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Chemical warfare agents represent a severe threat to mankind and their efficient decontamination is a global necessity. However, traditional disposal strategies have limitations, including high energy consumption, use of aggressive reagents and generation of toxic byproducts. Here, inspired by the compartmentalized architecture and detoxification mechanism of bacterial micro-compartments, we constructed oil-in-water Pickering emulsion droplets stabilized by hydrogen-bonded organic framework immobilized cascade enzymes for decontaminating mustard gas simulant (2-chloroethyl ethyl sulfide, CEES) under sweet conditions. Two exemplified droplet systems were developed with two-enzyme (glucose oxidase/chloroperoxidase) and three-enzyme (invertase/glucose oxidase/chloroperoxidase) cascades, both achieving over 6-fold enhancement in decontamination efficiency compared with free enzymes and >99% selectivity towards non-toxic sulfoxide. We found that the favored mass transfer of sugars and CEES from their respective phases to approach the cascade enzymes located at the droplet surface and the facilitated substrate channeling between proximally immobilized enzymes were key factors in augmenting the decontamination efficacy. More importantly, the robustness of immobilized enzymes enabled easy reproduction of both the droplet formation and detoxification performance over 10 cycles, following long-term storage and in far-field locations. [ABSTRACT FROM AUTHOR]

The application of ultraviolet (UV) light for the decontamination of chemical warfare agents (CWAs) has gained recognition as an effective method, especially for treating hard‐to‐reach areas where wet chemical methods are impractical. In this study, TiO2/Ti was employed as a model catalyst, which was contaminated with 2‐chloroethyl phenyl sulfide (CEPS), and subjected to photocatalytic decontamination using both UVB and UVC light. Additionally, photocatalytic decontamination efficiency by introducing Au, Pt, and Cu onto the TiO2/Ti surface was explored. During the photodecomposition process under UVC light, at least eight distinct secondary byproducts were identified. It was observed that the introduction of overlayer metals did not significantly enhance the photodecomposition under UVC light instead overlaid Au exhibited substantially improved activity under UVB light. Whereas, photodecomposition process under UVB light, only five secondary products were detected, including novel compounds with sulfoxide and sulfone functional groups. This novel study offers valuable insights into the generation of secondary products and sheds light on the roles of overlayer metals and photon wavelength in the photodecontamination process of CWA. [ABSTRACT FROM AUTHOR]

Chemical warfare agents pose a serious threat due to their extreme toxicity, necessitating swift the identification of chemical gases and individual responses to the identified threats. Fourier transform infrared (FTIR) spectroscopy offers a method for remote material analysis, particularly in detecting colorless and odorless chemical agents. In this paper, we propose a deep neural network utilizing a semi-supervised autoencoder (SSAE) for the classification of chemical gases based on FTIR spectra. In contrast to traditional methods, the SSAE concurrently trains an autoencoder and a classifier attached to a latent vector of the autoencoder, enhancing feature extraction for classification. The SSAE was evaluated on laboratory-collected FTIR spectra, demonstrating a superior classification performance compared to existing methods. The efficacy of the SSAE lies in its ability to generate denser cluster distributions in latent vectors, thereby enhancing gas classification. This study established a consistent experimental environment for hyperparameter optimization, offering valuable insights into the influence of latent vectors on classification performance. [ABSTRACT FROM AUTHOR]

Abstract The application of ultraviolet (UV) light for the decontamination of chemical warfare agents (CWAs) has gained recognition as an effective method, especially for treating hard‐to‐reach areas where wet chemical methods are impractical. In this study, TiO2/Ti was employed as a model catalyst, which was contaminated with 2‐chloroethyl phenyl sulfide (CEPS), and subjected to photocatalytic decontamination using both UVB and UVC light. Additionally, photocatalytic decontamination efficiency by introducing Au, Pt, and Cu onto the TiO2/Ti surface was explored. During the photodecomposition process under UVC light, at least eight distinct secondary byproducts were identified. It was observed that the introduction of overlayer metals did not significantly enhance the photodecomposition under UVC light instead overlaid Au exhibited substantially improved activity under UVB light. Whereas, photodecomposition process under UVB light, only five secondary products were detected, including novel compounds with sulfoxide and sulfone functional groups. This novel study offers valuable insights into the generation of secondary products and sheds light on the roles of overlayer metals and photon wavelength in the photodecontamination process of CWA.

New and efficient sensors of nerve agents are urgently demanded to prevent them from causing mass casualties in war or terrorist attacks. So, in this work, a novel hierarchical nanoheterostructure was synthesized via the direct growth of α-Fe2O3 nanorods onto multiwall carbon nanotube (MWCNT) backbones. Then, the composites were functionalized with hexafluoroisopropanol (HFIP) and successfully applied to detect dimethyl methylphosphonate (DMMP)-sarin simulant gas. The observations show that the HFIP-α-Fe2O3@MWCNT hybrids exhibit outstanding DMMP-sensing performance, including low operating temperature (220 °C), high response (6.0 to 0.1 ppm DMMP), short response/recovery time (8.7 s/11.9 s), as well as low detection limit (63.92 ppb). The analysis of the sensing mechanism demonstrates that the perfect sensing performance is mainly due to the synergistic effect of the chemical interaction of DMMP with the heterostructure and the physical adsorption of DMMP by hydrogen bonds with HFIP that are grafted on the α-Fe2O3@MWCNTs composite. The huge specific surface area of HFIP-α-Fe2O3@MWCNTs composite is also one of the reasons for this enhanced performance. This work not only offers a promising and effective method for synthesizing sensitive materials for high-performance gas sensors but also provides insight into the sensing mechanism of DMMP. [ABSTRACT FROM AUTHOR]

The proposal of a system for the safe recovery of unexploded ordnance (UXO), chemical weapons (CW) and chemical warfare agents (CWA) dumped at sea mainly after WWI and WWII is described in this work. The proposed solution addresses the tasks required to neutralise thousands of tons of dumped material and the currently available solutions and proposed ideas. Requirements concerning the features of a recovery system are defined and scrutinised, these being intended to ensure the safety of this phase of the UXO/CW neutralisation process. To meet this requirement, the concept of a remotely operated, two-component working size underwater vehicle is proposed, supplemented by a properly sized and outfitted surface platform that is an important part of the recovery system. Finally, the basic components of the proposed system configuration are characterised, together with their functions during the recovery of dangerous CWA-related objects.

