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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)
2
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
3
• 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
5
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
6
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
7
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
8
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
9
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
11
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 .
12
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
14
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
15
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
16
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
17
Project Outcome Research capacity
Shimadzu UV-VIS Spectrometer Rotary evaporator
New research facilities at Institute of Organic Chemistry, NAS Ukraine
18
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
19
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
20
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.
21
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.
23
Way Forward – SPS CBRN
Thank you very much for attention!