2-chloroethyl Ethyl Sulfide Research Articles

Improving the Selectivity of Metal Oxide Semiconductor Sensors for Mustard Gas Simulant 2-Chloroethyl Ethyl Sulfide by Combining the Laminated Structure and Temperature Dynamic Modulation.

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.

Cerium(III) Phosphinate and Cerium(IV) Phosphostibonate Acting as Catalysts for Mild, Selective Sulfoxidation.

A Ce(III) phosphinate and a Ce(IV) phosphostibonate have been assembled by the reaction of a phosphinic acid and phosphostibonate with Ce(III) salts. Single crystal X-ray diffraction (SCXRD) studies reveal the formation of a rare triangular Ce(III) oxo-cluster [CeIII3(Ph3CHPO2)]6Cl3(CH3OH)(H2O)8] (1) and a fascinating hexanuclear oxo-cluster containing Ce(IV) ions [CeIV6 (p-ClC6H4SbV)4(μ4-O)4(μ3-O)4(t-BuPO3)8(μ2-OCH3)8] (2). The molecular architecture of 2 showcased an interesting correlation with platonic solids, wherein the Ce(IV), Sb(V), and P(V) ions were found to be present in vertices of an octahedron, a tetrahedron, and a cube, respectively. Under mild conditions, 1 and 2 exhibited the capability to act as catalysts for sulfoxidation in the presence of hydrogen peroxide, with 1 acting as a homogeneous catalyst and 2 acting as a heterogeneous catalyst. Both 1 and 2 showed high conversion for various substrates, with 1 showing moderate selectivity while 2 showcased high selectivity. Moreover 1 and 2 catalyzed the oxidation of 2-chloroethyl ethyl sulfide (CEES) to nontoxic 2-chloroethyl ethyl sulfoxide (CEESO) with high selectivity.

Photocatalytic detoxification of a sulfur mustard simulant using donor-enhanced porphyrin-based covalent-organic frameworks.

Photocatalytic detoxification of sulfur mustards (e.g., bis (2-chloroethyl) sulfide, SM) is an effective approach for protecting the ecological environment and human health. In order to fabricate COFs with high performance for the selective transformation of the SM simulant 2-chloroethyl ethyl sulfide (CEES) to nontoxic 2-chloroethyl ethyl sulfoxide (CEESO), three porphyrin-based COFs with different donor groups (R = H, OH, and OMe) were synthesized. Among these COFs, COF-OMe, which possesses the strongest electron-donating ability, demonstrated a faster and higher detoxification rate of CEES at various concentrations, achieving selective oxidation of CEES to non-toxic CEESO with 99.2% conversion and 100% selectivity using white LED light irradiation within three hours. The facilitated charge transfer and separation as well as efficaciously produced reactive oxygen species (ROS), including singlet oxygen (1O2) and superoxide radical anions (O2˙-) are supposed to contribute to the excellent performance. The results demonstrated that the donor-enhanced porphyrin-based COFs could act as heterogeneous photocatalysts for visible light driven organic transformation and detoxification of sulfur mustards.

Exploring the Chemical Permeation Resistance and Surface Adsorption Properties of Polyurethane Coatings.

This work explores the adsorption and permeation of chemical warfare agents on polymer coatings to assess their protective potential. Two highly cross-linked aliphatic polyurethanes (PUs) were synthesized from two diisocyanate trimers, and their adsorption and permeation of dimethyl methylphosphonate (DMMP) and 2-chloroethyl ethyl sulfide (CEES) were analyzed using quartz crystal microbalance with dissipation and gas chromatography. The study revealed distinct adsorption properties for each agent and the PU. CEES, with higher polarity, exhibited greater readsorption compared to DMMP. IPtri-PU (alicyclic structure) showed negligible desorption and resorption, resulting in minimal permeation, unlike Htri-PU (aliphatic structure). Thus, alicyclic PUs are more promising for reducing adsorption and permeation.

