Chiral electrostatic interaction and cholesteric liquid crystals of DNA

Explicit expressions for electrostatic interaction between stiff DNA duplexes of finite length are obtained. These expressions allow for the helical symmetry of charge distribution on DNA molecules and reveal chiral and non-chiral interaction terms. Asymptotic expressions at small twist angles are applied to evaluate the cholesteric pitch and the twist elastic constant and their dependence on the length of DNA fragments. These estimates suggest an explanation for the large value of the cholesteric pitch and its nonmonotonic variation with the density of the liquid crystal. An analysis of biaxial correlations rationalizes the driving force of the transition from the cholesteric to hexagonal phase upon dehydration.     

Cholesteric–nematic transitions induced by a shear flow and a magnetic field

The untwisting of the helical structure of a cholesteric liquid crystal under the action of a magnetic field and a shear flow has been studied theoretically. Both factors can induce the cholesteric–nematic transition independently; however, the difference in the orienting actions of the magnetic field and the shear flow leads to competition between magnetic and hydrodynamic mechanisms of influence on the cholesteric liquid crystal. We have analyzed different orientations of the magnetic field relative to the direction of the flow in the shear plane. In a number of limiting cases, the analytic dependences are obtained for the pitch of the cholesteric helix deformed by the shear flow. The phase diagrams of the cholesteric–nematic transitions and the pitch of the cholesteric helix are calculated for different values of the magnetic field strength and the angle of orientation, the flow velocity gradient, and the reactive parameter. It is shown that the magnetic field stabilizes the orientation of the director in the shear flow and expands the boundaries of orientability of cholesterics. It has been established that the shear flow shifts the critical magnetic field strength of the transition. It is shown that a sequence of reentrant orientational cholesteric–nematic–cholesteric transitions can be induced by rotating the magnetic field in certain intervals of its strength and shear flow velocity gradients.     

Reentrant phases in compensated ferrocholesterics

Influence of magnetic field on orientation and magnetic properties of a compensated ferrocholesteric, a suspension of needle-like ferromagnetic particles in a cholesteric liquid crystal, was studied theoretically. A phase transition from a ferrocholesteric to a ferronematic state in a magnetic field oriented normally to the axis of the helical structure was considered. The dependences of the transition field to the ferronematic phase on the material parameters of the suspension and of the helical structure pitch and magnetization on the field strength were investigated. A possibility of existence of a reentrant ferrocholesteric phase was shown.

     

Light-induced instabilities driven by competing helical patterns in long-pitch cholesterics

We study theoretically the dynamical reorientation phenomena when a long-pitch cholesteric liquid-crystal film with homeotropic alignment is illuminated by a circularly polarized lightwave. In the present case, the natural cholesteric pitch is of the order of (or larger than) the film thickness. The helical cholesteric structure is thus frustrated by the boundary conditions without illumination. However, above a light intensity threshold reorientation occurs and the bifurcation scenario depends strongly on the natural cholesteric pitch. Recalling that a long-pitch cholesteric is achieved in practice by adding a small amount of chiral agents in a nematic liquid crystal, the observed dynamics can be viewed as the result of the competition between intrinsic and extrinsic unidimensional helical patterns. The intrinsic part consists of the helical deformations induced by the chirality of the dopant, whereas the extrinsic part is related to the chirality induced by the optical field through the non-uniform angular momentum transfer of light to a nematic. The all-optical analog in the case of a pure nematic (without chiral dopant), is also discussed.     

Theory for cholesteric ordering in lyotropic liquid crystals

Summary This paper presents an investigation of the chiral dispersion interaction between macromolecules in the solvent which is considered as a dielectric medium. In particular the results of the molecular statistical theory are reported. The expression for the helical pitch as a function of temperature on the solvent dielectric constant is used to interpret the experimental data. Moreover, the effect of the solvent chirality on the cholesteric ordering in polymer liquid crystals is considered. Finally the cholesteric ordering in the solution of chiral micelles is discussed. Work presented at the First USSR-Italy Bilateral Meeting on Liquid Crystals held in Portonovo, Ancona (Italy), September 30–October 2, 1987.     

