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YISAC 2010YISAC 2010YISAC 2010YISAC 2010

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ANALYTICAL ANALYTICAL ANALYTICAL ANALYTICAL CHEMISTRYCHEMISTRYCHEMISTRYCHEMISTRY

Venice, June 29Venice, June 29Venice, June 29Venice, June 29 th th th th ----July 1July 1July 1July 1stststst, 2010, 2010, 2010, 2010

BOOK BOOK BOOK BOOK OF OF OF OF ABSTRACTSABSTRACTSABSTRACTSABSTRACTS

YISAC 2010

Scientific Committee:

Bobrowski Andrzej University of Cracow Daniele Salvatore University of Venice

Francesconi Kevin University of Graz Goessler Walter University of Graz

Kalcher Kurt University of Graz Kolar Mitja University of Maribor

Lankmayr Ernst Technical University Graz Mladen Franko Politehnik Nova Gorica

Mocák Ján University of Ss. Cyril & Methodius, Trnava Moretto Ligia Maria University of Venice

Murkovic-Steinberg Ivana University of Zagreb Ogorevc Božidar National Institute of Chemistry, Ljubljana

Pihlar Boris University of Ljubljana Stibilj Vekoslava Institute Jozef Stefan, Ljubljana

Svegl Franc ZAG, Ljubljana Trebse Polonka Politehnik Nova Gorica

Turkusic Emir University of Sarajevo Ugo Paolo University of Venice

Veber Marjan University of Ljubljana Vytras Karel University of Pardubice

Organizers:

Moretto Ligia Maria Ongaro Michael Roman Marco

Silvestrini Morena Ugo Paolo (chair)

With the patronage of the University Ca’ Foscari of Venice

Sponsored by:

Dipartimento di Chimica Fisica

YISAC 2010 - Program

17th Young Investigators’ Seminar on Analytical Chemistry, June 29th – July 1st, 2010, Venice 1

YISAC 2010 – Scientific program

Tuesday, June 29th, 2010

18:00-19:00 Registration at Istituto Canossiano Fondamenta de le Romite, 1323 Dorsoduro – 30123 Venezia 19:00 Get-together

Wednesday, June 30th, 2010

08:30-09:00 Registration 09:00-09:15 Opening Session I – Chromatography Chair: Ovca Andrej

09:15-09:30 Papp Zsigmond (Novi Sad, Serbia)

Contribution to the Analytical Chemistry of Neonicotinoids: Spectrophotometric, Voltammetric and HPLC Measurements

09:30-09:45 Triglav Jure (Ljubljana, Slovenia)

Development of Software to Aid in the Optimization of Elemental Imaging by LA-ICP-MS

09:45-10:00 Soukup Jan

(Pardubice, Czech Republic)

Hydrophilic Interaction Liquid Chromatography for the Separation of Phenolic and Amino Acids on Three Silicagel Columns

10:00-10:15 Čáňová Eva


Lipidomic Analysis of Plant and Animal Tissues Using HPLC/MS

10:15-10:30 Ćirić Andrija (Kragujevac, Serbia)

Matrix Effect on Determination of Some Flavonoids in Real Samples by LC-UV and LC-MS/MS Method

10:30-10:45 Škeříková Veronika


Separation of Polar Compounds by HILIC

10:45-11:00 coffee break Session II – Electroanalysis Chair: Elcnerova Michaela

11:00-11:15 Šebez Bine (Ljubljana, Slovenia)

A Study on Selected Parameters for the Advanced Use of Antimony Film Electrode in anodic stripping

11:15-11:30 Bulíčková Jana


Characterization of Water-Soluble Fullerene Compounds by Electrochemical and Spectroscopic Techniques

11:30-11:45 Putek Maria (Kraków, Poland)

Voltammetric Studies of the Co(II)-Tris(hydroxymethyl)-Aminomethane and Sodium Perborate Volumetric Catalytic System

11:45-12:00 Stočes Matěj


Electrochemical Synthesis of Polyaniline Films at a Screen-Printed Carbon Electrode and their Potential Applicability in Biosensing

12:00-12:15 Haramustek Ivana (Zagreb, Croatia) Electrochemical Probing of Estradiol Antioxidant Capacity

12:15-12:30 Sopha Ingrid Hanna (Ljubljana, Slovenia) Recent Developments of Antimony- and Bismuth-Based Electrodes

12:30-13:45 lunch break Session III - Electroanalysis + Environment Chair: Skerikova Veronika

13:45-14:00 Jágerszki Gyula (Budapest, Hungary)

Ionophore-Gold Nanoparticle Conjugate as a Receptor in the Ion Selective Electrodes

14:00-14:15 Marecic Miroslav (Zagreb, Croatia)

Development of Conductometric Sensors for Organic Vapours Based on PEDOT-PSS Semiconductive Thin Films

14:15-14:30 Dožić Sanja (Novi Sad, Serbia)

Electrical Conductivity and Solvation Process Examination in Molten Salts

14:30-14:45 Masiol Mauro (Venice, Italy)

Analysis of Airborne Particulate Matter with the Combined Use of Particle Induced X-ray Emission, Ion Chromatography and Scanning Electron Microscopy

14:45-15:00 Brglez Polona (Maribor, Slovenia)

Determination of Oxygen in Biogas and Interference Study of Various Gases Using Ruthenium Complex Optical Sensor

15:00-15:15 Kitanovski Zoran (Ljubljana, Slovenia)

A Novel Method for Determination of Higher Carboxylic Acids in Atmospheric Aerosols Using Hydrophilic Interaction Liquid Chromatography Tandem Mass Spectrometry



coffee break 15:15-15:30 Session IV – Environment Chair: Triglav Jure

15:30-15:45 Zhuang Rensheng (Nova Gorica, Slovenia)

Photoreaction of BP-3 and BP-4 by Aqueous Chlorine- Products and Toxicity Studies

15:45-16:00 Barbaro Elena (Venice, Italy) Determination of Amino Acids in the Urban Aerosol in the Venice Lagoon

16:00-16:15 Berisha Fatlume (Graz, Austria)

Groundwater Situation in Kosova Investigated with Inductively Coupled Plasma Mass Spectrometry

16:15-16:30 Kavšek Darja (Maribor, Slovenia)

Multivariate Statistical Methods for Characterization of Waste Water Quality

16:30-16:45 Černe Marko (Ljubljana, Slovenia)

Determination of Radionuclides in Plants from the Area Around the Boršt Tailings Pile of the Former Uranium Mine at Žirovski vrh in Slovenia using Alpha-spectrometry

16:45-17:00 Žabar Romina (Nova Gorica, Slovenia)

Pesticide’s Transformation Products: Stability and Degradation Studies

17:30 Welcome by the vice-Rector in Ca’ Foscari

Thursday, July 1st, 2010

Session V - Nano-Micro Chair: Marecic Miroslav

09:15-09:30 Ongaro Michael (Venice, Italy)

TiO2 Nanofibers for Sensing Applications by Improved Sol-Gel Template Synthesis

09:30-09:45 Milutinovic Milena (Bourdeaux, France)

Photopatterning a Redox Polymer: Application to Electrogenerated Chemiluminescence Detection

09:45-10:00 Ičević Ivana (Novi Sad, Serbia)

Impact of Cosolvents and Additives to Change of Dimension and ζ-Potential of Fullerenol Nano Particles

10:00-10:15 Szűcs Júlia (Budapest, Hungary) Potentiometric Immunoassay Based on Sequential Flow Injection Analysis

10:15-10:30 Silvestrini Morena (Venice, Italy) Functionalization and Protection of Nanoelectrodes Ensembles by SAMs

10:30-10:45 coffee break Session VI – Spectrometry Chair: Palcic Marina

10:45-11:00 Panighello Serena (Venice, Italy)

Characterization of Polychrome pre-Roman Glasses by Laser Ablation ICP-MS

11:00-11:15 Fauland Alexander (Graz, Austria)

Shotgun Mass Spectrometry under Information Dependent Acquisition Control for Automated Lipidomic Analysis

11:15-11:30 Kokarnig Sabine (Graz, Austria) Investigation of Selenium Compounds in Human Serum

11:30- 11:45 Roman Marco (Venice, Italy) Selenium Speciation in Rat Colon Tissue

11:45-12:00 Jedličková Veronika


UHPLC/MS/MS Analysis of Anthelmintic Drugs and their Metabolites

12:00-12:15 Spolaor Andrea (Venice, Italy) Speciation Analysis of Fe2+ / Fe3+ in Antarctic Ice Core Samples

12:15-13:30 lunch break Session VII - Bioanalytical Chemistry Chair: Silvestrini Morena

13:30-13:45 Elcnerova Michaela


Activity Determination of Stearoyl-CoA-Desaturase 1 (SCD-1)

13:45-14:00 Donnarumma

Fabrizio (Graz, Austria)

Mechanism of Action and Pharmacokinetic Evaluation of a New Anti-Cancer Drug

14:00-14:15 Nemeček Peter (Trnava, Slovakia)

Prediction of HPLC Retention Factor of Compounds with Antituberculotic Activity

14:15-14:30 Hardt-Strehmayer

Magdalena (Graz, Austria)

Metabolism of 5-Hydroxymethylfurfural after Administration of a Novel Anticancer Infusion Solution

14:30-14:45 Zelenik Andreja (Ljubljana, Slovenia) Transformation of As2O3 in Cell Culture Studies

14:45- 15:00 Pfliger Heidelinde (Graz, Austria) Cell Culture Investigations with New Antitumoral Agents



15:00-15:15 coffee break Session VIII - Food Analysis Chair: Fauland Alexander

15:15-15:30 Vogrinčič Maja (Ljubljana, Slovenia)

Polyphenol Concentration and Antioxidant Activity of Tartary Buckwheat (Fagopyrum Tataricum) Bread

15:30-15:45 Bednárová Adriána (Trnava, Slovakia)

Multidimensional Analysis of Fatty Acid Composition of Beef Produced Under Grassland-Based Conditions in Austria

15:45-16:00 Ovca Andrej (Nova Gorica,

Slovenia)

Zinc Speciation in Pumpkin Seeds and Iceberg Lettuce Related to Plant Physiology and Human Health

16:00-16:15 Palčić Marina (Zagreb, Croatia)

Simultaneous Determination of Binary Dye Mixtures in Food Samples by Three Different Spectroscopic Methods

16:15-16:30 Štrekelj Petra (Ljubljana, Slovenia)

The Effect of Selenium in Seed Soaking Solution on Growth and Selenium Uptake in Tartary Buckwheat Sprouts

16:30-16:45 Closing ceremony

20:00 Conference Dinner

YISAC 2010 – Abstracts



ABSTRACTSABSTRACTSABSTRACTSABSTRACTS

YISAC 2010 – Session I: Chromatography


Session I

Chromatography



Contribution to the Analytical Chemistry of Neonicotinoids: Spectrophotometric, Voltammetric and HPLC Measurements

Zsigmond Papp, Valéria Guzsvány*

Department of Chemistry, Biochemistry and Environmental Protection, Faculty of Sciences, University of Novi Sad, Trg D. Obradovića 3, 21000 Novi Sad, Republic of

Serbia Abstract The aim of this work was to develop new, fast and simple analytical methods for the determination of selected neonicotinoid insecticides. First, a simple derivative spectrophotometric method was developed for the simultaneous determination of imidacloprid and 6-chloronicotinic acid (6-CNA), one of the synthetic precursors, and also an intermediate of imidacloprid decomposition [1]. The proposed method was applied for the determination of imidacloprid and 6-CNA in commercial insecticide formulations. A conventional spectrophotometric method was also employed for the determination of the content of imidacloprid in the same commercial formulations. As second, a differential pulse voltammetric method was developed for the determination of some neonicotinoid insecticides using a carbon paste electrode as working electrode [2-4]. The voltammetric procedure was applied for the monitoring of their photolytic and photocatalytic decomposition in aqueous solution. The applied voltammetric procedure was capable of measuring the concentration changes of the parent compound, both in the presence of degradation products and photocatalyst (in case of photocatalysis). In addition, voltammetric determination of neonicotinoids in commercial insecticide formulations was also performed. The results of both spectrophotometric and voltammetric methods were compared with those obtained by HPLC method. Acknowledgement Authors acknowledge financial support of the Secretariat for Science and Technological Development, AP Vojvodina, Republic of Serbia (Grant No. 114-451-02011/2007-02 and Grant No. 114-451-00663/2009-01) and Central European Exchange Program for University Studies (Project No. CII-CZ-0212-02-0910). References 1. Guzsvány V, Papp Zs, Lazić S, Gaál F, Bjelica L, Abramović B, J. Serb. Chem. Soc., 74,

1455 (2009) 2. Papp Zs, Švancara I, Guzsvány V, Vytřas K, Gaál F, Microchim. Acta, 166, 169 (2009) 3. Papp Zs, Guzsvány V, Kubiak Sz, Bobrowski A, Bjelica L, J. Serb. Chem. Soc., (2010),

accepted. 4. Papp Zs, Švancara I, Guzsvány V, Vytřas K, Gaál F, Bjelica L, Abramović B, in: Sensing

in Electroanalysis, Vol. 4., Vytřas K, Švancara I, eds., University of Pardubice, Pardubice, Czech Republic, 47 (2009)



Development of Software to Aid in the Optimization of Elemental Imaging by LA-ICP-MS

Jure Triglav1, Johannes T. van Elteren2*, Vid Šelih2

1 Medical faculty, University of Ljubljana, Vrazov trg 2, SI-1104 Ljubljana 2 Analytical Chemistry Laboratory, National Institute of Chemistry, Hajdrihova 19, SI-1000

Ljubljana Abstract LA-ICP-MS system is a robust sampling technique for elemental analysis of various inorganic and organic materials. The microbeam capabilities of the laser enable us to perform virtually non-destructive microanalysis for spatial resolution purposes (surface mapping and depth profiling) in the low mg kg-1 range for most elements of the periodic table. Using a 213 nm Nd-YAG laser with adjustable laser beam characteristics, coupled to a quadrupole ICP-MS, real-time elemental detection is possible, allowing rastering of a sample for elemental mapping purposes. Elemental mapping is prone to all kind of challenges, which may be related to the critical parameters sensitivity, resolution, noise and analysis time. Optimising the elemental mapping process is usually a matter of trial and error since all parameters are dependent of each other. A theoretical model we developed links these parameters to the LA-ICP-MS input settings (energy density, pulse rate, beam diameter, scanning speed, acquisition time) to get insight into the interactions of these settings with the fundamental analytical parameters. By careful assessment of the model we learnt that post-analysis resolution enhancement is possible using the model in reverse mode or even by using a genetic algorithm that runs through a process of simulated evolution. However, this can only be achieved with the development of dedicated software, enabling us to quickly compare these approaches and study the influence of various LA-ICP-MS settings on the image quality in a simulated rastering procedure. This presentation will focus on the use of computer programming to aid in the optimization of elemental imaging by LA-ICP-MS.

Figure 1. Simplified LA-ICP-MS model showing the transformation of the elemental concentrations in the sample to the ICP-MS response.



