27998-62-5Relevant articles and documents
Postsynthetic Incorporation of a Singlet Oxygen Photosensitizer in a Metal–Organic Framework for Fast and Selective Oxidative Detoxification of Sulfur Mustard
Howarth, Ashlee J.,Buru, Cassandra T.,Liu, Yangyang,Ploskonka, Ann M.,Hartlieb, Karel J.,McEntee, Monica,Mahle, John J.,Buchanan, James H.,Durke, Erin M.,Al-Juaid, Salih S.,Stoddart, J. Fraser,DeCoste, Jared B.,Hupp, Joseph T.,Farha, Omar K.
, p. 214 - 218 (2017)
A fullerene-based photosensitizer is incorporated postsynthetically into a Zr6-based MOF, NU-1000, for enhanced singlet oxygen production. The structural organic linkers in the MOF platform also act as photosensitizers which contribute to the o
Combining Two into One: A Dual-Function H5PV2Mo10O40?MOF-808 Composite as a Versatile Decontaminant for Sulfur Mustard and Soman
Gao, Qi,Huang, Chengcheng,Liu, Jie,Wang, Yong'An,Yu, Jialin,Zhang, Lijuan,Zhong, Yuxu,Zhou, Yuanyuan,Zhou, Yunshan
, (2020)
Due to the unpredictable nature of a battlefield environment, in the simultaneous degradation of sulfur mustard and nerve agents it is preferable to use just one decontaminant. Herein, the new composite HPVMo?MOF-808 (HPVMo = H5PV2Mo10O40) was deliberately synthesized via a simple impregnation method and thoroughly characterized. The results showed that the decontamination rate of the composites (30-40 mg) with optimal HPVMo loadings for HD (4 μL) and GD (4 μL) under ambient conditions was 97.2% (within 120 min) and 90.8% (within 30 min), respectively. Due to the combinational/synergistic effect of MOF-808 and encapsulated homogeneously dispersed HPVMo, the composite can very efficiently oxidize HD to nontoxic products in a single system, while retaining the inherent excellence of MOF-808 in hydrolytically degrading GD. The decontamination process was found to follow first-order reaction kinetics, and the rate constant and half-life of the composite for HD and GD were 0.0231 min-1, 30.13 min and 0.0795 min-1, 8.72 min, respectively. In addition, experimental results in guinea pigs and Kunming mice used as animal models showed that the composite provided effective skin protection against HD and GD, showing great potential for application in skin decontamination and protection.
A simple and controlled oxidative decontamination of sulfur mustard and its simulants using ozone gas
Ramakrishna,Krishna,Saini, Bijendra,Gopi,Swetha,Chandra Shekar
, p. 965 - 970 (2016)
A simple and efficient oxidative decontamination method was developed for sulfur mustard (HD), a potential chemical warfare agent. The method involves treatment of chemical warfare agent HD and its simulants, i.e., dimethyl sulfide, diethyl sulfide, and 2-chloroethyl ethyl sulfide with ozone gas at ambient conditions in acetonitrile solvent. Ozone gas readily oxidizes sulfur mustard in a controlled manner to give its corresponding nontoxic sulfoxide. This transformation is selective and takes place even at subzero temperatures. The oxidation products of HD and its simulants were monitored and quantified by gas chromatography and gas chromatography–mass spectrometry.
A novel polyoxovanadate-based Co-MOF: Highly efficient and selective oxidation of a mustard gas simulant by two-site synergetic catalysis
Dang, Tian-Yi,Li, Xiao-Hui,Liu, Shu-Mei,Liu, Shu-Xia,Lu, Ying,Tian, Hong-Rui,Zhang, Zhong
, p. 12398 - 12405 (2020)
Two novel polyoxovanadate-based metal-organic frameworks (MOFs), [Co(bib)]{V2O6} (V-Co-MOF) and [Ni(en)(bib)]{V2O6}·2H2O (V-Ni-MOF) (bib = 1,4-bis(1H-imidazoly-1-yl)benzene, en = ethylenediamine) were facilely synthesized under mild hydrothermal condition
V= O Functionalized {Tm2}-Organic Framework Designed by Postsynthesis Modification for Catalytic Chemical Fixation of CO2and Oxidation of Mustard Gas
Chen, Hongtai,Fan, Liming,Hu, Tuoping,Zhang, Xiutang
, p. 5005 - 5013 (2021)
In terms of recently documented references, the introduction of V= O units into porous MOF/COF frameworks can greatly improve their original performance and expand their application prospects due to a change in their electronegativity. In this work, by a cation-exchange strategy, a consummate combination of separate 4f [Tm2(CO2)8] SBUs and 3d [VIVO(H2O)2] units generated the functionalized porous metal-organic framework {(Me2NH2)2[VO(H2O)][Tm2(BDCP)2]·3DMF·3H2O}n (NUC-11), in which [Tm2(CO2)8] SBUs constitute the fundamental 3D host framework of {[Tm2](BDCP)2}n along with [VIVO(H2O)2] units being further docked on the inner wall of channels by covalent bonds. Significantly, NUC-11 represents the first example of V= O modified porous MOFs, in which uncoordinated carboxylic groups (-CO2H) further grasp the functional [VIVO(H2O)2] units on the initial basic skeleton along with the formation of covalent bonds as fixed ropes. Furthermore, activated samples of NUC-11 displayed a good catalytic performance for the chemical synthesis of carbonates from related epoxides and CO2 with high conversion rate. Moreover, by employing NUC-11 as a catalyst, a simulator of mustard gas, 2-chloroethyl ethyl sulfide, could be quickly and efficiently oxidized into low-toxicity products of oxidized sulfoxide (CEESO). Thus, this study offers a brand new view for the design and synthesis of functional-units-modified porous MOFs, which could be potentially applied as an excellent candidate in the growing field of efficient catalysis.
