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The threats to chemical warfare-associated agents (CWA), including nitrogen mustard, are increasing, and no direct antidote is currently available to mitigate the deleterious cutaneous and systemic responses to prevent mortality. Though most of these agents act as alkylating agents, a significant knowledge gap exists in the molecular mechanisms of how these vesicants cause toxic effects. Studies, including ours, have shown that exposure to reactive oxygen species (ROS)-generating stimuli, including alkylating chemotherapeutic agents, and thermal burn injuries with ethanol produce the potent family of lipid mediators, Platelet-activating factor (PAF) agonists that induce local inflammation, and multi-system organ dysfunction (MOD). Notably, nano-sized microvesicle particles (MVPs), released from cells in response to stimuli, carry PAF-agonists and act as potent signaling agents to induce the local (cutaneous) and systemic responses. The current review highlights mechanistic insights and applicable approaches to mitigate CWA-induced local and systemic toxic responses with implications in cellular senescence and aging. [Display omitted] • Chemical warfare-associated agents (CWA) can cause significant toxicities including death. • Currently, there is no antidote to mitigate CWA-induced toxic effects. • We propose that CWA act via oxidized lipids carried by subcellular particles and its targeting can mitigate CWA toxicities. • A substantial correlation also exists between CWA and cellular senescence in that both involve lipid oxidation. [ABSTRACT FROM AUTHOR]

Efficient degradation of sulfur mustard is essential owing to its extreme toxicity and widespread use as a chemical warfare agent. However, current degradation methods often lack selectivity and generate highly toxic by-products. Herein, we demonstrate an approach for the selective photodegradation of a sulfur mustard simulant using singlet oxygen (1O2) produced by a methylene blue (MB)-modified UiO-66-(COOH)2 (UC, a classical metal–organic framework) composite, termed as MB@UC. The composite was prepared via adsorption of MB onto the surface of UC through strong electrostatic interactions. The MB@UC composite demonstrates high 1O2 generation, enabling selective detoxification of a sulfur mustard simulant (2-chloroethyl ethyl sulfide) into relatively non-toxic sulfoxide, with a half-life of 1.8 minutes under ambient conditions. Compared to traditional detoxifying agents, the MB@UC composite offers superior selectivity, rapid degradation, and excellent recyclability, maintaining its performance over multiple cycles. This work presents a promising strategy for the development of advanced heterogeneous photosensitizers for the detoxification of chemical warfare agents. [ABSTRACT FROM AUTHOR]

In this study, the adsorption behavior of sulfur mustard on metal porphyrins replaced in carbon nanocone (M-PCNC, M = Fe2+ and Mg2+) is explored using density functional theory (DFT) calculations. Energetics, physical parameters, and electronic properties are determined utilizing the M06-2X approach and the 6-31G(d) basis set. Based on the obtained results, the sulfur mustard exhibits strong adsorption onto the M-PCNCs, which denotes a chemisorption process between species. Furthermore, the findings suggest that the M-PCNCs are effective adsorbents in eliminating undesired sulfur mustard molecules from the surroundings. The data also show that the energy gap (or work function) of the M-PCNC structures is not affected by the adsorption of sulfur mustard, suggesting that they are unsuitable for use as sensors for the sulfur mustard in terms of electronic conductivity or work function. The UV-visible spectra of bare Fe-PCNC are also compared to its corresponding complexes, which reveals the adsorption of sulfur mustard does not alter the spectra of the Fe-PCNC and cannot act as a UV-based sensitive material for detecting sulfur mustard. [ABSTRACT FROM AUTHOR]

Mustard gas (HD) is a well-known chemical warfare agent, recognized for its extreme toxicity and severe hazards. Metal–organic frameworks (MOFs), with their unique structural properties, show significant potential for HD adsorption applications. Due to the extreme hazards of HD, most experimental studies focus on its simulants, but molecular simulation research on these simulants remains limited. Simulation analyses of simulants can uncover structure–performance relationships and enable experimental validation, optimizing methods, and improving material design and performance predictions. This study integrates molecular simulations, machine learning (ML), and molecular fingerprinting (MFs) to identify MOFs with high adsorption performance for the HD simulant diethyl sulfide (DES), followed by in-depth structural analysis and comparison. First, MOFs are categorized into Top, Middle, and Bottom materials based on their adsorption efficiency. Univariate analysis, machine learning, and molecular fingerprinting are then used to identify and compare the distinguishing features and fingerprints of each category. Univariate analysis helps identify the optimal structural ranges of Top and Bottom materials, providing a reference for initial material screening. Machine learning feature importance analysis, combined with SHAP methods, identifies the key features that most significantly influence model predictions across categories, offering valuable insights for future material design. Molecular fingerprint analysis reveals critical fingerprint combinations, showing that adsorption performance is optimized when features such as metal oxides, nitrogen-containing heterocycles, six-membered rings, and C=C double bonds co-exist. The integrated analysis using HTCS, ML, and MFs provides new perspectives for designing high-performance MOFs and demonstrates significant potential for developing materials for the adsorption of CWAs and their simulants. [ABSTRACT FROM AUTHOR]

Insufficient selectivity is a major constraint to the further development of metal oxide semiconductor (MOS) sensors for chemical warfare agents, and this paper proposed an improved scheme combining catalytic layer/gas-sensitive layer laminated structure with temperature dynamic modulation for the Mustard gas (HD) MOS sensor. Mustard gas simulant 2-Chloroethyl ethyl sulfide (2-CEES) was used as the target gas, (Pt + Pd + Rh)@Al2O3 as the catalytic layer material, (Pt + Rh)@WO3 as the gas-sensitive layer material, the (Pt + Pd + Rh)@Al2O3/(Pt + Rh)@WO3 sensor was prepared, and the sensor was tested for 2-CEES and 12 battlefield environment simulation gases under temperature dynamic modulation. The results showed that the sensor only showed obvious characteristic peaks in the resistance response curves to HD under certain conditions (100–400 °C, the highest temperature was held for 1 s and the lowest temperature was held for 2 s), and its peak height reached 6.12, which was far higher than other gases, thus realizing the high selectivity of the MOS sensor to 2-CEES. Meanwhile, the sensor also showed good sensitivity, detection limits, response/recovery times, anti-interference, and stability, which further verified the feasibility of the improved scheme. [ABSTRACT FROM AUTHOR]

