Ultrafast infrared spectroscopy of N 2O is shown to be a sensitive probe of hydrophobic and aqueous sites in lipid bilayers. Distinct rates of VER of the nu 3 antisymmetric stretching mode of N 2O can be distinguished for N 2O solvated in the acyl tail, interfacial water, and bulk water regions of hydrated dioleoylphosphatidylcholine (DOPC) bilayers. The lifetime of the interfacial N 2O population is hydration-dependent. This effect is attributed to changes in the density of intermolecular states resonant with the nu 3 band ( approximately 2230 cm (-1)) resulting from oriented interfacial water molecules near the lipid phosphate. Thus, the N 2O VER rate becomes a novel and experimentally convenient tool for reporting on the structure and dynamics of interfacial water in lipids and, potentially, in other biological systems.
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http://dx.doi.org/10.1021/jp8012283 | DOI Listing |
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