Chemical shift extremum of 129Xe(aq) reveals details of hydrophobic solvation

Abstract The 129Xe chemical shift in an aqueous solution exhibits a non-monotonic temperature dependence, featuring a maximum at 311 K. This is in contrast to most liquids, where the monotonic decrease of the shift follows that of liquid density. In particular, the shift maximum in water occurs at a...

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Autores principales:	Petri Peuravaara, Jouni Karjalainen, Jianfeng Zhu, Jiří Mareš, Perttu Lantto, Juha Vaara
Formato:	article
Lenguaje:	EN
Publicado:	Nature Portfolio 2018
Materias:	Medicine R Science Q
Acceso en línea:	https://doaj.org/article/4902d5eb630c4358bff648489c14cc1b
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spelling	oai:doaj.org-article:4902d5eb630c4358bff648489c14cc1b2021-12-02T11:41:02ZChemical shift extremum of 129Xe(aq) reveals details of hydrophobic solvation10.1038/s41598-018-25418-42045-2322https://doaj.org/article/4902d5eb630c4358bff648489c14cc1b2018-05-01T00:00:00Zhttps://doi.org/10.1038/s41598-018-25418-4https://doaj.org/toc/2045-2322Abstract The 129Xe chemical shift in an aqueous solution exhibits a non-monotonic temperature dependence, featuring a maximum at 311 K. This is in contrast to most liquids, where the monotonic decrease of the shift follows that of liquid density. In particular, the shift maximum in water occurs at a higher temperature than that of the maximum density. We replicate this behaviour qualitatively via a molecular dynamics simulation and computing the 129Xe chemical shift for snapshots of the simulation trajectory. We also construct a semianalytical model, in which the Xe atom occupies a cavity constituted by a spherical water shell, consisting of an even distribution of solvent molecules. The temperature dependence of the shift is seen to result from a product of the decreasing local water density and an increasing term corresponding to the energetics of the Xe-H2O collisions. The latter moves the chemical shift maximum up in temperature, as compared to the density maximum. In water, the computed temperature of the shift maximum is found to be sensitive to both the details of the binary chemical shift function and the coordination number. This work suggests that, material parameters allowing, the maximum should be exhibited by other liquids, too.Petri PeuravaaraJouni KarjalainenJianfeng ZhuJiří MarešPerttu LanttoJuha VaaraNature PortfolioarticleMedicineRScienceQENScientific Reports, Vol 8, Iss 1, Pp 1-11 (2018)
institution	DOAJ
collection	DOAJ
language	EN
topic	Medicine R Science Q
spellingShingle	Medicine R Science Q Petri Peuravaara Jouni Karjalainen Jianfeng Zhu Jiří Mareš Perttu Lantto Juha Vaara Chemical shift extremum of 129Xe(aq) reveals details of hydrophobic solvation
description	Abstract The 129Xe chemical shift in an aqueous solution exhibits a non-monotonic temperature dependence, featuring a maximum at 311 K. This is in contrast to most liquids, where the monotonic decrease of the shift follows that of liquid density. In particular, the shift maximum in water occurs at a higher temperature than that of the maximum density. We replicate this behaviour qualitatively via a molecular dynamics simulation and computing the 129Xe chemical shift for snapshots of the simulation trajectory. We also construct a semianalytical model, in which the Xe atom occupies a cavity constituted by a spherical water shell, consisting of an even distribution of solvent molecules. The temperature dependence of the shift is seen to result from a product of the decreasing local water density and an increasing term corresponding to the energetics of the Xe-H2O collisions. The latter moves the chemical shift maximum up in temperature, as compared to the density maximum. In water, the computed temperature of the shift maximum is found to be sensitive to both the details of the binary chemical shift function and the coordination number. This work suggests that, material parameters allowing, the maximum should be exhibited by other liquids, too.
format	article
author	Petri Peuravaara Jouni Karjalainen Jianfeng Zhu Jiří Mareš Perttu Lantto Juha Vaara
author_facet	Petri Peuravaara Jouni Karjalainen Jianfeng Zhu Jiří Mareš Perttu Lantto Juha Vaara
author_sort	Petri Peuravaara
title	Chemical shift extremum of 129Xe(aq) reveals details of hydrophobic solvation
title_short	Chemical shift extremum of 129Xe(aq) reveals details of hydrophobic solvation
title_full	Chemical shift extremum of 129Xe(aq) reveals details of hydrophobic solvation
title_fullStr	Chemical shift extremum of 129Xe(aq) reveals details of hydrophobic solvation
title_full_unstemmed	Chemical shift extremum of 129Xe(aq) reveals details of hydrophobic solvation
title_sort	chemical shift extremum of 129xe(aq) reveals details of hydrophobic solvation
publisher	Nature Portfolio
publishDate	2018
url	https://doaj.org/article/4902d5eb630c4358bff648489c14cc1b
work_keys_str_mv	AT petripeuravaara chemicalshiftextremumof129xeaqrevealsdetailsofhydrophobicsolvation AT jounikarjalainen chemicalshiftextremumof129xeaqrevealsdetailsofhydrophobicsolvation AT jianfengzhu chemicalshiftextremumof129xeaqrevealsdetailsofhydrophobicsolvation AT jirimares chemicalshiftextremumof129xeaqrevealsdetailsofhydrophobicsolvation AT perttulantto chemicalshiftextremumof129xeaqrevealsdetailsofhydrophobicsolvation AT juhavaara chemicalshiftextremumof129xeaqrevealsdetailsofhydrophobicsolvation
_version_	1718395458578022400

Chemical shift extremum of 129Xe(aq) reveals details of hydrophobic solvation

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