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Solvation of Calcium–Phosphate Headgroup Complexes at the DPPC/Aqueous Interface
Author(s) -
Hua Wei,
Verreault Dominique,
Allen Heather C.
Publication year - 2015
Publication title -
chemphyschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.016
H-Index - 140
eISSN - 1439-7641
pISSN - 1439-4235
DOI - 10.1002/cphc.201500720
Subject(s) - chemistry , solvation , aqueous solution , calcium , sodium , phosphate , monolayer , solvation shell , analytical chemistry (journal) , inorganic chemistry , crystallography , ion , organic chemistry , biochemistry
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/CaCl 2 interface reorganizes and the resulting spectrum closely follows that of the bare air/CaCl 2 interface up to ∼3400 cm −1 . Most interesting is the appearance of a negative band at ∼3450 cm −1 in the DPPC/CaCl 2 Im χ s (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.

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