Exploring the (1->3)-β-D-glucan conformational phase diagrams to optimize the linear to macrocycle conversion of the triple-helical polysaccharide scleroglucan

摘要

The immunologically important (1->6) comb-like branched (1->3)-β-D-glucans scleroglucan, schizophyllan, lentinan, and others, exist mainly as linear triple-helical structures in aqueous solution. Partial interconversion from linear to circular topology has been reported to take place following conformational transition of the triple-helical structure and subsequent regeneration of the triplex conformation. We here report on experimental data indicating that complete strand separation of the triple-helical structure is required for this interconversion. NaOH or dimethylsulfoxide was used to induce dissociation of the triplex at combinations of concentrations and temperatures shown by calorimetry to yield a conformational transition of the triplex structures. For the alkaline treatment at 55 °C, it is found that up to about 30% of the material readily can be converted to the cyclic topology. This fraction increased to about 60% when the subsequent annealing of the scleroglucan in aqueous solution at pH 7 was carried out at 100 °C. Further increase of the annealing temperature yielded a smaller relative amount of cyclic species. The data indicate that the lower molecular weight fraction of the molecular weight distributions can be converted selectively to the macrocyclic topology by conditions that do not yield complete strand separation of the whole sample. These findings add to previous reports by providing more details about how the conditions required for the linear triplex to macrocycle interconversion relate to the conformational properties of the triple-helical structure.