The dependence of glucan conformational dynamics on linkage position and stereochemistry

The 13C NMR T1 relaxation times for the (1 → 4)-linked maltooligomers (Mi) and the (1 → 6)-linked isomaltooligomers (IMi) with i = 2, 4, 6, and 8 were measured in aqueous solution at 22 and 65°C at a concentration (3%) low enough to have removed concentration-dependent effects on the measured T1 values. Separate T1 values were measured for each carbon in the residue at the reducing end of the oligosaccharide, in the residue at the non-reducing end, and in the interior, i.e., non-terminal, residue(s). Analogous data for the corresponding high polymers show that at 22°C the relaxation times for the carbons of the interior residues of the oligomers have converged to their high chain length asymptotes at about i = 10. This observation suggests that at room temperature polymeric motions in the frequency domain effective for 13C NMR relaxation at a magnetic field strength of 11.7 T have a “wavelength” of the order of 10 residues. The relaxation times characterizing the two ends of the chain are different, with longer T1 values for the carbons of the reducing end than for those of the non-reducing end. Carbons of α-anomeric residues at the reducing end have shorter relaxation times than those of the corresponding β-anomeric reducing sugars. Carbons of the interior residues have T1 values shorter than the carbons of either type of terminal residue. For oligomers of a given dp there is no T1 difference between oligomers of the Mi and IMi series at room temperature. This observation is seemingly at odds with the great differences in the inherent conformational freedom of the (1 → 4)- and (1 → 6)-linkages. At elevated temperatures the orientational relaxation behavior of the two series of oligomers measured by 13C T1 values show interesting differences, and in the case of the Mi series, structure develops in the chain length dependence of the T1 values.