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The Chemical Communications journal, published by The Royal Society of Chemistry, features a variety of research articles on topics such as anion recognition, chemiluminescent systems, and ion-pair recognition. The journal includes contributions from researchers worldwide, covering areas like solar energy, biomedical advancements, and catalytic functionality. Articles in this issue discuss advancements in various chemical fields, including optical sensing, catalysis, and materials science, providing valuable insights for researchers and scholars in the chemistry community. [Extracted from the article]

A pillar[5]arene host, functionalised with halogen bonding (XB) recognition sites and BODIPY fluorophores, demonstrates strong binding and optical sensing of environmentally relevant dicarboxylates and a chemical warfare agent simulant, in organic and competitive aqueous-organic media – enabled by the unprecedented combination of fluorophore-conjugated XB interactions with the hydrophobic pillar[5]arene host cavity. [ABSTRACT FROM AUTHOR]

The risk of the use of toxic chemicals for unlawful acts has been a matter of concern for different governments and multilateral agencies. The Organisation for the Prohibition of Chemical Weapons (OPCW), which oversees the implementation of the Chemical Weapons Convention (CWC), considering recent events employing chemical warfare agents as means of assassination, has recently included in the CWC "Annex on Chemicals" some organophosphorus compounds that are regarded as acting in a similar fashion to the classical G- and V-series of nerve agents, inhibiting the pivotal enzyme acetylcholinesterase. Therefore, knowledge of the activity of the pyridinium oximes, the sole class of clinically available acetylcholinesterase reactivators to date, is plainly justified. In this paper, continuing our research efforts in medicinal chemistry on this class of toxic chemicals, we synthesized an A-230 nerve agent surrogate and applied a modified Ellman's assay to evaluate its ability to inhibit our enzymatic model, acetylcholinesterase from Electrophorus eel, and if the clinically available antidotes are able to rescue the enzyme activity for the purpose of relating the findings to the previously disclosed in silico data for the authentic nerve agent and other studies with similar A-series surrogates. Our experimental data indicates that pralidoxime is the most efficient compound for reactivating acetylcholinesterase inhibited by A-230 surrogate, which is the opposite of the in silico data previously disclosed. [ABSTRACT FROM AUTHOR]

The malfeasant usage of chemical warfare agents (CWAs) involved in the current world praxis poses a threat to humankind. Owing to their acute lethal toxicity, the pursuit of favorable approaches for their detoxification/degradation is making continuous progress. With this background, a series of UiO-66-NH2 metal–organic frameworks (MOFs) featuring structural defects were synthesized using a solvothermal technique by varying the modulator pKa, HCl modulator concentration, synthesis temperature and ligand ratio. The present study contributes additional evidence that the considered synthesis parameters outweigh the creation of an open framework in its own metrics. By fine tuning the synthesis practices, the formation of structural defects has been greatly induced. Furthermore, the impact of structural defects possessed by the synthesized samples was systematically investigated against methyl-paraoxon (DMNP), a CWA simulant. The coexistence of an amine group (–NH2) representing Brønsted basic sites, and Lewis acid sites of metal clusters in UiO-66-NH2 reveals a maximum conversion efficiency up to 93.6% with an ultrafast transient degradation rate (k) and shorter half-lives of 1.567 min−1 and 0.44 min, respectively. [ABSTRACT FROM AUTHOR]

Organophosphorus nerve agents (OPNA) are hazardous environmental exposures to the civilian population and have been historically weaponized as chemical warfare agents (CWA). OPNA exposure can lead to several neurological, sensory, and motor symptoms that can manifest into chronic neurological illnesses later in life. There is still a large need for technological advancement to better understand changes in brain function following OPNA exposure. The human-relevant in vitro multi-electrode array (MEA) system, which combines the MEA technology with human stem cell technology, has the potential to monitor the acute, sub-chronic, and chronic consequences of OPNA exposure on brain activity. However, the application of this system to assess OPNA hazards and risks to human brain function remains to be investigated. In a concentration-response study, we have employed a humanrelevant MEA system to monitor and detect changes in the electrical activity of engineered neural networks to increasing concentrations of the sarin surrogate 4-nitrophenyl isopropyl methylphosphonate (NIMP). We report a biphasic response in the spiking (but not bursting) activity of neurons exposed to low (i.e., 0.4 and 4 μM) versus high concentrations (i.e., 40 and 100 μM) of NIMP, which was monitored during the exposure period and up to 6 days post-exposure. Regardless of the NIMP concentration, at a network level, communication or coordination of neuronal activity decreased as early as 60 min and persisted at 24 h of NIMP exposure. Once NIMP was removed, coordinated activity was no different than control (0 mM of NIMP). Interestingly, only in the high concentration of NIMP did coordination of activity at a network level begin to decrease again at 2 days post-exposure and persisted on day 6 post-exposure. Notably, cell viability was not affected during or after NIMP exposure. Also, while the catalytic activity of AChE decreased during NIMP exposure, its activity recovered once NIMP was removed. Gene expression analysis suggests that human iPSC-derived neurons and primary human astrocytes resulted in altered genes related to the cell's interaction with the extracellular environment, its intracellular calcium signaling pathways, and inflammation, which could have contributed to how neurons communicated at a network level. [ABSTRACT FROM AUTHOR]

In this study, the production of activated carbon from wheat bran was carried out using the chemical activation method. ZnCl2 was used as the chemical agent in the chemical activation. The impregnation ratio was used as 2:1, and the activation temperature was set to 500 °C. The activated carbon (WB-500) was used to remove the deep red dye substance from aqueous solutions. The outcome of the adsorption studies revealed that the highest adsorption capacity was attained when the adsorbent was exposed for 24 hours, maintained at a temperature of 45°C, and a pH of 2.17. The adsorption process effectively removed 95.238 mg with 1 g WB-500. Adsorption study was determined to follow the pseudo-second-order kinetic model and Langmuir isotherm. According to the second order, the adsorption rate increased from 1.22.10-4 to 3.43.10-4 with the increase in temperature from 25 °C to 45 °C. According to adsorption thermodynamics, adsorption is endothermic (ΔH0, 41.08 kj mol-1) and occurs physically and chemically forces. Activated carbon produced from wheat bran can effectively remove the Deep red dye substance from wastewater. [ABSTRACT FROM AUTHOR]

This review article comprehensively explores the electrochemical detection of organophosphate-based agents, including warfare agents, pesticides, and simulants. It provides an in-depth analysis of their molecular structures, emphasizing the inherent toxicity and environmental risks posed by these compounds. The review highlights the significant role of flexible sensors in facilitating the electrochemical detection of organophosphate-based agents, offering insights into their design, development, and application in detection methodologies. Additionally, the article critically evaluates the challenges encountered in this field, such as sensor sensitivity and sample complexity, and discusses potential solutions to address these challenges. Furthermore, it outlines the future scope and opportunities for advancement in electrochemical detection technologies, including the integration of novel materials and the exploration of innovative detection strategies. By synthesizing current research findings and identifying future research directions, this review contributes to the ongoing discourse on the detection and mitigation of organophosphate-based agents' risks to human health and the environment. [ABSTRACT FROM AUTHOR]

