Structural analysis of permethylated oligosaccharides by electrospray tandem mass spectrometry

Viseux, N;de Hoffmann, Edmond;Domon, B
(1997) Analytical Chemistry — Vol. 69, n° 16, p. 3193-3198 (1997)

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Authors
  • Viseux, N
    Author
  • de Hoffmann, EdmondUCLouvain
    Author
  • Domon, B
    Author
Abstract
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 protonated 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 O-18-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.
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Viseux, N., de Hoffmann, E., & Domon, B. (1997). Structural analysis of permethylated oligosaccharides by electrospray tandem mass spectrometry. Analytical Chemistry, 69(16), 3193-3198. https://doi.org/10.1021/ac961285u (Original work published 1997)