Synthesis and Properties of High Tilted Antiferroelectric Esters with Partially Fluorinated Alkoxyalkoxy Terminal Chains

Novel chiral esters with partially fluorinated alkoxyalkoxy terminal chains are described. Their phase transition temperatures, enthalpies, and electrooptical properties are reported. A helical pitch in pure compounds and their mixtures based on selective reflection of light is also characterized

Switching dynamics of surface stabilized ferroelectric liquid crystal cells: effects of anchoring energy asymmetry

We study both theoretically and experimentally switching dynamics in surface stabilized ferroelectric liquid crystal cells with asymmetric boundary conditions. In these cells the bounding surfaces are treated differently to produce asymmetry in their anchoring properties. Our electro-optic measurements of the switching voltage thresholds that are determined by the peaks of the reversal polarization current reveal the frequency dependent shift of the hysteresis loop. We examine the predictions of the uniform dynamical model with the anchoring energy taken into account. It is found that the asymmetry effects are dominated by the polar contribution to the anchoring energy. Frequency dependence of the voltage thresholds is studied by analyzing the properties of time-periodic solutions to the dynamical equation (cycles). For this purpose, we apply the method that uses the parameterized half-period mappings for the approximate model and relate the cycles to the fixed points of the composition of two half-period mappings. The cycles are found to be unstable and can only be formed when the driving frequency is lower than its critical value. The polar anchoring parameter is estimated by making a comparison between the results of modelling and the experimental data for the shift vs frequency curve. For a double-well potential considered as a deformation of the Rapini-Papoular potential, the branch of stable cycles emerges in the low frequency region separated by the gap from the high frequency interval for unstable cycles.Comment: 35 pages, 15 figure

Induced Anticlinic Ordering and Nanophase Segregation of Bow-Shaped Molecules in a Smectic Solvent

Recent experiments indicate that doping low concentrations of bent-core molecules into calamitic smectic solvents can induce anticlinic and biaxial smectic phases. We have carried out Monte Carlo (MC) simulations of mixtures of rodlike molecules (hard spherocylinders with length/breadth ratio $L_{\rm rod}/D = 5$) and bow- or banana-shaped molecules (hard spherocylinder dimers with length/breadth ratio $L_{ban}/D = 5$ or 2.5 and opening angle $\psi$) to probe the molecular-scale organization and phase behavior of rod/banana mixtures. We find that a low concentration (3%) of $L_{ban}/D = 5$ dimers induces anticlinic (SmC$_A$) ordering in an untilted smectic (SmA) phase for $100^\circ \le \psi < 150^\circ$. For smaller $\psi$, half of each bow-shaped molecule is nanophase segregated between smectic layers, and the smectic layers are untilted. For $L_{ban}/D = 2.5$, no tilted phases are induced. However, with decreasing $\psi$ we observe a sharp transition from {\sl intralamellar} nanophase segregation (bow-shaped molecules segregated within smectic layers) to {\sl interlamellar} nanophase segregation (bow-shaped molecules concentrated between smectic layers) near $\psi = 130^\circ$. These results demonstrate that purely entropic effects can lead to surprisingly complex behavior in rod/banana mixtures.Comment: 5 pages Revtex, 7 postscript figure

Fractionation of cellulose nanocrystals : enhancing liquid crystal ordering without promoting gelation

Colloids of electrically charged nanorods can spontaneously develop a fluid yet ordered liquid crystal phase, but this ordering competes with a tendency to form a gel of percolating rods. The threshold for ordering is reduced by increasing the rod aspect ratio, but the percolation threshold is also reduced with this change; hence, prediction of the outcome is nontrivial. Here, we show that by establishing the phase behavior of suspensions of cellulose nanocrystals (CNCs) fractionated according to length, an increased aspect ratio can strongly favor liquid crystallinity without necessarily influencing gelation. Gelation is instead triggered by increasing the counterion concentration until the CNCs lose colloidal stability, triggering linear aggregation, which promotes percolation regardless of the original rod aspect ratio. Our results shine new light on the competition between liquid crystal formation and gelation in nanoparticle suspensions and provide a path for enhanced control of CNC self-organization for applications in photonic crystal paper or advanced composites

