Langmuir, Vol.10, No.6, 1871-1876, 1994
Effects of Metal-Ions on the Equilibrium Thicknesses of Foam Films Stabilized by Lysophosphatidylcholine as Studied by FT-Ir Spectroscopy
The core thicknesses of macroscopic, vertical foam films have been measured by FT-IR technique for the equilibrium films formed from palmitoyllysophosphatidylcholine (lysoPC) solutions in varying concentrations of NaCl and CaCl2. The addition of NaCl exhibits no effect on the core thicknesses of equilibrium films; Newton black films (NBF) with constant core thickness of 2.5 nm are observed in the range of the measured concentrations up to 1 M NaCl. Whereas, in CaCl2 the core thicknesses in equilibrium state strongly depend on CaCl2 concentrations. Consequently, the equilibrium films are NBF at below about 1.1 X 10(-3) M, silver films (SF) at about 1-4 X 10(-3) M, common black films (CBF) at about 5 X 10(-3) to 0.2 M and again NBF at higher concentrations than about 0.2 M. These transitions of film thickness are thought to be due to specific adsorption of Ca2+ on the zwitterionic head group. So, using the measured thickness of the film core and the Lifshitz theory applied for a triple-layer model, van der Waals dispersion forces (II(v)) were calculated and from the II(v) the effective Hamaker constants, A (h, 298 K), for a foam water film were simultaneously calculated. The values obtained vary from 2 X 10(-20) J to 4.5 X 10(-20) J in the range 5nm - 30nm of film thicknesses. Next, for the equilibrium SF and CBF, surface potential (psi0), surface charge density (sigma), and the binding constant (K) of Ca2+ to the equilibrium foam films were evaluated using the charge-regulation model taking account of the DLVO theory of colloid stability. At the thickness-transition concentration of 1.1 X 10(-3) M CaCl2 psi0 and sigma are 11 mV and 1.3 X 10(-3) C m-2, respectively. Further, K is almost independent of the CaCl2 concentration in the range 3 X 10(-2) M to 0.1 M, i.e., the binding constant of Ca2+ to the lysoPC foam film is given as 15 +/- 5 M-1 assuming a 2:1 stoichiometry for the PC/Ca2+.
Keywords:PHOSPHATIDYLCHOLINE BILAYER-MEMBRANES;DIVALENT-CATIONS;MAGNETIC-RESONANCE;VANDERWAALS FORCES;BINDING;CALCIUM;WATER;PHOSPHATIDYLETHANOLAMINE;SYSTEMS