academician alexander nikolayevich...

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Academician Alexander Nikolayevich Terenin (1896 – 1967)

Academician Alexander Nikolaevich Terenin was the leading scientist in the field of

photochemistry and photophysics in the former USSR. The scope of his scientific interests

was very broad, it extended from atoms to complex biological systems. His activity resulted

in a number of important scientific discoveries and in the inventions of new methods, which

now became conventional.

Suffice it to say about the experimental detection of photodissociation of simple molecules

by fluorescence of their radical products (1926), the discovery of extrafine structure of

atomic lines (1928), the hypothesis about triplet character of metastable state of aromatic

molecules (1943), the detection of spectral sensitization of internal photoeffect in

semiconductors (1948), the discovery of triplet-triplet energy transfer (1952) and pioneer

studies in the field of UV photoelectron spectroscopy (1961) and IR spectroscopy of surface

species (1940).

His works on photophysics and photochemistry of dyes, including chlorophyll and its

analogs, on photostimulated processes in heterogeneous systems, as well as on two-quanta

photoprocesses are widely known. His first paper, where IR spectroscopy was for the first

time applied to the study of adsorption, appeared already in 1940, much before such works

in other laboratories.

For many years A.N. Terenin was the scientific director of S.I. Vavilov State Optical

Institute, the head of the Spectroscopy Department of this Institute, and the head of

Department of Biomolecular and Photonic Physics in St.-Petersburg University.

A.N. Terenin took the active part in numerous international conferences and symposia. He

was a representative of the USSR in IUPAC (1957 – 1967) and a member of Advisory

Board of the international journal "Photochemistry and Photobiology" (1965 – 1967).

In 1958 A.N. Terenin was elected as a Honorary Member of the English Chemical Society

and the French Physico-Chemical Society. He was awarded with the Vavilov Gold Medal in

Physics (USSR, 1954), the Ciamician Gold Medal (Italy, 1959) and the Finzen Gold Medal

(England, 1964).

Now, a great number of Terenin's co-workers and followers, working now in many centres

of science of Russia, CIS and abroad, continue the development his scientific ideas.

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CONTENTS

PLENARY LECTURES

PERIODIC DFT AND VTIR STUDIES ON CO ADSORPTION IN ZEOLITES: SINGLE, DUAL

AND MULTIPLE CATION SITES

Arean C.O. .............................................................................................................................................. 21

PHOTOCHROMISM OF ORGANIC COMPOUNDS FOR INFORMATION PHOTONICS

Barachevsky V.A. .................................................................................................................................. 22

MOLECULAR SPECTROSCOPY WITH PLASMONIC EFFECTS

Gaponenko S.V. ..................................................................................................................................... 23

ACTUAL PROBLEMS OF PHOTONICS OF POLYMETHINE DYES AND LIGHT ENERGY

CONVERTERS BASED ON THEM

Ishchenko A.A. ....................................................................................................................................... 24

CONFORMATIONAL CHANGES IN CRYOGENIC MATRICES: MONOMERS, COMPLEXES,

AND REACTIONS

Khriachtchev L. ...................................................................................................................................... 25

LUMINESCENCE AND PHOTOCHEMICAL STUDIES OF SINGLET OXYGEN PHOTONICS

Krasnovsky A.A. .................................................................................................................................... 26

QUANTUM CONVERSION AND POWER GENERATION WITH DYE-SENSITIZED AND

HYBRID SEMICONDUCTOR PHOTOVOLTAIC CELLS

Miyasaka T. ............................................................................................................................................ 27

WHAT WE KNOW AND WE DO NOT KNOW IN PHOTOCATALYSIS: FROM

CONVENTIONAL TO PLASMONIC PHOTOCATALYSIS

Ohtani B. ................................................................................................................................................. 28

HISTORY AND DEVELOPMENT OF PHOTOCATALYSIS IN RUSSIA

Parmon V.N., Vorontsov A.V. .............................................................................................................. 29

SELF-CLEANING PROPERTIES OF TIO2-CONTAINING MATERIALS

Pichat P. .................................................................................................................................................. 30

ORALS

Section 1. Optical spectroscopy and photochemical processes in molecular and

supramolecular systems

IR SPECTRA OF OZONE IN LIQUID PHASE AND DISSOLVED IN LIQUID ARGON

Bulanin K.M., Kolomiitsova T.D., Bertsev V.V., Shchepkin D.N. .................................................... 31

LATERAL INTERACTIONS BETWEEN ADSORBED SF6 MOLECULES

Dobrotvorskaia A., Rudakova A., Shchepkin D., Kolomiitsova T., Petrov S., Volin R., Tsyganenko A. . 32

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SYSTEM OF DUPLEX ELECTRONIC LEVELS OF EOSIN

Goryachev N.S., Kotelnikov A.I., Schmitt F.-J., Renger G., Eichler H.J. ......................................... 33

ANALYSIS OF P-SYSTEM STRUCTURE FOR BRANCHED MACROMOLECULES ON THE

BASIS OF SPECTROPHOTOMETRY AND LUMINESCENCE DATA

Nurmukhametov R.N., Shapovalov A.V. ............................................................................................. 34

LUMINESCENCE AND ABSORPTION OF ACRIDINE HYDROGEN BONDED TO

CARBOXYLIC ACIDS AND ALCOHOLS

Rozhkova Y.A., Gurinov A.V., Tolstoy P.M., Shenderovich I.G., Korotkov V.I. ............................ 35

FTIR SPECTROSCOPY IN THE STUDIES OF SURFACE PHENOMENA

Tsyganenko A.A. ................................................................................................................................... 36

Section 2. Electron and energy transfer in molecular systems

PHOTOGENERATION OF CHARGE CARRIERS IN POLY-N-EPOXYPROPYLCARBAZOLE

FILMS DOPED WITH POLYMETHINE DYES

Afanasyev D.A., Ibrayev N.Kh., Ishchenko A.A., Davidenko N.A. .................................................. 37

SINGLET- SINGLET ENERGY TRANSFER BETWEEN TRYPTOPHANYL RESIDUE OF

HUMAN SERUM ALBUMIN AND EOSIN

Melnikov A.G., Melnikov G.V., Kochubey V.I., Pravdin A.B. ......................................................... 38

PHOTOPROCESSES IN SYNTHETIC AND NATURAL SENSITIZERS

Sokolova I.V., Tchaikovskaya O.N., Mayer G.V., Bryantseva N.G., Vershinin N.O., Nechaev L.V. ... 39

ABSORPTION SPECTROSCOPY OF CHARGE-TRANSFER COMPLEXES BETWEEN A

CONJUGATED POLYMER AND LOW-MOLECULAR-WEIGHT ACCEPTOR

Sosorev A. Yu., Kashtanov G.S., Zapunidy S.A., Paraschuk D.Yu. .................................................. 40

ENERGY MIGRATION IN NANOPARTICLES FROM LN(III) –ORGANIC COMPLEXES TO

DYES INCORPORATED IN THEM

Sveshnikova E.B., Ermolaev V.L., Mironov L.Yu., Dudar S.S. ......................................................... 41

Section 4. Photochemical processes in heterogeneous systems and heterogeneous

photocatalysis

ETHANOL VAPOR PHOTOCATALYTIC OXIDATION WITH URANYL MODIFIED SILICA,

ALUMINA AND TITANIA UNDER VISIBLE LIGHT

Filippov T.N., Kolinko P.A., Kozlov D.V. .......................................................................................... 42

SELF-SENSITIZATION OF PHOTOCATALYTIC PROPERTIES OF WIDE-BANDGAP

OXIDES USING INTRINSIC POINT DEFECTS

Lisachenko A.A. ..................................................................................................................................... 43

PHOTOINDUCED OXYGEN ISOTOPE EXCHANGE ON NANOSTRUCTURED METAL

OXIDES

Mikhaylov R.V., Titov V.V., Basov L.L., Lisachenko A.A. .............................................................. 44

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KINETICS OF CONTAMINANT ORGANIC FILM REMOVAL FROM PHOTOCATALYTIC

SELF-CLEANING SURFACES

Ollis D.F. ................................................................................................................................................ 45

PHOTOCATALYTIC ACTIVITY OF NANOSTRUCTURED CATION-ORDERED LAYERED

PEROVSKITE-TYPE TITANATES AND TANTALATES IN PROCESS OF WATER

SPLITTING

Rodionov I.A., Silyukov O.I., Zvereva I.A. ......................................................................................... 46

MECHANISMS OF RADICAL INTERMEDIATES FORMATION IN PHOTOSTIMULATED

PROCESSES ON OXIDE SURFACES

Volodin A.M., Malykhin S.E., Bedilo A.F. ......................................................................................... 47

TIO2-MXOY HETEROSTRUCTRUED PHOTOCATALYSTS. PREPARATION AND

PHOTOCATALYTIC STUDIES

Zhang X., Yang J., Wang C., Liu H., Liu Y. ........................................................................................ 48

Section 5. Photonics of model biological systems and biological molecules

PHOTOOXIDATION OF TETRAHYDROBIOPTERIN UPON UV-IRRADIATION: POSSIBLE

PATHWAYS AND MECHANISMS

Buglak A.A., Telegina T.A., Lyudnikova T.A., Vechtomova Y.L., Kritsky M.S. ............................ 49

EVIDENCE OF DNA MELTING IN BRILLOUIN LIGHT SCATTERING SPECTRA

Dmitriev A.V., Fedoseev A.I., Zakharov G.A., Lushnikov S.G., Savvateeva-Popova E.V. ............ 50

MODIFICATION OF PHOTONICS OF INDOLE CHROMOPHORE BY HALOGENATED

ORGANIC COMPOUNDS

Gurinovich V.V., Vorobey P.A., Pinchuk S.V., Vorobey A.V. .......................................................... 51

LIGHT INTERACTION WITH NUCLEIC ACIDS AND ORIGIN OF LIFE. TIGHTLY BONDED

STACKING AGGREGATES OF NUCLEIC BASES – THE FIRST LIFE SYSTEMS

Rapoport V.L. ......................................................................................................................................... 52

ULTRATHIN FILMS OF THE BACTERIORHODOPSIN AS PROMISING PHOTOSENSITIVE

NANOBIOMATERIALS

Solovyeva D.O., Zaitsev S.Yu. ............................................................................................................. 53

NON-PHOTOCHEMICAL FLUORESCENCE QUENCHING OF PHYCOBILISOMES IS A

NEW PHOTOBIOLOGICAL EFFECT FOUND IN CYANOBACTERIA

Stadnichuk I.N. ....................................................................................................................................... 54

PHOTOPHYSICAL PROPERTIES OF OLIGOMERIC CHAINS WITH PYRENE-MODIFIED

NUCLEOTIDES

Stasheuski A.S., Galievsky V.A. ........................................................................................................... 55

STUDY OF PHOTONICS OF POLYMETHINE DYES IN COMPLEXES WITH BIOMACRO-

MOLECULES FOR DEVELOPMENT OF NEW SPECTRAL-FLUORESCENT PROBES

Tatikolov A.S., Akimkin T.M., Pronkin P.G., Shvedova L.A., Yarmoluk S.M. ............................... 56

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LIGHT-DEPENDENT SYNTHESIS OF ATP FROM ADP ON PROTEINOID-SILICATE

MATRIX: A MODEL OF ABIOTIC PROCESS

Telegina T.A., Kolesnikov M.P., Buglak A.A., Vechtomova Yu.L., Kritsky M.S. .......................... 57

NANOBIOHYBRID STRUCTURES BASED ON ORGANIZED FILMS OF THE

PHOTOSENSITIVE MEMBRANE PROTEINS

Zaitsev S.Yu., Solovyeva D.O. ............................................................................................................. 58

Section 6. Photonics of molecular nano-systems

PHOTONICS OF UNSATURATED AND MACROCYCLIC COMPOUNDS. FROM

MOLECULES TO NANOSIZED SUPRAMOLECULAR SYSTEMS

Gromov S.P., Vedernikov A.I., Ushakov E.N., Kuzmina L.G., Alfimov M.V. ................................ 59

LUMINESCENCE QUENCHING OF CDSE/ZNS QUANTUM DOTS EMBEDDED IN POROUS

GLASS BY AMMONIA VAPOR

Gromova Yu. A., Orlova A.O., Maslov V.G., Baranov A.V., Andreeva O.V. .................................. 60

PHOTONICS OF MOLECULAR CLUSTERS IN RESTRICTED GEOMETRY SYSTEMS

Ibrayev N.Kh., Afanasyev D.A. ............................................................................................................ 61

PHOTONICS OF METAL ALKANOATE NANOCOMPOSITES

Klimusheva G.V., Mirnaya T.A., Garbovskiy Yu.A., Bugaychuk S.A., Melnik D.A., Tolochko A.S.,

Tokmenko I.I., Asaula V.V. .................................................................................................................. 62

HYBRID NANOSTRUCTURES ON THE BASIS OF WATER SOLUBLE FULLERENE

DERIVATIVES AND DAYS FOR PHOTODYNAMIC THERAPY

Kotelnikov A.I., Rybkin A.Yu., Goryachev N.S., Kornev A.B., Khakina E.A., Troshin P.A. ........ 63

MAGNETIC FIELD EFFECT ON INTERMOLECULAR RADIATIONLESS ENERGY

TRANSFER NEAR METALLIC NANOPARTICLE

Kucherenko M.G., Penkov S.A. ............................................................................................................ 64

THE EFFECT OF CYANINE DYES ON PHOTOREFRACTIVE PROPERTIES OF

COMPOSITES BASED ON CARBON NANOTUBES

Laryushkin A.S., Grishina A.D., Krivenko T.V., Savel’ev V.V., Vannikov A.V., Rychwalski R.W. 65

SPECTRAL AND PHOTOCHEMICAL PROPERTIES OF SEMICONDUCTOR QUANTUM

DOTS IN SELF-ORGANIZED STRUCTURES

Maslov V.G., Adrianov V.E., Orlova A.O., Baranov A.V., Fedorov A.V. ........................................ 66

THE DEMONSTRATION OF THE "QUASI-ATOMIC" STRUCTURE OF NANOPARTICLES

OF SILVER AND GOLD IN INORGANIC GLASSES

Nikonorov N.V., Sidorov A.I., Tsekhomsky V.A., Vartanjan T.A. ................................................... 67

HOW THE BINDING TYPE AFFECTS THE PHOTOPHYSICAL PROPERTIES OF THE

COMPLEXES OF QUANTUM DOTS WITH TETRAPYRROLES

Orlova A.O., Gubanova M.S., Martynenko I.V., Maslov V.G., Baranov A.V., Fedorov A.V. ........ 68

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CONTROL OF PHOTOCHEMICAL PROPERTIES OF ULTRATHIN FILMS OF AMPHIPHILIC

CROWN-SUBSTITUTED HEMICYANINE DYES

Selektor S.L., Silantyeva D.A., Batat P., Jonusauskas G., Arslanov V.V. ......................................... 69

Section 7. Photochromism of organic compounds

HYBRID PHOTOCHROMIC SYSTEMS: INSIGHTS INTO STRUCTURE AND MECHANISM

Fedorova O.A., Berdnikova D.V., Sergeeva A.N., Panchenko P.A., Fedorov Yu. V., Lokshin V.,

Delbaere S. ............................................................................................................................................. 70

FLUORESCENCE SWITCHING OF DYADS AND SILICA NANOPARTICLES BASED ON

PHOTOCHROME-FLUOROPHORE COMBINATION

Ouhenia K., Metivier R., Maisonneuve S., Jacquart A., Xie J., Leaustic A., Yu P., Nakatani K. .... 71

THE AMBIGUOUS ROLE OF WEAK IRREVERSIBLE CHANNEL IN A SYSTEM OF

REVERSIBLE PHOTOCONVERSIONS: PROVITAMIN D PHOTOISOMERIZATION

Terenetskaya I.P. .................................................................................................................................... 72

PHOTOPROCESSES IN NOVEL HYBRID COMPOUND INDUCED BY PHOTOEXCITATION

WITH LIGHT OF DIFFERENT WAVELENGTHS

Zaichenko N.L., Levin P.P., Tatikolov A.S., Shienok A.I., Koltsova L.S., Mardaleishvili I.R.,

Popov L.D., Levchenkov S.I., Berlin A.A. .......................................................................................... 73

Section 8. Applied molecular photonics

CYCLOMETALATED PLATINUM(II) COMPLEXES CONTAINING PYRAZOLONATE

LIGANDS AS HIGHLY LUMINESCENT EMITTERS FOR ORGANIC LIGHT-EMITTING

DIODES (OLEDS)

Begantsova Yu. E., Bochkarev L.N., Ilichev V.A. .............................................................................. 74

PHOTONIC MOLECULAR LOGIC GATES: HOW IT CAN BE DONE

Budyka M.F. ........................................................................................................................................... 75

PEG-ORGANIZED BIOCOMPATIBLE FLUORESCENT NANOPARTICLES DOPED WITH

NOVEL CYANOPORPHYRAZINE CHROMOPHORES FOR BIOPHOTONIC APPLICATIONS

Grigoryev I.S., Klapshina L.G., Lermontova S.A., Shirmanova M.V., Balalaeva I.V., Zagaynova E.V.,

Lekanova N.Yu. ...................................................................................................................................... 76

PHOTONICS OF DIPYRROMETHENE COORDINATING COMPLEXES FOR OPTICAL

DEVICES CREATION

Kuznetsova R.T., Aksenova Yu.V., Bashkirtsev D.E., Kopylova T.N., Mayer G.V., Telminov E.N.,

Antina E.V., Antina L.A., Berezin M.B., Guseva G.B., Yutanova S.L., Semeikin A.S. .................. 77

ALKOXYNAPHTHALIMIDE DERIVATIVES AS THE ACTIVE COMPONENTS OF OPTICAL

MOLECULAR DEVICES

Sergeeva A.N., Panchenko P.A., Fedorova O.A., Fedorov Yu.V. ...................................................... 78

LUMINESCENT HYBRID NANOCOMPOSITES AND PROSPECTS OF MOLECULAR AND

NANOPHOTONIC SYSTEMS IN MODERN PACKAGING AND PRINTING

Sherstyuk V.P., Sarapulova O.O., Shvalagin V.V. .............................................................................. 79

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PHOTOPHYSICAL PROPERTIES OF COPOLYFLUORENES IN SOLUTION AND BULK

Smyslov R.Yu., Nosova G.I., Solovskaya N.A., Zhukova E.V., Berezin I.A., Yakimansky A.V.,

Maltsev E.I., Lypenko D.A., Vannikov A.V. ....................................................................................... 80

SECOND-ORDER NON-LINEAR OPTICAL PROPERTIES OF CHROMOPHORE-

CONTAINING POLYIMIDES

Yakimansky A.V., Nosova G.I., Solovskaya N.A., Zhukova E.V., Smirnov N.N., Gorkovenko A.I.,

Simanchuk A.E., Plekhanov A.I. .......................................................................................................... 81

POSTERS

Section 1. Optical spectroscopy and photochemical processes in molecular and

supramolecular systems

PHOTOPROCESSES IN STYRYL DYES AND THEIR PSEUDOROTAXANE COMPLEXES

WITH CUCURBIT[7]URIL

Atabekyan L.S., Vedernikov A.I., Avakyan V.G., Lobova N.A., Gromov S.P., Chibisov A.K. ..... 82

IR SPECTRUM, HYDROGEN BOND AND STRUCTURE OF 2,3-DI-О-NYTRO-METHYL-

BETA-D-GLUCOPYRANOSIDE

Babkov L.M., Ivlieva I.V., Korolevich M.V. ....................................................................................... 83

LINKAGE ISOMERISM OF CO ADSORBED ON ALKALI-HALIDES

Belykh R.A., Tsyganenko A.A. ............................................................................................................ 84

EFFECT OF LINEAR AND ANGULAR BENZO-ANNELATION ON SPECTRAL AND

PHOTOCHEMICAL PROPERTIES OF 2-STYRYLQUINOLINE

Budyka M.F., Lee V.M., Potashova N.I., Gavrishova T.N. ................................................................ 85

POLYMORPHISM OF PHENYL-2-HYDROXYBENZOATE STUDIED BY LUMINESCENCE

AND IR SPECTROSCOPY

Davydova N.A., Klishevich G.V., Melnik V.I., Reznichenko V.Ya. ................................................. 86

N-METHYLAZACROWN-CONTAINING STYRYL DYES AS OPTICAL MOLECULAR

SENSORS FOR METAL CATION

Dmitrieva S.N., Ushakov E.N., Vedernikov A.I., Kurchavov N.A., Freidzon A.Ya., Kuzmina L.G.,

Sazonov S.K., Bagaturyants A.A., Alfimov M.V., Gromov S.P. ....................................................... 87

THE FLUORESCENCE QUENCHING OF TRYPTOPHAN BY GOLD NANOPARTICLES IN

COLLOIDS AND ON THE SURFACE OF AU/SIO2

Eremenko A.M., Smirnova N.P., Mukha I.P., Naumenko A.P., Belyy N.M. .................................... 88

SYNTHESIS AND LUMINESCENT PROPERTIES OF TRIS-DIKETONATE COMPLEXES OF

EU (III) AND TB (III) WITH PYRIDINE LIGANDS IN SOLUTIONS

Fomina M.V., Vannikov A.V., Lypenko D.A., Mal’tsev E.I., Pozin S.I., Koshkin A.V.,

Kuz’mina L.G., Alfimov M.V., Gromov S.P. ...................................................................................... 89

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SIMULATION OF ABSORPTION AND EMISSION SPECTRA OF NILE RED DYE AND ITS

COMPLEXES WITH SOME ANALYTES FOR VIRTUAL DESIGN OF MOLECULAR

CHEMOSENSORS

Freidzon A.Ya., Safonov A.A., Bagaturyants A.A. ............................................................................. 90

MULTISCALE APPROACH TO THE STRUCTURE AND SPECTRA OF NILE RED

ADSORBED ON POLYSTYRENE NANOPARTICLES

Freidzon A.Ya., Tikhomirov V.A., Odinokov A.V., Bagaturyants A.A. ........................................... 91

LUMINESCENCE OF SOLUTIONS OF THE N-PHENYLANTHRANILIC ACID

Galkin V.P., Klemesheva N.A., Mazyrin D.V., Nosova D.A., Rozhkova Y.A., Visotskaya S.O.,

Zarochentseva E.P., Korotkov V.I. ....................................................................................................... 92

FTIR STUDY OF ADSORBED CF4

Gatilova A.V., Shchepkin D.N., Kolomiitsova T.D., Tsyganenko A.A. ............................................ 93

THE COMPONENT ANALYSIS A EOSINE LUMINESCENCE

Goryachev N.S. ...................................................................................................................................... 94

THE EFFECT OF MEDIUM ACIDITY ON PHOTOPHYSICAL AND PHOTOCHEMICAL

PROPERTIES OF HEMIN IN AQUEOUS SOLUTIONS

Gradova M.A., Lobanov A.V. ............................................................................................................... 95

ABSORPTION OF GASEOUS NAPHTHALENE BY THE ORDERED LAYERS OF SUB-

MICROPARTICLES WITH THE NANOPOROUS SHELL OF POLY(ETHYLENE GLYCOL

DIMETHACRYLATЕ)

Grushnikova E.Yu., Koshkin A.V., Menshikova A.Yu., Lebedev-Stepanov P.V. ............................ 96

NEAR-INFRARED SQUARATE AND CROCONATE DIANIONS DERIVED FROM

TETRANITROFLUORENE

Ishchenko A.A., Kurdiukova I.V., Kulinich A.V. ............................................................................... 96

PHOTO-PHYSICAL PROPERTIES OF A FLUORESCENT CYANINE-DYE IN BINARY

MIXTURES OF IONIC LIQUIDS WITH DIMETHYL SULFOXIDE

Ivanov D.A., Petrov N.Kh., Klimchuk O., Billard I. ........................................................................... 98

AQUEOUS SOLUTIONS OF STYRYL DYE IN THE PRESENCE OF CUCURBIT[8]URIL:

PHOTO-PHYSICAL QUANTITATIVE PROPERTIES

Ivanov D.A., Petrov N.Kh., Vedernikov A.I., Gromov S.P. ............................................................... 99

PECULIARITIES OF PROVITAMIN D PHOTOCHEMISTRY IN LIQUID-CRYSTALLINE

MATRICES

Kapinos P.S., Orlova T.N., Terenetskaya I.P. .................................................................................... 100

QUANTUM- CHEMICAL INVESTIGATION OF SPECTRAL-LUMINESCENT PROPERTIES

OF SOME POLYMETHINE BIS-CHROMOPHORES AND BISMEROCYANINES LINKED BY

BUTADIENE SKELETON

Kashapova E.R., Artyukhov V.Ya., Mayer G.V. ............................................................................... 101

EFFECT OF INTERMOLECULAR INTERACTIONS ON SPECTRAL-LUMINESCENT

PROPERTIES OF POLYATOMIC MOLECULES

Komarov P.V., Plotnikov V.G. ........................................................................................................... 102

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SIMULATION OF THE RADIATION LIFETIME OF PHOSPHORESCENT EMITTERS BASED

ON CYCLOMETALLATED IRIDIUM COMPLEXES

Komarova K.G., Bagatur’yants A.A., Alfimov M.V. ........................................................................ 103

DETERMINE AND COMPARATIVE ANALYSIS OF PARAMETERS OF INTRAMOLECULAR

INTERACTION FROM SPECTRA OF ALL-TRANS-DIPHENYLBUTADIENES IN RIGID

MATRICES

Kompaneez V.V., Vasilyeva I.A. ......................................................................................................... 104

THEORETICAL AND EXPERIMENTAL STUDY OF PHOTOPHYSICAL PROPERTIES OF

SOME DERIVATIVES OF DIBENZOYLMETHANATOBORON DIFLUORIDE

Kopysov V.N., Sazhnikov V.A., Alfimov M.V. ................................................................................ 105

SPECTRAL-LUMINESCENT PROPERTIES OF LIGANDS IN STRUCTURE OF TRIS(8-

HYDROXYQUINOLINE)ALUMINUM(III)

Krivonogova K.Yu, Artyukhov V.Ya. ................................................................................................ 106

PHOTOSTABILITY STYRYLCYANINE DYE SBT AND ITS HOMODIMER IN SOLUTIONS

Kurtaliev E.N., Nizomov N. ................................................................................................................ 107

OPTICAL PROPERTIES OF NANODIAMOND OF DETONATION SYNTHESIS

Lapina V.A., Bushuk B.A., Bushuk S.B. ........................................................................................... 108

PHOTOSENSITIVE SYSTEMS BASED ON STYRYL DYES IN SOLID STATE AND IN

SOLUTION: DIMERIZATION AND AUTOPHOTOCYCLOADDITION

Lobova N.A., Vedernikov A.I., Kuz’mina L.G., Alfimov M.V., Gromov S.P. ............................... 109

LINKAGE ISOMERISM IN LAYERED SILICATES

Maevsky A.V., Tsyganenko A.A., Baskakova M.V. ......................................................................... 110

IN SITU RAMAN PROBE OF MOLECULAR ORDER IN ORGANIC PHOTOVOLTAIC CELL

Mannanov A.A., Bruevich V.V., Paraschuk D.Yu. ........................................................................... 111

THERMODYNAMIC STABILITY AND SPECTRAL PROPERTIES OF THE

SUPRAMOLECULAR COMPLEXES OF BIS(18-CROWN-6)AZOBENZENE WITH

AMMONIOALKYL DERIVATIVES OF HETEROCYCLIC COMPOUNDS

Martyanov T.P., Ushakov E.N., Efremova A.A., Gromov S.P. ........................................................ 112

QUANTUM-CHEMICAL INTERPRETATION OF THE SPECTROSCOPY OF HIGHLY

LUMINESCENT 1,3,5-TRIAZAPENTADIENE COMPLEXES OF PLATINUM(II)

Maslov V.G., Lyalin G.N. ................................................................................................................... 113

SPECTRAL AND ELECTROCHEMICAL PROPERTIES OF CRYSTAL VIOLET IN

COMPLEXES WITH ANIONIC CALIXRESORCIN[4]ARENES. SUPRAMOLECULAR

ENHANCERS OF RADIATION

Mironova D.A., Morozova Ju.E., Yanilkin V.V., Syakaev V.V., Kazakova E.Kh., Kazakova E.Kh.,

Konovalov A.I. ..................................................................................................................................... 114

APPLICATION OF ISOTOPIC SUBSTITUTION IN THE IR STUDIES OF LINKAGE

ISOMERISM

Petrov S.N., Tsyganenko A.A., Rudakova A.V., Smirnov K.S. ....................................................... 115

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LOCALIZATION OF WATER SOLUBLE POLYSUBSTITUTED FULLERENE DERIVATIVES

IN MEMBRANE OF PHOSPHATIDYLCHOLINE LIPOSOMES

Poletaeva D.A., Kotelnikova R.A., Kornev A.B., Khakina E.A., Troshin P.A., Kotelnikov A.I. .. 116

INVESTIGATION OF THE EXCITED STATE NATURE OF BORON DIFLUORIDE

ACETYLACETONATES

Portnyagin A.S., Korochentsev V.V., Shapkin N.P., Svistunova I.V. ............................................. 117

CLUSTERING OF ADSORBED ACRIDINE MOLECULES ON AMORPHOUS SILICA

SURFACES

Rozhkova Y.A., Gurinov A.V., Orlova A.O., Maslov V.G., Korotkov V.I. .................................... 118

FTIR STUDY OF OZONOLYSIS OF C2H4-XCLX ADSORBED ON WATER ICE, SIO2, AND TIO2

Rudakova A.V., Zakharov N.V., Tsyganenko N.M., Bulanin K.M., Tsyganenko A.A. ................. 119

FLUORESCENCE OF IRRADIATED POLYTETRAFLUOROETHYLENE

Sakhno T.V., Seliverstov D.I., Konova E.M., Sakhno Yu.E., Sychkova S.T., Khatipov S.A. ....... 120

PHOTOCORRELATION AND FLOURESCENCE SPECTRISCOPY METHODS OF

RHODAMINE 6G AND SILVER NANOPARTICLES DYNAMICS IN EVAPORATING DROP

Samusev I.G., Bryukhanov V.V., Myslitskaya N.A., Khitrin A.V., Ivanov A.M. .......................... 121

FLUORESCENCE ENHANCEMENT OF ORGANOLUMINOPHORES IN POLYMER AND ON

SILICON DIOXIDE SURFACE WITH GENERATION OF SURFACE PLASMONS IN ROUGH

SILVER FILM AND SILVER NANOPARTICLES

Samusev I.G., Bryukhanov V.V., Slezhkin V.A., Gorlov R.V., Tikhomirova N.S. ........................ 122

SYNTHESIS, STRUCTURE AND SPECTRAL PROPERTIES OF 9-DIARYLAMINO-

SUBSTITUTED ACRIDINES

Sazonov S.K., Vedernikov A.I., Sazhnikov V.A., Khlebunov A.A., Kuzmina L.G., Gromov S.P.,

Alfimov M.V. ....................................................................................................................................... 123

PECULIARITIES OF THE REFLECTION AND ABSORPTION SPECTRA OF LANGMUIR

MONOLAYERS UNDER NORMAL INCIDENCE OF LIGHT ONTO THE SAMPLE

Selektor S.L., Stuchebryukov S.D. ..................................................................................................... 124

SYNTHESIS AND PHOTOLUMINESCENT PROPERTIES OF LANGMUIR FILMS OF

COUMARIN DYES AND POLYAMPHOLYTIC POLYMER

Seliverstova E.V., Ibrayev N.Kh., Alekseeva V.I., Marinina L.E., Savvina L.P. ............................ 125

OPTICAL ABSORPTION AND PHOTOCATALYTIC PROPERTIES OF TITANIUM-

MANGANESE OXIDES

Shymanovska V.V., Kernazhitsky L.A., Gavrilko T.A., Naumov V.V., Khalyavka T.V.,

Kshnyakin V.C. ........................................................................................................................................................ 126

EFFECT OF STERIC STRUCTURE OF POLYMETHINE MOLECULES ON THE

COMPONENT COMPOSITION OF MOLECULAR LAYERS OF THESE COMPOUNDS

Starovoytov A.A., Kaliteevskaya E.N., Krutyakova V.P., Razumova T.K., Shchedrin P.V. ......... 127

NEAR INFRARED LIFETIME SPECTROMETER FOR SINGLET OXYGEN DETECTION

Stasheuski A.S., Galievsky V.A., Dzhagarov B.M. ........................................................................... 128

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PHOTONICS OF 5-FLUOROURACIL AND 5-HYDROXY-6-METHYL-(1-THIETANYL-

3)PYRIMIDINE-2,4(1Н,3Н)-DION IN SOLUTIONS

Sultanbaev M.V., Ostakhov S.S., Khursan S.L., Gantsev Sh.Kh. .................................................... 129

COMPARATIVE SPECTRAL-LUMINESCENT STUDY OF KETO-ENOL EQUILIBRIUM OF

5-FLUOROURACIL AND TEGAFUR IN WATER SOLUTIONS

Sultanbaev M.V., Ostakhov S.S., Khursan S.L., Gantsev Sh.Kh. .................................................... 130

PHTHALOCYANINE TRIPLET STATES ON THE NANO-SIZED SILICA IN AQUEOUS

SOLUTIONS

Sultimova N.B., Levin P.P., Lobanov A.V., Gradova M.A., Razina V.S. ....................................... 131

SPECTRAL-FLUORESCENT PROPERTIES AND ISOMERIZATION OF MEROCYANINES

CONTAINING NITRILE GROUPS AS ACCEPTORS

Tatikolov A.S., Shvedova L.A., Krasnaya Zh.A. .............................................................................. 132

LIGHT-INDUCED MID-INFRARED EMISSION OF LIQUID CARBON TETRACHLORIDE

AND BENZENE

Terpugova S.E., Degtyareva O.V., Savransky V.V., Terpugov E.L. ............................................... 133

MICROMACHINING OF THE TRANSPARENT LIQUIDS BY USE OF A LOW-INTENSE

VISIBLE LIGHT

Terpugova S.E., Degtyareva O.V., Savransky V.V., Terpugov E.L. ............................................... 134

A COMBINED THEORETICAL AND EXPERIMENTAL STUDY OF AN ORGANIC

MOLECULE – FLUORESCENT PROBE (LAURDAN)

Titova T.Yu., Artyukhov V.Y. ............................................................................................................ 135

PSEUDOROTAXANE COMPLEXES BETWEEN AZASTILBENES AND

CUCURBIT[N]URILS AND THEIR PHOTOCHEMISTRY

Vedernikov A.I., Lobova N.A., Kuzmina L.G., Sazonov S.K., Alfimov M.V., Gromov S.P. ....... 136

EFFECT OF POLYACRYLIC ACID SHELL ON LUMINESCENCE AND

PHOSPHORESCENCE OF ZNCDS NANOPARTICLES

Volkova E.K., Kochubey V.I., Konyukhova Ju.G. ............................................................................ 137

THE SPECTRAL AND LUMINESCENCE PROPERTIES OF METAL PHTHALOCYANINE

WITH STYRYL AND (THIOPHEN-2-YL)VINYL SUBSTITUENTS

Ziminov A.V., Bukov V.A., Yourre T.A., Ramsh S.M., Litke S.V. ................................................ 138

Section 2. Electron and energy transfer in molecular systems

PHOTOGENERATION OF CHARGE CARRIERS IN COPPER PHTHALOCYANINE–

ANTHRACENE HETEROSTRUCTURE

Aimukhanov A.K., Afanasyev D.A., Ibrayev N.Kh. ......................................................................... 139

PHOTONIC OF POLYPHENYLQUINOLINES – OPTOELECTRONIC MATERIALS WITH

EFFICIENT INTRAMOLECULAR CHARGE TRANSFER

Aleksandrova E.L., Svetlichnyi V.M., Miagkova L.A., Matyushina N.V., Nekrasova T.N.,

Smyslov R. Yu., Tameev A.R. ............................................................................................................ 140

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OPTIMALITY OF INTERFACING OF B740 , B798 AND B808 SUBANTЕNNAE IN LIGHT-

HARVESTING SUPERANTENNA OF THE PHOTOSYNTHETIC GREEN BACTERIUM

CHLOROFLEXUS AURANTIACUS

Fetisova Z.G., Yakovlev A.G., Taisova A.S., Novoderezhkin V.I. .................................................. 141

ENERGY TRANSFER IN HYDROGEN-BONDED DOPED POLYCRYSTALS OF BENZOIC

ACID DERIVATIVES

Galkin V.P., Klemesheva, N.A., Nosova D.A., Mazyrin D.V., Rozhkova Y.A., Vysotskaya S.O.,

Zarochentseva E.P. ............................................................................................................................... 142

MANIFESTATION OF THE INERTIAL COMPONENT OF MEDIUM RELAXATION IN

KINETICS OF NONEQUILIBRIUM ELECTRON TRANSFER IN RUTHENIUM(II)-

COBALT(III) COMPOUNDS

Kichigina A.O., Ivanov A.I. ................................................................................................................ 143

EXCIPLEX ELECTROLUMINESCENCE SPECTRA IN THE NEW ZINC COMPLEXES WITH

SULPHANYLAMINOSUBSTITUTED BENZOTHIAZOLES AND QUINOLINES

Krasnikova S.S., Kaplunov M.G., Yakushchenko I.K. ..................................................................... 144

EFFICIENCY OF THE ENERGY TRANSFER IN THE STRUCTURES BASED ON QUANTUM

DOTS CDSE/ZNS AND THE PORPHYRIN MOLECULES IN THE POLYMER PORE TRACK

MEMBRANES

Kurochkina M.A., Orlova A.O., Maslov V.G., Baranov A.V., Artemyev M.V. ............................. 145

THE NONEQUILIBRIUM ELECTRON PROCESSES IN THE PYROLYTIC CDS FILMS

Maiorova T.L., Klyuev V.G., Mihalevskiy A.A., Bezdetko J.S. ...................................................... 146

DECREASE OF INTER-MOLECULAR ENERGY LOSSES IN SOLUTIONS OF LANTHANIDE

COMPLEXES

Meshkova S.B., Kiriyak A.V., Topilova Z.M., Doga P.G. ............................................................... 147

ZINC COMPLEXES WITH SULFANILAMINOSUBSTITUTED LIGANDS: ELECTROLU-

MINESCENCE AND PHOTOSENSITIVITY

Nikitenko S.L., Kaplunov M.G. .......................................................................................................... 148

PHOTOLUMINESCENT PROPERTIES OF BLENDS OF COPOLYFLUORENES

CONTAINING BENZTHIADIAZOLE, NAPHTHALIMIDE, AND NILE RED FRAGMENTS

Nosova G.I., Smyslov R. Yu., Zhukova E.V., Solovskaya N.A., Berezin I.A., Yakimansky A.V. 149

PRINCIPLES OF CONTROL OF MOLECULAR SWITCHES OF "ON1-ON2-OFF" TYPE

Rogozina M.V., Mikhailova V.A., Ivanov A.I. ................................................................................. 150

THE INFLUENCE OF WATER ON PRIMARY CHARGE SEPARATION IN BACTERIAL

REACTION CENTERS

Yakovlev A.G., Shkuropatov A.Ya., Shuvalov V.A. ........................................................................ 151

Section 3. Gas-phase photoprocesses

HBR PHOTODISSOCIATION ANALYSIS AS THE CALIBRATION OF TWO-COLOR 3D

VELOCITY MAP IMAGING SETUP

Poretskiy M.S., Veckenstedt M., Maul H.C., Gericke K.-H. ............................................................ 152

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INVESTIGATION OF SUPEREXCITED STATES OF ORTHO-PARA DEUTERIUM

MOLECULES IN THE WAVELENGTH REGION FROM 70.8 TO 71.35 NM

Smolin A.G., Mo Y., Vasyutinskii O.S. ............................................................................................. 153

Section 4. Photochemical processes in heterogeneous systems and heterogeneous

photocatalysis

PHOTOPHYSICAL AND PHOTOCHEMICAL PROPERTIES OF COVALENT CONJUGATES

OF AQUA PLATINUM (II) AND OCTACARBOXY-SUBSTITUTED ZINC

PHTHALOCYANINE

Bulgakov R.A., Kuznetsova N.A., Dolotova O.V., Kaliya O.L., Nyokong T. ................................ 154

PHOTOSORPTION OF OXYGEN AND HYDROGEN ON THE SAMPLES OF MAGNESIA

OBTAINED IN DIFFERENT WAYS

Ekimova I.A., Minakova T.S., Ryabchuk V.K. ................................................................................. 155

SYNCHRONIZATION OF PHOTOCHEMICAL PROCESSES AND PHOTOINDUCED SELF-

ORGANIZATION IN DISPERSED SEMICONDUCTORS UNDER OPTICAL PUMPING

Gradov O.V., Gradova M.A. ............................................................................................................... 156

PHOTOACTIVE NANOCRYSTALLINE TIO2 BASED COATING FOR THE

PHOTOCATALYTIC DECOMPOSITION OF DYE IN A FLOW TYPE REACTOR

Kalinkina L.M., Rodionov I.A., Zvereva I.A. .................................................................................... 157

ANILINES PHOTOOXIDATION SENSITIZED BY IMMOBILIZED PHTHALOCYANINES

Kuznetsova N.I., Egorova O.Yu., Shevchenko E.N., Fedorova T.M., Derkacheva V.M., Kaliya O.L.

................................................................................................................................................................ 158

GAS AND IRRADIATION INFLUENCE ON THE PROPRIETIES OF THIN LAYERS OF TIO2

DEPOSITED ON SILICON BY ATOMIC LAYER DEPOSITION

Laptenkov D.V., Mikhaylov R.V., Basov L.L., Lisachenko A.A. .................................................... 159

INVESTIGATION OF THE FEATURES OF THE REACTION CO+NO+HV ->1/2N2+CO2 ON

TIO2 HOMBIFINE N UNDER VISIBLE LIGHT IRRADIATION

Mikhaylov R.V., Glazkova N.I., Nikitin K.V. ................................................................................... 160

FTIR AND TPD STUDY OF INTERACTION OF NO–OXYGEN MIXTURE AND NO2 WITH

TIO2 PHOTOCATALYST

Mikhaylov R.V., Lisachenko A.A., Shelimov B.N., Kazansky V.B., Martra G., Coluccia S. ....... 161

TIO2/SIO2 AND TIO2/AL2O3 PHOTOCATALYSTS FOR DEGRADATION OF WATER

POLLUTANTS

Nikitich M.P., Samoilov A.V., Vodyankin A.A., Emelyanova E.V., Vodyankina O.V. ................ 162

THE KINETICS OF COLOR CENTER FORMATION IN WIDE BAND GAP

PHOTOCATALYSTS AS A WAY TO DISTINGUISH BETWEEN CATALYTIC AND NON

CATALYTIC SURFACE PHOTO REACTIONS

Ryabchuk V.K., Kataeva G.V., Emeline A.V. ................................................................................... 163

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15

Section 5. Photonics of model biological systems and biological molecules

LUMINESCENCE QUENCHING OF ORGANIC DYES IN LIVING BIOLOGICAL TISSUES

Kuvandykova A.F., Letuta S.N., Pashkevich S.N. ............................................................................ 164

PRIMARY SITE OF NON-PHOTOCHEMICAL QUENCHING OF THE PHYCOBILISOME BY

ORANGE CAROTENOID PROTEIN IN THE CYANOBACTERIUM SYNECHOCYSTIS SP.

PCC 6803

Stadnichuk I.N., Yanyushin M.F., Maksimov E.G., Lukashev E.P., Zharmukhamedov S.K.,

Elanskaya I.V., Paschenko V.Z. .......................................................................................................... 165

ELECTRONIC EXCITATION ENERGY TRANSFER BETWEEN OXA- AND

THIACARBOCYANINE DYES IN COMPLEXES WITH DNA: FLUORESCENCE DECAY

KINETICS AND DISTANCE DISTRIBUTION IN DONOR–ACCEPTOR PAIRS

Tatikolov A.S., Pronkin P.G. ............................................................................................................... 166

Section 6. Photonics of molecular nano-systems

PROPERTIES OF DELAYED LUMINESCENCE OF MOLECULAR CLUSTERS EMBEDDED

INTO ANODIZED ALUMINUM PORES

Aimukhanov A.K., Zeinidenov A.K., Ibrayev N.Kh., Kubenova M.M., Seisenbayeva G.S. ......... 167

SPECTRAL PROPERTIES OF THE ORGANISED MOLECULAR SYSTEMS

Artyukhov V.Ya., Mayer G.V. ............................................................................................................ 168

THE PHOTOPHYSICAL PROPERTIES OF THE COMPLEXES CDSE/ZNS QUANTUM DOTS

WITH THE PTHALOCYANINE MOLECULES IN AQUEOUS MEDIA

Bakanov А.G., Оrlova A.O., Маslov V.G., Baranov A.V., Artemyev М.V. ................................... 169

ON THE FORM OF SIZE DISTRIBUTION FUNCTION OF QUANTUM DOTS

Bodunov E.N., Berberan-Santos M.N., Pogliani L. ........................................................................... 170

OPTICAL PROPERTIES OF TWO-DIMENSIONAL (2D) CDSE NANOSTRUCTURES

Cherevkov S.A., Baranov A.V., Artemyev M.V., Prudnikau A.V. .................................................. 171

OPTICAL LIMITING IN HYBRID SYSTEMS, INCLUDING SEMICONDUCTOR

NANOPARTICLES CDSE / ZNS

Danilov V.V., Panfutova A.S., Ermolaeva G.M., Vedenichev D.A., Gromova E.S., Khrebtov A.I.,

Shakhverdov T.A. ................................................................................................................................ 172

FUNDAMENTAL ABSORPTION OF NICKEL OXIDE NANOCRYSTALS

Kim G.A., Sokolov V.I., Druzhinin A.V., Gruzdev N.B., Yermakov A.Ye., Uimin M.A., Byzov I.V.

................................................................................................................................................................ 173

KINETIC LENS EFFECT IN INTERMOLECULAR ENERGY TRANSFER NEAR METALLIC

NANOPARTICLE WITH MACROMOLECULAR COVER

Kucherenko M.G., Izmodenova S.V., Chmereva T.M. ..................................................................... 174

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PHOTOPHYSICAL PROPERTIES OF COMPLEXES FORMED BY THE SEMICONDUCTOR

QUANTUM DOTS AND CHLORINE E6 MOLECULES

Martynenko I.V., Orlova A.O., Maslov V.G., Baranov A.V., Artemyev M.V. ............................... 175

PHOTONICS OF 6-PYRAZOLYL(ISOXAZOLYL)-7-HYDROXYCOUMARINS

Moskvina V.S., Khilya V.P., Ishchenko A.A. .................................................................................... 176

TUNABLE ORGANIC LASERS SIMULATION

Nikonov S.Yu., Gadirov R.M., Artukhov V.Ya., Kopylova T.N. .................................................... 177

STRUCTURE AND SPECTRAL-LUMINESCENT PROPERTIES OF

BISINDOTRICARBOCYANINE DYES WITH UNCONJUGATED CHROMOPHORES

Osmanova E.Ia., Derevyanko N.A., Ishchenko A.A. ........................................................................ 178

OPTICAL PROPERTIES OF ORGANOSILICON POLYMER NANOAGGREGATES

Ostapenko N.I., Kerita O., Ostapenko Yu.V. ..................................................................................... 179

DFT MODELING OF THE ADSORPTION OF AU ATOMS ON THE INAS(001) BETA2-

SURFACE: THE CLUSTER APPROACH

Podkopaeva O.Yu., Chizhov Yu.V., Krauklis I.V. ............................................................................ 180

THE NOVEL OPTICAL PROPERTY OF SUPRAMOLECULAR SYSTEMS INVOLVING

SILVER NANOPARTICLES AND IONIC SURFACTANTS

Romanovskaya G.I., Koroleva M.V. .................................................................................................. 181

HYBRID MOLECULAR SYSTEMS BASED ON FULLERENE DERIVATIVE AND DYE AS

POTENTIAL DRUGS FOR PHOTODYNAMIC THERAPY

Rybkin A.Yu., Barinov A.V., Goryachev N.S., Kornev A.B., Troshin P.A., Kotelnikov A.I. ....... 182

STRUCTURE AND SPECTRAL-LUMINESCENT PROPERTIES OF

INDODICARBOCYANINE AGGREGATES

Shargaeva A.Yu., Kulinich A.V., Slominskii Yu.L., Ishchenko A.A. ............................................. 183

OPTICAL PROPERTIES OF CYANINE DYE LAYERS MODIFIED BY PLASMONIC

NANOPARTICLES

Toropov N.A., Kaliteevskaya E.N., Leonov N.B., Vartanyan T.A. ................................................. 184

PHOTOCHROMIC HYBRID NANOSYSTEMS BASED ON DIARYLETHENES

Vasilyuk G.T., Maskevich S.A., Askirka V.F., German A.E., Kurkhuzenkov S.A., Sveklo I.F.,

Yasinsky V.M., Barachevsky V.A., Ayt A.O. ................................................................................... 185

PHOTONICS AND SINGLET OXYGEN GENERATION BY SEMICONDUCTOR QUANTUM

DOTS CDSE/ZNS SURFACELY PASSIVATED BY PORPHYRIN PHOTOSENSITIZERS

Zenkevich E.I., Sagun E.I., Knyukshto V.N., Stasheuski A.S., Galievsky V.A., Stupak A.P.,

Blaudeck T., Von Borczyskowski C. .................................................................................................. 186

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17

Section 7. Photochromism of organic compounds

PHOTOPHYSICAL AND PHOTOCHEMICAL PROPERTIES OF PLATINUM(II) COMPLEXES

WITH AZOMETHENE BASES

Ardasheva L.P. ..................................................................................................................................... 187

DEPENDENCE OF SPECTRAL-KINETIC PROPERTIES OF PHOTOCHROMIC BIS-

NAPHTOPYRANS FROM VARIATIONS OF SYMMETRY OF THE MOLECULAR

STRUCTURES

Ayt A.O., Gorelik A.M., Kobeleva O.I., Barachevsky V.A. ............................................................. 188

PHOTOCHROMIC ORGANIC SYSTEMS BASED ON NEW BIS-NAPHTHO- AND

ANTROPYRANS FOR OPTICAL METAL SENSING AND LIGHT MODULATION

Barachevsky V.A., Ayt A.O., Gorelik A.M., Venidiktova O.V., Kobeleva O.I., Valova T.M. ..... 189

PHOTOCHEMICAL PROPERTIES OF NOVEL HYDRAZONES DERIVATIVES OF

OXAINDANE SPIROPYRANS

Barachevsky V.A., Popov L.D., Kobeleva O.I., Valova T.M., Bulanov A.O., Shcherbakov I.N.,

Tsaturyan A.A., Karamanov A.A., Morozov A.N., Ivannikova E.V. .............................................. 190

SYNTHESIS AND PHOTOCHROMIC PROPERTIES OF NEW ANTHRAPYRANS

Barachevsky V.A., Venidiktova O.V., Gorelik A.M. ........................................................................ 191

SPECIFICITY OF PHOTOREACTION WITH THIADICARBOCYANINE DIMERS

Chibisov A.K., Zakharova G.V., Plotnikov V.G., Smirnov V.A. ..................................................... 192

STUDY OF SPECTRAL PROPERTIES OF LABELLED ISOXAZOLE DERIVATIVES

Demina O.V., Laptev A.V., Belikov N.E., Lukin A.Yu., Shvets V.I., Varfolomeev S.D., Levin P.P.,

Khodonov A.A. .................................................................................................................................... 193

ON SOLVATOFLUOROCHROMISM AND TWISTED INTRAMOLECULAR CHARGE

TRANSFER STATE OF THE NILE RED DYE

Freidzon A.Ya., Safonov A.A., Bagaturyants A.A. ........................................................................... 194

PHOTOSENSITIVITY OF THE LIQUID CRYSTALS DOPED WITH SPIROPYRANS

Japaridze K., Devadze L., Maisuradze J., Mzavanadze I., Sepashvili N., Zurabisvili Ts.,

Petriashvili G. ..................................................................................................................................... 195

STUDY OF SPECTRAL PROPERTIES OF SUBSTITUTED FORMYL-SPIROBENZOPYRANS

Khodonov A.A., Laptev A.V., Lukin A.Yu., Belikov N.E., Demina O.V., Shvets V.I., Levin P.P.

................................................................................................................................................................ 196

STUDY OF PHOTOCHROMIC PROPERTIES OF 5-VINYLSPIROBENZOPYRAN

DERIVATIVES

Khodonov A.A., Laptev A.V., Lukin A.Yu., Belikov N.E., Demina O.V., Shvets V.I., Levin P.P.

................................................................................................................................................................ 197

A NEW PHOTOCHROMIC (E)-2-STYRYLQUINAZOLIN-4(3H)-ONES AND THEIR CROWN-

ETHERS ANALOGUES

Kim G.A., Stupina T.V., Ovchinnikova I.G., Nosova E.V., Rusinov G.L. ...................................... 198

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18

PHOTOCHROMIC ORGANIC SYSTEMS WITH NONDESTRUCTIVE FLUORESCENCE

SWITCHING

Kobeleva O.I., Valova T.M., Perevoshikova A.Yu., Gorelik A.M., Ayt A.O., Vasilyuk G.T.,

Maskevich C.A., Yarovenko V.N., Krayushkin M.M., Barachevsky V.A. ..................................... 199

SPECTRAL-LUMINESCENT PROPERTIES OF HYDROXYAZOMETHINES OF INDOLINE

SPIROPYRANS IN FLUID SOLUTIONS AND SOLID MATRICES

Mardaleishvili I.R., Koltsova L.S., Zaichenko N.L., Shiyonok A.I., Tatikolov A.S., Levin P.P. .. 200

NEW ASYMMETRICAL BISSPIROPYRANS CONTAINING HYDROXYETHYL AND

CARBOXYETHYL SUBSTITUENTS IN THE INDOLINE FRAGMENT

Mukhanov E.L., Ozhogin I.V., Weibe V.V., Dorogan I.V., Besugly S.O., Chernyshev A.V.,

Lukyanov B.S. ...................................................................................................................................... 201

THERMODYNAMIC STABILITY AND PHOTOCHEMISTRY OF THE HETERODIMERIC

COMPLEXES OF STYRYLPYRIDINE DERIVATIVES

Savin I.V., Sazonov S.K., Ushakov E.N., Gromov S.P. .................................................................... 202

SYNTHESIS AND PHOTOCHROMISM OF NAPHTHO[1,8-BC]OXEPINE

Tyurin R.V. ........................................................................................................................................... 203

SYNTHESIS OF NEW MONO- AND DISUBSTITUTED PERFLUOROCYCLOPENTENE

PHOTOCHROMES

Yarovenko V.N., Bogacheva A.M., Krayushkin M.M., Charushin V.N., Platonova I.A.,

Barachevsky V.A. ................................................................................................................................ 204

SYNTHESIS OF CYCLOPENTENE DIHETARYLETHENES WITH THE PHOTOINDUCED

FLUORESCENT READING FOR OPERATIVE OPTICAL MEMORY

Yarovenko V.N., Khristoforova L.V., Krayushkin M.M., Platonova I.A., Barachevsky V.A. ...... 205

NEW CHROMONE BASED PHOTOSENSITIVE POLYMER FOR THREE-DIMENSIONAL

OPTICAL MEMORY

Yarovenko V.N., Levchenko K.S., Krayushkin M.M., Barachevsky V.A., Valova T.M., Kobeleva

O.I., Markova G.D., Vasnev V.A., Izmailov B.A. ............................................................................. 206

Section 8. Applied molecular photonics

HYDROGEN BONDING AND POLYMORPHISM AND THEIR APPEARANCE IN

VIBRATIONAL SPECTRA OF CYCLOHEXANOL

Babkov L.M., Davydova N.A., Moiseykina E.A. .............................................................................. 207

SYNTHESIS, PHOTO- AND ELECTROLUMINESCENT PROPERTIES OF NORBORNENE-

BASED IRIDIUM(III) COPOLYMERS

Begantsova Yu. E., Bochkarev L.N. ................................................................................................... 208

LANTHANIDEPORPHYRINS AS A NEW AGENTS FOR OPTICAL OXYGEN SENSORICS

Ermolina E.G., Kuznetsova R.T., Solodova T.A., Kopylova T.N., Ageeva T.A., Semenishin N.N.

................................................................................................................................................................ 209

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19

PHOTOEXCITED GENERATION AND ELECTROLUMINESCENCE IN THIN FILMS OF

COPOLYFLUORENES

Kopylova T.N., Telminov E.N., Degtyarenko K.M., Eremina N.S., Solodova T.A., Ponyavina E.N.,

Nosova G.I., Solovskaya N.A., Zhukova E.V., Berezin I.A., Yakimansky A.V. ............................ 210

GENERATION OF STIMULATED RADIATION BY ORGANIC SEMICONDUCTORS IN

THIN FILMS UNDER PHOTOEXCITATION

Kopylova T.N., Telminov E.N., Ponyavina E.N., Gadirov R.M., Solodova T.A., Polyanin N.V.,

Kaplunov M.G., Yakushchenko I.K. .................................................................................................. 211

SPONTANEOUS AND STIMULATED RADIATION OF BIPHENYLS UNDER PHOTO- AND

ELECTROEXCITATION

Kukhto A.V., Kopylova T.N., Degtyarenko K.M., Solodova T.A., Eremina N.S., Telminov E.N.,

Gadirov R.M., Ponyavina E.N. ........................................................................................................... 212

HIGH PRECISION FAST LUMINESCENT NO BAROMETRY

Lyalin G.N., Diekmann J. .................................................................................................................... 213

THREE COLOR LIGHT-EMITTING DIODES FROM A SINGLE POLYMER WITH

ALCOHOL-SOLUBLE POLYFLUORENE AS A HOLE-BLOCKING LAYER

Lypenko D.A., Maltsev E.I., Nosova G.I., Zhukova E.V., Smyslov R.Yu., Solovskaya N.A.,

Nekrasova T.N., Yakimansky A.V. .................................................................................................... 214

ENERGY TRANSFER IN DNA AND DETECTION OF THE PRESENCE OF THE SPECIFIC

SEQUENCES IN DNA

Malkin V.M. ......................................................................................................................................... 215

PHOTOCHEMICAL INFORMATION STORAGE ON THYMINE AND STACKING DIMERS

OF THYMINE IN POLY-T

Malkin V.M., Rapoport V.L. ............................................................................................................... 216

PRODUCING OF POLYMER COMPOSITES WITH VOLUME SPREAD METAL NANO-SIZE

PARTICLES AND ORGANIC PHOTOCHROMIC COMPOUNDS

Optov V.A., Barachevsky V.A., Ait A.O., Berlin A.A., Sabsai O.Yu. ............................................ 217

PHOTORESPONSE OF LIPOSOME-INCORPORATED FLUORESCENT DRUGS USED IN

THE PHOTODYNAMIC THERAPY OF CANCER

Reshetov V.A., Bezdetnaya L.N., Zorina T.E., Zorin V.P. ............................................................... 218

NON-LINEAR OPTICAL PROPERTIES OF PHOTOCONDUCTIVE POLYIMIDES AND

POLYURETHANES

Solovskaya N.A., Nosova G.I., Abramov I.G., Dobrokhotov O.V., Smirnov N.N., Zhukova E.V.,

Aleksandrova E.L., Yakimansky A.V. ............................................................................................... 219

SOLID-STATE ACTIVE MEDIA BASED ON HYBRID POLYMERS FOR TUNABLE LASERS

Telminov E.N., Kopylova T.N., Mayer G.V., Degtyarenko K.M., Solodova T.A., Samsonova L.G.,

Gadirov R.M., Nikonov S.Y. ............................................................................................................... 220

VITA-D: A NEW PERSONAL UV BIODOSIMETER FOR DIRECT MEASUREMENT OF THE

VITAMIN -D-SYNTHETIC CAPACITY OF SUNLIGHT AND ARTIFICIAL UV RADIATION

Terenetskaya I.P., Orlova T.M., Kirilenko E.K., Galich G.A. .......................................................... 221

Contents -------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------

20

SUPRAMOLECULAR CHEMOSENSORING SYSTEMS BASED ON PHOTOSENSITIVE

CROWN-ETHER DERIVATIVES

Zaitsev S.Yu., Zaitsev I.S., Tsarkova M.S., Solovyeva D.O., Sazonov S.K., Vedernikov A.I.,

Gromov S.P. ......................................................................................................................................... 222

PHOTOCHEMICALLY INDUCED GRATINGS AS OBSERVED USING CONFOCAL

LUMINESCENT SCANNING MICROSCOPE

Zakharov V.V., Angervaks A.E., Shcheulin A.S., Ryskin A.I., Veniaminov A.V. ......................... 223

PHOTOPHYSICAL AND KINETIC PROPERTIES OF PHOTOSENSITIZERS

ENCAPSULATED IN LIPID NANOVESICLES

Zorin V.P., Reshetov V.A., Zorina T.E., Bezdetnaya L.N. ............................................................... 224

AUTHORS INDEX ............................................................................................................................. 225

Plenary lectures ----------------------------------------------------------------------------------------------------------------------------- ------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------ --------------------------------------

21

PLENARY LECTURES

PERIODIC DFT AND VTIR STUDIES ON CO ADSORPTION IN ZEOLITES:

SINGLE, DUAL AND MULTIPLE CATION SITES

C.O. Arean

Department of Chemistry, University of the Balearic Islands, Spain

[email protected]

Increased knowledge about the structure of cation sites in zeolites would help to optimize use of

these materials in a wide range of technological processes; among them, gas separation and

purification, gas trapping for selective enhancement of chemical sensors and heterogeneous

catalysis. Infrared (IR) spectroscopy, using adequate probe molecules, constitutes a main

experimental technique currently used for investigating cationic gas adsorption sites in zeolites; and

CO is a very frequently used probe molecule. Based on a wealth of experimental data, often

combined with quantum chemical calculations on small clusters, the 1:1 adsorption model emerged;

meaning that each single cation site acts as an adsorbing site for the incoming probe molecule.

Nevertheless, recent research work combining variable temperature IR (VTIR) spectroscopy [1]

with DFT calculations on periodic zeolite models has clearly shown [2] that often nearby cations

are involved in a single adsorption process of the gas molecule, which can bridge two (or more) of

those cations, giving rise to dual-cation sites (or to multiple-cation sites). An example of a multiple-

cation site is shown in Figure 1. The number and relative situation of the zeolite cations that interact

with a single CO molecule is reflected in the structure and stability of the adsorption complex

formed, and hence on its vibrational dynamics and IR spectroscopic signature.

By using enlightening examples taken from the recent literature, the above research field will be

reviewed with a view to, (i) highlight the synergy between experimental work and theoretical

calculations for uncovering gas-solid interaction modes that go well beyond the 1:1 adsorption

model, (ii) clarify concepts, and (iii) pinpoint practical applications. Further developments in this

field, which holds the potential to open up a way leading to adsorption site engineering, will also be discussed.

Figure 1. Multiple-cation (yellow) adsorption complex of

CO (green and blue) on the zeolite Na-A, Si:Al = 1:1.

References

[1] E. Garrone, C. O. Arean, Chem. Soc. Rev., 34 (2005)

846-857.

[2] P. Nachtigall, M. R. Delgado, D. Nachtigallova, C. O.

Arean, Phys. Chem. Chem. Phys., 14 (2012) 1552-1569.


22

PHOTOCHROMISM OF ORGANIC COMPOUNDS

FOR INFORMATION PHOTONICS

V.A. Barachevsky

Photochemistry Center RAS, Moscow, Russia

[email protected]

Photochromic organic compounds and systems promise important application in the modern

information technique of a different type, especially optical memory, integrated optics, optical

sensors, because of reversibility of physical and chemical properties for two states experiencing

mutual photoinduced transformations. This paper presents the recent advances in the development

of photochromic systems and materials for application in above mentioned fields.

From the middle of the last century considerable attention has been paid to the development of

photochromic recording media for optical memory devices. Progress of the information technique

requires increasing its possibility to storage the large data massive and fast processing. It may be

achieved by the change of present two-dimensional (2D) optical memory by three-dimensional (3D)

one increasing the information capacity of optical disks more 1 TB. It is achieved by the use of two-

photon writing down of optical information in volume recording media instead of one-photon

recording. Photochromic recording media allow making the reversible multilayer optical disks

providing many-fold writing, erasure and readout of optical information (WERM). Realization of

this task was made possible in the case of application of photochromic compounds that undergo

photoinduced and thermally irreversible transformations, in particular diarylethenes. Based on these

compounds photochromic recording media with the refractive and fluorescent nondestructive readout for bitwise working optical memory have been developed.

The reversible photoinduced change of a refractive index and fluorescence provided application of

photochromic materials for making photoswitchable elements for optical communication devices.

Continuation of IC area density scaling with the use of optical lithography requires research and

development of novel materials with unique optical properties. One of the pathways to such optical

lithography extension is the use of materials exhibiting significant range of photoinduced

transmission modulation at 193 nm under excimer laser radiation of the same wavelength. For this

goal it was received masking polymer film based on one from photochromic diarylethenes with the

thickness of 450 nm. This film allows to increase a resolution of the photoresist layer up to 22 nm

and more by the photolithography method with the use of two exposures by radiation of the 193 nm excimer laser.

Practically important direction is the development of optical chemosensors for determination of the

content of ions in liquids of the different type including biological objects. This application is based

on complexation between molecules of photochromic spirocompounds as well chromenes and metal

ions as a result of an electrostatic interaction between the metal cation and the anionic sites of the

molecules, in particular phenoxide oxygen of the photoinduced merocyanine form. The

development of these photochromic sensors is based on the different efficiency of interaction

between the initial and the merocyanine form of spirocompounds or chromenes. These

photochromic compounds allows not only to determine the content of ions but also to transport metal ions in solutions with following their release in a given volume.

Finally, possible new directions of the development of photochromism research for application in

information photonics and nanophotonics, namely fluorescent biological labels, magneto-optical recording media, photoswitches of conductivity, etc. are discussed.


23

MOLECULAR SPECTROSCOPY WITH PLASMONIC EFFECTS

S.V. Gaponenko

B.I. Stepanov Institute of Physics NAS, Minsk, Belarus

[email protected]

A general consideration of nanoplasmonic enhancement of light–matter interaction is proposed in

terms of incident field concentration and photon density of states concentration providing a

rationale for huge enhancement factors for Raman scattering and noticeable enhancement factors

for luminescence[1].

Starting from a rather general and straightforward consideration which is valid for resonant

(Rayleigh-like) scattering, off-resonant (Raman) scattering and spontaneous emission

(luminescence) of incident photons, one readily arrives at the conclusion that not only the local field

enhancement in terms of excitation process but also photon density of states enhancement effect on

photon scattering/emission processes should occur. In this consideration, scattering of light

experiences enhancement as spontaneous emission does. Differences in scattering and luminescence

enhancement are due to quenching processes which are crucial for luminescence and less pronounced for scattering.

The proposed model sheds light on the so-called “hot spots”' as such places on a nanotextured metal

surface or near metal nanobodies where simultaneous spatial redistribution of electromagnetic field

occurs both at the frequency of the incident radiation ω and at the frequency of scattered radiation

ω’. Recalling the original Purcell's idea on Q-fold enhancement of spontaneous emission rate in a

cavity, local density of states enhancement can be treated as high Q-factor development in certain

portion of space near a metal nanobody. Therefore, a hot point in surface enhanced Raman

scattering can be treated as a place where high Q-factor develops simultaneously at the incident light frequency and emitted light frequency.

We consider ultimate experiments on single molecule detection by means of enhanced Raman

scattering and photoluminescence enhancement of atoms, molecules and quantum dots and the

approaches to efficient substrates fabrication for the purposes of ultrasensitive spectroscopy.

Feasibility of 10- to 102-fold enhancement is highlighted for luminescence. Rationale is provided

for 1014

enhancement factor for Raman scattering which has been claimed for the first time in 1997

based on experimental observation but has never been reported in the theory prior to our works.

1. S.V. Gaponenko, Introduction to Nanophotonics (Cambridge 2010).


24

ACTUAL PROBLEMS OF PHOTONICS OF POLYMETHINE DYES

AND LIGHT ENERGY CONVERTERS BASED ON THEM

A.A. Ishchenko

Institute of Organic Chemistry NAS, Kyiv, Ukraine

[email protected]

Polymethine dyes are unique converters of light energy. Therefore widely used in various fields of

science and technology.

Ways to structural modification of the dye molecules, allowing them to smoothly change the

electronic structure from the neutral polyene up polymethines and charged polyene demonstrated.

Features of photonics of these electronic structures using modern ab initio quantum chemical and

spectroscopic methods considered.

Problems creating photochemically stable dyes absorb light intensively in the near-infrared spectral range (800–1700 nm) were analyzed.

Structure and properties of the dyes with record Stokes shifts – 500 nm (6700 cm-1

) was discuss1ed.

Factors contributing to these changes are analyzed. Ways of Stokes shifts increasing were considered.

Posibility of change of the fluorescence quantum yields of 10-3

to 1 in polymethines shown. The

main nonradiative processes in their molecules are discussed.

Unusual effects of cationic polymethines solvatofluorohromism considered. We found that in

contrast to the absorption, in fluorescence is observed an excellent correlation between the maxima

of the bands and the one-parameter function of the universal interactions, despite the fact that the

dyes in the excited state as well as in the ground state have a system of strongly alternating charges.

Photonics of dyes with two chromophores considered.

It was discussed: buildup and quenching the luminescence in the low-polarity polymethines media,

including polymer matrices; Anomalously high hypsochromic (100-150 nm) and bathochromic

(200-250 nm) shifts of the dyes in these media; the role of the counterion in the deactivation of the

excited states polymethines.

Self-organized nanostructure photonics – J-aggregates of dyes discussed.

Intramolecular and intermolecular electron phototransfer in dyes and dye systems – photoconductive polymer is considered.

Light energy converters based on polymethine dyes for quantum electronics, nonlinear optics and optoelectronics analyzed.


25

CONFORMATIONAL CHANGES IN CRYOGENIC MATRICES:

MONOMERS, COMPLEXES, AND REACTIONS

L. Khriachtchev

Department of Chemistry, University of Helsinki, Finland

[email protected]

Conformational changes can be induced by vibrational excitation of molecules in cryogenic

matrices and studied by infrared spectroscopy. By vibrational excitation of the ground-state trans

conformers, the higher-energy cis forms of a number of carboxylic acids were prepared.1 For these

species, the higher energy cis conformer decays back to the ground state trans conformer via H-

atom tunneling mechanism, and the tunneling rates show remarkable host, isotope, and temperature

effects. We discuss the factors influencing the tunneling rates mainly for the case of formic acid (FA).

Intermolecular complexes of trans-FA and cis-FA with a number of species (water, nitrogen, xenon,

carbon dioxide) have been characterized. In most of the cases, cis-FA is stabilized upon formation

of the complexes. For example, the lifetime of cis-FA interacting with carbon dioxide in an argon

matrix is 130 times longer than that of the monomer and, moreover, the hydrogen bonding with

water stops the tunneling process completely.

Various trans-trans, trans-cis and cis-cis FA dimers have been studied. Some of the trans-cis dimers

decay to the corresponding trans-trans dimer; however, this tunneling process is slower than the

decay of the cis-FA monomer. Other trans-cis dimers are absolutely stable at low temperatures, due

to strong hydrogen bonding. Most of the theoretically predicted FA dimers have been experimentally characterized to date in cryogenic matrices.

Approaches to conformation-dependent reactions have been considered and a strong case of such a

reaction between FA and atomic oxygen has been found. The reaction surprisingly leads to

peroxyformic acid only from the ground-state trans conformer, and it results in the hydrogen-bonded complex for the higher-energy cis conformer.

The work was supported in part by the Academy of Finland through the Finnish Center of Excellence in Computational Molecular Science (2006-2011).

1 L. Khriachtchev, J. Mol. Struct. 880, 14 (2008).


26

LUMINESCENCE AND PHOTOCHEMICAL STUDIES

OF SINGLET OXYGEN PHOTONICS

A.A. Krasnovsky

A.N. Bach Institute of Biochemistry RAS, Moscow, Russia,

Biology Department M.V. Lomonosov State University, Moscow, Russia

[email protected]

It is known that oxygen molecules have the triplet ground state (3Σg

-) and the two low-lying singlet

states 1Δg and

1Σg

+. Luminescence of singlet oxygen in the solution phase has been studied in detail.

The absorption bands corresponding to the triplet-singlet transitions in dissolved oxygen molecules

are studied much worse because these bands are so weak that cannot be detected

spectrophotometrically under ambient conditions. The absorption spectra were recorded at very

high oxygen pressure (100-150 atm.). At this pressure, the absorption spectra are mostly determined

by dimols (dimers) of oxygen molecules. Recently, we developed a simple photochemical approach

to investigation of the absorption bands of oxygen dissolved in organic solvents and water at normal

atmospheric pressure. This method is based on measurement of photooxygenation rates of singlet

oxygen traps upon direct excitation of oxygen by IR laser radiation and on analysis of the action

spectra of the photooxygenation reactions. Using this method, we have shown that singlet oxygen is

readily formed upon laser excitation of the oxygen absorption bands at 765, 1073 and 1273 nm. The

obtained data allowed for estimation of the absorption spectra, optical densities and molar

absorption coefficients (ε) corresponding to the maxima of these bands in air-saturated organic

solvents and aqueous detergent dispersions. It was shown that relative intensities of the oxygen

absorption bands are markedly different from the data obtained at high pressure. Especially strong

difference was found in the intensity of the 1073 nm band. In monomeric oxygen molecules

(monomoles), this band was shown to be 50 times weaker than in dimols (O2)2. This conclusion

correlates with the spectrum of photosensitized luminescence of singlet oxygen dimols and

monomols. The molar absorption coefficients for the oxygen bands at 1273 and 765 nm were found

to correlate with the 1O2 radiative rate constants (kr) obtained from measurement of photosensitized

phosphorescence of singlet oxygen. It was demonstrated that in alcohol and aqueous systems,

vibrations of OH groups do not sensitize singlet oxygen formation. In aqueous detergent

dispersions, singlet oxygen has higher affinity to the hydrophobic micelles than to water. Within the

error limit, ε of the oxygen bands did not depend upon charge of the detergent micelles.

Significance of the obtained results for biomedical research and laser therapy of tumors will be

discussed.

References:

1. Krasnovsky A.A., Drozdova N.N., Ivanov A.V., Ambartzumian R.V. Biochemistry

(Moscow), 2003, 68, № 9, 963-966.

2. Krasnovsky A.A , Biochemistry Moscow, 2007, 72(10), 1311-1331.

3. Krasnovsky A.A., Kryukov I.V., Sharkov A.V., Proc. SPIE, 2007, 6535, 65351Q1- Q5.

4. Krasnovsky A.A., J. Photochem. Photobiol. A: Chem. 2008,196, 210-218.

5. Krasnovsky A.A., Rоumbal Ya.V., Strizhakov A.A., Chem. Phys. Lett., 2008, 458, 195-199.

6. Krasnovsky A.A., Kozlov A.S., Rоumbal Ya.V.. Photochem. Photobiol. Sciences, 2012,

DOI: 10.1039/c2pp05350k.


27

QUANTUM CONVERSION AND POWER GENERATION WITH DYE-

SENSITIZED AND HYBRID SEMICONDUCTOR PHOTOVOLTAIC CELLS

T. Miyasaka

Toin University of Yokohama, Graduate School of Engineering, Yokohama, Japan

[email protected]

Photoelectrochemistry of semiconductor electrodes has evolved to produce a dye-sensitized solar

cell (DSSC) of high power conversion efficiency up to 12% with respect to AM 1.5 solar irradiation

spectrum. Quantum conversion efficiency reaches nearly 100% which yields external efficiency

(EQE) of around 90%. These excellent performances were all realized with TiO2 mesoporous layers

with adsorbed dye molecules rather than ZnO and other oxide semiconductors. TiO2, however, is a

powerful photocatalyst which decomposes the surface organic dyes. In this aspect, durability of

DSSC cannot be compared with existing solid-state inorganic cells based on silicon and CIS.

Despite the lifetime issue, DSSC can meet the demand of low-cost production by simple printing

technologies. We have developed the methods to fabricate flexible plastic DSSCs based on low-

temperature printing of TiO2 layers on ITO-plastic films. In combination with organic dyes with

high absorption coefficients, thinner TiO2 layers (< 5 μm) are capable of high efficiency and

voltage. Indoline dye (D205)-sensitized 3.5 μm-thick TiO2 electrode yields 5.2% efficiency on

plastic DSSC.1 The efficiency increases with low intensity light without reduction of its output

voltage > 0.7V, indicating that the cell can be successfully applied to indoor light. This stable voltage is an essential advantage for charging the power in a secondary battery.

Currently we have devised a new type hybrid structured cell using a dye-coordinated TiO2 in

junction with an organic hole conductor, perylene, to achieve a high voltage of 1.2V.2 This trial

leads to design a solid-state DSSC with improved lifetime, by way of quick printing methods. Use

of quantum dots as inorganic sensitizers also proved to be effective in producing high voltage

>0.9V, where we sensitized a thin TiO2 layer with a perovskite

crystal, CH3NH3PbI3, by quick spin-coating and self-preparation of particle (2 nm in size) to obtain a cell yielding 4% efficiency.

3

Our proof-of-concept demonstration of the DSSC performance was

fabrication of thin flexible series-connection modules of DSSC on

ITO-polyethylene naphthalate film, which are capable of bifacial

power generation. Current trials and R&Ds of our DSSC and hybrid cell construction will be introduced in presentation.

References

1. T. Miyasaka, J. Phys. Chem. Lett. 2, 262-269 (2011).

2. A. Ishii and T. Miyasaka, submitted.

3. A. Kojima, K. Teshima, Y. Shirai, and T. Miyasaka, J, Am. Chem. Soc.,131, 6050 (2009).


28

WHAT WE KNOW AND WE DO NOT KNOW IN PHOTOCATALYSIS:

FROM CONVENTIONAL TO PLASMONIC PHOTOCATALYSIS

B. Ohtani

Hokkaido University, Catalysis Research Center, Sapporo, Japan

[email protected]

It is well known that heterogeneous photocatalysis is driven by a pair of a photoexcited electron in conduction band and a positive hole in valence band of semiconducting materials such as titania, and it is

also often claimed that the overall efficiency of photocatalysis is enhanced by efficient electron (positive hole) transfer at the surface and reduced by unfavorable recombination of electron–hole pairs at, presumably, a recombination center. At least for the present author, however, these interpretation seems to be only a speculation, which is consistent with experimental results reported so far. Here several topics related to the mechanism of this conventional photocatalysis, as well as recently developed non-conventional ones, are discussed [1,2]. Requites for Active Photocatalyst: Since conventional photocatalytic reactions are driven by photoexcited

electrons in a conduction band (CB) and positive holes in a valence band (VB), the CB bottom and VB top must be higher (more cathodic) and lower (more anodic) than standard potentials of redox species, respectively. It should be noticed that this is one of the requisites for a photocatalyst. A famous paper on photoelectrochemical water splitting by Fujishima and Honda published in Nature [3] suggested that charge separation can be achieved, at least for energy-storing reactions, only when bias voltage is applied between a photoanode (n-type semiconductor electrode) and a counter electrode to separate charge carriers. It is clear that such bias cannot be applied in particulate systems and almost all efficient photocatalytic reactions reported so far have been limited to energy-releasing reactions. Such energetics and strategies for giving an

internal electric field for charge separation are discussed. Light-intensity Dependence of Photocatalytic Reaction: It has been often claimed that heterogeneous photocatalysis can drive multielectron (hole) reactions in contrast to molecular systems in which only one-electron transfer occurs. Since photoexcited electrons and positive holes have appreciable life time, the efficiency of multielectron (hole) redox reactions induced by them must depend on the intensity (flux) of light producing them. Detailed analysis of light-intensity dependence as well as light-wavelength dependence of several photocatalytic reaction systems has revealed that a linear (first order) relation between

light intensity and reaction rate is observed, i.e., quantum efficiency is constant, for the photocatalytic reactions in which life time of active species is relatively short, while non linear relation is observed for the photocatalytic reaction including intermediate species of relatively long life time, such as peroxy radicals. Electron (Hole) Transfer Between Particles: One of the frequently claimed hypotheses in photocatalysis studies is transfer of electrons and/or positive holes between particles, especially different kinds of particles, to enhance the photocatalytic activity, though no direct evidence has been reported for the interparticle electron (hole) transfers. We have suggested that a synergetic effect including such electron transfer of anatase and rutile crystallites in Degussa (Evonik) P25 is negligible on the basis of experimental results

using isolated anatase and rutile particles [4]. Recent results on the analysis of action spectrum for mixed crystal photocatalyst systems are reported and discussed. Photocatalysis via Surface Plasmon Resonance Absorption by Gold Particles: Recently some approaches to develop novel photocatalytic reactions systems, in which non-band gap excitation is used, have been made. A representative one is gold particles loaded on titania particles that induce photoinduced oxidation of organic compounds via excitation at surface plasmon resonance (SPR) absorption wavelengths in the visible range [5]. The mechanism of this plasmon related photocatalysis has been still under

discussion, while some papers reported the speculations that electrons are injected from SPR-excited gold particles into titania particles to reduce molecular oxygen adsorbed on titania. However, our recent results suggest a different mechanism and will be discussed in detail.

