Lipids behavior

An essential component of cell membranes are the lipids, lecithins, or phosphatidylcholines (PC). The typical ir-a behavior shown in Fig. XV-6 is similar to that for the simple fatty-acid monolayers (see Fig. IV-16) and has been modeled theoretically [36]. Branched hydrocarbons tails tend to expand the mono-layer [38], but generally the phase behavior is described by a fluid-gel transition at the plateau [39] and a semicrystalline phase at low a. As illustrated in Fig. XV-7, the areas of the dense phase may initially be highly branched, but they anneal to a circular shape on recompression [40]. The theoretical evaluation of these shape transitions is discussed in Section IV-4F. 

The interest in vesicles as models for cell biomembranes has led to much work on the interactions within and between lipid layers. The primary contributions to vesicle stability and curvature include those familiar to us already, the electrostatic interactions between charged head groups (Chapter V) and the van der Waals interaction between layers (Chapter VI). An additional force due to thermal fluctuations in membranes produces a steric repulsion between membranes known as the Helfrich or undulation interaction. This force has been quantified by Sackmann and co-workers using reflection interference contrast microscopy to monitor vesicles weakly adhering to a solid substrate [78]. Membrane fluctuation forces may influence the interactions between proteins embedded in them [79]. Finally, in balance with these forces, bending elasticity helps determine shape transitions [80], interactions between inclusions [81], aggregation of membrane junctions [82], and unbinding of pinched membranes [83]. Specific interactions between membrane embedded receptors add an additional complication to biomembrane behavior. These have been stud-... 

Most of the Langmuir films we have discussed are made up of charged amphiphiles such as the fatty acids in Chapter IV and the lipids in Sections XV-4 and 5. Depending on the pH and ionic strength of the subphase, electrostatic effects can become quite important. Here we develop the theoretical foundation for charged films with the Donnan relationship. Then we mention the influence of subphase pH on film behavior. 

Muller M and Sohiok M 1998 Caloulation of the phase behavior of lipids Phys. Rev. E 57 6973... 

Two physically reasonable but quite different models have been used to describe the internal motions of lipid molecules observed by neutron scattering. In the first the protons are assumed to undergo diffusion in a sphere [63]. The radius of the sphere is allowed to be different for different protons. Although the results do not seem to be sensitive to the details of the variation in the sphere radii, it is necessary to have a range of sphere volumes, with the largest volume for methylene groups near the ends of the hydrocarbon chains in the middle of the bilayer and the smallest for the methylenes at the tops of the chains, closest to the bilayer surface. This is consistent with the behavior of the carbon-deuterium order parameters,. S cd, measured by deuterium NMR ... 

Lipids in model systems are often found in asymmetric clusters (see Figure 9.8). Such behavior is referred to as a phase separation, which arises either spontaneously or as the result of some extraneous influence. Phase separations can be induced in model membranes by divalent cations, which interact with negatively charged moieties on the surface of the bilayer. For example, Ca induces phase separations in membranes formed from phosphatidylserine (PS)... 

The sharpness of the transition in pure lipid preparations shows that the phase change is a cooperative behavior. This is to say that the behavior of one or a few molecules affects the behavior of many other molecules in the vicinity. The sharpness of the transition then reflects the number of molecules that are acting in concert. Sharp transitions involve large numbers of molecules all melting together. 

Some transport proteins merely provide a path for the transported species, whereas others couple an enzymatic reaction with the transport event. In all cases, transport behavior depends on the interactions of the transport protein not only with solvent water but with the lipid milieu of the membrane as well. The dynamic and asymmetric nature of the membrane and its components (Chapter 9) plays an important part in the function of these transport systems. 

There is a substantial weight of evidence for the cytoskeleton being responsible for the force production and control of cell locomotion. This view has not yet been accepted unanimously. However, an alternative hypothesis continues to be argued which states that membrane cycling is the motive force driving cell locomotion (Bretscher, 1987). One of the predictions of the membrane flow hypothesis is that there should be a discernible flow of lipid from the front to the rear of the cell. Lipid flow has proven very difficult to study, because of the lack of suitable methods to label single lipid molecules and the heterogenous behavior of membrane-associated proteins. The observation that particles were transported rearward when they bound... 

