Cholesteric phases temperatures

Several 4-(3-alkyl-2-isoxazolin-5-yl)phenol derivatives that possess liquid crystal properties have also been obtained (533-535). In particular, target compounds such as 463 (R = pentyl, nonyl) have been prepared by the reaction of 4-acetoxystyrene with the nitrile oxide derived from hexanal oxime, followed by alkaline hydrolysis of the acetate and esterification (535). A homologous series of 3-[4-alkyloxyphenyl]-5-[3,4-methylenedioxybenzyl]-2-isoxazolines, having chiral properties has been synthesized by the reaction of nitrile oxides, from the dehydrogenation of 4-alkyloxybenzaldoximes. These compounds exhibit cholesteric phase or chiral nematic phase (N ), smectic A (S4), and chiral smectic phases (Sc ), some at or just above room temperature (536). 

Thermotropic cholesterics have several practical applications, some of which are very widespread. Most of the liquid crystal displays produced use either the twisted nematic (see Figure 7.3) or the supertwisted nematic electrooptical effects.6 The liquid crystal materials used in these cells contain a chiral component (effectively a cholesteric phase) which determines the twisting direction. Cholesteric LCs can also be used for storage displays utilizing the dynamic scattering mode.7 Short-pitch cholesterics with temperature-dependent selective reflection in the visible region show different colors at different temperatures and are used for popular digital thermometers.8... 

Before attempting to develop any theory correlating molecular to cholesteric handedness, one must be completely sure of the experimental data. A cholesteric phase is fully described by its handedness and pitch, and often also knowledge of the pitch variations with temperature is fundamental. In particular, the determination of the handedness is quite a delicate matter. Before discussing the methods currently used to determine handedness and pitch, the principal textures of the cholesteric phase must be briefly reviewed The planar or Grandjean textures are obtained in thin cells by rubbing the cell walls (with... 

Sq and negative Hq (Figure 7.12), so the handedness of the polymers are correlated to those of the cholesteric phases and the apparent discrepancy depends only on the comparison of the two results at a single temperature. Also in these cases the most common model of Figure 1.9a seems to be followed.46 It should be remarked that in all these cases, Hq and Sq have opposite signs.41... 

The CD reflection spectra are quite sharp at all temperatures, and the reflection wavelength, corresponding to the optical pitch of the TChLC phase, increased progressively with temperature from 500 nm at 70 °C to 1,000 nm at 140 °C. It was considered that the positive sign of the CD reflection band indicated M screw sense helicity of the cholesteric phase. Very recently, a smectic A-cholesteric phase transition was also observed for PDMBS.348... 

Figure 54 (a) CD reflection bands of PDMBS cholesteric phases at various temperatures (cooling run) and (b) UV and CD absorption spectra at 80°C.346 Reprinted with permission from Watanabe, J. Kamee, H. Fujiki, M. Polymer J. 2001,33, 495-497, 2001 Society of Polymer Science Japan. 

Navard and Haudin studied the thermal behavior of HPC mesophases (87.88) as did Werbowyj and Gray (2), Seurin et al. (Sp and, as noted above, Conio et al. (43). In summary, HjPC in H2O exhibits a unique phase behavior characterized by reversible transitions at constant temperatures above 40 C and at constant compositions when the HPC concentration is above ca. 40%. A definitive paper has been recently published by Fortin and Charlet ( who studied the phase-separation temperatures for aqueous solutions of HPC using carefully fractionated HPC samples. They showed the polymer-solvent interaction differs in tiie cholesteric phase (ordered molecular arrangement) from that in the isotropic phase (random molecular arrangement). 

The macromolecular nature provides an interesting feature of LC polymeric cholesterics, namely the possibility of obtaining monochromic films. Thus for polymeric liquid crystals the helix pitch is practically not altered with temperature below Tg, when a cholesteric phase is frozen in a glassy matrix (Fig. 23a). This implies that fast cooling of polymeric films from a mesomorphic state (shown with arrows) fixes their optical properties, which makes it possible to use them at ordinary temperatures as selective monochromic reflectors. On the other hand, such polymeric films display the extraordinary polarizing properties of cholesterics, i.e. the different absorption... 