We present the fabrication of a novel Starfruit‐shaped metal‐organic framework (SMOF) composed of zirconium and Tetra(4‐carboxyphenyl)porphine linkers. The SMOF exhibits a unique morphology with edge‐sharing two‐dimensional (2D) nanosheet petals. Our investigation unravels a captivating transformation process, wherein three‐dimensional (3D) shuttle‐shaped MOFs form initially and subsequently evolve into 2D nanosheet‐based SMOF structures. The distinct morphology of SMOF showcases superior catalytic activity in detoxifying G‐type nerve agent and blister agent simulants, surpassing that of its 3D counterparts. This discovery of the 3D‐to‐2D transition growth pathway unlocks exciting opportunities for exploring novel strategies in advanced MOF nanostructure development, not only for catalysis but also for various other applications. [ABSTRACT FROM AUTHOR]

The development of porous adsorbents for removing hazardous chemicals is of paramount significance in mitigating the risks posed by these substances. Among these hazardous chemicals, chemical warfare agents (CWAs) are of primary concern due to their significant threat. Here, we report the development of porous metal–organic framework‐based adsorbents designed to efficiently adsorb CWA simulant, particularly during the early stages of exposure. We selected MIL‐68, which has a rigid Kagomé structure, as a model system for investigating the adsorption of 2‐chloroethyl ethyl sulfide (CEES). The introduction of a dangling hydroxyl (OH) group within the MIL‐68 framework significantly enhances CEES adsorption during the early stages of exposure to CEES vapors. However, it is crucial to note that an excessive presence of dangling OH groups can negatively impact adsorption ability. Therefore, it is imperative to carefully control the amount of dangling OH groups introduced into the MIL‐68 framework to optimize CEES adsorption performance. [ABSTRACT FROM AUTHOR]

Chemical warfare agents pose a serious threat due to their extreme toxicity, necessitating swift the identification of chemical gases and individual responses to the identified threats. Fourier transform infrared (FTIR) spectroscopy offers a method for remote material analysis, particularly in detecting colorless and odorless chemical agents. In this paper, we propose a deep neural network utilizing a semi-supervised autoencoder (SSAE) for the classification of chemical gases based on FTIR spectra. In contrast to traditional methods, the SSAE concurrently trains an autoencoder and a classifier attached to a latent vector of the autoencoder, enhancing feature extraction for classification. The SSAE was evaluated on laboratory-collected FTIR spectra, demonstrating a superior classification performance compared to existing methods. The efficacy of the SSAE lies in its ability to generate denser cluster distributions in latent vectors, thereby enhancing gas classification. This study established a consistent experimental environment for hyperparameter optimization, offering valuable insights into the influence of latent vectors on classification performance.

A facile, safe, and scalable method for fabricating electrically conductive-reduced graphene oxide (rGO) e-fabric using a plasma-assisted coating process has been demonstrated. A wearable sensor based on rGO e-fabric was fabricated and used to detect and distinguish deadly chemical warfare agents (CWAs). The rGO e-fabric-based CWA sensor exhibited consistent responses upon repeated exposure to chemicals, including dimethyl methylphosphonate (DMMP) and soman (GD), which is a nerve agent. A difference in responses of the sensor toward GD and DMMP was observed. Theoretical studies further confirmed the potential of the as-prepared device as an e-fabric sensor for the detection of nerve agents. This novel functional e-fabric holds promise for future applications of wearable chemical agent sensors in smart personal protective suits. [ABSTRACT FROM AUTHOR]

Field-level exercises with the purpose to assess remediation following the deliberate release of a highly toxic chemical in an indoor environment can be conducted using low-(er) toxicity simulants if they are closely linked to the behavior of the toxic chemical itself. Chemical warfare agent (CWA) simulants have been identified on their suitability based on chemical structural similarities and associated physical and chemical properties. However, there are no reported studies that combine measurement of simulant parameters like persistence on surfaces, ability to sample for, and capability to degrade during the decontamination phase such that the level of success of a field-level exercise can be quantified. Experimental research was conducted to assess these gaps using a select number of CWA simulants. The organophosphate pesticide malathion was found to be a suitable simulant for use in field-level exercises that simulate the release of the highly persistent nerve agent VX based on its high persistence, effective surface sampling and analysis using standard analytical equipment, and the in situ degradation in the presence of different oxidizing decontaminants. [ABSTRACT FROM AUTHOR]

The destruction of chemical warfare agents (CWAs) is a crucial area of research due to the ongoing evolution of toxic chemicals. Metal–organic frameworks (MOFs), a class of porous crystalline solids, have emerged as promising materials for this purpose. Their remarkable porosity and large surface areas enable superior adsorption, reactivity, and catalytic abilities, making them ideal for capturing and decomposing target species. Moreover, the tunable networks of MOFs allow customization of their chemical functionalities, making them practicable in personal protective equipment and adjustable to dynamic environments. This review paper focuses on experimental and computational studies investigating the removal of CWAs by MOFs, specifically emphasizing the removal of nerve agents (GB, GD, and VX) via hydrolysis and sulfur mustard (HD) via selective photooxidation. Among the different MOFs, zirconium-based MOFs exhibit extraordinary structural stability and reusability, rendering them the most promising materials for the hydrolytic and photooxidative degradation of CWAs. Accordingly, this work primarily concentrates on exploring the intrinsic catalytic reaction mechanisms in Zr-MOFs through first-principles approximations, as well as the design of efficient degradation strategies in the aqueous and solid phases through the establishment of Zr-MOF structure–property relationships. Recent progress in the tuning and functionalization of MOFs is also examined, aiming to enhance practical CWA removal under realistic battlefield conditions. By providing a comprehensive overview of experimental findings and computational insights, this review paper contributes to the advancement of MOF-based strategies for the destruction of CWAs and highlights the potential of these materials to address the challenges associated with chemical warfare. [ABSTRACT FROM AUTHOR]

