Premium
Ion‐Mobility Spectrometry Can Assign Exact Fucosyl Positions in Glycans and Prevent Misinterpretation of Mass‐Spectrometry Data After Gas‐Phase Rearrangement
Author(s) -
Sastre Toraño Javier,
Gagarinov Ivan A.,
Vos Gaël M.,
Broszeit Frederik,
Srivastava Apoorva D.,
Palmer Martin,
Langridge James I.,
AizpuruaOlaizola Oier,
Somovilla Victor J.,
Boons GeertJan
Publication year - 2019
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201909623
Subject(s) - chemistry , glycan , ion mobility spectrometry , fucosylation , mass spectrometry , tandem mass spectrometry , anomer , ion , gas phase , nucleophile , chromatography , stereochemistry , biochemistry , organic chemistry , catalysis , glycoprotein
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.