Structural analysis of a highly sulfated fucan from the brown alga Laminaria cichorioides by tandem MALDI and ESI mass spectrometry.

Water-soluble polysaccharide fractions were extracted from the brown alga Laminaria cichorioides. Samples were collected monthly from May to October in Troitsa Bay (Japan Sea, Russia). Analysis showed that the content and monosaccharide composition of the fractions changed with the collection season. Fucoidan was isolated and purified from the most fucose-rich fraction, collected in July, and subjected to autohydrolysis to obtain fucooligosaccharides, suitable for mass-spectrometric analysis. Both ESIMS and MALDI-TOFMS analyses show that multisulfated (up to 3) fucooligosaccharides with polymerization degree n from 2 to 5, including mono- and disulfated-fucose residues, were the major products of autohydrolysis. The structural features of the fucooligosaccharides and their alditol derivatives were elucidated by tandem MALDI-TOFMS and ESIMS. The results obtained allowed us to conclude that fragments of the fucoidan, collected in July, were predominantly linked with a (1→3)-type of linkage and that sulfate groups occupied mostly C-2 or C-2/C-4 of the α-l-fucose residues.