Chemical warfare agents (CWAs) are one of the most toxic compounds. Degradation of CWAs using decontamination agents is one of the few ways to protect human health against the harmful effects of CWAs. A ferrate (VI)-based potential chemical warfare agent decontaminant was studied for the degradation of persistent nitrogen mustard (tris(2-chloroethyl)amine, HN3). By optimizing the reaction conditions, the complete degradation of HN3 was achieved in 4 min. The degradation products contained mostly reduced Fe species, which confirmed the environmental friendliness of the proposed decontamination solution. [ABSTRACT FROM AUTHOR]

Handheld Raman spectrometers are commonly used as fast detectors for preliminary noncontact analysis of a number of chemicals. The article deals with their possible use for military identification of chemical warfare agents and their precursors. Spectra of 29 chemical substances were recorded. Based on the similarity of the spectra in the library, the device was able to automatically detect 20 substances in all measurement methods, 1 substance only in the most transparent containers. By means of external software and the creation of a user’s library, the vibrations of functional groups in the respective molecules were assigned to the individual Raman bands, thereby creating a database that enables the identification of toxic substances. [ABSTRACT FROM AUTHOR]

New and efficient sensors of nerve agents are urgently demanded to prevent them from causing mass casualties in war or terrorist attacks. So, in this work, a novel hierarchical nanoheterostructure was synthesized via the direct growth of α-Fe2O3 nanorods onto multiwall carbon nanotube (MWCNT) backbones. Then, the composites were functionalized with hexafluoroisopropanol (HFIP) and successfully applied to detect dimethyl methylphosphonate (DMMP)-sarin simulant gas. The observations show that the HFIP-α-Fe2O3@MWCNT hybrids exhibit outstanding DMMP-sensing performance, including low operating temperature (220 °C), high response (6.0 to 0.1 ppm DMMP), short response/recovery time (8.7 s/11.9 s), as well as low detection limit (63.92 ppb). The analysis of the sensing mechanism demonstrates that the perfect sensing performance is mainly due to the synergistic effect of the chemical interaction of DMMP with the heterostructure and the physical adsorption of DMMP by hydrogen bonds with HFIP that are grafted on the α-Fe2O3@MWCNTs composite. The huge specific surface area of HFIP-α-Fe2O3@MWCNTs composite is also one of the reasons for this enhanced performance. This work not only offers a promising and effective method for synthesizing sensitive materials for high-performance gas sensors but also provides insight into the sensing mechanism of DMMP.

Novichok is the name given to the group of nerve agents created stealthily in the later phases of the Cold War by the Soviet Union. Constitute the fourth generation of chemical warfare agents; like other nerve agents, they are organophosphorus compounds designed to be incurable and undetectable. The mechanism of action is based on the non-competitive and irreversible inhibition of acetylcholinesterase. Due to their enormous toxicity, Novichoks have become attractive targets for terrorists. However, little information is known about the identity of nerve agents. Furthermore, these compounds have never been submitted to the Chemical Weapons Convention. Our article aspires to provide a general overview of Novichoks knowledge. As part of this, we reviewed the available literature data to answer the question, what are Novichoks? In addition to the physical and chemical properties of A-agents, synthesis, mechanism of action, and toxicity of nerve agents were also reviewed. We hope that this review will highlight the tremendous threat posed by nerve agents and will inspire further studies on the interdisciplinary aspects of these compounds. Highlights: Novichoks, an extremely life-threatening nerve agents. General overview of the information on Novichoks: physical and chemical properties, mechanism of action and toxicity data. Novichoks should be treated as a separate group of chemical warfare compounds due to their hazardous properties. [ABSTRACT FROM AUTHOR]

Lewisite (Military Code: L) is an arsenical vesicant chemical warfare agent (CWA) that was developed in the United States during World War I. Even though its use has not been documented in warfare, large stockpiles were created and still exist in various locations around the world. Given that large quantities exist as well as the relative straightforward process for its creation, Lewisite still presents itself as a serious threat agent. In this study, we examined the effects of Lewisite on human dermal equivalent tissues (EpiDerm™/EpiDerm™-FT) through the evaluation of cellular viability, histology, and multiomic analysis. • Exposure to Lewisite reduces dermal cellular viability in a dose- and time-dependent manner. • Lewisite induces a mix of apoptosis and necrosis in human dermal tissue. • Multiomic analysis of human dermal equivalent samples exposed to Lewisite. • Lewisite activates several S100 proteins in human dermal tissue. [ABSTRACT FROM AUTHOR]

Effective control of toxic gaseous pollutants being emitted into the atmosphere has posed a critical and urgent challenge to deal with global climate change, protect the environment and human health as well as achieve clean and sustainable development. There remains a continuous threat to our human life from various toxic gaseous chemicals. Traditional methods for removing toxic gases usually suffer from shortcomings, such as low-capacity, energy-intensive, waste generation, and high cost. Metal-organic frameworks (MOFs), architected by various metal centers and organic ligands, represent a new type of adsorbent, which could readily offer a promising solution to capturing toxic gases. In this review, we provide detailed insights of the recent progress made on the adsorptive capture performance of MOF materials towards several critical toxic gases, such as SO₂, NO₂, NH₃, H₂S, sarin, CNCl, and CO. Considering the working condition and mixture components, the adsorption performance of various toxic gases are critically assessed and sorted. By comparing different modification strategies of a series of MOFs and corresponding performance manifestations, we make attempts to delineate future research directions to improve the adsorptive capture performance of MOFs toward toxic gases for real industrial applications. [Display omitted] • MOFs offer a promising solution to adsorbing toxic gases under ppm-level concentrations. • Fundamental separation mechanisms of MOFs toward critical toxic gases, such as SO₂, NO₂, NH₃, etc., are elucidated. • Innovative strategies enhancing the adsorptive gas separation performance of MOFs at ppm concentrations are pinpointed. • Future research directions for MOFs toward real industrial toxic gas separation applications are envisioned. [ABSTRACT FROM AUTHOR]

