Ultrathin free-standing polyelectrolyte nanocomposites: A novel method for preparation and characterization of assembly dynamics

We present a new opportunity for the investigation of the dynamics of electrostatic ultrathin-film assembly and the elucidation of time scales required for layer-by-layer adsorption of polyelectrolytes using a novel pendant drop technique which allows for the synthesis of free-standing nanocomposites. In short, a charged molecular template, i.e., a lipid monolayer, is deposited on a pendant drop and compressed to present a defined surface charge density to the subphase of the drop. The subphase, is then cycled alternatively between solutions of polycations, saline, and polyanions by injection and withdrawal of liquid from coaxial capillaries on which the drop was formed, resulting in encapsulation of the drop volume by a polymeric composite membrane. The in situ dynamics of the process are followed by axisymmetric drop shape analysis. As a model, nanocomposites of dimyristoyl phosphatidyl glycerol-(polyallylamine hydrochloride/polystyrene sulfonate)(n=1-3) were prepared. The characteristic time scales for assembly range from I to 4 min and increase with film thickness. It is also demonstrated that small-amplitude (> 1%) perturbations in the film density during adsorption prolong the assembly. Both these results underscore the nonequilibrium nature of these materials.