Dendrimer induced interaction forces between colloidal particles revealed by direct force and aggregation measurements

• Charge reversal of colloidal particles occurs due to adsorption of dendrimers.
• The adsorption leads to formation of surface charge heterogeneities.
• Forces originate from DLVO and attractive patch–charge interactions.
• The strength of patch–charge interactions increases with denrimer generation.
• Results from aggregation and direct force measurements agree reasonable well.

Interaction forces and aggregation rates were determined in order to characterize colloid stability of negative carboxyl latex particles in the presence of oppositely charged poly(amido amine) (PAMAM) dendrimers of three different generations G4, G7 and G10. The force profiles were measured by the atomic force microscopy (AFM) based on multi-particle colloidal probe technique. Close to the isoelectric point, the measured force profiles were more attractive than the pure van der Waals interactions. This behavior was rationalized in term of an additional electrostatic patch–charge contribution whose magnitude increases by increasing the dendrimer generation. The aggregation rates were calculated from these results using the classical theory developed by Derjaguin, Landau, Verwey and Overbeek (DLVO) as well as including the additional attractive term and a radially symmetric force field. The calculated aggregation rates were compared to the ones obtained directly from time-resolved dynamic light scattering (DLS) measurements using exactly the same latex particles as in the AFM study. The results from these two methods were in good agreement in the case of dendrimers of lower generation, while at higher generation, significant differences were found. In the latter case, the stability ratio in the slow aggregation regime extracted from direct force measurements was much higher than the one measured experimentally by DLS. Despite the fact that the additional attractive term was included in the calculation, the discrepancy between the two different stability ratios suggests that the assumption of radial symmetric interaction is weak.

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