Journal
ANALYTICAL CHEMISTRY
Volume 89, Issue 8, Pages 4540-4549Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acs.analchem.6b04998
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Funding
- Stichting voor Fundamenteel Onderzoek der Materie (FOM)
- University of Copenhagen Excellence Program for Interdisciplinary Research
- LABEX iMUST of Universite de Lyon within program Investissements d'Avenir [ANR-10-LABX-0064, ANR-11-IDEX-0007]
- Dutch-French Van Gogh program
- GENCI-CINES [087025]
- European Community [312284, 289217, 259869, 278832, 608381, 115360]
- BBSRC [BB/F017472/1, BB/L013762/1, BB/M027791/1]
- Royal Society
- Biotechnology and Biological Sciences Research Council [BB/M027791/1, BB/L013762/1, 1733990] Funding Source: researchfish
- Villum Fonden [00007523] Funding Source: researchfish
- BBSRC [BB/F017472/1, BB/L013762/1, BB/M027791/1] Funding Source: UKRI
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The lack of robust, high-throughput, and sensitive analytical strategies that can conclusively map the structure of glycans has significantly hampered progress in fundamental and applied aspects of glycoscience. Resolution of the anomeric a//3 glycan linkage within oligosaccharides remains a particular challenge. Here, we show that memory of anomeric configuration is retained following gas-phase glycosidic bond fragmentation during tandem mass spectrometry (MS2). These findings allow for integration of MS2 with-ion mobility spectrometry (IM-MS2) and lead to a strategy,to distinguish alpha- and beta-linkages within natural underivatized carbohydrates. We have applied, this fragment-based hyphenated MS technology to oligosaccharide standards and to de novo sequencing of purified plant metabolite glycoconjugates, showing that the anomeric signature is also observable in fragments derived from larger glycans. The discovery of the unexpected anomeric memory effect is further supported by IR-MS action spectroscopy and ab initio calculations. Quantum mechanical calculations provide candidate geometries for the distinct anomeric fragment ions, in turn shedding light on gas-phase dissociation mechanisms of glycosidic linkages.
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