Anion-cation contrast of small molecule solvation in salt solutions
Identifikátory výsledku
Kód výsledku v 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>
Výsledek na webu
<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>
Alternativní jazyky
Jazyk výsledku
angličtina
Název v původním jazyce
Anion-cation contrast of small molecule solvation in salt solutions
Popis výsledku v původním jazyce
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.
Název v anglickém jazyce
Anion-cation contrast of small molecule solvation in salt solutions
Popis výsledku anglicky
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.
Klasifikace
Druh
J<sub>imp</sub> - Článek v periodiku v databázi Web of Science
CEP obor
—
OECD FORD obor
10403 - Physical chemistry
Návaznosti výsledku
Projekt
<a href="/cs/project/GA20-24155S" target="_blank" >GA20-24155S: Studium preferenčních interakcí, přemosťování, a efektu kononsolvence na polymer PNIPAM pomocí experimentální a výpočetní termodynamiky</a><br>
Návaznosti
P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)
Ostatní
Rok uplatnění
2022
Kód důvěrnosti údajů
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů
Údaje specifické pro druh výsledku
Název periodika
Physical Chemistry Chemical Physics
ISSN
1463-9076
e-ISSN
1463-9084
Svazek periodika
24
Číslo periodika v rámci svazku
5
Stát vydavatele periodika
GB - Spojené království Velké Británie a Severního Irska
Počet stran výsledku
12
Strana od-do
3238-3249
Kód UT WoS článku
000744144800001
EID výsledku v databázi Scopus
2-s2.0-85124056388