Monolayers, insoluble phospholipid

A question of interest here is the origin of the DMPC molecules building up the bilayer, considering the low monomer concentration in the DMPC suspension and the small volume of the drop in the cell. However, as indicated in Section 3.4.3, NBF can be formed only at close packing at the interface (r ). A possible mechanism is the vesicle degradation at the surfaces, i.e. at the solution/air interface. An evidence of this mechanism are the kinetic studies of insoluble phospholipid monolayer of Ivanova et al. [291]. Nevertheless, NBF formation from vesicle suspensions needs further research. 

Cholesterol, which is largely insoluble in aqueous m a, travels through the blood circulation in the form of Upoprotein complexes. The plasma lipoproteins are a family of globular particles that share common structural features. A core of hydrophobic lipid, principally triacylglycerols (triglycerides) and cholesterol esters, is surrounded by a hydrophilic monolayer of phospholipid and protein (the apolipoproteins) [1-3]. Lipid-apolipoprotein interactions, facihtated byi amphi-pathic protein helices that segregate polar from nonpolar surfaces [2,3], provide the mechanism by which cholesterol can circulate in a soluble form. In addition, the apolipoproteins modulate the activities of certain enzymes involved in Upoprotein metabolism and interact with specific cell surface receptors which take up Upopro-teins by receptor-mediated endocytosis. Differences in the Upid and apoUpoprotein compositions of plasma Upoproteins determine their target sites and classification based on buoyant density. 

The pendent drop technique has also been extended to studies of insoluble monolayers of phospholipids at the water/n-dodecane interface (Li et al. 1994b). In these experiments first a monolayer is produced on a water drop surface as described above. Then, the water drop is gently immersed into the second liquid, for example n-dodecane. Then the change of the drop size enables one to compress and expand the interfacial film. Again, the isotherm obtained with ADSA shows the same type of dynamic behaviour as measured with the classic Langmuir-Blodgett trough technique (Thoma Mohwald 1994). 

It can be seen that Eq. (2.157) is just the ordinary Langmuir equation in its generalised form (2.40) which follow rigorously from the analysis of chemical potentials of the components of a mixed monolayer. It was demonstrated that Pethica s equation provides the description of quite complicated systems, including the penetration of a soluble protein into the monolayer of insoluble phospholipids able to form 2D aggregates [155]. In another paper, the case of mixed layers composed of a soluble and a 2D aggregating insoluble surfactant is considered [156]. 

Lipoproteins are molecular aggregates that transport water-insoluble lipids in the blood plasma they contain a core of neutral lipids, coated with a monolayer of phospholipids in which special proteins (apolipoproteins) and cholesterol are embedded. The interaction of apolipoprotein A-I with PC-coated mercury proceeds in steps when increasing progressively its bulk concentration, ca-i [48]. For ca-i < 4 pg cm the differential capacity minimum C is not affected, but the concomitant decrease in the orientation peaks of PC points to an interaction of apoA-I... 

The attachment of pyrene or another fluorescent marker to a phospholipid or its addition to an insoluble monolayer facilitates their study via fluorescence spectroscopy [163]. Pyrene is often chosen due to its high quantum yield and spectroscopic sensitivity to the polarity of the local environment. In addition, one of several amphiphilic quenching molecules allows measurement of the pyrene lateral diffusion in the mono-layer via the change in the fluorescence decay due to the bimolecular quenching reaction [164,165]. 

The effect is more than just a matter of pH. As shown in Fig. XV-14, phospholipid monolayers can be expanded at low pH values by the presence of phosphotungstate ions [123], which disrupt the stmctival order in the lipid film [124]. Uranyl ions, by contrast, contract the low-pH expanded phase presumably because of a type of counterion condensation [123]. These effects caution against using these ions as stains in electron microscopy. Clearly the nature of the counterion is very important. It is dramatically so with fatty acids that form an insoluble salt with the ion here quite low concentrations (10 M) of divalent ions lead to the formation of the metal salt unless the pH is quite low. Such films are much more condensed than the fatty-acid monolayers themselves [125-127]. 

The popular applications of the adsorption potential measurements are those dealing with the surface potential changes at the water/air and water/hydrocarbon interface when a monolayer film is formed by an adsorbed substance. " " " Phospholipid monolayers, for instance, formed at such interfaces have been extensively used to study the surface properties of the monolayers. These are expected to represent, to some extent, the surface properties of bilayers and biological as well as various artificial membranes. An interest in a number of applications of ordered thin organic films (e.g., Langmuir and Blodgett layers) dominated research on the insoluble monolayer during the past decade. 