胆甾相液晶激光器的调谐特性研究

基于胆甾相液晶螺距及折射率随温度与电场变化的特性, 研究了温度与电场对液晶染料可调谐激光器发射特性的影响. 首先探讨了手性剂浓度、温度与液晶螺距的关系, 制作了液晶染料可调谐激光器, 在温度23–35℃变化时, 其发射波长调谐范围为618.90–594.76 nm, 达到24.14 nm, 在电压0–9 V 变化时, 其发射波长调谐范围为617.40–608.11 nm, 共9.29 nm. 关键词： 可调谐激光器 胆甾相液晶 激光染料     

Transformation of cholesteric orientational structures and optical textures induced by the electric field–driven ionic modification of surface anchoring

The reorientation of a cholesteric liquid crystal with a large helical pitch induced by the electric field–driven modification of surface anchoring is investigated. In the initial state, the liquid crystal cell has a homeotropic alignment of the director. An applied dc electric field produced a twisted homeoplanar structure of the cholesteric.     

Zigzag instability of a χ disclination line in a cholesteric liquid crystal

We studied the formation of χ disclination lines in planar cholesteric samples placed in a temperature gradient near the cholesteric to smectic A phase transition. We observed that the first simple line which forms close to the smectic-cholesteric front zigzags when it is perpendicular to the direction of planar anchoring and is straight for other orientations. This instability is similar to Herring instability for crystalline surfaces. We show numerically that it originates from a strong increase of the elastic anisotropy close to the transition. In addition, we propose a new method to measure the pitch divergence at the smectic to cholesteric phase transition.     

The intrinsic pitch of cholesteryl nonanoate

The cholesteric pitch of mixtures of cholesteryl nonanoate and cholesteryl chloride has been measured as a function of temperature and concentration. The results are extrapolated to yield the intrinsic pitch of pure cholester nonanoate and its temperature coefficient. It is argued that this knowledge of the intrinsic pitch is important in analyzing the pitch divergence near the smectic-A transition.     

High resolution off-magic-angle spinning NMR for cholesteric liquid crystals

High resolution NMR of cholesteric liquid crystals is realized by off-magic-angle spinning (OMAS). Using the average potential theory, it is shown that the pitch axes of a cholesteric liquid crystal with a positive (negative) magnetic susceptibility anisotropy are aligned along the spinning axis with an OMAS angle larger (smaller) than the magic angle without any distortion of the helical structure, which is untwisted or distorted by the static magnetic field in some static samples. Hence, the line broadening due to the anisotropies of chemical shifts and/or quadrupole couplings is removed, while information of the anisotropies in cholesteric alignments can be obtained from the line positions. A detailed theoretical analysis of effects of spinning frequency and molecular diffusion along the pitch axis on the linewidth is given, predicting that the resolution is improved greatly at a spinning frequency much higher than the rotational diffusion coefficient. These theoretical results are verified by ¹³C OMAS experiments on a cholesteric liquid crystal of p-ethoxybenzyl-p-[(S)-2- methylbutyl]aniline (EBMBA) and cholesteric mixtures of p-methoxybenzylidene-p-n-butylaniline (MBBA) and cholesteryl chloride (CC).     

Steady low shear rate cholesteric flow normal to the helical axis

Steady cholesteric flow at low shear rate normal to the helical axis is studied analytically for shear flow and plane Poiseuille flow on the basis of Leslie’s continuum theory. For general asymmetric solutions the angle made by the director at the sample centre with the primary flow is found to profoundly affect the oscillations of the apparent viscosity with pitch for pitches of the order of the sample thickness. The velocity and orientation profiles are also found to change drastically. These considerations may be important in flow experiments on long pitch cholesterics.     

Twist in chiral interaction between biological helices

Using an exact solution for the pair interaction potential, we show that long, rigid, chiral molecules with helical surface charge patterns have a preferential interaxial angle approximately sqrt[RH]/L, where L is the length of the molecules, R is the closest distance between their axes, and H is the helical pitch. Estimates based on this formula suggest a solution for the puzzle of small interaxial angles in alpha-helix bundles and in cholesteric phases of DNA.     

