Differentiation of the fucoidan sulfated l-fucose isomers constituents by CE-ESIMS and molecular modeling

α- l-Fucose, the monosaccharide component of fucoidan, is found in the polysaccharide mainly as its sulfated form where sulfate groups are in position 2 and/or 4 and/or 3. The correlation between biological activities and structure of fucoidan requires the determination of the sulfation pattern of t...

Full description

Saved in:
Bibliographic Details
Published in:Carbohydrate research 2006-04, Vol.341 (5), p.598-609
Main Authors: Tissot, Bérangère, Salpin, Jean-Yves, Martinez, Michael, Gaigeot, Marie-Pierre, Daniel, Régis
Format: Article
Language:English
Subjects:
Capillary electrophoresis
Carbohydrate Sequence
Electrophoresis, Capillary
ESIMS
Fucoidan
Isomeric structures differentiation
Isomerism
Models, Molecular
Molecular modeling
Molecular Sequence Data
Molecular Structure
Polysaccharides - chemistry
Spectrometry, Mass, Electrospray Ionization
Sulfated fucose
Sulfuric Acid Esters - chemistry
Citations: Items that this one cites
Items that cite this one
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
Description
Summary:α- l-Fucose, the monosaccharide component of fucoidan, is found in the polysaccharide mainly as its sulfated form where sulfate groups are in position 2 and/or 4 and/or 3. The correlation between biological activities and structure of fucoidan requires the determination of the sulfation pattern of the fucose residues. Therefore, it is of importance to discriminate between the isobaric sulfated fucose isomers. For this purpose, the three isomers 2- O-, 3- O-, and 4- O-sulfated fucose have been analyzed using electrospray ion trap mass spectrometry and capillary electrophoresis. The results reported herein show that it is possible to differentiate between these three positional isomers of sulfated fucose based on their fragmentation pattern upon MS/MS experiments. 3- O-Sulfated fucose was characterized by the loss of the hydrogenosulfate anion HSO 4 - as the main fragmentation product, while the two other isomers 2- O-, and 4- O-sulfated fucose exhibited cross-ring fragmentation yielding to distinctive 0,2X and 0,2A daughter ion, respectively. A computational study of the conformation of the sulfated fucose isomers was carried out providing an understanding of the fragmentation pattern with respect to the position of the sulfate group.
ISSN:0008-6215
1873-426X
DOI:10.1016/j.carres.2005.11.029