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Influence of crowding on hydrophobic hydration-shell structure
1Purdue University, Department of Chemistry, West Lafayette, IN 47907, USA. bendor@purdue.edu.
Physical Chemistry Chemical Physics : PCCP
|May 16, 2020
Summary
Molecular crowding influences water structure, affecting hydration shells. This study quantifies how solute size and shape impact water
Area of Science:
- Physical Chemistry
- Solution Chemistry
- Spectroscopy
Background:
- Molecular crowding significantly alters solvent properties.
- Understanding water's structural changes in solutions is crucial for various chemical and biological processes.
Purpose of the Study:
- To quantify the influence of molecular crowding on water structure.
- To investigate the crossover behavior of hydration shells in aqueous alcohol solutions.
Main Methods:
- Utilized Raman multivariate curve resolution (Raman-MCR) spectroscopy.
- Analyzed hydration-shell OH stretch band shape and mean frequency.
- Studied aqueous solutions of tert-butyl alcohol, 2-butyl alcohol, and 2-butoxyethanol at varying concentrations and temperatures.
Main Results:
- Identified the crossover temperature where hydration shells shift from ordered to less ordered structures.
- Demonstrated that crowding's influence on crossover depends on solute size and shape.
- Observed that first hydration-shell spectra are similar to pure water, regardless of crowding.
Conclusions:
- The crossover temperature is primarily dictated by the enthalpic stabilization of more ordered hydration-shell structures.
- Solute properties significantly influence water structure reorganization under molecular crowding.
- Raman-MCR provides a quantitative method to probe hydration-shell dynamics.
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