ABSTRACT:Lentinan, β-(1 → 3)-D-glucan with (1 → 6) branching, was isolated from Lentinus edodes. Weightaverage molecular weight M w , radius of gyration < s 2 > 1/2 z and intrinsic viscosity [η] of Lentinan in 0.2 M NaCl aqueous solution, dimethylsulfoxide (DMSO) and water/DMSO mixtures were measured by light scattering (LS), size exclusion chromatography (SEC) combined with LS, and viscometry. The results indicated that the glucan exists mainly as triple-helical chains in 0.2 M NaCl aqueous solution and water/DMSO mixtures with over 20 wt% water content, and as single-flexible chain in DMSO. The data from SEC-LS, viscosity and 13 C NMR measurements proved strongly that the helix-coil conformation transition occurred in a narrow range from 80 to 85 wt% DMSO aqueous solution, accompanying with obvious changes of M w , < s Chihara et al. have reported that the β-(1 → 3)-Dglucan, Lentinan, obtained from Lentinus edodes has a strong antitumour activity against sarcoma 180 implanted subcutaneous in mice. 1 Thereby, the importance of the polysaccharides has provided a major impetus for increasing attention. Particularly mushroom polysaccharides have been used as functional food, and are developed in the field of new drugs. 2 The structural analysis may offer the most fundamental knowledge to understand the functions of polysaccharide, but the diversity and irregularity of polysaccharide chain make the structural analysis a formidable task. 3 Although a monosaccharide unit is common to many polysaccharides, its linkage mode varies and characteristic functions properties will appear accordingly. It is worth noting that polysaccharides in aqueous solution exhibit different chain conformation such as single helix, 4 triple helix, 5 random coil, 6 and aggregate, 7 even if their backbone all are β-(1 → 3)-D-glucan. However, conformation and its transition from an ordered state to a disordered for β-(1 → 3)-D-glucan in solution have not been fully investigated.Helix conformations of β-(1 → 3)-D-glucan with two (1 → 6)-glucosyl side groups for every five residues isolated from Lentinus edodes have been reported, based on analysis from the results of X-Ray diffraction 8 and 13 C NMR. 9-12 However, it has long been suspected to be a triple helix of the β-D-glucan in aqueous solution without strong evidence. In our recent work, 13 experimental results from light scattering have indicated that the predominant species of the β-D-glucan in 0.5 M NaCl aqueous solution exist as triple-helical chains with high rigidity, and in dimethylsulfoxide (DMSO) as single-flexible chains. The single or multiple helices of biopolymers in aqueous solution aggregate easily to form gel. The gelation and the helical state may be induced by lowering the temperature, by changing the solvent, or by adding salt. 14 The gel-forming ability of polysaccharide is of considerable importance in view of their biological functions. 15 Moreover, helixcoil transitions are important in biology, as they appear in proteins and DNA. 16 In this work, the conformation ...