Temperature dependence liquid crystalline phase modelling

It is not necessary to carry out synthesis, if the triggering photochromic compound has good affinity to the polymer matrix. A mixture of the polyacrylate with BMAB which exhibits an excellent function as trigger is equally photoresponsive. While the monomer model compound (i.e. the acrylate before polymerization) does not provide a liquid crystalline phase, the polymer shows a clear nematic - isotropic transition at ca. 61 °C and the glass transition temperature at 24 °C as shown in Fig. 4. Tj j depends very much on the length of the alkyl spacer. In comparison with the... 

The thermotropic liquid crystal, 4,4 -diheptylazoxybenzene (HAS), exhibiting isotropic, nematic and smectic phases, has been studied through e NMR. The temperature dependence of e chemical shifts and spin-lattice relaxation times of the Xe gas dissolved in HAS showed clear signatures of the phase transitions. Theoretical models have been used to understand the influence of the different phases on the isotropic and anisotropic parts of the chemical shielding. From the studies it is also inferred that in the smectic phase, Xe atoms preferentially occupy interlayer spacings rather than the interiors. Bent-core or banana-shaped molecules display an array of novel chiral liquid crystalline phases. NMR studies on two of the banana core moieties have been analyzed using ab initio structure calculations and the steric inertial frame model. ... 

We have therefore devised a new method for the determination of the temperatures for onset and end of melting, which is based on a simulation of the experimental DSC-curves. This procedure uses a regular solution model for nonideal mixing in both, the ordered and the liquid-crystalline phase, and incorporates the additional broadening by assuming a simple two-state transition of limited cooperativity, with the cooperative unit size c.u. as an adjustable parameter. This model is still a simplification of the real situation as it is based on the assumption that the cooperativity does not depend on temperature [84]. Nevertheless, this procedure seems to be more reliable for the determination of the phase boundaries as the arbitrariness in detennining the onset and end of melting temperatures is replaced by a more objective procedure. 

Whether polymerized model membrane systems are too rigid for showing a phase transition strongly depends on the type of polymerizable lipid used for the preparation of the membrane. Especially in the case of diacetylenic lipids a loss of phase transi tion can be expected due to the formation of the rigid fully conjugated polymer backbone 20) (Scheme 1). This assumption is confirmed by DSC measurements with the diacetylenic sulfolipid (22). Figure 25 illustrates the phase transition behavior of (22) as a function of the polymerization time. The pure monomeric liposomes show a transition temperature of 53 °C, where they turn from the gel state into the liquid-crystalline state 24). During polymerization a decrease in phase transition enthalpy indicates a restricted mobility of the polymerized hydrocarbon core. Moreover, the phase transition eventually disappears after complete polymerization of the monomer 24). 

A final example of induced mesogenicity in a multicomponent system is the well studied, but less well understood, carbonaceous mesophases which are comprised of a myriad of unidentified molecules which are created in situ as petroleum pitches are heated to temperatures where chemical transformations occur [163]. The processes leading to a mesophase involve decreases in both the elemental weight fraction of hydrogen and the group fraction of aliphatic carbon atoms [164]. Model studies have demonstrated that the component molecules of these phases are fused, polycyclic aromatic molecules with disk-like shapes the exact structures of the components depend upon the natures of the precursor molecules which are heated [164-167]. All of the carbonaceous mesophases somewhat resemble discotic nematic phases [168]. At least some of them probably represent another example of liquid crystallinity induced by mixing molecular components which, when separated, are not mesogenic. 

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