Phospholipid-water interface

From the experiments it is clear that poly electrolyte is adsorbed on the surface of the black lipid film. This applies both to the experiments with gelatin and bovine serum albumin, which gave no decrease of film resistance, and to the experiments with bovine erythrocyte ghost protein and polyphosphate. The adsorption of protein on the phospholipid-water interface may be controlled independently by investigating the electrophoretic behavior of emulsion droplets, stabilized by phospholipid, in a protein solution, as a function of pH. In this way Haydon (3) established protein adsorption on the phospholipid-water interface. If the high resistance (107 ohms per sq. cm.) of black lipid films is to be ascribed to the continuous layer of hydrocarbon chains in the interior of the film, as is generally done, an increase in film conductivity is not expected from adsorption without penetration. 

An important question to consider is where does metal catalysis takes place in multiphase systems In bulk oils systems, the hydrophilic metals would be oriented in the air-oil interface to catalyse lipid oxidation (Figure 10.7). In emulsions and liposomes, the metals would be in solution in the aqueous phases and oriented in either the oil-water or phospholipid-water interfaces, where they may have an affinity for the hydrated layer around the droplets (Figure 10.4). 

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. 

Stigter and Dill [98] studied phospholipid monolayers at the n-heptane-water interface and were able to treat the second and third virial coefficients (see Eq. XV-1) in terms of electrostatic, including dipole, interactions. At higher film pressures, Pethica and co-workers [99] observed quasi-first-order phase transitions, that is, a much flatter plateau region than shown in Fig. XV-6. 

Lipid bilayer (Section 26 4) Arrangement of two layers of phospholipids that constitutes cell membranes The polar termini are located at the inner and outer membrane-water interfaces and the lipophilic hydrocarbon tails cluster on the inside... 

It has been proposed that the a-tocopheroxyl radical can be recycled back to tocopherol by ascorbate producing the ascorbyl radical (Packer etal., 1979 Scarpa et al., 1984). The location of a-tocopherol, with its phytyl tail in the membrane parallel to the fatty acyl chains of the phospholipids and its phenolic hydroxyl group at the memisrane-water interface near the polar headgroups of the phospholipid bilayer, enables ascorbate to donate hydrogen atoms to the tocopheroxyl radical. The suitability for ascorbate and tocopherol as chain-breaking antioxidants is exemplified (Buettner,... 

Phospholipids are amphiphilic compoimds with high surface activity. They can significantly influence the physical properties of emulsions and foams used in the food industry. Rodriguez Patino et al. (2007) investigated structural, morphological, and surface rheology of dipalmitoylpho-sphatidylcholine (DPPC) and dioleoyl phosphatidylcholine (DOPC) monolayers at air-water interface. DPPC monolayers showed structural polymorphisms at the air-water interface as a function of surface pressure and the pH of the aqueous phase (Fig. 6.18). DOPC monolayers showed a... 

Since its first important flowering in the hands of purely physical chemists, interest in monolayers at the air-water interface has waxed and waned with a frequency of roughly 25 years. The first resurrection of interest came from biochemistry, primarily during the 1955-65 decade as phospholipid monolayers were studied as models for the cell membrane (see, for example, Chapman, 1968). This is still a very productive field of biophysical research. 

Unlike electron and scanning tunneling microscopy, the use of fluorescent dyes in monolayers at the air-water interface allows the use of contrast imaging to view the monolayer in situ during compression and expansion of the film. Under ideal circumstances, one may observe the changes in monolayer phase and the formation of specific aggregate domains as the film is compressed. This technique has been used to visualize phase changes in monolayers of chiral phospholipids (McConnell et al, 1984, 1986 Weis and McConnell, 1984 Keller et al., 1986 McConnell and Moy, 1988) and achiral fatty acids (Moore et al., 1986). 

The environment of a cell membrane is often modeled by a monolayer of phospholipid on the air-water interface. Our attempts to detect enantiomeric recognition in such films has largely involved dipalmitoylphosphatidyl choline (DPPC), which has a chiral headgroup situated at the junction of two 16-carbon unit chains. 

Equation 3-1 implies that the 7t-r relationship becomes MN -shaped when becomes sufficiently large. Indeed, Mingins et al. have reported that at the oil/water interface the n-A isotherms of the phospholipids with Ci, C20 and C22 alkyl chains show clear first-order transitions [37],... 

In the above subsection it was demonstrated that the inclusion of electrostatic interactions into the pressure-area-temperature equation of state provides a better fit to the observed equilibrium behavior than the model with two-dimensional neutral gas. Considering this fact, we would like to devote our attention now to the character of the lipid film under the dynamical, nonequilibrium conditions. In the following we shall describe the dynamical behavior of the phospholipid(l,2-dipalmitoyl-3-sn-phosphatidylethanolamines DPPE) thin films in the course of the compression and expansion cycles at air/water interface. 

J. R. Lakowicz, R. B. Thompson, and H. Cherek, Phase fluorometric studies of spectral relaxation at the lipid-water interface of phospholipid vesicles, Biochim. Biophys. Acta 734, 295-308 (1983). 

Pitcher WH III, Keller SL, Huestis WH. Interaction of nominally soluble proteins with phospholipid monolayers at the air-water interface. Biochim Bio-phys Acta 2002 1564 107. 

Figure 1. Various physical states of phospholipids in aqueous solution. Note the following features (a) phospholipids residing at the air/water interface are arranged such that their polar head groups maximize contact with the aqueous environment, whereas apolar side chains extend outward toward the air (b) solitary phospholipid molecules remain in equilibrium with various monolayer and bilayer structures (c) bilayer vesicles and micelles remain in equilibrium with solitary phospholipid molecules, provided that the total lipid content exceeds the critical micelle concentration.

A decrease in occupied area of the head group results in an increase in packing density of the molecules (45) exhibits only an expanded phase, (46) both a liquid and a solid-like phase, and (47) forms only a condensed film. Monolayer properties of many natural phospholipids and synthetic amphiphiles are described in the literature37 38. Especially the spreading behaviour of diacetylenic phospholipids at the gas-water interface was recently described by Hupfer 120). 

Structures formed by phospholipids in aqueous solution. Phospholipids may form a monomolecular layer at the air-water interface, or they may form spherical aggregations surrounded by water. A vesicle consists of a double molecular layer of phospholipids surrounding an internal compartment of water. 

Structures formed by (a) detergents and (b) phospholipids in aqueous solution. Each molecule is depicted schematically as a polar head-group ( ) attached to one or two long, nonpolar chains. Most detergents have one nonpolar chain phospholipids have two. At very low concentrations, detergents or phospholipids form monolayers at the air-water interface. At higher concentrations, when this interface is saturated, further molecules form micelles or bilayer vesicles (liposomes). 

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