Influence of an electric field on oriented films of DMPC/gramicidin bilayers: a circular dichroism study.

A film of oriented bilayers containing a mixture of gramicidin and dimyristoylphosphatidylcholine (DMPC) has been deposited on a fused-silica window coated with a 10 nm thick gold layer. The thin layer of gold allows the application of an electric potential across the film and the study of its influence on the structure and integrity of the bilayers. Electrochemical measurements, ellipsometry, and far-UV circular dichroism (CD) were employed to characterize the properties of the film of bilayers as a function of the potential applied to the gold electrode. For potentials across the film that are within the range approximately +300 to -150 mV the oriented film of bilayers is stable, and no change in the CD spectra of gramicidin molecule is observed. At more negative potentials, an increase in the film thickness and water content measured by ellipsometry indicated that the film swells and incorporates water, which causes a change in the circular dichroism spectrum of gramicidin molecules in the film. This transformation was interpreted as a change in the average orientation of gramicidin molecules within the film due to a decrease in the ordering of the molecules upon swelling.

Electrochemical and PM-IRRAS a glycolipid-containing biomimetic membrane prepared using Langmuir-Blodgett/Langmuir-Schaefer deposition.

Differential capacitance, chronocoulometry, and polarization modulation infrared reflection absorption spectroscopy (PM-IRRAS) measurements were used to characterize the structure and orientation of a DMPC + cholesterol + GM 1 (60:30:10 mol %) bilayer supported at a Au(111) electrode surface prepared using combined Langmuir-Blodgett/Langmuir-Schaefer (LB/LS) deposition. The electrochemical measurements indicate that the incorporation of ganglioside GM 1 into the membrane significantly improves the quality of the bilayer, reflected in the very low capacitance value of approximately 0.8 microF cm (-2). An analysis of the infrared data suggests that the incorporation of the glycolipid into the membrane changes both the orientation of the lipid acyl chains in the membrane and the hydration of the membrane, particularly with respect to the interfacial region of the lipids.

Influence of the electric field on a bio-mimetic film supported on a gold electrode.

A model biological membrane was formed by fusion of mixed cholesterol and DMPC (dimyristoylphosphatidylcholine) phospholipid vesicles onto a gold-coated quartz support. The gold surface was charged and the influence of the charge at the solid support on the structure and integrity of the phospholipid bilayer was investigated using the specular reflection of neutrons and electrochemical measurements. When the surface charge density is close to zero, the lipid vesicles fuse directly on the surface to form a bilayer with a small number of defects and hence low water content. When the support's surface is negatively charged the film swells and incorporates water due to the field driven poration of the membrane. When the charge density is more negative then -8 microC cm(-2) the bilayer is detached from the metal surface. However, it remains in close proximity to the metal electrode, suspended on a thin cushion of water. The film thicknesses, calculated from neutron reflectivity, have allowed us to determine the tilt angle of the lipid molecules as a function of the support's charge density. The lipid molecules are tilted 55 degrees from the surface normal at zero charge density but become significantly more perpendicular (30 degrees tilt angle) at charge densities more negative than -8 microC cm(-2). The tilt angle measurements are in very good agreement with previous IR studies. This paper describes the highlights of a more in-depth study which is fully described in [1].

Electric field-driven transformations of a supported model biological membrane--an electrochemical and neutron reflectivity study.

A mixed bilayer of cholesterol and dimyristoylphosphatidylcholine has been formed on a gold-coated block of quartz by fusion of small unilamellar vesicles. The formation of this bilayer lipid membrane on a conductive surface allowed us to study the influence of the support's surface charge on the structure and hydration of the bilayer lipid membrane. We have employed electrochemical measurements and the specular reflection of neutrons to measure the thickness and water content in the bilayer lipid membrane as a function of the charge on the support's surface. When the surface charge density is close to zero, the lipid vesicles fuse directly on the surface to form a bilayer with a small number of defects and hence small water content. When the support's surface is negatively charged the film swells and incorporates water. When the charge density is more negative than -8 micro C cm(-2), the bilayer starts to detach from the metal surface. However, it remains in a close proximity to the metal electrode, being suspended on a thin cushion of the electrolyte. The field-driven transformations of the bilayer lead to significant changes in the film thicknesses. At charge densities more negative than -20 micro C cm(-2), the bilayer is approximately 37 A thick and this number is comparable to the thickness determined for hydrated multilayers of dimyristoylphosphatidylcholine from x-ray diffraction experiments. The thickness of the bilayer decreases at smaller charge densities to become equal to approximately 26 A at zero charge. This result indicates that the tilt of the acyl chains with respect to the bilayer normal changes from approximately 35 degrees to 59 degrees by moving from high negative charges (and potentials) to zero charge on the metal.

Electrochemical and photon polarization modulation infrared reflection absorption spectroscopy study of the electric field driven transformations of a phospholipid bilayer supported at a gold electrode surface.

Electrochemistry and polarization modulation Fourier transform infrared reflection absorption spectroscopy (PM-FTIRRAS) was employed to investigate fusion of small unilamellar vesicles of 1,2dioyl-sn-glycero-3-phosphatidyl choline (DOPC) onto the Au(111) electrode. Electrochemical studies demonstrated that the DOPC vesicles fuse and spread onto the gold electrode surface at small charge densities -8 microC cm(-2)

Optical resolution of phosphorus containing calix[4]arenes by additive RP HPLC method.

The RP HPLC method (LiChrosorb RP18 or Separon SGX C18 column, acetonitrile-water 86:14 v/v mobile phase) was applied for enantiomeric separation of topologically chiral 5-bromo-25,26-bis(diethoxyphosphoryl)calix[4]arene 9 or 25-ethyl-26-dihydroxyphosphoryl-calix[4]arene 5. Separation of calixarene 9 was achieved by the addition of D-(-)-tartaric acid which formed hydrogen bonded diastereomeric associates with 9 to the mobile phase. Calixarenephosphoric acid 5 was transformed into diastereomeric salt 6 by addition of L-(-)-alpha-phenylethylamine before RP HPLC separation.

Structure of 3 beta-hydroxy-16-oxo-24-nor-17-azachol-5-eno-23-nitrile and its 20S epimer.

The structures of the title compounds have been investigated in solid state by X-ray and in solution by NMR methods. The configurations at C20 and the preferred conformations of both epimers were established. A full assignment of signals in 1H and 13C NMR spectra was done.