Laser-driven microflow-induced bistable orientation of a nematic liquid crystal in perfluoropolymer-treated unrubbed cells.

We demonstrate laser-driven microflow-induced orientational change (homeotropic to planar) in a dye-doped nematic liquid crystal. The homeotropic to planar director alignment is achieved in unrubbed cells in the thermal hysteresis range of a discontinuous anchoring reorientation transition due to the local heating by light absorption in dye-doped sample. Various bistable patterns were recorded in the cell by a programmable laser tweezers. The width of the patterns depend on the scanning speed of the tightly focussed laser beam and the minimum width obtained is approximately equal to 0.57µm which is about 35 times smaller than the earlier report in the rubbed cells. We show that the motion of the microbeam spot causes local flow as a result the liquid crystal director is aligned along that direction.

Spontaneous achiral symmetry breaking in liquid crystalline phases.

It is well known that spontaneous deracemization or spontaneous chiral resolution occasionally occurs when racemic molecules are crystallized. However, it is not easy to believe such phenomenon will occur when forming liquid crystal phases. Spontaneous chiral domain formation is introduced, when molecules form particular liquid crystal phases. Such molecules possess no chiral carbon but may have axial chirality. However, the potential barrier between two chiral states is low enough to allow mutual transformation even at room temperature. Therefore the systems are essentially not racemic but nonchiral or achiral. First, enhanced chirality by doping chiral nematic liquid crystals with nonchiral molecules is described. Emphasis is made on ester molecules for their anomalous behavior. Second, spontaneous chiral resolution is discussed. Three examples with rod-, bent-, and disk-shaped molecules are shown to give such phenomena. Particular attention will be paid to controlling enantiomeric excess (ee). Actually, almost 100% ee was obtained by applying some external chiral stimuli. This is very noteworthy in the sense that we can create chiral molecules (chiral field) without using any chiral species.

Distinctive thermal behavior and nanoscale phase separation in the heterogeneous liquid-crystal B4 matrix of bent-core molecules.

By means of high-resolution calorimetry, we studied thermodynamic properties of the liquid-crystal B(4) phase where bent-core molecules form a helical nanofilament structure. Distinctive thermal behavior characterizing the growth process of the B(4) phase was obtained in undergoing the phase transition with many sharp peaks, indicating a highly heterogeneous structure. It has been demonstrated that such unusual behavior is commonly seen for two types of rodlike molecules as well as for various mixture compositions. We speculate that mixture systems involve a nanoscale phase-separated structure due to the remarkable aggregation effect in the bent-core molecules and that the helical nanofilament structure independently grows in the isotropic state of rodlike molecules. We also propose that the asymmetry in viscoelastic property plays a role in yielding unusual behavior.

Quasi-two-dimensional Ising critical behavior of de Vries liquid crystals observed in the heat capacity and dielectric response.

Heat capacity and dielectric measurements have been made on a liquid crystal compound exhibiting de Vries type of smectic-A{*} (Sm-A{*}) phase. Heat capacity shows a significant anomaly which is almost symmetric for above and below the Sm-A{*}-Sm-C{*} transition temperature. The transition was found to be very weakly first order. The critical exponent gamma determined from the dielectric data lies 1.8+/-0.2. The present heat capacity data as well as former data for another compound of de Vries type have been analyzed in detail. It was found that the heat capacity data for both compounds are fitted well with a logarithmic divergence except in the immediate vicinity of the transition. These results agree with an expectation that de Vries Sm-A{*}-Sm-C-{*} transition can exhibit quasi-two-dimensional Ising critical behavior.

Critical behavior of layer compression modulus near the smectic- A-smectic- C(*)(alpha) transition

The layer compression modulus was measured near the smectic- A-smectic- C(*)(alpha) phase transition in a chiral smectic liquid crystal. The layer compression modulus B shows marked pretransitional effects above the phase transition. The critical softening of B can be fit to a simple power law. It is described by the theoretical description based on the renormalization-group method and seems to suggest a crossover behavior. These effects clearly show that the transition is not of the Landau mean-field type.

