Micron-sized cholesteric droplets dispersed in glycerol exhibit steady rigid rotation under a uniform temperature gradient about the axis parallel to the gradient. The rotational velocity is linear to the temperature gradient, and the chirality inversion reverses the rotational direction. The result clearly contrasts previous studies showing that cholesteric droplets in immiscible liquids such as glycerol and water never rotated under a temperature gradient. We demonstrated the steady and continuous rotation of the cholesteric droplets driven by a heat flux by hydrophilizing the substrate surface to adsorb the glycerol molecules. The thermomechanical coupling constant was found to be divide v divide >= 3 x 10-7 N m-1 K-1.

Induced smectic phases of 5CB-EBBA binary mixtures were investigated with respect to the structures, stabilities, and molecular motion. The highest stability of the ordered smectic phase was obtained when 5CB and EBBA were mixed at 1:2. At the same ratio, the transferred charges between 5CB and EBBA took the maximum, indicating the direct correlation of the induced phase to the charge-transfer interaction. Whereas, the molecular motion monotonically slowed down with increasing EBBA, which is ascribed to the decrease of the free volume. The stability and the slow molecular reorientation may be independently controlled in the induced smectics.

With a stochastic model based on self-avoiding walk of multi walkers, free radical polymerization in a confined system is numerically investigated. As a reaction field, we consider not a confined lattice but a graph to represent interactions between polymerizable molecules and possible networks. The result of calculation visualized how the individual polymer chains should grow from moment to moment, which can hardly be tracked by other statistic methods such as Monte Carlo simulation. The calculation also provided the effective chain length of polymers and the average polymerization time, both of which followed a log-normal distribution. With respect to the initial radical density, the effective polymer length monotonically decreased, while the average polymerization time exhibited a single maximum. Considering the probabilities for the multiple radicals to encounter, we derived an inequality that well explained these behaviors. The stochastic model combined with graphs can be a useful tool for analyzing confined polymerization system.

We investigated the steady unidirectional rotation of cholesteric (Ch) droplets driven by a heat flux. The droplets coexisted with the isotropic (Iso) phase and possessed a helical molecular arrangement. When a heat flux was transported along the helical axis, the droplets and their dumbbell-shaped aggregates exhibited steady rigid rotation. Our results are in contrast with those of previous reports in which Ch droplets in the same geometry exhibited pure director rotation. The fact that Ch droplets and their aggregates prefer rigid rotation can be ascribed to the orientational elasticity combined with the anchoring force at the Ch-Iso interface, which locks the director to the rotational flow in the droplets.

We show that cholesteric (Ch) liquid crystal droplets with cylindrically symmetric orientation dispersing in an isotropic (Iso) phase exhibited unidirectional rotation under a heat flux along the symmetry axis. By introducing colloidal particle adhesive to the Ch droplet surface, we traced the translational motion of the colloids and found that the colloids rotated unidirectionally around the center of each Ch droplet. The director configuration of the droplets was not distorted either spatially or temporally, while the colloids rotated constantly. The results suggest that the Ch droplets under the heat flux should rotate as a rigid body. Using this heat-driven rotation of the Ch droplets, we designed new geometries of various composites of Ch droplets and colloids and succeeded in driving intriguing complex dynamics.

Photopolymerization of Langmuir monolayers composed of bifunctional acrylic liquid crystalline (LC) compounds was observed in situ by polarizing optical microscopy. In a dark state, monolayers of the LC compounds formed at an air-water or liquid-liquid interface exhibited liquid-like fluidity and in-plane optical anisotropy because of the coherent molecular tilt from the surface normal. Irradiated by UV light, the in-plane anisotropy and the liquid fluidity gradually disappeared with time, indicating the formation of the polymerized monolayers. Because the constituent molecules possess polymerizable acryloyl groups, under UV light, they are combined by acrylic polymer chains grown on the interface, which decreases the intermolecular distance and disturbs the coherent molecular tilt, resulting in the evanescence of the in-plane optical anisotropy and the fluidity. In contrast to the classical model of radical polymerization, the time taken for the monolayers to be photopolymerized was inversely proportional to the UV intensity, which is ascribed to the ideal two dimensionality of the reaction field. Because the polymerization degree is quantitatively estimated from the in-plane optical anisotropy of the LC monolayers, the process is traced, from moment to moment, by in situ microscopy observation.

