Smolkin Boris, Levi Noam, Chen Ravit
Department of Organic Chemistry, Israel Institute for Biological Research, Ness Ziona 74100, Israel.
ACS Omega. 2022 Jul 15;7(29):25329-25336. doi: 10.1021/acsomega.2c02280. eCollection 2022 Jul 26.
The development of new and efficient decontamination methods has become more relevant in recent years, especially with regard to solid-based decontamination and detoxification systems. The majority of powders used today are dealing with the physical adsorption of chemical warfare agents (CWAs) and their removal from sites without actively destroying them. In this work, we have designed and developed an active solid composite matrix combining organic carboxylate salts and -iodosuccinimide (NIS) for HD decontamination oxidation. All the reactions and mechanistic studies for the sorption and degradation of CWAs were conducted using direct polarization and cross polarization solid-state magic-angle spinning nuclear magnetic resonance techniques. Performance toward the sorption and detoxification of HD was tested, exhibiting oxidation within minutes in a mild and selective manner to the nontoxic sulfoxide derivative followed by visible formation of iodine. The results indicate that carboxylate moieties in the matrix are important for stabilizing the positively charged sulfonium ion intermediate and for supplying oxygen for hydrolysis in a water-deficient environment. The NaOBz/NIS composite was shown to be the most efficient in sorbing and converting the water-insoluble agent HD to its nontoxic, water-soluble sulfoxide, which could then be removed from the site with mere water, resulting in less environmental damage and quick remediation.
近年来,新型高效去污方法的开发变得愈发重要,尤其是在基于固体的去污和解毒系统方面。如今使用的大多数粉末主要是通过物理吸附化学战剂(CWA)并将其从场地中去除,而不是主动销毁它们。在这项工作中,我们设计并开发了一种活性固体复合基质,它结合了有机羧酸盐和N-碘代琥珀酰亚胺(NIS)用于芥子气(HD)的去污氧化。所有关于化学战剂吸附和降解的反应及机理研究均采用直接极化和交叉极化固态魔角旋转核磁共振技术进行。测试了该基质对HD的吸附和解毒性能,结果表明它能在几分钟内以温和且选择性的方式将HD氧化为无毒的亚砜衍生物,随后可见碘的生成。结果表明,基质中的羧基部分对于稳定带正电荷的锍离子中间体以及在缺水环境中为水解提供氧至关重要。NaOBz/NIS复合材料在吸附和将水不溶性毒剂HD转化为其无毒、水溶性亚砜方面表现最为高效,然后仅用水就可将其从场地中去除,从而减少对环境的破坏并实现快速修复。