L-Gel Formulation and Decontamination Reaction of Its Active Ingredient (Oxone) Against Mustard and VX Nerve Agent Simulants

Abstract

L-Gel is an effective decontamination reagent against chemical and biological warfare agents. To achieve optimized formulation of L-Gel, several formulations with different proportional amounts of oxone (oxidizer) and Cab-O-Sil (gelling agent) were prepared and their viscosities and densities were measured. Final optimized formulation of gel was obtained as a 0.25 M aqueous solution of oxone gelled with 13%W/W of Cab-O-Sil EH-5. The L-Gel active ingredient (oxone) was tested against O,O,S-triethyl phosphorothioate (TEPT) as VX simulant and methyl phenyl sulfide (MPS) and chloroethyl phenyl sulfide (CEPS) as HD simulants. Decontamination of TEPT by a 10-fold excess amount of oxone was completed within 7.5 min with a kinetic rate constant of 0.097 S^?1. In the presence of oxone, MPS was converted to methyl phenyl sulfoxide and methyl phenyl sulfone with a higher reaction rate than CEPS, decontaminated product of which was chloroethyl phenyl sulfone.

Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file.

GRAPHICAL ABSTRACT      

Wearable membranes from zirconium-oxo clusters cross-linked polymer networks for ultrafast chemical warfare agents decontamination

The urgent need for immediate personal protection against chemical warfare agents （CWAs） spurs the requirement on robust and highly efficient catalytic systems that can be conveniently integrated to wearable devices.Herein,as a new concept for CWA decontamination catalyst design,sub-nanoscale,catalytically active zirconium-oxo molecular clusters are covalently integrated in flexible polymer network as crosslinkers for the full exposure of catalytic sites as well as robust framework structures.Th...     

Liquid permeation through nonporous barrier materials

Permeation of chemical warfare agents (CWAs) and relatively nontoxic simulants in several elastomer compounds is examined using a new design flooded surface, liquid permeation cell. Diffusivity (D) and permeability are determined for sulfur mustard and sarin CWA, and for the simulants: dichlorohexane, chloroethyl phenyl sulfide, diethyl methylphosphonate and diisopropyl methylphosphonate. Values of D calculated by several kinetic methods at different stages of the permeation process and from steady-state permeability are generally in agreement but lower than those obtained from immersion kinetics. Barrier effectiveness of the elastomer compounds towards the CWA and simulant liquids decreases in the order: butyl > EPDM > nitrile ≫ silicone. Simulant and CWA permeation are correlated in terms of relative permeability and reduced breakthrough time.     

Using Metal Complex Ion-Molecule Reactions in a Miniature Rectilinear Ion Trap Mass Spectrometer to Detect Chemical Warfare Agents

The gas-phase reactions of a series of coordinatively unsaturated [Ni(L)_n]^y+ complexes, where L is a nitrogen-containing ligand, with chemical warfare agent (CWA) simulants in a miniature rectilinear ion trap mass spectrometer were investigated as part of a new approach to detect CWAs. Results show that upon entering the vacuum system via a poly(dimethylsiloxane) (PDMS) membrane introduction, low concentrations of several CWA simulants, including dipropyl sulfide (simulant for mustard gas), acetonitrile (simulant for the nerve agent tabun), and diethyl phosphite (simulant for nerve agents sarin, soman, tabun, and VX), can react with metal complex ions generated by electrospray ionization (ESI), thereby providing a sensitive means of detecting these compounds. The [Ni(L)_n]²⁺ complexes are found to be particularly reactive with the simulants of mustard gas and tabun, allowing their detection at low parts-per-billion (ppb) levels. These detection limits are well below reported exposure limits for these CWAs, which indicates the applicability of this new approach, and are about two orders of magnitude lower than electron ionization detection limits on the same mass spectrometer. The use of coordinatively unsaturated metal complexes as reagent ions offers the possibility of further tuning the ion-molecule chemistry so that desired compounds can be detected selectively or at even lower concentrations.

