Search Results (181)

Iron-exchanged bentonites derived from a natural montmorillonite-rich clay (Taganskoe deposit, Kazakhstan) were prepared through a simple aqueous ion-exchange route using Fe(II) or Fe(III) inorganic salt precursors, yielding final Fe contents of ca. 5–7 wt.%, while preserving the smectite layered framework. A mild thermal treatment under air was applied to tune iron coordination without triggering major structural collapse. The resulting materials were characterized by ED-XRF, PXRD, FE-SEM/EDX, DLS/ζ-potential and DR UV–Vis–NIR spectroscopy, revealing predominantly exchanged Fe species with a limited fraction of surface iron-oxide clusters, whose contribution increases after activation. Structure–reactivity relationships were probed under mild conditions in liquid-phase ethyl acetate using dimethyl methylphosphonate (DMMP) and 2-chloroethyl ethyl sulfide (2-CEES) as organophosphorus and organosulfur hazardous chemicals and chemical warfare agent simulants, respectively. Fe(III)-bentonite enabled very fast DMMP removal (ca. 93% within 0.5 h) with a remarkable improved performance with respect to Fe(II)-bentonite and the pristine mineral clay. For 2-CEES, the presence of H₂O₂ markedly enhanced oxidation on Fe-containing clays, reaching quantitative abatement within 24 h (up to >90%), with strong retention of oxidized sulfur products by the clay matrix. These results highlight Fe-exchanged natural bentonites as robust, cheap and multifunctional adsorption/catalytic solids for decontamination and water-treatment applications. Full article

Melanin-like polymers, particularly polydopamine, have gained significant attention as photothermal materials due to their broad light absorption (ultraviolet to near-infrared), high photothermal conversion efficiency, negligible fluorescence, good biocompatibility regarding unmodified melanin-like polymers, and universal adhesion. Upon light irradiation, these bioinspired polymers convert absorbed optical energy into heat through molecular vibration and electron–phonon coupling, making them ideal for diverse photothermal applications. This review comprehensively summarizes recent advances in using melanin-like polymers for photothermal purposes. In biomedical engineering, they serve as efficient agents for photothermal therapy and synergistic antibacterial treatment. In catalysis, their photothermal effect enhances pollutant degradation, hydrogen production, and chemical warfare agent detoxification. For water remediation, melanin-like polymers are fabricated into evaporators, membranes, and aerogels for solar-driven steam generation, desalination, and oil spill cleanup. They also enable sensitive photothermal sensing, near-infrared imaging, and laser desorption ionization mass spectrometry imaging. Furthermore, these materials are incorporated into soft actuators and self-healing elastomers for light-controlled shape memory, programmable folding, and remote manipulation. Finally, we discuss remaining challenges such as long-term stability, biocompatibility, scalability, and color limitations and provide future perspectives for advancing melanin-like photothermal materials toward practical applications. Full article

The dangerous potential of chemical warfare requires immediate development of new materials capable of detecting and efficiently adsorbing the toxic nerve agents VX and Novichok (A-234). The current adsorbents fail to achieve sufficient detection efficiency and specific binding capabilities. Our research, conducted through advanced computational modeling, predicts that carbon nanocones (CNCs) could function as effective molecular traps for these toxic substances. The research combines density functional theory (DFT) with molecular dynamics (MD) and Monte Carlo (MC) simulations to explain the basic principles of molecular trapping by these agents. The nanocone shape produces two distinct and selective binding areas. MC shows preferential trapping VX molecules within the internal concave surface (P1), while A-234 molecules are strongly adsorbed on the external convex surface (P2). Docking results complement this by showing that A-234 exhibits stronger single-molecule binding on the more open surface, consistent with its preference for P2. The nanocone captures molecules through van der Waals forces, which produce measurable electronic changes that modify its electronic signature. The research demonstrates that carbon nanocones represent a promising candidate material for the future development of chemical defense systems, potentially including sensitive detection systems and advanced filtration technologies. Full article

