title: Electrospray ionization mass spectrometry of oligosaccharides derived from fucoidan of Ascophyllum nodosum.
abstract: Algal fucoidan is a complex sulfated polysaccharide whose structural characterization requires powerful spectroscopic methodologies. While most of the structural investigations reported so far have been performed using NMR as the main spectroscopic method, we report herein data obtained by negative electrospray ionization mass spectrometry. MS analysis has been carried out on oligosaccharides obtained by partial hydrolysis of fucoidan from the brown algae Ascophyllum nodosum. Oligosaccharide mixtures were fractionated by size exclusion chromatography, which allowed the analysis of oligomers ranging from monosaccharide to pentasaccharide. Monosaccharides were detected as monosulfated as well as disulfated forms. Besides, part of the oligosaccharides exhibited a high content of sulfate, evidencing that fucoidan contains disulfated fucosyl units. Fragmentation experiments yielded characteristic fragment ions indicating that the fucose units are mainly 2-O-sulfated. This study demonstrates that highly sulfated oligosaccharides from fucoidan can be analyzed by ESIMS which gives additional information about the structure of this highly complex polysaccharide.
authors.affiliation: CNRS, UMR 8587, Laboratoire Analyse et Modélisation pour la Biologie et l'Environnement, Université d'Evry Val d'Essonne, F-91025 Evry, France. regis.daniel@univ-evry.fr
authors.forename: Régis
authors.initials: R
authors.lastname: Daniel
authors.forename: Lionel
authors.initials: L
authors.lastname: Chevolot
authors.forename: Montse
authors.initials: M
authors.lastname: Carrascal
authors.forename: Bérangère
authors.initials: B
authors.lastname: Tissot
authors.forename: Paulo A S
authors.initials: PA
authors.lastname: Mourão
authors.forename: Joaquin
authors.initials: J
authors.lastname: Abian
mesh_terms: D044646:Ascophyllum / Q000737:chemistry*; D002236:Carbohydrate Conformation; D015394:Molecular Structure; D009844:Oligosaccharides / Q000032:analysis* / Q000737:chemistry; D011134:Polysaccharides / Q000737:chemistry*; D021241:Spectrometry, Mass, Electrospray Ionization / Q000379:methods*
chemical_list: D009844:Oligosaccharides; D011134:Polysaccharides; C007789:fucoidan