Templated nanofiber synthesis via chemical vapor polymerization into liquid crystalline films.

Extrusion, electrospinning, and microdrawing are widely used to create fibrous polymer mats, but these approaches offer limited access to oriented arrays of nanometer-scale fibers with controlled size, shape, and lateral organization. We show that chemical vapor polymerization can be performed on surfaces coated with thin films of liquid crystals to synthesize organized assemblies of end-attached polymer nanofibers. The process uses low concentrations of radical monomers formed initially in the vapor phase and then diffused into the liquid-crystal template. This minimizes monomer-induced changes to the liquid-crystal phase and enables access to nanofiber arrays with complex yet precisely defined structures and compositions. The nanofiber arrays permit tailoring of a wide range of functional properties, including adhesion that depends on nanofiber chirality.

Surface-Controlled Orientational Transitions in Elastically Strained Films of Liquid Crystal That Are Triggered by Vapors of Toluene.

We report the fabrication of chemically patterned microwells that enable the rapid and facile preparation (by spin coating and patterned dewetting) of thin films of liquid crystals (LCs) that have precise thicknesses (0.7-30 µm), are supported on chemically defined substrates, and have free upper surfaces. We use these microwells to prepare elastically strained nematic LC films supported on silica glass, gold, or polystyrene substrates and thereby characterize the response of the strained LC films to vapors of toluene. We report that low concentrations of toluene vapor (<500 ppm) can partition into the LC to lower the anchoring energy of the LC on these substrates, thus allowing the elastic energy of the strained LC film to drive the LC films through an orientational transition. The central role of the toluene-induced change in surface anchoring energy is supported by additional experiments in which the response of the nematic LC to changes in film thickness and substrate identity are quantified. A simple thermodynamic model captures these trends and yielded estimates of anchoring energies (8-22 µJ/m(2)). Significantly, the orientational transitions observed in these strained LC thin films occur at concentrations of toluene vapor that are almost 1 order of magnitude below those which lead to bulk phase transitions, and they are not triggered by exposure to water vapor. Overall, these results hint at principles for the design of responsive LC-based materials that can be triggered by concentrations of aromatic, volatile organic compounds that are relevant to human health.