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Profiling glycosphingolipid structural detail: Periodate oxidation, electrospray, collision‐induced dissociation and tandem mass spectrometry
Author(s) -
Reinhold Bruce B.,
Chan ShuiYung,
Chan Steven,
Reinhold Ver N.
Publication year - 1994
Publication title -
organic mass spectrometry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.475
H-Index - 121
eISSN - 1096-9888
pISSN - 0030-493X
DOI - 10.1002/oms.1210291206
Subject(s) - chemistry , tandem mass spectrometry , collision induced dissociation , mass spectrometry , electrospray ionization , fragmentation (computing) , glycosphingolipid , dissociation (chemistry) , glycosidic bond , electrospray , chromatography , organic chemistry , biochemistry , computer science , enzyme , operating system
Electrospray ionization mass spectrometry applied to methylated glycosphingolipid samples provides a sensitive molecular mass profile with no detectable fragmentation and little matrix background. In a bovine brain preparation, the components G M1a , G D1a/b and G T1a/b were characterized in detail and several minor entities, G T1 , G M3 , G A1 , G M2 , were mass profiled. Two additional materials, unrelated to the o‐, a‐, b‐ or c‐series, were characterized as hexosamine additions to G M1 and G D1a . Structural details of the major components within these samples were obtained by utilizing low‐energy collision tandem mass spectrometry and periodate oxidation, which could serve as a basis for more complex and higher molecular mass preparations. Fragment structures in the collision spectra were assigned with the assistance of C 1 H 3 and C 2 H 3 derivatization and by exploiting the natural carbohydrate and ceramide heterogeneity of the samples. Major fragments originate from C 1 O glycosidic rupture with few ring‐opening ions. Glycosidic fragments defined details that allow the determination of structural isomers, while specific fragments of the ceramide moiety differentiate sphingosine from N ‐acyl heterogeneity. When contrasted with high‐energy (8 keV) tandem mass spectrometry, low‐energy collision‐induced dissociation of multiply charged molecular ions provided more abundant structurally diagnostic fragments.