In light of the recent threat from chemical warfare agents (CWAs), the scientific community has focused extensively on developing effective and safe decontamination methodology for CWAs based on environmentally benign technology and the avoidance of corrosive and toxic chemicals. Herein, we report the decomposition of CWAs sarin and sulphur mustard on the hybrid material Zirconium hydroxide-granular activated carbon i.e. Zr(OH) 4 @GAC which is synthesized by utilizing the reactive zirconium hydroxide and high surface area carbon. In-situ zirconium hydroxide was generated in the pores of GAC by varying the precursor concentration i.e. zirconium oxychloride followed by hydrolysis. The morphology, structural, and textural properties of the reactive hybrid material Zr(OH) 4 @GAC were examined using several analytical techniques including powder x-ray diffraction, TGA, FT-IR, BET, SEM, EDX, and TEM. Furthermore, the degradation capability of Zr(OH) 4 @GAC was evaluated in the hydrolytic abatement of CWAs sarin and sulphur mustard. Under pristine laboratory conditions, the effectiveness of reactive hybrid material Zr(OH) 4 @GAC has been attributed due to a combination of defects and diverse surface hydroxyl species of Zr(OH) 4 , as well as a high surface area carbon matrix. The impact of water content and temperature on CWAs degradation was also investigated by altering the water percentage from 2 to 8 % and the temperature 25 °C to 45 °C. The GC–MS/GC technique was used to observe the kinetics of in-situ degradation of CWAs over Zr(OH) 4 @GAC The results indicated that the degradation process follows a first-order reaction kinetics. It is observed that higher water content along with elevated temperature enhance CWA decomposition on Zr(OH) 4 @GAC; conversely, at lower temperature, it slowed down the degradation of CWAs. This significant enhancement in the decontamination capability of hybrid materials Zr(OH) 4 @GAC towards CWAs was attributed to the synergistic effects of GAC (adsorption capacity) coupled with the reactive functional group of Zr(OH) 4. This strategy will pave the way for the development of self-detoxifying adsorbent material for environmental and defence purposes. [Display omitted] [ABSTRACT FROM AUTHOR]

The contamination of materials in urban areas by chemical weapons is a critical issue, especially as these materials can serve as key evidence in forensic investigations. Concrete, commonly found in urban environments, is highly porous and can retain chemical residues. However, its alkaline nature accelerates the degradation of chemical warfare agents, complicating the recovery of usable evidence. This study explores the recovery and persistence of alcohols and thiols, final degradation products of nerve and blistering agents, from two types of concrete matrices: lightweight concrete formworks and dense, steel-reinforced concrete blocks. Using an optimized method, uncrushed concrete fragments (up to 85 g) were extracted with acetone, monitoring two critical parameters: apparent recovery and persistence. The influence of external conditions, such as water addition, temperatures between 5°C and 35°C, and varying airflow speeds (1.7-5.1 m·s -1 ), was systematically evaluated. Reference conditions involved dried concrete at 22°C with no airflow. The findings revealed that alcohol recovery aligned with the volatility of the compounds, with denser concrete exhibiting lower recoveries but greater persistence. Thiols quickly converted to disulfides. Notably, temperature and moisture had the most profound effects on the recovery and persistence of the chemicals. These results highlight the importance of considering environmental factors when assessing chemical warfare agents and their degradation products in concrete, offering insights relevant to forensic science, environmental safety, and military defense. The study demonstrates how concrete's properties and external conditions can alter the forensic traceability of chemical contaminants., (© 2024 John Wiley & Sons Ltd.)

Ammunitions containing toxic chemical warfare agents (CWAs) that were seized from Germany at the end of World War II were disposed mainly by sea-dumping in the Skagerrak Strait and the Baltic Sea. In an area located 25 nautical miles south-east of Arendal, Norway, several ships carrying cargo of chemical munitions were scuttled. Previous investigations have revealed that CWAs are leaking from containers and munitions into surrounding sediments in the area, raising concerns of bioaccumulation of these chemicals in marine biota. In this study, Hagfish (Myxine glutinosa) was used as a model animal to investigate uptake of phenylarsenic CWAs by marine biota caught from the dumping area outside Arendal. Two laboratories analysed hagfish samples for primary degradation products of the phenylarsenic chemicals Clark I/II, namely diphenylarsinic acid and triphenylarsine oxide which have been previously found in sediment samples from the same area. The investigation showed that studied chemicals, originating from leaking munitions, are bioaccumulating in hagfish. These results support earlier findings of bioaccumulation of CWA-related phenylarsenic chemicals in different marine biota species living in the vicinity of dumping areas with increasing concern on environmental impacts caused by marine munitions. In addition, a novel biotransformation product of Clark I/II, methyldiphenylarsine oxide (MDPAO) was detected in studied fish samples for the first time. Based on findings reported in this study, biotransformation products of phenylarsenic CWAs should be considered as target chemicals in future evaluations of CWA exposure in marine biota. As the information on bioaccumulation and biological effects of CWAs in marine species are narrow, results gained in this study are essential for risk assessment related to marine munitions, as well as for future monitoring campaigns., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024. Published by Elsevier Ltd.)

The destruction of chemical warfare agents (CWAs) is a crucial area of research due to the ongoing evolution of toxic chemicals. Metal–organic frameworks (MOFs), a class of porous crystalline solids, have emerged as promising materials for this purpose. Their remarkable porosity and large surface areas enable superior adsorption, reactivity, and catalytic abilities, making them ideal for capturing and decomposing target species. Moreover, the tunable networks of MOFs allow customization of their chemical functionalities, making them practicable in personal protective equipment and adjustable to dynamic environments. This review paper focuses on experimental and computational studies investigating the removal of CWAs by MOFs, specifically emphasizing the removal of nerve agents (GB, GD, and VX) via hydrolysis and sulfur mustard (HD) via selective photooxidation. Among the different MOFs, zirconium-based MOFs exhibit extraordinary structural stability and reusability, rendering them the most promising materials for the hydrolytic and photooxidative degradation of CWAs. Accordingly, this work primarily concentrates on exploring the intrinsic catalytic reaction mechanisms in Zr-MOFs through first-principles approximations, as well as the design of efficient degradation strategies in the aqueous and solid phases through the establishment of Zr-MOF structure–property relationships. Recent progress in the tuning and functionalization of MOFs is also examined, aiming to enhance practical CWA removal under realistic battlefield conditions. By providing a comprehensive overview of experimental findings and computational insights, this review paper contributes to the advancement of MOF-based strategies for the destruction of CWAs and highlights the potential of these materials to address the challenges associated with chemical warfare.

