title: MS/IR, a new MS-based hyphenated method for analysis of hexuronic acid epimers in glycosaminoglycans.
abstract: We report an original MS-based hyphenated method for the elucidation of the epimerization in GAG fragments. It consists of measuring simultaneously the MS/MS spectrum and the gas phase IR spectrum to gain direct structural information. This is possible using a customized MS instrument, modified to allow injection of a tunable IR laser inside of the instrument for in situ spectroscopy of trapped ions. The proof of principle of this approach is performed in the case of a hyaluronic acid tetrasaccharide standard. In addition, we provide the reference IR fingerprint of glucuronic and Iduronic monosaccharide standards. Remarkably, we show that the gas phase IR fingerprint of reference hexuronic acid monosaccharides proves to be transposable to oligosaccharides. Therefore, the method presented here is predictive and allows structural elucidation of unknown GAG fragments, even in the absence of referenced standards.
authors.affiliation: Institut Lumière Matière, Univ Lyon, Université Claude Bernard Lyon 1, CNRS, F-69622, Villeurbanne, France.
authors.forename: Baptiste
authors.initials: B
authors.lastname: Schindler
authors.affiliation: Institut Lumière Matière, Univ Lyon, Université Claude Bernard Lyon 1, CNRS, F-69622, Villeurbanne, France.
authors.forename: Gina
authors.initials: G
authors.lastname: Renois-Predelus
authors.affiliation: Institut Lumière Matière, Univ Lyon, Université Claude Bernard Lyon 1, CNRS, F-69622, Villeurbanne, France.
authors.forename: Nassiba
authors.initials: N
authors.lastname: Bagdadi
authors.affiliation: Institut Lumière Matière, Univ Lyon, Université Claude Bernard Lyon 1, CNRS, F-69622, Villeurbanne, France.
authors.forename: Sihem
authors.initials: S
authors.lastname: Melizi
authors.affiliation: Institut Lumière Matière, Univ Lyon, Université Claude Bernard Lyon 1, CNRS, F-69622, Villeurbanne, France.
authors.forename: Loïc
authors.initials: L
authors.lastname: Barnes
authors.affiliation: Univ Lyon, INSA-Lyon, CNRS, Université Lyon 1, CPE Lyon, ICBMS, UMR 5246, Bâtiment Jules Verne, 20 avenue Albert Einstein, F-69621, Villeurbanne, France.
authors.forename: Stéphane
authors.initials: S
authors.lastname: Chambert
authors.affiliation: Institut Lumière Matière, Univ Lyon, Université Claude Bernard Lyon 1, CNRS, F-69622, Villeurbanne, France.
authors.forename: Abdul-Rahman
authors.initials: AR
authors.lastname: Allouche
authors.affiliation: Institut Lumière Matière, Univ Lyon, Université Claude Bernard Lyon 1, CNRS, F-69622, Villeurbanne, France. Isabelle.compagnon@univ-lyon1.fr.|Institut Universitaire de France IUF, 103 Blvd St Michel, 75005, Paris, France. Isabelle.compagnon@univ-lyon1.fr.
authors.forename: Isabelle
authors.identifier: 0000-0003-2994-3961
authors.initials: I
authors.lastname: Compagnon
mesh_terms: D006820:Hyaluronic Acid / Q000737:chemistry / Q000302:isolation & purification*; D007067:Iduronic Acid / Q000737:chemistry / Q000302:isolation & purification*; D009005:Monosaccharides / Q000737:chemistry; D009844:Oligosaccharides / Q000737:chemistry; D012996:Solutions; D013055:Spectrophotometry, Infrared / Q000295:instrumentation / Q000379:methods* / Q000592:standards; D053719:Tandem Mass Spectrometry / Q000379:methods* / Q000592:standards
chemical_list: D009005:Monosaccharides; D009844:Oligosaccharides; D012996:Solutions; D007067:Iduronic Acid; D006820:Hyaluronic Acid
keywords: GAG fragments; Mass spectrometry; gas phase IR spectroscopy; hexuronic acid epimers