Liquid crystalline systems transition between

An earlier study of the molecularly doped polymer liquid crystalline system shown in Figure 6.9 revealed more complex behavior (27, 32). In this study, the amount of induced nonlinearity was path dependent, with the largest observed value occurring when poling was done near Tg ( 25 C). The host polymer exhibits a nematic-to-isotropic transition at = 100 C and a nematic texture between Tg and. Poling at 50 C produces a decrease in approximately 1 order of magnitude. The l/T dependence... 

Figure 41.1 shows the gel-to-liquid crystalline phase transition temperatures (Tm) of DPPC-cholesterol mixtures as a function of the cholesterol-lipid molar ratio. The Tm of fully hydrated DPPC is 42°C (Crowe and Crowe, 1988 Vist and Davis, 1990 McMullen et al., 1993 Ohtake et al., 2004). Upon the addition of cholesterol, the transition enthalpy decreases continuously imtil it is no longer observable at 50 mol% cholesterol. The disappearance of the melting transition has been attributed to strong interactions between cholesterol and DPPC (McCoimell, 2003). Upon dehydration, the Tm for DPPC increases from 42 to 105°C (Crowe and Crowe, 1988 Ohtake et al., 2004). This Tm increase is caused by the reduction in the spacing between the phospholipids, which allows for increased van der Waals interactions between the lipid hydrocarbon chains (Koster et al., 1994). Between 10 and 70 mol% cholesterol, two endothermic transitions are observed, both lower than the Tm of the pure phospholipid (Figure 41.1). High-sensitivity DSC studies on fully hydrated DPPC-cholesterol systems reported endotherms consisting of two components, suggesting the existence of domains enriched/depleted in cholesterol (Vist and Davis, 1990 McMullen et al., 1993). The two peaks present in our freeze-dried systems also suggest the...

The first group includes liquid-crystalline systems based on polymers containing mesogenic groups in the main chain wh they alternate with flexible firagments, or in the side chains where they are joined to the main chain by flexible spacers. Phase equilibrium between these systems is due to thermal transitions from the crystalline state to some type of liquid-crystalline phase and subsequently to an isotropic melt. 

To this purpose, Fossheim et al. reported temperature sensitive liposomal Gd(III)-based probes (137-138). The composition of the liposomes was chosen in order to tune the temperature of transition between the gel-crystalline, where the liposome is water-impermeable, to the liquid-crystalline state, where water has free access to the interior of the liposome. This means that at temperatures below the transition, the relaxivity of the system is very low (paramagnetic contribution close to zero), whereas at higher temperature the Gd(III) complex ([GdDTPABMA(H20)] is the reference) is no longer silent... 

For the subject matter of this book, it is of particular interest to consider the situation for a non-crystalline system analogous to that of crystalline ytterbium or strontium under pressure, namely that when a valence and conduction band are separate or overlap slightly. If the degree of overlap can be changed by varying the mean distance between atoms, the composition or the coordination number then a metal-insulator transition can occur. Many examples will be discussed in this book, particularly amorphous films of composition (Mgi- )j(By3, liquid mercury at low densities, and liquid tellurium alloys in which the coordination number changes with temperature. The transition is, we believe, of Anderson type. 

Analysis of the results and comparison with the lipid phase transition observed iq the bulk lipid/water systems allows to conclude that the lowest temperature during heating at which measurable diffusion occurred correlates with the onset of formation of the lamellar Ln liquid crystalline phase of the given phospholipid. Therefore, the data support a correlation between the surface and bulk phase transitions. This was confirmed in recent studies where the lipid surface phase transition was successfully measured for the first time in foam film by independent means involving the detailed investigations of the temperature dependences of the W(C) curve for the foam film and its thickness. 

Hence, the interaction between lipid molecules is very similar in these foam bilayers and it can be supposed that the AF foam bilayers are in the liquid crystalline state within the temperature range studied. This assumption is in agreement with the fact that amniotic fluid contains substantial amount of unsaturated phospholipids, which as known [45], lower considerably the temperature of the chain-melting phase transition. Bearing in mind the similarity of the phase behaviour of a phosphatidylcholine aqueous dispersion and foam bilayers [38-40], it can be supposed that at the temperatures which are important for in vivo systems, the foam bilayers are in the liquid crystalline state. This assumption allows to determine the critical concentration of phosphatidylcholines in amniotic fluid, necessary for formation of a foam bilayer by extrapolation of the Arrhenius dependence of C, for AF foam bilayers to 37°C. Thus, at 37°C C, = 19.9 jxg cm 3 and d, = 1.47. This value of C, at 37°C corresponds to the lower limit (found by other methods [46,47]) of phosphatidylcholine concentration which permits to classify as mature a sample of amniotic fluid. The above value... 

Cho et al. described the synthesis and polymerization of 4,8-cyclododeca-dien-l-yl-(4 -methoxy-4-biphenyl) terephthalate VIII [54,55]. Polymerization was carried out with WCl4(OAr)2/PbEt4. The double bonds in the polymer backbone were subsequently hydrogenated with H2/Pd(C), leading to a SCLCP with a fully saturated hydrocarbon backbone. This polymer system had a very flexible polymer backbone but a stiff connection between the main chain and the mesogenic unit. The distance between two adjacent side chains was about 12 methylene units. This very flexible main chain allowed the polymer to organize into a LC mesophase. Both polymers - the unsaturated and the saturated -showed smectic liquid crystalline mesophases with almost the same transition temperatures (see Table 5). 

The transition moment directions of some of the absorption bands of PBLG in liquid crystalline state have been investigated in a CaF2 cell by means of the infra-red dichroic ratio (56). All the transition moment directions measured at 1 °C are very similar to those observed 32) on mechanically oriented films of PBLG (Table 2), verifying that all the polymer molecules present a parallel or nearly parallel orientation in the molecular cluster and that the main chain and the side chains of the polymer molecule are fixed as in the solid film. No significant difference is observed between the systems of solution testing. The orientation of the solvent molecules (methylene moletules) is detected in an electric field in accordance with the NMR observation (56). 

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