An alternative approach is the use of pH-sensitive fluorophores (Lichtenberg and Barenholz, lOSS). These probes are located at the lipid-water interface and their fluorescence behavior reflects the local surface pH, which is a function of the surface potential at the interface. This indirect approach allows the use of vesicles independent of their particle size. Recently, techniques to measure the C potential of Liposome dispersions on the basis of dynamic light scattering became commercially available (Muller et al., 1986). 

Biochemical studies with purified preparations incorporated into liposomes have also been performed [32,33,96-98]. Reconstituted receptors from skeletal muscle bound DHPs, PAAs and diltiazem with high affinity and in a 1 1 1 stoichiometry [97], In general, the reconstituted proteins exhibit the characteristic pharmacological properties expected for these channels. In recent studies, our laboratory has reconstituted partially purified channels into liposomes containing the Ca -sensitive fluorescent dye, fluo-3 [33,96]. These channels exhibit Ca influx that is sensitive to activation by Ca channel activators and inhibitors with affinities similar to those observed in intact cells, and the Ca influx is dependent on the establishment of a gradient in the presence of valinomycin [132]. This assay provides a convenient and rapid approach to obtaining a macroscopic picture of the activity of the channels under different conditions, while the more complex studies in lipid bilayers provide a more complete analysis of the single channel behavior. 

Figure 13.6 (a) Confocal micrograph of a circularly self-spreading lipid monolayer. A rhodamine-labeled lipid is doped to visualize the spreading behavior, (b) A schematic illustration of the front edge of the self-spreading lipid monolayer [51]. 

In addition to the self-spreading lipid bilayer, it was also found that a lipid mono-layer showed similar spreading behavior on a hydrophobic surface (Figure 13.6) [51]. By fabricating an appropriate hydrophobic surface pattern, the spreading area and direction can be easily controlled. For both the self-spreading bilayer and monolayer, non-biased molecular transportation is an important key concept for the next generation of microfiuidic devices. 

In addition to the spreading dynamics, the stacking structure of the self-spreading lipid bilayer is also controllable via the NaCl concentration [54, 55]. Further experimental and theoretical investigations regarding the control of self-spreading are required before we will be able to easily control the self-spreading behavior in microfluidic devices. 

Suzuki, K. and Masuhara, H. (2005) Groove-spanning behavior of lipid membranes on microfabricated silicon substrates. Langmuir, 21, 6487-6494. 

BCR RM 40 Wholemeal Wheat Flour a <0.03 w.c. = 1.70 + 0.04 %. It is important to note that this material is likely to have handling problems due to its hygroscopic behavior. The water activity is in the range where the monomolecular surface layer of water may be removed. Thus, deterioration of the lipids is hkely to occur during storage. 

With high-fat materials and small Dump volumes, the CPC eluate may contain more than 0.5 g of lipids. This may seriously affect the elution behavior of the analytes when the CPC eluate is cleaned up further with Modules Cl and C2. 

The lipases demonstrated very high stability in media partially or totally composed of organic solvent. In such media, the lipases catalyze esterification, transesterification, and resolution of enantiomers [19,45,75,97-100]. Nevertheless, several biphasic systems (organic-aqueous) are used for hydrolysis of lipid and fats [7,34,101]. Kinetic studies in biphase media or in inverted micelles demonstrate that the lipase behavior is different... 

Lipophilicity is a molecular property expressing the relative affinity of solutes for an aqueous phase and an organic, water-immiscible solvent. As such, lipophilicity encodes most of the intermolecular forces that can take place between a solute and a solvent, and represents the affinity of a molecule for a lipophilic environment. This parameter is commonly measured by its distribution behavior in a biphasic system, described by the partition coefficient of the species X, P. Thermodynamically, is defined as a constant relating the activity of a solute in two immiscible phases at equilibrium [111,112]. By convention, P is given with the organic phase as numerator, so that a positive value for log P reflects a preference for the lipid phase ... 

Lipids may be defined as a large group of molecules with a substantial portion of aliphatic or aromatic hydrocarbon. Included are molecules with diverse chemical characteristics, such as the hydrocarbons, soaps, detergents, acylglycerols, steroids, phospholipids, sphin-golipids, and fat-soluble vitamins, and, subsequently, with diverse physical behavior. One of the most important characteristics of lipids from a biological aspect is their behavior in aqueous environments, as all cells exist in an aqueous milieu. In this respect, the lipids range from almost total insolubility to nearly complete solubility. 

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