By addition of each of several diesters of isosorbide, isomannide, and isoidide to a nematic phase, cholesteric phases can be produced. All compounds exhibit a large twisting power. In the cholesteric phase, helix inversion, large or small temperature-dependencies of the pitch, and broad blue phases were achieved.183... 

We arrive at this conclusion from the lack of more than a slight atropisomeric excess (ca. 0.1% in all but one anomalous experiment) after equilibration of racemic BN in the cholesteric phases at several temperatures (TablelV). The lack of change in the ratio of atropisomers in the cholesteric phases is consistent with our observation that liquid-crystal induced circular dichroism spectra (67) of ISN in cholesteric mixture D are due to a macroscopic property of the solvent the LCICD spectra disappear when mixture D is heated to an isotropic temperature. 

The following table lists the liquid crystalline materials that are useful as gas chromatographic stationary phases in both packed and open tubular column applications. In each case, the name, structure, and transition temperatures are provided (where available), along with a description of the separations that have been done using these materials. The table has been divided into two sections. The first section contains information on phases that have either smectic or nematic phases or both, while the second section contains mesogens that have a cholesteric phase. It should be noted that each material may be used for separations other than those listed, but the listing contains the applications reported in the literature. 

It is possible to conceive of situations where the chemical linking of molecular components around a template is not as crucial as the formation of defined, non-covalent interactions during templating. This may be exemplified by the polymerisation of a nematic liquid crystalline crosslinker in the presence of a template, a non-polymerisable cholesteric mesogen [23]. The chiral dopant forces the crosslinker to form a cholesteric phase. After polymerisation of the crosslinker, the polymer still exhibits a helicoidal structure which is stable over a wider temperature range than the initial cholesteric phase. It is not reported in this work whether extraction of the chiral mesogen has been attempted or not. 

A similar thermally-induced inversion of the cholesteric sense was observed for the PBLG liquid crystal in benzyl alcohol. In this solution, a gel-like opaque phase coexists with the cholesteric phase at lower temperatures. The opaque phase disappears around 70 °C, where endothermic peaks are observed in the differential scanning calorimetry curve. The value of S below 70 °C remains constant, and then changes with temperature above 70 °C. The compensation occurs at about 103 °C, and the transition from biphasic phase to the isotropic phase is observed above 150 °C in this case. The results are summarized in Fig. 12, where the reciprocal of the half-pitch is plotted against temperature. The sign of 1/S is taken as positive when the cholesteric sense is the right-handed. 

Unfortunately, there is no report on the detailed physical characterization of these polymers. Such information as unidirectional twist angle and form optical rotation, as well as their dependence on chemical structures and temperature, can be very useful in further understanding the molecular orientations of the polymers in the cholesteric phase. In contrast, a number of studies have been made on the physical-chemical properties of cholesteric lyotropic polymer systems, especially polypeptides. 

Hgure 4.33 Representation of the local structure of some chiral mesophases on heating. The matches describe the relative orientations of chiral molecules in space. As the temperature is raised, the system transforms from a crystalline phase (left) to a cholesteric phase (centre) characterised by a single twist, to a double-twist blue" phase (right). 

Similar irradiation in the isotropic phase of CN/CC1 produces racemic hexahelicene. Studying the same system, but varying the pitch of the cholesteric phase with temperature. 

Temperature dependent steady state fluorescence spectra were recorded in the crystalline, cholesteric, and isotropic phases. Based upon relative emission intensities, excimer formation was most efficient in the cholesteric phase. Furthermore, plots of Ig/ M 1/T, from which Arrhenius activation energies could be extracted, were of dramatically... 

Subsequently, the kinetics of intramolecular pyrenyl excimer formation were examined in CH for a series of PnP which includes polymet - lene chains much longer than that of P3P (i.e., n-3, 5, 6, /, " 10, 11, 12, 13, 22). The dynamic behavior of these compo in normal isotropic solvents of low viscosity is known to be Vm j complex(45). However, in both the isotropic and cholesteric phases of CH, all of the temporal emission data for the PnP could be accommodated by Scheme 2. The pyrenyl decay waveforms were monoexponential and the excimer waveforms could be expressed as the difference between two exponentials (representing the growth and decay of excimer emission). Temperature dependent ki+k2 values for P3P were obtained as before from Z the ki+k2 for the other PnP were taken from experiments with 1-dodecyIpyrene (DP). 

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