Comparing the results of ESI–CID–MS/MS and NMR, all the deduced information from ESI–CID–MS/MS was validated by NMR. It showed that MS is an efficient and sample saving procedure for
structural investigation of SC-FUC oligosaccharides and could facilitate the resolution of NMR spectra, although complete clarification of fine structure required more proof from NMR. Combining the investigation of NMR and MS/MS, the fine structures of four major oligosaccharides in the enzymatic hydrolysate of SC-FUC were clarified and are shown in Fig. 4B.It was found that the structures of those four oligosaccharides are very similar. Fraction II could be composed of fraction I and a nonsuphated fucose residue. Fraction III could consist of fraction II and fraction I. Fraction IV could be composed of two moieties of fraction II. These results suggest that disulphated trisfuose and disulphated tetrafucose might constitute a large proportion of the structural backbone of A. Molpadioides SC-FUC.
Meanwhile, other fucoidan oligosaccharides obtained from sea cucumbers and algae have been reported. Chen et al. (2012) obtained [3-a-L-Fucp(2,4OSO23)-1 ? 3-a-L-Fucp-(2OSO23)1 ? 3-a-L-
Fucp-(2OSO23)-a-L-Fucp-1 ? ]n(n = 1,2) from sea cucumber Isostichopus badionotus by mild acid hydrolysis. In comparison with these oligosaccharides, 2-O-sulphation was absent in our oligosaccharides, which indicates that the sulphated pattern of fucoidans might be distinct in different species of sea cucumber. Many researchers have suggested that fucoidan oligosaccharides obtained from algae were heterogeneous with various sugar compositions, O-acetylated groups, glycosidic bonds and branching (Bakunina et al., 2002; Bilan et al., 2005; Clement et al., 2010; Ye et al., 2005). Compared with these algae-derived oligosaccharides, echinoderm-derived oligosaccharides were more simple and regular