Microscopic structure and solvation in dry and wet octanol
Microscopic structure and solvation in dry and wet octanol
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DOI：
10.1021/jp0548164
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发表时间：
2006-03-02
影响因子：
3.3
通讯作者：
Siepmann, JI
中科院分区：
文献类型：
--
作者：
Chen, B;Siepmann, JI
辛醇-水分配系数在关联和预测许多具有药理学和环境重要性的过程方面非常成功。1-辛醇分子的两亲性质允许辛醇相模拟从生物膜到土壤的许多不同环境的复杂性。然而，辛醇相的结构细节以及其结构是否在水饱和时改变尚未完全理解。吉布斯系综中的偏置蒙特卡罗模拟表明，在干和湿1-辛醇中存在不同的氢键聚集体光谱，并且水饱和度显著改变了1-辛醇环境，从干辛醇中的主要线性聚集体到湿辛醇中具有水核的较大圆柱形胶束。这些模拟结果是能够调和冲突的观点（链状或水为中心的聚集体与球形胶束）的1-辛醇结构推断从热力学参数，光谱测量，和衍射实验。计算的分配常数量化的水饱和度的干和湿辛醇相的溶解度特性的影响。
Octanol-water partition coefficients are extraordinarily successful for correlating and predicting numerous processes of pharmacological and environmental importance. The amphiphilic nature of the 1-octanol molecules allows the octanol phase to mimic the complexities of many different environments ranging from biomembranes to soil. However, the structural details of the octanol phase and whether its structure is altered upon water saturation are not yet fully understood. Configurational-bias Monte Carlo simulations in the Gibbs ensemble demonstrate, that a diverse spectrum of hydrogen-bonded aggregates exists in dry and wet 1-octanol, and that water saturation substantially alters the 1-octanol environment from predominantly linear aggregates in dry octanol to larger cylindrical micelles with water cores in wet octanol. These simulation results are able to reconcile the conflicting views (chainlike or water-centered aggregates vs spherical micelles) of the 1-octanol structure inferred from thermodynamic arguments, spectroscopic measurements, and diffraction experiments. Calculated partition constants quantify the influence of water saturation on the solubility characteristics of the dry and wet octanol phases.