Size distribution and chain conformation of six different fucoidans using size-exclusion chromatography with multiple detection.

Fucoidans represent an intriguing class of fucose-containing sulfated polysaccharides. The biological activities of these polysaccharides are related to their compositional and structural parameters, whereby their degree of sulfation, as well as molecular weight (MW) distribution and chain conformation play important roles. Modern NMR and mass spectrometry techniques allow elucidating details of the glycan structure, but not the structure of the whole molecules in their native state. Accordingly, the knowledge about the latter of the fucoidans is currently still limited. Contrary to traditional MW determination by SEC with column calibration, SEC with triple detection provides not only the absolute Mw, but can also give information on additional molecule characteristics. In the present study, we used this method to compare six fucoidans extracted from Fucus vesiculosus (FV), F. serratus (FS), F. evanescens (FE), Dictyosiphon foeniculaceus (DF), Laminaria digitata (LD), and Saccharina latissima (SL) concerning their molar mass (Mw, Mn, Mp, dispersity) and size (rms radius, Rh) characteristics and distribution as well as their chain conformation in solution. The tested fucoidans displayed considerable structural diversity including large differences in their MW profiles and showed to be heterogeneously composed. Fuc-FV and Fuc-SL showed the broadest MW distributions, those from Fuc-FE and Fuc-DF the narrowest ones. Most of the fucoidan fractions (except for Fuc-DF) turned out to exist as expanded flexible chains in PBS solution. The conformation data suggest branched structures with partly long side chains. The knowledge obtained by this study is useful for further fractionation and structural characterization as well as the interpretation of the bioactivity differences between the various fucoidans.