Hydrophilic Interaction Liquid Chromatography for the Separation of Phenolic and Amino Acids on Three Silicagel Columns

Jan Soukup, Pavel Jandera*

University of Pardubice, Studentská 95, Pardubice 2, 532 10, Czech Republic Faculty of Chemical Technology, Department of Analytical Chemistry

Abstract Hydrophilic interaction liquid chromatography (HILIC) methods with polar stationary phases and aqueous-organic mobile phases have become popular because of eliminating the disadvantages of both reversed phase (RP) liquid chromatography and normal phase (NP) liquid chromatography [1]. In RP mode, polar compounds elute too quickly whereas in non-aqueous NP adsorption liquid chromatography polar compounds elute too slowly and are often poorly soluble in purely organic mobile phases. In this work we investigated the influence of the HILIC conditions on the separation. We were primarily focused on temperature, concentration of buffer and its pH. The mobile phases contained acetonitrile and 10, 20 mM aqueous ammonium acetate buffer, 95:5, 90:10 (v/v) with pH adjusted to 2.5 – 3.5. Both isocratic and gradient elution were used for separation. Detection was carried out using an UV detector at 220 – 280 nm. 10 µL samples were injected into the chromatograph and the separations were performed at a constant flow rate of 0.5 mL/min and the temperature of column was set up to T = 40 - 80° C. Three columns (XBridge HILIC, Atlantis HILIC and hydrosilated Hydride silica column) have been used for separation of selected phenolic acids [2]. Both XBridge HILIC and Atlantis columns showed very low retention of phenolic acids and hence are not useful for their separation in the HILIC mode. Subsequently stronger retention was discovered on the Hydride silica column [3], where separation of some phenolic acids was achieved either in the isocratic or in the gradient modes, especially these embracing two or more phenolic groups, which are poorly retained in the RP systems. The Hydride silica column was also chosen for separation of amino acids. The attention was focused on the amino acids containing aromatic moieties, which show absorption in the UV region (tryptophan, tyrosine and phenylglycin). Possibilities of their separation at various operative conditions were studied as well as with the phenolic acids. Acknowledgement This work was financially supported by the Ministry of Education, Youth and Sports of Czech Republic under project MSM 0021627502 and by the Grant Agency of Czech Republic under project No. 203 / 07 / 0641. References 1. Alpert AJ, J. Chromatogr., 499, 177 (1990) 2. Pesek JJ, Matyska MT, J. Sep. Sci., 32, 1 (2009) 3. Jandera P, J. Sep. Sci., 31, 1421 (2008)



Lipidomic Analysis of Plant and Animal Tissues Using HPLC/MS

Eva Čáňová, Miroslav Lísa, Michal Holčapek*

University of Pardubice, Faculty of Chemical Technology, Department of Analytical Chemistry, Studentská 573, 53210 Pardubice, Czech Republic

Abstract Lipids are an important part of human diet and they play an essential role in many biochemical processes in the human organism. The disruption of lipid metabolism can lead to serious diseases (i.e., obesity, atherosclerosis, cancer, cardiovascular problems, etc.) and the characterization of lipid composition is necessary to describe their roles. For this purpose, lipidomic analysis using HPLC/MS was optimized. The total lipid extract containing all lipid species was prepared using chloroform/methanol/water extraction according to Folch procedure [1]. The total lipid extract was fractionated into individual lipid classes according to their polarity using the hydrophilic interaction liquid chromatography. The isolated fractions of individual lipid classes were separated using reversed-phase high-performance liquid chromatography with C18 porous shell particles column. Individual lipid species were separated according to the composition of fatty acids, i.e., their acyl chain lengths, number and position of double bonds. Individual lipids were identified using mass spectrometry. Electrospray ionization was used for polar lipids (phospholipids) and atmospheric pressure chemical ionization for non-polar lipids [2,3]. The lipid composition of various plant and animal tissues was characterized using optimized HPLC/MS method. The retention behavior and important fragment ions observed in mass spectra and their use for the identification of lipids was described.

Acknowledgement This work was supported by the grant project No. MSM0021627502 sponsored by the Ministry of Education, Youth and Sports of the Czech Republic and projects Nos. 203/09/P249 sponsored by the Czech Science Foundation. References 1. Folch J, Lees M, Stanley GHS, J. Biological Chem., 226, 497 (1957) 2. Holčapek M, Lísa M, Jandera P, Kabátová N, J. Sep. Sci., 28, 1315 (2005) 3. Lísa M, Holčapek M, J. Chromatogr. A, 1198, 115 (2008).



Matrix Effect on Determination of Some Flavonoids in Real Samples by LC-UV and LC-MS/MS Method

Andrija Ćirić1, Predrag Đurđević1, Helena Prosen2*

1 University of Kragujevac, Faculty of Science, P.O. Box 60, 34000 Kragujevac, Serbia 2 University of Ljubljana, Faculty of Chemistry and Chemical Technology, Aškerčeva 5, SI-

1000 Ljubljana, Slovenia Abstract LC-MS and especially LC-MS/MS methods have been accepted as the best tool to analyze a wide variety of samples due to their speed, sensitivity and selectivity. However, ionization suppression or enhancement in the interface due to visible and “invisible” matrix interferences is becoming a well-recognized problem [1, 2]. Matrix effects, mainly suppression of the ionization, have been noticed in our work on LC-MS/MS analysis of some naturally occurring compounds (morin, hesperetin, rutin and hespetidin) in various matrices. In the research we study their behaviour in MS source, influence of ionization conditions, solvent, carrying gas and excitation conditions on their fragmentation and co-extracted matrix from different samples. We explore these matrix effects for the extraction of some of the above compounds from food and plant samples. An HPLC method for determining flavonoids, morin, hesperetin, hesperidin and rutin, is presented with application to the real samples. The mobile phase was acetonitrile–2% acetic acid solution in gradient mode, using a Gemini column (150×4.6 mm, 3 µm particle size) for the quantitative analysis. The flow-rate was 0.7 mL/min and the detection wavelength was set at 280 nm. Calibration of the overall analytical procedure gave a linear signal (R2 = 0.9994 for rutin, 0.9984 for hesperidin, 0.9992 for hesperetin and 0.9997 for morin) over a concentration range of 0.5–20 mg/L of flavonoids in methanol. The full scan mass spectra from m/z 100–650 were acquired both in positive and negative ion modes. The optimum conditions of the interface were as follows: ESI-negative; ion spray voltage of -4500 V, the interface temperature was set at 500oC. The declustering and entrance potential were between -80 to -40 and -8 to -4. Calibration of the SRM method for rutin (m/z; 609/300, 609/271, 609/255, 609/150) gave a linear signal (R2 = 0.9987) over a concentration range of 0.01–20 mg/L of flavonoid in methanol. Ion suppression was studied for rutin in plant extract and found at lower concentration (below 1 mg/L) and its values were from 10 – 90%. Acknowledgement ERASMUS MUNDUS EXTERNAL COOPERATION WINDOW PROJECT BASILEUS References 1. Kralj Cigić, I, Prosen, H, Int. J. Mol. Sci., 10, 62 (2009) 2. Van Eeckhaut A, Lanckmans K, Sarre S, Smolders I, Michotte Y, J. Chroma. B, 877,

2198 (2009)



Separation of Polar Compounds by HILIC

Veronika Škeříková, Pavel Jandera* Department of Analytical Chemistry, Faculty of Chemical-Technology, University of

Pardubice, Stavařov 573, 532 10 – Pardubice Czech Republic, Abstract Columns containing zwitterionic sulfobetaine groups have been earlier applied for the separation of polar compounds by Hydrophilic Interaction LIquid Chromatography (HILIC) [1,2]. This work investigates separation of phenolic and flavone compounds as well as of amino acids and drugs on a zwitterionic organic polymer capillary column designed for HILIC. The monolithic column was prepared by “in-situ” radical polymerization in a fused-silica capillary (id = 320 µm). The polymerization mixture consist of 20% [2-(methacryloyloxy)ethyl]-dimethyl-(3-sulfopropyl)-ammonium hydroxide (monomer), 15% ethylene dimethacrylate (cross-linker), 25% 1-propanol, 25% 1,4-butanediol and 15% water. 2,2´-azo-bis-isobutyronitrile was used as the initiator of the polymerization reaction which performed at 60°C for 20 hours [3,4]. The polymethacrylate monolithic zwitterionic capillary column was used for separation of phenolic and flavone compounds, amino acids and drugs as the alternative to conventional ZIC-HILIC column [1]. The separation of these compounds depends on the pH of the mobile phase. Weakly acidic buffers as the mobile phases are generally required for separation of phenolic and flavone compounds and amino acids, whereas weakly basic or basic buffers as these mobile phases are required for separation of drugs. Due to differences in the dissociation constants of the individual compounds, even small changes in the mobile phase pH may cause significant differences in resolution. All experiments were carried out at temperature from 25 – 30°C; the flow rate was set in the range 3–30 µl min-1, according to the actual composition of the mobile phase. The capillary column was connected to UV-detector. Aqueous ammonium acetate or potassium hydrogen phosphate or dihydrogen phosphate, mixed with acetonitrile as organic modifier, were used as mobile phases. Isocratic conditions and gradient conditions were optimized to separate the maximum number of compounds in the shortest separation time. The monolithic column shows dual HILIC-RP mechanism, therefore isocratic and gradient separations were optimized also in RP-mode. Acknowledgement This work was supported by the Ministry of Education, Youth and Sports of the Czech Republic under the project MSM 0021627502 and by the Grant Agency of Czech Republic under the project No. 203/07/0641. References 1. Hemström P, Irgum K, J. Sep. Sci., 29, 1784 (2006) 2. Jiang Z, Smith NW, Ferguson PD, Tailor MR, Anal. Chem., 79, 1243 (2007) 3. Jandera P, Urban J, Škeříková V, Kubíčková R, Pospíšilová M, J. Sep. Sci., 32, 2530

(2009) 4. Jandera P, Urban J, Škeříková V, Langmaier P, Kubíčková R, Planeta J, J. Chromatgr.

A, 1273, 22 (2010)

YISAC 2010 – Session II: Electroanalysis


Session II

Electroanalysis



A Study on Selected Parameters for the Advanced Use of Antimony Film Electrode in Anodic Stripping Voltammetry

Bine Šebez, Božidar Ogorevc*, Samo Hočevar

Analytical Chemistry Laboratory, National Institute of Chemistry, Ljubljana, Slovenia

Abstract Anodic stripping voltammetry (ASV) is a powerful electroanalytical technique for trace metal measurements. A proper choice of the working electrode is a crucial factor for the good analytical performance. Recently there has been a major progress in development of new metal film electrodes that are nowadays already widely applied in electroanalysis. For example, a very recently introduced antimony film electrode (SbFE) revealed some attractive characteristics for use in electrochemical stripping analysis [1, 2]. In particular, favourable performance in more acidic solutions and wider useful potential window are some advantages of SbFE in comparison to the already established bismuth film electrode (BiFE). While basic studies for use of BiFE in ASV have been already published [3], similar studies for the optimal use of SbFE are still missing.

In this contribution, a preliminary study of several key experimental parameters on the performance of SbFE is presented. Effects of different substrate electrode materials and solution compositions (pH, ionic strength, anionic components) on analytical performance of test metal ions were thoroughly examined. The measurements were performed also in the presence of different surfactants and their effect on electroanalytical signals was investigated. The influence of the studied parameters on the performance of SbFE in ASV is discussed.

References 1. Hocevar SB, Svancara I, Ogorevc B, Vytras K, Anal. Chem., 79, 8639 (2007) 2. Jovanovski V, Hocevar SB, Ogorevc B, Electroanal., 21, 2321 (2009) 3. Hocevar SB, Ogorevc B, Wang J, Pihlar B, Electroanal.,14, 1707 (2002)



Characterization of Water-Soluble Fullerene Compounds by Electrochemical and Spectroscopic Techniques

J. Bulíčková1,3, M. Gál1, M. Hromadová1, L. Kavan1, L. Pospíšil1,2*, R. Sokolová1

1 J. Heyrovský Institute of Physical Chemistry, v.v.i., Prague, Czech Republic 2 Institute of Organic Chemistry and Biochemistry, v.v.i, Prague, Czech Republic

3 University of Pardubice, Faculty of Chemical Technology, Pardubice, Czech Republic Abstract Application of water-soluble fullerenes has been demonstrated recently in the fields of material sciences, catalysis and medicine. We have shown that water-soluble cyclodextrin-C60 complex is capable of the electrochemical conversion of N2 to ammonium ions in water [1]. Methanofullerene conjugates covalently-attached to cyclodextrins were scrutinized for a possible intramolecular complexation in aqueous environment [2]. This work is focused on the electrochemical and spectroscopic characterization of pristine C60 in water. Different approaches for preparation of aqueous solutions of C60 have been reported recently [3,4]. An ultrasonic treatment of a two-phase mixture of water and toluene containing C60 resulting in a brownish-yellow colloidal dispersion of C60 was used in the present study. Formal redox potentials of fullerene, fullerene-cyclodextrin complex and methanofullerene conjugates with cyclodextrins in aqueous solution were determined. The first part of the study was focused on the evaluation of the association constants of the complexes and/or conjugates from the shifts of the formal redox potentials of these compounds compared to uncomplexed C60. In this way an internal complexation can be investigated as well. The most suitable techniques for electrochemical characterization of fullerene derivatives proved to be the low-frequency phase-sensitive AC polarography and the steady-state voltammetry. The state of C60 in aqueous solution was characterized by UV-VIS, Raman and FTIR spectroscopies and AFM technique. Spectroscopic data confirm the presence of pristine C60 in aqueous samples. The sample forms a stable colloidal dispersion, whereas the voltammetry with 10 µm Pt ultramicroelectrode gave the formal redox potential of C60 -0.56 V against the Fc/Fc+ couple. The correlation of the redox potential of C60 with the donor number of a series of solvents is presented. Acknowledgement This work was supported by the Grant Agency of the Czech Republic (203/09/0705, 203/08/1157, 203/09/P502 and 203/09/1607) and the Ministry of Education (LC510 and COST OC140). References 1. Pospíšil L, Bulíčková J, Hromadová M, Gál M, Civiš S, Cihelka J, Tarábek J,

Chem.Commun., 2270 (2007) 2. Pospíšil L, Hromadová M, Gál M, Bulíčková J, Sokolová R, Filippone S, Yang J, Guan Z,

Rassat A, Zhang Y, Carbon, 48, 153 (2010) 3. Andrievsky GV, Kosevich MV, Vovk OM, Shelkovsky VS, Vashchenko LA, J. Chem. Soc.,

Chem.Commun., 1281 (1995) 4. Scharff P, Risch K, Carta-Abelmann L, Dmytruk IM, Bilyi MM, Golub OA, Khavryuchenko

AV, Buzaneva EV, Aksenov VL, Avdeev MV, Prylutskyy YuI, Durov SS, Carbon, 42, 1203 (2004)



Voltammetric Studies of the Co(II)-tris(hydroxymethyl)- aminomethane and Sodium Perborate Volumetric

Catalytic System

M. Putek, J. Zarębski, A. Królicka, A.Bobrowski Department of Building Materials Technology, Faculty of Materials Science and Ceramics, AGH – University of Science and Technology, Al. Mickiewicza 30, 30-059 Kraków, Poland

Abstract The results of voltammetric studies of a new volumetric catalytic system, in which the complex of Co(II) ions with tris(hydroxymethyl)-aminomethane (THAM) catalyzes oxidation of THAM by sodium perborate, have been shown. The reaction occurs at boiling temperature, and the product of the catalytic THAM oxidation, tris(hydroxymethyl)-nitrosomethane, gives a well-defined quasireversible cathodic wave preceding that of the Co(II) ions by about 160 mV. The voltammetric responses of this product are proportional to the amount of sodium perborate and to the concentration of Co(II) ions. The value and the shape of the observed catalytic signal also depend on the pH of the supporting electrolyte and the pH of the solution in which voltammetric measurements are carried out. In the volumetric catalytic system of Co(II) ions/THAM/sodium perborate, the sensitivity of the determination of Co(II) increases by one to two orders of magnitude, depending on the voltammetric technique used. Prior to the detection of tris(hydroxymethyl)nitrosomethane, EDTA was added to the solution to form voltammetrically inactive complexes with Co(II) and other interfering ions. Therefore, this method may be applied for the determination of Co(II) ions at low concentrations in the presence of a large excess of interfering ions, in particular Ni(II) and Zn(II).

Figure 1. DP polarograms: (1) 5 × 10–6 M Co(II) in the supporting electrolyte 0.1 M THAM, 2 × 10–3 M sodium perborate, 5 × 10–3 M Na2SO3; (2) the same solution as (1) and 2 × 10–3 M EDTA; (3) 5 × 10–6 M Ni(II) and Co(II) in the supporting electrolyte 0.1 M THAM; (4) the same solution as (3) and 2 × 10–3 M EDTA; (5) pure supporting electrolyte 0.1 M THAM, 2 × 10–3 M EDTA, 5 × 10–3 M Na2SO3. Solutions (1), (2): 10 min boiling. Acknowledgement Financial support from the Polish Ministry of Science and Higher Education (Project No. N50706332/1767) is gratefully acknowledged.



Electrochemical Synthesis of Polyaniline Films at a Screen-Printed Carbon Electrode and Their Potential Applicability in Biosensing

Matěj Stočes, Ivan Švancara, Karel Vytřas

Department of Analytical Chemistry, University of Pardubice, CZ-532 10, Pardubice, Czech Republic

Abstract Organic conducting polymers have attracted interest in recent years because they exhibit interesting electrochemical properties. One of the most studied substances is polyaniline (PANI) due to its unique properties and potential in commercial applications. Immobilization of enzymes in conducting polymers is a promising way for the development and fabrication of a new type of (bio)sensor. Conductive polymer polyaniline was electrochemically synthesized at a screen-printed carbon paste electrode (SPE) from different acid (HCl, H2SO4) aqueous solutions containing 0.25 M aniline monomer. The characterization of the SPE with PANI film was carried out by cyclic voltammetry in 1 M HCl exhibiting two distinct redox peaks that prove the electroactivity of PANI film. Glucose oxidase (GOD) was electrostatically immobilized onto the surface of CPE/PANI from 0.1 M phosphate buffer containing 0.75 mg/ml GOD. Optimal conditions of GOD immobilization were investigated (applied potential, time of deposition). The biosensors prepared in this way was tested for sensing glucose and experimental conditions were optimized. Preliminary tests and characterization of CPE / PANI / GOD electrode showed to be promising for the development of a new type of biosensors.

