Rigid bilayers

Liposomes are members of a family of vesicular structures which can vary widely in their physicochemical properties. Basically, a liposome is built of one or more lipid bilayers surrounding an aqueous core. The backbone of the bilayer consists of phospholipids the major phospholipid is usually phosphatidylcholine (PC), a neutral lipid. Size, number of bilayers, bilayer charge, and bilayer rigidity are critical parameters controlling the fate of liposomes in vitro and in vivo. Dependent on the preparation procedure unilamellar or multilamellar vesicles can be produced. The diameter of these vesicles can range from 25 nm up to 50 ym—a 2000-fold size difference. 

Bilayer rigidity is a parameter which influences biodistribution and biodegradation of liposomes. In vitro a hydrophilic marker molecule (carboxyfluorescein) leaked much faster from the vesicles with bilayers in a fluid state than from bilayers in a gel state (Crommelin and Van Bommel, 1984). An indication of the bilayer rigidity can... 

Figure 5 Snapshot of a lipid raft system studied through atomistic molecular dynamics simulations (42). Water is shown at the top and at the bottom in light color, while the membrane is in the middle of the figure. In the bilayer, rigid cholesterol molecules are shown in light grey, POPC in dark grey, and sphingomyelin in intermediate grey.

Dobretsov, G.E. Borschevskaya, T.A. Petrov, V.A. Vladimirov, Y. A. The increase of phospholipid bilayer rigidity after lipid peroxidation. FEBS Lett. 1977, 84, 125-134. 

CH has well-known effects on lipid bilayer rigidity and stability (17). Bilayer stability effects are reflected by the effect of CH concentration on phase transition temperature (18), saturated lipid segregation, bilayer fusion temperature and bilayer fluidity (19). 

The arrangement of hydrocarbon chains in the interior of a phospholipid bilayer varies from rigid to fluid, depending on the degree of unsaturation of the chains themselves. Saturated hydrocarbon chains tend to lie parallel and closely packed, making the bilayer rigid. 

The characteristics of the liposome membrane can be tuned by changing the lipid composition, thus achieving certain physicochemical properties, as size, surface charge (defined by the zeta potential), stabiUty, bilayer rigidity, and permeabiUty. In this way, liposomes can be classified according to their structural properties, that is, size and number of lamellae or charge. 

Many complex systems have been spread on liquid interfaces for a variety of reasons. We begin this chapter with a discussion of the behavior of synthetic polymers at the liquid-air interface. Most of these systems are linear macromolecules however, rigid-rod polymers and more complex structures are of interest for potential optoelectronic applications. Biological macromolecules are spread at the liquid-vapor interface to fabricate sensors and other biomedical devices. In addition, the study of proteins at the air-water interface yields important information on enzymatic recognition, and membrane protein behavior. We touch on other biological systems, namely, phospholipids and cholesterol monolayers. These systems are so widely and routinely studied these days that they were also mentioned in some detail in Chapter IV. The closely related matter of bilayers and vesicles is also briefly addressed. 

Phosphatidylcholine is an important component of cell membranes but cell mem branes are more than simply lipid bilayers Although their composition varies with their source a typical membrane contains about equal amounts of lipid and protein and the amount of cholesterol m the lipid fraction can approximate that of phosphatidylcholine The lipid fraction is responsible for the structure of the membrane Phosphatidyl choline provides the bilayer that is the barrier between what is inside the cell and what IS outside Cholesterol intermingles with the phosphatidylcholine to confer an extra measure of rigidity to the membrane... 

Bead-spring models without explicit solvent have also been used to simulate bilayers [40,145,146] and Langmuir monolayers [148-152]. The amphi-philes are then forced into sheets by tethering the head groups to two-dimensional surfaces, either via a harmonic potential or via a rigid constraint. 

Other examples of organized molecular assemblies of interest for photocatalysis are (1) PC-A, PC-D or D-PC-A molecules where PC, A and D fragments are separated by rigid bridges (2) host-guest complexes (3) micelles and microemulsions (4) surfactant monolayers or bilayers attached to solid surfaces, and (5) polyelectrolytes [19]. 

The half-life of liposomes administered in the blood stream is affected by the composition, size, charge, and fluidity. Liposomes with a small size or with a rigid lipid bilayer have a longer half-life (38 9). Large liposomes administered iv tend to accumulate at a lymph node near the injected site. This tendency can be useful for preventing metastases. Liposomes which pass through the lymph node have a tendency to accumulate in the RES, such as the liver and spleen (40,41). The disposition of liposomes is altered by the dose of liposomes as well as size or lipid composition of liposomes. Cholesterol rich liposomes are cleared slower due to... 

Several works have been reported for macroscopically orientated biological membranes.106-109 The biomembrane alignment can be carried out mechanically or magnetically. The first one relies on the deposition of lipid bilayers on the surface of a rigid support (glass plates) such that the bilayer normal is perpendicular to the surface of the support itself. Small peptides and the lipid bilayers can be dissolved in organic solvents which are successively removed under vacuum.105 The re-hydration of the system in a chamber of an optimized temperature, humidity and time gives rise to the desired orientation. 

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