Chemical warfare agents (CWAs) are one of the most toxic compounds. Degradation of CWAs using decontamination agents is one of the few ways to protect human health against the harmful effects of CWAs. A ferrate (VI)-based potential chemical warfare agent decontaminant was studied for the degradation of persistent nitrogen mustard (tris(2-chloroethyl)amine, HN3). By optimizing the reaction conditions, the complete degradation of HN3 was achieved in 4 min. The degradation products contained mostly reduced Fe species, which confirmed the environmental friendliness of the proposed decontamination solution.

Activated carbon fibers (ACFs) are extensively used to adsorb chemical warfare agents, including nerve agents. Cellulose-based materials are attractive precursors due to their low cost and abundant availability. However, the influence of the precursor material and fabric structure on the adsorption efficiency of ACFs remains unclear. This study investigates cellulose-based ACFs produced from different precursor materials and fabric structures, tested against the nerve agent simulant, dimethyl methylphosphonate (DMMP) to evaluate their adsorption capabilities. Cotton-based ACFs exhibited considerably higher specific surface area than lyocell-based ACFs, attributed to the higher molecular weight and crystallinity of cotton. Additionally, woven-type ACFs exhibited superior adsorption performance compared to commercial felt-type ACFs due to reduced DMMP migration, which prolonged contact time with adsorption sites. Reducing yarn diameter improved the adsorption performance by lowering the bed void fraction of the adsorption column and facilitating smoother DMMP penetration to the fiber's central region within the yarn. These findings offer valuable insights for applying cellulose-based ACFs in protective clothing against nerve agents. [Display omitted] • The most specific surface area of ACF, ever reported, with 3372 m2/g. • Cotton exhibited higher specific surface area as an ACF precursor than lyocell. • Woven-type ACFs exhibited superior adsorption performance compared to felt-type ACFs. • Smaller yarn diameters exhibited enhanced adsorption performance. [ABSTRACT FROM AUTHOR]

In this study, a potentiometric sensor was developed for the analysis of the parahtion which is a nerve agent simulant and pesticide. A molecularly imprinted polymer was used as the recognition layer in the electrode used in the potentiometric sensor. Parathion is also used as both an organophosphorus pesticide and a nerve agent simulant. For this reason, analysis methods to be developed for parathion are very important. The most important advantages brought by MIP-based sensor systems are; fast analysis, sensitive analysis, and the ability to analyze at very low concentrations. The sensor developed in our study was validated for parathion adsorption. In our study, first, Parathion imprinted polymers were synthesized. The synthesized MIPs are used as the recognition layer in the potentiometric sensor. The characterization of parathion imprinted polymers was done by FESEM, FT-IR, and zeta-sizer measurements. Optimization of the working conditions was carried out for the developed sensor system. The working pH was found to be 7.4.Measurements were taken for parathion samples with different concentrations under optimum operating conditions. When the results obtained were examined, a large linear range (10-8-10-4 mol L-1) and a satisfying detection limit against parathion (1.86 × 10-8 mol L-1) were calculated. Interference effect analysis was carried out within the scope of the performance tests of the potentiometric sensor. The analysis showed that interference did not affect the experimental results. In order to examine the matrix effect of the real sample environment, analyses were carried out in tap water and lake water. The recovery values in the analysis results are quite good. The results of the experiments show that the sensor we have developed can be used successfully in complex matrix environments. [ABSTRACT FROM AUTHOR]

The biocatalyzed oxidative detoxification of the V-series simulant PhX, by mean of the microperoxidase AcMP11, affords the corresponding phosphonothioate as the prominent product instead of the classical P-S and P-O bond cleavage. While PhX is structurally very close to the live agent VX (the methyl group is replaced by a phenyl), assessment with other surrogates missing the nucleophilic amino function displayed more resistance under the same conditions with no phosphonothioate observed. These encouraging results highlight 1) the efficacy of AcMP11 microperoxidase to efficiently detoxify V-series organophosphorus nerve agents (OPNA), and 2) the necessity to use representative alkyl or aryl phosphonothioates simulants such as PhX bearing the appropriate side chain as well as the P-O and P-S cleavable bond to mimic accurately the V-series OPNA to prevent false positive or false negative results., (© 2024 The Authors. ChemBioChem published by Wiley-VCH GmbH.)

The application of ultraviolet (UV) light for the decontamination of chemical warfare agents (CWAs) has gained recognition as an effective method, especially for treating hard-to-reach areas where wet chemical methods are impractical. In this study, TiO 2 /Ti was employed as a model catalyst, which was contaminated with 2-chloroethyl phenyl sulfide (CEPS), and subjected to photocatalytic decontamination using both UVB and UVC light. Additionally, photocatalytic decontamination efficiency by introducing Au, Pt, and Cu onto the TiO 2 /Ti surface was explored. During the photodecomposition process under UVC light, at least eight distinct secondary byproducts were identified. It was observed that the introduction of overlayer metals did not significantly enhance the photodecomposition under UVC light instead overlaid Au exhibited substantially improved activity under UVB light. Whereas, photodecomposition process under UVB light, only five secondary products were detected, including novel compounds with sulfoxide and sulfone functional groups. This novel study offers valuable insights into the generation of secondary products and sheds light on the roles of overlayer metals and photon wavelength in the photodecontamination process of CWA., (© 2024 The Authors. ChemistryOpen published by Wiley-VCH GmbH.)

