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

Eike Mucha; Maike Lettow; Mateusz Marianski; Daniel A Thomas; Weston B Struwe; David J Harvey; Gerard Meijer; Peter H Seeberger; Gert von Helden; Kevin Pagel

doi:10.1002/anie.201801418

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

Angew Chem Int Ed Engl. 2018 Jun 18;57(25):7440-7443. doi: 10.1002/anie.201801418. Epub 2018 May 25.

Authors

Eike Mucha^{1

2}, Maike Lettow^{1

2}, Mateusz Marianski¹, Daniel A Thomas¹, Weston B Struwe³, David J Harvey⁴, Gerard Meijer¹, Peter H Seeberger^{5

6}, Gert von Helden¹, Kevin Pagel^{1

2}

Affiliations

¹ Fritz-Haber-Institut der Max-Planck-Gesellschaft, Faradayweg 4-6, 14195, Berlin, Germany.
² Institut für Chemie und Biochemie, der Freien Universität Berlin, Takustraße 3, 14195, Berlin, Germany.
³ Oxford Glycobiology Institute, Department of Biochemistry, University of Oxford, Oxford, OX1 3QU, UK.
⁴ Target Discovery Institute, Nuffield Department of Medicine, University of Oxford, Roosevelt Drive, Oxford, OX3 7FZ, UK.
⁵ Max-Planck-Institut für Kolloid- und Grenzflächenforschung, Am Mühlenberg 1, 14476, Potsdam, Germany.
⁶ Institut für Chemie und Biochemie, der Freien Universität Berlin, Arnimallee 22, 14195, Berlin, Germany.

PMID: 29688603
DOI: 10.1002/anie.201801418

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.

Keywords: IR spectroscopy; carbohydrates; fucose; glycans; mass spectrometry.

Publication types

Research Support, Non-U.S. Gov't