Figure 1. Electrochemical synthesis of PANI. Experimental conditions: 0.2M aniline monomer in 1M HCl. Cyclic voltammetry Elow = -400 mV; Ehigh = +1200 mV; Estart = +1200 mV; scan rate = 100 mV·s-1; 10 cycles.

Acknowledgement Financial support from the Ministry of Education, Youth, and Sports of the Czech Republic (No. MSM0021627502 and Project No. LC 06035) is gratefully acknowledged.



Electrochemical Probing of Estradiol Antioxidant Capacity

Ivana Haramustek, Sanja Martinez Department of Electrochemistry, Faculty of Chemical Engineering and Technology, Savska

cesta 16, 10000 Zagreb, Croatia Abstract Electrochemistry is a useful technique for studying redox reactions, and the literature is replete with electrochemical methods applied to biology. In particular, cyclic voltammetry (CV) has been conveniently used and validated for the quantification of in vitro low molecular weight antioxidant (LMWA) capacity of biological fluids, tissue homogenates, various foods and beverages and of LMWA capacity in vivo [1 and references within]. CV provides biological oxidation potential which relates to the nature of the molecules and peak currents and areas of the anodic current waves that relate to the concentration of the antioxidant molecules. A few papers describe the application of CV to measure estradiol (E2) concentration and antioxidant properties [2-5]. Antioxidant capacity of E2 in plasma and different tissues is of particular interest due to the role of its natural loss in the etiology of many diseases [6] that are believed to be caused and/or aggravated by oxidative stress. In the present study, we investigate new experimental strategies for measuring the antioxidant capacity of E2 by cyclic voltammetry at electrodes of various sizes, made of various materials. Measurements were done in phosphate buffer saline solutions of E2, in the range of physiological concentrations and in blood plasma. The fabricated electrodes were shown to be active for both, the surface adsorption of E2 and its electrocatalytic oxidation, and can be used for determination of estrogens in real samples. The investigation was also aimed towards downsizing of the electrodes to micrometric [7] and nanometric [8] dimensions that would enable antioxidant probing of individual cells and of the local cell environment, respectively. References 1. Kohen R, Nyska A, Toxicol. Pathol., 30, 620 (2002) 2. Hea Q, Yuana S, Chena C, Hua S, Mater. Sci. Eng. C, 23, 621 (2003) 3. Ngundi MM, Sadik OA, Yamaguchi T, Suye S, Electrochem. Commun., 5, 61 (2003) 4. Xiangqin L, Yongxin L, Biosens. Bioelectron., 22, 253 (2006) 5. Jin G-P, Lin X-Q, Electrochim. Acta, 50, 3556 (2005) 6. Unfer TC, Conterato GMM, da Silva JCN, Duarte MMMF, Emanuelli T, Clin. Chim. Acta,

369, 73 (2006) 7. Amatore C, Arbault S, Melo DC, Tapsoba I, Verchier Y, J. Electroanal. Chem., 34, 615

(2008) 8. Sun P, Laforge FO, Abeyweera TP, Rotenberg SA, Carpino J, Mirkin MV, PNAS 105,

443 (2008)



Recent Developments of Antimony- and Bismuth-Based Electrodes

Hanna Sopha, Samo B. Hočevar*, Božidar Ogorevc

Analytical Chemistry Laboratory, National Institute of Chemistry, Hajdrihova 19, SI-1000 Ljubljana, Slovenia

Abstract Stripping voltammetry and chronopotentiometric stripping analysis are well-known as powerful techniques for trace measurements of heavy metal ions and some selected organic compounds in combination with most commonly used mercury-based working electrodes. However, due to their well-known toxicity, there were many attempts to replace mercury with some other non-toxic or less toxic electrode materials. In 2000, the bismuth film electrode (BiFE) was introduced as an efficient replacement for its mercury counterpart and it is now used in many electroanalytical laboratories worldwide [1]. Hitherto, numerous types/configurations of bismuth-based electrodes have been suggested, e.g. bismuth films prepared in-situ or ex-situ on glassy carbon, carbon paste, carbon fiber, screen printed carbon and boron doped diamond substrates, bismuth oxide and bismuth powder bulk modified carbon paste electrodes, bismuth bulk electrode etc., and have been employed in various electroanalytical applications. Current pioneering research on the recently emerged antimony film electrode, SbFE [2, 3], in electrochemical stripping analysis reveals that it is a valuable replacement for mercury and in certain cases even for bismuth electrodes. In this work, the applicability of antimony film electrodes has been expanded towards some other potentially interesting analytes in combination with potentiometric stripping analysis and adsorptive cathodic stripping voltammetry. The electroanalytical performance of the antimony film electrode was compared with its bismuth and mercury analogues. Moreover, a new type of bismuth electrode, the ammonium tetrafluorobismuthate bulk modified carbon paste electrode, is presented for measuring trace levels of cadmium(II) and lead(II). This electrode represents the first application of ionic liquids as a reservoir for the preparation of bismuth films and reveals a favorable electroanalytical performance in more acidic media (pH 1). Acknowledgement Financial support from the Slovenian Research Agency (P1-0034, and BI-CZ/09-10-004) is gratefully acknowledged. References 1. Wang J, Lu J, Hocevar SB, Farias PAM, Ogorevc B, Anal. Chem., 72, 3218 (2000) 2. Hocevar SB, Svancara I, Ogorevc B, Vytras K, Anal. Chem., 79, 8639 (2007) 3. Sopha H, Baldrianova L, Tesarova E, Hocevar SB, Svancara I, Ogorevc B, Vytras K,

Electrochim. Acta, (2010), doi:10.1016/j.electacta.2009.12.089

YISAC 2010 – Session III: Electroanalysis + Environment


Session III

Electroanalysis + Environment



Ionophore-Gold Nanoparticle Conjugate as a Receptor in the Ion Selective Electrodes

Gyula Jágerszki1*, Alajos Grün2, István Bitter2 Klára Tóth3, Róbert E. Gyurcsányi1,3

1 Department of Inorganic and Analytical Chemistry, Budapest University of Technology and Economics, Szt. Gellért tér 4, Budapest, 1111 Hungary

2 Department of Organic Chemistry and Technology, Budapest University of Technology and Economics, Budafoki út 8, 1111 Budapest, Hungary

3 Research Group for Technical Analytical Chemistry of the Hungarian Academy of Sciences,Szt. Gellért tér 4, Budapest, H-1111 (Hungary)

Abstract In our presentation we will show the synthesis and analytical application of ionophore-gold nanoparticle conjugates (IP-AuNP) based on the spontaneous self-assembly of Ag+-selective thiacalixarene [1] derivatives bearing dithiolane moieties onto the surface of gold nanoparticles. Using the IP-AuNP conjugates as a reduced mobility ionophore [2] we could make a ion selective electrode with low detection limit [3].

0 20 40 60 80 100 120

0

60

120

180

240

300

360

420

cAg+

=10-8 M

E, m

V

t, min.

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cAg+

=10-3 M

-9 -8 -7 -6 -5 -4 -3 -2

-100

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V

log(cAg+

)

IP-AuNPs IP

B

Figure 1. Potentiometric ion trace (figure A) and the calibration curve (figure B) of the IP-AuNP based Ag+-ion selective electrode (sign: IP-AuNPs) compared with an ISE contained free ionophore (sign: IP).

References 1. Szigeti Z, Malon A, Vigassy T, et al.,Anal. Chim. Acta, 572, 1 (2006) 2. Ceresa A, Sokalski T, Pretsch E, J. of Electroanal. Chem., 501, 70 (2001) 3. Jagerszki G, Grun A, Bitter I, et al., Chem. Commun., 46, 607 (2010)



Development of Conductometric Sensors for Organic Vapours Based on PEDOT-PSS Semiconductive Thin Films

Miroslav Marecic1, Matthew David Steinberg2, Ivana Murkovic Steinberg3*, Zorana

Grabaric1*

1 Faculty of Food Technology and Biotechnology, University of Zagreb, Pierottijeva 6, HR-10000 Zagreb, Croatia

2 Erasmus Technology LLP, 57A Moorfield Road, Duxford, Cambridge, CB22 4PP, UK 3 Faculty of Chemical Engineering and Technology, University of Zagreb, Marulicev trg 19,

HR-10000 Zagreb, Croatia Abstract The development of conductometric sensors for organic vapours based on organic semiconductive thin polymer films is presented. This work is part of a research project aimed to implement wireless data transmission from sensors to a PC using an ISO standard Radio Frequency IDentification, or RFID, protocol. Ethanol and Poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate), or PEDOT-PSS, were used in a model system as the organic vapour and as the conductive thin polymer film, respectively. PEDOT-PSS films spin-coated on planar substrates of gold electrodes were used as conductometric sensors. Several parameters were varied in order to investigate their influence on sensor calibration curves and dynamic response to ethanol vapour. Effects of the electrode geometry and the film thickness were studied using four different types of gold electrode structures. In order to determine the contribution of contact resistance in overall sensor response, 4-point resistance measurements were performed using the custom RFID card which includes a conductometric sensor interface and appropriate electronics for wireless data transmission. From the results obtained it can be observed that thicker films (3 layers of spin-coated PEDOT-PSS) show longer response time and about 10% smaller fraction of contact resistance in total resistance. Also, it was found that the contact resistance is critically dependent on electrode geometry. Acknowledgement The research presented here is supported by Erasmus Technology LLP, UK, the National Foundation for Science, Higher Education and Technological Development of the Republic of Croatia (NZZ), and the Ministry of science, education and sport of the Republic of Croatia (grant number: 125-0000000-3221, 058-0580000-3071).



Electrical Conductivity and Solvation Process Examination in Molten Salts

Sanja Dožić, Slobodan Gadžurić*, Milan Vraneš, Borko Matijević

Faculty of Sciences, Department of Chemistry, Biochemistry and Environmental Protection, Trg D. Obradovica 3, 21000 Novi Sad, Serbia

Abstract Calcium nitrate tetrahydrate and its mixtures with some other inorganic salts and organic compounds have high latent heat of fusion, low melting point and have been considered as phase change materials (PCM) for thermal energy storage [1]. The effect of increased absorbance with increased temperature and the high latent heat of fusion of the PCM are proposed for simultaneous control of temperature and insolation in solar heat storage systems, protecting the solar heated greenhouses from overheating [2]. In this paper, our research was focused in the transport and thermal properties of the calcium nitrate – ammonium nitrate – water and ammonium nitrate – dimethyl sulfoxide mixtures. Thus, additional data on mixed low temperature inorganic salts and inorganic – organic solvents, which are proposed as a suitable phase change materials, were provided. Electrical conductivity of liquid xCa(NO3)2·zH2O – (1–x)NH4NO3 and NH4NO3·xDMSO mixtures was measured as a function of temperature over the whole composition range. The specific conductivity data of liquid mixtures were fitted by the polynomial equation κ = A+BT+CT2. A new assessment and experimental confirmation of quasi crystal theory of molten salts was made using conductivity measurements as a suitable tool to show the difference between aqueous solutions and aqueous molten salt systems. Also, the influence of the electrolyte and water concentration on transport properties of the mixture was investigated.

Acknowledgement Authors acknowledge financial support of the Secretariat for Science and Technological Development, AP Vojvodina, Republic of Serbia (Grant No.114-451-00758/2009-05), Central European Exchange Programme forUniversity Studies (Project No. CII-CZ-0212-02-0910) and Ministry of Science and Environmental Protection of Republic of Serbia contract no. 14204B. References 1. Gadzuric S, Zsigrai I, Nikolic R, Z. Naturforsch., 56a, 832 (2001) 2. Marinkovic M, Nikolic R, Savovic J, Gadzuric S, Zsigrai I, Sol. Energy Mater. Sol. Cells,

51, 401 (1998)



Analysis of Airborne Particulate Matter with the Combined Use of Particle Induced X-Ray Emission, Ion Chromatography and

Scanning Electron Microscopy

Mauro Masiol1, Giancarlo Rampazzo1, Daniele Ceccato2, Bruno Pavoni1* 1 Dip. Scienze Ambientali, Università Ca’ Foscari Venezia

2 Dip. Fisica “Galileo Galilei”, Università di Padova Abstract The increasing atmospheric pollution is one of the most worrying problems in the world. Adverse health effects are associated to the air concentration of particulate matter with aerodynamic diameter less than 10 µm (PM10). The PM10 mass per m3 of air is one of the most important parameters used to estimate the air quality in Europe, since the European Directive 1999/30/EC became effective. This study presents the results of individual particle analyses performed on PM10 samples with different source contributions. The main objective is to characterize the chemical and mineralogical composition of the particulate matter in a coastal site near Venice, Italy. An extended PM10 sampling campaign was performed and concentrations of fifteen elements (Na, Mg, Al, Si, Cl, K, Ca, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn) and six inorganic ions (Cl−, NO3

−, SO42-, Na+, Mg2+, NH4

+) were determined using Particle Induced X-ray Emission (PIXE) and ion chromatography of water-soluble fractions, respectively. A varimax rotated factor analysis followed by a multi-linear regression analysis were performed on chemical data and five PM10 sources were identified and quantified: mineral dust, sea-salt, fossil fuel combustion, mixed anthropogenic pollution and secondary inorganic aerosol. A number of samples with very different source contributions to the daily levels of PM10 were also selected and an individual particle analysis by Scanning Electron Microscopy combined with Energy-Dispersive X-ray Spectrometry (SEM-EDS) was performed. Six different classes of particles were identified (mineral particles, chlorides, sulfates, elemental and organic carbon compounds, metals and biological particles) and an estimation of their abundance was made. Results show a relationship between source apportionment contributions and individual particle composition. This allows to extract further information on PM10 composition, source contributions, morphology, mineralogy and mixed state of particles and demonstrates the effectiveness of coupling the two approaches. Acknowledgement The authors gratefully acknowledge the support provided by Prof. P. Mittner (FISAMB-PD) and Laboratori Nazionali Legnaro – Istituto Nazionale di Fisica Nucleare (LNL-INFN) for PIXE and electron microscopy facilities, Dr. E. Ghedini, Prof. F. Pinna and Dr. M. Signoretto (Università Ca’ Foscari Venezia) for ion chromatography. The authors are also grateful to Comando Zona Fari e Segnalamenti Marittimi di Venezia for logistics.



Determination of Oxygen in Biogas and Interference Study of Various Gases Using Ruthenium Complex Optical Sensor

Polona Brglez1, Andrej Holobar1, Aleksandra Pivec2, Mitja Kolar3*

1 ECHO d.o.o., Stari trg 37, SI-3210 Slovenske Konjice, Slovenia 2 ZRS Bistra Ptuj, Slovenski trg 6, SI-2250 Ptuj, Slovenia

3 University of Maribor, Faculty of Chemistry and Chemical Engineering, Smetanova 17, SI-2000 Maribor, Slovenia

Abstract Biogas is a mixture of gases produced by the anaerobic fermentation. Biomass and animal waste decomposed by organisms such as bacteria mainly release methane (CH4) in the concentration range from 50% to 70% and carbon dioxide (CO2) in the concentration range from 30% to 40%. Biogas contains also hydrogen sulphide (H2S) in concentration around 2%, ammonia (NH3) and nitrogen (N2) in concentration less then 2% and hydrogen (H2) in concentration around 1% [1]. The biogas has also very high moisture content (about 80%), temperature up to 60° C and high pressure, and can contain corrosive gases (H2S and siloxanes). We searched for appropriate measuring system for determination of oxygen in biogas since the production process of biogas must run under anaerobic conditions; the presence of oxygen decrease the quality of biogas. For measuring various oxygen concentrations in the biogas, we have developed optical oxygen sensor based on fluorescence of ruthenium complex [2]. This optical oxygen sensor is suitable for various applications, such as for the in-situ determination of oxygen in the biogas. Ruthenium complex is widely used in this context due to its favourable properties: efficient quenching by molecular oxygen (O2), relatively long fluorescence lifetime, that is determined by the metal-to-ligand charge-transfer (MLCT) excited state, fast response time, strong visible absorption, delay times of few microseconds, absorption bands in the blue spectral range, high Stokes-shift and comparatively high photostability [1, 2]. In the present work we studied the effects of various gases on home made optical sensor based on ruthenium complex. We used different concentrations and studied the interference of gases CO, CO2, H2, H2S, NO, NO2 and SO2. The gas mixtures were prepared using a home made gas chamber-device, which was built up from several mass flow controllers connected and controlled by a special software. We found out that only NO2 interfere (in concentration above 500 ppm) when measuring oxygen with the described optical sensor; however this interfering gas is not present in the biogas. Therefore future work will be focused on optimisation of some optical sensor properties for final in-situ measurements of oxygen in biogas. Acknowledgement The authors would like to thank Slovenian Technology Agency (TIA) for financially supporting this work.