Synthesis of Na-A and/or Na-X zeolite/porous carbon composites from carbonized rice husk

Na-A and/or Na-X zeolite/porous carbon composites were prepared under hydrothermal conditions by NaOH dissolution of silica first from carbonized rice husk followed by addition of NaAlO₂ and in situ crystallization of zeolites i.e., using a two-step process. When a one-step process was used, both Na-A and Na-X zeolites crystallized on the surface of carbon. Na-A or Na-X zeolite crystals were prepared on the porous carbonized rice husk at 90 °C for 2-6 h by changing the SiO₂/Al₂O₃, H₂O/Na₂O and Na₂O/SiO₂ molar ratios of precursors in the two-step process. The surface area and NH₄⁺-cation exchange capacity (CEC) of Na-A zeolite/porous carbon were found to be 171 m²/g and 506 meq/100 g, respectively, while those of Na-X zeolite/porous carbon composites were 676 m²/g and 317 meq/100 g, respectively. Na-A and Na-X zeolites are well-known microporous and hydrophilic materials while carbonized rice husk was found to be mesoporous (pores of ∼3.9 nm) and hydrophobic. These hybrid microporous-mesoporous and hydrophilic-hydrophobic composites are expected to be useful for decontamination of metal cations as well as organic contaminants simultaneously.     

Fate of the chemical warfare agent O-ethyl S-2-diisopropylaminoethyl methylphosphonothiolate (VX) on soil following accelerant-based fire and liquid decontamination

In the event of alleged use of organophosphorus nerve agents, all kinds of environmental samples can be received for analysis. These might include decontaminated and charred matter collected from the site of a suspected chemical attack. In other scenarios, such matter might be sampled to confirm the site of a chemical weapon test or clandestine laboratory decontaminated and burned to prevent discovery. To provide an analytical capability for these contingencies, we present a preliminary investigation of the effect of accelerant-based fire and liquid decontamination on soil contaminated with the nerve agent O-ethyl S-2-diisopropylaminoethyl methylphosphonothiolate (VX). The objectives were (a) to determine if VX or its degradation products were detectable in soil after an accelerant-based fire promoted by aviation fuel, including following decontamination with Decontamination Solution 2 (DS2) or aqueous sodium hypochlorite, (b) to develop analytical methods to support forensic analysis of accelerant-soaked, decontaminated and charred soil and (c) to inform the design of future experiments of this type to improve analytical fidelity. Our results show for the first time that modern analytical techniques can be used to identify residual VX and its degradation products in contaminated soil after an accelerant-based fire and after chemical decontamination and then fire. Comparison of the gas chromatography–mass spectrometry (GC-MS) profiles of VX and its impurities/degradation products from contaminated burnt soil, and burnt soil spiked with VX, indicated that the fire resulted in the production of diethyl methylphosphonate and O,S-diethyl methylphosphonothiolate (by an unknown mechanism). Other products identified were indicative of chemical decontamination, and some of these provided evidence of the decontaminant used, for example, ethyl 2-methoxyethyl methylphosphonate and bis(2-methoxyethyl) methylphosphonate following decontamination with DS2. Sample preparation procedures and analytical methods suitable for investigating accelerant and decontaminant-soaked soil samples are presented. VX and its degradation products and/or impurities were detected under all the conditions studied, demonstrating that accelerant-based fire and liquid-based decontamination and then fire are unlikely to prevent the retrieval of evidence of chemical warfare agent (CWA) testing. This is the first published study of the effects of an accelerant-based fire on a CWA in environmental samples. The results will inform defence and security-based organisations worldwide and support the verification activities of the Organisation for the Prohibition of Chemical Weapons (OPCW), winner of the 2013 Nobel Peace Prize for its extensive efforts to eliminate chemical weapons.     