Synergistic effect of Lewis acid-base sites in Zr4+-doped layered double hydroxides promotes rapid decontamination of nerve and blister agents under ambient conditions

Nerve and blister agents are among the deadliest chemicals posing a major threat to the society, and the development of materials that can rapidly decontaminate them under solvent-free ambient conditions is a major societal challenge. In this paper, layered double hydroxides (ZnAlxZr1−x-LDH) with varying Zr4+ doping content were synthesized and the decontamination properties of nerve and blister agents were investigated under ambient conditions. The results show that, compared to ZnAl-LDH, the ZnAl0.4Zr0.6-LDH with the highest amount of Zr4+ dopant reduced the decontamination reaction half-life of sarin (GB) and soman (GD) by 10 and 9 times, respectively. Mechanism studies revealed that ZnAl0.4Zr0.6-LDH employs the synergistic effect of Lewis acid-base sites to catalyze the decomposition of GB and GD into hydrolysis products and surface-bound hydrolysis products. The study also showed that under ambient conditions, ZnAl0.4Zr0.6-LDH demonstrated superior decontamination performance for the sulfur mustard (HD) simulant 2-chloroethyl ethyl sulfide (CEES) compared to ZnAl-LDH, effectively catalyzing the detoxification of CEES into dehydrohalogenation (EVS) and 1,2-bis-(ethylthio) ethane (BETE). ZnAl0.4Zr0.6-LDH also had satisfactory decontamination performance against HD. This work provides not only a green and efficient catalyst with potential for practical applications but also new insights for constructing broad-spectrum, highly efficient self-detoxifying materials.

Leveraging Ligand Desymmetrization to Enrich Structural Diversity of Zirconium Metal-Organic Frameworks for Toxic Chemical Adsorption.

The discovery of metal-organic frameworks (MOFs) with novel structures provides significant opportunities for developing porous solids with new properties and enriching the structural diversity of functional materials for various applications. The rational design of building units with specific geometric conformations is essential to direct the construction of MOFs with unique properties. Herein, we leverage a ligand desymmetrization approach to construct a series of new MOFs. A flexible tetratopic carboxylate ligand with a tetrahedral geometry was designed and assembled with a Zr6 cluster, generating four Zr-based MOF structures: NU-2600, NU-2700, NU-2800, and NU-1802, in which the ligand configurations and Zr6 cluster connectivities can be controlled by varying solvents and modulators during synthesis. Except for NU-1802, these represent entirely new topologies. Notably, NU-1802 exhibits structural flexibility, with up to a 74 % reduction in the unit cell volume as confirmed by single-crystal X-ray diffraction studies. Given their microporous structures, we studied the adsorption behaviors of n-hexane and 2-chloroethyl ethyl sulfide to explore the structure-property relationships of these MOFs. Overall, this work highlights ligand desymmetrization as a powerful method to enrich MOF structural diversity and access complex MOFs with non-default topologies suitable for applications such as toxic gas capture.

Ultra-Fast Degradation of Mustard Gas Simulant by Titanium Dioxide-Phosphomolybdic Acid Sub-1nm Nanobelts.

The development of novel catalysts for the rapid detoxification of sulfur mustard holds paramount importance in the field of military defense. In this work, titanium dioxide-phosphomolybdic acid sub-1nm nanobelts (TiO2/PMA SNBs) are employed as effective catalysts for the ultra-fast degradation of mustard gas simulants (2-chloroethyl ethyl sulfide, CEES) with 100% selectivity and a half-life (t1/2, time required for 50% conversion) as short as 12 s, which is the fastest time to the best of the knowledge. Even in dark conditions, this material can still achieve over 90% conversion within 5min. A mechanism study reveals that the rapid generation rate of 1O2 and O2 •- in the presence of TiO2/PMA SNBs and H2O2 plays a crucial role in facilitating the efficient oxidation of CEES. A filter layer of a gas mask loaded with TiO2/PMA SNBs and H2O2/polyvinylpyrrolidone cross-linked complex (PHP) is constructed, which demonstrates remarkable stability and exhibits exceptional efficacy in the detoxification of CEES in the presence of a small amount of water. This innovation offers great potential for enhancing personal protective equipment in practical applications.

