title: Structural Analysis of the Minor Cerebrosides from a Glass Sponge Aulosaccus sp.
abstract: The minor cerebrosides from a Far-Eastern glass sponge Aulosaccus sp. were analyzed as constituents of some multi-component RP-HPLC fractions. The structures of eighteen new and one known cerebrosides were elucidated on the basis of NMR spectroscopy, mass spectrometry, optical rotation data and chemical transformations. These β-D-glucopyranosyl-(1→1)-ceramides contain sphingoid bases N-acylated with straight-chain (2R)-2-hydroxy fatty acids, namely, (2S,3S,4R,11Z)-2-aminoeicos-11-ene-1,3,4-triol, acylated with 15E-22:1, 16Z-21:1, 15Z-21:1, 15Z-20:1, 15E-20:1, 19:0, 18:0 acids, (2S,3S,4R)-2-amino-13-methyltetradecane-1,3,4-triol--with 19Z-26:1, 16Z-23:1, 23:0, 22:0 acids, (2S,3S,4R)-2-amino-14-methylpentadecane-1,3,4-triol--with 16Z-23:1, 16E-23:1, 15Z-22:1, 22:0 acids, (2S,3S,4R)-2-amino-14-methylhexadecane-1,3,4-triol, linked to 16Z-23:1, 15Z-22:1 acids, (2S,3S,4R)-2-amino-9-methylhexadecane-1,3,4-triol--to 16Z-23:1 acid, and (2S,3S,4R)-2-aminohexadecane-1,3,4-triol, attached to 15Z-22:1 acid. The 13-methyl and 9-methyl-branched trihydroxy sphingoid base backbones (C15 and C17, respectively) have not been found previously in sphingolipids. The ceramide parts, containing other backbones, present new variants of N-acylation of the marine sphingoid bases with the 2-hydroxy fatty acids. The combination of the instrumental and chemical methods used in this study improved the efficiency of the structural analysis of such complex cerebroside mixtures that gave more detailed information on glycosphingolipid metabolism of the organism.
authors.affiliation: G.B. Elyakov Pacific Institute of Bioorganic Chemistry, Far-Eastern Branch, Russian Academy of Sciences, Pr. 100 let Vladivostoku, 159, Vladivostok, 690022, Russia. santalova@piboc.dvo.ru.
authors.forename: Elena A
authors.initials: EA
authors.lastname: Santalova
authors.affiliation: G.B. Elyakov Pacific Institute of Bioorganic Chemistry, Far-Eastern Branch, Russian Academy of Sciences, Pr. 100 let Vladivostoku, 159, Vladivostok, 690022, Russia.
authors.forename: Vladimir A
authors.initials: VA
authors.lastname: Denisenko
authors.affiliation: G.B. Elyakov Pacific Institute of Bioorganic Chemistry, Far-Eastern Branch, Russian Academy of Sciences, Pr. 100 let Vladivostoku, 159, Vladivostok, 690022, Russia.
authors.forename: Pavel S
authors.initials: PS
authors.lastname: Dmitrenok
mesh_terms: D000215:Acylation; D000818:Animals; D002554:Cerebrosides / Q000737:chemistry* / Q000302:isolation & purification; D002851:Chromatography, High Pressure Liquid; D056148:Chromatography, Reverse-Phase; D045424:Complex Mixtures / Q000737:chemistry / Q000302:isolation & purification; D000431:Ethanol / Q000737:chemistry; D054878:Lipoylation; D015394:Molecular Structure; D019906:Nuclear Magnetic Resonance, Biomolecular; D009904:Optical Rotation; D010139:Pacific Islands; D010140:Pacific Ocean; D011161:Porifera / Q000737:chemistry* / Q000254:growth & development; D012426:Russia; D012997:Solvents / Q000737:chemistry; D021241:Spectrometry, Mass, Electrospray Ionization; D013237:Stereoisomerism; D053719:Tandem Mass Spectrometry
chemical_list: D002554:Cerebrosides; D045424:Complex Mixtures; D012997:Solvents; D000431:Ethanol
keywords: 2-Hydroxy fatty acid; Aulosaccus; Cerebroside; Glass sponge; Glycosphingolipid; Hexactinellida; Sphingoid base