A Polyoxoniobate–Polyoxovanadate Double‐Anion Catalyst for Simultaneous Oxidative and Hydrolytic Decontamination of Chemical Warfare Agent Simulants

A novel double‐anion complex, H₁₃[(CH₃)₄N]₁₂[PNb₁₂O₄₀(V^VO)₂⋅(V^IV₄O₁₂)₂]⋅22 H₂O ( 1 ), based on bicapped polyoxoniobate and tetranuclear polyoxovanadate was synthesized, characterized by routine techniques and used in the catalytic decontamination of chemical warfare agents. Under mild conditions, 1 catalyzes both hydrolysis of the nerve agent simulant, diethyl cyanophosphonate (DECP) and selective oxidation of the sulfur mustard simulant, 2‐chloroethyl ethyl sulfide (CEES). In the oxidative decontamination system 100 % CEES was transformed selectively to nontoxic 2‐chloroethyl ethyl sulfoxide and vinyl ethyl sulfoxide using nearly stoichiometric 3 % aqueous H₂O₂ with a turnover frequency (TOF) of 16 000 h⁻¹. Importantly, the catalytic activity is maintained even after ten recycles and CEES is completely decontaminated in 3 mins without formation of the highly toxic sulfone by‐product. A three‐step oxidative mechanism is proposed.     

Ultra‐Fast Degradation of Chemical Warfare Agents Using MOF–Nanofiber Kebabs

The threat associated with chemical warfare agents (CWAs) motivates the development of new materials to provide enhanced protection with a reduced burden. Metal–organic frame‐works (MOFs) have recently been shown as highly effective catalysts for detoxifying CWAs, but challenges still remain for integrating MOFs into functional filter media and/or protective garments. Herein, we report a series of MOF–nanofiber kebab structures for fast degradation of CWAs. We found TiO₂ coatings deposited via atomic layer deposition (ALD) onto polyamide‐6 nanofibers enable the formation of conformal Zr‐based MOF thin films including UiO‐66, UiO‐66‐NH₂, and UiO‐67. Cross‐sectional TEM images show that these MOF crystals nucleate and grow directly on and around the nanofibers, with strong attachment to the substrates. These MOF‐functionalized nanofibers exhibit excellent reactivity for detoxifying CWAs. The half‐lives of a CWA simulant compound and nerve agent soman (GD) are as short as 7.3 min and 2.3 min, respectively. These results therefore provide the earliest report of MOF–nanofiber textile composites capable of ultra‐fast degradation of CWAs.     

聚氨酯/分子筛复合材料的制备及性能

以聚对苯二甲酸乙二醇酯（PEA）、甲苯二异氰酸酯（TDI-80）、扩链剂（MOCA）、分子筛为原料,采用预聚体法制备了聚氨酯／分子筛复合材料．考察了分子筛的种类及加入量对聚氨酯／分子筛复合材料的耐溶剂性能、力学性能及热分解温度的影响．结果表明：在相同加入量的前提下,采用4A和13X分子筛制备的复合材料,前者的耐溶剂性能及力学性能要优于后者,当加入量为5％时,性能达到最佳．两者的加入均能提高复合材料的热分解温度,但影响相差不大．     

HFIP-Functionalized Co3O4 Micro-Nano-Octahedra/rGO as a Double-Layer Sensing Material for Chemical Warfare Agents

Semiconductor metal oxides (SMO)-based gas-sensing materials suffer from insufficient detection of a specific target gas. Reliable selectivity, high sensitivity, and rapid response–recovery times under various working conditions are the main requirements for optimal gas sensors. Chemical warfare agents (CWA) such as sarin are fatal inhibitors of acetylcholinesterase in the nerve system. So, sensing materials with high sensitivity and selectivity toward CWA are urgently needed. Herein, micro-nano octahedral Co₃O₄ functionalized with hexafluoroisopropanol (HFIP) were deposited on a layer of reduced graphene oxide (rGO) as a double-layer sensing materials. The Co₃O₄ micro-nano octahedra were synthesized by direct growth from electrospun fiber templates calcined in ambient air. The double-layer rGO/Co₃O₄-HFIP sensing materials presented high selectivity toward DMMP (sarin agent simulant, dimethyl methyl phosphonate) versus rGO/Co₃O₄ and Co₃O₄ sensors after the exposure to various gases owing to hydrogen bonding between the DMMP molecules and Co₃O₄-HFIP. The rGO/Co₃O₄-HFIP sensors showed high stability with a response signal around 11.8 toward 0.5 ppm DMMP at 125 °C, and more than 75 % of the initial response was maintained under a saturated humid environment (85 % relative humidity). These results prove that these double-layer inorganic–organic composite sensing materials are excellent candidates to serve as optimal gas-sensing materials.     

