| Electrochemical and PM-IRRAS Studies of the Effect of Cholesterol on the Structure of a DMPC Bilayer Supported at an Au (111) Electrode Surface, Part 1: Properties of the Acyl Chains Biophysical Journal, Volume 89, Issue 1, 1 July 2005, Pages 592-604 Xiaomin Bin, Sarah L. Horswell and Jacek Lipkowski Abstract Charge density measurements and polarization modulation infrared reflection absorption spectroscopy were employed to investigate the spreading of small unilamellar vesicles of a dimyristoylphosphatidylcholine (DMPC)/cholesterol (7:3 molar ratio) mixture onto an Au (111) electrode surface. The electrochemical experiments demonstrated that vesicles fuse and spread onto the Au (111) electrode surface, forming a bilayer, at rational potentials −0.4 V<()<0.4V or field strength <6×10 V m. Polarization modulation infrared reflection absorption spectroscopy experiments provided information concerning the conformation and orientation of the acyl chains of DMPC molecules. Deuterated DMPC was used to subtract the contribution of C-H stretching bands of cholesterol and of the polar head region of DMPC from spectra in the C-H stretching region. The absorption spectra of the C-H stretch bands in the acyl chains were determined in this way. The properties of the DMPC/cholesterol bilayer have been compared with the properties of a pure DMPC bilayer. The presence of 30% cholesterol gives a thicker and more fluid bilayer characterized by a lower capacity and lower tilt angle of the acyl chains. Abstract | Full Text | PDF (279 kb) |
| 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 Biophysical Journal, Volume 85, Issue 6, 1 December 2003, Pages 4055-4075 I. Zawisza, A. Lachenwitzer, V. Zamlynny, S.L. Horswell, J.D. Goddard and J. Lipkowski Abstract Electrochemistry and polarization modulation Fourier transform infrared reflection absorption spectroscopy (PM-FTIRRAS) was employed to investigate fusion of small unilamellar vesicles of 1,2dioyl--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 −8C cm<<0C cm(if the static electric field is <2×10 V/m) to form a bilayer. At <−8C cm, the film is detached from the electrode surface; however, the film remains in close proximity to the surface. The PM-FTIRRAS experiments demonstrated that the field-driven transformation of the film involves changes in hydration, orientation, and conformation in the polar headgroup region and that changes in the packing and tilt of the acyl chains are consequences of the headgroup rearrangements. Abstract | Full Text | PDF (572 kb) |
| Effect of Cationic Lipids in the Formation of Asymmetries in Supported Bilayers Biophysical Journal, Volume 76, Issue 5, 1 May 1999, Pages 2600-2605 M. Käsbauer, M. Junglas and T.M. Bayerl Abstract We have studied the formation of a supported bilayer containing both cationic and zwitterionic lipids by fusion of small unilamellar vesicles (SUV) onto the solid surface at low salt conditions using a combination of attenuated total reflection infrared (ATR-IR) and deuterium NMR spectroscopy with microcalorimetry. The data suggest that a significant cationic lipid asymmetry between the outer (distal) and the inner (proximal) monolayer of a supported bilayer results under conditions of prolonged incubation times of the solid support with the SUV coating solution. For a SUV composition of DPPC/DHDAB (4:1) we observed an enrichment of the cationic component in the proximal monolayer of up to 200% compared to the distal monolayer after 12h incubation. It is suggested that the electrostatic potential arising from the solid surface is the driving force for the creation of this asymmetry by means of directed flip-flop between the monolayers and/or by temporary fusion between SUV from the bulk with the supported bilayer. Abstract | Full Text | PDF (93 kb) |
Copyright © 1997 The Biophysical Society. All rights reserved.
Biophysical Journal, Volume 72, Issue 3, 1404-1413, 1 March 1997
doi:10.1016/S0006-3495(97)78787-3
Research Article
W. Xu, B.L. Blackford, J.G. Cordes, M.H. Jericho, D.A. Pink, V.G. Levadny and T. Beveridge
Department of Physics, Dalhousie University, Halifax, Nova Scotia, Canada.
The interaction of DMPC (L-alpha-dimyristoyl-1,2-diterradecanoyl-sn-glycero-3-phosphoch oli ne, C36H72NO8P) lipid-coated Si3N4 surfaces immersed in an electrolyte was investigated with an atomic force microscope. A long-range interaction was observed, even when the Si3N4 surfaces were covered with nominally neutral lipid layers. The interaction was attributed to Coulomb interactions of charges located at the lipid surface. The experimental force curves were compared with solutions for the linearized as well as with exact solutions of the Poisson-Boltzmann equation. The comparison suggested that in 0.5 mM KCl electrolyte the DMPC lipids carried about one unit of charge per 100 lipid molecules. The presence of this surface charge made it impossible to observe an effective charge density recently predicted for dipole layers near a dielectric when immersed in an electrolyte. A discrepancy between the theoretical results and the data at short separations was interpreted in terms of a decrease in the surface charge with separation distance.