Four metalloporphyrinic metal–organic frameworks (MOFs) were successfully synthesized and exhibited enhanced activities for the photooxidation of a sulfur mustard simulant, 2-chloroethyl ethyl sulfide (CEES). Among them, a Sn-porphyrin functionalized 2D MOF, namely CSLA-21-NH2(Sn), showed a half-life of 1.5 min for CEES oxidation under blue LED, featuring as one of the fastest photocatalysts for CEES degradation. [ABSTRACT FROM AUTHOR]

The use of chemical warfare agents (CWAs) in terrorist attacks remains a potential threat. Therefore, an updated wide-ranging database that contains details on the fate of CWAs on environmental surfaces is required, especially for the persistent blister agent sulphur mustard (HD). For this purpose, long-period evaporation rates measurements of HD from various common urban matrices were conducted from our specialised laboratory-designed wind tunnel. Small HD droplets were dispersed on each matrix surface, and then placed in the evaporation chamber. Samples of the target material were collected by continuous sampling on SPE (solid-phase extraction) tubes and analysed by GC (gas-chromatography) analytical method. Profiles of the air vapour concentrations as a function of time (up to four orders of magnitude) and the total mass balances were calculated at two temperatures. The results indicated fast clearance of HD together with a nearly full mass balance from stainless steel and smooth surface tiles, as these matrices are relatively inert. On the other hand, asphalt blocks relatively conserve HD, exhibiting a slow-release mode of action over 7–11 days until matching the GPL (General Population Limit) for HD. The concentration profile of commercial sidewalk bricks showed a moderate decay that characterises a semi-conserving matrix. These findings were compared to the evaporation profiles of the nerve agents sarin (GB) and VX from the same surfaces at the same experimental conditions. We can conclude that HD contamination can cause a secondary risk by a slow release into the atmosphere, especially from surfaces exhibiting conserving characteristics. [ABSTRACT FROM AUTHOR]

A series of porous organic polymers based on a singlet oxygen generating oxoporphyinogen ('OxP') has been successfully prepared from a pseudotetrahedral OxP-tetraamine precursor (OxP(4-NH2Bn)4) by its reaction with tetracarboxylic acid dianhydrides under suitable conditions. Of the compounds studied, those containing naphthalene (OxP-N) and perylene (OxP-P) spacers, respectively, have large surface areas (~530 m2 g−1). On the other hand, the derivative with a simple benzene spacer (OxP-B) exhibits the best 1O2 generating capability. Although the starting OxP-tetraamine precursor is a poor 1O2 generator, its incorporation into OxP POPs leads to a significant enhancement of 1O2 productivity, which is largely due to the transformation of NH2 groups to electron-withdrawing diimides. Overall 1O2 production efficacy of OxP-POPs under irradiation by visible light is significantly improved over the common reference material PCN-222. All the materials OxP-B, OxP-N and OxP-P promote oxidation of thioanisole involving conversion of ambient triplet state oxygen to singlet oxygen under visible light irradiation and its reaction with the sulfide. Although the reaction rate of the oxidation promoted by OxP POPs is generally lower than for conventional materials (such as PCN-222) or previously studied OxP derivatives, undesired overoxidation of the substrate to methyl phenyl sulfone is suppressed. For organic sulfides, selectivity of oxidation is especially important for detoxification of mustard gas (bis(2-chloroethyl)sulfide) or similarly toxic compounds since controlled oxidation leads to the low toxicity bis(2-chloroethyl)sulfoxide while overoxidation leads to intoxification (since bis(2-chloroethyl)sulfone presents greater toxicity to humans than the sulfide substrate). Therefore, OxP POPs capable of promoting selective oxidation of sulfides to sulfoxides have excellent potential to be used as mild and selective detoxification agents. IMPACT STATEMENT: Oxoporphyrinogen (OxP) is a unique chromophore compound in that it is intrinsically de-aggregated allowing large quantum yields of singlet oxygen generation. Due to its structure, OxP is also an ideal building block for porous systems. In this work, we describe the first incorporation of OxP in highly stable microporous polymers strongly enhanced singlet oxygen generation for selective oxidation of organic sulfides to sulfoxides (as a model reaction) under heterogeneous conditions. The novelty of this work lies in the high stability and easy recovery of the materials, the synergetic enhancement of singlet oxygen generation in the polymers over the starting OxP, and the excellent selectivity for the oxidation reaction. [ABSTRACT FROM AUTHOR]

Mustard gas keratopathy (MGK), a complication of exposure to sulfur mustard, is a blinding ocular surface disease involving key cellular pathways, including apoptosis, oxidative stress, and inflammation. Recent studies indicate that cellular senescence contributes to the pathophysiology of mustard gas toxicity. This study aimed to assess senescence and stress-related pathways—particularly mitogen-activated protein kinase (MAPK) signaling—in nitrogen mustard (NM)-induced corneal injury. In vitro, primary human corneal epithelial (P-HCECs), primary human corneal mesenchymal stromal cells (hcMSCs), and human corneal–limbal epithelial cell (HCLE) lines were exposed to varying concentrations of NM. The results demonstrated a dose-dependent increase in cellular senescence, characterized by reduced Ki67 expression, elevated p16, and p21 mRNA levels, as well as activation of the MAPK pathway activation. Treatment with a selective p38-MAPK inhibitor significantly reduced senescence markers and improved cell proliferation following exposure to NM. Overall, these studies indicate that NM exposure triggers cellular senescence and stress-related MAPK signaling, while p38-MAPK inhibition mitigates these effects, suggesting a potential therapeutic strategy. [ABSTRACT FROM AUTHOR]

Toxic epidermal necrolysis (TEN) is a severe skin reaction caused by extensive epidermal and mucosal necrosis. This clinical phenomenon is known as an acute syndrome of apoptotic pan‐epidermolysis (ASAP). The ASAP phenomenon is observed in conditions that mimic TEN, highlighting the challenge in distinguishing these conditions. While TEN is a well‐recognized entity, distinguishing it from other TEN‐like conditions presents significant diagnostic and treatment challenges. These conditions include drug rash with eosinophilia and systemic symptoms (DRESS), generalized bullous fixed drug eruption (GBFDE), acute generalized exanthematous pustulosis (AGEP), TEN‐like methotrexate toxicity, mustard gas toxicity, pseudoporphyria, mycoplasma‐induced rash and mucositis (MIRM), multisystem inflammatory syndrome in children (MIS‐C), graft versus host disease (GVHD), and acute cutaneous lupus erythematosus and subacute cutaneous lupus erythematosus. This review explores these ten separate entities and debates their clinical features, pathophysiology, diagnosis and management. [ABSTRACT FROM AUTHOR]

