Ion-Mobility Spectrometry Can Assign Exact Fucosyl Positions in Glycans and Prevent Misinterpretation of Mass-Spectrometry Data After Gas-Phase Rearrangement.

Autor: Sastre Toraño J; Department of Chemical Biology and Drug Discovery, Utrecht University, Universiteitsweg 99, 3584, CG, Utrecht, The Netherlands., Gagarinov IA; Department of Chemical Biology and Drug Discovery, Utrecht University, Universiteitsweg 99, 3584, CG, Utrecht, The Netherlands., Vos GM; Department of Chemical Biology and Drug Discovery, Utrecht University, Universiteitsweg 99, 3584, CG, Utrecht, The Netherlands., Broszeit F; Department of Chemical Biology and Drug Discovery, Utrecht University, Universiteitsweg 99, 3584, CG, Utrecht, The Netherlands., Srivastava AD; Department of Chemical Biology and Drug Discovery, Utrecht University, Universiteitsweg 99, 3584, CG, Utrecht, The Netherlands., Palmer M; Waters Corporation, Stamford Avenue, Altrincham Road, SK9 4AX, Wilmslow, UK., Langridge JI; Waters Corporation, Stamford Avenue, Altrincham Road, SK9 4AX, Wilmslow, UK., Aizpurua-Olaizola O; Department of Chemical Biology and Drug Discovery, Utrecht University, Universiteitsweg 99, 3584, CG, Utrecht, The Netherlands., Somovilla VJ; Department of Chemical Biology and Drug Discovery, Utrecht University, Universiteitsweg 99, 3584, CG, Utrecht, The Netherlands., Boons GJ; Department of Chemical Biology and Drug Discovery, Utrecht University, Universiteitsweg 99, 3584, CG, Utrecht, The Netherlands.; Complex Carbohydrate Research Center and Department of Chemistry, University of Georgia, 315 Riverbend Road, Athens, GA, 30602, USA.
Jazyk: angličtina
Zdroj: Angewandte Chemie (International ed. in English) [Angew Chem Int Ed Engl] 2019 Dec 02; Vol. 58 (49), pp. 17616-17620. Date of Electronic Publication: 2019 Oct 22.
DOI: 10.1002/anie.201909623
Abstrakt: 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.
(© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)
Databáze: MEDLINE
Externí odkaz: