Fragmentation and Modification of r‐Carrageenan and Characterisation of the Polysaccharide Order‐Disorder Transition in Solution

Abstract

A procedure is described in detail by which the algal polysaccharide, r‐carrageenan, can be modified and fragmented to products of more regular structure and shorter chain length. Since most chains of this product can form uninterrupted helices they undergo the disorder‐order transition without the gelation that is a feature of the behaviour of the natural polymer. The disorder‐order transition becomes much sharper and occurs at higher temperaturcs with increasing chain length. The sign and magnitude of the accompanying shift in optical rotation can be estimated satisfactorily from the solid‐state geometry of the helix using our semi‐empirical method for correlating optical rotation with the conformations at glycosidic linkages. In solutions of the helical form, but not the coil form, cationic dyes such as methylene blue or acridine orange show induced optical activity and a changed visible spectrum which we attribute to binding and stacking on the helix. This also causcs a shift in the temperature of the helix‐coil transition. We discuss the possibility that the tendency of dyes to stack could drive polysaccharides into conformations that they would not otherwise adopt, with implications for their use as ‘conformational probes’. Copyright © 1982, Wiley Blackwell. All rights reserved