References 1. Kolenc P, Holobar A, Pivec A, Kolar M; The possibility of using fluorescence sensor for

the determination of in-situ oxygen concentration in biogas; Lecture presented at Slovenian Chemical Days; Maribor; September 2009

2. Zhang H, Li B, Lei B, Li W, Lu S; Sensor. Actuator. B, 123, 508 (2007)



A Novel Method for Determination of Higher Carboxylic Acids in Atmospheric Aerosols Using Hydrophilic Interaction Liquid

Chromatography Tandem Mass Spectrometry

Zoran Kitanovski, Irena Grgić* Laboratory for Analytical Chemistry, National Institute of Chemistry, Hajdrihova 19, SI-1001,

Ljubljana, Slovenia Abstract Hydrophilic Interaction LIquid Chromatography (HILIC) was shown to be a suitable chromatographic technique for retention and thus analysis of polar ionized compounds using polar organic/aqueous mobile phases. Polar compounds usually have no retention under reversed-phase (RP) conditions or sometimes can be only retained using 100% aqueous mobile phases. Moreover, electro-spray ionization (ESI) process is highly enhanced using mobile phases containing high organic-to-water ratios, such as those commonly used in HILIC [1]. Carboxylic acids represent an important fraction of atmospheric organic aerosols [2]. Studying their chemistry is essential for understanding the physico-chemical properties of atmospheric aerosols and their role in atmospheric processes. For development of the HILIC-(-)ESI-MS/MS method an HPLC system (Agilent 1100) equipped with an XBridge Amide BEH column (Waters) and coupled with a linear ion trap (4000 QTRAP, Applied Biosystems/MDS Sciex) was used. Fifteen model compounds were therefore used: benzoic, glycolic, pyruvic, malonic, succinic, glutaric, adipic, pimelic, suberic, azelaic, maleic, fumaric, cis-pinonic, o-phthalic and trimesic acid. Aerosol samples (PM2,5 and PM10) were collected on quartz fiber filters in two of the largest cities in Slovenia, Ljubljana and Maribor. The deposits on the filters were extracted in Milli-Q water, lyophilized to dryness and dissolved in pure acetonitrile prior to HILIC-(-)ESI-MS/MS analysis. The retention behaviour of the model acids was studied under different chromatographic conditions. The influence of the buffer type, its pH and ionic strength were thoroughly studied along with gradient vs. isocratic elution. The best separation in the sense of good resolution and reasonable chromatographic analysis time was achieved using gradient elution with a mobile phase composed of 90/10 (v/v) acetonitrile/water mixture containing 10mM ammonium acetate (pH = 5) and 10 mM aqueous ammonium acetate (pH = 5). Using a Multiple Reaction Monitoring (MRM) and Neutral Loss (NL44, loss of CO2) scanning MS/MS, several carboxylic acids were identified in the urban PM2,5 and PM10 aerosols. Among them the most intense peaks were found for succinic, o-phthalic, maleic, azelaic and glutaric acid. Other detected carboxylic acids were pimelic, adipic, suberic and cis-pinonic acid. Acknowledgement This work was supported by the Slovenian Research Agency (Contract no. P1-0034-0104). The PM samples were provided by the Environmental Agency of the Republic of Slovenia. References 1. Nguyen HP, Schug KA, J. Sep. Sci., 31, 1465 (2008) 2. Sempéré R, Kawamura K, Global Biogeochem. Cy., 17, 1069 (2003)

YISAC 2010 – Session IV: Environment


Session IV

Environment



Photoreaction of BP-3 and BP-4 by Aqueous Chlorine - Products and Toxicity Studies

Rensheng Zhuang1,2, Jun Yao2, Polonca Trebše1*

1 Laboratory for Environmental Research, University of Nova Gorica, Nova Gorica, Slovenia 2 Key Laboratory of Biogeology and Environmental Geology Laboratory of Chinese Ministry

of Education, China University of Geosciences, Wuhan 430074, PR China Abstract Organic ultraviolet (UV) filters are widely used in sunscreens, lipsticks, shampoos, and other personal-care products, which may cause them easily to enter the aquatic environment (e.g., the swimming pool), where a really thorough protection is needed. Although UV filters must be stable under exposure to UV radiation, recent studies showed that several organic UV filters undergo degradation, mainly by photolysis, but also as a consequence of reaction with chlorine in chlorinated media (e.g., the sea or the swimming pool), because the energy absorbed cannot be internally converted quickly enough, and the molecule remains excited long enough to react chemically [1]. In the present study, benzophenone-3 (BP-3) and benzophenone-4 (BP-4) were applied as model compounds for the stability study of selected UV filters under different experimental conditions, such as pH and presence of sunlight. To simulate the natural sunlight, the set of 6 polychromatic low pressure mercury lamps (355 nm) in special quartz cell were used. We monitored the infuence of different chlorine compounds, such as NaOCl, trichloro isocyanuric acid, in the stability of BP-3 or BP-4 in the presence of sunlight. HPLC analysis was used for the monitoring of disappearance of parent compounds and appearance of products formed during irradiation. The results showed that BP-3 is highly stable within a broad range of pH (4.0−9.0), but may react with NaOCl and trichloro isocyanuric acid. In both cases two degradation products at retention times at 6.992 min and 8.055 min were observed. The mechanism of degradation is still under investigation. The experiments were evaluated in terms of toxicity applying Vibrio fischeri luminescent bacteria test. Acknowledgement This work was supported by the CMEPIUS Grant - Bilateral scolarships, provided by The Government of the Republic of Slovenia. References 1. Díaz-Cruz et al., Trend. Anal. Chem., 27, 873 (2008)



Determination of Amino Acids in the Urban Aerosol in the Venice Lagoon.

Elena Barbaro1 , Roberta Zangrando2, Silvia De Pieri1, Andrea Gambaro1,2, Carlo

Barbante1,2, Paolo Cescon1,2 1 Department of Environmental Sciences, University of Venice, Ca’ Foscari, Calle Larga

Santa Marta, 2137, 30123 Venice, Italy 2 Institute for the Dynamics of Environmental Processes CNR, Dorsoduro 2137, 30123,

Venice, Italy.

Abstract Organic nitrogen typically represents 20–80% of the total nitrogen in deposition, atmospheric drops, and airborne particles [1]. These results suggest that organic nitrogen compounds in the atmosphere might contribute to the nutrient budgets of ecosystems, due to the bioavailability of these compounds in deposition, their potential roles in ecological processes and their influence in atmospheric chemistry and air quality. Amino compounds could affect the atmospheric water cycle, the atmospheric radiation balance, and the scavenging of air pollutants. In addition, several amino acids, such as methionine, are rapidly transformed in water drops and particles during exposure to ozone and sunlight . Although detailed information on the chemical forms of organic N is required to understand its effects, currently very little is known about the composition and chemistry of this group of compounds in the atmosphere. The aim of this study is to determine amino acids (alanine (Ala), aspartic acid (Asp), glycine (Gly), glutammic acid (Glu), isoleucine (Ile), leucine (Leu), methionine (Met), phenylalanine (Phe), proline (Pro), serine (Ser), threonine (Thr), tyrosine (Tyr), valine (Val), asparagine (Asn), glutamine (Gln), trans-4-hydroxy-proline (4-Hyp), methionine solfoxide, methionine solfone) in TSP (Total Suspended Particulate) in the urban aerosol of the Venice Lagoon in order to better understand their chemistry and origin. The aerosol samples analysis was performed by using HPLC/ ESI-MS/MS. An Agilent 1100 series HPLC system (Agilent, Waldbronn, Germany) coupled to an API 4000 triple quadrupole mass spectrometer (Applied Biosystems/MDS SCIEX, Toronto, Ontario, Canada). In this work the internal standard method has been used and the analytical procedure was validated by evaluating the accuracy, precision and recovery. The particulate matter was collected using quartz fiber filters and extracted in methanol, after filtration the extract was directly analyzed. 39 samples were collected from April to October 2007, the average concentrations of amino acids in the aerosol of the Venice Lagoon were: alanine (Ala) 75.3 ng/m3, aspartic acid (Asp) 80.0 ng/m3, glycine (Gly) 493.1 ng/m3, glutammic acid (Glu) 203.0 ng/m3, isoleucine (Ile) 1.1 ng/m3, leucine (Leu) 1.4 ng/m3, methionine (Met) n.d., phenylalanine (Phe) 2.6 ng/m3, proline (Pro) 1171.2 ng/m3, serine (Ser) 13.9 ng/m3, threonine (Thr) 1.4 ng/m3, tyrosine (Tyr) 1.4 ng/m3, valine (Val) 3.1 ng/m3, asparagine (Asn) 376.0 ng/m3, glutamine (Gln) 459.3 ng/m3, trans-4-hydroxy-proline (4-Hyp) 5.8 ng/m3, methionine solfoxide 0.5 ng/m3, methionine solfone 0.015 ng/m3.

References 1. Zhang Q, Anastasio C, Atmos. Environ., 37, 2247 (2003)



Groundwater Situation in Kosova Investigated by Inductively Coupled Plasma Mass Spectrometry

Fatlume Berisha, Walter Goessler*

Karl-Franzens-University Graz, Institute for Chemistry – Analytical Chemistry, Universitatsplatz 1, 8010 Graz, Austria

Abstract Kosova declared independence on the 17th of February 2008. On its second birthday the youngest European country is still far beyond the central European standards. The lack of research and modern analytical facilities are of major concern for public health. Furthermore, Kosova has limited water resources which in the future will be a limiting factor for the economic and social development. Any new scientific findings and resources may be very useful to Kosovar authorities and to researchers into planning, constructing the future monitoring, and providing efficient protective measures for its own population and neighboring countries. An attempt to capture and study the groundwater situation in Kosova has not yet been conducted. It is well known that various elements occur naturally in the groundwater in many parts of the world and many people are unknowingly exposed to it. Even though, European Union (EU) and the World Health Organization (WHO) have set guidelines for the groundwater elemental exposure worldwide, in developing countries such as Kosova the lack of elemental groundwater monitoring to date continues to be an important health concern. During this study we collected field drinking water and groundwater samples for metal analysis throughout the territory of Kosova. The samples were analyzed using inductively coupled plasma mass spectrometry (ICP-MS). In the presentation we show the distribution of 33 elements in the drinking water of Kosova. Moreover, the strict QA/QC procedure for the measurements is discussed. Acknowledgement Austrian Exchange Service (OeAD) for the financial support.



Multivariate Statistical Methods for Characterization of Waste Water Quality

Darja Kavšek1, Tina Jerič2, Darinka Brodnjak Vončina3

1 Regional Technological Centre Zasavje, Chemical-Technological Laboratory, Nasipi 48, 1420 Trbovlje, Slovenia

2 Faculty of Mechanical Engineering, University of Maribor, Smetanova 17, 2000 Maribor, Slovenia

3 Faculty of Chemistry and Chemical Engineering, University of Maribor, Smetanova 17, 2000 Maribor, Slovenia

Abstract The objectives of chemometrics in analytical chemistry are focused on characterization and chemometrical classification of different samples. Environmental samples, namely industrial waste waters and textile waste waters were analyzed through longer time period. Environmental monitoring of industrial waste waters samples was performed in the region of Trbovlje, Slovenia, on two sampling sites and the measurements of physical and physicochemical variables were carried out. Parameters needed for assessment of water quality were selected and measured. For handling analytical results different chemometrics methods were employed, such as basic statistical methods for the determination of mean and median values, standard deviations, minimal and maximal values of measured parameters and their mutual correlation coefficients, the principal component analysis (PCA), cluster analysis (CA), and linear discriminant analysis (LDA). The study gives the opportunity to follow the quality of industrial waste waters at different sampling sites within the defined time period. Monitoring of general pollution of industrial waste waters and following measuring can be used to search the pollution source, to plan prevention measures and to protect from pollution, as well. Data from the physical and chemical characterization of the effluents were also used to identify a possible separation of waste water streams for reuse purposes. In one Slovene textile company analyzed, machineries are used to carry out different production processes such as sizing and desizing, weaving, scouring, bleaching, mercerizing, carbonizing, fulling, dyeing and finishing. Different process effluents from the same machinery were found to be very diverse in pollution level. Effluents from textile waste water streams were collected during two months period and data from the physical and chemical characterization of the effluents were elaborated. This was done with the aim of realizing a full scale characterization of effluents. Effluents have been characterized by different chemometrics methods to find hidden information about textile waste water quality for separation into treatable waste water streams for reuse purposes and into non treatable waste waters with selected technologies. Acknowledgement Operation part is financed by the European Union, European Social Fund. Operation implemented in the framework of the Operational Program for Human Resources Development for the Period 2007-2013, Priority axis 1: Promoting entrepreneurship and adaptability, Main type of activity 1.1.: Experts and researchers for competitive enterprises. and also this proposal is prepared by the thematic working group of the Water Supply and Sanitation Technology Platform (WSSTP) one of the EU Technology Platforms. The integrated research project AquaFit4Use (EU-FP7-ENV-211534) is being funded by the European Commission covering six Sub-Projects.



Determination of Radionuclides in Plants From The Area Around the Boršt Tailings Pile of the Former Uranium Mine at Žirovski vrh in

Slovenia Using Alpha-spectrometry

Marko Černe, Borut Smodiš Jožef Stefan Institute, Jamova 39, 1000 Ljubljana

Abstract Transfer of radionuclides into the environment is a common phenomenon and due to its potential harmful effect of particular scientific interest in the vicinity of uranium mines. Radionuclides, especially uranium decay products are discharged from U-mill tailings into the soil and water and consequently into vegetation where they accumulate. Radionuclide soil-to plant transfer was observed in many studies. Uranium mine at Žirovski vrh in Slovenia, which operated from 1985-1990, processed about 600,000 tons of U-ore. U mining and milling tailings were deposited at the Boršt and Jazbec site [1]. Plants that grow in the vicinity of U-mill tailings may accumulate radionuclides in their tissues and thus represent a possible transfer of radionuclides into the food chain [2]. Radionuclides in plants were determined by alpha-spectrometry with previous radio-chemical separation. Alpha-spectrometry is used for the measurement of alpha-emitting nuclides and has characteristics such as elimination of other possible interferences by chemical separation. In this study, the contents of 238U, 226Ra and 230Th are determined in different plants which were grown in the marsh beneath the Boršt tailings pile. Acknowledgement This work was supported by the Rudnik Žirovski vrh company. The Slovenian Research Agency (contrat no. P2-0075) is also acknowledged. References 1. Križman M, Byrne AR, Benedik.L, J. Environ. Radioactiv., 26, 223 (1995) 2. Shahandeh H, Hossner LR, Water Air. Sol. Poll., 141, 165 (2002)



Pesticide’s Transformation Products: Stability and Degradation Studies

Romina Žabar, Polonca Trebše*

University of Nova Gorica, Vipavska 13, 5000 Nova Gorica, Slovenia Abstract Pesticides have been used for more than 60 years and their consumption constantly grows. Following the legislation for the food safety and water quality, only the parent insecticides are monitored. But the most important and concerning is the fact that there is no control of the presence of transformation products which can be found after the application of pesticides. This research focused on three different transformation products (TPs): 2-isopropyl-6-methyl-4-pyrimidinol (IMP – TP of diazinon); 3,5,6-trichloro-2-pyridinol (TCP – TP of chlorpyrifos) and 6-chloronicotinic acid (6CNA – TP of acetamiprid and imidacloprid). In order to check the stability of selected TPs, aqueous samples were exposed for 90 days to sunlight at ambient temperature as well as kept in the dark in refrigerator at 5°C. The results of samples exposed to sunlight and ambient temperature showed that TCP is not stable within time, since 99.2% of initial concentration was transformed. In the case of IMP and 6CNA, the initial concentration did not change significantly, 1.9% and 9%, respectively. The samples kept in the dark at T= 5°C did not show significant change of concentration, varying of 1.8% for IMP, 1.7% for TCP and 9% for 6CNA. The degradation studies of aqueous solution of selected TPs were performed by photolysis and photocatalysis with immobilized TiO2. Photolysis experiments were performed with three fluorescent, 355nm polychromatic, low-pressure mercury lamps (20W) in special photocatalytic quartz cell. Samples were taken within the irradiation time and analyzed with HPLC, TOC, UV-Vis spectrophotometer and conductometer. All the experiments were performed in triplicates to evaluate the reproducibility of measurements. Photolytic experiment after 120 min revealed almost no degradation for 6CNA, but for IMP and TCP we observed significant disappearance of the parent compounds. In all three cases we did not notice mineralization, because the concentration of total organic carbon did not change during experiment. However, photocatalytic experiments with immobilized TiO2 revealed higher decrease of all three substances within 120 min as well as very high percentage of removal of total organic carbon which indicates the partial mineralization of selected TPs. In order to claim the efficiency of photocatalysis, the toxicity testing with luminescent bacteria Vibrio fischeri was applied. Acknowledgement This work was supported by the Ministry of Higher Education, Science and Technology of the Republic of Slovenia.

