title: Deciphering the structure of isomeric oligosaccharides in a complex mixture by tandem mass spectrometry: photon activation with vacuum ultra-violet brings unique information and enables definitive structure assignment.
abstract: Carbohydrates have a wide variety of structures whose complexity and heterogeneity challenge the field of analytical chemistry. Tandem mass spectrometry, with its remarkable sensitivity and high information content, provides key advantages to addressing the structural elucidation of polysaccharides. Yet, classical fragmentation by collision-activated dissociation (CAD) in many cases fails to reach a comprehensive structural determination, especially when isomers have to be differentiated. In this work, for the first time, vacuum ultra-violet (VUV) synchrotron radiation is used as the activation process in tandem mass spectrometry of large oligosaccharides. Compared to low energy CAD (LE-CAD), photon activated dissociation brought more straightforward and valuable structural information. The outstanding feature was that complete series of informative ions were produced, with only minor neutral losses. Moreover, systematic fragmentation rules could be drawn thus facilitating the definitive assignments of fragment identities. As a result, most of the structures present in a complex mixture of oligogalacturonans could be comprehensively resolved, including many isomers differing in the position of methyl groups along the galacturonic acid backbone.
authors.affiliation: INRA, UR1268 Biopolymers Interactions Assemblies, F-44316 Nantes, France. Electronic address: David.Ropartz@nantes.inra.fr.
authors.forename: David
authors.initials: D
authors.lastname: Ropartz
authors.affiliation: Institut des Sciences Analytiques, UMR 5280, Université Lyon 1-CNRS, Université de Lyon, F-69622 Villeurbanne cedex, France.
authors.forename: Jérôme
authors.initials: J
authors.lastname: Lemoine
authors.affiliation: Synchrotron SOLEIL, L'Orme des Merisiers, F-91190 Gif-sur-Yvette, France; UAR 1008 CEPIA, INRA, F-44316 Nantes, France.
authors.forename: Alexandre
authors.initials: A
authors.lastname: Giuliani
authors.affiliation: INRA, UR1268 Biopolymers Interactions Assemblies, F-44316 Nantes, France.
authors.forename: Yann
authors.initials: Y
authors.lastname: Bittebière
authors.affiliation: Institut des Sciences Analytiques, UMR 5280, Université Lyon 1-CNRS, Université de Lyon, F-69622 Villeurbanne cedex, France; Institut Lumière Matière, UMR5306, Université Lyon 1-CNRS, Université de Lyon, F-69622 Villeurbanne cedex, France.
authors.forename: Quentin
authors.initials: Q
authors.lastname: Enjalbert
authors.affiliation: Institut Lumière Matière, UMR5306, Université Lyon 1-CNRS, Université de Lyon, F-69622 Villeurbanne cedex, France.
authors.forename: Rodolphe
authors.initials: R
authors.lastname: Antoine
authors.affiliation: Institut Lumière Matière, UMR5306, Université Lyon 1-CNRS, Université de Lyon, F-69622 Villeurbanne cedex, France.
authors.forename: Philippe
authors.initials: P
authors.lastname: Dugourd
authors.affiliation: INRA, UR1268 Biopolymers Interactions Assemblies, F-44316 Nantes, France.
authors.forename: Marie-Christine
authors.initials: MC
authors.lastname: Ralet
authors.affiliation: INRA, UR1268 Biopolymers Interactions Assemblies, F-44316 Nantes, France.
authors.forename: Hélène
authors.initials: H
authors.lastname: Rogniaux
mesh_terms: D002851:Chromatography, High Pressure Liquid; D056148:Chromatography, Reverse-Phase; D007477:Ions / Q000737:chemistry; D007536:Isomerism; D009844:Oligosaccharides / Q000737:chemistry*; D017785:Photons; D021241:Spectrometry, Mass, Electrospray Ionization; D017356:Synchrotrons; D053719:Tandem Mass Spectrometry; D014466:Ultraviolet Rays; D014618:Vacuum
chemical_list: D007477:Ions; D009844:Oligosaccharides
keywords: CAD; DM; DPI; ECD; EDD; EID; ESI; ETD; HE; HILIC; HPAEC; Hhigh-energy; IC; IP; IVR; Isomers; LE; MALDI; MS; Oligogalacturonans; PD; PGC; RP; SEC; Structure; TOF; Tandem mass spectrometry; UHPLC; VUV; Vacuum ultra-violet synchrotron photon activation; collision activated dissociation; degree of methylation; dissociative photoionization; electron capture dissociation; electron detachment dissociation; electron induced dissociation; electron transfer dissociation; electrospray ionization; high-performance anionic exchange chromatography; hydrophilic interaction liquid chromatography; internal conversion; internal vibrational redistribution; ion pairing; low-energy; mass spectrometry; matrix assisted laser desorption ionization; photo-dissociation; porous graphitized carbon; reverse-phase; size exclusion chromatography; time of flight; ultra-high performance liquid chromatography; vacuum ultra-violet