Chemical Warfare Simulants Research Articles

Design Analysis of Mid IR DIAL System for Detection of Hazardous Chemical Species

Nowadays, both military and public agencies are concerned with the remote detection of toxic gases and chemical warfare agents in the atmosphere. A promising method for the remote detection of such harmful chemicals in the atmosphere is Differential Absorption Lidar (DIAL). In the current paper, system design analysis has been carried out to build a DIAL system for the detection of toxic chemical warfare agents, chemical warfare simulants, explosive precursors, and pollutants. The proposed DIAL system comprises an Optical Parametric Oscillator (OPO) based tuneable laser, a 203 mm diameter Cassegrain telescope, a TE-cooled MCT detector, suitable data acquisition hardware, etc. The DIAL output parameters like return signals, SNR, and minimum measurable concentrations have been simulated under different weather conditions such as clear sky, moderately hazy sky, and hazy atmospheric conditions for given system input parameters (pulse energy, detectivity, bandwidth, DAQ resolution, etc.). We have considered chemicals such as Sarin, Thiodiglycol (TDG), acetone, and methane to be detected using the system. Analysis has been carried out for these chemicals present at different locations with varying concentrations. Our analysis reveals that the DIAL system with a laser transmitter of 5 mJ energy and 203 mm receiver telescope is capable of detecting a few ppm concentrations of toxic chemicals present anywhere between the ranges from a few tens of meters to 2 km with topographic target present. The sensitivity of the system in terms of minimum detectable concentrations for the considered chemicals is also estimated for different atmospheric conditions. It is seen that the minimum detectable concentration of TDG is 3.2 ppm in clear weather conditions which increases to 9.2 ppm under a hazy atmosphere. A similar analysis has been carried out for other toxic chemicals and has been discussed in the paper.

Dark and UV-Enhanced Degradation of Dimethyl Methylphosphonate on Mesoporous CeO2 Aerogels

Our development of high surface-area mesoporous expressions of ceria (CeO2) is motivated by recent studies identifying CeO2 as one of the most reactive oxides for adsorbing and degrading toxic organophosphorus compounds, including chemical warfare simulants. We synthesize nanostructured CeO2 aerogels using a facile, scalable, and template-free sol–gel method to amplify the number of available and accessible surface sites for organophosphorus adsorption/degradation and then spectroscopically characterize the degradation of dimethyl methylphosphonate (DMMP) at the aerogel surface. The CeO2 aerogels retain high concentrations of surface-sited residual Cl from the chloride sol–gel precursors, which block DMMP binding sites and hinder the formation of surface hydroxyls (OH). We demonstrate that a simple alkaline soak removes surface-fouling Cl and creates a more OH-rich surface, thus unleashing the hydrolytic activity of the amplified CeO2 aerogel surfaces. Whereas the Cl-fouled CeO2 surface weakly and reversibly binds DMMP, the rinsed, OH-rich surface irreversibly binds DMMP and rapidly generates hydrolysis products. Exciting the CeO2 bandgap with UV light (390–400 nm) accelerates DMMP degradation and generates a higher proportion of mineralized POx products than the dark reaction. Our work marks the first-ever report of photodegradation of a chemical warfare simulant at CeO2 as well as the first report of mineralized POx formation at CeO2 at room temperature. The high surface-area CeO2 aerogels exhibit higher capacity than non-networked, nanoparticulate CeO2, thus highlighting the potential applicability of nanocrystalline CeO2 aerogels for protection against organophosphorus compounds.

