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  The role of the mobile proton in fucose migration

Lettow, M., Mucha, E., Manz, C., Thomas, D., Marianski, M., Meijer, G., et al. (2019). The role of the mobile proton in fucose migration. Analytical and Bioanalytical Chemistry, 411(19), 4637-4645. doi:10.1007/s00216-019-01657-w.

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Lettow2019_Article_TheRoleOfTheMobileProtonInFuco.pdf (Publisher version), 2MB
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 Creators:
Lettow, Maike1, 2, Author              
Mucha, Eike1, 2, Author              
Manz, Christian1, 2, Author              
Thomas, Daniel1, Author              
Marianski, Mateusz1, 3, Author              
Meijer, Gerard1, Author              
Helden, Gert von1, Author              
Pagel, Kevin1, 2, Author              
Affiliations:
1Molecular Physics, Fritz Haber Institute, Max Planck Society, ou_634545              
2Institute of Chemistry and Biochemistry, Freie Universität Berlin, BerlinGermany, ou_persistent22              
3Hunter CollegeThe City University of New York, New YorkUSA, ou_persistent22              

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Free keywords: Fucose migration Internal residue loss Infrared spectroscopy Mass spectrometry Carbohydrates
 Abstract: Fucose migration reactions represent a substantial challenge in the analysis of fucosylated glycan structures by mass spectrometry. In addition to the well-established observation of transposed fucose residues in glycan-dissociation product ions, recent experiments show that the rearrangement can also occur in intact glycan ions. These results suggest a low-energy barrier for migration of the fucose residue and broaden the relevance of fucose migration to include other types of mass spectrometry experiments, including ion mobility-mass spectrometry and ion spectroscopy. In this work, we utilize cold-ion infrared spectroscopy to provide further insight into glycan scrambling in intact glycan ions. Our results show that the mobility of the proton is a prerequisite for the migration reaction. For the prototypical fucosylated glycans Lewis x and blood group antigen H-2, the formation of adduct ions or the addition of functional groups with variable proton affinity yields significant differences in the infrared spectra. These changes correlate well with the promotion or inhibition of fucose migration through the presence or absence of a mobile proton.

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Language(s): eng - English
 Dates: 2018-11-162019-01-302019-03-022019-07
 Publication Status: Published in print
 Pages: 9
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1007/s00216-019-01657-w
 Degree: -

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Title: Analytical and Bioanalytical Chemistry
  Abbreviation : Anal. Bioanal. Chem.
Source Genre: Journal
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Publ. Info: Heidelberg : Springer-Verlag
Pages: 9 Volume / Issue: 411 (19) Sequence Number: - Start / End Page: 4637 - 4645 Identifier: ISSN: 1618-2642
CoNE: https://pure.mpg.de/cone/journals/resource/111006469468428