Chemical warfare agents (CWAs) are known as poor man's bombs because of their small lethal dose, cheapness, and ease of production. Therefore, the highly sensitive and rapid detection of CWAs at room temperature (RT = 25 °C) is essential. In this paper, we have developed a resistive semiconductor sensor for the highly sensitive detection of CWAs at RT. The gas-sensing material is SnS2/rGO nanosheets (NSs) prepared by hydrothermal synthesis. The lower detection limits of the SnS2/rGO NSs-based gas sensor were 0.05 mg/m3 and 0.1 mg/m3 for the typical chemical weapons sarin (GB) and sulfur mustard (HD), respectively. The responsivity can reach −3.54% and −10.2% in 95 s for 1.0 mg/m3 GB, and in 47 s for 1.0 mg/m3 HD. They are 1.17 and 2.71 times higher than the previously reported Nb-MoS2 NSs-based gas sensors, respectively. In addition, it has better repeatability (RSD = 6.77%) and stability for up to 10 weeks (RSD = 20.99%). Furthermore, to simplify the work of later researchers based on the detection of CWAs by two-dimensional transition metal sulfur compounds (2D-TMDCs), we carried out calculations of the SnS2 NSs-based and SnS2/rGO NSs-based gas sensor-adsorbing CWAs. Detailed comparisons are made in conjunction with experimental results. For different materials, it was found that the SnS2/rGO NSs-based gas sensor performed better in all aspects of adsorbing CWAs in the experimental results. Adsorbed CWAs at a distance smaller than that of the SnS2 NSs-based gas sensor in the theoretical calculations, as well as its adsorption energy and transferred charge, were larger than those of the SnS2 NSs-based gas sensor. For different CWAs, the experimental results show that the sensitivity of the SnS2/rGO NSs-based gas sensor for the adsorption of GB is higher than that of HD, and accordingly, the theoretical calculations show that the adsorption distance of the SnS2/rGO NSs-based gas sensor for the adsorption of GB is smaller than that of HD, and the adsorption energy and the amount of transferred charge are larger than that of HD. This regularity conclusion proves the feasibility of adsorption of CWAs by gas sensors based on SnS2 NSs, as well as the feasibility and reliability of theoretical prediction experiments. This work lays a good theoretical foundation for subsequent rapid screenings of gas sensors with gas-sensitive materials for detecting CWAs. [ABSTRACT FROM AUTHOR]

[Display omitted] Selective oxidation of sulfur mustard gas (HD) to non-toxic sulfoxide by the visible-light-catalyzed generation of singlet oxygen (1O 2) is a promising degradation strategy. Although PCN-224 can absorb visible light, it suffers from rapid electron-hole recombination and low redox capacity, which limits the performance of HD degradation. Titanium dioxide (TiO 2) is an excellent photocatalyst but it lacks visible-light-activity in degrading HD. In this study, PCN-224@TiO 2 heterojunction with S-type core–shell structure was synthesized by in-situ growth method to prolong the visible light absorption capacity of TiO 2 and inhibit the rapid recombination of PCN-224. The interface formation and internal electric field were optimized by adjusting the Zr/Ti ratio to enhance the charge transfer, redox capacity, electron-hole separation, and visible light absorption. In this study, the formation of heterojunction composites based on Zr-O-Ti linkages is demonstrated by a series of characterization methods. It is demonstrated by experiments and theoretical calculations that PCN-224@TiO 2 can generate nearly 100 % 1O 2 under visible light conditions without a sacrificial agent, resulting in efficient and selective oxidation of 2-chloroethyl ethyl sulfide (CEES), a simulant of HD, to non-toxic sulfoxide form. [ABSTRACT FROM AUTHOR]

The highly blistering sulfur mustard analogue agent T (bis(2-chloroethylthioethyl) ether), also known as O-mustard or oxy-mustard, is a common impurity in military grade sulfur mustard (SM) and a component of mixtures such as "HT" that are still found in old munitions. Together with sesquimustard (Q), it is the most important SM analogue and tightly regulated as a Schedule 1 chemical under the Chemical Weapons Convention. We report the adducts of T with nucleophilic Cys34 and other residues in human serum albumin (HSA) formed in vitro. A micro liquid chromatography electrospray ionization high-resolution tandem-mass spectrometry method (µLC-ESI MS/HR MS) was developed for the detection and identification of biomarker peptides alkylated by a T-derived hydroxyethylthioethyloxyethylthioethyl (HETEOETE)-moiety (as indicated by an asterisk below). Following proteolysis of T-exposed human plasma with pronase, the dipeptide Cys34*Pro and the single amino acid residue His* were produced. The use of proteinase K yielded Cys34*ProPhe and the use of pepsin generated ValThrGlu48*Phe, AlaGlu230*ValSerLysLeu, and LeuGlyMet329*Phe. Corresponding peptide-adducts of SM and Q were detected in a common workflow that in principle allowed the estimation of the mustard or mustard composition encountered during exposure. Novel adducts of Q at the Glu230 and Met239 residues were detected and are reported accordingly. Based on molecular dynamics simulations, we identified regular interactions of the Cys34(-HETEOETE)-moiety with several glutamic acid residues in HSA including Glu86, which is not an obvious interaction partner by visual inspection of the HSA crystal structure. The existence of this and other intramolecular cross-links was experimentally proven for the first time. [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]

Atomic‐level modulation of covalent organic frameworks (COFs) structure for enhanced photocatalytic oxidation is highly important but still challenging. Herein, a series of β‐ketoenamine‐linked COFs have been synthesized by using 2,4,6‐triformyl‐phloroglucinol (Tp) as a modular molecule, 5,5′‐Diamino‐2,2′‐bipyridine (Bpy), and 3,6‐Pyridazinediamine (Dz) linkers with atomic level N sites substitute 4,4′‐diamino‐bipheny (BD) and 1,4‐phenylenediamine (Pa) to construct COFs with adjustable photocatalytic performance. Mechanism study reveals that in COFs with N sites‐based linkers, 1O2 adsorbed on the pore walls of TpBpy‐COF (−4.23 kcal mol−1) and TpDz‐COF (−4.63 kcal mol−1) with higher adsorption energy than on TpBD‐COF (−2.73 kcal mol−1) and TpPa‐COF (−2.17 kcal mol−1), enabling 1O2 activation and high catalytic performance toward thioether oxidation with almost >99% conversion, outperforming most reported organic photocatalysts. Notably, TpBpy‐COF exhibits a superior catalytic activity for thioether oxidation (e.g., aromatic thioethers, aliphatic sulfide, and Mustard Gas sulfide) because of its narrow bandgap, fast charge separation and transfer ability, and single‐ended activation ability. This study provides a novel and effective strategy for modulating exciton effects and photocatalytic activity of COFs‐based organic photocatalysts at the atomic level. [ABSTRACT FROM AUTHOR]