Effect of Ischaemia-Reperfusion on Rabbit Kidney and Human Brain

Free radicals are produced in various organs at ischaemia-reperfusion. The final stage in radical damage is lipid peroxidation. We have demonstrated previously that a lipid-soluble antioxidant improves restoration of bioenergetics in rabbit kidneys after ischaemia, as reflected in 31P spectrometry. Radical production in the brain during surgery for carotid artery stenosis can be measured using an ex vivo spin trap method. Aims of the present study: 1. To examine whether pretreatment with a combination of a lipidsoluble and a water-soluble antioxidant causes improved restoration of bioenergetics in rabbit kidneys after ischaemia compared to single treatment with a lipid soluble antioxidant. 2. To examine whether pretreatment with allopurinol or acetylcysteine influences radical production in conjunction with surgery for carotid artery stenosis. 3. To study the relationship between various markers for arteriosclerosis and the production of free radicals in conjunction with surgery for carotid artery stenosis. Methods: New Zealand white rabbits were used for the NMR experiments. Volume-selective 31P spectrometry was used to determine changes in bioenergetics during and after ischaemia following various pretreatments. An ex vivo spin trap method was used to measure radical production in the brain during carotid endarterectomy in control patients as well as patients pretreated with allopurinol or acetylcysteine. ICAM-1, MCP-9, MMP-1 and oxLDL serum levels were determined in the control patients. Results: Pretreatment with a combination of a lipid-soluble and a water-soluble antioxidant resulted in improved restoration in cell bioenergetics after ischaemia compared to single treatment with a lipid-soluble antioxidant. Production of radicals can be measured reproducibly using the ex vivo spin trap method. Pretreatment with allopurinol eliminated the strong correlation between e.g. degree of stenosis and leucocyte counts and radical production, which might indicate a beneficial effect of pretreatment with a xanthine oxidase inhibitor. Pretreatment with acetylcysteine on the other hand appeared to increase radical production. High levels of MMP-1 and low levels of ICAM-1 were associated with high radical production. Conclusion: A combination of a lipid-soluble and a water-soluble antioxidant is most effective in improving cell bioenergetics after ischaemia in rabbit kidneys. Allopurinol appears to have a beneficial effect in conjunction with carotid endarterectomy while acetylcysteine appears to increase radical production. MMP-1 is associated with increased radical production

Tilt plane orientation in antiferroelectric liquid crystal cells and the origin of the pretransitional effect

The optic, electro-optic, and dielectric properties of antiferroelectric liquid crystals AFLCs are analyzed and discussed in terms of the local tilt plane orientation. We show that the so-called pretransitional effect is a combination of two different electro-optic modes: the field-induced antiphase distortion of the antiferroelectric structure and the field-induced reorientation of the tilt plane. In the presence of a helix, the latter corresponds to a field-induced distortion of the helix. Both electro-optic modes are active only when the electric field has a component along the tilt plane. Thus, by assuring a horizontal surface-stabilized condition, where the helix is unwound by surface action and the tilt plane is everywhere parallel to the cell plates, the pretransitional effect should be suppressed. We also discuss the dielectrically active modes in AFLCs and under which circum- stances they contribute to the measured dielectric permittivity

Electrolyte effects on the nematic-isotropic phase transition in lyotropic liquid crystals

A phenomenological approach to the description of the electrolyte effect on the nematic– isotropic phase transition in lyotropic liquid crystals is proposed. The influence of the electrolyte is discussed by varying the coupling between the concentration variables and the orientational order parameter. The analysis shows that the discontinuity in the first order nematic–isotropic phase transition as measured by TNI{T0 increases as a function of the NI weight fraction of the electrolyte. Here TNI is the first order nematic–isotropic phase transition temperature and TN0I is the extrapolated supercooling limit. The electrolyte dependence of the Cotton–Mouton coefficient and the non-linear dielectric effect in the isotropic phase above the nematic–isotropic phase transition are calculated. The theoretical predictions are found to be in good agreement with experimental results