Adsorption of poly(amido amine) (PAMAM) dendrimers on silica: importance of electrostatic three-body attraction.

Adsorption of poly(amido amine) (PAMAM) dendrimers to silicon oxide surfaces was studied as a function of pH, ionic strength, and dendrimer generation. By combining optical reflectometry and atomic force microscopy (AFM), the adsorbed layers can be fully characterized and an unequivocal determination of the adsorbed mass becomes possible. For early stages, the adsorption process is transport limited and of first order with respect to the dendrimer solution concentration. For later stages, the surface saturates and the adsorbed dendrimers form loose but correlated liquidlike surface structures. This correlation is evidenced by a peak in the pair correlation function determined by AFM. The maximum adsorbed amount increases with increasing ionic strength and pH. The increase with the ionic strength is explained by the random sequential adsorption (RSA) model and electrostatic repulsion between the dendrimers. The adsorbing dendrimers interact by the repulsive screened Coulomb potential, whose range decreases with increasing ionic strength and thus leads to increasing adsorbed densities. The pH increase is interpreted as an effect of the substrate and is quantitatively explained by the extended three-body RSA model. This model stipulates the importance of a three-body interaction acting between two adsorbing dendrimers and the charged substrate. The presence of the charged substrate weakens the repulsion between the adsorbing dendrimers and thus leads to higher surface densities. This effect can be interpreted as an additional attractive three-body interaction, which acts in addition to the usual two-body repulsion and originates from the additional screening of the Coulomb repulsion by the counterions accumulating in the diffuse layer.