Sulfur mustard (SM) is an established chemical weapon that can result in severe damage to parts of the body. Currently, there are no effective treatments available for SM-caused damage. We aimed to investigate the therapeutic potential of adipose-derived mesenchymal stromal cells (AD-MSCs) and conditioned medium (CM-MSCs) in acute and chronic pulmonary mouse models caused by 2- chloroethyl ethyl sulfide (CEES), an SM analog. The mice were divided into 4 experimental groups:(1) CEES+AD-MSCs, (2) CEES+CMMSCs, (3) CEES, and (4) control. The model observation time was divided into 7 days for the short and 6 months for the long term. AD-MSCs were injected into mice via intraperitoneal injection 24 hours after CEES exposure. The therapeutic effects of AD-MSCs on pulmonary tissue damage were assessed using a histopathologic assay, measuring the neutrophil count, and bronchial alveolar lavage fluid (BALF) protein level. The levels of inflammatory and anti-inflammatory cytokines were evaluated using the enzyme-linked immunosorbent assay as the outcomes of interest. Lung damage progression was reduced by AD-MSC treatment in mice after CEES injection into the peritoneum. The proportion of CD11b+F4/80+ macrophages in the peritoneum was significantly lowered by AD-MSC treatment following CEES exposure. AD-MSC administration also reduced the level of pro-inflammatory cytokines, BALF protein, and nitric oxide levels in the peritoneal cavity. By reducing inflammation and enhancing tissue healing, AD-MSCs and CM-MSC help prevent acute lung damage caused by CEES. The current study supports the use of a mouse model as a solid experimental foundation and indicates potential use for future cell treatment. [ABSTRACT FROM AUTHOR]

Copyright of Journal of Tiangong University is the property of Journal of Tianjin Polytechnic 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.)

Simultaneously fabricating a fibrous structure and phase junction has the potential to improve the separation of nano titanium oxide, catalytic activity, and catalytic power. It is important to maintain an easy and environmentally-friendly fabrication process. This research led to the successful creation of a sophisticated type of titanium oxide, featuring a TiO2/anatase phase interface and a significant unique outer layer. A unique exterior level was created using an eco-friendly method and modification of deep tunable solvents. This resulted in a 3D structure made of 2D ultrathin nanosheets with mesopores. We synthesized Dy2Sn2O7 nanoparticles and combined them with aromatic ring-doped C3N4 nanosheets (Ar-C3N4; Ar = Ph, Pm, Py,) which were deposited onto nanofibrous titanium (Dy2Sn2O7@Ar-C3N4/NFT) as a nanoceramic. The employment of NFT was discovered to supply numerous hydroxyl groups, enabling consistent loading of Ar-C3N4 via molecular binding engagement. By exploring the potential of fibrous structure in nanoceramic production, a novel and innovative approach is being pursued, which has the potential to revolutionize the field of catalysis in the petroleum industry. Moreover, Ar-C3N4 could adjust fibre sizes and offer active amino group adsorption sites, aiding in chemisorption with organic compounds. The surface features and porous architecture of the Dy2Sn2O7@Ar-C3N4/NFT composite were preserved after Dy2Sn2O7@Ar-C3N4 loading, suggesting the maintained crystalline form. This remarkable catalyst, displays an impressive capability in facilitating the desulfurization process, all while adhering to environmentally friendly conditions. Moreover, in order to further enhance its sustainability credentials, this catalyst has been crafted with the support of oxygen green oxidant, ensuring a greener approach to the desulfurization process. Remarkably, this entire process is carried out at atmospheric pressure and at low temperatures, ensuring energy conservation and minimizing any potential adverse effects. [ABSTRACT FROM AUTHOR]

Sesquimustard (Q) is a powerful blistering agent that contains additional sulfur atoms. Sulfur mustard causes covalent bonding by alkylating nucleophilic groups of biologically important macromolecules such as lipids, proteins, DNA, or RNA. Most cells maintain relatively high amounts of a unique tripeptide called glutathione (GSH) (γ-glutamyl-cysteinyl glycine), which possesses a free thiol group, to prevent unwanted reactions caused by reactive chemical entities. Moreover, these thiol groups on cysteines (Cys) are the main target for alkylation. Although Q is the most potent vesicant among sulfur mustards, research studies identifying biomarkers of Q are very limited. Therefore, here in this study, we aimed to identify the GSH and Cys conjugates of Q using mass spectrometric methods and to observe the formation of these conjugates in HaCat cell culture following exposure to different doses. We identified four different conjugates of Q, which are bis-glutathionyl ethylthioethylthioethyl conjugate (GSH-ETETE-GSH), hydroxyethylthioethylthioethyl glutathione conjugate (HETETE-GSH), bis-cysteinyl ethylthioethylthioethyl conjugate (Cys-ETETE-Cys), and hydroxyethylthioethylthioethyl cysteine conjugate (HETETE-Cys). The identity of the conjugates was elucidated using liquid chromatography–high-resolution mass spectrometry (LC-HRMS). We also investigated changes in conjugate formation with exposure concentration and time elapsed after exposure in the cell culture. After exposure, GSH conjugates decreased until 1st hour, while Cys conjugates increased until 6th hour. We also observed that conjugate formation depended on the concentration of Q. This is the first study to elucidate the conjugates of Q dependent on GSH conjugation. As biomarkers are essential tools for evaluating exposure to Q, this study contributes to the limited number of studies identifying biomarkers for Q. [ABSTRACT FROM AUTHOR]

"The Bolsheviks and Britain During the Russian Revolution and Civil War, 1917–1924" by Evgeny Sergeev provides a new account of Anglo-Soviet relations during this period, drawing on previously inaccessible Soviet archives. Sergeev reveals Trotsky's friendlier stance towards Britain compared to Lenin, and sheds light on the alleged "Lockhart plot" as a counterintelligence operation. The book also explores Churchill's advocacy for poison gas use in the Russian Civil War and Lloyd George's pursuit of a trade deal with the Bolsheviks. However, the text is critiqued for the author's imperfect English, which may impact its reliability as a reference source." [Extracted from the article]

