title: Glycosphingolipids in insects. Chemical structures of two variants of a glucuronic-acid-containing ceramide hexasaccharide from a pupae of Calliphora vicina (Insecta: Diptera), distinguished by a N-acetylglucosamine-bound phosphoethanolamine sidechain.
abstract: The two major components of the acidic glycolipid fraction from the pupae of Calliphora vicina were isolated using high-performance liquid chromatography. The acidic moiety was identified as glucuronic acid by beta-glucuronidase cleavage and gas chromatographic analysis as the pentafluoropropionyl derivative. The structures of the carbohydrate moiety were elucidated by peracetylation, methylation, exoglycosidase cleavage, fast-atom-bombardment mass spectrometric and 1H-nuclear magnetic resonance spectroscopic analysis. The only difference between the two hexasaccharide variants was the presence, in one of them, of a between the two hexasaccharide variants was the presence, in one of them, of a phosphoethanolamine (AeP) sidechain on the third sugar of the sequence, i.e. N-acetylglucosamine. The composition of the ceramide moiety was dominated by a C20:0 fatty acid (arachidic acid) and a C14:1 sphingoid base (tetradecasphing-4-enine). The chemical structures of the two insect acidic glycosphingolipids were determined to be: GlcA(beta 1-3)Gal-(beta 1-3)GalNAc(beta 1-4)GlcNAc(beta 1-3)Man (beta 1-4)Glc(beta 1-1)Cer; GlcA(beta 1-3)Gal(beta 1-3)GalNAc(beta 1-4)[2AeP-6]-GlcNAc(beta 1-3) Man(beta 1-4)Glc(beta 1-1)Cer. Such glucuronic-acid-containing insect glycosphingolipids have been given the generic name arthrosides, with the implied synonymity to the gangliosides.
authors.affiliation: Institut für Physiologische Chemie, Universität Marburg, Federal Republic of Germany.
authors.forename: B
authors.initials: B
authors.lastname: Weske
authors.forename: R D
authors.initials: RD
authors.lastname: Dennis
authors.forename: F
authors.initials: F
authors.lastname: Helling
authors.forename: M
authors.initials: M
authors.lastname: Keller
authors.forename: G A
authors.initials: GA
authors.lastname: Nores
authors.forename: J
authors.initials: J
authors.lastname: Peter-Katalinic
authors.forename: H
authors.initials: H
authors.lastname: Egge
authors.forename: U
authors.initials: U
authors.lastname: Dabrowski
authors.forename: H
authors.initials: H
authors.lastname: Wiegandt
mesh_terms: D000117:Acetylglucosamine / Q000032:analysis*; D000818:Animals; D001665:Binding Sites; D002236:Carbohydrate Conformation; D002240:Carbohydrate Sequence; D002518:Ceramides / Q000032:analysis*; D002855:Chromatography, Thin Layer; D004175:Diptera / Q000032:analysis*; D004983:Ethanolamines / Q000032:analysis*; D005944:Glucosamine / Q000031:analogs & derivatives*; D005965:Glucuronates / Q000032:analysis*; D020723:Glucuronic Acid; D006026:Glycoside Hydrolases; D006028:Glycosphingolipids / Q000302:isolation & purification*; D006863:Hydrogen-Ion Concentration; D009682:Magnetic Resonance Spectroscopy; D013058:Mass Spectrometry; D011134:Polysaccharides / Q000032:analysis*
chemical_list: D002518:Ceramides; D004983:Ethanolamines; D005965:Glucuronates; D006028:Glycosphingolipids; D011134:Polysaccharides; C005448:phosphorylethanolamine; D020723:Glucuronic Acid; D006026:Glycoside Hydrolases; D005944:Glucosamine; D000117:Acetylglucosamine