Carboxylated cellulose nanocrystal films with tunable chiroptical properties

Carboxylated cellulose nanocrystals prepared by TEMPO-mediated oxidation exhibit a distinct ability to form nematic order, however, their ability to form chiral nematic films remains relatively unexplored. In this study, bleached cotton pulp hydrolyzed with hydrochloric acid and oxidized by TEMPO-mediated oxidation produce carboxylated cellulose nanocrystals with different aspect ratios 33.1, 32.8, 30.9, 29.0 and 28.9, and surface charge densities 0.16, 0.56, 1.00, 1.25, and 1.42 e·nm^-2. By tuning the aspect ratio and surface charge density, the optimal carboxylated cellulose nanocrystals producing left-handed chiral nematic films by evaporation-induced self-assembly are obtained. The left-handed chiral nematic films enable selective reflection of left-handed circularly polarized light with the peak wavelength tunable from the visible to the near-infrared regime by modifying the characteristics of nanorods and suspensions. Such carboxylated cellulose nanocrystal films transform spontaneous luminescence to right-handed circularly polarized luminescence with the peak luminescence dissymmetry factor of -0.51.