Electropolymerization of Metal Clusters Establishing a Versatile Platform for Enhanced Catalysis Performance

AbstractAtomically precise metal clusters are attractive as highly efficient catalysts, but suffer from continuous efficiency deactivation in the catalytic process. Here, we report the development of an efficient strategy that enhances catalytic performance by electropolymerization (EP) of metal clusters into hybrid materials. Based on carbazole ligand protection, three polymerized metal‐cluster hybrid materials, namely Poly‐Cu14cba, Poly‐Cu6Au6cbz and Poly‐Cu6Ag4cbz, were prepared. Compared with isolated metal clusters, metal clusters immobilizing on a biscarbazole network after EP significantly improved their electron‐transfer ability and long‐term recyclability, resulting in higher catalytic performance. As a proof‐of‐concept, Poly‐Cu14cba was evaluated as an electrocatalyst for reducing nitrate (NO3−) to ammonia (NH3), which exhibited ≈4‐fold NH3 yield rate and ≈2‐fold Faraday efficiency enhancement compared to that of Cu14cba with good durability. Similarly, Poly‐Cu6Au6cbz showed 10 times higher photocatalytic efficiency towards chemical warfare simulants degradation than the cluster counterpart.

Electropolymerization of Metal Clusters Establishing a Versatile Platform for Enhanced Catalysis Performance.

Atomically precise metal clusters are attractive as highly efficient catalysts, but suffer from continuous efficiency deactivation in the catalytic process. Here, we report the development of an efficient strategy that enhances catalytic performance by electropolymerization (EP) of metal clusters into hybrid materials. Based on carbazole ligand protection, three polymerized metal-cluster hybrid materials, namely Poly-Cu14 cba, Poly-Cu6 Au6 cbz and Poly-Cu6 Ag4 cbz, were prepared. Compared with isolated metal clusters, metal clusters immobilizing on a biscarbazole network after EP significantly improved their electron-transfer ability and long-term recyclability, resulting in higher catalytic performance. As a proof-of-concept, Poly-Cu14 cba was evaluated as an electrocatalyst for reducing nitrate (NO3 - ) to ammonia (NH3 ), which exhibited ≈4-fold NH3 yield rate and ≈2-fold Faraday efficiency enhancement compared to that of Cu14 cba with good durability. Similarly, Poly-Cu6 Au6 cbz showed 10 times higher photocatalytic efficiency towards chemical warfare simulants degradation than the cluster counterpart.

A continuous flow generator of organic hypochlorites for the neutralization of chemical warfare agent simulants

On-demand organic hypochlorites for the neutralization of sulfur-based chemical warfare simulants.

Gold nanoparticle nanofibres as SERS substrate for detection of methylene blue and a chemical warfare simulant (methyl salicylate)

Flexible polymer (polyvinyl alcohol, PVA) nanofibres achieved with electrospinning and loaded with picosecond laser-ablated gold nanoparticles (Au NPs) were utilized as surface-enhanced Raman scattering (SERS) substrates. The fabricated polymer nanofibres and Au NPs were characterized by UV–Visible absorption, field emission scanning electron microscope, transmission electron microscopy and X-ray diffraction techniques. The PVA–Au NPs SERS substrates were used to detect the dye methylene blue (MB 5 µM) and a chemical warfare agent simulant (methyl salicylate) using a portable Raman spectrometer. The flexible PVA–Au NPs nanofibre exhibited a good sensitivity with enhancement factors of >104 and a high reproducibility (RSD ~10%). These flexible substrates could be extended for SERS studies of various explosive and other hazardous molecules.

Sonochemical synthesis of Zr-based porphyrinic MOF-525 and MOF-545: Enhancement in catalytic and adsorption properties

Abstract The synthesis of metal-organic frameworks (MOFs) with in-built porphyrin units remains challenging. It takes long synthesis time under carefully controlled reaction conditions, and a mixed-phase with different crystal morphologies is still frequently observed. In this work, Zr-based porphyrinic MOF-525 and MOF-545 in high purity and uniform size were produced through a sonochemical route in 2.5 and 0.5 h, respectively, using zirconyl chloride octahydrate and tetrakis (4-carboxyphenyl) porphyrin. Benzoic acid was used as a modulator for MOF-525, and trifluoroacetic acid for MOF-545. The physicochemical properties of the MOF products were examined by X-ray diffraction, scanning electron microscopy, and N2 adsorption-desorption isotherms. Additionally, the defect sites in the MOF samples were analyzed by UV–vis spectrometry, thermogravimetric analysis, and inductively coupled plasma mass spectrometer. The sonochemically synthesized MOF samples had more defect sites than the conventionally prepared ones and exhibited improved textural properties. In particular, the MOF-545 had a significantly smaller (ca. 1.0 μm) particle size than the conventionally prepared sample (ca. 4.8 μm). The MOF-525 and MOF-545 prepared by the sonochemical route exhibited enhanced hydrolysis of the chemical warfare simulant dimethyl-4-nitrophenyl phosphate (DMNP) and a faster and higher bisphenol-A adsorption than the conventionally prepared MOF samples.

