Ion-Mobility Spectrometry Can Assign Exact Fucosyl Positions in Glycans and Prevent Misinterpretation of Mass-Spectrometry Data After Gas-Phase Rearrangement
| Autor: | Sastre Toraño, Javier, Gagarinov, Ivan A, Vos, Gaël M, Broszeit, Frederik, Srivastava, Apoorva D, Palmer, Martin, Langridge, James I, Aizpurua-Olaizola, Oier, Somovilla, Victor J, Boons, Geert-Jan, Afd Chemical Biology and Drug Discovery, Sub Chemical Biology and Drug Discovery, Chemical Biology and Drug Discovery |
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| Jazyk: | angličtina |
| Rok vydání: | 2019 |
| Předmět: |
Glycan
Anomer Ion-mobility spectrometry Stereochemistry rearrangement carbohydrates 010402 general chemistry Tandem mass spectrometry Mass spectrometry on-mobility spectrometry massspectrometry 01 natural sciences Mass Spectrometry Catalysis Fucose Acetylglucosamine Small Molecule Libraries chemistry.chemical_compound Isomerism Nucleophile fucose Polysaccharides Fucosylation Ions Molecular Structure biology 010405 organic chemistry General Chemistry N-Acetylneuraminic Acid 0104 chemical sciences carbohydrates (lipids) chemistry biology.protein Gases |
| Zdroj: | Angewandte Chemie-International Edition, 58(49), 17616. John Wiley and Sons Ltd |
| ISSN: | 1433-7851 |
| Popis: | The fucosylation of glycans leads to diverse structures and is associated with many biological and disease processes. The exact determination of fucoside positions by tandem mass spectrometry (MS/MS) is complicated because rearrangements in the gas phase lead to erroneous structural assignments. Here, we demonstrate that the combined use of ion-mobility MS and well-defined synthetic glycan standards can prevent misinterpretation of MS/MS spectra and incorrect structural assignments of fucosylated glycans. We show that fucosyl residues do not migrate to hydroxyl groups but to acetamido moieties of N-acetylneuraminic acid as well as N-acetylglucosamine residues and nucleophilic sites of an anomeric tag, yielding specific isomeric fragment ions. This mechanistic insight enables the characterization of unique IMS arrival-time distributions of the isomers which can be used to accurately determine fucosyl positions in glycans. |
| Databáze: | OpenAIRE |
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