In this manuscript, we present in detail the design and implementation of the hardware and software to produce a standalone wireless sensor node, called SensorQ system, for the detection of a toxic chemical agent. The proposed wireless sensor node prototype is composed of a micro-controller unit (MCU), a radio frequency (RF) transceiver, a dual-band antenna, a rechargeable battery, a voltage regulator, and four integrated sensing devices, all of them integrated in a package with final dimensions and weight of 200 × 80 × 60 mm and 0.422 kg, respectively. The proposed SensorQ prototype operates using the Long-Range (LoRa) wireless communication protocol at 2.4 GHz, with a sensor head implemented on a hetero-core fiber optic structure supporting the surface plasmon resonance (SPR) phenomenon with a sensing section (L = 10 mm) coated with titanium/gold/titanium and a chemically sensitive material (zinc oxide) for the detection of Di-Methyl Methyl Phosphonate (DMMP) vapor in the air, a simulant of the toxic nerve agent Sarin. The transmitted spectra with respect to different concentrations of DMMP vapor in the air were recorded, and then the transmitted power for these concentrations was calculated at a wavelength of 750 nm. The experimental results indicate the feasibility of detecting DMMP vapor in air using the proposed optical sensor head, with DMMP concentrations in the air of 10, 150, and 150 ppm in this proof of concept. We expect that the sensor and wireless sensor node presented herein are promising candidates for integration into a wireless sensor network (WSN) for chemical warfare agent (CWA) detection and contaminated site monitoring without exposure of armed forces. [ABSTRACT FROM AUTHOR]

In a chemical mass casualty incident requiring skin decontamination, dry removal using absorbent materials may be beneficial to enable immediate decontamination. The efficacy of absorbent materials has therefore been evaluated, alone or procedures including both dry and wet decontamination, following skin exposure to two low volatile toxic chemicals using an in vitro human skin penetration model. Additionally, removal using active carbon wipes was evaluated with or without the Dahlgren Decon solution. All dry decontamination procedures resulted in a significantly decreased skin penetration rate of the industrial chemical 2‐butoxyethanol compared to the control without decontamination. Wet decontamination following dry absorption significantly improved the efficacy compared to dry removal alone. Dry decontamination post‐exposure to the chemical warfare nerve agent VX showed no decontamination efficacy. However, dry and wet decontamination resulted in a decreased agent skin penetration rate during the last hour of the experiment. At −15°C, significantly reduced VX skin penetration rates were demonstrated for both dry decontamination alone and the dry and wet decontamination procedure. The Dahlgren Decon solution significantly reduced the amount of VX penetrating the skin, but the active carbon wipe alone did not impact the skin penetration rate. In conclusion, absorbent materials are beneficial for the removal of low‐volatile chemicals from the skin, but the degree of efficacy varies between chemicals. Despite the variability, immediate dry decontamination using available absorbent materials prior to wet decontamination is recommended as a general procedure for skin decontamination. The procedure should also be prioritized in cold‐weather conditions to prevent patient hypothermia. Skin decontamination is important in a chemical mass casualty incident, including toxic, low‐volatile chemicals. In vitro human skin studies displayed the beneficial impact of dry decontamination prior to wet decontamination, however, the degree of efficacy varies post‐exposure to the industrial chemical 2‐butoxyethanol and the nerve agent VX. In cold air temperatures, dry removal was efficient post‐exposure to VX. Immediate dry removal using available absorbent materials prior to wet decontamination is therefore recommended as a general procedure for skin decontamination. [ABSTRACT FROM AUTHOR]

Chemical warfare agents (CWAs) are very toxic and dangerous to all forms of life. With the purpose of protecting environment and human health, it is essential to identify and eliminate these threats quickly and effectively. B38 nanocage as a sensor is rarely discussed therefore the detection of harmful CWAs (phosgene and thiophosgene) by using the B38 nanocage has been examined using density functional theory (DFT) parameters. Optimized geometries, adsorption energies, NCI, NBO, FMO and QTAIM studies have been used to analyze the interactions between CWAs and the B38 nanocage. The adsorption energy values indicate that CWAs are adsorbed on the B38 nanocage in a stable manner and the reaction is exothermic. The complex T-S@B38-B have the greatest conductivity, lowest stability and maximum sensitivity due to its narrow energy gap of 1.9648 eV while complex T-S@B38-6r, with the highest energy gap of 1.9988 eV is the most stable. The global reactivity parameters indicate that the complex T-S@B38-B has the highest electrophilicity index, the lowest chemical hardness and the highest chemical softness and resultantly leads to highest sensitivity. Van der Waals forces are present between the B38 nanocage and CWAs as shown by NCI and QTAIM studies. The formation of new energy level in PDOS of B38 results into the interaction of CWAs with the surface of B38. Nanocage sensing capacity is evaluated by measuring Eg value, sensitivity and recovery time of the complex. B38 has the highest sensitivity and shortest recovery time for T-S@B38-B and P-Cl@B38-B complex with 5.90 × 10−3 and 2.78259 × 10−12 s values which results the B38 nanocage is more effective sensor for detecting CWAs. Consequently, B38 nanocage is recommended as fine future sensor for the sensing of phosgene and thiophosgene. [ABSTRACT FROM AUTHOR]

Lewisite is a representative chemical warfare agent that contains arsenic. Thermal decomposition is an essential method for Lewisite destruction, and appropriate destruction conditions can enhance the environmental friendliness of this method by minimizing the hazards of destruction products. In this study, the variation of Lewisite during pyrolysis and incineration was calculated, with particular emphasis on the evolution behaviors of arsenic and chloride with temperature, pressure, and molar ratio. The main products identified during pyrolysis were HCl(g), C, As, and AsCl3(g). Under anoxic conditions, AsCl3(g) and As were the dominant species. In oxygen‐enriched conditions, arsenic existed primarily as AsCl3(g), As2O5, As2O4, and AsOCl. Below 600 °C, arsenic predominantly existed in high valence forms such as As2O5. Above 600 °C, the binding capacity of chlorine and arsenic was stronger than that of oxygen, resulting in an AsCl3(g) molar fraction exceeding 75 % at 1200 °C. The primary chlorides in oxygen‐enriched conditions were Cl2(g), HCl(g), AsCl3(g), and Cl(g). Lower incineration temperatures (around 500 °C), sufficient oxygen conditions (molar ratio above 4 : 1), and positive pressures were conducive to reducing the toxicity of destruction products. The results are in good agreement with the experimental data. [ABSTRACT FROM AUTHOR]

