Physical Adsorption of Bilayer Membranes on Silica

Abstract

Isotherms for adsorption of bilayer-forming synthetic amphiphiles or phospholipids from vesicles onto hydrophilic silica particles (Aerosil OX-50) are obtained over a range of experimental conditions. Phosphatidylcholine (PC), dipalmitoylphosphatidylcholine (DPPC), dihexadecylphosphate (DHP), and dioctadecyldimethylammonium bromide (DODAB) dispersed in 10 mMTris, pH 7.4, as small unilamellar vesicles present affinities for silica following the sequence DODAB > DPPC > PC > DHP. Among these, only DHP adsorption is below that expected for one bilayer deposition. Interaction at 65°C for 1 h between DPPC (or, at 25°C, for PC) vesicles and silica efficiently leads to bilayer deposition at maximal adsorption, if Tris is the buffer used. Preliminary centrifugation of the PC or DPPC vesicle dispersion is necessary to prevent overestimated adsorption. PC affinity for silica and its deposition as a bilayer depend on the nature of buffer used being much higher for Tris than for Hepes at pH 7.4. Formation of ion pairs between protonated amino groups in Tris and silanol groups on silica may lead to Tris adsorption and an increase in density of –OH groups on the solid surface. Therefore, formation of cooperative hydrogen bridges between –P=O in the phosphatidyl of the phospholipid bilayer and the –OH groups of Tris adsorbed on silica increases PC affinity for silica in the presence of Tris. For Hepes as buffer, PC affinity for silica is much lower and no plateau indicative of bilayer deposition is observed in the adsorption isotherm. Stabilization of supported phospholipid bilayers on solid surfaces requires several cooperative hydrogen bridges between the phospholipid and the solid surface. DODAB adsorption was unaffected by vesicle age and physical state of the bilayer vesicle. Adsorption isotherms for DODAB are of the high-affinity type with a maximum indicative of competition between intervesicle interactions and DODAB deposition on silica. Stabilization of DODAB bilayer deposition requires surface charge densities on silica higher than −1 μC/cm2.