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.
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.
Weske
B
B
Institut für Physiologische Chemie, Universität Marburg, Federal Republic of Germany.
Dennis
R D
RD
Helling
F
F
Keller
M
M
Nores
G A
GA
Peter-Katalinic
J
J
Egge
H
H
Dabrowski
U
U
Wiegandt
H
H
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*
D002518:Ceramides; D004983:Ethanolamines; D005965:Glucuronates; D006028:Glycosphingolipids; D011134:Polysaccharides; C005448:phosphorylethanolamine; D020723:Glucuronic Acid; D006026:Glycoside Hydrolases; D005944:Glucosamine; D000117:Acetylglucosamine