Molecular dynamics of polycrystalline cellobiose studied by solid-state NMR

Molecular motions of polycrystalline cellobiose have been investigated by measuring proton spin–lattice relaxation times, T₁ and T_1ρ, and the second moment, M₂, in both protonated and D₂O exchanged forms over the temperature range 120–380 K. T₁ relaxation is dominated by the motions of hydroxyl groups between 150 and 380 K, characterised by an activation energy of about 8.74 kJ/mol, whereas T_1ρ relaxation is driven by the motions of the same groups between 120 and 300 K. T_1ρ results suggest that hydroxyl groups have a distribution of dynamics. Motion of methylene groups was detected in the second-moment experiments at about 350 K, characterised by activation energy of about 40 kJ/mol. Consideration of the calculated and observed rigid-lattice second moments suggests that the reported X-ray data are incorrect for the inter-proton distance on C6′. ¹³C CPMAS spectra of both protonated and deuterated cellobiose have also been measured. Spectra of the deuterated material showed the existence of a second crystalline form in addition to the normal form.     

C CPMAS studies of plant cell wall materials and model systems using proton relaxation-induced spectral editing techniques

The solid state ¹³C CPMAS NMR spectra of plant cell walls are often complex owing to superposition of resonances from different polysaccharides and the heterogeneity of the cell wall assembly. In this paper, we describe the application of a set of proton relaxation-induced spectral editing (PRISE) experiments which combine ¹H relaxation properties (T₁, T_1ρ, T₂) with ¹³C high resolution spectroscopy (CPMAS) to relate the dynamics of the plant cell walls and model systems to their domain structural details. With PRISE it has been found that in plant cell wall materials, cellulose is always associated with the long components of spin–lattice relaxation in both the laboratory and rotating frames whereas non-cellulose polysaccharides (pectin and hemicellulose) are associated with the short ones. For the proton T₂ relaxation, cellulose is only associated with the short component (below 20 μs), pectin contributes to both the short component and the long one.