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  • Title: Cholesterol decreases the interfacial elasticity and detergent solubility of sphingomyelins.
    Author: Li XM, Momsen MM, Smaby JM, Brockman HL, Brown RE.
    Journal: Biochemistry; 2001 May 22; 40(20):5954-63. PubMed ID: 11352730.
    Abstract:
    The interfacial interactions of cholesterol with sphingomyelins (SMs) containing various homogeneous acyl chains have been investigated by Langmuir film balance approaches. Low in-plane elasticity among the packed lipids was identified as an important physical feature of the cholesterol-sphingomyelin liquid-ordered phase that correlates with detergent resistance, a characteristic property of sphingolipid-sterol rafts. Changes in the in-plane elastic packing, produced by cholesterol, were quantitatively assessed by the surface compressional moduli (C(s)(-1)) of the monolayer isotherms. Of special interest were C(s)(-1) values determined at high surface pressures (>30 mN/m) that mimic the biomembrane situation. To identify structural features that uniquely affect the in-plane elasticity of the sphingomyelin-cholesterol lateral interaction, comparisons were made with phosphatidylcholine (PC)-cholesterol mixtures. Cholesterol markedly decreased the in-plane elasticity of either SM or PC regardless of whether they were fluid or gel phase without cholesterol. The magnitude of the reduction in in-plane elasticity induced by cholesterol was strongly influenced by acyl chain structure and by interfacial functional groups. Liquid-ordered phase formed at lower cholesterol mole fractions when SM's acyl chain was saturated rather than monounsaturated. At similar high cholesterol mole fractions, the in-plane elasticity within SM-cholesterol liquid-ordered phase was significantly lower than that of PC-cholesterol liquid-ordered phase, even when PCs were chain-matched to the SMs. Sphingoid-base functional groups (e.g., amide linkages), which facilitate or strengthen intermolecular hydrogen bonds, appear to be important for forming sphingomyelin-cholesterol, liquid-ordered phases with especially low in-plane elasticity. The combination of structural features that predominates in naturally occurring SMs permits very effective resistance to solubilization by Triton X-100.
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