Sulfated fucans from marine invertebrates are composed of regular repetitive fucose building-blocks with sulfation patterns differing in a species-specific manner. These polysaccharides can act as mediators of the acrosome reaction of sea-urchins or play a structural role in the body-wall of sea-cucumbers. Other fucose-rich polysaccharides found in the body-wall of sea-cucumbers are the fucosylated chondroitin sulfates composed of a vertebrate-like chondroitin sulfate decorated with species-specific fucose branches. Fine-tuning structural determinations of these polysaccharides have been accomplished since the 1980s almost exclusively via high-resolution NMR. In this review, we present an overview on NMR-based structural and conformational analyses of these sulfated fucose-rich polysaccharides. This constitutes an outstanding example of the potential of NMR in studying the chemical aspects of complex carbohydrates.
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