110-77-0Relevant academic research and scientific papers
Synthesis, characterization, and heterobimetallic cooperation in a titanium-chromium catalyst for highly branched polyethylenes
Liu, Shaofeng,Motta, Alessandro,Delferro, Massimiliano,Marks, Tobin J.
, p. 8830 - 8833 (2013)
A heterobimetallic catalyst, {Ti - Cr}, consisting of a constrained-geometry titanium olefin polymerization center (CGCEtTi) covalently linked to a chromium bis(thioether)amine ethylene trimerization center (SNSCr) was synthesized and fully characterized. In ethylene homopolymerizations it affords linear low-density polyethylene with molecular weights as high as 460 kg·mol-1 and exclusively n-butyl branches in conversion-insensitive densities of ～18 branches/1000 carbon atoms, which are ～17 and ～3 times (conversion-dependent), respectively, those achieved by tandem mononuclear CGCEtTi and SNSCr catalysts under identical reaction conditions.
Nanosized inorganic metal oxides as heterogeneous catalysts for the degradation of chemical warfare agents
Bisio, Chiara,Carniato, Fabio,Palumbo, Chiara,Safronyuk, Sergey L.,Starodub, Mykola F.,Katsev, Andrew M.,Marchese, Leonardo,Guidotti, Matteo
, p. 192 - 199 (2016)
Nanosized inorganic metal oxides, such as TiO2, ZnO, γ-Al2O3, are proposed as heterogeneous catalysts for the oxidative degradation of chemical warfare agents (CWA), particularly of organosulfur toxic agents, into oxidised products with reduced toxicity. The morphology, structural and textural properties of the catalysts were investigated. Furthermore, their catalytic properties were evaluated in the oxidative abatement of (2-chloroethyl)ethylsulfide, CEES, a simulant of sulfur mustard (blistering CWA). Their performance was also compared to a conventional decontamination powder and a commercial Nb2O5 sample. The metal oxides powders were then employed in the active oxidative decontamination of CEES from a cotton textile substrate, mimicking a real contamination occurrence. Remarkable results in terms of abatement and degradation into desired products were recorded, achieving good conversions and decontamination efficiency with Nb2O5, TiO2 and γ-Al2O3, under very mild conditions, with hydrogen peroxide (as aqueous solution or as urea-hydrogen peroxide adduct), at room temperature and ambient pressure. In the aim of a real on-field use, the potential environmental impact of these solids was also evaluated by bioluminescence toxicity tests on reference bacteria (Photobacterium leiognathi Sh1), showing a negligible negative impact for TiO2, γ-Al2O3, and Nb2O5. A major biotoxic effect was only found for ZnO.
Decontamination of 2-chloro ethyl ethyl sulphide and dimethyl methyl phosphonate from aqueous solutions using manganese oxide nanostructures
Verma, Monu,Chandra, Ramesh,Gupta, Vinod Kumar
, p. 285 - 292 (2016)
Current study investigates the efficiency of reactive adsorbent composed of MnO2 nanoparticles and nanorods for the detoxification of 2-chloro ethyl ethyl sulphide (CEES) and dimethyl methyl phosphonate (DMMP), well-known simulants of sulphur mustard and sarin, respectively. The MnO2 nanoparticles and nanorods were synthesised using novel reactive magnetron sputtering technique and then characterised by powder XRD, Raman spectroscopy, FE-SEM, TEM, BET, FT-IR and Thermogravimetry (TG) analysis. Powder XRD and Raman results confirm the formation of pure tetragonal phase of MnO2 nanostructure material. The FE-SEM and TEM analysis exhibited the formation of aggregate MnO2 nanoparticles and nanorods. The surface area of the synthesised aggregate MnO2 nanoparticles and nanorods (164.28 m2/g) was found to be enhanced significantly in comparison with what was reported in the literature. Decontamination reactions of synthesised nanostructure material were examined by GC equipped with FID and the products obtained after reaction were analysed by GC-MS and FT-IR techniques. It was observed that the currently synthesised MnO2 nanoparticles and nanorods exhibit much better decontamination results towards CEES as well as DMMP in comparison to or as per existing solid decontaminants. The reactions exhibited pseudo first order kinetic behaviour with rate constant and half life value 0.267 h- 1 and 2.58 h for CEES and 0.068 h- 1 and 10.10 h for DMMP, respectively. The data exhibits the formation of non-toxic hydrolysis products in the detoxification of CEES as well as DMMP.
