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Diagnostic ions for the rapid analysis by nano‐electrospray ionization quadrupole time‐of‐flight mass spectrometry of O ‐glycans from human mucins
Author(s) -
Robbe Catherine,
Capon Calliope,
Coddeville Bernadette,
Michalski JeanClaude
Publication year - 2004
Publication title -
rapid communications in mass spectrometry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.528
H-Index - 136
eISSN - 1097-0231
pISSN - 0951-4198
DOI - 10.1002/rcm.1352
Subject(s) - chemistry , mass spectrometry , oligosaccharide , electrospray ionization , glycan , glycosidic bond , fragmentation (computing) , tandem mass spectrometry , electrospray , ion , chromatography , time of flight mass spectrometry , fast atom bombardment , protein mass spectrometry , analytical chemistry (journal) , ionization , organic chemistry , biochemistry , glycoprotein , computer science , enzyme , operating system
Abstract Nano‐electrospray ionization quadrupole time‐of‐flight mass spectrometry (nanoESI‐Q‐TOFMS) was used for sensitive mapping and sequencing of underivatized oligosaccharide alditols obtained from human mucins. Using subnanomolar amounts of oligosaccharides previously analyzed by nuclear magnetic resonance (NMR), series of diagnostic ions relevant to the structural characterization of O ‐glycans were deduced. Determination of the core type as well as positions and partial linkages of fucose residues could be readily obtained from the dominant [M+Na] + ions. Differentiation of isomeric structures and glycosidic linkages were defined by the characteristic cross‐ring 0,2 A‐type cleavages in the negative ion mode. Tandem (MS/MS) mass spectra of [MH] − ions from sialylated or sulfated O ‐glycans revealed information concerning the position and linkage of such residues. These fragmentation rules were further applied in the structural determination of glycans from human colonic mucins. All these findings indicated the efficiency of ESI‐Q‐TOFMS for the determination of oligosaccharide composition, sequence, partial linkage and substitution, providing a wealth of structural information with sensitivity sufficient for the analysis of quantities as obtained from natural sources. Copyright © 2004 John Wiley & Sons, Ltd.