Molecular architecture of a galactoglucan from Rhizobium meliloti.

Rhizobium meliloti mutants produce a linear, acidic exopolysaccharide with alternating galactopyranosyl and glucopyranosyl units having (1-->3) linkages. It has a 4,6-O-pyruvic cyclic acetal group on the alpha-galactosyl and 6-O-acetyl ester group on the beta-glucosyl units. X-ray diffraction patterns from polycrystalline and well oriented specimens of its potassium salt indicate that the polymer forms a 2-fold helix of pitch 15.89 A. The three-dimensional structure has been determined and refined by using the X-ray intensities and the linked-atom least-squares technique. The details of the antiparallel packing arrangement of two helices in an orthorhombic unit cell, a = 14.49, b = 9.79, and c = 15.89 A, reveal that each disaccharide repeating unit is associated with one potassium and three water molecules. The helices are interconnected by a series of ...COO- ...K+ ...W ...COO- ... interactions. Both pyruvyl and acetyl groups, which are on the periphery of the helix, are involved in the association of the polysaccharide chains and thus appear to be an integral component of the galactoglucan in the nodule invasion process.