YISAC 2010 – Session V: Nano-Micro


Session V

Nano-Micro



TiO2 Nanofibers for Sensing Applications by Improved Sol-Gel Template Synthesis

Michael Ongaro, Andrea Mardegan, Paolo Ugo*

Department of Physical Chemistry, University of Venice, S. Marta 2137, Venezia, Italy

Abstract Over the last decades, the increasing concern on pollution and its effects on human health pushed many research groups to develop sensors for monitoring atmospheric pollutants. Nanostructured metal oxides, such as TiO2, are promising materials in this field, since their semiconductor nature makes it possible to monitor changes in the surrounding atmosphere by measuring changes in their electrical conductivity. The detection mechanism is based on phenomena which take place at the gas/solid interface, therefore an increase in the surface-to-volume ratio should improve significantly the sensitivity of the sensing device. In this prospect, obtaining sensors based on ensembles of quasi-1-D TiO2 nanostructures is highly desirable [1]. In this work, TiO2 nanofibers have been successfully synthesized by an improved sol–gel template method, where an organic additive, has been used to slow down the kinetics of the hydrolysis of the TiO2 precursor. Nanorods were synthesized through repeated injection of TiO2-sol into the pores of microporous templating membranes. Two different templates were tested and compared, namely, microporous aluminium oxide or track-etched polycarbonate membranes. The template method allowed the preparation of TiO2 nanowire with an aspect ratio (length/diameter) of about 50. Special effort has been put in the development of etching methods to obtain self-standing arrays of TiO2 nanowires, by suitable removal of the templating membrane. To this aim chemical and plasma etching methods have been examined and relevant results are discussed.

Figure1. SEM images of TiO2 nanorods arrays synthesized by improved sol–gel template deposition.

Acknowledgements Discussion and skilful assistance in some experiments by Dr. P. Scopece and Dr. A. Patelli (CIVEN, Venezia-Marghera, Italy) is gratefully acknowledged. References 1. Huang X-J, Choi Y-K, Sensor. Actuator. B, 122 (2007) 659-671



Photopatterning a Redox Polymer: Application to Electrogenerated Chemiluminescence Detection

Milena Milutinovic1,2, Emmanuel Suraniti1,3, Sébastien Sallard1, Dragan Manojlovic2,

Nicolas Mano3, Neso Sojic1*

1 University of Bordeaux, Institut des Sciences Moléculaires, ENSCBP, 33607 Pessac, France

2 Department of Chemistry, University of Belgrade, 11000, Belgrade, Serbia 3 Centre de Recherche Paul Pascal, CNRS UPR 8641, 33600 Pessac, France

Abstract Electrogenerated chemiluminescence (ECL) of Ru(bpy)3

2+ is being used in a wide range of analytical applications [1]. Derivatives of Ru(bpy)3

2+ have been immobilized in polymer and silica sol-gels films, attached to nanoparticles and covalently bound to substrates. Here we report the electrodeposition of an ECL-exhibiting Ru2+/3+ complex-containing hydrogel under physiological conditions [2]. We used for our studies the [poly(4-vinylpyridine)-Ru(2,2'-bipyridine)2Cl-ethylamine] [3].

Figure 1. A) Cyclic voltammogram (red) and ECL emission (blue) of the electrodeposited film in PBS with 10 mM TPrA. Scan rate: 10 mV/s. B) Dependence of the ECL signal on the glucose concentration (mM) with the glucose dehydrogenase immobilized in the electrodeposited film.

In the presence of tri-n-propylamine (TPrA), the wave of electrocatalytic oxidation (red curve) of TPrA appeared and light (blue curve) is simultaneously emitted due to generated light-emitting Ru(II)*. Chloride ligand exchange by histidine, lysine or arginine protein residues is likely to allow the co-electrodeposition of biologically active proteins, such as NAD+ depended dehydrogenases, which would produce NADH, a known ECL co-reactant. Figure 1B shows the dependence of the ECL emission on the glucose concentration when the glucose dehydrogenase is immobilized in the film. The intensity increase linearly in the certain region of glucose concentration which can be explained like combination of ECL response, enzyme kinetics and mass transfer effects. In order to improve the properties of deposited film, redox polymer was also photodeposited together with PEGDA in presence of DAROCUR (photoinitiator). By this way we obtained system with much better stability and longer lifetime.

References 1. Richter MM, Chem. Rev., 104, 3003 (2004) 2. Gao Z, Binyamin G, Kim HH, Barton SC, Zang Y, Heller A, Angew. Chem. Int. Ed., 41, 810

(2002) 3. Sallard S, Soukharev V, Heller A, Mano N, Sojic N, Electrochem. Commun., 11, 599

(2009)



Impact of Cosolvents and Additives to Change of Dimension and ζ-Potential of Fullerenol Nano-particles

Ivana Ičević1, Aleksandar Djordjevic*1, Milan Nikoloć2, Milica Vučinić-Vasić3

1 Faculty of Sciences, Department of Chemistry, Trg Dositeja Obradovića 3, Novi Sad, Serbia. 2 Faculty of Technology, Department of Ceramics, Trg Cara Lazara 1, Novi Sad, Serbia

3 Faculty of Technical Sciences, Trg Dositeja Obradovića 6, Novi Sad, Serbia

Abstract Chemical modification of fullerenes C60 into water soluble polyhydroxylated nano-clusters fullerenols, make them interesting for biological research [1,2]. Bio-nano research of fullerenols (C60(OH)24) nano-particles aims to investigate numerous of its applications as antioxidative [3], cell protective [4], radioprotective [5], geno-protective agent [6] and cardio and hepato-protector in doxorubicin-induced stress in vivo models [7]. In this paper, we present the impact of cosolvent and additives in the dimension and ζ- potential change of fullerenol (C60(OH)24) nano-particles (FNP). The measurements were made on Mastersizer 2000, Zetasizer Nano. The dimensions of FNP (pH=5.1) were 50.3, 60.0, 71.5 and 85.4 nm, with average dimension 61.1 nm. FNP (pH=5.1) had two values for ζ-potential, -51.4 mV and -26.4 mV. The average value of ζ-potential was -47.2 mV. Change in pH value determined different values of FNP ζ-potential. In the pH range from 1.76 to 9.87, ζ-potential of FNP was -13.4 to -53.2 mV. Addition of cosolvent DMSO in water solution of FNP decreased the ζ-potential. The increase of concentration of FNP (10, 14.4 and 21.2 mg/ml) in a water / DMSO solution (w/w 20%) caused the decrease of ζ-potential and particles size of FNP. We did not detect significant changes in FNP dimensions (in water and water / DMSO solution) by adding different amounts of cyclodextrin. Addition of Fe3+ at pH 2.5 caused the increase in dimensions of nano-particle aggregates in correlation with Fe3+ concentration rise. When the concentration of Fe3+ ions went above 0.025 mol/l precipitation of fullerenol nano-particles larger than 1.5 nm was detected in the solution. Addition of Ca2+ at concentrations higher than 0.01 mol/l led to total deposition of fullerenol nano-particles. Acknowledgement Authors acknowledge financial support of the Secretariat for Science and Technological Development, AP Vojvodina, Republic of Serbia (grant No. 114-451-02011/2007-02) and Central European Excange Programme for University Studies (Project No. CII-CZ-0212-02-0910) and the Ministry of Science, Republic of Serbia, Grant no. 142076. References 1. Djordjevic A, Bogdanovic G, Dobric S, J. BUON, 11, 391 (2006) 2. Injac R, Radic N, Govedarica B, Afr. J. Biotechnol., 25, 4940 (2008) 3. Mirkov S, Djordjevic A, Andric N, Nitric Oxide-Biol. Ch., 11, 201 (2004) 4. Bogdanovic G, Kojic V, Djordjevic A, Toxicol. in vitro, 18, 629 (2004) 5. Trajkovic S, Dobric S, Jacevic V, Colloid. Surf. B, 58, 39 (2007) 6. Mrdjanovic J, Solajic S, Bogdanovic V, Mutat. Res.—Gen. Tox. En., 680, 25 (2009) 7. Injac R, Perse M, Cerne M, Potocnik N, Radic N, Biomaterials, 30, 1184 (2009)



Potentiometric Immunoassay Based on Sequential Flow Injection Analysis

Júlia Szűcs1, Tom Lindfors2, Róbert E. Gyurcsányi1

1 Research Group of Technical Analytical Chemistry of the Hungarian Academy of Sciences, Budapest University of Technology and Economics

1111-Budapest, Szent Gellért tér 4, Hungary 2 Process Chemistry Group, c/o Laboratory of Analytical Chemistry,

Åbo Akademi University 20500-Turku/Åbo, Biskopsgatan 8, Finland

Abstract A potentiometric sandwich immunoassay was developed based on bioreagent conjugated silver nanoparticle labels. Since the detection is based on the oxidative dissolution of silver nanoparticles with the generated silver ions to be detected by silver selective electrodes (ISE) the sensitivity of the assay could have been very much increased with the reduction of the reaction volume. For complete automatization and controlled handling of volumes in the lower microliter range Sequential Injection Analysis (SIA) was used. The benefits of this enzyme free amplification lay in potentiometry, that is the instrumental method with one of the simplest and cost –effective methodologies. The time required for the dissolution of the nanoparticle is shorter by a factor of 6 than the incubation times used for detection in commonly used optical immunoassays.

Figure1. A new detection scheme based on potentiometric monitoring of silver nanoparticles genereted by oxidative dissolution.

Acknowledgement This work has been supported by the Johan Gadolin Scholarship Foundation of Åbo Akademy. References 1. Basu S, Jana S, Pande S, Pal T, J. Coll. Inter. Sci., 321, 288 (2008) 2. Szucs J, Pretsch E, Gyurcsanyi RE, Analyst, 134, 1601 (2009)



Functionalization and Protection of Nanoelectrodes Ensembles by SAMs

Morena Silvestrini1, Piero Schiavuta2, Dino Paladin3, Paolo Ugo1*

1Department of Physical Chemistry, University of Venice, Santa Marta 2137, 30123 Venice, Italy

2CIVEN association, via delle Industrie 5, 30175 Venice, Italy 3AB ANALITICA s.r.l., via Svizzera 16, 35127 Padova, Italy

Abstract Nanoelectrode ensembles (NEEs), introduced by Chuck Martin’s group in the mid nineties [1], have shown properties useful for several applications. In the electroanalytical and sensor field, NEEs are particularly attractive since they are characterized by highly improved signal-to background currents ratio [1], extremely low detection limits [2-4] and they are suitable to extreme miniaturization since their signal/background ratio is independent on the overall size [3]. Functionalization of NEEs with biorecognition elements allows us to fabricate electrochemical biosensors useful for protein and DNA detection. An approach for the modification of the surface of the NEEs was introduced recently and exploits the possibility to immobilize the biorecognition layer onto the wide polycarbonate surface surrounding the nanoelectrodes [5,6]. Gold nanodisks are only used for the electrochemical signal transduction by a redox mediator that shuttles electrons from the gold electrodes to the biorecognition layer, both elements being in strict spatial proximity. In the present work we study the possibility to use self-assembled monolayers (SAMs) of thiols to protect the surface of nanoelectrodes ensembles (NEEs) from the undesired adsorption of biomolecules, in particular, proteins. Thioctic acid and 2-mercaptoethanesulfonic acid were chosen to this aim. The behaviour of SAM-modified NEEs was studied by cyclic voltammetry as a function of the solution pH using ferrocenecarboxylate as anionic redox probe and (ferrocenylmethyl) trimethylammonium (FA+) as cationic redox probe. It was observed that, when the SAM is negatively charged it repels the negative redox probes from the surface of the nanoelectrodes, while the voltammetry of FA+ remain unchanged. The protective role of the SAM was confirmed by studying the voltammetric signals recorded with NEEs dipped in solutions of high adsorbable proteins, such as Bovine Serum Albumin and Casein, comparing signals recorded at bare NEEs vs. signals at SAM-modified NEEs, in different experimental conditions. AFM measurements in semi-contact mode confirmed that SAMs prevent the undesired adsorption of the proteins on the nanoelectrodes surfaces. References 1. Menon VP, Martin CR, Anal. Chem., 67, 1920 (1995) 2. Ugo P, Moretto LM, Bellomi S, Menon VP, Martin CR, Anal. Chem., 68, 4160 (1996) 3. Moretto LM, Pepe N, Ugo P, Talanta, 62, 1055 (2004) 4. Pereira FC, Moretto LM, De Leo M, Boldrin Zanoni MV, Ugo P, Anal. Chim. Acta, 575,

16 (2006) 5. Pozzi Mucelli S, Zamuner M, Tormen M, Stanta G, Ugo P, Biosens. Bioelectron., 23,

1900 (2008) 6. Zamuner M, Pozzi Mucelli S, Tormen M, Stanta G, Ugo P, Eur. J. Nanomed., 1, 33

(2008)

YISAC 2010 – Session VI: Spectrometry


Session VI

Spectrometry



Characterization of Polychrome pre-Roman Glasses by Laser Ablation ICP-MS

Serena Panighello1, Vid S. Šelih2, Johannes T. van Elteren2, Emilio F. Orsega1*

1 Department of Physical Chemistry, University Ca’ Foscari of Venice, Italy 2 National Institute of Chemistry, Ljubljana, Slovenia

Abstract The wide period from the end of the 3rd millennium to the end of 1st millennium B.C. (bronze and iron ages) is considered the first step in the history of the technology of the ancient glass production. There are several papers about the chemical composition of the bronze-age glasses, mainly from Egypt, Near-East and Aegean area, but only few physico-chemical studies about the glasses of the iron age [1-4]. This work presents the preliminary study of a small set of polychrome glass samples - fragments (glass vessels and ewers) from 5th to 2nd century B.C., made with the so called "core forming" technique. They were found in an Etruscan archaeological site of Adria in North-East Italy, but were probably produced in the Aegean area. All the samples feature different decorative coloured glass patterns on the surface of a main blue glass core and show inhomogeneous morphologies, with many bubbles and inclusions. The aim of this work was the elemental analysis of the samples, in order to get information about the nature and the origin of the sands, fluxes, chromophores and opacifiers used for their production. This can help to state the points of continuity with the production technology of the glasses on the previous and following periods. The glass samples were analyzed by the ICP-MS technique with solid sampling by laser ablation (LA). 54 elements were measured, forming matrix, major, minor and trace constituents of the samples. The experimental procedure uses the advantage of the sum-normalization calibration approach, developed at the L-04 Laboratory of the National Institute of Chemistry in Ljubljana, Slovenia, using a high quality set of glass standards for the calibration purpose [5]. Bivariate and multivariate analysis of the data obtained by LA-ICP-MS may help us in the characterization of the glasses in terms of the production technology and possible provenance. A further characterization of samples was attempted by LA-ICP-MS surface rastering to obtain high quality elemental maps. Acknowledgement We are grateful to Dr. Simonetta Bonomi, former Director of the Museo Archeologico Nazionale di Adria and now Soprintendente ai Beni Archeologici della Calabria, for the supplying of the glass samples and the related cultural support. References 1. Arletti R, Maiorano C, Ferrari D, Vezzalini G, Quartieri S, J. Archaeol. Science, 37, 712

(2010) 2. Gratuze B, Annales du 17eme Congrès de l’ AIHV, Antwerp, 8 (2009). 3. Gratuze B, Lorenzi F, Bulletin de la Société Préhistorique Française, 103, 379 (2006) 4. Hartmann G, Kappel I, Grote K, Arnold B, J. Archaeol. Science, 24, 547 (1997) 5. van Elteren JT, Tennent NH, Šelih VS, Anal. Chim. Acta, 644, 1-2, 1 (2009)



Shotgun Mass Spectrometry under Information Dependent Acquisition Control for Automated Lipidomic Analysis

Alexander Fauland 1, Xinghua Guo1, Martin Trötzmüller2, Harald Köfeler2, Ernst Lankmayr1