We investigated molecular diffusion in charge-transferred (CT) liquid crystalline (LC) mixtures composed of a cyanobiphenyl compound (8CB, electron acceptor) and an azobenzene derivative (7AB7, electron donor). When the molar ratio of 7AB7 is as small as 0-0.1, the mixture forms a uniform two-dimensional (2D) fluid phase called induced SmA. Statistically, the induced SmA phase possesses the same structure as pure 8CB, but in the dynamics, it shows unusual molecular diffusion. With hemispherical bubbles made of the induced SmA phase, we examined gas transport across the films, and found that the oxygen diffusion abruptly fell when the 7AB7 ratio exceeded 0.05. The result suggests that even in the macroscopically uniform 2D fluid phase, small CT crystalline domains can be formed and stably dispersed, which should disturb the one-dimensional molecular transport normal to the smectic layer.

We fabricated aggregates of cholesteric cylinders coexisting with the isotropic phase and investigated their dynamics under a temperature gradient. Each constituent cylinder possessed the double-twist (DT) structure, and when a heat flux was applied, the whole aggregates rotated as a rigid-body without changing the DT orientation. The angular velocity was proportional to the heat flux and the rotational direction was determined by the molecular chirality and the flux direction. The result suggests that the rigid-body rotation was driven by the thermomechanical cross-correlation in chiral LCs. We also succeeded in switching the rotation by changing the illumination onto the sample.

Droplets of cholesteric liquid crystals rotate their helical structure when subjected to a thermal gradient perpendicular to their helical axes. Concerning the interpretation of their dynamics, there has been an argument whether the textural rotation indicates rigid-body rotation of the droplets or pure director rotation. To clarify this, we dispersed micron-size particles in a cholesteric-isotropic coexisting sample and traced their motion, and found that the particles adhering onto a cholesteric droplet rotated together with the helix in phase. This observation provided clear evidence of the rigid-body rotation of the droplet, and we also revealed an unusual hydrodynamic flow in the coexisting phase.

We made aggregates of cholesteric liquid crystalline Cylinders with Double-Twist orientational structure (DTC) and investigated their rigid-body rotation under a temperature gradient, focusing on how the rotational speed should depend on the cylinder size. The experimental results showed that the angular velocity of the DTC aggregates linearly increased with the height of the cylinders and was inversely proportional to the base area. With a phenomenological equation, we analyzed the torque caused by the heat flux and its balance with the viscous friction, and found that the simple analysis well explained the size-dependence of the rotation of the DTC aggregates. The coupling constant between the heat flux and the torque to drive the rigid-body rotation was in the same order of magnitude as that for the director rotation.

We succeeded in driving the unidirectional rigid-body rotation of cholesteric (Ch) double-twist cylinder (DTC) droplets under a heat flux along the cylindrical symmetry axis.

The flexible control of nanopatterns by a bottom-up process at the nanometer scale is essential for nanofabrication with a finer pitch. We have previously reported that for the fabrication of linear nanopatterns with sub-5 nm periodicity on Si substrates the outermost surfaces of assembled micelles facing the substrates can be replicated with soluble silicate species generated from the Si substrates under basic conditions. In this study, concentrically arranged nanogrooves with a sub-5 nm periodicity were prepared on Si substrates by replicating the outermost surfaces of bent micelles guided by silica particles. The Si substrates, where silica particles and surfactants films were deposited, were exposed to an NH3-water vapor mixture. During the vapor treatment, cylindrical micelles became arranged in concentric patterns centered on the silica particles, and their outermost surfaces facing the substrates were replicated by soluble silicate species on the Si substrates. The thinness of the surfactant film on the substrate is crucial for the formation of concentric silica nanogrooves because the out-of-plane orientations of the micelles are suppressed at the interface. Surprisingly, the domains of the concentric silica nanogrooves spread to much larger areas than the maximum cross-sectional areas of the particles, and the size of the domains increased linearly with the radii of the particles. The extension of concentric nanogrooves is discussed on the basis of the orientational elastic energies of the micelles around one silica particle. This study of the formation of bent nanogrooves guided by the outlines of readily deposited nanoscale objects provides a new nanostructure-guiding process.

