Jump to main content
Jump to site search
Access to RSC content Close the message box

Continue to access RSC content when you are not at your institution. Follow our step-by-step guide.


Issue 20, 2020
Previous Article Next Article

Influence of crowding on hydrophobic hydration-shell structure

Author affiliations

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

Back to tab navigation

Supplementary files

Article information


Submitted
07 Feb 2020
Accepted
27 Apr 2020
First published
15 May 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

Social activity

Search articles by author

Spotlight

Advertisements