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Anal Chim Acta. 2014 Jan 7;807:84-95. doi: 10.1016/j.aca.2013.11.018. Epub 2013 Nov 16.

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.

Author information

  • 1INRA, UR1268 Biopolymers Interactions Assemblies, F-44316 Nantes, France. Electronic address: David.Ropartz@nantes.inra.fr.
  • 2Institut des Sciences Analytiques, UMR 5280, Université Lyon 1-CNRS, Université de Lyon, F-69622 Villeurbanne cedex, France.
  • 3Synchrotron SOLEIL, L'Orme des Merisiers, F-91190 Gif-sur-Yvette, France; UAR 1008 CEPIA, INRA, F-44316 Nantes, France.
  • 4INRA, UR1268 Biopolymers Interactions Assemblies, F-44316 Nantes, France.
  • 5Institut 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.
  • 6Institut Lumière Matière, UMR5306, Université Lyon 1-CNRS, Université de Lyon, F-69622 Villeurbanne cedex, France.

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.

Crown Copyright © 2013. Published by Elsevier B.V. All rights reserved.

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

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