Simulation studies of high-field EPR spectra of spin-labeled lipids in membranes.
The high-field (i.e., 94 GHz) membrane EPR spectra of lipids spin labeled in their fatty acid chains have been simulated by using two limiting motional models. The aim was to identify the dynamic origin of the residual (g(xx) - g(yy)) anisotropy observed in the nonaxial EPR spectra of cholesterol-containing membranes. It is concluded that the residual spectral anisotropy arises from in-plane ordering of the lipid chains by cholesterol. The partial averaging of the (g(xx) - g(yy)) anisotropy was best described by restricted axial rotation with a frequency in the region of tau(-1)(R||) approximately 0.5-1 x 10(9) s(-1). Simulations for slower axial rotation of unrestricted amplitude produced less satisfactory fits. In phospholipid membranes not containing cholesterol, the nonaxial anisotropy is completely averaged in the fluid phase and substantially reduced even in the gel phase. The unrestricted axial rotation in the gel phase is of comparable frequency to that of the limited axial rotation in the liquid-ordered phase of membranes containing cholesterol. These results on in-plane ordering by cholesterol in the liquid-ordered phase could be significant for current proposals regarding domain formation in cellular membranes.
Livshits
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VA
Abteilung Spektroskopie, Max-Planck-Institut für biophysikalische Chemie, Göttingen, D-37070, Germany.
Marsh
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D
D000465:Algorithms; D002462:Cell Membrane / Q000737:chemistry; D002784:Cholesterol / Q000737:chemistry; D003198:Computer Simulation; D004134:Dimyristoylphosphatidylcholine / Q000737:chemistry; D004578:Electron Spin Resonance Spectroscopy; D008051:Lipid Bilayers; D008563:Membrane Lipids / Q000737:chemistry*; D008954:Models, Biological; D008968:Molecular Conformation; D013113:Spin Labels
D008051:Lipid Bilayers; D008563:Membrane Lipids; D013113:Spin Labels; D002784:Cholesterol; D004134:Dimyristoylphosphatidylcholine