Induced antiferroelectric smectic- C(*)(A) phase by doping ferroelectric- C* phase with bent-shaped molecules

Doping of the ferroelectric Sm-C(*) phase with bent-shaped molecules induces the antiferroelectric Sm-C(*)(A) phase. The effect was observed by means of electro-optic and dielectric measurements in systems with weak interlayer interactions in which the relative strength of anticlinic-synclinic order between molecules in adjacent layers is easily controlled by external factors. Fourier-transform infrared spectroscopy studies suggest that the bent-shaped molecules are not flat. They reorient upon the electric field-induced antiferroelectric-ferroelectric transition to adopt a position in which the average direction of the carbonyl groups is in the smectic plane and a bending tip along the C2 symmetry axis.

Dynamic kerr effect measurements on photoreceptor disk membrane vesicles.

Dynamic Kerr effect measurements were performed with dilute aqueous suspensions of monodisperse spherical vesicles (approximately 1 micron diameter), isolated from the rod outer segment of bovine retina. A large birefringence, amounting to the specific Kerr constant of 10(-3) esu, can be observed. When a sufficiently long duration pulse (1 s) is applied, the decay of birefringence can be represented by a single exponential profile, yielding a relaxation time of 100 +/- 20 ms in 1 mM imidazole buffer. This is consistent with the rotatory relaxation time of these spherical membrane vesicles. When a short duration is applied, the birefringence increases more steeply and the decay profile contains several components. The slowest (terminal) relaxation time is 86 +/- 15 ms is due to the same process as the one observed in the slow pulse case.

Electric and optical anisotropy and their osmotically induced changes of photoreceptor disk membrane vesicles.

Electro-optical characterization of the photoreceptor disk membrane vesicle is performed by examining the electric field and concentration dependence of the study-state birefringence of aqueous suspensions of the vesicles. The electric polarizability anisotropy is found to be negative and of large magnitude: alpha 1 - alpha 2 = -(1-3) X 10 cm3. The optical anisotropy is determined to be also negative but of small magnitude: g 1 - g 2 = -1 X 10(-7). The specific Kerr constant deduced from the concentration dependence of the Kerr constant is found to be very large: Ksp = 7 X 10(-4) e.s.u. Upon deforming the vesicles osmotically from the spherical shell to the disk structure, the steady-state birefringence increases by an order of magnitude which is attributed solely to the increase in optical anisotropy attending the corresponding change in the geometric eccentricity of the vesicle. A plausible birefringence mechanism based on the known structural features of the vesicles is proposed, which would account for these findings.

A potent antimalarial activity of Hydrangea macrophylla var. Otaksa leaf extract against Plasmodium yoelii 17XL in mice.

The antimalarial activity of the hot-water extract of Hydrangea macrophylla var. Otaksa leaves was evaluated against Plasmodium yoelii 17XL in mice. Non-treated control mice died from 6 to 7 days after infection, but mice treated with the leaf extract survived during the experiment. Mice given the extract orally showed low parasitemia levels during administration. Following a transient recrudescence of malaria parasites in the bloodstream of treated mice, no parasites could be detected by a microscopic examination. Furthermore, the 30% MeOH aq. eluate and 50% MeOH aq. eluate from dried leaves of H. macrophylla var. Otaksa showed an antimalarial activity in vivo. Sulfamonomethoxine was orally given to infected mice to compare with the antimalarial activity of the hot-water extract of leaves. Sulfamonomethoxine given orally reduced parasitemia, but no complete cure of mice was observed.

Generalized mean-field potential description for ferroelectric ordering in nematic liquid crystals.

Ferroelectric ordering in a nematic liquid crystal system is described using a generalized mean-field potential including effective potentials for both axial and polar interactions. From a self-consistent numerical analysis, a complete phase diagram is obtained as a function of the axial and polar interaction potential strengths. The obtained phase diagram exhibits not only the usual isotropic-nematic phase transition but also nematic-ferroelectric nematic and direct isotropic-ferroelectric nematic phase transitions with a tricritical point among the phases. The phase transition behaviors and the angular orientational distribution function of the molecules were investigated by studying the dependence of the polar and the axial order parameters on the reduced temperature. Moreover, the other polar order parameters responsible for second-harmonic generation (SHG) were also investigated in the generalized mean-field potential description. As a concrete example, we performed a quantitative analysis of the SHG signal reported previously in a lyotropic poly L-glutamate system, detailing the relationship between the angular distribution function and the order parameters based on our potential model. This clarifies the nature of the ferroelectric phase responsible for SHG in nematics.

