Polymerized phospholipid vesicles

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... 

Polymeric phospholipids based on dioctadecyldimethylammonium methacrylate were formed by photopolymerization to give polymer-encased vesicles which retained phase behavior. The polymerized vesicles were more stable than non-polymerized vesicles, and permeability experiments showed that vesicles polymerized above the phase transition temperature have lower permeability than the nonpolymerized ones [447-449]. Kono et al. [450,451] employed a polypeptide based on lysine, 2 aminoisobutyric acid and leucine as the sensitive polymer. In the latter reference the polypeptide adhered to the vesicular lipid bilayer membrane at high pH by assuming an amphiphilic helical conformation, while at low pH the structure was disturbed resulting in release of the encapsulated substances. 

Phospholipid vesicles form spontaneously when distilled water is swirled with dried phospholipids. This method of preparation results in a highly polydisperse array of multicompartment vesicles of various shapes. Extrusion through polymeric membranes decreases both the size and polydispersity of the vesicles. Ultrasonic agitation is the most widely used method for converting the lipid dispersion into single-compartment vesicles of small size. 

Hydrophobically modified polybetaines combine the behavior of zwitterions and amphiphilic polymers. Due to the superposition of repulsive hydrophobic and attractive ionic interactions, they favor the formation of self-organized and (micro)phase-separated systems in solution, at interfaces as well as in the bulk phase. Thus, glasses with liquid-crystalline order, lyotropic mesophases, vesicles, monolayers, and micelles are formed. Particular efforts have been dedicated to hydrophobically modified polyphosphobetaines, as they can be considered as polymeric lipids [5,101,225-228]. One can emphasize that much of the research on polymeric phospholipids was not particularly focused on the betaine behavior, but rather on the understanding of the Upid membrane, and on biomimicking. So, often much was learnt about biology and the life sciences, but little on polybetaines as such. 

A EXPERIMENTAL FIGURE 17-8 Vesicle buds can be visualized during in vitro budding reactions. When purified COPII coat components are incubated with isolated ER vesicles or artificial phospholipid vesicles (liposomes), polymerization of the coat proteins on the vesicle surface induces emergence of highly curved buds. In this electron micrograph of an in vitro budding reaction, note the distinct membrane coat, visible as a dark protein layer, present on the vesicle buds. [From K. Matsuoka etal., 1988, Ce//93(2) 263.[... 

A comparison of the synthesis of metal nanoparticles at the surfaces of polymerized and unpolymerized phospholipid vesicles has been undertaken. Vesicles were prepared from mixtures of charge-neutral phospholipid, 1,2-Z> w(tricosa-10,12-diynoyl)- -glycero-3-... 

In this chapter, we overviewed several fluorescence techniques suitable for studies of colloidal particles in aqueous solutions and discussed their application in the research of amphiphilic block copolymer micelles. Unlike surfactant micelles or phospholipid vesicles, amphiphilic block copolymer micelles have no sharp interface between the hydrophobic interior of the particles and the bulk solution, which results in greater heterogeneity of localization sites of fluorescent probes in the polymeric micelles and consequently in more difficult interpretation of data in comparison with surfactant micelles and phospholipid vesicles. 

In order to determine whether these surfactant vesicles were of polymerized vesicle forms, a 25% V/V ethanol (standard grade) was added to the three year old sample solution. Alcohols are known (34) to destroy surfactant vesicles derived from natural phospholipids, however, synthetically prepared polymerized vesicles are stable in as much as 25% (V/V) alcohol addition. Photomicrographs shown in Figures 7c and 7d indicate that these vesicles partially retain their stability (being mesomorphic) and therefore are suspected to be polymerized surfactants. Whether surfactant molecules of these vesicles are single or multipla bonds in tail, or in head groups remains to be seen. 

Polymerization in Bilayers. Upon irradiation with UV light the monomer vesicles are transferred to polymer vesicles (Figure 12.). In the case of the diyne monomers (2,5-9,12,13,14) the polyreaction can again be followed by the color change via blue to red except phospholipids (5,6), which turn red without going through the blue intermediate as observed in monolayers. The VIS spectra of these polymer vesicle dispersions are qualitatively identical to those of the polymer monolayers (Figure 13.). 

There are several methods to selectively open up closed polymeric membrane compartments in order to release entrapped substances (Fig. 37). For uncorking a polymerized vesicle, its membrane has to contain destabilizable areas which could possibly be opened up by variation of pH 70), temperature increase71), photochemical destabilization 72), or enzymatic processes. Such an enzymatic process is the hydrolysis of a natural phospholipid by phospholipase A2 (Fig. 38). This enzyme cleaves the ester bond in position two of a natural phosphoglyceride producing a lysophospholipid and a fatty acid which are both water soluble. This leads to complete destruction of the membrane. 

Vesicle and micelles are considered to be useful models for minimum protocells that had emerged in prebiotic times [200]. One of their properties should have been to sequester other molecules, including macromolecules, for self-replication. A central enigma to be addressed is related to various routes by which the enantiopure homochiral biopolymers were formed within such architectures. Polymerization of NCA of natural hydrophobic amino acids in water in the presence of phospholipids by Luisi et al. [201] has demonstrated that the hydrophobic environment enhances their rate of polymerization. 

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-... 

Metallization of Polymerized Vesicles Formed from Mixtures of Zwitterlonic and Negatively Charged Phospholipids... 

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