In vivo molecular evaluation of guinea pig skin incisions healing after surgical suture and laser tissue welding using Raman spectroscopy

The healing process in guinea pig skin following surgical incisions was evaluated at the molecular level, in vivo, by the use of Raman spectroscopy. After the incisions were closed either by suturing or by laser tissue welding (LTW), differences in the respective Raman spectra were identified. The study determined that the ratio of the Raman peaks of the amide III (1247 cm⁻¹) band to a peak at 1326 cm⁻¹ (the superposition of elastin and keratin bands) can be used to evaluate the progression of wound healing. Conformational changes in the amide I band (1633–1682 cm⁻¹) and spectrum changes in the range of 1450–1520 cm⁻¹ were observed in LTW and sutured skin. The stages of the healing process of the guinea pig skin following LTW and suturing were evaluated by Raman spectroscopy, using histopathology as the gold standard. LTW skin demonstrated better healing than sutured skin, exhibiting minimal hyperkeratosis, minimal collagen deposition, near-normal surface contour, and minimal loss of dermal appendages. A wavelet decomposition–reconstruction baseline correction algorithm was employed to remove the fluorescence wing from the Raman spectra.     

Zeolite-Polymer Composite Materials as Water Scavenger

The influence of the charge compensating cation nature (Na⁺, Mg²⁺) on the water adsorption properties of LTA-type zeolites used as filler in composite materials (zeolite/polymers) was investigated. Large scale cation exchanges were performed on zeolite powder at 80 °C for 2 h using 1 M magnesium chloride (MgCl₂) aqueous solutions. XRF, ICP, and EDX analyses indicate a successful cationic exchange process without the modification of the zeolite structure as shown by XRD and solid-state NMR analyses. Composite materials (granulates and molded parts) were manufactured using to extrusion and injection processes. In the case of MgA zeolite, nitrogen adsorption–desorption experiments allowed us to measure a microporous volume, unlike NaA zeolite, which is non-porous to nitrogen probe molecule. SEM and EDX analyses highlighted the homogeneous distribution of zeolite crystals into the polymer matrix. Water adsorption capacities confirmed that the trends observed in the zeolite powder samples are preserved after dragging zeolites into composite formulations. Granulates and molded parts composite samples containing the magnesium exchanged zeolite showed an increase of their water adsorption capacity up to +27% in comparison to composite samples containing the non-exchanged zeolite. The MgA composite is more promising for water decontamination applications due to its higher water adsorption properties than the NaA composite.     

Synthesis of HZSM-5 zeolites with excellent DME aromatization properties by orthogonal test

Abstract

The synthesis conditions of HZSM-5 zeolite, including crystallization temperature, crystallization time and raw material ratio, were investigated by L₃₂ (4⁸) orthogonal test to specifically optimize its performance in dimethyl ether (DME) aromatization for the first time. Based on the total yield of aromatic products, the synthesis conditions of HZSM-5 zeolite with the best DME aromatization properties were obtained by comprehensive analysis and validation experiments. The relationship between the aromatization performance, crystalline structure, pore structure, and acidity of HZSM-5 zeolite were analyzed. The results showed that the HZSM-5 zeolite accompanied by hierarchical structure, an appropriate Brønsted and Lewis acid content and uniform crystal morphology, was successfully synthesized under optimized conditions. Over this unmodified and un-doped catalyst, the conversion of DME approached to 99.3% and the total yield of aromatics reached was 53.5%.     

