Binding of carboxylate and water to monovalent cations†

IF 2.9 3区 化学 Q3 CHEMISTRY, PHYSICAL Physical Chemistry Chemical Physics Pub Date : 2023-10-20 DOI:10.1039/D3CP04200F
Mark J Stevens and Susan L. B. Rempe
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Abstract

The interactions of carboxylate anions with water and cations are important for a wide variety of systems, both biological and synthetic. To gain insight on properties of the local complexes, we apply density functional theory, to treat the complex electrostatic interactions, and investigate mixtures with varied numbers of carboxylate anions (acetate) and waters binding to monovalent cations, Li+, Na+ and K+. The optimal structure with overall lowest free energy contains two acetates and two waters such that the cation is four-fold coordinated, similar to structures found earlier for pure water or pure carboxylate ligands. More generally, the complexes with two acetates have the lowest free energy. In transitioning from the overall optimal state, exchanging an acetate for water has a lower free energy barrier than exchanging water for an acetate. In most cases, the carboxylates are monodentate and in the first solvation shell. As water is added to the system, hydrogen bonding between waters and carboxylate O atoms further stabilizes monodentate structures. These structures, which have strong electrostatic interactions that involve hydrogen bonds of varying strength, are significantly polarized, with ChelpG partial charges that vary substantially as the bonding geometry varies. Overall, these results emphasize the increasing importance of water as a component of binding sites as the number of ligands increases, thus affecting the preferential solvation of specific metal ions and clarifying Hofmeister effects. Finally, structural analysis correlated with free energy analysis supports the idea that binding to more than the preferred number of carboxylates under architectural constraints are a key to ion transport.

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羧酸盐和水与单价阳离子的结合。
羧酸根阴离子与水和阳离子的相互作用对于各种生物和合成系统都很重要。为了深入了解局部络合物的性质,我们应用密度泛函理论来处理络合物的静电相互作用,并研究具有不同数量的羧酸根阴离子(乙酸根)和与单价阳离子Li+、Na+和K+结合的水的混合物。总体自由能最低的最佳结构包含两种醋酸盐和两种水,使得阳离子是四重配位的,类似于早期发现的纯水或纯羧酸盐配体的结构。更一般地,与两种醋酸盐的络合物具有最低的自由能。在从总体最佳状态转变的过程中,用乙酸盐交换水比用水交换乙酸盐具有更低的自由能垒。在大多数情况下,羧酸盐是单齿的并且在第一溶剂化壳中。当向系统中加入水时,水和羧酸盐O原子之间的氢键进一步稳定了单齿结构。这些结构具有强烈的静电相互作用,涉及不同强度的氢键,它们被显著极化,ChelpG部分电荷随着键合几何形状的变化而显著变化。总的来说,这些结果强调了随着配体数量的增加,水作为结合位点组分的重要性越来越大,从而影响了特定金属离子的优先溶剂化,并澄清了Hofmeister效应。最后,与自由能分析相关的结构分析支持这样一种观点,即在结构约束下与超过优选数量的羧酸盐结合是离子传输的关键。
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来源期刊
Physical Chemistry Chemical Physics
Physical Chemistry Chemical Physics 化学-物理:原子、分子和化学物理
CiteScore
5.50
自引率
9.10%
发文量
2675
审稿时长
2.0 months
期刊介绍: Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.
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