Robust Chiral Organization of Cellulose Nanocrystals in Capillary Confinement.

We showed large area uniformly aligned chiral photonic bioderived films from a liquid crystal phase formed by a cellulose nanocrystal (CNC) suspension placed in a thin capillary. As a result of the spatial confinement of the drying process, the interface between coexisting isotropic and chiral phases aligns perpendicular to the long axis of the capillary. This orientation facilitates a fast homogeneous growth of chiral pseudolayers parallel to the interface. Overall, the formation of organized solids takes hours vs weeks in contrast to the slow and heterogeneous process of drying from the traditional dish-cast approach. The saturation of water vapor in one end of the capillary causes anisotropic drying and promotes unidirectional propagation of the anisotropic phase in large regions that results in chiral CNC solid films with a uniformly oriented layered morphology. Corresponding ordering processes were monitored in situ at a nanoscale, mesoscale, and microscopic scale with complementary scattering and microscopic techniques. The resulting films show high orientation order at a multilength scale over large regions and preserved chiral handedness causing a narrower optical reflectance band and uniform birefringence over macroscopic regions in contrast to traditional dish-cast CNC films and those assembled in a magnetic field and on porous substrates. These thin films with a controllable and well-identified uniform morphology, structural colors, and handedness open up interesting possibilities for broad applications in bioderived photonic nanomaterials.

Effect of collective molecular reorientations on Brownian motion of colloids in nematic liquid crystal.

In the simplest realization of Brownian motion, a colloidal sphere moves randomly in an isotropic fluid; its mean squared displacement (MSD) grows linearly with time τ. Brownian motion in an orientationally ordered fluid--a nematic--is anisotropic, with the MSD being larger along the axis of molecular orientation, called the director. We found that at short time scales, the anisotropic diffusion in a nematic becomes anomalous, with the MSD growing slower or faster than τ; these states are respectively termed subdiffusion and superdiffusion. The anomalous diffusion occurs at time scales that correspond to the relaxation times of director deformations around the sphere. Once the nematic melts, the diffusion becomes normal and isotropic. Our experiment shows that the deformations and fluctuations of long-range orientational order profoundly influence diffusive regimes.