After the use of chemical weapons, there is a gradual spontaneous decomposition of chemical warfare agents (CWAs), and only degradation products can be present at the time of sample collection. Depending on the type of parent compound, these are most often acids, alcohols, or thiols. This article deals with the development and optimization of methods for the trimethylsilylation of controlled alcohols that outperforms the currently widely used method with N,O-bis(trimethylsilyl)trifluoroacetamide (BSTFA) prior to gas chromatographic identification. Thiodiglycol (TDG) was chosen as a model alcohol for the development and optimization of methods. Nine trimethylsilylating agents were tested as derivatization agents. For each reagent, the method was optimized in terms of reaction medium (seven tested solvents), reaction time, and temperature. The temporal stability of the resulting derivatives and the effect of the addition of the reaction catalyst were also monitored. Subsequently, optimal methods were applied in the derivatization of N-ethyldiethanolamine, N-methyldiethanolamine, triethanolamine, 2-diisopropylaminoethanol (DIAE), and 3-quinuclidinol. The developed methods were compared in all monitored properties with the standard BSTFA-method (in acetonitrile for 30 min at 60 °C). From the developed methods, three were selected that showed similar or better sensitivity parameters than BSTFA, and at the same time were less demanding to perform. Trimethylsilylation via trimethylsilyl cyanide (TMSCN) appears to be the most successful method. In conclusion, the selected methods were applied in the analysis of contaminated environmental and urban samples – sand, acrylic paint, asphalt-aluminum paint, and concrete. The samples were measured on both a benchtop and a field gas chromatograph. [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]

The neutralization of organophosphorous (OP) chemical agents used in modern warfare is a growing concern due to their extreme toxicity to human cells. In several previous works, although the capability of several Zr‐MOF‐based catalysts has been showcased to facilitate hydrolysis of OP agents in heterogeneous pathways, their usage appeared to be limited by very slow kinetics at neutral pH. There is still a lack of MOF based catalysts that can detoxify OPs at physiological pH. The recycling ability of MOF‐based catalysts has also not been greatly explored. Thus, herein, we explored a Zr‐based MOF, MOF‐801(Zr) for the detoxification of a series of OP nerve agents and a pesticide with simultaneous adsorption and degradation at pH 7.5 in a buffer solution, close to physiological conditions. This MOF‐based catalyst demonstrates significant hydrolysis activity towards several nerve agents, with up to 99 % conversion within 2 h and an excellent half‐life of less than 5 minutes. In addition, it can be recycled at least 5 times consecutively with a residual activity of at least 90 %. [ABSTRACT FROM AUTHOR]

In the field of chemical warfare agents (CWAs), ethanolamines are important building blocks for the preparation of nerve agents belonging to the V-series such as VX and VR as well as the nitrogen-based mustards. In this work, the determination of three members in this class of Schedule 2B reportable chemicals, namely N,N-dimethylethanolamine (DMEA), N,N-diethylethanolamine (DEEA), and N,N-diisopropylethanolamine (DIEA) by electron ionization gas chromatography-mass spectrometry (EI-GC-MS) is presented. The three dialkylethanolamines were spiked in a high organic content soil matrix featured during the 45th Organization for the Prohibition of Chemical Weapons (OPCW) proficiency test (PT) at two separate concentrations each (1 and 10 µg/g separately), simulating values often encountered during these tests. The N,N-dialkylethanolamines were O-alkylated using benzyl bromide and sodium carbonate at 55 °C and were detected as their benzylated versions by electron ionization GC-MS. The benzylation of each dialkylethanolamine yielded derivatives with higher molecular weight and therefore different GC-MS profiles such as longer retention times and sharper peak chromatography relative to their unmodified counterparts. These characteristics enable the analytical chemist to detect and confirm these important CWA-related chemicals specifically in instances where they are present in low concentrations (i.e. <10 µg/g) among more abundant interferences. [ABSTRACT FROM AUTHOR]

This review article comprehensively explores the electrochemical detection of organophosphate-based agents, including warfare agents, pesticides, and simulants. It provides an in-depth analysis of their molecular structures, emphasizing the inherent toxicity and environmental risks posed by these compounds. The review highlights the significant role of flexible sensors in facilitating the electrochemical detection of organophosphate-based agents, offering insights into their design, development, and application in detection methodologies. Additionally, the article critically evaluates the challenges encountered in this field, such as sensor sensitivity and sample complexity, and discusses potential solutions to address these challenges. Furthermore, it outlines the future scope and opportunities for advancement in electrochemical detection technologies, including the integration of novel materials and the exploration of innovative detection strategies. By synthesizing current research findings and identifying future research directions, this review contributes to the ongoing discourse on the detection and mitigation of organophosphate-based agents’ risks to human health and the environment.

Chemical warfare agents (CWAs) pose a threat as gaseous substances and as liquid aerosols, necessitating chemical warfare-protective clothing for soldiers. The paramount consideration lies in the effectiveness of the clothing as a barrier against the pertinent CWAs. This paper presents a dynamic swatch test method aimed at evaluating the performance of such clothing against liquid-phase aerosol penetration. Central to the methodology is a specialized test cell designed to rotate to the left and right, integrated within a laboratory wind tunnel, replicating mission-relevant conditions with varying wind speeds. Utilizing di(2-ethylhexyl) sebacate particles as liquid aerosols, tests were conducted at wind speeds of 1.0, 3.0, and 5.0 m/s. Penetration assessment relied on analyzing particle counts downstream and upstream of the fabric, with preliminary studies showing that higher wind speeds and fabric air permeabilities increase penetration at an equivalent face velocity of 5.0 cm/s. Interestingly, penetration decreased when fabric samples were subjected to rotation. The system and methodology devised demonstrated consistent and repeatable results, offering valuable insights into optimizing the effectiveness of chemical warfare-protective clothing. This research contributes to advancing methodologies for testing protective clothing, crucial for ensuring the safety of military personnel in hazardous environments. [ABSTRACT FROM AUTHOR]

In this work, we test metal–organic frameworks (MOFs) as sorbents in the solid-phase extraction (SPE) technique to determine chemical warfare agents (CWAs) and their related compounds in water samples. During this study, we used 13 target compounds to test the selectivity of MOFs thoroughly. Three MOFs were used: MIL-100(Fe), ZIF-8(Zn), and UiO-66(Zr). The obtained materials were characterized using FT-IR/ATR, SEM, and XRD. CWA's and related compounds were analyzed using gas chromatography coupled with tandem mass spectrometry (GC-MS/MS). The effect of the type of elution solvent and the amount of sorbent (MOFs) in the column on the efficiency of the conducted extraction were verified. The LOD ranged from 0.04 to 7.54 ng mL−1, and the linearity range for the analytes tested extended from 0.11/22.62 (depending on the compound) to 1000 ng mL−1. It was found that MOFs showed the most excellent selectivity to compounds having aromatic rings in their structure or a "spread" spatial structure. The best recoveries were obtained for DPAA, CAP, and malathion. Environmental water samples collected from the Baltic Sea were analyzed using an optimized procedure to verify the developed method's usefulness. [ABSTRACT FROM AUTHOR]

