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• W2004967342 abstract "In the solid state most polysaccharides adopt regular chain geometry corresponding to fixed values of the angles between adjacent residues. Such ordered conformations may persist in solution or as the fundamental structural unit in polysaccharide gels or biological tissue. Physical techniques may be used (1) to detect conformational order in solution, (2) to characterise chain geometry and packing, often by reference to known solid-state conformations, and (3) to monitor order-disorder transitions. Characterisation of solution conformation is often facilitated by the use of structurally regular short chain segments, which show the same conformational behaviour as the intact polymer, but are capable of participating in only one ordered intermolecular junction zone. Nmr relaxation behaviour, measured either directly from the exponential decay of magnetisation, or indirectly from high resolution linewidth, provides a convenient index of conformational rigidity. Polysaccharides show two conformation-sensitive circular dichroism (cd) bands in the vacuum uv at about 150 and 170 nm. These are inaccessible to commercial cd instruments, but may be monitored indirectly by optical rotation, which shows a simple quantitative correlation with the linkage geometry between adjacent sugars in the polymer chain. Accessible pendant chromophores, in particular carboxy groups, also show conformation-sensitive cd behaviour and provide a direct probe of specific cation chelation. The masking effect of such chromophores on the optical activity of the polymer backbone may be eliminated by Kronig-Kramers transform of their observed cd spectra. Order-disorder transitions are conveniently monitored by discontinuities in optical rotation behaviour, intensity of discernible high resolution nmr resonances, differential scanning calorimetry, solution viscosity and, for segments, by light scattering. Transition kinetics show the number of chains involved in the fundamental ordered structure, a source of frequent difficulty in solid-state x-ray analysis. Further association of ordered structures may be probed by competitive inhibition studies with short chain segments or, where appropriate, by the stoichiometry of cation chelation." @default.
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• W2004967342 date "1980-10-01" @default.
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• W2004967342 title "Physical probes of polysaccharide conformation and interactions" @default.
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• W2004967342 doi "https://doi.org/10.1016/0308-8146(80)90004-7" @default.
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