[1] B. Ohtani Chem. Lett. 37 (2008) 216. [2] B. Ohtani J. Photochem. Photobiol. C Photo- chem. Rev. 11 (2010) 157.

[3] A. Fujishima, K. Honda Nature 238 (1972) 37. [4] B. Ohtani, O.O. Prieto-Mahaney, D. Li, R. Abe J. Photochem.

Photobiol. A Chem. 216 (2010) 179. [5] For example, (a) E. Kowalska, R. Abe, B. Ohtani Chem. Commun. 45 (2009) 241. (b) E. Kowalska, O.-O. Prieto-Mahaney, R. Abe, B. Ohtani Phys. Chem. Chem. Phys. 12 (2010) 2344.


29

HISTORY AND DEVELOPMENT OF PHOTOCATALYSIS IN RUSSIA

V.N. Parmon, A.V. Vorontsov

Boreskov Institute of Catalysis SB RAS, Novosibirsk, Russia

[email protected]

Photocatalysis as phenomenon is present on the Earth for billions of years inside photosynthesizing

organisms and probably was functioning long time before in stellar dust clouds as surface reactions.

It is deemed that research on photocatalysis was started by Carl Renz at the beginning of the

previous century and he published his work on photoreduction of oxides inside organic fluids in

1921 (1). In Russia, the start of research on photocatalysis was given by academician Terenin who

directed studies on photoprocesses in gases, organic compounds and processes of photodesorption

and photoadsorption over solid surfaces (2). In 1960 he initiated creation of laboratory of

photocatalysis in Leningrad University. In 1964, gas phase photocatalytic oxidation of organic

vapors over metal oxides was carried out (3), a reaction that is widely used now in commercially

produced photocatalytic air cleaners.

In 70th, the development of photocatalysis has gained big attention due to the energy deficit and

prospects of using solar energy for photocatalytic processes of hydrogen and electricity production.

Academician N.N. Semenov created scientific council of AS USSR for search on new ways to

utilize solar energy in which actively worked academicians K.I. Zamaraev, A.E. Shilov, A.A.

Krasnovsky. During these time, several research teams have emerged in Novosibirsk, Moscow,

Chernogolovka, Kiev, Minsk, Erevan who worked on solar energy transformation. Several new

research directions has appeared (4) – photoelectrochemistry, photocatalysis in microheterogeneous

systems. However, the vivid development of the field was disrupted by lowered oil prices. The research decline was caused by economic crises in former USSR as well in 80-90

th.

At the beginning of 90th of 20

th century, there appeared a new research direction in photocatalysis

related with the removal of air and water pollutants. Starting in 90th, the research on gas and liquid

phase photocatalytic oxidation has been carried out at Boreskov Institute of Catalysis (Novosibirsk)

and IPCP (Chernogolovka). The research was carried out for both fundamental and applied

purposes from the very beginning. As a result of joint research and development efforts with OOO

“ITI”, the production of the first commercial photocatalytic air purification devices was started in

Moscow in 1997. These air purifiers are still produced and besides complete oxidation of molecular air pollutants drive the air disinfection.

In the present time, photocatalysis in Russia is developed in the following directions: photocatalytic

oxidation, photocatalytic production of hydrogen from water, photocatalytic synthesis of organic compounds, and development as well as improvement of photocatalytic materials.

All these directions have commercial value. The most marked example is photocatalytic oxidation

which is used in air purification devises produced commercially in Moscow, Lipetsk, Novosibirsk.

The good prospects are confirmed by large investments into the production increase and diversification.

Literature [1] C. Renz, Lichtreactionen der Oxyde des Titans, Cers und der Erdsäuren, Helv. Chim. Acta, 1921, v. 4, p. 961.

[2] Теренин А.Н., Избранные труды. В 3-х томах. Л.: Наука, 1972. [3] В.Н. Филимонов, Исследование фотокаталитического окисления органических соединений на

ZnO, TiO2, Al2O3 и SiO2 по спектрам поглощения адсорбированных молекул в ИК области, ДАН, 1964, т. 158, сс. 1408–1411.

[4] Photocatalytic transformation of solar energy, parts 1 and 2, K.I. Zamaraev, V.N. Parmon (Eds.), Novosibirsk, Nauka, 1985.


30

SELF-CLEANING PROPERTIES OF TIO2-CONTAINING MATERIALS

P. Pichat

“Photocatalysis and Environment”, CNRS / Ecole Centrale de Lyon, France

[email protected]

The use of photocatalytic self-cleaning materials based on coated or incorporated TiO2 for the

facades of buildings aims at decreasing the periodicity of cleaning and/or renovation of these

facades, while maintaining a visual aspect as constant as possible. Accordingly, efficient self-

cleaning materials present both aesthetic and economical interests. These interests will likely grow

because, first, a higher fraction of the world population lives in city buildings, and, second, air

pollution due to traffic of vehicles and industrial activities generally increases in spite of stricter

regulations. Therefore, facades' soiling by solid deposits generated by combustions tends to occur more rapidly than ever before.

The sun-light-induced phenomena at the origin of the self-cleaning effect of TiO2-containing

materials are: (i) the photocatalytic oxidation of the organic compounds and carbon deposited, and

(ii) the spreading of water droplets (i.e. hydrophilicity). Also, the adhesion of deposited inorganic

salts is supposed to be decreased as a result of the hydrophilicity and the removal of the organic layer.

These phenomena and the other properties (viz. mechanical and optical characteristics, durability

and cost) required for self-cleaning materials to be used outdoors in the construction area will be

presented. In particular, a discussion about the suggested origins of the light-induced hydrophilicity

will be included. The question of increasing the self-cleaning efficacy, especially by making TiO2

capable of being activated by solar irradiation in the visible spectral region, will briefly be addressed.

The significance of the potential impact of self-cleaning materials on outdoor air quality will also be discussed.

References

- http://www.eolss.net/sample-chapters/c08/e6-106-14.pdf: P. Pichat, 2008, Solar irradiation and

TiO2 render materials self-cleaning, in Solar energy conversion and photo-energy systems,

Encyclopedia of Life Support Systems, Eolss Publishers, Oxford, UK.

- P. Pichat, Self-cleaning materials based on solar photocatalysis, in New and future developments

in catalysis: solar photocatalysis, ed. S.I. Suib, Elsevier, to be published.

Orals Optical spectroscopy and photochemical processes in molecular and supramolecular systems ----------------------------------------------------------------------------------------------------------------------------- ---------------------------------------------------------------------------------------------------------------------------- ----------------------------------------------------------------------------------------------------------------

31

ORALS

SECTION 1. OPTICAL SPECTROSCOPY AND PHOTOCHEMICAL

PROCESSES IN MOLECULAR AND SUPRAMOLECULAR SYSTEMS

IR SPECTRA OF OZONE IN LIQUID PHASE

AND DISSOLVED IN LIQUID ARGON

K.M. Bulanin, T.D. Kolomiitsova, V.V. Bertsev, D.N. Shchepkin

Department of Physics, St.-Petersburg State University, Russia

[email protected]

IR spectra of liquid ozone deposited as a film on a pre-cooled BaF2 window (O3liq

) and of ozone

dissolved in liquid argon (O3sol

) at concentrations of 3∙10-5

÷ 3∙10-4

mole fractions were recorded in

the 78÷90 К temperature range. Evidence of the spectral effects due to persisted rotation of O3sol

molecules in Ar was detected in the form of intensity redistribution between the absorption bands:

ν3 to ν1 and from ν1+ ν3 to 2 ν1 transitions, caused by the Coriolis vibration-rotational coupling (see

Table). The presence of wings in the band shapes for the ν1, 2ν1, and 2ν3 spectral features in O3sol

and their absence in the spectrum of O3liq

also support evidence of the residual molecular rotation

on the spectral parameters for O3sol

. At the same time, in the spectrum of O3liq

3 band has

complicated profile due to the resonance dipole-dipole interaction (RDD) in pure liquid. The

measured ν3 band spectral moments for O3sol

are: M1 = 1030.6 cm-1

, M2 = 240cm-2

. The value of the

M2 is in accord with an estimate M2 = M2rotational + M2RDD

≈ (100 + 130) cm-1

for O3liq

.

Band positions in O3sol

spectrum are shifted towards lower frequencies versus gas phase values by

about Δνi = 1÷30 cm-1

, which corresponds to harmonic frequency shifts Δω –1.85(5) cm-1

,

Δω –0.67(7) cm-1

, Δω –7.20(5) cm-1

.

Table. Experimental vibrational frequencies (ν cm-1

) and relative intensities (I, in km/mole) of O3sol

(Arliq) at 90.5 K. Experimental (I) and calculated (Icalc) relative intensities for ozone in liquid argon

(Arliq) and oxygen (O2liq) solutions, in liquid (liq) and gas (gas) phases at temperatures indicated are presented for comparison.

Assign-

ment ν (Arliq)

T = 90.5 K

(this work)

I(Arliq)

T = 90.5 K

(this work)

I(Arliq)

T = 84K

[1]

I(liq)

T = 78 K

(this work)

Icalc,

[2], pure

vibrational

Icalc,

free rotation

T = 90K

I (gas)

T = 300K

[1]

I (O2liq)

T = 77K

[3]

010 (A1) 700.2 0.50(3) 0.41 0.49(2) 0.49 -- 0.55 0.55

001 (B1) 1034.4 10.7(8) 11.1 9.8(8) 11.5 10.9 10.9 10.9

100 (A1) 1101.9 0.13(3) 0.063 0.085(3) 0.081 0.22 0.32 0.075

002 (A1) 2044.3 0.036(6) -- 0.039(6) 0.039 0.06 -- --

101 (B1) 2101.2 1 1 1 1 1 1 1

200 (A1) 2197.2 0.0035(10) -- 0.0032(10) 0.008 0.01 -- 0.00325

003 (B1) 3026.2 0.11(1) 0.11 0.14(2) 0.12 0.13 0.09 0.11

Acknowledgement: This work was financially supported by the Ministry of Education and Science

of the Russian Federation, grant 11.23.845.2012.

References: 1. P.F. Zittel, J.Phys. Chem., V. 95, № 18, pp. 6802–6811 (1991). 2. J.-M. Flaud, C. Camy-Peyret, A.Barbe, C. Secroun, P. Jouve, J. Mol. Spectr., V. 80, pp. 185–199

(1980).

3. K.M. Bulanin, M.O. Bulanin, A.A. Tsyganenko, Chem. Phys., V. 203, pp.127–136 (1996).


32

LATERAL INTERACTIONS BETWEEN ADSORBED SF6 MOLECULES

A. Dobrotvorskaia, A. Rudakova, D. Shchepkin,

T. Kolomiitsova, S. Petrov, R. Volin, A. Tsyganenko

V.A. Fock Institute of Physics, St.Petersburg State University, Russia

[email protected]

Lateral interactions, studied in detail by IR spectroscopy for CO adsorbed on metаls [1] and oxides

[2], affect greatly the adsorption and catalytic properties of solid surfaces. The method of isotopic

dilution enables us to distinguish between two kinds of interactions: static effect, which accounts

for the energetics and geometry of adsorbed layer, and the dynamic interaction, referred also as

resonance dipole-dipole (RDD) interaction. The latter modifies the positions, shapes and widths of

absorption bands in the spectra of adsorbed molecules. Up to now, the dynamic interaction was

observed only for CO molecules somehow oriented with respect to the flat surface of crystals.

Recently it was shown, however, that complex bandshapes in the spectra of such symmetric

molecules as SF6 in liquid or dissolved state can be explained by RDD interaction [3]. The aim of

this work was to find out the manifestations of such interactions in the spectra of SF6 adsorbed on the surface of amorphous or crystalline oxide adsorbents.

Spectra of adsorbed SF6 and solid SF6 film were obtained at 77 K. The spectra markedly differ from

one another (see Fig.1). Experiments with isotopic dilution show that complex bandshapes in the

spectra of studied systems are rather due to strong intermolecular RDD interaction than caused by

surface heterogeneity. The studied systems can be classified into three types depending on the

mutual arrangement of SF6 molecules. Thus, we have a three-dimensional system of SF6 in solid

film on cell windows, a two-dimensional layers on SiO2, ZnO, CaO and MgF2, and one-dimensional chains in the channels of silicalite.

To simulate the band shapes of adsorbed SF6 we used the modificated model developed in the previous study [3].The results obtained are in quantitative agreement with the experimental data.

Acknowledgement. The work was supported by the Ministry of Education and Science of Russian

Federation, Grant 11.38.38.2011.

Fig.1. Absorption spectra of SF6: solid

film on cell windows (1) and adsorbed on

silicalite (2), SiO2 (3), CaO (4), MgF2 (5),

and ZnO (6). All the spectra are

normalized to the common integrated

intensity.

References:

[1] Ermoshin V.A., Kazanskii A.K. Opt. and Spectrosc., 75 (1993), p.719

[2] Tsyganenko A.A., Denisenko L.A., Zverev S.M., Filimonov V.N. J. Catal., 94 (1985), p.10.

[3] Andrianov D.S., Cherevatova A.N., Kolomiitsova T.D., Shchepkin D.N. Chem. Phys., 364

(2009) 69.

1000 960 920 880

0

2

4

6

65

43

2

Wavenumvers, cm-1

Rel.

Un

its

1


33

SYSTEM OF DUPLEX ELECTRONIC LEVELS OF EOSIN

N.S. Goryachev1, A.I. Kotelnikov

1, F.-J. Schmitt

2, G. Renger

2, H.J. Eichler

3

1 - Institute of Problems of Chemical Physics RAS, Chernogolovka, Russia

2 - Max-Volmer-Laboratories for Biophysical Chemistry, Berlin Institute of Technology, Germany

3 - Institute of Optics and Atomic Physics, Berlin Institute of Technology, Germany

[email protected]

Nonexponential kinetics of eosin phosphorescence spectrum decay in 66 % water glycerine solution

was detected in temperature range 90–250 K. The component analysis of results has shown, that the

phosphorescence spectrum consists of two identical spectrums with different times of signal

attenuation. Both spectrums have identical vibrational structure and are shifted from each other on

11 nm.

These results could be explained by weak asymmetry of eosin molecule structure. As a result the

degeneration of basic and excited electronic levels is removed and system of pair electronic levels is formed.

Activation temperature of transitions between these levels was measured. The kinetic model of a

phosphorescence lifetime dependence on temperature was created. Within the framework of kinetic

model the data on kinetics of spectra phosphorescence decay in a broad temperature range were analysed.

It is supposed the availability of such systems of pair electronic levels for all molecules having

feeble asymmetry, in particular for fluorone dyes.

This property can serve as one of the reasons of red-edge excitation shifts (REES) effect, which one is usually featured by properties of a solvent.

This work was supported by the RFBR (grant 10-03-00687), the Presidium of Russian Academy of

Sciences (Research program No 24 “Fundamental research in the field of nanotechnology and

nanomaterials”) and International Bureau of BMBF (Project No RUS 10/026).


34

ANALYSIS OF P-SYSTEM STRUCTURE FOR BRANCHED

MACROMOLECULES ON THE BASIS OF SPECTROPHOTOMETRY AND

LUMINESCENCE DATA

R.N. Nurmukhametov1, A.V. Shapovalov

2

1 – L.Ya. Karpov Physicochemical Institute, Moscow, Russia

2 – A.N. Nesmeyanov Institute of Organoelement Compounds RAS, Moscow, Russia

[email protected]

Many organic compounds possessing bright fluorescence have found different applications as

phosphors, fluorescent probes, fluorescent additives and activators of plastic scintillators. The

molecules of such phosphors have a conjugated system of π-bonds with a rigid coplanar or chain-

like structure. The aim of this work was to obtain and investigate the optical properties of brightly

fluorescing macromolecules with branched structure in which the branching points are 1,3,5 -

trisubstituted benzene rings.

UV-absorption and fluorescence spectra, quantum yields and fluorescence lifetimes were

determined for the branched compounds of poly-p-phenylene's type, some of which had been

obtained earlier [1]. The general structural formula of the investigated compounds was the

following (Fig. 1).

Fig. 1.

The absorption spectra of solutions and thin transparent

films of these compounds have been studied.

Spectrophotometric analysis of macromolecules OPh4-1

― OPh6 based on the principle of conjugation

interruption at the meta-substituted benzene ring, which

had been previously set for linear meta- and para-

polyphenyls [2], was also performed. This allowed us to

identify the main chromophoric and fluorochromic groups

in the structure of branched macromolecules. It was shown

that the absorption spectra of the compounds studied was a

superposition of the absorption bands of isolated

chromophoric groups [3]. Obtained result allowed to

specify the number of units in the macromolecules

containing π-conjugated p-quaterphenyl fragments (OPh4-

1 and OPh4-2) and to find out the differences of the main

absorption maxima of these compounds.

[1] Khotina I.A., Lepnev L.S., Burenkova N.S., Valetsky P.M., Vitukhnovsky A.G. Phenylene

dendrimers and novel hyperbranched polyphenylenes as light emissive materials for blue OLEDs //

Journal of luminescence. 2004. V. 110. № 4. P. 232 – 238.

[2] Stern E., Timmons К. Electronic absorption spectroscopy in organic chemistry. – М.: Mir, 1974.

296 p.

[3] Nurmukhametov R.N., Shapovalov A.V., Sergeev A.M., Kushakova N.S., Khotina I.A.

Analysis of branched oligophenylene by absorption and fluorescence spectra // Journal of Applied

Spectroscopy. 2011. V. 78. № 1. P. 31 – 37.


35

LUMINESCENCE AND ABSORPTION OF ACRIDINE HYDROGEN

BONDED TO CARBOXYLIC ACIDS AND ALCOHOLS

Y.A. Rozhkova1, A.V. Gurinov

2, P.M. Tolstoy

1, I.G. Shenderovich

3, V.I. Korotkov

1

1 – Department of Physics, St.-Petersburg State University, Russia

2 – Department of Chemistry, St.-Petersburg State University, Russia

3 – University Regensburg, Germany

[email protected]

Protonation of acridine by strong acids results in a characteristic extension of its absorption

spectrum, intensity increase and shift to longer waves of its luminescence spectrum. A considerably

more challenging task today is elucidation of the structures of complexes of acridine hydrogen

bonded to weaker acids, when the formation of hydrogen bond complexes of acridine with proton

transfer are unlikely, especially in non-polar solvents. The goal of studies was to inspect the

possibility to elucidate the geometry of hydrogen-bonded complexes formed by acridine using

features of its luminescence and absorption spectra. Acridine (pKa = 5.56) complexes with

trifluoroacetic acid (pKa = 0.05), dichloroacetic acid (pKa = 1.37), chloroacetic acid (pKa = 2.65),

acetic acid (pKa = 4.80), perfluorotertbutanol (pKa = 7.05), hexafluoropropanol (pKa = 9.75) and ethanol (pKa = 15.24) were investigated in solutions.

The most important preliminary result is that the positions of the luminescence maxima correlate

with the pKa values of the proton donors. The stronger is the proton donor the stronger is the long-

wave shift of the luminescence as compared to free acridine. The shift is accompanied by a

progressive increase of the luminescence intensity. Thus, both the intensity and the shift of the

luminescence of acridine upon hydrogen bonding can be potentially used to estimate the geometry

of the forming bonds.

The difference in the luminescence maxima of complexes with different acetic acids concentrations

reflects the fact that the geometry of the corresponding hydrogen bonds are differ as well. This

observation might indicate that acridine – acetic acid hydrogen bonded complexes of other

composition than 1:1 are formed. Such systems were described in [1]. The absorption spectrum of

acridine in ethanol resembles the absorption spectrum of acridine in dichloromethane. The same is

true for the luminescence except a dramatical increase of its intensity. For the systems of acridine –

hexafluoropropanol and acridine – perfluorotertbutanol in dichloromethane an increase of the

luminescence intensity is accompanied by a long-wave shifts of the spectra (13 nm and 50 nm, correspondingly).

Acridine hydrogen bonded to perfluorotertbutanol was investigated in different solvents. It was

supposed, that the formation of hydrogen-bonded complexes occurs by different mechanisms in

different solvents. In a low polar solvents (similar to dichloromethane, polarity is 3.1) complexes

with proton shared hydrogen bonds are formed in the darkness. In contrast, such complexes has not

been observed in ethanol (polarity 4.3) in the darkness, although proton transfer can occur after

photo excitation. Probably in this case the formation of hydrogen-bonded complex between acridine

and perfluorotertbutanol requires overcoming an energy barrier to that expended energy of the

absorbed photon.

This work is supported by the German-Russian Interdisciplinary Science Center (G-RISC) funded

by the German Federal Foreign Office via the German Academic Exchange Service (DAAD).

References

1. N.S. Golubev, S.N. Smirnov, P. Shah-Mohammedi, I.G. Shenderovich, G.S. Denisov, H.-H.

Limbach // Journal of general physic, 1997, v. 67/7, pp. 1150 – 1155.


36

FTIR SPECTROSCOPY IN THE STUDIES OF SURFACE PHENOMENA

A.A. Tsyganenko


[email protected]

The paper deals with the advances in the application of IR spectroscopy for the studies of

adsorption, mechanism of lateral interaction between the adsorbed molecules and linkage isomerism in the adsorbed state.

Spectroscopy at low and variable temperatures enable us to broaden the number of test molecules

for surface sites and instead of ammonia, pyridine and nitriles, to use simple molecules that do not

adsorb at 300 K, such as CO, NO, H2 to characterize acidic (electron-accepting) sites, while for

basic (electron-donating) centers low-temperature adsorption of weak CH proton-donors like CHF3

can be used. Quantitative measurements reveal a correlation between the frequency shifts and absorption coefficients of adsorbed molecules.

The strength of surface sites is affected by lateral interactions between the adsorbed species, which

can be repulsive or attractive. Static interaction changes the energies of adsorption and shifts the

bands of test molecules. Dynamic interaction accounts for the changes in the bandshape and half-

width and for splitting of the bands. It manifests itself even in the spectra of symmetric molecules weakly adsorbed on zeolites or amorphous adsorbents.

Some molecules, such as CO, reveal linkage isomerism and form with the cations in Y or ZSM-5

zeolites, besides the usual C-bonded species, the energetically unfavorable O-bonded complexes.

Besides the frequencies, different geometry of isomeric species leads to dissimilarity in the isotopic

shifts on 13

C or 18

O substitution. The linkage isomerism can be explained by electrostatic model,

which also accounts for the absence of this phenomenon for oxides or X-zeolites, where formation

of side-on complexes with surface anions or interaction with dual cationic sites is preferable.

According to the model, isomerism is possible for halogenides or layered alumosilicates where

negative charge of anions is lower or is delocalized over the polyanionic layers, that was recently

confirmed by variable temperature FTIR measurements. Surface isomeric states were established for some other adsorbed species, such as cyanide ion CN

- produced by HCN dissociation.

Acknowledgements

The work was supported by the Ministry of Education and Science of the Russian Federation, grant

11.38.38.2011

Orals Electron and energy transfer in molecular systems --------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------- ----------------------------

37

SECTION 2.

ELECTRON AND ENERGY TRANSFER IN MOLECULAR SYSTEMS

PHOTOGENERATION OF CHARGE CARRIERS

IN POLY-N-EPOXYPROPYLCARBAZOLE FILMS

DOPED WITH POLYMETHINE DYES

D.A. Afanasyev1, N.Kh. Ibrayev

1, A.A. Ishchenko

2, N.A. Davidenko

3

1 – Institute of Molecular Nanophotonics, E.A. Buketov State University, Karaganda, Kazakhstan

2 – Institute of Organic Chemistry NAS, Kiev, Ukraine

3 - Taras Shevchenko National University, Kiev, Ukraine

[email protected]

Photosensitive polymeric semiconductors may have a significant impact on the efficiency of solar

energy converters, electrophosphorescence light-emitting devices and other applications. Creation

of materials with high efficiency of generation and transport of charge carriers is important.

Polymer films based on photoconductive polymer doped with ionic polymethine dyes can be one of the most promising materials.

Investigation of the role of triplet states of polymethine dyes in charge carriers photogeneration is

shown in this paper. The influence of the chemical nature of the dye was studied in the efficiency

development of electron-hole pair in a matrix of poly-N-epoxypropylcarbazole.

The results of studies of the decay kinetics of delayed luminescence of ion (cationic and anion) and

neutral polymethine dyes in polymer matrices with photoconductive and non-photoconductive

properties are given in this paper. Polymer films based on polyvinylbutyral (PVB) and

photoconductive poly-N-epoxypropylcarbazole (PEPC) with additives of polymethine dyes were prepared.

Photoexcitation of the samples was performed using a laser LCS-DTL-374QT (λ= 532 nm, E = 60

uJ, τ = 7 ns). Delayed luminescence was observed for all polymethine dyes at the excitation in the

absorption band of dyes in polymer films. Delayed luminescence spectra coincided with the spectra

of fast fluorescence. Delayed fluorescence is related to the inverse interconversion of the lowest

triplet state T1 to the singlet excited state S1. Time-resolved phosphorescence spectra were obtained

for polymer-dye film with a heavy atom.

Poly-N-epoxypropylcarbazole films doped with dyes have recombination luminescence. The

intensity of recombination luminescence depends on the chemical nature of the dye. The highest

yield of charge pair is achieved by using cationic dye, which has energetically more favorable

arrangement of the HOMO energy level with respect to the HOMO energy level of poly-N-

epoxypropylcarbazole. The Coulomb interaction between carbazole fragment and anionic fragment of dye molecules plays an important role.

Measurement of the magnetic field effect on the delayed luminescence kinetics of dyes in the

polymer films showed that magnetic field has no recorded influence (B = 0–0.47 T) for all dyes in

the PVB polymer. The intensity of recombination luminescence of cationic dyes and neutral dyes in

PEPC decreases in external magnetic field. The maximum negative magnetic effect is 26%. It is

observed for the cationic dye, in the magnetic field 0.47 T. The magnetic effect is time-based

nature. This is due to competition between the singlet and triplet channels the appearance charge

pair. The role of the singlet channel is enhanced in the presence of a heavy atom in sample. This is

due to the increase in the rate of triplet-singlet transitions in the molecules of the dye.


38

SINGLET- SINGLET ENERGY TRANSFER BETWEEN TRYPTOPHANYL

RESIDUE OF HUMAN SERUM ALBUMIN AND EOSIN

A.G. Melnikov1, G.V. Melnikov

1, V.I. Kochubey

2, A.B. Pravdin

2

1 – Saratov State Technical University, Russia

2 – Saratov State University, Russia

[email protected]

We have studied the singlet-singlet energy transfer of electronic excitation from tryptophanyl

residue of human serum albumin (HSA) to the eosin molecule noncovalently bound to the protein.

Measurements were carried out both on the initial system which contained 15∙10-6

M (1 mg/ml)

solution of HSA in the pH 7.4 phosphate buffer with the addition of eosin in the total concentration

of 4∙10-6

M and the solutions obtained by sequential dilution of initial system with the phosphate

buffer. Excitation of the donor of energy – tryptophanyl residue – was performed within its absorption band at 280 nm.

The energy transfer was revealed from the quenching of HAS intrinsic (mainly originated from

tryptophan) fluorescence at 360 nm after the introduction of eosin into the albumin solution. When

introduced into the water-protein system eosin concentrated in protein globules, which was

indicated by a long-wavelength shift of the dye absorption band and a relative increase in its dimer

content in comparison with the aqueous solution of eosin. Analogous shift into the long-wave

region, upon transfer from water to albumin solution, underwent the maximum of eosin fluorescence spectrum with 480 nm excitation.

During the dilution of initial solution (water-protein-dye) by the buffer the absorption band of dye

somewhat shifted to the short-wave region, which might be indicative of an increase of the fraction

of total eosin in the aqueous phase (eosin partition ratio did not change under dilution, but the

water/protein volume ratio grew). This assumption is also confirmed by a short-wave shift of eosin luminescence band during the dilution of initial system.

We also compared the sensitivity of singlet-singlet and triplet-triplet [1] energy transfer to structural

rearrangements in albumin globule caused by the addition of sodium dodecylsulfate in solution.

The obtained results suggest that the effectiveness of singlet-singlet energy transfer between the

tryptophanyl residue of HSA and the eosin molecule noncovalently bound to the protein depends on

the distribution of the dye between aqueous macrophase and protein micro-phase, which

distribution may change during the significant dilution of blood serum (plasma) specimen with added dye.

According to the theory of the singlet-singlet resonance energy transfer, proposed by Förster, and

taking into account the nonuniform distribution of the molecules of acceptor we estimated the

critical distance of transfer (the Förster distance) in the system of HSA tryptophanyl residue as a

donor of energy and eosin as an acceptor and obtained the value R0 ≈ 9 ± 2 Å. This value of the

distance of transfer attests to the fact that eosin in HSA globule is localized in the nonpolar vicinity

of tryptophanyl residue.

1. A.G. Mel’nikov, A.M. Saletskii, V.I. Kochubey, A.B. Pravdin, I.S. Kurchatov and G.V.

Mel’nikov. Triplet-triplet energy transfer between luminescent probes bound to albumins //

Optics and Spectroscopy Volume 109, Number 2 (2010), 188–192.


39

PHOTOPROCESSES IN SYNTHETIC AND NATURAL SENSITIZERS

I.V. Sokolova, O.N. Tchaikovskaya, G.V. Mayer, N.G. Bryantseva, N.O. Vershinin, L.V. Nechaev

Tomsk State University, Russia

[email protected]

Sensitizers are used in different fields of science and technology, but their choice is mostly random.

Many natural substances exhibit photosensitizing properties. The electronic processes in organic

substrates using light activation of photosensitizer are of increasing interest. Sensitizers have been

widely employed for many purposes, and the development of the understanding of their

photophysics and photochemistry is still in progress. The study of the dependence of spectral and

luminescent properties of organic compounds on their structure makes the search for new efficient

sensitizers more purposeful.

Purpose of present work – a study of photophysical, photochemical properties and molecular

interactions of synthetic and natural sensitizers. Psoralens (furocoumarins) are substances exhibiting

photosensitizing properties in the UV radiation range 320-400 nm. The combined action of

psoralens and UV radiation on skin or blood components (photopheresis) is used to treat many skin

diseases and autoimmune disorders [1]. The particular photophysical and photochemical processes

relevant to phototherapy are still under study. In this work, we performed quantum-chemical

calculations and experimental study on the molecules of psoralen, its isomers, methoxy and other

coumarin derivatives in order to reveal the specifics of the electronic structure and to study

photophysical processes occurring in systems after absorption of a quantum of light. Schemes of

photophysical processes were analysed and detailed. Effects of isomerism and methoxysubstitution

on the energy level diagram are demonstrated. The rate constants of intersystem and internal

conversions are calculated. We obtained rather high intersystem conversion constant that influences

on the fluorescent yield of psoralens. In addition, the reactive species, such as singlet oxygen and

hydroxyl radicals produced by irradiation of various psoralens were characterized. The fluorescence

efficiency of investigated coumarins is rather small and highly dependent on the polarity and hydrogen-bonding capabilities of solvents.

Humic substances representing the main fraction of organic matter receive increased attention

because their reactivity as light absorbers. Depending on their origin, humic acids have a

remarkable ability to absorb light and transfer this energy to other substrates and in some cases

strongly affect photolysis of xenobiotics [2]. In water and in soils humic acids have been found to

act as photosensitisers and they have also been reported to produce oxygen species upon irradiation,

and be able to photoinduce the transformation of ecotoxicants. In the report the results of

investigations of molecular interactions of humic acids in water with phenols and

chlorophenoxyacetic acids are considered. The results in a flow reactor for photodegradation of

ecotoxicants are presented. A specific feature of the reactor is the use of three excilamps [3] with

different radiation wavelengths (λ = 172 nm, λ = 222 nm, λ =308 nm). The discussion includes

comparative analysis of the direct and indirect photolysis.

The work is supported by Grant of the President of the Russian Federation for Support of Leading Schools (project No. NSh-512.2012.2).

1. J.J. Serrano-Perez, R. Gonzalez-Luque, M. Merchan, L. Serrano-Andres J. Photochem.

Photobiol. A: Chem. 2008, V. 199, P. 34–41.

2. O. Tchaikovskaya, I. Sokolova, G.V. Mayer, E. Karetnikova, E. Lipatnikova, S. Kuzmina, D.

Volostnov Luminescence, 2011, V. 26, P. 156–161.

3. Sosnin E.A., Sokolova I.V., Tarasenko V.F., In Book: Photochemistry Research Progress (Eds

by A. Sanchez, S.J. Gutierrez). Nova Science Publishers, 2008, 225–269.


40

ABSORPTION SPECTROSCOPY OF CHARGE-TRANSFER COMPLEXES

BETWEEN A CONJUGATED POLYMER AND LOW-MOLECULAR-

WEIGHT ACCEPTOR

A.Yu. Sosorev, G.S. Kashtanov, S.A. Zapunidy, D.Yu. Paraschuk

M.V. Lomonosov State University, Moscow, Russia

[email protected]

Donor-acceptor blends of conjugated polymers (CP) with low-molecular acceptors are the heart of

organic solar cells. The interface between donor and acceptor phases plays here an important role,

as it governs the processes of exciton dissociation into free charges and charge recombination. It

was noticed earlier that in some of the blends charge-transfer complexes (CTC) are formed between

donor and acceptor molecules in the ground electron state. CTC formation alters blend

photophysics, as it can widen absorption spectrum, facilitates exciton dissociation, enhances

photostability and affects conformation of the polymer molecules and blend morphology [1].

However, CTC formation between a CP and low-molecular acceptor is not well studied.

Here, we present the information about CTC formation in the solutions of CP donor-acceptor blends

that can be extracted from the absorption spectroscopy data. We used blends of the model CP

MEH-PPV with different fluorene acceptors and two acceptors with different molecular skeleton

(TCNQ and DNAQ). We have found that in most of the blends, additional absorption band appears

as a result of CTC formation. Interestingly, spectra of the blends with fluorene acceptors are almost

similar, while electron affinity differs by c.a. 0.5 eV. At the same time, spectra of the CP blends

with DNAQ and TCNQ have qualitatively different shape. It indicates that the shape of the CTC

spectra depends rather on the geometry of the molecular skeleton, than on the electron affinity or

substituents of the acceptor molecule.

We paid special attention to the spectral changes with acceptor concentration (Ca) increase. We

have found that the in the solution, the spectra can be considered as a superposition of the non-

shifted polymer and CTC spectra, while in the film, polymer spectrum is shifted with Ca increase.

Interestingly, that polymer peak of the film spectra “squeezes” at some acceptor concentration.

Considering that optical properties of the single CTC do not depend on acceptor concentration, we

can obtain the dependence of CTC concentration (CCTC) on Ca. For most of the fluorene acceptors,

this dependence has a threshold character, in correspondence with studies on MEH-PPV:TNF blend

[2]. As we have shown earlier, this threshold-like behavior can be explained by the presence of the

neighbor effect during CP complexation. It means, that new CTCs are formed preferentially near

the existing ones. We have also suggested before the original statistical model of the neighbor

effect, which has three parameters: E0, the energy of isolated CTC formation; E, the energy gain in

the case of two neighboring CTC formation; and n, the CTC stoichiometry. In the current study, we

applied this model to the analysis of absorption data on the fluorene series. It was found that E0

differs in about two times, while E values are equal in the error limits. In contrast to the fluorene

series, in the blends of MEH-PPV with DNAQ and TCNQ, the CCTC(Ca) dependence is almost

linear, indicating weak neighbor effect. We conclude therefore that the magnitude of the neighbor

effect in CP complexation also depends rather on the molecular skeleton than on the electron

affinity or substituents of the acceptor molecule.

So, we argue that a simple method of absorption spectroscopy applied to the solutions and films of

CP blends can provide rich information about CTC formation.

1. Bakulin A.A., et al., Weak charge-transfer complexes based on conjugated polymers for plastic solar cells. Synthetic Metals, 2004. 147(1-3): p. 221–225. 2. Parashchuk, O.D., V.V. Bruevich, and D.Y. Paraschuk, Association function of conjugated polymer charge-transfer complex. Phys. Chem. Chem. Phys., 2010. 12(23): p. 6021–6026.


41

ENERGY MIGRATION IN NANOPARTICLES FROM LN(III) –

ORGANIC COMPLEXES TO DYES INCORPORATED IN THEM

E.B. Sveshnikova, V.L. Ermolaev, L.Yu. Mironov, S.S. Dudar

National Research University of Information Technologies, Mechanics and Optics, St. Petersburg, Russia

[email protected]

The method of dopant fluorescence sensitization in nanoparticles (NP’s) is applied more and more

for the enhancement of sensitivity of luminescent analysis and for creature of brightly luminescent

markers in biology analysis. In 2008 we found that under self-formation of NP’s of lanthanide beta-

diketonate complexes in aqueous solutions dye molecules are captured from the solution and

sensitization of their fluorescence (cofluorescence) takes place [1]. The construction of such NP’s

demands understanding of the relation between the length of singlet exciton diffusion path (L) and

the size (D) of NP’s. It was shown that L–variation, caused by decrease of τfl of complexes from 0.1

ns to 3 ps doesn’t influence markedly on sensitized fluorescence intensity (Icofl) of dyes in NP’s

with D~10-30 nm. Consequently, L values are comparable with D as in NP’s from complexes of

light and heavy ions. The substitution of La(III) or Lu(III) by Ln(III) ions absorbing in the region of

complex fluorescence may initiate further decrease of τfl of complexes and incorporated dyes.

The effect of absorbing ions on Icofl of coumarin 30 (C30) and rhodamine 6G (R6G) was examined

in NP’s from Ln(PhBTA)3phen (where Ln – Nd, Pr, Er, Eu, Sm, Yb, PhBTA – p-

phenylbenzoyltrifluoroacetone) at different dye concentrations. To estimate the influence on Icofl

values of only the decrease of τfl of complexes under their interaction with Nd(III), Pr(III), Er(III) it

is necessary to exclude Icofl diminution under these ions interaction with dyes in NP’s. The

possibility to separate reliably these two processes gives examination of cofluorescence and

fluorescence of C30 in NP’s. The comparison of the dependence on C30 concentration of the

spectra sensitized and usual fluorescence of this dye in solutions of NP’s from La or

Lu(PhBTA)3phen complexes has shown that C30 molecules completely pass from solution to NP’s

up to dye concentration – 1μM. There is no concentration quenching of C30 fluorescence in such

systems so as C30 comes into NP’s not only as admixture, but also as Ln(PhBTA)3C30 complexes.

After exclusion of absorbing ion influence on intensity of own C30 fluorescence we found ~ tenfold

decrease of dye Icofl as a result of decrease of τfl of complexes in NP’s from Nd, Pr, Er, complexes

in comparison with NP’s from complexes nonabsorbing ions. This means that further fall of τfl of

complexes to ~ 0.1 ps makes L < D of NP’s and leads to diminution of energy migration

contribution into dye Icofl value. However the observed dependence of fluorescence excitation

spectra of C30 on the relation of C30 and complex concentrations gives strong evidence that S1 – S1

energy migration occurs even in NP’s from complexes with ~0.1 ps. Consequently, the rate of S1 –

S1 energy migration is ≥ 1013

c-1

, and jump time is shorter than 10-13

s. A clear knowledge of

migration laws in NP’s helps to choose such NP’s which allows controlling the minimal dye

concentrations in solutions. It is essential that this work demonstrate the way of elimination of

fluorescence concentration quenching of a set of coumarin dyes in NP’s, and such NP’s promise to be bright markers for biology.

[1] V.L. Ermolaev, E.B. Sveshnikova, L.Yu. Mironov. Nanotechnologies in Russia. 2012. V. 7. No

3-4. P. 110–116 (and references in it).

Orals Photochemical processes in heterogeneous systems and heterogeneous photocatalysis ----------------------------------------------------------------------------------------------------------------------------- --------------------------------------------------------------------------------------------------------------------------------------------- -----------------------------------------------------------------------------------------------

42

SECTION 4. PHOTOCHEMICAL PROCESSES IN HETEROGENEOUS

SYSTEMS AND HETEROGENEOUS PHOTOCATALYSIS

ETHANOL VAPOR PHOTOCATALYTIC OXIDATION WITH URANYL

MODIFIED SILICA, ALUMINA AND TITANIA UNDER VISIBLE LIGHT

T.N. Filippov1, P.A. Kolinko

2, D.V. Kozlov

2

1 – Novosibirsk State University, Russia

2 – G.K. Boreskov Institute of Catalysis SB RAS, Novosibirsk, Russia

[email protected]

Today the problem of environmental pollution is very actual. A lot of industrial companies,

development of poultry and livestock farming, a high level of human mobility result in that people

are exposed to variety of toxic species and harmful microorganisms.

As a result a universal air purifying methods are of interest. The most promising one is

photocatalysis. Titanium dioxide is well-known photocatalyst because it is inexpensive, chemically

and photochemically stable and could provide photocatalytic oxidation of almost any organic

species. Carbon dioxide and water are the ultimate products of photooxidation. Unfortunately, TiO 2

works only in the near-ultraviolet region (λ<380 nm), which takes about 4% of the solar spectrum.

At the same time visible light occupies about 43% of sun irradiation. This is the reason of

increasing interest to visible light photocatalysis.

Earlier it was found that uranyl ions in water can be sensitized by visible light [1] but the gas phase

photocatalytic oxidation of organic species with uranyl-modified photocatalysts was not investigated.

In the current work photocatalyst samples were synthesized by incipient wetness impregnation

method with the use of TiO2, γ-Al2O3 and SiO2 as support. The UO2(NO3)2 content was varied from 0.2 to 10 wt.%.

The activity of catalysts was measured in the reaction of ethanol vapor oxidation in the static reactor

at room temperature. The high pressure Xe-lamp was used as the light source. The visible regions of

the spectrum (λ > 420 nm) was cutoff with the optical glass filter ZhS-11. Ethanol, acetaldehyde and CO2 gas concentration were measured with gas chromatograph equipped with FID.

Results of investigation demonstrated that:

1) Acetaldehyde was registered as the intermediate and CO2 as the final products of C2H5OH photooxidation;

2) Although TiO2 was not active under visible light (λ>420 nm) it was found to be the best support

for uranyl nitrate and demonstrated highest photooxidation rate up to 470 nm incident light wavelength.

Further research of action spectra and FTIR (Fourier transform infrared spectroscopy) in situ

mechanistic investigations should be conducted to reveal the role of uranyl species.

[1]. E. Rabinowitch, R.L. Belford Spectroscopy and Photochemistry of Uranyl Compounds

Pergamon, London (1964)

http://lingvopro.abbyyonline.com/ru/Search/GlossaryItemExtraInfo?text=%d1%81%d0%b5%d0%bd%d1%81%d0%b8%d0%b1%d0%b8%d0%bb%d0%b8%d0%b7%d0%b8%d1%80%d0%be%d0%b2%d0%b0%d1%82%d1%8c&translation=sensitize&srcLang=ru&destLang=en


43

SELF-SENSITIZATION OF PHOTOCATALYTIC PROPERTIES

OF WIDE-BANDGAP OXIDES USING INTRINSIC POINT DEFECTS

A.A. Lisachenko

V.A. Fock Institut of Physics, St.-Petersburg State University, Russia [email protected]

In 1930ties professor A.N. Terenin had discovered the photo-activated dissociation of NH3

molecules adsorbed on nominally pure Al2O3 under UV-irradiation in sub-bandgap oxide region.

Terenin has supposed that light absorption was due to defects in crystal structure. Since then the

program of experimental step-by-step investigations of interrelated quantum photo-stimulated

surface processes in electronic and atomic subsystems is developed in his laboratory in the Institute

of Physics of Leningrad (St.-Petersburg) University.

While the excitations under inter-band absorption are delocalized, the excitations in the sub-

bandgap region are localized, spectral-selective and site-sensitive. The irradiation disturbs the

equilibrium distribution of point electron/hole donor/acceptor defects over charge states, thus

transferring system into a metastable state. There are slow relaxation channels with characteristic

times exceeding 105 s. Such long living-time of excited states provides a high efficiency of photo-

activation. It is shown that chemical processes successively compete with radiative and

thermoactivated channels of electron subsystem deexcitation.

In our report the interplayed physical and chemical processes on irradiated oxide surface are

analysed in the framework of a 3-step model: 1. Fast initial electronic excitation; 2. Energy or charge transfer, energy relaxation channels; 3. Chemical bonds breaking/making.

The detailed experimental investigations of mechanisms of interrelated spectral selective and site-

sensitive processes in electronic and atomic subsystems on UV-VIS illuminated surface of wide band-gap oxides are presented [1,2].

It is shown that the most active in photoadsorption/desorption and in photochemical processes are

point defects of F-type (oxygen vacancy – empty or 1 or 2 electrons localized) and V-type (cation

vacancy – 1 or 2 holes localized) which are responsible for photon absorption in the sub-bandgap

region. The key parameters of the surface active centers are follow:

– the absorption region and the nature of the optical transition;

– the positions of local levels in the electron energy structure;

– the pathways of electronic energy deexcitation; – the values of cross sections of the interaction with molecular reactants.

The in situ investigations are carried out in three phases: gas–adsorbat–surface. A variety of

complementary in situ experimental methods were used:

– mass-spectrometry (gas phase monitoring, Thermo- Desorbtion Spectroscopy),

– optical (Diff. Reflectance spectroscopy, photo- and thermo-stimulated luminescence),

– ESR spectroscopy, – UV-photoelectron spectroscopy.

The applied aspects are exemplified by photoinduced interaction of air pollutants NOx with mineral

dust aerosols, optical degradation of spacecraft thermal control coatings (TCC), sensitizing of

TiO2-x photocatalysts to visible light-irradiation.

This work was supported by RFBR under grant 09-03-00795-a.

References.

1. A.A. Lisachenko. Journal of Photochemistry and Photobiology A: Chemistry, (2008), v.196, pp. 127–137. 2. A.A. Lisachenko. Physica B: Condensed Matter, Volume 404, Issues 23-24, 2009, P. 4842-4845.


44

PHOTOINDUCED OXYGEN ISOTOPE EXCHANGE

ON NANOSTRUCTURED METAL OXIDES

R.V. Mikhaylov, V.V. Titov, L.L. Basov, A.A. Lisachenko


[email protected]

The understanding of the interaction between photoactivated metal oxides and oxygen is of great

importance since oxides are widely used as photocatalysts [1]. Photoactivation of adsorbed (or

lattice) oxygen species is an essential step in photocatalytic oxidation reactions. The two main forms of photoactivated surface oxygen are atomic O

- and molecular O2

- species.

The aim of this work was to investigate oxygen photoadsorption (PA) and photodesorption (PD), as

well as photoinduced oxygen isotopic homo- (16

O2(gas) + 18

O2(gas) ↔ 216

O18

O(gas)) and hetero-

(16

O(surf) + 18

O2(gas) → 16

O18

O(gas) + 18

O(surf)) exchange (POIE) on wide-bandgap oxides. Mass-

spectrometric kinetic measurements and thermo-programmed desorption (TPD) were used in this

work. The setup and techniques are described elsewhere [2].

TiO2-x. Two kinds of sample treatment were used. The “oxidized” samples were obtained by

annealing TiO2 at 820 K in 0.5 Torr O2 for 30 min and subsequent cooling down to 470 K in

oxygen and further down to the room temperature in ultra-high vacuum (UHV). The “reduced”

samples were obtained by annealing at 870 K in UHV for 30 min.

It was found by TPD that O2- species is formed on reduced samples upon exposure to O2, while no

adsorption was detected on the oxidized samples.

The irradiation of TiO2 in UHV was found to cause oxygen desorption with vacancy formation. In

contrast, the UV or VIS irradiation of TiO2 in O2 results in vacancy healing, formation of atomic

oxygen species and homo- and heteroexchange via O3- intermediate complexes. Spectral and kinetic

features of POIE were determined. The mechanism proposed is in complete accordance with those features.

O2 photoadsorption, photodesorption and POIE were also revealed on ZnO, moreover dissociative

PA of H2 and methane were found. The activation spectra of these processes extend to the sub-

bandgap region and quantum yields of these processes reach 0.2. Similarly to TiO2, long-living

photoinduced anions O–struct are considered to be responsible for POIE and O2 and methane PA on

ZnO.

The formation of such photoinduced centers is a typical for wide-bandgap oxides (ZrO2, Al2O3,

La2O3, Ga2O3, Sc2O3, MgO). The results obtained for Ga2O3 suggest the appearance of two types of

O–struct centers and, as a consequence, two species of adsorbed oxygen with the desorption activation

barriers of 36.5 and 125 KJ/mol. The photoinduced centers can survive multiple adsorption/desorption cycles.


References.

1. U. Diebold. Surface Science Report, Vol. 48, 2003, p. 53-230.

2. Lisachenko, A. A.; Kuznetsov, V. N.; Zakharov, M. N.; Mikhailov, R. V. Kinet. Catal. 2004, 45,

189.


45

KINETICS OF CONTAMINANT ORGANIC FILM REMOVAL

FROM PHOTOCATALYTIC SELF-CLEANING SURFACES

D.F. Ollis

North Carolina State University, Chemical and Biomolecular Engineering, Raleigh, USA

[email protected]

Photocatalytic titania-containing, powders and nanomaterials have been incorpo-rated into office

window glass, ceramic tiles, cementitious building materials, and road paving blocks (1,2), among

other possibilities, to yield air-solid surfaces which are “self-cleaning” when subjected to bandgap

illumination, because they can oxidatively remove deposited organic contaminants. While kinetic

rate laws for destruction of air and water contaminants have been widely studied, the less-studied

kinetics of organic contaminant film removal present distinctive challenges, leading frequently to

kinetic disguises and the requirement for careful analysis to obtain fundamental kinetic rate

constants.

We discuss kinetic models for the following organic film configurations:

1. non-porous catalyst, continuous organic film deposit

2. porous surface continuous organic film deposited within catalyst

3. non-porous surface, discontinuous film (island) deposits

4. organic dye deposits on non-porous surface

5. organic dye deposits within porous catalyst

6. organic soot deposits on non-porous catalyst surface

With simple models which account for contaminant surface coverage, and light absorption by

catalyst or contaminant, we demonstrate model results which fit a considerable set of data from

multiple laboratories and rationalize the following observed reaction orders:

Catalyst Organic film Reaction kinetic order

Porous? Continuous? Intrinsic(true) order Apparent (observed) order

NO YES 1(submonolayer) 1

NO YES 0(multilayers) 0

NO NO 0(islands) 0 to 1

YES YES 1(submonolayer) 2

YES YES 0(multilayer) 1

These circumstances include deposits of non-volatile hydrocarbons (e.g., stearic acid), colored

contaminants (organic dyes), and environmental particulates (soot). They demonstrate that a

reliable understanding of organic film removal kinetics requires knowledge of film thickness

(submonolayer vs. multi-layers), location (on or within porous catalyst), state of dispersions

(continuous layers vs. islands), and size distribution of initial (island) deposits, if present. We also

demonstrate that these models of disguised kinetics may be used to recover the values of the

intrinsic(true) rate constants.

(1)Auguliaro, et al (eds), Clean by Light Irradiation: Practical Applications of Supported TiO2,

RSC Publishing, Cambridge, UK, 2010.

(2)Ohama, Y. and van Gemert, D (eds), Application of Titanium Dioxide Photocatalysis to

Construction Materials, Springer, Dordrecht, 2011.


46

PHOTOCATALYTIC ACTIVITY OF NANOSTRUCTURED CATION-

ORDERED LAYERED PEROVSKITE-TYPE TITANATES AND

TANTALATES IN PROCESS OF WATER SPLITTING

I.A. Rodionov, O.I. Silyukov, I.A. Zvereva

Department of Chemistry, St.-Petersburg State University, Russia

[email protected]

The presentation focuses on the structural design and catalytic properties of materials based on

perovskite-type layered oxides. Photocatalytic properties are discussed in comparison with relative

binary oxides and oxides with 3D perovskite structure. The reactions of photocatalytic degradation

of dyes and water splitting are considered as example. There was a much attention to the application

of TiO2 as a catalyst in various photochemical processes (water splitting or decomposition of

organic chemicals in wastewater).

In last decade one of the main directions of the searching of novel photocatalysts is the study of

catalytic activity of perovskite-type layered oxides with 3d, 4d, 5d- and 4f-elements. The structure

and electronic properties of layered phases should strongly influence on the electron-hole

recombination process and the nature of interlayered space. Use of layered materials of complex

cationic content is especially promissing because of the possibility of modifying the chemical

composition as well as microstructure by means of ion-exchange or intercalation, which is useful

for designing photocatalysts based on semiconducting metal oxide sheets.

The current report presents results of the development of the photocatalytic systems based on

nanostructured cation-ordered layered oxides and investigation of their catalytic activity in the

reactions of model organic water contaminants degradation and photocatalytic water splitting under

the UV-light irradiation.

In our work we consider the wide range of oxides which belong to layered perovskite-type

structures (Ruddlesden-Popper, Dion-Jacobson and Aurivillius phases with various thickness of

perovskite slabs) on the base of our experimental data. A main attention will be devoted to series

A2Ln2Ti3O10 and ALnTa2O7 (A= Li, Na, K, Rb, Cs) which exhibit a complete ordering of A+ and

Ln3+

cations inside the rock salt layers owing to essential differences in charge. New data on band

gap energy, quantitative characteristics of water intercalation in layered structure and ion-exchange

reactions in the water medium are reported. On the base of these sets of data the link between

structural particularities and catalytic activity will be discussed. Unexpected high photocatalytic

activity of some members of the series under investigation can be clear from point of a prominent

role of the water intercalation into the interlayer space of the crystal structure.

This work has been supported by the RFBR (Grant 12-03-00761) and Saint-Petersburg State

University (Research grant 12.0.105.2010).


47

MECHANISMS OF RADICAL INTERMEDIATES FORMATION

IN PHOTOSTIMULATED PROCESSES ON OXIDE SURFACES

A.M. Volodin, S.E. Malykhin, A.F. Bedilo

G.K. Boreskov Institute of Catalysis SB RAS, Novosibirsk, Russia

[email protected]

Radicals and ion-radicals are possible intermediates in many photochemical and photocatalytic

reactions taking place on the surface of heterogeneous materials. In the current study we

investigated by “in situ” EPR and quantum chemistry the mechanisms of photostimulated processes

resulting in the formation of such intermediates after illumination with photon energies lower than

the band gap of the solids. It was shown that on partially hydroxylated surface of alkaline-earth

metal oxides such light absorption is caused by the presence of specific surface complexes

consisting of the surface low-coordinated atoms and chemisorbed water.

hν

[OH-…Mg

2+-O

2-…H

+]LC [OH

-…Mg

+-O

-…H

+]LC* [OH

-…Mg

2+-O

-]LC +

•H

The formed holes [OH-…Mg

2+-O

-]LC are electrically neutral and can be attributed to O

-LC radical

anions detected by EPR. Formally, the formation of such electron-deficient sites (holes) can be

described as stabilization of a neutral •OH radical on a low-coordinated surface structure

[Mg2+

-O2-

]LC. Electron-rich sites can be formed in the same process by [Mg2+

-O2-

]LC interaction

with a neutral •H radical.

This original mechanism for the generation of ion-radicals on the MgO surface under illumination

[1] does not include the charge separation. Instead, it involves separation of neutral radicals (see

Figure) resulting from homolytic photodissociation of chemisorbed water. In this presentation we

shall discuss the thermodynamic aspects of such processes and possibility of their occurrence on the surface of oxide semiconductors (TiO2, ZnO).

The study was supported by RFBR (Grant 10-03-00691).

[1] S.E. Malykhin, A.M. Volodin, A.F. Bedilo, G. M. Zhidomirov, J. Phys. Chem. C, 113 (2009)

10350–10353.


48

TIO2-MXOY HETEROSTRUCTRUED PHOTOCATALYSTS.

PREPARATION AND PHOTOCATALYTIC STUDIES

X. Zhang, J. Yang, C. Wang, H. Liu, Y. Liu

Northeast Normal University, China

[email protected]

TiO2 is the most investigated photocatalyst over the past decades in the field of environmental

cleanup including purification of indoor and outdoor air, self-cleaning, bactericidal, as well as water

purification. [1-2]

Various approaches have been examined to extend the spectral response of TiO2 to

the visible spectrum in order to utilize solar irradiation better. We, however, focus herein on

enhancing the photo-stimulated charge separation of anatase TiO2 via forming heterostructure with

other oxide materials, including SnO2, WO3, rutile TiO2 and TiO2 (B), so as to obtain higher

photocatalytic performance.[3-4]

The motivation of our work is encouraged by the fact that solar

light actually contains a considerable amount of ultraviolet photons (1-3 mW cm-2

) dependent on

weather condition in urban area) and the recent development in low cost UV-LED has made it

possible to have low-cost, high output and miniatured UV light sources in the near future. We are

also interested in identifying the factors that influence the photocatalytic performance of

heteostructure systems. One example of the research is TiO2-WO3 composite porous microsphere

photocatalysts prepared by the ultrasonic spray pyrolysis method. We observed faster photocatalytic

decomposition of acetaldehyde for three sample compositions, TiO2-2% WO3 (TW-2), TiO2-

4%WO3 (TW-4) and TiO2-10%WO3 (TW-10), than TiO2 (TW-0) only. However, only the TW-2

sample was better than pristine TiO2 (TW-0) in both CO2 production and acetaldehyde degradation.

Under UV illumination, TW-4 and TW-10 samples both showed apparent photochromic behavior in

methanol solution (5% v/v), evidenced the electron accumulation in WO3 phase, whereas TW-2 and

TW-0 showed negligible color change. These results suggest that the amount of WO3 deposited in

TiO2 microsphere is a critical factor that influences charge acceptance and accumulation in WO3.

Correlation of photochromic behavior with photocatalytic activity of TW samples thus suggests that

charge accumulation in TiO2-based photocatalysts is not good for the complete mineralization of

organic pollutants.

Acknowledgements. The work was supported by NSFC (Grants No. 51072032) the Program for

New Century Excellent Talents in University (NECT-10-0320).

References

[1] A. Fujishima, X. Zhang, D. A. Tryk, Surf. Sci. Rep. 2008 (63) 515-582.

[2] A. Fujishima, X. Zhang, C. R. Chim. 2006 (9) 750-60.

[3] C. Wang, X. Zhang, Y. Zhang, Y. Jia, J. Yang, P. Sun, Y. Liu, J. Phys. Chem. C 2011 (115)

22276-22285.

[4] J. Yang, X. Zhang, C. Wang, H. Liu, S. Liu, P. Sun, L. Wang, Y. Liu, Catal. Today 2012, in

press

Orals Photonics of model biological systems and biological molecules ----------------------------------------------------------------------------------------------------------------------------- --------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------

49

SECTION 5. PHOTONICS OF MODEL BIOLOGICAL SYSTEMS

AND BIOLOGICAL MOLECULES

PHOTOOXIDATION OF TETRAHYDROBIOPTERIN UPON

UV-IRRADIATION: POSSIBLE PATHWAYS AND MECHANISMS

A.A. Buglak, T.A. Telegina, T.A. Lyudnikova, Y.L. Vechtomova, M.S. Kritsky

A.N. Bach Institute of Biochemistry RAS, Moscow, Russia

[email protected]

Tetrahydrobiopterin (H4Bp) is known to serve as a cofactor for several enzymes such as aromatic

amino acid hydroxylases (including phenylalanine-4-hydroxylase which is involved in

melanogenesis), nitric oxide synthases, glyceryl-ether monooxygenase. Cyanopterin, which is a

glycosylated form of H4Bp, acts as a chromophore in photoreceptors of some cyanobacteria. Pterins

absorb ultraviolet, including UV-A photons, and in addition to their functions in photoreceptors

they are unspecific molecular targets of UV-radiation in organism. In this context, we investigated photooxidation of H4Bp and examined the mechanisms involved in this process.

Irradiation of pterin solutions was performed by using high-pressure mercury-vapor lamp with UFS-

6 filter (transmission range from 290 to 400 nm) or Xenon arc lamp as a source of 300 nm or 350

nm monochromatic light. Identification of the reaction products was based on HPLC separation,

using photometric, fluorometric and amperometric detection of eluted compounds in combination

with the analysis of their absorption and fluorescence spectra. To study the mechanism of H4Bp

photooxidation we also performed quantum-chemical calculations using Density Functional Theory (DFT) method.

After 60 seconds of 350 nm irradiation oxidation of H4Bp accelerated, leading to dihydrobiopterin

formation. At the same time concentration of biopterin (Bp) coincidentally increased. Addition of

Bp to the initial H4Bp solution dramatically increased the rate of H4Bp oxidation. Thus, the

presence of excited Bp enhanced H4Bp oxidation. By using the DFT method we have found that

photosensitization of O2 proceeds through energy transfer from 3Bp and results in formation of

1O2,

and does not involve electron transfer and formation of superoxide-anion radical. Basing on

calculations of Gibbs free energy of reactions between H4Bp derivatives and reactive oxygen

species (ROS) we proposed a mechanism of H4Bp photooxidation.

Under 350 nm monochromatic irradiation, the quantum yield of H4Bp photooxidation reaction was

1.5±0.6. This high quantum yield value prompted us to suggest that photooxidation of H4Bp is a

chain process. The quantum chemical calculations support this hypothesis. It is known that

autooxidation of H4Bp in absence of irradiation is a radical chain process. We believe that photoreactions supplement the H4Bp autooxidation and also proceed as radical chain process.

Our results show that there are at least two pathways that participate in H4Bp photooxidation: 1)

direct H4Bp photooxidation; 2) reactions of H4Bp with ROS which depend on 1O2 generated by

oxidized pterins.

Our data may shed light on causes of melanogenesis disorder such as vitiligo pathology, and also on the role of pterins in photoreception.

Supported by the Program of Basic Research №28 of the Presidium of Russian Academy of

Sciences and Russian Foundation for Basic Research. Grant 11-04-01007-a.


50

EVIDENCE OF DNA MELTING

IN BRILLOUIN LIGHT SCATTERING SPECTRA

A.V. Dmitriev1, A.I. Fedoseev

2, G.A. Zakharov

3, S.G. Lushnikov

2, E.V. Savvateeva-Popova

3


2 – A.F. Ioffe Physical-Technical Institute RAS, St.Petersburg, Russia

3 – I.P. Pavlov Physiology Institute RAS, St.Petersburg, Russia

[email protected]

During the last decade researchers actively studied phase transformations of DNA, proteins, and

other biopolymers that can lead to changes in activity and functions. Phase transformations of

biopolymers mean changes in the spatial structure of a macromolecule under the action of external

factors (temperature, pressure, etc.). One of the least studied problems is how the vibrational

spectrum of a macromolecule behaves when its spatial structure changes or, in other words,

dynamics of a macromolecule at phase transformation. Our work was aimed at studying the low-

frequency (frequency range from 1 to 1000 GHz) dynamics of DNA at melting. It is known that the

low-frequency dynamics of biopolymers typically reflects local conformational changes, i.e., hops

of atoms from one configuration to another and collective excitations. Dynamics of biopolymers in

this frequency range has many common features with the dynamics of glasses, supercooled liquids,

and other condensed media. One of the most promising techniques that gives valuable information

on the low-frequency dynamics of biopolymers is Brillouin light scattering [1,2].

We employed this techniques to investigate the low-frequency DNA dynamics at its melting. The

sample was a DNA solution in a sodium-phosphate buffer (pH = 7.5). The DNA sample 120

nucleotides in length was obtained from a genome DNA of drosophila by a polymerase chain

reaction.

Experiments were carried out in a 180° scattering geometry by a three-pass piezo-scanned Fabry-

Perrot interferometer. The light source was an argon laser with wavelength λ = 488 nm. The objects

of measurements were solutions with a DNA concentration of 100 mcg/ml, the temperature range

was 20–90° С.

It has been shown that the hypersound velocity exhibits an anomaly in the region of the theoretical

melting temperature. At this temperature, an anomaly in damping of hypersonic waves is also observed.

1) S. A. Lee, S. M. Lindsay, J.W. Powell, T. Weidlich, N. J. Tao, G. D. Lewen. Biopolymers, Vol.

26, 1637-1665 (1987).

2) A. V. Svanidze, S. G. Lushnikov, S. Kojima. Pis`ma v ZhETF, Vol. 90, iss. 1, 85-89 (2009).


51

MODIFICATION OF PHOTONICS OF INDOLE CHROMOPHORE

BY HALOGENATED ORGANIC COMPOUNDS

V.V. Gurinovich1, P.A. Vorobey

2, S.V. Pinchuk

3, A.V. Vorobey

4

1 – Faculty of physics, Belarus State University, Minsk, Belarus

2 – National Anti-Doping Laboratory, Minsk District, Belarus

3 – Institute of Biophysics and Cell Engineering NAS, Minsk, Belarus

4 – Institute of Physics NAS, Minsk, Belarus

[email protected]

Photophysical processes and photochemical reactions of tryptophan and tryptophan residues of

proteins, in aqueous solutions and isolated erythrocyte membranes, in the presence of halogenated

organic compounds (HOC) chloroform, trichloroethanol and sodium trichloroacetate has been investigated.

It was found that HOC (in millimole concentrations) significantly modify photonics of UV-induced

(λ = 270–300 nm) degradation of tryptophan in solution. There has been an increase in the quantum

yield of photodegradation, and the formation of photoproducts which are different from products of

UV-induced degradation of tryptophan in the absence of HOC. The observed effects are due to

electron transfer from the excited tryptophan molecule to the HOC molecule, with the formation of

a free radical of one-electron reduction of HOC and an unidentified product of the photochemical

degradation of tryptophan. Electron transfer occurs from the singlet excited state of amino acid by a

tunneling mechanism. Similar photophysical processes and photochemical reactions occur upon

irradiation of tryptophan-containing proteins in solution and in membranes in the presence of HOC.

The free radicals of one-electron reduction of HOC are highly reactive to various biological

substrates. When tryptophan-containing proteins, such as enzymes, are irradiated in solutions in the

presence of HOC, their inactivation is observed. The presence of HOC in suspensions of isolated

membranes under irradiation lead to significant enhancement of peroxidation of membrane lipids due to formation of HOC radicals involving excited tryptophan residues of membrane proteins.

The products of photodegradation of tryptophan and tryptophan residues of proteins, which are

formed in the presence of HOC, are able to generate singlet oxygen while absorbing UVA radiation

(315–400 nm). Thus, these products may act as sensitizers of photodynamic damage of biological molecules and membranes under the effect of solar UV radiation in real environmental conditions.

The possible significance of the observed phenomena for human health and environment under increased exposure to UV radiation in the presence of technogenic HOC pollutants is discussed.


52

LIGHT INTERACTION WITH NUCLEIC ACIDS AND ORIGIN OF LIFE.

TIGHTLY BONDED STACKING AGGREGATES OF NUCLEIC BASES –

THE FIRST LIFE SYSTEMS

V.L. Rapoport

V.A. Fock Institute of Physics, St.-Petersburg State University, Russia

[email protected]

The results of the series of work of author and co-workers, devoted to the study of luminescence of

dinucleosides, dinucleotides, polynucleotides and stacking aggregates of nucleic bases in water are

discussed. In these works has been shown the existence of tightly bonded densely packed stacked

dimers of nucleic bases and other stable at high temperatures stacking aggregates. These dimers and

aggregates are stable at temperatures up to the 90°C in water [1]. These luminescence and

excitation spectra are similar to the same spectra, observed for their dinucleosides and

polynucleotides. For example, for adenosine dimers spectra is practically the same, as for ApA and

poly-A: luminescence maximum at 400–500 nm and excitation with exciton splitting 4000 cm-1

[2]. The same results were observed for adenine, uracil and thymine [3].

These stable at high temperatures dimers and aggregates of nucleic bases could be precursors of

RNA in the role of first genetic matrix [1]. It was supposed that they could multiple in mixed water

solutions of complementary nucleic bases during the cyclic growing and falls of temperatures (from 1–2°C to 6–7°C).

Here discussed the results, which support this idea. In mixed adenine and uracil (thymine) solutions

(10-3

М, рН 7.0) were observed stacking aggregates formation at the temperatures about 2°С (in the

time about 0.5 h, it can be forced by the heating) and little duplexes from stacked dimers and

aggregates, bonded with monomers, other dimers and aggregates by the H-bonds. During the cyclic

heating (up to 6–7°С) and cooling (to 1–2°С) of the mixture the increasing of the stacking

aggregates concentration (up to 15% during 5-6 cycles) is observed. This increasing are caused by

the self-assembling of the new stacking dimers (or higher aggregates) from the monomers (and less

aggregates) on the initial matrix. Now the proposed schema of stacking dimers (aggregates) multiplication are supported by these results.

It should be pointed out, that stable at high temperatures stacking dimers (aggregates) are instable at UV irradiation at 300–320 nm, there these dimers absorb light, but monomers – not.

Here discussed the properties of stable at high temperatures stacking aggregates, similar to the

properties of the living systems:

1. ability to matrix multiplication with errors;

2. dense packing – inter plane distance ≈ 2.9–3 Å (from exciton splitting);

3. high stabilization energy in gas phase 0.5 eV (I.V. Krauklis, quantum chemistry);

4. adaptivity (a plenty of different conformers);

5. the exchange of matter and energy with external (water) environment (reproduction and

luminescence quenching);

6. ability to absorb and emit 2 photons (bifotons = biofotons);

7. evolution-like growth of the stacking aggregates size with an increase in numbers of heating-

cooling cycle.

The possibility of life based on other chemistry (for example, aromatic amino acids), is discussed.

1. Рапопорт В.Л. и др. Доклады Академии наук, 2006, том 406, №3, с.402–406. 2. Рапопорт В.Л. и др. В кн.: Происхождение и эволюция биосферы. Сборник трудов П/программы 1

Программы №18 Президиума РАН. П/ред. акад. Э.М. Галимова. М: УРСС, 2008), с. 169–178. 3. Rapoport V.L., et all. Biophysics, 2012, 57 (1), pp. 9–13.


53

ULTRATHIN FILMS OF THE BACTERIORHODOPSIN

AS PROMISING PHOTOSENSITIVE NANOBIOMATERIALS

D.O. Solovyeva, S.Yu. Zaitsev

Laboratory of Nano-Bioengineering, Moscow Engineering Physics Institute, Russia

[email protected]

Preparation and application of the membrane-like systems based on photosensitive membrane

protein - bacteriorhodopsin (bR) is an interesting field at the interface of materials and life sciences

[1-3]. Purple membranes (PMs) are the fragments of membranes of the bacteria Halobacterium

salinarum, in which bR is the main protein component. They are the most typical and well-

described examples of such membrane-like systems. It is known that bR is transforming physical

energy (light quanta) into chemical energy of macroergic compounds (e.g., ATP) or mechanical

energy (e.g., flagellar movement in bacteria). It should be emphasized that bR and PMs possesses

unique physicochemical properties and fulfils three main molecular functions that are crucial in

terms of fundamental studies and technological applications: photoelectric, photochromic, and

proton-transporting [2-5].

The fabrication of ultrathin and highly oriented bR films is one of the key tasks for prospective

applications of bioinspired hybrid materials and devices. One of the most promising methods is the

preparation of bR monolayers at the liquid/air or solid/air interfaces by Langmuir–Blodgett,

Langmuir–Schaefer or self-assembly methods [1, 2].

In the first experiments on obtaining bR monolayers, bR patches were applied to the liquid/gas

interface from an organic solvent (hexane) or a mixture of bR and soybean lecithin dispersed in

hexane [6]. More than 85% of bR were found to be oriented with their cytoplasmic (inner) side

facing the water subphase [6]. When PM monolayers were transferred onto glass, the same

percentage of PMs was adsorbed with their cytoplasmic side facing the glass substrate surface [6].

Later, a number of studies demonstrated that PMs were partly denatured when organic solvents

were mixed with the water subphase [7], which could be related to either disruption of hydrophobic

interactions within the protein or exclusion of lipid molecules from its three-dimensional structure.

In most cases, to apply bR from water dispersions is the best method for obtaining their monolayers

[7]. In our experiments the area per bR molecule in a monolayer (upon extrapolation to a zero

pressure) on the surface of a 100 mM KCl solution has been estimated to be 8 nm2 [1], which agrees

with the X-ray data on the protein structure in the membrane obtained by Henderson et al. using

elementary cell 2.5 × 3.5 × 4.5 nm in size [4]. A steep rise of the isotherm of surface pressure

versus area per protein molecule and a high monolayer collapse pressure (higher than 45 mN/m)

indicate the formation of sufficiently strong bR monolayers on concentrated salt subphases. In

addition, these structures have been found to have a high photopotential when illuminated through a

filter with a bandpass of 570 ± 15 nm. Such ultrathin and oriented bR films are considered as

promising nano-biomaterials for photovoltaic, biosensing, and development of optoelectronic

devices [2, 5].

This study was partly supported by the Ministry of Higher Education and Science of the Russian Federation (grant no. 11.G34.31.0050) and RFBR (10-03-00711).

1. Birdi KS: Lipid and Biopolymer Monolayers at Liquid Interfaces. Plenum Press; 1989. 2. Zaitsev SYu: Supramolecular Nanodimensional Systems at the Interfaces: Concepts and Prospects for

Bionanotechnology. Mosbook–Librocom; 2010.

3. Hampp N, Osterhelt D. In Protein Science Encyclopedia. Wiley Online Library; 2008. 4. Henderson R, Baldwin JM, Ceska TA, Zemlin F, Beckmann E, Downing KH, J Mol Biol, 1990; 213: 899. 5. Vsevolodov NN: Biomolecular Electronics. An introduction via photosensitive proteins. Birkhauser; 1998. 6. Hwang S, Korenbrot JT, Stoeckenius W, J Membr Biol, 1977; 36: 115. 7. Furuno T, Sasabe H, J Colloid Interface Sci, 1991; 147: 225.


54

NON-PHOTOCHEMICAL FLUORESCENCE QUENCHING

OF PHYCOBILISOMES IS A NEW PHOTOBIOLOGICAL EFFECT

FOUND IN CYANOBACTERIA

I.N. Stadnichuk

A.N. Bakh Institute of Biochemistry RAS, Moscow, Russia

[email protected]

Phycobilisomes (PBS) are giant phycobiliprotein complexes with the molecular mass of about 3

million Daltons that play the role of photosynthetic antenna in the cyanobacterial pigment

apparatus. Light energy absorbed by PBS is transferred to photosynthetic reaction centers with 95-

100% efficiency [1]. It has long been assumed that cyanobacteria do not have the possibility of

dissipating excess energy as heat at the antennal level although the overexcitation of PBS which

includes hundreds of pigment molecules can result in damage of the antenna itself or the reaction

centers. In these photosynthetic prokaryotes, an effect of a blue light on the variability of

chlorophyll and the PBS fluorescence emission was mentioned in 2001 [2] but the corresponding

short-term light adaptation process of PBS quenching (non-photochemical fluorescence quenching)

was found later, in 2004 [3]. According to a current report this mechanism is evolutionarily rather

old [4]. Illumination of the cyanobacterium Synechocystis sp. with strong blue-green light led to

about 40-80% diminishing of PBS-fluorescence emission. The action spectrum of this quenching

with three characteristic bands in the region of 450-550 nm indicated that the phenomenon is

triggered by an unidentified carotenoid [3]. In 2006, it was shown that it is a ketocarotenoid,

hydroxyechinenone, present as a single chromophore molecule in the water-soluble orange

carotenoid protein (OCP) [5]. OCP was demonstrated to exist in two forms: inactive dark-adapted

OCP orange form and induced by strong blue-green light metastable active OCP red form with the

phototransformed ketocarotenoid molecule [6]. Effective docking of OCP red form to isolated PBS,

using an in vitro reconstituted system and corresponding fluorescence methods, provided direct

evidence that OCP is not only a photosensor in this process, but acts also as an effector [7,8]. To

localize the primary site of quenching, we have analyzed the role of all chromophorylated

polypeptides within the PBS using an in vitro isolated PBS components. The data suggest that the

long-wavelength LCM-polypetide besides a key structural function in the PBS and the central role in

excitation energy transfer is the site of photoprotective excitation quenching influenced by OCP.

Various other chromophorylated components of the PBS are not directly subjected to quenching.

According to the Strern-Volmer theory the quenching of LCM has a static character, while the

corresponding secondary quenching of assembled PBS is of a dynamic type. A model for OCP-LCM

interaction within the PBS is proposed based on the 3D structures of the corresponding proteins.

The distance between the phycocyanobilin chromophore of LCM and the ketocarotenoid

chromophore of OCP is estimated as about 15 Å being available for quenching.

References [1] I.N. Stadnichuk, Phycobilisomes, VINITI Publ. Moscow, 1991, 176 pp.

[2] K. El Bissati, E Delphin, N. Murata et al., Biochim. Biophys. Acta 2000, 1457, 229-242. [3] M. Rakhimberdieva, I. Stadnichuk, I. Elanskaya, N. Karapetyan, Febs Lett. 2004, 45, 85-88. [4] G. Bernát, U. Schreiber, E Sendtko et al., Plant Cell Physiol. 2012, 53, 528-542. [5] A. Wilson, G. Ajlani, J.-M. Verbavatz, et al., Plant Cell 2006, 18, 992-1007. [6] A. Wilson, C. Punginelli, A. Gall, et al., Proc. Natl. Acad. Sci. U. S. A. 2008, 33, 12075-12080. [7] I. Stadnichuk, M. Yanyushin, S. Zharmukhamedov et al., Dokl. Biochem. Biophys. 2011, 439, 167-170. [8] M. Gwizdala, A. Wilson, D. Kirilovsky, Plant Cell, 2011, 23, 2631-2643. [9] I. Stadnichuk, M. Yanyushin, E. Maksimov et al., Biochim. Biophys. Acta, 2012,

doi:10.1016/j.bbabio.2012.03.023.


55

PHOTOPHYSICAL PROPERTIES OF OLIGOMERIC CHAINS

WITH PYRENE-MODIFIED NUCLEOTIDES

A.S. Stasheuski, V.A. Galievsky

Institute of Physics NAS, Minsk, Belarus [email protected]

Binding of nucleotides with polyaromatic labels provides easy way for DNA- or RNA-associated

processes visualization and may be applied for nucleic sequences analyses. For example, pyrene-

based probes may form excimers and exciplexes with fluorescent band shifted up to 100nm from

the monomeric band. Due to their utilization wide group of hybridization probes have been

originated and based on luminescence wavelength switching after binding with target nucleotide

sequence. Incorporation of label into the probe may be realized in different ways, among them the

most prominent is replacement of natural bases by non-nucleoside pyren-based units.

In present work photophysical properties of oligonucleotide modified by pyrene building blocks

were investigated. Influence of molecular structure of using pyrene label and adjacent nucleic bases

on rising and decay of monomeric and excimeric luminescence is studied by methods of laser

kinetics spectroscopy. Characteristics of new building blocks in model single- and dublestranded

sequences are described.

Oligonucleotide hybridization brings two pyrene molecules to each other and leads to red shift of

pyrene band in absorption spectra. Also intensity of absorption is reduced. These features are

because of pi-pi interaction of pyrene molecule in ground state.

Kinetic data were treated by maximum entropy and global analysis methods (figure 1).

