New approach to the equilibrium of D-glucaric acid in water: DFT study of tetrahedral intermediates

IF 1.2 4区综合性期刊 Q3 MULTIDISCIPLINARY SCIENCES

Kuwait Journal of Science Pub Date : 2024-05-22 DOI:10.1016/j.kjs.2024.100254

Sarah Amara

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Abstract

The present study aims at investigating, for the first time, the formation of tetrahedral intermediates during the equilibrium mechanism of D-glucaric acid in water. In this work, carried out at B3LYP/6-31+G(d,p) computational level in vacuum and using the polarizable continuum model, two systems are proposed and simulated: the first describes an intramolecular proton transfer, and the second requires the intervention of solvent molecules for the proton transfer. The second system, simulated in vacuum, indicates greater ease in establishing this equilibrium due to a significant reduction in angular tensions. Also, the idea of a tetrahedral intermediate carrying two geminal diol groups constitutes a favorable hypothesis due to the low energy barriers calculated as well as a better structural flexibility generated following the equilibrium of the tetrahedral intermediates between them. Experimental confirmation of the presence of such a powerful tetrahedral intermediate would be a considerable advance in resolving the equilibrium mechanisms of D-glucaric acid.

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研究 D-葡糖酸在水中平衡的新方法：四面体中间体的 DFT 研究

本研究旨在首次探究 D-葡糖酸在水中的平衡机制中四面体中间体的形成。这项工作在 B3LYP/6-31+G(d,p)计算水平下于真空中进行，并使用可极化连续体模型，提出并模拟了两个体系：第一个体系描述了分子内质子转移，第二个体系则需要溶剂分子的介入来进行质子转移。在真空中模拟的第二个系统表明，由于角张力的显著降低，更容易建立这种平衡。此外，由于计算出的能障较低，以及四面体中间体之间的平衡后产生的更好的结构灵活性，携带两个二元醇基团的四面体中间体的想法构成了一个有利的假设。通过实验证实这种强大的四面体中间体的存在，将是解决 D-葡糖酸平衡机制问题的一大进步。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

Kuwait Journal of Science MULTIDISCIPLINARY SCIENCES-

CiteScore

1.60

自引率

28.60%

发文量

132

期刊介绍： Kuwait Journal of Science (KJS) is indexed and abstracted by major publishing houses such as Chemical Abstract, Science Citation Index, Current contents, Mathematics Abstract, Micribiological Abstracts etc. KJS publishes peer-review articles in various fields of Science including Mathematics, Computer Science, Physics, Statistics, Biology, Chemistry and Earth & Environmental Sciences. In addition, it also aims to bring the results of scientific research carried out under a variety of intellectual traditions and organizations to the attention of specialized scholarly readership. As such, the publisher expects the submission of original manuscripts which contain analysis and solutions about important theoretical, empirical and normative issues.