Decoding the Fucose Migration Product During Mass-Spectrometric Analysis of Blood Group Epitopes

Overview

Journal Angew Chem Int Ed Engl

Specialty Chemistry

Date 2023 Mar 20

PMID 36939315

Authors

Maike Lettow

Kim Greis

Eike Mucha

Tyler R Lambeth

Murat Yaman

Vasilis Kontodimas

Christian Manz

Waldemar Hoffmann

Gerard Meijer

Ryan R Julian

Gert von Helden

Mateusz Marianski

Kevin Pagel

Affiliations

Soon will be listed here.

Abstract

Fucose is a signaling carbohydrate that is attached at the end of glycan processing. It is involved in a range of processes, such as the selectin-dependent leukocyte adhesion or pathogen-receptor interactions. Mass-spectrometric techniques, which are commonly used to determine the structure of glycans, frequently show fucose-containing chimeric fragments that obfuscate the analysis. The rearrangement leading to these fragments-often referred to as fucose migration-has been known for more than 25 years, but the chemical identity of the rearrangement product remains unclear. In this work, we combine ion-mobility spectrometry, radical-directed dissociation mass spectrometry, cryogenic IR spectroscopy of ions, and density-functional theory calculations to deduce the product of the rearrangement in the model trisaccharides Lewis x and blood group H2. The structural search yields the fucose moiety attached to the galactose with an α(1→6) glycosidic bond as the most likely product.

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