DS0901 - Sécurité des citoyens, lutte contre le crime et le terrorisme

Bio-inspired nanostructured and functionalized cantilevers for sensitive and selective chemical warfare agent detection – BIONANODETEC

Bio-inspired nanostructured and functionalized cantilevers for sensitive and selective detection of chemical warfare agent s.

Elaboration of a very sensitive (below the lethality level) and selective (exhibiting only affinity toward organophosphorous chemical agents) sensor .

Elaboration of a sensitive and selective sensor for organophosporous chemical agents detection that could be implemented onto mobile devices

The final goal of the BIONANODETEC project is the elaboration of an organophosphorus chemical agents sensor working under ambiant air and able to reach very low detection threshold with high selectivity level. The final aim would be the implementation of this sensor onto mobile and reactive (within 10 minutes) devices, which could be deployed into sensitive places (airports, subways, trains, ...). The lethality level for 10 minutes of exposure is: 110 pp. for tabun, 64 pp. for sarin, 49 ppb for someone and 2,7 pp. for VX. We have to reach lower thresholds. Thus, the desired threshold for 10 min of exposure is : 100 ppb for tabun, 50 ppb for sarin, 40 ppb for someone and 2 ppb for VX.

To reach these objectives the project is organized into 5 main tasks, (1) Nanostructuration of micro-cantilevers with TiO2 and CuO nanorods/nanotubes to increase the sensitivity of detection (2) Functionalisation of the nanostrucured cantilevers with specific molecules exhibiting high affinity toward organophosphorus agents (3) Optimisation of the generation of organophosphorous agents simulants (from tens to hundred of ppb) (4) Quantification toward the detection of chemical warfare agents simulants and real agents (5) Implementation onto devices and drones.

Microcantilever nanostructuration either with TiO2 or CuO nanorods/nanotubes allowed to increase the surface of the cantilevers by a factor going from 15 to 100 times. This resulted in higher capture of organophosphorus molecules. Furthermore, chemical functionnalisation of the nanostructured cantilevers with specific chemical ligands still led to decrease the detection thresholds to 80 ppb. The first detection tests also highlighted a very good selectivity in the prsence of humidity in air.

The optimisation of the nanostructuration in terms of length, diameter of the TiO2 and CuO nanorods/nanotubes and of thetering ligands might lead to further decrease the detection threshold and increase the selectivity level to reach detection threshold below the lethality level. At the end of the project we hope to be able to implement these sensors onto drones for remote detection of chemical warfare agents.

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There is a great need for efficient – rapid, sensitive and selective – detection of Chemical Warfare Agents (more especially OP – OrganoPhosphorous agents) both during terrorist attacks or for post-use decontamination purposes to make sure that ambient areas are no more contaminated. Sensitivity is determined by the lowest concentration of OP agent that can be detected with confidence. Selectivity is determined by the ability to respond only to the targeted OP agents, i.e. to be able to distinguish only targeted compounds over a broad range of concentrations, from any other substances present in the environment. The ability for rapid detection, to identify and to monitor OP agents is imperative for the efficient use of both military and civilian defense, in order to identify areas that are definitely unpolluted or no more contaminated.

The BIONANODETEC project is clearly devoted to the detection of ultra-trace quantities in vapor phase (for the first time under the lethal limit, lower than the ppb level to reach the ppt level never reached before) of OrganoPhosphorous substances acting as chemical warfare agents. Compared to existing technologies, it is novel and innovative because it starts from a disruptive concep tof cantilever nano-structuration – with vertically oriented TiO2and CuO nanotubes -, enabling to reduce the detection threshold. Nevertheless, in addition to this concept, this project displays further disruptive progresses and breakthroughs:
(1) Nano-structuration of piezoresistive cantilevers, allowing miniaturization and easier prototyping of the sensing system. This first additional breakthrough is to replace classical cantilever design i.e. with an optical readout by Laser beam, by cantilevers using piezoresistive readout. With this kind of cantilevers, it may be possible (thanks to nanostructuration on both sides) to increase the capturing surface and thus to enhance detection threshold.
(2) Scaling-up of nanostructuration step of piezoresistive microlevers to produce the sensors in large scale to ensure high dissemination.The choosen solution consists in combining the nanotubes synthesis to the cantilever fabrication process. Piezoresistive cantilevers are made from a 4 inches wafer. More than 300 nanostructured cantilevers could thus be produced at the same time.
(3) Functionalization of the nanostructured cantilevers with self-assembled monolayers (SAMs) of oxime sto reach high selectivity towards OP agents. Original bifunctional molecules composed with pyridinaldoxime or pyridinalamidoxime sensing chemical function (SCF), and a functional Attachment Group (FAG) able to link covalently to TiO2 and CuO surfaces will be synthetized and used for the chemical functionalization.

As a consequence and considering the current terrorist threat through chemical warfare, these three previously mentioned and novel approaches represent the bottlenecks to overcome to reach this important challenge. The project is really ambitious as the objectives to reach high selectivity and sensitivity (below the lethality level, as never reached before) are highly challenging. The benefit and the impact for society will be very significant.

Project coordination

Valérie KELLER-SPITZER (Institut de Chimie et des Procédés pour l'Energie, l'Environnement et la Santé)

The author of this summary is the project coordinator, who is responsible for the content of this summary. The ANR declines any responsibility as for its contents.

Partner

ICPEES Institut de Chimie et des Procédés pour l'Energie, l'Environnement et la Santé
NS3E Nanomatériaux pour Systèmes Sous Sollicitations Extrêmes

Help of the ANR 496,216 euros
Beginning and duration of the scientific project: September 2015 - 42 Months

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