The past few decades have witnessed encouraging progress in the development of high-performance film-based fluorescent sensors (FFSs) for detecting explosives, illicit drugs, chemical warfare agents (CWAs), and hazardous volatile organic chemicals (VOCs), among others. Several FFSs have transitioned from laboratory research to real-world applications, demonstrating their practical relevance. At the heart of FFS technology lies the sensing films, which play a crucial role in determining the analytes and the resulting signals. The selection of sensing fluorophores and the fabrication strategies employed in film construction are key factors that influence the fluorescence properties, active-layer structures, and overall sensing behaviors of these films. This review examines the progress and innovations in the research field of FFSs over the past two decades, focusing on advancements in fluorophore design and active-layer structural engineering. It underscores popular sensing fluorophore scaffolds and the dynamics of excited state processes. Additionally, it delves into six distinct categories of film fabrication technologies and strategies, providing insights into their advantages and limitations. This review further addresses important considerations such as photostability and substrate effects. Concluding with an overview of the field's challenges and prospects, it sheds light on the potential for further development in this burgeoning area. [ABSTRACT FROM AUTHOR]

A promising, but not yet practiced, approach to the treatment of neurotoxic organophosphate poisoning is the administration of a scavenger that rapidly deactivates the nerve agent before it can exert its toxic effects. The detoxification rates required for successful use of this therapy can currently only be achieved with enzymes, but synthetic scavengers, whose mode of action is based on key concepts of supramolecular chemistry, are an attractive alternative. Considerable progress has recently been made in the development of such scavengers, and compounds from several receptor classes are now available that not only bind nerve agents but also degrade them at promising rates. This review provides an overview of the field and highlights recent developments. [ABSTRACT FROM AUTHOR]

In the present study, we used two popular radio communication SAW resonators as a base for gas sensors and tested their performance. Taking into account issues related to sensor sensitivity, the possibility of applying a sensor layer, the availability of devices, and other related issues, we selected two popular single-port resonators with center frequencies of 315 and 433 MHz (models R315 and R433, respectively) for testing purposes. Both resonators were equipped with a sensitive film of hexafluoroisopropanol-substituted polydimethylsiloxane, a material that selectively absorbs molecules with a high ability to form basic hydrogen bonds. Fabricated sensors were used to detect trace amounts of dimethyl methylphosphonate (DMMP) vapor, which has often been used in similar studies as a nerve chemical warfare agent simulant. Sensors using both devices loaded with sensor layers of an optimal thickness rapidly reacted to a gas containing DMMP at a concentration of 3 mg/m3, generating a stable analytical signal ranging from several to several dozen kilohertz. In the case of R433, the frequency signal was 20.5 kHz at 1 min from the beginning of exposure to DMMP. The obtained results showed that the used transducers exhibited good performance as a base for gas sensors. Finally, their suitability for sensing applications was confirmed by a comparison with the results obtained in previous similar studies. [ABSTRACT FROM AUTHOR]

Oxidized organosulfur compounds and, in particular, sulfoxides are of interest as solvents in the semiconductor and pharmaceutical industry, environmental contaminants, and simulants in deactivation of chemical warfare agents. An experimental study is reported of the interaction of porphyrin aluminum metal–organic framework Al-MOF-TCPPH2 (Compound 2) with diethyl sulfoxide (DESO) in pure form and in aqueous solution. First, the suitability of Compound 2 as sorbent in aqueous solution was assessed; namely, its long-term stability (up to 15 days) in liquid water has been investigated at room temperature and under stirring. Here, a novel facile spectroscopic method has been used, a periodic micro-sampling of sorbent from suspension, followed by vacuum mini-filtration and an ex situ time-dependent attenuated total reflection Fourier transform infrared spectroscopy (ATR FT-IR) analysis. Next, the interaction of Compound 2 with pure liquid DESO under ambient conditions was investigated, which yields the stoichiometric adsorption complex (Al-MOF-TCPPH2)1(DESO)2 denoted Compound 3. In this adsorption complex, molecules of DESO interact with the OH group and carboxylate group of the sorbent. Then, the removal of DESO from Compound 3 was assessed, using facile treatment with warm water in the micro Soxhlet apparatus followed by the ATR FT-IR analysis. Finally, Compound 2 was tested in sorption of DESO from diluted aqueous solution. In the initial step, the sorption proceeds very quickly (in <1 min the concentration of DESO decreases by about 20%) followed by a much slower step. The maximum amount of adsorbed DESO corresponds to half of the amount adsorbed from pure DESO as found by the high-performance liquid chromatography–ultraviolet detection method. This adsorbed amount corresponds to 1 mol DESO adsorbate per mol of sorbent. Porphyrin aluminum metal–organic framework Compound 2 is promising for the removal of DESO from diluted aqueous solution, and it is of interest for the removal of similar oxidized organosulfur compounds. [ABSTRACT FROM AUTHOR]

Chemical warfare agents primarily comprise organophosphorus nerve agents, saliva alkaloids, cyanides, and mustard gas. Exposure to these agents can result in severe respiratory effects, including spasms, edema, and increased secretions leading to breathing difficulties and suffocation. Protecting public safety and national security from such threats has become an urgent priority. Porous metal–organic framework (MOF) materials have emerged as promising candidates for the degradation of chemical warfare agents due to their large surface area, tunable pore size distribution, and excellent catalytic performance. Furthermore, combining MOFs with polymers can enhance their elasticity and processability and improve their degradation performance. In this review, we summarize the literature of the past five years on MOF-based composite materials and their effectiveness in degrading chemical warfare agents. Moreover, we discuss key factors influencing their degradation efficiency, such as MOF structure, pore size, and functionalization strategies. Furthermore, we highlight recent developments in the design of MOF–polymer composites, which offer enhanced degradation performance and stability for practical applications in CWA degradation. These composite materials exhibit good performance in degrading chemical warfare agents, playing a crucial role in protecting public safety and maintaining national security. We can expect to see more breakthroughs in the application of metal–organic framework porous materials for degrading chemical warfare agents. It is hoped that these innovative materials will play a positive role in achieving social stability and security. [ABSTRACT FROM AUTHOR]

Nonsyndromic orofacial clefts (nsOFCs) are the most prevalent congenital craniofacial abnormalities, significantly impacting an individual's overall health. They are clinically presented as an incomplete separation of the lips, palate, or both. NsOFC occurs as a separate entity and is not associated with any other syndromic abnormalities. Epigenetics has been regarded as a key factor in increasing the prevalence of orofacial clefts. Studies in the past have aimed to explain the involvement of epigenetics in the formation of nsOFCs. Researchers have also well-investigated and documented certain environmental factors and chemical agents that could influence the occurrence of orofacial clefts. Understanding the role and effect of the etiological factors will directly support postulating preventative measures to minimize the occurrence of clefts. This review article will offer a comprehensive overview of the epigenetics, environmental factors, and chemical agents linked to developing nsOFCs. The article will also focus on the promising epigenetic biomarkers that can potentially detect clefts early. [ABSTRACT FROM AUTHOR]