-0.5 0.0 0.5 1.0 1.5 2.0 2.5 3.00

1

2

3

4

f[log ]

log( )

monomer decay

excimer rising

excimer decay

AGC TCG GTC A C GAG AGT GCA

TCG AGC CAG T G CTC TCA CGT

-0.5 0.0 0.5 1.0 1.5 2.0 2.5 3.00

1

2

3

4

AGC TCG GTC A C GAG AGT GCA

TCG AGC CAG T G CTC TCA CGT

f[log ]

log( )

monomer decay

excimer rising

excimer decay

Figure 1 – Lifetime distributions for monomer (at 400nm) and excimer (at 540nm) luminescence. Capital

letters – nucleotides. α and β – 1,6- and 1,8-bistriazolylpyrene. τ in ns

Multiple bands in the distributions indicate about several physical processes affecting the luminescence. Excimer rising part is overlapped with monomer decay. In the studied systems are implemented two

pathways for excimer formation: from the coupling of monomers in the excited and ground states and from the direct photoexcitation of a ground state dimer.

Label incorporation inside of nucleic chain isolates substantially excited pyrene molecules from

interaction with water environment and oxygen quenching. Previously single- and doublestranded

oligonucleotide based on carboxyamidpyrene building blocks were studied [1]. For buffer solutions in

presence of oxygen excimer fluorescence quantum yields were up to 26%. In new substances with bistriazolylpyrenes and bisbutynylpyrenes excimer fluorescence quantum yields are more than 50%.

Lifetime of dominant component from excimer decay is more than 60ns, and almost one order higher

than monomer luminescence lifetime. Therefore during experiments in vivo excimeric luminescence may be surely separated from obstructing autofluorescence by spectral and kinetic techniques.

Obtained photophysical characteristics of nucleotides with pyrene building blocks enable to utilize such

supramolecular structure as frameworks for construction of new highly sensitive fluorescence probes.

References: 1. Galievsky V.A. et al. Photochem. Photobiol. Sci., 2009, 8, 1448.


56

STUDY OF PHOTONICS OF POLYMETHINE DYES

IN COMPLEXES WITH BIOMACROMOLECULES

FOR DEVELOPMENT OF NEW SPECTRAL-FLUORESCENT PROBES

A.S. Tatikolov1, T.M. Akimkin

1, P.G. Pronkin

1, L.A. Shvedova

1, S.M. Yarmoluk

2

1 – N.M. Emanuel Institute of Biochemical Physics RAS, Moscow, Russia

2 – Institute of Molecular Biology and Genetics NAS, Kiev, Ukraine

[email protected]

The method of spectral-fluorescent probes is a powerful tool for studying biological systems. As we

showed earlier, meso-substituted polymethine dyes are promising as such probes. To develop new probes for biomolecules, we studied spectral-fluorescent properties and photochemistry of carbocyanine

dyes, both meso-substituted and, for comparison, without a meso-substituent, in complexes with

biomacromolecules.

3,3’,9-trimethylthiacarbocyanine (Cyan 2), 3,3’-dimethylthiacarbocyanine (Cyan 45), and 3,3’-diethyl-9-methylthiacarbocyanine (DMTC) were shown to form H-aggregates on hyaluronic acid (HA)

molecules, which is reflected in the appearance of a short-wavelength absorption band with a maximum

at 440–450 nm in the presence of HA (the initial monomeric dye has an absorption maximum at 535

nm). By the tendency to H-aggregation in the presence of HA, the dyes can be arranged in the series Cyan 2 > Cyan 45 > DMTC > DTC (DTC is 3,3’-diethylthiacarbocyanine). Since the H-aggregates

formed are nonfluorescent, fluorescence does not appear. The aggregation number for Cyan 2 was

determined: n = 3. Since noticeable changes in the absorption spectrum of Cyan 2 are observed even at a sufficiently low concentration of HA (about 5∙10–7 mol l–1), we suggested this dye as a spectral probe to

detect HA in biological objects and successfully used it in detection of HA in the vitreous body of the

eye.

Despite the fact that HA and chondroitin-4 sulfate (C4S) have similar structures of their monomeric units, the interaction of Cyan 2 with these biopolymers is completely different: its binding to HA results

in a long-wavelength shift of the absorption spectrum and a fluorescence growth. From the

mathematical modeling of the fluorescence buildup, we obtained the association constants K of Cyan 2

with C4S at different pH: K = 5∙105 – 1∙106 M–1 and n = 70–230 (n is the number of C4S monomeric units in the complex). The dependence of the fluorescence quantum yield of Cyan 2 in the complex with

C4S on pH is unusual: it reaches a minimum (0.24) at pH 7 and maximums (0.64–0.69) at low (pH 4.5)

and high (pH 9.0) pH values. This is explained by changing the biopolymer charge and conformation

upon changing pH. Therefore, Cyan 2 can serve as a probe for conformational changes in such biopolymers.

To determine peculiarities of the interaction of polymethine dyes with DNA, we studied electronic

excitation energy transfer (EEET) between donor and acceptor dye molecules, both noncovalently bound to DNA. Oxacarbocyanine dyes were used as donors and DTC as an acceptor dye. Along with

steady-state fluorescent measurements, we measured fluorescence decay kinetics of the donors in the

presence of different acceptor concentrations. To describe the EEET process, two alternative models

were used: the stoichiometric complex model and the microphase (pseudophase) model. We showed that the microphase model, which assumes concentrating of donor and acceptor dye molecules close to

DNA molecules, adequately explains the experimental data. The deviation of the fluorescence decay

kinetic curves from exponentials was explained by distribution of the distances in donor–acceptor pairs

upon EEET. The results show that the dye molecules in complexes with DNA have sufficient rotational freedom to provide the random orientation factor κ (2/3).

Using the method of flash photolysis, the photochemical processes of polymethine dyes in complexes

with biomacromolecules were studied. Along with generation of the dye triplet states, we found an

unusual effect: enhancement of photoisomerization of the dyes stimulated by bimolecules. The effect was considered with relation to potential energy curves for isomerization.

This work was supported by the Russian Foundation for Basic Research (project no. 10-03-00647).


57

LIGHT-DEPENDENT SYNTHESIS OF ATP FROM ADP

ON PROTEINOID-SILICATE MATRIX: A MODEL OF ABIOTIC PROCESS

T.A. Telegina, M.P. Kolesnikov, A.A. Buglak, Yu.L. Vechtomova, M.S. Kritsky

A.N. Bach Institute of Biochemistry RAS, Moscow, Russia

[email protected]

In organisms there exist mechanisms converting light energy into energy of macroergic bonds of

adenosine triphosphate (ATP). In photosynthetic phosphorylation light energy is converted into the

electronic excitation energy of the photoreceptor, then, to the electrochemical energy and, further, to mechanochemical energy that provides the operation of ATP synthase and formation of ATP.

We have developed a model in which the conversion of photon energy into the energy of

macroergic bonds of ATP is performed by abiogenic pigments which are the products of thermal

condensation of amino acids mixture (Glu, Gly, Lys). The pigments are conjugated with amino acid

polymer molecules (proteinoids) also formed in process of thermolysis. Two-dimensional scanning

of excitation and emission fluorescence spectra of pigment material revealed the presence of two

groups of pigments – flavins and pteridines. Substitution in mixture of glycine to alanine resulted in

a prevailing formation of pteridine, not flavin. Consequently, the long wavelength maximum of the

photophosphorylation action spectrum shifted from 450 nm to 350 nm.

These proteinoid-bound pigments sensitized efficient phosphorylation of ADP to ATP only when

staying in complex with the colloidal silicate particles. Electron donor used in experiments was Na2-EDTA and the electron acceptor was atmospheric oxygen.

The analysis of photophosphorylation showed that flavin-conjugated proteinoids were more

effective as photoreceptors than pterin-conjugated proteinoids (the yield of ATP was 20% and 9%,

respectively). We performed quntum chemical calculations of basic photochemical properties (S0-

T1 energy gap, electron affinity of T1 and ionization potential of T1) of pteridine and isoalloxazine

containing structures. The obtained values allowed us to compare ability of investigated pigments to

transport electron from donor (EDTA) to acceptor(O2). Flavin molecules when excited were shown

to have a higher electron affinity than pterins (–4.14 eV and –3.56 eV, respectively). This difference

correlates with a higher activity of flavins in photophosphorylation process that involves electron transfer.

The studied model of abiotic photophosphorylation can be regarded as a functional prototype of

biological photophosphorylation. We believe that the presence on the primitive Earth of

photoactivated supramolecular matrices was an important prerequisite for the development of various processes of prebiological evolution dependent on the formation of ATP.

Supported by the Program of Basic Research № 28 of the Presidium of Russian Academy of Sciences and Russian Foundation for Basic Research. Grant 11-04-01007-а.


58

NANOBIOHYBRID STRUCTURES BASED ON ORGANIZED FILMS

OF THE PHOTOSENSITIVE MEMBRANE PROTEINS

S.Yu. Zaitsev, D.O. Solovyeva

Laboratory of Nano-Bioengineering, Moscow Engineering Physics Institute, Russia [email protected]

The development and study of hybrid nanostructures and biomaterials engineered from

photosensitive membrane proteins (the key functional elements of various biomembranes) and

nanoheterostructures (inorganic nanoparticles, transparent electrodes and films, quantum dots, etc.)

is a rapidly growing field at the interface of materials and life sciences, with potential implications

for nanotechnology and biomedicine [1-3]. The energy harvesting in plants has a maximum

efficiency of 5%, whereas bacteriorhodopsin (bR), in the absence of a specific light-harvesting

system, allows bacteria to utilize only 0.1–0.5% of the solar light. Recent nano-bioengineering

approaches employing colloidal semiconductor and metal nanoparticles conjugated with biosystems

permit the enhancement of the light-harvesting capacity of photosensitive proteins, thus providing a strong impetus to protein-based device optimisation [1].

The main achievements in this field is connected with the organized films prepared from purple

membranes (PMs) and bR, reaction center proteins of some bacteria and plants (RCs), etc. [2]. Such

ultrathin and highly oriented PMs, bR or RC films can be considered as prototypes of

photosensitive hybrid nano-biomaterials with photovoltaic, energy transfer and optical switching

properties. Comparison of the techniques for obtaining thin films and their structural and functional

characteristics leads to the conclusion that the homogeneity and orderliness of PMs, bR or RCs in

these films depend on the method of their fabrication and increase in the following order:

electrophoretic sedimentation < Langmuir–Blodgett (Schaefer) method < self-assembly and layer-

by-layer methods [2]. Techniques of preparation of nano-biohybrid structures which were

composed of PMs, bR or RC films and semiconductor fluorescent quantum dots or plasmonic nanoparticles and demonstrated advanced photovoltaic properties have been analysed [3].

It should be emphasised that the future work on optimisation of hybrid material efficiency should

include development of highly oriented hybrid films with enhanced light harvesting, energy

transfer, photovoltaic, and optical switching properties. In these films, the internal filter effect

should be decreased and higher efficiency should be achieved at a higher nano-to-bio-material

ratios. In addition, hybrid materials can be further optimised by using QDs or metal nanoparticles

with stronger absorptions or by forming hybrid materials from biological systems and nanowires or

nanorods, whose absorption is typically much greater than that of spherical nanoparticles of the

same diameter [1, 3]. Biotechnological approaches, such as site-directed mutagenesis, permit fine

adjustment of some parameters of biological functions, e.g., the sensitivity of bR to electric field

and pH, or photochromic characteristics. Spatially and optically controlled binding of

functionalized nanomaterials with the selected molecular groups of various photosensitive proteins

followed by preparation of oriented homogeneous films will permit the development of materials with considerably improved biological functions useful for industrial applications.

This study was partly supported by the Ministry of Higher Education and Science of the Russian

Federation (grant no. 11.G34.31.0050) and RFBR (10-03-00711).

1. Nabiev I, Sukhanova A, Artemyev M, Oleinikov V. In Elaissari A (editors) Colloidal

Nanoparticles in Biotechnology. Wiley&Sons Inc; 2008.

2. Zaitsev SYu: Supramolecular Nanodimensional Systems at the Interfaces: Concepts and

Prospects for Bionanotechnology. Mosbook–Librocom; 2010.

3. Nabiev I, Rakovich A, Sukhanova A, Lukashev E, Zagidullin V, Pachenko V, Rakovich Y,

Donegan JF, Rubin AB, Govorov AO, Angewandte Chemie Intl Ed, 2010; 49:7217.

Orals Photonics of molecular nano-systems ---------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------- ---------------------------------------------

59

SECTION 6. PHOTONICS OF MOLECULAR NANO-SYSTEMS

PHOTONICS OF UNSATURATED AND MACROCYCLIC COMPOUNDS.

FROM MOLECULES TO NANOSIZED SUPRAMOLECULAR SYSTEMS

S.P. Gromov1, A.I. Vedernikov

1, E.N. Ushakov

2, L.G. Kuzmina

3, M.V. Alfimov

1

1 – Photochemistry Center RAS, Moscow,Russia

2 – Institute of Problems of Chemical Physics RAS, Chernogolovka, Russia

3 – N.S. Kurnakov Institute of General and Inorganic Chemistry RAS, Moscow, Russia [email protected]

A new trend is being currently formed in nanotechnology “bottom-up”, namely, organic nanophotonics.

We propose a new unique class of polyfunctional light-sensitive compounds: crown-containing

unsaturated dyes functioning as photochromes, fluorophores and ionophores. A large body of

research has been performed for their synthesis, determination of their spatial structures, study of

self-assembly features to give supramolecular systems, and also study of fluorescent, photochemical and complexing properties.

Resulting from the research, we elaborated for the first time universal molecular meccano, allowing

one to accomplish building-up, with using a limited number of complementary compounds, light-

sensitive and light-emissive nanosized supramolecular systems of varied architecture with adjusted

properties. Within the same class of compounds one can construct in solution, solid and at the air-

water interface new types of molecular switches, photocontrolled molecular machines, photosensitive monolayers and monocrystals susceptible to all of the key photoprocesses.

molecular devicesmolecular machines

cucurbituril

h

PHOTOANTENNA

displacement

h

CROWNPHOTOANTENNA

Mn+

The high practical value of these studies deserves attention. They provide a new strategy for the

design of materials for nanophotonics, which was demonstrated, first of all, by the creation of

practically important sensor and photochromic materials.

This work was supported by the Presidium and the Division of the RAS, the Ministry of Science and

Education, the Russian Foundation for Basic Research, the Moscow Government, the INTAS, the

CRDF and International Science Foundation (ISF), the DFG, and the Royal Society.


60

LUMINESCENCE QUENCHING OF CDSE/ZNS QUANTUM DOTS

EMBEDDED IN POROUS GLASS BY AMMONIA VAPOR

Yu. A. Gromova, A.O. Orlova, V.G. Maslov, A.V. Baranov, O.V. Andreeva


[email protected]

The problem of volatile compound vapor detection is extremely important in the modern world.

One of the detection methods is the registration of luminescence intensity changing when

luminescent particle react with target compound. Colloidal semiconductor quantum dots (QDs)

have a number of unique properties: optical characteristics depending on core size, a high

luminescence quantum yield, the extended absorption spectrum, high photostability. So, QDs are

widely used as luminescent markers and sensory elements in ecological monitoring and medicine.

In particulars, in case of semiconductor CdSe/ZnS quantum dots the interaction with vapors of

nitrogen containing compounds was observed by QDs luminescence quenching and the degree of quenching correlated with concentration of detected agent vapor [1].

In this work hydrophobic semiconductor CdSe/ZnS QDs was embedded in borosilicate porous glass. The dependence of photophysical properties on presents of ammonia vapor is investigated.

Investigation of optical properties QDs embedded in porous glass demonstrated, that absorption and

luminescence spectra are the same as that in solution in chloroform. Simultaneously, an average

time of luminescence decay became is one and a half time longer. Such a significant average time-

decay growing in the sample (from 22 ns in solution to 30 ns in porous glass) is an evidence of

partial passivation QDs surface. The reason of passivation is the nanocrystal adsorption on the

sample inner pore surfaces. Also, decay time QDs luminescence does not depend on luminescence

registration wavelength. These data indicate that QDs embedded in porous glass from chloroform

solution is isolated and do not interac with each other.

For reseach of the interaction of the porous glass with

embedded QDs with ammonia vapor our sample was

placed into the hermetic box (of 20 ml volume) containing

5 mkl of 10% water solution of ammonia on its bottom. It

should be noted that the sample did not contact with

ammonia solution. As it is clearly seen from the Figure,

increasing the time which the sample interacts with

ammonia vapors leads to a successive symbate shortening

decay time and luminescence intensity in the sample. The

observed changing of QDs photophysical properties gives an evidence of ammonia interaction with

the QDs surface that is the reason of partial quenching of QDs luminescence. The physical

mechanism of QDs luminescence quenching is not clear yet, it is a goal of the following researches.

It was found, that degassing the sample having no luminescent signal after interaction with

ammonia vapor results in recovering QDs time decay and luminescence intensity to the previous level.

Present data confirm remarkable perspective of using porous glass with embedded semiconductor

QDs as high sensitive luminescent sensory elements for detection of vapor of nitrogen containing

compounds.

1. Nazzal A. Y., Qu L., Peng X., Xi M., Photoactivated CdSe Nanocrystals as Nanosensors for

Gases//Nano Lett., Vol. 3, No. 6, 2003 P. 819-822

0 5 10 15 200,0

0,2

0,4

0,6

0,8

1,0< >/<

0>

I/I0I/

I 0, <

t>/<

t 0>

Time, min


61

PHOTONICS OF MOLECULAR CLUSTERS

IN RESTRICTED GEOMETRY SYSTEMS

N.Kh. Ibrayev, D.A. Afanasyev

E.A. Buketov State University, Institute of Molecular Nanophotonics, Karaganda, Kazakhstan [email protected]

This paper presents the results of a research of the magnetic field effect and temperature on triplet-

triplet annihilation (TTA) in solid Langmuir-Blodgett (LB) films of amphiphilic coumarin dye. LB

films of coumarin dye is observed anisotropy of light absorption. This is evidence of the dominating

spatial molecules orientation in the monolayer. Mixed thin films obtained by the LB technology,

consisting of molecules of palmitic acid and amphiphilic coumarin dye (7-decyloxy-3 (4'-

ethoxyphenyl)-coumarin) have been used as the research objects.

When the coumarin dye LB films was excited by laser pulses at T = 100 K both delayed

luminescence (λmax = 460 nm) and phosphorescence (λmax = 530 nm) were observed. Decay kinetics

of annihilation delayed fluorescence (ADF) of LB film has a non-exponential form. In the chosen

temperature range the initial part of kinetic curves (t <0.5 ms) is approximated by exponential function, and the long-term – by the exponent.

Our results demonstrate that TTA process is the one way of deactivation of T1 centers in Langmuir-

Blodgett films of the coumarin dye. TTA is the intra-layer and inter-layer process. The existing of

the inhomogeneity of the films leads to the existence two types of structures with different values of

the inhomogeneous broadening of triplet energy levels. TTA process realized in these structures with different thermal activation energy.

Modulation of the TTA rate constant by the external magnetic field at T = 100 K for multilayer

films shows the dependence as for crystals. Monolayers shows only the negative magnetic effect.

The large magnitude of the positive magnetic effect shows a higher order structure for the 10 layer

film compared to the two layer film. The absence of a positive magnetic effect for the monolayer

films shows that structure is present in the largest disorder.

Changing the magnetic effect occurs with increasing temperature for the multilayer films. The

dependence of g(B) from the time of registration ADF signal was observed. When the signal was

recorded up to 0.5 ms, the magnetic effect remains positive but decreases in magnitude. At the time

of registration of more than 0.5 ms the positive part of the magnetic effect is absent. It becomes completely negative.

The resulting time dependence of the magnetic effect indicates that the coumarin dye LB films

consist of clusters of ordered and chaotic distribution of molecules. In clusters with ordered

molecules TTA triplet annihilation is similar to triplet annihilation in crystalline environments. The

triplet annihilation in these clusters gives the largest contribution to the intensity of the ADF at the

initial moments after excitation). The dominant contribution to the kinetics of ADF give clusters

with a disordered distribution of molecules when treg ≥ 0.5 ms.

The temperature dependence of g(B) correlates with the temperature dependence of the ADF

intensity. This fact is additional evidence of the important role of thermal activation of triplet excitons migration in the clusters with the orderly and chaotic distribution of molecules.

TTA kinetics of aromatic molecules was studied in nanoporous silicate glasses. Thus two types of

clusters of aromatic molecules form in porous glasses. Clusters with the crystal structure dominate

in the ADF decay kinetics in the initial period of time (a fraction of a millisecond) after excitation.

Amorphous clusters determine the form of fluorescence decay in the millisecond range. The

increase in the pore size and concentration of the adsorbate lead to the dominance of crystalline

components.


62

PHOTONICS OF METAL ALKANOATE NANOCOMPOSITES

G.V. Klimusheva1, T.A. Mirnaya

2, Yu.A. Garbovskiy

3, S.A. Bugaychuk

1,

D.A. Melnik1, A.S. Tolochko

1, I.I. Tokmenko

2, V.V. Asaula

2

1 – Institute of Physics NAS, Kyiv, Ukraine

2 – Institute of General and Inorganic Chemistry NAS, Kyiv, Ukraine

3 – University of Colorado at Colorado Springs, CO, USA

[email protected]

The class of metal alkanoates possesses a set of advantage properties [1]. They can form ionic lyotropic and thermotropic liquid crystals, anisotropic glasses based on a pure metal alkanoate or their mixtures, serve as

universal matrices for organic and inorganic impurities, and also for semiconductor or metal nanoparticles. Because of this, cells with photoelectrochromic properties and highly effective luminescent and nonlinear optical characteristics can be created on the base of metal alkanoates.

In the present work spectral and nonlinear optical properties of photoelectrochromic cells on the base of lyotropic liquid crystals of potassium caprylate with viologen impurities (1), photosensitive cells on the base of homologous series of cobalt alkanoate anisotropic glasses (2) are researched. Cells of cadmium alkanoate composites with semiconductor nanoparticles (3) demonstrate quantum size effects in absorption and luminescence spectra of CdS nanocrystalls, which are also considered in this work.

By the methods of small angle X-ray scattering we found out, that lyotropic liquid crystalls (LLC) of potassium caprylate form mesophase, namely a smectic A, and viologens (2-4 weight %) imbedded naturally into electrostatic layers of ionic liquid crystalline matrix. Photoelectric composite cells (1) demonstrate colouring in different ranges of spectrum in dependence of the value of applied direct electric field. By the absorption spectra one can monitor electrochemical reduction processes of viologen molecules in liotropic a liquid crystal matrix. Under the action of laser irradiation (second harmonic at wavelength of λ = 539.8 nm

of Nd:YAP impulse laser) a dynamic holographic grating is recorded in the composites (1) and (2) [2]. We propose the mechanism of the dynamic grating recording in the composites (1) that lies in a reversible photoconversion between dimers and radical cations, which are the reduction products of the viologen molecules, in LLC.

Thermotropic liquid crystal phase of cobalt alkanoates can be easily supercooled and form anisotropic glasses with a smectic A structure at room temperature, that was proved by the X-ray method. Cobalt alkanoate homologues with different alkanoate chain lengths as well as binary and ternary mixtures of different metal alkanoates containing a cobalt alkanoate absorb light in the visible range of spectrum. The mechanism of absorption is due to excitation of d-electrons of cobalt ions that form octahedron coordination with alkanoate ligands. We found out that a nonlinear process of the dynamical grating recording in the anisotropic glasses of the coordination complexes of the cobalt alcanoates (2) is characterized by cubic

electronic susceptibility and high coefficient of the nonlinear refraction. High value of the hyperpolarizability of the absorption centers is connected with the delocalization of d-electrons of cobalt ions, which are located in the electrostatic layers of the matrices and linked by the coordination bonds with the ligands.

Quantum size effects that are observed in absorption and luminescence spectra of CdS nanocrystals, being synthesized in ionic liquid crystals of cadmium alkanoates (3) [3], are discussed in the work. It is shown that CdS nanocrystals in the new matrices have small dispersion of sizes, their shapes are close to spherical, and they are stable in time. Average sizes of CdS nanocrytals (2.5–4.0 nm) in the new matrices are determined by the methods of transmission electronic microscopy, by the X-ray methods and by absorption spectra.

The received results of researches of the new materials present a great scientific and practical interest. New composite materials can be used as an element base for devices of high-speed photonics, holography, nonlinear optical information processing, optical switches, light modulators, photoelectrochromic filters and sensors. References 1. T.A. Mirnaya. S.V. Volkov, in: R.D. Rogers. K.R. Seddon, S.V. Volkov. (Eds.), Green industrial applications of ionic liquids,

Kluwer Academic Publishers, London, 2002, pp.439-456. 2. Nonlinear optics of electrochromic and photosensitive cells of ionic liquid crystals and mesomorphic glasses, G. Klimusheva, Yr.

Garbovskiy, S. Bugaychuk, A. Tolochko, D. Melnik, I.Tokmenko, and T.Mirnaya, Mol.Cryst.Liq.Cryst., vol.541: pp. 142/380 -151/389, 2011

3. Т.А Мirnaya, В.V. Аsаula, G.G. Yaremchuk, A.A. Ponomarenko, S.V. Volkov, Ukrainian Chemistry Journal, 75, № 5: pp. 3–6, 2009.


63

HYBRID NANOSTRUCTURES ON THE BASIS

OF WATER SOLUBLE FULLERENE DERIVATIVES AND DYES

FOR PHOTODYNAMIC THERAPY

A.I. Kotelnikov, A.Yu. Rybkin, N.S. Goryachev, A.B. Kornev, E.A. Khakina, P.A. Troshin

Institute of Problems of Chemical Physics RAS, Chernogolovka, Russia

[email protected]

It is known that [60]fullerene exhibits exciting photophysical and electronic properties due to its

unique three-dimensional structure. Pristine fullerene and its derivatives are efficient electron

donors in photoexcited state and rather strong electron acceptors in the ground state. They generate

efficiently singlet oxygen 1О2 under light excitation. The fullerene-based systems generate

superoxide radical anion О2- and other active radical species in the presence of electron donors and

depending on the solvent polarity. Recently, many papers have been published on a photodynamic

effect of fullerenes and their derivatives resulting in the damage of DNA, proteins and membranes,

as well as a suppression of tumor cells, viruses and bacteria growth. Unfortunately, the application

of fullerenes and their derivatives for photodynamic therapy in clinical practice is strongly limited

by a weak absorption of fullerenes at long wavelengths in the visible and near infrared spectral

ranges. The short wavelength absorptions characteristic for fullerenes are hardly suitable for the

photodynamic therapy since they do not penetrate deep in the living tissues. Efficiency of the

photodynamic action of fullerenes can be greatly enhanced by using hybrid nanostructures (HNS)

composed of the fullerene derivatives bearing appended dye molecules absorbing the light in the

VIS and NIR spectral ranges.

A novel type of photoactive architectures has been successfully designed by two methods: by

creation of complex between cationic fullerene derivative and anionic chromophore (xanthene or

phthalocianine dye) and by covalent conjugating the other chromophore – anticancer anthracycline

antibiotic ruboxyl with the water soluble fullerene derivatives. Both type of nanostructures create

the associates in water solution, investigated by fluorescence quenching and by dynamic light

scattering. The dynamic light scattering experiments have shown that the synthesized conjugates

undergo association in the aqueous solutions with the formation of supramolecular nanostructures

with the characteristic hydrodynamic sizes of 85 and 98 nm. The photophysical properties and the

photodynamic action of different nanostructures: complexes of cationic fullerene derivative with

eosine, anionic derivative of phthalocianine and the ruboxyl-fullerene covalent conjugat were

extensively investigated. It has been shown unambiguously that all chromophores: the anthracycline

chromophore of the ruboxyl (having no photodynamic activity), eosine or phthalocianine derivative

behave as an efficient photosensitizers for the fullerene core operating via the energy and/or the

electron transfer pathways. The presented approach opens up wide opportunities for the design of

various fullerene-based donor-acceptor systems with photodynamic properties for biomedicinal

applications.

This work was supported by the RFBR (grant 10-03-00687), the President Science Foundation

(MK-4916.2011.3) and the Presidium of Russian Academy of Sciences (Research program No 24

“Fundamental research in the field of nanotechnology and nanomaterials”).


64

MAGNETIC FIELD EFFECT ON INTERMOLECULAR RADIATIONLESS

ENERGY TRANSFER NEAR METALLIC NANOPARTICLE

M.G. Kucherenko, S.A. Penkov

Orenburg State University, Russia

[email protected]

It is well known that the magnetic field can have an effect on spin-selective molecular processes. As

an example of this influence is the magnetic modulation of excited electron states triplet-triplet

annihilation rate. Нowever, the magnetic sensitivity can be appear in processes with the

participation of singlet electronic states of molecules if the electronic excitations energy

transformation is carried out in special conditions. Thus, in the dipole-dipole energy transfer

between electronic excitation molecules near a metal nanoparticle the reaction between molecules depends on whether the conductor plasma magnetized or not?

In this case radiationless energy transfer rate U is presented by three terms

2 2 *~ ( ) ( ) ( ) ( ) 2Re{( ( ) )( ( ) ( ) ( ) ) }D DA A D D A A D DA A D D A AU r r r r r rp T p p T α T p p T p p T α T p . (1)

The first term corresponds to the usual Forster dipole-dipole direct energy transfer. The second term

represents itself the energy transfer by means the metal nanoparticle and the third term is the

interference between these transfer channels. Vectors AD pp , are transient electric dipole moments

of donor and acceptor molecules; 3( ) ( ) (3 )i j ijr ij rT T n n is the configuration tensor of the dipole-

dipole electronic interaction on the distance r.

The polarizability of the metal nanoparticle is determined by the dielectric permeability of the

corresponding bulk conductor. Dielectric permeability of the magnetized plasma differs from the

permeability of plasma in the absence of the magnetic field. For the frequency-dependent

polarizability tensor α(ω)of the anisotropic spherical particles can write

1( ) ( ) ( ) ( ) 3( ) ( ) ( ) 2i e i e Rα ε 1 ε 1 . (2)

All non-zero dielectric permeability two-rank tensor ( ) ( )iε components are accepted as

corresponding values of the Ginzburg plasma theory

2

2 2

( )1

[( ) ]

p

xx yy

L

i

i,

2

1( )

p

zzi

, xy yx ig ,

2

2 2[( ) ]

p L

L

gi

. (3)

Parameters 24 /p ee n m and / ( )L eB mc in (3) are Langmuir and Larmor frequencies of

electrons; γ is the electrons collision frequency; B – magnetic field induction. Tensor 1

L in (2) is

the inverse tensor to L : 1LL 1 . Conducted calculations gave the presentation on the magnetic

field dependence for the energy transfer rate ( )U B . It was obtained a complicated behavior of the

rate ( )U B in different relative orientations of AD pp , vectors. 1–10% increasing of the magnetic

field dependence of the rate ( )U B was observed for ones geometrical configuration as well as an

expressing fall of this dependence – for others relative directions.

This work was supported by the Russian Foundation for Basic Research (project no. № 10-02-96021-r_ural_а) and the Ministry of Education and Science of the Russian Federation (under assignment no.

1.3.06).


65

THE EFFECT OF CYANINE DYES ON PHOTOREFRACTIVE

PROPERTIES OF COMPOSITES BASED ON CARBON NANOTUBES

A.S. Laryushkin1, A.D. Grishina

1, T.V. Krivenko

1,

V.V. Savel’ev1, A.V. Vannikov

1, R.W. Rychwalski

2

1 – A.N. Frumkin Institute of Physical Chemistry and Electrochemistry RAS, Moscow, Russia

2 – Department of Materials and Manufacturing Technology, Chalmers University of Technology, Göteborg, Sweden

[email protected]

Analysis of photoelectric, photorefractive, and nonlinear optical properties showed that introduction

of a cyanine dye with high electron affinity (low reduction potential) into the composite of

polyvinyl carbazole (PVC) and closed single_walled carbon nanotubes (PVC/SWCNT) composite

results in a two-fold increase in amplification factor g0 and therefore in an increase in the two-beam

amplification factor Γ. Herewith, the quantum efficiency of free charge carrier formation increases

nearly 14-fold. These effects are related to the dye trapping electrons in photogenerated electron–

hole pairs of PVC+•…SWCNT–•. This decreases the probability of reverse recombination PVC+•…SWCNT–• → PVC + SWCNT leading to an increase in the number of free holes in PVC.

Besides, electron trapping by the dye decreases the electron track length, which results in an

increase in phase shift ψ in the direction of hole movement. Introduction of the dye leads to a fivefold decrease in bulk susceptibility.

The two-beam amplification factor and effective factor are Γ = 80 cm–1

and Γ – α= 70 cm–1

,

accordingly, with field Е0 = 100 V/mm and I(0)1 = I(0)2 =0.24 W/cm2. Preillumination (exposure to

the laser (633 nm) at the dye absorption band before measurement of photorefractive properties)

leads in a further, nearly two-fold increase in the amplification factor, probably, due to the filling of

deep hole traps and increase in the hole rack length (phase shift ψ) before trapping.


66

SPECTRAL AND PHOTOCHEMICAL PROPERTIES

OF SEMICONDUCTOR QUANTUM DOTS

IN SELF-ORGANIZED STRUCTURES

V.G. Maslov, V.E. Adrianov, A.O. Orlova, A.V. Baranov, A.V. Fedorov

National Research University of Information Technologies, Mechanics and Optics, St.Petersburg, Russia

[email protected]

Semiconductor quantum dots (QDs) are intensively investigated during last years, owing to their

unique photophysical properties and wide sphere of potential or real practical applications. Self-

organized structures of QDs are of special interest because self-organization is considered as one of

main ways of creation of supramolecular structures. In this work the spectral, luminescent and

photochemical properties of self-organized structures obtained by evaporation of colloid solution of

semiconductor quantum dots (QDs) have been investigated. The main morphological types of

structures are considered. On the basis of direct measurement of absorption spectra it is shown that

in dendrite-like structures the QDs occupy no more than 20% of the structure volume. Such

structures thus should be considered being formed by supplementary components of colloid solutions (solubilizers, stabilizers etc.), where QDs are incorporated as into matrix.

It is shown that the spectral properties of QDs in self-organized structures, in particular the position

of the luminescence band maximum is mainly determined by two factors: (1) QD size separation

under incorporation into the structure and (2) the spectral changes caused by QD photodestruction. The latter factor is absent for QDs with shells or in absence of illumination.

The main peculiarities and spectral appearance of two types of photochemical processes of QDs

within self-organized structures are considered: (i) QD photodestruction and (ii) photoinduced

change of luminescence quantum yield (PCLQY) of QD. On the example of shell-less water soluble

CdTe QDs it is shown that in self-organized structures the QD photodestruction leads to irreversible

blue shift of the QD luminescence maximum to a certain limit position. Such a shift may reach 50

nm or even more and is evidently caused by decreasing the effective QD size as the result of

photooxidation of surface layers of the QD matter. It was also found that this process is

accompanied by the appearance of very long component (tens of ns) in luminescence decay

kinetics, that is evidently caused by passivation of QD surface by the photodestruction products.

The processes of QD PCLQY in contrast to QD photodestruction are partially or completely

reversible ones, and are not accompanied by any luminescence spectral shifts. We considered two

main cases when the QD PCLQY could be observed without any complications caused by

simultaneously occurring photodestruction: (1) when the photodestruction reached the limit and

further luminescence band shift does not take place and (2) in the case of shelled QDs, for which

the blue luminescence spectrum shift under illumination does not take place. Evidently, the effects

of photoinduced QD luminescence quantum yield change are caused by the processes of reversible recharging of QD surface local states under illumination.


67

THE DEMONSTRATION OF THE "QUASI-ATOMIC" STRUCTURE

OF NANOPARTICLES OF SILVER AND GOLD IN INORGANIC GLASSES

N.V. Nikonorov, A.I. Sidorov, V.A. Tsekhomsky, T.A. Vartanjan

Institue of Nanophtonics and Optoelectronics

of National Research University of Information Technologies, Mechanics and Optics, St.Petersburg, Russia

[email protected]

We have investigated the X-rays interaction with gold and silver nanoparticles (NP) in inorganic

glasses. In the studied glasses a shape of NP’s is close to spherical and their sizes do not exceed 10

nm.. This allows the analysis of absorption spectra by quasi-static approximation of Mie theory,

according to which the position of the maximum of surface plasmon resonance (SPR) does not

depend on the NP’s size. At the same time, the spectral width of SPR is determined by the NP’s size and can be used for evaluation [1].

It is shown that the effect of X-rays at room temperature leads to an increase of the NP’s size, and

the appearance of luminescence. In the case of the glass with Au, the size of Au NP’s increases up

to ~ 25%. This behavior of NP’s at high density of electron-hole pairs is explained by quasi-atomic

structure of NP’s. According to modern concepts [2] the free conduction electrons are distributed in

shells 1s, 1p, 1d, 2s, 1f, 2p, ..., and below the vacuum level they may be partially filled, and empty.

At high density electron-hole pairs produced in the matrix during X-ray irradiation, electrons can be

captured in these shells.. Naturally, these additional electrons exceeding positive charge of the core, should lead to a series of kinetic effects in the matrix and change the size of NP’s.

It is shown that heat treatment of the glass reduces the NP’s size and decrease the luminescence..

The negative charge on the NP’s during heat treatment can be compensated by the thermal emission

of electrons, as well as the approach to such particles of mobile ions Ag+, Na

+, Li

+. Silver ions are

reduced on the negatively charged NP’s (the growth of NP’s), and the Na+ and Li

+ drew off the

electrons (the decrease of NP’s). Interaction between Na+ and Li

+ with the negatively charged

particles explains catalytic effect of the NP’s, which leads to local inhomogeneity of glass and

precipitation of crystalline phases. Particularly interesting is the interaction of Li+ ions with the

negatively charged NP’s. Li+ ions having a higher coefficient of diffusion than Ag

+, surrounds the

NP’s and prevents the approach of silver ions. This results in the preservation of the luminescence in lithium-containing glasses up to 400°C.

1. Kreibig U., Vollmer M. Optical Properties of Metal Clusters (Springer Series in Materials

Science) Springer-Verlag, p. 532, 1995.

2. Alonco J.A. Structure and properties of atomic nanoclusters, Imperial College Press, p.410, 2005.


68

HOW THE BINDING TYPE

AFFECTS THE PHOTOPHYSICAL PROPERTIES

OF THE COMPLEXES OF QUANTUM DOTS WITH TETRAPYRROLES

A.O. Orlova, M.S. Gubanova, I.V. Martynenko, V.G. Maslov, A.V. Baranov, A.V. Fedorov

National Research University of Information Technologies, Mechanics and Optics, S. Petersburg, Russia

[email protected]

The idea of creating complexes where tetrapyrroles can enhance the generation of the singlet oxygen

due to the effective energy transfer from the donor energy to the tetrapyrrole molecules seems very attractive. This explains a great attention to such complexes during last decade [1]. Colloidal

semiconductor quantum dots (QDs) have interesting properties: the optical characteristics of QDs

depend on their core size; they have broad absorption spectrum with high extinction, a high quantum

yield of luminescence (QY) and a high photostability. Today the synthesis and solubilization of the quantum dots allow obtaining water-soluble QDs with charged group on their surface. So, quantum dots

are perfect for the role of the energy donor in complexes with the tetrapyrroles. The simplest way to

enable the energy transfer from QDs to molecules in complexes consists in providing the conditions for

realization of the effective dipole-dipole Förster Resonance Energy Transfer (FRET) in them.

Here we have analyzed the photophysical properties of complexes of the CdSe/ZnS and CdTe quantum

dots with three different tetrapyrroles: chlorine e6, metal-free porphyrin meso-tetra(p-trimethylaminophenyl)porphine (TAPP) and Al-tetrasulphophtalocyanine (Al-TSPc). It has been found

that binding the tetrapyrroles in complexes with QDs via their charged group leads to change of the

spectral form of the tetrapyrrole molecules in all our complexes. This is accompanied by the reduction

of the luminescence quantum yields of the tetrapyrroles. So, in our complexes tetrapyrroles have QY which amounts 30%, 20% and 4% from that of free chlorine e6, TAPP and Al-TSPc correspondingly.

The FRET conditions: the distance from QDs to molecules and overlap of the absorption spectra of

tetrapyrroles with luminescence spectra of QDs were practically the same in our complexes. However, it has been found that if we use charged group of tetrapyrroles for binding to QDs, the FRET efficiency

depends on a concentration of tetrapyrroles in solution and can change over a wide range (from 1% up

to 50%). Thus the increase of concentration of Al-TSPc in solution leads to formation of nonluminescent pthalocyanine aggregates on the QDs surface. These aggregates create the competitive

channel of the QD exited state deactivation and at the same time they can quench the luminescence of

the other Al-TSPc molecules bound to the same QD.

In the case of Al-TSPc we have another principal way to create complex. It is possible to coordinate the

carboxyl group of the solubilasier of the QDs to the Al atom of the Al-TSPc. For such complexes, we

should use QDs with the charge of the same sign as that of Al-TSPc. Due to Coulomb interaction

between similarly charged particles in solution this leads to incomplete binding in complexes QDs with molecules. Our research has shown that in such complexes Al-TSPc does not change its spectral form or

QY. The experimental efficiency of the energy transfer from QDs to phtalocyanine in these complexes

is equal to 80% that is close to theoretical FRET efficiency (97%).

Our data clearly evidence that the binding type of the tetrapyrroles with QDs in complexes affects the

photophysical properties of these complexes. It is apparent that using charged groups of the tetrapyrroles

can bring to zero all the advantages of the effective FRET in the QD-tetrapyrrole complex. It seems a promising to create complexes of QDs with the tetrapyrrole molecules without the involvement of

charged groups of the tetrapyrroles.

1. Maslov V., Orlova A., Baranov A., “Photosensitisers in medicine, Environment, and Security”.

T. Nyokong, V. Ahsen, Eds. Part II, Chapter 3//Springer-Verlag. 1st Edition. 2011. 699 p.


69

CONTROL OF PHOTOCHEMICAL PROPERTIES OF ULTRATHIN FILMS

OF AMPHIPHILIC CROWN-SUBSTITUTED HEMICYANINE DYES

S.L. Selektor1, D.A. Silantyeva

1, P. Batat

2, G. Jonusauskas

3, V.V. Arslanov

1


2 – Chemistry department, Koc University, Istanbul, Turkey

3 – Laboratoire Ondes et Matiere d’Aquitaine, Bordeaux University, France

[email protected]

The control of structure and structure-dependent photophisycal properties of ultrathin films is

largely demanded for the implementing of the advantages of planar supramolecular systems as basic

elements of nanoscale information devices.

In the present study, we investigated structure and optical properties of Langmuir monolayers of

amphiphilic chromoionophores ChI and ChII containing crown-ether moieties by fiber-optic

spectrophotometry in situ directly during the process of formation of monolayer. The possibility to

control the degree and the type of molecular aggregation in the monolayer and in the Langmuir-

Blodgett films (LBF) was proven, as well as the influence of monolayer structure on the processes of the cations recognition was revealed.

It was shown that the fluorescence signal is highly sensitive to different types of aggregation of the

organized planar system. It was established that the introduction of alkali and alkali-earth cations

into the subphase inhibits H-aggregation of crown-substituted dyes and results in a significant enhancement of fluorescence signal of the monolayer.

We found a reversible formation of excimers under cyclic monolayer compression-expansion,

characterized by a 100 nm red-shifted emission band relative to that of monomer (700 and 600 nm

correspondingly) in monolayers of ChI on water subphase containing metal cations. The optical characteristics of monolayers are maintained after their transfer onto solid support.

The dependences of fluorescence intensity of excimers on concentration of Ва2+, Са2+, Mg2+, К+

in water subphase were obtained. It was shown that efficiency of dye excimer formation in the

monolayer depends on cation charge, its radius and binding constant with crown-ether moiety. At

the same time, the X-ray photoelectron spectroscopy proved that cations promoting excimer

formation are not contained in LBFs transferred on solid supports. It was found that interaction

between cations and crown-ether groups of dyes takes place in the presence of chloroform upon

spreading dye solution over the cation-containg subphase surface at the initial stage of monolayer

formation. Apparently these interactions determine the structure of monolayer and the efficiency of excimer formation in it.

Thus, the possibilities of control of structure and photophysical characteristics of Langmuir

monolayers of amphiphilic crown-substituted hemicyanine dyes by changing the subphase

composition are demonstrated in this study.

This work has been done with the support of Russian Foundation for Basic Research (project № 09-

03-93118-НЦНИЛ_а) and the Program 7(5) of Presidium RAS

Ch1

Ch2

Orals Photochromism of organic compounds ----------------------------------------------------------------------------------------------------------------------------- --------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------

70

SECTION 7. PHOTOCHROMISM OF ORGANIC COMPOUNDS

HYBRID PHOTOCHROMIC SYSTEMS:

INSIGHTS INTO STRUCTURE AND MECHANISM

O.A. Fedorova1, D.V. Berdnikova

1, A.N. Sergeeva

1, P.A. Panchenko

1,

Yu. V. Fedorov1, V. Lokshin

2, S. Delbaere

3

1 – A.N. Nesmeyanov Institute of Organoelement compounds RAS, Moscow, Russia

2 – CNRS UPR 3118, Interdisciplinary Center of Nanoscience CINaM, Marseille, France

3 – CNRS UMR 8516, Université Lille Nord de France, Lille, France

[email protected]

In the last few years, naphthopyrans have evolved as a fascinating family of commercially-used

photochromic molecules because of their synthetic availability, ease of modification, durable

persistency and addressable bleaching kinetics. The hybrid biphotochromic systems involving

naphthopyran species have generated substantial research interest because they allow a possible

sequential control of electronic properties thus leading to potential applications as new generation

of smart materials, such as high-density data storage systems or the optical equivalent of field-effect

transistors and logical gates. Therefore, a better understanding of photochemical pathways,

including identification of stable intermediates, is critical for learning how to construct and

manipulate these synthetic hybrid biphotochromic systems. In this context, the hybrid

biphotochromic system consisting of a styryl, stylbene or naphthlimide unit tethered to a

naphthopyran was prepared and studied.

The resulting cross-validation of the data obtained by UV/Vis and by using multinuclear NMR

monitoring technique gave a highly reliable and comprehensive picture of the thermodynamic

stability and photochemical behavior of this hybrid system in acetonitrile solution.

Acknowledgments to RFBR program (10-03-93105), the International Research Group “PHENICS”

and French CNRS for financial support.


71

FLUORESCENCE SWITCHING

OF DYADS AND SILICA NANOPARTICLES

BASED ON PHOTOCHROME-FLUOROPHORE COMBINATION

K. Ouhenia1, R. Metivier

1, S. Maisonneuve

1, A. Jacquart

1,

J. Xie1, A. Leaustic

2, P. Yu

2, K. Nakatani

2

1 – PPSM, ENS Cachan, Chemistry department, Cachan, France

2 – LCI, ICMMO, CNRS, Université Paris-Sud, Paris, France

[email protected]

Molecular systems based on photochrome entities are sought for their switching stimulated by light.

These molecules have the functionality of switch and memory. Each molecule can potentially be a

"bit". However, in the objective of miniaturization, it is necessary to couple, to these photochromic

molecules, entities with properties detectable at small scales, for example fluorescence. [1] We

synthesized multichromophoric molecules and nanoparticles containing both photochromic (P) and fluorescent (F) moieties, and studied the interactions in these multifunctional systems.

The presentation focuses on the fabrication and study of:

- Photochrome-fluorophore dyads. The fluorescence of F can be switched upon UV and visible

irradiation, while P shuttles between its open form (OF) and closed form (CF). We demonstrated

that this phenomenon is based on the quenching of the fluorescence by Förster resonance energy

transfer (FRET) from F to P, when P is in its CF. No such effect is observed when P is in the OF

state. Interestingly, P-OF is also fluorescent, and a reverse FRET from P to F is detectable when P

is in its OF.

- Photochrome and fluorophore moieties grafted on silica nanoparticles (Si-NP). In addition to the

fluorescence switching observed in the dyads, the confinement of the chromophores on Si-NP

enables the quenching of the fluorescence of several F moieties by a single P moiety in its CF form.

This leads to a nonlinear relationship between the OF-CF conversion extent and the fluorescence intensity.

Photochrome Fluorophore

Figure 1 : Photochrome-fluorophore dyad (left) and silica nanoparticle (right)

1. J. Piard, R. Métivier, M. Giraud, P. Yu, K. Nakatani (2009), New J. Chem. 33:1420.


72

THE AMBIGUOUS ROLE OF WEAK IRREVERSIBLE CHANNEL

IN A SYSTEM OF REVERSIBLE PHOTOCONVERSIONS:

PROVITAMIN D PHOTOISOMERIZATION

I.P. Terenetskaya

Institute of Physics NAS, Kiev, Ukraine

[email protected]

The synthesis of vitally important vitamin D3 in skin induced by solar ultraviolet (UV) irradiation is

a two-stage process which begins with the production of previtamin D from the steroidal precursor

7-dehydrocholesterol (7-DHC). Then vitamin D3 itself is formed upon reversible thermal

rearrangement of the previtamin D via [1,7]-sigmatropic hydrogen migration.

In solutions, the photosynthesis of previtamin D is a complex branched network of isomerization

reactions, with conformationally flexible molecule of previtamin D occupying the central position.

A dynamic equilibrium between the four principal photoisomers, - photostationary state, - is

established after some time of UV irradiation, and its composition strongly depends on the

irradiation spectrum applied. This well-known wavelength effect is caused mainly by the different

absorbances of the photoisomers involved in the reaction network.

In commercial production of vitamin D the maximization of the yield is achieved by control of the

irradiation wavelength and the extent of the irradiation. So, monochromaticity of laser radiation was

of prime interest to the investigators. Using tunable laser irradiation within 295-305nm another,

more complicated, wavelength effect in previtamin D photochemistry has been revealed by Dauben:

a sudden increase in the efficiency of ring closure into lumisterol at the wavelengths between 302

and 305nm. One of the most logical explanations involved selective excitation of different

previtamin D conformers possessing different absorption spectra and photoreactivity. However,

sudden change within narrow spectral range around 300nm was not fully understood.

Despite it is generally accepted that above mentioned reversible photoreactions of previtamin D

play a determining role in the photoreaction kinetics, there are also irreversible photoconversions

into so-called over-irradiation products toxisterols. Nevertheless, it is usually assumed that due to

the low quantum yield toxisterols accumulate on prolonged exposure after complete conversion of

the initial provitamin D. Therefore, as a rule the irreversible channel does not appear on the reaction

scheme, and the presence of toxisterols is disregarded, i.e. the total concentration of the four main

photoisomers is taken as 100%.

In this presentation based on our studies [1] on laser initiation of provitamin D photoisomerization

we will show the limitations of the photostationary approximation and explain the little-known

wavelength dependence of the irreversible channel efficiency with a using both the simplified

model and computer simulations of the photoreaction kinetics. The data on the photoreaction

kinetics initiated with UV lasers will illustrate the importance of the wavelength effect revealed.

Particular attention will be given to original spectrophotometric analysis of the multicomponent

mixture of the vitamin D photoisomers which does take into account irreversible degradation of the

photoisomer mixture and has most relevant applications in an in situ monitoring of biologically

active antirachitic solar UV radiation. Characterization of the ‘Vitamin D’ biodosimeter will be

described in detail with focus on the difference between the in vivo and the in vitro action spectra of

vitamin D synthesis.

In summary, disregard of the irreversible channel with low quantum yield in a system of reversible

photochemical reactions is not always justified over a wide spectral range.

1. I. Terenetskaya, Photochemistry: UV/ VIS spectroscopy, Photochemical Reactions and

Photosynthesis, Nova Science Publishers Inc., 2011, chapter 6, p.238-270.


73

PHOTOPROCESSES IN NOVEL HYBRID COMPOUND INDUCED

BY PHOTOEXCITATION WITH LIGHT OF DIFFERENT WAVELENGTHS

N.L. Zaichenko1, P.P. Levin

2, A.S. Tatikolov

2, A.I. Shienok

1, L.S. Koltsova

1,

I.R. Mardaleishvili1, L.D. Popov

3, S.I. Levchenkov

3, A.A. Berlin

1

1 – N.N. Semenov Institute of Chemical Physics RAS, Moscow, Russia


3 – Southern Federal University, Rostov-on-Don, Russia

[email protected]

Novel hybrid compound (HC), which molecule contains three photochromic fragments of different

nature, was investigated by the microsecond pulse photolysis techniques using excitation with UV

and visible light in methanol. In the HC molecule the photochromic spironaphthoxazine fragment,

capable to form a colored merocyanine form, is linked to the hydroxynaphthylmethylenimine (NA)

fragment, in which intramolecular proton transfer can occur in the ground and excited (ESIPT)

states of the molecule. The NA fragment contains a phenylazo substituent prone to trans-cis

photoisomerization. This HC was synthesized according to the sequence of chemical reactions:

N

Me

MeMe

N

O

N CH

HO NN

N

Me

MeMe

N

O

HO NN

HNO 3, H2SO4

-5oC N

Me

MeMe

N

ONO2

N2H4 H2O

Ni- Raney

CHO

N

Me

MeMe

N

ONH2

Spectral-kinetic characteristics of photoproducts were studied. A significant effect of the excitation

light wavelength on the relative yield of the photoproducts of different nature was found.

N

Me

MeMe

N

O

N

HO NN

AE

trans

BE

trans

UV VISIBLE

BK

trans

BE

trans

AE

cis

600 nm

600 nm

650 nm

450 nm

This work was financially supported by the Russian Academy of Sciences (Presidium Program No. 8).

Orals Applied molecular photonics ------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------- ------------------------------------------------------------------------------------

74

SECTION 8. APPLIED MOLECULAR PHOTONICS

CYCLOMETALATED PLATINUM(II) COMPLEXES CONTAINING

PYRAZOLONATE LIGANDS AS HIGHLY LUMINESCENT EMITTERS

FOR ORGANIC LIGHT-EMITTING DIODES (OLEDS)

Yu. E. Begantsova, L.N. Bochkarev, V.A. Ilichev

G.A. Razuvaev Institute of Organometallic Chemistry RAS, Nizhny Novgorod, Russia

[email protected]

Last decade square planar Pt(II) compounds have attracted considerable attention due to their

efficient electroluminescent properties [1]. In the present work a series of novel phenylpyridine

Pt(II) complexes with isopropyl- (iPr) and norbornenyl-substituted (NBE) pyrazolonate ancillary

ligands were synthesized:

Compounds 1 and 2 were used as emissive materials in OLED devices with the structure of

ITO/TPD/1 or 2/BATH/Yb (TPD – N,N΄-bis(3-methylphenyl)-N,N΄-di(phenyl)benzidine).

Electroluminescence (EL) of orange color was observed and assigned to eximer emission of

platinum complexes. The maximum of brightness of 5300 cd/m2 and current efficiency of 16.47

cd/A were reached. When complexes 1 and 2 were doped into poly-9-vinylcarbozole (PVK) (1-10

%) color of EL were found to depend on the dopant concentration and changed from green to

yellow to white.

Complexes 3 and 4 were copolymerized with carbazole functionalized NBE monomers using third-

generation Grubbs` catalyst. Pt(II)-containing copolymers with different ratio of monomer units

were obtained. OLED with configuration of ITO/Pt(II)copolymer/BATH/Alq3/Yb (ITO - indium tin

oxide, BATH – bathophenanthroline, Alq3 - tris(8-hydroxyquinolinato)aluminium) were fabricated.

The emission colors of the copolymer-based devices changed from yellowish green to white to

yellow depending on the ratio of carbazole- and Pt(II)-containing units. The maximum brightness of

400 cd/m2 and current efficiency of 3.90 cd/A were observed.

Photoluminescent properties of synthesized Pt(II) complexes and polymeric materials will be

discussed also.

[1] J. Kalinowski, V. Fattori, M. Cocchi, J.A.G. Williams, Coord. Chem. Rev. 255 (2011) 2401.

This work was supported by the Russian Foundation for Basic Research (Project No. 12-03-

00250_a)


75

PHOTONIC MOLECULAR LOGIC GATES: HOW IT CAN BE DONE

M.F. Budyka


[email protected]

Since previous 2-nd symposium "MOLECULAR PHOTONICS" three years ago there is consistent

growth of papers in the field of molecular logic gates (MLGs) published in different countries, but

Russia does not belong to this community. To make up for this deficiency, in this report the recent

achievements in investigations of various molecular systems capable of performing logic operations are discussed, and algorithm of MLG design is also considered.

Logic gate is a switch, whose input and output signals can accept only values of "0" or "1".

Dependence of numerical value of output signal on inputs is defined by the truth table of the logic

(Boolean) function.

Majority of known MLGs use chemical inputs – addition of an acid or alkali, ions of metals, other

reagents. The output is usually absorbance or luminescence. Therefore, inputs and outputs are non-

identical so that MLGs don’t interact with each other, and it is one of the main problems. It is

difficult to pass the output from one molecular gate as the input to the second for the physical integration (concatenation) of many logic gates in arrays.

One approach to overcome this problem is functional integration. This means that a unimolecular

system can mimic a complex logic circuit, composed of various logic gates, without the necessity of

representing each logic gate by a different structural feature. For example, a molecular half-adder is

a combination of AND and XOR logic gate functions in the same molecule, and some molecular

systems capable of performing this simple arithmetic were synthesized and investigated. This

unique property - compatibility of several logic gates in one device or reconfigurability of logic gate

on different type of work - is essentially unattainable for currently used semiconductor elements where the separate device is demanded for each logic operation.

Another and more universal approach to overcome the problem of gate concatenation in array is

design of molecular systems with homogeneous inputs and outputs. In this case the output signal

from one molecular gate can be directed straight to the input of the second gate.

All-photonic MLGs satisfy the principle of homogeneity of input and output signals. The impact on

the system consists in irradiation by light of definite wavelength, and readout is made on optical

density or luminescence. The switching of the gate between different states is performed by

photoisomerization of photoactive receptor. There are known examples of completely photonic

supramolecular gates which are capable of performing "AND", "OR", "XOR", "INHIBIT" logic

operations, and more complex functions of half-adder and half-subtractor,

multiplexer/demultiplexer, encoder/decoder.

In the report the algorithm of photonic MLG design is considered using styrylquinoline-based

supramolecular dyad and two-addressable logic gate as an example. Every from four possible gate

states (00, 01, 10, 11) should be correlated with definite state of molecular system. An input

stimulus (for photonic gate it is irradiation wavelength) should be chosen to switch gate from one

state to another and to reset. Then threshold value of optical density or luminescence intensity

should be defined to transform measured analogue output signal to binary (digital) one. Finally,

using correspondence between input and output signals (truth table) one can define the type of logic operation producible by MLG.

The work was supported by the Russian Foundation for Basic Research (grant no. 10-03-00751).


76

PEG-ORGANIZED BIOCOMPATIBLE FLUORESCENT NANOPARTICLES

DOPED WITH NOVEL CYANOPORPHYRAZINE CHROMOPHORES

FOR BIOPHOTONIC APPLICATIONS

I.S. Grigoryev1, L.G. Klapshina

1, S.A. Lermontova

1, M.V. Shirmanova

2,

I.V. Balalaeva3, E.V. Zagaynova

2, N.Yu. Lekanova

2

1 – G.A. Razuvaev Institute of Orgamometallic Chemistry RAS, Nizhny Novgorod, Russia

2 – State Medical Academy, Nizhny Novgorod, Russia

3 – N.I. Lobachevsky State University, Nizhny Novgorod, Russia

[email protected]

Tetrapyrrolic macrocycles and their metal complexes occupy a central place in bioorganic

chemistry since they are used in important biomedical applications, particularly in the fields of

neoplastic tissue detection and photodynamic therapy.

A series of novel

tetraaryltetracyanoporphyrazine chromophors (free bases and ytterbium complexes) showing high

light absorption and emission in the wavelength range 600-680 nm has been prepared by use of the

new synthetic approach [1,2] . All the prepared compounds showed photophysical behaviors

which was not typical for the majority of the known macrocyclic dyes: fluorescent quantum yield

very strongly increased in higher-viscosity solvents. We established that macrocycle red

fluorescence quantum yield ( F) and bulk viscosity (η) follow a power-law relationship that is

widely referred to as the Forster-Hoffmann equation:

lg F = C + x lg η,

where C and x solvent- and chromophor dependent constants.

Our efforts to develop short and simple routes to biologically relevant forms of novel porphyrazine

dyes gave rise to two one-pot strategies: (i) encapsulation of that into non-toxic biocompatible

water soluble polyethylene glycol (PEG) macromolecule aggregates, and (ii) the preparation of

biocompatible water soluble uniform disk-shaped nanoparticles consisting of a PEG core framed with fluorinated hybrid silica nanolayers doped with porphyrazine metal complex [3].

A large enhancement of red emission for all the types of nanoparticles is observed in physiological

liquids (serum and 10% aqueous human albumin solution) owing to their binding to biomolecules.

The novel uniform disk-shaped nanoparticles incorporating fluorinated functionalized hybrid silica

show an enhanced chemical compatibility with serum proteins because of a combination of their lipophilic properties with additional binding with biomolecules through the amide groups.

Prepared nanoparticles were tested as fluorescent markers for tumour in vivo diagnostics. By using

transplantable mouse cervical carcinoma as a tumour model we have demonstrated selective red-emitting nanoparticle accumulation in the tumour tissue.

References

[1] L. G. Klapshina, I. S. Grigoryev, W. E. Douglas, A. A. et al. Chem. Commun., 2007, 1942-1944

[2] L. G. Klapshina, W. E. Douglas, I. S. Grigoryev et al , J. Mater. Chem., 2009, 19, 3668–3676.

[3] L. G. Klapshina, W. E. Douglas, I. S. Grigoryev, E. Yu. Ladilina et al, Сhem. Comm., 2010, 46,

8398-8400.


77

PHOTONICS OF DIPYRROMETHENE COORDINATING COMPLEXES

FOR OPTICAL DEVICES CREATION

R.T. Kuznetsova1, Yu.V. Aksenova

1, D.E. Bashkirtsev

1, T.N. Kopylova

1,

G.V. Mayer1, E.N. Telminov

1, E.V. Antina

2, L.A. Antina

2, M.B. Berezin

2,

G.B. Guseva2, S.L. Yutanova

2, A.S. Semeikin

3

1 – Tomsk State University, Tomsk, Russia

2 – G.A. Krestov Institute of Solution Chemistry RAS, Ivanovo, Russia

3 – State University of Chemical Technology, Ivanovo, Russia [email protected]

The facilities of purposeful syntheses of complicated molecules which exhibit undoubted physical-chemical properties at the last years are increased [1]. Comprehensive study of processes of interactions of such systems with light and solvate cores at the ground and electron excited states would be forecast its

applications in modern technologies and the various optical deviсes.

The spectroscopic characteristics at the ground and electron-excited states, photochemical, nonlinear-optical, lasing properties of coordinating complexes of BF2- dipyrromethene (BODIPY1, BODIPY2, BODIPY3 on fig.) and binuclear complexes of Zn(II) and B(III) with bis(dipyrromethene) ([Zn2L2] and bis-BODIPY on fig.) in solvents of the different species at the room temperature (297) and in frozen solutions (77K) are researched.

NN

CH3

NN

CH3

CH3H3C

CH3

H3C

CH3

CH3

CH3

CF3

H

H3CBB

F FF F

[Zn2L2]: R=H or CF3 bis-BODIPY

N NB

F F

C2H5

CH3

H3C

H5C2

H3C

CH3

N NB

F F

C2H5

CH3

H3C

H5C2

H3C

CH3

N NB

F F

Br

CH3

H3C

Br

H3C

CH3

BODIPY1 BODIPY2 BODIPY3

It is established that CF3-substitutor into spacer moves absorption to shortwave (6-7 nm) and emission to

longwave (3nm), absorbance decreases slightly. Replacing of Zn(II) with BF2 in binuclear complexes moves absorption (18 nm) and emission (2 nm) to longwave. Absorbance intensity of bis-BODIPY decreases on two compared with [Zn2L2], because number of chromophore units decrease. Complexes BODIPY1 and

BODIPY2 independently on solvents exhibit the high fluorescence efficiency and are used as laser-active media for retune lasers at the region 550-570 nm. These compounds are comparable to commercial pyrromethenes on efficiency [1] and exceed their on photostability. BODIPY3 exhibits small quantum yield of fluorescence and long lived luminescence as phosphorescence (790 nm, 3.5 ms) and delay fluorescence (540nm, 1-1.2 ms). These properties propose further study of oxygen effect and possibility for creation of optical oxygen sensors on the base this compound and getting of electrophosphorescence for OLEDs creation. Binuclear complexes [Zn2L2] and bis-BODIPY have different structure: double-helical “ridger-tile”

ligands at the [Zn2L2] and mono-helical – at bis-BODIPY, however, these compounds exhibit similar absorption and the same decreasing fluorescence efficiency (<0.1) in specific solvents compare with nonpolar media (up to 1). At the frozen ethanol solutions of [Zn2L2] and bis-BODIPY fluorescence efficiency increases to 1. Therefore solutions of [Zn2L2] and bis-BODIPY in cyclohexene may be used as laser media. Ethanol solution of these compounds may be apply as optical sensor on temperature in interval 77-200K and for limiting of power pulsed radiation on 355 and 480-500 nm, because absorption in excited states at these regions is higher compared with the ground state.

These researches are supported by grants of RF President (SS-512.2012.2).

1. M.Bemstead, G.H.Mehl, R.W.Boyle //Tetrahedron. 2011. 67. 3573-3601.


78

ALKOXYNAPHTHALIMIDE DERIVATIVES

AS THE ACTIVE COMPONENTS OF OPTICAL MOLECULAR DEVICES

A.N. Sergeeva, P.A. Panchenko, O.A. Fedorova, Yu.V. Fedorov

A.N. Nesmeyanov Institute of Organoelement compounds RAS, Moscow, Russia

[email protected]

In recent years great interest of researchers attracted to functional organic compounds that can

change their optical characteristics upon the irradiation or as a result of complex formation. It is

known that organic luminophores based on 1,8-naphthalimide have a unique set of photophysical

and photochemical properties [1], so they often act as active components in the systems which can

find applications in many disciplines such as clinical and environmental sciences, analytical chemistry and biochemistry [2].

In this paper we present a synthesis of the naphthalimide derivatives containing electron-donating

methoxy group in the fourth position naphthalimide core (1) (fig. 1), as well as photochromic

fragment in the molecule (2), (3) (fig. 2).

N

O

O

MeO

SO

OS

N

Mn+

1Ar

SO

SO

O

Hg2+, Ag+, Cu2+ =

Ar =

N

O

O

Ph

O

Ph Ph

N

O

O

Ph

OPh

Ph

N

O

O

Ph

2

OPh

Ph3

hv

Fig.1. Optical sensors. Fig. 2. Fluorescent photochromes.

The study of spectral properties of 4-methoxyderivatives (1) showed that the presence of crown

ether receptor in the N-aryl moiety leads to selective fluorescent sensors toward the transition metal

cations, which demonstrate the enhancement of fluorescence upon complexation in acetonitrile and

aqueous solutions.

Compounds (2) and (3) containing benzopyran moiety showed the ability to switch fluorescence

characteristics as a result of the photochemical isomerization in the open form upon irradiation with

UV light. The specified property makes photochromes (2) and (3) perspective compounds for use as

components in optical filters and elements of optical memory.

Thus, a method for the synthesis of 4-methoxy-1.8-naphthalimide derivatives containing a fragment

of benzoditia-15-crown-5 ether and N-phenyl-azaditia-15-crown-5 ether as an N-aryl substituent of

the naphthalimide core was developed, as well as was studied the complexation of these compounds

with the transition metal cations. Also isomeric N-phenylnaphthalimides containing photochromic benzopyran fragment in the molecule were obtained.

References

1) Б.М. Красовицкий, Б.М Болотин. Органические люминофоры. М.: Химия, 1984, p.336

2) Valeur B. Molecular Fluorescence: Principles and Applications. Wiley: VCH Verlag CmbH,

2001, p.273-350.

Acknowledgments to RFBR program (09-03-00041, 09-03-93116), GDRI “SUPRACHEM” and

Russian Ministry of Education and Sciences for financial support.


79

LUMINESCENT HYBRID NANOCOMPOSITES AND PROSPECTS

OF MOLECULAR AND NANOPHOTONIC SYSTEMS

IN MODERN PACKAGING AND PRINTING

V.P. Sherstyuk, O.O. Sarapulova, V.V. Shvalagin

National Technical University of Ukraine “KPI”

[email protected]

Nanotechnology began to be used widely in printing and packaging technology for producing micro- and nanoelectronics, devices for photonics, security elements in forgery-proof printed products etc. and

in printing materials production too. For example, inks for ink-jet printing containing silver, gold, and

copper nanoparticles are used to fabricate printed devices for photonics. There are of essential interest

hybrid organic-inorganic luminescent nanocomposites.

Multifunctional materials for inks, including in a part luminescent-magnetic nanocomposites, have a great potential in printing industry. Forgery-proof inks with both magnetic and luminescent properties

can be used for printing visible or invisible in daylight elements and detected on different levels from

ultraviolet lamps for currency and special tags testing to special laboratory equipment for detailed checking of magnetic and spectral characteristics of the inks. Multifunctional inks are considerably

more difficult to forge, at least because it will be unknown for forgers how the problem of quenching of

luminescent emission by magnetic material and additives is solved for particular luminophores and

magnetic compositions, not to mention other technical problems which emerge when the attempts to

forge such inks and print with them are made.

The use of multifunctional nanosized materials is promising for active and intelligent packaging

systems. Active systems can change the environment inside a package, for example, absorb oxygen,

humidity, ethylene or emit ethanol or anti-microbial components. Intelligent packaging systems are

aimed to monitor quality of food product of the surrounding environment and alert a consumer to contamination or presence of pathogens. Therefore, these systems extend product shelf-life, enhance

food quality and safety, efficiently preserve flavour and color, and facilitate transportation and usage.

Luminescent and magnetic materials can be used as such systems. If nanosized ZnO is used as luminophore in combination with Fe3O4, they serve as non-toxic anti-microbial agents and forgery-proof

measures at the same time. They can be incorporated into polymer films or printed onto their surface. In

addition, ZnO prevents UV light from entering package environment and can be used as protein detector. Luminophores, inorganic or organic also can change the intensity of luminescence in presence

of compounds, which emerge in packed products during their storage or as a result of food spoilage, as

well as changes of pH. The luminescent-magnetic materials have thus a great potential in use as active

and intelligent systems for food packaging. The investigated metal oxides have anti -fungal and UV-

protecting properties.

The experiments were carried out in order to produce components for multifunctional luminescent-

magnetic nanocomposites and their spectral and printing properties were investigated. When an attempt

to combine luminescent materials (organic and inorganic luminophores) and magnetic materials

(magnetic fluid – nanosized magnetite Fe3O4) is made, the problem emerges concerning the phenomenon that magnetic material quenches the luminescence. It was discovered that this phenomenon

occurs basically as a result of chemical interaction between active centres Fe3+ and Fe2+ of Fe3O4 and

organic and inorganic luminophores in excited states, and partly because of optical adsorption of light by magnetite. The Stern-Folmer dependences obtained confirmed that. The way to overcome this

problem was shown and employed by incorporating magnetic nanoparticles into a polymer matrix and

placing luminescent nanoparticles onto the surface of magnetic-polymer particles. Created varnish and

ink compositions can be printed onto surface of forgery-proof products or packaging materials by

flexography, inkjet printing, pad (indirect gravure) printing and screen printing.

To sum up, the development of printing technology and materials and packaging is strongly connected

to the development of nanotechnology, and luminescent-magnetic organic-inorganic nanocomposites

are very promising for printing technology and packaging systems.


80

PHOTOPHYSICAL PROPERTIES OF COPOLYFLUORENES

IN SOLUTION AND BULK

R.Yu. Smyslov1, G.I. Nosova

1, N.A. Solovskaya

1, E.V. Zhukova

1, I.A. Berezin

1,

A.V. Yakimansky1, E.I. Maltsev

2, D.A. Lypenko

2, A.V. Vannikov

2

1 – Institute of Macromolecular Compounds RAS, St. Petersburg, Russia


[email protected]

One of the tasks of molecular photonics is the development of highly efficient electroluminescent

devices for illuminating panels, optoelectronic systems, etc. A possible solution, meeting the

modern challenges, is the use of thin polymer electroluminescent films instead of light-emitting

layers on the basis of low-molecular weight luminophores. An advantage of the approach is an

abandonment of a costly vacuum deposition of phosphors to simple solution procedures compatiple with spin-coating, ink jet, screen, and web printing technologies [1].

In the present paper, photoluminescence properties of new low band gap copolymers of 9,9 -

dioctylfluorene are investigated in both solution and bulk. This type of materials is promising as

light-emitting layers due to rather high quantum yield and thermal stability [2]. The aim of the

present paper is a tuning of photo- and electroluminescence spectra of the synthesized polymers for

an efficient white-light emission, varying the chemical structure and composition of

copolyfluorenes. Three basic approaches to white-light emitting copolyfluorene materials were

given a try: 1) combining triple copolymers, containing blue-, green, and red-emitting comonomer

units in one macromolecule; 2) blending homopolymers, emitting in blue, green, and red spectral

ranges; 3) blending two or three copolymers, consisting of two comonomers, emitting in different spectral ranges of the visible light.

In the present work, new copolyfluorenes (blue emitter), containing electron-donor carbazole and

electron acceptor 2,1,3-benzthiadiazole (green emitter) fragments in their backbones, and Nile red

(red emitter) or naphthalimide (green emitter) derivatives in side chains. The resulting emission

color is determined by the efficiency of excitation energy migration along the conjugated backbone,

exciton trapping, and excimer formation. A control of energy migration is realizable at different

levels of the material structural organization. First, a microblock or an alternating copolyfluorene

structure may be attained via the use of Yamamoto or Suzuki cross-coupling polycondensations,

respectively. A strengthening or weakening of the excitation energy transfer is provided by

variations of a balance between inter- and intramolecular interactions, owing to the use of double

and triple copolyfluorene blends and the transfer from synthetically cumbersome individual triple

copolymers to blends of much more feasible double copolymers. It is shown that a distribution of

amorphous and crystalline phases is affected by annealing of the material. The indicated factors

may be used to control photoluminescence spectra. Sample light-emitting diodes prepared on the

basis of the synthesized materials showed a rather high brightness (1000 cd/m2).

[1] Vannikov A.V. // Vysokomolek. soed. Ser. А. 2009. T. 51. № 4. S. 547.

[2] Lee J.-I., Klaerner G., Davey M. H., Miller R.D. // Synthetic Metals 102(1999) 1087—1088.

This work is supported by the Scientific Program “Multifunctional materials for molecular

electronics” of the Presidium of the Russian Academy of Sciences (coordinator – academician S.M.

Aldoshin) and by Ministry of Education and Science of the Russian Federation in the framework of

the Federal Targeted Program “Investigation on prioritized directions of development of the

scientific and technological complex of Russia for 2007-2012” (State contract no. 16.516.11.6072).


81

SECOND-ORDER NON-LINEAR OPTICAL PROPERTIES

OF CHROMOPHORE-CONTAINING POLYIMIDES

A.V. Yakimansky1, G.I. Nosova

1, N.A. Solovskaya

1, E.V. Zhukova

1,

N.N. Smirnov1, A.I. Gorkovenko

2, A.E. Simanchuk

2, A.I. Plekhanov

2


2 – Institute of Automation and Electrometry SB RAS, Novosibirsk, Russia

[email protected]

Non-linear optical (NLO) nanostructured materials are of great interest for optoelectronics because

they make it possible to change the frequency of the propagating light and to realize a

communication between electric and optical signals through their light-perturbed electronic

distribution.

In the present work, thermally stable and heat resistant polyimides with covalently attached

chromophore groups were synthesized by Mitsunobu reactions between OH- or COOH-

functionalized polyimide and OH-containing chromophores in the presence of diethyl-

azodicarboxylate (DEAD) and triphenylphosphine (PPh3),

N

Q

N

OH

O

O

O

O

n n

ROH

DEAD,

PPh3

N

Q

N

OR

O

O

O

O

where Q is a bridge group, chromophores R include various commercial and synthetic azo-

chromophores, and two 2-[3-[2-[4-(N,N-diethylamino)-phenyl]ethenyl]-5,5-dimethyl-2-cyclohexen-

1-ylidene]- propanedinitrile chromophores. Some of the used azo-chromophores contained

carbazole fragments to enhance polymer photoconductivity properties, which is necessary to create

photorefractive holographic polymer media, or bulky side groups, preventing an undesirable

centrosymmetric aggregation of chromophore groups. Second harmonic generation (SHG)

coefficients, d33, for corona-poled films of these polymers were measured. Films with the thickness

of 0.1–2.0 μm were spin-cast on glass substrates from polymer solutions in cyclohexanone. Corona-

poling was performed for 40–60 min at 150–200ºC (depending on glass transition temperature of a

particular chromophore-containing polymer). Rather high d33 values (>50 pm/V) were achieved.

For some azo-chromophore containing polyimides, the refractive index dispersion and frequency

dependences of d33 values were measured in the fundamental frequency range from 800 to 1400 nm.

All studied samples possessed a rather high beam resistance at the fundamental wavelength, their

nonlinear optical properties remaining unchanged after the action of more than 104 pulses. It was

shown that the frequency dependence of d33 is red-shifted with respect to the absorption spectrum.

Therefore, there is a frequency range where the polymer is practically transparent, while the d33

values are still rather high.

This work is supported by the Russian Foundation for Basic Research, project no. 12-03-00709-а,

by the Scientific Program “Multifunctional materials for molecular electronics” of the Presidium of

the Russian Academy of Sciences (coordinator – academician S. M. Aldoshin)


82

POSTERS

SECTION 1. OPTICAL SPECTROSCOPY AND PHOTOCHEMICAL

PROCESSES IN MOLECULAR AND SUPRAMOLECULAR SYSTEMS

PHOTOPROCESSES IN STYRYL DYES AND THEIR

PSEUDOROTAXANE COMPLEXES WITH CUCURBIT[7]URIL

L.S. Atabekyan, A.I. Vedernikov, V.G. Avakyan, N.A. Lobova, S.P. Gromov, A.K. Chibisov


[email protected]

The formation of inclusion complexes between styryl dyes with dimethylamino and azocrown ether

residue as substituent and cucurbit[7]uril (CB[7]) was studied by 1H NMR spectroscopy and

quantum chemistry in water. Complexes are characterized by 1:1 composition and pseudorotaxane structure that is confirmed by quantum-chemical calculations.

Triplet-triplet absorption spectra and the life-time of the dyes and complexes dye@CB[7] tiplets

were measured by means of ns-laser photolysis. Dyes exhibited a P-type delayed fluorescence, an

increasing of intersystem crossing and an enhancement of prompt fluorescence.

NEt

NMe2

ClO4

_

+

NEt

ClO4

_

+

O O

N

O O

O

The formation of pseudorotaxane complexes of guest-host type with dimethylamino and azocrown

ether residue as substituent and cucurbit[7]uril (CB[7]) was found to result in decreasing of

conformation mobility of dye molecules and their relative isolation by molecule of cavitande. As a

consequence it results in a increase of both luminescence intensity of the dye and the probability of

intersystem crossing. The finding of delayed fluorescence of the dye makes it possible to explain a

noticeable increase of fluorescence intensity in the presence of CB[7] as well as the intersystem

crossing.

The work was supported from RFBR (projects № 12-03-00107-а and № 12-03-00491-a).


83

IR SPECTRUM, HYDROGEN BOND AND STRUCTURE

OF 2,3-DI-О-NYTRO-METHYL-BETA-D-GLUCOPYRANOSIDE

L.M. Babkov1, I.V. Ivlieva

1, M.V. Korolevich

2


2 – Institute of Physics NAS, Minsk, Belarus

[email protected]

The IR spectrum of the 2,3-di-O-nytro-methyl-β-D-glucopyranoside have been measured by room

temperature. The analysis of the IR spectrum measured at the room temperature indicates the

presence of H-bonds. How the H-bonds influence to the structure of the sample? What structure do

the formed H-complexes have and what is the probability of their realization? Can we identificate

the H-complexes and, if we can, in what areas of the spectrum could be revealed their structural differences?

