Collision-Induced Dissociation of Branched Oligosaccharide Ions with Analysis and Calculation of Relative Dissociation Thresholds

• Published in: Analytical chemistry (Washington) Vol. 68; no. 14; pp. 2331 - 2339
• Main Authors: Penn, Sharron G, Cancilla, Mark T, Lebrilla, Carlito B
• Format: Journal Article
• Language: English
• Published: Washington, DC American Chemical Society 15-07-1996
• Subjects: Carbohydrate Sequence; Carbohydrates; Chemistry; Exact sciences and technology; Ions; Kinetics; Lasers; Mass spectrometry; Molecular Sequence Data; Oligosaccharides - chemistry; Organic chemistry; Reactivity and mechanisms; Scientific imaging; Spectrometry, Mass, Matrix-Assisted Laser Desorption-Ionization; Matrix isolation; Branched chain; Fourier transformation; Collisional activation; Aldose; Photoionization; Aminoglycoside; Mass spectrometry MS/MS; Oligoholoside; Fragmentation pattern; Mass spectrometry; Laser desorption
• ISSN: 0003-2700; 1520-6882
• DOI: 10.1021/ac960155i

Collision-induced dissociation (CID) is used in an external source Fourier transform mass spectrometer (FTMS) equipped with matrix-assisted laser desorption/ionization (MALDI) to study a number of complex, branched oligosaccharides. The relative dissociation thresholds for various oligosaccharide fragmentation pathways have been calculated in terms of kinetic and center-of-mass frame energy. For two isomers of difucosyllacto-N-hexaose, the loss of the fucose sugar is always the lowest energy fragment observed and occurs at the same energy for both isomers when the oligosaccharide is coordinated to a sodium ion. When the oligosaccharide is complexed to cesium, the threshold for the removal of the fucose moiety increases, indicating that the cesium is involved in a coordination complex that stabilizes the sugar. MS/MS/MS is performed on a sugar, mannose core, which does not readily fragment during MALDI. In all the sugars examined, CID produces additional structural information relative to MALDI/FTMS.