Structural analysis of a fucoidan from the brown alga Fucus evanescens by MALDI-TOF and tandem ESI mass spectrometry

A fucoidan, a heterogeneous sulfated polysaccharide from the brown alga Fucus evanescens, was depolymerized under solvolytic conditions, and its ethanol-extracted low-molecular-weight fraction was analyzed by MALDI-TOFMS and ESIMS/MS. it was found that the mixture contained unsulfated oligosaccharides including some monosulfated components, which were shown to consist of mainly (1 -> 3)-linked 2-O-sulfonated fucose residues (from 1 to 4). Minor components of the mixture were shown to contain 2-O- and 4-O-sulfonated xylose and galactose residues. Among them, mixed monosulfonated fucooligosaccharides were detected and characterized: Xyl-(1 -> 4)-Fuc, Gal-(1 -> 4)-Fuc, Gal(1 -> 4)-Gal-(1 -> 4)-Fuc, Gal-(1 -> 4)-Gal. Fucose, galactose, and xylose residues were shown to be mainly 2-O-sulfonated with traces of 4-O-sulfonation. Glucuronic acid was also found as a part of non-sulfated fucooligosaccharicles: Fuc-(1 -> 3)-GlcA, Fuc-(1 -> 4)-Fuc-(1 -> 3)-GlcA, Fuc-(1 -> 3)-Fuc-(1 -> 4)-Fuc-(1 -> 3)-GlcA. (C) 2009 Elsevier Ltd. All rights reserved.