Invited Lecture. Helical twisting in cholesteric mesophases: Molecular structure and microscopic description

Recent studies of cholesteric systems are briefly reviewed, with special attention paid to the relationship between the molecular structure of the optically active molecules and the helical twisting features. Microscopic models are presented which provide an account of specific intermolecular interactions, conformational equilibria, etc. Mechanisms of dopant-induced helix distortions are discussed based on N.M.R. studies. The use of cholesteric systems as solvents for selective reflection spectroscopy is considered.     

Anomalous optical properties of photoactive cholesteric liquid crystal doped with single-walled carbon nanotubes

Optical transmission and selective reflection data are reported for suspensions of single-walled carbon nanotubes (CNTs) in photoactive nematic material ZhK-440 with a mesogenic chiral dopant M5. At small concentrations of CNTs (C ≈ 0.01–0.05%), the preferential localisation of CNTs at oily sticks (cholesteric topological defects) and suppression of the network of oily streaks by CNTs were observed. At the same time, the optical density D was shown to be essentially non-linear and a minimum at certain concentration of CNTs, C ≈ 0.05–0.08%, was observed. This anomalous behaviour was explained by the presence of the structural transition from the loose (ramified) aggregates with highly anisotropic shape (oriented along the anchoring direction on rubbed polyvinyl alcohol) to the compact aggregates with denser packing. The location of this minimum, as well as the selective reflection maximum (helical pitch), was sensitive to partially reversible UV-induced trans–cis–trans isomerisation effects. The UV-controlled helical pitch variation was shown to be only slightly affected by introduction of CNTs.     

Anomalous selective reflection in cholesteryl oleyl carbonate – nematic 5CB mixtures and effects of their doping by single-walled carbon nanotubes

Liquid crystalline (LC) mixtures of cholesteryl oleyl carbonate (COC) and 4-pentyl-4'-cyanobiphenyl (5CB) as well as dispersions of single-walled carbon nanotubes (NTs) in these mixtures were studied by means of selective reflection measurements, differential scanning calorimetry (DSC) and optical microscopy. The relative mass of COC in a mixture X was varied between 0.4 and 1.0, the temperature range of measurements was between 284 and 314 K, and concentration of NTs was fixed at 0.1%. Two important anomalies were noted: (1) the cholesteric to smectic-A transition temperature increased on dilution of COC by non-smectogenic 5CB in the concentration range 0.8 < X < 1 and (2) the reciprocal pitch versus 5CB concentration dependence was essentially linear, in contrast to behaviour commonly observed in nematic-cholesteric mixtures. A model of molecular arrangement in the mixtures, accounting for the possibility of integration of 5CB dimers and monomers between COC molecules and presumably explaining the experimental data, was proposed. The helical pitch of the cholesteric mixtures remained practically unchanged upon doping by NTs, and only slight widening of the selective reflection peaks was noted. The obtained results allow considering the COC + 5CB mixtures as promising matrices for composite materials on the basis of liquid crystals and NTs.     

A TEM and XRD study of the SbNbSe3 misfit layer structures

Two new misfit layer structures have been synthesized within the Sb-Nb-Se system. Powder X-ray diffraction and electron microscopy techniques (electron diffraction, HREM, XEDS) have been used to determine the nature of their structure. According to TEM and XEDS data (for more than 15 crystals studied) both phases are monolayer type, i.e. (SbSe)1+delta (NbSe2). Electron microscopy reveals a composite modulated structure that consists of the periodical intergrowth of a pseudotetragonal SbSe layer, denominated as Q, and a pseudohexagonal layer NbSe2, denominated as H. Both layers fit along b, stack along c and do not fit along a (misfit) giving rise to an incommensurate modulation along this direction. The two phases differ in the symmetry of the Q layers being in one case orthorhombic (for delta = 0.17) and monoclinic in the other (for delta = 0.19). After the characterization of the sample by electron microscopy the unit cells of the basic layers could be refined for both phases by powder X-ray diffraction: aQ = 5.824(2) A, bQ = 5.962(5) A, cQ = 23.927(6) A, alpha = 90 degrees, beta = 90 degrees and gamma = 90 degrees and aH = 3.415(5) A, bH = 5.962(6) A,, cH = 11.962(1) A, alpha = 90 degrees, beta = 90 degrees and gamma = 90 degrees for the orthorhombic phase; aQ = 5.844(2) A, bQ = 5.981(1) A, cQ = 23.919(5) A, alpha = 90 degrees, beta = 90 degrees and gamma = 96.00(3)degrees and aH = 3.439(1) A, bH = 5.994(2) A, cH = 11.956(3) A, alpha = 90 degrees, beta = 90 degrees and gamma = 90 degrees for the monoclinic phase. The phase with the monoclinic Q-sublattice often appears as twinned crystals. The more abundant crystals are disordered intergrowths of both monolayer phases.     

Aggregation of Anthraquinone Dye Molecules in a Nematic Liquid Crystal

We report an experimental evidence that molecules of anthraquinone dye aggregate in an anisotropic solvent, a nematic liquid crystal (NLC). We observe strong nonlinear dependencies of the dielectric permittivity and anisotropy of light absorption on the dye concentration c. Moreover, the data suggest that the aggregates are linear, but, in contrast to the isotropic case, their formation in a NLC undergoes two different concentration regimes with a well pronounced crossover. These effects are explained by the interplay between the aggregates’ lengths and their orientational ordering due to the interaction with the nematic director.     

Studies of phase transformations in the gelatine-water system using near-IR spectroscopy

Near-IR spectroscopy studies of gel formation mechanism are reported for gelatin-water systems. Relative absorbance in 1.4-μm and 1.9-μm bands was shown to be sensitive to the helix to coil phase transition in the pre-melting region. The formation mechanism of a metastable “coil” phase is in agreement with DSC and TGA data obtained in parallel experiments on the 10% gelatin gel. Received: 12 April 2000 Accepted: 4 October 2000     

Cooperative domains in lipid membranes

Journal of Thermal Analysis and Calorimetry - Phase transitions of multibilayer structures of hydrated L-α-dipalmitoyl- and L-α-dimyristoylphosphatidylcholine (DPPC and DMPC) were studied...     

Cholesteric liquid Crystals: Physical Properties and Molecular-Statistical Theories

It seems certain now that cholesteric liquid crystals (cholesterics, or CLC, for short) have been the first examples of mesomorphic state of matter known to humankind. Apart from the well-known discovery of the two-stage melting of cholesteryl benzoate made by Reinitzer in 1888¹ and cited in almost all the textbooks, one may recall some other papers where the authors, quite unaware of the real significance of their observations, presented undeniable evidence of the liquid crystalline state of matter. E.g., Professor Planer from the Lvov University as early as in 1861 did observe, putting it in the presentday terms, selective reflection from the planar texture of cholesteryl chloride forming a monotropic cholesteric mesophase on cooling.² One should also note that the works of Fergason^3,4 outlining the prospects of practical applications for CLC, did, in fact, precede similar endeavors by Heilmeier in the field of nematics. From the viewpoint of organic chemistry, a number of mesogenic cholesterol derivatives had been already synthesized and thoroughly studied⁵ by the time the name of MBBA (p-methoxybenzylidene-p′-n-butylaniline), to say nothing about cyanobiphenyls, was not yet known to anybody. The mere listing of CLC prospective applications^6,7. seems so impressive that, keeping in mind the above-described historical background, one should expect to find cholesterics in a key position in the field of liquid crystal science.