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Matrix‐assisted laser desorption/ionization in‐source decay combined with tandem time‐of‐flight mass spectrometry of permethylated oligosaccharides: targeted characterization of specific parts of the glycan structure
Author(s) -
Wuhrer Manfred,
Deelder André M.
Publication year - 2006
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.2390
Subject(s) - chemistry , mass spectrometry , fragmentation (computing) , oligosaccharide , time of flight mass spectrometry , tandem mass spectrometry , glycan , glycomics , glycosidic bond , structural isomer , characterization (materials science) , matrix assisted laser desorption/ionization , molecule , protein mass spectrometry , tandem , time of flight , chromatography , desorption , ionization , stereochemistry , ion , organic chemistry , nanotechnology , biochemistry , materials science , glycoprotein , enzyme , computer science , composite material , operating system , adsorption
Abstract Matrix‐assisted laser desorption/ionization tandem time‐of‐flight mass spectrometry (MALDI‐TOF/TOF‐MS) has been introduced in recent years as a valuable tool for the structural characterization of permethylated oligosaccharides. In this report, we describe the combination of MALDI in‐source decay (ISD) with the subsequent TOF/TOF‐MS analyses of specific fragments, allowing the detailed characterization of the selected part of the oligosaccharide molecule. Part of the second‐generation fragment ions were different from those observed in conventional MALDI‐TOF/TOF‐MS experiments. Other fragments, which had already been observed in conventional MALDI‐TOF/TOF‐MS and again showed up in second‐generation fragment analysis, could be assigned to specific parts of the molecule. Our approach disclosed different structural features of the oligosaccharides: due to permethylation, the glycosidic linkage fragments allowed the distinction between terminal, monosubstituted and disubstituted monosaccharides and indicated the oligosaccharide sequence. Moreover, substitution positions were deduced based on characteristic cross‐ring fragmentation by high‐energy collision‐induced fragmentation. In conclusion, combination of MALDI‐ISD with TOF/TOF‐MS allows the detailed characterization of specific moieties of permethylated oligosaccharides and is, therefore, a powerful technique for structural glycomics. Copyright © 2006 John Wiley & Sons, Ltd.