Chen Jie, Trout Bernhardt L
Department of Chemical Engineering, Massachusetts Institute of Technology, Cambridge, MA 02139, USA.
J Phys Chem B. 2008 Jul 3;112(26):7794-802. doi: 10.1021/jp7106582. Epub 2008 Jun 5.
The solution behavior of a model compound, tetrolic acid (TTA), is studied via molecular dynamics simulations in four organic solvents. The results suggest that strong interactions between TTA and solvent molecules (ethanol or dioxane) prevent the formation of carboxylic acid dimers in solution and thus promote the crystallization of TTA in a catemer-based form or a solvate form. Weak interactions, however, between TTA and solvent molecules (carbon tetrachloride or chloroform) facilitate the formation of carboxylic acid dimers in solution and thus promote the crystallization of a dimer-based crystal. Detailed solvent structure plays an important role in determining the relative stability of various growth synthons in solution and also the barriers along the pathway connecting them. This work illustrates the potential of molecular simulations to aid in the rational selection of solvents to obtain desired polymorphs during crystallization.
通过在四种有机溶剂中的分子动力学模拟，研究了模型化合物四炔酸（TTA）的溶液行为。结果表明，TTA与溶剂分子（乙醇或二氧六环）之间的强相互作用会阻止溶液中羧酸二聚体的形成，从而促进TTA以基于三聚体的形式或溶剂化物形式结晶。然而，TTA与溶剂分子（四氯化碳或氯仿）之间的弱相互作用则有利于溶液中羧酸二聚体的形成，进而促进基于二聚体的晶体的结晶。详细的溶剂结构在确定溶液中各种生长合成子的相对稳定性以及连接它们的途径中的势垒方面起着重要作用。这项工作说明了分子模拟在帮助合理选择溶剂以在结晶过程中获得所需多晶型物方面的潜力。
