“NanoContraChem”

Science for Peace and Security Programme

Multi-year Projects

proposal no. 984481

Science for Peace and Security Programme

Multi-year Projects

NPD: Dr. Matteo GUIDOTTI, CNR-ISTM

Milano, ITALY

PPD: Prof. Mykola STARODUB, Nat. Univ. Life and Env, Sciences,

Kiev, UKRAINE

Prof. Andrew KATSEV, Crimean State Medical Univ.

Simferopol, UKRAINE

Dr. Chiara BISIO, Univ. of Eastern Piedmont,

Alessandria, ITALY

Conventional Decontamination

Conventional decontamination is based on:

- Dissolution

organic solvents, petrol, paraffin, etc.

- Removal

bentonite, magnesia, absorbing powders

- Destruction

basic solutions, detergents, chlorinated lime, decon solutions

- Combustion

• Both physical and chemical actions

• Large amounts of water

• Oxidising agents

All these methods need huge amounts of reactants and/or energy and

pose several problems in terms of safety, environmental and economical

sustainability, costs and disposal of the detoxified by-products

• Formation of hazardous by-products

as dangerous as Chem Bio agents

Current status and needs

a reliable catalyst must be

1) robust, under re-use conditions 2) cheap, for production and scale-up 3) active, as immediate as possible 4) selective, avoid hazardous by-products 5) versatile, for a wide range of aggressives 6) safe and non-toxic 7) effective under mild conditions, as close as possible to ambient conditions

From

stoichiometric to

catalytic decontamination

Main Objectives of the Project

- Development of effective, cheap and reliable nanostructured inorganic solid systems for the catalytic decontamination of chemical warfare agents (CWA) - Evaluation of the large-scale use of these materials in decontamination devices, assessing their toxicological impact on living organisms by rapid and reliable biological tests

CNR – Institute of Molecular Sciences and Technologies (ISTM)

National University of Life and Environmental Sciences of Ukraine

(NULES)

University of Eastern Piedmont (NanoSISTEMI)

Crimean State Medical University of Ukraine

(CSMU)

- testing of solid catalysts in liquid-phase catalytic oxidation of nerve agent and blistering agent simulants

- Preparation of nanostructured synthetic clays and inorganic nanostructured oxides

- Physico-chemical characterization of solids

- Development of biosensors and enzymatic methods for toxicity

assessment -Evaluation of toxicity on health and

the environment

- Estimation of toxicity (ecotoxicity) of all species will be estimated using

bioluminescent bacteria technology.

The Participants

Transdisciplinary approach to the problem

Phase 1: Design, synthesis and characterization of nanostructured metal-containing inorganic oxides

Definition and selection of materials Synthesis and characterization of nanostructured oxides and layered materials nanometric oxides (Al2O3, TiO2, ZnO, WO3 or MgO) layered solids (smectite clays: saponite and hectorite)

Preparation of metal-supported inorganic catalysts single-site catalysts containing redox-active centres (Ti, Nb, V, W, Fe, ...)

Silicon Aluminum Oxygen Hydroxyl

M n + • X H 2 O

~ 1 nm

Nanostructured TiO2

Synthetic clay

Phase 2: Testing the materials in the oxidative decontamination of a blistering agent simulant and of a nerve agent simulant

Catalytic tests on the detoxification of blistering and nerve agent simulants CWA simulants for evident health and safety reasons

Study of the chemical mechanism of the catalytic oxidation on the most promising solids

Catalytic evaluation of selected materials under real working conditions with genuine CWA in collaboration with CeTLI Italian Armed Forces Technical Centre

ClS

ClS

Cl

CEES

Sulfur Mustard

P

O

OO P

O

F

O

DMMP Sarin

Environmentally friendly oxidants

H2O2, O2, air

Phase 3: Optimization of biosensor methods for the evaluation of environmental and toxicological impact.

Development of enzymatic biosensors for the determination of organophosphorous substances

Elaboration of optical systems for the express evaluation of the total toxicity with living micro-organisms determination of chemiluminescence of Daphnia magna

Development of a biological system for the express control of the effect of CWA degradation products on vegetables “Floratest” to estimate the influence of toxics on plants

Development and validation of a special cytological test for the control of mutagenic effects of CWA simulants by-products

Models of multi-electrochemical

biosensors

Daphnia magna

Phase 4: Environmental and toxicological impact of the solids and on the decontamination by-products

Toxicological evaluation of selected materials impact of nanosized solids on living organisms

Determination of the total toxicity of CWA simulants after detoxification treatment evaluation of side-production of hazardous compounds

Estimation of the possible mutagenic effects of selected materials “Studying chronic effects on living organisms

Evaluation of the effect on vegetables

NanoHazard ? Nanotoxicology ?