Monolayers are best formed from water-insoluble molecules. This is expressed well by the title of Gaines s classic book Insoluble Monolayers at Liquid-Gas Interfaces [104]. Carboxylic acids (7-13 in Table 1, for example), sulfates, quaternary ammonium salts, alcohols, amides, and nitriles with carbon chains of 12 or longer meet this requirement well. Similarly, well-behaved monolayers have been formed from naturally occurring phospholipids (14-17 in Table 1, for example), as well as from their synthetic analogs (18,19 in Table 1, for example). More recently, polymerizable surfactants (1-4, 20, 21 in Table 1, for example) [55, 68, 72, 121], preformed polymers [68, 70, 72,122-127], liquid crystalline polymers [128], buckyballs [129, 130], gramicidin [131], and even silica beads [132] have been demonstrated to undergo monolayer formation on aqueous solutions. 

Amphiphilic molecules form monomolecular films on liquid surfaces. Some amphiphiles, such as phospholipids, with a large hydrophobic tail are practically insoluble in water and therefore form insoluble monolayers at the air-water interface. 

It is well known that water dispersions of amphiphile molecules may undergo different phase transitions when the temperature or composition are varied [e.g. 430,431]. These phase transitions have been studied systematically for some of the systems [e.g. 432,433]. Occurrence of phase transitions in monolayers of amphiphile molecules at the air/water interface [434] and in bilayer lipid membranes [435] has also been reported. The chainmelting phase transition [430,431,434,436] found both for water dispersions and insoluble monolayers of amphiphile molecules is of special interest for biology and medicine. It was shown that foam bilayers (NBF) consist of two mutually adsorbed densely packed monolayers of amphiphile molecules which are in contact with a gas phase. Balmbra et. al. [437J and Sidorova et. al. [438] were among the first to notice the structural correspondence between foam bilayers and lamellar mesomorphic phases. In this respect it is of interest to establsih the thermal transition in amphiphile bilayers. Exerowa et. al. [384] have been the first to report such transitions in foam bilayers from phospholipids and studied them in various aspects [386,387,439-442]. This was made possible by combining the microscopic foam film with the hole-nucleation theory of stability of bilayer of Kashchiev-Exerowa [300,402,403]. Thus, the most suitable dependence for phase transitions in bilayers were established. 

TiTuch of our understanding of the phase behavior of insoluble - monolayers of lipids at the air-water interface is derived from Adam s studies of fatty acid monolayers (I). It is now clear that the phase behavior of phospholipid monolayers (2) parallels that of the fatty acids we make use of these structure variations in our study of the interactions of phosphatidylcholine (lecithin) monolayers with proteins. Because of the biological significance of the interfacial behavior of lipids and proteins, there is a long history of studies on such systems. When Adam was studying lipid monolayers, other noted contemporary surface chemists were studying protein monolayers (3) and the interactions of proteins with lipid monolayers (4). The latter interaction has been studied by many so-called 4 penetration experiments where the protein is injected into the substrate below insoluble lipid monolayers that are spread on the... 

The theory which describes the penetration of a soluble surfactant into a monolayer formed by molecules possessing equal partial molar area (mixtures of homologues), was extended recently to include the actual process of protein penetration into 2D aggregating phospholipid monolayer [155, 157]. This extension was based on the concept of independent segments of the protein molecules, occupying an area equal to that of the phospholipid molecule. In the theoretical models, various mechanisms for the effect of the soluble surfactant on the aggregation of the insoluble component can be considered ... 

PHA synthases are members of a new family of enzymes with unique features, considering the functional role in biogenesis of these water-insoluble subcellular structures, also called PHA granules, as well as the possible association with a phospholipid monolayer. The self-assembly of the PHA particles... 

Plasma lipoproteins (LPs) are soluble aggregates of lipids and proteins that deliver hydrophobic, water-insoluble lipids (triglycerides and cholesteryl esters) from the liver and intestine to other tissues in the body for storage or utilization as an energy source [60]. All LP particles have a common structure of a neutral lipid core surrounded by a surface monolayer of amphipathic lipids (phospholipids and unesterified cholesterol) and some specific apoproteins (Fig. 14). The LPs are usually classified according to density, from very low-density lipoprotein (VLDL) to high-density lipoprotein (HDL). The size of LPs varies from 5-12 nm for HDL to 30-80 nm for VLDL. 

Artificial lipid vesicles, termed liposomes, are colloid particles in which phospholipid bilayers or tetraether monolayers encapsulate an aqueous medium. Because of their physicochemical properties, liposomes are widely used as model systems for biological membranes and as delivery systems for biologically active molecules. In general, water-soluble molecules are encapsulated within the aqueous compartment whereas water insoluble substances may be intercalated into the liposomal membrane [147]. 

Plasma lipoproteins are uniquely endowed with the ability to transport large quantities of water-insoluble lipids through an aqueous environment. This because the nonpolar lipids (triglyceride and cholesterol ester Fig. 2) are buried in the core of the lipoprotein, surrounded by a monolayer of amphipathic lipids, phospholipid, andunes-terified cholesterol (Fig. 3). 

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