Graphene-based sensors and biosensors are attractive candidates for chemical and biological threat detection due to their high surface sensitivity, rapid transduction, and low-power operation, yet real-world deployment remains constrained by cross-sensitivity, interface instability in biosensing, and limited validation under operational conditions. This review consolidates key requirements for Chemical, Biological, Radiological, and Nuclear (CBRN) detection and proposes a structured roadmap to guide the transition from laboratory demonstrations to field-relevant sensing systems. The roadmap is explicitly modular and non-linear, integrating (i) qualitative research planning and gap analysis, (ii) computational screening via molecular docking as a hypothesis-generation tool with well-defined limitations, (iii) graphene electrode fabrication and functionalization using pulsed laser deposition (PLD) to enable tunable thickness/defect engineering and strong interface control, (iv) multiscale characterization combining laboratory methods with in situ/portable diagnostics, and (v) field-oriented performance evaluation focused on response time, stability, selectivity against industrial interferents, and false-positive/false-negative behavior. Iterative feedback loops connect all modules, enabling progressive refinement of material processing, recognition chemistry, and device architecture. By framing success in terms of technology-maturity progression and operational metrics, this roadmap provides a practical, defense-relevant framework for developing deployable graphene-based CBRN sensing platforms. Full article

Background: Lewisite, a potent chemical warfare agent, induces rapid and progressive cutaneous damage, necessitating treatment strategies that offer both immediate decontamination and prolonged therapeutic action. This study aimed to develop and evaluate a composite topical formulation comprising 4-phenylbutyric acid (4-PBA)-loaded emulsomes embedded within a foam vehicle to address both aspects of vesicant-induced skin injury intervention. Methods: Emulsomes composed of a stearic acid–cholesterol solid lipid core stabilized by a lecithin shell were prepared via thin film hydration and optimized by varying lipid ratios and drug loading parameters. Formulations were characterized for drug loading, particle size, and zeta potential. Physicochemical compatibility was assessed using Fourier transform infrared spectroscopy (FTIR) and differential scanning calorimetry (DSC) analyses. Stability was evaluated under accelerated refrigerated (25 °C/60% RH) and room temperature (40 °C/75% RH) conditions. The optimized formulation was incorporated into a foam base and evaluated for decontamination efficiency, drug release kinetics, in vitro permeation, and in vivo efficacy. Results: The selected formulation (E2) exhibited high drug loading (17.01 ± 0.00%), monodisperse particle size (PDI = 0.3 ± 0.07), and stable zeta potential (−40 ± 1.24 mV). FTIR and DSC confirmed successful encapsulation with amorphous drug dispersion. The emulsome-foam demonstrated dual functionality: enhanced decontamination (66.84 ± 1.27%) and sustained release (~30% over 24 h), fitting a Korsmeyer–Peppas model. In vitro permeation showed significantly lower 4-PBA delivery from E2 versus free drug, confirming sustained release, while in vivo studies demonstrated therapeutic efficacy. Conclusions: This emulsome-foam system offers a promising platform for topical treatment of vesicant-induced skin injury by enabling both immediate detoxification and prolonged anti-inflammatory drug delivery. Full article

Of the Cytochrome P450 enzymes, the CYP2C9 variant is very important in the metabolism of several human drugs, acting as a natural bioscavenger. Previously, CYP2C9 was shown to convert the thion (P=S) to the oxon (P=O) form for some organophosphorus (OP) pesticides, such as dimethoate, diazinon, and parathion. In this study, we tested the ability of CYP2C9 to degrade other OP compounds. We investigated the metabolism of OP compounds by CYP2C9 using LC-MS/MS as well as time-dependent inhibition using the previously developed pFluor50 fluorogenic assay. We found that CYP2C9 metabolizes thions preferentially over oxons, and that many OP compounds inhibit CYP2C9 activity in a time-dependent manner. Additionally, we performed molecular docking based on the crystal structure (1OG5) of the CYP2C9 receptor. We observed a positive, though moderate, correlation between the calculated binding energy and the CYP2C9 metabolism of various OP compounds (R = 0.59). These in vitro data, combined with further analysis and additional OP derivatives, could potentially be used to develop artificial intelligence (AI)/machine learning (ML) models to predict the metabolism of specific OP compounds by CYP2C9. This type of approach could be particularly relevant for the prediction of the metabolism of current and emerging chemical warfare agents. Full article

