Hypothesis: Adsorption of weak polyelectrolytes onto charged nanoparticles, and concurrent effects such as spatial partitioning of ions may be influenced by details of the polyelectrolyte structure (linear or star-like) and size, by the mobility of the nanoparticle surface charge, or the valence of the nanoparticle counterions.
Experiments: Ionization and complexation of weak polyelectrolytes on spherical macroions with monovalent and divalent countrions has been studied with constant-pH Monte Carlo titrations and primitive electrolyte models for linear and star-like polymers capable, also, of forming charged hydrogen bonds. Nanoparticles surface charge has been represented either as a single colloid-centered total charge (CCTC) or as surface-tethered mobile monovalent spherical charges (SMMSC).
Findings: Differences in the average number of adsorbed polyelectrolyte arms and their average charge, and in the relative amount of macroion counterions (m-CI's) released upon polymer adsorption are found between CCTC and SMMSC nanoparticles. The amount of the counterions released also depends on the polymer structure. As CCTC adsorbs a lower number of star-like species arms, the degree of condensation of polymer counterions (p-CI's) onto the polyelectrolyte is also substantially higher for the CCTC colloid, with a concurrent decrease of the osmotic coefficient values.
Keywords: Counterion desorption; Monte Carlo simulations; Nanoparticles; Polyelectrolytes; Polymer adsorption; Titrations.
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