Chemical Structure of a Branched α-d-Glucan from the Eggs of Sea Urchin Tripneustes gratilla

A water-soluble high-molecular neutral polysaccharide (NP) was isolated from the eggs of the sea urchin Tripneustes gratilla. The formation of glucose only upon the treatment of NP by amyloglucosidase and the value of its optical rotation [α]D +233.5 (c 0.2, water) confirmed its belonging to the family of α-d-glucans. According to the results of NMR spectroscopy and methylation analysis, the chains of NP are built up of non-reducing terminal, 4-linked and 4,6-disubstituted glucose residues at a ratio of 1:8:1. A branched structure with an average linear chain length of about five glucose residues was calculated from the spectrum of iodine complex. Contrary to the previously published structure of branched α-d-glucan from the sea urchin Strongylocentrotus nudus bearing single glucose units as branches, the polysaccharide NP contains oligosaccharide branches at position 6, which was confirmed by NMR data. Hence, NP has a glycogen-like structure with a rather high degree of branching, which markedly exceeds that of usual mammalian or fungal glycogens.