Abstract
Hydrophobic hydration is considered to have a key role in biological processes ranging from membrane formation to protein folding and ligand binding1. Historically, hydrophobic hydration shells were thought to resemble solid clathrate hydrates2,3,4, with solutes surrounded by polyhedral cages composed of tetrahedrally hydrogen-bonded water molecules. But more recent experimental5,6,7,8 and theoretical9,10,11,12,13,14,15,16 studies have challenged this view and emphasized the importance of the length scales involved. Here we report combined polarized, isotopic and temperature-dependent Raman scattering measurements with multivariate curve resolution (Raman-MCR)17,18,19 that explore hydrophobic hydration by mapping the vibrational spectroscopic features arising from the hydrophobic hydration shells of linear alcohols ranging from methanol to heptanol. Our data, covering the entire 0–100 °C temperature range, show clear evidence that at low temperatures the hydration shells have a hydrophobically enhanced water structure with greater tetrahedral order and fewer weak hydrogen bonds than the surrounding bulk water. This structure disappears with increasing temperature and is then, for hydrophobic chains longer than ∼1 nm, replaced by a more disordered structure with weaker hydrogen bonds than bulk water. These observations support our current understanding of hydrophobic hydration, including the thermally induced water structural transformation that is suggestive of the hydrophobic crossover predicted to occur at lengths of ∼1 nm (refs 5, 9, 10, 14).
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Acknowledgements
This work was supported by the National Science Foundation (CHE-0847928). We thank B. Widom, D. Chandler, M. Fayer and S. Granick for comments and suggestions; D. Wilcox for writing the SMCR code used in this work; B. Rankin for performing molecular dynamics simulations to determine the number of water molecules in the first hydration shells of n-alcohols (as further described in Supplementary Methods); and D. L. McCaffrey, S. Zukowski and C. DeShaw (undergraduate research students) for assistance in collecting experimental results relevant to this work.
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J.G.D. and K.P.G. performed experimental measurements and reproducibility validations. J.G.D. further contributed to the SMCR data analysis and manuscript writing. P.W. designed and constructed the high-performance Raman system that facilitated these studies. D.B.-A. conceived and supervised the work, and contributed to the data analysis and manuscript preparation.
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This file contains Supplementary Figures 1-8, a Supplementary Discussion, Supplementary Methods and additional references. (PDF 719 kb)
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Davis, J., Gierszal, K., Wang, P. et al. Water structural transformation at molecular hydrophobic interfaces. Nature 491, 582–585 (2012). https://doi.org/10.1038/nature11570
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DOI: https://doi.org/10.1038/nature11570
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