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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.
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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.
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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.
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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.
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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. To directly observe the rigid-body rotation of DTC droplets, in each of which the center of the rotation and the symmetry axis of the structure correspond, we fabricated DTC aggregates that comprise several DTCs with intact structures. Given a steady heat flux, the DTC aggregates metastabilized by the shape and the surface anchoring show a unidirectional rigid-body rotation with a constant angular velocity. The rotational direction is determined by the molecular chirality and the direction of the heat flux, and the rotational velocity increases with the temperature gradient and decreases with the aggregation number N of the DTCs as 1 + 2/sin2(π/N). The behavior agrees with a simple model based on the linear phenomenological equation.
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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.
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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.
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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.
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When a chiral liquid crystal is given a transport current, a unidirectional molecular motion is known to take place, which is called the Lehmann effect. In this paper, we study the mysterious heat-current-driven Lehmann effect using two types of hemispherical cholesteric droplets using polarizing, reflecting, confocal and fluorescent microscopies. Both the droplets, coexisting with the isotropic phase and contacting on a glass substrate, are characterized by the concavo-convex modulated surface and the inside orientational helix. Further, the only difference between them is the helical axis direction; i.e., one is perpendicular and the other is parallel to the substrate. Under the temperature gradient perpendicular to the substrate, the droplet whose helical axis is parallel to the heat current exhibited pure director rotation, while that with the axis perpendicular to the current rotated independently as a rigid body. In the two droplets, the rotational conversion efficiency from the temperature gradient into the angular velocity showed very different dependences on the chirality strength and on the droplets' size, suggesting that the rotations of the two droplets may be driven by independent torques with different origins. This is the first observation that the cholesteric droplets under the temperature gradient exhibit the two rotational modes, the pure director rotation and the molecular barycentric motion, which can be switched to each other by changing the heat-current direction parallel and perpendicular to the helical axis.
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Orientational correlations in Langmuir monolayers of nematic and smectic-C liquid crystal (LC) phases are investigated by molecular dynamics simulation. In both phases, the orientational correlation functions decay algebraically yet with the different exponents of 1.9 and 0.2 for the nematic and the smectic-C monolayers, respectively. The power law decay, i.e., the absence of long-range orientational order, means the both monolayers should be the ideal 2D system with a continuous symmetry, whereas the large difference in the exponents of power law gives rise to the crucial difference in their optical properties; the nematic monolayer is optically isotropic while the smectic-C monolayer exhibits an anisotropy on the length scale of visible light. Since the exponent is inversely proportional to the molecular exchange energy, the averaged molecular interaction in the nematic monolayer should be an order of magnitude smaller than that in the smectic-C monolayer, which is ascribed to the low molecular density and the weak molecular dipole due to the water molecule. The relation between the molecular interaction and the orientational correlation calculated for the 2D LC system offers much information not only about the 2D LCs but also on the bulk system.
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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.
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Photoinduced orientational waves in illuminated liquid-crystalline monolayers is one of the most remarkable far-from-equilibrium phenomena that systems of soft condensed matter exhibit. We model this behavior from a phenomenological point of view, taking the anisotropic photoexcitation of molecules into account. Numerical simulations as well as theoretical analyses of the model reveal that the intricate interplay between the spontaneous splay deformation of the liquid-crystalline order and the anisotropy of the photoexcitation can lead to the generation and propagation of orientational waves. The model can explain all the salient features of the phenomenon-in particular, the anomalous reversal of the propagation direction upon 90 degrees rotation of the polarization direction of illumination, which evaded theoretical explanation for nearly a decade.
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Surface-specific sum-frequency vibrational spectroscopy has been used to study the structure of alkyl chains of azobenzene molecules at the air/water interface. The results show that the alkyl chains are well aligned before UV irradiation and protruding out of the surface with a certain distribution. Although the alkyl chains become less ordered by UV irradiation following dynamical motion due to cis-trans isomerization of the azobenzene core, the alkyl chains show anisotropy in the direction perpendicular to that of the azobenzene core by linearly polarized UV irradiation.
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A phenomenological model of wave propagation in photo-excited liquid-crystalline Langmuir monolayers is constructed. The spontaneous splay deformation of the liquid-crystalline order and the anisotropy of photo-excitation of molecules are taken into account in this model. Numerical simulations of the model well reproduce qualitative features of the wave propagation phenomenon observed in recent experiments. A linear stability analysis of the model equations reveals that an interplay between the spontaneous splay deformation and the anisotropy of the photo-excitation can lead to the wave propagation.
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Modelos Teóricos , Cristalización , FotoquímicaRESUMEN
Free-standing films composed of several layers of chiral smectic liquid crystals (SmC*) exhibited unidirectional director precession under various vapor transfers across the films. When the transferred vapors were general organic solvents, the precession speed linearly depended on the momentum of the transmembrane vapors, where the proportional constant was independent of the kind of vapor. In contrast, the same SmC* films under water transfer exhibited precession in the opposite direction. As a possible reason for the rotational inversion, we suggest the competition of two origins for the torques, one of which is microscopic and the other macroscopic. Next, we tried to move an external object by making use of the liquid crystal (LC) motion. When a solid or a liquid particle was set on a film under vapor transfer, the particle was rotated in the same direction as the LC molecules. Using home-made laser tweezers, we measured the force transmitted from the film to the particle, which we found to be several pN.
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Membrana Celular/química , Gases/química , Cristales Líquidos/química , Agua/química , Propiedades de SuperficieRESUMEN
Successful attempts to manufacture synthetic molecular motors have recently been reported. However, compared with natural systems such as motor proteins, synthetic motors are smaller molecules and are therefore subject to thermal fluctuations that prevent them from performing any useful function. A mechanism is needed to amplify the single molecular motion to such a level that it becomes distinguishable from the thermal background. Condensation of molecular motors into soft ordered phases (such as liquid crystals) will be a feasible approach, because there is evidence that they support molecularly driven non-equilibrium motions. Here we show that a chiral liquid-crystalline monolayer spread on a glycerol surface acts as a condensed layer of molecular rotors, which undergo a coherent molecular precession driven by the transmembrane transfer of water molecules. Composed of simple rod-like molecules with chiral propellers, the monolayer exhibits a spatiotemporal pattern in molecular orientations that closely resembles 'target patterns' in Belousov-Zhabotinsky reactions. Inversion of either the molecular chirality or the transfer direction of water molecules reverses the rotation direction associated with switching from expanding to converging target patterns. Endowed only with the soft directional order, the liquid crystal is an optimal medium that helps molecular motors to manifest their individual motions collectively.