Identification of complexes formed between sulphur mustards and arsenic-containing chemical warfare agents

Large quantities of toxic chemical warfare material, such as mixtures of sulphur mustard (HD) and arsenic-containing chemical warfare agents (As-CWAs) have been submerged in the Baltic Sea region after World War II. Little is known about the possible reactivity between HD and As-CWAs. In this study, we used simple reaction mixtures and ultra-high performance liquid chromatography combined with mass spectrometric techniques to study the reactivity of HD and the half-mustard 2-chloroethyl ethyl sulphide (CEES) with As-CWAs. Altogether 22 novel As-CWA-HD- and As-CWA-CEES-complexes were identified. Eight of the As-CWA-HD-complexes were also detected in environmental samples collected from known CWA dumping sites in the Baltic Sea region. Because the As-CWA-HD- and As-CWA-CEES-complexes have structural moieties of both S-mustards and As-CWAs, they might have toxic properties of both CWA-types. Therefore, their occurrence in the environment is concerning and their potential negative effect on the wellbeing of marine biota and humans should be investigated in the future. This is the first time alkylation of As–CWAs is reported, providing new knowledge on the reactivity of S-mustards. The results increase the understanding of the environmental fate of HD and is valuable for the assessment of the environmental threat of sea-dumped CWAs.

Mesenchymal Stem Cell Therapy Mitigates Acute and Chronic Lung Damages of Sulfur Mustard Analog Exposure.

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+CM-MSCs, (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 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 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.

Microwave-assisted hydrothermal synthesis of highly dispersed cerium–zirconium solid solution on Ti3C2Tx nanosheets as an efficient decontamination towards sulfur mustard simulants

The microwave-assisted hydrothermal method has facilitated the straightforward and efficient production of nanoscale CexZr1−xO2/Ti3C2Tx composites. This technique has greatly shortened the synthesis time several hours required by conventional hydrothermal method to merely 10 min. Due to the unique mechanism of microwave-hydrothermal synthesis, composites with excellent crystallinity, uniform particle size, and superior degradation capabilities can be obtained without calcination. Our investigation systematically explores the influence of various factors including mineralizer concentration, dispersant types, synthesis duration, cerium-to-zirconium ratio, as well as MXene content on the material properties. Optimal degradation of 2-chloroethyl ethyl sulfide (2-CEES), sulfur mustard simulants, is achieved using PEG1000 as the dispersant, a cerium-to-zirconium ratio of 1:2, along with 15 mL of MXene, resulting in a remarkably short half-life of only 6.5 min. Furthermore, it is confirmed that the incorporation of cerium atoms into ZrO2 lattice, forming a solid solution that is deposited onto the interlayer and surface of Ti3C2Tx nanosheets, with the composite particles measuring approximately 5.01 nm. The reduced size and increased specific surface area, coupled with the synergistic effects of oxygen vacancies and acid-base sites, ultimately contribute to the hydrolysis and elimination reactions occurring on 2-CEES. This research offers fresh perspectives on the development of novel materials for the degradation of chemical warfare agents.

Ambidextrous approach in action: Mg(OMe)2-doped hierarchical porous zirconium MOFs for decontaminating toxic chemical agents in nonbuffered systems

Utilizing a ligand-truncation strategy, a hierarchically porous structure was engineered within MOF-808, designated as HP-MOF-808. Furthermore, Mg(OMe)2 doping yielded HP-MOF-808@Mg(OMe)2, materials with both hierarchical porosity and basic character, for decontamination of two types of toxic chemical agents in nonbuffered solutions. In aqueous solution, the HP-808-2 exhibited decontamination rate constants for dimethyl-4-nitrophenyl phosphate (DMNP) and the nerve agent soman (GD) that were 3.13 and 1.98 times higher than MOF-808, respectively. The decontamination half-lives of HP-808-2@Mg(OMe)2 1:2 for DMNP and GD were further reduced by 13.87 and 36.82 times compared to HP-808-2. The material retains its decontamination efficacy for DMNP even after 60-days exposure in air and maintains structural integrity in solvents devoid of labile hydrogen for at least 24 h. In methanol, HP-808-2@Mg(OMe)2 achieved 100% DMNP decontamination in 25 min, outperforming HP-808-2 at 31.8%, marking it as the fastest DMNP decontamination material in methanol. Theoretical simulations confirmed the experimental findings, clearly demonstrating the energy changes during reactions with various nucleophiles and revealing the degradation process and mechanism of DMNP on the active sites of MOFs. Moreover, these materials rapidly degraded 2-chloroethyl ethyl sulfide (CEES) through hydrolysis, dehydrohalogenation, and heterolytic cleavage, demonstrating great potential for dual decontamination of toxic chemical agents in unbuffered systems.