Electrocatalysis of Chemical Warfare Agent Sulfur Mustard in Room Temperature Ionic Liquid

Room temperature ionic liquids (RTILs) have the potential for being ideal alternatives for organic solvents in chemical warfare agent (CWA) electrochemical reactions. In this paper, electrocatalysis of CWA sulfur mustard (SM) was achieved by exploring the potential advantage of RTIL methyltrioctylammonium bis (trifluoromethylsulfonyl) imide and further this methodology was used for the detection of CWA. The hydrophobicity of this RTIL offers the opportunity to use this methodology in field condition without environmental humidity effect. The diffusion coefficient calculated for SM in RTIL was 0.196×10⁻⁹ cm²/s. The electrochemical parameters deduced from cyclic voltammetry such as electron transfer coefficient (α), electron transfer number (n) and heterogenous rate constant were estimated 0.11, 2 and 4.41 s⁻¹, respectively. The electrocatalytic activity of the RTIL toward the electrochemical reduction and oxidation of CWA is evidenced, showing the potential of this novel approach for the oxidation of other toxic CWAs. The new RTIL based strategy provides an opportunity to develop field deployable detection of CWA and could provide a new paradigm shift in CWA detection approach, addressing the escalating threat of CWA.     

Electrochemical Behavior and Determination of Rutin at the Copper Nanoparticles-Doped Zeolite A/Graphene Oxide-Modified Electrode

In this work, a novel Cu?zeolite A/graphene modified glassy carbon electrode was applied for the determination of rutin. The Cu?zeolite A/graphene composites were prepared using copper doped zeolite A and graphene oxide as the precursor, subsequently reduced by chemical agents. Based on the Cu?zeolite A/graphene modified electrode, the overpotential of the rutin oxidation was lowered by ~300 mV. Also the proposed Cu?zeolite A/graphene modified electrode showed higher electrocatalytic performance than zeolite A/graphene electrode or graphene modified electrode. The electrochemical behavior of copper incorporated in the zeolite A modified electrode illustrated the adsorption-controlled reaction at the modified electrode. The behavior of electrocatalytic oxidation of rutin at the modified electrode was investigated. The diffusion coefficient of rutin was equal to 4.2 × 10^–7 cm²/s. A linear calibration graph was obtained for rutin over the concentration range of 2.3 × 10^–7–2.5 × 10^–3 M. The detection limit for rutin was 1.2 × 10^–7 M. The RSDs of 10 replicate measurements performed on a single electrode at rutin concentrations between 2.3 × 10^–7–2.5 × 10^–3 M were between 1.1 and 2.1%. Study of the influence of potentially interfering substances on the peak current of rutin showed that the method was highly selective. The proposed electrode was used for the determination of rutin in real samples with satisfactory results.     

The effect of triethyl citrate on the dispersibility and water vapor sorption behavior of polylactic acid/zeolite composites

The aim of this study was to investigate the water vapor adsorption behavior and mechanical properties of poly (lactic acid) (PLA)/zeolite (5, 10, or 15 phr) composites prepared with triethyl citrate (TEC; 20 phr) via a melting process. TEC was used to improve the flexibility of the PLA and the dispersibility of the zeolite in TEC-zeolite suspensions that were ultra-sonicated. It was found that zeolite was uniformly dispersed in the PLA matrix, and the interfacial adhesion between the PLA matrix and zeolite was enhanced by TEC. In addition, the tensile strengths and Young's modulus of the composites improved with increasing zeolite content. The PLA/zeolite composites prepared with TEC had increased water vapor permeability and contact angles compared to neat PLA and standard PLA/zeolite due to the presence of TEC. In particular, TEC accelerated the hydrolysis of the PLA surface in a high humidity environment, resulting in an improvement in water vapor sorption capacity. At the same zeolite content of 15 phr, the equilibrium moisture content (EMC) values of PLA/zeolite films prepared with TEC increased by up to 39.25 mg/g whereas those prepared without TEC only increased by up to 24.33 mg/g. The results suggest the possibility of applying PLA/zeolite films prepared with TEC as a flexible active packaging material.     