This study describes the development of hydrogel formulations with ionic crosslinking capacity and photocatalytic characteristics. The objective of this research is to provide an effective, accessible, "green", and facile route for the decontamination of chemical warfare agents (CWAs, namely the blistering agent—mustard gas/sulfur mustard (HD)) from contaminated surfaces, by decomposition and entrapment of CWAs and their degradation products inside the hydrogel films generated "on-site". The decontamination of the notorious warfare agent HD was successfully achieved through a dual hydrolytic–photocatalytic degradation process. Subsequently, the post-decontamination residues were encapsulated within a hydrogel membrane film produced via an ionic crosslinking mechanism. Polyvinyl alcohol (PVA) and sodium alginate (ALG) are the primary constituents of the decontaminating formulations. These polymeric components were chosen for this application due to their cost-effectiveness, versatility, and their ability to form hydrogen bonds, facilitating hydrogel formation. In the presence of divalent metallic ions, ALG undergoes ionic crosslinking, resulting in rapid gelation. This facilitated prompt PVA-ALG film curing and allowed for immediate decontamination of targeted surfaces. Additionally, bentonite nanoclay, titanium nanoparticles, and a tetrasulfonated nickel phthalocyanine (NiPc) derivative were incorporated into the formulations to enhance absorption capacity, improve mechanical properties, and confer photocatalytic activity to the hydrogels obtained via Zn2+—mediated ionic crosslinking. The resulting hydrogels underwent characterization using a variety of analytical techniques, including scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), viscometry, and mechanical analysis (shear, tensile, and compression tests), as well as swelling investigations, to establish the optimal formulations for CWA decontamination applications. The introduction of the fillers led to an increase in the maximum strain up to 0.14 MPa (maximum tensile resistance) and 0.39 MPa (maximum compressive stress). The UV-Vis characterization of the hydrogels allowed the determination of the band-gap value and absorption domain. A gas chromatography–mass spectrometry assay was employed to evaluate the decontamination efficacy for a chemical warfare agent (sulfur mustard—HD) and confirmed that the ionic crosslinked hydrogel films achieved decontamination efficiencies of up to 92.3%. Furthermore, the presence of the photocatalytic species can facilitate the degradation of up to 90% of the HD removed from the surface and entrapped inside the hydrogel matrix, which renders the post-decontamination residue significantly less dangerous. [ABSTRACT FROM AUTHOR]

This comprehensive review explores the diverse applications of defective zirconium-based metal–organic frameworks (Zr-MOFs) in energy and environmental remediation. Zr-MOFs have gained significant attention due to their unique properties, and deliberate introduction of defects further enhances their functionality. The review encompasses several areas where defective Zr-MOFs exhibit promise, including environmental remediation, detoxification of chemical warfare agents, photocatalytic energy conversions, and electrochemical applications. Defects play a pivotal role by creating open sites within the framework, facilitating effective adsorption and remediation of pollutants. They also contribute to the catalytic activity of Zr-MOFs, enabling efficient energy conversion processes such as hydrogen production and CO2 reduction. The review underscores the importance of defect manipulation, including control over their distribution and type, to optimize the performance of Zr-MOFs. Through tailored defect engineering and precise selection of functional groups, researchers can enhance the selectivity and efficiency of Zr-MOFs for specific applications. Additionally, pore size manipulation influences the adsorption capacity and transport properties of Zr-MOFs, further expanding their potential in environmental remediation and energy conversion. Defective Zr-MOFs exhibit remarkable stability and synthetic versatility, making them suitable for diverse environmental conditions and allowing for the introduction of missing linkers, cluster defects, or post-synthetic modifications to precisely tailor their properties. Overall, this review highlights the promising prospects of defective Zr-MOFs in addressing energy and environmental challenges, positioning them as versatile tools for sustainable solutions and paving the way for advancements in various sectors toward a cleaner and more sustainable future. [ABSTRACT FROM AUTHOR]

Simple and efficient sample pretreatment methods are important for analysis and detection of chemical warfare agents (CWAs) in environmental and biological samples. Despite many commercial materials or reagents that have been already applied in sample preparation, such as SPE columns, few materials with specificity have been utilized for purification or enrichment. In this study, ionic magnetic mesoporous nanomaterials such as poly(4-VB)@M-MSNs (magnetic mesoporous silicon nanoparticles modified by 4-vinyl benzene sulfonic acid) and Co2+@M-MSNs (magnetic mesoporous silicon nanoparticles modified by cobalt ions) with high absorptivity for ethanol amines (EAs, nitrogen mustard degradation products) and cyanide were successfully synthesized. The special nanomaterials were obtained by modification of magnetic mesoporous particles prepared based on co-precipitation using -SO3H and Co2+. The materials were fully characterized in terms of their composition and structure. The results indicated that poly(4-VB)@M-MSNs or Co2+@M-MSNs had an unambiguous core-shell structure with a BET of 341.7 m2·g−1 and a saturation magnetization intensity of 60.66 emu·g−1 which indicated the good thermal stability. Poly(4-VB)@M-MSNs showed selective adsorption for EAs while the Co2+@M-MSNs were for cyanide, respectively. The adsorption capacity quickly reached the adsorption equilibrium within the 90 s. The saturated adsorption amounts were MDEA = 35.83 mg·g−1, EDEA = 35.00 mg·g−1, TEA = 17.90 mg·g−1 and CN−= 31.48 mg·g−1, respectively. Meanwhile, the adsorption capacities could be maintained at 50–70% after three adsorption–desorption cycles. The adsorption isotherms were confirmed as the Langmuir equation and the Freundlich equation, respectively, and the adsorption mechanism was determined by DFT calculation. The adsorbents were applied for enrichment of targets in actual samples, which showed great potential for the verification of chemical weapons and the destruction of toxic chemicals. [ABSTRACT FROM AUTHOR]

