Summary
The surface charge density resulting from the adsorption of hydrophobic anions of dipicrylamine onto dioleyl-lecithin bilayer membranes has been measured directly using a high field pulse method. The surface charge density increases linearly with adsorbate concentration in the water until electrostatic repulsion of impinging hydrophobic ions by those already adsorbed becomes appreciable. Then Gouy-Chapman theory predicts that surface charge density will increase sublinearly, with the power [z +/(z ++2)] of the adsorbate concentration, wherez + is the cation valence of the indifferent electrolyte screening the negatively charged membrane surface. The predicted 1/3 and 1/2 power laws for univalent and divalent cations, respectively, have been observed in these experiments using Na+, Mg++, and Ba++ ions. Gouy-Chapman theory predicts further that the change from linear to sublinear dependence takes place at a surface charge density governed by the static dielectric constant of water and the concentration of indifferent electrolyte. Quantitative agreement with experiment is obtained at electrolyte concentrations of 10−4 m and 10−3 m, but can be maintained at higher concentrations only if the aqueous dielectric constant is decreased. A transition field model is proposed in which the Gouy-Chapman theory is modified to take account of dielectric saturation of water in the intense electric fields adjacent to charged membrane surfaces.
Similar content being viewed by others
References
Andersen, O., Feldberg, S., Nakadomari, H., Levy, S., McLaughlin, S. 1977. Electrostatic potentials associated with the absorption of tetraphenylborate into lipid bilayer membranes.In. Ion Transport Across Membranes. D.C. Tosteson, Yu.A. Ovchinnikov and R. Latorre, editors. p. 325. Raven Press, New York
Andersen, O.S., Fuchs, M. 1975. Potential energy barriers to ion transport within lipid bilayers.Biophys. J. 15:795
Aveyard, R., Haydon, D.A. 1973. An Introduction to the Principles of Surface Chemistry. Cambridge University Press, Cambridge
Barthel, J., Schmithals, F., Behret, H. 1970. Untersuchungen zur Dispersion der komplexen Dielektrizitäts-Konstante wäßriger und nichtwäßriger Elektrolytlösungen.Z. Phys. Chem. (Frankfurt am Main) 71:115
Booth, F. 1951. The dielectric constant of water and the saturation effect.J. Chem. Phys. 19:391, 1327, 1615
Böttcher, C.J.F. 1973. Theory of Electric Polarization (2nd Ed.). Vol. 1, Ch. VII. Elsevier Scientific, Amsterdam
Bruner, L.J. 1975. The interaction of hydrophobic ions with lipid bilayer membranes.J. Membrane Biol. 22:125
Bruner, L.J. 1977. Self-limited adsorption of ions onto bilayer membrane surfaces.In: Ion Transport Across Membranes. D.C. Tosteson, Yu.A. Ovchinnikov and R. Latorre, editors. p. 91. Raven Press, New York
Carroll, B.J., Haydon, D.A. 1975. Electrokinetic and surface potentials at liquid interfaces.J. Chem. Soc. Faraday Trans. 1. 71:361
Cohen, L.A. 1970. Chemical modification as a probe of structure and function.In: The Enzymes (3rd Ed.). P.D. Boyer, editor. Vol. 1, Ch. 3. Academic Press, New York
Conway, B.E., Bockris, J.O'M., Ammar, I.A. 1951. The dielectric constant of the solution in the diffuse and Helmholtz double layers at a charged interface in aqueous solution.Trans. Faraday Soc. 47:756
Davies, M. 1971. Electric field effects in biomolecular systems.Acta Phys. Pol. A40:561
Davies, M. 1976. Some aspects of recent high electric field studies in molecular systems.Acta Phys. Pol. A50:241
Gaboriaud, R. 1966. Sur le compartement des acides non chargés dans les milieux eauméthanol.C. R. Acad. Sci. Ser. C 263:991
Giese, K., Kaatze, U., Pottel, R. 1970. Permittivity and dielectric and proton magnetic relaxation of aqueous solutions of the alkali halides.J. Phys. Chem. 74:3718
Grahame, D.C. 1947. The electrical double layer and the theory of electrocapillarity.Chem. Rev. 41:441
Grahame, D.C. 1950. Effects of dielectric saturation upon the diffuse double layer and the free energy of hydration of ions.J. Chem. Phys. 18:903
Hasted, J.B. 1973. Aqueous Dielectrics. Ch. 2. Chapman and Hall, London
Haydon, D.A., Myers, V.R. 1973. Surface charge, surface dipoles and membrane conductance.Biochim. Biophys. Acta 307:429
Ketterer, B., Neumcke, B., Läuger, P. 1971. Transport mechanism of hydrophobic ions through lipid bilayer membranes.J. Membrane Biol. 5:225
Kirkwood, J.G. 1939. The dielectric polarization of polar liquids.J. Chem. Phys. 7:911
Klotz, I.M., Stellwagen, E.C., Stryker, V.H. 1964. Ionic equilibria in protein conjugates: Comparison of proteins.Biochim. Biophys. Acta 86:122
Kolodziej, H.A., Parry-Jones, G., Davies, M. 1975. High field dielectric measurements in water.J. Chem. Soc. Faraday Trans. 2 71:269
Levine, S., Mingins, J., Bell, G.M. 1967. The discrete-ion effect in ionic double-layer theory.J. Electroanal. Chem. 13:280
Malmberg, C.G., Maryott, A.A. 1956. Dielectric constant of water from 0° to 100°C.J. Res. Nat. Bur. Stand. 56:1
McClellan, A.L. 1974. Tables of Experimental Dipole Moments. Vol. 2, p. 25. Rahara Enterprises, El Cerrito, Calif.
McLaughlin, S. 1972. The mechanism of action of DNP on phospholipid bilayer membranes.J. Membrane Biol. 9:361
McLaughlin, S.G.A., Szabo, G., Eisenman, G. 1971. Divalent ions and the surface potential of charged phospholipid membranes.J. Gen. Physiol. 58:667
McLaughlin, S.G.A., Szabo, G., Eisenman, G., Ciani, S.M. 1970. Surface charge and the conductance of phospholipid membranes.Proc. Nat. Acad. Sci. USA 67:1268
Muller, R.U., Finkelstein, A. 1972. The effect of surface charge on the voltage-dependence conductance induced in thin lipid membranes by monazomycin.J. Gen. Physiol. 60:285
Onsager, L. 1936. Electric moments of molecules in liquids.J. Am. Chem. Soc. 58:1486
Querry, M.R., Curnutte, B., Williams, D. 1969. Refractive index of water in the infrared.J. Opt. Soc. Am. 59:1299
Robinson, R., Levine, S. 1973. The discreteness-of-charge effect at charged aqueous interfaces. III. Smoothly varying dielectric constant in inner region at mercury interface.J. Electroanal. Chem. Interfacial Electrochem. 47:395
Schwarzenbach, G. 1970. Electrostatic and non-electrostatic contributions to ion association in solution.Pure Appl. Chem. 24:307
Tanford, C. 1962. The interpretation of hydrogen ion titration curves of proteins.Adv. Protein Chem. 17:69
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Wang, C.C., Bruner, L.J. Dielectric saturation of the aqueous boundary layers adjacent to charged bilayer membranes. J. Membrain Biol. 38, 311–331 (1978). https://doi.org/10.1007/BF01870149
Received:
Revised:
Issue Date:
DOI: https://doi.org/10.1007/BF01870149