Infrared laser desorption mass spectrometry of oligosaccharides: Fragmentation mechanisms and isomer analysis

Bernhard Spengler, Joseph W. Dolce, Robert J. Cotter

Research output: Contribution to journalArticle

Abstract

Infrared laser desorption/ionization of oligosaccharides and their naturally occurring derivatives leads to a distinctive fragmentation pattern, which is useful both for the analysis of functional groups (e.g., the positions of fatty acyl groups in lipid A and other glycolipids) and for distinguishing isomers of underivatized oligosaccharides with different glycosidic linkages. The predominant mechanism of fragmentation can be understood as a pericyclic hydrogen rearrangement of the retro-aldol reaction type, leading to fragmentation of the sugar ring. A prerequisite for this process appears to involve opening of the hemiacetal saccharide ring to the linear saccharide form by rapid heating from the infrared laser irradiation. Saccharides derivatized at the anomeric hydroxyl group (i.e., cyclic acetals) normally do not undergo this ring opening and thus do not exhibit ring fragmentation reactions. This fragmentation mechanism can be used to predict and interpret fragmentation patterns of unknown oligosaccharides, glycosides, lipid A, and other glycoconjugates.

Original languageEnglish (US)
Pages (from-to)1731-1737
Number of pages7
JournalAnalytical Chemistry
Volume62
Issue number17
StatePublished - Sep 1 1990

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Infrared lasers
Oligosaccharides
Isomers
Mass spectrometry
Desorption
Lipid A
Acetals
Glycoconjugates
Glycolipids
Laser beam effects
Glycosides
Sugars
Hydroxyl Radical
Functional groups
Ionization
Hydrogen
Derivatives
Heating

ASJC Scopus subject areas

  • Analytical Chemistry

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Infrared laser desorption mass spectrometry of oligosaccharides : Fragmentation mechanisms and isomer analysis. / Spengler, Bernhard; Dolce, Joseph W.; Cotter, Robert J.

In: Analytical Chemistry, Vol. 62, No. 17, 01.09.1990, p. 1731-1737.

Research output: Contribution to journalArticle

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