Structure and Fluctuations of Charged Phosphatidylserine Bilayers in the Absence of Salt

Horia I. Petrache*, Stephanie Tristram-Nagle, Klaus Gawrisch, Daniel Harries, V. Adrian Parsegian, John F. Nagle

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

247 Scopus citations

Abstract

Using x-ray diffraction and NMR spectroscopy, we present structural and material properties of phosphatidylserine (PS) bilayers that may account for the well documented implications of PS headgroups in cell activity. At 30°C, the 18-carbon monounsaturated DOPS in the fluid state has a cross-sectional area of 65.3 Å2 which is remarkably smaller than the area 72.5 Å2 of the DOPC analog, despite the extra electrostatic repulsion expected for charged PS headgroups. Similarly, at 20°C, the 14-carbon disaturated DMPS in the gel phase has an area of 40.8 Å 2 vs. 48.1 Å2 for DMPC. This condensation of area suggests an extra attractive interaction, perhaps hydrogen bonding, between PS headgroups. Unlike zwitterionic lipids, stacks of PS bilayers swell indefinitely as water is added. Data obtained for osmotic pressure versus interbilayer water spacing for fluid phase DOPS are well fit by electrostatic interactions calculated for the Gouy-Chapman regime. It is shown that the electrostatic interactions completely dominate the fluctuational pressure. Nevertheless, the x-ray data definitively exhibit the effects of fluctuations in fluid phase DOPS. From our measurements of fluctuations, we obtain the product of the bilayer bending modulus KC and the smectic compression modulus B. At the same interbilayer separation, the interbilayer fluctuations are smaller in DOPS than for DOPC, showing that B and/or K C are larger. Complementing the x-ray data, 31P-chemical shift anisotropy measured by NMR suggest that the DOPS headgroups are less sensitive to osmotic pressure than DOPC headgroups, which is consistent with a larger KC in DOPS. Quadrupolar splittings for D2O decay less rapidly with increasing water content for DOPS than for DOPC, indicating greater perturbation of interlamellar water and suggesting a greater interlamellar hydration force in DOPS. Our comparisons between bilayers of PS and PC lipids with the same chains and the same temperature enable us to focus on the effects of these headgroups on bilayer properties.

Original languageAmerican English
Pages (from-to)1574-1586
Number of pages13
JournalBiophysical Journal
Volume86
Issue number3
DOIs
StatePublished - Mar 2004
Externally publishedYes

Bibliographical note

Funding Information:
We acknowledge use of the F1 and D1 stations of the Cornell High Energy Synchrotron Facility (National Science Foundation grant DMR-9311772). The Carnegie Mellon University authors and the initial data collection by Dr. Petrache were supported by National Institutes of Health grant GM44976 (JFN-PI).

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