Free-Radical Formation by the Peroxidase-Like Catalytic Activity of MFe2O4 (M = Fe, Ni, and Mn) Nanoparticles

Ferrite magnetic nanoparticles (MNPs) have peroxidase-like activity and thus catalyze the decomposition of H2O2-producing reactive oxygen species (ROS). Increasingly important applications of these ferrite MNPs in biology and medicine require that their morphological, physicochemical, and magnetic properties need to be strictly controlled. Usually, the tuning of their magnetic properties is achieved by the replacement of Fe by other 3d metals, such as Mn or Ni. Here, we studied the catalytic activity of ferrite MNPs (MFe2O4, M = Fe2+/Fe3+, Ni, and Mn) with the mean diameter ranging from 10 to 12 nm. Peroxidase-like activity was studied by electron paramagnetic resonance (EPR) using the spin-trap 5,5-dimethyl-1-pyrroline N-oxide at different pHs (4.8 and 7.4) and temperatures (25 and 40 degrees C). We identified an enhanced amount of hydroxyl ((OH)-O-center dot) and perhydroxyl ((OOH)-O-center dot) radicals for all samples, compared to a blank solution. Quantitative studies show that [(OH)-O-center dot] is the dominant radical formed for Fe3O4, which is strongly reduced with the concomitant oxidation of Fe2+ or its substitution (Ni or Mn). A comparative analysis of the EPR data against in vitro production of ROS in microglial BV2 cell culture provided additional insights regarding the catalytic activity of ferrite MNPs, which should be considered if biomedical uses are intended. Our results contribute to a better understanding of the role played by different divalent ions in the catalytic activity of ferrite nanoparticles, which is very important because of their use in biomedical applications.