- Wearable membranes from zirconium-oxo clusters cross-linked polymer networks for ultrafast chemical warfare agents decontamination
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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. The obtained membrane catalysts exhibit high swelling ratio with aqueous content as 84 wt% and therefore, demonstrate quasi-homogeneous catalytic activity toward the rapid hydrolysis of both CWA, soman (GD) (t1/2 = 5.0 min) and CWA simulant, methyl paraoxon (DMNP) (t1/2 = 8.9 min). Meanwhile, due to the covalent nature of cross-linkages and the high flexibility of polymer strands, the membranes possess promising mechanical strength and toughness that can stand the impact of high gas pressures and show high permeation for both CO2 and O2, enabling their extended applications in the field of collective/personal protective materials with body comfort.
- Chen, Likun,Fan, Zhiwei,Li, Heguo,Lu, Lin,Ma, Litao,Xie, Jiamin,Xin, Yi,Yan, Xiaoshan,Yin, Panchao
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supporting information
(2021/12/09)
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- Polyoxometalate-based gelating networks for entrapment and catalytic decontamination
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We report the synthesis and characterization of a new class of organic/inorganic hybrid polymers composed of covalently-bound 1,3,5-benzenetricarboxamide linkers and anionic polyoxovanadate clusters with varying counter-cations. These materials form gels within seconds upon contact with polar aprotic organic liquids and catalyze the degradation of odorants and toxic molecules under mild conditions including aerobic oxidation of thiols, hydrogen peroxide-catalyzed oxidation of sulfides, and hydrolysis of organophosphate chemical warfare agent analogues.
- Sullivan, Kevin P.,Neiwert, Wade A.,Zeng, Huadong,Mehta, Anil K.,Yin, Qiushi,Hillesheim, Daniel A.,Vivek, Skanda,Yin, Panchao,Collins-Wildman, Daniel L.,Weeks, Eric R.,Liu, Tianbo,Hill, Craig L.
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supporting information
p. 11480 - 11483
(2017/10/23)
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- The influence of gold(i) on the mechanism of thiolate, disulfide exchange
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The mechanism of gold(i)-thiolate, disulfide exchange was investigated by using initial-rate kinetic studies, 2D (1H-1H) ROESY NMR spectroscopy, and electrochemical/chemical techniques. The rate law for exchange is overall second order, first order in gold(i)-thiolate and disulfide. 2D NMR experiments show evidence of association between gold(i)-thiolate and disulfide. Electrochemical/chemical investigations do not show evidence of free thiolate and are consistent with a mechanism involving formation of a [Au-S, S-S], four-centered metallacycle intermediate during gold(i)-thiolate, disulfide exchange.
- Garusinghe, Gamage S. P.,Bessey, S. Max,Bruce, Alice E.,Bruce, Mitchell R. M.
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supporting information
p. 11261 - 11266
(2016/07/26)
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- THE EFFECTIVENESS OF A WEAK BASE IN THE OLEFIN SYNTHESIS FROM β-HYDROXYALKYLPHOSPHONATES
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β-Hydroxyalkylphosphonates were treated with a weak base such as potassium carbonate in N,N-dimethylformamide to give the corresponding olefins in good yields.
- Kawashima, Takayuki,Ishii, Takafumi,Inamoto, Naoki
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p. 1097 - 1100
(2007/10/02)
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- Nucleophilic Reactions of Anions with Trimethyl Phosphate in the Gas Phase by Ion Cyclotron Resonance Spectroscopy
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The gas-phase ion-molecule reactions of several negative ions (SF6-, SF5-, SO2F-, F2-, F-, CF3Cl-, Cl-, CD3O-, DNO-, OH-, and NH2-) with trimethyl phosphate are investigated using ion cyclotron resonance techniques.Nucleophilic attack on OP(OCH3)3 occurs chiefly at carbon, resulting in displacement of O2P(OCH3)2-.This behavior contrast with that observed in solution, where attack at phosphorus is favored for hard nucleophiles.This difference is ascribed to solvation energetics for the intermediates involved in the two reactions.The failure of SF6- to transfer F- to OP(OCH3)3 places an upper limit of 11 +/- 8 kcal/mol on the fluoride affinity of OP(OCH3)3.The significance of the results for the negative chemical ionization mass spectrometry of phosphorus esters is briefly discussed.
- Hodges, Ronald V.,Sullivan, S. A.,Beauchamp, J. L.
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p. 935 - 938
(2007/10/02)
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