1 Graz University of Technology, Institute of Analytical Chemistry and Food Chemistry, Graz Austria

2 Medical University of Graz, Center for Medical Research, Graz Austria Abstract The entire composition of all lipid classes and lipid molecular species within each class is called lipidome. Lipidomic research, defined as the large – scale study of the pathways and networks of cellular lipids in biological systems, is an emerging and rapidly expanding research field. In the present study a shotgun mass spectrometry method for the automated identification of different lipid molecular species based on Information Dependent Acquisition (IDA) in combination with the flexible LipidX software is reported [1]. The instrumentation used for this approach is a Q-Trap 4000 mass spectrometer. The combined ion trap and triple quadrupole scan functions make it a useful system for lipidomic research. For the identification and quantification of the analytes the flexible LipidX software platform (Andrej Shevchenko, Max Planck Institute of Molecular Cell Biology and Genetics, Dresden) is used. The software is designed with the straightforward Molecular Fragmentation Query Language (MFQL) and can be easily adapted by an operator according to given requirements. LipidX especially enables an interpretation of data received under Information Dependent Acquisition control, but is also applicable to other scan types and instruments. Measuring under IDA increases the throughput by combining different scan modes in a sequential fashion for the same run. Moreover the use of neutral loss scans and precursor ion scans as survey scans in IDA experiments with Linear Ion Trap (LIT) scan functions greatly reduce the nonrelevant data obtained and allows the detection of the analytes of interest at much lower concentrations [2]. References 1. Matyash V, Liebisch G, Kurzchalia T, Shenchenko A, Schwudke D, J. Lipid Res., 49, 5,

1137 (2008) 2. Schwudke D, Liebisch G, Herzog R, Schmitz G, Shevchenko A, Method. Enzymol.,

Elsevier, Amsterdam, 175 (2007)



Investigation of Selenium Compounds in Human Serum

Sabine Kokarnig, Kevin Francesconi, Doris Kuehnelt Karl-Franzens-University Graz, Institute for Chemistry – Analytical Chemistry,

Universitatsplatz 1, 8010 Graz, Austria Abstract Selenium is known as an essential trace element which has been ascribed beneficial health effects as well as toxic properties at elevated intake. To understand the role of selenium in human metabolism it is essential to have reliable analytical methods for the determination of selenium compounds in different body fluids. In serum, selenium mainly occurs in the two selenoproteins, glutathione peroxidase and selenoprotein P as well as bound to albumin [1]. So far research has mainly focused on determination of these three selenium compounds. There is the possibility that also smaller non-protein bound molecules containing selenium are present in human serum. In this work a method using HPLC coupled to ICP MS was investigated for the determination of non protein bound selenium compounds following removal of proteins in human serum. References 1. Dumont E, Vanhaecke F, Cornelis R, Anal. Bioanal. Chem., 385, 1304 (2006)



Selenium Speciation in Rat Colon Tissue

Marco Roman1, María Luisa Fernández Sánchez2, Alfredo Sanz-Medel2, Carlo Barbante1,3

1 University Ca’ Foscari of Venice, Department of Environmental Sciences, Dorsoduro 2137, 30123 Venice, Italy

2 University of Oviedo, Department of Physical and Analytical Chemistry, C/ Julián Clavería 8, 33006 Oviedo, Spain

3 Institute for the Dynamics of Environmental Processes (IDPA-CNR), Dorsoduro 2137, 30123 Venice, Italy

Abstract Selenium (Se) is an essential trace element in animals and humans. About 25 Se- proteins have been identified in human proteome and 24 in rat and mice proteome, but still few of them have been fully characterized. Nevertheless, some of these proteins showed to carry out an important role in biological functions among which oxidative stress control, thyroid hormone regulation, insulin mimesis, and anticarcinogenic action [1]. Such Se-proteins constitute promising biomarkers for both global oxidative stress status, and organ-specific diseases. In this field, early cancer detection is one of the most promising applications, particularly for the forms that showed to be correlated with total Se levels in tissue and blood, as is the case of colorectal cancer. The aim of this study was the development of a methodology for speciation of Se in colon tissues. Healthy rat colon samples were used as model for humans in the first stage of the investigation presented here. Se compounds extraction procedures based on stirring, ultrasonication and dispersion (by Ultra-Turrax® disperser) have been evaluated in terms of total element recovery and species preservation. Total Se in tissue and extracts was determined by inductively coupled mass spectrometry (ICP-MS) recurring to isotope dilution analysis (IDA). The selected and optimized extraction protocol allowed a recovery of 43%, while continuously bubbling N2 in the solution during the procedure showed to be mandatory to prevent the oxidative degradation of Se-proteins. Speciation analysis was then performed on the extracts, by separating the species using orthogonal (size-exclusion and anion-exchange) high performance liquid chromatography (HPLC). A number of Se compounds were detected in rat colon extracts, and individually quantified by HPLC-ICP-MS coupling, and species-unspecific on-line (post-column) IDA [2]. Amongst the isolated Se species, the two major proteins glutathione peroxidase 1 and thioredoxin reductase 1 [3] have been identified by fractions collection and MALDI-TOF characterization.

References 1. Hatfield DL, Berry MJ, Gladyshev VN, , Selenium: Its molecular biology and role in

human health, 2nd edition edition, Springer, New York (2006) 2. Hinojosa Reyes L, Marchante-Gayón JM, García Alonso JI, Sanz-Medel A, J. Anal. At.

Spectrom., 18, 11 (2003) 3. Irons R, Carlson BA, Hatfield DL, Davis CD, J. Nutr., 136, 1311 (2006)



UHPLC/MS/MS analysis of anthelmintic drugs and their metabolites

Veronika Jedličková1, Robert Jirásko1, Michal Holčapek1, Lenka Skálová2 1 University of Pardubice, Faculty of Chemical Technology, Department of Analytical

Chemistry, Studentská 573, 53210 Pardubice, Czech Republic 2 Charles University, Faculty of Pharmacy, Department of Biochemical Sciences,

Heyrovského 1203, 500 05 Hradec Králové, Czech Republic Abstract Anthelmintic drugs (anthelmintics) are used for the treatment of infections caused by parasitic helminths (Dicrocoelium dendriticus, Haemonchus contortus, etc.). The capability of parasites to survive the medical treatment is a serious problem due by a frequent resistance to common anthelmintic agents [1]. The analysis of drugs and the identification of their metabolites [2] can provide information about biotransformation paths in the metabolism of parasites and hosts. In our study, selected parasites were cultivated in flasks with a medium enriched by praziquantel (or ivermectin) and subsequently analyzed using UHPLC/MS/MS with the electrospray ionization. Both ESI polarity modes are used to obtain complementary information. Particular emphasis was given on the optimum calibration of the mass scale to achieve the high mass accuracy, which resulted in the determination of ions elemental composition observed in full-scan and tandem mass spectra. Moreover, advanced software tools were used for the prediction and identification of possible metabolites. Acknowledgement This work was supported by MSM0021627502 (Ministry of Education, Youth and Sports of the Czech Republic) and P502/10/0217 (Czech Science Foundation). References 1. Cvilink V, Lamka J, Skálová L, Drug Metabol. Rev., 41, 8 (2009) 2. Holčapek M, Kolářová L, Nobilis M, Anal. Bioanal. Chem., 391, 59 (2008)



Speciation Analysis of Fe2+ / Fe3+ in Antarctic Ice Core Samples

Andrea Spolaor1, Paul Vallelonga2, Vania Gaspari1, Martina Ranaldo1, Marco Roman1, Andrea Gambaro1, Carlo Barbante1,3

1 University Ca’ Foscari of Venice, Department of Environmental Sciences, Dorsoduro 2137, 30123 Venice, Italy

2 Centre for Ice and Climate, Niels Bohr Institute, Juliane Maries Vej 30, 2100 Copenhagen Ø, Denmark

3 Institute for the Dynamics of Environmental Processes (IDPA-CNR), Dorsoduro 2137, 30123 Venice, Italy

Abstract Iron is an element of great interest for its role in the oceanic carbon cycle and for its capacity to regulate primary production [1]. The low iron concentrations in a few oceanic areas are able to limit phytoplankton production and in part control the atmospheric carbon dioxide (CO2) concentration. It is possible that past changes in iron deposition influenced primary production and the capacity of the ocean to store CO2. The biological and environmental activity and iron behaviour depend strongly on the oxidation state; for example, the solubility and the capability to form complexes depend upon iron speciation. Distinguishing between the two iron species, Fe(II) and Fe(III), is necessary to estimate bioavailability as Fe(II) species are more soluble and therefore more readily available for phytoplankton uptake and growth [2]. In this work we studied the Fe speciation in the Talos Dome Antarctic ice core. We used a FIA-ICP-SFMS system with a particular resin, Ni-NTA Superflow, to separate the Fe2+ and Fe3+ by pH variation [3]. The pH 2 resin is capable of retaining Fe3+ with no retention of Fe2+. However, Fe2+ species are unstable and rapidly oxidize. After the initial separation we oxidized the Fe2+ using H2O2, and estimated the concentration by the difference between the two measurements. To minimize the oxidation of Fe2+ to Fe3+, samples must be melted in the absence of light and acidified to pH 2. Samples were immediately analyzed after melting in order to minimize oxidation. The detection limit of this method is 1 ppt. Our results show more Fe2+ during glacial periods than during interglacial periods. These results suggest that more iron may be available for phytoplankton growth during a glacial maximum. References 1. Martin JH, Fitzwater SE, Nature, 331, 341 (1988) 2. Maldonado MT and Prince NM, Deep Sea Res., 2, 2447 (1999) 3. Lohan MC, Anal. Chim. Acta, 530, 121 (2005)

YISAC 2010 – Session VII: Bioanalytical Chemistry


Session VII

Bioanalytical Chemistry



Activity Determination of Stearoyl-CoA-Desaturase 1 (SCD-1)

Michaela Elcnerova1, Alexander Cegan2, Karel Komarek1*, Lukas Cegan3, Veronika Novotná2

1 University of Pardubice, Faculty of Chemical Technology, Department of analytical chemistry, Studentska 95, 532 10 Pardubice, Czech Republic

2 University of Pardubice, Faculty of Chemical Technology, Department of biological and biochemical sciences, Studentska 95, 532 10 Pardubice, Czech Republic

3 University of Pardubice, Faculty of Electrial Engeneering and Informatics, Department of information technology, Studenska 95, 532 10 Pardubice, Czech Republic

Abstract SCD-1 is an enzyme necessary for the biosynthesis of unsaturated fatty acids

(palmitoleic acid (C16:1, n=7) and oleic acid (C18:1, n=9)) from saturated fatty acids (palmitic acid (C16:0) and stearic acid (C18:0)). The unsaturated fatty acids are important substrates for esters of triglycerides and cholesterol synthesis. These compounds are the main components of very low density lipoprotein (VLDL) fraction of human plasma which enables the transport of these acids from liver to fatty tissue and to other organs. The rate of oleic and stearic acid or palmitoleic and palmitic acid is a standard value of SCD-1 activity in human plasma (Fig. 1).

The plasma VLDL fraction was isolated by ultracentrifugation. The VLDL fraction was divided into five subfractions (phospholipids (PL), diglycerides (DG), free fatty acids (FFA), triglycerides (TG) and cholesterol (CE)) using thin-layer chromatography (TLC). The TG fraction was scraped off the TLC plate, dissolved in methanol-toluol mixture and subjected to direct transesterification. The fatty acid methylesters were quantified with cis-13, 16, 19-docosatrienoic acid as the internal standard using gas chromatography with a flame ionization detector. The GC column was programmed from 130° C (0.2 min), 2 °C min-1 to 258° C (6 min). The temperature of the injector was 280° C, the temperature of the detector was 250° C. The SCD-1 activity values in TG were correlated with the patient’s physiological values using multivariable statistical analysis. It was established that the SCD-1 activity correlates with liver damage and insulin resistance in obese diabetic patients. The SCD-1 activity can be used as a diagnostic marker for insulin resistant type 2 diabetes.

Values of plasma Patient n. 1 TRIG = 179 mg/ml CHOL = 218 mg/ml HDL = 51 mg/ml Patient n. 2 TRIG = 96 mg/ml CHOL = 133 mg/ml HDL = 34 mg/ml

Figure 1. Spectrum VLDL-TG fraction of patient´s and healthy individual and the standard value of SCD-1 activity.



Mechanism of Action and Pharmacokinetic Evaluation of a New Anti-Cancer Drug.

F. Donnarumma1, J. Greilberger2, V. Matzi3, J. Lindenmann3, A. Maier3, H-J. Leis4, R.

Wintersteiger1* 1 Inst. of Pharmaceutical Sciences, University of Graz, Austria;

2 Inst. of Physiological Chemistry, Medical University of Graz, Austria; 3 Dept. of Thoracic and Hyperbaric Surgery, Medical University of Graz, Austria;

4 Research Unit of Osteology and Analytical Mass Spectrometry, University Children's Hospital, Medical University Graz, Austria.

Abstract A newly developed anti-cancer drug is currently under investigation in a phase II clinical study. Designed as an infusion solution, this new chemotherapeutical approach is meant to be used by patients for whom other conventional treatments are no longer indicated. Its combination consists of four active agents: alpha-ketoglutaric acid (KG), hydroxymethylfurfural (HMF), N-acetyl-L-methionine (NALM) and N-acetyl-L-selenomethionine (NASeLM) with concentrations of 9 g/L, 3 g/L, 0.1 g/L and 0.002 g/L respectively. The mechanism of action of the drug consists of different effects including angiogenesis suppression and disruption of the tumour cells metabolism. KG and HMF are especially interesting in regard to their synergistic effect, involving a specific acidification of the tumour cells together with a decrease of ammonia and primary amines concentration in the body by this resulting in apoptosis. NASeLM acts as a suitable source of selenium, an element already well known for its anti-tumour properties that in addition is supported by the presence of NALM. A pilot pharmacokinetic study is presented concerning the analytical data of KG in blood samples of patients affected by lungs tumour with interpretation and strategy planning for a future study. Measurements were performed with two different methods. The first involved a SPE purification of the plasma samples by two different cartridges, an ion exchange cartridge for KG, NALM and NASeLM and a polymeric hydrophobic cartridge for HMF. Afterwards, eluates containing KG were derivatised with dansylhydrazine leading to the formation of a hydrazone derivative analyzed via fluorescence detection. In the second method GS-MS was used for detection. A derivatisation step was directly applied to plasma samples using O-(2,3,4,5,6-pentafluorobenzyl) hydroxylamine (PBFHA). The oxime derivative of KG was extracted with hexane and further derivatised with (N-methyl-N-[tert-butyldimethylsilyl] trifluoroacetimide (MTBSTFA) as silylation agent. Both methods involve reaction with carbonyl groups and therefore they were developed for the contemporary analysis of KG and HMF. No free HMF was found in plasma samples thus necessitating further tests for the evalutation of its protein binding rate and metabolism. Acknowledgement This project was funded by C.Y.L. Pharmazeutika GmbH.



Prediction of HPLC Retention Factor of Compounds with Antituberculotic Activity

Peter Nemeček1, Jan Mocak1,2,*, Jozef Lehotay2, Karel Waisser3

1 Department of Chemistry, University of Ss. Cyril and Methodius, J. Herdu 2, Trnava, SK-91701, Slovak Republic

2 Institute of Analytical Chemistry, Slovak University of Technology, Radlinskeho 9, Bratislava, SK-81237, Slovak Republic

3 Faculty of Pharmacy, Charles University, Heyrovskeho 1203, CZ-50005 Hradec Králové, Czech Republic

Abstract The study of compounds inhibiting the growth of mycobacteria is important with respect to their danger for humans. With regard to the role of mycobacteria in human infection the threat of tuberculosis is constantly a serious problem in contemporary medicine. Worldwide, tuberculosis (TB) remains the most frequent and important infectious disease causing morbidity and death. One-third of the world's population is infected with Mycobacterium tuberculosis, the etiologic agent of TB. Mycobacterium avium and M. kansasii, in addition to M. tuberculosis, are most widespread strains of nontuberculous mycobacteria among the HIV infected patients and all three strains are the main cause of their mortality. The search for new effective antimycobacterial compounds and design of their optimum molecular structure is therefore a challenging task for current chemistry [1]. 3-phenyl-2H-1,3-benzoxazin-2,4(3H)-dione (PBOD) derivatives have been found to be very effective agents inhibiting the growth of the mentioned mycobacteria [2-4]. Quantitative structure–retention relationships (QSRRs) represent a powerful tool in chromatography. The main aim of QSRR is to predict retention data from the molecular structure so that QSRRs allow the prediction of retention data of novel, not yet synthesized compounds, just using their structural descriptors. The chief goal of this work is the investigation of relationships among HPLC retention characteristics of sixty-two 3-phenyl-2H-1,3-benzoxazin-2,4(3H)-dione derivatives and calculated compound properties (QSRR variables or descriptors) using artificial neural networks as the main calculation tool for prediction of the HPLC retention factor, k. For this purpose, a relatively wide choice of QSRR variables was used (e.g. lipophilicity solubility, dipole moment, polarizability, molar weight, hydration energy, simulated NMR data, etc.). As target variables several forms of retention factor, namely k and log k corresponding to two mobile phases (methanol – water and acetonitrile – water) were utilized. Acknowledgement Support of Slovak research grant VEGA 1/1005/09 is highly acknowledged. References 1. Nemecek P, Durcekova T, Mocak J, Waisser K, Chem. Pap., 63, 84 (2009) 2. Waisser K, Gregor J, Holy P, Kubicova L, Klimesova V, Kaustova J, Cesk. Slov. Farm., 50,

148 (2001) 3. Waisser K, Perina M, Kunes J, Klimesova V, Kaustova J, Farmaco, 58, 1137-1149 (2003) 4. Waisser K, Hladuvkova J, Gregor J, Rada T, Kubicova L, Klimesova V, Kaustova J, Arch.

