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.

Stick-slip water penetration into capillaries coated with swelling hydrogel.

We have observed intriguing stick-slip behavior during capillary pressure driven filling of borosilicate microtubes coated with hydrogel on their inner wall. Swelling of hydrogel upon exposure to a translating waterfront is accompanied by "stick-and-slip" motion. This results in the macroscopic filling velocity for water penetration into glass capillaries coated with poly(N-isopropylacrylamide) (PNIPAM) being constant throughout the filling process, and reduced by three orders of magnitude when compared to filling of uncoated capillaries. A simple scaling analysis is used to introduce a possible explanation by considering the mechanisms responsible for pinning and unpinning of the contact line. The explanation assumes that the time scale for water diffusion into a hydrogel film and the resulting swelling/change of the local meniscus contact angle define the duration of each "stick" event. The "slip" length scale is in turn established by the elastocapillary deformation of dry hydrogel at the pinning point of the contact line. The sequential dynamics of these processes then determine the rate of water filling into a swelling capillary. Collectively, these experimental and theoretical results provide a new conceptual framework for liquid motion confined by soft, dynamically evolving polymer interfaces, in which the system creates an energy barrier to further motion through elasto-capillary deformation, and then lowers the barrier through diffusive softening. This insight has implications for optimal design of microfluidic and lab-on-a-chip devices based on stimuli-responsive smart polymers.

Remote Giant Multispectral Plasmonic Shifts of Labile Hinged Nanorod Array via Magnetic Field.

We report a remotely mediated and fast responsive plasmonic-magnetic nanorod array with extremely large variability in optical appearance (up to 100 nm shifts in scattering maxima) and concurrently for multiple wavelengths in a broad range from UV-vis to near-infrared (at 450, 550, and 670 nm) with an external magnetic field with variable direction. The observed phenomenon demonstrates a rapid, wide-range response controlled via a noninvasive remote stimulus. The remotely controlled system suggested here is a magnetic field-directed assembly of an ordered monolayer array of unipolar oriented magnetic-plasmonic nickel-gold nanorods flexibly hinged to a sticky substrate. The unique geometry of the mobile nanorod array allows for the instant alteration of the surface plasmon polariton modes in the gold segment of the controllably tilting nanorods. This design demonstrates the utility of hybrid bimetallic nanoparticles and gives a novel approach to the design of fast-acting, remotely controlled color-changing nanomaterials for sensing and interfacial transport.