Controlling surface mobility in interdiflusing polyelectrolyte multilayers

The phenomenon of interdiffusion of polyelectrolytes during electrostatic layer-by-layer assembly has been extensively investigated in the past few years owing to the intriguing scientific questions that it poses and the technological impact of interdiffusion on the promising area of electrostatic assembly processes. In particular, interdiffusion can greatly affect the final morphology and structure of the desired thin films, including the efficacy and function of thin film devices created using these techniques. Although there have been several studies on the mechanism of film growth, little is known about the origin and controlling factors of interdiffusion phenomena. Here, we demonstrate a simple but robust method of observing the process of polyelectrolyte interdiffusion by adsorbing charged viruses onto the surface of polyelectrolyte multilayers. The surface mobility of the underlying polycation enables the close-packing of viruses adsorbed electrostatically to the film so as to achieve a highly packed structure. The ordering of viruses can be controlled by the manipulation of the deposition pH of the underlying polyelectrolyte multilayers, which ultimately controls the thickness of each layer, effective ionic cross-link density of the film, and the surface charge density of the top surface. Characterization of the films assembled at different pH values were carried out to confirm that increased quantities of the mobile polycation LPEI incorporated at higher pH adsorption conditions are responsible for the ordered assembly of viruses. The surface mobility of viruses atop the underlying polyelectrolyte multilayers was determined using fluorescence recovery after photobleaching technique, which leads to estimate of the diffusion coefficient on the order of 0.1 mu m(2)/sec for FITC-labeled viruses assembled on polyelectrolyte multilayers.