Bilayer, phospholipid

In an extensive SFA study of protein receptor-ligand interactions, Leckband and co-workers [114] showed the importance of electrostatic, dispersion, steric, and hydrophobic forces in mediating the strong streptavidin-biotin interaction. Israelachvili and co-workers [66, 115] have measured the Hamaker constant for the dispersion interaction between phospholipid bilayers and find A = 7.5 1.5 X 10 erg in water. 

There has been a surge of research activity in the physical chemistry of membranes, bilayers, and vesicles. In addition to the fundamental interest in cell membranes and phospholipid bilayers, there is tremendous motivation for the design of supported membrane biosensors for medical and pharmaceutical applications (see the recent review by Sackmann [64]). This subject, in particular its biochemical aspects, is too vast for full development here we will only briefly discuss some of the more physical aspects of these systems. The reader is referred to the general references and some additional reviews [65-69]. 

Procarione W L and Kauffman J W 1974 The electrical properties of phospholipid bilayer Langmuir films Chem. Phys. Lipids 12 251-60... 

Brent et al., 1989] Brent, G. A., Dunn, M. K., Harney, J. W., Gulick, T., and Larsen, P. R. Thyroid hormone aporeceptor represses Ta inducible promoters and blocks activity of the retinoic acid receptor. New Biol. 1 (1989) 329-336 [Cevc and Marsh, 1987] Cevc, G., and Marsh, D. Phospholipid Bilayers Physical Principles and Models. John Wiley Sons, New York, 1987. 

This chapter has given an overview of the structure and dynamics of lipid and water molecules in membrane systems, viewed with atomic resolution by molecular dynamics simulations of fully hydrated phospholipid bilayers. The calculations have permitted a detailed picture of the solvation of the lipid polar groups to be developed, and this picture has been used to elucidate the molecular origins of the dipole potential. The solvation structure has been discussed in terms of a somewhat arbitrary, but useful, definition of bound and bulk water molecules. 

B Roux, TB Woolf. Molecular dynamics of Pfl coat protein in a phospholipid bilayer. In KM Merz Ir, B Roux, eds. Biological Membranes A Molecular Perspective from Computation and Experiment. Boston Birkhauser, 1996, pp 555-587. 

In 1972, S. J. Singer and G. L. Nicolson proposed the fluid mosaic model for membrane structure, which suggested that membranes are dynamic structures composed of proteins and phospholipids. In this model, the phospholipid bilayer is a fluid matrix, in essence, a two-dimensional solvent for proteins. Both lipids and proteins are capable of rotational and lateral movement. 

Particular phospholipids display characteristic transition temperatures (Tm). As shown in Table 9.1, increases with chain length, decreases with unsaturation, and depends on the nature of the polar head group. For pure phospholipid bilayers, the transition occurs over a narrow temperature range. The phase transition for dimyristoyl lecithin has a peak width of about 0.2°C. 

While recent attention has been largely on proteins, it should be borne in mind that membrane fusion ultimately involves the merger of phospholipid bilayers. However, little is known about the specific membrane lipid requirements. When membranes fuse, energetically unfavorable transition states are generated that may require specific lipids and lipid domains for stabilization. Although there is some evidence for a specific influence of lipids on exocytosis, it is still unclear whether specific lipid metabolites are needed or even generated at the site of membrane merger. 

The passage of a small and/or highly lipophilic molecule through the membrane phospholipid bilayer according to the gradient of its concentrations across the plasma membrane. It is slower than facilitated diffusion, which, however, also follows the gradient of solute concentrations across the membrane. 

Crowe, J.H., Crowe, L.M., Carpenter, J.F. Aurell Wistrom, C. (1987). Stabilization of dry phospholipid bilayers and proteins by sugars. Biochemical Journal, 242, 1-10. 

Boden, N., and Sixtl, F. (1986). Forces between phospholipid bilayers, Faraday Disc. Chem. Soc.. 81. 1-9. 

Rand, R. P. (1981). Interacting phospholipid bilayers Measured forces and induced structural changes, Ann. Rev. Biophys. Bioeng.. 10. 277-314. 

Langmuir films have been generated not only from phospholipids but also from tetraether lipids (Fig. 14b). Tetraether glycerophospho- and glycoUpids are typical for ar-chaea, where they may constitute the only polar lipids of the cell envelope [154,155]. Tetraether lipids are membrane-spanning lipids, a single monolayer has almost the same thickness as a phospholipid bilayer. 

Planar phospholipid bilayer [137], tetraether lipid monolayer [21]... 

Spherical unilamellar liposomes [119] Planar phospholipid bilayer [141,142]... 

Modeling Pardaxin Channel. The remarkable switching of conformation in the presence of detergents or phospholipid vesicles (5) suggests that pardaxin is a very flexible molecule. This property helps to explain the apparent ability of pardaxin to insert into phospholipid bilayers. In addition, it is consistent with the suggestion that the deoxycholate-like aminoglycosteroids (5,7) present in the natural secretion from which pardaxin is purified (5) serve to stabilize its dissociated conformation. The question of the mechanism by which pardaxin assembles within membranes is important for understanding pore formation and its cytolytic activity (5). 

TERAO J, PiSKULA M and YAO Q (1994) Protective effect of epicatechin, epicatechin gallate, and quercetin on lipid peroxidation in phospholipid bilayers , Arch Biochem Biophys, 308, 278-84. 

Liposomes — These are synthetic lipid vesicles consisting of one or more phospholipid bilayers they resemble cell membranes and can incorporate various active molecules. Liposomes are spherical, range in size from 0.1 to 500 pm, and are thermodynamically unstable. They are built from hydrated thin lipid films that become fluid and form spontaneously multilameUar vesicles (MLVs). Using soni-cation, freeze-thaw cycles, or mechanical energy (extrusion), MLVs are converted to small unilamellar vesicles (SUVs) with diameters in the range of 15 to 50 nm. ... 

Tamm, L. K. and McConnell, H. M. (1985) Supported phospholipid bilayers. Biophys. 

Zhang, L., Longo, M. L. and Stroeve, P. (2000) Mobile Phospholipid Bilayers Supported on a Polyion/Alkyllhiol Layer Pair. Langmuir, 16, 5093—5099. ... 

Megli and Sabatini [55] studied the phospholipid bilayers after lipoperoxidation. Phospholipids were oxidized, and the oxidized phospholipid species were separated by PLC and estimated by EPR. It was shown that the early stages of lipoperoxidation brought about disordering of the phospholipid bilayer interior rather than fluidity alterations and that prolonged oxidation may result in a loss of structural and chemical properties of the bilayer until the structure no longer holds. 

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,... 

TABLE 5 NMR Characterization of Thermal Phase Transition in Zones I III of Phospholipid Bilayers... 

---