Thermotropic mesophase crystal

The separation of Hquid crystals as the concentration of ceUulose increases above a critical value (30%) is mosdy because of the higher combinatorial entropy of mixing of the conformationaHy extended ceUulosic chains in the ordered phase. The critical concentration depends on solvent and temperature, and has been estimated from the polymer chain conformation using lattice and virial theories of nematic ordering (102—107). The side-chain substituents govern solubiHty, and if sufficiently bulky and flexible can yield a thermotropic mesophase in an accessible temperature range. AcetoxypropylceUulose [96420-45-8], prepared by acetylating HPC, was the first reported thermotropic ceUulosic (108), and numerous other heavily substituted esters and ethers of hydroxyalkyl ceUuloses also form equUibrium chiral nematic phases, even at ambient temperatures. 

The prime requirement for the formation of a thermotropic liquid crystal is an anisotropy in the molecular shape. It is to be expected, therefore, that disc-like molecules as well as rod-like molecules should exhibit liquid crystal behaviour. Indeed this possibility was appreciated many years ago by Vorlander [56] although it was not until relatively recently that the first examples of discotic liquid crystals were reported by Chandrasekhar et al. [57]. It is now recognised that discotic molecules can form a variety of columnar mesophases as well as nematic and chiral nematic phases [58]. 

The mesophases of thermotropic liquid crystals are described as calamitic if the constituent molecules are rod-like and columnar, if the constituent molecules, which often have a disc like shape(discotic), stack into columns. 

The family of primary silver thiolate compounds AgSC H2n+1 ( = 4, 6, 8, 10, 12, 16, or 18), which in the solid state consists of 2x,[AgSR] layers, behaves as thermotropic liquid crystals. On heating, they display successively lamellar (smectic A), cubic, and micellar mesophases.969... 

A preliminary analysis of the features of thermotropic mesophases of flexible polymers we just described, leads us to envisage a path of polymer crystallization different from chain-folded, fold-preserving crystallization in-... 

Experimental Data from Polymer Thermotropic Mesophases and Conformationally Disordered Crystals... 

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... 

To understand how chirality is expressed, it is important to first describe the different thermotropic mesophase assemblies which can be formed by chiral discotics. Even though expression of chirality has been observed in thermotropic mesophases, the chiral expression occurs in a rather uncontrolled manner, and systems which are suitable for applications, for example, easily switchable columns/ferroelectric discotic liquid crystals, consequently have not yet been developed. Hence, the assembly of discotics in solution has received considerable attention. Supramolecular assemblies of discotic molecules in solution are still in their infancy and have not yet found commercial application, but they are of fundamental importance since they allow a detailed and focused investigation of the specific interactions that are required to express chirality at higher levels of organization. As such, the fundamental knowledge acquired from supramolecular assemblies in solution might formulate the design criteria for thermotropic chiral discotic mesophases and provide the necessary tools for the creation of functional systems. 

Thermotropic liquid crystals, 15 86-98 bent-core, 15 98 discotic phases of, 15 96 frustrated phases of, 15 94-96 metallomesogens, 15 97 nematic liquid crystals, 15 86-92 smectic liquid crystals, 15 92-94 Thermotropic mesophases, 20 79 Thermotropic polycarbonates, 19 804 Thermotropic polyesters, liquid-crystalline, 20 34... 

Starting with the crystalline state, the mesophase is reached by increasing the temperature or by adding a solvent. Accordingly, a differentiation can be made between thermotropic and lyotropic liquid crystals, respectively. As with thermotropic liquid crystals, a variation of the temperature can also cause a phase transformation between different mesophases with lyotropic liquid crystals. 

The smectic mesophases of the thermotropic liquid crystals show a variety of textures but resemble mainly the fan-shape texture of the lyotropic hexagonal meso-phase. For further reading more comprehensive literature is recommended [11]. 

The molecular structure of arsphenamin is a typical representative of a thermotropic mesogen. With its symmetrical arrangement of the atoms the same holds for disodium cromoglycate, DNCG [20], which forms both thermotropic liquid crystals and lyotropic mesophases in the presence of water. Micronized DNCG powder applied to the mucosa of the nose or the bronchi absorbs water from the high relative humidity of the respiration tract and is first transformed into a lyotropic mesophase and then into a solution depending on the amount of water available. 

The mesogenic structures of glycolipids are due to the occurrence, on the same molecule, of a hydrophilic and a hydrophobic moiety often referred to as head and tail respectively. As a result, glycolipids are able to self-organize into a large variety of mesophases also called liquid crystals (Fig. 2) [ 10]. Supramolecular assemblies of mesogenic compounds can be caused by a rise in temperature (thermotropic liquid crystals) or by the addition of water (lyotropic liquid crystals) they result from different responses of the carbohydrate and the alkyl chain to temperature or solvent (water), respectively. 

When they are heated, mesogenic compounds do not melt directly from the highly ordered crystalline state to an isotropic liquid. They form instead, intermediate phases in which the molecules are orientated in a parallel direction and referred to as smectic (centers of the molecules organized in layers) or nematic (centers of the molecules distributed at random). Smectic and nematic mesophases are in turn divided into a variety of subgroups of thermotropic liquid crystals which will not be dealt with in detail in the present article. 

Melting point the temperature at which a thermotropic liquid crystal passes from the solid to the mesophase (or to an isotropic liquid). 

Thermotropic liquid crystals are divided into two principal types, by considering the shape of the units forming the mesophase (Figure 7.1) ... 

The thermotropic mesophases are well enough understood to propose a subdivision into six types. Depending on the type of disorder, they are called liquid crystals, plastic crystals or condis crystals (positional and if applicable conformational disorder, orientational disorder, and conformational disorder, respectively). For the corresponding glasses, which represent the frozen-in mesophases, the names LC-, PC-, and CD-glasses are proposed (Fig. 2). For macromolecules not only equilibrium... 

Mesophases Induced by Association of Complementary Molecular Components. A common type of molecular species that form thermotropic liquid crystals possesses an axial rigid core fitted with flexible chains at each end. One may then imagine splitting the central core into two complementary halves e and 3, whose association would generate the mesogenic supermolecule, as schematically represented in Figure 38. 

Liquid crystalsare an intermediate state in which the molecules in a crystal can undergo a secondary phase transition to a mesophase, which gives them mobility in 1-2 directions. They are birefringent, but possess low properties like a liquid phase. Lyotropic liquid crystals form on uptake of water into a system that increases its mobility, and thermotropic liquid crystals can be disrupted by heating above a transition temperature. Cromolyn sodium (Cox et al., 1971), the HMG-CoA reductase inhibitor SQ33600 (Brittain et al., 1995), and the leukotriefienffagonist L-660,711 (Vadas et al., 1991) are examples of pharmaceuticals that can form liquid crystals. 

One of the most classic examples of chiral expression in thermotropic liquid crystals is that of the stereospecific formation of helical fibres by di-astereomers of tartaric acid derivatised either with uracil or 2,6-diacylamino pyridine (Fig. 9) [88]. Upon mixing the complementary components, which are not liquid crystals in their pure state, mesophases form which exist over very broad temperature ranges, whose magnitude depend on whether the tartaric acid core is either d, l or meso [89]. Electron microscopy studies of samples deposited from chloroform solutions showed that aggregates formed by combination of the meso compounds gave no discernable texture, while those formed by combinations of the d or l components produced fibres of a determined handedness [90]. The observation of these fibres and their dimensions makes it possible that the structural hypothesis drawn schematically in Fig. 9 is valid. This example shows elegantly the transfer of chirality from the molecular to the supramolecular level in the nanometer to micrometer regime. 

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