title: Partial synthesis of ganglioside and lysoganglioside lipoforms as internal standards for MS quantification.
abstract: Within recent years, ganglioside patterns have been increasingly analyzed by MS. However, internal standards for calibration are only available for gangliosides GM1, GM2, and GM3. For this reason, we prepared homologous internal standards bearing nonnatural fatty acids of the major mammalian brain gangliosides GM1, GD1a, GD1b, GT1b, and GQ1b, and of the tumor-associated gangliosides GM2 and GD2. The fatty acid moieties were incorporated after selective chemical or enzymatic deacylation of bovine brain gangliosides. For modification of the sphingoid bases, we developed a new synthetic method based on olefin cross metathesis. This method was used for the preparation of a lyso-GM1 and a lyso-GM2 standard. The total yield of this method was 8.7% for the synthesis of d17:1-lyso-GM1 from d20:1/18:0-GM1 in four steps. The title compounds are currently used as calibration substances for MS quantification and are also suitable for functional studies.
authors.affiliation: Life & Medical Sciences, Membrane Biology and Lipid Biochemistry Unit, Kekulé-Institut für Organische Chemie und Biochemie, Universität Bonn, D-53115 Bonn, Germany.
authors.forename: Martin
authors.initials: M
authors.lastname: Gantner
authors.affiliation: Life & Medical Sciences, Membrane Biology and Lipid Biochemistry Unit, Kekulé-Institut für Organische Chemie und Biochemie, Universität Bonn, D-53115 Bonn, Germany.
authors.forename: Günter
authors.initials: G
authors.lastname: Schwarzmann
authors.affiliation: Life & Medical Sciences, Membrane Biology and Lipid Biochemistry Unit, Kekulé-Institut für Organische Chemie und Biochemie, Universität Bonn, D-53115 Bonn, Germany.
authors.forename: Konrad
authors.initials: K
authors.lastname: Sandhoff
authors.affiliation: Life & Medical Sciences, Membrane Biology and Lipid Biochemistry Unit, Kekulé-Institut für Organische Chemie und Biochemie, Universität Bonn, D-53115 Bonn, Germany.
authors.forename: Thomas
authors.initials: T
authors.lastname: Kolter
mesh_terms: D000215:Acylation; D000581:Amidohydrolases / Q000378:metabolism; D000818:Animals; D001921:Brain / Q000378:metabolism; D002138:Calibration; D002417:Cattle; D005732:Gangliosides / Q000737:chemistry* / Q000302:isolation & purification / Q000378:metabolism / Q000592:standards; D006868:Hydrolysis; D050356:Lipid Metabolism; D008055:Lipids / Q000737:chemistry* / Q000302:isolation & purification / Q000592:standards; D008297:Male; D015394:Molecular Structure; D009474:Neurons / Q000737:chemistry; D012015:Reference Standards; D013237:Stereoisomerism; D013737:Testis / Q000201:enzymology; D014020:Tissue Extracts / Q000737:chemistry; D001616:beta-Galactosidase / Q000378:metabolism
chemical_list: D005732:Gangliosides; D008055:Lipids; D014020:Tissue Extracts; C037470:cronassial; D001616:beta-Galactosidase; D000581:Amidohydrolases; C096410:sphingolipid ceramide N-deacylase
keywords: brain lipids; chemical synthesis; glycolipids; lipidomics; mass spectrometry; olefin metathesis; sphingolipids