Transitions lyotropic

Thus, the terms thermotropic and lyotropic transitions are correct, but there are no grounds behind the division of liquid crystalline polymers into lyotropic and thermotropic (with the exception of block copolymers which form, in selective solvents, systems that can conventionally be referred to as liquid crystals... 

Pure phospholipids all undergo a transition from crystalline to the liquid crystalline phase many degrees below the capillary melting point. In the liquid crystalline phase the hydrocarbon chains are in a fluid condition. In the presence of water this transition temperature is lowered. At this temperature myelin tubes are formed, and the phospholipids can be more easily dispersed. The temperature for lyotropic transitions from lamellar to hexagonal phases is alsoTelated to this temperature. 

Amphotropic behavior can be found for a large number of different chemical structures. Additional information is given in other chapters of this Handbook. Typical classes of amphotropic materials are for instance classical soaps (see lyotropics), transition metal soaps (see metallomesogens), viologens, quartemary amines and other ionic surfactants (see lyotropics), block copolymers (see polymer liquid crystals), cellulose derivatives (see cellulose liquid crystals) and partially fluorinated paraffines, diols, peptide surfactants, lecithins, lipids, alkylated sugars and inositols, naturally occurring glycosides and silanols, which are discussed in this chapter. 

The mesomorphic behavior of a solution of rigid rods has been studied by several authors.i-iZ-Ll In particular, for long rods of length b and radius a, OnsagerL has shown that the effective excluded volume per rod in the isotropic phase is of order b a. The actual volume occupied per rod is ira b. A lyotropic transition to a nematic phase occurs at a rod concentration O given by... 

Figure 2. Difference in free energy between nematic and isotropic phases of a rigid rod solution for different values of the monomer concentration c. There is a predicted first-order lyotropic transition at c =...

Some molecules ia a solvent form phases with orientational and/or positional order. In these systems, the transition from one phase to another can occur due to a change of concentration, so they are given the name lyotropic Hquid crystals. Of course temperature can also cause phase transitions ia these systems, so this aspect of thermotropic Hquid crystals is shared by lyotropics. The real distinctiveness of lyotropic Hquid crystals is the fact that at least two very different species of molecules must be present for these stmctures to form. 

M. Allain, P. Oswald, J. M. di Meglio. Structural defects and phase transition in a lyotropic system optical birefringence and order parameter measurements. Mol Cry St Liq Cryst 7625 161-169, 1988. 

L. Sallen, P. Sotta, P. Oswald. Pretransitional effects near the hexagonal-micellar phase transition of the CnEOA/HoO lyotropic mixture. J Phys Chem 707 4875-4881, 1997. 

We have examined a number of different salts and have shown that the transition temperature can almost be altered at will (12), in many cases in line with the Hofmeister or lyotropic series (13-15J, a relationship found for many other aqueous systems such as hydrocarbon solubility and protein stability. 

Surfactant blends of interest will exhibit clouding phenomena in aqueous solutions undergoing a phase transition from a one phase system to a two phase system at a discrete and characteristic temperature, referred to as the Cloud Point (CP). This value indicates the temperature at which sufficient dehydration of the oxyethylene portion of the surfactant molecule has occurred and this results in its "displacement" from solution. The addition of lyotropic salts will depress the CP, presumably due to the promotion of localised ordering of water molecules near the hydrophilic sheath of the surfactant molecule (8). Furthermore, the addition of different oils to surfactant solutions can induce either an elevation or a depression of the recorded CP and can be used to qualitatively predict the PIT (8x9). 

In addition to the cubic and/or inverse cubic forms described above, further transitional forms exist between the lamellar phase and the hexagonal mesophase (cubic, type II) or inverse hexagonal mesophase (cubic, type III) [6]. In contrast to the discontinuous phases of types I and IV, cubic mesophases of type II and III belong to the bieontinuous phases (Fig. 4f). A range of lyotropic mesophases are possible, depending on the mesogen concentration, the lipophilic or hydrophilic characteristics of the solvent, and the molecule itself [6]. 

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. 

Thermotropic LCs exhibit the phase transition into the LC phase as temperature is changed, whereas lyotropic LCs exhibit it as a function of concentration of the... 

A very simple model that predicts lyotropic phase transitions is the hard-rod model proposed by Onsager (Friberg, 1976). This theory considers the volume excluded from the center-of-mass of one idealized cylinder as it approaches another. Specifically, if the cylinders are oriented parallel to one another, there is very little volume that is excluded from the center-of-mass of the approaching cylinder (it can come quite close to the other cylinder). If, however, the cylinders are at some angle to one another, then there is a large volume surrounding the cylinder where the... 

Other cases, polymers can undergo lyotropic or thermotropic liquid crystalline phase transitions, which can often be observed and recorded in a polarized light microscope. 

Large numbers of functionalized LB films have been prepared. Highly ordered LB films have been formed by the inclusion of surface-active cobaltous phthalocyanine [168] amphiphilic TCNQ was assembled to function as conducting LB films [169] liquid-crystalline LB films, potentially capable of undergoing thermotropic or lyotropic phase transitions [170, 171], have also been generated. Spacer groups introduced into polymeric surfactants (23) helped to stabilize the LB films which they formed by decoupling the motion of pendant polymers (see Fig. 13) [172]. 

The appearance of tubular myelin-like structures in swollen lecithin was observed by light microscopy well before the systematic investigation of liposomes [351-352]. Similarly, it was also demonstrated some time ago that the addition of calcium ions converted phospholipid liposomes to cochleate cylinders [353]. Subsequent studies have, however, revealed that the system is extremely complex. For example, examination of the phase-transition behavior of synthetic sodium di-n-dodecyl phosphate [(C12H2sO)2PO2Na+ or NaDDP] and calcium di-n-dodecyl phosphate [Ca(DDP)2] showed the presence of many diverse structures [354]. In particular, hydrated NaDDP crystals were shown to form lyotropic liquid-crystalline phases which transformed, upon heating to 50 °C, to myelin-like tubes. Structures of the tubes formed were found... 

We could show that the modification of transition metal alkoxides is a versatile tool to adjust the reactivity of precursors for the needs in lyotropic crystalline templating processes. In case of high surfactant concentrations where the liquid crystalline template is formed prior to the addition of the precursor the use of a modifier may become unnecessary. The synthesis of nanostructured rhenium dioxide and the utilization of MTO as precursor for this purpose clearly shows that in some cases the use of unusual specialized compounds is imperative. First promising results in the synthesis of nanostructured chromium oxide surfactant composites have been displayed although hydrolysis of the precursor seems to be still uncompleted within the nanostructure. The possibility of tailoring the d-values in a desired way besides the synthesis of certain particle morphologies encourages for further work in the future. 

Both polymer melts and polymer solutions sometimes form phases with orientational and positional ordci. Thermotropic polymer liquid crystals possess at least one liquid crystal phase between the glass-transition temperature and the transition temperature to the isotropic liquid. Lyotropic polymer liquid crystals possess at least one liquid cry stal phase for certain ranges of concentration and temperature. 

In this review we are mainly concerned with thermotropic materials, i.e. with liquid crystals and LC-glasses which do not contain a solvent. The transitions of the macro-molecular, thermotropic liquid crystals are governed then by temperature, pressure and deformation. In lyotropic liquid crystals and LC-glasses a solvent or dispersing agent is present in addition. The transitions then also become concentration dependent. 

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