| Article ID | Journal | Published Year | Pages | File Type |
|---|---|---|---|---|
| 1251957 | Chemistry and Physics of Lipids | 2012 | 14 Pages |
An analysis of electron spin resonance (ESR) spectra from compositions along the liquid-ordered (Lo) and liquid-disordered (Ld) coexistence curve from the brain-sphingomyelin/dioleoylphosphatidylcholine/cholesterol (SPM/DOPC/Chol) model lipid system was performed to characterize the dynamic structure on a molecular level of these coexisting phases. We obtained 200 continuous-wave ESR spectra from glycerophospholipid spin-labels labeled at the 5, 7, 10, 12, 14, and 16 carbon positions of the 2nd acyl chain, a sphingomyelin spin-label labeled at the 14 carbon position of the amide-linked acyl chain, a headgroup-labeled glycerophospholipid, a headgroup-labeled sphingomyelin, and the cholesterol analogue spin-label cholestane all within multi-lamellar vesicle suspensions at room temperature. The spectra were analyzed using the MOMD (microscopic-order macroscopic-disorder) model to provide the rotational diffusion rates and order parameters which characterize the local molecular dynamics in these phases. The analysis also incorporated the known critical point and invariant points of the neighboring three-phase triangle along the coexistence curve. The variation in the molecular dynamic structures of coexisting Lo and Ld compositions as one moves toward the critical point is discussed. Based on these results, a molecular model of the Lo phase is proposed incorporating the “condensing effect” of cholesterol on the phospholipid acyl chain dynamics and ordering and the “umbrella model” of the phospholipid headgroup dynamics and ordering.
► Molecular dynamic structure of coexisting 3 component lipid phases was determined. ► Distinct differences in behavior of upper and lower part of acyl chain in Lo phase. ► The condensing effect of cholesterol on phospholipid chains was inferred. ► Substantial support was obtained for the umbrella model of the Lo phase. ► Continuous transition through the critical point in molecular structural dynamics.
