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Tuning the Stereo and Solvation Selectivity at Interfacial and Bulk Environments by Changing Solvent Polarity: the Isomerization of Glyoxal in Different Solvent Environments
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2018-04-05 , DOI: 10.1021/jacs.8b01503 Jie Zhong 1 , Marcelo A. Carignano 2 , Sabre Kais 3 , Xiao Cheng Zeng 1 , Joseph S. Francisco 1 , Ivan Gladich 2
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2018-04-05 , DOI: 10.1021/jacs.8b01503 Jie Zhong 1 , Marcelo A. Carignano 2 , Sabre Kais 3 , Xiao Cheng Zeng 1 , Joseph S. Francisco 1 , Ivan Gladich 2
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Conformational isomerism plays a central role in organic synthesis and biological processes; however, effective control of isomerization processes still remains challenging and elusive. Here, we propose a novel paradigm for conformational control of isomerization in the condensed phase, in which the polarity of the solvent determines the relative concentration of conformers at the interfacial and bulk regions. By the use of state-of-the-art molecular dynamics simulations of glyoxal in different solvents, we demonstrate that the isomerization process is dipole driven: the solvent favors conformational changes toward conformers having molecular dipoles that better match its polar character. Thus, the solvent polarity modulates the conformational change, stabilizing and selectively segregating in the bulk vs the interface one conformer with respect to the others. The findings in this paper have broader implications affecting systems involving compounds with conformers of different polarity. This work suggests novel mechanisms for tuning the catalytic activity of surfaces in conformationally controlled (photo)chemical reactions and for designing a new class of molecular switches that are active in different solvent environments.
中文翻译：
通过改变溶剂极性调节界面和本体环境中的立体和溶剂化选择性：乙二醛在不同溶剂环境中的异构化
构象异构在有机合成和生物过程中起着核心作用；然而，异构化过程的有效控制仍然具有挑战性和难以捉摸。在这里，我们提出了一种新的缩合相异构化构象控制范式，其中溶剂的极性决定了界面和本体区域构象异构体的相对浓度。通过使用最先进的乙二醛在不同溶剂中的分子动力学模拟，我们证明异构化过程是偶极驱动的：溶剂有利于构象变化，使其具有更好地匹配其极性特征的分子偶极子的构象异构体。因此，溶剂极性调节构象变化，稳定和选择性地在体与界面中分离一个构象异构体。本文的发现具有更广泛的影响，影响涉及具有不同极性构象异构体的化合物的系统。这项工作提出了在构象控制（光）化学反应中调节表面催化活性的新机制，以及设计一类在不同溶剂环境中具有活性的新型分子开关。
更新日期：2018-04-05
中文翻译：
通过改变溶剂极性调节界面和本体环境中的立体和溶剂化选择性：乙二醛在不同溶剂环境中的异构化
构象异构在有机合成和生物过程中起着核心作用；然而，异构化过程的有效控制仍然具有挑战性和难以捉摸。在这里，我们提出了一种新的缩合相异构化构象控制范式，其中溶剂的极性决定了界面和本体区域构象异构体的相对浓度。通过使用最先进的乙二醛在不同溶剂中的分子动力学模拟，我们证明异构化过程是偶极驱动的：溶剂有利于构象变化，使其具有更好地匹配其极性特征的分子偶极子的构象异构体。因此，溶剂极性调节构象变化，稳定和选择性地在体与界面中分离一个构象异构体。本文的发现具有更广泛的影响，影响涉及具有不同极性构象异构体的化合物的系统。这项工作提出了在构象控制（光）化学反应中调节表面催化活性的新机制，以及设计一类在不同溶剂环境中具有活性的新型分子开关。
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