Interface lipid bilayer

SERS has been employed to monitor incorporation of some molecules, such as medicament pirambicin (Heywang et al. 1996) or photosensitizer hypericin (Lajos et al. 2009) inside the membranes. In order to interface lipid bilayers with solid substrates, many groups employ tethered lipid bilayers. In these systems, a lipid... 

Schwarz G 1996 Peptides at lipid bilayers and at the air/water interface Ber. Bunsenges. Rhys. Chem. 100 999-1003... 

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... 

NMR Studies on Lipid Bilayer Interfaces Coupled with Anesthetics and Endocrine Disruptors... 

Molecular study of lipid bilayer interfaces is necessary for a better understanding of the membrane-drug interaction and DD into biomembranes. The points to be clarified are (1) How can we determine DD sites at the bilayer interface (2) What kind of method is advantageous (3) Is it possible to unambiguously specify the bilayer interfacial portion coupled with drugs (4) What are most important characteristics of DD at the bilayer interface In order to answer these important questions, this chapter has been planned. We will emphasize the significance of the molecular level information obtainable from NMR studies. 

IV. LIPID BILAYER INTERFACES COUPLED WITH ANESTHETICS... 

General anesthetics are usually small solutes with relatively simple molecular structure. As overviewed before, Meyer and Overton have proposed that the potency of general anesthetics correlates with their solubility in organic solvents (the Meyer-Overton theory) almost a century ago. On the other hand, local anesthetics widely used are positively charged amphiphiles in solution and reversibly block the nerve conduction. We expect that the partition of both general and local anesthetics into lipid bilayer membranes plays a key role in controlling the anesthetic potency. Bilayer interfaces are crucial for the delivery of the anesthetics. 

Basic concepts and the methods for determining DD sites in lipid bilayer membranes have been developed by NMR on the atomic site level. Lipid bilayer interfaces as delivery sites can be specified by taking advantage of the site selectivity of NMR. DD sites can be generally classified into the three categories in Fig. 6. The distinction is based on the difference in the micropolarity in membranes around the drug. It has been briefly mentioned how to evaluate dynamic properties of drugs in membranes. 

Lessard, J. G. Fragata, M., Micropolarities of lipid bilayers and micelles. 3. Effect of monovalent ions on the dielectric constant of the water-membrane interface of unilamellar phosphatidylcholine vesicles, J. Phys. Chem. 90, 811-817 (1986). 

Fig. 6 The electrical potential, ij/, profile across a lipid bilayer. The transmembrane potential, Aij/, is due to the difference in anion and cation concentrations between the two bulk aqueous phases. The surface potential, ij/s, arises from charged residues at the membrane-solution interface. The dipole potential, J/d, results from the alignment of dipolar residues of the lipids and associated water molecules within the membrane...

Models of lipid bilayers have been employed widely to investigate diffusion properties across membranes through assisted and non-assisted mechanisms. Simple monovalent ions, e.g., Na+, K+, and Cl, have been shown to play a crucial role in intercellular communication. In order to enter the cell, the ion must preliminarily permeate the membrane that acts as an impervious wall towards the cytoplasm. Passive transport of Na+ and Cl ions across membranes has been investigated using a model lipid bilayer that undergoes severe deformations upon translocation of the ions across the aqueous interface [126]. This process is accompanied by thinning defects in the membrane and the formation of water fingers that ensure appropriate hydration of the ion as it permeates the hydrophobic environment. 

A second approach with respect to anisotropic flavin (photo-)chemistry has been described by Trissl 18°) and Frehland and Trissl61). These authors anchored flavins in artificial lipid bilayers by means of C18-hydrocarbon chains at various positions of the chromophore. From fluorescence polarization analysis and model calculations they conclude, that the rotational relaxation time of the chromophore within the membrane is small compared to the fluorescence lifetime (about 2 ns74)). They further obtain the surprising result that the chromophore is localized within the water/lipid interface, with a tilt angle of about 30° (long axis of the chromophore against the normal of the membrane), irrespective of the position where the hydrocarbon chain is bound to the flavin nucleus. They estimate an upper limit of the microviscosity of the membrane of 1 Poise. 

In the literature, one can find many more interesting MD studies concerning lipid bilayers with additives. In particular, a wealth of MD simulations of such systems is in the field of anaesthetics (for a review see [142]). Many anaesthetics tend to accumulate at the membrane/water interface, implying that their potencies are not related to their ability to cross the membrane. Instead, it seems to be more likely that their functioning is via binding to membrane receptors. Generally, they have an effect opposite to that of cholesterol, i.e. they increase the membrane fluidity and permeability. 

Chiu, S. W., Clark, M., Balaji, V., Subramaniam, S., Scott, H. L. and Jakobsson, E. (1995). Incorporation of surface tension into molecular dynamics simulation of an interface a fluid phase lipid bilayer membrane, Biophys. J., 69,1230-1245. 

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