Structural analysis of permethylated oligosaccharides by electrospray tandem mass spectrometry.
Electrospray tandem mass spectrometry used in conjunction with reversed-phase liquid chromatography was applied to characterize permethylated oligosaccharides. N-Acetylhexosamine-containing carbohydrates yielded under these conditions promoted molecular ions which underwent extensive fragmentation, even under low-energy collision-induced dissociation. MS/MS spectra of [M + H]+ ions are characterized by simple fragmentation patterns which result from cleavage of the glycosidic bonds and thus allow a straightforward interpretation. A systematic study of various oligosaccharides showed that information on sugar sequence and branching could be obtained. The nature of the substituent linked in position 3 of HexNAc-containing fragments could easily be assigned as the result of a specific secondary fragmentation process. The nature of some internal fragments was established on the basis of MS/MS spectra of derivatives 18O-labeled at the reducing end. Furthermore, MS/MS experiments carried out on fragment ions were proven to be useful for the structural characterization of oligosaccharide subunits. Thus, this approach constitutes a powerful tool for the structural assignment of moieties derived from larger glycans.
Viseux
N
N
Laboratoire de Chimie Biologique, UMR du CNRS No. 111, Université des Sciences et Technologies de Lille, France.
de Hoffmann
E
E
Domon
B
B
D002236:Carbohydrate Conformation; D002240:Carbohydrate Sequence; D013058:Mass Spectrometry / Q000379:methods*; D008969:Molecular Sequence Data; D009844:Oligosaccharides / Q000737:chemistry*
D009844:Oligosaccharides