Four donor‐acceptor (D‐A) polymers are synthesized by combining two different electron donors (truxene and its more electron rich triaza analogue, triindole) with an electron‐deficient monomer (benzothiadiazole) through two different positions (2,7,13 or 3,8,13) and their optoelectronic properties are studied by theoretical and experimental methods. One of the polymers exhibits remarkable sensing capabilities for explosive nitraoaromatics while another demonstrated efficient photocatalytic activity in the aerobic sulfoxidation of the sulfur mustard simulant 2‐chloro‐ethyl ethyl sulfide (MGS) sulfoxidation. These results highlight their potential applications in defense‐related areas. Moreover, the structure‐performance relationships observed among the four polymers have enabled us to deepen the understanding of the mechanisms underlying the performance of these polymers in the aforementioned applications, thereby providing valuable insights to further improve their properties. [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]

Sulfur mustard (SM) is a highly potent alkylating vesicant agent and remains a relevant threat to both civilians and military personnel. The eyes are the most sensitive organ after airborne SM exposure, causing ocular injuries with no antidote or specific therapeutics available. In order to identify relevant biomarkers and to obtain a deeper understanding of the underlying biochemical events, we performed an untargeted metabolomics analysis using liquid chromatography coupled to high-resolution mass spectrometry of plasma samples from New Zealand white rabbits ocularly exposed to vapors of SM. Metabolic profiles (332 unique metabolites) from SM-exposed (n = 16) and unexposed rabbits (n = 8) were compared at different time intervals from 1 to 28 days. The observed time-dependent changes in metabolic profiles highlighted the profound dysregulation of the sulfur amino acids, the phenylalanine, the tyrosine and tryptophan pathway, and the polyamine and purine biosynthesis, which could reflect antioxidant and anti-inflammatory activities. Taurine and 3,4-dihydroxy-phenylalanine (Dopa) seem to be specifically related to SM exposure and correspond well with the different phases of ocular damage, while the dysregulation of adenosine, polyamines, and acylcarnitines might be related to ocular neovascularization. Additionally, neither cysteine, N-acetylcysteine, or guanine SM adducts were detected in the plasma of exposed rabbits at any time point. Overall, our study provides an unprecedented view of the plasma metabolic changes post-SM ocular exposure, which may open up the development of potential new treatment strategies. [ABSTRACT FROM AUTHOR]

Cutting off refractory organosulfur compounds is an immense need in the modern age of petroleum refineries. The oxidation of these hard organosulfur compounds is dynamic in the course of deep oxidative desulfurization. Atmospheric molecular oxygen is an organic, innocuous, abundant, and economical oxidant. Microorganisms synthesize dendritic fibrous nanoparticles (DFNPs) in exposure to metal ions. In this research, microorganisms were used to produce Zn2MnO4 DFNPs in a biological process instead of a chemical method as a nanocatalyst. This biogenic nanoparticle has been used for the first time as a recyclable catalyst with external magnet and efficient in desulfurization process under environmentally friendly conditions with support of oxygen green oxidant, at atmospheric pressure, at low temperature, green water extraction agent, Distilled with the help of ultrasound as a source of green energy in a shorter time. This strategy has marvelous profits, including high economic yield and tolerance of functional groups. The present study underscores how metabolic processes in anaerobic bacteria could be mixed with green chemical technologies to generate extremely efficient catalytic reactions for ultrasound-assisted oxidative desulfurization of simulated fuel, natural gasoline, and sulfur mustard analogs. [ABSTRACT FROM AUTHOR]

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The objective of the present review is to list, describe, compare, and critically analyze the main procedures developed in the last 20 years for the analysis of digested alkylated peptides, resulting from the adduction of albumin by different mustard agents, and that can be used as biomarkers of exposure to these chemical agents. While many biomarkers of sulfur mustard, its analogues, and nitrogen mustards can easily be collected in urine such as their hydrolysis products, albumin adducts require blood or plasma collection to be analyzed. Nonetheless, albumin adducts offer a wider period of detectability in human exposed patients than urine found biomarkers with detection up to 25 days after exposure to the chemical agent. The detection of these digested alkylated peptides of adducted albumin constitutes unambiguous proof of exposure. However, their determination, especially when they are present at very low concentration levels, can be very difficult due to the complexity of the biological matrices. Therefore, numerous sample preparation procedures to extract albumin and to recover alkylated peptides after a digestion step using enzymes have been proposed prior to the analysis of the targeted peptides by liquid chromatography coupled to mass spectrometry method with or without derivatization step. This review describes and compares the numerous procedures including a number of different steps for the extraction and purification of adducted albumin and its digested peptides described in the literature to achieve detection limits for biological samples exposed to sulfur mustard, its analogues, and nitrogen mustards in the ng/mL range. [ABSTRACT FROM AUTHOR]

Nerve agents are the most notorious substances, which can be fatal to an individual because they block the activity of acetylcholinesterase. Fighting against unpredictable terrorist assaults and wars requires the simple and quick detection of chemical warfare agent vapor. In the present contribution, we have introduced a rhodamine-based chemosensor, BDHA, for the detection of nerve gas-mimicking agents diethylchlorophosphate (DCP) and diethylcyanophosphonate (DCNP) and mustard gas-mimicking agent 2-chloroethyl ethyl sulfide (CEES), both in the liquid and vapor phase. Probe BDHA provides the ability for detection by the naked eye in terms of colorimetric and fluorometric changes. It has been revealed that the interaction between nerve agents mimics and probe BDHA facilitates spirolactam ring opening due to the phosphorylation process. Thus, the highly fluorescent and colored species developed while probe BDHA is colorless and non-fluorescent due to the intramolecular spirolactam ring. Moreover, probe BDHA can effectively recognize DCP, DCNP, and CEES in the µM range despite many toxic analytes and could be identified based on the response times and quantum yield values. Inexpensive, easily carried paper strips-based test kits were developed for the quick, on-location solid and vapor phase detection of these mustard gas imitating agents (CEES) and nerve gas mimicking agents (DCP and DCNP) without needing expensive equipment or skilled personnel. More remarkably, the test strips' color and fluorescence can be rapidly restored, exposing them to triethyl amine (TEA) for cyclic use, suggesting a potential application in the real-time identification of chemical warfare agents. To accomplish the on-location application of BDHA, we have experimented with soil samples to find traces of DCP. Therefore, the chromo-fluorogenic probe BDHA is a promising, instantaneous, and on-the-spot monitoring tool for the selective detection of DCP, DCNP, and CEES in the presence of others. [ABSTRACT FROM AUTHOR]

