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The conformational behavior of the capsular polysaccharide obtained from a fast‐growing soybean‐nodulating rhizobia (strain B33) isolated from Xinjiang Autonomous Region (Eastern China) has been analyzed by NMR and molecular mechanics simulations. This polysaccharide has the repeating unit →6)‐4‐O‐Me‐α‐d‐Glcp‐(1→4)‐3‐O‐Me‐β‐d‐GlcpA‐(1→. The NMR results indicate that the α‐(1→4) linkage may adopt a variety of conformations, and that at least two of the resulting minima must exist in solution. NOE data agree with an 85:10:5 ratio for the lowest‐energy conformations. In the case of the β‐(1→6) linkage, NMR indicates that the rotamer gg is highly populated. Experimental and calculated NOE intensities match well when the global energy minimum conformation for this linkage has exclusively the gg orientation. The influence of the adjacent methyl group on the glycosyloxymethyl population has been evaluated by simulation of a disaccharide without this group. A relative destabilization of gt rotamer has been found....

The conformational behaviour of the major trisaccharide repeating unit (α-D-Galp-(1→2)-β-D-Ribf-(1→9)-α-5-O-Me-Kdnp-) of the polysaccharide from Sinorhizobium fredii SVQ293, a mutant derivative has been analysed by NMR spectroscopy and extensive molecular dynamics simulations. The results obtained indicate that the five-membered ring adopts an almost unique conformation as do the pyranose rings. The Ribf-(1→9)-α-5-O-Me-Kdnp linkage may adopt a variety of conformations while the α-D-Galp-(1→2)-β-D-Ribf- also populates an extended surface of the Φ/Ψ map. Two 10 ns MD simulations using the GB/SA continuum solvent model for water and the MM3* force field provides a population distribution of conformers which satisfactorily agrees with the experimental NMR data for both the glycosidic linkages and the hydroxymethyl groups.