Structural–dynamic models of the molecule of 2,3-di-O-nytro-methyl-β-D-glucopyranoside and its

H-complexes are constructed by density functional method in bases 6-31 G(d) [1-3]. Their

energies, structures, dipole moments, polarizabilities have been calculated. Using the results of the

quantum chemistry calculations and the calculations of the IR spectrum of H-complexes of the 2,3-

di-O-nytro-methyl-β-D-glucopyranoside and ethanol the following conclusions can be made.

The complexing influence only the geometry of the fragments bordering with the core of the H-

complex. The lengths of the bonds О-Н of hydroxyl groups in the transition of the molecules to the

complexes are increasing by 0.1 Å and make up 0.98 Å. The energies of hydrogen bonds are

different: from 7.4 to 10 kcal/mol (dimers) and from 5.7 to 10.2 kcal/mol (complexes with ethanol).

The changes of frequencies of valent oscillations of the O-Н bonds are 108 cm-1

and 216 cm-1

,

which qualitatively consistent with the obtained data for the energies of hydrogen bonds. The

difference of the frequencies of valent oscillations of the O-H bonds at the H-complexes with

difference at the structure was 110 cm-1

. It is possible to held their spectroscopic identification. The

results of the modeling allowed to interpret the measured IR spectrum of the 2,3-di-O-nytro-methyl-

β-D-glucopyranoside taking the H-complexes into account.

1. Кон В. // УФН. – 172 (2002), №3, c. 336–348.

2. Попл Дж. // УФН. – 172 (2002), c. 349–356.

3. Frisch M.J., Trucks G.W., Schlegel H.B. et al. Gaussian03, Revision B.03; Gaussian, Inc.,

Pittsburgh PA (2003).


84

LINKAGE ISOMERISM OF CO ADSORBED ON ALKALI-HALIDES

R.A. Belykh, A.A. Tsyganenko


[email protected]

The effect of linkage isomerism was first observed for CO on Y- and ZSM5- zeolites with alkali

cations [1, 2]. The molecule was shown to form with the same adsorption site complexes of two

types, bound via carbon or oxygen atoms. No linkage isomerism was found for CO adsorbed on X

zeolites or for metal oxides, apparently, because of strong interaction of CO with oxygen anions [3].

Since halogen anions have lower charge and greater size, one could anticipate the manifestations of

linkage isomerism for CO adsorbed on disperse alkali halides. The search of this phenomenon for thin evaporated films of NaCl and KBr was the aim of the present study.

Fig.1 Evolution of the spectrum of CO adsorbed on NaCl on heating from 87 (top curve) to 133 K (bottom).

Fig.1 shows the changes in the spectra of CO adsorbed on NaCl film, sputtered at room

temperature, observed on raising the temperature. Intensity decrease of the main band at 2153-2155

cm-1

is accompanied by proportional diminution of the peak of 13

CO at 2102 cm-1

. Unlike the latter,

a weak band at 2124 cm-1

first grows on heating the sample, then start to decrease, exhibiting

exactly the behavior of M-OC isomeric structure in zeolites. The bands referred to linkage isomers

were found on both surfaces.

More detailed analysis of temperature dependence of band intensities, as well as the positions of the

bands persuade us that isomerism occurs only on the strongest sites, apparently, those, which

account for the band at 2170–2172 cm-1

and can be associated with the three-coordinated Na+

cations at the kinks of rock salt microcrystals.

Almost the same results were obtained for KBr films. The presented results support our notion

about the conditions for isomerism on adsorption. The phenomenon that can be of a great

importance for catalysis, because the energetically less favourable structure can act as activated

state in catalytic reactions. Structures with two stable states can also be considered as promising

units for the optoelectronic devices.

Acknowledgement The work was supported by the Ministry of Education and Science of the

Russian Federation, grant 11.38.38.2011.

References 1. Otero Arean C., Tsyganenko A.A., Escalona Platero E., Garrone E., Zecchina A. Angew. Chemie. Intern. Ed., 37 (1998),3161. 2. Tsyganenko A.A., Storozhev P.Yu., Otero Areán C., Kinet. Catalysis 45 (2004) 530. 3. Storozhev P.Yu., Yanko V.S., Tsyganenko A.A., Turnes Palomino G., Rodriguez Delgado M., Otero Areán C. Appl. Surface Sci., 238 (2004) 390.


85

EFFECT OF LINEAR AND ANGULAR BENZO-ANNELATION

ON SPECTRAL AND PHOTOCHEMICAL PROPERTIES

OF 2-STYRYLQUINOLINE

M.F. Budyka, V.M. Lee, N.I. Potashova, T.N. Gavrishova


[email protected]

In previous investigations we have found that 2-styrylquinoline (2SQ), due to its photochemical

activity and stability, can be used to design molecular logic gates. The purpose of the present work

is to study spectral and photochemical properties of benzo-annelated derivatives of 2SQ, linear

derivative 2-styrylbenzo[g]quinoline (2SBQ) and angular derivative 3-styrylbenzo[f]quinoline

(3SBQ). For comparison, properties of 3-styrylacridine (3SA) are also studied. Both 2SBQ and 3SA

are the hetero analogues of 2-styrylanthracene (2SA), the latter possessing an interesting property,

one-way photoisomerization: there is no reaction in the trans → cis direction (quantum yield φtc <

10-3

) but in the cis → trans direction only (quantum yield φct > 0.1).

N

N

NN

2SBQ

3SA

3SBQ2SQ

2SA

Benzo-annelation of 2SQ resulted in bathochromic shift of absorption band and bathofluoric shift of

emission band with simultaneous increase in the fluorescence quantum yield. All compounds on

protonation demonstrated red shifts of absorption and emission bands and essential decrease in emission intensity.

2SBQ and 3SA (trans-isomers) proved to be photoinert in both neutral and protonated forms (φtc <

10-3

), and in this respect resemble homoaromatic analogue, 2SA. 3SBQ underwent reversible

photoisomerization with quantum yields φtc = 0.19 and φct = 0.38, which increased in protonated form (3SBQ

.HCl) to φtc = 0.44 and φct = 0.47.

For the explanation of the effects observed, quantum-chemical calculations were performed using

PM3 method for the S0 state and PM3-CI (with configuration interaction) for the S1 state,

MOPAC09 program. Difference in photochemical properties of linear and angular annelated

styrylbenzoquinolines is determined by the difference in the structure of the frontier molecular

orbitals, that gives rise to difference in the shape of potential energy surfaces (PESs) of the S1

excited states. In the case of 2SBQ, the S1-term of the trans-isomer lies below the term of the

perpendicular conformer that results in high activation barrier for twisting around the central double

bond in the excited state. In the case of 3SBQ, the S1-term of the trans-isomer lies above the term of

the perpendicular conformer, the latter is a global minimum on the S1 PES that favours the diabatic photoisomerization.

Comparison of properties of 2SBQ and 3SBQ with those of 2SQ reveals the size and topological effects in photochemistry of aza-diarylethylenes.

The work was supported by the Russian Foundation for Basic Research (grant no. 10-03-00751).


86

POLYMORPHISM OF PHENYL-2-HYDROXYBENZOATE

STUDIED BY LUMINESCENCE AND IR SPECTROSCOPY

N.A. Davydova, G.V. Klishevich, V.I. Melnik, V.Ya. Reznichenko

Institute of Physics NAS, Kyiv, Ukraine

[email protected]

Phenyl-2-hydroxybenzoate, or phenyl salicylate (HO–C6H4COOC6H5) has diversified applications,

namely as a stabilizer for cellulosic and vinyl plastics, as an ingredient for suntan preparations, and

also as an analgesic and antipyretic.

In our previous studies of phenyl-2-hydroxybenzoate using Raman and DSC methods [1] it was

experimentally illustrated that different crystalline modifications can be obtained upon variation of

crystal growth conditions. To our knowledge, no work on the luminescence study of phenyl-2-

hydroxybenzoate has been performed so far. This provides a stimulus to the detailed luminescence

study, which can give interesting information on the different crystal polymorphs of phenyl-2-hydroxybenzoate.

The luminescence spectra of different modifications of phenyl-2-hydroxybenzoate and their

temperature dependencies have been studied for the first time. It has been found that luminescence

spectra appear fairly similar, are asymmetric and broad, and have the vibronic structure. Gaussian

decomposition of the luminescence band shows the four components. The vibrational spacing

between the first three components was found to be at about 1250 cm-1

. The spectrum of the stable

phase has a full width at half-maximum (fwhm) amplitude of 2500 cm-1

. The luminescence

spectrum of the metastable phase has the fwhm = 3500 cm-1

, and is down-shifted by 760 cm-1

relative the stable phase. That fact gives the possibility to identify each modification of phenyl-2-

hydroxybenzoate according to the position of the first emission band in the luminescence spectra.

The progression interval in the luminescence spectra was combined with data from the IR

transmittance spectra. It has been found that the vibration that gives rise to the vibronic structure on

the luminescence band corresponds to the (C–OH) stretching vibration. Obviously, the presence of

an OH group in the orto-position on the OH-substituted ring asymmetrizes the molecule, localizing

the electronic excitation to the substituted ring.

[1] J. Baran, N.A. Davydova, M. Drozd. J. Phys.: Cond. Matter 22, 155108 ( 2010).


87

N-METHYLAZACROWN-CONTAINING STYRYL DYES

AS OPTICAL MOLECULAR SENSORS FOR METAL CATION

S.N. Dmitrieva1, E.N. Ushakov

2, A.I. Vedernikov

1, N.A. Kurchavov

1, A.Ya. Freidzon

1,

L.G. Kuzmina3, S.K. Sazonov

1, A.A. Bagaturyants

1, M.V. Alfimov

1, S.P. Gromov

1

1 – Photochemistry Center RAS, Moscow, Russia


3 – N.S. Kurnakov Institute of General and Inorganic Chemistry RAS, Moscow, Russia

[email protected]

Synthesis of new styryl dyes of 2-benzothiazole, 2- and 4-quinoline, and 4-pyridine series,

containing a fragment of N-methylbenzoaza-15(18)-crown-5(6) ether, was developed. The dyes

were obtained by condensation reaction of quaternary heterocyclic salts with formyl derivatives of

benzoazacrown ethers.

Y

N

EtOO

O

N O

O

Me

ClO4

_

OO

O

N O

O

Me

NMe

X_

n = 0 , 1

+

n n

+

Y = CH=CH, S X = I, ClO4

Fig. 1. Absorption spectra of dye (Y = S, n = 1) and its metal complexes in MeCN.

Fig. 2. Structure of dye (Y = CH=CH, n = 0).

The complex formation, ionophoric and ionofluorophoric properties of azacrown-containing styryl

dyes were investigated. It was shown that such dyes are highly effective optical molecular sensors

(OMS) for alkali and alkaline-earth metal cations. They are characterized by an enormous

ionochromic effect, high selectivity and can operate as «switched on» luminescent sensors of new

type. These new donor-acceptor OMS were established to exceed greatly similar OMS on the basis

of N-phenylazacrown ethers both in thermodynamic stability of the complexes with metal cations

and in value of ionochromic effect. The structures of azacrown-containing styryl dyes and their

metal complexes were studied by NMR, X-ray diffraction, and quantum chemical calculations

(DFT). A considerable degree of pre-organization of N-methylazacrown fragment toward the

formation of complexes with metal and ammonium cations was noted, that causes high complexation ability of these dyes.

New OMS, elaborated on the basis of N-methylbenzoazacrown ethers, can be used as components

of sensor materials for alkali and alkaline-earth metal cations.

This work was supported by the RFBR and the Russian Academy of Sciences.


88

THE FLUORESCENCE QUENCHING OF TRYPTOPHAN

BY GOLD NANOPARTICLES IN COLLOIDS

AND ON THE SURFACE OF AU/SIO2

A.M. Eremenko1, N.P. Smirnova

1, I.P. Mukha

1, A.P. Naumenko

2, N.M. Belyy

2

1 – O.O. Chuiko Institute of Surface Chemistry NAS, Kyiv, Ukraine

2 – Physical Dept. of Taras Shevchenko National University of Ukraine

[email protected]

In recent years, the fluorescence quenching technique was applied extensively to study the

interactions of biomolecules with noble metal nanoparticles. Extensive experimental and theoretical

data on the electronic spectra of amino acids, enzymes, proteins, etc., located near the surface of

nanoscale metal particles appeared in the literature. These studies are based usually on the

assumption about the formation of so-called “labeled” or “marked” particles, marking the material

by the direct addition of molecules to the NPs’ surface. The strong reduction of fluorescence

intensity experienced by the fluorophores when bound to Au NPs and quenching process is usually

attributed by many authors to energy transfer [S. Mayilo, 2009, M. Iosin, 2009]. In this work,

tryptophan (Trp), an essential amino acid in human nutrition, which has high affinity to the gold, at

the same time is able to act as a stabilizer of NPs and reduce its toxic effect on living cells, was

used.

The goal of this work was to study the interaction of gold NPs with Trp molecules in solution and

immobilized on the surface of dispersed SiO2, by the methods of electron spectroscopy. Colloidal

solutions of Au NPs were prepared via reduction of tetrachlorauratic acid using Trp as

reducing/stabilization agent. Heterogeneous composites Trp/Au/SiO2 were obtained by adsorption

of colloidal solution of complex of gold NPs with tryptophan on the SiO2 surface (Au-Trp/SiO2). In

the presence of Au NP solution, the fluorescence (FL) spectrum of Trp consists of two bands - the

FL of the molecular Trp with λmax = 360 nm and a new band, referred by us to the FL of charge-transfer complex (CTC) between Trp and Au NPs with λmax = 450 nm.

Luminescence excitation spectrum of Trp associated with Au NPs consists of two bands – one

belonging to the free molecule in solution shifted by 5 nm in the "red" region relative to the position

in pure Trp solution (λmax = 303 nm), and excitation band of CTC (λmax = 373 nm).

As well as in the solution of Trp with gold NPs, on the surface of Au/SiO2 the emission band of

CTC is registered at the maximum of 450-490 nm. Short-wave shift of the main FL maximum of

adsorbed Trp on the initial SiO2 and Au/SiO2 (334 nm) compared with that in solution Trp (360 nm)

is due to protonation of the amino group of Trp by acidic OH groups of silica surface. Such short -

wave shift is typical for the electronic spectra of aromatic molecules containing an amino group in

acidic medium and evidenced on the participation of NH2 group in the interaction with the surface.

Despite the slightly acidic function of the OH groups of silica it is well-known the ability of OH

groups to dissociate and to ion exchange. Reduction of gold ions by Trp occurs due to the π-electron system of indole ring.

Thus, based on the effective quenching of fluorescence of Trp molecules bound to the gold NPs

both in solution and on the surface of dispersed silica we assume the mechanism of quenching as

charge-transfer process between Trp and Au NPs. The fluorescent charge-transfer complex

between Trp and Au NPs is observed in the spectra.


89

SYNTHESIS AND LUMINESCENT PROPERTIES

OF TRIS-DIKETONATE COMPLEXES OF EU (III) AND TB (III)

WITH PYRIDINE LIGANDS IN SOLUTIONS

M.V. Fomina1, A.V. Vannikov

2, D.A. Lypenko

2, E.I. Mal’tsev

2, S.I. Pozin

2,

A.V. Koshkin1, L.G. Kuz’mina

3, M.V. Alfimov

1, S.P. Gromov

1

1 – Photochemisry Center RAS, Moscow, Russia

2 – Institute of Physical Chemistry and Electrochemistry RAS, Moscow, Russia

3 – Institute of General and Inorganic Chemistry RAS, Moscow, Russia

[email protected]

A novel trivalent lantanide complexes 1 and 2 were prepared by the reaction of Eu(III) or Tb(III)

chloride (LnCl3) with β-diketone (dikH) and pyridine-containing ligands Q at the presence of

sodium hydroxide:

LnCl3

n QNaOH

+ +3 dikH Ln(dik)3Qn

n = 1, 2; Ln = Eu(III), Tb(III)

All complexes were prepared in good yields (40–88%).

N O

O

CF3

S

Eu

N

N

N

Me

R

O

O

R

R

Ln

3

2

1

1

3

2

R = Me, 2- naphthyl; R1 = Me, 2-thienyl, Ph; R

2 = CF3, Ph; Ln = Eu

3+, Tb

3+

The structures of the synthesized complexes Eu(III) and Tb(III) were established by X-ray diffraction and confirmed by the data elemental analysis.

The electronic absorption and luminescence spectra of the complexes 1 and 2 were studied in

solutions. The complexes have high molar absorption coefficients and display strong visible (red or

green) luminescence, depending on the choice of the lanthanide. The quantum yield of

luminescence reach tens of percent, which indicates the efficient transfer of energy from organic

ligands to the lanthanide cation. The spectral properties of the complexes 1 and 2 were studied at

the presence of amines and ketones.

This work was financially supported by the Ministry of Education and Science and by the Presidium

of the Russian Academy of Sciences.


90

SIMULATION OF ABSORPTION AND EMISSION SPECTRA

OF NILE RED DYE AND ITS COMPLEXES WITH SOME ANALYTES

FOR VIRTUAL DESIGN OF MOLECULAR CHEMOSENSORS

A.Ya. Freidzon, A.A. Safonov, A.A. Bagaturyants

Photochemisry Center RAS, Moscow, Russia

[email protected]

The absorption and emission spectra of Nile Red dye used as an indicator in molecular

chemosensors and its intermolecular complexes with a number of small analyte molecules are

simulated by TDDFT with the PBE0 functional and Grimme's dispersion correction. It is found that

complexation with analytes only slightly influences the position of the absorption band as well as

the locally excited (LE) fluorescence band. However, the emission from the twisted intramolecular

charge transfer (TICT) state is affected by the complexation. The most prominent effect was

observed with alcohols and, to the less extent, with water. Hence, it was found that TICT

fluorescence of Nile Red could be an analytical signal in the determination of alcohols in air.


91

MULTISCALE APPROACH TO THE STRUCTURE AND SPECTRA

OF NILE RED ADSORBED ON POLYSTYRENE NANOPARTICLES

A.Ya. Freidzon, V.A. Tikhomirov, A.V. Odinokov, A.A. Bagaturyants

Photochemisry Center RAS, Moscow, Russia

[email protected]

The structure and absorption spectra of Nile Red (NR) dye adsorbed on the surface of polystyrene (PS) nanoparticles is studied by DFT.

Polystyrene nanoparticle with an adsorbed NR molecule was simulated by a large cluster consisting

of PS chains using molecular dynamics in the OPLS-aa force field in the NVT ensemble at 298 K.

Different surface models were tried: a surface of a single-chain coil (up to 1000 monomeric units)

and of a periodic box. Next, the surface was truncated so that only the nearest-neghiboring phenyl

rings surrounding the chromophore (bold lines in the figure) were treated either explicitly by DFT

or as effective fragment potentials (EFP). The structure of the dye from MD calculation was re-

optimized by DFT in the frozen environment, and its absorption and emission spectra of were

calculated by TDDFT in this environment and compared with those in vacuo and in toluene

(simulated through polarizable continuum model). It is shown that the transition energies calculated

in an explicit environment and in EFP are almost the same, but EFP makes the calculation cheaper.

The positions of the absorption, locally excited (LE) and twisted intramolecular charge transfer state

fluorescence bands are in good agreement with the experiment.

Fig.1 Polystyrene cluster with adsorbed Nile Red dye considered at different level of theory: thin lines, molecular

dynamics; bold lines, effective fragment potentials; balls-and-sticks, quantum mechanics


92

LUMINESCENCE OF SOLUTIONS

OF THE N-PHENYLANTHRANILIC ACID

V.P. Galkin, N.A. Klemesheva, D.V. Mazyrin, D.A. Nosova, Y.A. Rozhkova,

S.O. Visotskaya, E.P. Zarochentseva, V.I. Korotkov


[email protected]

Luminescence studies of chromophore-bearing systems are a useful source of dynamic [1] and

structural information [2]. The present work is concerned with the phenomena of the solute

concentration on the solution luminescence spectra. To make clear this influence luminescence

spectra and luminescence excitation spectra of the N-phenylanthranilic acid (NPA) solutions in

dichloromethane has been investigated at room temperature. NPA has been choused because of its tendency to form aggregates. NPA concentrations were 10

-2, 10

-3, 10

-4 and 10

-5 M.

Luminescence spectra under excitation by three wavelengths (λex = 280, 330 and 340 nm) of

individual molecules (C = 10-5 M) consists of one band near 450 nm and luminescence excitation

spectra detected in maximum of luminescence spectrum (λreg = 450 nm) expose two bands near 280

and 343 nm.

New long-wave band at 390 nm appears in excitation spectrum after increasing concentration up to

C = 10-4

M and two other bands move to short-wave side up to 260 and 318 nm. Luminescence

spectra don’t change under excitation by short-wave radiation, but long-wave excitation (λex = 390

nm) results in red shift of luminescence maximum to 460 nm.

Further concentration growth until C = 10-3M leads to luminescence intensity reduction. Excitation

by 400 nm gives another long-wave shift of luminescence maximum up to 473 nm. Three maxima

of excitation spectrum (detected at 473 nm) become more sharp and blue-shifted – 257, 315 and

400 nm. Relative intensity of long-wave maximum rises.

Sample with concentration C = 10-2M gives luminescence maximum at 476 nm. Excitation spectrum consists of single very narrow band at 423 nm.

Changes in luminescence and excitation spectra appear under concentration rising usually owing to

reabsorption effect. But those phenomena begin play role at concentration more than 10-3

-10-2

M.

In addition in our experiments long-wave band arises in excitation spectrum lies out-of single

molecule absorption diapason. The excitation spectra changed from those characteristic of a

individual molecule (C = 10-5 M) to red-shifted narrow band (C = 10-2M) typical of J aggregates.

Between these concentrations, the two maxima of excitation spectra split into three blue- and red-

shifted bands. Relative intensities of these bands changes with concentration for benefit of long-

wave band. Analogical results for ionic liquids were described in [3]. Authors explained changes in

excitation and fluorescence spectra provided concentration rising molecules rearranging in their clusters from head-to-head to head-to-tail aggregates.

References 1. Jin H, Baker G, Arzhantsev S, Dong J, Maroncelli M, (2007) J Phys Chem B 111:7291-7302.

2. Serrano B, Baselga J, Bravo J, Mikes F, Sese L, Esteban I, Pierola IF, (2000) J Fluorescence,

10:135-139.

3. Pierola, Ines F.; Pacios, Isabel E. (2012), J of fluorescence22 (1), 145-150.


93

FTIR STUDY OF ADSORBED CF4

A.V. Gatilova, D.N. Shchepkin, T.D. Kolomiitsova, A.A. Tsyganenko


[email protected]

Lateral interactions, studied in detail for adsorbed CO, affect greatly the spectra of molecules

adsorbed on the surfaces of metаls [1] and oxides [2]. Static effect accounts for the energetics and

geometry of adsorbed layer and changes the vibrational frequencies of individual molecules.

Dynamic interaction, referred also as dipole coupling or resonance dipole-dipole (RDD) interaction,

modifies the positions, shapes and widths of the absorption bands in the spectra of adsorbed layers,

where the vibrations are delocalized over the ensembles of surface species.

Up to now, the dynamic interaction was observed mostly for CO molecules somehow oriented with

respect to the flat surface of metals, crystalline oxides or halides. Recently it was shown, however,

that complex bandcontour in the spectra of CF4 or SF6 molecules dissolved in liquid noble gases

can be explained by RDD interaction [3]. The aim of this work was to find out the manifestations of

such interactions in the spectra of adsorbed CF4, almost not studied spectroscopically in adsorbed

state.

Figure 1. FTIR spectra of 12

CF4 gas (1),

solid film at 60 K (2), and adsorbed at 77 K

on MgO pretreated at 773 K (3) and CaO

pretreated at 973 K (4), and NaX zeolite

evacuated at 623 K (5). Background

absorption of samples before adsorption is

subtracted.

Figure 1 shows the region of ν3 vibration in

the spectra of CF4 adsorbed on several

adsorbents at 77K. For comparison spectra

of CF4 gas and solid film on cell windows are given at the same picture. In all the spectra at about

1259 cm-1

the “Evans hole” can be seen caused by Fermi resonance of ν3 vibration with 2ν4 mode,

observed in the spectrum of gas as a doublet at 1265–1257 cm-1

.

The band of ν3 vibration of adsorbed CF4 is split in two maxima with more intense high-frequency

constituent. The separation is not the same for different adsorbents and increases in the sequence:

MgO, CaO, NaX zeolite, following the basicity of surface anions. The position of the high-

frequency constituent slightly shifts to higher wavenumbers with the increasing coverage. The

position of ν3 band of 12

CF4 admixed in 13

CF4 adsorbed on MgO coincides with that of pure 12

CF4 at

the lowest coverage, thus indicating of RDD interaction as a reason of coverage-induced frequency

shift.

Acknowledgement. The work was financially supported by the Ministry of Education and Science

of the Russian Federation , grant 11.38.38.2011.

References

[1] Hollins P., Pritchard J., in Vibrational Spectroscopy of Adsorbates, Ed. by Willis R.F. (Springer-

Verlag Berlin Heidelberg, New York, 1980), pp.125-144.

[2].Tsyganenko A., Denisenko L., Zverev S., Filimonov V., J. Catal., 94, p.10-15 (1985).

[3].Cherevatova A., et. al, J. Mol. Spectr., 238, p.64–71 (2006).


94

THE COMPONENT ANALYSIS A EOSINE LUMINESCENCE

N.S. Goryachev


[email protected]

The component analysis is the most widely applied in spectroscopic studies for definition of a

qualitative and quantitative composition of optically active substances. Our research use method of

fundamental component to analysis of kinetics of a phosphorescence spectrum and fluorescence

spectrums. It has allowed us to increase precision and quality of measurements and also to receive

dates unapproachable by other methods. We explored a phosphorescence kinetics of eosin recorded

on different wavelengths of emission. All data array was decomposed with the use of singular

decomposition. We was taken the first two components take into account contribution, which one described all massive of measurements with good precision.

The obtained basis kinetics was analysed in two-exponential approach. In result obtained separate

two monoexponential phosphorescence spectrums of eosin.

The emission spectrums and excitation spectrums similarly parsed. In result we discovered a system of pair electronic levels of eosin.

This work was supported by the RFBR (grant 10-03-00687) and the Presidium of Russian Academy

of Sciences (Research program No 24 “Fundamental research in the field of nanotechnology and

nanomaterials”).


95

THE EFFECT OF MEDIUM ACIDITY ON PHOTOPHYSICAL AND

PHOTOCHEMICAL PROPERTIES OF HEMIN IN AQUEOUS SOLUTIONS

M.A. Gradova, A.V. Lobanov

N.N. Semenov Institute of Chemical Physics RAS, Moscow, Russia

[email protected]

Photophysical and photochemical properties of metal porphyrins are known to be strongly affected

by the coordination number of metal ions, the nature of extraligands and the aggregation state of the

pigment [1]. In the present work we study the effect of medium acidity on the aggregation state of hemin (Fe

III-protoporphyrin IX, FePP) in aqueous solutions and its catalase and peroxidase activity.

Catalytic activity in hydrogen peroxide decomposition together with the resistance to oxidative

destruction was found to depend on the aggregation state of the pigment [2]. The aggregation

process of FePP usually results in a blue shift and a significant broadening of the absorption band.

In addition to the aggregation process the absorption spectrum of FePP is strongly affected by the

number and nature of axially coordinated ligands especially in the Q-band region. Coordination of

extraligands prevents aggregation of FePP and causes a red shift of the Soret band indicating the

predominance of a monomeric form of hemin. A similar effect is observed in the presence of surfactants at concentrations above cmc due to solubilization of the pigment in micellar phase [3].

In alkaline solutions hemin molecules mainly exist in a bipyramidal dimeric form and each

molecule contains negatively charged propionic acid residues, which prevent further aggregation,

whereas in acidic medium oligomer formation is observed due to charge neutralization. During the

transition from alkaline to acidic medium dimeric hemin species undergo molecular transformations

accompanied by the monomer formation with an absorption maximum at 392 nm. Dimeric form of

hemin in alkaline solutions was found to be the most active in catalytic H2O2 decomposition and

resistant to oxidation. Thus catalase activity prevails over peroxidase one in alkaline solutions of

FePP. Acidic solutions of hemin provide an extremely low yield of molecular oxygen and a low rate

of the pigment oxidative decomposition.

In micellar solutions of surfactants the transition from alkaline to acidic forms of hemin is

influenced by interactions with the micellar surface charge, but in all cases no short-wavelength

aggregated species are observed in acidic medium. Cationic surfactants reduce the rate of H2O2

decomposition and inhibit oxidative destruction of FePP, while anionic surfactants retain the high rate of oxidative destruction of hemin but have little effect on its catalase activity.

The data obtained provide new approaches for biomimetic modeling of redox enzymatic activity

and contribute to better understanding of the mechanism of intermolecular interactions between

redox cofactors and their macromolecular environment in vivo.

References:

[1] The porphyrin handbook: Inorganic, organometallic and coordination chemistry. Ed. by K. M.

Kadish, K. M. Smith, R. Guilard. Elsevier, 1999, 425 p.

[2] Lobanov A.V., Vasiliev S.M., Komissarov G.G. Interaction of Hemin and Hydrogen Peroxide:

Effect of Media. Macroheterocycles, 2009, 2 (3-4), 268-270.

[3] Toader A.M., Volanschi E. Electrochemical and Spectral Study of the Hemin-Surfactant

Interactions in Solution. Revue Roumaine de Chimie, 2007, 52(1–2), 159–167.


96

ABSORPTION OF GASEOUS NAPHTHALENE BY THE ORDERED

LAYERS OF SUB-MICROPARTICLES WITH THE NANOPOROUS SHELL

OF POLY(ETHYLENE GLYCOL DIMETHACRYLATЕ)

E.Yu. Grushnikova1, A.V. Koshkin

1, A.Yu. Menshikova

2, P.V. Lebedev-Stepanov

1


2 – Institute of macromolecular compounds RAS, St. Petersburg, Russia

[email protected]

A new model describing the kinetics of absorption of naphthalene vapor from the atmosphere in

three-ordered arrays of polymer submicroparticles (400-450 nm) with simple and porous (modified)

shell and an impenetrable core was proposed. The experiment examined the layers of polymer

particles made of poly(ethylene glycol dimethacrylatе) (PEGDM). Processing of the experiment

using a physical model yielded the rate naphthalene absorption constants for the polymer and the

polymer template pores. Based on these results the effective thickness of the particle shells (about

20 nm), the diffusion coefficient of the analyte in the polymer and the enthalpy of dissolution of

naphthalene in the polymer were evaluated. It was shown the model efficiently describes the two-

stage absorption of the analyte by layers of sub-microparticles with nanoporous surface.

Study of sorption of polycyclic aromatic hydrocarbons (PAHs) were performed on samples of

sensor layers, prepared from an aqueous emulsion with a particle concentration of 5-10% by weight.

Scheme of the experiment was as follows (Fig. 1). The layers were obtained by the drop method on

quartz substrates. At the pre-washed substrate was placed in a water emulsion volume of 10 ml.

Drop evenly distributed over the surface of the substrate. Layers were dried for 1-2 hours at room

temperature. In the course of the experiment was obtained the dependence of the fluorescence

intensity of the time (Fig. 2) during the sorption of naphthalene and was conducted by recording the

intrinsic fluorescence spectra of analytes.

Fig. 1. The scheme for obtaining the structure and selective sensor layer from an aqueous emulsion of a submicroparticles.

Fig. 2. The kinetics of intensity of fluorescence

for sample 1-4 (1-3 samples – submicro-particles with template pores, 4-th sample – model submicroparticles) at a wave-length of 323 nm, in the form of normalized curves.

0 500 1000 1500 2000

0,0

0,2

0,4

0,6

0,8

1,0

1

I, a.u.

2

3

4

time, sec

Posters Optical spectroscopy and photochemical processes in molecular and supramolecular systems -------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------- -----------------------------------

97

NEAR-INFRARED SQUARATE AND CROCONATE DIANIONS

DERIVED FROM TETRANITROFLUORENE

A.A. Ishchenko, I.V. Kurdiukova, A.V. Kulinich

Institute of Organic Chemistry NAS, Kyiv, Ukraine

[email protected]

Two unusual squarylium and croconium dianionic dyes with 2,4,5,7-tetranitrofluorene (TNF)

terminal groups dyes were synthesized by condensation of TNF with squaric and croconic acid

respectively in the presence of organic bases. In spite of their dianionic nature, they are rather stable

both in a solid state and in solutions. To date mainly neutral (intra-ionic) squarylium and croconium

dyes were studied. In their molecules the negative charge of the central "olate" fragment is

compensated with the positive charge of the terminal heterocyclic group. To the best of our

knowledge, only two dianionic squarate and croconate dyes comprising malononitrile residues were

described hitherto. But their absorption bands lie in the yellow range of spectrum. TNF's expanded

π-system, high symmetry, and strong electron-acceptor ability favor the delocalization of a negative

charge in the chromophore and thus significantly enhance their color and chemical stability.

The carbocyclic TNF terminal nuclei brought qualitatively new features to the absorption spectra of

synthesized dyes. First, the compounds obtained have a record-deep color among all known dyes of

this class. Second, they present a unique case of the squarate colored deeper (1058 nm in DMF)

than the corresponding croconate (1052 nm). Another distinctive feature of their absorption, viz.,

multiple fairly intense bands in the VIS and NIR regions, is characteristic neither for the other

squarylium and croconium compounds nor for typical organic dyes at all.

An up-to-date quantum chemical approach at the DFT/B3LYP/6-31G(d,p) level was used to

interpret their unusual optical behavior. The probable reason of rather complicated absorption

spectra of synthetic dyes was found from the analysis of their MOs energy diagram: a great number

of the vacant levels, close by energy to the LUMO+1, are localized on the nitro-groups of fluorene

residues, thus increasing the number of long-wavelength electronic transitions. Therefore,

practically all long-wavelength transitions in studied dyes are accompanied with a transfer of

electron density from the central core and C9-atoms of fluorene onto the nitro-groups.

Also the PCM/TDDFT calculations (polarizing continuum model simulation of solvent effect) were

performed to explain deeper coloring of the squarate dye. They predict the bathochromic shift of the

long-wavelength band in the electronic spectrum of the squarate dye in going from vacuum to polar

solvents while for the croconate the opposite shift should take place. Probably, the solvation plays a

decisive role in the inversion of the experimental absorption maxima of the synthesized compounds in comparison with the calculated ones.


98

PHOTO-PHYSICAL PROPERTIES OF A FLUORESCENT CYANINE-DYE

IN BINARY MIXTURES OF IONIC LIQUIDS

WITH DIMETHYL SULFOXIDE

D.A. Ivanov1, N.Kh. Petrov

1, O. Klimchuk

2, I. Billard

2


2 – Institut Pluridisciplinaire Hubert Curien, CNRS/IN2P3 and University of Strasbourg, France

[email protected]

The photophysics of 3,3'-diethylthiacarbocyanine iodide (DTCI), as a fluorescence probe, in liquid

mixtures of dimethyl sulfoxide (DMSO) with either trimethyl(butyl)ammonium

bis((trifluoromethyl)sulfonyl)imide ([N(4)111] [Tf2N]) or 1-butyl-3-methylimidazolium

bis((trifluoromethyl)sulfonyl)imide ([bmim] [Tf2N]) was studied by means of steady-state and

time-resolved fluorescence spectroscopy. Steady-state properties as functions of the mixture

composition, i.e. DTCI absorption and fluorescence spectra, and fluorescence depolarization, were

found to be fairly similar to both mixtures. On the contrary, the DTCI fluorescence decay was

observed to be double-exponential in mixtures with ([N(4)111] [Tf2N]) for DMSO volume

fractions less than ca. 0.5 while that is single exponential in mixtures with [bmim] [Tf2N] under

the same conditions.

These findings are explained in terms of the Hildebrand solubility model by assuming the existence

of coursed-grained spatial micro-heterogeneities, clusters of DMSO molecules, in ammonium-based

ionic liquid/DMSO mixtures. The condition for the observation such micro-segregation is

V1(δ1 – δ1)2 ≈ RT, where 1V is the molar volume of DMSO, R is the universal gas constant,

T is the absolute temperature, δ1 and δ2 are solubility parameters for DMSO and IL respectively.


99

AQUEOUS SOLUTIONS OF STYRYL DYE IN THE PRESENCE OF

CUCURBIT[8]URIL: PHOTO-PHYSICAL QUANTITATIVE PROPERTIES

D.A. Ivanov, N.Kh. Petrov, A.I. Vedernikov, S.P. Gromov

Photochemistry center RAS, Moscow, Russia

[email protected]

Pumpkin-shaped macrocycle of cucurbit[8]uril (CB[8]) has a rigid cavity (the internal diameter is

8.8 Å, the portal diameter, 6.5 Å, the height, 9.1 Å) that allows producing 1:1 and 2:1 complexes

with styryl dye as the guest-molecule [1]. The purpose of this work was to study photo-physical

properties of aqueous solution of styryl dye (12 μM) in the presence of CB[8] by means of

fluorescence spectroscopy.

Figure 1. Fluorescence titration of styryl dye by cucurbit[8]uril.

The complexation of dye by CB[8] results in the variation of the dye-fluorescence intensity. There

is a decrease in fluorescence upon increasing the CB[8] concentration in the range from 0 to 50 µM

(Fig.1). A further increase in CB[8] concentration leads to a significant fluorescence enhancement.

One can rationalize it assuming that 2:1 complexes largely exist for low CB[8] concentration and

1:1 complexes, for high CB[8] concentration. This model is in agreement with results on

fluorescence anisotropy and lifetime measurements. It was found that association constant for

complexes 2:1 is 4E8 M-2

and for complexes 1:1 is 2.5E-3 M-2

. Illumination of the complexes 2:1

leads to the dimerization of dye with quantum yield of ca 5%.

Support from the Russian Foundation for Basic Research and the Russian Academy of Sciences is

gratefully acknowledged.

References: [1] S. P. Gromov, et al., Eur. J. Org. Chem., 13 (2010) 2587–2599.


100

PECULIARITIES OF PROVITAMIN D PHOTOCHEMISTRY

IN LIQUID-CRYSTALLINE MATRICES

P.S. Kapinos, T.N. Orlova, I.P. Terenetskaya


[email protected]

Cis-trans isomerization is a ubiquitous photochemical process which forms the fundamental step in

many important biological processes, such as vitamin D synthesis, vision, phototaxis, etc. The

influence of ordered anisotropic liquid-crystalline (LC) microenvironment on the

photoisomerization reactions of biologically active molecules is in the spotlight of molecular

photochemistry over last decade.

It is known that previtamin D plays a central role in the complex network of vitamin D3 synthesis. It

is formed from initial provitamin D3 (7-DHC, 7-dehydrocholesretol) by the UV induced hexadiene

ring opening, and its subsequent cis-trans isomerization into tachysterol is the most efficient side

photoconversion [1]. The accumulation of trans-isomer is accompanied by significant increase of the maximum absorbance over UV exposure.

Kinetics of 7-DHC photoisomerization in mesophase and isotropic phase of LCs was studied using

UV absorption spectroscopy. At room temperature it was found that the efficiency of cis-trans

isomerization increased significantly with raising of the 7-DHC concentration from 0.04 wt.-% to 3 wt.-% in both nematic LCs MLC-6815 [2, 3] and ZhK-805 (Fig.1a, 1b).

With the temperature rising up to the isotropic phase transition the remarkable reduction of the cis-

trans isomerization efficiency was established (Fig.1c) [2, 3]. Finally, in isotropic LC phase the

increase of maximum absorbance was significantly lower than in ethanol (Fig.1c).

240 260 280 300 320 3400,0

0,1

0,2

0,3

0,4

0,5

0,6

Ab

so

rba

nce

, nm

0 min

30'

1 min

1 min 30'

2 min

5 min

a)

240 260 280 300 320 3400,0

0,4

0,8

1,2

1,6

Ab

so

rba

nce

, nm

0 min

30'

1 min

2 min

3 min

9 min

b)

0 2 4 6 8 10 12

1,0

1,2

1,4

1,6

1,8

2,0

2,2

2,4

2,6

RA

(2

82

nm

)

UV irradiation time, min

1

2

3

4

5

c)

Figure 1a,b). Transformation of initial 7-DHC absorption spectrum under UV irradiation (254 nm) at room

temperature up to the quasi-photostationary state: a) C7-DHC = 0.5 wt.-%, b) C7-DHC = 1.6 wt.-%.

Figure 1c). Dependences of maximum relative absorbance (RA) on the UV exposure in mesophase (curves 1, 2) and isotropic LC phase (curves 3, 4) at C7-DHC = 1.6 wt.-% (curves 1, 3) and C7-DHC = 0.5 wt.-% (curves 2, 4) in comparison with ethanol (curve 5).

Altogether, the results obtained indicate the collective character of previtamin D cis-trans

isomerization in liquid-crystalline matrices due to the medium ordering.

References:

[1] Jacobs H.J.C., Havinga E., Adv. Photochem. 11, 305 (1979).

[2] Orlova T., Terenetskaya I., Opt.Spectr. 108, 608 (2010).

[3] Terenetskaya I.P., Orlova T.N., Mol.Cryst.Liq.Cryst. 541 96 [334] – 103 [341] (2011).


101

QUANTUM-CHEMICAL INVESTIGATION

OF SPECTRAL-LUMINESCENT PROPERTIES

OF SOME POLYMETHINE BIS-CHROMOPHORES AND

BISMEROCYANINES LINKED BY BUTADIENE SKELETON

E.R. Kashapova, V.Ya. Artyukhov, G.V. Mayer

National Research Tomsk State University, Russia

[email protected]

Investigation of photophysical processes and photochemical reactions of polymethine dyes (PD) is

of importance due to their wide use in the photographic process and laser technology . A study of

the photoprocesses in PD dimers is motivated in many respects. Dimers may be considered as the

simplest associates in the course of the formation of higher aggregates, which are formed when the

dye concentration is increased; dimerization is usually considered as the first step of aggregation.

The study of aggregates may meet some difficulties when interpreting the results due to different

aggregation numbers and because in solution the equilibrium exists between aggregates of different

compositions including those with monomers. Bis-chromophores which are monomeric forms in

reasonably diluted solutions are free from these disadvantages [1].

In the present work, we report results of a comparative investigation of photoprocesses in monomer

molecules of indocarbocyanine properties in monomer of indocarbocyanine, its bis-derivatives in

which two chromophores are connected by one (angular dimers) and two (cyclic dimers) chains

consisting of various number of methylene groups and bismerocyanines linked by butadiene

skeleton.

Calculations were carried out with use of semiempirical method of intermediate neglect of

differential overlap (INDO) with spectroscopic parameterization [2], TDDFT method and CIS

method [3, 4]. All calculations were carried out with use of the geometry received from X-ray data

for a related class of compounds. Rate constants of photophysical processes, the quantum yield of

fluorescence from the first singlet state were estimated by INDO method.

Bis-dyes manifest the characteristic changes for dimers in absorption and fluorescence spectra due

to splitting of the Sl-level (Davydov splitting) into levels with higher (S1’-level) and lower (Sl

’’-

level) energies. This leads to a difference in photophysical properties between dye monomers and

dimers. The more rigid structure of dimers, as compared to monomers, brings about steric

hindrances of trans↔cis-photoisomerization of bismerocyanines and, consequently, cause an

increase in quantum yield of fluorescence.

It is established that the reason of a low quantum yield in cyclic polymethine bis-chromophores is a

reduction of a rate constant of radiation decay by two order and an increase of a rate constant of

internal conversion, the rate constant of intersystem crossing increases in comparison with that for a

monomer, but still can't compete to a rate constant of internal conversion. It is shown that the

increase in number of the methylene groups connecting two chromophores, leads to increase in the

energy gap between S1 and S2 states that is connected with reduction of resonant interaction

between two chromophores.

Work is executed with support of the grant of the President of the Russian Federation (SS-

512.2012.2.).

1. Chibisov A.K., Zakharova G.V., Gerner H. et all // J. Phys. Chem. 1995. Т.99. С.886.

2. Mayer G.V, Artyuhov V.Ya, Bazyl’ O.K. et all. Electron-excited states and photochemistry of organic compounds. Novosibirsk: Science: 1997. 232 p.

3. Alex A. Granovsky, Firefly version 7.1.G, http://classic.chem.msu.su/gran/firefly/index.html 4. GAMESS: Schmidt, M.W.; Baldridge, K. K.; Boatz, J.A.; Elbert,T.S.; Gordon, M.S.; Jensen, J.H.; Koseki

S.; Matsunaga,N. et all.1993.14.1347.


102

EFFECT OF INTERMOLECULAR INTERACTIONS

ON SPECTRAL-LUMINESCENT PROPERTIES

OF POLYATOMIC MOLECULES

P.V. Komarov, V.G. Plotnikov


[email protected]

Theoretical analysis of a dependence of spectral-luminescent properties of heteroaromatic

molecules on interactions with solvent and other dissolved molecules was carried out. It was shown

that the order of the singlet and triplet electronic states of the molecule might be altered alone by dipole-dipole (non-specific) interactions [1].

It was shown that the impact of protic solvents on the spectral-luminescent properties of

heteroaromatic molecules cannot be reduced only to the specific interactions (H-bond formation)

between the luminophore molecule and the solvent molecules because its effect is comparable to the

effect of non-specific interactions [2]. So commonly used approach based on taking into account

only specific interactions, reasonable only in the case of 1:1 complexes in a non-polar solvent or in

a gas phase. Moreover, specific interaction leads to a substantial increase in the non-specific

interaction magnitude (probably, it is due to an increase in polarizability of a complex in contrast

with the lone molecule). This is an instance of a more general phenomenon of synergy between the

non-specific and specific (H-bond, exciplex, charge-transfer complexes) intermolecular

interactions. The spectral-luminescent properties of heteroaromatic molecules are changed in a

natural manner under the influence of the intermolecular interactions [2,3]. The examples of the

usage of changes in the spectral-luminescent properties of the molecules under the influence of

intermolecular interactions for the goals of molecular optical sensing (MOS) are suggested [4]. It is

stressed that the results obtained imply for MOS design the need to reckon in all types of

intermolecular interactions.

[1] P.V. Komarov, V.G. Plotnikov, V.Y. Artyukhov, G.V. Mayer, Dokl. Phys. Chem. 431 (2010) 63

[2] P.V. Komarov, V.G. Plotnikov, Journal of Luminescence 132 (2012) 1139–1143

[3] P.V. Komarov, V.G. Plotnikov Int.J. Quant. Chem. (In press)

[4] V.G. Plotnikov; V.A. Sazhnikov, M.V. Alfimov, High Energy Chemistry, 41 (2007), 299-311.


103

SIMULATION OF THE RADIATION LIFETIME OF PHOSPHORESCENT

EMITTERS BASED ON CYCLOMETALLATED IRIDIUM COMPLEXES

K.G. Komarova, A.A. Bagatur’yants, M.V. Alfimov

Photochemistry Center of RAS, Moscow, Russia

[email protected]

The effect of different substituents in the ligand on radiative rate constants for a series of

phosphorescent cyclometallated iridium(III) complexes (Scheme 1) is studied. It was found

previously [1] that the phosphorescence quantum yield for the bis-terdentate complex

Ir(dpyx)(dppy)* (I) is very low even at low temperatures. A change of the diphenylpyridine ligand

in I for its tetrafluoro-substituted analog (II) or passing to the Ir(dpyx)(ppy)Cl (III) complex results

in a significant increase in the quantum yield.

Scheme 1

N

Ir

3 I Ir(dpyx)(dppy) * II Ir(dpyx)(F4dppy) III Ir(dpyx)(ppy)Cl Ir(ppy)3

Our calculations reveal that the molecular orbitals involved in the T1-S0 transition in the bis-

terdentate complexes are π orbitals delocalized on the dpyx ligand and the dxz orbital of the iridium

atom (figure 1). Strong electron-acceptor substituents (F, Cl) in the ligand cause a decrease in the

HOMO π character, which leads to an increase in the spin-orbit coupling effect on the radiative rate

constant of the transition.

HOMO LUMO

Figure 1. Molecular orbitals involved in T1-S0 transition in complex I.

The spin-orbit coupling effects are taken into account through the HSO1-Zeff approximation based

on the multi-configurational wave-function approach. The radiative rate constants are evaluated

using the first order perturbation theory expansion for the T1 and S0 wave function.

_______________ * – dpyx = 1,3-di(2-pyridyl)-4,6-dimethylbenzene; dppy = 2,6-diphenylpyridine; ppy = phenylpiridine

[1] A.J. Wilkinson, H. Puschmann, J.A.K. Howard, C.E. Foster, J.A.G. Williams./ Inorg. Chem.,

2006. Vol. 45, № 21, P.8685.


104

DETERMINE AND COMPARATIVE ANALYSIS OF PARAMETERS

OF INTRAMOLECULAR INTERACTION FROM SPECTRA

OF ALL-TRANS-DIPHENYLBUTADIENES IN RIGID MATRICES

V.V. Kompaneez, I.A. Vasilyeva

Moscow Pedagogical State University, Moscow, Russia

[email protected]

The fluorescence and fluorescence excitation spectra of all-trans diphenylbutadiene (DPB) and two

its push-pull substituted compounds were measured in n-paraffins at 4.2 K. The chemical structure

of these substances:

(DPB) N

H

H

(DPBI) N

CH3

CH3

(DPB2)

The spectra have a pronounced violation of bilateral symmetry between the conjugated spectra. In

these spectra vibronic peaks are stayed on the intensive background and the task of evaluation of

FC- and HT- parameters are very difficult. To determine the true relative intensities of the vibronic

transitions of DPB and two substituted derivatives, we modeled conjugate fluorescence and

fluorescence excitation spectra of studied connections by a series of vibronic bands, each of which

is the sum of a zero-phonon line and a phonon wing [1]. By choosing the necessary parameters (a

width of the zero-phonon line, a width of the phonon wings and a Debye–Waller factor) a nearly

complete coincidence between the experimental and model spectra was achieved. The large width

and considerable intensity of the phonon wings indicate that the electron–phonon interaction

between impurity molecules and the environment is more strong in the case of push-pull substituted

compounds. In addition, the calculated spectrum takes into account the deviations of the band

maxima from their true positions upon intensity summation of closely spaced lines; consequently, the band positions are refined.

Based on the calculated spectra, the relative intensities of the vibronic transitions were determined.

The parameters of the Franck--Condon (a) and Herzberg–Teller (α) interactions in the molecules

considered are calculated [2]. For all the basic normal vibrations, the parameter a greatly exceeds

α. The comparative analysis of the received parameters for the main normal vibronic transitions from connection structure is carried out.

1. N.L. Naumova, I.A. Vasil'eva, I.S. Osad'ko, and A.V. Naumov // Opt. Spektrosk. v.98 (4), p.586

(2005) [Opt. Spectrosc. v.98 (4), p.535 (2005)].

2. I.S. Osad'ko, Usp. Fiz. Nauk // V. 128 (1), p. 31 (1979) [Sov. Phys. Usp. v.22, p. 311 (1979)].


105

THEORETICAL AND EXPERIMENTAL STUDY OF PHOTOPHYSICAL

PROPERTIES OF SOME DERIVATIVES OF

DIBENZOYLMETHANATOBORON DIFLUORIDE

V.N. Kopysov, V.A. Sazhnikov, M.V. Alfimov


[email protected]

It is well known that dibenzoylmethanatoboron difluoride (DBMBF2) is able to form exciplexes with methylsubstituted benzenes [1]. Recently, it has also been shown that silica nanoparticles with DBMBF2 covalently grafted on their surface can be used as the basis of selective sensor materials capable of detecting benzene, toluene and xylene vapors [2]. One way to develop highly sensitive and selective sensor is to use various fluorophores as the indicator molecules. In this respect one can single out a number of important properties of such molecules. First and foremost it is a fluorescence wavelength (λfl) and an electron affinity (EA), because they influence both the efficiency of exciplex formation and its photophysical properties.

Fluorescence lifetime (τfl) should be not too small so that an analyte molecule has time to interact with an excited fluorophore. Finally, since the absorption maximum (λabs) of DBMBF2 lies at about 365 nm it is desirable from practical point of view to use indicators with absorption spectrum shifted to longer wavelengths.

In recent years quantum chemical methods have become a powerful tool widely used in chemical design.

The aim of this study was to experimentally investigate photophysical properties of some derivatives of DBMBF2 in solution and to demonstrate that computational techniques can be successfully exploited to predict them.

By means of steady-state and time-resolved spectroscopy, absorption and fluorescence spectra, quantum

yields and fluorescence lifetimes of several mono- and disubstituted DBMBF2 in cyclohexane and acetonitrile solutions have been obtained. With respect to DBMBF2 one can see certain spectral shifts of absorption and fluorescence spectra (as well as changes in their shape) of its derivatives, however the substitution has a great impact on quantum yields and fluorescence lifetimes. Since the radiative rate constants only slightly vary for these compounds, this fact indicates that even minor shifts of singlet and triplet levels result in considerable changes in non-radiative decay rates.

The equilibrium geometries of the ground and the first excited singlet states have been optimized using B3LYP functional and 6-31G(d,p) basis set. Calculated absorption maxima and fluorescence wavelengths are in a good agreement with experimental data (calculated values are blue-shifted by about 2000 cm-1). Using 6-311(d,p) basis of triple-zeta quality does not appreciably improve these results. In principle, one can use linear regression model to account for this discrepancy. Radiative rate constants k r and spin-orbit couplings Hso have been calculated at CAS(12,12)/6-31G(d,p) level of theory. Experimental and calculated kr values are of the same order of magnitude. As concerns the intersystem crossing rate, the situation is much

more complicated because of the small energy gaps between S1 and low-lying triplet states. In this case kISC is determined by the Franck-Condon factor which could not be precisely evaluated. However, a comparison with experimental data reveals that at least in polar solvents experimental values are approximately by an order of magnitude greater that the estimated kISC (S1→T2) values. Electron affinities are known experimentally only for several 1,3-diketonatoboron difluorides [3]. EAs calculated at B3LYP/6-31G+(d,p)//B3LYP/6-31G(d,p) level of theory linearly correlate with experimental values. For the large molecules using 6-31G+(d,p) basis becomes very time-consuming and it is also known that the importance

of diffuse functions decreases with the size of the molecule. So, for all the fluorophores under study 6-31G(d,p) basis has been used.

Thereby, ab initio calculations adequately describe photophysical properties of DBMBF2 and its derivatives as well as their electron affinities. Absolute values of such estimations, of course, cannot be used directly because of the errors inherent to these techniques. However, one can use the relations deduced in this work

to quantitatively predict the properties of a given derivative of DBMBF2 and therefore to efficiently pick out the most prospective fluorophores.

1. Y.L. Chow, X. Cheng, C.I. Johansson. Journal of Photochemistry and Photobiology A: Chemistry, 1991, 57, 247-255.

2. V.A. Sazhnikov et al. Nanotechnologies in Russia, 2012, 7, 6-14.

3. Y.L. Chow et al. Journal of Physical Organic Chemistry, 1996, 9, 7-16.


106

SPECTRAL-LUMINESCENT PROPERTIES OF LIGANDS IN STRUCTURE

OF TRIS(8-HYDROXYQUINOLINE)ALUMINUM(III)

K.Yu Krivonogova, V.Ya. Artyukhov

National Research Tomsk State University

[email protected]

Tris(8-hydroxyquinoline)aluminum(III) due to its properties such us high quantum yield (even in

the solid state), high electron–hole recombination efficiency, and etc. is used as a component for

optoelectronic devices (for example, photodetectors, organic electroluminescent (light-emitting) diodes (OLEDs)) flat and flexible displays and etc.) [1].

In resent papers the electronic spectrum of AlQ3 has been investigated by experimental and

theoretical studies [2,3] with a view to understand the uniqueness of the electronic and photonic

properties of AlQ3 with the relation to other molecules of this type and to predict structural modifications that will improve the favourable properties further.

This paper contains theoretical investigations of electronic spectra of ligands (8- hydroxyquinoline)

in different ionic states: the neutral form, protonated (cation) form, deprotonated (anion) form, and zwitter ion form.

The role of the spectral characteristics of the ligands (8- hydroxyquinoline) in the formation of

absorption and emission spectra of molecules AlQ3 was shown. Experimental data for comparison

with the results of the calculation were taken from [4].

Calculations of the geometry of the compounds and the spectra were estimated in a software

package based on the semiempirical method of intermediate neglect of differential overlap (INDO)

[5] with the original spectroscopic parametrization and the software package based on density

functional theory – Amsterdam Density Functional (ADF). Was also used semiempirical method

ZINDO/S.

The work was supported by the Grant of the President of the Russian Federation (NSh-512.2012.2).

[1] Tang, C. W.; Van Slyke, S. A. // Appl. Phys. Lett. 1987. V. 51. P. 913.

[2] A. Curioni, M. Boero, W. Andreono, Chem. Phys. Lett. 294 (1998) 263.

[3] I.G. Hill, A. Kahn, J. Cornil, D.A. dos Santos, J.L. Bredas, Chem. Phys. Lett. 317 (2000) 444.

[4] V.V.N. Ravi Kishore et al. // Synthetic Metals 2002. V. 126. P. 199-205.

[5] Mayer G.V., Artyukhov V.Ya., Bazyl O.K. et al, "Electron-excited states and photochemistry of

organic compounds", Nauka, Novosibirsk in 1997. C. 232.


107

PHOTOSTABILITY STYRYLCYANINE DYE SBT

AND ITS HOMODIMER IN SOLUTIONS

E.N. Kurtaliev, N. Nizomov

Samarkand State University, Uzbekistan

[email protected]

Depending on the sphere of application of fluorophores [1,2], their following properties are

important: the quantum yield, photostability, pH dependence, fluorescence lifetime and etc. In

medicine and biology in recent years as the fluorescent probes and labels increasingly are widely

used styrylcyanine dyes [3,4]. During use of the dye solutions, photostability is significant

parameter in determining their working life alongside with the spectral-luminescent characteristics.

Therefore, studying the spectral-luminescent characteristics and mechanisms of photochemical

destruction organic dyes is of great scientific and practical importance. The aim of this work is to

study the photostability solutions of the styrylcyanine dye Sbt and homodimers1 - dyes with two

chromophores (Dbt-5, Dbt-10, D-179, D-180, D-182, D-183, S-37 and S-39) in solvents of different nature.

It is established, that in the process of the light irradiation of solutions of binary mixtures:

water+DMF and water+dioxane, there is a decrease in the intensity of the main absorption and

emission of fluorescence. In this case, significant changes in the shape of the spectra do not occur, i.

e the process of bleaching of the dye solution takes place. Intensity of the longwave absorption band

decreases in absorption spectra of aqueous solutions and binary mixtures of water+ethanol as the

irradiation takes place, and a new band with λmax=354 nm is observed by the shorter wavelengths;

its intensity increases with increasing exposure time of solutions. The shape of the fluorescence

spectra remains constant, a decrease of light intensity and a hypsochromic shift is about 7 -12 nm.

The exposure time required for the bleaching solution depends on the structure of the dye molecules

and the nature of the solvent. This means that the decay occurs in the photolysis of the dye

molecule. Nature of the photobleaching of the studied solutions, apparently, can be explained by the

fact that the photodegradation of solvent molecules [5]. Further, the formed radicals interact with

the active part of the dye molecules, while the conjugation chain of the dye molecules is disturbed,

which leads to destruction of the dye and the bleaching of solution.

This work was supported by grant U3104 (STCU, Ukraine).

References

1. V.A. Svetlichnyi, O.K. Bazyl, E.R. Kashapova, N.A. Derevyanko, A.A. Ishchenko. Quantum

Electron. 39 (8) (2009) 739–744.

2. P. Imon, M. Landl, M. Breza, F. Kvasnik. Sens. Actuators, B 90 (1–3) (2003) 9-14.

3. E.N. Kurtaliev, N. Nizomov, Sh.N. Nizamov, G. Khodjayev, J. Mol. Struct. 936 (2009) 199-205.

4. Matiukas, B.G. Mitrea, M. Qin, et all. Heart Rhythm 4 (11) (2007) 1441-1451.

5. J.G. Calvert, J.N. Pitts. Photochemistry. Wiley & Sons, New York, 1966.

1 We kindly acknowledge Prof. S.M. Yarmoluk of the Institute of Molecular Biology and Genetics, NAS Ukraine for

the dye samples.


108

OPTICAL PROPERTIES OF NANODIAMOND

OF DETONATION SYNTHESIS

V.A. Lapina, B.A. Bushuk, S.B. Bushuk

Institute of Physics NAS, Minsk, Belarus

[email protected]

Luminescenting nanomaterials draw much attention in connection with their potential application as

optical markers in the biology and medicine. In recent years a great number of works is devoted to

nanodiamonds of various origins. Diamond nanoparticles possess a number of unique properties:

nanosizing, chemical and radiating stability, inertness, bio-compatibility, non-toxicity. These

properties define their huge potential for the purposes of biomedical optics.

The objects of our investigations are nanodiamonds of detonation synthesis. This kind of diamonds

has the developed chemistry of the surface, which is capable to various functionalization. This fact

allows one to modify these particles with various bio-ligands. Besides, at present it is known, that

these particles can enter the cells. For their visualization the study of their own spectral-luminescent properties is extremely important.

The purpose of our work is the investigation of the fluorescence of nanodiamonds of various

modifications. Spectral-luminescent characteristics of nanodiamonds have been investigated with

the method of stationary optical spectroscopy and the method of confocal laser scanning

microscopy Either the fluorescence spectra or fluorescence excitation spectra and optical images of

nanoparticles ensembles of various sizes have been measured. Position and the form of fluorescence

spectra and excitation fluorescence had insignificant differences for all samples. However, it is

possible to mark out some general features, which nanodiamonds possess. It has been established,

that the short-wave emission band in the region of 460–560 nm is the superposition of two wide

bands with their maxima at 484 and 530 nm. The long-wave part of the emission spectrum

represents a wide band with its maximum at 640 nm. It has been shown, that fluorescence excitation

spectra allow one to choose an optimal range of wavelengths of nanodiamonds excitation for the

obtaining of maximal fluorescence intensity. Excitation spectrum of the short-wave luminescence in

the area of 460–480 nm is localized in the near UV-region with its maximum at 360 nm. In the

same spectral range the excitation spectrum of the red luminescence (640 nm) is also localized. It

allows one to assume, that this luminescence is caused by non-radiating energy transfer from the

blue luminescence centers to the red ones. The excitation spectrum of green-orange luminescence is

localized in the region of 460 nm. It is possible to assume, that the observed luminescence of

nanodiamonds is connected with the surface defects, caused by the presence of sp2 hybrids of

carbon, creating the branched out p-electronic system which is modified by the presence of the

admixtures arising in the process of synthesis. The observed luminescence for the all samples

possesses high stability, but insignificant intensity. For intensity amplification the powders of

nanodiamonds have been irradiated with the stream of electrons with the energy of about 5 Меv and

the subsequent annealing at the temperature of 800 °C. After this, the luminescence intensity has

considerably been increased, about 10 times without the change of spectral-luminescent characteristics.

Thus, nanodiamonds of detonation synthesis are the perspective optically active material and can

find wide applications in biophotonics.


109

PHOTOSENSITIVE SYSTEMS BASED ON STYRYL DYES

IN SOLID STATE AND IN SOLUTION:

DIMERIZATION AND AUTOPHOTOCYCLOADDITION

N.A. Lobova1, A.I. Vedernikov

1, L.G. Kuz’mina

2, M.V. Alfimov

1, S.P. Gromov

1

1 – Photochemistry Centre of the RAS, Moscow, Russia

2 – N.S. Kurnakov Institute of General and Inorganic Chemistry RAS, Moscow, Russia

[email protected]

Synthesis of novel styryl dyes 1 containing terminal NH3+

group was elaborated. Dyes 1

spontaneously form stable dimeric complexes 2 in both solid state and MeCN solution due to

complexation of crown-ether moiety with NH3+ group. The dimers have a head-to-tail stacking

structure. Stability constants of dimers 2 were estimated by 1H NMR titration in MeCN-d3 (lgKd up

to 8.0).

N N

S

N,,Het =

HetRAr

ClO4

_

OO

O

OO

O

m

N

OO

O O

O

+

1

m = 0, 1

Ar = ,

= (CH2)nNH3

+= heterocyclic moiety

h

1 2 3

(spontaneously)

MeCN

2

= crown-ether fragment

Irradiation of dimers 2 by visible light in solution, thin polycrystalline film or monocrystal leads to

efficient stereospecific reaction of [2+2]-photocycloaddition giving single rctt-isomer of

cyclobutane derivative 3. The possibility and the efficiency of cycloaddition depend on nature of

heterocyclic moiety, length of ammonioalkyl substituent, size and type of crown-ether fragment.

Structures of 1-3 were studied using X-ray diffraction and NMR spectroscopy. Dyes 1 can be

utilized in systems of registration and storage of information.

This work was financially supported by the Russian Foundation for Basic Research, the Russian

Academy of Sciences and the Royal Society of Chemistry.


110

LINKAGE ISOMERISM IN LAYERED SILICATES

A.V. Maevsky, A.A. Tsyganenko, M.V. Baskakova

V.A. Fock Institute of Physics of St.Petersburg State University, Russia

[email protected]

Linkage isomerism of adsorbed molecules, recently established for CO bound to cationic sites or

hydroxyl groups of ZSM5 and Y zeolites [1, 2], is of a great interest for catalysis and nanophotonics.

The purpose of this work was a search of isomerism for the layered analogs of zeolites - clay minerals of montmorillonite group, where this phenomenon could be

anticipated according to the electrostatic model [3]. For that,

variable- temperature FTIR spectra of CO adsorbed on mica

(muscovite), commercial blue clay, natural bentonite, and synthetic Ca-montmorillonite were studied.

The cell construction has been described elsewhere [4]. In the

spectrum of CO adsorbed on mica two bands were visible at

2156 and 2142 cm-1, whose temperature depen-dence сould not be followed because of too low intensity.

Spectrum of CO adsorbed on blue clay exhibits a band at

2161 cm-1, which moves to 2165.5 cm-1 with the de-crease of

coverage, and a band at 2125 cm-1. The intensity of the latter first grows on raising the temperature and then diminishes, so

that the intensity ratio of it (LF band) to that of the high-

frequency (HF) band at 2165 cm-1 constantly increases. The

slope of the intensity ratio dependence on the reciprocal temperature (the van’t Hoff plot) leads to the estimated

isomerisation enthalpy of 3.8 ± 0.8 kJ mol-1. CO adsorption on bentonite is illustrated in Fig.1. In the equilibrium with gas at 77 K, besides the HF

band at 2164 cm-1 of molecules bonded to cations via C atom, a strong band at 2142 cm-1 can be seen

(Fig. 1a). With the increasing temperature the latter band, assigned to physisorption, is the first to

disappear. On heating the sample, the maximum of the HF band shifts to 2176 cm-1 and the LF band appears at 2121 cm-1. If the spectral curves are normalized to the same intensity of the HF band (Fig.

1b), one can see the monotonous increase in the relative intensity of this band with temperature. The

estimated isomerisation enthalpy in this case is 5.6 ± 0.4 kJ mol-1. Thus, both for the blue clay and bentonite samples spectra of CO at variable temperatures provide

evidence for the linkage isomerism of molecules coordinately bound to the cations. Higher position of

the HF band and greater isomerisation enthalpy value for bentonite as compared with those of blue clay are naturally due to different cationic composition of the samples, mostly Ca for the former and K for

the latter. Experiments with Ca-montmorillonite and Zn-exchanged bentonite confirm the sensitivity of

band position to the cations. This first observation of linkage isomerism for the layered silicate systems

enable us to measure the isomerisation enthalpy, but not the height of potential barrier between the two states. To estimate the latter, quantum-chemical calculations of model clusters have been carried out.

The results provide information on the temperatures, when the transitions between the isomeric states

can be frozen or when the equilibrium can be set in.

Acknowledgments. The work was supported by the Ministry of Education and Science of the Russian Federation, grant 11.38.38.2011.

References

1. C. Otero Areán, G. Turnes Palomino, A.A. Tsyganenko and E. Garrone, Intern. J. Mol. Sci., 3 (2002) 764. 2. A.A. Tsyganenko, P.Yu. Storozhev, C. Otero Areán, Kinet. Catalysis 45 (2004) 530.

3. P.Yu. Storozhev et al, Appl. Surface Sci., 238 (2004) 390. 4. С. Otero Areán et al, Eur. J. Inorg. Chem., 2001, No 7, 1739.

Figure 1: FTIR spctrum of CO adsorbed on bentonite at 77–193 K (a), and the same spectra normalized to common

intensity of the HF band (b).


111

IN SITU RAMAN PROBE OF MOLECULAR ORDER

IN ORGANIC PHOTOVOLTAIC CELL

A.A. Mannanov, V.V. Bruevich, D.Yu. Paraschuk

Faculty of Physics & International Laser Center, M.V. Lomonosov State University, Moscow, Russia

[email protected]

Organic photovoltaic cells (OPC) show high potential to convert solar energy into electricity in a

cost-effective way. To date, the best polymer OPC achieved the efficiency of solar energy

conversion of 10%, and significant efforts are underway to increase their efficiency to the level of

practical applications. One of the key parameters determining the OPC efficiency is the morphology

of the active layer on the molecular scale. Specifically, the order of molecules in semiconducting polymeric materials has significant effects on their optoelectronic properties.

Raman spectroscopy allows the control of conjugated polymer P3HT (poly(3-hexylthiophene))

molecular order in blends with PCBM ([6,6]-phenyl-C61-butyric acid methyl ester) [1]. In a spin

cast film P3HT has a high content of the amorphous phase due to the PCBM intercalation. Post

deposition treatment of these blends, e.g., thermal annealing, is frequently used to achieve ordering

of P3HT chains and, therefore, to optimize the bulk heterojunction morphology. The partially

crystalline polymer phase is characterized by both better absorption at longer wavelength and charge carrier mobility resulting in a significant increase in the power conversion efficiency.

In this work, we have developed a technique for in situ probing the degree of molecular order in

OPCs by Raman spectroscopy during annealing. Raman spectra are measured during film annealing

directly inside a temperature controlled stage and then fitted by a superposition of two components -

amorphous and quasi crystalline phases. From those data the fraction of quasi crystalline polymer phase is evaluated giving a dynamics of molecular ordering upon annealing.

Various fullerene derivatives (methanofullerenes, metal complexes of fullerenes, fluorine fullerene

derivatives) are studied as an acceptor component for OPC. We show that several fullerene types

act similarly to PCBM in decreasing the molecular order of polymer by intercalating in its phase.

Annealing is turned out to be efficient to achieve the partially crystalline polymer domains. The

developed technique is used to determine the optimum annealing parameters by in situ monitoring evolution of the Raman spectra.

As many new polymer and low-molecular-weight organic materials for solar cells are being developed, the applicability of the proposed technique for their optimization is discussed.

[1] Wing C. Tsoi et al., J. Am. Chem. Soc. 2011, 133, 9834 –9843


112

THERMODYNAMIC STABILITY AND SPECTRAL PROPERTIES OF THE

SUPRAMOLECULAR COMPLEXES OF BIS(18-CROWN-6)AZOBENZENE

WITH AMMONIOALKYL DERIVATIVES

OF HETEROCYCLIC COMPOUNDS

T.P. Martyanov1, E.N. Ushakov

1, A.A. Efremova

2, S.P. Gromov

2

1 - Institute of Problems of Chemical Physics, Chernogolovka, Russia

2 - Photochemistry Center RAS, Moscow, Russia

[email protected]

In supramolecular chemistry, much attention is paid to organic compounds that are able to change

essentially their spectral and photochemical properties upon complex formation with metal ions or

organic cations. Previously, the supramolecular charge-transfer (CT) complexes between bis(18-

crown-6)stilbene and ammonioalkyl derivatives of heterocyclic compounds (dipyridylethylene,

viologen, diazapyrene, etc.) have been synthesized in Photochemistry Center of RAS [1]. It was

found that in acetonitrile solutions the supramolecular CT complexes of 1:1 composition have a

pseudocyclic structure and are characterized by very high thermodynamic stability due to ditopic

macrocycle–ammonium cation interaction.

A spectrophotometric study of similar supramolecular complexes involving bis(18-crown-

6)azobenzene was carried out.

The stability constants and the absorption spectra of 1:1 complexes were measured. The

thermodynamic stability of supramolecular complexes was found to decrease on changing from the

stilbene fragment to the azobenzene one.

This work was supported by RFBR and the Russian Academy of Sciences.

[1] A.I. Vedernikov, E.N. Ushakov, A.A. Efremova, L.G. Kuz’mina, A.A. Moiseeva, N.A. Lobova,

A.V. Churakov, Yu.A. Strelenko, M.V. Alfimov, J.A.K. Howard and S.P. Gromov. Synthesis,

Structure, and Properties of Supramolecular Charge-Transfer Complexes between Bis(18-crown-

6)stilbene and Ammonioalkyl Derivatives of 4,4’-Bipyridine and 2,7-Diazapyrene. J. Org. Chem.

2011, 76, 6768-6779.


113

QUANTUM-CHEMICAL INTERPRETATION

OF THE SPECTROSCOPY OF HIGHLY LUMINESCENT

1,3,5-TRIAZAPENTADIENE COMPLEXES OF PLATINUM(II)

V.G. Maslov1, G.N. Lyalin

2

1 – National Research University of Information Technologies, Mechanics and Optics, St. Petersburg, Russia

2 - Department of Physics, St.-Petersburg State University, Russia

[email protected]

Highly luminescent square-planar complexes of platinum(II) have attracted a great deal of interest

because of their promising photophysical and photochemical properties, such as a high

luminescence quantum yield and long lifetime of the emissive states, as well as due to their

potential applications in many fields, such as creation of luminescence sensors, organic light-

emitting diodes (OLEDs), light-emitting electrochemical cells (LECs), and photovoltaic cells and

photocatalysis. Furthermore, these complexes are biologically active and are capable of binding and

interacting with DNA and protein substrate. Previously, we described of photophysical behaviors of two representatives of a new class of luminescent 1,3,5-triazapentadiene complexes of Pt(II)—

[Pt{NH=C(Ph)–NC(Ph)=NPh}2] (1) and [Pt{NH=C(Ph)NC(NHPh)=NPh}2] (2)—which possess

the most intense luminescence [1]. Now, we present a quantum-chemical interpretation of the

photophysical properties of these complexes. The equilibrium geometries of the ground and the

lowest triplet states of complexes were calculated by the DFT/B3LYP/LACVP** method using the

program GAMESS [2]. In the calculation of the ground state, the total spin was set at zero. In the

calculation of the triplet state, the spin was set to be S=1 and we used the spin unrestricted Kohn–

Sham (UKS) method. The LACVP** basis set [3] was applied with the use of the pseudopotential

for the Pt atom. Upon consideration of the nature of excited states, the calculations were performed

both by the DFT/B3LYP method and by the ordinary HF method in the SBKJC basis set [4]. The

GAMESS program was used [2]. The excitation energies and oscillator strengths for several

transitions to the lowest singlet excited states were calculated both by the TDDFT and by the

HF/CIS methods. Our calculations of the equilibrium geometry of complexes 1 and 2 showed that

the geometry of complexes 1 in the ground and lowest triplet states differ little from each other. In

case of complexes 2, difference is very significant, and, in the triplet state, the planar structure of

the central part of the complex is distorted. This difference in the behavior can determine the

difference in the phosphorescence quantum yields of complexes 1 and 2, at least due to the

difference between the Franck–Condon factors. The pair of the highest occupied orbitals of the two

complexes is mainly a pair of π orbitals of ligands, but containing a contribution of 15–30% from

the dxz/dyz AOs of the metal atom. The pair of the lowest unoccupied orbitals complexes are

described by an asymmetric (LUMO) and symmetric (LUMO+1)(with respect to the inversion

center) combinations of the lowest unoccupied π orbitals of ligands. The calculation of the energies

of the triplet states of the complexes shows that the energies T1 and T2 are close, due to which the T2

can be thermally populated if the complex is in the T1 state, which can lead to dual

phosphorescence at room temperature. The calculation of the energies and intensities of transitions

to singlet excited states shows that, among the lowest singlet–singlet transitions, only the transitions

that contain considerable contributions from the excitations 0 → 1 and –1 → 1 (the latter transition

can combine with other excitations of the π–π* type) have any noticeable intensity. The same range

of the spectrum can also contain low intensity transitions of the π–π* type and transitions with

charge transfer to phenyl substituents.

1. P.V.Gushin,et al abstr. of Intern. Conf. “Organic Nanophotonics”, p.211 SPb,Rus.,2009; 2.M. W.

Schmidt et al, J. Comput. Chem.14, 1347 (1993).3. P. J. Hay et al, Chem. Phys. 82, 299 (1985).; 4.

T. R. Cundari et al, J. Chem. Phys. 98, 5555 (1993).


114

SPECTRAL AND ELECTROCHEMICAL PROPERTIES OF CRYSTAL

VIOLET IN COMPLEXES WITH ANIONIC CALIXRESORCIN[4]ARENES.

SUPRAMOLECULAR ENHANCERS OF RADIATION

D.A. Mironova, Ju.E. Morozova, V.V. Yanilkin, V.V. Syakaev, E.Kh. Kazakova, A.I. Konovalov

A.E. Arbuzov Institute of Organic and Physical Chemistry of Kazan SC RAS, Kazan, Russia

[email protected]

Triphenylmethane dyes are an important class of synthetic compounds,

and have interesting spectroscopic properties, such as photo- and thermo-

chromism, non-Beer’s law behavior, and ability to form inclusion

complexes with a variety of macromolecules such as n-p-doping additives

in organic semiconductors.

The association effect of the Crystal violet (CV) with the amphiphilic calix[4]resorcinarenes, with differ length of the alkyl substituents at the

lower rim, determining their ability to self-association, on the

spectroscopic and photophysical properties of CV was studied.

It was found an unprecedented stabilizing CV+ , unstable in the

strong basic conditions, in nanoscale containers, formed by the macrocycle C11 and C12.

It was shown that encapsulating the dye by the macrocyclic

nanocontainers, make it fluorescent active.

They play the role of supramolecular radiation

«enhancers» on the association with the third

component - the protein molecule, bovine serum

albumin.

The main structural features of nanoscale aggregates were suggested by the analysis of the

spectrophotometric , DLS, NMR spectroscopy and electrochemical data, are discussed.

Financial support was provided by the grants of the RFBR, № 10-03-00266a, and Program 7 of the

Division of Chemistry and Material Science RAS.


115

APPLICATION OF ISOTOPIC SUBSTITUTION

IN THE IR STUDIES OF LINKAGE ISOMERISM

S.N. Petrov1, A.A. Tsyganenko

1, A.V. Rudakova

1, K.S. Smirnov

2

1 – V.A. Fock Institute of Physics, St.Petersburg State University, Russia

2 – LASIR, University Lille 1, Villeneuve d’Ascq, France

[email protected]

The phenomenon of linkage isomerism of adsorbed molecules, first established for CO bound to

cationic sites of ZSM5 and Y zeolites [1], is of a great interest for catalysis and nanophotonics.

However, the assignment of the bands of isomeric forms was based mostly on the intensity

measurements as a function of temperature, while the results of quantum mechanical calculations

are often controversial. In this work we applied isotopic substitution to obtain the most direct data on the structure of surface complexes with linkage isomerism.

Formation of a new bond between a certain atom of diatomic species and the surface results in the

deviations of the isotopic shift from the value observed for a free molecule of gas. Model

calculations show that these deviations are not the same for isomeric structures bound to the surface

via different atoms. Indeed, for CO adsorbed on Zn–Na–Y, Cs–X and CaY zeolites, as well as for γ-

Al2O3 the high-frequency bands assigned to C-bonded species exhibit the shift caused by 13

C

substitution 1.0–1.8 cm-1

greater, while for C18

O it is 1.1–1.9 cm-1

smaller than it follows from the

reduced mass ratio. For the low-frequency band of O-bonded species, on the contrary, in the

spectrum of CaY zeolite, the positions of maxima for adsorbed 13

C16

O and 12

C18

O are 0.4 below or

1.5 cm-1

above the calculated values, respectively.