Sulfur mustard (SM, bis[2‐chloroethyl]‐sulfide) is a banned chemical warfare agent that was frequently used in recent years and led to numerous poisoned victims who developed painful erythema and blisters. Post‐exposure analysis of SM incorporation can be performed by the detection of human serum albumin (HSA)‐derived peptides. HSA alkylated by SM contains a hydroxyethylthioethyl (HETE)‐moiety bound to the cysteine residue C34 yielding the dipeptide biomarker C(‐HETE)P after pronase‐catalyzed proteolysis. We herein present a novel procedure for the selective precolumn nicotinylation of its N‐terminus using 1‐nicotinoyloxy‐succinimide. The reaction was carried out for 2 h at ambient temperature with a yield of 81%. The derivative NA‐C(‐HETE)P was analyzed by micro liquid chromatography‐electrospray ionization tandem‐mass spectrometry working in the selected reaction monitoring mode (μLC‐ESI MS/MS SRM). The derivative was shown to be stable in the autosampler at 15°C for at least 24 h. The single protonated precursor ion (m/z 428.1) was subjected to collision‐induced dissociation yielding product ions at m/z 116.1, m/z 137.0, and m/z 105.0 used for selective monitoring without any plasma‐derived interferences. NA‐C(‐HETE)P showed a mass spectrometric response superior to the non‐derivatized dipeptide thus yielding larger peak areas (factor 1.3 ± 0.2). The lower limit of identification corresponded to 80 nM SM spiked to plasma in vitro. The presented procedure was applied to real case plasma samples from 2015 collected in the Middle East confirming SM poisoning. [ABSTRACT FROM AUTHOR]

Sulfur mustard (SM) is a banned chemical warfare agent recently used in the Syrian Arab Republic conflict causing erythema and blisters characterized by complicated and delayed wound healing. For medical and legal reasons, the proof of exposure to SM is of high toxicological and forensic relevance. SM reacts with endogenous human serum albumin (HSA adducts) alkylating the thiol group of the cysteine residue C34, thus causing the addition of the hydroxyethylthioethyl (HETE) moiety. Following proteolysis with pronase, the biomarker dipeptide C(-HETE)P is produced. To expand the possibilities for verification of exposure, we herein introduce a novel biomarker produced from that alkylated dipeptide by derivatization with propionic anhydride inducing the selective propionylation of the N-terminus yielding PA-C(-HETE)P. Quantitative derivatization is carried out at room temperature in aqueous buffer within 10 s. The biomarker was found to be stable in the autosampler at 15 °C for at least 24 h, thus documenting its suitability even for larger sets of samples. Selective and sensitive detection is done by micro liquid chromatography-electrospray ionization tandem-mass spectrometry (μLC-ESI MS/MS) operating in the selected reaction monitoring (SRM) mode detecting product ions of the single protonated PA-C(-HETE)P (m/z 379.1) at m/z 116.1, m/z 137.0, and m/z 105.0. The lower limit of detection corresponds to 32 nM SM in plasma in vitro and the limit of identification to 160 nM. The applicability to real exposure scenarios was proven by analyzing samples from the Middle East confirming poisoning with SM. [ABSTRACT FROM AUTHOR]

Oxide aerogels are pore–solid networks notable for their low density, large pore volume, and high surface area. This three-dimensional arrangement of pore and solid provides critical properties: the high surface area required to maximize the number of active sites and a through-connected porosity that plumbs reactants to the active interior. In decontamination applications where reactivity beyond adsorption is desired to degrade deleterious molecules, oxide aerogels offer multiple avenues to add oxidative power to this unique arrangement of pore and solid. For protection against chemical warfare agents or toxic industrial chemicals, metal-oxide aerogels with their oxide/hydroxide surfaces afford stability under ambient conditions against competing sorbents such as water and oxygen. In this review, strategies to maximize sorptive capacity and degradation rate by modifying surface functionality, compositing with dissimilar oxides, or adding metallic nanoparticles and the subsequent impact on decontamination performance will be summarized and expected directions for future research will be discussed based on the observed trends.

A low-cost differential mobility spectrometer (DMS) was constructed using polytetrafluoroethylene printed circuit boards with two pairs of gold electrodes. The printed circuit boards were used to construct the drift tube into which the gas samples are introduced by a carrier gas and ionized. The ionized gas moves toward the gold electrode to which an asymmetric voltage is applied. Only the ionized gas with the proper ion mobility leaves the electrode region and reach the detection electrodes to form the ion current. Traces of five chemical warfare agents, including dimethyl methylphosphonate, triethylamine, 2-diisopropylaminoethanol, diethylaminoethanol, and N, N-dimethylethanolamine, were prepared using the permeation tube method and introduced into the sensor. All of the chemicals show characteristic ion peak shifts in the electric field. The limits of detection for the analytes are less than 1 ng/L. The recovery time was less than 10 s and the response time is 2 s. The developed sensor exhibits the ability to detect and distinguish between these chemical warfare agents. [ABSTRACT FROM AUTHOR]

The primary aim of this study was to identify biomarkers of exposure to some so-called Schedule 1 sulfur mustard (HD) analogues, in order to facilitate and expedite their retrospective analysis in case of alleged use of such compounds. Since these HD analogues can be regarded as model compounds for possible impurities of HD formed during synthesis processes, the secondary aim was to explore to which extent these biomarkers can be used for chemical provenancing of HD in case biomedical samples are available. While the use of chemical attribution signatures (CAS) for neat chemicals or for environmental samples has been addressed quite frequently, the use of CAS for investigating impurities in biomedical samples has been addressed only scarcely. Human plasma was exposed to each of the five HD analogues. After pronase or proteinase K digestion of precipitated protein and sample work-up, the histidine (His) and tripeptide (CPF) adducts to proteins were analyzed, respectively. Adducts of the analogues could still be unambiguously identified next to the main HD adducts in processed plasma samples after exposure to HD mixed with each of the analogues, at a 1% level relative to HD. In conclusion, we have identified plasma protein adducts of a number of HD analogues, which can be used as biomarkers to assess an exposure to these Schedule 1 chemicals. We have shown that adducts of these analogues can still be analyzed after work-up of plasma samples which had been exposed to these analogues in a mixture with HD, supporting the hypothesis that biomedical sample analysis might be useful for chemical provenancing. [ABSTRACT FROM AUTHOR]

Organophosphorus (OP) chemical warfare agents (CWAs) represent an ongoing global threat, through either purposeful environmental release or the need to dispose of historic stockpiles. This presents a need for the development of novel decontamination technologies. Due to the toxic nature and legal limitations placed on OP CWAs, the use of appropriate OP simulants that mimic the reactivity but not the toxicity of the agents themselves is vital to decontamination studies. Herein, we show that association constants derived from non-specific hydrogen bonded complexation events may be used as parameters within models to predict simulant reactivity. We also discuss the limitations that should be placed on such data. [ABSTRACT FROM AUTHOR]

