环状和非环状葫芦脲对化学战剂 VX 降解途径的影响。,Organic & Biomolecular Chemistry

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环状和非环状葫芦脲对化学战剂 VX 降解途径的影响。
Organic & Biomolecular Chemistry ( IF 2.9 ) Pub Date : 2020-06-23 , DOI: 10.1039/d0ob01167c
Beatrice Andrae ₁ , Daniel Bauer ₁ , Patrick Gaß ₁ , Marianne Koller ₂ , Franz Worek ₂ , Stefan Kubik ₁

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剧毒神经毒剂 VX 是一种甲基硫代磷酸酯，可通过降解水溶液中的三种途径，即通过 P-O 或 P-S 键的水解，或在 2-氨基乙基残基处裂解 C-S 键。在后一种情况下，形成氮丙啶鎓离子和硫代膦酸酯。此处表明，无环或环状葫芦脲在生理 pH 值下抑制磷酸盐缓冲液中的这些反应，从而稳定神经毒剂。然而，当使用未缓冲的碱性溶液作为反应介质时，其中 P-S 或 P-O 键通常优先水解，结果显示葫芦脲强烈地将 VX 降解转向 C-S 键的裂解。尤其是葫芦[7]uril，在合适的条件下具有如此显着的效果，它几乎完全抑制了由其他降解途径产生的产物的形成。涉及 VX 类似物与计算方法相结合的研究表明，葫芦脲施加反应控制的一个原因是 VX 对氮丙啶离子形成的预组织。此外，葫芦[7]脲还通过稳定生成产物过程中产生的正电荷来降低反应的过渡态。因此，葫芦脲对剧毒神经毒剂的反应性有显着影响，这可能允许将它们用于净化目的。

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Influence of cyclic and acyclic cucurbiturils on the degradation pathways of the chemical warfare agent VX.

The highly toxic nerve agent VX is a methylphosphonothioate that degrades via three pathways in aqueous solution, namely through the hydrolysis of the P–O or P–S bonds, or the cleavage of the C–S bond at the 2-aminoethyl residue. In the latter case, an aziridinium ion and a phosphonothioate is formed. Here it is shown that acyclic or cyclic cucurbiturils inhibit these reactions in phosphate buffer at physiological pH and thus stabilise the nerve agent. When using unbuffered basic solutions as the reaction medium, however, in which the P–S or P–O bonds are normally hydrolysed preferentially, cucurbiturils turned out to strongly shift VX degradation towards the cleavage of the C–S bond. Cucurbit[7]uril, in particular, has a so pronounced effect under suitable conditions that it almost completely suppresses the formation of products resulting from the other degradation pathways. Investigations involving VX analogues in combination with computational methods suggest that one reason for the reaction control exerted by the cucurbiturils is the preorganisation of VX for aziridinium ion formation. In addition, cucurbit[7]uril also lowers the transition state of the reaction by stabilising the positive charge developing on the way to the product. Cucurbiturils thus have a marked effect on the reactivity of a highly toxic nerve agent, which potentially allows using them for decontamination purposes.

更新日期：2020-07-15

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