HCN interaction with oxides and zeolites could lead to different isomeric species both for molecular

and dissociative adsorption [3]. Then, admitting of the deuterated compound enables us to

distinguish between the bands of molecules and CN- ions, while the choice between the isomeric

structures can be done using the results of 13

C and 15

N substitution. Such data show that HCN

dissociation on γ-Al2O3 and MgO leads first to the formation of M–NC species, which after raising

the sample temperature transform to M–CN, in agreement with the assignment proposed by Yates et

al [4].

References

[1] A.A.Tsyganenko, E. Escalona Platero, C.Otero Arean, E.Garrone, A.Zecchina, Catalysis Letters,

61 (1999), 187.

[2] A.A.Tsyganenko, P.Yu.Storozhev, C.Otero Areán, Kinet. Catal., 45 (2004), 530.

[3] A. A. Tsyganenko, A. M. Chizhik and A. I. Chizhik, PCCP 12 (2010), 6387.

[4] J Sunhee Kim, D.C.Sorescu, J. T. Yates, Jr., J. Phys. Chem. C, 111 (2007), 5416.


116

LOCALIZATION OF WATER SOLUBLE

POLYSUBSTITUTED FULLERENE DERIVATIVES

IN MEMBRANE OF PHOSPHATIDYLCHOLINE LIPOSOMES

D.A. Poletaeva, R.A. Kotelnikova, A.B. Kornev, E.A. Khakina, P.A. Troshin, A.I. Kotelnikov


[email protected]

Fullerenes and their derivatives are of great interest to researchers to be used in medicinal chemistry due to the unique structure of the fullerene spheroid and the donor-acceptor properties. Studying of

biological effects of chemical compounds, mechanisms of their penetration into living cells is one of the

most important subjects. This study is devoted to the membranotropic properties of water soluble

polysubstituted fullerene derivatives (PFD) possessed a high solubility (about 10-2 M) having five or eight ligands with charged (carboxyl or amine) groups.

Interaction of PFD with amphiphilic fluorescent probes: eosin Y, methyl eosin, 2.7-Br-proflavine and

riboflavin, which have a charges (-2), (-1), (1) and (0) respectively at neutral pH was studied in this

work by fluorescence and phosphorescence methods. In addition, we have studied the interaction of PFD with nonpolar probe pyrene in the hydrophobic zone of lipid bilayer of phosphatidylcholine

liposomes by recording the fluorescence spectra of the probe. Rate constants for the phosphorescence

quenching of probes by PFD in aqueous solution and in the area of lipid hydrophilic heads have been

determined. Phosphorescence quenching of eosin Y by one of the studied compounds, which has negative charges on the ligands, rate constants have the values about 107 M-1s-1. Such values are about 3

orders lower than diffusion constant, due to mutual repulsion of chromophore electrostatic charges and

the PFD.

The essential role of electrostatic interactions in the phosphorescence quenching of probes is confirmed by the fact that quenching rate constant for another PFD, which has one electron located directly on a

fullerene spheroid, decreases more than one order, to values <106 M-1s-1, and repulsion effect increases.

At the same time for the derivatives, which have several positive charges on ligands, the process of

phosphorescence quenching of eosin Y is absolutely different. This effect can be explained by the formation of stable complex [chromophore]:[PFD] due to electrostatic interactions. For such derivatives

the quenching rate constant is about 109 M-1s-1 like diffusion one.

It was found that the introduction of fullerene derivatives with a charges, which are opposite to the

charge of chromophore in aqueous chromophore solution leads to an effective decline of the fluorescence amplitude. Moreover, the quenching occurs at concentrations of PFD ~ 10-6 M. So we can

conclude that the quenching occur not due to diffusion interactions, but as a result of the formation of

long-lived complex [chromophore]:[PFD], and through the mutual electrostatic attraction of opposite

charges of the chromophore and PFD.

The value of the equilibrium constant K, which characterizes the strength of the complex, can be found

from the slope of linear anamorphosis in the Stern-Volmer coordinates. For a number of oppositely

charged chromophores and PFD values of K are in the range 105 – 106 M-1. This parameter is suggested

for quantitative assessment of membranotropic of PFD.

The fluorescent probe pyrene was used to study the processes in the hydrophobic area of the membrane.

This probe is located in the area of fatty acid phospholipids residues. Efficient quenching of its

fluorescence was observed during the titration of pyrene by different PFD because of formation of long-

lived complexes [pyrene]:[PFD]. In this case we can also determine the equilibrium constant of the [pyrene]:[PFD]. PFD interaction with pyrene reflects membranotropic of compounds in terms of their

ability to penetrate into the hydrophobic membrane zone or to penetrate the lipid bilayer, parameter K

reflects membranotropic level of PFD.

The investigations are supported by the RFBR grant 10-03-00687 and by the Research program of Presidium of Russian Academy of Sciences No 24 “Fundamental research in the field of nanotechnology and nanomaterials”.


117

INVESTIGATION OF THE EXCITED STATE NATURE

OF BORON DIFLUORIDE ACETYLACETONATES

A.S. Portnyagin, V.V. Korochentsev, N.P. Shapkin, I.V. Svistunova

Far Eastern Federal University, Vladivostok, Russia

[email protected]

By the means of quantum chemistry in the approximation of nonstationary density functional theory

(TD DFT, B3LYP5 functional, def2-TZVPP Ahlrich's basis set), the electronic structure and the

excited state nature of boron difluoride acetylacetonate F2BacacH (fig. 1) and its sulphurcontaining

γ-substituted derivatives were investigated [1].

Fig.1. Molecule of boron difluoride acetylacetonate.

The geometrical optimization of the substituted complexes showed changes in the conformation of

methyl groups as compared with the unsubstituted one and increased value of planar deformation

that consists in boron atom moving out of the ligand plane. Influence of γ -substituents on the order

and energy of MO and distribution of electronic density on atoms were investigated.

By the calculated transition energies and oscillator strength the absorption spectra modeling in

shortwave field was carried out. Modelled spectra are compared to the expetimental one's, obtained

in solution. It is showed that in the absorption spectra of γ-substituted complexes the batochromic

shift of π3-π4 transition is observed and new transitions, caused by the charge transfer from π3 MO

to the antibonding MO's of the substituent, are appeared.

1. Vovna V.I., Tikhonov S.A. and L'vov I.B. Photoelectron spectra and electron structure of boron

difluoride ethyl acetonate, boron difluoride benzoyl acetonate, and its derivatives // J. of phys.

Chem., V.85, №11, 2011, p. 2082-2088.


118

CLUSTERING OF ADSORBED ACRIDINE MOLECULES

ON AMORPHOUS SILICA SURFACES

Y.A. Rozhkova1, A.V. Gurinov

2, A.O. Orlova

3, V.G. Maslov

3, V.I. Korotkov

1


2 – Department of Chemistry, St.-Petersburg State University, Russia


[email protected]

The specific current aim of this work is to inspect the effect of adsorbate-adsorbent interactions on

the luminescence of acridine adsorbed on silica surfaces. The goal is to study the feasibility of

spectral methods to characterize adsorbate-adsorbent interactions and the dynamics of complex

heterocycles loaded into silica pores of 4 to 20 nm in diameter. The temperature at which the silica was trained was insufficient to complete water desorption.

Obtained results afford ground for assumption that acridine forms strong ionic hydrogen bonds with

the hydroxyl part of silanol groups. This conclusion was made from smaller long-wave shift of

luminescence spectrum of adsorbed acridine as compared to its protonated form. By comparing the

luminescence spectra of acridine in water and acridine adsorbed on silica from vacuum it was

concluded that silica surface, dried in high vacuum at 420 K, contained a variety of adsorption

centers, including adsorbed water. The proton transfer to the nitrogen of acridine happens in the dark process, without the promoting photo excitation.

Previous investigations of acridine adsorbed from chloroform solution showed that acridine formed

excimers on the surface. This conclusion was made based on lifetime’s data and the position and the

shape of the luminescence band. Excimers can be formed in the case of island-type of adsorption,

when acridine aggregates can be organized on the silica surface. Therefore, acridine polycrystals

were investigated particularly. Considerable long-wave (crystalline) shift was observed. It can be

supposed that being adsorbed from solution acridine aggregates on the surface as islands, but

individual molecules present on the surface when adsorption occurs from vacuum. Difference in the

maxima positions in the luminescence spectra of acridine adsorbed from vacuum obtained at

different excitation wavelengths can mean that there are present both hydrogen-bonded and aggregated acridine.


119

FTIR STUDY OF OZONOLYSIS OF C2H4-XCLX

ADSORBED ON WATER ICE, SIO2, AND TIO2

A.V. Rudakova, N.V. Zakharov, N.M. Tsyganenko, K.M. Bulanin, A.A. Tsyganenko


[email protected]

Surface chemistry of halogenated hydrocarbons attracts significant attention due to their important

role in stratospheric ozone destruction. The aim of this work was to study surface reactions of

chloroethenes with ozone at 77-300 K on water ice, silica, and titania which could be considered as

model atmospheric aerosols. The effect of UV irradiation on the studied processes was also

investigated.

The cell designed for spectral studies of adsorbed species at variable temperatures (55-370 K) [1]

was used in the studies of C2H4-xClx ozonolysis on SiO2, and TiO2. To prepare water ice films the

cell was equipped with a device for water vapour deposition onto the inner BaF2 windows at

cryogenic temperatures [2]. A 120-W high-pressure mercury lamp was used in photochemistry

experiments.

It was found that at low temperatures all chlorinated ethenes (C2H3Cl, trans-, cis-, and gem- isomers

of C2H2Cl2, C2HCl3 and C2Cl4) were molecularly adsorbed on H2O ice, TiO2 and SiO2 surfaces

forming H-bonds with surface hydroxyls.

Studies of ozonolysis on ice and silica surfaces enable us to conclude that these adsorbents do not

reveal any catalytic activity with respect to chloroethenes, but participate as condensors of reagents

and products. Ozone co-adsorption with C2H4 or C2H3Cl even at 77 K leads to ozonolysis reaction,

which also takes place for C2H2Cl2 isomers, but only at elevated temperatures (120 –150 K). Co-

adsorption of O3 with C2HCl3 or C2Cl4 molecules does not lead to any noticeable spectral changes.

At the same time, TiO2 exhibits higher activity towards ozonolysis of chloroethenes. For all the

studied adsorbates, weak bands of products start to grow already at 77 K. Preliminary water

adsorption decreases the activity of titania. The reactions in this case starts only at 100–140 K.

The bands of initial products, i. e. primary and secondary ozonides, were identified. The final

products (formaldehyde H2CO (bands at 1720 and 1500 cm-1

), phosgene COCl2 (1805 cm-1

) and

formyl chloride HClCO (features at 1731–1754 cm-1

spectral range) – on ice and silica surfaces, and

H2O, CO2 and surface carboxylate-like species – on titania surface) were detected. The reaction

mechanism is consistent with Criegee’s scheme [3].

We also studied the effect of UV irradiation upon adsorbed halogenated hydrocarbons and their

reactions on TiO2, SiO2 and water ice surfaces. On TiO2 irradiation of gem-C2H2Cl2 in the presence

of O2 at 300 K results in the decrease of the band intensities of adsorbed species and the appearance

of new bands of products, thus testifying for photooxidation. The products of photooxidation and

ozonolysis of gem-C2H2Cl2 are not the same. Though SiO2 and ice are inert in photooxidation

reaction, simultaneous action of ozone and UV irradiation upon C2H2Cl2 isomers and C2Cl4 on both

the surfaces results in spectral changes already at 77 K. Spectral dependence of C2Cl4

photoozonolysis on ice surface at 77 K shows that photoexcitation and dissociation of ozone

evidently account for the observed processes.

Acknowledgments. The work was supported by the Ministry of Education and Science of the

Russian Federation, grant 11.38.38.2011.

References:

1. Otero Areán С., et al. Eur. J. Inorg. Chem., 2001, 7, 1739.

2. Rudakova A.V., Sekushin V.N., Marinov I.L., Tsyganenko A.A., Langmuir, 2009, 25, 1482.

3. Criegee R., Werner G., Justus Liebigs Ann. Chem., 1949, 546, 9.


120

FLUORESCENCE OF IRRADIATED POLYTETRAFLUOROETHYLENE

T.V. Sakhno1, D.I. Seliverstov

2, E.M. Konova

2, Yu.E. Sakhno

1, S.T. Sychkova

1, S.A. Khatipov

2

1 – University of Economics and Trade, Poltava, Ukraine

2 – L.Ya. Karpov Institute of Physical Chemistry, Moscow, Russia

[email protected]

It is well known that the side/main-chain chromophores are responsible for fluorescent properties of

polymer based materials. The commonly used polymers as polyethylene, polytetrafluoroethylene,

PMMA do not contain chromophoric groups and their luminescence resulted by the admixtures as a

side effect. Luminophores in polymer matrix can be as a mechanical mixture or covalently bounded

to the main chain. Among all available methods used for variety of polymer studies in industry the investigation of their photoluminescence is not frequently applied.

Only few works has described the fluorescence of such broadly applied materials as PTFE. We have

found that low doses of g-irradiation at melting point to PTFE induce the fluorescent properties of

such material [1]. The cause and origin of fluorescence [2,3], possible mechanisms of active centre

formation [4], quantum-chemical calculations [5] has been described. In this work we've analyzed

theoretically the fluorescence spectra of PTFE obtained by some of authors when treated surface of

materials by radiation with different linear energy transfer. Obtained fluorescence spectra of PTFE

affected by a-irradiation in vacuum; with xenon excimer lamp in atmosphere of ammonium at wave

length maximum 172 nm [7]; forming thin films by use of pulse laser deposition [8] has been

analyzed in detail. We've demonstrated that independently on a source of irradiation the surface of

PTFE dominated with identical by it nature optical centers but different by their ratio and

concentration. 1. Khatipov S.A., Nurmukhametov R.N., Seliverstov D.I., Sergeev A.M. Spectrophotometric and

Luminescent Analysis of Polytetrafluoroethylene Treated by g-Irradiation near the Melting Point. Vysokomol Soedin, Ser A 2006;48(2):153–158.

2. Nurmukhametov R.N., Klimenko V.G., Seliverstov D. I., Sergeev A. M., and Khatipov S. A. Luminescence and Color of Radiation-Modified Polytetrafluoroethylene in Blocks. Polymer Science, Ser.

A, 2008;50(12):1226–1232. 3. Seliverstov D.I., Nurmukhametov R.N., Sergeev A.M, Klimenko V.G. and. Khatipov S. A. Formation of

optical color and fluorescence centers in polytetrafluoroethylene under γ-irradiation. Journal of Applied Spectroscopy, 2011;78(4):512-517.

4. Khatipov S., Nurmukhametov R., Sakhno Yu., Klimenko V., Seliverstov D., Sakhno T. Fluorescent Analysis of Polytetrafluoroethylene Treated by γ-Irradiation Near the Melting Point. Rad. Phys. Chem. 2011;80(3):522-528.

5. Sakhno Yu.E., Klimenko V.G., Seliverstov D.I., Sakhno T.V., Khatipov S.A. The Nature of Color Centers in g-Irradiated Poly(tetrafluoroethylene) Polymer Science, Ser. B, 2008, 50(5–6):117–119.

6. Pugmire D.L., Wetteland C.J., Duncan W.S., Lakis R.E., Schwartz D.S. Cross-linking of polytetrafluoroethylene during room-temperature irradiation. Polym. Degradation Stability 2009;94(9):1533–1541.

7. a)Heitz J., Svorcík V., Bacáková L., Rocková K., Ratajová E., Gumpenberger T., Bäuerle D., Dvoránková B., Kahr H., Graz I., Romanin C. Cell adhesion on polytetrafluoroethylene modified by UV-irradiation in an ammonia atmosphere. J. Biomed. Mater. Res. A. 2003;67(1):130-137.b) Svor ík V., Ro ková K.,

Ratajová E., Heitz J., Huber N., Bäuerle D., Ba áková L., Dvo ánková B.and. Hnatowicz V. Cell proliferation on UV-excimer lamp modified and grafted polytetrafluoroethylene. Nuclear Instruments and Methods in Physics Research Section B: Beam Interactions with Materials and Atoms, 2004;217(2):307-313.

8. Heitz1 J., Arenholz E., Dickinson J.T. Particles in laser ablation of polytetrafluoroethylene. Appl. Phys. A 1999;69:S467–S470.


121

PHOTOCORRELATION AND FLOURESCENCE SPECTRISCOPY

METHODS OF RHODAMINE 6G AND SILVER NANOPARTICLES

DYNAMICS IN EVAPORATING DROP

I.G. Samusev1, V.V. Bryukhanov

2, N.A. Myslitskaya

1, A.V. Khitrin

1, A.M. Ivanov

1

1 – Kaliningrad State Technical University, Russia

2 – Immanuel Kant Baltic Federal University, Kaliningrad, Russia

[email protected]

Scientific interest to an evaporating multicomponent liquid drop is caused by its numerous

applications in micro- and nanotechnological problems, chemical and biological substances

development, and structural analysis in medical diagnostics. The evaporating drop of a pure solvent

is known to keep the edge angle unchanged, but the area of its contact with the solid substrate

decreases with evaporation time. If molecular substances (suspensions, colloidal solutions etc.) are

dissolved in the liquid drop, there are the drop base area remains unchanged during evaporation (the

pinning phenomenon), but the edge angle decreases. In this case, there are capillary flows toward

the drop edge that transfer the dissolved substances or suspended particles to the drop edge causing

pinning phenomena of the boundary after liquid evaporation. Colloid silver nanoparticles and its

competition with the capillary flow in an evaporating drop using the method of photocorrelation

spectroscopy of light molecular scattering has been obtained. The method of laser photocorrelation

spectroscopy was used to calculate the parameters of diffusion motion of colloid silver

nanoparticles in an evaporating water drop. A single-mode He-Ne laser (W = 25 mW, λ = 632.8 nm,

and the beam cross-sectional diameter was ~100 μm) was used for the radiation source. Laser

radiation was scattered by nanoparticles participating in the Brownian motion. Fluctuations of the

laser light intensity were investigated on a setup built around an optical goniometer produced by

JSC “LOMO”. Scattered light was registered by a Photocor-FC system operating in the photon

counting regime. The correlation function of the scattered light intensity was calculated using a

Photocor-FC 32-bit 282-channel correlator. The decrease of the nanoparticle diffusion coefficients

D is caused first, by the increase in the particle concentration as a result of water evaporation and

hence decrease of the drop volume and second, by substance transfer to the drop edge as a result of

the capillary flow that is confirmed by a significant increase in scattering particle sizes at the drop

edge for the following reasons: association of the colloid silver nanoparticles and increase in the

viscosity of the medium are observed in the drop. Rhodamine 6G (R6G) molecules and its

aggregates capillary flow in an evaporating water drop by means of molecular fluorescence

spectroscopy have also been investigated. The initial concentration of R6G in an aqueous solution

was 5∙10-4

M. The intensity of R6G stationary fluorescence was studied be means of optical fiber

attachment to “Fluorat-PANORAMA-02”. Dye molecules fluorescence excitation was carried out at

530 nm. The samples was in a cave where the temperature was remained constant and equaled 22.0

± 0.1°C. The observation time was 4 hours (the period of time which corresponded to 90% decrease

of drop height after evaporation). R6G molecules fluorescence intensity appeared to linear-

decreasing with evaporation time: its decrease rate at the pinning line was three times higher than

the one in the center of the drop. It has been suggested that a more intense fluorescence quenching

on the drop edge can be associated with the processes of dye molecules association and

concentration quenching of fluorescence near the pinning line is caused by the dye molecules

removal from the drop center to its periphery. We simulated the dynamics of mass transfer in the

evaporation drop based on convection-diffusion differential equations model (R6G molecules

concentration distribution dynamics estimation) and compared analytical expressions with the

experimental data on R6G molecules fluorescence concentration quenching in the drop center and

at the pinning line.


122

FLUORESCENCE ENHANCEMENT OF ORGANOLUMINOPHORES

IN POLYMER AND ON SILICON DIOXIDE SURFACE

WITH GENERATION OF SURFACE PLASMONS

IN ROUGH SILVER FILM AND SILVER NANOPARTICLES

I.G. Samusev1, V.V. Bryukhanov

2, V.A. Slezhkin

1, R.V. Gorlov

1, N.S. Tikhomirova

1

1 – Kaliningrad State Technical University, Russia

2 – Immanuel Kant Baltic Federal University, Kaliningrad, Russia

[email protected]

Increasing interest to metal-dielectric, containing metals nanoparticles, is connected with their

unique optical properties in consequence of surface plasmon absorption formation in ultraviolet,

visible and near infrared areas of a spectrum. Among which the structures containing nanoparticles

of Ag, possess the unique physical and chemical properties caused by surface plasmons (SP)

generation, have practical application in nano-plasmonic and nano-photonics. Structures with

particles of noble metals on the basis of porous materials, in particular silicon dioxide, are

investigated intensively for the purpose of growth of chemical and biological sensor controls. In the

present work transfer of electronic energy of SP on electronic conditions of rhodamine 6G (R6G)

molecules, introduced in polymeric films of polyvinyl alcohol (PVA), deposited on Ag films with a

various roughness has been investigated; in films of R6G molecules PVA and eosin with Ag

nanoparticled, and also in the presence of Ag hydrosol nanoparticles with adsorbates of R6G on

silicon dioxide (silochrom) surface. Ag films were produced by electrochemical reduction Ag+ on

copper from cyanide rhodanate electrolyte. Roughness of Ag surface (creation modeling

nanoparticles on a surface) was varied by anode dissolution. Ag film coated with R6G water

solution with PVA, dried up at 60°С and produced films PVA of a various thickness (6–25 μm) in

concentration of dye 1.5∙10-3

M. Morphology (an estimation of the sizes and the form of cambers)

of Ag surface was investigated by means of scanning electronic microscope JSM-6390 and

tunneling microscope SMM-2000. In the first series of experiments it has been established that with

excitation of R6G fluorescence in PVA at 400 nm depending on a roughness of Ag surface various

enhancement of fluorescence intensity occured. Thus, the spectral structure of fast fluorescence of

dye did not change. In experiments with change of polarisation and an excitation corner it has been

shown, what the greatest effect is observed with excitation p-polarisation and at angles 42–44°.

Comparison of the received results with the literary data and their analysis shows that fluorescence

enhancement is caused by carrying over of energy of SP on electronic conditions of luminophore

molecules, and the sizes of films roughness averaged 50–200 nm, and the effect of enhancement

depended on average distance of molecules to a rough surface. By means of method of pulse laser

excitation of dye films on surface of Ag it has been found out that singlet-triplet annihilation

between molecules of singlet O2 and triplet dye molecules, as a result of generation singlet O2 in a

time of film Ag. Experiments with PVA films with dye eosin and organoluminophores hydrosol Ag

showed that in the presence of Ag at certain concentration enhancement of fluorescence of

molecules of dye was observed. Simultaneously there is a change of speed of deactivation triplet

conditions of molecules of the dye, the intensity of the slowed down fluorescence measured on

change and a dye phosphorescence. In the second series of experiments for the first time it has been

shown that at consecutive equilibrium adsorption of molecules of R6G dye and hydrosol Ag on the

surface silicon dioxide there is a enhancement of fast fluorescence intensity. It is thus shown that

the effect of enhancement is observed only at a certain parity of concentration of dye and hydrosol.


123

SYNTHESIS, STRUCTURE AND SPECTRAL PROPERTIES

OF 9-DIARYLAMINOSUBSTITUTED ACRIDINES

S.K. Sazonov1, A.I. Vedernikov

1, V.A. Sazhnikov

1, A.A. Khlebunov

1,

L.G. Kuzmina2, S.P. Gromov

1, M.V. Alfimov

1



[email protected]

The synthesis of three 9-diarylaminosubstituted acridines was elaborated. These compounds of the

donor-acceptor type – N,N-diphenylacridin-9-amine (1), 2,7-dimethyl-N,N-bis(4-methyl-

phenyl)acridin-9-amine (2), and 2,7-bis(1-methyl-1-phenylethyl)-N,N-bis[4-(1-methyl-1-phenyl-

ethyl)phenyl]acridin-9-amine (3) were characterized by IR, 1H,

13C NMR, mass-spectral and

elemental analysis. The crystal structures of compounds 1–3 and their protonated forms were

determined by X-ray diffraction analysis. Their absorption and fluorescence spectra in various

solvents at room temperature and the phosphorescence spectra in CHBr3 at 77 K were measured.

Solvatochromic shifts and dependence of the fluorescence quantum yields on the solvent polarity

and protonation suggest the use of these compounds as chemical sensors. An example of a sensor

material based on compound 2 is presented.

N

H

R R

N

R R

N

R R

Me

Me

R = H (1), Me (2), (3)

hexane

CBr4, h

Yield 16- 21%

Fig. 1 Structure of 1.

12000 12800 13600 14400 15200 16000

0,0

0,2

0,4

0,6

0,8

1,0

Inte

nsity,

a.u

.

Wavenumber, cm-1

123

Fig. 2 Absorption spectra of protonated 1 (a), 2 (b), 3 (c) in methanol with added 1 M HCl.

Fig. 3 Phosphorescence spectra (excitation at 430 nm) of 2 (1), 1 (2) and 3 (3) in CHBr3 at 77 K.

This work was supported by the Russian Academy of Sciences.


124

PECULIARITIES OF THE REFLECTION AND ABSORPTION SPECTRA

OF LANGMUIR MONOLAYERS UNDER NORMAL INCIDENCE

OF LIGHT ONTO THE SAMPLE

S.L. Selektor, S.D. Stuchebryukov

A.N. Frumkin Institute of Physical Chemistry and Electrochemistry RAS, Moscow, Russia

[email protected]

UV-Vis spectroscopy is well-known as one of the most informative methods of investigation of

compounds and materials. But application of this method to ultrathin films is limited by the

necessity to record the very weak signals and to take account of quite a number of possible

distortions and peculiarities. The prospects of the study of optically anisotropic, in the general case

biaxial, monolayers by means of linearly polarized light were analyzed. It was shown that upon

normal incidence of the probe radiation onto the sample under consideration, it is possible to

estimate the extinction coefficients of monolayer both in the line of its compression and in

orthogonal direction. This possibility can be realized by means of linearly polarized radiation with two different mutually orthogonal polarization states.

In order to obtain the quantitative description of transmission spectra of Langmuir monolayers on

the water subphase or ones transferred onto the surface of transparent quartz plate the three-layer

system was considered. These layers are: ambient medium – monolayer – substrate. The

expressions for Absorbance in transmission spectra of such optical system were obtained. These

formulas were compared with the expressions derived earlier by W.N. Hansen for the Absorbence

in the reflection-absorption spectra of the analogues three-layer system. It was shown that at all

other conditions being equal the measurement in reflection mode made possible to obtain much

more higher amplitude spectra. The peak intensities of these spectra (expressed in the units of the Absorbance) are almost one order higher than those in transmission mode.

300 400 500 600 700

0,00

0,01

0,02

0,03

0,04

2

absorbance

wavelength, nm

1

300 400 500 600 700

0,00

0,02

0,04

0,061

2

ab

sorb

ance

wavelength, nm

Fig. 1. UV-Vis spectra of Ce(R4Pc)2 (Pc = phthalocyaninate ion, R = 15-crown-5) (a) and crow-substituted oligothiophene (b) monolayers at air/water interface at 25 mN/m (1) and 6-layer LB films on the quartz plates transferred at 25 mN/m (2).

The revealed dependences were proved by experimental results for monolayers of different

surfactant compounds: crown-substituted oligothiophenes, amphiphilic hemicyanine dyes,

amphiphilic fluorophores and sandwich-type phthalocyanine complexes of lanthanides (fig.1). The

fairly good agreement between the theory and the experimental results was demonstrated for all systems under investigation.

This work has been done with the support of Russian Foundation for Basic Research (project № 11 -

03-12124-офи-м) and the Program P7(5) of Presidium RAS

a b


125

SYNTHESIS AND PHOTOLUMINESCENT PROPERTIES OF LANGMUIR

FILMS OF COUMARIN DYES AND POLYAMPHOLYTIC POLYMER

E.V. Seliverstova1, N.Kh. Ibrayev

1, V.I. Alekseeva

2, L.E. Marinina

2, L.P. Savvina

2

1 - E.A. Buketov State University, Institute of Molecular Nanophotonics, Karaganda, Kazakhstan

2 - NPO Organic Intermediaries and Dyes (NIOPIC), Moscow, Russia

[email protected]

Nanodimensional films on a basis of synthesized non-amphiphilic molecules of coumarin-7

derivatives: chromene-3 (3-diethilamyno-7-imino-7H-chromene[3',2'-3,4]pyrido[1,2-а]-

benzimidazole-6-carbonitrile) and chromene-13 (3-diethilamyno-7-oxo-7H-chromene[3',2'-

3,4]pyrido[1,2-а]- benzimidazole-6-carbonitrile) and hydrophobic-modified polyampholytic

polymer have been received by Langmuir-Blodgett (LB) technique. Mixed monolayers were formed

at water–air interface using Langmuir trough. Monolayers were transferred onto quartz substrates

by vertical dipping according to Y type transfer at surface pressure of π = 21 mN/m and the dipping

speed through the monolayer 0.02 mm/s. The thickness of the films consisted of 20 monolayers.

The relative concentrations of dye molecules in films were equal to 0.2, 10, 33 and 50 mol%.

Behavior of monolayers was studied by measuring the dependence of surface pressure-specific

molecular area (π-А–isotherm).

Spectral and luminescent properties of obtained LB films were investigated. The absorption spectra

of ethanol solutions of dye represents as a broad band at the region of 450-600 nm with two distinct

maxima at 517 and 551 nm for chromene-3, and 517 and 550 nm for chromene-13. The

fluorescence spectra of dyes in ethanol exhibits a maximum at 573 nm with the shoulder at 615-630 nm.

Absorption spectra of LB films of dyes are broadened and shifted to the red region of spectrum

(λmax = 555 nm for chromene-3 and λmax = 558 nm for chromene-13) in the comparison with

absorption spectra of dyes ethanol solutions. Fluorescence spectra of films also broadened and

shifted to the long-wave region. Fluorescence band of film containing 10 mol% of cromene-3 was

observed with the maximum at 577 nm and shoulder at the 623 nm. With increasing of

concentration of dye molecules in the film the maxima of absorption bands shifted

hypsochromically (to 580 and 625 nm for dye concentration C = 33 mol%; 581 nm and 631 nm for

C = 50 mol%). Fluorescence spectra of LB films of chromene-13 markedly deformed with the

increasing of concentration of dye. The maximal value of fluorescence quantum yield for LB films

was obtained at 10 mol% dye concentration. Maximum of fluorescence band of dye was observed at

583 nm with the shoulder at 617 nm. Increasing of dye concentration in film leads to quenching of

the intensity of fluorescence. Obtained data indicate the presence of aggregation of dye molecules

within LB films.

Properties of long-lived luminescence LB films of coumarin dyes were investigated. Spectra of

luminescence exhibits two bands with the maxima at 730 and 670 nm. It is found, that short -wave

band of emission is the thermoactivated delayed fluorescence (E-type). The band with the

maximum at 740 nm is belong to phosphorescence of dye.


126

OPTICAL ABSORPTION AND PHOTOCATALYTIC PROPERTIES

OF TITANIUM-MANGANESE OXIDES

V.V. Shymanovska1, L.A. Kernazhitsky

1, T.A. Gavrilko

1,

V.V. Naumov1, T.V. Khalyavka

2, V.C. Kshnyakin

3

1 – Institute of Physics NAS, Kiev, Ukraine

2 – Institute for Sorption and Problems of Endoecology NAS, Kyiv, Ukraine

3 – Sumy State Pedagogical University, Ukraine

[email protected]

Prospects for wide practical application of wide-band semiconductor TiO2 as an efficient converter

of solar energy and the photocatalyst are restricted by large value of TiO2 band gap (3 eV for rutile

and 3.2 eV for anatase). To improve the photocatalytic activity and increase the operating range of

the material in the visible region of the solar spectrum are used by different TiO2 doping elements,

such as transition metal cations, nitrogen, sulfur, etc. [1, 2].

We have studied the optical and photocatalytic properties of titanium-manganese mixed oxide

(TiO2/Mn2O3), which are of practical interest. The absorption spectra in the UV-vis range for pure

TiO2 (rutile and anatase) and Ti-Mn oxides were measured in 2.5–6.0 eV range. In the range of 2.5–

3.0 eV there is a "tail" of absorption of TiO2, caused by optical transitions between the states,

located above the valence band (from 0 to 0.5 eV) and the bottom of the conduction band. These

states may be associated with structural defects in the bulk TiO2 and can be populated by thermal

excitation of electrons from the valence band. It is found that the absorption intensity of Ti-Mn

oxides is about 10 times higher than that of pure anatase and there is a significant red shift of the

absorption edge. The presence of manganese oxides in TiO2 leads to the creation of additional

defect states, resulting in the absorption intensity increases. In the range of 3–4 eV the absorption

edge is shifted into the visible region of more than 0.5 eV compared to pure rutile. This red shift

and increased absorption associated with charge transfer between the Mn 3d-electrons and the TiO2

conduction band.

The activity for Ti-Mn mixed oxides and surface-doped TiO2 by Mn2+

-cation samples in

photocatalytic destruction of the safranine dye under UV irradiation was studied. A great

improvement of photocatalytic activity is registered for Mn2+

-doped TiO2 (anatase and rutile) as

well as for rutile-Mn2O3 oxides. We believe that these Ti-Mn oxide materials can be promising

photocatalysts for degradation of organic pollutants under UV and visible light irradiation.

1. A. Fujishima, X. Zhang, D.A. Tryk, Surface Science Reports 63, 515–582 (2008).

2. O. Carp, C.L. Huisman, A. Reller, Prog. Solid State Chem. 32, 33–1771 (2004).

This work was supported in part by the Academy of Science of Ukraine under the "Nanophysics and

Nanoelectronics" Program (project No. VC-153).


127

EFFECT OF STERIC STRUCTURE OF POLYMETHINE MOLECULES

ON THE COMPONENT COMPOSITION OF MOLECULAR LAYERS

OF THESE COMPOUNDS

A.A. Starovoytov, E.N. Kaliteevskaya, V.P. Krutyakova, T.K. Razumova, P.V. Shchedrin


[email protected]

Molecular layers of polymethine compounds with long conjugation chain on glass contain several

types of molecular nanocomponents. The number and type of the components depend on the

thickness of a layer. In thin layers, only monomolecular components (all-trans-isomers and cis-

isomers) are present. Cis-isomers are formed from all-trans-isomer upon rotation around various

bonds in the polymethine chain. The spectral parameters of the components are significantly

different. The relative surface concentration of the stereoisomers is determined by the thickness of a

layer and chemical structure of a molecule. We studied a series of four dicarbocyanines

(diethylthiodicarbocyanine iodide, DTDCI, and its derivatives differing in the substituents and their

positions in the polymethine chain) and determined the steric structure of the nanocomponents of

the layers. The absorption spectra of the dye solutions were compared with the spectra of layers of

different thicknesses. It was shown that the layers of less than 1 monolayer thick contain up to 4

monomeric components. The spectral shifts of the long-wave singlet bands of the isomers with

respect to the all-trans isomer band (∆νca) are within 1600 – 6500 cm–1

, depending on the type of

the isomer. In a series of the dyes studied, the differences in ∆νca between the same components are

considerably lesser than those between the different components of the same layer. For monocis-

and dicis-isomers of the dyes studied, which are obtained from the all-trans form upon rotation of

fragments of a molecule around different C-C bonds in the polymethine chain, the steric models

were constructed. It was shown that in the series of cyanine molecules differing in the substituents

and their positions in the polymethine chain there is a correlation between the intensity of the

absorption bands of the certain components and the steric hindrance of molecular isomers. The

above correlation may be used for the determination of the steric structure of monomeric

components of the layer.


128

NEAR INFRARED LIFETIME SPECTROMETER

FOR SINGLET OXYGEN DETECTION

A.S. Stasheuski, V.A. Galievsky, B.M. Dzhagarov

Institute of Physics NAS, Minsk, Belarus

[email protected]

In recent years, studying the luminescence dynamics in the near infrared (NIR) spectral region has

become especially important in connection with the appearance of new medicines–sensitizers for photodynamic therapy, which is based on singlet oxygen formation after photoexcitation.

Singlet oxygen luminescence is quite weak in condensed media. Its lifetime is varied from tens of

milliseconds in some organic solvents to hundreds of nanoseconds in biological environments,

where singlet oxygen is substantially quenched. For pure water singlet oxygen luminescence

quantum yield is only 6.5∙10–7

and lifetime is about 3.6 microseconds. Advanced photon counting methods are necessary for such kind of low level and relatively fast luminescence measurements.

We have created NIR lifetime spectrometer using the multichannel scaling technique [1]. The

spectrometer has an ultra fast multiscaler (P7888-2, FAST ComTec GmbH), which digitizes with a

time resolution of 1 ns all output pulses from the highly sensitive photomultiplier (H10330-45,

Hamamatsu Photonics K.K.) operating in single photon counting mode and enables to count up to

2 s signals. Special collecting optics, 90˚ image rotator maximizing the overlap of the excited

volume within the sample and the monochromator entrance slit provide high optical efficiency.

Diode pumped solid state laser operating at 1 kHz repetition rate is the source of sub-nanosecond

531 nm excitation pulses. Their energy may be lowered by the computer-controlled attenuator.

Transmittance of the sample at excitation wavelength is monitored by the ratio of photodiode

signals before and after the cell. It allows checking photodegradation of the sample during the

measurement. In addition to a standard sample holder for 1×1 cm fluorescence cells, which is

equipped with a magnetic stirrer, there is an option to set up a thermostat to maintain the sample

temperature in a range from –100 to +100°С. The software controlling the spectrometer provides

automatic measurements of luminescence kinetics at different wavelengths with the subsequent

reconstruction of luminescence spectra by integrating the areas under kinetic curves within a specified time window.

In solutions the spectrometer allows measurements of quenched luminescence of singlet oxygen

with a total quantum yield (product of formation and luminescence yields) up to 6∙10–9

.

Dynamics and efficiency of photosensitized production of singlet oxygen by water-soluble

porphyrins and commercial drugs based on chlorin e6 are investigated [2, 3]. Studies of benzo-fused

hydroporphyrazines [4], nanocomposites consist of quantum dot and porphyrin [5] and other extra

sensitive 1O2 measurements were performed with the developed spectrometer.

References:

1. V.A. Galievsky et al., Instruments and Experimental Techniques, 2010, V. 53, No. 4, P. 568.

2. M.V. Parkhats et al., Optics and Spectroscopy, 2009, V. 107, No. 6, P. 974.

3. M.V. Parkhats et al., Journal of Applied Spectroscopy, 2011, V. 78, No. 2, P. 278

4. Р.Р. Pershukevich et al., Journal of Applied Spectroscopy, 2011, V. 77, No. 6, P. 790.

5. E.I. Zenkevich et al., Journal of Physical Chemistry C, 2011, V. 115, No. 44, P. 21535.


129

PHOTONICS OF 5-FLUOROURACIL AND 5-HYDROXY-6-METHYL-

(1-THIETANYL-3)PYRIMIDINE-2,4(1Н,3Н)-DION IN SOLUTIONS

M.V. Sultanbaev1, S.S. Ostakhov

1, S.L. Khursan

1, Sh.Kh. Gantsev

2

1 – Institute of Organic Chemistry, Ufa RC RAS, Russia

2 – Bashkir State Medical University, Ministry of Health of Russian Federation, Ufa, Russia

[email protected]

This paper deals with a number of fundamental issues of the photonics of the synthetic analogues of

uracil and thymine (DNA and RNA structural elements) – 5-fluorouracil (FU) and 5-hydroxy-6-

methyl-(1-thietanyl-3)pyrimidine-2,4(1Н,3Н)-dion (TOMU). The sequence of pyrimidine and

purine bases in a polynucleotide chain predetermines the genetic information in the DNA and the

matrix RNAs.

The author of the paper has conducted spectral-luminescent research of tautomeric equilibrium of

FU in neutral aqueous solutions. Upon selective light excitation of λex. = 265, 305, 320 and 340 nm

the first experimental records of the individual emission spectra of 2,4-dioxo (A), 2-hydroxy-4-oxo

(B), 4-hydroxy-2-oxo (D) и 2,4-dihydroxy (E) tautomers of 5-fluorouracil with corresponding

maximum fluorescence (FL) values of 340, 380, 410 and 440 nm were made. The quantum yields

(φ) of the fluorescence (FL) of the tautomers in question were estimated: 1.5×10-4

(A), 2.1×10-2

(B),

0.16 (D), 0.35 (E), as well as their percentage values: 99.5 (A), 0.4 (B), 0.03 (D), 0.008 (E).

In recent years the progressive development of femtosecond technologies has made possible the

direct measurements of the lifetimes of the fluorescence of pyrimidine bases. On the one hand, the

extremely short lifetimes of the S1 → S0 fluorescence of uracil (0.1 ps), thymine (0.2 ps) and FU

(0.65 ps) determine the high photochemical stability of nucleic acids under the damaging effect of

UV light; on the other hand, they presuppose the possibility of recording the radiative S2 → S0

transition from the second excited singlet S2-level to the ground level (violation of Vavilov’s law).

The influence of the length of an excitation light wave on the fluorescence spectra of FU in acid

aqueous solutions (pH 2.5) and of TOMU in acetonitrile solutions has been studied upon excitation

in the absorption band of the S2←S0 transition. It was discovered that upon direct photoexcitation in

the second or further short-wave absorption bands fluorescence of FU and TOMU is observed not

only from the first excited S1-level (FU: λmax. = 340 nm, φ(S1 → S0) = (0.6 ± 0.05)∙10-3

; TOMU:

λmax. = 350 nm, φ(S1 → S0) = (4.5 ± 0.5) × 10-3

), but also upon transition from the second S2-level to

the ground level (FU: λmax. = 300 nm, φ(S2 → S0) = (1.25 ± 0.1)∙10-3

; TOMU: λmax. = 305 nm, φ(S2 → S0) = (1.0 ± 0.1)∙10

-3).

The obtained results and literary data analysis lead to the suggestion that observing radiative

transitions from highly excited singlet Sn-states in organic molecules with extremely short lifetimes

of the S1-state (< 1 ps) is more of a regularity than of an exception.

The research was supported by the Russian Academy of Science (project no. OKh – 01).


130

COMPARATIVE SPECTRAL-LUMINESCENT STUDY OF KETO-ENOL

EQUILIBRIUM OF 5-FLUOROURACIL AND TEGAFUR IN WATER

SOLUTIONS

M.V. Sultanbaev1, S.S. Ostakhov

1, S.L. Khursan

1, Sh.Kh. Gantsev

2

1 - Institute of Organic Chemistry, Ufa Research Center, Russian Academy of Sciences, Ufa, Russia

2 - Bashkir State Medical University, Ministry of Health of Russian Federation, Ufa, Russia

[email protected]

The antitumor drugs 5-fluorouracil (FU) and tegafur (TF) are synthetic analogs of uracil and

thymine being structural components of nucleic acids and posses fluorescence (FL).

The comparative spectral-luminescent research of the tautomeric equilibrium of FU and TF has

been carried out in neutral aqueous solutions. We were the first to detect experimentally the

individual FL spectra of four among the six theoretically possible FU tautomers and two among of

three possible TF tautomers and to determine their fluorescence quantum yields (φ) and

percentages.

Fluorescence with emission maxima (λem.) at 340, 380, 410 and 440 nm which are attributed to 2,4-

dioxo (FU-A), 2-hydroxi-4-oxo (FU-B), 4-hydroxi-2-oxo (FU-D) and 2,4-dihydroxi (FU-E)

tautomers of FU was detected in aqueous solution of FU. The FL quantum yields of the tautomers

in question were estimated: 1.5∙10-4

(FU-A), 2.1∙10-2

(FU-B), 0.16 (FU-D), 0.35 (FU-E), as well as

their percentage values: 99.5 (FU-A), 0.4 (FU-B), 0.03 (FU-D), 0.008 (FU-E).

FL with λem. = 340 and 410 nm which we attributed to 2,4-dioxo (TF-A), 4-hydroxi-2-oxo (TF-D)

was detected in aqueous solution of TF. Unlike FU, TF has not 2-hydroxi-4-oxo and 2,4-dihydroxi

tautomers therefore FL of TF with λem. = 380 and 440 nm is undetectable. The FL quantum yields of

the tautomers of TF in question were estimated: 1.5∙10-4

(TF-A), 0.16 (TF-D), as well as their

percentage values: 99.77 (TF-A), 0.23 (TF-D). The comparison of spectral-luminescent data of FU

and TF FL shows, that the presence of tetrahydrofurane cycle in TF does not practically effect the

spectral composition and φ of their tautomeric A and D forms.

The comparative analysis of experimental data combined with results of quantum-chemical

calculations [1] allows to attribute the spectra, φ as well as the percentage of tautomers to following

forms: FU-A, FU-B, FU-D, FU-E for 5-fluorouracil and TF-A, TF-D for tegafur.

The research was supported by the Russian Academy of Science (project no. OKh – 01).

References

1. Makarova N., Enchev V., Ivanova G. Tautomeric Equilibria of 5-Fluorouracil Anionic

Species in Water. J. Phys. Chem. A. 2010. V.114. P.13154-13162.


131

PHTHALOCYANINE TRIPLET STATES

ON THE NANO-SIZED SILICA IN AQUEOUS SOLUTIONS

N.B. Sultimova1, P.P. Levin

1, A.V. Lobanov

2, M.A. Gradova

2, V.S. Razina

2



[email protected]

The preparation of nanostructured tetrapyrrolic complexes has received considerable attention in

recent years because of their potential applications in diverse fields, such as artificial light-

harvesting antenna [1], molecular wires [2], non-linear optics [3] and photodynamic therapy [4].

Well-designed molecular nano-assemblies based on phthalocyanines (Pc) can produce desirable

new functions that are not observed in the corresponding monomers. Thus the efficient photo-

induced energy transfer, electron and charge transport, and non-linear optics are of particular

interest in the development of new nano-Pc-based materials. The preservation of photoactivity

within nano-Pc is a critical factor in the design of applicable nano-Pc molecular assemblies. A

photoactive species is the one that efficiently forms long-lived excited singlet and triplet states upon photoexcitation, which can be optically responsive to appropriate physical and chemical effects.

The electronic absorption spectra of zinc phthalocyanine (ZnPc) and aluminum phthalocyanine

(AlPc) on the nano-sized silica surface (diameter of silica particles is 60 nm) in aqueous solutions

indicate various phthalocyanine aggregates formation. Those aggregates can be classified as «face-

to-face» H-type aggregates (new blue-shifted band appears at 640 nm), pure «head-to-tail» J-type

aggregates (significant red-shifted band appears at 740 nm) and slipped cofacial J-type aggregates

(absorption band is at 770 nm). The triplet state of AlPc J-type aggregates (TJ), characterized by a

broad absorption spectrum in the range of 400-800 nm and lifetimes of 360 μs was observed by the

nanosecond laser photolysis. It was found that the yield of TJ is significantly lower than the yield of

the monomeric triplet state (TM) in DMF. The described J-aggregates represent a new category of

Pc-nano-assemblies that possess a significant potential for use in a variety of optoelectronic devices and photodynamic therapy of tumors.

The authors thank Academician A.M. Muzafarov for kindly providing of nano-sized silica and

fruitful discussion. The work was supported by the Grant of the President of the Russian Federation

for State Support of Young Russian Scientists – Candidates of Sciences No MK-227.2011.3,

Russian Foundation for Basic Research No 12-03-01081-а, RAS Presidium Program No 28,

Project of International Science and Technology Center No 3910 and Grant for State Support of

Leading Scientific Schools No NSh-6605.2012.3.

References:

[1] Walter M.G., Rudine A.B., Wamser C.C. Porphyrins and phthalocyanines in solar photovoltaic

cells. Journal of porphyrins and phthalocyanines, 14 (2010), 759-792.

[2] Functional Phthalocyanine Molecular Materials (Ed. by J.Jiang). Springer, 2010, 336 p.

[3] Youssef T.E. Advanced Designed Phthalocyanine Materials for Nonlinear Optics: Novel

Designed Phthalocyanines and their possibilities to use as Optical Limiters. Suedwestdeutscher

Verlag fuer Hochschulschriften, 2011, 120 p.

[4] Wainwright M. Photosensitisers in Biomedicine. Wiley, 2010, 296 p.


132

SPECTRAL-FLUORESCENT PROPERTIES AND ISOMERIZATION

OF MEROCYANINES CONTAINING NITRILE GROUPS AS ACCEPTORS

A.S. Tatikolov1, L.A. Shvedova

1, Zh.A. Krasnaya

2


2 – N.D. Zelinsky Institute of Organic Chemistry RAS, Moscow, Russia

[email protected]

The spectral, fluorescent, and photochemical properties of new merocyanines containing nitrile

groups as acceptors have been studied:

Me2N

O

CN

CN

CN

Me2N

NC CN

Me2N

O

K1

Me2NCN

CN

Me2NCN

CN

Me2NCN

CN

Ph

Positive solvatochromism is observed for most of these compounds; however, for the dye

containing three nitrile groups as acceptors—polyenic aminotrinitrile K1—negative

solvatochromism is observed: the absorption spectrum is shifted to shorter wavelengths with

increasing the solvent polarity. This is explained with respect to the limiting resonance structures of

the compound. In all solvents used, the fluorescence and fluorescence excitation spectra of the

merocyanines almost do not depend on the excitation and fluorescence registration wavelengths,

respectively. At the same time, the NMR spectroscopic data indicate the presence of two isomers (E

and Z in the 2:1 ratio) of merocyanine K1 in DMSO solution. The discrepancy is probably due to

very similar fluorescent properties (the fluorescence spectra and quantum yields) of both isomeric forms.

Using the flash photolysis method, the formation of photoisomers of the merocyanines has been

detected and the kinetics of their decay in solvents of different polarity has been studied. Backward

(dark) isomerization of the photoisomers has been shown to take place more slowly in nonpolar

solvents.

This work was supported by the Russian Foundation for Basic Research, project no. 10-03-00647.


133

LIGHT-INDUCED MID-INFRARED EMISSION

OF LIQUID CARBON TETRACHLORIDE AND BENZENE

S.E. Terpugova1, O.V. Degtyareva

2, V.V. Savransky

1, E.L. Terpugov

2

1 – Natural Sciences Center A.M. Prokhorov General Physics Institute RAS, Moscow, Russia

2 – Institute of Cell Biophysics RAS, Pushchino, Russia

[email protected]

Light-induced infrared emission is a novel technique, which is promising tool in the studies novel

spectral properties of practically all materials. The high-quality vibrational spectra are produced

without the heating of the organic as well as nonorganic materials [1-3]. The emission arises in the

excited molecules of the sample during optical excitation by a low intense visible light. The IR-

radiation usually was trapped from a front surface of the sample. The intensity of vibration modes is sensitive to the channels and the mechanism of energy flow following a vibrational excitation.

In this work, we present spectral analysis of transparent liquids (carbon tetrachloride and benzene)

by the light-induced infrared emission spectroscopy. We used wavelengths at 532 and 1064 nm

(continuous-wave diode Nd:YAG laser ) and broadband visible light (320–700) nm) (continuous-

wave 100 W Xenon lamp) for a illumination of liquid samples (carbon tetrachloride and benzene).

Our experiments were carried out in the reflection geometry which is generally used in surface

measurements. Infrared absorption spectra as well as emission (Raman and infrared emission)

spectra were recorded in the range 1700–500cm-1

with a resolution of 4 cm-1

by using the FT-IR

technique (FS-02 spectrometer, Russia). All emission peaks displayed in the 1600–400 cm-1

region

in the emission spectra of investigated liquids can be identified with infrared and Raman peaks. The

emission spectra of both (carbon tetrachloride and benzene) demonstrated a good agreement with

the IR-absorption spectra in a set and peak positions of spectral bands, however, the spectra differ in

relative intensity of spectral lines. It is important, because it permit to determine the precise peak

position of the weak spectral bands or resolve the broad absorption bands of a sample investigated.

The detailed characteristics of the infrared emission produced by different wavelength radiation on

liquids are presented

[1] E.L. Terpugov, O.V. Degtyareva, Proc. of SPIE 4129 (2000) 659-665

[2] V.S. Gorelik, A.G. Gagrinov, O.V. Degtyareva, V.V. Savransky , E.L.Terpugov, Inorgan.

Mater. 42 (2006) 1251-1254

[3] A.G. Gagarinov, O.V. Degtyareva, A.A. Khodonov, E.L. Terpugov, Vibrat. Spectrosc. 42

(2006) 231-238


134

MICROMACHINING OF THE TRANSPARENT LIQUIDS

BY USE OF A LOW-INTENSE VISIBLE LIGHT

S.E. Terpugova1, O.V. Degtyareva

2, V.V. Savransky

1, E.L. Terpugov

2

1 – Natural Sciences Center A.M. Prokhorov General Physics Institute RAS, Moscow, Russia

2 – Institute of Cell Biophysics RAS, Pushchino, Russia

[email protected]

During the last decades much attention has been paid to investigation of the structural changes

induced by intense ultrashot laser pulses. The interaction of these pulses has potential uses in

materials processing and micromachining of photonic devices [1-2]. The mechanism by which

permanent structural changes are induced by the deposited high energy has not, however, been

firmly established.

In this communication we report that one can produce a nucleation and the permanent structural

changes inside a transparent material by use of only a low intense continuous-wave (CW)- laser.

Light-induced patterning was demonstrated in unsaturated solution of amino acids (L-lysine

monohydrochloride or glycine). Aqueous lysine (or glycine) solution was prepared in the

spectroscopic cuvette. The reagents, lysine monohydrochloride (Sigma), glycine (Sigma) and water

(Millipor, Environmental Grade = 18M cm), were used without further purification. To investigate

the structural changes inside an aqueous amino acid solution, a simple in situ optical imaging setup

was employed using a light beam from a CW-laser ( He-Ne: λ = 633 nm or Nd:YAG: λ = 532 nm at

an intensity of I = 80–720 mW cm-2

) and a CCD camera. Such setup permitted a real-time

observation of the structural dynamics in various transparent molecular systems. The laser beam

was focused into the surface of quartz cuvette filled with liquids examined to a spot with a diameter

of 1.5 mm. Structural modification both of the surface and inside bulk of transparent materials has

been demonstrated. Under these conditions the structural changes on the surface as well as inside

the beam appearing within ~ 1 s. We find that the laser beam produce structures with a diameter of

less than 0.5 μm, which in time can noticeably increase. Beside domains, we observed the

structures, which can be linked together during irradiation yielding visible optical waveguide in

bulk liquid. We attribute this effect to the electric-field-induced orientation of the highly polar

molecules of lysine (or glycine) in large preexisting solute clusters, helping them organize into a

crystalline structure. This result is an experimental evidence of a nonphotochemical generation of

laser-induced structural changes under given experimental conditions. Although the precise

mechanism by which structural changes are induced by the deposited energy had to be established,

this phenomenon may one day be used as waveguides in optical circuits. This is important because

it is possible easy to design optical systems that can manipulate with low- intense visible light

without causing of any sample damage.

[1] M. Makakura, M. Terazima, Y. Shimotsuma, K. Miura, and K. Hirao, Optics Express 15, 5674-

5686 (2007).

[2] C.B. Schaffer, J.F. Garcia, E.Mazur, Appl.Phys. A 76, 351-354(2003).


135

A COMBINED THEORETICAL AND EXPERIMENTAL STUDY

OF AN ORGANIC MOLECULE – FLUORESCENT PROBE (LAURDAN)

T.Yu. Titova, V.Y. Artyukhov

National research Tomsk State University

[email protected]

The information of molecular system can be received after probe introduction – a fluorescing

organic molecule with electron – donor and electron – acceptor groups. Such method of artificial

fluorescent probes takes an important place among physical methods of studying of fluorescence of

various biological objects. The method is applied to research of structure and properties of

biological liquids and tissues. Thus because of the small size of such molecular units

(suprastructure) and low concentration the probe causes the minimum infringements of structure of investigated object.

In this connection perspective object of research is the fluorescent probe – a molecule of laurdan (6-

dodecanoyl-2-dimethylaminnaphtalene).

A theoretical study on the photonics of polyatomic molecules is based on the laws of spectroscopy

and luminescence, the theory of electronic transitions, and methods of quantum chemistry (quantum

mechanics of molecules). Performing a complete and detailed investigation on molecular

photoprocesses requires knowledge of the energy-level diagram of electronic states and of the

probabilities (rate constants) of different processes: light absorption and emission, intramolecular

absorbed-energy conversion (internal conversion and intersystem crossing, intermolecular energy

transfer, and photochemical reactions in each of the electronic states of examined molecules) [1].

Dependence of fluorescence spectra in homogenous and binary solvents with exciting lengthwave was studied.

It is known that one of requirements to fluorescent probes is them multicentered which cannot be

established only by means of experimental methods, therefore spectroscopically – luminescent

characteristics of a molecule – a probe have been studied semiempirical and ab initio quantum-chemical methods of calculation [2].

Influence nonrigid structures on distribution of charges in a molecule, the dipole moments and

power levels is studied. On the basis of the received data by means of method MEP assumptions on

interaction of laurdan with various solvents have been put forward.

It is necessary to notice that spectra of fluorescence of a molecule of laurdan reacts not only to

polarity and viscosity of solvents, but also on a phase condition of a solution that testifies to strong

sensitivity of this probe to effects of solvatochromism and dynamics of a microstructure in its the

first solvation sphere.

In this connection application of an investigated probe for an estimation of polarity of solvents on

fluorescence spectra is offered to work.

This work is executed with support of the Grant of the President of the Russian Federation (NSh-

512.2012.2) and The Dynasty Foundation's Grant of non-profit program «Dynasty».

[1] V. Ya. Artyukhov, T. N. Kopylova, L. G. Samsonova, N. I. Selivanov, V. G. Plotnikov, et al.,

Russian Physics Journal, V.51, №. 10 (2008)

[2] Dobretsov G.E. Fluorescence probes during investigation of cells, membranes and lypoproteins.

– Moscow: Nauka, 1989


136

PSEUDOROTAXANE COMPLEXES BETWEEN AZASTILBENES

AND CUCURBIT[N]URILS AND THEIR PHOTOCHEMISTRY

A.I. Vedernikov1, N.A. Lobova

1, L.G. Kuzmina

2, S.K. Sazonov

1, M.V. Alfimov

1, S.P. Gromov

1

1 – Photochemistry Centre RAS, Moscow, Russia


[email protected]

A series of viologen vinylogs 1 and styryl dyes 2 bearing various N-substituents were synthesized.

Complex formation features of compounds 1, 2 with cucurbit[n]urils (CB[n], n = 7, 8) was studied

using NMR, UV/Vis spectroscopy, and X-ray diffraction. In water, CB[7] and planar trans isomers

of compounds 1 form relatively stable pseudorotaxane complexes 1@CB[7] (logK1:1 ≥ 3.2).

N RNRN R

NR

NOMe

OMeR

NOMe

OMeR

NMeO

MeOR

N

N

R

R

OMe

OMe

MeO

MeO

NN

N N

O

O

NN

N N

O

O

CB[7] ++

1: R = Et + ClO4-, (CH2)3NH3

+ + 2ClO4-,

(CH2)nSO3-, n = 2-4, o-CH2C6H4SO3

-

+

+

1@CB[7]

H2O

7

{2}2@CB[8]

+

2: R = Et, (CH2)3NH3+, (CH2)3SO3

-

+

+

h

+

+

- CB[8]

rctt-3

CB[8]

8

H2O

Dyes trans-2 and CB[n] also demonstrate pseudorotaxane-type complex formation. Under

irradiation with visible light, 2 and their complexes with CB[7] undergo only reversible E–Z

photoisomerization. With CB[8], dyes 2 are able to give both bimolecular 2@CB[8] (logK1:1 ≥ 4.0)

and termolecular {2}2@CB[8] (logK2:1 ≥ 2.6) complexes. Within termolecular complexes, two

organic cations are arranged according to syn-head-to-tail pattern thus enabling the efficient

stereospecific [2+2]-photocycloaddition (PCA) reaction to proceed to form rctt isomers of

cyclobutane derivatives 3. The stability of rctt-3@CB[8] complexes (logK1:1 ≥ 3.2) is lower than

that of 2@CB[8]. This makes it possible to use CB[8] as a supramolecular catalyst in order to attain

complete photoconversion of 2. Thus, CB[8] is a photocontrolled molecular assembler for

cyclobutanes. Such systems can be used for optical recording and storage of information, for

creation of molecular machines driven by light.

This work was supported by the Russian Foundation for Basic Research and the Russian Academy

of Sciences.


137

EFFECT OF POLYACRYLIC ACID SHELL ON LUMINESCENCE

AND PHOSPHORESCENCE OF ZNCDS NANOPARTICLES

E.K. Volkova, V.I. Kochubey, Ju.G. Konyukhova

N.G. Chernyshevsky State University, Saratov, Russia

[email protected]

Polymer nanocomposites attract attention of researchers because of possibility of stabilization of

different nanoparticles in polymer matrices. It is known that the interaction between the

nanoparticles and the polymer affects the properties of the polymer nanocomposite. Changes in the

structural, dynamic, thermodynamic and rheological properties of polymeric matrix occur as a result

of this interaction. Nevertheless the influence of polymeric matrix on the optical properties of nanoparticles is an area studied by other authors insufficiently.

We have investigated changes in the optical characteristics of ZnCdS semiconductor nanoparticles

of the mixed type as a result of coating them with polymeric shell. ZnCdS nanoparticles were

synthesized from a mixture of aqueous solutions of cadmium chloride (CdCl2) and zinc chloride

(ZnCl2) by addition of sodium sulphide solution at room temperature. The nanoparticles were not

stabilized. Acrylic acid aqueous solution contained 200 ppm p-methoxyphenol inhibitor that was

not removed before use was added into the nanoparticle suspension. The polymerization was

induced by unfiltered radiation of 250 W mercury lamp during 15 minutes with continuous mixing

of the solution. It should be noted that, under irradiation of acrylic acid solution in the same regime,

no polymerization occurred without the ZnCdS nanoparticles. The activation of polymerization with

the presence of the nanoparticles is explained by the capability of semiconductor nanoparticles for

photoinitiating polymerization via a free-radical pathway. To complete the photopolymerization

processes, the suspension was held in the light at room temperature for several days under periodic intensive mixing. In parallel a part of the suspension was held in the dark.

The fundamental absorption edge of the ZnCdS nanoparticles has been shown to shift into the short-

wave spectral region by several nanometers and to become more gently sloping as a result of

coating the nanoparticles with the polymer. The edge shift into the short-wave region can be

explained by photochemical "etching" based on the reactions of the oxidizing photocorrosion of

semiconductor nanoparticles in aqueous solutions. It is also possible that the polymer separates the

nanoparticle aggregates formed in synthesis.

It has been shown that, for the ZnCdS nanoparticles without polymer coating, in the fluorescence

spectra a complex band in the region of 640 nm is observed. After polymerization its amplitude

rises by an order of magnitude. The fluorescence in this spectral region can be attributed to vacancy

complexes containing interstitial cadmium atoms. The nanoparticles also phosphoresce in the region

of 705 nm. Earlier we revealed a phosphorescence in this region in the ZnS nanoparticles [1]. After

coating of the ZnCdS nanoparticles with polymer, the maximum of the complex phosphorescence

band is shifted into the region of 660 nm, and the band amplitude rises several times.

Phosphorescence decay has complex multi-exponential nature, which indicates participation of

several types of deep non-luminescent defects in the process. The coating with polymer changes the

phosphorescence decay times. This can be explained by both change in the types of defects and

change in the depth of the electronic levels. The last of the changes is caused by change in the

energy bandgap, in its turn.

[1] Volkova E.K., Konyukhova Ju.G., Kochubey V.I. Synthesis, surface morphology, optical and

structural properties of CdS and ZnS nanoparticles // Optics and Spectroscopy. 2012 (accepted for

publication).


138

THE SPECTRAL AND LUMINESCENCE PROPERTIES

OF METAL PHTHALOCYANINE WITH STYRYL

AND (THIOPHEN-2-YL)VINYL SUBSTITUENTS

A.V. Ziminov1, V.A. Bukov

1, T.A. Yourre

1, S.M. Ramsh

1, S.V. Litke

2

1 – State Institute of Technology (Technical University), St. Petersburg, Russia

2 – V.A. Fock Institute of Physics, St.-Petersburg State University, Russia

[email protected]

The unique properties of phthalocyanines have been studied over recent decades. These compounds

have found use in many areas of science and technology. Recently, these complexes also have

found applications as promising second-generation photosensitizers and luminescent markers for

photodynamic therapy (PDT) [1]. The introduction oh various substituents in the periphery of

phthalocyanines has a significant effect on they optical characteristics [2]. It is know styryl

fragments have been introduced onto periphery of pyrazinoporphyrazine macroheterocycle leads to

a bathochromic shift of the Q-band in absorption spectrum [3]. In the present work the absorption,

excitation and emission spectra of solution earlier not described metal phthalocyanines (I-IV) with

different substituents (fig.1) have been studied.

R=

N

N

N

N

N

N

N

NM

R

NO2

R

NO2R

O2N

R

O2N

I-IV

S

M= Zn (I, III), Mg (II, IV)

(I, II)

(III, IV)

The electronic spectra of the complexes showed characteristic absorption in the Q band region. The

Q band positions of substituted complexes (I-IV) are significant bathochromic shifted relative to

that of unsubstituted ZnPc due to introduction of styryl and thiophen-2-yl-vinyl π-cojugated

fragments. This bands are very broad due to processes of aggregation in solution. All the complexes

showed similar fluorescence behavior in DMF. Stokes shifts were 19-12 nm are typical of MPc

complexes. The fluorescence quantum yields of all complexes are similar and values of substituted

complexes are lower compared to standart (ZnPc Φ = 0.17). The nature of central metal ion very smal affect the fluorescence properties.

Table 1. Spectral-luminescent properties solutions of studied complexes I-IV in DMF.

Compound Q band / λA, nm

lg(ε) Excitation /

λex, nm Emission /

λF, nm Stokes shift /

∆, nm ΦF

I 733 4,597 733 752 19 0,106 II 736 4,633 733 752 19 0,098

III 733 4,404 717; 729 742 13 0,112 IV 732 4,038 717; 730 742 12 0,113

This work was partially supported by RFBR (Grant № 11-02-00162а).

[1] I. Gurol, M. Durmus, V. Ahsen, T. Nyokong, Dalton Trans., 2007, 3782-3791. [2] E.A. Lukyanets, V.N. Nemykin. J. Porphyrins Phthalocyanines, 2010, 14, 1–40. [3] L.A. Tomachinskaya, I.N. Tretyakova, Theoretical and Experimental Chemistry, 2007, 43(2), 125-130.

Posters Electron and energy transfer in molecular systems ----------------------------------------------------------------------------------------------------------------------------- --------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------

139

SECTION 2.

ELECTRON AND ENERGY TRANSFER IN MOLECULAR SYSTEMS

PHOTOGENERATION OF CHARGE CARRIERS IN COPPER

PHTHALOCYANINE–ANTHRACENE HETEROSTRUCTURE

A.K. Aimukhanov, D.A. Afanasyev, N.Kh. Ibrayev

E.A. Buketov State University, Institute of Molecular Nanophotonics, Karaganda, Kazakhstan

[email protected]

This paper presents the results of a study current-voltage and spectral characteristics of the layered

structure of ITO/polyethylenedioxythiophene/copper phthalocyanine/anthracene/Al heterojunction.

Polyethylenedioxythiophene (PEDOT) are used as p-channel organic polymer. Heterojunction

based organic molecules of copper phthalocyanine (CuPc) and anthracene.

CuPc and anthracene was used as the electron donor and electron acceptor respectively. This is due

to the fact that the energy between the highest occupied molecular orbital CuPc and lowest

unoccupied molecular orbital of anthracene corresponds to the condition of charge separation at the

boundary layer of CuPc and anthracene. Electron-hole pairs generated in the CuPc layer by photon

absorption. Next charge pairs is separated into free charge carriers.

Conducting polymer (PEDOT) film were cast on glass substrates coated with a transparent

conductive film of indium tin oxide (ITO). The resistance of ITO was R = 60 Ohm/cm. CuPc and

anthracene films were obtained by vacuum evaporation at a residual pressure of not more than 10-5

Pa. The anthracene films doesn't absorb light in the 450–780 nm region, that allows CuPc film

absorbed more sunlight. The total thickness of the films is of the order of 80–100 nm. The film

thickness is chosen to maximize generation and separation of charge carriers.

A thin film of aluminum deposited on the surface of the organic layered structure in vacuum.

Aluminum film thickness was less than 0.2 μm. Aluminum and ITO contact layers form a good

ohmic contact with the film and a good value for the electron work function. Current-voltage

characteristics and spectral dependence of photosensitivity was measured for the organic

heterostructure. Measurements were made under illumination heterostructure from the ITO. The

light source was a halogen lamp with the power of 50 mW/cm2. Measurements were performed in

the wavelength range 350–750 nm. Measurements were carried out in the photovoltaic mode at

room temperature.

The range of photovoltaic sensitivity has a broad structureless band in the range from 450 nm to

780 nm. The maximum photovoltaic sensitivity was at 590 nm. These maximum matches with the

maximum of the absorption spectrum of the CuPc film.

Spectral of photovoltaic sensitivity of the heterostructure allows to determine the photoprocesses

taking place in the sample. When light is absorbed by a CuPc layer electron is transferred to the

lower free molecular orbital of the molecule CuPc. Then anthracene is taken electron, which leads

to the formation of bound electron-hole pair. In this case PEDOT was a hole transport material with

good conductive properties. Carriers are localized in ITO after passing through the polymer layer.

Thus, we conclude that the center of the charge generation is excited molecule of CuPc.

Current-voltage characteristics of the heterostructure was determined under illumination by the ITO

(P = 50 mW/cm2). The current-voltage characteristic is nonlinear. From the current-voltage

characteristics were determined values of the open circuit voltage, short-circuit current density and

fill factor. The value of the power conversion efficiency of the heterostructure was determined by

the values of open circuit voltage, short-circuit current density and fill factor. The value of the

power conversion efficiency of the heterostructure was 0.6%.


140

PHOTONIC OF POLYPHENYLQUINOLINES –

OPTOELECTRONIC MATERIALS

WITH EFFICIENT INTRAMOLECULAR CHARGE TRANSFER

E.L. Aleksandrova1, V.M. Svetlichnyi

2, L.A. Miagkova

2, N.V. Matyushina

2,

T.N. Nekrasova2, R. Yu. Smyslov

2, A.R. Tameev

3

1 – A.F. Ioffe Physical–Technical Institute RAS, St. Petersburg, Russia



[email protected]

Multifunctional ambipolar materials (i.e., capable of bipolar charge transport) Polyphenylquinolines

(PPQs) of the general formula:

N

X

N Arn ,

containing between acceptor phenylquinoline moieties a bridging resorcinol (-R-), oxygen (-О-) or

phenylamino (-FА-) group Х and aromatic Ar fragment of carbazole (CAR) or indolo[3,2-

b]carbazole (ICZ), are the intramolecular charge-transfer complexes ((ICTC)). Due to the high

values of sensitivity and mobility of charge carriers and the presence of "white" luminescence, they

are of interest for optoelectronics as materials for light-emitting diodes, photovoltaic cells,

holography, etc.

In this paper we attempt with an analysis of the absorption spectra, quantum yield of

photogeneration of charge carriers and luminescence to clarify the nature of the charge-transfer to

determine which of the fragments of the monomer unit are the donor and acceptor fragments of

what ICTC and to determine the energy structure of newly synthesized compounds.

It is shown that the replacement (-R-), (-O-) or (-FA-) group at the bridge between the quinoline

cycle leads to an increase in the photophysical properties: the values of the quantum yield of

photogeneration of charge carriers η up to 5 times or more, and the integrated light sensitivity S of

more than one order of magnitude. Introduction to the arylene fragment Ar acceptor substituents

leads to an increase of S and η values in 2-3 times as compared with values for PPQs, containing

only the N-alkyl (octyl, dodecyl) fragments CAR8, CAR12 and ICZ fragments, as well as the

luminescence quenching in the case of N-nonafluorinediphenyl deputy and its complete

disappearance in the case of N-nitrophenyl deputy.

The results also show the possibility for carbazole containing PPQs, and especially for their

mixtures with intense luminescent PPQs containing diphenyl oxide (DPO) fragment in Ar to

achieve emission polymer films throughout the visible spectrum, i.e. "White". For the studied PPQs

were determined the energy gap (Eg) and showed that the characteristics have the greatest light-

sensitive ICZ-containing PPQs with FA bridge group with Eg = 2.3 eV. PPQs, which have high

charge carrier mobility (~ 10-5

cm2 / V∙s) when the "white" luminescence make them promising for

the creation of LED-based devices that are not inferior to the parameters of the dual polyICZ,

fluorene, and other organic materials used in such devices.

The study was supported by the Russian Foundation for Basic Research (project no. 10 03 00439 a).


141

OPTIMALITY OF INTERFACING OF B740 , B798 AND B808

SUBANTЕNNAE IN LIGHT-HARVESTING SUPERANTENNA

OF THE PHOTOSYNTHETIC GREEN BACTERIUM

CHLOROFLEXUS AURANTIACUS

Z.G. Fetisova, A.G. Yakovlev, A.S. Taisova, V.I. Novoderezhkin

M.V. Lomonosov State University, A.N. Belozersky Institute of Physico-Chemical Biology, Moscow, Russia

[email protected]

This work continues the series of our studies on the basic principles in the organization of natural

light-harvesting antennae, which we theoretically predicted for the optimal model light-harvesting

systems, initiated by our concept of the rigorous optimization of photosynthetic apparatus structure

by functional criteria [Fetisova Z.G., Fok M.V., 1984]. This work deals with the problem of the

structure optimization of Chloroflexus (Cf.) aurantiacus heterogeneous superantenna, consisting of

several uniform subantennae, which raises the problem of their optimal interfacing. Here we used

mathematical modeling of the functioning of this natural superantenna to consider possible

optimization of this process via optimizing the mutual spatial orientation of Qy transition dipole

moments vectors of the light-harvesting molecules in adjacent subantennae, namely, BChl c B740,

BChl a B798 and BChl a B808. Only the orientation of B798 BChl a dipoles is unknown. Our

model calculations for a single Cf.aurantiacus chlorosome have shown that the optimal mutual

orientation of B740, B798 and B808 dipoles leads to stable minimization of the time of excitation

energy transfer B740→ B798→B808, which is a criterion for optimization of the antenna

functioning. The predicted by us model of optimal orientation of BChl a dipoles in the baseplate

implies the B798 BChl a Qy transition dipoles, randomly distributed around the normal to the

baseplate, to form the angle φopt = 54°±3 with the plane of the baseplate. To examine this model,

absorption difference spectra of Cf. aurantiacus chlorosomes were measured on the fs- through ps-

time scales for the B798 BChl a Qy band upon direct excitation of the band at two different

temperatures, T = 293K and T = 90K. The anisotropy parameter value r was constant within the

B798 band at both temperatures and decayed from r = 0.4 (at 200 fs delay time) to r = 0.100 at T =

293K and to r = 0.094 at T=90K (at 100 ps delay time). The theoretical dependence of the steady

state anisotropy parameter r on the sought angle φ for the examined model was shown to be

described by the equation: r(φ)=0.1(3cosφ×cosφ–2)×(3cosφ×cosφ–2). According to this

dependence, the angle φ, corresponding to the experimental steady state value r = 0.1 , was found

to equal the angle φ = 54.7±0.05° at T = 293K. As the temperature drops from T = 293K to T = 90K

the angle φ slightly decreases to φ = 54.2 ± 0.05°. Thus, the findings are in complete agreement

with our theoretically predicted model of optimal orientation of B798 BChl a dipoles in

Cf.aurantiacus chlorosome, in which the BChl a Qy transition dipoles, randomly distributed around

the normal to the baseplate, form the angle φopt ≈ 54° with the subantenna plane, i.e., the angle φopt

≈ 36° with the normal to the plane.

The work was supported by the Russian Foundation for Basic Research (Grant 08-04-01587a).


142

ENERGY TRANSFER IN HYDROGEN-BONDED

DOPED POLYCRYSTALS OF BENZOIC ACID DERIVATIVES

V.P. Galkin, N.A. Klemesheva, D.A. Nosova, D.V. Mazyrin,

Y.A. Rozhkova, S.O. Vysotskaya, E.P. Zarochentseva


[email protected]

This work is concerned with the role of hydrogen bonds on luminescence properties of the benzoic

acid polycrystals doped N–phenylanthranilic (NPA) and niflumic acids (NA). Molecules of these

acids have slightly different energy levels. These differences of energy levels play role in energy

transfer in molecular crystals. Guest molecule concentration was 10-2

M/M.

Benzoic acid samples doped NA display intensive guest emission around 445 nm under excitation

in absorption band of the host (280 nm) and the guest (340 nm). Luminescence of host molecules

don’t occurs. Doped probe luminescence intensity three times more than luminescence intensity of

pure NA polycrystals and position of spectrum maximum blue shifted at 5 nm. Excitation spectrum

is superposition of excitation spectra of host and guest. Therefore one can see energy transfer from benzoic acid to niflumic acid.

Specimens doped NPA demonstrate luminescence spectrum represents superposition of the

luminescence spectra of benzoic acid and NPA. Under excitation in absorption band of the host

(260 nm) host luminescence intensity four times less than guest intensity. Guest luminescence

intensity five times more than luminescence intensity of pure NPA polycrystals. Under excitation in

absorption band of the guest (330 nm) guest luminescence intensity six times more than

luminescence intensity of pure NPA polycrystals. Position of spectrum maximum red shifted at 8

nm. We see energy transfer too. Excitation spectrum is overlap of host and guest excitation spectra .

It is known that NPA and NA in crystalline state are strong emitters because of intramolecular N-

H...

O and intermolecular O-H…

O hydrogen bonds [1]. Due to these hydrogen bonds the carboxylic

acids form dimers, which arrange J-type stacking aggregates. Aggregation-induced emission were

attributed to the restriction of intramolecular rotations, intramolecular planarization, inhibition of

photoisomerization and photocyclization and blockage of non-radiative pathways of the excited

species [2]. In our case more intensive luminescence of doped samples suppose that guest acid

molecules produce dimers with host acid molecules. These dimers form J-aggregates in which the

molecules are arranged head-to-tail. This structural feature increases the rigidity of the molecules by

restricting vibration and rotation of the acid groups and thus could improve the luminescence

quantum yield. Close packing of the molecules simplifies energy transfer from upper energy levels

of the host molecules to lower levels of the guest molecules.

References 1. Tianlei Zhou, Feng Li, Yan Fan, Weifeng Song, Xiaoyue Mu, Hongyu Zhang, Yue Wang, (2009)

Chem. Commun., 3199-3201.

2. Y. Ren, J.W.Y. Lam, Y.Q. Dong, B.Z. Tang, K.S. Wong, (2005), J. Phys. Chem. B, 109, 1135.


143

MANIFESTATION OF THE INERTIAL COMPONENT OF MEDIUM

RELAXATION IN KINETICS OF NONEQUILIBRIUM ELECTRON

TRANSFER IN RUTHENIUM(II)-COBALT(III) COMPOUNDS

A.O. Kichigina, A.I. Ivanov

Volgograd State University, Russia

[email protected]

Ultrafast photoinduced electron transfer is central to understanding fundamental chemical reaction

dynamics and natural and artificial light harvesting. A molecular level understanding of the coupled electron and nuclear dynamics following the absorption of a photon is crucial for our ability to control

charge transfer, charge separation, and charge recombination for efficient energy conversion

applications. From a fundamental perspective, studies of charge transfer processes are essential for developing a microscopic understanding of chemical reactions in solution. In the condensed phase,

multiple solute and solvent degrees of freedom intertwine to determine the efficacy of the electron

transfer process, making this a multidimensional problem spanning various length and time scales.