Pharm. Pharm. Med. Chem., 331, 3-6 (1998)



Metabolism of 5-Hydroxymethylfurfural after Administration of a Novel Anticancer Infusion Solution

M. Hardt-Stremayr1, J. Greilberger2; V. Matzi3; J. Lindenmann3; A. Maier3; H-J. Leis4;

R. Wintersteiger1* 1 Inst. of Pharmaceutical Sciences, University of Graz, Austria;

2 Inst. of Physiological Chemistry, Medical University of Graz, Austria; 3 Dept. of Thoracic and Hyperbaric Surgery, Medical University of Graz, Austria;

4 Research Unit of Osteology and Analytical Mass Spectrometry, University Children's Hospital, Medical University Graz, Austria.

Abstract The Karal® infusion solution can be seen as a new strategy against cancer as its action towards tumor cells is based on differential metabolism. Four different substances are used exhibiting specific mechanisms and 5-hydroxymethylfurfural (HMF) is meant to be one of the main acting agents. Therefore, its metabolism has to be investigated. So far three main metabolites are supposed to be found in human urine samples: the monocarboxylic acid 5-hydxroxymethyl furoic acid (HMFA), its dicarboxylic acid 2,5-furanodicarboxylic acid (FDCA) and the phase-II conjugate N-(5-hydroxymethyl-2-furoyl)glycine (HMFG). Furthermore, the presence of HMF is not expected within the samples. Potential metabolites are detected via HPLC/UV and peak identification ensues through standartized substances. Purification of urine samples is conducted by means of SPE. Structural elucidation of further metabolites in human samples will be performed using LC/MS.

Figure 1. Metabolites of HMF: HMFA, FDCA and HMFG

Acknowledgement This project was supported by C.Y.L. Pharmazeutika GmbH.



Transformation of As2O3 in Cell Culture Studies Andreja Zelenik1, Zdenka Šlejkovec1, Ingrid Falnoga1*, Magda Tušek Žnidarič2, Irena

Zajc2

1 Institute Jožef Stefan, Jamova 39, 1000 Ljubljana, Slovenia 2 National Institute of Biology, Večna pot 111, 1000 Ljubljana, Slovenia

Abstract Since the last decade arsenic trioxide (As2O3) is used to treat patients with acute promyelocytic leukemia (APL). APL is often cured by As2O3 in cases when patients do not respond to, or have relapsed from, retinoid and anthracycline chemotherapy (first line therapy) [1]. As2O3 has been shown to induce cell death in different malignant cell lines, therefore many clinical trials are currently in progress to evaluate their usefulness in cancer treatment, among them is the treatment of glioblastoma [2, 3]. In the case of anticancer therapy different resistance mechanisms in cells can prevent successful treatment with As2O3. If during the process of methylation, trivalent methylated species are formed, these would enhance its toxicity and potentiate its anticancer effects. The transformation of trivalent to pentavalent As points to a protective mechanism since As(V) is less effective. The influence of dissolved As2O3 (As(III)) on malignant cells is often studied in cell culture experiments. Cells are cultivated in growth media with or without addition of As(III). The aim of this study was to investigate the chemical stability of As(III) in different growth media and the transformation of As(III) inside cells. We investigated the time-dependent transformation of As(III) in different growth media (MEM, with different amounts of aminoacids, with and without addition of serum or vitamin C) with or without cells (cell line U87 MG). The cells were treated with 0.6, 2 and 7 µM As(III) for different time intervals (0-72 h); the media without cells served as controls. We followed the four main metabolites in growth media during cell exposure and As(III/V) conversion during media incubation. Metabolites were followed with high-performance liquid chromatography directly coupled to a hydride generation-atomic fluorescence spectrometry system (HPLC-HG-AFS). At given conditions we noticed considerable transformation of As(III) to As(V) in growth media without cells (up to 30 %). In growth media with cells the amount of As(V) rose up to 10 % and only in one case the presence of dimethylarsinic acid was observed (3 %, 48 h exposure of cells). The time-dependent As(III/V) conversion in various media without cells requires routine checking of the As speciation during cell culture experiments, otherwise the results of biological effects attributed to As(III) should be interpreted with caution. References 1. Cell Therapeutics, Trisenox, Cell Therapeutics Inc, London (2002) 2. Ning S, Knox SK, Int. J. Radiat. Oncol. Biol. Phys. 60, 197 (2004) 3. Ning S, Knox SK, Int. J. Radiat. Oncol. Biol. Phys. 65, 493 (2006)



Cell Culture Investigations with New Antitumoral Agents

H. Pfliger1, J. Greilberger2, P. B. Stiegler3, S. Koestenbauer3, R. Wintersteiger1* 1 Inst. of Pharmaceutical Chemistry, Univerity of Graz, Austria

2 Inst. of Physiological Chemistry, Medical University of Graz, Austria; 3 Dept. of Surgery Div. of Transplantation Surgery, Medical University of Graz, Austria

Abstract Recently new substances have been investigated for cancer treatment. These substances are α- ketoglutarate (KG), 5- hydroxymethylfurfural (HMF), N- acetyl-L-methionine (NALM), N-acetylseleno- L- methionine (NASeLM) acting specificly on tumor cells. The ability of these four compounds to influence cell proliferation, mitochondrial activity and apoptosis is going to be tested by performing cell culture studies. Preliminary studies showed highly promising inhibiting effects with respect to some cancer types. In order to know which substances in which concentration or combination are mainly responsible therefore, Jurkat cells (T-cell- leukemia) were firstly investigated. Later on cell lines from non-small cell lung- cancer, prostate cancer, hepatocellular cancer and melanoma are going to be used. To measure the metabolic and mitochondrial activity of viable cells, more precisely the activity of mitochondria dehydrogenases, the WST-1 reagent is applied. 200.000/mL cells in a 24 well plates are treated with different concentrations of the anticarcinogenic substances (0 - 500 µg/mL) and incubated up to 72 hours at 37°C, 5% CO2. Then 100 µL of the suspension is transformed into 96 well- plates, treated with WST reagent and again incubated for 45 min. Later on the plate is mixed and the absorbance is determined by using a 96 well plate ELISA reader. The FITC active caspase-3 apoptosis kit is used for the detection of tumor cell apoptosis. Caspase-3 is part of the family of cysteine proteases and is activated in the early steps of apoptosis. 2.000.000 cancer cells/mL are treated with different concentrations (0 - 500µg/mL) of the substances under investigation and following the caspase- 3- activity is measured on a flow cytometer. The JC-1 assay kit is also related to apoptosis because it measures the mitochondrial membrane potential. Again 2.000.000 tumor cells/m are incubated in 96 well plates with different concentrations of KG, HMF, NALM and NASeLM for up to 72 hours and at the end of the procedure the mitochondrial membrane potential is analyzed by flow cytometry. During apoptosis several events in the mitochondria occur, like release of caspase- activators, changes in electrone transport and loss of mitochondrial membrane potential. This loss is an important parameter of mitochondrial function and an indicator of cell death. Healthy cells show a high mitochondrial membrane potential, so that JC- 1 forms aggregates that cause red fluorescence. On the other hand apoptotic cells suffer from a low potential, so that JC- 1 remains monomeric and causes green fluorescence. The differences in terms of the membrane potential of healthy and apoptotic cells can be also quantified and qualyfied by fluorescence microscopy or fluorescence plate readers. All things considered, just the complexity of analytical methods including immunoassays, photometric and fluorometric measurements, guarantee significance of results in a highly interesting scientific field.

YISAC 2010 – Session VIII: Food Analysis


Session VIII

Food Analysis



Polyphenol Concentration and Antioxidant Activity of Tartary Buckwheat (Fagopyrum Tataricum) Bread

Maja Vogrinčič1, Maria Timoracka2, Silvia Melichacova2, Alena Vollmannova2, Ivan

Kreft1 1 Biotechnical Faculty, University of Ljubljana, Jamnikarjeva 101, SI-Ljubljana, Slovenia

2 Department of Chemistry, Slovak Agricultural University of Nitra, Tr. A. Hlinku 2, SK-4976 Nitra, Slovak Republic

Abstract Polyphenols are a group of chemical substances found in plants, characterized by the presence of more than one phenol unit per molecule. They are secondary plant metabolites that play an important role in the protection of plants against ultraviolet radiation, pathogens, and herbivores. Polyphenols have antioxidant properties that may inhibit lipid peroxidation, decrease capillary fragility associated with hemorrhagic changes, and reduce high blood pressure and the risk for arteriosclerosis. The aim of our work was to investigate the impact of bread making procedure on rutin (Figure 1), quercetin (Figure 1) and total polyphenols concentration and on antioxidant activity of tartary buckwheat (Fagopyrum tataricum) bread and breads made of mixtures of tartary buckwheat and wheat flour. The following freeze dried and milled samples were analysed: tartary buckwheat flour (Tf), wheat flour (Wf; which served as a control), yeast and bread samples made of Tf and Wf in following ratios: 100:0, 70:30, 50:50 and 0:100. Sample extracts were prepared with 80% methanol. For the analysis of free radical scavenging activity, 2,2-diphenil-1-pycrilhydrazyl (DPPH) was used; the amount of total polyphenols was determined using Folin-Ciocalteau reagent (FCR), rutin and quercetin concentrations were analysed by HPLC. Methods are described in more details elsewhere [1]. A decrease in polyphenol concentration through baking was observed in all samples. The high DPPH (2,2-diphenyl-1-picrylhydrazyl) scavenging capacity in mixed breads (32-56 %) and in tartary buckwheat bread (85-90 %) decreased slightly through bread making process, while an increase of antioxidant activity in bread made of 100 % wheat flour during bread making was observed. With the addition of water to mixtures containing tartary buckwheat during preparation of the dough, rutin concentration decreased while quercetin concentration increased. The rutin concentration continued to decrease during the bread baking process, while the concentration of quercetin remained stable. After baking rutin (0.47 mg/g) was present only in bread made of 100% tartary buckwheat flour along with quercetin (4.83 mg/g).

Figure 1. Rutin (left) and quercetin (right) molecules. References 1. Vogrinčič M, Timoracka M, Melichacova S, Vollmannova A, Kreft I, J. Agric. Food Chem.,

DOI:10.1021/jf9045733, (2010)



Multidimensional Analysis of Fatty Acid Composition of Beef Produced Under Grassland-Based Conditions in Austria

Adriána Bednárová1, Viera Mrázová1, Ján Mocák1,*, Kathrin Ertl2, Walter Goessler2

1 Department of Chemistry, Faculty of Natural Sciences, University of Ss. Cyril and Methodius in Trnava, Nám. J. Herdu 2, SK- 917 01, Trnava, Slovakia

2 Institute of Chemistry - Analytical Chemistry, Karl-Franzens-University Graz, Universitätsplatz 1, A- 8010 Graz, Austria

Abstract The content of nutrients, of possible harmful residuals and the additive, as well as nutritional value, are substantial factors influencing the consumer behaviour on the meat market. The nutritional value is an important feature of beef quality which is, among other things, connected to efforts to improve the fatty acid composition of beef. Dietary intake of unsaturated fatty acids (UFA) has been shown to reduce the risk of cardiovascular disease (CVD) and possibly the incidence of some kind of cancer, asthma and diabetes [1]. Increasing the content of n-3 (or omega-3) polyunsaturated fatty acids (PUFA) and conjugated linolenic acids (CLA) and reduction of the saturated fatty acids (SFA) content are important priorities leading to the net effect of increasing the PUFA/SFA ratio and reducing the n-6/n-3 PUFA ratio [2]. Beef can be enriched with dietary fatty acids within wide limits depending on animal species and technology [3]. The objective of this study is the chemometrical assessment of the fatty acid composition in relation to the way of feeding by using several methods of multidimensional data analysis, like principal component analysis (PCA), linear discrimination analysis (LDA), partial least squares regression (PLS) and artificial neural networks (ANN). For this purpose 68 samples of carcase was used originated from six known Austrian beef labels and four Austrian provinces [4]. Among the used variables were: (a) 33 fatty acids and CLA, (b) content of proteins, fat, ash and dry-mass, (c) total content of SFA, MUFA (monounsaturated fatty acids) and PUFA, (d) total content of n-3 and n-6 fatty acids and their ratio n-6/n-3, (e) 24 trace or minor elements, and (f) age, race and sex of animals. The important task was to find associations among the variables and to determine their importance in order to eliminate less important or unimportant ones. Acknowledgement Support of Slovak grants VEGA 1/1005/09 and VVCE-0004-07 is highly acknowledged. References 1. Simopoulos AP, Am. J. Clin. Nutr., 70, 560 (1999) 2. Moloney AP, Scollan ND, Miles L, Nutrition Bulletin, 33, 374 (2008) 3. French P, Stanton C, Lawless F, O’Riordan EG, Monahan FJ, Caffrey PJ, Moloney AP,

J. Anim. Sci., 78, 2849 (2000) 4. Velik M, Steinwidder A, Frickh JJ, Ibi G, Kolbe-Roemer A, Zuechtungskunde, 80, 378

(2008)



Zinc Speciation in Pumpkin Seeds and Iceberg Lettuce Related to Plant Physiology and Human Health

Andrej Ovca1,2,3, Vid Simon Šelih3, Michael Beeston3, Ingrid Falnoga4, Janez Štupar1,

Johannes Teun van Elteren3* 1 University of Nova Gorica, Vipavska 13, Rožna Dolina,

SI-5000 Nova Gorica, Slovenia 2 University of Ljubljana, Faculty of Health Sciences, Poljanska 26a,

SI-1000 Ljubljana, Slovenia 3 Analytical Chemistry Laboratory, National Institute of Chemistry, Hajdrihova 19,

SI-1000 Ljubljana, Slovenia 4 Department of Environmental Sciences, Institute Jožef Štefan, Jamova 39

SI-1000 Ljubljana Slovenia

Abstract Zn plays a key role in plants as a structural constituent or regulatory co-factor of a wide range of different enzymes and proteins in many important biochemical pathways. While some of the biological functions of essential elements are quite well understood, the chemical form in which elements naturally occur in plants is mostly unknown. In plants the water-soluble Zn fraction is widely considered to be the most physiologically active and is regarded as a better indicator of plant Zn status than total Zn content. While plants constitute important components of ecosystems as they provide the transport pathway from the abiotic to the biotic environment, Zn and its species are also interesting from a nutritional point of view. The aim of this work is to gain information about zinc and its different chemical forms in iceberg lettuce (Lactuca sativa) and pumpkin seeds (Cucurbita pepo), regarding their importance for plant physiology and human health. A sequential analytical approach was applied focusing on total Zn, spatial Zn distribution, extractability of Zn, speciation of Zn and bioaccessibility of Zn. The presentation will focus on results obtained by ultrafiltration, size-exclusion chromatography hyphenated with ICP-MS and in vitro gastrointestinal extraction tests (PBET). Analytical results show that pumpkin seeds and iceberg lettuce have different Zn species fingerprints (in water extracts) with a high (ca. 70%) low-MW fraction (ca. 500Da) in iceberg lettuce and a high (ca. 70%) intermediate/high-MW fraction (>10,000Da) in pumpkin seeds. When these Zn species are subjected to conditions simulating the human stomach (pH ~ 1) they break down completely. This disproofs conclusions of Zn speciation studies done in the past (on plants which are used for nutritional purposes) that low-MW Zn species may have nutritional importance. However, these findings open up a wide range of further interesting research possibilities, especially in the case of pumpkin seeds, where results evidence that anti-nutrients (e.g. naturally present phytate) can reduce the uptake of Zn by complexing with Zn2+ in the intestines (pH ~ 7). Acknowledgement Financial support of experimental work is acknowledged to the programme group P1-0034 (Analytics and chemical characterization of materials and processes).



