title: Identification of Lewis and Blood Group Carbohydrate Epitopes by Ion Mobility-Tandem-Mass Spectrometry Fingerprinting.
abstract: Glycans have several elements that contribute to their structural complexity, involving a range of monosaccharide building blocks, configuration of linkages between residues and various degrees of branching on a given structure. Their analysis remains challenging and resolving minor isomeric variants can be difficult, in particular terminal fucosylated Lewis and blood group antigens present on N- and O-glycans. Accurately characterizing these isomeric structures by current techniques is not straightforward and typically requires a combination of methods and/or sample derivatization. Yet the ability to monitor the occurrence of these epitopes is important as structural changes are associated with several human diseases. The use of ion mobility-mass spectrometry (IM-MS), which separates ions in the gas phase based on their size, charge and shape, offers a new potential tool for glycan analysis and recent reports have demonstrated its potential for glycomics. Here we show that Lewis and blood group isomers, which have identical fragmentation spectra, exhibit very distinctive IM drift times and collision cross sections (CCS). We show that IM-MS/MS analysis can rapidly and accurately differentiate epitopes from parotid gland N-glycans and milk oligosaccharides based on fucosylated fragment ions with characteristic CCSs.
authors.affiliation: Fritz Haber Institute of the Max Planck Society , Faradayweg 4-6, 14195 Berlin, Germany.|Institut für Chemie und Biochemie, Freien Universität Berlin , Takustrasse 3, 14195 Berlin, Germany.
authors.forename: Johanna
authors.initials: J
authors.lastname: Hofmann
authors.affiliation: Institut für Chemie und Biochemie, Freien Universität Berlin , Takustrasse 3, 14195 Berlin, Germany.
authors.forename: Alexandra
authors.initials: A
authors.lastname: Stuckmann
authors.affiliation: Oxford Glycobiology Institute, Department of Biochemistry, University of Oxford , OX1 3QU Oxford, United Kingdom.
authors.forename: Max
authors.initials: M
authors.lastname: Crispin
authors.affiliation: Oxford Glycobiology Institute, Department of Biochemistry, University of Oxford , OX1 3QU Oxford, United Kingdom.
authors.forename: David J
authors.initials: DJ
authors.lastname: Harvey
authors.affiliation: Fritz Haber Institute of the Max Planck Society , Faradayweg 4-6, 14195 Berlin, Germany.|Institut für Chemie und Biochemie, Freien Universität Berlin , Takustrasse 3, 14195 Berlin, Germany.
authors.forename: Kevin
authors.initials: K
authors.lastname: Pagel
authors.affiliation: Oxford Glycobiology Institute, Department of Biochemistry, University of Oxford , OX1 3QU Oxford, United Kingdom.
authors.forename: Weston B
authors.identifier: 0000-0003-0594-226X
authors.initials: WB
authors.lastname: Struwe
mesh_terms: D000939:Epitopes / Q000032:analysis*; D006801:Humans; D007477:Ions / Q000737:chemistry; D007983:Lewis Blood Group Antigens / Q000378:metabolism*; D009844:Oligosaccharides / Q000737:chemistry; D011134:Polysaccharides / Q000737:chemistry; D053719:Tandem Mass Spectrometry / Q000379:methods*
chemical_list: D000939:Epitopes; D007477:Ions; D007983:Lewis Blood Group Antigens; D009844:Oligosaccharides; D011134:Polysaccharides