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Fucose Migration in Intact Protonated Glycan Ions: A Universal Phenomenon in Mass Spectrometry

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Mucha,  Eike
Molecular Physics, Fritz Haber Institute, Max Planck Society;
Institut für Chemie und Biochemie der Freien Universität Berlin;

Lettow,  Maike
Molecular Physics, Fritz Haber Institute, Max Planck Society;
Institut für Chemie und Biochemie der Freien Universität Berlin;

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Marianski,  Mateusz
Molecular Physics, Fritz Haber Institute, Max Planck Society;

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Thomas,  Daniel
Molecular Physics, Fritz Haber Institute, Max Planck Society;

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Meijer,  Gerard
Molecular Physics, Fritz Haber Institute, Max Planck Society;

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Seeberger,  Peter H.
Peter H. Seeberger, Biomolekulare Systeme, Max Planck Institute of Colloids and Interfaces, Max Planck Society;
Institut für Chemie und Biochemie der Freien Universität Berlin;

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Helden,  Gert von
Molecular Physics, Fritz Haber Institute, Max Planck Society;

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Pagel,  Kevin
Molecular Physics, Fritz Haber Institute, Max Planck Society;
Institut für Chemie und Biochemie der Freien Universität Berlin;

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Citation

Mucha, E., Lettow, M., Marianski, M., Thomas, D., Struwe, W. B., Harvey, D. J., et al. (2018). Fucose Migration in Intact Protonated Glycan Ions: A Universal Phenomenon in Mass Spectrometry. Angewandte Chemie International Edition, 57. doi:10.1002/anie.201801418.


Cite as: https://hdl.handle.net/21.11116/0000-0001-69C1-F
Abstract
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.