PH and Surface Charge Switchability on Bifunctional Charge Gradients.

Abstract

Multifunctionalized pH-sensitive silica gradients containing acidic and basic functional groups have been prepared to evaluate how the spatial arrangement of active sites on a surface influences the surface charge and pH switchability. The gradient surfaces were prepared using controlled rate infusion in such a manner that the individual gradients in the strong acid (sulfonic acid) and in the weak base (propylamine) align, whereas a gradient in the weakly acidic silanol groups opposes them. The relative amounts of the three species were varied by controlling the composition of the deposition solution, whereas the hydrophobicity of the underlying surface was set by using base layer-coated substrates prepared from either tetramethoxysilane or tetramethoxysilane/octyltrimethoxysilane mixtures. Results from X-ray photoelectron spectroscopy confirm that aligned gradients are formed in both amine and sulfonic acid groups, and the relative amounts bound to the surface follow that expected from the solution composition. Water contact angle measurements show a 40°-50° change across the length of the gradient, the exact values being dependent on the hydrophobicity of the base layer. Zeta potential measurements on gradient mimics reveal that there is a pH where the net charge on the gradient surface is predicted to have a constant but nonzero value. Static contact angle measurements and modeling confirm this prediction. At a pH acidic of this value, the gradient in charge runs in one direction, whereas at a pH basic of this value, the gradient in charge runs in the other direction. This point can be strategically moved from acidic values to basic values by changing the relative amounts of acidic and basic functionalities on the surface. The origin of this unique pH switchability can be found in acid-base chemistry. By modeling the charge along the gradient surface using a simple equilibrium model, a distribution of pKa values were noted in these materials.