Investigating structural and dynamic changes in cellulose due to nanocrystallization.

Cellulose nanocrystals (CNCs) is synthesized from alpha-cellulose by acid hydrolysis method, and formation of nanocrystallization is comprised by using various microscopic and spectroscopic techniques like PXRD, XPS, Raman, FTIR, PL, UV-Vis, DSC, TGA, DLS, SEM, TEM. Nanocrystalline cellulose shows a notably higher photoluminescence (PL) intensity than cellulose, which enhances its ability to absorb and emit visible light. This increase in PL intensity is attributed to a smaller particle size of CNCs, greater surface area, and quantum confinement effects. The higher intensity of the XPS spectrum further supports the larger surface area of CNCs. PXRD and Raman spectroscopy results show that CNCs has a higher crystallinity index than cellulose. Through deconvolution of the ¹³C CP-MAS SSNMR spectrum, we confirmed a significant reduction in the relative abundance of the amorphous region of cellulose (43.61%) to just 4.97% in CNCs. The ¹³C CP-MAS SSNMR spectrum of CNCs, at the C4, C6, C2C3C5 nuclei sites, can be fitted by two distinct lines for both amorphous and crystalline region, indicating the formation of a co-crystal from two nanocrystallites. Despite this, the principal components of the CSA (chemical shift anisotropy) tensor remain unchanged, suggesting similar electronic environments for these two nanocrystallites. The spin-lattice relaxation time and local correlation time of cellulose and CNCs are determined for chemically distinct carbon nuclei residing on D-glucopyranose units. It is noteworthy that the ¹³C spin-lattice relaxation time and ¹³C local correlation time are longer for each chemically distinct nucleus in CNCs compared to cellulose. It can be predicted by observing the NMR relaxometry data that the longer relaxation time in CNCs is due to the enhancement of crystallinity index. Hence, a correlation between the crystallinity index and nuclear spin dynamics can be established by NMR relaxometry measurements. These findings offer significant insights into the intricate structure and dynamic behavior of cellulose and nanocrystalline cellulose (CNCs), crucial for advancing biomimetic material design, which has huge applications across the pharmaceutical, textile, and cosmetics industries.