Effective sampling is a key step in the process of proving the use of chemical weapons. An alternative to collecting the respective sample is to perform a wipe of surface contamination. This work deals with the optimization of the wiping process of the surfaces of selected matrices contaminated with bis(2-chloroethyl)sulfide and tris(2-chloroethyl)amine. Optimization of the procedure was carried out in terms of the choice of wiping material, wetting solvent and extraction of the wiped contaminant. Furthermore, the time decrease of surface contamination was monitored. The effect of transport on the change in the observed recovery value was investigated and the measurement deviations of the wipe method were discussed. The resulting values of observed recovery were negatively influenced by the volatility of the analyte, the porosity of the matrix and the time that passed since the contamination. Viscose was evaluated as the most effective wipe material. Low relative standard deviations (≤7 %) were achieved with this material. The optimal wetting solvent was dichloromethane. There was no degradation of contaminants on the surface of the matrices, so the fate was only affected by evaporation and penetration into the material. [ABSTRACT FROM AUTHOR]

Sulfur mustard (SM) is a highly toxic blister agent which has been used many times in several wars and conflicts and caused heavy casualties. Ease of production and lack of effective therapies make SM a potential threat to public health. SM intoxication causes severe damage on various target organs, such as the skin, eyes, and lungs. In addition, SM exposure can also lead to hepatotoxicity and severe liver injuries. However, despite decades of research, the molecular mechanism underlying SM-induced liver damage remains obscure. SM can be converted into various products via complex hepatic metabolism in vivo. There are some pieces of evidence that one of the oxidation products of SM, divinyl sulfone (DVS), exhibits even more significant toxicity than SM. Nevertheless, the molecular toxicology of DVS is still hardly known. In the present study, we confirmed that DVS is even more toxic than SM in the human hepatocellular carcinoma cell line HepG2. Further mechanistic study revealed that DVS exposure (200 μM) promotes pyroptosis in HepG2 cells, while SM (400 μM) mainly induces apoptosis. DVS induces gasdermin D (GSDMD) mediated pyroptosis, which is independent of caspases activation but depends on the large amounts of reactive oxygen species (ROS) and severe oxidative stress produced during DVS exposure. Our findings may provide novel insights for understanding the mechanism of SM poisoning and may be helpful to discover promising therapeutic strategies for SM intoxication. [ABSTRACT FROM AUTHOR]

The design and synthesis of a bifunctional catalyst to tackle environmental pollution caused by 2-chloroethyl ethyl sulfide (CEES) and phenolic compounds is meaningful. In this study, a new three-dimensional (3D) polyoxovanadate (POV)-based metal–organic framework, [Co(L)(V4O12)0.5(H2O)]·2H2O (1; L = N,N’-bis(3-methylpyridin-3-yl)-2,6-naphthalenediamide), was synthesized under hydrothermal conditions. 1 was characterized using single-crystal X-ray diffraction analysis, infrared spectroscopy, and powder X-ray diffraction. Structural analysis shows that the [V4O12]4– clusters and pairs of Co2+ cations are alternately connected to form a one-dimensional inorganic chain, eventually generating a 3D (4,4)-connected framework through the expansion of L, which exhibits a two fold interpenetration array. As a bifunctional catalyst, 1 exhibits satisfactory catalytic properties for the selective oxidation of 2-chloroethyl ethyl sulfide to the corresponding sulfoxide, with an effective conversion of > 99% and selectivity of 97%. Furthermore, 1 exhibits excellent photocatalytic degradation activity toward phenol, 2-chlorophenol, and m-cresol under visible light. The degradation efficiencies were above 92.6% for 140 min. The photocatalytic reaction kinetics, mechanisms of photodegradation, and recycling capability of phenol were also investigated in detail.

There have been many studies on surface acoustic wave (SAW) sensors for detecting sulfur-containing toxic or harmful gases. This paper aims to give an overview of the current state of polymer films used in SAW sensors for detecting deleterious gases. By covering most of the important polymer materials, the structures and types of polymers are summarized, and a variety of devices with different frequencies, such as delay lines and array sensors for detecting mustard gas, hydrogen sulfide, and sulfur dioxide, are introduced. The preparation method of polymer films, the sensitivity of the SAW gas sensor, the limit of detection, the influence of temperature and humidity, and the anti-interference ability are discussed in detail. The advantages and disadvantages of the films are analyzed, and the potential application of polymer films in the future is also forecasted. [ABSTRACT FROM AUTHOR]

This communication introduces a highly efficient, safe and sustainable flow protocol for the oxidative neutralization of sulfur-based chemical warfare agent simulants using ozone. The methodology employs preliminary in silico mechanistic studies and chemical analogy studies with DFT to scout reaction profiles and kinetics. It unveils crucial parameters that guide selectivity and prevent the formation of undesirable overoxidized by-products. This computational foundation is seamlessly translated into real-world neutralization experiments conducted under flow conditions, yielding remarkably swift neutralization rates under mild conditions. Full oxidative neutralization of CWA simulants with ozone is achieved within a second, without the need for additives or catalysts, in an EtOH/water mixture. This convergence of computational insights and experimental validation provides a promising avenue toward new neutralization protocols, foreseeing transformative possibilities with low waste generation and high safety. [ABSTRACT FROM AUTHOR]

Vesicating chemicals like sulfur mustard (SM) or nitrogen mustard (NM) can cause devastating damage to the eyes, skin, and lungs. Eyes, being the most sensitive, have complicated pathologies that can manifest immediately after exposure (acute) and last for years (chronic). No FDA-approved drug is available to be used as medical counter measures (MCMs) against such injuries. Understanding the pathological mechanisms in acute and chronic response of the eye is essential for developing effective MCMs. Here, we report the clinical and histopathological characterization of a mouse model of NM-induced ocular surface injury (entire surface) developed by treating the eye with 2% (w/v) NM solution for 5 min. Unlike the existing models of specific injury, our model showed severe ocular inflammation, including the eyelids, structural deformity of the corneal epithelium and stroma, and diminished visual and retinal functions. We also observed alterations of the inflammatory markers and their expression at different phases of the injury, along with an activation of acidic sphingomyelinase (aSMase), causing an increase in bioactive sphingolipid ceramide and a reduction in sphingomyelin levels. This novel ocular surface mouse model recapitulated the injuries reported in human, rabbit, and murine SM or NM injury models. NM exposure of the entire ocular surface in mice, which is similar to accidental or deliberate exposure in humans, showed severe ocular inflammation and caused irreversible alterations to the corneal structure and significant vision loss. It also showed an intricate interplay between inflammatory markers over the injury period and alteration in sphingolipid homeostasis in the early acute phase. [ABSTRACT FROM AUTHOR]

