Kinetics of Macroion Adsorption on Silica: Complementary Theoretical and Experimental Investigations for Poly-l-arginine.

A comprehensive approach enabling a quantitative interpretation of poly-l-arginine (PARG) adsorption kinetics at solid/electrolyte interfaces was developed. The first step involved all-atom molecular dynamics (MD) modeling of physicochemical characteristics yielding PARG molecule conformations, its contour length, and the cross-section area. It was also shown that PARG molecules, even in concentrated electrolyte solutions (100 mM NaCl), assume a largely elongated shape with an aspect ratio of 36. Using the parameters derived from MD, the PARG adsorption kinetics at the silica/electrolyte interface was calculated using the random sequential adsorption approach. These predictions were validated by optical reflectometry measurements. It was confirmed that the molecules irreversibly adsorbed in the side-on orientation and their coverage agreed with the elongated shape of the PARG molecule predicted from the MD modeling. These theoretical and experimental results were used for the interpretation of the quartz crystal microbalance measurements carried out under various pH conditions. A comprehensive analysis unveiled that the results stemming from the hydrodynamic theory postulating a lubrication-like (soft) contact of the macroion molecules with the sensor adequately reflect the adsorption kinetics. The range of validity of the intuitively used Sauerbrey model was also estimated. It was argued that acquired results can be exploited to control macroion adsorption at solid/liquid interfaces. This is essential for the optimum preparation of their supporting layers used for bioparticle immobilization and shell formation at nanocapsules in targeted drug delivery.