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Eur. J. Mass Spectrom. 9, 45 - 60 (2003)
DOI: 10.1255/ejms.526

Structural characterisation by both positive- and negative-ion electrospray mass spectrometry of partially methyl-esterified oligogalacturonides purified by semi-preparative high-performance anion-exchange chromatography

Bernard Quéméner, Cédric Désiré and Marc Lahaye
Institut National de la Recherche Agronomique, Unité de Recherche sur les Polysaccharides, leurs organisations et leurs Interatctions (URPOI), rue de la Géraudiêre, BP 71627, 44316 Nantes, France
Laurent Debrawer
Institut National de la Recherche Agronomique, Laboratoire des xênobiotiques, chemin de Tournefeuille, St-Martin-du-Touch, BP 3, 31931 Toulouse, France
Luc Negroni
Institut National de la Recherche Agronomique, Plate-forme de protéomique, IFR87, Ferme du Moulon, 91190 Gif-sur-Yvette, France

ABSTRACT:
The off-line coupling of high-performance anion-exchange chromatography (HPAEC) to electrospray ionisation/ion trap mass spectrometry (ESI-ITMS) is described. The Dionex carbohydrate membrane desalter (CMD) has been assessed as an on-line chromatographic desalting system to remove the high sodium concentration necessary for the HPAEC separation of partially methyl-esterified oligogalacturonides. The developed HPAEC configuration proved to be suitable for indirect coupling with ESI-ITMS. This paper provides some interesting features of positive- and negative-ion multistage tandem mass spectrometry (MSn) analysis of these acidic oligosaccharides. The spectra acquired in both negative- and positive-ion modes show characteristic fragment ions resulting from glycosidic bond and cross-ring cleavages. Some new mass spectrometric fragmentation routes are also described. The positive-ion mode gave more complex spectra but was as informative as the negative-ion mode. ESI-ITMS was revealed to be, as previously reported from direct use on an unseparated enzymatic digest, a powerful sequencing technique for the determination of linkage type and the methyl ester distribution of partially methyl-esterified oligogalacturonides. Moreover, unlike matrix-assisted laser desorption/ionisation time-of-flight mass spectrometry (MALDI-ToF MS), it gives valuable information on the elution behaviour of these oligomers in relation to their structure, namely the HPAEC co-elution of isomeric structures.

Keywords: pectins, endogalacturonase, partially-esterified oligogalacturonides, structural characterisation, HPAEC, ESI-ITMS

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