Solvation of Calcium-Phosphate Headgroup Complexes at the DPPC/Aqueous Interface.
The effects of sodium (Na(+) ) and calcium (Ca(2+) ) cations on model zwitterionic dipalmitoylphosphatidylcholine (DPPC) monolayers spread on metal chloride salt solutions are investigated by means of vibrational sum frequency generation (VSFG) and heterodyne-detected (HD)-VSFG spectroscopy. VSFG and HD-VSFG spectra in the OH stretching region reveal cation-specific effects on the interfacial water's H-bonding network, knowledge of which has been limited to date. It is found that low-concentrated Ca(2+) more strongly perturbs interfacial water organization relative to highly concentrated Na(+) . At higher Ca(2+) concentrations, the water H-bonding network at the DPPC/CaCl2 interface reorganizes and the resulting spectrum closely follows that of the bare air/CaCl2 interface up to ∼3400 cm(-1) . Most interesting is the appearance of a negative band at ∼3450 cm(-1) in the DPPC/CaCl2 Im χs ((2)) spectra, likely arising from an asymmetric solvation of Ca(2+) -phosphate headgroup complexes. This gives rise to an electric field that orients the net OH transition moments of a subset of OH dipoles toward the bulk solution.
Department of Chemistry & Biochemistry, The Ohio State University, 100 West 18th Avenue, Columbus, OH, 43210, USA.
Wei
W
Hua
Department of Chemistry & Biochemistry, The Ohio State University, 100 West 18th Avenue, Columbus, OH, 43210, USA.
Dominique
D
Verreault
Department of Chemistry & Biochemistry, The Ohio State University, 100 West 18th Avenue, Columbus, OH, 43210, USA. allen@chemistry.ohio-state.edu.
Heather C
HC
Allen
VSFG spectroscopy; calcium; sodium; water; zwitterionic lipid monolayers