Department of Chemistry, Cherry L. Emerson Center for Scientific Computation, Emory University, 1515 Dickey Dr., Atlanta, Georgia, 30322, USA.
X-ray Crystallography Center, Emory University, 1515 Dickey Dr., Atlanta, Georgia, 30322, USA.
Angew Chem Int Ed Engl. 2016 Jun 20;55(26):7403-7. doi: 10.1002/anie.201601620. Epub 2016 Apr 9.
A wide range of chemical warfare agents and their simulants are catalytically decontaminated by a new one-dimensional polymeric polyniobate (P-PONb), K12 [Ti2 O2 ][GeNb12 O40 ]⋅19 H2 O (KGeNb) under mild conditions and in the dark. Uniquely, KGeNb facilitates hydrolysis of nerve agents Sarin (GB) and Soman (GD) (and their less reactive simulants, dimethyl methylphosphonate (DMMP)) as well as mustard (HD) in both liquid and gas phases at ambient temperature and in the absence of neutralizing bases or illumination. Three lines of evidence establish that KGeNb removes DMMP, and thus likely GB/GD, by general base catalysis: a) the k(H2 O)/k(D2 O) solvent isotope effect is 1.4; b) the rate law (hydrolysis at the same pH depends on the amount of P-PONb present); and c) hydroxide is far less active against the above simulants at the same pH than the P-PONbs themselves, a critical control experiment.
在温和条件下和黑暗中，一种新型一维聚合多铌酸盐（P-PONb）K12 [Ti2 O2 ][GeNb12 O40 ]⋅19 H2 O（KGeNb）可催化降解多种化学战剂及其模拟剂。独特的是，KGeNb 可促进沙林（GB）和梭曼（GD）（及其反应性较低的模拟剂二甲甲基膦酸酯（DMMP））在液相和气相中于环境温度和无中和碱或光照条件下发生水解。三条证据表明 KGeNb 通过广义碱催化去除 DMMP，从而可能去除 GB/GD：a）溶剂同位素效应 k(H2 O)/k(D2 O)为 1.4；b）速率定律（在相同 pH 下水解取决于 P-PONb 的量）；c）在相同 pH 下，与 P-PONb 本身相比，氢氧化物对上述模拟剂的活性要低得多，这是一个关键的对照实验。
