Fast-forward approach of time-domain NMR relaxometry for solid-state chemistry of chitosan

Abstract

Chitosans with different average degrees of acetylation and weight molecular weight were analyzed by time-domain NMR relaxometry using the recently proposed pulse sequence named Rhim and Kessemeier - Radiofrequency Optimized Solid-Echo (RK-ROSE) to acquire ¹H NMR signal of solid-state materials. The NMR signal decay was composed of faster (tenths of μs) and longer components, where the mobile-part fraction exhibited an effective relaxation transverse time assigned to methyl hydrogens from N-acetyl-d-glucosamine (GlcNAc) units. The higher intrinsic mobility of methyl groups was confirmed via DIPSHIFT experiments by probing the ¹H-¹³C dipolar interaction. RK-ROSE data were modeled by using Partial Least Square (PLS) multivariate regression, which showed a high coefficient of determination (R² > 0.93) between RK-ROSE signal profile and average degrees of acetylation and crystallinity index, thus indicating that time-domain NMR consists in a promising tool for structural and morphological characterization of chitosan.

Keywords: Chitosan; Crystallinity; Degree of acetylation; Relaxometry; TD-NMR.