Rational fabrication of two polyoxovanadate-based frameworks for efficient detoxifying mustard gas simulant

Two polyoxovanadates (POVs)-based cobalt–organic frameworks, namely [H2Co2(p-bix)4][V8O23] (1) and [Co(o-bix)][V2O6] (2) (where p-bix = 1,4-bis(imidazol-1-ylmethyl)benzene and o-bix = 1,2-bis(imidazol-1-ylmethyl)benzene), were synthesized via a hydrothermal process and thoroughly characterized structurally. Compound 1 features a three-dimensional framework where the inorganic layers {V8Co2}, containing circular [V4O12]4− ({V4}) dimers, are interconnected by p-bix ligands. While compound 2 forms a two-dimensional layer structure where the inorganic {V4} clusters are linked by four binuclear [Co2O3(o-bix)2]2− units through the sharing of O atoms from {V4} clusters. Given the catalytic prowess of POVs in oxidizing various organic substrates, we evaluated the catalytic performance of these two compounds as heterogeneous catalysts for detoxifying mustard gas simulant CEES (2-chloroethyl ethyl sulfide) into the non-toxic CEESO (2-chloroethyl ethyl sulfoxide). The catalytic tests revealed that both compounds effectively catalyze the oxidation of CEES, yielding solely CEESO. Particularly, catalyst 2 exhibited excellent catalytic properties, achieving nearly 100 % conversion and selectivity within just 40 min at room temperature. The prominent performance of 2 remains consistent through at least five recycling cycles, showcasing its durability and effectiveness. This exceptional performance of 2 was achieved due to the synergistic interaction between V and coordinatively unsaturated Co sites within the structure, as confirmed by detailed comparative studies of structure and catalytic activity as well as density functional theory (DFT) calculations.

Effects of Titanium Dioxide (TiO2) on Physico-Chemical Properties of Low-Density Polyethylene.

Hazardous chemicals are transported on rail and road networks. In the case of accidental spillage or terror attack, civilian and military first responders must approach the scene equipped with appropriate personal protective equipment. The plausible manufacturing of chemical protective polymer material, from photocatalyst anatase titanium dioxide (TiO2) doped low-density polyethylene (LDPE), for cost-effective durable lightweight protective garments against toxic chemicals such as 2-chloroethyl ethyl sulphide (CEES) was investigated. The photocatalytic effects on the physico-chemical properties, before and after ultraviolet (UV) light exposure were evaluated. TiO2 (0, 5, 10, 15% wt) doped LDPE films were extruded and characterized by SEM-EDX, TEM, tensile tester, DSC-TGA and permeation studies before and after exposure to UV light, respectively. Results revealed that tensile strength and thermal analysis showed an increasing shift, whilst CEES permeation times responded oppositely with a significant decrease from 127 min to 84 min due to the degradation of the polymer matrix for neat LDPE, before and after UV exposure. The TiO2-doped films showed an increasing shift in results obtained for physical properties as the doping concentration increased, before and after UV exposure. Relating to chemical properties, the trend was the inverse of the physical properties. The 15% TiO2-doped film showed improved permeation times only when the photocatalytic TiO2 was activated. However, 5% TiO2-doped film exceptionally maintained better permeation times before and after UV exposure demonstrating better resistance against CEES permeation.

The role of carbon textile surface functionalities in reactive adsorption of vapor and liquid 2-chloroethyl ethyl sulfide: Evaluating interactions at the interface

A carbon textile (CT) was chemically modified to increase its surface activity and promote the adsorption and degradation of 2-chloroethyl ethyl sulfide (CEES) - a surrogate for mustard gas. CT was initially subjected to oxidation (CTO), and then heated under ammonia (CTON) or hydrogen sulfide (CTOS) atmosphere to incorporate nitrogen or sulfur functionalities, respectively. Detoxification experiments were performed in closed vials using either vapor or liquid forms of CEES. The maximum vapor weight uptakes on CT, CTO, CTOS, and CTON were 399, 372, 434, and 489 mg/g, respectively. All textiles were able to prevent the vaporization of CEES liquid droplets. Although similar reaction products were detected in both vapor and liquid systems, the marked differences in the extent of CEES chemical transformation on the surfaces of the textiles indicate distinct detoxification pathways influenced by surface chemistry. Even though the heterogeneous surface of CTO, enriched with oxygen surface groups, facilitated various reactions, hydrolysis was the predominant pathway. The thermal treatment, regardless of the atmosphere, reduced the oxygen content, decreasing the extent of hydrolysis. However, incorporating basic surface groups such as pyridines, amines, or weak acids such as thiols promoted dehydrohalogenation as the main detoxification pathway on these samples.

