Packing constraints and electrostatic surface potentials determine transmembrane asymmetry of phosphatidylethanol
| Autor: | Nathan Janes, Theodore F. Taraschi, Jan B. Hoek, Alexander V. Victorov |
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| Jazyk: | angličtina |
| Předmět: |
Steric effects
Magnetic Resonance Spectroscopy Surface Properties Lipid Bilayers Static Electricity Analytical chemistry Biophysics Ionic bonding Phosphatidic Acids Glycerophospholipids In Vitro Techniques Biophysical Phenomena chemistry.chemical_compound Membrane Lipids Phosphatidylcholine Particle Size Chemistry Bilayer Vesicle Osmolar Concentration Resonance Electrostatics Membrane Models Chemical Chemical physics Liposomes Phosphatidylcholines Thermodynamics lipids (amino acids peptides and proteins) Research Article |
| Zdroj: | Scopus-Elsevier |
| ISSN: | 0006-3495 |
| DOI: | 10.1016/S0006-3495(97)78902-1 |
| Popis: | 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 (4.8–9.1%) and low salt concentrations, where electrostatic repulsion becomes a dominant factor, the asymmetry was markedly reduced and an almost even distribution across the bilayer was obtained. In less curved, large vesicles, where packing constraints in the two leaflets are approximately the same, the PtdEth distribution was almost symmetrical. This study is the first quantitative analysis of the balance between steric and electrostatic factors that determines the equilibrium transbilayer distribution of charged membrane constituents. |
| Databáze: | OpenAIRE |
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