Liquid crystals cholesteric mesophase

Liquid crystals represent a transition between solid crystalline substances and isotropic liquids. On heating, mesophases are formed that have ordered structures which can be nematic, smectic or cholesteric. On further heating, the orientation is disturbed and the phases are converted into an isotropic liquid. The long structure of liquid crystals causes isomers with more drawn-out shapes to be readily dissolved in the ordered liquid crystal substrate ( mesophase ) thus yielding stronger sor-bat-sorbent interactions,... 

Rod-like liquid crystals [1] have been known for more than a hundred years, the first one, cholesteryl benzoate, being discovered in 1888 by Reinitzer. In materials of this type, nematic N, cholesteric N and different lamellar mesophases such as SmA, SmC, SmF, and SmI are obtained. Beside these classical liquid crystals, thermotropic mesophases - consisting of two-dimensional aromatic flat molecules - that exhibit various columnar phases (e.g., Col, Coif, Colob) have been known since 1977 [2, 3], In these two types of systems, the lamellar and columnar phases are observed separately. So, it was interesting to examine the mesomorphic properties of the hybrid molecules, i.e., molecules with a long rodlike rigid core ending in two half-disc moieties (Fig. 1). In fact, the phasmids [4,5] fill... 

Some liquid crystals exhibit mesophases between the isotropic phase and the chiral nematic (or cholesteric) phase. There may be up to three different spatial structures in a temperature interval as small as 1 K. These phases are optically not birefringent and they reflect preferentially short wavelengths that is why they are called blue phases. ... 

Reinitzer discovered liquid crystallinity in 1888 the so-called fourth state of matter.4 Liquid crystalline molecules combine the properties of mobility of liquids and orientational order of crystals. This phenomenon results from the anisotropy in the molecules from which the liquid crystals are built. Different factors may govern this anisotropy, for example, the presence of polar and apolar parts in the molecule, the fact that it contains flexible and rigid parts, or often a combination of both. Liquid crystals may be thermotropic, being a state of matter in between the solid and the liquid phase, or they may be lyotropic, that is, ordering induced by the solvent. In the latter case the solvent usually solvates a certain part of the molecule while the other part of the molecule helps induce aggregation, leading to mesoscopic assemblies. The first thermotropic mesophase discovered was a chiral nematic or cholesteric phase (N )4 named after the fact that it was observed in a cholesterol derivative. In hindsight, one can conclude that this was not the simplest mesophase possible. In fact, this mesophase is chiral, since the molecules are ordered in... 

Thermotropic cholesterics were officially discovered2 in 1888 by the Austrian botanist Friederich Reinitzer, while studying the melting of cholesterol esters cholesteryl benzoate first melted to give a cloudy liquid that, at higher temperature, turned into an ordinary clear liquid. The cloudy liquid (the mesophase) was a thermotropic cholesteric liquid crystal. These phases... 

Discotic liquid crystals arise from disk-shaped molecules as nematic or cholesteric mesophases. Their structural characteristics are similar to the respective ealamitie mesophases, that is, the normals of the disks are oriented parallel. Instead of the smectic mesophases, diseotie columnar liquid crystals arise from eonnecting the disks to each other. The columns of the discotic columnar mesophase form a two-dimensional lattice whieh is in a hexagonal or rectangular modification. In addition, the columns may be tilted (Fig. 2f,g). 

Solvent viscosity vs, concentration plots for cellulose dissolved in TFA-CH2CI2 (70/30, v/v) do not exhibit a maximum (1I,S1) in contrast to the typicid behavior of polymer liquid crystal solutions. This same behavior is exhibited by other cellulose-solvent systems (52,fiQ). Conio et al. (59) si gest that due to the close proximity of the cholesteric mesophase to its solubility limit, it is only observed in a metastable condition. 

Price and Wendorff31 > and Jabarin and Stein 32) analyzed the solidification of cholesteryl myristate. Under equilibrium conditions it changes at 357.2 K from the isotropic to the cholesteric mesophase and at 352.9 K to the smectic mesophase (see Sect. 5.1.1). At 346.8 K the smectic liquid crystal crystallized to the fully ordered crystal. Dilatometry resulted in Avrami exponents of 2, 2, and 4 for the respective transitions. The cholesteric liquid crystal has a second transition right after the relatively quick formation of a turbid homeotropic state from the isotropic melt. It aggregates without volume change to a spherulitic texture. This process was studied by microscopy32) between 343 and 355.2 K and revealed another nucleation controlled process with an Avrami exponent of 3. 

The main feature identifying a cholesteric mesophase in polymers is the presence of optical texture with selective circularly-polarized light reflection. This indicates the formation of 1-helical cholesteric structure in LC copolymers. The X-ray patterns of actually all cholesteric copolymers described (with the exclusion of polymers 3.1 and 4.1, Table 13) correspond to those of nematic and cholesteric low-molecular liquid crystals, which is manifested in a single diffuse reflex at wide scattering angles. At the same time, for copolymers 3.1 and 4.1 (Table 13) small angle reflexes were observed 123), that are usually missing in low-molecular cholesterics. 

The role of supramolecular chemistry in materials is perhaps expressed most impressively in liquid crystals, in which slight variations of chiral content can lead to dramatic influences in the properties of the mesophases. The helical sense of these mesophases is determined not only by intrinsically chiral mesogens but also by the use of dopants which more often than not interact with achiral host LCs to generate chiral phases (Fig. 7). These phenomena are important both scientifically and technologically, most notably for the chiral smectic and cholesteric liquid crystal phases [68-71]. These materials—as small molecules and as polymers [72,73]—are useful because their order... 

The liquid crystal melt, which comes into being at the glass-rubber transition or at the crystal-melt transition, may have several phase states (Mesophases) one or more smectic melt phases, a nematic phase and sometimes a chiral or cholesteric phase the final phase will be the isotropic liquid phase, if no previous decomposition takes place. All mesophase transitions are thermodynamically real first order effects, in contradistinction to the glass-rubber transition. A schematic representation of some characteristic liquid crystal phase structures is shown in Fig. 6.13, where also so-called columnar phases formed from disclike molecules is given. 

Cholesteric liquid crystals are optically active nematic phases as a result of their gradual twist in orientational alignment. Therefore, cholesteric liquid-crystalline solvents are expected to induce enantioselectivity in chemical reactions see reference [713] for a review on photoasymmetric induction by chiral mesophases. The existing results are not very promising. So far, the maximum photoasymmetric induction reported has... 

There is as yet no clear-cut relationship between the molecular structure of the mesogenic..unit and the type of mesophase it forms, but several generalizations can be made. Gray and Winsor have divided these factors into how the molecular structure (1) is conducive to liquid crystal formation, (2) affects the thermal stability of the mesophase, and (3) favors the occurrence of smectic versus nematic or cholesteric liquid crystals. 

It is also known that in side-chain LC polymers the copolymerization of optically active monomers with mesogenic monomers, in the same manner as the mixing of optically active compounds with nematic low molecular weight compounds, can induce the formation of a cholesteric mesophase. Therefore, it is expected that inclusion of chiral spacers in main chain liquid crystal polymers, which would be nematic... 

Discotic liquid crystals arise from disc-shaped molecules as nematic or cholesteric mesophases. Their structural characteristics are similar to that of their respective calamitic mesophases, that is, the normals... 

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