Cross-Ring Fragmentation Patterns in the Tandem Mass Spectra of Underivatized Sialylated Oligosaccharides and Their Special Suitability for Spectrum Library Searching

Reference spectral library searching, while widely used to identify compounds in other areas of mass spectrometry, is not commonly used in glycomics. Building on a study by Cotter and coworkers on analysis of sialylated oligosaccharides using atmospheric pressure-matrix-assisted laser-induced tandem...

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Bibliographic Details
Published in:Journal of the American Society for Mass Spectrometry 2019-03, Vol.30 (3), p.426-438
Main Authors: De Leoz, Maria Lorna A., Simón-Manso, Yamil, Woods, Robert J., Stein, Stephen E.
Format: Article
Language:English
Subjects:
Analytical Chemistry
Bioinformatics
Biotechnology
Chemistry
Chemistry and Materials Science
Fragmentation
Glycan
Ions
Isomers
Libraries
Mass spectra
Mass spectrometers
Mass spectrometry
Monosaccharides
Oligosaccharides
Organic Chemistry
Proteomics
Research Article
Scientific imaging
Search methods
Spectrometers
Spectroscopy
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Summary:Reference spectral library searching, while widely used to identify compounds in other areas of mass spectrometry, is not commonly used in glycomics. Building on a study by Cotter and coworkers on analysis of sialylated oligosaccharides using atmospheric pressure-matrix-assisted laser-induced tandem mass spectrometry (MS/MS), we show that library search methods enable the automated differentiation of such sialylated oligosaccharide isomers using MS/MS derived from electrospray collision-induced dissociation in ion trap and beam-type fragmentation mass spectrometers. We compare MS/MS spectra of five sets of native sialylated oligosaccharide isomers and show a spectral library search method that can distinguish between these isomers using the precursor ion [M+2X-H] + , where X=Li, Na, or K. Sialic acid linkage (α2,3 vs. α2,6) is known to have a dramatic effect on the fragmentation of the sialylated compounds. We found that 2,4 A3 cross-ring fragment at the terminal monosaccharide in sialyllactoses, sialyllactosamines, and sialyl pentasaccharides is highly abundant in the MS/MS spectra of [M+2X-H] + species of α2,6-NeuAc glycans, while ( 2,4 A3-H2O) fragment is highly abundant in α2,3-NeuAc moiety. The 2,4 A3-H2O peak is specific to NeuAc-α2,3-Gal-β1,4-Y (Y=GlcNAc or Glc). To our knowledge, this observation was not reported previously. Theoretical calculations reveal major conformational differences between α2,6-NeuAc and α2,3-NeuAc structures that provide reasonable explanations for the observed fragmentation patterns. Other singly-charged ions ([M+X] + ) do not show similar cross-ring cleavages. Implemented in a searchable library, these spectral differences provide a facile method to distinguish sialyl isomers without derivatization. We also found good spectral matching across instruments. MS/MS spectra and tools are available at http://chemdata.nist.gov/glycan/spectra . Graphical Abstract
ISSN:1044-0305
1879-1123
DOI:10.1007/s13361-018-2106-8