Development of helical cholesteric structure in a nematic liquid crystal due to the dipole-dipole interaction

A nematic liquid crystalline phase is considered whose rod-like non-centrosymmetric molecules possess a permanent dipole moment. This phase is a “liquid ferroelectric” if all the molecules are oriented along the same “preferred” direction. It is shown that a liquid ferroelectric can not exist in a homogeneous nematic state. It is transformed into a more stable helical structure (the vector of the spontaneous polarization of such a structure rotates aroung the helical axis). There is a variety of domain structures for the specific case when the anisotropy coefficient of the polarization is equal to zero. Since each elementary dipole moment is rigidly bound to its molecule, the “preferred” alignment direction of the rod-like molecules as well as the polarization vector rotates with respect to the same axis in a helical manner. Therefore a nematic phase with a nonzero spontaneous polarization has a cholesteric structure. Its helical pitch is determined by the geometric size of the sample, the absolute value of the spontaneous polarization, and the elastic moduli. Apparently, we can consider some cholesteric phases to be liquid ferroelectrics with helical domain structure.     

Chiral nematic phase of suspensions of rodlike viruses: left-handed phase helicity from a right-handed molecular helix

We report a study on charged, filamentous virus called M13, whose suspensions in water exhibit a chiral nematic (cholesteric) phase. In spite of the right-handed helicity of the virus, a left-handed phase helicity is found, with a cholesteric pitch which increases with temperature and ionic strength. Several sources of chirality can be devised in the system, ranging from the subnanometer to the micrometer length scale. Here an explanation is proposed for the microscopic origin of the cholesteric organization, which arises from the helical arrangement of coat proteins on the virus surface. The phase organization is explained as the result of the competition between contributions of opposite handedness, deriving from best packing of viral particles and electrostatic interparticle repulsions. This hypothesis is supported by calculations based on a coarse-grained representation of the virus.     

Study on optical characterization of TGB and reentrant smectic-A phases in binary mixture of two liquid crystals

In this work, our investigation is to study the optical and thermal properties of the binary mixture of cholesteric and nematic compounds, namely, cholesteryl nonanoate and p-methoxybenzylidene-p-ethylaniline, which exhibits a very interesting liquid crystalline twisted grain boundary (TGB) phase and reentrant smectic-A phase. The chiral liquid crystalline TGB phases and reentrant smectic-A phases have been observed at different concentrations and at different temperatures. The existence of TGB and reentrant smectic-A phases is confirmed by differential scanning calorimetry and optical microscopic studies. The variation of optical anisotropy has been discussed. The helical pitch of the cholesteric phase has also been discussed.     

Cholesteric pitch of cholesteryl decanoate near the smectic-a transition

The temperature dependence of the cholesteric pitch in cholesteryl decanoate has been measured near the smectic-A transition. The data show a power-law divergence with a critical exponent v = 0.67 ± 0.03, in agreement with previous results in cholesteryl nonanoate.     

A simple molecular statistical treatment of a model for cholesterics

The cholesteric state is discussed in terms of a model consisting of the Maier-Saupe and a twist interaction. The model can be easily solved in the mean field approximation. In the practical case of a large pitch analytical expressions are obtained for relevant quantities like the order parameters and the free energy. Then it appears that the pitch is temperature independent, which is a general result, and does not influence the discontinuity of the main (nematic) order parameter at the isotropic-cholesteric transition. Interactions giving rise to a temperature-dependent pitch are discussed briefly.     

Reflection spectrum of a cholesteric liquid crystal with structural defects

An expression is obtained for the reflection coefficient of circularly polarized light normally incident on the film of a cholesteric liquid crystal with a variable helix pitch. It is shown that, in the case of a single defect (local change in the helix pitch), the spectrum of light reflection from a cholesteric acquires a dip corresponding to the defect mode. New qualitative features appear in the reflection spectrum of a cholesteric with two defects as the distance between them varies.     

Group theory and experiments on helical and linear distributed feedback gas lasers

This study puts forward the concept of helical distributed feedback (DFB) lasers. The basic features of this new type of laser are derived by group theoretical considerations on cylindrical, circular linear periodic, and helical waveguide and laser structures. It is demonstrated that not only linear periodic structures but also helical structures show Bragg and DFB effects. Microwave and far-infrared experiments on passive helical metal waveguides reveal Bragg resonances in transmission. These results initiated the first experimental realization of a helical DFB gas laser, i.e. an optically pumped 496m CH₃F laser with a helical metal waveguide of a pitch close to 250m. This helical DFB laser shows higher-mode selectivity than the corresponding linear DFB laser. Finally, we show that the concept of helical DFB also applies to dye lasers with internal DFB incorporated by a mixture of the dye with a cholesteric liquid crystal.On leave from the Polish Academy of Sciences, Gdansk, Poland