Interactions of phosphororganic agents with water and components of polyelectrolyte membranes.
Interactions of phosphororganic agents with water and components of polyelectrolyte membranes.
复制标题
有机磷试剂与水和聚电解质膜组分的相互作用。
DOI：
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发表时间：
2011
影响因子：
3.3
通讯作者：
A. Neimark
中科院分区：
文献类型：
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作者：
Ming;A. Vishnyakov;G. Gor;A. Neimark
采用量子化学从头计算方法，结合真实溶剂类导体筛选模型(COSMO-RS)，研究了神经G毒剂(沙林和梭曼)及其模拟物DMMP(二甲基甲基膦酸二甲酯)和DIFP(氟磷酸二异丙酯)与水和聚电解质膜组分的相互作用。为了检验COSMO-RS计算的可靠性，我们测量了DMMP-水混合物中的汽液平衡，并发现计算结果与实验结果定量一致。利用COSMO-RS研究了含磷有机试剂与全氟化和磺化聚苯乙烯(SPS)聚电解质特征碎片的相互作用，探索了用于防护服膜的有机磷化合物。我们发现，DIFP和DMMP这两个模拟剂都相当好地模拟了G-试剂的热力学性质；但也有一些具体的差异被讨论。我们还认为，与类似Nafion的预氟化聚电解质相比，SPS基聚电解质对含磷有机试剂的亲和力较低。
Interactions of nerve G-agents (sarin and soman) and their simulants DMMP (dimethyl methylphosphonate) and DIFP (diisopropyl fluorophosphate) with water and components of polyelectrolyte membranes are studied using ab initio calculations in conjunction with thermodynamic modeling using the conductor-like screening model for real solvents (COSMO-RS). To test reliability of COSMO-RS calculations, we measured the vapor-liquid equilibrium in DMMP-water mixtures and found quantitative agreement between computed and experimental results. Using COSMO-RS, we studied the interactions of phosphororganic agents with the characteristic fragments of perfluorinated and sulfonated polystyrene (sPS) polyelectrolytes, which are explored for protective clothing membranes. We found that both simulants, DIFP and DMMP, mimic the thermodynamic properties of G-agents reasonably well; however, there are certain specific differences that are discussed. We also suggested that sPS-based polyelectrolytes have less affinity for phosphorganic agents compared to prefluorinated polyelectrolytes similar to Nafion.