Na+ and Ca2+ Effect on the Hydration and Orientation of the Phosphate Group of DPPC at Air-Water and Air-Hydrated Silica Interfaces

被引:89
作者
Casillas-Ituarte, Nadia N. [1 ]
Chen, Xiangke [1 ]
Castada, Hardy [1 ]
Allen, Heather C. [1 ]
机构
[1] Ohio State Univ, Dept Chem, Columbus, OH 43210 USA
基金
美国国家科学基金会;
关键词
SUM-FREQUENCY GENERATION; MOLECULAR-DYNAMICS SIMULATION; PHOSPHOLIPID-BILAYERS; METAL-CATIONS; GEL-PHASE; DIPALMITOYLPHOSPHATIDYLCHOLINE BILAYER; PHOSPHATIDYLCHOLINE BILAYERS; VIBRATIONAL-SPECTRA; MAGNETIC-RESONANCE; MEMBRANE-FUSION;
D O I
10.1021/jp1022357
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Hydration and orientation of the phosphate group of dipalmitoylphosphatidylcholine (DPPC) monolayers in the liquid-expanded (LE) phase and the liquid-condensed (LC) phase in the presence of sodium ions and calcium ions was investigated with vibrational sum frequency generation (SFG) spectroscopy at the airaqueous interface in conjunction with surface pressure measurements. In the LE phase, both sodium and calcium affect the phosphate group hydration. In the LC phase, however, sodium ions affect the phosphate hydration subtly, while calcium ions cause a marked dehydration. Silica-supported DPPC monolayers prepared by the Langmuir-Blodgett method reveal similar hydration behavior relative to that observed in the corresponding aqueous subphase for the case of water and in the presence of sodium ions. However, in the presence of calcium ions the phosphate group dehydration is greater than that from the corresponding purely aqueous CaCl2 subphase. The average tilt angles from the surface normal of the PO2- group of DPPC monolayers on the water surface and on the silica substrate calculated from SFG data are found to be 59 degrees +/- 3 degrees and 72 degrees +/- 5 degrees, respectively. Orientation of the phosphate group is additionally affected by the presence of ions. These findings show that extrapolation of results obtained from model membranes from liquid surfaces to solid supports may not be warranted since there are differences in headgroup organization on the two subphases.
引用
收藏
页码:9485 / 9495
页数:11
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