Chemical warfare agents (CWAs) threaten peace and global security due to their extreme toxicity and devastating effects. Prompt discovery and detoxification are imperative to protect ourselves from these perilous agents. Metal–organic frameworks (MOFs), characterized by high specific surface areas, tunable porosities, and chemical stability, have attracted growing interest for the catalytic degradation of CWAs. However, the powder form of MOFs hinders their application in protection, and it is challenging to combine them with flexible carriers to protect humans. In this context, we provide an update on the recent development of MOF textile materials for the efficient degradation of CWAs. The research progress on different technologies for the catalytic degradation of CWAs and their simulants in MOF textiles in recent years is presented. Furthermore, challenges in developing MOF textiles for the catalytic degradation of CWAs and their simulants are highlighted. It is expected that these useful insights will be beneficial in constructing relevant MOF textiles for the degradation of CWAs. Full article

Organophosphorus chemical warfare agents such as sarin (GB), soman (GD), and cyclosarin (GF) rank among the most toxic substances known, making trace-level detection critical for public and military safety. In this study, we compared the sensitivity of two analytical techniques for determining these nerve agents: gas chromatography with flame-photometric detection (GC-FPD) and gas chromatography coupled to inductively coupled plasma mass spectrometry (GC-ICP-MS). Diluted samples of sarin, soman, and cyclosarin were prepared under controlled laboratory conditions and then analyzed by both methods. Limits of detection, calibration linearity, and selectivity of the two approaches were evaluated. It was shown that GC-ICP-MS enabled detection of sarin, soman, and cyclosarin at ≈0.12–0.14 ng/mL (LOD), whereas GC-FPD achieved LODs of ≈0.36–0.43 ng/mL. The obtained results confirm that GC-ICP-MS exhibits significantly higher sensitivity than GC-FPD in the analysis of the chemical warfare agents under study. This advantage indicates strong application potential of GC-ICP-MS as a technique for ultra-sensitive detection of trace amounts of chemical warfare agents (CWAs) in environmental samples and in confirmatory testing for compliance with the CWC, while simultaneously employing GC-FPD for rapid preliminary monitoring. Full article

Chlorpyrifos CPF (O,O-diethyl O-(3,5,6-trichloro-2-pyridyl) phosphorothioate), known also as Chlorpyrifos-ethyl, is one of the most utilized organophosphorus pesticides worldwide. Additionally, CPF could be used as a chemical warfare agent surrogate. Although its acute toxicity is not high, it is responsible for both a large number of intoxications and chronic, delayed neurological effects. In this work, it is reported for the first time the qualitative and quantitative response produced by CPF vapors, using a pocket-held Time-of-Flight Ion Mobility Spectrometer (ToF IMS) with a non-radioactive ionization source and ammonia doping, model LCD-3.2E (Smiths Detection Ltd.), operated near ambient temperature (below 30 °C). Spectra of CPF in positive ion mode included two distinct product ion peaks; thus, identification of CPF vapors by IMS relies on these peaks—the monomer M·NH₄⁺ with reduced ion mobility K₀ = ca. 1.76 cm² V⁻¹ s⁻¹ and the dimer M₂·NH₄⁺ with K₀ = ca. 1.47 cm² V⁻¹ s⁻¹ (where M may be assignable to CPF molecule)—and positive reactant ions (Pos RIP) have K₀ = ca. 2.25 cm² V⁻¹ s⁻¹. Excellent sensitivity, with a limit of detection LOD of 0.72 ppb_v (10.5 μg m⁻³) and a limit of quantification LOQ of 2.41 ppb_v (35.1 μg m⁻³), has been noticed; linear response was up to 100 ppb_v, while saturation occurs over ca. 1000 ppb_v (14.6 mg m⁻³). Our results demonstrate that this method provides a robust tool for both off-site and on-site detecting and quantifying CPF vapors at trace levels, which has strong implications for either industrial hygiene or forensic investigations concerning the pesticide Chlorpyrifos, as well as for monitoring of environmental contamination by organophosphorus pesticides. Full article