The development of lightweight and wearable fabrics that can rapidly degrade chemical warfare agents (CWAs) is highly desirable. Two-dimensional (2D) metal–organic framework (MOF) nanosheets are distinguishingly attractive due to their better accessible catalytic active sites for CWAs degradation and smaller diffusion barriers compared to their three-dimensional (3D) counterparts. However, ultrathin 2D MOF nanosheets uniformly and vertically grown on fabrics remain a challenge. Herein, we have grown ultrathin 2D Zr-BTB metal–organic framework (MOF) nanosheets, composed of 6-connected Zr6O4(OH)412+ and 1,3,5-tris-(4-carboxyphenyl)-benzene (BTB), vertically on polypropylene fabrics using a microwave-assisted solvothermal method. We have optimized the modulator, reaction temperature, and time to achieve a loading rate of up to 50%. The resulting composite fabric exhibits superior catalytic performance in degrading dimethyl methylphosphonate, a nerve agent stimulant, with half-lives of 0.77 min in bulk solution and 0.1 min in the surface contact state. This is due to the better accessible catalytic active sites and smaller diffusion barriers of the separate vertically grown 2D MOF nanosheets. The composite also shows a good filtration detoxification performance, with a single filtration detoxification rate above 88%. It demonstrates good reusability, making it competitive for environmental purification and chemical protective applications, such as gas filters, protective suits, and clothing. [ABSTRACT FROM AUTHOR]

Metal‐organic frameworks (MOFs) are a promising class of materials for catalysis, offering unique opportunities for designing efficient and selective catalysts. In this study, we have focused on the synthesis and catalytic activity of a novel mixed metal MOF, Ce/Zr−UiO‐66@LiOtBu, designed for the rapid hydrolysis of chemical warfare agents simulants: dimethyl 4‐nitrophenyl phosphate (DMNP) and 2‐chloroethyl ethyl sulfide (CEES). This MOF was thoroughly characterized using powder X‐ray diffraction (PXRD), BET surface area, and inductively coupled plasma optical emission spectrometry (ICP‐OES). The catalytic performance of Ce/Zr−UiO‐66@LiOtBu was monitored in the hydrolysis of DMNP and CEES by using 31P NMR and GC‐MS respectively. Remarkably, the MOF demonstrated rapid and efficient catalytic activity, breaking the P−O bond in DMNP with 2 min and the hydrolysis of CEES was observed in less than 45 min The results suggest the potential application of Ce/Zr−UiO‐66@LiOtBu as a robust catalyst in the detoxification of chemical warfare agent simulants. Our findings highlight the novelty of Ce/Zr−UiO‐66@LiOtBu as a catalytically active MOF, showcasing the successful integration of cerium ions and lithium tert‐butoxide to enhance basicity. [ABSTRACT FROM AUTHOR]

This study addresses a comprehensive assessment of the interaction between chemical warfare agents (CWA) and acetylcholinesterase (AChE) systems, focus on the intriguing pnictogen‐bond interaction (PnB). Utilizing the crystallographic data from the Protein Data Bank pertaining to the AChE‐CWA complex involving Sarin (GB), Cyclosarin (GF), 2‐[fluoro(methyl)phosphoryl]oxy‐1,1‐dimethylcyclopentane (GP) and venomous agent X (VX) agents, the CWA is systematically displaced by increments of 0.1 Å along the PO bond axis, extending its distance by 4 Å from the original position. The AIM analysis was carried out and consistently revealed the presence of a significant interaction along the PO bond. Investigating the intrinsic nature of the PnB, the NBO and the EDA analysis unearthed the contribution of orbital factors to the overall energy of the system. Strikingly, this observation challenges the conventional σ‐hole explanation commonly associated with such interactions. This finding adds a layer of complexity to understanding of PnB, encouraging further exploration into the underlying mechanisms governing these intriguing chemical phenomena. [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]

The idea of this study was the estimation of the theoretical acute toxicity (t-LD50, rat, oral dose) of organophosphorus-based chemical warfare agents from the G-series (n = 12) using different in silico methods. Initially identified in Germany, the G-type nerve agents include potent compounds such as tabun, sarin, and soman. Despite their historical significance, there is a noticeable gap in acute toxicity data for these agents. This study employs qualitative (STopTox and AdmetSAR) and quantitative (TEST; CATMoS; ProTox-II and QSAR Toolbox) in silico methods to predict LD50 values, offering an ethical alternative to animal testing. Additionally, we conducted quantitative extrapolation from animals, and the results of qualitative tests confirmed the acute toxicity potential of these substances and enabled the identification of toxicophoric groups. According to our estimations, the most lethal agents within this category were GV, soman (GD), sarin (GB), thiosarin (GBS), and chlorosarin (GC), with t-LD50 values (oral administration, extrapolated from rat to human) of 0.05 mg/kg bw, 0.08 mg/kg bw, 0.12 mg/kg bw, 0.15 mg/kg bw, and 0.17 mg/kg bw, respectively. On the contrary, compounds with a cycloalkane attached to the phospho-oxygen linkage, specifically methyl cyclosarin and cyclosarin, were found to be the least toxic, with values of 2.28 mg/kg bw and 3.03 mg/kg bw. The findings aim to fill the knowledge gap regarding the acute toxicity of these agents, highlighting the need for modern toxicological methods that align with ethical considerations, next-generation risk assessment (NGRA) and the 3Rs (replacement, reduction and refinement) principles. [ABSTRACT FROM AUTHOR]

Ultraviolet (UV) curing is an efficient and environmentally friendly curing method. In this paper, UV-cured polyurethane acrylates (PUAs) were investigated as potential military coatings to serve as barriers against chemical warfare agents (CWAs). Seven UV-cured PUA coatings were formulated utilizing hydroxyethyl methacrylate-capped hexamethylene diisocyanate trimer (HEMA-Htri) and trimethylolpropane triacrylate-capped polycarbonate prepolymer (PETA-PCDL) as the PUA monomers. Isobornyl acrylate (IBOA) and triethyleneglycol divinyl ether (DVE-3) were employed as reactive diluents. Gas chromatography was utilized to investigate the constitutive relationships between the structures of the PUA coatings and their protective properties against simulant agents for CWAs, including dimethyl methylphosphonate (DMMP), a nerve agent simulant, and 2-chloroethyl ethyl sulfide (CEES), a mustard simulant. The glass transition temperature (Tg) and crosslinking density (υe) of PUAs were found to be crucial factors affecting their ability to serve as barriers against CWAs. The incorporation of IBOA units led to enhanced Tg and barrier performance of the PUAs, resulting in a DMMP retention of less than 0.5% and nearly 0 retention of CEES. However, an excessive introduction of polycarbonate chains decreased the υe and barrier performance of the PUAs. These findings may offer valuable insights for enhancing the protection of UV-cured PU coatings against CWAs. [ABSTRACT FROM AUTHOR]

