Liquid crystalline mesophases thermotropic

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. 

This family of noncovalently bonded PLCs may also include polyelectrolyte + surfactant complexes which, as will be seen, can also give rise to liquid crystalline mesophases. In these complexes there is only a flexible alkyl chain attached to the ionic head group in the small molecule constituent, with no rigid aromatic core present. Since surfactants themselves are frequently thermotropic liquid crystals, it is not surprising that their complexes with polyelectrolytes may produce PLCs, in both cases driven by the incompatibility between the ionic and aliphatic parts leading to amphitropic systems [27]. 

Thermotropic liquid crystalline mesophases are usually recognized because the materials exhibiting them melt into a fluid which maintains the birefringent and light scattering... 

Equation 27 is also known to reliably predict Vf for polymers that are not true rods if, as Flory [193] suggested, the aspect ratio of the Kuhn segment is utilized [175, 194, 195]. Furthermore, Eq. 27 provides some insight into the minimum aspect ratio for thermotropic liquid crystal formation. Most of the polymers of Table 3 are known to form liquid crystalline mesophases under appropriate conditions. 

Partial to complete 3-0-octadecylated polysaccharides exhibited characteristic solution and solid properties based on hydrophilic-hydrophobic structures. These polymers are suggested to form micellar conformations in water and in chloroform polysaccharide-coated liposomes, polymeric membranes, and thermotropic liquid-crystalline mesophase, depending on the octadecyl content. Hydrolysis of 3-deoxygenat-ed, 3-0-methylated, and 3-0-octadecylated dextrans by an endo-acting dextrans is compared. The possibility of a combshaped branched polysaccharide toward cell-specific biomedical materials is discussed. 

Thermotropic liquid-crystalline properties of different metal alkanesulfonates are studied by microscopy and X-ray diffraction [59]. Sodium soaps show smectic polymorphism of smectic A and smectic B phases. Ammonium soaps only show smectic A phases but polymorphism in the crystalline state. Calcium soaps show columnar mesophases. In Figs. 32 and 33 some textures and x-ray diffraction patterns are depicted. 

A review of the literature demonstrates some trends concerning the effect of the polymer backbone on the thermotropic behavior of side-chain liquid crystalline polymers. In comparison to low molar mass liquid crystals, the thermal stability of the mesophase increases upon polymerization (3,5,18). However, due to increasing viscosity as the degree of polymerization increases, structural rearrangements are slowed down. Perhaps this is why the isotropization temperature increases up to a critical value as the degree of polymerization increases (18). 

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 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... 

Thermotropic liquid crystalline (LC) phases or mesophases are usually formed by rod-like (calamitic) or disk-like (discotic) molecules. Spheroidal dendrimers are therefore incapable of forming mesophases unless they are flexible, because this would allow them to deform and subsequently line up in a common orientation. However, poly(ethyleneimine) dendrimers were reported to exhibit lyotropic liquid crystalline properties as early as 1988 [123],... 

There are now numerous examples of cellulose derivatives that form both lyotropic and thermotropic mesophases. Of course, cellulose itself is unlikely to form a thermotropic liquid crystalline phase because it decomposes prior to melting. 

The structure and function of cell membranes have long been associated with lyotropic liquid crystalline phases. Since most of the glycolipids are amphitropic (both thermotropic and lyotropic) their was an increase of interest in the comparison of the structures of both types of mesophases formed by the same compound. 

The development is reviewed of liquid-crystalline polymers whose mesophase formation derives from the nature of the chemical units in the main chain. The emphasis lies primarily on highly aromatic condensation polymers and their applications. The general properties of nematic phases formed by such polymers are surveyed and some chemical structures capable of producing nematic phases are classified in relation to their ability to form lyotropic and thermotropic systems. The synthesis, properties, physical structure and applications of two of the most important lyotropic systems and of a range of potentially important thermotropic polymers are discussed with particular reference to the production and use of fibres, films and anisotropic mouldings. 

The article covers synthesis, structure and properties of thermotropic liquid-crystalline (LC) polymers with mesogenic side groups. Approaches towards the synthesis of such systems and the conditions for their realization in the LC state are presented, as well as the data revealing the relationship between the molecular structure of an LC polymer and the type of mesophase formed. Specific features of thermotropic LC polymers and copolymers of nematic, smectic and cholesteric types are considered. 

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