Organophosphates (OPs) are potent anti-acetylcholinesterase compounds historically used as pesticides and exploited in chemical warfare. Exposure to OPs initiates cholinergic crisis with both peripheral and central effects such as salivation, lacrimation, urination, and defecation (SLUD), and status epilepticus (SE), a prolonged state of seizure. Standard medical countermeasures atropine, oximes, and benzodiazepines reduce mortality, control peripheral symptoms, and terminate SE. However, they do not attenuate the consequences of SE, including neurodegeneration, oxidative stress, neuroinflammation, epilepsy, and associated comorbidities such as cognitive dysfunction. SE induces excessive NADPH oxidase (NOX) synthesis and production of reactive oxygen species, which is a key driver of neurodegeneration and epilepsy. Furthermore, inhibition of NOX in SE-induced epilepsy models reduces neuroinflammation, neurodegeneration, and seizure frequency. Following OP toxicity, treatment with NOX inhibitors diapocynin and mitoapocynin reduced oxidative stress and astrocyte reactivity. This review summarizes the history and development of OPs and the current knowledge on OP toxicity, emphasizing the role of NOX, and the therapeutic potential of NOX inhibitors in treating long-term consequences of acute exposure to OPs. Full article

Rapid on-site detection of chemical warfare agents (CWAs) is vital for security and environmental monitoring. In this work, copper(I) oxide (Cu₂O) nanowire (NW) chemiresistors were investigated as gas sensors for low-concentration organophosphorus chemical warfare agent (CWA) simulants. The NWs were hydrothermally synthesized and deposited onto microheater platforms, enabling them to operate at elevated working temperatures. Their sensing performance was tested against a range of vapor-phase simulants, including dimethyl methylphosphonate (DMMP), triethyl phosphate (TEP), diethyl ethylphosphonate (DEEP), diphenyl phosphoryl chloride (DPPCl), parathion, diethyl phosphite (DEP), diethyl adipate (DEA), and cyanogen chloride (ClCN). Fully oxidized P(V) simulants (DMMP, DEEP, TEP) produced modest, predominantly reversible responses (~3–6% RR). On the contrary, DPPCl and DEP induced the strongest relative responses (RR −94.67% and >200%, respectively), accompanied by irreversible surface modification as revealed by SEM and EDS. ClCN produced a substantial but reversible negative response (RR −9.5%), consistent with transient oxidative interactions. Surface poisoning was confirmed after exposure to DEP and DPPCl, which left phosphorus or chlorine residues on the Cu₂O surface. These results highlight both the promise and limitations of Cu₂O NW chemiresistors for selective CWA detection. Full article

This study explores the physicochemical and toxicological properties of six G-series and A-series chemical warfare agents (Sarin, Soman, Tabun, A230, A232, and A234) using an integrated computational approach combining molecular dynamics (MD) simulations and Quantitative Structure–Activity Relationship (QSAR) modeling. For the A-series nerve agents, both Ellison–Hoenig and Mirzayanov structural proposals were examined. MD simulations (10 ns, NPT ensemble) provided key thermodynamic properties, including density, molar heat capacity, and diffusivity. Simulated densities for G-agents (e.g., Sarin: 1.09 g/cm³, Soman: 1.03 g/cm³) and A-agents (e.g., A230: 1.608 g/cm³, Ellison–Hoenig model) closely matched experimental data. Heat capacities ranged from 258 to 462 J/mol·K, and self-diffusion coefficients revealed lower mobility for A-agents, especially under the Ellison–Hoenig configurations. QSAR modeling focused on lipophilicity (LogP) and acute toxicity (LD₅₀). Predicted LD₅₀ values ranged from 0.012 to 0.017 mg/kg for G-agents and up to 1.23 mg/kg for A-agents. A-234 showed the highest lipophilicity (LogP = 2.97) and toxicity (LD₅₀ = 0.51 mg/kg) within its group. Additional descriptors, such as molecular weight and polar surface area, supported toxicity predictions. Strong correlations emerged between MD-derived properties and QSAR outputs, validating the integrated approach. The combined use of MD and QSAR techniques provided a comprehensive view of the agents’ environmental behavior and toxicological impact, supporting safer assessment strategies and reinforcing the importance of multidisciplinary modeling for chemical threat mitigation. Full article

