A set of seven different palladium nanoparticle (PdNP) systems stabilized by small amounts (1.0 mg/mL) of structurally related macromolecular capping agents were comparatively tested as catalyst in p-nitrophenol (Nip) reduction and Suzuki cross-coupling reactions. The observed rate constants (k(obs)) for Nip reduction were in the range of 0.052-3.120 x 10(-2) s(-1), and the variation reflected the effects of polymer chain conformation, ionic strength and palladium-polymer complex coordination. Macromolecules featuring pendant pyridyl moieties or inverse temperature-dependent solubility were found to be unsuitable capping agents for PdNPs catalysts, despite being active. The catalytic activity in Suzuki cross-coupling reactions followed the same behavior; the most active particles in the Nip reaction also mediated the cross-coupling reaction providing the expected products in quantitative yields under relatively mild conditions after only 4 h at 50 degrees C. Experiments involving the successive addition of reactants and catalyst recovery/re-use indicated that the recycling potential was comparable to those of the standards used in this field. (C) 2014 Elsevier Inc. All rights reserved.