Anion-cation contrast of small molecule solvation in salt solutions

Result code in IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F60461373%3A22340%2F22%3A43924995" target="_blank" >RIV/60461373:22340/22:43924995 - isvavai.cz</a>

Result on the web

<a href="https://pubs.rsc.org/en/content/articlelanding/2022/CP/D1CP04129K" target="_blank" >https://pubs.rsc.org/en/content/articlelanding/2022/CP/D1CP04129K</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1039/d1cp04129k" target="_blank" >10.1039/d1cp04129k</a>

Result language

angličtina

Original language name

Anion-cation contrast of small molecule solvation in salt solutions

Original language description

The contributions from anions and cations from salt are inseparable in their perturbation of molecular systems by experimental and computational methods, rendering it difficult to dissect the effects exerted by the anions and cations individually. Here we investigate the solvation of a small molecule, caffeine, and its perturbation by monovalent salts from various parts of the Hofmeister series. Using molecular dynamics and the energy-representation theory of solvation, we estimate the solvation free energy of caffeine and decompose it into the contributions from anions, cations, and water. We also decompose the contributions arising from the solute-solvent and solute-ions interactions and that from excluded volume, enabling us to pin-point the mechanism of salt. Anions and cations revealed high contrast in their perturbation of caffeine solvation, with the cations salting-in caffeine via binding to the polar ketone groups, while the anions were found to be salting-out via perturbations of water. In agreement with previous findings, the perturbation by salt is mostly anion dependent, with the magnitude of the excluded-volume effect found to be the governing mechanism. The free-energy decomposition as conducted in the present work can be useful to understand ion-specific effects and the associated Hofmeister series. This journal is © the Owner Societies.

Czech name

—

Czech description

—

Type

J_imp - Article in a specialist periodical, which is included in the Web of Science database

CEP classification

—

OECD FORD branch

10403 - Physical chemistry

Project

<a href="/en/project/GA20-24155S" target="_blank" >GA20-24155S: Insight in preferential interactions, bridging, and cononsolvency on PNIPAM by experimental and computational thermodynamics</a><br>

Continuities

P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)

Publication year

2022

Confidentiality

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Name of the periodical

Physical Chemistry Chemical Physics

ISSN

1463-9076

e-ISSN

1463-9084

Volume of the periodical

24

Issue of the periodical within the volume

5

Country of publishing house

GB - UNITED KINGDOM

Number of pages

12

Pages from-to

3238-3249

UT code for WoS article

000744144800001

EID of the result in the Scopus database

2-s2.0-85124056388