Expulsion of Hydroxide Ions from Methyl Hydration Shells
Expulsion of Hydroxide Ions from Methyl Hydration Shells
复制标题
从甲基水合壳中驱逐氢氧根离子
DOI：
10.1021/acs.jpcb.1c08420
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发表时间：
2022
期刊：
影响因子：
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通讯作者：
Ben-Amotz, Dor
中科院分区：
文献类型：
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作者：
Bredt, Aria J.;Kim, Yongbin;Mendes de Oliveira, Denilson;Urbina, Andres S.;Slipchenko, Lyudmila V.;Ben-Amotz, Dor
采用实验和理论相结合的方法对叔丁醇（TBA）在纯水、NaOH和NaI水溶液中的溶解过程进行了分析，研究了氢氧根离子对甲基水合壳层的亲合力。实验结果得到使用拉曼多变量曲线分辨率（拉曼MCR）和一个新的三组分总最小二乘（拉曼TLS）光谱分解策略，用于突出TBA和水溶液离子之间的相互作用产生的振动扰动。实验的解释和扩展的帮助下，有效的碎片势分子动力学（EFP-MD）模拟，以及Kirkwood-Buff计算和辛醇/水分配测量，TBA-离子分布函数TBA溶解度的变化。实验和模拟结果表明，甲基水合壳比碘阴离子更强烈地排出氢氧化物，预计碘阴离子在TBA甲基附近的分布与TBA羟基附近的钠反离子定位相关。
The affinity of hydroxide ions for methyl hydration shells is assessed using a combined experimental and theoretical analysis oftert-butyl alcohol (TBA) dissolved in pure water and aqueous NaOH and NaI. The experimental results are obtained using Raman multivariate curve resolution (Raman-MCR) and a new three-component total least squares (Raman-TLS) spectral decomposition strategy used to highlight vibrational perturbations resulting from interactions between TBA and aqueous ions. The experiments are interpreted and extended with the aid of effective fragment potential molecular dynamics (EFP-MD) simulations, as well as Kirkwood–Buff calculations and octanol/water partition measurements, to relate TBA-ion distribution functions to TBA solubility changes. The combined experimental and simulation results reveal that methyl group hydration shells more strongly expel hydroxide than iodide anions, whose populations near the methyl groups of TBA are predicted to be correlated with sodium counterion localization near the TBA hydroxyl group.