We investigated the novel photo-induced dynamics of azobenzene-doped cholesteric (Ch) droplets coexisting with the isotropic (Iso) phase. When the hemispherical Ch droplets initially stuck to glass substrates were irradiated by UV-light, they were parted from the substrates due to the surface disordering caused by the photo-isomerization of azobenzene. Then, the spherical droplets floating in the Iso phase exhibited an unexpected motion - a continuous and unidirectional rotation along the light propagation direction. The rotational direction was reversed by the inversion of either the sample's chirality or the UV irradiation direction, and the rotational velocity increased with both the UV-light intensity and the concentration of the doped azobenzene, the dependences of which were described by linear and relaxation functions, respectively. We proposed a possible scenario based on Leslie's theory combining mass fluxes and torques, which well explained the photo-driven rotation of the Ch droplets.

When a cholesteric liquid crystal (LC) is submitted to a thermal gradient, it exhibits continuous director rotation. The phenomenon is called the Lehmann effect and is understood as a thermomechanical coupling in chiral LCs without mirror symmetry. Since the Lehmann effect is considered to possess time-reversal symmetry, one can expect the inverse process, i.e., rotating chiral LCs to pump heat along the rotational axis. We report the first observation of heat transport driven by rotating cholesteric droplets. This result suggests a new function of the cholesterics as a micro heat pump.

We revealed the detailed structures of induced smectic liquid crystal (LC) phases composed of a binary mixture of charge-transfer (CT) LC substances. Although neither of the constituents had highly ordered smectic phases, the mixture exhibited smectic-E (SmE) or smectic-B (SmB) phases when mixed at ratios of 1 : 1 and 2 : 3, respectively. The results of polarized optical microscopy, differential scanning calorimetry, X-ray diffraction, and infrared spectroscopy indicated that the induced smectic phases were stabilized by an exquisite balance between the CT interactions, dipolar interactions, and excluded volume effects. We proposed a possible model for the molecular arrangements in the SmE and SmB phases, which consistently explained the experimental results including the stoichiometric ratios.

We found for the first time the stabilization of a double twisted structure in cholesteric liquid crystals confined to small spherical droplets under weak anchoring conditions. The direct observation of the droplets using a polarized microscope revealed the physical properties of the structure. The experimental results showed that the stability of the double twisted structure is determined by the relationship between the helical pitch length and the droplet size. We theoretically analyzed the structural stability by the calculation of the Frank elastic free energy including the surface elastic term, and succeeded in explaining the experimental results. In this paper, we concluded that the stability of the double twisted structure is determined by the competition between the surface and the bulk elasticity.

In an isotropic-cholesteric coexistence system, a single-helix structure is formed in the cholesteric droplets, and when a temperature gradient is applied, unidirectional rotations are induced in these droplets. However, in a previous work, we showed that a double twisted structure was also formed in the droplets by changing droplet size or chirality. In this paper, we find that unidirectional rotations are also induced by applying a temperature gradient to droplets with a double twisted structure. Here, however, the rotational behavior is strongly dependent on the relationship between the direction of the helical axis and the temperature gradient. Unidirectional rotation is induced when one of the helical axes is parallel to the gradient, whereas no rotation is found when all of the axes are perpendicular to the temperature gradient. These results suggest that the macroscopic helix plays a significant role in the heat-driven rotational dynamics of cholesteric droplets.