Influence of crowding on hydrophobic hydration-shell structure

文献情報

出版日 2020-05-15

DOI 10.1039/D0CP00702A

インパクトファクター 3.676

著者

Aria J. Bredt, Dor Ben-Amotz

原文を見る

要旨

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.

掲載誌

Physical Chemistry Chemical Physics

CiteScore: 5.5

自己引用率: 10.3%

年間論文数: 3036

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.