Dorosh T, Mangin T, Engler E, Schurhammer R, Chaumont A
Université de Strasbourg, CNRS, CMC UMR 7140, Laboratoire MSM, 4 rue B. Pascal, F-67000, Strasbourg, France.
Chemphyschem. 2025 Jan 2;26(1):e202400768. doi: 10.1002/cphc.202400768. Epub 2024 Nov 19.
Using classical molecular dynamics, we have investigated the solvation of catechol, resorcinol, hydroquinone and 1,4-benzoquinone at infinite dilution, in a series of menthol - thymol mixtures in which the molar fraction of thymol (x) has been increased by steps of 0.1, from 0 (pure menthol) to 1 (pure thymol). The evolution of the solvation shell around the solutes reveals that when x is increased, the average number of hydrogen bonds (HB) where the solute acts as HB acceptor (HBA) and the solvent as HB donor (HBD) increases, while the amount of HB, in which the solute acts as HBD and the solvent as HBA, decreases. Overall, the total number of HBs between the different benzenediols and the solvent decreases with an increase of x, while for benzoquinone the total number of HB increases. This points to the fact that "acidic" or HBD molecules are better solvated in mixtures with high menthol proportion, while "basic" or HBA molecules, are better solvated in thymol rich mixtures. The results reported herein follow the same trends as experimentally reported Kamlet-Taft parameters and present insights on how the composition of these "deep eutectic" mixtures maybe tweaked in order to optimize their solvation properties.
我们使用经典分子动力学方法，研究了儿茶酚、间苯二酚、对苯二酚和1,4 - 苯醌在一系列薄荷醇 - 百里酚混合物中无限稀释时的溶剂化情况。在这些混合物中，百里酚的摩尔分数（x）以0.1的步长从0（纯薄荷醇）增加到1（纯百里酚）。溶质周围溶剂化壳层的演变表明，当x增加时，溶质作为氢键受体（HBA）且溶剂作为氢键供体（HBD）的氢键（HB）平均数量增加，而溶质作为氢键供体且溶剂作为氢键受体的氢键数量减少。总体而言，不同苯二酚与溶剂之间的氢键总数随x的增加而减少，而对苯醌的氢键总数增加。这表明“酸性”或氢键供体分子在薄荷醇比例高的混合物中溶剂化效果更好，而“碱性”或氢键受体分子在富含百里酚的混合物中溶剂化效果更好。本文报道的结果与实验报道的Kamlet - Taft参数遵循相同趋势，并为如何调整这些“低共熔”混合物的组成以优化其溶剂化性质提供了见解。
