Anomeric configuration, glycosidic linkage, and the solution conformational entropy of O-linked disaccharides

Oligosaccharides perform a large number of biological roles, as dictated by their chemical structure and spatial arrangement. While conformational entropies are usually determined in vacuo by computer modeling, molecular recognition processes normally take place in solution. Here I show results of experiments using size-exclusion chromatography (SEC), an entropically driven solution technique. These clearly differentiate the individual contributions of the alpha and beta anomeric configurations and of the (1 --> 4) and (1 --> 6) glycosidic linkages to the solution conformational entropy of O-linked disaccharides. I also distinguish between the members of the epimeric disaccharide pair isomaltose-melibiose and trace the difference to that between their constituent monosaccharides, alpha-glucose and alpha-galactose.