Packing constraints and electrostatic surface potentials determine transmembrane asymmetry of phosphatidylethanol

Biophysical Journal
A V VictorovJ B Hoek

Abstract

The energetic determinants of the distribution of anionic phospholipids across a phosphatidylcholine (PtdCho) bilayer with different packing constraints in the two leaflets were studied, using (13)CH2-ethyl-labeled phosphatidylethanol (PtdEth) as a (13)C NMR membrane probe. PtdEth is unique in exhibiting a split (13)CH2-ethyl resonance in sonicated vesicles, the two components originating from the inner and outer leaflets, thus permitting the determination of the PtdEth concentration in each leaflet. Small and large unilamellar PtdEth-PtdCho vesicles were prepared in solutions of different ionic strengths. A quantitative expression for the transbilayer distribution of PtdEth, based on the balance between steric and electrostatic factors, was derived. The transbilayer difference in packing constraints was obtained from the magnitude of the PtdEth signal splitting. The electrostatic contribution could be satisfactorily described by the transmembrane difference in Gouy-Chapman surface potentials. At low (0.1-0.25%) PtdEth levels and high (up to 500 mM) salt concentrations, PtdEth had a marked fivefold preference for the inner leaflet, presumably because of its small headgroup, which favors tighter packing. At higher PtdEth content...Continue Reading

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Citations

May 16, 2000·Chemistry and Physics of Lipids·M Langner, K Kubica
Nov 15, 2008·Langmuir : the ACS Journal of Surfaces and Colloids·Andrew P ShreveAtul N Parikh
Mar 21, 2009·Biochimica Et Biophysica Acta·Shamshad Cockcroft

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