Membrane lipid bilayers phase transitions

Hydrated bilayers containing one or more lipid components are commonly employed as models for biological membranes. These model systems exhibit a multiplicity of structural phases that are not observed in biological membranes. In the state that is analogous to fluid biological membranes, the liquid crystal or La bilayer phase present above the main bilayer phase transition temperature, Ta, the lipid hydrocarbon chains are conforma-tionally disordered and fluid ( melted ), and the lipids diffuse in the plane of the bilayer. At temperatures well below Ta, hydrated bilayers exist in the gel, or Lp, state in which the mostly all-trans chains are collectively tilted and pack in a regular two-dimensional... 

Cholesterol also affects the fluidy of lipid bilayers while increasing disorder in the low temperature plrase, and the order in the high temperature phase. The phase transition and the intensity are reduced. Generally speaking cholesterol reduces the fluidity of membranes above the phase transition temperature, and the permeability to aqueous solutes. 

V. F. Antonov, V. V. Petrov, A. A. Molnar, D. A. Predvoditelev, and A. S. Ivanov, The Appearance of Single-ion Channels in Unmodified Lipid Bilayer Membranes at the Phase Transition Temperature, Nature 283, 585-586 (1980). 

Membranes are composed of phospholipids and proteins. The fatty acid composition of the phospholipids in a membrane influences how it is affected by the cold. In general, as the temperature of a cell is lowered the lipids in the membrane bilayer undergo a phase transition from a liquid crystalline (fluid) state to a gel (more solid) state. The temperature at which this transition takes place is very narrow for phospholipids composed of a simple mixture of fatty acids, but is quite broad for the phospholipids in cellular membranes. It is usually implied from various methods... 

Major determinants of membrane fluidity may be grouped within two categories [53] (1) intrinsic determinants, i.e., those quantifying the membrane composition and phase behavior, and (2) extrinsic determinants, i.e., environmental factors (Table 1). In general, any manipulation that induces an increase in the molal volume of the lipids, e.g., increase in temperature or increase in the fraction of unsaturated acyl chains, will lead to an increase in membrane fluidity. In addition, several intrinsic and extrinsic factors presented in Table 1 determine the temperature at which the lipid molecules undergo a transition from the gel state to liquid crystalline state, a transition associated with a large increase in bilayer fluidity. 

Recently, due to increased interest in membrane raft domains, extensive attention has been paid to the cholesterol-dependent liquid-ordered phase in the membrane (Subczynski and Kusumi 2003). The pulse EPR spin-labeling DOT method detected two coexisting phases in the DMPC/cholesterol membranes the liquid-ordered and the liquid-disordered domains above the phase-transition temperature (Subczynski et al. 2007b). However, using the same method for DMPC/lutein (zeaxanthin) membranes, only the liquid-ordered-like phase was detected above the phase-transition temperature (Widomska, Wisniewska, and Subczynski, unpublished data). No significant differences were found in the effects of lutein and zeaxanthin on the lateral organization of lipid bilayer membranes. We can conclude that lutein and zeaxanthin—macular xanthophylls that parallel cholesterol in its function as a regulator of both membrane fluidity and hydrophobicity—cannot parallel the ability of cholesterol to induce liquid-ordered-disordered phase separation. 

The formalism sketched above has been used in the literature in more or less the same detail by many authors [87-92]. The predicted membrane structure that follows from this strategy has one essential problem the main gel-to-liquid phase transition known to occur in lipid membranes is not recovered. It is interesting to note that one of the first computer models of the bilayer membrane by Marcelja [93] did feature a first-order phase transition. This author included nematic-like interactions between the acyl tail, similar to that used in liquid crystals. This approach was abandoned for modelling membranes in later studies, because this transition was (unfortunately) lost when the molecules were described in more detail [87]. 

From the modelling results for bilayers composed of unsaturated lipids one can begin to speculate about the various roles unsaturated lipids play in biomembranes. One very well-known effect is that unsaturated bonds suppress the gel-to-liquid phase transition temperature. Unsaturated lipids also modulate the lateral mobility of molecules in the membrane matrix. The results discussed above suggest that in biomembranes the average interpenetration depth of lipid tails into opposite monolayers can be tuned by using unsaturated lipids. Rabinovich and co-workers have shown that the end-to-end distance of multiple unsaturated acyl chains was significantly less sensitive to the temperature than that of saturated acyls. They suggested from this that unsaturated... 

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