Dynamics of photoinduced electron transfer in II III 5+[(tpy)Ru (L-L)Co (tpy)]

(L-L: tpy-tpy (tpy = 2, 2 :6 , 2 terpyridine, tpy tpy = 6 ,6 bis (2 pyridyl) 2, 2 : 4 ,4 : 2 ,2

quarter - pyridyne), tpy-ph-tpy (tpy = 2,2 : 6 ,2 terpyridine, tpy ph tpy = 1, 4 bis [ 2, 2 :6 ,

2 terpyridine 4 yl] benzene)) complexes reported in papers [1] have been described in the framework of the stochastic point-transition model [2]. The model involves the medium and

intramolecular high frequency vibrations and the explicit description of the medium relaxation and has

allowed reproducing the low quantum yields of the charge separated state. The experimentally observed significant decrease of the product yield in more viscous solvents has been shown to be a direct

consequence of the hot transition efficiency increase. A weak opposite dependence, also revealed in

experiments, has been elucidated in terms of two time scales of the solvent relaxation. Solvent

relaxation is well-known to involve at least two stages: the inertial one (fast) and the diffusive one (slower) [3]. The solvent relaxation function can be well approximated by the equation

2 21 //

1

1

( ) ,k

Mtt

k

k

X t x e x e

where the first Gauss term describes the fastest relaxation, the sum of exponential functions corresponds

to slower diffusion relaxation, and M is the number of solvent relaxation modes. The possibility and

conditions of the replacement of the inertial by diffusion relaxation component were studied in the simulation of electronic transition kinetics in real solvents [4]. For the systems considered here the

difference between possibilities of hot electronic transitions for inertial and diffusion polar solvent

relaxation modes is insignificant. This allows the whole relaxation process to be described in terms of

several diffusive modes.

So, the model considered in this paper has allowed reproducing the experimental data of forward and

backward electron transfer kinetics, including the low yield of electron transfer products and its variation with solvent. When hot transitions are terminated at the stage of the inertial relaxation, the

yield of the electron transfer products is nearly independent of the diffusive timescale; otherwise a

strong increase of the yield in more viscous solvents should be observed.

This work was financially supported by the Ministry of Education and Science of Russian Federation (state contract nos. 14.740.11.037).

1. Torieda H., Nozaki K., Yoshimura A., Ohno T. // J. Phys. Chem. A. 2004. V.108. P.4819.

2. Feskov S.V., Kichigina A.O., Ivanov A.I. // Phys. Chem. A. 2011. V. 115. P. 1462. 3. Horng M.L., Gardecki J.A., Papazyan A., Maroncelli M. // J. Phys. Chem. 1995. V. 99. P. 17311. 4. Kichigina A.O., Ivanov A.I. // Russian Journal of Physical Chemistry B. 6. В.31. № 2. С. 175.


144

EXCIPLEX ELECTROLUMINESCENCE SPECTRA

IN THE NEW ZINC COMPLEXES WITH

SULPHANYLAMINOSUBSTITUTED BENZOTHIAZOLES

AND QUINOLINES

S.S. Krasnikova, M.G. Kaplunov, I.K. Yakushchenko


[email protected]

We found that for the new electoluminescent materials based on the zinc complexes with

sulphanylaminosubstituted benzothiazoles and quinolines, the electroluminescence (EL) spectra can

significantly differ from their photoluminescence (PL) spectra [1,2]. EL was observed for the

layered structures which contain the organic hole-transporting layer of triaryl derivative (PTA,

NPD) and the luminescent layer of one of the studied complexes. Typical spectra are shown in the

figure for the zinc complex of phenylsulphanylamino substituted 2-phenyl-benzothiazole Zn(PSA-

BTZ)2 for the structure ITO/PTA/NPD/Zn(PSA-BTZ)2/Al:Ca. The EL spectrum (curve 1) exhibit

two bands: comparatively narrow band in the region of 450 nm and wide band in the region of 550-

600 nm.

The 450 nm band is present also in the PL spectrum

of Zn(PSA-BTZ)2 powder (curve 2) and can be

attributed to the intrinsic electronic transitions in the

zinc complex molecule. The 550-600 nm bands may

be due to the formation of exciplex between excited

states of the molecules of hole-transporting and

luminescent materials at the interface of the two

layers. The exciplex band in the EL spectra can be

eliminated by introducing the additional layer

between the hole transporting and the luminescent

layers (curve 3 – the EL spectrum of the structure

ITO/PTA/NPD/CBP/Zn(PSA-BTZ)2/Al:Ca).

1. S. S. Krasnikova, M. G. Kaplunov, and I. K. Yakushchenko // High Energy Chemistry, 2009, 43,

536-539.

2. M. G. Kaplunov, S. S. Krasnikova, I.O.Balashova, I. K. Yakushchenko // Mol. Cryst. Liq. Cryst.,

2011, 535, 212–219.

400 450 500 550 600 650 7000,0

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0,4

0,6

0,8

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145

EFFICIENCY OF THE ENERGY TRANSFER IN THE STRUCTURES

BASED ON QUANTUM DOTS CDSE/ZNS AND THE PORPHYRIN

MOLECULES IN THE POLYMER PORE TRACK MEMBRANES

M.A. Kurochkina1, A.O. Orlova

1, V.G. Maslov

1, A.V. Baranov

1, M.V. Artemyev

2


2 – Institute of Physics-Chemical Problems, Belarusian State University, Minsk, Belarus

[email protected]

Today intensive researches are underway for developing supramolecular structures based on organic

molecules and inorganic nanoparticles. In such structures it is possible to combine the unique optical, electrical and magnetic properties of inorganic particles with functional properties of molecules. As

inorganic particles the semiconductor quantum dots (QDs) can be used in such structures. Owing to

their optical properties, such as the dependence of the spectral characteristics on the particle sizes, an

extended range of absorption, high quantum yield of luminescence, QD can be used as an effective energy donor. In the structures including QDs and molecules it is possible to create conditions under

which the energy transfer from QDs to the molecule will lead to improved functional properties of the

molecule. In particular, there is a large class of organic compounds – tetrapyrroles, which are

characterized by a high quantum yield of singlet oxygen generation. Creation of structures involving tetrapyrrole molecules and QDs may lead to a marked increase of the efficiency of

generation of singlet oxygen by tetrapyrrole molecules due to the photoexcitation energy transfer from

the QDs to the molecules. Developing the structures with QDs and tetrapyrrole molecules without the formation of complexes is possible with the use of polymer track membranes.

In this paper we have investigated the photophysical properties of structures with the

hydrophobic semiconductor quantum dots CdSe / ZnS and molecules of tetra(p-trimethylamine) phenylporphin (TAPP) embedded in poly(ethylene terephthalate) track membranes (PET TM). In the

process of formation of PET TM the carboxyl groups are formed on the inner surface of the pores. This

leads to the appearance of uncompensated negative charge on the inner surface of the pores and in the

region adjacent to the inner surface of the pores. Therefore, when impregnating track membranes by an aqueous solution of TAPP, the binding of molecules to TAPP with dissociated carboxyl groups takes

place in the PET membrane due to the electrostatic interaction.

The conducted investigation of photophysical properties of the samples of track membranes with

embedded hybrid structures based on quantum dots and porphyrin molecules has shown that a consistent

increase of the concentration of porphyrin molecules in the samples of membranes with embedded QDs

leads to a significant decrease of the intensity of the luminescence and the reduction of the decay time of the luminescence of nanocrystals. The combination of these data indicates that in the track membranes

the efficient long-range resonance energy transfer of the photoexcitation (FRET, Förster Resonant

Energy Transfer) from the quantum dots to TAPP molecules is observed. It was found that changing

the QD core diameter from 2.5 nm to 5.0 nm leads to a noticeable change of the experimental efficiency of energy transfer from QDs to porphyrin molecules. So, the maximum efficiency of energy transfer for

the structures with QDs with a diameter of 2.5 nm core was 50%, whereas for QDs 3.5 nm and 5.0nm,

it was 41% and 31% respectively. Such a dependence of the efficiency of energy transfer is consistent with the values of the spectral overlap integrals for the corresponding donor-acceptor pair. An

effective energy transfer from QDs to porphyrin molecules leads to a 40% increase of the intensity of

the porphyrin molecules’ luminescence. It should be noted that as the result of the introduction of the

TAPP molecules in the track membrane the quantum yield of luminescence does not change. The combination of these data implies the real increase of the intensity of the porphyrin molecules’

luminescence in comparison to their free form in aqueous solution.


146

0

100

200

300

400

500

600

700

1 10 19 28 37 46 55 64 t,s

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A

1

2

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100

200

300

400

500

600

700

1 9 17 25 33 41 49 57 65t,s

I,н

А

1

2

3

THE NONEQUILIBRIUM ELECTRON PROCESSES

IN THE PYROLYTIC CDS FILMS

T.L. Maiorova1, V.G. Klyuev

2, A.A. Mihalevskiy

2, J.S. Bezdetko

2

1 – Voronezh State Academy of Forestry Engineering, Russia

2 – Voronezh State University, Russia

[email protected]

Recently the investigation of properties of the filmative semiconductive CdS structures pays

attention in connection with opportunity of their wide application in the different area of the modern technique.

Early we have shown that the pyrolitic CdS films have got the row of interesting

photoluminescence and photoelectrical properties [1]. It is worth noticing that such structures have

been prepared by enough simple and economical method – the pyrolize method. At present this

method allows to control the contain and the defect structure of the deposition films and to get films with grain size order of 10

1 – 10

2 nm[2].

This work is dedicated to the investigation of the behavior of the nonequilibrium current carriers in

the pyrolitic CdS films both pure and alloyed by alkaline metals. So the measurements of current

have been carried out during the excitation and after its switch off. The samples was illuminated by

the light diode with λ=465 nm and J= 0.72 cd. At that the voltage in the samples was 3 V.

Fig. 1. The dependence of the current on time a) during the excitation, and b) after excitation switch off for CdS – 1, CdS:Li – 2, CdS:Na – 3.

The increase of the photoexcitation conductivity of CdS films has been observed at the alloying

them by alkaline metals. In addition, the photoexcitation conductivity kinetic has got the row of the

features. For the alloyed samples the excitation curves of the conductivity are slow threshold-shape

or in same case S-shape (fig.1a). The relaxation curves of the photoexcitation conductivity have a complete nonexponentional character (fig 1b).

The such features of the photoexcitation conductivity kinetics in the pyrolitic CdS films indicate the

substantial role of the captures centers with different deep and captures section for the

nonequilibrium electron processes in the investigation structures. Also so long photocurrent

relaxation may be due to the presence of the biographical recombination barriers, which arise between areas of the different own conductivity.

1. Maiorova T.L., Klyuev V.G. Physics and technique of semiconductors, V. 43, № 3, 2009, p.

311-315 (in Russia)

2. Samofalova T.V., Semenov V.N., Naumov A.V., Choviv A.M., Charin A.N., Lebedeva T.S.

V. 13, №4, 2011, p. 504-509 (in Russia)


147

DECREASE OF INTER-MOLECULAR ENERGY LOSSES

IN SOLUTIONS OF LANTHANIDE COMPLEXES

S.B. Meshkova, A.V. Kiriyak, Z.M. Topilova, P.G. Doga

A.V. Bogatsky Physico-Chemical Institute NAS, Odessa, Ukraine

[email protected]

Unremitting interest to compounds of lanthanides (Ln) is related to its peculiar characteristics and

photophysical properties. Because of these characteristics Ln(III) ions are widely used in dedicated

fields such as telecommunications, lasers, photovoltaics (solar-energy conversion), lighting

(fluorescent lamps and OLEDs), luminescent probes for bio-analyses, ets. For the synthesis of Ln

(III) organometallic compounds uses the reagents of different classes: beta-diketones,

acylpyrazolones, cyclic carboxylic acids, other. However the nonradiative intra- and inter-molecular

energy losses limit an observation possibility of their intensive luminescence. On the example of

complexes of Tb(III) with pyrazolones-5 and pyrazol-5-carboxylic acids it was shown [1], that

inter-molecular energy losses, conditioned diffusion in solutions, exceed more on an order the intra-

molecular energy losses, caused the high-frequency vibrations of OH-groups of water molecules,

included in the internal coordinating sphere of complex, and also N–H, C–H and non-connected

OH–groups of ligand. The role of diffusion in the processes of energy transfer in liquid solutions is

considered in works of V.L. Ermolaev with collaborates [2], and connection of it with viscosity of

solutions is mentioned in [3].

A purpose of work is research of influence of viscous environments of water-soluble polymers

(WSP) on luminescence intensity of Eu(III) and Tb(III)complexes in a row: water solution of

complex → a complex in solution of WSP → a complex in film of WSP.

Water solutions of WSP are used: polyvinyl alcohol (PVA), methylcellulose (MC), ksantane gum

(KG), poly(vinylpyrrolidone) (PVP), poly(vinylcaprolaktame) (PVCL). In solutions and films of

these WSP entered solutions of complex compounds of Eu(III) and Tb(III) with the organic

reagents of different classes. As molecules of WSP are contained by functional groups (–OH,

=C=O, –COOH), with them additional coordination of ions of Ln(III) is possible. Thus the even

distribution of complex in viscous solution and film of WSP will provide the decrease of diffusion,

inter-molecular energy losses and, respectively, increase of luminescence intensity.

Experimentally established that luminescence intensity of beta-diketonates, amino- and

oxibenzoates, pyridinkarboxylates, other complex compounds of Ln(III) in solutions of WSP

increased to 10 times, and in films of WSP (at that mass of complex) – on 2-3 orders of size.

Literature

1. V.L. Ermolaev, E.N. Bodunov, E.B. Sveshnikova and T.A. Shahverdov. Nonradiative energy

transfer of electronic excitation. Nauka, 1977. 311 p.

2. S.B. Меshkova, А.V. Кiriyak, Z.M. Topilova, V.P. Gorodnyuk. Opt. and spectr (Russ). – 2006. –

V. 100, № 6. – P. 908-912.

3. G.G. Guilbault. Practical fluorescence: Theory, Methods and Techniques. Marcel Dekker, INC.,

N.Y. 1973, 664 p.


148

ZINC COMPLEXES WITH SULFANILAMINOSUBSTITUTED LIGANDS:

ELECTROLUMINESCENCE AND PHOTOSENSITIVITY

S.L. Nikitenko, M.G. Kaplunov


[email protected]

Organic light-emitting diodes (OLED) are promising as energy-efficient sources of illumination. So

the interest to the subject in scientific publications in the world is still very high.

Light-emitting diode based on organic materials is a multi-layered thin-film (thickness of each layer

is a few tens of nanometers) heterostructure, containing various organic and inorganic materials.

Schematic diagram of a typical organic electroluminescent device, used in our work, and the

structure of zinc complexes with sulfanilaminosubstituted ligands, which we used as materials for a light-emitting layers are shown in Figure 1.

Figure 1. The scheme of electroluminescent devices and structural formulae of zinc complexes

with sulfanilaminosubstituted ligands. (a - Zn(TSA-BTZ)2 b - Zn(POPS-BTZ)2)

This new class of metal complexes is suitable for the manufacture of OLEDs. And the metal

complexes possesses interesting properties, in particular, an unusual spectra of radiation in

electroluminescent devices with some hole-transporting materials arise due to formation of

exciplexes, which allows the LEDs to produce color characteristics similar to the white, although the complexes emit in the blue region.

We found that the material of the hole-transporting layer is crucial for the formation of exciplexes.

Triarilamine derivatives apparently are the most suitable material for the formation of exciplexes

with the complexes. Also we found that the exciplex bands in the spectra of electroluminescence

disappear if there are no amino groups in the hole-transporting material (for example CBP on

Fig.2).

PTA (n=8-9)

α-NPD

CBP Figure 2. Electroluminescence spectra and current-voltage characteristics under illumination AM1.5

(100 mW/cm2) of devices based on the Zn(TSA-BTZ)2 complex with different hole-transporting layers and the structural formulas of the materials of the hole-transporting layers.

We also found that the electroluminescent structures based on the complexes exhibit double

function properties – electroluminescence, and photovoltaic properties. The photosensitivity is

influenced by formation of exciplexes. The photocurrent density in systems with exciplexes is much

higher (see Fig.2).


149

PHOTOLUMINESCENT PROPERTIES OF BLENDS

OF COPOLYFLUORENES CONTAINING BENZTHIADIAZOLE,

NAPHTHALIMIDE, AND NILE RED FRAGMENTS

G.I. Nosova, R. Yu. Smyslov, E.V. Zhukova, N.A. Solovskaya, I.A. Berezin, A.V. Yakimansky

Institute of Macromolecular Compounds RAS, St. Petersburg, Russia

[email protected]

Structural tuning of conjugated polymers makes it possible to create materials with new optical and

electric properties, meeting the requirements of optoelectronics, in particular, for manufacturing

efficient white-light emitting diodes. One of the ways to achieve this goal is to design and

synthesize conjugated polymers, containing simultaneously blue, green, and red luminophores and possessing high charge-transport characteristics.

In the present work, new polyfluorenes (PF) (blue emitter), containing both electron-donor

carbazole and electron-acceptor 2,1,3-benzthiadiazole (green emitter) fragments in the backbone

and Nile Red (red emitter) or naphthalimide (green emitter) moieties – in side chains, were

synthesized via Suzuki polycondensation reactions. Studies of photoluminescent (PL) properties of

co-PF films of different compositions showed a virtually complete quenching of blue emission of

the PF backbone by 2,1,3-benzthiadiazole green luminophore fragments, resulting in green or

yellow-green glow of co-PF films in most cases. Introduction of naphthalimide green luminophore

fragments into side chains of co-PF instead of 2,1,3-benzthiadiazole comonomer in the backbone led to a partial but not sufficient retention of blue emission of the PF backbone.

In order to overcome this problem, two methods of preparation of co-PF blends were used, aiming at the tuning the system for white-light emission.

According to the first method, co-PF, containing simultaneously all luminophores, was diluted with

the pure PF and composite films obtained from these blends were annealed at 85°C. PL spectra of

the films showed an enhanced blue band of PF, and CIE coordinates (0.3009; 0.3845) of the emitted light were achieved.

Within the second approach, two co-PF, one doped with a green luminophore (2,1,3-thiadiazole or

naphthalimide) and the other doped with the red luminophore (Nile Red), were both blended with

the matrix co-PF, containing hole-transporting 2,7-carbazole-diyl comonomer units. In these blends,

the content of the red luminophore was varied at a constant content of the green luminophore. The

composite films obtained from the blends were annealed at 80, 100, and 115°С. After the annealing,

an increase in the blue emission band was observed in PL spectra. Mixing the polymers of the same

nature made it possible to obtain uniform blends without a phase separation of the components. It is

assumed that the film annealing above the co-PF softening temperatures may result to formation of nanoaggregates or nanocrystallites, enhancing the blue emission component.

During further investigations, an optimization of the co-PF compositions, temperature and time of

the annealing will be performed. Electron-transporting properties of the polymers will be improved

due to end-capping with electron-acceptor fragments or the use of an electron-acceptor water-soluble coating.

This work is supported by the Scientific Program “Multifunctional materials for molecular

electronics” of the Presidium of the Russian Academy of Sciences (coordinator – academician S. M.

Aldoshin) and by Ministry of Education and Science of the Russian Federation in the framework of

the Federal Targeted Program “Investigation on prioritized directions of development of the

scientific and technological complex of Russia for 2007-2012” (State contract no. 16.516.11.6072).


150

PRINCIPLES OF CONTROL OF MOLECULAR SWITCHES

OF "ON1-ON2-OFF" TYPE

M.V. Rogozina, V.A. Mikhailova, A.I. Ivanov

Volgograd State University, Russia [email protected]

Modern femtosecond laser technology allows studying the dynamics of molecules in real time.

Recently, the researches of the dynamics of electron transfer from higher excited states were

reported [1, 2]. These researches form the foundation for the creation of element base of molecular

optoelectronics. Only recently, molecular switches that represent the triads including a molecule of

zinc−porphyrin and two acceptors covalently bound to it, located on opposite sides of the porphyrin

ring have been synthesized and investigated [1]. The parameters of triads were selected so that the

second 2S and the first 1S excited states were quenched by electron transfer on different acceptors

[1]. This opens the possibility of control of an electron transfer direction by variation of wavelength

of exciting impulses so that one of the acceptors is occupied that allows creating a molecular

switch of "on1-on2-off" character.

Unfortunately, the synthesized molecular triads have relatively low selectivity due to the ultrafast

hot charge recombination (CR). To ensure efficient operation of molecular switches, one should

solve the problem of the suppression of the hot charge recombination to the first excited state of Zn-

porphyrins, which is the main reason for the low yield of thermalized charge separated (CS) state.

Our investigations of the influence of different parameters of electron transfer reactions on the

kinetics of charge separation from the second excited state and the following CR into the first

excited state in Zn−porphyrin derivatives allowed formulating the recommendations for the

development of molecular switches with given dynamic properties [3, 4].

Controlling hot recombination by variation of the solvent properties.

To reduce the efficiency of hot recombination one should use: less viscous solvents, which have the

lowest dielectric relaxation time, with minimal solvent reorganization energy, i.e. solvents with low polarity.

Controlling hot recombination by variation of the energy parameters of the triad.

To reduce the efficiency of hot recombination one needs to select triad with a minimum energy gap

between the states 2S and S1; with the maximum value of the energy gap –ΔGCS; the electronic

matrix element of the transition CS→ S1 should be much smaller than that for 2S →CS.

A cardinal solution to the problem could be associated with a design of molecular compounds in

which imide acceptors are not used, because in all known Zn-porphyrin compounds covalently

linked to various imides, electronic transition matrix elements CSV and

CRV are almost the same.

Kinetics of processes considered are described in terms of the stochastic model that includes three

electronic states (the first and second singlet excited and the charge separated state), as well as their

vibrational sublevels [5]. This model is right for the problem that was validated in many ultrafast charge transfer processes [6].

This work was supported by the Ministry of education and science of the Russian Federation (contract 14.740.11.0374) and the Russian foundation for basic research (Grant No. 11- 03-00736).

Literature: [1] Wallin S., Monnereau C., Blart E. et al. // J. Phys. Chem. A. 2010. V. 114. P. 1709. [2] Mataga N., Shibata Y., Chosrowjan H. et al. // J. Phys. Chem. B. 2000. V. 104. P. 4001. [3] Rogozina M.V., Ionkin V.N., Ivanov A.I. // J. Phys. Chem. A. 2012. V. 116. P. 1159. [4] Rogozina M.V., Ionkin V.N., Ivanov A.I. // Russ. J. Phys. Chem. A. 2012. V. 86. P. 667. [5] Ionkin V.N., Ivanov A.I. // J. Phys. Chem. A. 2009. V. 113. P. 103. [6] Ivanov A.I., Mikhailova V.A. // Russ. Chem. Rev. 2010. V. 79. P. 1047.


151

THE INFLUENCE OF WATER ON PRIMARY CHARGE SEPARATION

IN BACTERIAL REACTION CENTERS

A.G. Yakovlev1, A.Ya. Shkuropatov

2, V.A. Shuvalov

2

1 – M.V. Lomonosov State University, A.N. Belozersky Institute of Physico-Chemical Biology, Moscow, Russia

2 – Institute of Basic Biological Problems RAS, Pushchino, Russia

[email protected]

The influence of the crystallographic water on electron transfer between primary electron donor P

and acceptor BA was studied in reaction centers (RCs) of the purple bacterium Rhodobacter

sphaeroides and the green bacterium Chloroflexus aurantiacus. Charge separation kinetics

measured with 20-fsec resolution are compared between dry film RCs and RCs in glycerol–water

buffer at 90 K. A result of the drying of the RCs is slowing of the charge separation process,

decrease in amplitude of the oscillatory components of the kinetics, and the rarefaction of its

spectrum. The time constant of stimulated emission decay of P* is increased from 1.1 psec for

water-containing Rba. sphaeroides RCs to 1.9 psec for dry films of these RCs (from 3.5 to 4.2 psec

in Cfx. aurantiacus RCs). In dry films of Rba. sphaeroides RCs, the amplitude of coherent

oscillations of the absorption band of BA– at 1020 nm is 1.8 times less for the 130-cm

–1 component

and 2.3 times less for the 32-cm–1

component than the analogous amplitudes for water-containing

RCs. Measurements in the Cfx. aurantiacus RCs reveal ~5-10 times decrease of the BA– absorption

band and ~4 times slowing of BA– accumulation together with ~3-fold decrease in oscillation

amplitude on drying of these RCs. The overtones of the 32-cm–1

component disappeared from the

oscillations of the kinetics after drying of the RCs. The results are in agreement with the results for

GM203L mutant of Rba. sphaeroides in which the HOH55 water molecule is sterically removed

(Yakovlev, A. G., et. al. (2005) Chem. Phys., 319, 297-307) and with the results for dry films of

pheophytin-modified RCs of Rba. sphaeroides R-26 and for YM210W and YM210L Rba.

sphaeroides mutant RCs (Yakovlev, A. G., et. al. (2003) J. Phys. Chem. A, 107, 8330-8338). The

data are discussed in terms of the influence (or participation) of the HOH55 water molecule on

electron transfer along the chain of polar atomic groups N–Mg(PB) –N–C–N(HisM202) –HOH55–

O=(BA) connecting PB and BA in Rba. sphaeroides RCs.

Posters Gas-phase photoprocesses -------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------

152

SECTION 3. GAS-PHASE PHOTOPROCESSES

HBR PHOTODISSOCIATION ANALYSIS AS THE CALIBRATION

OF TWO-COLOR 3D VELOCITY MAP IMAGING SETUP

M.S. Poretskiy, M. Veckenstedt, H.C. Maul, K.-H. Gericke

Technische Universität Braunschweig, Deutschland

[email protected]

Imaging experiments in chemical dynamics provide dynamical information about elementary

chemical processes, e.g. whether a reaction product is translationally or internally excited, what is

the nature of the internal excitation, and whether or not the spatial product distribution is

anisotropic. In many experiments two lasers system have to be used. But in this case the problem of

the overlap of laser beams in space has to be considered. To solve this problem the HBr

photodissociation can be analyzed:

HBr + hν → H + Br (2PJ)

In a one color experiment HBr is photolyzed at a wavelength of 243.12 nm, which is also used for

[2+1]-REMPI of resulting H-atoms. The dye laser was scanned over the REMPI-transition in order

to eliminate any bias in the detection from the Doppler effect. The distribution of the velocity vector

of H atoms emerging from photodissociation of HBr is presented by two concentric spheres, which

correspond to two channels of measured H atoms, which are different due to the spin orbit state of the bromine partner fragment i.e. Br(

2P3/2) and Br(

2P1/2).

In two color experiment the fact that HBr can be photolyzed both at the REMPI detection

wavelength 243.12 nm and at 193 nm (produced by an ArF excimer laser) was used. The H atoms

produced by both wavelengths are subsequently ionized only by 243.12 nm radiation. As a result

two new channels of H+ are observed in the H atoms velocity distribution by new spheres, sensitive

to the position of the excimer laser beam. The position of the excimer laser beam is changed until it

is overlapped with the beam of dye laser (243.12 nm). In case of the overlap of both laser beams in

space the spheres, which appears in two color experiment have to be concentric with these from the

one color experiment.

Posters Gas-phase photoprocesses -------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------

153

INVESTIGATION OF SUPEREXCITED STATES

OF ORTHO-PARA DEUTERIUM MOLECULES

IN THE WAVELENGTH REGION FROM 70.8 TO 71.35 NM

A.G. Smolin1, Y. Mo

2, O.S. Vasyutinskii

1

1 – A.F. Ioffe Physical-Technical Institute RAS, St. Petersburg, Russia

2 – Department of Physics, Tsinghua University, Beijing, China

[email protected]

As the simplest neutral molecule deuterium and hydrogen plays an important role as a testing

ground for fundamental quantum theory calculations. The molecular deuterium provides

information on massdependent effects in the molecular level structure. Furthermore, the deuterium

has a number of scientific and commercial uses. In particularly, the deuterium is used as non-

radioactive, stable isotopic tracer in chemistry, biochemistry and environmental sciences. The

study of photon-induced ion-pair formation provides information on the dynamics of molecular

dissociation. The deuterium molecules can be excited into superexcited states by ionizing radiation

that can result in ionization or dissociation of these superexcited states into various fragments. Such

superexcited molecules play important roles in radiation physics and chemistry as well as in various molecular processes which are important in related scientific fields and astrophysical studies.

The present work reports the photoionization efficiency curve for ion-pair formation from ortho-

para D2 at supersonic molecular beam experiment taken at a wavelength resolution of 0.00027 A,

approximately a factor of 50 improvement over the previous measurements [1]. Our experimental

and theoretical studies have been carried out on the one-photon photoionization of high Rydberg

states of D2 molecules in the wavelength region from 70.8 to 71.35 nm. High resolution VUV

(vacuum ultra violet) laser in combination with the velocity map imaging method [2, 3] provides us

with a new tool to study the very details of the spectroscopy and the dynamics of the molecular

superexcited states. The coherent VUV radiation was generated by using resonance-enhanced four-

wave sum mixing in a pulsed Kr jet and the monochromonator chamber, which is equipped a gold

coated toroidal grating. The temperature of the supersonic-cooled D2 beam was less than 10 K

which guarantees that the ortho-para D2 molecules were in rotational ground state. Spectra were

obtained by monitoring the negative ion D^- signal as a function of the wave number. It was

pointed out previously [1] that ion-pair formation results almost exclusively from predissociating

Rydberg states of the parent molecule H2 and D2 rather than from direct dissociation. In our

experiment the Rydberg state assignments were made for ortho-para-D2, based on the results of an

analysis using multichannel quantum defect theory. Possible photolysis channels have been

investigated and important information on the photolysis mechanism has been obtained. In the case

of ortho-D2, the np_0,2 Rydberg series have been investigated for the transition between ortho-D2

ground state X (v=0, N=0) and Rydberg state belonging to a series converging on the X^+ (v+,

N+=0,2) level of ortho-D2^+. In the case of para-D2, the np_1,3 Rydberg series have been

investigated for the transition between para-D2 ground state X (v=0, N=1) and Rydberg state

belonging to a series converging on the X^+ (v+, N+=1,3) level of para-D2^+.

[1] W.A. Chupka, P.M. Dehmer, W.T. Jivery // J. Chem. Phys. V. 63, p. 3929, 1975

[2] Y.S. Hao, C. Zhou, and Y.X. Mo // J. Phys. Chem. A, v. 109, p. 5832, 2005

[3] Y.S. Hao, C. Zhou, and Y.X. Mo // J. Phys. Chem. A, v. 111, p. 10887, 2007

Posters Photochemical processes in heterogeneous systems and heterogeneous photocatalysis -------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------

154

SECTION 4. PHOTOCHEMICAL PROCESSES IN HETEROGENEOUS

SYSTEMS AND HETEROGENEOUS PHOTOCATALYSIS

PHOTOPHYSICAL AND PHOTOCHEMICAL PROPERTIES

OF COVALENT CONJUGATES OF AQUA PLATINUM (II)

AND OCTACARBOXY-SUBSTITUTED ZINC PHTHALOCYANINE

R.A. Bulgakov1, N.A. Kuznetsova

1, O.V. Dolotova

1, O.L. Kaliya

1, T. Nyokong

2

1 – “Niopik” Organic Intermediates and Dyes Institute, Moscow, Russia

2 – Department of Chemistry, Rhodes University, South Africa

[email protected]

Photophysical and photochemical properties of new covalent conjugates of aqua platinum (II) and

octacarboxy-substituted zinc phthalocyanine, bearing one, two, three and four aqua platinum

fragments, were evaluated in DMSO solutions, where they showed monomeric behaviour evidenced

by a single narrow Q band. In DMSO, four conjugates and unconjugated octacarboxy-substituted

zinc phthalocyanine have similar electronic absorption and fluorescence spectra as well as

fluorescence lifetimes. Hence, electronic structure of octacarboxy-substituted zinc phthalocyanine

remains practically unchanged by aqua platinum coordination on periphery. Investigation of excited

triplet state properties also showed that aqua platinum moieties on the zinc

octacarboxyphthalocyanine periphery have low effect on the dynamics of excited states – quantum

yields of excited triplet state and singlet oxygen generation. The photostability of parent zinc

octacarboxyphthalocyanine and conjugates in aerated DMSO is rather high (photobleaching

quantum yields are in the range (1.8–2.3)∙10-6

). The conjugates were found to possess high ability to

sensitize the singlet oxygen formation (quantum yields ΦΔ 0.51–0.62) and thus show potential as

sensitizers for PDT. The low effect of aqua platinum fragments on photophysical and

photochemical properties of conjugates will be discussed.

Acknowledgements

This work was supported by Russian Foundation for Basic research (project No. 11-03-93960

UARa), by the Department of Science and Technology (DST) and National Research Foundation

(NRF), South Africa through DST/NRF South African Research Chairs Initiative for Professor of

Medicinal Chemistry and Nanotechnology as well as Rhodes University.


155

PHOTOSORPTION OF OXYGEN AND HYDROGEN

ON THE SAMPLES OF MAGNESIA OBTAINED IN DIFFERENT WAYS

I.A. Ekimova1, T.S. Minakova

1, V.K. Ryabchuk

2

1 – Tomsk State National Research University, Russia

2 – Saint-Petersburg National Research University, St. Petersburg, Russia

[email protected]

Photosorption of oxygen and hydrogen on the samples of magnesia (№1 − №4 in table 1) that differ

in the ways of obtaining, the values of specific surface area (52–155 m2/g), acid-base properties [1]

and adsorptive capability in relation to water vapour [2], were investigated in this paper. It was

shown on the basis of photosorption investigation that photosorption on all the samples of MgO had

an irreversible character at room temperature; while irreversibility was revealed at 373 K and it

reached 100 % at 573 K. The separation of photosorbed molecules of O2 and partially H2 occurs in

the same temperature interval. For all the samples of MgO in relation to the photosorption of О2 and

Н2 the effect of “memory” to preliminary irradiation at room temperature (before gas affluxion) is

observed. In the course of increasing irradiation temperature, this effect becomes less and finally

disappears at temperatures higher than 333 K. The increased photosorption capability of MgO in

relation to О2 was educed. The diagrams of initial rate of photosorption dependency from pressure

were constructed and quantitative features were counted on the basis of photosorption barograms.

The analysis of the experimental and estimated data obtained in the experiment showed the

difference in photosorption activity in relation to acceptor (О2) and donative (Н2) gases in samples

of MgO which were obtained in different ways, i.e. the decrease of О2 photosorption in the line of

МgО №1 >МgО №4 >МgО №2 and the increase of Н2 photosorption were observed. The reduction

of sample МgО №2 photosorption activity in relation to oxygen was caused by the presence of the

amorphous phase in its structure. While comparing the values which characterize acid-base

properties of the surface with photosorption parameters (table 1) the following dependence was

found: the lower the basicity of MgO surface, the higher the photosorption activity in relation to О2

and the lower this activity in relation to Н2.

Table 1 – The parameters which characterize acid-base and photosorption properties of magnesia samples surface, obtained in different ways.

Oxide

МgО№1

(from МgСО3)

МgО №2 (from

(МgОН)2СО3 with m. r. МgСО3/Мg(ОН)2=3.89)

МgО №3 (from

(МgОН)2СО3 with m. r. МgСО3/Мg(ОН)2=1.74)

МgО №4

(from МgSО4)

рНiis 10.2 10.9 10.8 10.5

τ, sec (О2) 0.72∙10-3 0.76∙10-3 1.33∙10-3 1.65∙10-3

τ, sec (Н2) 0.42∙10-3 0.58∙10-3 0.25∙10-3 0.25∙10-3

Vмах, Pa/sec (Р = 1 Pa О2) 0.124 0.034 – 0.074

Vмах, Pa/sec (Р = 1 Ра Н2) 0.002 0.006 – 0.004

∆Р∞(О2), Pa 7 5 – 6

∆Р∞(Н2), Pa 2 3 – 3

Note: рНiis – рН of isoionic state; τ – time of active centers living; Vмах – maximum rate of photosorption; ∆Р∞ – photosorption capacity.

Literature 1. The investigation of alkaline-earth metals oxides and fluorides surface properties / I. А. Ekimova, Т. S.

Minakova, V.V. Kozik, R.V. Osvald, V.V. Shagalov // Polzunovsky vestnik. – 2009. № 3. P. 256–258.

2. Ekimova I. A. Adsorption of water vapours on oxides and fluorides of magnesium, strontium, calcium and barium. / I.A. Ekimova, T.S. Minakova, E.A. Lyapina // Materials of XIV All-Russian symposium with participation of foreign scientists “Actual problems of adsorption theory, porosity and adsorption

selectivity”. – Moscow ; Klyazma, 2010. P. 191.


156

SYNCHRONIZATION OF PHOTOCHEMICAL PROCESSES

AND PHOTOINDUCED SELF-ORGANIZATION

IN DISPERSED SEMICONDUCTORS UNDER OPTICAL PUMPING

O.V. Gradov, M.A. Gradova

N.N. Semenov Institute of Chemical Physics RAS, Moscow, Russia

[email protected]

To date photoinduced oscillatory processes in a nonlinear medium [1], methods of laser ablation

and laser modification [2] and optical pumping of nonlinear media (including semiconductors) [3]

are rather common. These methods lead to either phase separation and formation of products of

nonspecific thermal effect under irradiation, or initiate photoinduced self-oscillatory processes in

active medium without stable structure formation, or provide optical pumping of the medium

followed by radiative energy dissipation.

We propose to combine the course of several photoinduced processes in one system: photo-induced

self-organization in semiconductors, accompanied by self-oscillations due to generation-

recombination processes, self-oscillatory photochemical processes, which occur according to the

potential gradient, caused by autowave processes in a semiconductor, and a number of

physicochemical processes, initiated by optical pumping and leading to spectrally nonspecific

excitation of a dispersed semiconductor precursor. This approach requires photoinitiation of

generation-recombination processes in semiconductor medium, described by the brusselator model

[4], where the function of charge carriers is performed by oppositely charged ions involved in the

diffusion process. Reaction-diffusion processes in active medium coupled with generation-

recombination of charge carriers induce morphogenetic processes in the precursor, according to the gradient of photoinduced charge transfer.

The efficiency of self-organization and the contribution of each of these processes can be evaluated

by measuring radiation power and energy and comparing them with the respective

electrochemical/electrophysical parameters of semiconductor precursor, which undergoes chemical

transformations under irradiation due to local change of phase composition of the medium. Local

phase separation is governed by reaction-diffusion processes and leads to the formation and

separation of areas with different conductivity, which can be considered as conductors,

semiconductors and insulators respectively. The application of the above principle of simultaneous

phase separation, structure formation and photoinitiation of self-oscillatory reactions in active

medium was described in [5, 6].

References:

[1] Adamatsky A., Costello B.D.L., Asai T. Reaction-Diffusion Computers. Elsevier, 2005, 348 p.

[2] Gladush G.G., Smurov I. Physics of Laser Materials processing: Theory and Experinent.

Springer, 2011, 552 p.

[3] Rostami A., Baghban H., Maram R. Nanostructure Semiconductor Optical Amplifers: Building

Blocks for All-Optical Processing. Springer, 2010, 192 p.

[4] Scholl E. Nonequilibrium Phase Transitions in Semiconductors: Self-Organization Induced by

Generation and Recombination Processes. Springer, 1987, 313 p.

[5] Gradova M.A., Gradov O.V. Photoinduced Self-Oscillatory Processes in Hydrolyzed Ferric

Chloride Solutions, Proc. 1st Int. Conf. "Reaction Kinetics in Condensed Matter", P –S7, pp. 120–

121 (2010).

[6] Gradov O.V., Gradova M.A. Photoinduced Biomimetic Self-Oscillatory Processes in

Biopolymer-Immobilized Silver Halides. Proc. 1st Int. Conf. "Reaction Kinetics in Condensed

Matter", P – S7, pp. 118–119 (2010).


157

PHOTOACTIVE NANOCRYSTALLINE TIO2 BASED COATING

FOR THE PHOTOCATALYTIC DECOMPOSITION

OF DYE IN A FLOW TYPE REACTOR

L.M. Kalinkina, I.A. Rodionov, I.A. Zvereva

Department of Chemistry, St.-Petersburg State University, Russia

[email protected]

Heterogeneous photocatalysis using TiO2 is a promising method of organic pollutants removal from

water. Slurry reactors which utilize powder were found to possess the largest photocatalytic

activity. However such systems require separation of nanosized particles from the treated water

which decreases the economical viability of water purification. Therefore photocatalytic reactors with immobilized photocatalyst are preferred for practical applications [1].

The majority of methods to immobilize photocatalytic TiO2 coatings developed so far utilizes

conditions of ultrahigh vacuum. Therefore they are rather complicated, expensive and sensitive

even to a small variation of conditions [2]. The main purpose of this research work is to propose an

effective, simple, cheap and ecological method to immobilize nanocrystalline titania on quartz glass

so that morphology, particle size and phase composition of initial photocatalytic powder would be invariable when coated.

In our work we consider the dependence of hydromechanical stability of coating on the suspension composition, mainly content of TiO2 in suspensions.

The proposed method includes deposition from water suspension of nano-TiO2 (Degussa P25)

which contains organic dispergator (acetylacetone) to quartz glass and annealing at 450°С. The

morphology of coatings is examined by scanning electron microscopy (Zeiss ORION). The main

advantages of our method are good uniformity and continuity of coatings, keeping fixed size and

phase composition of initial titania nanoparticles and stability under hydromechanical treatment of

coating. Photocatalytic activity of resulted coatings is investigated in a flow-type reactor using

methyl orange dye (MOD) as a model organic contaminant. The dependence of MOD conversion

on irradiation time for different initial concentrations and flow rates is reported. The first order

kinetic constants of MOD degradation are calculated. The presence of photocatalyst is found to

increase of the kinetic constant of MOD degradation at least by one order of magnitude.

This work has been supported by the RFBR (Grant 12-03-00761) and Saint-Petersburg State

University (Research grant 12.0.105.2010).

References

[1] H. De Lasa, B.Serrano, M.Salaices, Photocatalytic Reaction Engineering, NY, Springer, 2005

[2] V. I. Shapovalov, Glass Phys. Chem, 36 (2010) 121.


158

ANILINES PHOTOOXIDATION

SENSITIZED BY IMMOBILIZED PHTHALOCYANINES

N.I. Kuznetsova, O.Yu. Egorova, E.N. Shevchenko, T.M. Fedorova, V.M. Derkacheva, O.L. Kaliya

“Niopik” Organic Intermediates and Dyes Institute, Moscow, Russia

[email protected]

Aniline and its derivatives are widely used in many manufacturing processes to produce products

such as antioxidants, dyes, rubbers, pharmaceuticals, and so on. Some quantity of these toxic and

hazardous water pollutants is presented in wastewaters of these factories. Therefore, it is need to

remove anilines from wastewaters before being released them into the environment. Among the

wastewaters treatment techniques (biodegradation, adsorption, O3/Fe+2

, H2O2/Fe+2

, UV irradiation

and others) photooxidation of organic water pollutants under visible light irradiation with using

metal phthalocyanines (PcM) as sensitizers of singlet oxygen (1O2) seems to be effective and

promising because the last one is active oxidizing specie [1, 2]. For practical application the photosensitizer needs to be immobilized on carrier for easy separation and reuse.

In this report, substituted PcM (M=Zn, AlX) immobilized on different carriers have been examined

as heterogeneous sensitizers (HS) for aniline and its methyl and chloroderivatives oxidation under

visible light irradiation. HS were prepared by both equilibrium adsorption of PcM from solution into carrier surface and covalent attaching of PcM sulfochlorides to 3-aminopropyl-modified SiO2.

The photoreaction has been carried out in glass reactor surrounded by a water jacket to keep the

content cool. The mixture of substrate water solution and sensitizer was saturated with dioxygen

and illuminated with a halogen lamp (150-500 W) through a filter (λ > 450 nm). At the certain intervals the sample aliquots have been taken out and examined by HPLC measurements.

The catalytic activity and stability of HS in photooxidation of aniline depend both on the nature of

substituents and metal atom in R4PcM (R=3-PhSO2-5-t-Bu, 3-PhSO2, 3-PhS, 4-t-Bu; M=Zn, AlCl)

as well as on the carrier structure (Amberlite 7HP, 3-aminopropyl-modified SiO2 and others). It has

been shown that HS obtained by adsorption of complex (3-PhSO2-5-t-Bu)4PcZn on Amberlite 7HP is the most active. It can be used at least in 5 photooxidation cycles.

The low-molecular compounds are the final products of anilines degradation in this reaction.

The arrangement of increasing rates of anilines photooxidation is as follows: o-, p-, m-

chloroanilines < aniline < m-, p-, o-toluidines.

The photooxidation of aniline in the presence of (3-PhSO2-5-t-Bu)4PcZn/Amberlite 7HP has been

carried out in H2O, D2O and in NaN3 containing water solution. The initial rate is increased in D2O,

but decreased in NaN3 solution. These facts confirm the participation of singlet oxygen in this

reaction.

Thereby, the photooxidation of anilines in the presence of heterogeneous sensitizers on the base of

zinc phthalocyanines can be used for wastewaters cleaning.

References

[1] D. Wöhrle, M. Kaneko, K. Nagai, R. Gerdes, O. Suvorova, Environmental cleaning by

molecular photocatalysis (in Molecular Catalysis for Energy Conversion), Springer Series in

Material Science, (2008) 263.

[2] K. Ozoemena, N. Kuznetsova, T. Nyokong, J .Photochem. Photobiol. A: Chem. 139 (2001) 217.


159

GAS AND IRRADIATION INFLUENCE ON THE PROPRIETIES

OF THIN LAYERS OF TIO2 DEPOSITED ON SILICON

BY ATOMIC LAYER DEPOSITION

D.V. Laptenkov, R.V. Mikhaylov, L.L. Basov, A.A. Lisachenko

V.A. Fock Institut of Physics, St.-Petersburg State University, St.-Petersburg, Russia

[email protected]

Atomic layer deposition (ALD) technique based on sequential self-terminating gas–solid reactions

is widely used for the design of inorganic material layers with nanometer thickness. However the

physico-chemical processes that control ALD growth are rather poorly understood.

The aim of this work was to investigate the effect of gas and UV-VIS irradiation on the proprieties

of thin layers of photocatalysts TiO2 and Al2O3 deposited on silicon by ALD. The UV PES and

UV VIS spectroscopy were used. The photoinduced hydrophilicity of surface films was of special

interest.

The following samples were investigated: TiO2/Si, Al2O3/TiO2/Si, Ta2O5/Si.

The obtained results are follow:

1. On smooth layers of nanoscale TiO2 the effect of super-hydrophilicity was attained under UV

irradiation as well as in VIS region (436 nm).

2. The electrons emitted from the silicon substrate practically do not penetrate through even thin (25

nm) films of TiO2.

3. It is shown that the intensity of the VUV (hv=8.43eV) probe beam is sufficiently small, that

allows to observe the effect of UV-VIS irradiation on tested structure. The changes in the electron

structure are induced during irradiation in the inter-band as well as in the sub-bandgap region of

TiO2.

4. UV-VIS irradiation reduces the surface because of oxygen losses that results in a shift of the

Fermi level towards the bottom of the conduction band for 0.6-0.7 eV.

5. The deposition of thin (2 nm) dielectric film Al2O3 on TiO2 surface protects TiO2 in course of

heating and irradiation in vacuum or gas atmosphere. The photoelectrons tunnel through this film

Al2O3 into vacuum.

6. The deposition of a thin dielectric film Al2O3 on TiO2 surface leads to the formation of filled

charge states pinning the Fermi level .

7. Oxygen strongly changes the PES spectra of TiO2 samples without Al2O3 layer but does not

change the PES spectra of protected TiO2 surface.

8. The effect of photoinduced super-hydrophilicity of smooth nanosized Ta2O5 layers was observed

under UV irradiation.



160

INVESTIGATION OF THE FEATURES OF THE REACTION

CO+NO+hν → ½N2+CO2 ON TIO2 HOMBIFINE N

UNDER VISIBLE LIGHT IRRADIATION

R.V. Mikhaylov, N.I. Glazkova, K.V. Nikitin


[email protected]

Introduction. Photocatalytic removal of organic and inorganic pollutants from indoor air is being intensively investigated. In most cases, TiO2 is used as a photocatalyst owing to its high activity,

versatility, non-toxicity and low cost. Early we showed that the reaction

CO+NO+hν → ½N2+CO2 (1)

occurs under UV and/or VIS light irradiation on TiO2 Degussa P25 (anatase 75%, rutile 25%) [1, 2].

The reaction (1) was divided into two consequent stages: the first one includes the NO photoadsorption

(PA) and N2O appearing, while the second stage includes the N2O adsorption and N2 appearing. The

selectivity of the photoreaction to N2 production attains 90-95%. Mass-spectrometric analysis of the gas phase showed that the CO2 formed by the reaction does not desorb at 300 K suggesting formation of

some carbonate or carboxylate stable surface structures which are detected by IR spectroscopy [2].

However, the CO2 produced could be quantitatively desorbed after completion of the photoreaction by

heating TiO2 to ~500 K. It is found that the photocatalytic reduction of NO can occur on TiO2 catalysts both upon UV (λ < 380 nm) and visible light (λ > 380 nm) irradiation, in the latter case owing to the

presence of electron-donor centers (Ti3+, F and F+ centers) in nonstoichiometric TiO2-x capable of

absorbing visible light [3]. The mechanism of reaction (1) was proposed [1, 2].

The aim of the present work was to investigate the features of photoreaction CO+NO+hν → ½N2+CO2 (1) on TiO2 (Hombifine N, anatase, S = 320 m2/g) under UV and visible irradiation by means

of kinetic mass-spectrometry and thermo-programmed desorption spectroscopy (TPD). An experimental methods and a setup for mass-spectrometric measurements in the course of kinetic runs under static

conditions and TPD measurements was described previously [1]

Results. It was shown that the reaction (1) occurs on TiO2 Hombifine N under both UV and VIS light

irradiation. The reaction (1) can be divided into two consequent stages (NO PA, and N2 appearing). The intermediate N2O does not appear in gaseous on the first stage due to the formation of two strong N2O

species adsorbed on the TiO2 Hombifine N surface. CO2 was found to remain on the TiO2 surface, and

its desorption obeys to the second-order kinetic. The TPD spectra of forming CO2 are well fitted by

Polanyi-Wigner equation with Edes = 0.9 eV and factor ν = 2.5∙1012 s-1.

An influence of both CO and NO amounts and the spectral composition of the light on the reaction

course were investigated. More effective spectral region was found to includes the emission lines λ =

365 and 404 nm of high-pressure Hg lamp. The increase in CO pressure leads to increase in the rates of

processes of both stages. Moreover the presence of CO drastically changes the NO PA kinetic: it has a linear part and, as CO amounts increases it has a clear S-shape.

Two channels of NO PA (fast and slow) were revealed. The fast channel leads to the formation of NOads

species, which rapidly turn into two adsorbed species of N2O. The slow channel provides the

accumulation of strongly bonded NO-species on the TiO2 surface, which react with CO in the second stage of reaction (1) forming the intermediate NOads, N2O and then N2. The model describing the S-

shape of NO PA kinetic in CO presence is proposed.


References [1] A.A. Lisachenko, R.V. Mikhailov, L.L. Basov, B.N. Shelimov, M. Che, J. Phys. Chem. C, 111 (2007), 14440.

[2] R.V. Mikhaylov, A.A. Lisachenko,

B.N. Shelimov, V.B. Kazansky, G. Martra, G. Alberto, and S. Coluccia. J. Phys.

Chem. C, 113 (2009), 20381.

[3] A. A. Lisachenko, V. N. Kuznetsov, M. N. Zakharov, and R. V. Mikhailov. Kinetics and Catalysis, Vol. 45, No. 2,

2004, pp. 189-197.


161

FTIR AND TPD STUDY OF INTERACTION OF NO–OXYGEN MIXTURE

AND NO2 WITH TIO2 PHOTOCATALYST

R.V. Mikhaylov1, A.A. Lisachenko

1, B.N. Shelimov

2, V.B. Kazansky

2, G. Martra

3, S. Coluccia

3

1 – V.A. Fock Institut of Physics, St.-Petersburg State University, Russia


3 – Dept. of IPM Chemistry & Interdipartimental NIS Centre of Excellence, UniVersity of Torino, Italy

[email protected]

Kinetics and mechanism of NO and oxygen coadsorption on TiO2 which is a key step in the

photocatalytic removal of NOx pollutants from air have been studied. NO adsorption on TiO2 is

found to strongly increase in the presence of oxygen, the (NO ads)/(О2 ads) ratio in the course of adsorption being constant and very close to three.

It is shown by FTIR that the amount and composition of nitrogen-containing species on the TiO2

surface are strongly dependent on the adsorption time and composition of initial NO–O2 mixture. At

relatively small exposures, absorption bands of NO– and nitrosyl complexes Ti

n+–NO (n = 3-4) are

predominant. With increasing contact time, the NO– band disappears and the bands arising from

NO3– and possibly NO2

– species appear and grow in the IR spectra. An unambiguous assignment of

all the IR bands observed is however not possible, as the stretching vibration frequencies of NO3–

and NO2– species fall into the same wavenumber interval. The thermal stability of the surface

nitrates and nitrites is found to correlate with their structure.

The IR spectrum after NO2 adsorption on TiO2 is similar to that after exposure to the NO–O2

mixture. The bands of N–OH groups, NO+, broad bands of nitrosyl complexes Ti

n+–NO or adsorbed

N2O3 as well as those of NO3– and NO2

– were detected in the IR spectra. Subsequent exposure to

15NO for 2-30 min results in some change of the IR spectrum evidencing an isotopic replacement of

14N with

15N in the surface species.

In TPD profiles, mainly NO and NO2 peaks are observed which presumably arise from thermal decomposition of NO3

– (NO2

–) and Ti

n+–NO nitrosyls.

On the basis of the results obtained in this study, a multistep reaction scheme of NO and O2

interaction with TiO2 surface is proposed.



162

TIO2/SIO2 AND TIO2/AL2O3 PHOTOCATALYSTS

FOR DEGRADATION OF WATER POLLUTANTS

M.P. Nikitich, A.V. Samoilov, A.A. Vodyankin, E.V. Emelyanova, O.V. Vodyankina

Tomsk State University, Russia [email protected]

It is well-known that TiO2 is used for photooxidation of volatile organic compounds (VOC). Using

UV irradiation (λ < 388 nm) TiO2 produced conduction band electrons (eCB–) and valence band

holes (hVB+) which quickly recombined at the surface. Electron-hole recombination is always a

critical issue in the efficiency of TiO2 photocatalyst systems, regardless of the application [1-3].

However, titania can be modified to improve its photocatalytic properties.

This work deals with preparation and investigation of physical-chemical and catalytic properties of

TiO2/SiO2 and TiO2/Al2O3 catalysts. Two series of TiO2/SiO2 and TiO2/Al2O3 photocatalysts were

prepared by heterogeneous deposition [4]. TTIP (98 %), TEOS (99 %) and γ-Al2O3 were selected as

precursors of titania, silica and alumina, respectively. The content of active component TiO2 was

varied from 3 to 15 % wt. Physical-chemical properties and structures of the prepared catalysts were

studied using XRD, FTIR and UV-Vis spectroscopy. According to TEM and XRD data the average

size of TiO2 particles is 9-10 nm. Also these methods were shown that 99,9% of TiO2 phase

obtained by our method is amorphous.

The photocatalytic activity of prepared systems was studied in the photodegradation reaction of

methanol solutions. The DKSh-250 lamp was used as source of irradiation, the radiation was not

filtered. An aqueous solution of methanol required amount of catalysts were placed into reactor

with a quartz window. The suspension was treated in ultrasonic bath for 10 min for

homogenization. The activity of prepared samples was compared with the activity of titania

Degussa P 25 (45 m2g

-1, nonporous, 70 % anatase and 30 % rutile, purity 99,5%).

The model reactions of photochemical deposition of cationic Ag+ and Pb

2+ were used for

identification of a character of the free charge carrier distribution on the photocatalyst surface

according to [5].

Ag+ + e–

CB → Ag0 (1)

Pb2+

+ 2H2O + 2h+VB → PbO2 + 4H

+ (2)

These reactions are used as testing for determination a presence and concentration of free electrons

(1) and holes (2) on the surface of samples. A degree of photoelectrochemical deposition is

identified by the ICP emission method from liquid phase (mother liquor) and solid phase (samples).

Determination of the selectivity on the basis of the ability to generate electronic vacancy is carried

out according to (3):

Sh+VB = [qPb

4+/(qPb

4+ + qAg)]∙100% (3)

qPb4+

= quantity of lead cations deposited on the surface, mg-eqv and qAg = amounts of silver

deposited on the surface, mg-eqv.

According to experimental results the photocatalytic activity of modified TiO2/SiO2 and TiO2/Al2O3

systems is higher than TiO2 Degussa P25.

This work was supported by the grant of the Russian Federal purposeful program “Scientific and scientific -educational personnel of innovative Russia” (16.740.11.0604).

References: C. Gu, C. Shannon, J. Mol. Catal. A: Chem. 2007. V. 262. P. 185-189.

S. Goldstein, D. Behar, J. Rabani, J. Phys. Chem. C, 2008. V. 112. No 39. P. 15134-15139 C. L. Flakker, D.S. Muggli, Appl. Catal. B: Environmental, 2008 V. 84. P. 706-714 M. Fedotova, G.Voronova, E. Emel’yanova, N. Radishevskaya, O. Vodyankina, Rus. J. Phys. Chem. A. 2009. V. 83. No 8. P. 1371-1375. A. Evstratov, K. Kish, A. Malygin et al., Rus. Chem. J. 2007. V. 51. No 6. P. 52-60.


163

THE KINETICS OF COLOR CENTER FORMATION IN WIDE BAND GAP

PHOTOCATALYSTS AS A WAY TO DISTINGUISH BETWEEN

CATALYTIC AND NON CATALYTIC SURFACE PHOTO REACTIONS

V.K. Ryabchuk1, G.V. Kataeva

2, A.V. Emeline

1

1 – V.A. Fock Institute of Physics, St. Petersburg State University, Russia

2 – Institute of Engineering and Technology, Dimitrovgrad, Russia

[email protected]

The problem of experimental distinguishing between photocatalytic and non photocatalytic

reactions (i.e. stoichiometric reactions such as photoadsorption) is examined. The determination of

turnover number (TON) is a direct way to confirm the photocatalytic character of a given surface

photoreaction [1, 2]. Here we consider the alternative way to distinguish between photocatalytic and

non photocatalytic reactions, which is based on the effect of surface photoreactions on color centers

formation in near surface area of wide band gap solids [3]. Taking as examples the reactions of

hydrogen oxidation over ZrO2 and ammonia decomposition on MgAl2O4, it is demonstrated that

the saturation level of color centers formation kinetics for both F- and V-type centers is approaching

to that for UV coloration in vacuo in a case of photocatalytic reaction only. In contrast, for non

photocatalytic reactions (such as ammonia decomposition on MgAl2O4 and probably, ammonia

decomposition over Al2O3 [4]) the saturation levels of F- and V-type centers significantly differ

from achieved under vacuum conditions. The difference depends on the type of surface active

centers (electron or hole traps) involved into non catalytic surface reaction. The effect is similar to

that for photoadsorption of either acceptor or donor molecules typically reacting with surface

trapped electrons and holes respectively [3].

References

1. Emeline A.V., Ryabchuk V.K. Salinaro A., Serpone N. Turnovers and Photocatalysis.

A Mathematical Description. J. Photochemistry and Photobiology. A: Chem. 2000. Vol. 130,

issue: (2-3), pp. 83–94.

2. Emeline, A.V.; Kataeva, G.V.; Panasuk, A.V.; Ryabchuk, V.K.; Sheremetyeva, N.; Serpone, N.

Effect of surface photoreactions on the photocoloration of a wide band gap metal oxide: probing

whether surface reactions are photocatalytic, J. Phys. Chem. B 2005, 109, pp.5175–5185.

3. Emeline A.V., Kataeva G.V., Ryabchuk V.K., Serpone N. Photostimulated gen-eration of defects

and surface reactions on a series of wide band-gap metal-oxide solids // J. Phys.Chem. B. 1999.

Vol.103. N 43. pp. 9190–9199.

4. Kasparov, K.Ya.; Terenin, A.N. Optical investigations of activated adsorption. I. Photo-

decomposition of NH3 adsorbed on catalysts. Acta Physicochim. USSR, 1941, 15, pp. 343–365.

Posters Photonics of model biological systems and biological molecules ----------------------------------------------------------------------------------------------------------------------------- -------------------------------------------------------------------------------------------------------------------------------------------------------- ------------------------------------------------------------------------------------

164

SECTION 5. PHOTONICS OF MODEL BIOLOGICAL SYSTEMS

AND BIOLOGICAL MOLECULES

LUMINESCENCE QUENCHING OF ORGANIC DYES

IN LIVING BIOLOGICAL TISSUES

A.F. Kuvandykova, S.N. Letuta, S.N. Pashkevich


[email protected]

This paper presents the results of a study of the kinetics of delayed fluorescence (DF) and

phosphorescence of exogenous fluorophores in tumor and normal breast tissues mice BYRB. Xanthene dyes – erythrosine and eosin as an exogenous fluorophores were used.

Decay kinetics of DF and phosphorescence of the dye molecules experimentally were measured.

The second harmonic of a neodymium laser with a wavelength of 532 nm for excitation of the dye

molecules was used. Kinetics of delayed luminescence was recorded by PMT-84 with

monochromator MDR-41. Installation allowed to digitize the recorded signals and automatically processed.

Tissue cells contain a variety of triplet state dye molecules quencheries. It is shown that the most

efficient quenching of triplet states of the fluorophores is molecular oxygen 3Σg

– (O2). As a result of

quenching T1-states of dye molecules formed by singlet oxygen 1Δg(O2). The remaining non

quenching triplet states of dye molecules can be annihilated with the singlet oxygen.

As a result of singlet-triplet annihilation T1 → 1Δg(O2) singlet S1-state of fluorophores are formed.

Such molecules giving an additional contribution to the overall signal DF. Therefore, the recorded

DF kinetics of dye is composed of three signals of different nature - the thermally activated DF

resulting from the reverse T1→S1 intersystem crossing, as well as the emission due to singlet-triplet

and triplet-triplet annihilation of the T1-T1.

It is shown that in tissues at short times, the greatest contribution to the total signal makes the

singlet-triplet annihilation. At the same time in both normal and pathogenic tissue kinetics of

delayed luminescence is different. The contribution of the singlet-triplet annihilation to the total

signal of the DF in tumor tissues significantly greater than in normal tissues, indicating a more effective interaction between the triplet states of dye molecules with singlet oxygen.

Unlike DF the phosphorescence intensity of dye molecules decreases monotonously with the period

of time. Phosphorescence kinetics as well as DF differs within different tissues. The luminescence

peculiarity depends on the phase of the tumour, the biotissue condition and other factors. However

in all our experiments the common regularity is evident, namely the phosphorescence lifetime in tumours is shorter than that in normal tissues.

Reliable registered differences in the dye tissue delayed luminescence kinetics can be used when

developing an alternative method of optical diagnosis of biotissues. We assume that the method

based on the measurement of lifetime of the delayed luminescence phosphor is fairly promising.

Any combinations possessing delayed luminescence and meeting the requirements set to such

specimen may serve as exogenous phosphor.


165

PRIMARY SITE OF NON-PHOTOCHEMICAL QUENCHING

OF THE PHYCOBILISOME BY ORANGE CAROTENOID PROTEIN

IN THE CYANOBACTERIUM SYNECHOCYSTIS SP. PCC 6803

I.N. Stadnichuk1, M.F. Yanyushin

2, E.G. Maksimov

3, E.P. Lukashev

3,

S.K. Zharmukhamedov2, I.V. Elanskaya

3, V.Z. Paschenko

3

1 – A.N. Bakh Institute of Biochemistry RAS, Moscow, Russia

2 – Institute of Fundamental Problems of Biology RAS, Puschino, Russia

3 – Faculty of Biology, M.V. Lomonosov State University, Moscow, Russia

[email protected]

Phycobilisomes are phycobiliprotein antenna complexes associated with the cytoplasmic surface of

the thylakoid membrane in the pigment apparatus of cyanobacteri. The thermal dissipation of excess

absorbed energy at the level of the phycobilisome-antenna is triggered by absorption of strong blue-

green light by the photoactivated orange carotenoid protein (OCP). This process known as non-

photochemical quenching, whose molecular mechanism remains in many respects unclear, is

revealed in vivo as a decrease in phycobilisome fluorescence. In vitro reconstituted system on the

interaction of the OCP and the phycobilisomes isolated from the cyanobacterium Synechocystis sp.

PCC 6803 presents direct evidence that the OCP is not only a photosensor, but also an effecter that

makes direct contacts with the phycobilisome and causes dissipation of absorbed energy. To

localize the site(s) of quenching, we have analyzed the role of chromophorylated polypeptides of

the phycobilisomes using phycobilisome-deficient mutants in conjunction with in vitro systems of

assembled PBS and of isolated components of the phycobilisome core. The results demonstrated

that LCM, the core-membrane linker protein and terminal emitter of the phycobilisome, could act as

the docking site for OCP. Bulk allophycocyanin trimers as well as other terminal emitters of the

phycobilisome core are not directly subjected to quenching. The data suggest that besides its central

role in excitation energy transfer and as a key structural element in the phycobilisome, LCM is the

primary site of photoprotective excitation quenching in the phycobilisome core. Changes in

fluorescence lifetime of the fully assembled phycobilisomes and isolated LCM and linear

dependences of fluorescence intensity on OCP concentration indicate that the quenching of LCM has

a static character, while the corresponding secondary quenching of assembled phycobilisomes is of

a dynamic type. The data suggests that there could be close contact between the phycocyanobilin

chromophore of LCM and the 3´-hydroxyechinenone chromophore present in OCP. A model for

OCP-phycobilisome interaction is proposed based on the crystallographic structures of the

corresponding proteins. According to the model the OCP molecule is wedged between the

chromophorylated domain of LCM inside the phycobilisome core and the surface of the thylakoid

membrane and there could be a direct contact between the phycocyanobilin chromophore of LCM

and the ketocarotenoid chromophore of OCP. The distance between these chromophores is

estimated as about 15 Å and two-fold longer in the unquenched state respectively.

Reference

I. Stadnichuk, M. Yanyushin, E. Maksimov, E. Lukashev, S. Zharmukhamedov, I.V. Elanskaya,

V.Z. Paschenko, Biochim. Biophys. Acta Bioenergetics (2012) doi: 10.1016/j.bbabio. 2012.03.02.


166

ELECTRONIC EXCITATION ENERGY TRANSFER BETWEEN

OXA- AND THIACARBOCYANINE DYES IN COMPLEXES WITH DNA:

FLUORESCENCE DECAY KINETICS AND DISTANCE DISTRIBUTION

IN DONOR–ACCEPTOR PAIRS

A.S. Tatikolov, P.G. Pronkin

N.M. Emanuel Institute of Biochemical Physics RAS, Moscow, Russia

[email protected]

Electronic excitation energy transfer (EEET) between molecules of carbocyanine dyes, which form

noncovalent complexes with DNA, has been studied by steady-state and time-resolved techniques.

The oxacarbocyanine dyes 3,3’-dimethyl-9-ethyloxacarbocyanine iodide (D1), 3,3’,9-triethyl-5,5’-

dimethyloxacarbocyanine iodide (D2), and 3,3’,9-triethyl-6,6’-dimethoxyoxacarbocyanine iodide

(D3) were used as the dyes–donors of electronic excitation energy, and 3,3’-

diethylthiacarbocyanine (A) served as the acceptor dye. In dye–DNA complexes, the DNA helix

acts as a matrix for embedding dye molecules, which facilitates EEET, since the dye ligands in such

a system are located close to one another. Furthermore, in DNA matrix spatial fixation of cyanine

molecular fragments occurs, which is accompanied by a tenfold rise in the fluorescence quantum

yield. Since the fluorescence spectra of D1–D3 overlap well with the absorption spectrum of the

acceptor, we considered the energy transfer process to occur by the Förster inductive-resonance

mechanism. We showed that the microphase model, which assumes concentrating of donor and acceptor dye molecules close to DNA molecules, adequately explains the experimental data.

An increase in the DNA concentration leads to a decrease in the values of the EEET efficiency r:

for D1 from 0.59 (at cDNA = 5.0∙10–6

mol l–1

) to 0.36 (at cDNA = 1.25∙10–4

mol l–1

); for the dye pair

D3–A, r decreases from 0.49 to 0.42 (with an increase in cDNA from 6.2∙10–6

to 5.0∙10–5

mol l–1

).

The steady-state experiments were shown that upon D1–D3 fluorescence quenching by A, the

dynamic (diffusion) quenching does not play a significant role, and the quenching occurs mainly by

the static mechanism, which causes an upward deviation and concavity of the experimental Stern–

Volmer plots. Therefore the fluorescence is emitted by the donor molecules located beyond the

quenching sphere of the acceptor (Perrin model).

The EEET kinetics was measured by a picosecond spectrofluorometer. In the presence of the

quencher, the fluorescence decay kinetics for D1–D3 differ noticeably from the exponentials, which

cannot be explained using the Perrin model and simple numerical modeling by the Monte Carlo

method (without considering of distribution of acceptor positions around of the donor). The analysis

of the kinetic data permitted us to determine the characteristics of the distribution of acceptor

molecules with respect to the donor in the DNA microphase. For dyes D1–D3, an increase in the

acceptor concentration leads to a decrease in the dispersion of distribution of the random function

P(RD–A) and is accompanied by a decrease in the values characterizing the average distances in the

D–A pairs. The change in the dispersion can be explained by the decrease in the Debye radius due

to the local (in the biopolymer microphase) increase in the ionic strength of the solution with

growing the concentration of acceptor dye molecules in the DNA microphase. It can be seen that

the expected value M[X] of P(RD–A) is much the same for the three compounds and satisfactorily

corresponds to the energy transfer distance R (~30–40 Å) under these conditions.

The results show that the dye molecules in complexes with DNA, in spite of spatial fixation, have

sufficient rotational freedom to provide the random orientation factor κ (2/3).

We thank Prof. B.I. Shapiro (NIIKHIMFOTOPROEKT Research Center) for providing the polymethine dyes

and V.Yu. Gak (Institute of Problems of Chemical Physics, Russian Academy of Sciences) for the help in measuring fluorescence kinetics.

This work was supported by the Russian Foundation for Basic Research, project no. 10-03-00647.

Posters Photonics of molecular nano-systems ----------------------------------------------------------------------------------------------------------------------------- ----------------------------------------------------------------------------------------------------------------------------- ---------------------------------------------------------------------------------------------------------------

167

SECTION 6. PHOTONICS OF MOLECULAR NANO-SYSTEMS

PROPERTIES OF DELAYED LUMINESCENCE OF MOLECULAR

CLUSTERS EMBEDDED INTO ANODIZED ALUMINUM PORES

A.K. Aimukhanov, A.K. Zeinidenov, N.Kh. Ibrayev, M.M. Kubenova, G.S. Seisenbayeva

Institute of Molecular Nanophotonics, E.A. Buketov State University, Karaganda, Kazakhstan

[email protected]

There are the results of the research of spectral, kinetic, and magnetic properties of delayed

luminescence of organic luminophors embedded into nanoscale pores of anodized aluminum oxide.

Obtaining of porous aluminum oxide was done by anodic oxidation of polished aluminum plates in

solutions of phosphoric acid. The sorption of eosin molecules in porous aluminum oxide was

carried out from ethanol solutions of phosphors, and anthracene – from hexane solution. The

concentration of phosphor molecules in the pores was estimated according to the change in optical

density of the solutions before and after sorption. The number of adsorbed molecules of eosin were

kept constant, while anthracene was varied from 2∙103 mol/nm

2 to 4.8∙10

3 mol/nm

2. To remove the

traces of solvent, the substrate was kept at 80°C in vacuumed exsiccator during the 24 hours.

Photoexcitation of the samples was carried out by the second harmonic of the laser energy LCS-

DTL-374QT (λexc = 532 nm, E = 60 mkJ at τ = 7 ns). The time of measurements starts from the

moment of arrival time of laser pulse and it was 2 μks. To obtain a satisfactory level of signals there

were at least 2,000 accumulations produced.

At excitation of porous aluminum oxide with adsorbed molecules of eosin (C = 4∙103 mol/nm

2) the

spectrum which consists of strips of delayed fluorescence (DF) (λmax = 580 nm) and

phosphorescence (λmax = 720 nm) is observed. Both types of luminescence decay exponentially with

a lifetime of τ = 1.6 ms. Lowering the temperature of the sample led to an increase in the intensity

of the phosphorescence intensity and falling DF intensity. Analysis of properties DF shows that this luminescence is due to the intercombinational conversion of molecules from Т1 to S1 state.

At embedding into aluminum oxide pores with the molecules of eosin the molecules of anthracene

the phosphorescence quenching of the staining agent is observed both in intensity and time of life.

When the concentration of anthracene in the pores from 2∙103 mol/nm

2 to 4.8∙10

3 mol/nm

2 duration

of phosphorescence is reduced to τ = 1.3 ms.

In this concentration range the intensity of anthracene increases into 1.2 times, and the lifetime of

DF drops to τ = 0.6 ms. With further increase of the concentration of anthracene the quenching of

the phosphorescence and the buildup of the staining agent increases. In addition, the observed the sensibilized annihilation of anthracene with τ = 0.5 ms.

The observed changes in the phosphorescence and DF eosin at the sorption into the pores of

anthracene molecules are connected with the processes of triplet-triplet energy transfer from eosin to anthracene and subsequent heteroannihilation of triplet excitons of eosin and anthracene.

The impact of magnetic field onto the phosphorescence and DF molecules of eosin adsorbed in the

pores of aluminum oxide is studied. The magnetic influence was not observed in both cases. In the

system of eosin-anthracene there was observed negative magnetic effect (9%) for DF eosin and (6%) for ADF.

The obtained data show that in mixed molecular clusters formed in nanosized pores of aluminum

oxide pores flow processes of triplet-triplet energy transfer and triplet-triplet annihilation.


168

SPECTRAL PROPERTIES OF THE ORGANISED MOLECULAR SYSTEMS

V.Ya. Artyukhov, G.V. Mayer

Tomsk state university, Russia

[email protected]

The ordered (specially spatially organised) molecular structures and supramolecules draw the

increasing attention of researchers of physics and chemistry of molecules. In live matter such

structures (biopolymers, organelles and membranes) visually show high functional and power

efficiency. Whether it is impossible to use such principles of construction at creation of optical

devices? In the last two decades, there has been increasing interest in the design and synthesis of

stable multidimensional molecular systems (or supramolecules) as precursors to materials with

unusual properties. There is a considerable progress in technologies of creation of ultrathin films

and monolayer nanodimensional materials for the molecular photonics. Methods and the equipment

for experimental studying of physical and chemical characteristics of such materials actively

develop also. Thanks to achievements of chemical synthesis there is a possibility to use various

molecules and structures. The main interest in such systems arises from their magnetic and optical properties.

At the same time theoretical (including, quantum chemical) researches of spectral properties of

molecular systems basically are limited by studying and their comparison in monomers and dimers.

Our idea consists in studying of spectral-luminescent properties of the molecules organized in certain plane structures.

In the present work the modelling molecular systems constructed on the basis of naphthalene are

investigated. Spectral-luminescent properties of this molecule are well studied both experimentally,

and theoretically. It is important, that two low excited singlet states of naphthalene have the same

ππ*-type of orbital origin and different photophysical characteristics of a absorption spectrum

(oscillator strength and polarization), that allows to spend useful comparisons. It is known, that

electronic transition in S1 state is polarized on a long axis of a molecule and has weak intensity. On

the contrary, electronic transition in S2 state is polarized on a short axis of a molecule and has high intensity.

Electronic states of two plane supramolecular structures of a "chained" structure (n = 1–10) with

orientation of molecules on a long and short axis have been calculated. Molecules either took places as isolated or connected the cyclobutyl bridge not transferring π-conjugation.

Change of molecular orbital structure, arrangement and the nature of bands of absorption depending

on mutual orientation of molecules and the sizes of system have been analyzed. The analysis of a

spatial structure of molecular orbitals of the investigated structures has shown, that they are delocalized on all structure.

Because of intermolecular interaction there is a splitting and shift of energies for electronic states of

supramolecular structures. Each electronic state of a monomer is split on n states. Meanwhile

oscillator strength for one of these states becomes n times more of that in a monomer. The

arrangement of the allowed state depends on orientation of molecules in structure and polarization

of electronic transition in a monomer. Other states have considerably smaller oscillator strength.

Features of formation of spectral-luminescent properties of the investigated molecular systems are

established. Their properties can differ considerably from those of monomers and dimers. This

circumstance gives the chance to create purposefully materials with demanded optical properties.

This work was supported in part by the President of the Russian Federation (grant NSh-

512.2012.2).


169

THE PHOTOPHYSICAL PROPERTIES OF THE COMPLEXES CDSE/ZNS

QUANTUM DOTS WITH THE PTHALOCYANINE MOLECULES

IN AQUEOUS MEDIA

А.G. Bakanov1, A.O. Orlova

1, V.G. Mаslov

1, A.V. Baranov

1, М.V. Artemyev

2


2 – Institute for Physico-Chemical Problems Belarusian State University, Minsk, Belarus

[email protected]

Combination of the optical, electrical and magnetic properties of inorganic particles and organic

molecules can be realized in supramolecular structures. This allows to create the structures with

intriguing properties. Complexes of the semiconductor quantum dots (QDs) with tetrapyrrole

molecules belong to these structures. The quantum dots posses some remarkable features: a high

extinction in a wide spectral range, a high photoluminescence quantum yield (PLQY) and a high

photostability. In addition, their spectral properties depend on a size of the quantum dot. QDs can

serve as an effective donor of the energy due to its photophysical properties.

Singlet forms of the oxygen have a wide range of applications: a cleaning of waste water, a creation

of the pure medicines, sterilization of blood plasma, diagnostic and therapy of the oncological

diseases [1]. Therefore the task of searching a new type of substances with a high quantum yield of

singlet oxygen remains relevant. Tetrapyrroles can very effectively generate singlet oxygen and

today they are widely used as photosensitizes in diagnostics and photodynamic therapy of cancer.

Combination in the complexes the remarkable features of the QDs and tetrapyrroles can

significantly improve the singlet oxygen generation by the tetrapyrroles in such complexes.

Here we have investigated of the formation and the photophysical properties of the complexes of

the cationic CdSe/ZnS QDs with the Al-tetrasulphophtalocyanine (Al-TSPc) in aqueous media. In

these complexes the effective Förster Resonance

Energy Transfer (FRET) from QDs to pthalocyanine

molecules has been observed. This can be illustrated by

the Figure, where it is shown that the PL intensity of the

Al-TSPc (1) has improved significantly after addition the CdSe/ZnS QDs (2) in solution.

In our complexes the pronounced dependence of the

energy transfer efficiency and PLQY of the Al-TSPc on

the pthalocyanine concentration in the solution has been

found. The maximum intracomplex energy transfer

efficiency (~ 50%) with unchanged PLQY of pthalocyanine bound with QDs has been observed at

the lower Al-TSPc concentration in the solution. However, the increasing concentration of

pthalocyanine in solution leads to dramatic fall of the energy transfer efficiency (up to 4%) and PLQY of the Al-TSPc in the complexes.

Our data have shown that the formation of nonluminescence pthalocyanine aggregates on the QDs

surfaces occurs with the increasing of the Al-TSPc concentration in solution. These aggregates form

the nonradiative channel of the deactivation of the exited state of the QDs and can quench another pthalocyanine molecules attached to the same QD.

In summary, in the complexes of the CdSe/ZnS QDs with Al-TSPc molecules the effective FRET

(up to 50%) can be realized. At the same time, if we want to use these complexes as a real system

for effective generation of singlet oxygen, the problem of the formation the nonluminescence pthalocyanine aggregates on the QDs surfaces should be solved.

1. F. Hul, Y. Ran, Z. Zhou, and M. Gao, Nanotechnology 17, 2972 (2006).

500 600 700 800

0

10

20

PL

, a

.u.