Portable chronofluorometer “Floratest”

Implementation of the Results

• Publications and presentations at international level (peer-reviewed journals and international congresses on CBRN topics)

• Deliverables in form of demonstrators

the preparation on multigram-scale of at least two solids for the total and safe detoxification of CWA (blistering and nerve agents)

will be the most relevant deliverable

real application to new tools for CBRN Defence

• Patents for the most promising findings in catalytic materials and novel biosensors and detection tools

• Communication Plan Internet website, divulgation papers and video through NATO Press

media office (dual-use of Chemistry)

strong contacts with OPCW, IUPAC, Italian Society of Chemistry and National Academy of Sciences of Ukraine

Nanosized metal oxides

Nanocatalysts for abatement

Key role of homogeneously dispersed and

accessible oxidation and acid

sites

Abatement of CEES (chloroethyl ethyl

sulfide; HD mustard simulant) in the

presence of H2O2 over Nb-containing saponite

clays

0 5 10 15 20 25 30

0.0

0.2

0.4

0.6

0.8

1.0Blank

Na-SAP

H-SAP

Na-NbSAP-Et

Na-NbSAP-Cl

NbSAP-Cl

NbSAP-EtCE

ES

mo

lar

ratio

Time (h)

Oxidative degradation of CEES

at 25°C with H2O2 (70mM)

to be published soon work in progress for toxicological evaluation

Relevance to Security Issues

• Fully consistent with the Key Priorities of the SPS Programme

(1.d) Defence against CBRN Agents

(1.d.i) Methods and technology regarding the protection against,

diagnosing effects, detection, decontamination, destruction, disposal and containment of CBRN agents

Strengthen national and international preparedness and response to non-conventional threats

Improve security in terms of 1) reduced risks of illegal uses (better prevention)

2) reduced vulnerability for the civilian population (better protection) 3) improved risk management (minimization of negative

consequences).

Valid for NATO countries, but particularly relevant for Italy and Ukraine, in its strategic role between European and Asian scenarios

Strong points of the Projects

Transdisciplinary approach to the problem

Large participation of young researchers

Safety issues for nanosized compounds - “Nanotoxicology” NanoREG

Cradle-to-grave evaluation

Deep interest by governmental end-users in Ukraine, Italy and USA

Focus on one well-defined final product - tool for decontamination of CBRN agents

• What research in CBRN Defence requires urgent and substantial

attention?

• problem of dual use (for peaceful or illicit purposes) of emerging

disciplines (nanosciences, nanotech, biotech, information tech,

cognitive sciences) is real and is a source of concern.

• New scientific advances mean new technological capabilities to set up

unexpected threats to global and/or local security.

• A strategic study of the potential misuse of new discoveries should in

developing adequate countermeasures to new threats.

Way Forward – SPS CBRN

“Traditional” non-toxic

compounds

Nanosystems as new aggressives

Risk of uncontrolled production of nanosized hazardous compounds

Nanoshaped or nanosized

materials

Results within parameters

NO VIOLATION

OF REGULATIONS

Uncontrolled manufacture

National or international “traditional”

analytical control

Novel hazardous

or toxic materials

OK for production

No macroscopic difference in chemical composition between the “raw material” and the final product

• What should be the focus of the SPS Programme in CBRN

Defence?

Way Forward – SPS CBRN

• “Preventing is better than curing”

• Not only support to pure and applied research or high-level

specialization, but also to fundamental education and formation

about the ethical use and study of Sciences

• NATO-ASI or ARW Books are fundamental textbooks at graduate

level too

• A plan for discussing and highlighting these fundamental issues should

deserve more attention, at educational level with schools and

universities

• Ideas for potential SPS activities in the CBRN field (according to

your expertise)

• Converging efforts

Academy, Education institutions, First

Responders, Military, Industrial manufacturers

• These are domains that possess top-level

capabilities but that, too often, do not interact

• National Scientific Societies, IUPAC, OPCW are

already active to bridge the gap

Way Forward – SPS CBRN

Thank you for your attention …

… and let’s keep fingers crossed