Chemical sensing of harmful species released either from natural or anthropogenic activities is critical to ensuring human safety and health. Over the last decade, conjugated microporous polymers (CMPs) have been proven to be potential sensor materials with the possibility of realizing sensing devices for practical applications. CMPs found to be unique among other porous materials such as metal–organic frameworks (MOFs) and covalent organic frameworks (COFs) due to their high chemical/thermal stability, high surface area, microporosity, efficient host–guest interactions with the analyte, efficient exciton migration along the π‐conjugated chains, and tailorable structure to target specific analytes. Several CMP‐based optical, electrochemical, colorimetric, and ratiometric sensors with excellent selectivity and sensing performance were reported. This review comprehensively discusses the advances in CMP chemical sensors (powders and thin films) in the detection of nitroaromatic explosives, chemical warfare agents, anions, metal ions, biomolecules, iodine, and volatile organic compounds (VOCs), with simultaneous delineation of design strategy principles guiding the selectivity and sensitivity of CMP. Preceding this, various photophysical mechanisms responsible for chemical sensing are discussed in detail for convenience. Finally, future challenges to be addressed in the field of CMP chemical sensors are discussed. [ABSTRACT FROM AUTHOR]

Ocular tissue, especially the cornea, is overly sensitive to chemical exposures. The availability and adoption of chemical threat agent chloropicrin (CP) is growing in the United States as a pesticide and fumigant; thereby increasing the risk of its use in warfare, terrorist attacks and non-intentional exposure. Exposure to CP results in immediate ocular, respiratory, and dermal injury; however, we lack knowledge on its mechanism of toxicity as well as of its breakdown products like chlorine and phosgene, and effective therapies are elusive. Herein, we have reviewed the recent findings on exposure route, toxicity and likely mechanisms of CP induced ocular toxicity based on other vesicating chemical warfare agents that cause ocular injury. We have focused on the implication of their toxicity and mechanistic outcomes in the ocular tissue, especially the cornea, which could be useful in the development of broad-spectrum effective therapeutic options. We have discussed on the potential countermeasures, overall hallmarks and challenges involved in studying ocular injuries from chemical threat agent exposures. Finally, we reviewed useful available technologies and methods that can assist in the identification of effective medical countermeasures for chemical threat agents related ocular injuries. [Display omitted] • Chloropicrin, a warfare agent, is used as a pesticide and fumigating agent. • Chloropicrin is a choking chemical threat agent that caused severe ocular injury. • The mechanism of ocular injury from chloropicrin exposure is unknown. • There is currently no available targeted treatment for chloropicrin induced injuries. [ABSTRACT FROM AUTHOR]

Rapid and accurate on-site detection of chemical warfare agents (CWAs) could defend military and civilian populations against current and emerging chemical weapons. With the development of ambient ionization and linear ion trap technology, the rapid and accurate quantitative determination method of CWAs based on direct ionization and multistage mass spectrometry has attracted widespread attention. In this study, a microliter electrospray ionization-miniature linear ion trap mass spectrometry (LIT-MS) instrument was designed and constructed, and the effects of quadrupole enhanced dipole resonance excitation on the resolution and sensitivity were investigated; consequently, the parameters of CWAs detection were optimized. Based on the broad time-frequency ion excitation technology, accurate multiple reaction monitoring (MRM) quantitative analysis of DMMP (G-series agent simulants, m/z 125 → m/z 93) was obtained. The linear correlation coefficient in the concentration range of 1 to 20 μg/mL could reach 99.02%, and the relative standard deviations (RSD) of continuous repeatability, interday repeatability, and intraday repeatability were all less than 10%. The results showed that the accurate pseudo-MRM detection method based on miniature linear ion trap mass spectrometry for CWAs detection was feasible. [ABSTRACT FROM AUTHOR]

Background and Aim: Triage is a dynamic process of the patient care chain that is used to determine priority for treatment, evacuation, and decontamination. The preparation of military nurses is essential for the isolation and triage of chemical casualties. The purpose of this study is to determine the impact of the triage training of chemical casualties using a multimedia method on the attitude of nurses of a selected military hospital. Methods: In this semi-experimental study, 54 nurses working in a military hospital in Mashhad, Iran in 2022 were selected and randomly allocated to intervention and control groups. The data collection tool included two sections of demographic information and a researcher-made questionnaire. Nurses' attitudes were measured in three stages before, after, and one month after the intervention. Then the data were analyzed using SPSS software ver.21 and with independent t-tests and analysis of variance of repeated measures. Results: There was no statistically significant difference in the average attitude score between the two groups before the intervention (P>0.180) but, a significant increase in the mean scores of nurses' attitude in the test group was observed after the intervention (P = 0.001) and one month later (P = 0.009), and the effect size of the attitude level was estimated in the medium range. Conclusion: The results show the effectiveness of multimedia training on improving nurses' attitudes in the triage of chemical casualties; Therefore, it is suggested to use multimedia training in continuous training to improve the knowledge and attitude of nurses in response to disasters, especially chemical, microbial and nuclear events. [ABSTRACT FROM AUTHOR]

Copyright of Journal of Defense Sciences / Savunma Bilmleri Dergisi is the property of Turkish Military Academy Defense Sciences Institute and its content may not be copied or emailed to multiple sites or posted to a listserv without the copyright holder's express written permission. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)

Copyright of Journal of Faculty of Pharmacy of Ankara University / Ankara Üniversitesi Eczacilik Fakültesi Dergisi is the property of Ankara University and its content may not be copied or emailed to multiple sites or posted to a listserv without the copyright holder's express written permission. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)

The interest in characterization of drugs abused started in 1948 with the aim of determining the origin of opium. After 75 years there is still a great interest in this approach, called geo-profiling, chemical or forensic profiling in the following decades. Recently chemical attribution signatures (CAS) were proposed by the authors who studied “synthesis precursors and byproducts, impurities, degradation products, and metabolites in various biological matrices” of fentanyl. Forensic profiling evolved during these decades: new analytical approaches were tested and it was applied to more and more products, which threaten the health and security of citizens worldwide.In substances of natural origins (e.g. opium, cannabis and cocaine), it is possible to exploit the great variability of both elements and organic chemical compounds and to study chemical compounds such as reagents and solvents, by-products, and cutting agents used in the production chain. Profiles can be used to classify products from different seizures into groups of similar samples (tactical intelligence) or to determine the origin of samples (strategic intelligence).Chromatographic approaches coupled to mass spectrometry are very common to determine organic profiles, while elemental profiles are obtained by nuclear activation analysis, inductively coupled plasma mass spectrometry or ion beam analysis. A very important role in the field is played by isotope ratio analysis. Approaches to obtain forensic profiles are available also for chemical warfare agents, explosives, illegal medicines, doping agents, supplements, food. Chemometrics can be particularly useful to establish the authenticity of products and for the interpretation of large amount of forensic data. The future of forensic profiling is a challenge for forensic sciences. Organized crime is involved in the manufacturing of a large number of illegal products and forensic profiling is a very powerful tool to support the health of citizens and the administration of justice worldwide.