Selective visible-light-driven toxicity breakdown of nerve agent simulant methyl paraoxon over a photoactive nanofabric

An efficient photocatalytic nanofabric (NbOFe-NF) based on polycaprolactone (PCL) and immobilized iron niobate (NbOFe) nanoparticles was produced through the electrospinning technique and applied to the photodegradation of methyl paraoxon (MP), a highly neurotoxic chemical warfare simulant. Photocatalytic tests were conducted in the absence of any solvent, relying only on the fabric, substrate, and visible light radiation. As a result, an excellent conversion of 94.5 % of MP was obtained in 48 h of photocatalysis. Furthermore, the photoactive nanofabric proved to be extremely selective, converting MP and its original organophosphate product into less toxic compounds. This entire process was exclusively photocatalytic, through h+ and OH produced from ambient humidity.

Function-Topology Relationship in the Catalytic Hydrolysis of a Chemical Warfare Simulant in Two Zr-MOFs.

Owing to their high surface area, high concentration of active metal sites, and water stability, zirconium(VI)-based metal-organic frameworks (Zr-MOFs) have shown excellent activity in the hydrolysis of organophosphorus nerve agents (OPNs). In this regard, for the first time, two topologically different Zr-MOFs (Zr-fcu-tmuc and Zr-bcu-tmuc, constructed from the same organic and inorganic building blocks; fcu=face-centered cubic, bcu=body-centered cubic) have been rationally chosen to investigate the effect of network topology on the catalytic hydrolysis of the nerve agent simulant, dimethyl 4-nitrophenyl phosphate (DMNP). A remarkable enhancement in the hydrolysis rate of DMNP was observed with Zr-bcu-tmuc, reducing the half-life more than three-fold compared with Zr-fcu-tmuc. Greater accessibility of the active ZrVI sites in the 8-connected bcu net compared with the 12-connected fcu leads to a faster hydrolysis of DMNP on Zr-bcu-tmuc. Interestingly, the higher activity of Zr-bcu-tmuc was also confirmed by its higher fluorescence sensitivity towards DMNP (limit of detection (LOD)=0.557 μm) compared with Zr-fcu-tmuc (LOD=1.09 μm). The results show that controlling the desired topology of Zr-MOFs is a useful strategy for improving their performance in the detection and catalytic detoxification of OPNs.

Effect of superabsorbent polymers (SAP) and metal organic frameworks (MOF) wiping sandwich patch on human skin decontamination and detoxification in vitro

Most chemical warfare agents partition rapidly into stratum corneum (SC) and subsequently slowly diffuse through – or are retained in the membrane. Since chemicals can interact with SC components during the process, skin decontamination poses a challenging yet important problem. To address these issues, we have developed a new method in combination with wet and dry decon technologies with new materials for emergency or delayed contamination scenarios. An in vitro human skin diffusion system was employed to model various dermal exposures of radiolabeled chemical warfare simulants, followed by surface decontamination with metal organic frameworks (MOFs), super-absorbent polymers (SAP), and/or dermal decontamination gel (DDGel). All samples measured for radioactive recovery and acetylcholinesterase activity to ascertain relative decon efficacy. Results demonstrated powerful water absorption of SAP, strong catalysis of UiO-66 MOF, and decon enhancement of pre-wetting surface contaminants. SAP had no interfering interactions with MOF yet provided additional benefits as porosity and reactivity that allowed for fast liquidized chemical transportation, absorption, and degeneration. We then designed a cotton-based SAP/MOF patch that worked cooperatively in decontamination and detoxification. Together with pre-wet, SAP/MOF wipe, and DDGel applications, maximum effect was observed in early and/or extended dermal exposure, and no “wash-in” effect occurred.

