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NATO

Science for Peace and Security (SPS) Programme

Workshop on CBRN Defence – 22-24 October 2013 – Brussels

Emerging Security Challenges Division

NATO

Novel Macromolecular Complexes for Rapid Detection of Hazardous Agents

SPS Project Number: 984189 (05.2012-04.2014)

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Institute of Physics, National Academy of Science (NAS), Kiev, Ukraine

Dr Anatoli Verbiysky PPD

Dr Yuri Piryatinski, Senior Scientist

Dr Petro Lutsyk

Mr Raimond Perminov Young Scientists

Mr Anatoli Bukivskii

Institute of Organic Chemistry, NAS, Kiev, Ukraine

Dr Mykola Shandura, Co Director

Dr Yuri Kovtun Senior Scientist

Prof Oleksiy Kachkovski Senior Scientist

Dr Viktor Iakubovski Young Scientist

Aston University, Birmingham, UK

Dr Alex Rozhin, NPD

Dr Mykhaylo Dubov, Senior Scientist

Mrs Raz Arif, Young Scientist

Mr Jan Hruby, Erasmus visiting student (Brno University of Technology, Czech Republic)

Project Description

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• Heavy metal global production has reaching 90 millions metric tons

The contents of heavy metals in the environment can be determined by different electrochemical methods, atomic emissive/adsorption analysis, spectrophotometry, mass-spectrometry, X-ray fluorescence analysis. Such methods are very sensitive but can’t be used for rapid detection in the non-laboratory conditions.

• There are numerous large-scale ammonia production plants worldwide, producing a total of 146.5 millions metric tons of ammonia in 2006

The Nessler’s reagent and the indophenol method are common for the

ammonia detection. These methods are very complex, have low sensitivity and can’t be used for rapid detection.

Project Description

4

•World production capacity for multi-wall carbon nanotubes exceeded 3,400 tons per year in 2010.

•Production capacity for MWNT is projected to reach 9,400 tons by 2015.

There are no sensors for rapid detection of Carbon Nanotubes!

http://www.electroiq.com/articles/stm/2010/04/mwnts--leaders-move.html

Project Description

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The major advantage of the new detection method is the possibility to use the same class of materials for the detection of various hazardous compounds by chemical engineering of macromolecular complexes.

The project objectives are the development of a new detection method combining

• the chemical synthesis of sensor/probe molecules such as Polymethine Dyes (PDs),

• development of optical spectroscopy methods for their detection

• fabrication the sensor device by using novel photonics micro-fabrication tools.

•this will ensure the required spectral characteristics of the fluorophore and the high

selectivity of the receptor part of the molecular fluorescent (FL) sensors.

Project Description

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This project addresses the problem of rapid portable sensors for the detection of dangerous environmental polluters

In the frame of the project we plan to create sensor systems for the spectroscopic detection of four major types of the polluters:

• ammonia, aliphatic primary and secondary amines;

• heavy metals (mercury, lead, zinc, cadmium);

• hydrogen sulfide and mercaptanes.

• sensor for recognition of carbon nanotubes, which are toxic and will be potential industrial polluter in the near future.

Project Description

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hν

e-

FLUOROPHORE N..

N..

Me+FLUOROPHORE

hν

hν`

Principle of molecule recognition by fluorescent sensor

• the lone electron pair of the donor can quench the fluorescence at the time of fluorescence excitation (left part).

• the fluorescence intensity can be drastically enhanced due to detected ion binding (right part).

The detection of the hazardous objects molecules based on the following main concept:

Project Description

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S

NN

S

C2H5

C2H5

X_

+ ( )n

n = 1, 2, 3, 4, 5

The synthesis of new macromolecular complexes to detect hazardous agents:

• fluorescent substances for the detection of amines including ammonia;

• new ionoflurophores and ionchromogens based on chinoline podands;

• new boron-dipyrromethene dyes for detection of hydrogen sulphide and mercaptanes;

• fluorescent substances for the detection of nanotubes

Project Description

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O

OO

O

BFF

R

O

OO

O

BFF

R

NHRRNH

2

weak fluorescence strong fluorescence

RNH3

+

1 2

O

O

O

BO

F F

N

ST

Project Outcome

600 650 700 750 8000

10

20

1

4

3PL (

a.u

.)

(nm)

2

Dye ST

Photoluminescence (PL) changes for the dye ST (1, СМ = 1×10-6) in 50% aqueous ethanol in 10 min after the admixture of ammonia solution (2, СМ = 4×10-6; 3, СМ = 6×10-6, 4, СМ = 1×10-5).

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Our Method

The limit of sensitivity – 1 µM (0.017 mg/l)

Time – 10 min

Neßler's reagent

The limit of sensitivity – 60 µM (1 mg/l)

Time – 10 min

Indophenol method

The limit of sensitivity– 1 µM (0.017 mg/l)

Time – 60 min

Project Outcome

0 3 6 9 120

1000

2000

PL

max (

a.u

.)

amine concentration (10-6, mol/l)

dye ST {CM = 2.5 x 10

-6 } + amine

CLOD

= 0.6 x 10-6

The calibration curve plotted as a dependence of PL @ 620 nm, PLmax, for dye ST in 50% aqueous ethanol on amine concentration

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Project Outcome

N

N

O

S

NN

OHC Hg2+

ON N+

RO

SX Xant

300 400 500 600 700

0,0

0,5

1,0

1,5

2,0

2,5

Absorp

tio

n

nm

1

2

3

4

5

SX

The changes of absorption spectra of SX compound (30 µM) in 50% aquatic acetonitrile by adding of mercury (II) perchlorate : 1,2 (5 µM), 1 – fresh solution, 2 - for ten minutes, 3,4,5 (10 µM), 3 – fresh solution, 4 – for ten minutes, 5 – for fifteen minutes

Transformation of a colorless spiroxantene (SX) into xantene dye (Xant) in

the presence of salts of mercury .