Catalytic is a crucial reaction for environmental detoxication of pesticides and neutralization of various molecules classified as chemical warfare agents. Herein, we report on a series of tunable Ce−Zr‐based metal oxides, (ZraCe1–aOx) prepared using a facile biomineralization technique, as catalysts for organophosphates dephosphorylation. Synchrotron scattering and spectroscopy methods showcase that ZraCe1–aOx catalysts are highly defective and exhibit an abundance of Ce3+ sites that promote oxygen vacancies needed for enhanced dephosphorylation reactions. The catalytic performance was assessed using a model para‐nitrophenyl phosphate reaction and showcases a strong dependence on Zr dopant concentration and subsequent tuning of the Ce3+/Ce4+ ratio. Analysis of synchrotron datasets allowed structure‐performance correlations between the Ce3+ concentration and associated oxygen vacancies, the dephosphorylation rate constant, and Zr concentration to be established, confirming that Ce3+ as active sites is positively correlated with the rate constant. We envision that similar biomineralization approaches can be used to fabricate Ce3+‐rich Ce−Zr oxide for environmental application in dephosphorylation and other hydrolysis reactions. [ABSTRACT FROM AUTHOR]

This investigation delves into the development of cupric oxide functionalized activated carbon fabrics (ACF@CuO) as a filter material for self-decontaminating protective clothing designed to counter chemical warfare agents (CWAs). Three variants of samples were developed by controlling functionalization levels (7.5%, 13.0%, 16.0% w/w) through optimized precursor concentrations, integrating CuO particles onto ACF surfaces. Comprehensive analysis using techniques like FTIR, BET surface area, SEM, EDX, STEM, XRD, TGA, and XPS explored the material’s properties. The studies concentrated on evaluating the performance through kinetic studies of self-detoxification of CWA Sarin (GB) using developed ACF@CuO materials analyzed by Gas Chromatography-Mass Spectrometry (GC-MS). ACF@CuO with 16% w/w functionalization exhibited superior self-decontamination against GB, achieving 92.87% efficiency within 18 hours, in contrast to 26.55% for ACF alone. Additionally, materials were tested for tensile strength, air-permeability, and Sulfur Mustard breakthrough time (HDBTT) as per IS 17377:2020 standard. The material with 13% w/w functionalization emerged as the recommended filter layer for CWA protective clothing designed for defense and civilian safety applications. The significant improvements in the self-decontamination efficiency of the material were attributed to the synergistic effects of ACF’s adsorption capabilities combined with the decontamination properties of CuO rod-shaped crystals embedded in the surface of ACF. [ABSTRACT FROM AUTHOR]

The latest trends in the field of the on-site detection of chemical warfare agents (CWAs) involve increasing the availability of point detectors to enhance the operational awareness of commanders and soldiers. Among the intensively developed concepts aimed at meeting these requirements, wearable detectors, gas analyzers as equipment for micro- and mini-class unmanned aerial vehicles (UAVs), and distributed sensor networks can be mentioned. One of the analytical techniques well suited for use in this field is surface acoustic wave sensors, which can be utilized to construct lightweight, inexpensive, and undemanding gas analyzers for detecting CWAs. This review focuses on the intensively researched and developed variant of this technique, utilizing absorptive sensor layers dedicated for nerve CWAs' detection. The paper describes the mechanism of the specific interaction occurring between the target analyte and the sensing layer, which serves as the foundation for their selective detection. The main section of this paper includes a chronological review of individual achievements in the field, largely based on the peer-reviewed scientific literature dating back to the mid-1980s to the present day. The final section presents conclusions regarding the prospects for the development of this analytical technique in the targeted application. [ABSTRACT FROM AUTHOR]

A green synthesis of UiO-66-NH2 embedded in chitosan and deposited on textiles has been investigated for the degradation of chemical warfare agents. This method requires no heating or use of toxic solvents. The composite synthesized presents an interesting efficiency in detoxifying common simulants of chemical warfare agents, such as DMNP. In parallel, resistance and permeability tests were also realized in order to confirm the suitability of the composites for further applications. [ABSTRACT FROM AUTHOR]

Thermocatalytic decomposition is an efficient purification technology that is potentially applicable to degrading chemical warfare agents and industrial toxic gases. In particular, ZrO2 has attracted attention as a catalyst for the thermocatalytic decomposition of dimethyl methylphosphonate (DMMP), which is a simulant of the nerve gas sarin. However, the influence of the crystal phase and morphology on the catalytic performance of ZrO2 requires further exploration. In this study, monoclinic- and tetragonal-phase ZrO2 (m- and t-ZrO2, respectively) with nanoparticle, flower-like shape and hollow microsphere morphologies were prepared via hydrothermal and solvothermal methods, and their thermocatalytic decomposition of DMMP was systematically investigated. For a given morphology, m-ZrO2 performed better than t-ZrO2. For a given crystalline phase, the morphology of hollow microspheres resulted in the longest protection time. The exhaust gases generated by the thermocatalytic decomposition of DMMP mainly comprised H2, CO2, H2O and CH3OH, and the by-products were phosphorus oxide species. Thus, the deactivation of ZrO2 was attributed to the deposition of these phosphorous oxide species on the catalyst surface. These results are expected to help guide the development of catalysts for the safe disposal of chemical warfare agents. [ABSTRACT FROM AUTHOR]

Chemical warfare agents (CWAs) refer to toxic chemical substances used in warfare. Recently, CWAs have been a critical threat for public safety due to their high toxicity. Metal–organic frameworks have exhibited great potential in protecting against CWAs due to their high crystallinity, stable structure, large specific surface area, high porosity, and adjustable structure. However, the metal clusters of most reported MOFs might be highly consumed when applied in CWA hydrolysis. Herein, we fabricated a two-dimensional piezoresponsive UiO-66-F4 and subjected it to CWA simulant dimethyl-4-nitrophenyl phosphate (DMNP) detoxification under sonic conditions. The results show that sonication can effectively enhance the removal performance under optimal conditions; the reaction rate constant k was upgraded 45% by sonication. Moreover, the first-principle calculation revealed that the band gap could be further widened with the application of mechanical stress, which was beneficial for the generation of 1O2, thus further upgrading the detoxification performance toward DMNP. This work demonstrated that mechanical vibration could be introduced to CWA protection, but promising applications are rarely reported. [ABSTRACT FROM AUTHOR]

The adsorption properties of benzyl chloride and benzyl bromide on tetragonal silicane (tetra-silicane) are studied based on the density functional theory. The tetra-silicane possesses a stable structure with an energy band gap of 2.887 eV. Besides, the hydrogenation along the vertical directions increases the band gap of tetra-silicane suitable as an adsorbing material for benzyl chloride and benzyl bromide molecules. We observed the changes in the electronic properties of tetra-silicane due to target molecules' adsorption, which is evident from charge transfer, electron density difference diagrams, band structure, and projected density of states spectrum. The tetra-silicane exhibits chemo-resistive properties owing to benzyl chloride and benzyl bromide molecular adsorption. The current report will open the gate in the new sensing material towards benzyl chloride and benzyl bromide molecules, which are classified under chemical warfare agents. [ABSTRACT FROM AUTHOR]