Follicular pathway role in chemical warfare simulants percutaneous penetration.

Chemical warfare (CW) exposure could be fatal to military and civilians through skin contamination. Our work and others focus on investigating stratum corneum reservoir with less regards to skin appendageal routes including hair follicles. Here, C-14 CW simulants (CWS) with specific activity of 0.1 mCi/ml were tested on abdominal and scalp human cadaver skin using flow-through diffusion system. Quantitative analysis of simulants in skin compartments were performed using scintillation counter. Scalp permeation of dipropylene glycol monomethyl ether (DPGME), diisopropyl methylphosphonate (DIMP) and methyl salicylate (MeS) exceed abdominal skin by 8%, 15%, and 6% (p value < 0.05) of applied dose, respectively. DPGME and DIMP (most hydrophilic) showed earlier permeation peak time (Tmax) through scalp skin at 2 and 4 h, respectively, comparing with 6 h with abdominal skin. The percentage of applied dose of DPGME and DIMP retained in human skin membrane (SC, epidermis, and viable dermis) showed no statistically significant difference between tested abdominal and scalp skin samples (p value >0.05). The percentage of applied dose of MeS in scalp showed higher partitioning in stratum corneum and viable epidermis than abdominal skin (p value <0.05). In conclusion, human scalp showed greater total skin absorption than abdominal skin. This work points to a qualitative importance of high follicular density body regions in percutaneous penetration and suggests that transfollicular pathway might have a significant role in early stage permeation of chemical warfare simulants. However, the difference noticed here between scalp and abdominal skin could be attributed to regional variability in anatomy, physiology, and barrier characteristics.

Colloidal crystal engineering with metal\u2013organic framework nanoparticles and DNA

Colloidal crystal engineering with nucleic acid-modified nanoparticles is a powerful way for preparing 3D superlattices, which may be useful in many areas, including catalysis, sensing, and photonics. To date, the building blocks studied have been primarily based upon metals, metal oxides, chalcogenide semiconductors, and proteins. Here, we show that metal–organic framework nanoparticles (MOF NPs) densely functionalized with oligonucleotides can be programmed to crystallize into a diverse set of superlattices with well-defined crystal symmetries and compositions. Electron microscopy and small-angle X-ray scattering characterization confirm the formation of single-component MOF superlattices, binary MOF–Au single crystals, and two-dimensional MOF nanorod assemblies. Importantly, DNA-modified porphyrinic MOF nanorods (PCN-222) were assembled into 2D superlattices and found to be catalytically active for the photooxidation of 2-chloroethyl ethyl sulfide (CEES, a chemical warfare simulant of mustard gas). Taken together, these new materials and methods provide access to colloidal crystals that incorporate particles with the well-established designer properties of MOFs and, therefore, increase the scope of possibilities for colloidal crystal engineering with DNA.

Direct soil analysis by paper spray mass spectrometry: Detection of drugs and chemical warfare agent hydrolysis products

There is a significant concern about the accumulation of hazardous chemicals in the environment. Pharmaceuticals and drugs of abuse (DOA) can reach high levels in waste water and industrial or hospital effluents, for example. Another group of chemicals of concern are organophosphate compounds. Although the stockpiling and manufacture of chemical warfare agents (CWA) has substantially decreased due to the Chemical Weapon’s Convention, nerve agents continue to be used by rogue states and other actors. In this study, two paper spray MS screening procedures were developed to detect these hazardous chemicals in soil without sample preparation. Central nervous system (CNS) depressants, opiates, stimulants, and tricyclic antidepressants were included in the pharmaceutical/DOA screening method. Chemical warfare simulants and hydrolysis products were analyzed using a separate screening method which utilized polarity switching to detect positive and negative ions associated with this class of molecules. For both methods, an aliquot of soil was weighed into a well pressed against the paper spray substrate. A dual extraction/spray solvent was then applied to the soil, extracting the analytes and facilitating electrospray ionization from the paper. A quadrupole-orbitrap mass spectrometer was utilized in MS/MS mode for detection. Limits of detection for the pharmaceuticals and DOA ranged between 0.3 and 40 ng/g for three different soil types. The CWA simulants had limits of detection of 50 ng/g while the hydrolysis products were detected between 1 and 5 ng/g. In order to improve quantitative performance, an offline salting out liquid-liquid (SALLE) extraction with internal standardization was also performed.

