Thermotropic liquid crystalline states

Some drug substances can form mesophases with or without a solvent [19-26]. In the absence of a solvent, an increase in temperature causes the transition from the solid state to the liquid crystalline state, called thermotropic mesomorphism. Lyotropic mesomorphism occurs in the presence of a solvent, usually water. A further change in temperature may cause additional transitions. Thermotropic and/or lyotropic liquid crystalline mesophases of drug substances may interact with meso-morphous vehicles as well as with liquid crystalline structures in the human organism. Table 1 presents drug substances for which thermotropic or lyotropic mesomorphism has been proved. 

Unusual properties of fully aromatic polyesters are observed if they have at least partially a rigid planar chain structure. In particular, they can form thermotropic liquid crystalline states (see Example 4-5). As already discussed in Sect. 1.2.4 an important structural prerequisit for LCPs of Type A in order to attain the liquid crystalline state of aromatic polyesters (and aromatic polyamides, see Example 4-14), is a rigid main chain according to the following construction principle ... 

The structures of liquid crystals are intermediate between the amorphous and crystalline states. They have some short-range orientational order. Some also have positional order. Thousands of organic compounds exhibit liquid crystal structures. Most have molecules that are very long and thin, but some have molecules that are flat and pancake shaped. Many compounds may exist in more than one liquid crystalline state. Transitions from one state to another may be thermotropic (caused by temperature change) or lyotropic (caused by change of solute concentration). 

Gray has provided an excellent book on the liquid crystalline state as known in 196222. It includes many detailed definitions. Although he notes the wide occurrence of liquid crystals in biological tissue, he limited his discussion of such crystals to the introduction. Materials in the liquid crystalline state can be divided into two major groups, those that are thermotropic and lyotropic. 

The liquid crystalline state is frequently recognized most simply by heating a thermotropic solid. If the solid transitions to a turbid system before becoming an isotropic liquid, the turbid system is most likely a liquid crystalline system. On cooling, the liquid may revert to the turbid system on the way to the solid phase. However, if heated above a molecular transition point, the material may not return to the turbid state on the way to becoming a solid. 

In addition to this thermotropic mesomorphism, a lysotropic mesomorphism is observed [98]. The phase transition temperature, Tt, for the transition from the crystalline to the liquid crystalline state decreases as a function of water content. The decrease in Ttis due to destabilization of the crystal lattice in the head group region by water molecules. This, in turn, decreases the interaction between the fatty acid chains. When the water content reaches a certain level, the phospholipids assume a thermodynamically optimal arrangements whereby the fatty acids are directed to the... 

In order to understand the basic principles of operation of the many different kinds of LCDs being developed and/or manufactured at the present time, it is necessary to briefly describe the liquid crystalline state and then define the physical properties of direct relevance to LCDs. First, the nematic, smectic and columnar liquid crystalline states will be described briefly. However, the rest of the monograph dealing with liquid crystals will concentrate on nematic liquid crystals and their physical properties, since the vast majority of LCDs manufactured operate using mixtures of thermotropic, non-amphiphilic rodlike organic compounds in the nematic state. 

Both theoretical approaches qualitatively describe the "thermotropic" and "lyotropic" liquid crystalline state of rod-like molecules ( see also D.B. DuPre, R. Parthasarathy, this book). Combination of both theories (Flory, Ronca)(7) slightly improves the predictions compared to the experimental findings. Anisotropic dispersion interactions and/or anisometric molecular shape can thus be the basis for explaining theoretically the appearance of "lyotropic" and "thermotropic" liquid crystalline phases. 

For example, if the polymer is diluted by introducing a solvent to the concentration v , the system gets into the liquid crystalline state at the temperature (route I). Upon further diluting the polymer at the same temperature the system goes over to the isotropic state with the polymer concentration Vj. Similar transitions, however, can take place by heating the system at a given polymer concentration. For example, when the temperature is increased at the concentration V2 (route II), the successive transitions c Ic (at and Ic i (at take place. Just as in the case of a pure polymer, such transitions should be regarded as thermotropic. 

Further theoretical studies by Floryconcerned the clarification of phase transitions for the systems with a definite distribution of macromolecules over the length and also the analysis of equilibrium for a model system composed of macromolecules in which rigid blocks are separated by flexible units. An example of such systems are copolyesters exhibiting the thermotropic transition into the liquid crystalline state in the absence of a solvent... 

When a thermotropic liquid crystal is heated, it passes from the crystalline state into the liquid-crystalline state at a point called the melting point. By further heating, the birefringent (anisotropic) liquid crystal is transformed at the clearing point into an isotropic fluid the birefringent fluid becomes clear and all molecular order is lost. 

At 80°C, the polymers with more than 10 carbon atoms are in the liquid crystalline state. Low mobility of the side chain prevents the polymers of n 9 to be in the thermotropic liquid crystal. The existence of the discontinuity is evidence for the solvent like nature of the side chains in the thermotropic liquid crystalline phase. 

The amphiphilic molecules can occur in lyotropic and thermotropic mesomorph, and the organization of lipid bilayers such as liposomes can exist in a temperature range where all the mesophases from gel stale to liquid crystal state are favored. In the gel state the phospholipid acyl chains are closely packed and the molecular movements are deteriorized, while in the liquid crystalline state, the faity acid moieties are in a more fluid state and are able to move more freely. 

Since the discovery of Kevlar, scientists world-wide have attempted to synthesize many thermotropic LCPs that the liquid crystalline state can be formed in a melt instead of in a solution as lyotropic LCPs. Generally, two kinds of thermotropic LCPs can be prepared depending on the position of mesogens (J9.) ... 

Thermotropic liquid crystal polymers (LCI ) are of considerable current interest, because of their theoretical and technological aspects [1-3]. Evidently, a new class of polymers has been developed, combining anisotropic physical properties of the liquid crystalline state with diaracteristic polymer features. This unique combination promises new and interesting material properties with potential ai lications, for example in the field of high modulus fibers [4], storage technology, or non-linear optics [5]. 

V.Frosini, A.Marchetti, and S.De Petris, Low temperature phase transition in some thermotropic polyesters quenched from the liquid crystalline state, Makromol.Chem., Rapid Commun. 3 795 (1982),... 

The influence of chain packing (Le. free volume) on solubility, diffusivity and permeability in liquid crystalline polymers can be studied by comparing properties of LCPs in the disordered, isotropic state with those in the ordered, liquid crystalline state. HIQ-40 is a random, glassy, thermotropic, nematogenic terpolymer synthesized from 40 mole percent p-hydroxybenzoic acid and 30 mole percent each of isophthalic acid and hydroquinone. The chemical structures of the constituent monomers for fflQ-40are ... 

The three elastic constants of a liquid crystal are important physical parameters which depend on the interaction between the molecules in the liquid crystalline state. While a large number of theoretical and experimental investigations on the elastic constants are contained in the literature for thermotropic liquid crystals, very little is known about them in the case of lyotropic polymer liquid crystals such as those formed by poly-Y-benzyl-L-glutamate (PBLG) in various organic solvents. Some theoretical investigations have been carried out 3 the experimental data is limited largely to measurements of the twist elastic constant and a few recent measurements of the bend and splay constants. ... 

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