Objective: Disasters increase the incidence of infectious and contagious diseases, non-communicable diseases, and trauma. This systematic review aims to investigate the impact of man-made disasters on cardiovascular diseases (CVDs). Methods: This is a systematic review conducted following the PRISMA protocol. The population, intervention, control, outcome (PICO) framework utilized for this research is as follows: P: people with CVDs; I: various manmade disasters; C: no intervention is being compared; O: prevalence, treatment, and management of the disease. In the present study, English-language articles published until November 9, 2022 that investigated CVDs in human-made disasters were included. We conducted an extensive search in Medline, Web of Science, Embase, and SCOPUS. Results: The primary search of the databases resulted in 1878 articles, from which 1219 non-duplicate records. Finally, 18 articles were included; 13 studies were in the area of nuclear and atomic accidents, four studies were related to the sulfur mustard gas, and one was related tomethyl chloride. Conclusion: CVDs increased in prevalence after man-made disasters, particularly among high-risk individuals. The likelihood of developing CVDs is higher with increasing dose, intensity, and duration of exposure. [ABSTRACT FROM AUTHOR]

Although chemical and radiological agents cause toxicity through different mechanisms, the multiorgan injuries caused by these threats share similarities that convene on the level of basic biological responses. This publication will discuss these areas of convergence and explore "multi-utility" approaches that could be leveraged to address common injury mechanisms underlying actions of chemical and radiological agents in a threat-agnostic manner. In addition, we will provide an overview of the current state of radiological and chemical threat research, discuss the US Government's efforts toward medical preparedness, and identify potential areas for collaboration geared toward enhancing preparedness and response against radiological and chemical threats. We also will discuss previous regulatory experience to provide insight on how to navigate regulatory paths for US Food and Drug Administration (FDA) approval/licensure/clearance for products addressing chemical or radiological/nuclear threats. This publication follows a 2022 trans-agency meeting titled, "Overlapping Science in Radiation and Sulfur Mustard Exposures of Skin and Lung: Consideration of Models, Mechanisms, Organ Systems, and Medical Countermeasures," sponsored by the National Institute of Allergy and Infectious Diseases (NIAID), a part of the National Institutes of Health (NIH). Discussions from this meeting explored the overlapping nature of radiation and chemical injury and spurred increased interest in how preparedness for one threat leads to preparedness for the other. Herein, subject matter experts from the NIAID and the Biomedical Advanced Research and Development Authority (BARDA), a part of the Administration for Strategic Preparedness and Response (ASPR), summarize the knowledge gained from recently funded biomedical research, as well as insights from the 2022 meeting. These topics include identification of common areas for collaboration, potential use of biomarkers of injury to identify injuries caused by both hazards, and common and widely available treatments that could treat damage caused by radiological or chemical threats. [ABSTRACT FROM AUTHOR]

Nuclear and chemical weapons of mass destruction share both a tragic and beneficial legacy in mankind's history and health. The horrific health effects of ionizing radiation and mustard gas exposures unleashed during disasters, wars, and conflicts have been harnessed to treat human health maladies. Both agents of destruction have been transformed into therapies to treat a wide range of cancers. The discovery of therapeutic uses of radiation and sulfur mustard was largely due to observations by clinicians treating victims of radiation and sulfur mustard gas exposures. Clinicians identified vulnerability of leukocytes to these agents and repurposed their use in the treatment of leukemias and lymphomas. Given the overlap in therapeutic modalities, it goes to reason that there may be common mechanisms to target as protective strategies against their damaging effects. This commentary will highlight oxidative stress as a common mechanism shared by both radiation and sulfur mustard gas exposures and discuss potential therapies targeting oxidative stress as medical countermeasures against the devastating lung diseases wrought by these agents. [ABSTRACT FROM AUTHOR]

Development of medical countermeasures (MCM) to mitigate and/ or treat the pulmonary complications associated with exposure to chemical, radiological, and/ or nuclear weapons is a national, public health preparedness posture priority in the United States (US). Pulmonary exposure to either sulfur mustard vapor or radiation causes oxidative damage, vascular injury, hyperinflammation, and pro-fibrotic signaling cascades that lead to life-threatening and potentially debilitating lung disease. There is no MCM currently approved by the US Food and Drug Administration (FDA) to mitigate and/ or treat lung injury caused by sulfur mustard or radiation exposure. Thus, there remains a major unmet public health need for development of threat-agnostic, host-directed therapeutics that target common pathophysiological mechanisms underlying the progression of acute and/ or late lung injury independent of the etiology of disease. This review describes the clinical manifestations and underlying mechanisms of sulfur mustard and radiation-induced lung injury and regulatory considerations for MCM development under the non-traditional Animal Rule pathway. [ABSTRACT FROM AUTHOR]

The detection and monitoring of toxic and harmful gases play a vital role in environmental protection, human health, and industrial and agricultural production. However, it is still challenging to develop gas sensors for the detection of toxic and harmful gases with high sensitivity, good recovery and excellent selectivity. In this study, WO3/Al2O3/graphite composite materials were used for an MEMS 2-CEES gas sensor (dichlorodiethyl sulfide simulation), and the corresponding sensing properties were explored. The experimental results show that when the working temperature is 340 °C, the response of the sensor to 2-CEES gas with a concentration of 5.70 ppm is 69%, the response time is 5 s and the recovery time is 42 s. The sensor also has the advantages of long-term stability and high selectivity. Furthermore, the MEMS gas sensor array based on WO3/Al2O3/graphite composite materials has been achieved and also exhibits excellent sensing performance. Overall, this study provides a strategy for realizing high-performance dichlorodiethyl sulfide gas sensors. [ABSTRACT FROM AUTHOR]