Special phase matching of second-harmonic generation in helical ferroelectric liquid crystal cells.

The helical structures in ferroelectric liquid crystals can be utilized to realize a special phase matching for second-harmonic generation (SHG) when two counter fundamental waves propagate along the helical axis and the wavelength of SHG is near the photonic (selective reflection) band edge. On the basis of the exact theory [Drevensek-Olenik and Copic, Phys. Rev. E 56, 581 (1997)], a simple analytical description is derived and some characteristic features of the special phase matching are shown. (1) Special phase matching is definitely achieved under particular combinations of polarization. (2) The SH spectrum is related to a subsidiary oscillating structure in the selective reflection spectrum. The maximum SH intensity is realized at the first dip of the oscillation near one of the edges in the selective reflection band. (3) The thickness (d) dependence of the maximum SH intensity is d4 in thick cells, while it is d2 for conventional phase matching. (4) The linewidth for the SH peak is d(-3) dependent, which is much narrower than in conventional phase matching.

Holes and disclinations in hybrid nematic liquid crystal films.

Defect patterns in hybrid nematic liquid crystal films of pentylcyanobiphenyl (5CB) on a glycerol surface were studied with polarized transmission and monochromatic reflected light microscopy. We report that disclinations of apparent topological strength zero, stable pairs of +1 and -1 disclinations, and higher strength defects found in these films are stabilized by holes in the liquid crystal film. These holes are produced by a monolayer of surfactant on the glycerol surface. In addition, we describe the topology of the director field in the film during the coalescing of two such holes.

Observation of a soft smectic liquid-crystal phase in a mixture showing V-shaped switching.

We present the experimental observation of a soft smectic liquid crystal phase in a three-component liquid crystal mixture reported to exhibit V-shaped switching. Unlike the layer compression modulus B of the usual smectic phase, B of the soft smectic phase has a peculiar temperature and frequency dependence. It was found that this characteristic feature is one of the main driving force to realize an ideal V-shaped switching.

Molecular orientation near the surface of a smectic liquid crystal cell showing V-shaped switching by means of attenuated total internal reflection ellipsometry.

Attenuated total internal reflection ellipsometry was used to probe the molecular orientation and switching near the surface of a smectic liquid crystal cell showing V-shaped switching. We find that the switching occurs collectively near the surface as in the bulk. The molecules form a twisted state, but the twist angle relative to the bulk layer normal is small because of compensating twist of the smectic layer normal. As a result, a rather uniform molecular orientation is produced, resulting in high extinction and a high contrast ratio in the absence of a field.

Observation of a pretransitional effect near a virtual smectic-A--smectic-C* transition.

Unusual softening of the layer compression modulus B has been observed near the phase boundary where the smectic-C* phase vanishes in a naphtalene-based liquid crystal mixture. From the systematic study of x-ray and layer compression measurements, this unusual effect is attributed to the pretransitional softening near a virtual smectic-A-smectic-C* phase transition in the smectic-A phase, which no longer appears on the thermoequilibrium phase diagram. This phenomenon is similar but not equivalent to supercritical behavior.

Enhanced chirality by adding achiral molecules into the chiral system.

It is generally accepted that the doping of chiral materials with achiral molecules diminishes the chirality of the system. Here we report the opposite phenomenon. It was found that the structural chirality of smectic phases made of rodlike molecules, Sm-C(*) or Sm-C(*)(A) phases, measured as the reverse length of the helical pitch, is enhanced by adding small amount of achiral bent-shaped molecules. The effect is due to the chirality transfer between host and guest systems. Achiral bent-shaped molecules become structurally chiral due to the interactions with the chiral host that induces tilt and polar order of bent-shaped molecules. This induced chirality is then transferred back to the host.

Spontaneous Enantiomeric Resolution in a Fluid Smectic Phase of a Racemate.

