Single Molecule Desorption Studies on Immobilized Nanoclay Particle Surfaces

AFM-based single molecule force spectroscopy was performed on sheetlike inorganic particles of Na-montmorillonite to study the pH-dependent adsorption and desorption behavior of polyelectrolytes in aqueous solutions. Polyallylamine macromolecules were covalently attached on gold-coated AFM cantilevers. Heterogeneous surfaces were formed by immobilizing the nanoclay sheets on mica-stripped ultraflat Au(111) surfaces using aminothiol chemistry. Because of the constant surface charge of the particles over a wide pH range, polymer line charge density was the only parameter that affected the adsorption and desorption behavior when the ionic concentration was kept constant. Polarization modulation infrared-reflection absorption spectroscopy (PM-IRRAS) was performed on cast polyallylamine films to study the pH-dependent charge density of polyallylamine molecules. A good correlation was found between the line charge density and the adsorption characteristics of polyallylamine.