The electrostatic origins of specific ion effects: quantifying the Hofmeister series for anions.
The electrostatic origins of specific ion effects: quantifying the Hofmeister series for anions.
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DOI：
10.1039/d1sc03568a
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发表时间：
2021-11-24
期刊：
影响因子：
8.4
通讯作者：
Page AJ
中科院分区：
文献类型：
--
作者：
Gregory KP;Wanless EJ;Webber GB;Craig VSJ;Page AJ
我们所知道的生命依赖于水，或更具体地说是咸水。如果没有溶解的离子，生物分子之间的相互作用就不够复杂，不足以维持生命。这种复杂性与不同离子的存在引起的性质变化密切相关。这些特定的离子效应（广泛称为霍夫迈斯特效应）已为人所知 100 多年。它们在化学、生物和物理科学中无处不在。这些效应的起源及其相对强度仍然存在激烈争论。在这里，我们通过库仑相互作用的视角重新考虑特定离子效应的起源，并为水性和非水性环境中的阴离子效应奠定基础。我们表明，对于阴离子，可以通过考虑位点特异性静电相互作用来解释和量化霍夫迈斯特级数。这可以简单地通过阴离子的径向电荷密度来近似，我们已经为常见报道的离子计算了该密度。这广泛地量化了以前不可预测的特定离子效应，包括已知影响溶液性质、病毒活性和反应速率的离子效应。此外，在非水溶剂中，阴离子系列的相对大小取决于溶剂的路易斯酸度，通过古特曼受体数测量。阳离子的类似 SIE 与其径向电荷密度的相关性有限，凸显了由于竞争的非库仑现象，阴离子和阳离子的特定离子效应起源的基本不对称性。对离子径向电荷密度的分析表明它们与许多特定的离子效应相关，并为解释和量化已有 130 年历史的阴离子霍夫迈斯特级数提供了新的基础。
Life as we know it is dependent upon water, or more specifically salty water. Without dissolved ions, the interactions between biological molecules are insufficiently complex to support life. This complexity is intimately tied to the variation in properties induced by the presence of different ions. These specific ion effects, widely known as Hofmeister effects, have been known for more than 100 years. They are ubiquitous throughout the chemical, biological and physical sciences. The origin of these effects and their relative strengths is still hotly debated. Here we reconsider the origins of specific ion effects through the lens of Coulomb interactions and establish a foundation for anion effects in aqueous and non-aqueous environments. We show that, for anions, the Hofmeister series can be explained and quantified by consideration of site-specific electrostatic interactions. This can simply be approximated by the radial charge density of the anion, which we have calculated for commonly reported ions. This broadly quantifies previously unpredictable specific ion effects, including those known to influence solution properties, virus activities and reaction rates. Furthermore, in non-aqueous solvents, the relative magnitude of the anion series is dependent on the Lewis acidity of the solvent, as measured by the Gutmann Acceptor Number. Analogous SIEs for cations bear limited correlation with their radial charge density, highlighting a fundamental asymmetry in the origins of specific ion effects for anions and cations, due to competing non-Coulombic phenomena. Analysis of ions’ radial charge densities reveals they correlate with many specific ion effects, and provides a new basis to explain and quantify the 130-year-old Hofmeister series for anions.
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影响因子：
9.2
作者：
Eftekhari, A
通讯作者：
Eftekhari, A
影响因子：
64.8
作者：
CRAIG, VSJ;NINHAM, BW;PASHLEY, RM
通讯作者：
PASHLEY, RM
影响因子：
2.9
作者：
Gregory, Kasimir P.;Webber, Grant B.;Page, Alister J.
通讯作者：
Page, Alister J.
DOI：
10.1016/0005-2744(73)90132-0
发表时间：
1973-01-01
期刊：
BIOCHIMICA ET BIOPHYSICA ACTA
影响因子：
--
作者：
HAYASHI, M;UNEMOTO, T;HAYASHI, M
通讯作者：
HAYASHI, M
DOI：
10.1002/anie.201611335
发表时间：
2017-03-20
期刊：
Angewandte Chemie (International ed. in English)
影响因子：
--
作者：
Gurnev PA;Roark TC;Petrache HI;Sodt AJ;Bezrukov SM
通讯作者：
Bezrukov SM