Wavelength, nm

2

1


170

ON THE FORM OF SIZE DISTRIBUTION FUNCTION

OF QUANTUM DOTS

E.N. Bodunov1, M.N. Berberan-Santos

2, L. Pogliani

3

1 – D epartment of Physics, St. Petersburg State Transport University, Russia

2 – Centro de Quimica-Fisica Molecular and Institute of Nanoscience and Nanotechnology,

Instituto Superior Tecnico, Lisboa, Portugal

3 – Dipartimento di Chimica, Universitá della Calabria, Rende, Italy

[email protected]

Distribution functions play an important role in physics and, in particular, optical spectroscopy, by

connecting the observables that characterize the whole system with quantities related to its

particular elements. One of them is the Lifshits–Slyozov function (LS) [1, 2], which is used as the

size distribution function of quantum dots.

In the classical works [1, 2], the formation of a new phase (e.g., quantum dots in a solid solution or

liquid drops in a gas) in an oversaturated solution at a late stage of coalescence has been

theoretically studied in which a key role is played by the surface tension and conservation laws. A

specific property of this phase is that the mean size of the grain increases due to the diffusive mass

transfer of the substance from smaller to larger particles (small particles are dissolved, while large

particles grow). It was concluded that, regardless of the initial size distribution of the grains, the

size distribution function of the grains transforms in time into a universal function controlled by the

mechanism of mass transfer acting inside the system.

In recent years, mathematicians have shown interest in the LS equations (see [3] and references

therein). The search for new asymptotic solutions to the generalized LS equations has been

undertaken. In this report, we show that, along with the function found in [1, 2], other solutions can

exist depending on initial conditions. We present qualitative forms of these functions based on the

physical meaning of the processes of the evaporation and condensation of grains in a solution

described by LS equations and show that the following conclusions are valid [4].

1. The solution of LS basic equations for the initial volume distribution function as a sum of δ-

functions allows a qualitative forecasting of the behavior of the distribution function for any initial

condition. 2. If the initial distribution function is continue and it is concentrated in a small volume

domain and the number of droplets is small, then all droplets dissolve and the distribution function

never approached the LS asymptotic solution (as contrasted to statement [1, 2]). 3. After

comparatively short time, the distribution function can be approximated (in small volume domain)

by a series; the inverse number of droplets and the average droplet volume become linear functions

of time in agreement with the LS asymptotic solution, but over all the volume domain, the

distribution function approaches the asymptotic solution only at very large time. 4. If the initial

distribution function has a sharp boundary from the side of large volumes (derivative of the

distribution function is a δ-function at this boundary), this sharp boundary continues to exist (the

derivative continues to be a δ-function) for every time (as contrasted to statement [1, 2] and in

agreement with obtained results [3]). Thus, such distribution function never approaches the LS

asymptotic solution, but in a small volume domain, this distribution function can be approximated

by the series. 5. If precipitation is taken into account, the distribution function can be approximated

by the series at large times, the number of droplets decreases almost exponentially, and the average

droplet volume approaches a constant value.

1. Lifshitz I. M., Slyozov V. V. // Zh. Eksp. Teor. Fiz. 1958. V. 35. P. 479. 2. Lifshitz I. M., Slyozov V. V. // J. Phys. Chem. Solids. 1961. V. 19. P. 35. 3. Carrillo J. A., Goudon T. // J. Sci. Computing. 2004. V. 20. P. 69.

4. Bodunov E.N., Berberan-Santos M.N., Pogliani L. // Opt. Spectrosc. 2011. V. 111. No 1. P.61; MATCH Commun. Math. Comput. Chem. 2012. V. 67. No. 3. P. 563.


171

OPTICAL PROPERTIES OF TWO-DIMENSIONAL (2D)

CDSE NANOSTRUCTURES

S.A. Cherevkov1, A.V. Baranov

1, M.V. Artemyev

2, A.V. Prudnikau

2

1 – National Research University of Information Technologies, Mechanics and Optics, Saint-Petersburg, Russia

2 – Institute for Physico-Chemical Problems Belarussian State University, Minsk, Belarus

[email protected]

Two-dimensional colloidal anisotropic inorganic crystal nanostructures, especially those with

thickness < 10 nm [1, 2], have recently emerged as a novel class of material with unusual electronic

and optical properties resulting from their exceptionally small thickness and their lateral dimensions

that can reach several micrometers. In the past few years, the interest to ultrathin 2D nanosheets has

grown rapidly.

One type of 2D materials of particular interest are the CdSe nanoplatelets (NPs). Expected what 2D

CdSe nanostructures with thickness of several monolayers are semiconductor analogies of

graphene, and have extraordinary electrical and optical properties. In particular, their optical

properties should be similar to those predicted for CdSe quantum well, where the exciton energy

depends on the thickness of the well: 22 2 2 * 2 2 2 2 *

2 / 2g hhn cn hhn g cE E E E n m d n m d ,

where Eg is the semiconductor bandgap, n is the number of the interband transition, *

hhm and *

cm are

the heavy hole and electron effective masses, and d is the thickness of the quantum well. On the

other side, the 2D colloidal nanocrystals, similar to colloidal nanocrystals - quantum dots, provide

the ability to create on their basis of self-organized nanostructures more complex with unusual

optical properties. However, most of the work published so far focuses primarily on the growth

mechanisms and the structural characterization of these 2D nanocrystals. Works devoted to the

study of the electronic and phonon structure and its dependence on the thickness of the

nanocrystals, are practically absent.

In this work, the resonance Raman scattering (RS) spectra of 2D CdSe nanocrystals with a thickness

of 5 and 6 monolayers (ML) with the fundamental exciton transition at 460 nm and 515 nm,

respectively were obtained. Absorption spectra of the samples are shown in Fig.1a. Excitations at

wavelengths of 457 nm, 514.5 nm and 632.8 nm were used. The first and second are in resonance

with the NPs exciton transitions while the latter can be regarded as non-resonant for all three

samples. The spectra were obtained using a micro-Raman spectrometer "inVia Renishaw" at room

temperature.

In the spectra of samples of micro-Raman NPs CdSe with different numbers of monolayers are

observed characteristic peaks at frequencies of ~ 180, 203, 230, 370, 406 and 470 cm-1

, where the

peak of ~ 180 cm-1

and 203 cm-1

comply with SO and LO phonon modes of the material, as well as

their overtones (370 cm-1

and 406 cm-1

). The assignment of the bands 230, 370 and 470 cm-1

, and

the band 276cm-1

is not so obvious. It is assumed that they are linked to the flat shape of the

nanoparticles. When the thickness of nanoplatelets reliably observed a slight decrease in the

frequency bands of LO-phonon and its overtone, which is associated with the effect of spatial

confinement of optical phonons. Thus, it is shown that resonance Raman spectroscopy opens up

new possibilities for obtaining information on the structural parameters of 2D CdSe nanocrystals

and their phonon spectra.

References:

1. S. Ithurria, G. Bousquet, B. Dubertret, J. Am. Chem. Soc. 2011, 133, 3070–3077

2. S. Ithurria and B. Dubertret, J. Am. Chem. Soc. 2008, 130, 16504–16505


172

OPTICAL LIMITING IN HYBRID SYSTEMS,

INCLUDING SEMICONDUCTOR NANOPARTICLES CDSE / ZNS

V.V. Danilov1, A.S. Panfutova

2, G.M. Ermolaeva

2, D.A. Vedenichev

2,

E.S. Gromova3, A.I. Khrebtov

2, T.A. Shakhverdov

2

1 – S.I. Vavilov State Optical Institute, St. Petersburg, Russia, St. Petersburg State Transport University, Russia

2 – S.I. Vavilov State Optical Institute, St. Petersburg, Russia

3 – St. Petersburg State Transport University, Russia

[email protected]

We consider the possibility of use as optical limiters of hybrid systems, including semiconductor

nanoparticles CdSe / ZnS, as well as the C60 and perylene (Per), which forming with nanoparticles

so-called "a contact complexes." The feature of selected composites is to realize the effect of optical

limiting at a photoinduced electron transfer. In the literature (for example [1]) are known the

research of the charge separation in a mixture of colloidal solutions of semiconductor quantum dots

(QDs) CdSe and C60. It was demonstrated that in such system at the excitation of QDs in the area

of a resonance excitonic transition, the electron transfer with the formation of ion-radical pair is a

possible. QDs and C60 play the role of a donor and acceptor of electron, respectively. The

passivation of the surface of QDs the molecules of perylene needed as shown in [2] for to improve

the efficiency of charge separation on the QDs. Per is a good electron donor, and we assume the

possibility the phototransfer of electron from the Rer on QDs • which should help increase the

number of not recombined radical anions of C60. The probable course of the reaction can be

represented by the following scheme:

(C60~•-, QDs •

+ ) + Реr → C60

~•

- + QDs + Реr•

+ .

In [2] it was shown that the use of intermediate

products of reversible photochemical reaction

leads to improved optical limiting parameters.

The maximum of the absorption band of

cation-radical Rer • lies on the λ = 535 nm,

and extinction coefficient (ε) Rer • at this

wavelength is 50000 cm-1

M-1

, which is ideal

for limiting on the wavelength of the second

harmonic YAG: Nd+3

laser [11]. All

experiments were performed in solutions in

toluene, T532 ~ 50%. The obtained values of the

constants of quenching of the luminescence

QDs components of the mixture confirmed

the formation of the “contact complexes” in

solution. For the model solutions were obtained

curves of limitations for various combinations

of mixture components (Fig.1). It is shown that

the introduction of perylene leads to a

significant increase in the efficiency of limitation. The nature of the curves of limitation confirms

the existence of electron transfer and the proposed reaction scheme.

References:

1. P. Brown and P.V. Kamat // J. Am. Chem. Soc. 2008 V.130 P.8890-8891.

2. M.V.Gryaznova, V.V. Danilov, T.A. Shahverdov // Opt. and spectr. 2008, v.105 №6. p.874–880.

Fig. 1. The curves of limitations : 1 – CdSe / ZnS, 2 – C60 + CdSe/ZnS, 3 – C60; 4 – C60 + CdSe/ZnS + Per. Initial transmission of all solutions T = 50%. All in toluene.


173

FUNDAMENTAL ABSORPTION OF NICKEL OXIDE NANOCRYSTALS

G.A. Kim1, V.I. Sokolov

2, A.V. Druzhinin

2, N.B. Gruzdev

2,

A.Ye. Yermakov2, M.A. Uimin

2, I.V. Byzov

2

1 – I.Ya. Postovsky Institute of Organic Synthesis UB RAS, Ekaterinburg, Russia

2 – Institute of Metal Physics UB RAS, Ekaterinburg, Russia

[email protected]

Nickel oxide is an actively studying material with strong electronic correlations what significantly

transform the crystal energy spectrum. The fundamental absorption of NiO is formed by p-d- and

d-d- charge transfer transitions. The absorption coefficient α value exceeds 105 cm

-1 thus the NiO

absorption spectrum has not been registered yet.

Earlier the absorption of Cu2O and ZnO nanocrystals placed to a transparent medium or deposited

to a transparent substrate was observed for studying of high absorption band [1,2]. Oxide compound

nanocrystals were synthesized by the gas-phase method [2]. Cu2O intensive exciton lines in blue

and indigo regions of spectra [1] and strong exciton lines at the ZnO and Zn0.99Mn0.01O absorption

edge [2] were registered by adjusting the amount of nanopowder.

This work deals with NiO nanocrystals, the size of nanocrystals is (5-25) nm. They were placed

between two quartz plates. The absorption spectra of 5 nm nanocrystal (curve 1) and 25 nm ones

(curve 2) are shown in Figure 1.

2 4 60,0

0,2

0,4

0,6

0,8

1,0

1,2

1,4

1,6

1,8

2,0

Op

tic

al

de

ns

ity

Energy , eV

1

2

Figure 1

Absorption spectra of NiO nanocrystals. The size of nanocrystals are 5 nm (curve 1) and 25 nm (curve 2)

Some differences of spectra are observed in high absorption region. They will be discussed in the

report on the basis of conception that absorption is the sum of contributions of p-d- and d-d-charge

transfer transitions.

References:

1. V. I. Sokolov, A. Ye. Yermakov, M. A. Uimin, A. A. Mysik, V. B. Vykhodets, T. E. Kurennykh,

V. S. Gaviko, N. N. Shchegoleva, N. B. Gruzdev. JETP, 2007, 105, 1, 65–68. 2. N. B. Gruzdev, V. I. Sokolov, A. Ye. Yermakov, M. A. Uimin, A. A. Mysik, V. A. Pustovarov.

JETP, 2010, 111, 2, 231-235.


174

KINETIC LENS EFFECT IN INTERMOLECULAR ENERGY TRANSFER

NEAR METALLIC NANOPARTICLE WITH

MACROMOLECULAR COVER

M.G. Kucherenko, S.V. Izmodenova, T.M. Chmereva


[email protected]

Dipole-dipole radiationless electron excitation energy transfer between two molecules (donor (D)

and acceptor (A)) near a spherical metallic nanoparticle (NP) is considered. In such system, the

energy transfer rate depends on the distance between the D(A) molecule and nanoparticle center as

well as some set of angular parameters. In closed D-NP-A complexes with an optimal geometrical

configuration the radiationless energy transfer is carried out by an assistant of localized plasmons.

Because the observed luminescent quenching kinetics is presented as some superposition of

different local time resolution signals with corresponding profiles. Polymeric chain linkers can be

used for D and A molecules confinement in the near particle area. Analytical expressions for

composite matrix elements of the donor-acceptor dipole-dipole interaction, including intermediate

local plasmonic states are obtained. Estimates of an intermolecular energy transfer rate in the presence of metal nanoparticles are yielded in the approximation of dipole plasma oscillations.

In addition, the dynamical polarizability of the nanosphere in the case of degenerate electronic gas

is considered and the degeneracy role in plasmonic mechanism of the D-A energy transfer is

indicate. It is shown, as a degeneracy of the electronic gas in a spherical metallic nanoparticle will

influence on a resonant behaviour of its dipole polarizability in the monochromatic electromagnetic

field on optical frequencies at presence of dissipative processes in the conductor (complexity of the

dielectric permeability). Frequency dependencies of real and imaginary parts of the spherical

nanoparticle polarizability are received in the manner of graphs for different values of radius of

particles, lengths of Thomas-Fermi’s screening and decay constant. Expressions for the

radiationless energy transfer rate between molecules near nanoparticle and the D-NP energy transfer

rate, including itself the nanosphere dynamic polarizability with the degenerate electronic gas are

obtained.

Performed estimate of the “kinetic lens” effect is used for the preparation of the experimental

observation of the inductive-resonant energy transfer between organic dyes molecules connected with the metal nanoparticles in colloidal solutions.

Spin-forbidden triplet-singlet energy transfer kinetics was considered in addition to the singlet-

singlet reaction as an example of another process formed by “kinetic lens”.

This work was supported by the Russian Foundation for Basic Research (project no. № 10-02-

96021-r_ural_а) and the Ministry of Education and Science of the Russian Federation (under

assignment no. 1.3.06 from the Federal Agency of Education).

1. Kucherenko M. G., Chmereva T. M., Kislov D. A. Energy Transfer in Molecular Systems at the

Surface of Metal Solids and Nanoparticles // High Energy Chemistry. 2009. Vol. 43. -No. 7. -P.

587-591.

2. Kucherenko M.G., Chmereva T.M. Processes with participation of electron-excited molecules

on solid adsorbent surfaces. Orenburg: Orenburg State University. 2010. -346 p. (in Russian).


175

PHOTOPHYSICAL PROPERTIES OF COMPLEXES FORMED BY THE

SEMICONDUCTOR QUANTUM DOTS AND CHLORINE E6 MOLECULES

I.V. Martynenko1, A.O. Orlova

1, V.G. Maslov

1, A.V. Baranov

1, M.V. Artemyev

2

1 – National Research University of Information Technologies, Mechanics and Optics, Saint-Petersburg, Russia 2 – Institute for Physical-Chemical Problems of the Belarusian State University, Minsk, Belarus

[email protected]

Interest in tetrapyrrole compounds and complexes based on both fundamental and applied

viewpoints has been sparked by their photophysical properties, such as high quantum yield of

singlet oxygen generation, oncotropic properties (tetrapyrroles show preferential accumulation in

target tissues) and suitable spectral characteristics (high specific absorption coefficient at

wavelengths longer than 630 nm and preferably above 700 nm) [1].

In the past decade the complexes formed by the colloidal quantum dots (QD) and tetrapyrrol

substances in liquid solutions have been actively investigated [2]. QDs are the semiconductor

nanocrystals with the typically sizes of 2–10 nm. QDs have unique optical properties such as

dependence between the wavelength of the QD fluorescence maximum and its size, high quantum

yield of fluorescence, broad excitation spectra with extremely high extinction coefficient over a

wide wavelength range. Due to this, it’s possible to use the QD as the energy donor in complexes

with organic molecules. Particularly, in QD/tetrapyrrole complexes an efficient photoexcitation

energy transfer from QD to molecule can significantly increase the efficiency of singlet oxygen

generation compared with the free tetrapyrroles.

In this work we present the study of photophysical properties of two types of complexes formed by

water-soluble CdSe/ZnS QDs and chlorine e6, binding by different mechanisms such as covalent

bonding and electrostatic interaction. Chlorine e6 is one of the tetrapyrrole compounds and today is

widely used as the main component of drugs for photodynamic therapy (Photoditazin, Photostim,

Radachlorin, etc.).

Covalent binding of the QD with chlorine e6 molecules using 1-Ethyl-3-(3-Dimethylaminopropyl)

carbodiimide hydrochloride (EDAC) as a cross-linking reagent has been performed. Previously the

hydrophobic CdSe / ZnS / TOPO QDs were solubilized by standard method by cysteine, then

cysteine was replaced by the polyethylene glycol (PEG). Also the QD/chlorine complex formation

via electrostatic interactions between the peripheral negatively charged carboxyl chlorine groups

and positive QD solubilizer molecules groups was studied.

Analysis of the photophysical properties of two types of complexes showed that the spectral form of

chlorine e6 bound in a complex with QD is different from the free molecular form. At the same

time there was a 30% decrease in its quantum yield of luminescence compared to the unbound

form. In both types of complexes the sensitized luminescence of chlorine e6 was observed. This

indicates an efficient energy transfer from the QD to the molecules. It was found that the

experimental efficiency of energy transfer in covalently bound complexes is equal to 8%, that

amounts 30% of the theoretical FRET efficiency. Meanwhile, for the complexes derived from the

electrostatic interaction between QDs and chlorine e6, the experimental efficiency of energy

transfer was two times lower – 4%. The low efficiency of the experimental energy transfer in both

cases is associated with the formation of a competitive channel of nonradiative energy transfer. This

leads to a decrease in the luminescence of chlorine by 30% of the maximum possible for the

covalent binding, and 90% in the case of electrostatic interaction.

1. Warren, M. J., and A. G. Smith. 2008. Tetrapyrroles: birth, life and death. Landes Bioscience, Springer Science and Business Media, New York, NY.

2. Maslov V., Orlova A., Baranov A., Combination Therapy: Complexing of QDs with tetrapyrrols and

other dyes. In: “Photosensitisers in medicine, Environment, and Security”. T. Nyokong, V. Ahsen, Eds. Part II, Chapter 3//Springer-Verlag. 1st Edition. 2011. 699 p. ISBN: 9789048138708.


176

PHOTONICS OF

6-PYRAZOLYL(ISOXAZOLYL)-7-HYDROXYCOUMARINS

V.S. Moskvina1, V.P. Khilya

1, A.A. Ishchenko

2

1 – Taras Shevchenko National University, Ukraine

2 – Institute of Organic Chemistry NAS, Kyiv, Ukraine

[email protected]

Derivatives of 7-hydroxycoumarins, due to their wide set of spectral, biological, and chemical

properties, are being widely applied as active laser media, fluorescence labels and probes, and

luminescent solar concentrators and optical bleaches. Up to date compounds with heterocyclic

substituents in the 3rd

position of the coumarin system were obtained and their spectral-luminescent

properties were studied. In this work we present a study of spectral-luminescent properties of

coumarins with residues of pyrazol (compound 1) and isoxazol (compound 2) in the 6th

position,

and effects of electron structure and medium on them.

O

Me

OOH

N

NH

O

Me

OOH

O

N

1 2

The fluorescence spectra of compounds 1, 2 in CH2Cl2 mirror the absorption spectra. The principle

of mirror symmetry is violated in DMSO because of the emergence of the new long-wavelength

fluorescence band, accompanied by a sharp rise in Φf (to 43 and 70%, respectively) and an increase

in SS (for 1: 2119 and 7140 cm-1

both at λex = 310 and λех = 370 nm; for 2: 1783 and 7472 cm-1

at

λех=310, 1928 and 7817 cm-1

at λех=370 nm). Regardless of the excitation wavelength, compounds

1 and 2 display long-wavelengeth fluorescence almost exclusively in MeOH (for 1: λfmax = 469 nm,

SS = 7664 cm-1

; for 2: λfmax = 470 nm, SS = 4697 cm

-1). The addition of Et3N to the methanol

solution suppresses the insignificant short-wavelength emission and has no effect on the position or

shape of the long-wavelength emission band. Conversely, addition of HCl to the solution restores

the short-wavelength fluorescence with the maximum corresponding to the emission range of this

compound in CH2Cl2. In addition, the long-avelength fluorescence band undegoes a bathochromic

shift. Both this shift and the fact that the long-avelength absorption is suppressed by acidification result in SS values of 10422 and 10016 cm

-1 for compounds 1 and 2, respectively.

Upon electronic excitation of 6-hetarylcoumarins 1, 2, their electronic charges and bond orders

experience a strong redistribution, which causes a considerable increase in SS. A decrease in the

charge on the oxygen atom of the hydroxyl group and its increase on the oxygen atom of the

carbonyl group in the excited state of compound 1 in polar and proton-donor solvents lead to the

phototransfer of proton from the hydroxyl group to the carbonyl group, as a result of which anionic

and tautomeric forms are created (ab initio quantum-chemical calculations were performed using

the PC Gamess/Firefly software package by the DFT and TDDFT methods in the B3LYP/6-31G

(d,p) basis set with preliminary geometry optimization).

Therefore, by varying the nature and pH of medium, one can in a directed fashion control the

proportion between the neutral, anionic, and tautomeric forms and, consequently, their spectral–

luminescent properties. This implies good prospects for their wide application for solving diverse

applied problems.


177

TUNABLE ORGANIC LASERS SIMULATION

S.Yu. Nikonov, R.M. Gadirov, V.Ya. Artukhov, T.N. Kopylova

Syberian physical technical institute Tomsk State University

[email protected]

A software package designed for the simulation of the fluorescence and generation of optical

radiation in plane-parallel resonator with transverse pumping by a pulsed monochromatic light source with a rectangular cross section.

For the simulation scheme with five electronic levels (3 singlets and 2 triplets) is used (Img. 1).

5

1

3

4

2 νг νн

Img. 1 – Energy levels of the dye molecule.

On the left shows the singlet levels (S0, S1 and S2 – 1, 3 and 5 respectively), on the right T1 and T2 –

(2 and 4).

Populations of the levels are described by a system of five differential equations:

)(**),(*

)(**),(*

)(**),()(**),()(**),(*)(**

)(**),(***

)(**),()(**),(*)(*

3535355

2424244

313353131323313135353

2423232124242

131313212313131

NtIkNdt

dN

NtIkNdt

dN

NtINtINtIkNkkNkNdt

dN

NtIkNkNkNdt

dN

NtINtIkNkkNdt

dN

ic

ic

STflicic

STSTic

STflic

where kic – internal 3→1 crossing, kfl – fluorescence rate constant 3→1, kTS – nonradiative rate

constant 2→1, kST – intersystem crossing 3→2, kphs – phosphorescence rate constant (2→1), k53 и

k24 – non-optical transitions between the corresponding states.

Solving the system, we find the level populations. After this, other parameters are calculated (lasing wavelength, efficiency, dynamics, losses etc.

This approach has shown high efficiency and now it’s adapted to perform calculations on a

supercomputer SKIF “Cyberia”. Simulation can be performed both on the experimental spectra of

organic dyes, and on the calculated spectra from quantum-chemical theory. It’s possible to perform

a series of calculations with varying input parameters (dye concentration, reflection factor etc.) for

parameters optimization.

This work was supported by Federal Program «Innovative laser, optical and optoelectronic

technologies – photonics», GC №07.514.11.4057.


178

STRUCTURE AND SPECTRAL-LUMINESCENT PROPERTIES

OF BISINDOTRICARBOCYANINE DYES

WITH UNCONJUGATED CHROMOPHORES

E.Ia. Osmanova1, N.A. Derevyanko

2, A.A. Ishchenko

2

1 – Institute of High Technologies, Taras Shevchenko National University, Kyiv, Ukraine


[email protected]

The phenomenon of chromophore-chromophore interaction in the biscyanine dyes with

unconjugated chromophores to date was studied just for dyes with a short polymethine chain as

carbocyanines [1]. The new types of bisindotricarbocyanines with a general structure shown below

were synthesized.

1, m=1; 2, m=2; 3, m=3; 4, m=5.

There are two clearly resolved absorption bands in the spectra of all these compounds. The

interactions between chromophores are most distinctly manifested in the dye 1. The distance

between the absorption maxima (Δυ) which (shows the degree) is related to degree of the

chromophores interaction is more than 2200 cm-1

. This indicates that the absorption bands belong to

different electronic transitions. This conclusion is confirmed by the fluorescence spectra data; there is only one band which corresponds to the long-wavelength transition.

The increase of the number of CH2 groups in the insulating polymethylene bridge decreases the

value of Δυ.

When m > 1 it is difficult to make unequivocal conclusions about the degree of chromophores

interaction by using the absorption maxima because short-wave transition band significantly

overlaps with vibrational maximum of the long-wave transition. Therefore, to examine the

chromophores interaction in dyes 1-4 we analysed the shapes of bands (in particular, the bandwidth)

using the moments method [1]. In this way, the dependence of the degree of chromophores interaction from the length of the polymethylene bridge was clearly defined.

The long-wavelength band is more intensive than the short-wavelength band. This indicates that the

angle between the chromophores is obtuse.

[1] A.A. Ishchenko. Structure and spectral-luminescent properties of polymethine dyes. – Kiev:

Naukova Dumka, 1994.


179

OPTICAL PROPERTIES OF ORGANOSILICON

POLYMER NANOAGGREGATES

N.I. Ostapenko, O. Kerita, Yu.V. Ostapenko


[email protected]

The organic/nanosize inorganic hybrid materials have a prominent role in the forefront of research

due to combining the advantages of organic and inorganic materials and open up countless possibilities for application.

In this work novel composite films based on poly (di-n-hexylsilane) (PDHS) incorporated into SiO2

[1] and TiO2 nanoporous films were fabricated. Photoelectronic properties of these composites

have been studied using optical spectra and photoluminescence decay measurements in the wide

temperature range (5-330) K as well as refractive index of inorganic matrix and composites. It was

proved that the polymer chains are localized into the nanopores of inorganic films. These

measurements demonstrate essential influence of inorganic matrixes on the polymer chains

conformation and the emission properties. Temperature dependence of photoluminescence

intensities enabled us to establish the nature of the conformational structure of the polymer chains

as well as to obtain information about the thermochromic transition of the confined PDHS and the excitation energy transfer pathways.

The fabricated composite films were proved to have peculiarities associated with the domination of

the nanoaggregates formation over the other conformations of the polymer chains as well as the

existence of the intense FL band of the nanoaggregates even at room temperature. The aggregates

lifetime is independent of temperature in 5-200 K, while surprisingly increases above the trans-

gauche transition temperature, what is in contrast to the results obtained for polymer films and

solutions. These characteristics of nanocomposites are expected to be promising for their

application in optoelectronic units as organic LEDs.


180

DFT MODELING OF THE ADSORPTION OF AU ATOMS

ON THE INAS(001) BETA2-SURFACE: THE CLUSTER APPROACH

O.Yu. Podkopaeva, Yu.V. Chizhov, I.V. Krauklis

Department of Physics, St. Petersburg State University, Russia

[email protected]

It is well known that the materials based on АIII

ВV semiconductor heterostructures are the most

prospective materials for solid state photonics, microelectronics, optoelectronics, and

nanobiotechnology [1]. The last decade the interest has been focused on studying threadlike

nanocrystals or nanowhiskers. The participation of Au as a catalyst is one of the success factors in

the process of epitaxial growth of nanowhiskers. Surface reconstructions on pure InAs(001) are

well studied [2]. However, the adsorption of metal submonolayers on semiconductor surfaces leads

to more diverse surface configurations than in the case of pure surfaces [3].

In the present project, we use the quantum chemical cluster approach for modeling the InAs surface.

The InAs(001) β2-surface commonly obtained under standard conditions of epitaxial growth is

modeled by In44As44H56 stoichiometric cluster. This cluster is a seven-layer cluster where all the

dangling bonds, except for those of the first two top layers, are passivated by H-atoms, and the

uppermost layer is formed by typical As surface dimers (Fig.1a). In geometry optimization, the

three lower atomic layers of In44As44H56 cluster were frozen, which however did not cause

significant changes of its electronic spectrum. The Au atoms (indicated by numbers 1–4 in Fig. 1b)

were added successively to the most energetically favorable positions over the nanocluster surface.

The adsorption energies of Au adatoms were estimated as the differences between the total energies

of the resulting and initial structures. It turned out that the barrierless insertion of Au atoms is

possible only into positions 1 and 2: ΔEB(Au1) = –1.82 eV and ΔEB(Au2) = –1.67 eV, and

considerable extension of the surface As-dimer bonds from R = 2.62 Å to R = 2.84Å takes place.

This, in turn, leads to the possibility of a further barrierless bonding of Au adatoms in positions 3

and 4 with a considerable gain in total energy: ΔEB(Au3) = –2.36 eV and ΔEB(Au4) = –2.33 eV.

At the same time, the two remaining As-dimer bonds shrink from R = 2.84 Å to R = 2.61 Å.

All quantum-chemical calculations were carried out by Gaussian 03 [4] package using the

mPW1PW91 DFT method in the LanL2DZ pseudopotential basis. This work was performed in the

framework of SPbSU project “The study of the functional properties of semiconductor nanoclusters

by DFT methods”, contract No.11.37.25.2011.

а) In44As44H56_Fz3 nanocluster: initial structure

б) In44As44H56_Fz3 + 4 Au nanocluster

Fig.1. a) Optimized geometry of the initial In44As44H56 nanocluster with three frozen lower atomic layers; b) The structure of the resulting In44As44H56Au4 nanocluster with four successively inserted Au adatoms.

[1] V.G. Dubrovskii et al., Fizika i tekhnika poluprovodnikov, 2009, V. 43, N. 12, p. 1585-1628. [2] W.G. Schmidt, III−V compound semiconductor (001) surfaces, Appl. Phys. A 75, 89–99 (2002). [3] T.Zhe, Y.Shen-Yuan, J.Ying at al. Chin.Phys.Lett. V. 25, No. 8 (2008), p. 2977. [4] Gaussian 03, Revision B.05, Frisch M.J. et al. Gaussian, Inc., Pittsburgh PA, 2003.


181

THE NOVEL OPTICAL PROPERTY OF SUPRAMOLECULAR SYSTEMS

INVOLVING SILVER NANOPARTICLES AND IONIC SURFACTANTS

G.I. Romanovskaya, M.V. Koroleva

V.I. Vernadsky Institute of Geochemistry and Analytical Chemistry RAS, Moscow, Russia

[email protected]

It was shown by spectral-luminescent investigations of the silver aqua sols in presence ionic

surfactants that new supramolecules were formed.

It was observed that these Supramolecular systems were generated at critical micellar

concentrations (CMC) of the anionic surfactant, namely sodium dodecyl sulfate (SDS), adding to

dilute silver aqua sol (≤ 0.16 mM), stabilized by a cationic surfactant, namely cetyltrimethyl-

ammonium bromide (CTAB)

The novel optical property the resulting supramolecular systems – a linear dichroism was revealed.

On an example of one of representations of polycyclic aromatic hydrocarbons (PAHs) – pyrene it was established that investigated systems variously absorb its own polarized fluorescence.

It is standard practice to use pyrene as fluorescence probe. Its fluorescence spectra are highly

sensitive to changes in the nearest environment. In addition the fluorescence spectrum of pyrene is two linearly-polarized perpendicularly one to another components in viscous medium.

It is possible to explain the observed phenomenon by presence in investigated systems the

homogeneously spatial arrangement of silver nanoparticles dipoles. It is known that dipoles of metal

nanoparticles, in particular silver, are formed at their interaction with electromagnetic radiation.

In our work necessary orientation of silver nanoparticles dipoles carried out by means of optical

influence (the polarized fluorescence of pyrene), changing concentration of present SDS. It was

established that at SDS concentration much less that CMC except radiationless electron density

transfer from excited pyrene molecules (donor) to silver nanoparticles (acceptor), before [1] found

out by us, it is observed the pyrene fluorescence transmittion in violet spectral range. At

concentration of the SDS exceeding value CMC, it is pyrene fluorescence transmittion in blue

spectral range.

In all cases the most contrast by found out novel property of the resulting supramolecular systems is observed in presence CTAB (C = 0.19 mM).

The given systems can be used as polarizing medium, for example, for creation polarizing optical

filters.

1. A. Yu. Olenin, G.I. Romanovskaya, A. Yu Krutyakov, et al., Dokl. Akad. Nauk. 419, 508-511

(2008).


182

HYBRID MOLECULAR SYSTEMS BASED ON FULLERENE DERIVATIVE

AND DYE AS POTENTIAL DRUGS FOR PHOTODYNAMIC THERAPY

A.Yu. Rybkin, A.V. Barinov, N.S. Goryachev, A.B. Kornev, P.A. Troshin, A.I. Kotelnikov


[email protected]

Photodynamic therapy (PDT) is a new fast-developing approach of cancer treatment, and much

attention paid nowadays to create new photosensitizers. Fullerene (C60) derivatives as

photosensitizers are attractive due to their high quantum yield of singlet oxygen or superoxide and

lack of acute toxicity in the absence of the light. Pure fullerene has very low absorption of the

wavelength from 650 to 1000 nm, however this absorption range is the most suitable for PDT

because of the low absorption of red light by cells and tissues. This problem may be solved by using

complex of the fullerene with a dye which has high red light absorption and dumps excitation

energy to fullerene core effectively.

In the present work we have studied photophysical properties and photodynamic action of

complexes of polycationic fullerene derivative with xanthene dye eosine Y, commercial drug

«Photosens» and hybrid molecular structure of fullerene with anthracycline antibiotic «Ruboxile»

bonded covalently.

Water-soluble polycationic fullerene derivative (PFD) and hybrid molecular structure fullerene-

Ruboxile was synthesized as described at [2]. Molecular structure was studied by IR and UV-

absorption spectroscopy, electrospray mass spectrometry analysis, nuclear magnetic resonance

spectroscopy on 1Н and

13С nuclei.

Photodynamic activity of the compounds under study was estimated by generation of О2-

under

visible light irradiation (450–550 nm for eozine Y and Ruboxile, > 640 nm for Photosens) in water solution with NADH, NBT and EDTA as described in method [1].

By steady-state fluorimetry and kinetic phosphorescent spectroscopy it was shown that the PFD

forms complexes with eosine Y and commercial drug Photosens (equilibrium constant Кe = 1.02∙106

М-1

and Кe = 1.5∙105 М

-1, for eosine Y and Photosens, respectively) due to electrostatic interactions

in solution. It was found that the excited states of a dye are effectively quenched either due to

excitation energy transfer or electron transfer from a dye to the fullerene core. And it can’t be specified which way is more likely.

Apparently that is the reason for a substantial increase of photodynamic activity of the PFD when

PFD forms complex with the dye and this complex is excited by the light in the absorption band of

the dye. We have observed increase of photodynamic activity compared to pure dye/fullerene

derivative. It was about 10 times more for complex PFD-eozine Y and ~100 times more for

complex PFD-Photosens. Same result was obtained for hybrid molecular structure fullerene-

Ruboxile (more than three times increase).

Given results showed availability of such structures as potential drugs for photodynamic therapy.

This work was supported by the RFBR (grant 10-03-00687), the President Science Foundation

(MK-4916.2011.3) and the Presidium of Russian Academy of Sciences (Research program No 24

“Fundamental research in the field of nanotechnology and nanomaterials”).

1. Yamakoshi Y., Umezawa N., Ryu A., et al. Active Oxygen Species Generated from

Photoexcited Fullerene (C60) as Potential Medicines: O2- versus

1O2 // J. Am. Chem. Soc. 2003.

Vol. 125. P. 12803-12809.

2. Troshin P.A., Troshina O.A., Peregudova S.M., et al. // Mendeleyev Commun. 2006. P. 206.


183

STRUCTURE AND SPECTRAL-LUMINESCENT PROPERTIES

OF INDODICARBOCYANINE AGGREGATES

A.Yu. Shargaeva1, A.V. Kulinich

2, Yu.L. Slominskii

2, A.A. Ishchenko

2

1 – Taras Shevchenko National University, Kyiv, Ukraine


[email protected]

Aggregation - one of the areas of supramolecular chemistry as a method to obtain materials with

predetermined properties. The aim of this research was to determine the regularities of

indodicarbocyanines 1-6 aggregation in depending on their structure in solutions of DMF, water,

and mixtures thereof.

N+

N

R3

R1 R1

R2 R2

(Et)3NH+

N+

N

R3R2 R2

(Et)3NH+

1-5 6

1 R1 = H, R2 = (CH2)4SO3-, R3 = H; 2 R1 = H, R2 = (CH2)3SO3

-, R3 = Ph; 3 R1 = H, R2 =

(CH2)3SO3-, R3 = Naph; 4 R1 = H, R2 = (CH2)4SO3

-, R3 = Naph; 5 R1 = SO3

-, R2 = Et, R3 = Naph;

6 R2 = (CH2)3SO3-, R3 = Naph.

It is found that a compound 1 with unsubstituted polymethine chain in these environments are not

prone to aggregation at concentrations up to 2∙10-5

mol/l. With the introduction of bulky

substituents in the meso-position of the polymethine chain (compound 2) arises a new absorption

band in the shortwave region. With the increasing water content in the DMF-water mixture

increases its intensity and the fluorescence quench of the monomer band. This indicates to the

formation of H-aggregate. In the presence of singly charged cations of salts (KCl, LiClO4)

decreases the intensity of the absorption bands of the monomer and H-aggregate as well the

appearance of high-intensity narrow band in the wavelength region, which coincides with the

resonance fluorescence band. This indicates to the formation of J-aggregate dye. With the

increasing the volume of meso-substituent, the formation of J-aggregate takes place even in the

absence of salt additives. By changing the position of sulfo-groups (their introduction into

heterocyclic nuclei – compound 4) J-aggregation does not occur, but it promotes the formation of

H-aggregate. The going from dye 3 to isomeric compounds 5 leads to a decrease the area of

interaction between molecules and the output of sulfonic groups from the plane of the polymethine

chromophore, that prevents to the aggregates formation.


184

OPTICAL PROPERTIES OF CYANINE DYE LAYERS

MODIFIED BY PLASMONIC NANOPARTICLES

N.A. Toropov, E.N. Kaliteevskaya, N.B. Leonov, T.A. Vartanyan


[email protected]

Optical properties of the dyes molecules covering a granular metal film can be largely modified

provided the metal nanoparticles comprising the film support plasma oscillations. In our

experiments silver was used as a nanoparticle material. The granular film was obtained via thermal

evaporation on a sapphire substrate in high vacuum conditions. Mono- and dicarbocyanine dye

molecules were spread over the silver nanoparticle arrays by spin-coating technique. The samples

were characterized by scanning electron microscopy, optical spectroscopy, and laser scanning

fluorescent microscopy. Significant enhancements of the dye absorption, fluorescence as well as the

shifts of the spectral positions of plasmon resonances were observed. The character and the rate of

the photoinduced transformations of the dye molecules are found to differ significantly for the samples prepared on the silver granular films and the bare sapphire substrates.

The extinction spectrum of the hybrid material was rationalized as a result of mutual interactions

between the plasma oscillations localized in the metal nanoparticles and resonance absorption and

refraction of dye molecules. Plasmon resonances are shifted due to the anomalous refraction of the

dye molecules. Depending on the spectral position of the dye absorption band relative to the

inhomogeneously broadened plasmon band, this shift can lead to considerable clarification or darkening of the sample at particular wavelengths. Both effects were observed experimentally.

On the other hand, the absorption of dye molecules is enhanced due to the incident field

amplification in the near field of metal nanoparticles. Even when the dye absorption band overlaps

with the tail of the plasmon band of silver nanoparticles, 3 to 5 times enhancement of the dye absorption was obtained.

The fluorescent images of the samples reveal the presence of dye microcrystals on their surface.

The regions containing such microcrystals were excluded from the further analysis of the

fluorescent band of the molecular dye layers. A nearly 4-fold increase of cyanine dyes fluorescence intensity in the presence of metal nanoparticles was observed.

The photoinduced transformations of the dye molecular layers under the action of ruby and

Nd:YAG-laser irradiation were studied. The mono- and dicarbocyanine dye layers were found to

behave differently under the laser action.


185

PHOTOCHROMIC HYBRID NANOSYSTEMS

BASED ON DIARYLETHENES

G.T. Vasilyuk1, S.A. Maskevich

1, V.F. Askirka

1, A.E. German

1,

S.A. Kurkhuzenkov1, I.F. Sveklo

1, V.M. Yasinsky

2, V.A. Barachevsky

3, A.O. Ayt

3

1 – Ya. Kupala State University, Grodno, Belarus

2 – B.I. Stepanov Institute of Physics NAS, Minsk, Belarus


[email protected]

Designing of the reversible photochromic switchers based on hybrid organic-inorganic systems

uppermost from nanoparticles of noble metals and molecules of photochromic compounds is new

intensively developing nanotechnological trend. These kinds of photo-switchers are of special

interest for using in informational technologies developing sensors and photosensitive detecting

mediums for optical memory of superhigh capacity.

In the present work with developed technology solid-phase hybrid nanostructured systems “metallic

particle–photochrome” (composed of Ag and Au nanoparticles with photochromic diarylethene

molecules shell) are obtained. Structure and optical properties of mentioned hybrid systems as well

as features of their photochromic transformations were investigated by means of methods of kinetic

spectral photometry, surface enhanced Raman scattering (SERS) spectroscopy, luminescence,

quantum chemistry, scanning probe microscopy (SPM).

It was shown, that investigated hybrid nanostructures display photochromic properties (both in

solutions and solid-phase state) similar to photochromic properties of diarylethene in solutions and

solid-phase layers. Using of SERS spectroscopy and luminescence methods shown that valency

interaction of the diarylethene molecules with Ag nanoparticles become apparent only for

functionalized compounds (containing NH groups).

Work was supported by BRFFI (grant F10R-241), RFFI (grant 10-03-90023 Bel_a).


186

PHOTONICS AND SINGLET OXYGEN GENERATION

BY SEMICONDUCTOR QUANTUM DOTS CDSE/ZNS

SURFACELY PASSIVATED BY PORPHYRIN PHOTOSENSITIZERS

E.I. Zenkevich1, E.I. Sagun

2, V.N. Knyukshto

2, A.S. Stasheuski

2, V.A. Galievsky

2,

A.P. Stupak2, T. Blaudeck

3, C. von Borczyskowski

4

1 – National Technical University of Belarus, Minsk, Belarus


3 – Linkoping University, Sweden

4 – Institute of Physics, Chemnitz University of Technology, Germany

[email protected]

Photodynamic therapy makes use of the so-called photodynamic effect in which singlet oxygen

(1O2) is generated in the target tissue via Foerster resonance energy transfer (FRET) from the first

excited triplet state of a photosensitizer to molecular oxygen in its triplet ground state.

Semiconductor nanocrystals, otherwise known as quantum dots (QDs), are promising for such

applications because of their size-dependent optical properties, wide intense absorption bands and

relatively narrow, tunable emissions. The shell of ligand molecules surrounding QDs allows their

chemical properties to be adjusted through relatively straightforward solution-based surface

chemistry with the driven FRET efficiency. QDs are impacting the areas of photonics, electronics, bio-imaging as well as hold great potential for applications in nanomedicine.

In the report, we describe photonics of self-assembled nanocomposites “CdSe/ZnS QD – Porphyrin”

in toluene at 295 K. We discuss the results on quantitative experimental evaluation of exciton

relaxation pathways (using steady-state and time-resolved spectroscopy) as well as direct

measurements of singlet oxygen generation efficiencies (near-IR region) published in [1].

QD photoluminescence quenching in the nanocomposites under study is caused by two main

reasons: the electron tunneling in the conditions of quantum confinement (the efficiency of 0.85–

0.90) as well FRET QD→porphyrin (the efficiency of 0.10–0.15). The experimental efficiencies γΔ

of 1O2 generation by “QD-Porphyrin” nanocomposites are essentially higher with respect to those

obtained for alone QDs. For nanocomposites, the non-linear decrease of 1O2 generation efficiency

γΔ on the laser pulse energy increase is caused by non-radiative intraband Auger processes, realized

in QD counterpart. Finally, within the accuracy of the independent experiments, FRET efficiencies

found from the direct sensitization data for porphyrin fluorescence in nanocomposites (ΦFRET = 0.14

± 0.02) are in a good agreement with the corresponding values obtained via the direct 1О2

generation measurements at low laser excitation (ΦΔ

FRET = 0.12 ± 0.03). These quantitative results

provide for the first time strong evidence that namely FRET QD→Porphyrin is a main reason of 1O2

generation by the above nanocomposites.

References: 1. E.I. Zenkevich, E.I. Sagun, V.N. Knyukshto, A.S. Stasheuski, V.A. Galievsky, A.P.

Stupak, T. Blaudeck, C. von Borczyskowski, J. Phys. Chem. C. 2011, 115, No 44, P. 21535

3O2(

3Σg–) 1

O2(1Δg)

CdSe

ZnS FRET

EET

1225 1250 1275 1300 1325 1350

0

2

4

6

8

10

12

1O

2,

Lu

min

es

ce

nc

e,

a.u

.

Wavelength, nm

Experimental points

Fitted curve

Posters Photochromism of organic compounds ---------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------- ---------------------------------------------------------------------------------------------------------------------------------------

187

Pt

HC

O

H3CO

NNCH

O

OCH3

SECTION 7. PHOTOCHROMISM OF ORGANIC COMPOUNDS

PHOTOPHYSICAL AND PHOTOCHEMICAL PROPERTIES

OF PLATINUM(II) COMPLEXES WITH AZOMETHENE BASES

L.P. Ardasheva

Department of Inorganic Chemistry, A.I. Herzen State Pedagogical University of Russia, Saint-Petersburg, Russia

[email protected]

In recent decade, we have been engaged in the development of procedure of electrochemical

synthesis of thin-film polymers based on transitional metal complexes. They show electric

conductivity and photoelectric activity due to their ability to the reversible photo- and

electroinduced charge transfer [1].

Selection of objects for the synthesis of such thin-film polymers requires studying of photophysical

and photochemical properties of initial monomer compounds because photoactive and luminescent

polymers are perspective materials for creation of photogalvanic cells, luminophors, photocatalysts

and other nano-devices. In this connection the square-planar Pt(II) complexes [2] including those

with Salen-type ligands (Salen = N,N'-ethylene-bis(salicylideneimine) are the most attractive for the

photoactive systems development.

In this report the data describing the luminescence and photochemical properties of [Pt(3-

MeOSalen)] where 3-MeOSalen = N,N´-bis(3-methoxysalicylidine)ethylenediamine and [Pt(3-

MeOSaltMe)] where 3-MeOSaltMe = N,N ´-bis(3-methoxysalicylidine)butane-2,3-diamine is

presented.

[Pt(3-MeOSalen)] [Pt(3-MeOSaltMe)]

The results concerning the influence of donor-acceptor properties of Salen-type ligands on

photophysical and photochemical properties of the corresponding Pt(II) complexes in acetonitrile,

dimethylformamide, dimethyl sulfoxide, dichloromethane, ethanol solutions at Т = 298 К is

discussed.

It has been stated that both [Pt(3-MeOSalen)] and [Pt(3-MeOSaltMe)] exhibits luminescence at T =

298 and 77 K which proceeds from a lowest-lying triplet electronically excited state (ees) attributed

to a metal-to-ligand charge transfer.

Also, it was found that for [Pt(3-MeOSalen)] photochemical reaction proceeds from the same

lowest-lying triplet ees at T = 298 K in addition to the radiating ad nonradiating deactivation. The

quantum yield of the photoreaction depends on the nature of a solvent and concentration of the

complex, but is independent of the energy and intensity of the exciting light. The similar character

of absorption spectra transformation in all used solvents demonstrates the presence of the only

single dimeric product of photolysis.

In contradistinction to [Pt(3-MeOSalen)], the formation of excimers in solutions provides an

additional completing channel of degradation on the lowest-lying ees for [Pt(3-MeOSaltMe)] that

decreases the possibility of photochemical reaction occurrence.

On the basis of the experimental data and the calculated integrated quantum yield it was concluded

that efficiency of the photochemical reaction decreases in the series [Pt(Salen)] › [Pt(3-MeOSalen)]

> [Pt(3-MeOSaltMe)] due to the decrease in the π-acceptor properties of the corresponding ligands.

[1] Shagisultanova G., Orlova I., Ardasheva L., Popova E., J. Macromol. Phys. Macromol. Symp., 136 (1998). P.91. [2] Demas J.N., DeGraff B.A., Coord. Chem. Rev. 211 (2001). P. 317.

Pt

HC

O

H3CO

NNCH

O

OCH3


188

DEPENDENCE OF SPECTRAL-KINETIC PROPERTIES

OF PHOTOCHROMIC BIS-NAPHTOPYRANS

FROM VARIATIONS OF SYMMETRY

OF THE MOLECULAR STRUCTURES

A.O. Ayt, A.M. Gorelik, O.I. Kobeleva, V.A. Barachevsky


[email protected]

Photochromic naphthopyrans are an important class of photosensitive organic compounds of

supramolecular chemistry for production of nanostructured photosensitive materials. Photochromic

transformations of the compounds include the reversible photoinduced formation of merocyanine

colored form B from the colorless spiro form A under UV irradiation.

darkO

R2

R1

UV light

OR1

R2

A B

A comparative spectral-kinetic investigation of properties of synthesized both unsubstituted and

substituted naphthopyrans and bis- naphthopyrans was carried out. An absorption spectra, kinetics

of photocolouring and thermal relaxation, and also kinetics of photodegradation of the

compounds in toluene solution have been investigated. Analysis of the influence of structure factors on spectral-kinetic properties of the investigated compounds has been made.

With molecular modelling methods there was studied a dependency of location of absorption bands

and thermal stability of photoinduced merocyanine on a structure of substituted bis-naphthopyrans

which have various locations of pyrane cycles relatively to the central naphthalene ring and

substitutes with various electronic-donor properties in phenyl rings.


189

PHOTOCHROMIC ORGANIC SYSTEMS

BASED ON NEW BIS-NAPHTHO- AND ANTROPYRANS

FOR OPTICAL METAL SENSING AND LIGHT MODULATION

V.A. Barachevsky, A.O. Ayt, A.M. Gorelik, O.V. Venidiktova, O.I. Kobeleva, T.M. Valova

Photochemistry Center RAS, Novatorov st. 7a, Moscow, Russia

[email protected]

Photochromic naphthopyrans are an important class of photosensitive organic compounds and the

particular interest of them due to their efficient colorability, rapid reversibility, good fatigue

resistance, photostability with relation to irreversible photochemical reaction and light-sensitivity.

Usually application of such compounds is rather wide and has rendered these compounds invaluable

to the ophthalmic photochromic sun and contact lens industries. There are other application of

photochromic pyrans, for example, in fuel, security markers, as UV light intensity indicators, optical information technologies.

This paper is devoted to the development of photochromic systems base on derivatives of

naphthopyrans synthesized by us for making reversible optical chemosensor on metal ions.

Photochromic transformations of these compounds include reversible the photoinduced formation

of merocyanine colored form B from the colorless pyran form A under UV irradiation. This

application is based on a complexation of only photoinduced form B with metal ion. The sensing

effect is manifested in a change of absorption band position and, consequently, a solution color

depending on the metal nature.

O

Ph

Ph

HO

O

Ph

Ph

OAr1

Ar2

C

Ar1

Ar2

C CHO

Ph

Ph

OAr1

Ar2

UV

heat

In the frame of this science line 5 new functionalized bis-naphtho- and antropyrans and studied of

their functional properties in toluene, acetonitrile and poly(viny lbutiral). The long-wavelength

absorption of the spiropyran form is found to be in the range of 360-365 nm and is not significantly

affected by the compound structure. The photoinduced merocyanine form is characterized by

absorption band maxima at the spectral range 460-510 nm. It was found that over metal ions this

absorption band is moved to the long-wave spectral diapason (595-730 nm). The values of the

bathochromic shift depend on an ion type and may be used for selective optical sensing each cation in solution.

It was found that the complexation process is realized in the polymer matrix namely poly

(vinylbutiral). It is very important that unlike photochrochromic solutions photochromic polymer

systems containing metal ions are characterized drastically enhances of photostability to irreversible

photochemical transformations of photochromic naphthopyrans.


190

PHOTOCHEMICAL PROPERTIES OF NOVEL HYDRAZONES

DERIVATIVES OF OXAINDANE SPIROPYRANS

V.A. Barachevsky1, L.D. Popov

2, O.I. Kobeleva

1, T.M. Valova

1, A.O. Bulanov

2,

I.N. Shcherbakov2, A.A. Tsaturyan

2, A.A. Karamanov

2, A.N. Morozov

2, E.V. Ivannikova

2


2 – Department of Chemistry, Southern Federal University, Rostov-on-Don, Russia

[email protected]

Photochromic organic compounds or their various combinations are able to possess specific

physical and chemical properties which permit to consider them as optically active substances for

applications in different optical devices. Spiropyrans are organic photochromes which undergo the

reversible structural transformations activated by light irradiation of various spectral regions. The

synthesis of a new spirocompounds containing free functional groups allow to enter different

substitutients into molecules and to obtain the derivatives with a number of donor centers for using

them as ligands for obtaining both mono- and polynuclear complexes.

O

OCH3

CH3

OH

N

NH

O

R R = a) H, b) CH3, c) Cl, d) Br, e) NO2, f) N(CH3)2

We have obtained a number of novel hydrazones based on 3,3-dimethyl-7-hydroxi-8-formyl-[2Н-

1-benzopyrane-2,1-[2]-oxaindane] and hydrazide of substituted benzoic acid. The structures of spiropyrane and its hydrazones a – b were established by the X-ray method [1,2].

Photochemical properties of these new spiropyranes were studied in presence of metal ions. It was

established that photochemical activity is stronger for compounds having the substituent in the

benzopyranic part of 3,3-dimethyl-7-hydroxi-8-formyl-[2Н-1-benzopyrane-2,1-[2]-oxaindane].

Besides, the quantum-chemical modeling the structure was carried out and the geometry of the most

stable conformers of spiropyran hydrazone derivatives was revealed.

References.

1. A.O. Bulanov, I.N. Shcherbakov, Y.P. Tupolova, L.D.Popov, V.V. Lukov, V.A. Kogan, P.A.

Belikov. Acta Cryst. C. 65, 618–620 (2009).

2. A.O. Bulanov, I.N. Shcherbakov, L.D.Popov, E.Y. Shasheva, P.A. Belikov, Z.A. Starikova.

Acta Cryst. C. 67, 85–88 (2011).


191

SYNTHESIS AND PHOTOCHROMIC PROPERTIES

OF NEW ANTHRAPYRANS

V.A. Barachevsky, O.V. Venidiktova, A.M. Gorelik


[email protected]

Photochromic compounds from the chromene class are very perspective for application because of

the high cyclic recurrence of photochromic transformation. Unfortunately, these compounds are

characterized by the restricted photoinduced absorption in the range of 400-500 nm. In order to

extend the spectral range of light-induced absorption were at the first time synthesized and

investigated by the spectral-kinetic method of new photochromic anthrapyrans: 3,3-diphenyl-3H-

anthra[2,1-b]pyran (I) and 3-ferrocenyl-3-phenyl-3H-anthra[2,1-b]pyran (II).

Compounds I and II were prepared by reacting 2-anthrol and the corresponding by a propargyl

alcohol.

Investigations were carried out in solutions of acetonitrile without and in the presence of perchloric

acid and.

Spectral-kinetic characteristics of compounds I and II were measured before and after irradiation

with UV light. It was found that photoinduced transformations of these compounds is held by the

scheme:

Introduction of small concentration of perchloric acid in solution containing the compound I gives

rise to the photoinduced appearance two absorption bands in the visible spectral region. The new intense long-wavelength band is not observed in solution without acid.

The similar result is achieved by introduction of the ferrocenyl fragment R1 into the antrapyran

structure (II). The new absorption band is located in the near infrared spectral range too.

Thus, widening the spectral range of photoinduced absorption for antrapyrans may be achieved by

using perchloric acid as a component of photochromic systems or introduction of the ferrocenyl

substituent into the molecule structure.


192

SPECIFICITY OF PHOTOREACTION

WITH THIADICARBOCYANINE DIMERS

A.K. Chibisov1, G.V. Zakharova

1, V.G. Plotnikov

1, V.A. Smirnov

2



[email protected]

The primary steps of photoreaction of 3,3'-disulfopropyl-9,11-[ββ-

dimethyltrimethylene]thiadicarbocyanine (Dye 1) and 3,3'-disulfopropyl-5,5'-dichloro-9,11-[ββ-

dimethyltrimethylene]thiadicarbocyanine triethylammonium (Dye 2) dimers were studied in water

by ns-laser photolysis. The formation of the dimers (M22-

) is concluded from the analysis of

absorption spectra. Upon laser pulses (532 nm, 10 ns) of the Dye 1 and Dye 2 dimers a short-lived

transient (lifetime is 2∙10-4

s) with λmax = 520 nm was observed both in deairated and air saturated

aqueous solutions. The transient was found to be quenched by electron

(CH2)

3SO

3

S

N

S

N

(CH2)

3SO

3

Me Me

(C2H

5)

3NH

+

+--

Dye 1

(CH2)

3SO

3

S

N

ClS

N

(CH2)

3SO

3

Cl

Me Me

(C2H

5)

3NH

+

+--

Dye 2

donor (ascorbic acid) but not electron acceptors (p-nitroacetophenon, pNAP). The transient was

assigned to one-electron oxidized dimer M2-· formed as a result of two-quantum photoionization of

M22-

via the triplet state. The yield of M2-·

was found to be proportional to laser intensity in the

second power and took place at high light intensity. At lower pulse intensity the yield of M2-· is

proportional to laser intensity in the first power. Along with photoionization the M22-

exhibited the

intersystem crossing. The triplet of the dimers was quenched by pNAP that resulted in the formation

of M2-·.

References

1. Chibisov А.К., Zakharova G.V. Photochem.Photobiol. Sciences, 2011, DOI: 10.1039/

c1pp05273j.

The work was supported by the Division of chemistry and material sciences of the Russian

Academy of Sciences, program № 1 OXНМ.


193

STUDY OF SPECTRAL PROPERTIES

OF LABELLED ISOXAZOLE DERIVATIVES

O.V. Demina1, A.V. Laptev

1, N.E. Belikov

2, A.Yu. Lukin

1, V.I. Shvets

1,

S.D. Varfolomeev2, P.P. Levin

2, A.A. Khodonov

1

1 - M.V. Lomonosov State University of Fine Chemical Technologies, Moscow, Russia


[email protected]

The investigation of the regulation of ligand – receptor or ligand-enzyme interactions by the usage

of organic compounds with photochromic labels on the subcellular or molecular levels is one of the

significant tasks of bionanophotonics. The search of new effective variants of the direct regulation

of the human hemostasis system definite stages is the important medicine problem, because the

mortality from cardio-vascular diseases takes first place in the world. It was shown by us that a

number of 3,5-substituted isoxazoles were potent anti-aggregatory compounds [1,2,3]. A few 3,5-

substituted isoxazole analogs contained photochromic label – spiropyran moiety at 3- or 5-position

of isoxazole ring were synthesized by us for the determination of molecule pharmacophoric

fragment detail structure and the investigation of the action mechanism of this class compounds.

Photochromic and fluorescence properties of synthesized compounds were investigated. The

possibility of specific bonding of these substances with human platelets was demonstrated.

This work was partly supported by State contract № 16.740.11.0177 of FCP «Scientific and

scientific-pedagogical staff of innovational Russia» 2009-2013, Grant of President of RF for young

scientists support МК-6877.2012.4.

1. O.V. Demina, A.A. Khodonov, V.I. Shvets, S.D. Varfolomeev. (2002) Biological membranes

(Rus.), 10: 115-152.

2. O.V. Demina, P.V. Vrzhesch, A.A. Khodonov, V.I. Kozlovsky, S.D. Varfolomeev. (1995)

Bioorganic Chem. (Rus.), 21: 933-940.

3. O.V. Demina, A.V. Laptev, A.Yu. Lukin, A.A. Khodonov, N.E. Belikov, M.A. Fomin, I.V.

Gribkova, V.I. Shets, S.D. Varfolomeev. (2011) Biological membranes (Rus.), 28: 243-253.


194

ON SOLVATOFLUOROCHROMISM AND TWISTED INTRAMOLECULAR

CHARGE TRANSFER STATE OF THE NILE RED DYE

A.Ya. Freidzon, A.A. Safonov, A.A. Bagaturyants


[email protected]

The structure of Nile Red dye in the first excited state is studied by TDDFT and

XMCQDPT2/CASSCF. It is shown that the profile of the S1 potential energy surface along the NEt2

twisting coordinate has two minima, a locally excited (LE) planar one and a twisted intramolecular

charge transfer (TICT) one. TDDFT data show that this profile depends on the weight of HF

exchange in the functional: at 0% exchange, only the TICT minimum exists, while at 50% exchange

and more there is only the LE minimum. XMCQDPT2/CASSCF data show that the picture obtained

at 20–25% HF exchange is qualitatively correct. This multireference study showed that the energy

of the CT state is lowered due to the participation of doubly excited configurations and dynamic

correlation, which is implicitly included in the density functionals. Solvent effects on the relative

energies of the LE and TICT states and the barrier height are studied using polarizable continuum

model. The effect of hydrogen bonds is studied for a complex of Nile Red with two water

molecules. The solvatofluorochromism of Nile Red is explained both by nonspecific solvation,

which stabilizes the LE state and causes solvatofluorochromism in aprotic polar solvents, and by

hydrogen bonds in water and alcohols, which stabilize the TICT state and facilitate the transition

from LE to TICT.


195

PHOTOSENSITIVITY OF THE LIQUID CRYSTALS

DOPED WITH SPIROPYRANS

K. Japaridze, L. Devadze, J. Maisuradze, I. Mzavanadze,

N. Sepashvili, Ts. Zurabisvili, G. Petriashvili

Institute of Cybernetics, Tbilisi, Georgia

[email protected]

Spiropyrans are an important class of organic photochromic, bistable compounds. Bistable

molecules and molecule ensembles can exist in two thermodynamic stable states divided by a

certain energy barrier. Switching from one state to another occurs via external stimulation (light,

heat, mechanical stress, electric and magnetic fields, etc.). An uncolored spiropyran molecule with a

bulky structure by the influence of ultraviolet light (UV) is transformed into a coplanar, colored

merocyanine form with a high dipole moment. Such bipolar molecules under certain circumstances

easily selforganize, i.e. create nanoparticles. The merocyanine, coplanar, bipolar molecules

originated at inducing the spiropyran molecules with UV rays, in case of presence of a long alkyl

radical at nitrogen atom may be considered as a diphyl particle, with a head with a high dipole

moment and a long alkyl radical tail.

Such a molecule with its structure is similar to the surfactant molecules with micelle-originating

capability what makes us suppose that a merocyanine form of a spiropyran when placed in the

matrix with a certain order, e.g. in a liquid crystal, may be structured as micelle. A trigger of

micelle or nanoreactors origination in this case is the UV light (λ = 365 nm). At the given

temperature, prior to irradiation, the solution is made up of the matrix and spiropyran and

merocyanine-form molecules, which are in thermodynamic equilibrium with spiropyran. The

constant of thermo-dynamic equilibrium KT is less than the constant of photo-chemical equilibrium

KPH (KT<KPH). In case of exposition with the UV light, the thermo-dynamic equilibrium of the

composition is violated and inclines to the merocyanine-form molecules, and the solution gets

colored. The processes of photoinduction and micelle formation are noninertial, i.e. they are

initiated as soon as the trigger is started. There is one more pseudophase – the micelle originated at

the microlevel in the base solution. In the process of micelle formation, the base solution is depleted

with merocyanine molecules and the spiropyran molecules start to transform to the merocyanine

ones to restore the thermodynamic equilibrium. The merocyanine molecules, which are originated

in a photochemical manner, are added by the merocyanine form molecules originated to restore the

thermodynamic equilibrium. The given process increases the number of absorbing centers in the

composition what in the final account increases the effective photosensitivity of the system.

Spiropyran Merocyanine form

Non-polar tail

Polar head

I II


196

STUDY OF SPECTRAL PROPERTIES

OF SUBSTITUTED FORMYL-SPIROBENZOPYRANS

A.A. Khodonov1, A.V. Laptev

1, A.Yu. Lukin

1, N.E. Belikov

2,

O.V. Demina1, V.I. Shvets

1, P.P. Levin

2

1 – M.V. Lomonosov State University of Fine Chemical Technologies, Moscow, Russia


[email protected]

Indoline spirobenzopyrans are one of the most studied photochromic compound classes. Their

spectral properties and photochromic transformations parameters greatly depend on substituent

nature, thus variation of their substituent nature allows to make pointed search of photochromes

with defined properties. In present work we studied substituted spirobenzopyrans formylation process regioselectivity with different substituents in pyran cycle at Duff reaction conditions.

N O

R

3'5

6'

8'

N O

O

H

RSP-5-CHO

We have found out that Duff formylation of photochromic spiropyrans having electron-acceptor

substituents at the pyran part of molecule (R 6’NO2; 8’NO2; 6’CHO; 6’CO2Et; 6’CO2H) mainly

proceeds to C5-position of indoline fragment [1]. However, another two main products – 8’-formyl-

and 5,8’-bisformylderivatives at 1:3 ratio have been isolated upon Duff formylation of 6’-

halogensubstituted spiropyrans. 5,7’-Bisformylderivative is the main reaction product for

spiropyrans with R 8’OH, and two main products – 5-monoformyl- and 5,6’-bisformylderivatives have been isolated with 1:2 ratio in case of R 8’OMe under the same reaction conditions.

This kind of spiropyran core modification is quite promising for design of new photochromic

materials and systems containing substituents at C5-position of indoline moiety of photochrome

molecule, thus new photochromic labels and photosynthetic systems models based on vitamin A

photochromic analogs have been obtained by us on basis of new formyl spiropyran derivatives [2].

Spirobenzopyrans and their derivatives mentioned above have been prepared in preparative

quantities, characterized by range of physical-chemical analysis methods, as well as their

photochromic behavior studies have been carried out.

This work was partly supported by the Grant of President of RF for young scientists support

(project No. МК-6877.2012.4), State contract № 16.740.11.0177 of FCP «Scientific and scientific-

pedagogical staff of innovational Russia» 2009–2013.

1. Laptev A.V., Lukin A.Yu., Belikov N.E., Shvets V.I., Demina O.V., Barachevsky V.A.,

Khodonov A.A. 2009, Patent RU2358977.

2. (a). Laptev A.V., Belikov N.E., Lukin A.Yu., Barachevsky V.A., Alfimov M.V., Demina O.V.,

Varfolomeev S.D., Shvets V.I., Khodonov A.A. High Energy Chemistry 2008, 42 (suppl.), 601-

603. (b) Laptev A.V., Lukin A.Yu., Belikov N.E., Zemtsov R.V., Barachevsky V.A., Demina

O.V., Varfolomeev S.D., Shvets V.I., Khodonov A.A. High Energy Chemistry 2010, 44, 211-215.


197

STUDY OF PHOTOCHROMIC PROPERTIES

OF 5-VINYLSPIROBENZOPYRAN DERIVATIVES

A.A. Khodonov1, A.V. Laptev

1, A.Yu. Lukin

1, N.E. Belikov

2,

O.V. Demina1, V.I. Shvets

1, P.P. Levin

2

1 – M.V. Lomonosov State University of Fine Chemical Technologies, Moscow, Russia


[email protected]

N O NO2

R1

R2N O NO2

O

H

(1)

Spectral properties and photochromic

transformations parameters of indoline

spirobenzopyrans drastically depend on substituent

nature, thus variation of their substituent nature

allows to make pointed search of photochromes

with defined properties.

№ R1 R2

2 H H

3 NO2 H

4 CN CN

5 CO2Me CN

6 -C(O)-O-C(Me)2-O-(O)C-

7 -C(O)-CH2-C(Me)2-CH2-(O)C-

Previously we have developed the process of direct formylation at C5-position of the

spirobenzopyran derivatives with electron-acceptor substituents [1].

In present work we studied the spectral properties of 5-vinyl-6’-nitrospirobenzopyran derivatives

(2-7). These compounds were prepared by direct 5-formyl function modification with usage of

modern and efficient synthetic methods (olefination by Wittig or Horner-Emmons reactions,

nucleophilic addition on the carbonyl group with reagent family, possessing an active methyl or methylene groups).

Spirobenzopyrans (2-7) have been prepared in preparative quantities, characterized by range of

physical-chemical analysis methods, as well as their photochromic behavior in toluene and ethanol

solutions have been studied.

This work was partly supported by the Grant of President of RF for young scientists support

(project No. МК-6877.2012.4), State contract № 16.740.11.0177 of FCP «Scientific and scientific-

pedagogical staff of innovational Russia» 2009–2013.

1. Laptev A.V., Lukin A.Yu., Belikov N.E., Shvets V.I., Demina O.V., Barachevsky V.A.,

Khodonov A.A. 2009, Patent RU2358977.


198

A NEW PHOTOCHROMIC (E)-2-STYRYLQUINAZOLIN-4(3H)-ONES

AND THEIR CROWN-ETHERS ANALOGUES

G.A. Kim1, T.V. Stupina

2, I.G. Ovchinnikova

1, E.V. Nosova

2, G.L. Rusinov

1

1 – I.Ya. Postovsky Institute of Organic Synthesis UB RAS, Ekaterinburg, Russia

2 – Department of Organic Chemical Technology Institute, Ural Federal University, Ekaterinburg, Russia

[email protected]

A polyfunctional light-sensitive heterocyclic analogues of stilbenes is an important structural base

of a modern optical materials used in various fields including light emitting diodes, photovoltaic

cells, field effect transistors, and nonlinear optics. The quinazolin-4-one core is able to have

perspective in design of these ‘push–pull’ dyes due to convenient methodology allowing to tune the

fluorescent property by combination of a certain functional groups.1,2

The macroheterocyclic

systems capable to photoinduced selective recognition and self-assemblage in supramolecular

assemblies were obtained by means of the introduction of 2-hydroxyaryl substituent and crown-

ether fragment on the electron-withdrawing quinazolin-4-one core.

NH2

OH

O

N

N

O

R

N

N

O

R'

R =

R' =

OO

O O

n

O

O

O

O

O

O

n

OH

OH

During photophysical and photochemical researches it has been found the influence of attached aryl

substitutes on bathochromic and bathofluoric shift of the absorption and emission bands in UV-Vis

absorption and fluorescence spectra of these dyes. Moreover, the fact of luminescence quenching

process, connected with the solvent nature and OH–groups, was established. However, the addition

of strong (inorganic and organic) bases to investigated solutions led to disappearance of this effect

and essential increase of the emission observed at 500–750 nm in the fluorescent spectra of

hydroxyarylquinazolin-4-ones, in comparison with their unsubstituted analogues.

This work was supported by the Russian Foundation for Basic Research (grant 11-03-00718), the

Grant of the Leading Scientific Schools NSh-65261.2010.3.

References:

1. T.V. Trashakhova, E.V. Nosova, M.S. Valova, P.A. Slepukhin, G.N. Lipunova and V.N.

Charushin, “Synthesis and Photophysical Properties of 2-Styrylquinazolin-4-ones”, Russian

Journal of Organic Chemistry, 2011, 47, № 5, 753–761.

2. E.V. Nosova, T.V. Stupina, G.N. Lipunova, M.S. Valova, P.A. Slepukhin, V.N. Charushin, 3 -

Phenyl/Pyridinyl Derivatives of Trans-2-(aryl/heteryl)vinyl-3H-quinazolin-4-ones: Synthesis and

Fluorescent Properties, International Journal of Organic Chemistry, 2012, 2, 56–63.


199

PHOTOCHROMIC ORGANIC SYSTEMS

WITH NONDESTRUCTIVE FLUORESCENCE SWITCHING

O.I. Kobeleva1, T.M. Valova

1, A.Yu. Perevoshikova

2, A.M. Gorelik

1, A.O. Ayt

1, G.T. Vasilyuk

3,

C.A. Maskevich3, V.N. Yarovenko

4, M.M. Krayushkin

4, V.A. Barachevsky

1


2 – M.V. Lomonosov State Academy of Fine Chemical Technology, Moscow, Russia

3 – Yanko Kupala State University, Grodno, Belarus


[email protected]

This paper presents own latest results in the development of reversible photochromic organic liquid

and polymer systems based on thermal irreversible photochromic compounds and fluorophores

providing fabrication of recording media for 3D bitwise working optical memory with the information capacity more 1 TB and nondestructive fluorescent readout of optical information.

Diarylethenes (I) manifesting photoinduced reversible valence isomerization between two thermal

stable states A and B were selected as photochromic compounds:

For fluorophores laser dyes from the phenalenone class (II) as well as quantum dots CdSe/ZnS

were used.

The photochromic and fluorescent components of these systems were selected according to rules

providing fluorescent resonance energy transfer (FRET) from fluorophore to the cyclic form of

diarylethene. It was achieved by a coincidence of the absorption band of diaryethenes and

fluorescence one of fluorophores. Nondestructive fluorescence readout was provided by disposition

of the absorption band of fluorophore between absorption bands open A and cyclic forms of

diarylethenes. The photoinduced reversible transformations between two forms of photochromic

compounds provide reversible modulation of intensity of fluorescence (Fig.1).

Fig.1. Fluorescence modulation of the polymer system based on diarylethene and phenalenone

under light absorbed by the cyclic (1) and open (2) forms of the photochromic compound

These photochromic systems were used for preparation of polymer materials and multilayer

recording media acceptable for two-photon 3D bitwise working optical memory with fluorescent

nondestructive readout of optical information.


200

SPECTRAL-LUMINESCENT PROPERTIES OF HYDROXYAZOMETHINES

OF INDOLINE SPIROPYRANS IN FLUID SOLUTIONS

AND SOLID MATRICES

I.R. Mardaleishvili1, L.S. Koltsova

1, N.L. Zaichenko

1, A.I. Shiyonok

1, A.S. Tatikolov

2, P.P. Levin

2



[email protected]

Spectral-luminescent properties of novel bifunctional compounds (BFs)1-3 based on indole

spiropyrans and o-hydroxyazomethines have been investigated in fluid solutions and in solid phase

–in crystalline powder, polymethylmethacrylate (PMMA) and polyvinylbutyral (PVB) films at 293

K, 77 K and in frozen 2,4- dimethylpentane and methanol solutions at 77 K.

OH

N

O

Me Me

Me

R

OH

N

N

Me Me

O R

Me

BF2, R=NO2

BF1, R=BrBF3

Depending on the substituent in the para-position to the hydroxyl-group and spiro O-atom various

combinations of the structures of the chromophore fragments are observed in solutions:

keto- (K-) or enol- (E-) forms of azomethine fragment and spirocyclic or merocyanine form of the

spiropyran fragment. In all matrices BFs 1,2 exist mainly with the E-form of azomethine fragment.

On passing from liquid solutions to frozen glasses the K-E tautomeric equilibrium of BF3 is fully

shifted towards K-form. However in PMMA films obtained by solvent evaporation at 293 K the

E/K tautomers ratio practically does not change and corresponds to the solutions used for

preparation of the film samples.

Under nanosecond laser flash photolysis (λ = 337 nm) of BFs 1,2, two short-lived products,

assigned to compounds with merocyanine form of spiro-fragment and trans-K-form of azomethine

fragment are observed both in solutions and solid matrix. Solid matrix can hinder the

comformational motions needed for isomerization reactions and so affect the yield of photochromic

products, which formation is connected with processes of isomerization in both fragments. In solid

state in comparison with solutions the yield of merocyanine form of BFs 1-3 decreased, but the PL

efficiency of BFs 1-3 in polymer films due to ESIPT in azomethine fragment is significantly higher

than that in the solutions.

Under excitation with λ in the absorbance band of azomethine fragment, PL quantum yields of BFs

1,3 in fluid and frozen solutions and in PMMA films were determined. For example the PL

quantum yield of BF 1 in methanol at 77 K increased about 30 times in comparison with 293 K.

The growth of luminescence intensity of BF 1 is observed in PMMA matrix too, and cooling the

PMMA film leads to an additional intensity increase.

Analysis of quantum yields of luminescence and photochromic products in the solid phase shows

the change of the ratio between two photochemical reaction ways –cleavage of the spiro-linkage

and ESIPT in azomethine fragment and following luminescence.

The different photochemical behavior in solid phase may be related to K-E equilibrium change,

decreasing the nonradiative deactivation processes, and different mechanisms of photochemical

transformations, connected with conformational constrains due to the solid phase environment and

specific for solid phase reactions.

This work was financially supported by the Russian Academy of Sciences (Presidium Program No. 8).


201

NEW ASYMMETRICAL BISSPIROPYRANS CONTAINING

HYDROXYETHYL AND CARBOXYETHYL SUBSTITUENTS

IN THE INDOLINE FRAGMENT

E.L. Mukhanov, I.V. Ozhogin, V.V. Weibe, I.V. Dorogan,

S.O. Besugly, A.V. Chernyshev, B.S. Lukyanov

Institute of Physical and Organic Chemistry, South Federal University, Rostov-on-Don, Russia

[email protected]

Photochromic compounds are capable to intramolecular isomerisation with simultaneous shifting of

the longwave absorption maxima under irradiation in various spectral regions [1]. Such structures

could be discussed as obvious cores for the different molecular switching systems. Bisphotochromic

compounds contain two different photochromic units in the individual molecule. Ultimately such

structures are able to switch between four distinguished states that make them quite perspective for the development of multi-level molecular switches [2].

On the basis of 2,4-dihydroxy-iso-phtalic aldehyde we have synthesized new systematic series of

bisspiropyrans (1) – photochromic compounds with two spirochromenic moieties in the molecule

and with hydroxethyl/carboxyethyl substituents in the indoline fragment..

N

OO

N

O

O

CH3

CH3

R3

R1

R2

(1)

,a) R1= -CH3, R2= -H, R3= -CH2-CH2-OH,

b) R1= -CH3, R2= -H, R3= -CH2-CH2-COOH,

c) R1= CH2-Ph, R2= -7,8-бензо,R3= -CH2-CH2-COOH,

d) R1= -CH2-Ph, R2= -7,8-бензо, R3= - CH2-CH2-OH

Comprehensive photochemical investigations of the compounds supplemented with high-level DFT

calculations allowed detecting two kinds of different photoinduced isomers – where one or both

photocontrolled pyran cycles are opened. Also influence of the different substituents on the photo-

dynamical and spectral parameters have been investigated. It allowed us to formulate the most

perspective way of structural modifications in order to obtain bisspiropyran-based multi-state molecular switches.

It was shown that obtained compounds are characterized by the higher lifetimes of the photoinduced

isomers in comparison to the previously obtained bisspiropyrans of the same structure type [3].

This work have been financially supported by Grants of the Russian Federation

President NSh 927.2012.3 and MK-1629.2012.3, RFFI 12-03-90017 Bel_a

References:

[1] Durr H., Bouas-Lauren, Т.Н. Photochromism: molecules and systems. – Amsterdam: Elsevier

Science, 1990.

[2] Feringa B.L.. Molecular Switches. – Weinheim: Wiley-VCH, 2001.

[3] Mukhanov E., Alekseenko Yu., Luk’yanov B., Dorogan I., Bezuglyi S. //High Energy

Chemistry, V. 44, 3, P. 220 - 223, 2010.


