title: IRMPD Spectroscopy Sheds New (Infrared) Light on the Sulfate Pattern of Carbohydrates.
abstract: IR spectroscopy of gas-phase ions is proposed to resolve positional isomers of sulfated carbohydrates. Mass spectrometric fingerprints and gas-phase vibrational spectra in the near and mid-IR regions were obtained for sulfated monosaccharides, yielding unambiguous signatures of sulfated isomers. We report the first systematic exploration of the biologically relevant but notoriously challenging deprotonated state in the near IR region. Remarkably, anions displayed very atypical vibrational profiles, which challenge the well-established DFT (Density Functionnal Theory) modeling. The proposed approach was used to elucidate the sulfate patterns in glycosaminoglycans, a ubiquitous class of mammalian carbohydrates, which is regarded as a major challenge in carbohydrate structural analysis. Isomeric glycosaminoglycan disaccharides from heparin and chondroitin sources were resolved, highlighting the potential of infrared multiple photon dissociation spectroscopy as a novel structural tool for carbohydrates.
authors.affiliation: Univ Lyon, Université Claude Bernard Lyon 1, CNRS, Institut Lumière Matière , F-69622 VILLEURBANNE, France.
authors.forename: B
authors.initials: B
authors.lastname: Schindler
authors.affiliation: Univ Lyon, Université Claude Bernard Lyon 1, CNRS, Institut Lumière Matière , F-69622 VILLEURBANNE, France.
authors.forename: L
authors.initials: L
authors.lastname: Barnes
authors.affiliation: School of Chemistry & Manchester Institute of Biotechnology, The University of Manchester , 131 Princess Street, Manchester M1 7DN, United Kingdom.
authors.forename: C J
authors.initials: CJ
authors.lastname: Gray
authors.affiliation: Univ Lyon, INSA-Lyon, Université Lyon 1, CPE Lyon, ICBMS, UMR 5246 , Bâtiment Jules Verne, 20 avenue Albert Einstein, F-69621 Villeurbanne, France.
authors.forename: S
authors.initials: S
authors.lastname: Chambert
authors.affiliation: School of Chemistry & Manchester Institute of Biotechnology, The University of Manchester , 131 Princess Street, Manchester M1 7DN, United Kingdom.
authors.forename: S L
authors.identifier: http://orcid.org/0000-0003-3974-646X
authors.initials: SL
authors.lastname: Flitsch
authors.affiliation: Institute for Molecules and Materials, FELIX Laboratory, Radboud University , Toernooiveld 7c, Nijmegen 6525ED, The Netherlands.|Van't Hoff Institute for Molecular Sciences, University of Amsterdam , Science Park 904, Amsterdam 1098XH, The Netherlands.
authors.forename: J
authors.initials: J
authors.lastname: Oomens
authors.affiliation: CNRS, UMR 8587, Laboratoire Analyse et Modélisation pour la Biologie et l'Environnement, Université Evry-Val-d'Essonne , Evry 91025, France.
authors.forename: R
authors.initials: R
authors.lastname: Daniel
authors.affiliation: Univ Lyon, Université Claude Bernard Lyon 1, CNRS, Institut Lumière Matière , F-69622 VILLEURBANNE, France.
authors.forename: A R
authors.initials: AR
authors.lastname: Allouche
authors.affiliation: Univ Lyon, Université Claude Bernard Lyon 1, CNRS, Institut Lumière Matière , F-69622 VILLEURBANNE, France.|Institut Universitaire de France IUF , 103 Boulevard St Michel, Paris 75005, France.
authors.forename: I
authors.identifier: http://orcid.org/0000-0003-2994-3961
authors.initials: I
authors.lastname: Compagnon
mesh_terms: D002241:Carbohydrates / Q000737:chemistry*; D007259:Infrared Rays; D017785:Photons; D011789:Quantum Theory; D013055:Spectrophotometry, Infrared; D013431:Sulfates / Q000737:chemistry*
chemical_list: D002241:Carbohydrates; D013431:Sulfates