Hydrolysis of Mustard Derivatives in Aqueous Acetone-Water and Ethanol-Water Mixtures
Yang, Yu-Chu,Ward, J. Richard,Luteran, Thomas
, p. 2756 - 2759 (1986)
The hydrolyses of two mustard derivatives, 2-chloroethyl ethyl sulfide (CEES) and 2-chloroethyl methyl sulfide (CEMS), were investigated and compared with the hydrolysis of tert-butyl chloride (TBC) in aqueous binary mixtures of acetone and ethanol from 0 to 45 deg C.The solvent effect on rates and on activation parameters provided further evidence for an SN1 mechanism with anchimeric assistance of the sulfur atom to form a cyclic sulfonium ion as the reaction intermediate.Lower ΔH(excit.) and ΔS(excit.) values of both CEES and CEMS relative to that of TBC reflected the S-C bond formation and the strained structure of the intermediate.A finite and negative ΔCp(excit.) was detected.The observed ΔH(excit.) was corrected for the cosolvent effect by adopting Fagley's model and was consistent with the value in pure water.
Effect of crystallographic structure of MnO2 on degradation of 2-CEES
Guo, Yueting,Kong, Lingce,Lei, Meiling,Xin, Yi,Zuo, Yanjun,Chen, Wenming
, (2021)
In this study, four MnO2 samples with different crystallographic structures (α-, β-, δ- and γ-MnO2) were synthesized by the hydrothermal method. The relationship between the characteristics of the four crystalline samples and their degradation ability against 2-chloroethyl ethyl sulfide (2-CEES), a simulant of the chemical warfare agent sulfur mustard, and the relevant reaction mechanism were investigated. Characterization data indicated that the various crystal types displayed different specific surface areas, frequency of lattice defects, amounts of adsorbed/inserted water, and numbers and strength of basic sites. The combined effects of these differences caused different degradation activity in 2-CEES degradation to be observed. The reaction followed pseudo-first-order kinetics, whereby γ-MnO2 exhibited the highest degradation activity. The mechanism of 2-CEES degradation was studied by gas chromatography and infrared spectroscopy methods, and data indicated the key role played by substrate hydrolysis and oxidation in the degradation process.
A New Hexa-TiIV-Substituted Sandwich-Type Polyoxotungstate: Hydrothermal Synthesis, Structure, and Oxidative Decontamination of Chemical Warfare Agent Simulant
Qin, Dan,Sun, Jun-Jun,Wang, Yue-Lin,Yang, Guo-Yu
, p. 475 - 479 (2020)
A new hexa-TiIV-substituted sandwich-type silicotungstate, Na2(H2enMe)4[Ti6(μ-O)9(A-α-SiW9O34H2)2]·16H2O (1, enMe = 1,2-diaminopropane) has been synthesized under mild hydrothermal conditions and characterized by FT-IR spectroscopy, elemental analysis, thermogravimetric analysis, single-crystal and powder X-ray diffraction. Compound 1 contains a dimeric polyoxoanion with two [A-α-SiW9O34]10– Keggin moieties sandwiching a trigonal-prismatic [Ti6(μ-O9)]6+ cluster. The catalytic performance of 1 was evaluated for the oxidative decontamination of chemical warfare agent, i.e. sulfur mustard simulant, 2-chloroethyl ethyl sulfide (CEES), using H2O2 under ambient conditions, showing that 1 is an excellent catalyst for the rapid and complete transformation from CEES to nontoxic 2-chloroethyl ethyl sulfoxide (CEESO) with 100 % selectivity. In addition, 1 exhibits good stability and recyclability.
Preparation of a porphyrin-polyoxometalate hybrid and its photocatalytic degradation performance for mustard gas simulant 2-chloroethyl ethyl sulfide
Tao, Fangsheng,Tian, Shubo,Wang, Yong'an,Yang, Ying,Zhang, Lijuan,Zhong, Yuxu,Zhou, Yunshan
supporting information, (2022/01/03)
By combining 5,10,15,20-tetra(4-chlorine)phenylporphyrin (TClPP) and α-Keggin polyoxometalate H5PV2Mo10O40 (H5PVMo) via a simple ion-exchange method, an organic-inorganic hybrid material [C44H28N4Cl4]1.5[H2PMo10V2O40]·2C2H6O (H2TClPP-H2PVMo) was prepared and thoroughly characterized by a variety of techniques. The homogeneous photocatalytic degradation of 2-chloroethyl ethyl sulfide (CEES) (5 μL) by H2TClPP-H2PVMo (1 × 10?6 mol/L) was studied in methanol and methanol-water mixed solvent (v/v = 1:1), in which the degradation rate of CEES reached 99.52% and 99.14%, respectively. The reaction followed first-order reaction kinetics, and the half-life and kinetic constant in methanol and the mixed solvent were respectively 33.0 min, ?0.021 min?1 and 15.7 min, ?0.043 min?1. Mechanism analysis indicated that under visible light irradiation in the air, CEES was degraded via oxidation and alcoholysis/hydrolysis in methanol and the mixed solvent. O2·? and 1O2 generated by H2TClPP-H2PVMo selectively oxidized CEES into a nontoxic sulfoxide. Singlet oxygen capture experiments showed that H2TClPP-H2PVMo (? = 0.73) had a higher quantum yield of singlet oxygen than TClPP (? = 0.35) under an air atmosphere and visible light irradiation.