We studied the stability of plasma samples spiked with sulfur mustard (SM) and urine samples spiked with the SM metabolite, 1,1'-sulfonylbis[2-(methylsulfinyl)ethane] (SBMSE), upon long-term storage. The stability of biomarkers in biomedical samples was evaluated by measuring the concentrations of spiking chemicals during the storage at 4 and 30°C. Plasma samples were analyzed by GC–MS/MS for SM regenerated from protein adducts under the action of conc. HCl and by HPLC–HR-MS/MS for albumin adduct [S-HETE]-CPF. Urine was analyzed for intact SBMSE by HPLC–HR-MS/MS, and SBMSE reduced to 1,1'-sulfonylbis[2-(methylthio)ethane] was determined after its conversion with TiCl3 followed by GC–MS/MS measurements. A reference compound of SBMSE was synthesized and characterized in terms of authenticity and quantitative content. Procedures for the quantification of SM markers in biomedical samples in the concentration range 1–100 ng mL–1 were validated. The plasma samples were stable upon storage at 4 and 30°С for at least 41 days after spiking, whereas the urine samples proved to be unstable upon long-term storage at elevated temperatures. The results of the present study can be taken into account in selecting conditions for the transportation and storage of biosamples and for interpreting the results of the determination of the SM biomarker in samples from individuals affected in incidents related to exposure to sulfur mustard. [ABSTRACT FROM AUTHOR]

Caenorhabditis elegans (C. elegans) is gaining recognition and importance as an organismic model for toxicity testing in line with the 3Rs principle (replace, reduce, refine). In this study, we explored the use of C. elegans to examine the toxicities of alkylating sulphur mustard analogues, specifically the monofunctional agent 2-chloroethyl-ethyl sulphide (CEES) and the bifunctional, crosslinking agent mechlorethamine (HN2). We exposed wild-type worms at different life cycle stages (from larvae L1 to adulthood day 10) to CEES or HN2 and scored their viability 24 h later. The susceptibility of C. elegans to CEES and HN2 paralleled that of human cells, with HN2 exhibiting higher toxicity than CEES, reflected in LC50 values in the high µM to low mM range. Importantly, the effects were dependent on the worms' developmental stage as well as organismic age: the highest susceptibility was observed in L1, whereas the lowest was observed in L4 worms. In adult worms, susceptibility to alkylating agents increased with advanced age, especially to HN2. To examine reproductive effects, L4 worms were exposed to CEES and HN2, and both the offspring and the percentage of unhatched eggs were assessed. Moreover, germline apoptosis was assessed by using ced-1p::GFP (MD701) worms. In contrast to concentrations that elicited low toxicities to L4 worms, CEES and HN2 were highly toxic to germline cells, manifesting as increased germline apoptosis as well as reduced offspring number and percentage of eggs hatched. Again, HN2 exhibited stronger effects than CEES. Compound specificity was also evident in toxicities to dopaminergic neurons–HN2 exposure affected expression of dopamine transporter DAT-1 (strain BY200) at lower concentrations than CEES, suggesting a higher neurotoxic effect. Mechanistically, nicotinamide adenine dinucleotide (NAD+) has been linked to mustard agent toxicities. Therefore, the NAD+-dependent system was investigated in the response to CEES and HN2 treatment. Overall NAD+ levels in worm extracts were revealed to be largely resistant to mustard exposure except for high concentrations, which lowered the NAD+ levels in L4 worms 24 h post-treatment. Interestingly, however, mutant worms lacking components of NAD+-dependent pathways involved in genome maintenance, namely pme-2, parg-2, and sirt-2.1 showed a higher and compound-specific susceptibility, indicating an active role of NAD+ in genotoxic stress response. In conclusion, the present results demonstrate that C. elegans represents an attractive model to study the toxicology of alkylating agents, which supports its use in mechanistic as well as intervention studies with major strength in the possibility to analyze toxicities at different life cycle stages. [ABSTRACT FROM AUTHOR]

Sulfur mustard (SM) is a chemical warfare agent with well-known severe toxic effects and may cause long-term debilitating injuries. We aimed to evaluate aging and longevity in Iranian SM-exposed survivors using some endocrine and molecular biomarkers for the first time. Dehydroepiandrosterone (DHEA), prolactin (PRL), cortisol, testosterone, and luteinizing hormone (LH) were measured in 289 male SM-veterans and 66 age-matched males using the ELISA method. Leukocyte Telomere Length (LTL) measurement and p16INK4a expression were measured in the peripheral blood leukocytes of 55 males who were exposed to SM. We found a significantly lower serum DHEAS level and higher serum PRL level in SM-exposed groups (without any related to the severity of lung injuries) compared to healthy controls, but no significant difference in serum levels of cortisol, testosterone, and LH. The molar ratio of DHEAS/cortisol was significantly higher in controls compared to the SM-exposed individuals especially those with severe lung damage. Some biological parameters of allostatic load score such as DHEAS and DHEAS/cortisol ratio significantly decreased long-term after the SM exposure. Additionally, we found that LTL was shorter in SM-exposed veterans rather than unexposed controls while p16INK4a gene expression significantly increased in these groups. It seems that DHEAS, DHEAS/cortisol ratio, LTL, and p16INK4a gene expression have changed significantly in favor of cellular senescence in SM-exposed patients. Therefore, it seems that SM exposure increases biological age compared to chronological age in SM-exposed survivors. [ABSTRACT FROM AUTHOR]

Precise synthesis of topologically predictable and discrete molecular crystals with permanent porosities remains a long‐term challenge. Here, we report the first successful synthesis of a series of 11 isoreticular multivariate hydrogen‐bonded organic frameworks (MTV‐HOFs) from pyrene‐based derivatives bearing −H, −CH3, −NH2 and −F groups achieved by a shape‐fitted, π–π stacking self‐assembly strategy. These MTV‐HOFs are single‐crystalline materials composed of tecton, as verified by single‐crystal diffraction, nuclear magnetic resonance (NMR) spectra, Raman spectra, water sorption isotherms and density functional theory (DFT) calculations. These MTV‐HOFs exhibit tunable hydrophobicity with water uptake starting from 50 to 80 % relative humidity, by adjusting the combinations and ratios of functional groups. As a proof of application, the resulting MTV‐HOFs were shown to be capable of capturing a mustard gas simulant, 2‐chloroethyl ethyl sulfide (CEES) from moisture. The location of different functional groups within the pores of the MTV‐HOFs leads to a synergistic effect, which resulted in a superior CEES/H2O selectivity (up to 94 %) compared to that of the HOFs with only pure component and enhanced breakthrough performance (up to 4000 min/g) when compared to benchmark MOF materials. This work is an important advance in the synthesis of MTV‐HOFs, and provides a platform for the development of porous molecular materials for numerous applications. [ABSTRACT FROM AUTHOR]