Enhanced interfacial charge transfer in WO3-Bi2WO6 heterostructures: Toward trace detection of mustard gas simulant

Developing reliable and portable sensors for detection of highly toxic mustard gas is extremely important for public security. However, gas sensors based on pristine metal oxide semiconductors often suffer from high working temperature, inferior response, and inadequate detection limit owing to their poor intrinsic conductivity and weak adsorption toward target gases, thereby hindering their wide application. Herein, hierarchical WO3-Bi2WO6 heterostructures were fabricated as sensing materials to comprehensively improve their sensing properties to 2-chloroethyl ethyl sulfide (2-CEES, a mustard gas simulant). The optimized sensor based on WO3-Bi2WO6-2 displayed short response time of 1.4 s and high sensing response (Ra/Rg = 63) to 50 ppm 2-CEES at 133 °C, together with an ultra-low detection limit of 10 ppb. The improvement of WO3-Bi2WO6-2 in sensing properties are synergistically attributed to the amount of heterojunction and surface adsorption sites, which were proved by DFT calculations and a series of characterizations. This work might pave the way for further developing heterostructure-based sensors for 2-CEES detection with superior sensing properties.

Doxycycline versus Curcumin for Inhibition of Matrix Metalloproteinase Expression and Activity Following Chemically Induced Inflammation in Corneal Cells.

Sulfur mustard (SM) is a potent blistering agent. This alkylating chemical agent has extremely toxic effects on the eye. MMP-2 and MMP-9 are the two most important matrix metalloproteinase enzymes involved in the pathology of chemical eye injuries. Curcumin is regarded as a natural anti-inflammatory agent. This study aims to compare the anti-inflammatory effects of curcumin versus doxycycline on chemically induced corneal injuries. The HCE-2 cell line was used as a model for corneal cells. The effective concentrations of 2-chloroethyl ethyl sulfide (CEES) - as an analog of SM - doxycycline, and curcumin were determined using the MTT assay. The gene expression of MMP-2, MMP-9, and tissue inhibitors of metalloproteinase (TIMP-1) was evaluated by the real-time PCR method. Also, the activity of MMP-2 and MMP-9 enzymes was determined by zymography. The expression of the MMP-2 and MMP-9 genes increased 5- and 3.3-fold after exposure to CEES, respectively. Following the treatment with curcumin and doxycycline, MMP-2 expression decreased significantly. Also, after treatment with curcumin and doxycycline, the MMP-9 expression decreased 2.5- and 1.6-fold, respectively. The reduction in activity was 32% for MMP-2 and 56% for MMP-9 after treatment with curcumin. The corresponding values were 12% and 40% following doxycycline treatment. There was no significant difference between the effects of curcumin and doxycycline on reducing MMP-2 expression, but the difference was statistically significant in the case of MMP-9. Doxycycline and curcumin can inhibit MMP expression and activity in chemically exposed corneal cells. Curcumin has a greater ability than doxycycline to inhibit MMP-2 and MMP-9 enzymes; however, the difference is statistically significant only in the case of MMP-9. After further validation, these substances can be introduced as anti- inflammatory agents to treat corneal chemical burns.