A dual-function all-inorganic intercluster salt comprising the polycation ?-[Al13O4(OH)24(H2O)12]7+and polyanion α-[PMo10V2O40]5-for detoxifying sulfur mustard and soman
Gao, Qi,Tao, Fangsheng,Wang, Yong'An,Yin, Jianbo,Yu, Jialin,Zhang, Lijuan,Zhong, Yuxu,Zhou, Yuanyuan,Zhou, Yunshan
, p. 8122 - 8135 (2020/07/10)
?-[Al13O4(OH)24(H2O)12]7+, which shares similarity with the phosphotriesterase active site ZnII-OH-ZnII, was specially chosen to interact with the cluster α-PMo10V2O405- to form a new three-dimensional intercluster, which crystallized in the monoclinic space group P21/m with Z = 2, for the decontamination of chemical warfare agents. The experimental results showed that 50 mg of the compound decontaminated 96.4percent (within 120 min) and 99.5percent (within 40 min) of sulfur mustard (HD) (4 μL) and soman (GD) (4 μL), respectively, in ambient conditions. The decontamination processes followed first-order reaction kinetics with a rate constant and half-life of 0.01234 min-1 and 56.15 min for HD and 0.1198 min-1 and 5.78 min for GD, respectively. It was concluded that the α-PMo10V2O405- moiety was responsible for the catalytic oxidation of HD into non-toxic sulfoxide, while the ?-[Al13O4(OH)24(H2O)12]7+ moiety was responsible for the catalytic hydrolysis of HD and GD into nontoxic hydrolysates. Besides, the compound showed notable efficacy for the decontamination of HD on guinea pig skin and of GD on Kunming mouse skin, indicating high potential for use in human skin protection and treatment. This journal is
(POLY)THIOL COMPOUND PRODUCTION METHOD
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Paragraph 0085; 0088-0093; 0096-0104; 0107-0108, (2019/12/15)
PROBLEM TO BE SOLVED: To provide a production method capable of realizing a (poly)thiol compound of interest with high yields efficiently and inexpensively in a simple manner. SOLUTION: The (poly)thiol compound production method comprises reacting hydrogen sulfide with an organic halogen compound represented by the general formula (1) defined by Q1-(X)n in the presence of one or more base compounds having a pKa from 4 to 13 inclusive, thereby producing a (poly)thiol compound represented by the general formula (2) defined by Q2-(SH)n. SELECTED DRAWING: None COPYRIGHT: (C)2020,JPOandINPIT
Textile/metal-organic-framework composites as self-detoxifying filters for chemical-warfare agents
L?pez-Maya, Elena,Montoro, Carmen,Rodríguez-Albelo, L. Marleny,Aznar Cervantes, Salvador D.,Lozano-Pérez, A. Abel,Cenís, José Luis,Barea, Elisa,Navarro, Jorge A. R.
supporting information, p. 6790 - 6794 (2015/06/08)
Abstract The current technology of air-filtration materials for protection against highly toxic chemicals, that is, chemical-warfare agents, is mainly based on the broad and effective adsorptive properties of hydrophobic activated carbons. However, adsorption does not prevent these materials from behaving as secondary emitters once they are contaminated. Thus, the development of efficient self-cleaning filters is of high interest. Herein, we report how we can take advantage of the improved phosphotriesterase catalytic activity of lithium alkoxide doped zirconium(IV) metal-organic framework (MOF) materials to develop advanced self-detoxifying adsorbents of chemical-warfare agents containing hydrolysable P-F, P-O, and C-Cl bonds. Moreover, we also show that it is possible to integrate these materials onto textiles, thereby combining air-permeation properties of the textiles with the self-detoxifying properties of the MOF material. The silk of human kindness: Insertion of lithium alkoxides in zirconium metal-organic frameworks (MOF) which are then deposited on silk fibers gives rise to protective fabrics capable of self-detoxifying chemical-warfare agents. The fabrics combine the air-permeation properties of the textiles with the highly active phosphotriesterase catalytic activity of the MOF for the hydrolysis of P-F, P-O, and C-Cl bonds.
