Phospholipid vesicles transition properties

Seki and Tirrell [436] studied the pH-dependent complexation of poly(acrylic acid) derivatives with phospholipid vesicle membranes. These authors found that polyfacrylic acid), poly(methacrylic arid) and poly(ethacrylic acid) modify the properties of a phospholipid vesicle membrane. At or below a critical pH the polymers complex with the membrane, resulting in broadening of the melting transition. The value of the critical pH depends on the chemical structure and tacticity of the polymer and increases with polymer hydro-phobicity from approximately 4.6 for poly(acrylic acid) to approximately 8 for poly(ethacrylic acid). Subsequent photophysical and calorimetric experiments [437] and kinetic studies [398] support the hypothesis that these transitions are caused by pH dependent adsorption of hydrophobic polymeric carboxylic acids... 

Table I. Transition Properties of DPPE-DVBA and DLPE-DVBA Phospholipids and Vesicles...

The chemical compositions and isomeric structures of the fatty acid chains of phospholipids is well known to have large effects on the physical properties of lipid bilayers, such as the temperatures of endothermic chain melting phase transitions. Lipid vesicles sensitized with lipid haptens can be agglutinated with specific antibodies directed against the haptens (see Fig. 1). 

Up until 1977, the non-covalent polymeric assemblies found in biological membranes rarely attracted any interest in supramolecular organic chemistry. Pure phospholipids and glycolipids were only synthesized for biophysical chemists who required pure preparations of uniform vesicles, in order to investigate phase transitions, membrane stability and leakiness, and some other physical properties. Only very few attempts were made to deviate from natural membrane lipids and to develop defined artificial membrane systems. In 1977, T. Kunitake published a paper on A Totally Synthetic Bilayer Membrane in which didodecyl dimethylammonium bromide was shown to form stable vesicles. This opened the way to simple and modifiable membrane structures. Since then, organic chemists have prepared numerous monolayer and bilayer membrane structures with hitherto unknown properties and coupled them with redox-active dyes, porous domains and chiral surfaces. Recently, fluid bilayers found in spherical vesicles have also been complemented by crystalline mono-... 

We note here that systematic studies of the melting transition of dry or nearly dry phospholipids bilayers (e.g., vesicles) have been scarce. While there is an abundant experimental and theoretical literature concerning the structure and properties of bilayers in water, less is known about their behavior when water is removed. We have therefore initiated a systematic experimental study of the gel-liquid crystal transition of pure DPPC and DPPC-cholesterol vesicles freeze-dried with and without disaccharides and oxyanion-disaccharide complexes. Some of our results to date are shown in Figure 9.3. 

The structural and dynamic properties of polymerized surfactant aggregates such as detergent micelles, vesicles and bilayers have been studied extensively (32). From a biological aspect, it is of interest to determine in which way these structures mimic the properties of natural membranes (33). Most luminescent anisotropy studies of lipid rotation have employed the fluorescence characteristics of incorporated probes (34,35), as the time scales of lipid rotation are usually in the ns regime. However, a recent electron spin study using incorporated phospholipid spin-labels (36), indicated that rotation about the long axis of dimyristoyl-phosphatidylcholine (DMPC) lipids below the phase transition occurrs with time constants of about 60-100 is. Such values lie within the time domain of phosphorescence anisotropy measurements. 

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