Photothermal-enhanced detoxification metal-organic framework microneedle array for 2-chloroethyl ethyl sulfide-poisoned wound healing

Sulfur mustard (2,2′-dichloroethylsulfide; SM) is a bifunctional alkylating agent that can easily penetrate skin and cause persistent pain and damage. Effective biological dressings are required to treat wounds caused or poisoned by SM. Though the use of SM is regulated under the Chemical Weapons Convention, it is still a threat during wars and terrorist attacks. Herein, we present a photothermal-enhanced detoxification microneedles array (MNA) encapsulated with ZnIn2S4@UiO-66-NH2 (ZnInS/UIO) catalysts for the treatment of 2-chloroethyl ethyl sulfide (CEES, SM analog)-poisoned wounds under simulated sunlight (SSL) irradiation. Due to the excellent photothermal detoxification capability possessed by ZnInS/UIO, the conversion rate of CEES can be significantly increased under SSL exposure. When encased in a polyvinyl alcohol (PVA) MNA and piercing into the skin, ZnInS/UIO catalysts can be released quickly from MNA for detoxification. After applying the resultant ZnInS/UIO-MNA to the CEES-poisoned wound bed, acceleration of the wound healing process and a reduced inflammatory response can be confirmed. In conclusion, ZnInS/UIO-MNA has encouraging potential as a first-aid dressing for CEES-poisoned wound healing in battlefields and injuries related to acts of terrorism.

New two fold interpenetrating 3D polyoxovanadate-based metal–organic framework as bifunctional catalyst for the removal of 2-chloroethyl ethyl sulfide and phenolic compounds

New two fold interpenetrating 3D polyoxovanadate-based metal–organic framework as bifunctional catalyst for the removal of 2-chloroethyl ethyl sulfide and phenolic compounds

Unveiling Ru(bpy)3 2+-Encapsulated Zeolite Y as Photocatalyst: Harnessing Photocatalytic Singlet Oxygen Generation for Mustard Gas Simulant Detoxification.

This study explores the encapsulation of Ru(bpy)3 2+ within Zeolite Y (ZY) to improve photocatalytic singlet oxygen generation for the degradation of a mustard gas simulant, namely 2-chloroethyl ethyl sulfide (CEES). Mustard gas simulants are known to disrupt several biological processes; thus, their effective degradation is essential. Zeolite Y, with its hierarchical structure and adjustable Si/Al ratios, is an ideal host for Ru(bpy)3 2+, significantly improving its photocatalytic efficiency and stability. It is demonstrated through XRD and spectroscopic analyses that encapsulated Ru(bpy)3 2+ maintains its structural and photophysical properties, which are essential for generating singlet oxygen. Ru(bpy)3(1.0) loaded ZY(15) (where 1.0 and 15 represent the encapsulated amount of Ru(bpy)3 2+ and Si/Al ratio, respectively) outperforms other investigated photocatalytic systems in the oxidation of CEES, demonstrating high conversion rates and selectivity toward nontoxic sulfoxide products. Immobilization of Ru(bpy)3 2+-encapsulated zeolite Y onto cotton fabric results in effective degradation of CEES. The experimental results, validated by theoretical calculations, indicate an improved oxygen affinity and accessibility in zeolites with higher Si/Al ratios. This study advances the design of photocatalytic materials for environmental and defense applications, providing sustainable solutions for hazardous chemical degradation.

Permeable Self-Association of Metal-Organic Framework 808/Ag-Based Fiber Membrane for Broad-Spectrum and Highly Efficient Degradation of Biological and Chemical War Agents.

The threat posed by biological and chemical warfare agents (BCWA) to national security, the environment, and personal health underscores the need for innovative chemical protective clothing. To address the limitations of conventional activated carbon materials, which are prone to falling off and adsorption saturation, an efficient self-association approach was introduced. In this study, we proposed the immobilization of metal-organic framework (MOF) 808 and Ag nanoparticles onto a polypropylene (PP) fiber membrane using a rapid self-association method facilitated by chitosan (CS). The MOF 808/Ag-based (PP-CS/808-Ag) fiber membrane demonstrated exceptional degradation efficiency, achieving a remarkable rate of t1/2 within 2 h for the mustard simulant 2-chloroethyl ethyl sulfide (2-CEES) and a rate of t1/2 = 4.12 min for the G-series simulant dimethyl 4-nitrophenylphosphate (DMNP). A theoretical computational model was developed to determine the overall reaction mechanism, and it was verified that MOF 808 and Ag nanoparticles were mainly involved in the hydrolysis process against 2-CEES and DMNP. The PP-CS/808-Ag composite fiber film was prepared as the core layer, and the fracture strength, bending resistance, and moisture permeability were better than those specified by many countries for biochemical protective clothing, showing that it has a broad application prospect in developing a generation of broad-spectrum bioprotective clothing.