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Fucose Migration in Intact Protonated Glycan Ions: A Universal Phenomenon in Mass Spectrometry
Author(s) -
Mucha Eike,
Lettow Maike,
Marianski Mateusz,
Thomas Daniel A.,
Struwe Weston B.,
Harvey David J.,
Meijer Gerard,
Seeberger Peter H.,
von Helden Gert,
Pagel Kevin
Publication year - 2018
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.201801418
Subject(s) - fucose , chemistry , tandem mass spectrometry , glycan , mass spectrometry , intramolecular force , protonation , glycoconjugate , dissociation (chemistry) , ion , chromatography , biochemistry , stereochemistry , organic chemistry , galactose , glycoprotein
Fucose is an essential deoxysugar that is found in a wide range of biologically relevant glycans and glycoconjugates. A recurring problem in mass spectrometric analyses of fucosylated glycans is the intramolecular migration of fucose units, which can lead to erroneous sequence assignments. This migration reaction is typically assigned to activation during collision‐induced dissociation (CID) in tandem mass spectrometry (MS). In this work, we utilized cold‐ion spectroscopy and show for the first time that fucose migration is not limited to fragments obtained in tandem MS and can also be observed in intact glycan ions. This observation suggests a possible low‐energy barrier for this transfer reaction and generalizes fucose migration to an issue that may universally occur in any type of mass spectrometry experiment.