202

THERMODYNAMIC STABILITY AND PHOTOCHEMISTRY OF THE

HETERODIMERIC COMPLEXES OF STYRYLPYRIDINE DERIVATIVES

I.V. Savin1, S.K. Sazonov

2, E.N. Ushakov

3, S.P. Gromov

2

1 – Moscow Institute of Physics and Technology, Dolgoprudny, Russia



[email protected]

Ammonioalkyl (A) and crown-containing (B) derivatives of styrylpyridine were synthesized

(examples are given in the figure).

The main photochemical and photophysical properties of these compounds were studied in

solutions. The quantum yields of both the forward and reverse trans-cis photoizomerizations were

measured in acetonitrile. It was found by spectrophotometry that compounds A and B are able to

form heterodimers due to the intermolecular interaction between the macrocycle and the ammonium

cation. The absorption spectra of heterodimeric complexes as well as the complex stability constants were determined at a fixed ionic strength of solution.

The effect of complex formation on the photochemistry of styrylpyridine derivatives was

investigated. Some of the heterodimeric complexes were found to undergo the stereospecific [2+2]

photocycloaddition reaction.

This work was supported by RFBR and the Russian Academy of Sciences.


203

SYNTHESIS AND PHOTOCHROMISM OF NAPHTHO[1,8-BC]OXEPINE

R.V. Tyurin

Chromtech Ltd., Rehovot, Israel

[email protected]

Peri-annealated naphto[1,8-bc]oxepine (3) was prepared in the coarse of studies of photochromism

of steric hindered spirochromenes. The synthesis of the chromene was carried out in presence of

acetic acid, however the main product was naphtho[1,8-bc]oxepine (3). Apparently, the main factor,

which determines the reaction direction is the space hindrance of propargyl alcohol.

N

O

O

O

O

OF

O

O

N

O

O

O

1

32

456

78

9

10

OH

O

O O

O

F

+

1 2 3

The NMR analysis of the product shows the lack of the singlet signal, corresponding to the proton

in 8-position of the naphthalene ring and the appearance of the singlet signal in 2-position, which is in the agreement with the oxepine structure of our product.

Stabilization of the photo-activated "open" form of (3) may be explained as a result of the

delocalization of the positive charge on the dimethylamino group.

N

O

O

O

OF

O

OO

+

_

N

O

O

O

O

OF

O

O

N

O

O

O

OF

O

OO

+_


204

SYNTHESIS OF NEW MONO- AND DISUBSTITUTED

PERFLUOROCYCLOPENTENE PHOTOCHROMES

V.N. Yarovenko1, A.M. Bogacheva

2, M.M. Krayushkin

1,

V.N. Charushin2, I.A. Platonova

3, V.A. Barachevsky

3


2 – I.Ya. Postovsky Institute of Organic Synthesis UB RAS, Yekaterinburg, Russia


[email protected]

Photochromic compounds have attracted considerable attention because of their potential

application to photonic devices, such as optical memories and photoswitches. Photochromic 1,2-

dithienylethenes containing perfluorocyclopentene as a linking bridge are considered as promising

components of light-sensitive recording media. Under UV irradiation these compounds can

repeatedly undergo, without decomposition, photochemical transformations to form thermally

stable open (A) and cyclic (B) forms.

A B

hv

hv 1

F F

We developed methods for the synthesis of unknown perfluorocyclopentene photochromes 2,3 and

showed that these compounds can be used for the design of various mono- and disubstituted

perfluorocyclopentene photochromes containing heterocycles.

123

8 a) R=Cl b) R=NO2

6 a) R= furan-2-yl b) R= thiophen-2-yl c) R= Ph

7 a) R= furan-2-yl b) R= thiophen-2-yl c) R= Ph

4 a) R = NH2

b) R= Ph 5 a) R = NH2

b) R= Ph

1. M.M. Krayushkin and M.A. Kalik, Syntheses of Photochromic Dihetarylethenes. In: Katritzky,

editors: Advances in Heterocyclic Chemistry, Vol 103, Oxford: Academic Press; 2011, p. 1 -59.


205

SYNTHESIS OF CYCLOPENTENE DIHETARYLETHENES

WITH THE PHOTOINDUCED FLUORESCENT READING

FOR OPERATIVE OPTICAL MEMORY

V.N. Yarovenko1, L.V. Khristoforova

1, M.M. Krayushkin

1, I.A. Platonova

2, V.A. Barachevsky

2



[email protected]

Photochromic 1,2-dithienylethenes containing cyclopentene as a linking bridge are considered as

promising components of light-sensitive recording media. Under UV irradiation these compounds

can repeatedly undergo, without decomposition, photochemical transformations to form thermally

stable open (A) and cyclic (B) forms.

A B

hv

hv 1

We developed methods for the synthesis of a wide range of new cyclopentene photochromes and

showed that these compounds can be used for the design of recording media with the photoinduced

fluorescent readout of optical information. Unsymmetrical cyclopentene photochrome containing

sulfur and amino derivatives 2, which may be of interest as linkers for nanothechnology, and

photochrome having coordination ligand moiety 3 were synthesized. A photochromic recording

media with nondestructive optical data reading was designed based on thermally irreversible

diarylethene 4 and the fluorescent derivative of phenalenone 5.

1 2

3 4 5

1. M.M. Krayushkin and M.A. Kalik, Syntheses of Photochromic Dihetarylethenes. In: Katritzky,

editors: Advances in Heterocyclic Chemistry, Vol 103, Oxford: Academic Press; 2011, p. 1-59.

2. M.M. Krayushkin, V.N. Yarovenko, L.V. Christoforova, A.S. Shashkov, E.P. Grebennikov, A.G.

Devyatkov, G.E. Adamov, K.S. Levchenko, P.S. Shmelin, V.A. Barachevsky, T.M. Valova, O. I.

Kobeleva. Russ. Chem. Bull., 2011, № 12, 2487-2494.


206

NEW CHROMONE BASED PHOTOSENSITIVE POLYMER

FOR THREE-DIMENSIONAL OPTICAL MEMORY

V.N. Yarovenko1, K.S. Levchenko

2, M.M. Krayushkin

1, V.A. Barachevsky

3,

T.M. Valova3, O.I. Kobeleva

3, G.D. Markova

4, V.A. Vasnev

4, B.A. Izmailov

4


2 – ОJSC CSRIТ «Technomash», Moscow, Russia


4 – A.N. Nesmeyanov Institute of Organoelement Compounds RAS, Moscow, Russia

[email protected]

Considerable attention is given to the creation of novel photosensitive recording media for archival

three-dimensional optical memory on multilayer discs with fluorescence information reading. We

proposed a method for the synthesis of earlier unknown derivatives of 3-acetyl-2(2’-

hetaryl)chromone (A) capable of undergoing irreversible changes under UV irradiation to form

photoluminescent products (B) that provide optical information reading.

A B

Methods were developed for the synthesis of previously unknown halogenated derivatives of 3-

acyl-2-hetaryl chromones 1-3 and photosensitive polymer I which are of interest as photosensitive

components of recording media for multilayer optical disks used for three-dimensional optical memory suitable for archival storage.

X = O, S1 2 3

\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\

140 oC

20 min

DMF, r.t

140 oC

\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\\

I 1. V.A.Barachevsky, O.I. Kobeleva, T.M.Valova, A.O. Ait, A.A.Dunaev, A.M. Gorelik, M.M.

Krayushkin, K.S. Levchenko, V.N. Yarovenko, V.V. Kiyko, E.P.Grebennikov. Optical Memory &

Neural Networks (Information Optics), v.19, №2, 187–195, 2010.

Posters Applied molecular photonics ----------------------------------------------------------------------------------------------------------------------------- ------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------- -------------------------

207

SECTION 8. APPLIED MOLECULAR PHOTONICS

HYDROGEN BONDING AND POLYMORPHISM AND THEIR

APPEARANCE IN VIBRATIONAL SPECTRA OF CYCLOHEXANOL

L.M. Babkov1, N.A. Davydova

2, E.A. Moiseykina

1


2 – Institute of Physics NAS, Kyiv, Ukraine

[email protected]

By neutron diffraction investigation and X-ray diffraction analysis the polymorphisms in

cyclohexanol was researched [1]: it found the existence plastic, crystal (II) and metastable (III, III ')

phases, in which formation hydrogen bonding played the crucial role; the presence of four

conformers of the molecule with different orientation(axial and equatorial) of the hydroxyl group relatively carbon ring of the molecule was established.

In a wide range of temperatures infrared absorption spectra of cyclohexanol in the plastic (I) and

crystalline (II, III) phases were measured. The measured spectra differ from each other. These

differences are due to their belonging to the different polymorphic modifications. In this connection

the question about detailed study of polymorphism by quantum theory and vibrational spectroscopy methods and identification of polymorphic modification become more actual problem.

By density functional method [2] using the functional B3LYP in the basis 6-31G (d) structural-

dynamic models of conformers of cyclohexanol molecule and its H-complexes (dimmer, trimmer,

tetramer1, tetramer2) were constructed. Energies were minimized, structures were optimized,

mechanical and electro – optical parameters, the normal modes frequencies in the harmonic

approximation and the intensity distribution in the IR spectra were calculated.

On the basis of the analysis of calculated IR spectra of the conformers and the measured spectra

their preliminary interpretation was given. The spectral and structural characteristics (frequencies)

allowing to distinguish between conformers with different structures were determined. Vibrations

which sensitive to the orientation of the hydroxyl group relatively the carbon ring of the molecule were identified.

On the basis of the analysis of the structure and spectra simulation results of the H-complexes

conclusions about implementation of conformers with the equatorial orientation of the hydroxyl

group in the crystalline phases II, III and about implementation of conformers with different

orientation in the plastic phase. It was theoretically justified that the crystalline phases II and III are

formed by the H-complexes representing tetramers of the molecules: in phase II – cyclical, in phase

III – chained, like a wave ("wave-like" chain). In the phase III' formation of trimmer is

possible. Plastic phase probably contains all of the H-complexes and its IR spectrum in the 3200-

3700 cm-1

has a broad, structureless band. By complexing the geometry of the fragments of the

molecule forming the core of the H-complex is changed, the conformation of the "chair" of

hydrocarbon ring is retained.

1. Richard M. Ibberson, Simon Parsons, David R. Allan, Anthoni M.T. Bell. ActaCryst.2008, B64,

573-582.

2. Frisch J., Trucks G.W., Schlegel H.B. et al., Gaussian03, Revision B.03; Gaussian, Inc.,

Pittsburgh PA, 2003.


208

SYNTHESIS, PHOTO- AND ELECTROLUMINESCENT PROPERTIES

OF NORBORNENE-BASED IRIDIUM(III) COPOLYMERS

Yu. E. Begantsova, L.N. Bochkarev

G.A. Razuvaev Institute of Organometallic Chemistry RAS, Nizhny Novgorod, Russia

[email protected]

Novel cyclometalated Ir(III) complexes with norbornene-substituted pyrazolonate ligand were

synthesized and structurally characterized:

Compound 1 and 2 were copolymerized with carbazole-functionalized norbornene by ring-opening

metathesis polymerization.

Photoluminescent spectra of synthesized Ir(III)-containing copolymers consist of broad bands at

500-520 nm assigned to metal to ligand charge transfer transition. The relative quantum yields were

found to be in the range 6-8 %. Light-emitting diodes with the configuration of ITO/Ir(III)-

copolymer/BATH/Alq3/Yb (ITO - indium tin oxide, BATH – bathophenanthroline, Alq3 - tris(8-

hydroxyquinolinato)aluminium) produced yellowish-green light. Maximum brightness of 800 cd/m2

and current efficiency of 1.85 cd/A were reached.

This work was supported by the Russian Foundation for Basic Research (Project No. 11-03-97021 r

povolzje_a)


209

LANTHANIDEPORPHYRINS AS A NEW AGENTS

FOR OPTICAL OXYGEN SENSORICS

E.G. Ermolina1, R.T. Kuznetsova

1, T.A. Solodova

1,

T.N. Kopylova1, T.A. Ageeva

2, N.N. Semenishin

3

1 – Tomsk State University, Russia

2 – Ivanovo State University of Chemistry and Technology, Ivanovo, Russia

3 – A.V. Bogatskii Physical-Chemical Institute NAS, Odessa, Ukraine

[email protected]

Methods of determining oxygen in gas mixtures are widely used in science, technology and clinical

analysis. At nowadays the optical direction of oxygen sensorics based on quenching of organic dye luminescence by O2 molecules is the most perspective.

The matrix is of great importance for high material sensitivity to oxygen. It must be technological,

highly porous and transparent in a wide spectral range and must not provoke photochemical

degradation of the dye molecule.

In this paper different polymer films with doping by lanthanideporphyrines were synthesized and

their sensor abilities were studied. Lanthanideporphyrines as optical sensorics agents for oxygen

were studied for the first time. Polymers are copolymers of tert-butylmethacrylate or styrene with

propylmethacrylate, comprising octa(propylmethacrylate) polyhedral oligomerous silsesquioxane

(POSS) as a lateral substituent, polyvinylchloride, polycarbonate, methyl- and diacetylcellulose, also sol-gel by different methods.

The main sensor characteristics are the system response time to incoming analyte, range of

measurable concentrations, and primarily the sensitivity to analyte determined by the ratio I0/I100 for

optical sensors, where I0 and I100 are the luminescence intensities for analyte concentrations of 0 and

100%, respectively. The most outstanding result was received for methylcellulose film with

ClLuTPP as a dopant – 40. This value I0/I100 was close to the best results obtained for PdOEP and

PtOEP in organically modified sol-gel films. Futhermore this material is distinguished by short

enough response time of about 1.0 s lying within the range 0.04–35.0 s presented in the literature.

For the materials obtained, the Stern-Volmer dependence deviates from the linear one at the O2

concentration of ~ 40% for ClGdTPP and 10% for ClLuTPP. Moreover, it seems most likely that

the dependence for the polymeric films is saturated at oxygen concentrations smaller than those for

the films based on methylcellulose due to complete quenching of the triplet-excited complexes

accessible for the oxygen molecules. This allows us to consider ClLuTPP as new available agent for

optical oxygen sensorics.


210

PHOTOEXCITED GENERATION AND ELECTROLUMINESCENCE

IN THIN FILMS OF COPOLYFLUORENES

T.N. Kopylova1, E.N. Telminov

1, K.M. Degtyarenko

1, N.S. Eremina

1,

T.A. Solodova1, E.N. Ponyavina

1, G.I. Nosova

2, N.A. Solovskaya

2,

E.V. Zhukova2, I.A. Berezin

2, A.V. Yakimansky

2

1 – Siberian Physical Technical Institute of Tomsk State University, Russia


[email protected]

Emitting organic semiconductor polymers open great possibilities for creation of organic optical materials and devices on their basis (organic light-emitting diodes, photoexcited organic semiconductor

lasers, etc.). The problem of creation of an organic semiconductor injection laser has not yet been solved

in the world and calls for comprehensive investigations of photoexcited generation and

electroluminescence of organic thin-film structures on their basis.

In the present work, photoexcited generation and electroluminescence of two copolyfluorenes (Fig. 1)

are investigated.

It was established that the absorption spectra of the examined copolymers in films were similar, while in

the fluorescence spectrum of copolymer 1, radiation in blue and green regions of the spectrum was

observed.

Upon excitation of stimulated radiation of copolymers in solution (c = 2 10-3 M) by radiation of the third harmonics of Nd3+:YAG laser using the transverse scheme, generation was observed in the region of polyfluorene emission λgen = 440 nm with efficiency = 12% (W = 10 МW/cm2) for copolymer 1 and

efficiency = 5% (W = 7 MW/cm2) for copolymer 2. In films, both CP1 and CP2 generate in the region of

polyfluorene emission, λgen = 448 nm.

The electroluminescence of copolyfluorens was studied for the ITO/PEDOT/CP1/MgAg and ITO/PEDOT/CP2/MgAg structures (prepared by the spin-casting method). The threshold voltage levels

for these structures were 4.2 and 4.4 V; bands with maxima at 434, 462, 494, and 584 nm were observed

in the electroluminescence spectrum of CP1, and bands with maxima at 428, 450, 486, and 523 nm were

observed for CP2. (Fig. 2).

0

2

4

6

8

10

12

14

16

0 2 4 6 8Voltage, V

Curr

ent,

mA

0

20

40

60

80

100

120

140

160

180

Bri

ghtn

ess,

Kd/m

2

Volt-Current

Volt-Brightness

0

1

2

3

4

5

6

7

8

9

10

400 500 600 700 800

wavelength, nm

Inte

nsi

ty, u

W/(

cm

2*

nm

)

a b

Figure 2 – Voltage-current (VC) and voltage-brightness (VB) plots (a) and electroluminescence spectrum (b)

for an OLED with the architecture: ITO/PEDOT (80 nm)/CP2 (100 nm)/MgAg (150 nm)

This work is supported by the Scientific Program “Multifunctional materials for molecular electronics” of the Presidium of RAS.

C8H17 C8H17

1-X X

NNS

n

Х = 0.01, polymer 1 (CP1)

C2H17C2H17

1-X N Xn

CH2 CH

C2H5

(CH3)2CH3

Х = 0.1, polymer 2 (CP2)

Figure 1 – Structural formulas of copolyfluorenes 1 and 2


211

GENERATION OF STIMULATED RADIATION BY ORGANIC

SEMICONDUCTORS IN THIN FILMS UNDER PHOTOEXCITATION

T.N. Kopylova1, E.N. Telminov

1, E.N. Ponyavina

1, R.M. Gadirov

1,

T.A. Solodova1, N.V. Polyanin

1, M.G. Kaplunov

2, I.K. Yakushchenko

2



[email protected]

Investigation of generation of stimulated radiation by organic semiconductors in thin films under

photoexcitation is urgent from the viewpoint of creating organic semiconductor injection lasers that

have not yet been created. It’s known that, organic semiconductors, which are used for OLED

fabrication, are the most suitable types of materials for organic semiconductor lasers [1]. In the

present work, DA-BuTAZ [2] and a metallo-organic complex with Zn(DFP-SAMQ)2 [3] were

chosen as objects for investigation. Both compounds have a high quantum yield of fluorescence in

blue region of spectra: λmax = 430 nm, Δλ = 70 nm, η = 90 % for DA-BuTAZ and λmax = 465 nm, Δλ = 90 nm, η = 90 % for Zn(DFP-SAMQ)2.

It was established that BuTAZ excited by radiation of the 3rd

harmonics of a Nd3+

:YAG laser with

transverse pumping scheme generated stimulated radiation in TGF solutions (λgen = 450 nm) and

films (λgen = 412 nm). A dependence of output radiation on the BuTAZ concentration and power

density of exciting radiation was investigated (Fig. 1). It can be seen that for power density of

8 MW/cm2 and BuTAZ concentration of 5∙10

–3 M, the amplified spontaneous emission (ASE) is

observed (curves 1 and 2) that is transformed into generation (curve 4) when the concentration

decreases to 2.5∙10-3

M. It should be noted that the film absorbed only 39% of the pump energy (it

was 3 mJ for generation threshold level of 1.17 mJ). Durations of pump and generation pulses coincided (8.5 ns), which demonstrated low intramolecular losses in the molecule.

wavelength, nm

Inte

nsi

ty,

a.u

.

0

0,5

1

1,5

2

2,5

3

400 450 500 550 600 650 700 750

Wpump = 31,4 MW/cm2

W = 21,5 2pump MW/cm

W = 15,7 2pump MW/cm

W = 8,4 2pump MW/cm

W = 5,5 2 pump MW/cm

W = 2,4 2 pump MW/cm

wavelength, nm

Inte

nsi

ty,

a.u

.

Figure 1 – BuTAZ generation (film). 1 and 2

were drawn for the same film; c = 5 10–3

M

(W = 8 MW/cm2); 3 and 4 were drawn for the

same film; c = 2.5 10–3

M (W = 8 MW/cm2)

Figure 2 – Dependence of the radiation

intensity of the zinc complex pumped by laser

radiation with the indicated power Wpump

The Zn(DFP-SAMQ)2 complex did not generate radiation even in solutions when the pump power

density changed from 2.4 to 31.4 MW/cm2 and the radiation pulse duration exceeded twice the

pump pulse duration (Fig. 2). Investigation of the nature of the radiative state for this compound will be continued.

1. Hide F, DiazGarcia M.A., et al., Science 273, 1833 (1996)

2. I.K.Yakushchenko, M.G.Kaplunov, et al. Phys. Chem. Chem. Phys., 1, 1783 (1999).

3. Якущенко И.К., Каплунов М.Г. и др, Коорд. химия, 35, 316 (2009).


212

SPONTANEOUS AND STIMULATED RADIATION

OF BIPHENYLS UNDER PHOTO- AND ELECTROEXCITATION

A.V. Kukhto1, T.N. Kopylova

2, K.M. Degtyarenko

2, T.A. Solodova

2,

N.S. Eremina2, E.N. Telminov

2, R.M. Gadirov

2, E.N. Ponyavina

2



[email protected]

Substituted biphenyls are well known as laser active media radiating in the blue range of the

spectrum and as emitters of organic light-emitting diodes. After vacuum deposition and centrifuging, they form amorphous transparent films.

In the present work, spontaneous radiation and stimulated radiation of some substituted biphenyls

excited by light and electric current are investigated. The results obtained are presented in Table 1.

Table 1 – Spectral, luminescent, generation, and electroluminescent properties of biphenyls

№ 256 199 197 200

Structural

formula NN

S

O O

OCH3

SO O

O

SO O

O

CH3

F

F

Concentration, M

2 10-3

in TGF

film

2 10-3

in TGF

2.5 10-5

in TGF toluene

film

2 10-3

in TGF toluene

film

2 10-3

in TGF toluene

film

λn

(ε), nm 298

406 346

390 346

391 346

λfl(γ), nm 480 456 (0.63)

436 (0.63) 456 (0.68) 472 (0.63)

EL Structure ITO/PEDOT

/PVK:256/Al ITO/PEDOT



/PVK:200/Al Uthr, V 7.0 6.9 5.9 4.4

λel 474 476 476 451

λgen, (Δλ), nm 485 (4)

480 (7) 460 (5)

463 (5) 459 (5)

464 (6) 454 (2)

463(8) Uthr, MW/cm

2 0.3 0.5 0.25 0.3 Efficiency, % 17 (8) 19.8 (5.4) 24 (5.4) 31 (4.5)

It can be seen that well radiating biphenyls in the simplest compositions under photoexcitation have

both low-threshold generation and electroluminescence that are of undoubted interest for

investigation of deactivation of the excitation energy of various types in such structures and creation

of organic injection lasers.

This work was supported by Federal Program «Innovative laser, optical and optoelectronic

technologies – photonics», GC №07.514.11.4057 and Grant of President НШ-512.2012.2


213

HIGH PRECISION FAST LUMINESCENT NO BAROMETRY

G.N. Lyalin1, J. Diekmann

2


2 – University of Bielefeld, Germany [email protected]

A method for spatially resolved pressure mappings based on laser-induced photoluminescence and

imaging techniques was described in [1]. The method of measurement uses the fact that the

luminescence of special organic dye molecules([Ru(Ph2Phen)3]Cl2- Ru(II)) adsorbed on specially

prepared aluminum porous plate(Al2O3) or porous polyacrylonitrile film(PAN)-pressure sensitive

coating(PSC) is quenched by molecular oxygen.

One of most tempting application of PSC is their application as detectors for quantification of

oxygen in gas mixture. Such detectors could be applied in medicine, particularly in pulmonology, or

in moto-car-construction for analysis of exhaust gas. Therefore the knowledge of influence some

gas components on luminescence of coatings is one of the interesting task. For this aim it was

chosen NO gas which is contained in ambient air and exhaust gas.

Knowing the mechanism of luminescence quenching of the coatings by oxygen it is not difficult to

predict beforehand that paramagnetic molecular NO with doublet ground state (X2Π) [2] should

have a strong influence on luminescence of Ru(II) adsorbed on Al2O3 or PAN.

In Fig there are represented the time response (ms) and quenching of luminescence of PSC on

aluminium by NO. The amount of NO is 3 ppm in the flow of pure nitrogen. The influence of NO

on the luminescence intensity at PSC on polymer foil is in the same range. Intensity variation is

about 0.9% at a 1 ppm NO concentration. The accuracy of detection allows to estimate the detection

limit for concentration of nitrogen monoxide with the help of luminescent dyes as1 ppm.

0 20 40 60 80

6000

6050

6100

6150

6200

I=2.6%

=> 0.87% per ppm

(1)

(1)

(2)

Luminescence Intensity from PSC on Aluminium at Nitrogen (1) and 3 ppm NO (2)

Lum

inescence Inte

nsity

time

The mechanism of quench by NO could not be the same as a mechanism quenching of

luminescence by O2 because there are no suitable excited electronic states of NO, in contrast to O2,

which could be able to except of electronic energy from excited CTML state of Ru(II) due to

transfer of energy. Therefore one of the possible mechanism might be consist of very strong

perturbation electronic system of Ru(II) by doublet paramagnetic NO molecule which causes strong

mixing CTML state with ground state increasing nonradiative intramolecular intersystem

conversion [3]. The other possible mechanism could be transfer of electronic energy from excited

CTML state of Ru(II) to high vibrational levels of NO [4]. To clear which mechanism is true it

should be made, for example, additional experiments such as attempt of finding out NO-

luminescence in far infrared range sensibilized by Ru(II). 1.H. Spieker et al Opt.and Spectr. V.83,

p.639,1997; 2.Hideo Okabe "Photochemistry of small molecules" interscience Publication-John

Wiley and Sons,N-Y-Chichester-Brisbane-Toronto.; 3.GijzemanO.L. J.Chem.Soc., Farad.Trans.II.

70, (1974),p.1143. ; 4. Hawks M. et al" Infrared fluorescence study of electronic-to-vibrational

energy transfer in the Br(2P1/2)-NO system" Chem.Phys. 195, (1995), p.395


214

THREE COLOR LIGHT-EMITTING DIODES FROM A SINGLE POLYMER

WITH ALCOHOL-SOLUBLE POLYFLUORENE

AS A HOLE-BLOCKING LAYER

D.A. Lypenko1, E.I. Maltsev

1, G.I. Nosova

2, E.V. Zhukova

2, R.Yu. Smyslov

2, N.A. Solovskaya

2,

T.N. Nekrasova2, A.V. Yakimansky

2



[email protected]

In the last few years, white polymer light-emitting diodes (PLED) have attracted increasing

attention due to their potential applications for paper-thin next generation light sources and other

illumination purposes. Here we report on the study of a series newly synthesized polyfluorene-

based derivatives (PF) containing three different types of organic fragments as EL color tuning

substituents in their back-bones. Best results were obtained on polymers structures shown below.

All the three fragments emitted light in different regions of the visible range. It was demonstrated

that the emission color of PLEDs based on this polymers could be tuned by changing molar

concentration of the chromophore groups in the polymer chain. Moreover incorporation in main

polymer chain different charge transporting moieties significantly affected EL spectra and luminous

efficiency of the PLEDs. EL spectra (Fig. 2a) and CIE diagram (Fig. 2b) for the PLEDs based on

the studied EL polymers are shown below. Employing alcohol-soluble poly[9,9-bis(6’-diethoxyl-

phosphorylhexyl)fluorene] (PF3) as hole-blocking layer resulted in the increase of luminous (LE)

and power (PE) efficiency of studied PLEDs by one order of magnitude.

(a) Fig. 2 (b)

The PLEDs had the following structure: ITO/PEDOT (60nm)/ EL polymer (80 nm)/PF3

(15nm)/LiF/Al. Main PLEDs characteristics are given in the Tab.1

Emitting layer CIE coordinates Max. brigtness, cd/m2 Max. PE (cd/A) Max. LE (lm/W)

PF 1 (0.313, 0.484) 3620 (at 16 V) 2.48 0.67

PF2 (0.306, 0.377) 1000 (at 17V) 0.83 0.28

0

0.5

1

350 450 550 650 750

Wavelength, nm

EL, a.u

.

PF1

PF2

N

(CH2)6

N

N OO

N

(CH2)6

N OO

N

O

R

C8H17C8H17

z100-x-y-z

n

x y

A R

R=

R=PF1: A=

N N

PF2: N

A=

N (CH2)6 O

N N

O

Fig. 1


215

ENERGY TRANSFER IN DNA AND DETECTION OF THE PRESENCE

OF THE SPECIFIC SEQUENCES IN DNA

V.M. Malkin


[email protected]

It is well known that energy transfer between donor and acceptor via the nucleic bases of double

DNA helix is possible [1,2]. Energy transfer efficiency depends on the distance between the donor

and acceptor, the correctness of the structure of the double helix, the sequence of base pairs between the donor and acceptor. The role of sugar-phosphate chain could be neglected.

Now observed high interest to so-called peptide-nucleic acids (PNA). This interest caused by their

high affinity of PNA to DNA. High affinity and specific (Watson-Crick) pairing make possible PNA using for the testing for the presence of the specific sequences in DNA [3-6].

Here proposed the idea of using the PNA molecules, marked on N and C ends by a coupe dyes and

energy transfer between these dyes (donor and acceptor), for analysis of the nucleotide sequences of

DNA (RNA). For example, we can use fluorescein derivatives as a donor and rhodamine derivatives

as an acceptor.

In DNA solution labeled PNA molecules should form a double helix with complementary to them

DNA sites. That should lead to the increasing of the energy transfer efficiency from the donor to

the acceptor. It could be observed by the appearance (increasing) of the acceptor luminescence,

caused by the excitation in the donor's absorption band. If there is not DNA sites, complementary to

the labeled PNA, the mentioned above luminescence changes could not be observed. So, the

appearance of the acceptor luminescence, caused by the donor excitation, can be used as a proof of

the specific sequence presence in the DNA (RNA) sample.

I suppose, that this method could be useful for different applications.

2. J. Ju, Ch. Ruan, C.W. Fuller, A.N. Glazed and R.A. Mathies. Proc. Natl. Acad. Sci. USA. Vol.

92, pp. 4347-4351, May 1995, Biophysics.

3. Da-Guang Xu and Th. M. Nordlund. Biophysical Journal. Vol. 78 Feb. 2000, pp. 1042-158

4. P.E. Nielsen, M.Egholm, R.H. Berg, O. Buchardt. Science. Vol. 254. Dec. 1991, pp. 1497-1500

5. P.E. Nielsen and M. Egholm. Bioorg. Med. Chem. Vol 9, 2001, pp. 2429-2434

6. K. Kaihatsu, B.A. Janovski, D.R. Corey. Chemistry&Biology, Vol. 11, 749-758, June 2004

7. A.Tovar-Salazar, J. Dhawan, A. Lovejoy, Q. Alison Liu, A.N. Gifford. Anal. Biochem., Vol.

360, 2007, pp. 92-98


216

PHOTOCHEMICAL INFORMATION STORAGE ON THYMINE

AND STACKING DIMERS OF THYMINE IN POLY-T

V.M. Malkin, V.L. Rapoport


[email protected]

The idea of reversible information storage based on the cyclobutane photodimerisation of thymine

(CPT) was independently proposed in [1] and [2]. In [2] was experimentally studied possibility of

the reversible information storage based on CPT in Langmuir-Blodgett films of dodecylthymine on

water. CPT was not completely reversible in mentioned system, but authors supposed, that it is

rather perspective for information storage. In [1] proposed the idea of using for information storage

CPT in stacking dimers of thymine, similar to the observed for dimethylthymine (DMT) (EG:water,

77 K) with quantum yield of CPT equal to 1.0 [3]. It was shown in [4], that CPT in water solutions

of poly-T are many times reversible. The action spectra of CPT in poly-T [4] was similar (by the

maximum, at 260 nm) to the absorption spectra of stacking dimers of DMT (EG:water, 77K)[3].

The difference between the action spectra of CPT and absorption spectra of poly-T (maximum at

268 nm) [4] demonstrate heterogeneity of these solutions. Ours main aim was to find out in poly-T stacking dimers of thymine, similar to the observed for DMT (EG:water, 77 K).

We had shown, that in poly-T water solutions exists the more photoactive (shortly – “photoactive”)

and less photoactive (shortly – “photoresistent”) fractions of the thymine chromophores

(thymines).

“Photoactive” fraction consists of stacking dimers with optimal for CPT structures, which are not

luminescent. They was discovered by studying the differential absorption spectra of these solutions,

which were found by substraction between absorption spectra, obtained on different stages of UV

irradiations. For these stacking dimers we found absorption bands at 250, 260, 280 and 290 nm. We suppose, that some of these stacking dimers are similar to the observed for DMT (EG:water, 77 K).

One part of the "photoresistent" thymines are relatively isolated and have absorption band at 270

nm and luminescence band at 338 nm. The other part are luminescent dimers with bad for CPT

structures. They have luminescence band at 350 nm and absorption bands at 255 nm and 280–300 nm.

We had shown that during the UV irradiation, after the exhaustion of the "photoactive" fraction, the

"photoresistent" fraction became involved in CPT. This contradicts with [5]. We also had observed,

that the irreversibility of CPT is caused by photoadducts and phototrimer formation during UV

irradiation of poly-T water solutions.

We suppose that for the realization of the idea of information storage based on the reversible CPT

it is necessary to fix the positions of poly-T on the surface or in the rigid medium.

[1] Рапопорт В.Л. Тезисы докладов Всесоюзной школы-семинара по биомолекулярному

компьютингу. 27-31 Мая 1991, Москва, стр.40.

[2] Yano Ei, S.Tatsuura Thin Solid Films 1991, V.196, N01, pp. 147-151

[3] Lamola A.A., J.Eisinger. Proc. of the Nat.Acad. of Sciences USA.V.55, №1, 1968, pp.46–51.

[4] Deering R.A., Setlow, R.B. Biochimica et Biophysica Acta 1963, V.68, №4, pp.526–534.

[5] A.T. Johnson, O.Wiest. J.Phys.Chem. B 2007, V. 111, pp. 14398-14404


217

PRODUCING OF POLYMER COMPOSITES

WITH VOLUME SPREAD METAL NANO-SIZE PARTICLES

AND ORGANIC PHOTOCHROMIC COMPOUNDS

V.A. Optov1, V.A. Barachevsky

2, A.O. Ait

2, A.A. Berlin

1, O.Yu. Sabsai

1



[email protected]

After condensation of a metal vapour on a polymer surface and consecutive polymer melt

processing in extruder a composite material with nano-sized metal particles was obtained (5 x 50

nm according to PEM data). On this method of composite materials producing a Patent RF № 2412050 was obtained.

After diffusion penetration of organic photochrome molecules in a surface polymer layer from

solutions, powders, in a super critical carbon dioxide medium and consecutive polymer melt

processing in extruder polymer composites with volume spread photochrome molecules on a base

of polyolefines, polyurethane, ethylcellulose and polycarbonate were prodused.

Both methods may be realized on existing. industrial equipment.


218

PHOTORESPONSE OF LIPOSOME-INCORPORATED FLUORESCENT

DRUGS USED IN THE PHOTODYNAMIC THERAPY OF CANCER

V.A. Reshetov1, L.N. Bezdetnaya

2, T.E. Zorina

1, V.P. Zorin

1

1 – Belarusian State University, Minsk, Belarus

2 – Centre de Recherche en Automatique de Nancy, Nancy-Universite, CNRS, France

[email protected]

Photodynamic therapy is based on application of light-activatable photosensitizing drugs. Among

the second-generation photosensitizing pigments is meso-tetrahydroxyphenylchlorin (mTHPC) that

shows a high efficacy in animals models and in clinical studies. Since mTHPC is insoluble in

aqueous media, the drug is formulated with conventional or pegylated nano-sized lipid vesicles. The

purpose of this study was to examine structural, photophysical and photochemical properties of

mTHPC embedded into DPPC lipid vesicles and estimate the rate of the sensitizer transfer from its lipid based formulations.

Spectroscopic measurements in liposomes with different drug:lipid molar ratios revealed several

mTHPC fluorescence features which could be attributed to the influence of microenvironment and

dye-dye interactions in lipid membrane. Exposure of mTHPC loaded liposomes to a small laser

light dose (< 50 mJ/cm2, 650 nm laser) resulted in a substantial drop in fluorescence, which,

however, was restored after addition of a non-ionic surfactant to the sample and subsequent

disruption of liposomal structure. We attributed this behavior to photoinduced fluorescence

quenching. This effect strongly depends on the molar drug:lipid ratio and was revealed only for

high local drug concentrations. The results were interpreted supposing energy migration between

closely located mTHPC molecules with its subsequent dissipation by the molecules of photoproduct

formed during laser irradiation acting as excitation energy traps. The range of effective

photoinduced quenching was consistent with the decreased quantum yield of singlet oxygen

generation.

We further developed a model to apply the effect of photoinduced fluorescence quenching to the

study of drug release kinetics from liposomes in biological media. Compared to other spectroscopic

techniques, photoinduced fluorescence quenching provides a wider dynamic sensitivity range while

indicating the same characteristic time of redistribution. The data obtained with these experimental

approaches suggest that mTHPC molecules extremely slow remove from liposomal carriers.

Therefore, the process of mTHPC release from lipid vesicles appears to be an important

determinant controlling pharmacokinetics of the photosensitizer liposomal formulation. Our recent

results show that this factor may play significant role in the application of the mTHPC

photosensitizer liposomal formulations and make possible to assume the possibility of sensitizer

biodistribution control at the expense of the carrier nature.


219

NON-LINEAR OPTICAL PROPERTIES OF PHOTOCONDUCTIVE

POLYIMIDES AND POLYURETHANES

N.A. Solovskaya1, G.I. Nosova

1, I.G. Abramov

2, O.V. Dobrokhotov

2, N.N. Smirnov

1,

E.V. Zhukova1, E.L. Aleksandrova

1, A.V. Yakimansky

1

1 – Institute of Macromolecular Compounds RAS, Saint-Petersburg, Russia

2 – Yaroslavl State Technical University, Russia

[email protected]

Heat-resistant polymers, containing covalently bound side-chain chromophores, are of interest as promising materials for applications in non-linear optics.

In the present paper, OH- and COOH-functionalized polyimides on the basis of a series of

dianhydrides (4,4'-(1,3-diphenoxy)-bis(phthalic anhydride), 4,4'-(hexafluoroisopropylidene)-

bis(phthalic anhydride), 4,4'-(4,4'-isopropylidenediphenoxy)-bis(phthalic anhydride)) and diamines

(3,3'-dihydroxy-4,4'-diaminodiphenylmethane, 3,5-diaminobenzoic acid, 4,4'-diaminotriphenyl-

amine) were synthesized. OH-containing azo-chromophores with bulky substituents,

N

OH

NNNC

NC

N

OH

NN OH

O2N Cl

N

N

N

OH O

CN

CN

preventing an undesirable centrosymmetric aggregation of chromophores, were covalently attached

to the synthesized polyimides via Mitsunobu reactions. These structural features of the

chromophores made it possible to enhance the second-order NLO-properties of the synthesized

chromophore-containing polyimides and to achieve the values of the second harmonic generation

coefficient d33 = 32–60 pm/V.

Composite film coatings of the obtained chromophore-containing polyurethanes with the polyimide,

containing photoconductive triphenylamine groups, were prepared in order to improve

photorefractive properties of the polymers. Spectral electrophotographic photosensitivity of the

prepared compositions is studied. It was shown that d33 values for the compositions are only slightly

lower but their spectral electrophotographic photosensitivities are much higher as compared to the

corresponding properties of pure chromophore-containing polyimides.

This work is supported by the Russian Foundation for Basic Research, project no. 12-03-00709-а

and by the Scientific Program “Multifunctional materials for molecular electronics” of the

Presidium of the Russian Academy of Sciences (coordinator – academician S. M. Aldoshin).


220

SOLID-STATE ACTIVE MEDIA BASED ON HYBRID POLYMERS

FOR TUNABLE LASERS

E.N. Telminov, T.N. Kopylova, G.V. Mayer, K.M. Degtyarenko,

T.A. Solodova, L.G. Samsonova, R.M. Gadirov, S.Yu Nikonov

Syberian Physical Technical Institute of Tomsk State University, Russia

[email protected]

The development of methods of synthesis and preparation of solid-state active media based on organic compounds for tunable lasers is still urgent due to the possibility of their application in compact solid-state tunable lasers, including thin-film ones. In this work, 8 batches of solid-state active media based on PM 567 in PMMA-8POSS were synthesized and investigated, where 8POSS is polyhedral silsesquioxane (Fig. 1). The influence of the concentration of the initiator of polymerization reaction (AIBN), active substance (PM 567), and 8POSS on the generation characteristics of active media was studied.

CH3

C CH2C O CH3

O PM567 8POSS MMA

Figure 1 – Structural formulas of the materials used to prepare solid-state active media

The technology of preparing polymeric active elements with minimum changes of the material composition was developed. The media were excited by radiation of the 2nd harmonic of a Nd3+:YAG laser (30 mJ), pulse duration of 10 ns, and pulse repetition frequency up to 10 Hz. The radiation spectrum of the active elements, efficiency of radiation transformation, and operating lifetime

(the number of pulses before the efficiency decrease by the preset percent of its initial value) were registered. The data obtained are presented in Table 1.

Table 1. Lasing characteristics of the solid-state active media based on pyrromethene 567

Sample No. (Batch No.)

Concentration Efficiency, %

W, MW/cm

2

Np × 103

(efficiency/ efficiency0)

C(PM 567), M C(8POSS), % C(AIBN), %

2 (IV) 10-3

0 0.5 50

58 10 8

135 (0.67) 63 (0.75)

4 (IV) 10-3

0 0.2 46 58

10 8

90 (0.62) 47 (0.81)

5 (IV) 10-3

3.25 0.2 54 59

10 8

90 (0.56) 65.6 (0.81)

2 (VII) 1.5 × 10-3

0 0.1 51 43

10 8

140 (0.55) 128 (0.80)

4 (VII) 1.5 × 10-3

5 0.1 53 39

10 8

200 (0.50) 66 (0.83)

6 (VIII) 4 × 10-4

0 0.1 68 8 104 (0.80)

4 (VIII) 1.5 × 10-3

13 0.5 60 8 124 (0.60)

5 (VIII) 1.5 × 10-3

5 0.1 58 8 83 (0.70)

8 (VIII) 10-4

13 0.1 68 8 90 (0.54)

It can be seen that the prepared solid-state active media have the transformation efficiency up to 68%, their operating lifetime reached 105 at one point before the ratio efficiency/efficiency0 decreased by 20–50%. The synthesized active media based on organic and hybrid polymers have high characteristics. The

reproducibility of the characteristics of solid-state active media was investigated for different batches. It was noted that with increasing 8POSS concentration, inhomogeneities arose in the material; they could be avoided only in the process of synthesis in the water thermostat. The technology of synthesis of active media based on organic polymers has been protected by know-how.


221

VITA-D: A NEW PERSONAL UV BIODOSIMETER

FOR DIRECT MEASUREMENT OF THE VITAMIN-D-SYNTHETIC

CAPACITY OF SUNLIGHT AND ARTIFICIAL UV RADIATION

I.P. Terenetskaya1, T.M. Orlova

1, E.K. Kirilenko

2, G.A. Galich

1

1 – Institute of Physics NAS, Kiev, Ukraine

2 – VIRIA Ltd, Kiev, Ukraine

[email protected]

It is well-known that the biological activity of ultraviolet (UV) radiation can produce both positive

(synthesis of vitamin D3 in skin) and negative health effects (erythema and skin aging, immune

suppression, etc.). That is why monitoring of acquired UV doses of ultraviolet radiation is essential.

To date a number of UV dosimeters have been developed to measure erythemic biological activity of UV radiation for prevention of potentially harmful UV doses.

As known, lack of vitamin D3 causes rickets in children and osteoporosis in adults. Moreover, as

revealed recently, many serious diseases of heart and internal organs may also be caused by the

vitamin D3 deficiency [1]. With due regard to the above, monitoring of specific antirachitic

biological activity of ultraviolet radiation, i.e. its vitamin-D-synthetic ability, is gained in

importance, especially in view of current pandemy of vitamin D deficiency [2]

In view of significant distinction between erythemic and ‘antirachitic’ action spectra standard

personal UV dosimeters (for example, polysulphone film) don't give adequate information on the

vitamin D3 quantity synthesized during an UV exposure. What is needed is a dosimetric approach

that is similar to the actual process being measured. Therefore a UV biodosimeter has been

developed whose operation is based on the same photoreaction that occurs in human skin, thereby ensuring an accurate and reliable basis for measurement.

This bioequivalent process, – photosynthesis of previtamin D3 from 7-dehydrocholesterol (7-DHC,

provitamin D3) in a polymeric film, – is used in the original personal UV biodosimeter VITA-D [3],

capable to define a vitamin-D-synthesizing dose in situ. Clearly, the action spectrum of the

photosensitive material, - the polymeric film enriched with 7-DHC molecules, - corresponds to the

antirachitic one, and the quantity of previtamin D3, formed during an exposure to sunlight or artificial UV source, is a measure of received antirachitic biodose.

For an in situ measurements a portable optoelectronic device has been developed, allowing to

register the film transparency at λ = 280 nm (corresponding to maximum of the absorption band of

7-DHC). The change in transparency before and after an exposure caused by the 7 -DHC

photoconvertion is directly linked to the quantity of synthesized previtamin D3 which can be

determined using a calibration chart. Such measurements open the way for adequate correlation

between the quantities of photosynthesized vitamin D3 and daily recommended intake.

1. Norman A.W. Contribution of vitamin D to good health, Exp. Biol. and Med. 2010; 235: 1034–1045. 2. Holick M.F. The Vitamin D epidemic and its health consequences. J. Nutr., 2005, 135:2739S-2748S. 3. Terenetska I.P., Orlova Т.M., Kirilenko I.К., Galich G.А., Eremenko А.М., Ukrainian Patent

№ 93569, 24.03.2009; PCT/US10/28268, 23-MAR-2010.


222

SUPRAMOLECULAR CHEMOSENSORING SYSTEMS

BASED ON PHOTOSENSITIVE CROWN-ETHER DERIVATIVES

S.Yu. Zaitsev1, I.S. Zaitsev

1, M.S. Tsarkova

1, D.O. Solovyeva

2,

S.K. Sazonov3, A.I. Vedernikov

3, S.P. Gromov

3

1 – Moscow State Academy of Veterinary Medicine and Biotechnology, Russia

2 – Laboratory of Nano-Bioengineering, Moscow Engineering Physics Institute, Russia

3 – Photochemistry Center RAS, Moscow, Russia [email protected]

Design and preparation of the multifunctional supramolecular systems (MSS) based on crown-

containing dyes is currently one of the rapidly developing areas of research at the “junction” of

chemical physics & photonics, polymers & colloids, organic & biological chemistry, bio- &

nanotechnology [1-4]. The properties of a new class of photochromic materials synthesized at the

Photochemistry Center of the Russian Academy of Sciences [3,4], such as crown-containing dyes,

have recently become the subject of intense studies [1,2]. The presence of a crown ether fragment in

the dyes facilitates their selective bonding to metal cations. Spectral measurements taken in organic

and water-organic media have shown cation influences on the physical-chemical properties of the

sensor molecule [3,4]. There are three functional parts in the structure of the amphiphilic pyridinium

benzodithia-18-crown-6 (dye 1) (Figure 1): an ion-selective part of the dithia-containing macrocycle,

a photosensitive benzo-C=C-pyridinium part, and a lipid-like hydrophobic “tail” (C18).

Figure 1. The structure of the amphiphilic pyridinium benzodithia-18-crown-6 (dye 1).

N C18

H37

S

O

O S

O

O

ClO4

_

+

The dye 1 monolayers at the air/water interface were prepared by Langmuir technique and

characterized by surface pressure area and surface potential-area isotherms (on pure water and on

various salt solutions), reflection spectroscopy, Brewster angle microscopy. Transfer of dye 1

monolayers from the air/water interface onto optically transparent substrates (like glass and quartz

plates) was fulfilled by Langmuir-Blodgett (LB) method to obtain LB-films of desirable thickness;

absorption and fluorescence spectral properties. After structural modification of the LB films it was

possible to enhance the interaction with cations in the adjacent aqueous phase. In particular, the

capability of the obtained LB-films to form complexes with particular heavy metal cations, e.g.

Hg2+

, was demonstrated and detected by specific changes of the absorption and emission spectrum (on 10-13 nm in the shortwave range) of these nanofilms.

The particular interest to such MSS is due to their fundamental importance and great potential for

application in chemical and biological sensors; filters, membranes, electrodes, photochromic and

photorefractive elements, materials recording, for processing and storage of optical information.

This study was partly supported by the Ministry of Higher Education and Science of the Russian

Federation (Project No. 02.740.11.0718) and RFBR (Project No. 10-03-00711).

1. Zaitsev S.Yu. Supramolecular nanodimentional systems at the interfaces: concepts and

perspectives for bio nanotechnology. Moscow:LENAND, 2010, 208 p. (Russian).

2. Zaitsev S.Yu. Russian nanotechnologies, 2009, v.4, N.7-8, p.6-18 (Russian).

3. Gromov S.P. Russ. Chem. Bull., Int. Ed., 2008, v.57, p.1325-1340 (Russian).

4. Ushakov E.P.; Alfimov M.V.; Gromov S.P. Russian Chemical Reviews 2008, v.77, N.1, p.39–59.


223

PHOTOCHEMICALLY INDUCED GRATINGS AS OBSERVED

USING CONFOCAL LUMINESCENT SCANNING MICROSCOPE

V.V. Zakharov, A.E. Angervaks, A.S. Shcheulin, A.I. Ryskin, A.V. Veniaminov


[email protected]

The microscopic structures of holographic gratings written in an additively colored crystal of

fluorite and in a glassy polymer with phenanthrenequinone, known also as PQ:PMMA, are

observed with the help of confocal luminescent scanning microscope Zeiss LSM 710. The

mechanisms of hologram recording in the two materials concerned are based on photoinduced

transformation and spatial transfer (diffusion) of color centers and organic molecules, respectively.

In both cases, the phototransformed species (color centers and phenanthrene groups bound to

macromolecules) produce photoluminescence that makes it possible to detect their spatial

distribution with the help of luminescent microscopy, and the confocal scanning technique allows for high spatial resolution in all 3 dimensions.

While the hologram in polymeric material demonstrates nearly sinusoidal profile similar to that of

intensity in the recorded interference pattern, the profile observed in the crystalline material is

strictly non-sinusoidal, in agreement with the supposed mechanism of hologram formation and with

the observation of light diffraction from its several spatial harmonics with comparable amplitudes.

Another difference between the two cases is that the locations of maximum intensities of

luminescence coincide with the maxima of absorption in the crystal, but with its minima in the

polymer material. Contrary to the idea of phase nature of holograms recorded in polymers with

phenanthrenequinone, strong periodic absorption structures are observed within the whole visible

spectral range.

Along with direct imaging of holograms, scanning luminescent microscopy is used to measure quantum yields of the photoprocesses responsible for recording.

Luminescent images of gratings holographically imprinted in the bulks of additively colored

fluorite crystal (left) and polymeric glass with phenanthrenequinone (right).


224

PHOTOPHYSICAL AND KINETIC PROPERTIES

OF PHOTOSENSITIZERS ENCAPSULATED IN LIPID NANOVESICLES

V.P. Zorin1, V.A. Reshetov

1, T.E. Zorina

1, L.N. Bezdetnaya

2

1 – Belarussian State University, Minsk, Belarus

2 – Centre de Recherche en Automatique de Nancy, Nancy-Universite, CNRS, France

[email protected]

Photodynamic therapy (PDT) was shown to be highly effective in the curative and palliative

treatment of malignant tumors and other diseases. The effect of PDT involves a complex

combination of events, where highly reactive singlet oxygen generated by the photodynamic action

plays a major role to achieve therapeutic effect. Porphyrins are the most popular photosensitizing

agents for PDT. The most important limitation on their clinical application is low water solubility.

To overcome these problems, the photosensitizer could be loaded into nanosized drug delivery

systems, which enhances drug solubility and bioavailability. Liposomes are often used as

pharmaceutical carriers for poorly soluble drugs, since they can be solubilized in the hydrophobic

lipid core. Because of their characteristic small size (between 40 and 100 nm), good solubilization

efficiency and stability, liposomes may represent an ideal delivery system for apolar PDT drugs.

Incorporation into lipid vesicles allows keeping a monomeric state for many tetrapyrrolic

sensitizers, providing a high photosensitizing activity. The application of liposomal formulations in PDT requires the development of methods for sensitizer release control.

In our study, several chlorin-type photosensitizers (meta-tetra(hydroxyphenyl)chlorin, chlorin e6,

chlorin e6 dimethylester and chlorin e6 trimethylester) have been loaded into conventional or

PEGylated unilamellar phosphatidylcholine-based vesicles. All these sensitizers, while possessing

similar spectral properties, are quite different in their behavior in solutions and biological systems.

A comparison of dye spectral properties in liposomes with lipid/pigment ratio from 20 to 10000

strongly supports a monomeric state of all photosensitizers. For liposomes with high lipid/pigment

ratio different effects are observed: a) laser fluorometry shows a significant decrease in the quantum

yield of the photosensitized generation of singlet oxygen by chlorins; b) fluorescence depolarization

for sensitizer bound to lipid vesicles, c) a decrease in relative fluorescence quantum yield, d)

significant increase of FRET between lipid vesicle-bound probes and chlorins. All these

concentration-dependent fluorescence characteristics may be used for analyzing the rate of pigment

release from lipid carriers. We developed different techniques to analyze the redistribution of

sensitizer from liposomes to biological substrates: chlorins anisotropy measurements, photoinduced

fluorescence quenching and excitation energy transfer from the fluorescent probe (DPH, pyrene) to

chlorin. Despite the fact that each of the techniques shows similar results in the assessment of

chlorins redistribution, they have their own sensitivity limitations. The fluorescence anisotropy

technique is capable of measurements in the range of 1:100–1:1000 chlorin:lipid ratios, FRET-

based technique is sensitive at chlorin concentrations less than 1:200. Our experiments show that photoinduced quenching is sensitive in the range of 1:10–1:500 chlorin:lipid ratios.

The developed experimental approaches have been used to compare the rates of chlorins release

from lipid vesicles. According to the data obtained characteristic values of retention time changes in

very wide range, from seconds for chlorin e6 to several hours for meta-tetra(hydroxyphenyl)chlorin.

Authors Index -------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------

225

AUTHORS INDEX

A

Abramov I.G. ............................................... 219

Adrianov V.E................................................. 66

Afanasyev D.A. ............................... 37, 61, 139

Ageeva T.A.................................................. 209

Aimukhanov A.K. ............................... 139, 167

Ait A.O. ....................................................... 217

Akimkin T.M. ................................................ 56

Aksenova Yu.V. ............................................ 77

Aleksandrova E.L................................ 140, 219

Alekseeva V.I. ............................................. 125

Alfimov M.V. . 59, 87, 89, 103, 105, 109, 123,

136

Andreeva O.V................................................ 60

Angervaks A.E. ........................................... 223

Antina E.V. .................................................... 77

Antina L.A. .................................................... 77

Ardasheva L.P. ............................................ 187

Arean C.O. ..................................................... 21

Arslanov V.V................................................. 69

Artemyev M.V. ...........................145, 171, 175

Artemyev М.V. ........................................... 169

Artukhov V.Ya. ........................................... 177

Artyukhov V.Y. ........................................... 135

Artyukhov V.Ya. .........................101, 106, 168

Asaula V.V. ................................................... 62

Askirka V.F. ................................................ 185

Atabekyan L.S. .............................................. 82

Avakyan V.G. ................................................ 82

Ayt A.O............................... 185, 188, 189, 199

B

Babkov L.M........................................... 83, 207

Bagatur’yants A.A. ..................................... 103

Bagaturyants A.A. .................... 87, 90, 91, 194

Bakanov А.G. .............................................. 169

Balalaeva I.V. ................................................ 76

Barachevsky V.A. ....... 22, 185, 188, 189, 190,

191, 199, 204, 205, 206, 217

Baranov A.V. ... 60, 66, 68, 145, 169, 171, 175

Barinov A.V. ............................................... 182

Bashkirtsev D.E............................................. 77

Baskakova M.V. .......................................... 110

Basov L.L. ............................................. 44, 159

Batat P. ........................................................... 69

Bedilo A.F. .................................................... 47

Begantsova Yu. E. ................................. 74, 208

Belikov N.E. ................................193, 196, 197

Belykh R.A. ................................................... 84

Belyy N.M. .................................................... 88

Berberan-Santos M.N. ................................ 170

Berdnikova D.V. ........................................... 70

Berezin I.A. ...................................80, 149, 210

Berezin M.B. ................................................. 77

Berlin A.A. ............................................ 73, 217

Bertsev V.V. .................................................. 31

Besugly S.O. ................................................ 201

Bezdetko J.S. ............................................... 146

Bezdetnaya L.N. .................................. 218, 224

Billard I. ......................................................... 98

Blaudeck T................................................... 186

Bochkarev L.N. ..................................... 74, 208

Bodunov E.N. .............................................. 170

Bogacheva A.M........................................... 204

Bruevich V.V............................................... 111

Bryantseva N.G. ............................................ 39

Bryukhanov V.V. ................................ 121, 122

Budyka M.F. ............................................ 75, 85

Bugaychuk S.A.............................................. 62

Buglak A.A. ............................................. 49, 57

Bukov V.A. .................................................. 138

Bulanin K.M. ......................................... 31, 119

Bulanov A.O. ............................................... 190

Bulgakov R.A. ............................................. 154

Bushuk B.A. ................................................ 108

Bushuk S.B. ................................................. 108

Byzov I.V..................................................... 173

C

Charushin V.N. ............................................ 204

Cherevkov S.A. ........................................... 171

Chernyshev A.V. ......................................... 201

Chibisov A.K. ........................................ 82, 192

Chizhov Yu.V.............................................. 180

Chmereva T.M. ........................................... 174

Coluccia S. ................................................... 161

D

Danilov V.V. ............................................... 172

Davidenko N.A.............................................. 37

Davydova N.A. ...................................... 86, 207

Authors Index -------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------

226

Degtyarenko K.M........................210, 212, 220

Degtyareva O.V................................... 133, 134

Delbaere S...................................................... 70

Demina O.V.................................193, 196, 197

Derevyanko N.A. ........................................ 178

Derkacheva V.M. ........................................ 158

Devadze L. ................................................... 195

Diekmann J. ................................................. 213

Dmitriev A.V. ................................................ 50

Dmitrieva S.N................................................ 87

Dobrokhotov O.V........................................ 219

Dobrotvorskaia A. ......................................... 32

Doga P.G. .................................................... 147

Dolotova O.V. ............................................. 154

Dorogan I.V. ................................................ 201

Druzhinin A.V. ............................................ 173

Dudar S.S. ...................................................... 41

Dzhagarov B.M. .......................................... 128

E

Efremova A.A. ............................................ 112

Egorova O.Yu.............................................. 158

Eichler H.J. .................................................... 33

Ekimova I.A. ............................................... 155

Elanskaya I.V. ............................................. 165

Emeline A.V. ............................................... 163

Emelyanova E.V. ........................................ 162

Eremenko A.M. ............................................. 88

Eremina N.S. ....................................... 210, 212

Ermolaev V.L. ............................................... 41

Ermolaeva G.M. .......................................... 172

Ermolina E.G. .............................................. 209

F

Fedorov A.V. ........................................... 66, 68

Fedorov Yu. V. .............................................. 70

Fedorov Yu.V. ............................................... 78

Fedorova O.A. ......................................... 70, 78

Fedorova T.M. ............................................. 158

Fedoseev A.I. ................................................. 50

Fetisova Z.G. ............................................... 141

Filippov T.N. ................................................. 42

Fomina M.V. ................................................. 89

Freidzon A.Ya. ......................... 87, 90, 91, 194

G

Gadirov R.M. ...................... 177, 211, 212, 220

Galich G.A. .................................................. 221

Galievsky V.A. ..............................55, 128, 186

Galkin V.P. ............................................ 92, 142

Gantsev Sh.Kh. .................................... 129, 130

Gaponenko S.V. ............................................ 23

Garbovskiy Yu.A. ......................................... 62

Gatilova A.V. ................................................ 93

Gavrilko T.A. .............................................. 126

Gavrishova T.N. ............................................ 85

Gericke K.-H. .............................................. 152

German A.E. ................................................ 185

Glazkova N.I. .............................................. 160

Gorelik A.M. ...................... 188, 189, 191, 199

Gorkovenko A.I............................................. 81

Gorlov R.V. ................................................. 122

Goryachev N.S. ........................ 33, 63, 94, 182

Gradov O.V. ................................................ 156

Gradova M.A. ................................95, 131, 156

Grigoryev I.S. ................................................ 76

Grishina A.D. ................................................ 65

Gromov S.P. 59, 82, 87, 89, 99, 109, 112, 123,

136, 202, 222

Gromova E.S. .............................................. 172

Gromova Yu. A. ............................................ 60

Grushnikova E.Yu. ........................................ 96

Gruzdev N.B. ............................................... 173

Gubanova M.S. .............................................. 68

Gurinov A.V. ......................................... 35, 118

Gurinovich V.V. ............................................ 51

Guseva G.B.................................................... 77

I

Ibrayev N.Kh. ................. 37, 61, 125, 139, 167

Ilichev V.A. ................................................... 74

Ishchenko A.A. ......... 24, 37, 97, 176, 178, 183

Ivannikova E.V............................................ 190

Ivanov A.I. ........................................... 143, 150

Ivanov A.M.................................................. 121

Ivanov D.A. ............................................. 98, 99

Ivlieva I.V. ..................................................... 83

Izmailov B.A. .............................................. 206

Izmodenova S.V. ......................................... 174

J

Jacquart A. ..................................................... 71

Japaridze K. ................................................. 195

Jonusauskas G. .............................................. 69

Authors Index -------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------

227

K

Kalinkina L.M. ............................................ 157

Kaliteevskaya E.N. .............................. 127, 184

Kaliya O.L. .......................................... 154, 158

Kapinos P.S. ................................................ 100

Kaplunov M.G. ............................144, 148, 211

Karamanov A.A. ......................................... 190

Kashapova E.R. ........................................... 101

Kashtanov G.S. .............................................. 40

Kataeva G.V. ............................................... 163

Kazakova E.Kh............................................ 114

Kazansky V.B.............................................. 161

Kerita O. ...................................................... 179

Kernazhitsky L.A. ....................................... 126

Khakina E.A. ......................................... 63, 116

Khalyavka T.V. ........................................... 126

Khatipov S.A. .............................................. 120

Khilya V.P. .................................................. 176

Khitrin A.V. ................................................. 121

Khlebunov A.A. .......................................... 123

Khodonov A.A. ...........................193, 196, 197

Khrebtov A.I. ............................................... 172

Khriachtchev L. ............................................. 25

Khristoforova L.V. ...................................... 205

Khursan S.L. ........................................ 129, 130

Kichigina A.O. ............................................ 143

Kim G.A. ............................................. 173, 198

Kirilenko E.K. ............................................. 221

Kiriyak A.V. ................................................ 147

Klapshina L.G. .............................................. 76

Klemesheva N.A. .......................................... 92

Klemesheva, N.A. ....................................... 142

Klimchuk O. .................................................. 98

Klimusheva G.V. ........................................... 62

Klishevich G.V. ............................................. 86

Klyuev V.G.................................................. 146

Knyukshto V.N............................................ 186

Kobeleva O.I. ............. 188, 189, 190, 199, 206

Kochubey V.I. ....................................... 38, 137

Kolesnikov M.P............................................. 57

Kolinko P.A. .................................................. 42

Kolomiitsova T. ............................................. 32

Kolomiitsova T.D.................................... 31, 93

Koltsova L.S. ......................................... 73, 200

Komarov P.V. .............................................. 102

Komarova K.G. ........................................... 103

Kompaneez V.V. ......................................... 104

Konova E.M. ............................................... 120

Konovalov A.I. ............................................ 114

Konyukhova Ju.G........................................ 137

Kopylova T.N. .... 77, 177, 209, 210, 211, 212,

220

Kopysov V.N. .............................................. 105

Kornev A.B....................................63, 116, 182

Korochentsev V.V. ...................................... 117

Koroleva M.V.............................................. 181

Korolevich M.V. ........................................... 83

Korotkov V.I. .................................. 35, 92, 118

Koshkin A.V. ........................................... 89, 96

Kotelnikov A.I. ....................... 33, 63, 116, 182

Kotelnikova R.A. ........................................ 116

Kozlov D.V.................................................... 42

Krasnaya Zh.A. ........................................... 132

Krasnikova S.S. ........................................... 144

Krasnovsky A.A. ........................................... 26

Krauklis I.V. ................................................ 180

Krayushkin M.M. ............... 199, 204, 205, 206

Kritsky M.S. ............................................ 49, 57

Krivenko T.V................................................. 65

Krivonogova K.Yu ...................................... 106

Krutyakova V.P. .......................................... 127

Kshnyakin V.C. ........................................... 126

Kubenova M.M. .......................................... 167

Kucherenko M.G. .................................. 64, 174

Kukhto A.V. ................................................ 212

Kulinich A.V. ........................................ 97, 183

Kurchavov N.A. ............................................ 87

Kurdiukova I.V.............................................. 97

Kurkhuzenkov S.A. ..................................... 185

Kurochkina M.A. ........................................ 145

Kurtaliev E.N............................................... 107

Kuvandykova A.F. ...................................... 164

Kuz’mina L.G........................................ 89, 109

Kuzmina L.G. ......................... 59, 87, 123, 136

Kuznetsova N.A. ......................................... 154

Kuznetsova N.I. ........................................... 158

Kuznetsova R.T. .................................... 77, 209

L

Lapina V.A. ................................................. 108

Laptenkov D.V. ........................................... 159

Laptev A.V. .................................193, 196, 197

Laryushkin A.S.............................................. 65

Leaustic A. ..................................................... 71

Lebedev-Stepanov P.V. ................................ 96

Lee V.M. ........................................................ 85

Lekanova N.Yu. ............................................ 76

Leonov N.B. ................................................ 184

Lermontova S.A. ........................................... 76

Letuta S.N. ................................................... 164

Authors Index -------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------

228

Levchenko K.S. ........................................... 206

Levchenkov S.I.............................................. 73

Levin P.P. .............73, 131, 193, 196, 197, 200

Lisachenko A.A...................... 43, 44, 159, 161

Litke S.V. ..................................................... 138

Liu H. ............................................................. 48

Liu Y. ............................................................. 48

Lobanov A.V. ........................................ 95, 131

Lobova N.A. ..................................82, 109, 136

Lokshin V. ..................................................... 70

Lukashev E.P. .............................................. 165

Lukin A.Yu. .................................193, 196, 197

Lukyanov B.S. ............................................. 201

Lushnikov S.G. .............................................. 50

Lyalin G.N. .......................................... 113, 213

Lypenko D.A. .................................. 80, 89, 214

Lyudnikova T.A. ........................................... 49

M

Maevsky A.V............................................... 110

Maiorova T.L............................................... 146

Maisonneuve S. ............................................. 71

Maisuradze J. ............................................... 195

Maksimov E.G. ........................................... 165

Mal’tsev E.I. .................................................. 89

Malkin V.M. ........................................ 215, 216

Maltsev E.I. ........................................... 80, 214

Malykhin S.E. ................................................ 47

Mannanov A.A. ........................................... 111

Mardaleishvili I.R. ................................ 73, 200

Marinina L.E. .............................................. 125

Markova G.D. .............................................. 206

Martra G....................................................... 161

Martyanov T.P. ............................................ 112

Martynenko I.V. .................................... 68, 175

Maskevich C.A. ........................................... 199

Maskevich S.A. ........................................... 185

Maslov V.G. .... 60, 66, 68, 113, 118, 145, 175

Matyushina N.V. ......................................... 140

Maul H.C. .................................................... 152

Mayer G.V. ..................... 39, 77, 101, 168, 220

Mazyrin D.V. ......................................... 92, 142

Melnik D.A. ................................................... 62

Melnik V.I. .................................................... 86

Melnikov A.G................................................ 38

Melnikov G.V................................................ 38

Menshikova A.Yu. ........................................ 96

Meshkova S.B. ............................................ 147

Metivier R. ..................................................... 71

Miagkova L.A. ............................................ 140

Mihalevskiy A.A. ........................................ 146

Mikhailova V.A........................................... 150

Mikhaylov R.V. .................... 44, 159, 160, 161

Minakova T.S. ............................................. 155

Mirnaya T.A. ................................................. 62

Mironov L.Yu................................................ 41

Mironova D.A. ............................................ 114

Miyasaka T. ................................................... 27

Mo Y. ........................................................... 153

Moiseykina E.A........................................... 207

Morozov A.N............................................... 190

Morozova Ju.E. ........................................... 114

Moskvina V.S. ............................................. 176

Mukha I.P. ..................................................... 88

Mukhanov E.L. ............................................ 201

Myslitskaya N.A. ........................................ 121

Mzavanadze I. ............................................. 195

Mаslov V.G. ................................................ 169

N

Nakatani K. .................................................... 71

Naumenko A.P. ............................................. 88

Naumov V.V. .............................................. 126

Nechaev L.V. ................................................. 39

Nekrasova T.N. ................................... 140, 214

Nikitenko S.L. ............................................. 148

Nikitich M.P. ............................................... 162

Nikitin K.V. ................................................. 160

Nikonorov N.V. ............................................. 67

Nikonov S.Yu .............................................. 220

Nikonov S.Yu. ............................................. 177

Nizomov N. ................................................. 107

Nosova D.A. .......................................... 92, 142

Nosova E.V.................................................. 198

Nosova G.I. ............. 80, 81, 149, 210, 214, 219

Novoderezhkin V.I. ..................................... 141

Nurmukhametov R.N. ................................... 34

Nyokong T. .................................................. 154

O

Odinokov A.V. .............................................. 91

Ohtani B. ........................................................ 28

Ollis D.F. ....................................................... 45

Optov V.A. .................................................. 217

Orlova A.O. ..... 60, 66, 68, 118, 145, 169, 175

Orlova T.M. ................................................. 221

Orlova T.N. .................................................. 100

Osmanova E.Ia. ........................................... 178

Authors Index -------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------

229

Ostakhov S.S. ...................................... 129, 130

Ostapenko N.I.............................................. 179

Ostapenko Yu.V. ......................................... 179

Ouhenia K. ..................................................... 71

Ovchinnikova I.G. ....................................... 198

Ozhogin I.V. ................................................ 201

P

Panchenko P.A. ....................................... 70, 78

Panfutova A.S.............................................. 172

Paraschuk D.Yu..................................... 40, 111

Parmon V.N. .................................................. 29

Paschenko V.Z. ........................................... 165

Pashkevich S.N............................................ 164

Penkov S.A. ................................................... 64

Perevoshikova A.Yu. .................................. 199

Petriashvili G. .............................................. 195

Petrov N.Kh. ............................................ 98, 99

Petrov S. ......................................................... 32

Petrov S.N.................................................... 115

Pichat P. ......................................................... 30

Pinchuk S.V. .................................................. 51

Platonova I.A. ...................................... 204, 205

Plekhanov A.I. ............................................... 81

Plotnikov V.G...................................... 102, 192

Podkopaeva O.Yu. ...................................... 180

Pogliani L. ................................................... 170

Poletaeva D.A.............................................. 116

Polyanin N.V. .............................................. 211

Ponyavina E.N. ............................210, 211, 212

Popov L.D.............................................. 73, 190

Poretskiy M.S. ............................................. 152

Portnyagin A.S. ........................................... 117

Potashova N.I. ............................................... 85

Pozin S.I......................................................... 89

Pravdin A.B. .................................................. 38

Pronkin P.G. .......................................... 56, 166

Prudnikau A.V. ............................................ 171

R

Ramsh S.M. ................................................. 138

Rapoport V.L. ........................................ 52, 216

Razina V.S. .................................................. 131

Razumova T.K. ........................................... 127

Renger G. ....................................................... 33

Reshetov V.A. ..................................... 218, 224

Reznichenko V.Ya. ....................................... 86

Rodionov I.A. ........................................ 46, 157

Rogozina M.V. ............................................ 150

Romanovskaya G.I. ..................................... 181

Rozhkova Y.A. ....................... 35, 92, 118, 142

Rudakova A. .................................................. 32

Rudakova A.V. .................................... 115, 119

Rusinov G.L. ............................................... 198

Ryabchuk V.K. .................................... 155, 163

Rybkin A.Yu. ........................................ 63, 182

Rychwalski R.W. .......................................... 65

Ryskin A.I.................................................... 223

S

Sabsai O.Yu. ................................................ 217

Safonov A.A. ......................................... 90, 194

Sagun E.I. .................................................... 186

Sakhno T.V. ................................................. 120

Sakhno Yu.E. ............................................... 120

Samoilov A.V. ............................................. 162

Samsonova L.G. .......................................... 220

Samusev I.G. ....................................... 121, 122

Sarapulova O.O. ............................................ 79

Savel’ev V.V. ................................................ 65

Savin I.V. ..................................................... 202

Savransky V.V. ................................... 133, 134

Savvateeva-Popova E.V. .............................. 50

Savvina L.P.................................................. 125

Sazhnikov V.A. ................................... 105, 123

Sazonov S.K. ................ 87, 123, 136, 202, 222

Schmitt F.-J.................................................... 33

Seisenbayeva G.S. ....................................... 167

Selektor S.L. .......................................... 69, 124

Seliverstov D.I. ............................................ 120

Seliverstova E.V. ......................................... 125

Semeikin A.S. ................................................ 77

Semenishin N.N. ......................................... 209

Sepashvili N. ............................................... 195

Sergeeva A.N........................................... 70, 78

Shakhverdov T.A. ....................................... 172

Shapkin N.P. ................................................ 117

Shapovalov A.V. ........................................... 34

Shargaeva A.Yu. ......................................... 183

Shchedrin P.V.............................................. 127

Shchepkin D. ................................................. 32

Shchepkin D.N. ....................................... 31, 93

Shcherbakov I.N. ......................................... 190

Shcheulin A.S. ............................................. 223

Shelimov B.N. ............................................. 161

Shenderovich I.G........................................... 35

Sherstyuk V.P. ............................................... 79

Shevchenko E.N. ......................................... 158

Authors Index -------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------

230

Shienok A.I. ................................................... 73

Shirmanova M.V. .......................................... 76

Shiyonok A.I. .............................................. 200

Shkuropatov A.Ya. ...................................... 151

Shuvalov V.A. ............................................. 151

Shvalagin V.V. .............................................. 79

Shvedova L.A. ....................................... 56, 132

Shvets V.I. ...................................193, 196, 197

Shymanovska V.V. ..................................... 126

Sidorov A.I. ................................................... 67

Silantyeva D.A. ............................................. 69

Silyukov O.I. ................................................. 46

Simanchuk A.E.............................................. 81

Slezhkin V.A. .............................................. 122

Slominskii Yu.L. ......................................... 183

Smirnov K.S. ............................................... 115

Smirnov N.N. ........................................ 81, 219

Smirnov V.A. .............................................. 192

Smirnova N.P. ............................................... 88

Smolin A.G. ................................................. 153

Smyslov R. You. ........................................... 80

Smyslov R. Yu. ................................... 140, 149

Smyslov R.Yu. ............................................ 214

Sokolov V.I.................................................. 173

Sokolova I.V. ................................................. 39

Solodova T.A.............. 209, 210, 211, 212, 220

Solovskaya N.A...... 80, 81, 149, 210, 214, 219

Solovyeva D.O. ............................... 53, 58, 222

Sosorev A. Yu. .............................................. 40

Stadnichuk I.N. ...................................... 54, 165

Starovoytov A.A. ........................................ 127

Stasheuski A.S. ..............................55, 128, 186

Stuchebryukov S.D. .................................... 124

Stupak A.P. .................................................. 186

Stupina T.V.................................................. 198

Sultanbaev M.V................................... 129, 130

Sultimova N.B. ............................................ 131

Sveklo I.F..................................................... 185

Sveshnikova E.B. .......................................... 41

Svetlichnyi V.M. ......................................... 140

Svistunova I.V. ............................................ 117

Syakaev V.V. ............................................... 114

Sychkova S.T............................................... 120

T

Taisova A.S. ................................................ 141

Tameev A.R................................................. 140

Tatikolov A.S. ................ 56, 73, 132, 166, 200

Tchaikovskaya O.N....................................... 39

Telegina T.A. ........................................... 49, 57

Telminov E.N. .............. 77, 210, 211, 212, 220

Terenetskaya I.P. ...........................72, 100, 221

Terpugov E.L....................................... 133, 134

Terpugova S.E. .................................... 133, 134

Tikhomirov V.A. ........................................... 91

Tikhomirova N.S. ........................................ 122

Titov V.V. ...................................................... 44

Titova T.Yu. ................................................ 135

Tokmenko I.I. ................................................ 62

Tolochko A.S................................................. 62

Tolstoy P.M. .................................................. 35

Topilova Z.M............................................... 147

Toropov N.A. .............................................. 184

Troshin P.A....................................63, 116, 182

Tsarkova M.S. ............................................. 222

Tsaturyan A.A. ............................................ 190

Tsekhomsky V.A........................................... 67

Tsyganenko A. .............................................. 32

Tsyganenko A.A. ..... 36, 84, 93, 110, 115, 119

Tsyganenko N.M. ........................................ 119

Tyurin R.V. .................................................. 203

U

Uimin M.A. ................................................. 173

Ushakov E.N. ......................... 59, 87, 112, 202

V

Valova T.M......................... 189, 190, 199, 206

Vannikov A.V. .................................. 65, 80, 89

Varfolomeev S.D......................................... 193

Vartanjan T.A. ............................................... 67

Vartanyan T.A. ............................................ 184

Vasilyeva I.A. .............................................. 104

Vasilyuk G.T. ...................................... 185, 199

Vasnev V.A. ................................................ 206

Vasyutinskii O.S. ........................................ 153

Vechtomova Y.L. .......................................... 49

Vechtomova Yu.L. ........................................ 57

Veckenstedt M............................................. 152

Vedenichev D.A. ......................................... 172

Vedernikov A.I. 59, 82, 87, 99, 109, 123, 136,

222

Veniaminov A.V. ........................................ 223

Venidiktova O.V. ................................ 189, 191

Vershinin N.O. .............................................. 39

Visotskaya S.O. ............................................. 92

Vodyankin A.A. .......................................... 162

Vodyankina O.V. ........................................ 162

Authors Index -------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------

231

Volin R........................................................... 32

Volkova E.K. ............................................... 137

Volodin A.M. ................................................ 47

Von Borczyskowski C. ............................... 186

Vorobey A.V. ................................................ 51

Vorobey P.A. ................................................. 51

Vorontsov A.V. ............................................. 29

Vysotskaya S.O. .......................................... 142

W

Wang C. ......................................................... 48

Weibe V.V. .................................................. 201

X

Xie J. .............................................................. 71

Y

Yakimansky A.V. ... 80, 81, 149, 210, 214, 219

Yakovlev A.G...................................... 141, 151

Yakushchenko I.K. .............................. 144, 211

Yang J. ........................................................... 48

Yanilkin V.V. .............................................. 114

Yanyushin M.F. ........................................... 165

Yarmoluk S.M. .............................................. 56

Yarovenko V.N. ................. 199, 204, 205, 206

Yasinsky V.M.............................................. 185

Yermakov A.Ye. ......................................... 173

Yourre T.A. ................................................. 138

Yu P. .............................................................. 71

Yutanova S.L. ................................................ 77

Z

Zagaynova E.V. ............................................. 76

Zaichenko N.L. ...................................... 73, 200

Zaitsev I.S. ................................................... 222

Zaitsev S.Yu. ................................... 53, 58, 222

Zakharov G.A. ............................................... 50

Zakharov N.V. ............................................. 119

Zakharov V.V. ............................................. 223

Zakharova G.V. ........................................... 192

Zapunidy S.A................................................. 40

Zarochentseva E.P. ................................ 92, 142

Zeinidenov A.K. .......................................... 167

Zenkevich E.I. ............................................. 186

Zhang X. ........................................................ 48

Zharmukhamedov S.K. ............................... 165

Zhukova E.V. ......... 80, 81, 149, 210, 214, 219

Ziminov A.V. .............................................. 138

Zorin V.P. ............................................ 218, 224

Zorina T.E............................................ 218, 224

Zurabisvili Ts. ............................................. 195

Zvereva I.A. ........................................... 46, 157

academician alexander nikolayevich...

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