Efficacy of Different Hair and Skin Decontamination Strategies with Identification of Associated Hazards to First Responders

Background: Established procedures for mass casualty decontamination involve the deployment of equipment for showering with water (such as the ladder pipe system [LPS] and technical decontamination [TD]). This necessarily introduces a short, but critical delay. The incorporation of dry decontamination to the incident response process offers the potential to establish a more rapid and timely intervention. Objectives: To investigate the effectiveness of various dry (DD) and wet decontamination strategies for removing a chemical warfare simulant (methyl salicylate; MS) from the hair and skin of human volunteers. Methods: The simulant was applied to volunteers via whole body exposure to an aerosol. Three decontamination protocols (dry, LPS and technical decontamination) were applied, singly and in various combinations. The efficacy of the protocols was evaluated by fluorescent photography and analysis of residual MS from skin/hair swabs, decontamination materials and air samples. Results: Dry decontamination was effective, with the greatest reduction in skin and hair contamination arising from the "Triple Protocol" (DD+LPS+TD). Secondary hazards associated with contaminated individuals and equipment decreased as the number of decontamination procedures increased. In particular, dry decontamination reduced the potential contact and inhalation hazard arising from used washcloths, towels and vapor within the TD units. Discussion: The introduction of dry decontamination prior to wet forms of decontamination offers a simple strategy to initiate treatment at a much earlier opportunity, with a corresponding improvement in clinical outcomes and substantial reduction of secondary hazards associated with operational processes.

Evaluation and application of gas chromatography - vacuum ultraviolet spectroscopy for drug- and explosive precursors and examination of non-negative matrix factorization for deconvolution.

Since the introduction of a benchtop vacuum ultraviolet (VUV) absorption spectroscope with an increased wavelength range towards to the high energetic ultraviolet radiation, gas chromatography coupled to VUV has been proven a powerful tool in several fields of application such as petroleomics, permanent gas analytic, pesticide analytic and many more. In this study, the potential of GC-VUV for investigations was examined, focusing on drug- and explosive precursors as well as chemical warfare simulants. The ability of VUV absorption spectra to differentiate isomers is presented, among others for nitroaromatics. In addition, the limit of detection for target compounds was determined to 0.7 ng absolute on column. Furthermore, non-negative matrix factorization (NMF) was successfully implemented as alternative deconvolution approach and evaluated for the deconvolution of unknown substances. In comparison, the spectral library-based deconvolution was applied to a standard mixture and a simulated case study. The results reveal that the NMF is a useful additional tool for deconvolution because, unlike library-based deconvolution, it allows to investigate unknown substances as well.

Nylon-MOF Composites through Postsynthetic Polymerization.

Hybridization of metal-organic frameworks (MOFs) and polymers into composites yields materials that display the exceptional properties of MOFs with the robustness of polymers. However, the realization of MOF-polymer composites requires efficient dispersion and interactions of MOF particles with polymer matrices, which remains a significant challenge. Herein, we report a simple, scalable, bench-top approach to covalently tethered nylon-MOF polymer composite materials through an interfacial polymerization technique. The copolymerization of a modified UiO-66-NH2 MOF with a growing polyamide fiber (PA-66) during an interfacial polymerization gave hybrid materials with up to around 29 weight percent MOF. The covalent hybrid material demonstrated nearly an order of magnitude higher catalytic activity for the breakdown of a chemical warfare simulant (dimethyl-4-nitrophenyl phosphate, DMNP) compared to MOFs that are non-covalently, physically entrapped in nylon, thus highlighting the importance of MOF-polymer hybridization.

