Cooling Disorder, chain

The phase behavior of a synthetic lecithin, dipalmitoyllecithin, as analyzed by Chapman and co-workers (5), is diagrammed in Figure 3. The main features are the same as in the phase diagram of egg lecithin a mixture of numerous homologs. As a consequence of the variation in fatty acid chain length, the chain melting point is lowered which means that the critical temperature for formation of liquid crystalline phases is reduced. This temperature is about 42 °C for dipalmitoyllecithin, and, if the lamellar liquid crystal is cooled below this temperature, a so-called gel phase is formed. The hydrocarbon chains in the lipid bilayers of this phase are extended, and they can be regarded as crystalline. The gel phase and the transitions between ordered and disordered chains are considered separately. 

Fig. 1 Melting temperatures of polymers k%Tm/Ec) with variable Ev/Ec values. The line is calculated from Eq. 10 and the circles are the simulation results obtained from the onset of crystallization on the cooling curves of disorder parameters, in a short-chain (r = 32) system (occupation density is 0.9375 in a 32-sized cubic box) with a template substrate (Hu and Frenkel, unpublished results)...

Fig. 6 Simulational cooling curves of disorder parameters (solid lines) and mixing parameters (dashed lines) for 32-mers with different sets of energy parameters in a 64-sized cubic box (the concentration is fixed at 0.150). The mixing parameter is defined as the mean fraction of neighboring sites occupied by the solvent for each chain unit [84]... 

Lipid assemblies of the lamellar type, such as lipid bilayers, can feature a true phase transition in which the topology does not change. Upon cooling, the bilayer goes from the fluid phase to the gel phase. In the fluid phase, the acyl chains are disordered, in the sense that there is enough free volume around the chains to allow for chain conformation variations. In the gel phase, the acyl chains are more densely packed and believed to be ordered in an all-trans (straight) configuration. For very pure systems, at temperatures below this sharp gel-to-liquid phase transition, there are several other states and distinct transitions detectable (pre-transition, ripple phase, etc.). These phases will not be reviewed here. In biomembranes, many type of lipids (and other molecules) occur, and it is known that for this reason the gel-to-liquid phase transition is... 

For polycatenar hydrogen bonded complexes with fluorinated chains at both ends (e.g., 138,139, see Fig. 36) formation of columnar phases was observed [246]. However, compound 137, having a branched Rp-chain at one end and three RH-chains at the other has a sequence of three distinct phases in the unusual sequence Cub-Col-SmA-Iso. For the SmA phase of compound 137 a structure with intercalated aromatic cores and RF-chains and separated layers of the hydrocarbon chains was proposed. At lower temperature, when incompatibility rises and the aromatics and Rp-chains disintegrate, all three components form their own layers. However, this produces interface curvature and a columnar phase with square lattice is formed. On further cooling a transition to a cubic phase with Im3m lattice takes place which is most likely of the bicontinuous type [262]. This leads to the unusual phase sequence Cubv-Col-SmA where the positions of the Cubv and Col phases are exchanged with respect to the usually observed phase sequences. The Col-Cub transition at lower temperature could be the result of the decreased conformational disorder of the terminal chains which reduces the steric frustration and hence reduces the interface curvature. 

---