Deployable chemical laboratories are considered a highly specific part of the Armed Forces of the Czech Republic, intended for Chemical, Biological, Radiological and Nuclear Defence in operations. Their professional activity is determined by a number of scientific and technical requirements, which are formulated by standards for sample identification. To achieve the required degree of credibility, it is particularly important to have specific technical capacities. This instrumentation is crucial for the implementation of laboratory analyzes. The article describes the state of chemical laboratories of the Chemical Corps in the context of standardized requirements and discusses some points of selected Alliance agreements which the Armed Forces of the Czech Republic have signed. [ABSTRACT FROM AUTHOR]

Ideal mixed‐matrix composites fabricated from metal–organic frameworks (MOFs) and polymers should exhibit good compatibility between components, high adsorptivity, and fast and efficient reactivity. Often, poor compatibility between MOFs and polymers results in interfacial defects, which lead to underperforming materials. In this work the MOF UiO‐66‐NH2 was modified using various acyl chlorides to tailor MOF compatibility and dispersion within mixed‐matrix composites and electrospun fibers to enable better protective suits and filters. MOF crystal structures were unaffected and high surface areas were present after acyl chloride treatment. Most treated MOFs had increased reactivity towards soman (GD) and the simulant dimethyl p‐nitrophenylphosphate relative to the baseline MOF, and this enhanced reactivity was probably because of better wetting behavior towards the agents. Chlorine and 2‐chloroethyl ethyl sulfide uptake of modified MOFs was similar to uptake in the baseline MOF, while nitrogen dioxide and GD sorption capacity decreased for all modified MOFs due to exhaustion of amine sites and pore blockage, respectively. Overall, modification of the MOF with acyl chlorides resulted in better polymer compatibility, retained adsorption capacity for multiple chemicals and even increased reactivity towards GD. The structure–activity processing insights gained from this work will lead to the design of more effective protection equipment such as filters, clothing/suits and membranes. Published 2020. This article is a U.S. Government work and is in the public domain in the USA [ABSTRACT FROM AUTHOR]

Phosgene is a gas crucial to industrial chemical processes with widespread production (∼1 million tons/year in the USA, 8.5 million tons/year worldwide). Phosgene's high toxicity and physical properties resulted in its use as a chemical warfare agent during the First World War with a designation of CG ('Choky Gas'). The industrial availability of phosgene makes it a compound of concern as a weapon of mass destruction by terrorist organizations. The hydrophobicity of phosgene exacerbates its toxicity often resulting in a delayed toxidrome as the upper airways are moderately irritated; by the time symptoms appear, significant damage has occurred. As the standard of care for phosgene intoxication is supportive therapy, a pressing need for effective therapeutics and treatment regimens exists. Proposed toxicity mechanisms for phosgene based on human and animal exposures are discussed. Whereas intermediary components in the phosgene intoxication pathways are under continued discussion, generation of reactive oxygen species and oxidative stress is a common factor. As animal models are required for the study of phosgene and for FDA approval via the Animal Rule; the status of existing models and their adherence to Haber's Rule is discussed. Finally, we review the continued search for efficacious therapeutics for phosgene intoxication; and present a rapid post-exposure response that places exogenous human heat shock protein 72, in the form of a cell-penetrating fusion protein (Fv-HSP72), into lung tissues to combat apoptosis resulting from oxidative stress. Despite significant progress, additional work is required to advance effective therapeutics for acute phosgene exposure. [ABSTRACT FROM AUTHOR]

Hydrogen peroxide (H 2 O 2 ) is a highly effective decontaminant against chemical warfare agents (CWAs) when present both in a liquid and as a solid powder. For the latter, this can be in the form of H 2 O 2 being complexed to a polymer, such as polyvinylpyrrolidone (PVP). While a H 2 O 2 -PVP complex is indeed effective at decontaminating CWAs, it is vulnerable to environmental conditions such as high relative humidities (RH), which can dissociate the H 2 O 2 from the complex before it is given the opportunity to react with CWAs. In this paper, we demonstrate that the cross-linked version of PVP forms a highly stable complex with H 2 O 2 , which can withstand both high (40 °C) and low (-20 °C) temperatures as well as maintain stability at high RH up to 90% over several days. Collectively, this lays the framework for processing the H 2 O 2 -PVP complex in a variety of form factors that can maintain efficacy under a wide range of real-world environmental conditions.

Abstract AEOL-10150 is a broad-spectrum metalloporphyrin superoxidase dismutase (SOD) mimic specifically designed to neutralize reactive oxygen and nitrogen species. Research has shown that AEOL-10150 is a potent medical countermeasure against national security threats including sulfur mustard (SM), nerve agent exposure and radiation pneumonitis following a radiological/nuclear incident sufficient to cause acute radiation syndrome (ARS). AEOL-10150 performed well in animal safety studies, and two completed phase 1 safety studies in patients demonstrated that the drug was safe and well tolerated, indicating that AEOL-10150 has potential as a new catalytic antioxidant drug. In this article, we review improvements in AEOL-10150 in preclinical pharmacodynamic studies, especially regarding anti-SM, chlorine gas and radiation exposure studies.