Nylon–MOF Composites through Postsynthetic Polymerization

AbstractHybridization of metal–organic frameworks (MOFs) and polymers into composites yields materials that display the exceptional properties of MOFs with the robustness of polymers. However, the realization of MOF–polymer composites requires efficient dispersion and interactions of MOF particles with polymer matrices, which remains a significant challenge. Herein, we report a simple, scalable, bench‐top approach to covalently tethered nylon–MOF polymer composite materials through an interfacial polymerization technique. The copolymerization of a modified UiO‐66‐NH2 MOF with a growing polyamide fiber (PA‐66) during an interfacial polymerization gave hybrid materials with up to around 29 weight percent MOF. The covalent hybrid material demonstrated nearly an order of magnitude higher catalytic activity for the breakdown of a chemical warfare simulant (dimethyl‐4‐nitrophenyl phosphate, DMNP) compared to MOFs that are non‐covalently, physically entrapped in nylon, thus highlighting the importance of MOF–polymer hybridization.

Shape-selective synthesis of nanoceria for degradation of paraoxon as a chemical warfare simulant.

Repeated attacks using organophosphorus compounds, in military conflicts or terrorist acts, necessitate developing inexpensive and readily available decontamination systems. Nanosized cerium oxide is a suitable candidate, acting as a heterogeneous catalyst for the degradation of organophosphorus compounds such as VX agent or sarin. However, the reaction mechanism of the phosphatase mimetic activity of CeO2 nanoparticles is not fully described. Adsorption, surface-promoted hydrolysis, and desorption cycles strongly depend on the physico-chemical characteristics of the facets. In this study, CeO2 nanoparticles with different shapes were elaborated by hydrothermal synthesis. Nano-octahedra, nanocubes, or nanorods were selectively obtained under different conditions (temperature, concentration and nature of the precursors). The degradation activity according to the crystal faces was evaluated in vitro by measuring the degradation kinetics of paraoxon organophosphate in the presence of CeO2 nanoparticles. The results show an influence of both specific surface area and crystal faces of the nanoparticles, with higher activity for {111} facets compared to {100} facets at 32 °C. The relative activity between the facets is ascribed to the adsorption probability, assuming coordination between the phosphoryl oxygen and cerium atoms, but also to the surface density of the Ce doublets with relevant spacing for phosphatase mimetic activity.

Fate of Some Chemical Warfare Simulants Adsorbed on an Inert Surface when Exposed to Rapid Laser Initiated Heating

The pyrolysis products resulting from the rapid laser heating of low concentrations of adsorbed chemical warfare simulants have been examined. Specifically, three GB simulants were reacted in this ...

Direct Analysis of Aerosolized Chemical Warfare Simulants Captured on a Modified Glass-Based Substrate by "Paper-Spray" Ionization.

Paper spray ionization mass spectrometry offers a rapid alternative platform requiring no sample preparation. Aerosolized chemical warfare agent (CWA) simulants trimethyl phosphate, dimethyl methylphosphonate, and diisopropyl methylphosphonate were captured by passing air through a glass fiber filter disk within a disposable paper spray cartridge. CWA simulants were aerosolized at varying concentrations using an in-house built aerosol chamber. A custom 3D-printed holder was designed and built to facilitate the aerosol capture onto the paper spray cartridges. The air flow through each of the collection devices was maintained equally to ensure the same volume of air sampled across methods. Each approach yielded linear calibration curves with R2 values between 0.98-0.99 for each compound and similar limits of detection in terms of disbursed aerosol concentration. While the glass fiber filter disk has a higher capture efficiency (≈40%), the paper spray method produces analogous results even with a lower capture efficiency (≈1%). Improvements were made to include glass fiber filters as the substrate within the paper spray cartridge consumable. Glass fiber filters were then treated with ammonium sulfate to decrease chemical interaction with the simulants. This allowed for improved direct aerosol capture efficiency (>40%). Ultimately, the limits of detection were reduced to levels comparable to current worker population limits of 1 × 10-6 mg/m3.