Effect of the reducing-terminal substituants on the high energy collision-induced dissociation matrix-assisted laser desorption/ionization mass spectra of oligosaccharides

Bernhard Küster, Thomas J.P. Naven, David J. Harvey

Research output: Contribution to journalArticlepeer-review

43 Scopus citations

Abstract

High-energy collision-induced dissociation (CID) matrix-assisted laser desorption/ionization mass spectra of N-linked oligosaccharides bearing different, commonly encountered, reducing terminal modifications (hydroxyl, 2-aminobenzamide, asparagine and a tetrapeptide) were recorded on a magnetic sector instrument equipped with an orthogonal-acceleration time-of-flight (OA-TOF) analyser. All the compounds formed abundant molecular (MNa+) and fragment ions, the latter corresponding to glycosidic and cross-ring cleavages as well as to internal fragment ions, all of which provided much insight into the oligosaccharide structure. The nature of the modification considerably influenced the CID behaviour. The strongest and most complete series of glycosidic cleavage ions (mainly Y and B - Domon and Costello nomenclature) was formed by the underivatized oligosaccharide whereas most cross-ring fragment ions, diagnostic of linkage, were found in the spectra of the glycopeptides. A-type cross-ring cleavage ions were particularly abundant in the spectrum of the asparagine derivative. Reductive amination using 2-aminobenzamide resulted in an opened reducing-terminal sugar ring and suppression of the cross-ring fragment ions carrying information associated with that ring. This information was present in the spectra of the free carbohydrate and the peptide derivatives.

Original languageEnglish
Pages (from-to)1645-1651
Number of pages7
JournalRapid Communications in Mass Spectrometry
Volume10
Issue number13
DOIs
StatePublished - 1996
Externally publishedYes

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