Self-assembled microstructures from 1,2-ethanediol suspensions of pure and binary mixtures of neutral and acidic biological galactosylceramides.
Optical and electron microscopy were employed to characterize microstructures formed by thermal mechanical treatment of glycol suspensions of various pure and binary mixtures of the brain-derived galactosphingolipids hydroxy fatty acid cerebroside (HFA-Cer), non-hydroxy fatty acid cerebroside (NFA-Cer) and sulfatide (S-Cer). Negative staining indicated some new features of the neutral cerebroside suspensions in glycol. HFA-Cer formed a small fraction of both unilamellar cylinders (ULCs) (lumina ca. 27 nm) and giant multilamellar cochleates in addition to the typical nonhelical multilamellar cylinders (MLCs) (lumina ca. 10-30 nm). NFA-Cer formed a gel composed of a significant fraction of very long ULCs (lumina ca. 17 nm) without helical substructure, in addition to multilamellar helical structures such as ribbons and cylinders (lumina ca. 70 nm). Anisotropic lamellar micelle-shards of NFA-Cer were also detected by negative staining. S-Cer formed short ULCs (lumina ca. 44 nm) with no obvious helical substructure. Complex mixture data are thought to result from thermodynamic and kinetic factors. HFA-Cer is highly insoluble and promotes a network of rigid intralamellar hydrogen bonding that tends to exclude other lipids. NFA-Cer stabilizes helical defects in the lamellae, and S-Cer enhances disorder or micellization. The processes of microstructure nucleation and lipid phase separation were affected by mixtures such that metastable microstructures were trapped or the length of lamellar cylinders was altered.
Archibald
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School of Chemistry, University of Bath, United Kingdom.
Mann
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D000818:Animals; D055592:Biophysical Phenomena; D001703:Biophysics; D001923:Brain Chemistry; D002417:Cattle; D002554:Cerebrosides / Q000737:chemistry; D055598:Chemical Phenomena; D002627:Chemistry, Physical; D005026:Ethylene Glycols; D005699:Galactosylceramides / Q000737:chemistry*; D066298:In Vitro Techniques; D008051:Lipid Bilayers / Q000737:chemistry; D046911:Macromolecular Substances; D008823:Micelles; D008854:Microscopy, Electron; D008968:Molecular Conformation; D015394:Molecular Structure; D013433:Sulfoglycosphingolipids / Q000737:chemistry; D013535:Suspensions; D013816:Thermodynamics; D014867:Water
D002554:Cerebrosides; D005026:Ethylene Glycols; D005699:Galactosylceramides; D008051:Lipid Bilayers; D046911:Macromolecular Substances; D008823:Micelles; D013433:Sulfoglycosphingolipids; D013535:Suspensions; D014867:Water