4.8 Article

Water dynamics at neutral and ionic interfaces

出版社

NATL ACAD SCIENCES
DOI: 10.1073/pnas.0907875106

关键词

reverse micelles; ultrafast IR experiments; interfacial water; hydrogen bond dynamics

资金

  1. Department of Energy [DE-FG03-84ER13251]
  2. National Institutes of Health [2-R01GM061137-09]
  3. National Science Foundation [DMR 0652232]
  4. Stanford Graduate Research Fellowship

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The orientational dynamics of water at a neutral surfactant reverse micelle interface are measured with ultrafast infrared spectroscopy of the hydroxyl stretch, and the results are compared to orientational relaxation of water interacting with an ionic interface. The comparison provides insights into the influence of a neutral vs. ionic interface on hydrogen bond dynamics. Measurements are made and analyzed for large nonionic surfactant Igepal CO-520reverse micelles (water nanopool with a 9-nm diameter). The results are compared with those from a previous study of reverse micelles of the same size formed with the ionic surfactant Aerosol-OT (AOT). The results demonstrate that the orientational relaxation times for interfacial water molecules in the two types of reverse micelles are very similar (13 ps for Igepal and 18 ps for AOT) and are significantly slower than that of bulk water (2.6 ps). The comparison of water orientational relaxation at neutral and ionic interfaces shows that the presence of an interface plays the dominant role in determining the hydrogen bond dynamics, whereas the chemical nature of the interface plays a secondary role.

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