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Issue 20, 2020
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Influence of crowding on hydrophobic hydration-shell structure

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Abstract

The influence of molecular crowding on water structure, and the associated crossover behavior, is quantified using Raman multivariate curve resolution (Raman-MCR) hydration-shell vibrational spectroscopy of aqueous tert-butyl alcohol, 2-butyl alcohol and 2-butoxyethanol solutions of variable concentration and temperature. Changes in the hydration-shell OH stretch band shape and mean frequency are used to identify the temperature at which the hydration-shell crosses over from a more ordered to less ordered structure, relative to pure water. The influence of crowding on the crossover is found to depend on solute size and shape in a way that is correlated with the corresponding infinitely dilute hydration-shell structure (and the corresponding first hydration-shell spectra are invariably very similar to pure water). Analysis of the results using a Muller-like two-state equilibrium between more ordered and less ordered hydration-shell structures implies that crossover temperature changes are dictated primarily by enthalpic stabilization of the more ordered hydration-shell structures.

Graphical abstract: Influence of crowding on hydrophobic hydration-shell structure

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Article information


Submitted
07 2 2020
Accepted
27 4 2020
First published
15 5 2020

Phys. Chem. Chem. Phys., 2020,22, 11724-11730
Article type
Paper

Influence of crowding on hydrophobic hydration-shell structure

A. J. Bredt and D. Ben-Amotz, Phys. Chem. Chem. Phys., 2020, 22, 11724
DOI: 10.1039/D0CP00702A

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