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Project Outcome

500 520 540 560 580 600 620 640 660 680 700

400

420

440

460

480

500

520

540

560

580

600

Emission Wavelength [nm]

Astraphloxin 0.01 3-6-2013

0.0E+00

2.0E+05

4.0E+05

6.0E+05

8.0E+05

1.0E+06

1.2E+06

1.3E+06

Excitation W

avele

ngth

[nm

]

Photoluminescence (PL) excitation emission maps of Dye

Strong visible PL in the spectral range 540-640 nm

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PL excitation emission maps of Dye with CNT in visible spectral range

Project Outcome

500 520 540 560 580 600 620 640 660 680 700

400

420

440

460

480

500

520

540

560

580

600

Excitatio

n W

ave

leng

th [n

m]

Emission Wavelength [nm]

Astraphloxin 0.01 + CNT (1:4 from 29-4-2013) 3-6-2013

0

30000

60000

90000

120000

150000

180000

210000

240000

270000

300000310000

Efficient quenching of PL in short wavelength range around 560nm

Change of colour of dye due to aggregation of dyes molecules on

CNT-surfactant complexes

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Project Outcome

1000 1100 1200 1300 1400

300

400

500

600

700

800

Emission Wavelength [nm]

Excita

tio

n W

ave

len

gth

[n

m]

CNT +H2O D(1:4) 29-4-2013 1-5-2013

3000

9267

15533

21800

28067

34333

40600

46867

50000

1000 1100 1200 1300 1400

300

400

500

600

700

800

Excita

tio

n W

ave

len

gth

[n

m]

Emission Wavelength [nm]

Astraphloxin 0.01 + CNT (1:4 from 29-4-2013) 3-6-2013

3000

9400

15800

22200

28600

35000

41400

47800

51000

Enhancement of PL of CNT due to complexes formation with dyes

PL excitation emission maps of Dye with CNT in the IR spectral range

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Project Outcome

Current challenges in design and fubrication of opto-fluidic components

Transverse geometry of inscription. The focal spot is shifted (along Z-axis) into the glass sample (15-300mm).

The sample is scanned using 2D (X,Y) translation stages.

Scan

Fibre Microchannels

Top view Lateral view

Micro-resonator

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The Edinburgh Iinstruments LifeSpec II high performance fluorescence lifetime spectrometer

New research facilities at Institute of Physics, NAS Ukraine

He cryostat

Project Outcome Research capacity

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Project Outcome Research capacity

Shimadzu UV-VIS Spectrometer Rotary evaporator

New research facilities at Institute of Organic Chemistry, NAS Ukraine

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Project Outcome Educational successes

Training of Young Scientists in the Framework of NATO project at Aston University (Birmingham, UK)

1. Dr Petro Lutsyk (IoP, NAS Ukraine) - 2 months

2. Mr Raimond Perminov (IoP, NAS Ukraine) - 1 month

3. Mrs Raz Arif (PhD student sponsored by Iraq Government)- continuous

4. Mr Jan Hruby (Erasmus Student, Brno University for Technologies, Czech Republic)- 6 months

5. Mr Anatoli Bukivskii (IoP, NAS Ukraine) - will spend 3 week at Aston in Nov-Dec 2013

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Project Outcome Educational successes

Training of Young Scientists in the NATO Partner Countries

• Organisation (IoP team) of the 9-th International Conference

ELECTRONIC PROCESSES IN ORGANIC MATERIALS (ICEPOM-9)

May 20 – 24, 2013, Lviv, Ukraine.

Plenary Lecture by Dr A Rozhin “Carbon nanomaterials as a future

platform for photonics: promises and risks”

• The British Council Researcher Links 2014 Conference “New Advanced Materials for Photonics and Sensors” Novosibirsk, Russia (17-20 March, 2014). Chairs A. Rozhin and A.I. Plekhanov.

80% of participants will be young scientists from Russia and the UK Special grants for participation of young scientists

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Project Outcome Public Communication

Dr Petro Lutsyk and Mr Raimond Perminov described the NATO SPS project #984189 at the Minor Academy of Science, Kiev Ukraine November 2011.

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Project Outcome Public Communication

Dr Petro Lutsyk & Mr Raimond Perminov described the NATO SPS project #984189 at the Minor Academy of Science, Kiev Ukraine November 2011.

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What research in CBRN Defence requires urgent and substantial attention?

Substantial attention have to be paid for security and protection of critical infrastructure: water resources, agricultural land, oil/gas pipelines, energy and transport networks

Development of sensitive tools for detection of hazardous CBRN agents . Focusing on simple “on-place” test-methods, like colorimetric and luminescent detection of harmful substances by organic/inorganic nanomaterial sensors which offer significant advantages (very high sensitivity and fast response) over standard analytical methods using expensive laboratory equipment.

What should be the focus of the SPS Programme in CBRN Defence?

Ideas for potential SPS activities in the CBRN field (according to your expertise)

Way Forward – SPS CBRN

Prevention and minimization of impact of technological catastrophes and natural disasters, like natural resources spill out, hazardous chemical pollutions at mills, and so on.

Bio-security associated with nanomaterials pollutants.

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Way Forward – SPS CBRN

Thank you very much for attention!