title: ESI-MS differential fragmentation of positional isomers of sulfated oligosaccharides derived from carrageenans and agarans.
abstract: We have prepared a number of isomeric red seaweed galactan-derivative sulfated oligosaccharides to determine whether there were diagnostic differences among the isomeric mass spectra obtained using ESI CID MS/MS (triple quadrupole instrument). Fragmentation of the single or multicharged molecular ions from di-, tetra-, and hexasaccharides indicated that the relative positioning of the sulfate groups and type of monosaccharide unit affect the rate of cleavage of the glycosidic bonds. We also performed a comparative [M-Na](-) fragmentation study of positional isomers of sulfated disaccharides that present all four monosulfation possibilities on the galactopyranosidic ring. In this case, negative-ion ESI CID MS/MS approach gave diagnostic product ions from cross-ring cleavages along with the same main B(1) ion (from sulfated Galp), at m/z 241, for all isomers. The isomeric disaccharides were also submitted to increased spray energy conditions inducing in-source fragmentation; preformed B(1) ions were then fragmented to give similar product ions as those found in [M-Na](-) analysis. Evaluation of the relative abundances mainly for cross-ring fragment ions at m/z 138, 139, 151, 153 allowed clear distinction among the members of the disaccharide series. The different ratios for m/z 151/153 ions were consistent with the predominance of m/z 153 being related to the cases when the bond involved in the cleavage process links a sulfated carbon. A quadrupole ion trap instrument (MS(n) analysis) was also utilized to compare the results obtained with the triple quadrupole instrument.
authors.affiliation: Departamento de Farmácia, Universidade Federal do Paraná, Paraná, Brazil.
authors.forename: Alan G
authors.initials: AG
authors.lastname: Gonçalves
authors.forename: Diogo R B
authors.initials: DR
authors.lastname: Ducatti
authors.forename: T Bruce
authors.initials: TB
authors.lastname: Grindley
authors.forename: M Eugênia R
authors.initials: ME
authors.lastname: Duarte
authors.forename: Miguel D
authors.initials: MD
authors.lastname: Noseda
mesh_terms: D000362:Agar / Q000737:chemistry*; D002240:Carbohydrate Sequence; D002351:Carrageenan / Q000737:chemistry*; D008969:Molecular Sequence Data; D009844:Oligosaccharides / Q000737:chemistry*; D012624:Seaweed / Q000737:chemistry; D021241:Spectrometry, Mass, Electrospray Ionization / Q000379:methods*; D013402:Sugar Alcohols / Q000737:chemistry; D013431:Sulfates / Q000737:chemistry*
chemical_list: D009844:Oligosaccharides; D013402:Sugar Alcohols; D013431:Sulfates; D002351:Carrageenan; D000362:Agar
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