Energetics of cross-ring cleavages and their relevance to the linkage determination of oligosaccharides

James A. Carroll, Dale Willard, Carlito B Lebrilla

Research output: Contribution to journalArticle

68 Scopus citations

Abstract

The decomposition of oligosaccharide anions is investigated using the low energy collisional activation and Fourier transform mass spectrometry. The dissociation of the anion, specifically the monosaccharide rings, provides information on the types of linkage that form the glycosidic bonds. The fragment ions observed under liquid secondary ion mass spectrometry ionization and low energy collisional activation conditions show that the deprotonation of the anomeric position is necessary for cleaving the saccharide ring. For this reason, fragmentation occurs readily on the reducing end of the molecule. When the reducing ring is derivatized, or linked so that deprotonation of the anomeric ring is not possible, cross-ring fragmentation is not observed. A mechanism for cross ring cleavage is proposed based on experimental results. Molecular orbital calculations are performed to predict the activation barrier of each step and the overall dissociation process.

Original languageEnglish (US)
Pages (from-to)431-447
Number of pages17
JournalAnalytica Chimica Acta
Volume307
Issue number2-3
DOIs
StatePublished - May 30 1995

Keywords

  • Cross-link cleavages
  • Oligosaccharides

ASJC Scopus subject areas

  • Biochemistry
  • Analytical Chemistry
  • Spectroscopy
  • Environmental Chemistry

Fingerprint Dive into the research topics of 'Energetics of cross-ring cleavages and their relevance to the linkage determination of oligosaccharides'. Together they form a unique fingerprint.

  • Cite this