The reactions of singlet oxygen with β-chlorosulfides. The role of hydroperoxy sulfonium ylides in the oxidative destruction of chemical warfare simulants
Toutchkine, Alexei,Clennan, Edward L.
, p. 6519 - 6522 (1999)
The reactions of singlet oxygen with 2-chloroethyl ethyl sulfide and 3- chlorothiane are reported, In both cases elimination of HCl to produce α,β- unsaturated sulfoxides is observed. The experimental results implicate a hydroperoxy sulfonium ylide as a transition state or intermediate in an E2 or E1cb elimination, respectively.
Hollow Lindqvist-like-Shaped {V6} Cluster-Based Metal-Organic Framework for the Highly Efficient Detoxification of Mustard Gas Simulant
Tian, Hong-Rui,Zhang, Zhong,Dang, Tian-Yi,Liu, Shu-Mei,Lu, Ying,Liu, Shu-Xia
, p. 840 - 845 (2021)
A polyoxovanadate-based nickel-organic framework, [Ni(bib)2]{V2O6}({V6}-MOF, bib = 1,4-bis(1H-imidazoly-1-yl)benzene), was facilely prepared under gentle hydrothermal conditions and structurally characterized. Single-crystal X-ray diffraction analysis ind
Efficient and selective oxidation of sulfur mustard using singlet oxygen generated by a pyrene-based metal-organic framework
Liu, Yangyang,Buru, Cassandra T.,Howarth, Ashlee J.,Mahle, John J.,Buchanan, James H.,Decoste, Jared B.,Hupp, Joseph T.,Farha, Omar K.
, p. 13809 - 13813 (2016)
A pyrene-based metal-organic framework (MOF) NU-1000 was used as a heterogeneous photocatalyst for the degradation of a sulfur mustard simulant, 2-chloroethyl ethyl sulfide (CEES). Using irradiation from a commercially available and inexpensive ultraviole
Chemoselective Oxidation of Sulfides to Sulfoxides with Urea-Hydrogen Peroxide Complex Catalysed by Diselenide
Bulman Page, Philip C.,Buckley, Benjamin R.,Elliott, Claire,Chan, Yohan,Dreyfus, Nicolas,Marken, Frank
, p. 80 - 82 (2016)
A highly selective catalytic oxidation system has been developed for the conversion of sulfides into the corresponding sulfoxides using urea-hydrogen peroxide as stoichiometric oxidant in the presence of a catalytic quantity of diphenyl diselenide.
Electropolymerization of Metal Clusters Establishing a Versatile Platform for Enhanced Catalysis Performance
Cai, Jinmeng,Gong, Chun-Hua,Han, Zhen,Li, Si,Li, Yao,Mak, Thomas C. W.,Wang, Qian-You,Wang, Shan,Wang, Yi-Man,Zang, Shuang-Quan
supporting information, (2022/01/20)
Atomically precise metal clusters are attractive as highly efficient catalysts, but suffer from continuous efficiency deactivation in the catalytic process. Here, we report the development of an efficient strategy that enhances catalytic performance by electropolymerization (EP) of metal clusters into hybrid materials. Based on carbazole ligand protection, three polymerized metal-cluster hybrid materials, namely Poly-Cu14cba, Poly-Cu6Au6cbz and Poly-Cu6Ag4cbz, were prepared. Compared with isolated metal clusters, metal clusters immobilizing on a biscarbazole network after EP significantly improved their electron-transfer ability and long-term recyclability, resulting in higher catalytic performance. As a proof-of-concept, Poly-Cu14cba was evaluated as an electrocatalyst for reducing nitrate (NO3?) to ammonia (NH3), which exhibited ≈4-fold NH3 yield rate and ≈2-fold Faraday efficiency enhancement compared to that of Cu14cba with good durability. Similarly, Poly-Cu6Au6cbz showed 10 times higher photocatalytic efficiency towards chemical warfare simulants degradation than the cluster counterpart.
Covalent Organic Frameworks toward Diverse Photocatalytic Aerobic Oxidations
Liu, Shuyang,Tian, Miao,Bu, Xiubin,Tian, Hua,Yang, Xiaobo
supporting information, p. 7738 - 7744 (2021/05/07)
Photoactive two-dimensional covalent organic frameworks (2D-COFs) have become promising heterogenous photocatalysts in visible-light-driven organic transformations. Herein, a visible-light-driven selective aerobic oxidation of various small organic molecules by using 2D-COFs as the photocatalyst was developed. In this protocol, due to the remarkable photocatalytic capability of hydrazone-based 2D-COF-1 on molecular oxygen activation, a wide range of amides, quinolones, heterocyclic compounds, and sulfoxides were obtained with high efficiency and excellent functional group tolerance under very mild reaction conditions. Furthermore, benefiting from the inherent advantage of heterogenous photocatalysis, prominent sustainability and easy photocatalyst recyclability, a drug molecule (modafinil) and an oxidized mustard gas simulant (2-chloroethyl ethyl sulfoxide) were selectively and easily obtained in scale-up reactions. Mechanistic investigations were conducted using radical quenching experiments and in situ ESR spectroscopy, all corroborating the proposed role of 2D-COF-1 in photocatalytic cycle.