Right- and left-handed homochiral domains segregate in a fluid smectic phase of the racemic (R*,S*)-beta-Me-TFMHPOBC analogue shown. This CF(3)-containing liquid crystalline compound exhibits an electrooptic response in a homogeneous cell, although no macroscopic dipole is expected to exist. Moreover, the homeotropic cells of this material exhibit striped domains, which are associated with fine stripes having two opposite tilt senses with respect to the predominant stripes.

Viscoelasticity of ambient-temperature nematic binary mixtures of bent-core and rodlike molecules.

We report measurements of the temperature variations of physical parameters in ambient-temperature nematic liquid crystal mixtures of bent-core (BC) and rodlike molecules (5CB): birefringence Δn; static dielectric constants ε(||) and ε(⊥); splay K(11) and bend K(33) elastic constants; rotational viscosity γ(1); and diffusion coefficients D(||) and D(⊥) of a microsphere. Both Δn and ε(||) decreases rapidly with increasing BC concentration, whereas ε(⊥) remains almost constant. At a shifted temperature (e.g., T-T(NI)=-10 °C), K(11) increases by ~50% and K(33) decreases by ~80% compared to pure 5CB when the BC concentration is increased to ~43 mol % in the mixture. Viscosities parallel and perpendicular to the director, η(||), η(⊥), which are nearly equal to the Miesowicz viscosities η(2) and η(3), respectively, were obtained by D(||) and D(⊥) using the Stokes-Einstein relation. Both the viscosities at room temperature increase by 60 and 50 times, respectively, whereas γ(1) increases by 180 times (at ~43 mol %) compared to the corresponding values of pure 5CB. The stiffening of K(11) and exorbitantly large enhancement in all the viscosities at a higher mol % of BC indicate that the viscoelastic properties are highly impacted by the presence of smectic clusters of BC molecules that results from the restricted free rotation of the molecules along the bow axis in the nematic phase. A possible attachment model of smectic type clusters of BC molecules surrounding the microparticle is presented.

High-resolution calorimetric study of phase transitions in chiral smectic-C liquid crystalline phases.

We carried out an improved characterization of phase transitions among chiral smectic-C subphases observed for various antiferroelectric liquid crystals by precise heat capacity measurements. It was found that the phase transitions are intrinsically first order exhibiting a remarkable heat anomaly which involves little pretransitional thermal fluctuation and a finite thermal hysteresis. On the other hand, we also noticed that the critical point of the smectic-C(α)(*)-smectic-C* transition is induced by the destabilization of the smectic-C(α)(*) phase which couples with the fluctuation associated with the smectic-A-smectic-C(α)(*) phase transition.

Calorimetric study of the effect of bent-shaped dopant molecules on the critical behavior at the nematic-smectic-Ad phase transition.

We report results of calorimetric studies for the binary mixture of rodlike host n-alkyloxy-cyanobiphenyl (nOCB, n=8,9) and bent-shaped guest 1,3-phenylene-bis[4-(3-methylbenzoyloxy)]-4'-n-dodecylbiphenyl-4'-carboxylate (BC12). The effect of bent-shaped dopant molecules on the critical behavior associated with the nematic-smectic-A(d) phase transition has been studied in detail. The transition temperature for the nematic-smectic-A(d) phase sharply decreases as the increase of the mole fraction of the dopant concentration (denoted X for the BC12/9OCB mixture and Y for the BC12/8OCB mixture). The dependence of the critical exponent α on X and Y is well explained in terms of the McMillan ratio. A nearly tricritical exponent has been obtained for the X=0.01 mixture. X=0.02-0.03 mixtures, pure 8OCB, and Y=0.01-0.03 mixtures exhibit nonuniversal behaviors with effective exponents lying between the 3D-XY and tricritical exponents. The heat capacity anomaly for Y=0.05 has been well described with the 3D-XY exponent. The critical amplitude ratio A(-)/A(+) is close to 1 and insensitive to the dopant concentration. No Fisher renormalization of the critical exponent has been observed even for nearly tricritical compositions, which indicates the smallness of the concentration plays a decisive role rather than the steepness of the N-SmA(d) phase boundary.