Sorption characteristics of uranium onto composite ion exchangers

The composite ion exchangers were tested for their ability to remove UO₂ ²⁺ from aqueous solutions. Polyacrylonitrile (PAN) composites having natural zeolite, clinoptilolite, and synthetic zeolite, zeolite X, were used as an adsorbents. The influences of pH, U(VI) concentration, temperature and contact time on the sorption behavior of U(VI) were investigated in order to gain a macroscopic understanding of the sorption mechanism. The optimum adsorption conditions were determined for two composites. The sorption behaviors of uranium on both composites from aqueous systems have been studied by batch technique. Parameters on desorption were also investigated to recover the adsorbed uranium.     

Desorption electrospray ionization mass spectrometric analysis of organophosphorus chemical warfare agents using ion mobility and tandem mass spectrometry

Desorption electrospray ionization mass spectrometry (DESI‐MS) has been applied to the direct analysis of sample media for target chemicals, including chemical warfare agents (CWA), without the need for additional sample handling. During the present study, solid‐phase microextraction (SPME) fibers were used to sample the headspace above five organophosphorus CWA, O‐isopropyl methylphosphonofluoridate (sarin, GB), O‐pinacolyl methylphosphonofluoridate (soman, GD), O‐ethyl N,N‐dimethyl phosphoramidocyanidate (tabun, GA), O‐cyclohexyl methylphosphonofluoridate (cyclohexyl sarin, GF) and O‐ethyl S‐2‐diisopropylaminoethyl methyl phosphonothiolate (VX) spiked into glass headspace sampling vials. Following sampling, the SPME fibers were introduced directly into a modified ESI source, enabling rapid and safe DESI of the toxic compounds. A SYNAPT HDMS? instrument was used to acquire time‐aligned parallel (TAP) fragmentation data, which provided both ion mobility and MSⁿ (n = 2 or 3) data useful for the confirmation of CWA. Unique ion mobility profiles were acquired for each compound and characteristic product ions of the ion mobility separated ions were produced in the Triwave? transfer collision region. Up to six full scanning MSⁿ spectra, containing the [M + H]⁺ ion and up to seven diagnostic product ions, were acquired for each CWA during SPME fiber analysis. A rapid screening approach, based on the developed methodology, was applied to several typical forensic media, including Dacron sampling swabs spiked with 5 µg of CWA. Background interference was minimal and the spiked CWA were readily identified within one minute on the basis of the acquired ion mobility and mass spectrometric data. Copyright © 2010 Crown in the right of Canada. Published by John Wiley & Sons, Ltd.     

溶胶-凝胶法合成硅溶胶包覆型均分散纳米β分子筛

在系统考察铝源、反应体系硅铝比、钠离子、反应温度等对分子筛粒度影响的基础上,优化合成条件合成出了粒径为100 nm左右的β分子筛。利用XRD和TEM对所合成样品进行了表征。采用溶胶凝胶法研究了硅溶胶包覆的均分散纳米β分子筛复合材料的合成,结果表明合成产物为纳米β分子筛均匀分散于硅溶胶基质中的微孔-介孔双孔复合材料。     

The effects of natural zeolite and silane coupling agents on melting and crystallization behaviour of polypropylene

The thermal characterization of polypropylene (PP) composites containing untreated and treated zeolite with different silane coupling agents was carried out using thermogravimetric analysis (TG) and differential scanning calorimetry (DSC) to investigate the effects of natural zeolite and surface modifiers on melting, crystallization and degradation behaviour of PP. 3-aminopropyltriethoxysilane (AMPTES), methyltriethoxysilane (MTES) and 3-mercaptopropyltrimethoxysilane (MPTMS) were used as surface modifiers at four different concentrations (0.5–2.0 mass%). Thermal analyses indicated that silane treatment and 2–6 mass% zeolite addition have no significant effect on the melting and degradation temperatures of the composites. The crystallization temperatures of the composites were increased due to the nucleating effect of the zeolite. The influence of the modifiers on the interactions between PP and zeolite was determined by the activities of untreated and treated zeolite. The maximum interactions leading to good adhesion were observed in the AMPTES treated composites. Also, non-isothermal crystallization kinetics of the composites was analyzed using Avrami and Kissinger models.