The poor selectivity of metal oxide semiconductor sensors is a major constraint to their application in the detection of chemical warfare agents. We prepared a (Pt+Pd+Rh)@Al₂O₃/(Pt+Rh)-WO₃ sensor by using (Pt+Pd+Rh)@Al₂O₃ as a catalytic film material and (Pt+Rh)-WO₃ as a gas-sensitive film material. Using temperature dynamic modulation, the (Pt+Pd+Rh)@Al₂O₃/(Pt+Rh)-WO₃ sensor was realised to improve the selectivity for mustard. Due to the catalytic effect of the (Pt+Pd+Rh)@Al₂O₃ catalytic film on mustard, mustard was able to be catalytically generated into mustard sulphoxide after passing through the (Pt+Pd+Rh)@Al₂O₃ catalytic film. Under a certain temperature dynamic modulation, the mustard concentration on the surface of the (Pt+Rh)-WO₃ gas-sensitive film showed an increase and then a decrease. Since the resistance response of the (Pt+Rh)-WO₃ gas-sensitive film to mustard was much higher than that of mustard sulphoxide, the change in the resistance of the (Pt+Rh)-WO₃ gas-sensitive film was mainly determined by the change in the concentration of mustard, which led to the peak signal in the curve of its resistance response to mustard. The experimental results showed that the (Pt+Pd+Rh)@Al₂O₃/(Pt+Rh)-WO₃ sensor had peak signals in the resistance response to mustard only, and not in the resistance response to 12 interfering gases, such as carbon monoxide. Full article

The historical use of toxic chemicals to cause intentional harm has evolved from blister agents in World War I to highly lethal organophosphates and emerging families of chemicals, such as Novichok. In turn, medical or recreational substances like fentanyl, lysergamides, and phencyclidine pose a growing risk of hostile use, particularly related to the rapid proliferation of new psychoactive substances (NPSs). A narrative literature review was conducted covering specialized databases (PubMed, ScienceDirect, SciELO, Google Scholar) and sources from international organizations (OPCW, UNODC, ONU), analyzing historical and recent cases of the use of nerve agents in conflicts and the use of NPSs for hostile purposes. The main families of conventional agents (G, V, A series, and Novichok) and NPSs (lysergamides, PCP, fentanyl derivatives) were identified, highlighting their ease of synthesis, high toxicity profiles, and the regulatory gaps that facilitate their illicit production. In this scenario, it is essential to strengthen regulatory frameworks, surveillance systems, and ethical protocols in chemical research, as well as to promote international cooperation to prevent these substances from becoming chemical threats. Full article

Alkylating agents, historically employed as chemical warfare agents and currently used as chemotherapeutic drugs, are known to induce significant pulmonary toxicity. Current clinical interventions often fail to fully prevent or reverse these pathological changes, highlighting the urgent need for safe, broad-spectrum therapeutic agents that are effective across diverse exposure scenarios. Melatonin has emerged as a promising protective agent due to its antioxidant, anti-inflammatory, and immunomodulatory properties, along with a well-established safety profile. This systematic review evaluates the potential of melatonin in mitigating vesicant-induced pulmonary damage, synthesizing and critically analyzing preclinical evidence in accordance with the PRISMA guidelines. Three in vivo rodent studies met the inclusion criteria and were analyzed. In all cases, melatonin demonstrated protective effects against alkylating agents such as mechlorethamine (HN2) and cyclophosphamide (CP). These effects were dose-dependent and observed across various animal models, administration protocols, and dosages (ranging from 2.5 to 100 mg/kg), highlighting the importance of context-specific considerations. The human equivalent doses (HEDs) ranged from 12 to 973 mg per day, suggesting that the effective doses may exceed those typically used in clinical trials for other conditions. Melatonin’s pleiotropic mechanisms, including a reduction in oxidative stress, the modulation of inflammatory pathways, and support for tissue repair, reinforce its therapeutic potential in both prophylactic and treatment settings for alkylating agent exposure. Nonetheless, this review underscores the critical need for further randomized clinical trials to establish the optimal dosing strategies, refine treatment protocols, and fully elucidate melatonin’s role in managing alkylating-agent-induced pulmonary toxicity. Full article