Structural Dynamics of Hydrated Phospholipid Surfaces Probed by Ultrafast 2D Spectroscopy of Phosphate Vibrations

The properties of biomembranes depend in a decisive way on interactions of phospholipids with hydrating water molecules. To map structural dynamics of a phospholipid-water interface on the length and time scale of molecular motions, we introduce the phospholipid symmetric and asymmetric phosphate stretch vibrations as probes of interfacial hydrogen bonds and electrostatic interactions. The first two-dimensional infrared spectra of such modes and a line shape analysis by density matrix theory reveal two distinct structural dynamics components; the first 300 fs contribution is related to spatial fluctuations of charged phospholipid head groups with additional water contributions at high hydration levels; the second accounts for water-phosphate hydrogen bonds persisting longer than 10 ps. Our results reveal a relatively rigid hydration shell around phosphate groups, a behavior relevant for numerous biomolecular systems.