New materials and chemical knowledge for improved personal protection are among the most pressing needs in the international community. Reported attacks using chemical warfare agents (CWAs,) including organophosphate soman (GD) and thioether mustard gas (HD) are driving research in field‐deployable catalytic composites for rapid toxin degradation. In this work, we report simple template‐free low temperature synthesis that enables for the first time, a deployable‐structured catalytic metal‐organic framework/polymer textile composite "MOF‐fabric" showing rapid hydrolysis and oxidation of multiple active chemical warfare agents, GD and HD, respectively, and their simulants. Our method yields new zirconium–porphyrin based nano‐crystalline PCN‐222 MOF‐fabrics with adjustable MOF loading and robust mechanical adhesion on low‐cost nonwoven polypropylene fibers. Importantly, we describe quantitative kinetic analysis confirming that our MOF‐fabrics are as effective as or better than analogous MOF powders for agent degradation, especially for oxidation. Faster oxidation using the MOF‐fabrics is ascribed to the composite geometry, where active MOF catalysts are uniformly displayed on the MOF‐textile enabling better reactant transport and reactive oxidant generation. Furthermore, we note the discovery of visible photo‐activation of GD hydrolysis by a MOF‐fabric, which is ascribed to oxidation at the active metal node site, significantly increasing the rate over that observed without illumination. These results provide important new insights into the design of future materials and chemical systems to protect military, first‐responders, and civilians upon exposure to complex chemical toxins. [ABSTRACT FROM AUTHOR]

The threat from chemical warfare agents (CWAs) imparts an alarming call for the global community not limited to human being but also extends as unprecedented environmental threat, hence, timely detection and degradation in the event of CWAs attack is very crucial. Herein, we describe a hybrid material of 3‐aminopropyltriethoxysilane (APTES) modified graphene oxide (GO) on glassy carbon (GC) electrode along with electrodeposited silver nanodendrimers (AgNDs) for the electrochemical detection and degradation of CWA sulphur mustard (HD). The AgNDs/APTES‐GO hybrid material was characterized by SEM, EDX, BET, TGA, Raman, UV‐Vis, XPS and XRD techniques. The AgNDs/APTES‐GO modified GC electrode was also characterized by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). Electrochemical studies indicated presence of electrocatalysis owing to the synergistic effect of AgNDs and GO for sensing CWA HD via reductive dehalogenation. The AgNDs/APTES‐GO modified GC electrode exhibited linearity for CWA HD from 5.3 μM to 42.4 μM. Constant potential electrolysis was performed with modified electrode and degradation products were analysed using GC‐MS, highlighting the great potential of graphene based hybrid material. This new strategy provides an opportunity for the development of "detect and destroy" system for the CWAs and other environmental toxic pollutant, which could help in mitigation of on‐ site events for first responders. [ABSTRACT FROM AUTHOR]

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High-efficiency decomposition technology for volatile chemical warfare agent sarin was developed using a dielectric-barrier discharge (DBD). The power consumptions of the developed device for which the gap lengths of the plasma-generation sites were 1.0–2.0 mm, were found to be 22–27 W, respectively. The DBD driven sarin-decomposition amount per unit time and the decomposition efficiency in the optimized condition were obtained to be 2.05 × 10−3 mg/s and 1.38 × 10−4 mg/W, respectively, measured by ion mobility spectrometer. Sarin-decomposition products were investigated using a gas chromatography–mass spectrometry with tert-butyldimethylsilylation derivatization, indicating that isopropyl methylphosphoric acid (IMPA), methylphosphoric acid (MPA), and phosphoric acid (PA) were generated during sarin decomposition by DBD. The decomposition efficiency at 37 W decreased by 41% molar concentration compared with that at 15 W, but the production levels of IMPA, MPA and PA were changed from 10.0%, 41.5% and 3.9% to 7.2%, 21.3% and 6.4%, respectively. [ABSTRACT FROM AUTHOR]

Agent BZ (3‐quinuclidinyl benzilate) is a centrally acting synthetic anticholinergic agent, considered as a potential military incapacitating chemical warfare agent. Despite its significance as a model compound in pharmacological research and its potential misuse in chemical attacks, few modern analytical methods for BZ determination in biological samples have been published. The goal of the present work is to develop and validate a sensitive and rapid LC–MS/MS method for the determination of agent BZ in rat plasma. The sample preparation was based on solid‐phase extraction on C‐18 cartridges. The reversed‐phase HPLC coupled with the mass spectrometer with electrospray ionization in the positive ion‐selective reaction monitoring mode was employed in the BZ analysis. Atropine was used as an internal standard. The presented method is selective, accurate, precise, and linear (r2 = 0.9947) in a concentration range from 0.5 ng/mL to 1 000 ng/mL and sensitive enough (limit of detection 0.2 ng/mL; limit of quantification 0.5 ng/mL) to determine the BZ plasma levels in rats exposed to 2 mg/kg and 10 mg/kg of BZ. The highest level of BZ in plasma was observed 5 minutes after intramuscular administration (154.6 ± 22.3 ng/mL in rats exposed to 2 mg/kg of BZ and 1024 ± 269 ng/mL in rats exposed to 10 mg/kg). After 48 h, no BZ was observed at detectable levels. This new method allows the detection and quantification of BZ in biological samples after exposure of an observed organism and it will be further optimized for other tissues to observe the distribution of BZ in organs. [ABSTRACT FROM AUTHOR]

A three-layered composite wipe was fabricated by laminating individual layers of non-woven polypropylene, activated carbon fabric (ACF) and aramid fabric for the sampling and investigation of chemical warfare agents (CWA)-contaminated urban porous and non-porous surfaces. The material of main ACF layer was characterized to ascertain its suitability to act as an efficient adsorbent for the surface wipe sampling. The performance of ACF-based composite wipe was determined by evaluating its extraction efficiency, wiping efficacy and adsorption capacity for the sampling of blister and nerve agent class of CWA-contaminated surfaces using gas chromatography-mass spectrometry (GC-MS). Parameters like amount of wipe required, solvent selection, amount of solvent, time of extraction etc. were optimized to achieve the maximum recovery of contaminating analytes required for the forensic investigations. Overall recoveries of contaminating analytes after sampling and extraction were found to be in the range of 45–85% for all types of surfaces. No breakthrough in wiping process was noticed up to contamination density (CD) 1.6 mg/cm2 for non-porous surface and 3.2 mg/cm2 for porous surfaces. ACF-based wipe was found capable to significantly reduce the vapour hazards from liquid sulphur mustard (HD) and sarin (GB). Contamination from surfaces could be preserved within the wipe up to 15 days for the extended forensic investigation purposes. Limit of detections (LOD) of contaminants was determined in the range of 0.8–6.8 ng/cm2 while limit of quantitation (LOQ) was achieved up to the range of 2.4–14.4 ng/cm2 for wipe sampling of different surfaces. [ABSTRACT FROM AUTHOR]