Elucidating the internal structure and dynamics of α-chitin by 2DPASS-MAS-NMR and spin-lattice relaxation...

The structure and dynamics of the second most abundant biopolymer α-chitin were studied by high resolution solid state ¹³C cross-polarization magic angle spinning nuclear magnetic resonance (CP-MAS-NMR) spectral analysis, ¹³C relaxation measurements at eight chemically different carbon sites and chemical shift anisotropy measurement by two-dimensional phase-adjusted spinning sidebands (2DPASS) magic angle spinning (MAS) solid state NMR method.¹³C spin-lattice relaxation time was measured by high resolution Torchia CP method. Spin-lattice relaxation rate (1/T₁) of side chain carbon nuclei were remarkably high, because those nuclei possess higher degree of motional freedom. Chemical shift anisotropy parameters of eight chemically different carbon nuclei were determined by 2DPASS-MAS-NMR experiment. Large value of chemical shift anisotropy was observed for carbonyl group carbon (C₇) nuclei, because of electrostatic effect, hydrogen bonding and molecular magnetic susceptibility. ¹³C relaxation mechanism is mainly governed by chemical shift anisotropy interaction, especially at high value of external magnetic field (11.74 T). Thus, the correlation time at different carbon sites were also calculated by using the spin-lattice relaxation times and chemical shift anisotropy values. The correlation time of side chain carbon (C₈) was two orders of magnitude less than the carbonyl group carbon. These types of investigations would enlighten the correlation between the structure and dynamics of long polysaccharide chain compound.