Simultaneous Determination of Binary Dye Mixtures in Food Samples by Three Different Spectroscopic Methods

Marina Palčić, Darija Ilijaš, Ivana Pranjić, Božidar S. Grabarić, Zorana Grabarić*

Department of Chemistry and Biochemistry, Faculty of Food Technology and Biotechnology, University of Zagreb, Pierottijeva 6, Zagreb, Croatia

Abstract Overlapping signals can be resolved by using methods based on purely mathematical curve resolution techniques such as logarithmic, Fourier or derivative transformations, the last one being improved using measurement at selected “zero-crossings” of derivative, mainly spectrophotometric, signals. For signals and systems where conventional resolution techniques are not very suitable, multivariate calibrations using a family of factor analysis techniques can be used as general selectivity and reliability enhancement tools. In this work a simple method based on signals ratio resolution (SRR) has been fully investigated and some new criteria are established, which enable the determination of two components in mixture from one set of the experimental data. The procedure consists of using several different resolving functions and plotting the difference of the mean of absolute and non absolute values of pseudo signals ([PDMMV(PS)) against analyte concentration obtained with each of the resolving functions. Minimum value of concentration for which PDMMV(PS)=0 represents concentration of one dye. Concentration of the other dye is calculated by multiplying the concentration of resolving function with resolving factor, obtained as the maximum value of resolving factor for which is PDMMV(PS)=0. The results obtained with SRR method were compared with Vierordt’s method in which absorbance of the mixed sample solutions were measured at two wavelengths and then the concentration of each dye was calculated from the following simultaneous equations:

Aλmax1 = αλmax1 c1 + βλmax1 c2 Aλmax2 = αλmax2 c1 + βλmax2 c2 where c1 and c2 are the concentrations of two dyes, A denotes the absorbance of the mixture solution, and α and β represent the values of molar absorption coefficient for individual dye at measured wavelengths. A first-derivative spectrophotometric method using a zero-crossing technique of measurement for simultaneous determination of binary dye mixture was used, too. The selectivity in derivative spectrophotometry is increased because bands that are overlapped in zero-order absorption spectra can be separated in the derivative mode. Mean recoveries, relative standard deviations and linearity ranges in calibration graphs of the methods are compared and discussed. Acknowledgement The financial support by the Croatian Ministry of Science, Education and Sport (grant number: 058-0580000-3071) is gratefully acknowledged.



The Effect of Selenium in Seed Soaking Solution on Growth and Selenium Uptake in Tartary Buckwheat Sprouts

Petra Štrekelj1, Ivan Kreft1, Vekoslava Stibilj2*

1 Biotechnical Faculty, University of Ljubljana, Jamnikarjeva 101, SI-1000 Ljubljana 2 Department of Environmental Sciences, Jožef Stefan Institute, Jamova 39, SI-1000

Ljubljana Abstract Selenium (Se) is an essential trace element for mammals with a very narrow concentration range between insufficiency and toxicity. The availability and toxicity both depend on the chemical form of Se in food. The essentiality of selenium in higher plants has not yet been confirmed. Tartary buckwheat (Fagopyrum tataricum Gaertn.) is an important alternative crop because of high content of proteins, fiber, vitamins and antioxidants (rutin), which have positive impact on human health. Tartary buckwheat is used as sprouts, leafy vegetable, tea or flour from milled grain [1]. The aim of this study was to determine the impact of various concentrations (5, 10, 30 mg/l) of Se(IV) and Se(VI) in seed soaking solution on dry matter and its Se content in tartary buckwheat sprouts. For the control group, the seeds soaked in distilled water were used. Sprouts were exposed to various growing conditions: dark, day light without UV radiation and daylight with short exposure to UV radiation (five hours). Sampling was done when the sprouts developed two extended cotyledon leaves. Samples were lyophilized and milled. For sample digestion H2SO4, HNO3 and HF were used. A solution of 6 M HCl was used for reduction of Se(VI) to Se (IV). Sensitive detection was achieved by HG-AFS with the chemicals and instrumental operating conditions according to Smrkolj and Stibilj [2]. During the plant growth no toxic signs, like leaf necrosis, drying or plant death were noticed. The Se(VI) and Se(IV) in soaked solution had a positive impact on sprouts growth, and Se(IV) has higher impact on the sprouts dry mass than Se(VI), with the exception for sprouts growing on daylight with UV radiation. For these sprouts the positive effect on dry mass was the most pronounced at Se (VI) soaking solution. The results showed that the uptake of Se was dependent on the form and concentrations of Se in the solution used for soaking seeds. The Se content in sprouts raised by increasing concentration of Se in soaking solution. When seeds were soaked at the same concentration and sprouts exposed to various growing conditions similar Se uptake was observed. The lowest amount of Se was obtained in sprouts, from seeds soaked in 5 mg Se(VI)/l solution and growing in the dark (0.94 µg Se/g DM). The highest amount of Se (13.83 µg Se/g DM) was found in sprouts grown in daylight with UV radiation from seeds soaked in 30 mg Se(VI)/l. The lowest amount of Se (4.82 µg Se/g DM) was found in sprouts, from seeds soaked in 5 mg Se(IV)/l and grown in the daylight. Sprouts grown from seeds soaked in 30 mg Se(IV)/l and grown in the dark, contained the highest Se content (37.05 µg Se/g DM). We can conclude that sprouts uptake the higher amount of Se in the form of selenite than in the form of selenate.

References 1. Bonafaccia G, Gambelli L, Fabjan N, Kreft I, Food Chem., 83, 1 (2003) 2. Smrkolj P, Stibilj V, Anal. Chim. Acta, 512, 11 (2004)

YISAC 2010 – Index of papers



INDEX OF PAPERSINDEX OF PAPERSINDEX OF PAPERSINDEX OF PAPERS

(a(a(a(according to the alphabetical order of young investigators’ surnames)ccording to the alphabetical order of young investigators’ surnames)ccording to the alphabetical order of young investigators’ surnames)ccording to the alphabetical order of young investigators’ surnames)



Page

Elena Barbaro, Roberta Zangrando, Silvia De Pieri, Andrea Gambaro, 28 Carlo Barbante, Paolo Cescon

Adriána Bednárová, Viera Mrázová, Ján Mocák, Kathrin Ertl, Walter Goessler 55

Fatlume Berisha, Walter Goessler 29

Polona Brglez, Andrej Holobar, Aleksandra Pivec, Mitja Kolar 24

J. Bulíčková, M. Gál, M. Hromadová, L. Kavan, L. Pospíšil, R. Sokolová 14

Eva Čáňová, Miroslav Lísa, Michal Holčapek 9

Marko Černe, Borut Smodiš 31

Andrija Ćirić, Predrag Đurđević, Helena Prosen 10

F. Donnarumma, J. Greilberger, V. Matzi, J. Lindenmann, A. Maier, 48 H-J. Leis, R. Wintersteiger

Sanja Dožić, Slobodan Gadžurić, Milan Vraneš, Borko Matijević 22

Michaela Elcnerova, Alexander Cegan, Karel Komarek, Lukas Cegan, 47 Veronika Novotná

Alexander Fauland, Xinghua Guo, Martin Trötzmüller, Harald Köfeler, Ernst Lankmayr 41

Ivana Haramustek, Sanja Martinez 17

M. Hardt-Stremayr, J. Greilberger, V. Matzi, J. Lindenmann, A. Maier, 50 H-J Leis, R. Wintersteiger

Ivana Ičević, Aleksandar Djordjevic, Milan Nikoloć, Milica Vučinić-Vasić 36

Gyula Jágerszki, Alajos Grün, István Bitter, Klára Tóth, Róbert E. Gyurcsányi 20

Veronika Jedličková, Robert Jirásko, Michal Holčapek, Lenka Skálová 44

Darja Kavšek, Tina Jerič, Darinka Brodnjak Vončina 30

Zoran Kitanovski, Irena Grgić 25

Sabine Kokarnig, Kevin Francesconi, Doris Kuehnelt 42

Miroslav Marecic, Matthew David Steinberg, Ivana Murkovic Steinberg, 21 Zorana Grabaric

Mauro Masiol, Giancarlo Rampazzo, Daniele Ceccato, Bruno Pavoni 23

Milena Milutinovic, Emmanuel Suraniti, Sébastien Sallard, Dragan Manojlovic, 35 Nicolas Mano, Neso Sojic

Peter Nemeček, Jan Mocak, Jozef Lehotay, Karel Waisser 49

Michael Ongaro, Andrea Mardegan, Paolo Ugo 34

Andrej Ovca, Vid Simon Šelih, Michael Beeston, Ingrid Falnoga, Janez Štupar, 56 Johannes Teun van Elteren

Marina Palčić, Darija Ilijaš, Ivana Pranjić, Božidar S. Grabarić, Zorana Grabarić, 57

Serena Panighello, Vid S. Šelih, Johannes T. van Elteren, Emilio F. Orsega 40

Zsigmond Papp, Valéria Guzsvány 6

H. Pfliger, J. Greilberger, P.B. Stiegler, S. Koestenbauer, R. Wintersteiger 52

M. Putek, J. Zarębski, A. Królicka, A. Bobrowski 15



Marco Roman, María Luisa Fernández Sánchez, Alfredo Sanz-Medel, 43 Carlo Barbante

Bine Šebez, Božidar Ogorevc, Samo Hočevar 13

Morena Silvestrini, Piero Schiavuta, Dino Paladin, Paolo Ugo 38

Veronika Škeříková, Pavel Jandera 11

Hanna Sopha, Samo B. Hočevar, Božidar Ogorevc 18

Jan Soukup, Pavel Jandera 8

Andrea Spolaor, Paul Vallelonga, Vania Gaspari, Martina Ranaldo, 45 Marco Roman, Andrea Gambaro, Carlo Barbante

Matěj Stočes, Ivan Švancara, Karel Vytřas 16

Petra Štrekelj, Ivan Kreft, Vekoslava Stibilj 58

Júlia Szűcs, Tom Lindfors, Róbert E. Gyurcsányi 37

Jure Triglav, Johannes T. van Elteren, Vid Šelih 7

Maja Vogrinčič, Maria Timoracka, Silvia Melichacova, Alena Vollmannova, 54 Ivan Kreft

Romina Žabar, Polonca Trebše 32

Andreja Zelenik, Zdenka Šlejkovec, Ingrid Falnoga, Magda Tušek Žnidarič, 51 Irena Zajc

Rensheng Zhuang, Jun Yao, Polonca Trebše 27

YISAC 2010 – List of participants


List of participants

Young Investigators

Barbaro Elena [email protected] Department of Environmental Sciences, University Ca’ Foscari of Venice, Italy Bednárová Adriána [email protected] University of Ss. Cyril & Methodius, Trnava, Slovakia Berisha Fatlume [email protected] Karl-Franzens University, Graz, Austria Brglez Polona [email protected] Faculty of Chemistry and Chemical Engineering, Maribor, Slovenia Bulíčková Jana [email protected] Department of Analytical Chemistry, University of Pardubice, Czech Republic Čáňová Eva [email protected] University of Pardubice, Czech Republic Černe Marko [email protected] Jozef Stefan Institute, Ljubljana, Slovenia Ćirić Andrija [email protected] Department of Chemistry, University of Kragujevac, Serbia Donnarumma Fabrizio [email protected] Karl-Franzens University, Graz, Austria Dožić Sanja [email protected] Department of Chemistry, Biochemistry and Environmental Protection, University of Novi Sad, Serbia Elcnerova Michaela [email protected] Department of Analytical Chemistry, University of Pardubice, Czech Republic Fauland Alexander [email protected] University of Technology, Graz, Austria Haramustek Ivana [email protected] Faculty of Chemical Engineering and Technology, University of Zagreb, Croatia Hardt-Stremayr Magdalena [email protected] Karl-Franzens University, Graz, Austria Ičević Ivana [email protected] Department of Chemistry, University of Novi Sad, Serbia



Jágerszki Gyula [email protected] University of Technology and Economics, Budapest, Hungary Jedličková Veronika [email protected] University of Pardubice, Czech Republic Kavšek Darja [email protected] Faculty of Chemistry and Chemical Engineering, University of Maribor, Slovenia Kitanovski Zoran [email protected] University of Ljubljana, Slovenia Kokarnig Sabine [email protected] Karl-Franzens University, Graz, Austria Marecic Miroslav [email protected] Faculty of Food Technology and Biotechnology, University of Zagreb, Croatia Masiol Mauro [email protected] Department of Environmental Sciences, University Ca’ Foscari of Venice, Italy Milutinovic Milena [email protected] University of Bordeaux, France Nemeček Peter [email protected] University of Ss. Cyril & Methodius, Trnava Ongaro Michael [email protected] Department of Physical Chemistry, University Ca’ Foscari of Venice, Italy Ovca Andrej [email protected] University of Nova Gorica, Slovenia and National Institute of Chemistry, Slovenia Palčić Marina [email protected] Faculty of Food Technology and Biotechnology, University of Zagreb, Croatia Panighello Serena [email protected] Department of Physical Chemistry, University Ca’ Foscari of Venice, Italy Papp Zsigmond [email protected] University of Novi Sad, Serbia Pfliger Heidelinde [email protected] Karl-Franzens University, Graz, Austria Putek Maria [email protected] University of Science and Technology, Krakòw, Poland Roman Marco [email protected] Department of Environmental Sciences, University Ca’ Foscari of Venice, Italy Šebez Bine [email protected] National Institute of Chemistry, Ljubljana, Slovenia



Silvestrini Morena [email protected] Department of Physical Chemistry, University Ca’ Foscari of Venice, Italy Škeříková Veronika [email protected] Department of Analytical Chemistry, University of Pardubice, Czech Republic Sopha Ingrid Hanna [email protected] National Institute of Chemistry, Ljubljana, Slovenia Soukup Jan [email protected] University of Pardubice, Czech Republic Spolaor Andrea [email protected] Department of Environmental Sciences, University Ca’ Foscari of Venice, Italy Stočes Matěj [email protected] University of Pardubice, Czech Republic Štrekelj Petra [email protected] Biotechnical Faculty, University of Ljubljana, Slovenia Szűcs Júlia [email protected] University of Technology and Economics, Budapest, Hungary Triglav Jure [email protected] University of Ljubljana, Slovenia Vogrinčič Maja [email protected] Biotechnical Faculty, University of Ljubljana, Slovenia Žabar Romina [email protected] University of Nova Gorica, Slovenia Zelenik Andreja [email protected] Jozef Stefan Institute, Ljubljana, Slovenia Zhuang Rensheng [email protected] University of Nova Gorica, Slovenia



Participating Supervisors

Barbante Carlo [email protected] Department of Environmental Sciences, University Ca’ Foscari of Venice, Italy Brodnjak Vončina Darinka [email protected] Faculty of Chemistry and Chemical Engineering, University of Maribor, Slovenia Gadžurić Slobodan [email protected] University of Novi Sad, Serbia Goessler Walter [email protected] Karl-Franzens University, Graz, Austria Grabarić Zorana [email protected] University of Zagreb, Croatia Grgić Irena [email protected] National Institute of Chemistry, Liubljana, Slovenia Guo Xinghua [email protected] University of Technology, Graz, Austria Guzsvany Valeria [email protected] University of Novi Sad, Serbia Hočevar Samo [email protected] National Institute of Chemistry, Ljubljana, Slovenia Kalcher Kurt [email protected] Karl-Franzens University, Graz, Austria Kolar Mitja [email protected] University of Maribor, Slovenia Kreft Ivan [email protected] University of Ljubljana, Slovenia Lankmayr Ernst [email protected] University of Technology, Graz, Austria Martinez Sanja [email protected] University of Zagreb, Croatia Mocák Ján [email protected] University of Ss. Cyril & Methodius, Trnava Moretto Ligia Maria [email protected] Department of Physical Chemistry, University Ca’ Foscari of Venice, Italy Ogorevc Božidar [email protected] National Institute of Chemistry, Ljubljana



Orsega Emilio [email protected] Department of Physical Chemistry, University Ca’ Foscari of Venice, Italy Pavoni Bruno [email protected] Department of Environmental Sciences, University Ca’ Foscari of Venice, Italy Prosen Helena [email protected] University of Ljubljana, Slovenia Šelih Vid Simon [email protected] National Institute of Chemistry, Ljubljana, Slovenia Šlejkovec Zdenka [email protected] Jozef Stefan Institute, Ljubljana, Slovenia Smodiš Borut [email protected] Jozef Stefan Institute, Ljubljana, Slovenia Stibilj Vekoslava [email protected] Jozef Stefan Institute, Ljubljana, Slovenia Tóth Klára [email protected] University of Technology and Economics, Budapest, Hungary Ugo Paolo [email protected] Department of Physical Chemistry, University Ca’ Foscari of Venice, Italy van Elteren Johannes T. [email protected] National Institute of Chemistry, Ljubljana, Slovenia Wintersteiger Reinhold [email protected] Karl-Franzens University, Graz, Austria

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