Structure, Ecotoxicity, Redox and Bactericidal Activity of Cu-Containing Nanocrystalline Ferrites

Cu-modified ferrites, prepared by solvothermal syntheses, at up to 200 °C, show the presence of copper metal particles, embedded in ferrite nanocrystalline particle agglomerates. Notably, these metallic copper micron-sized crystallites were dramatically reduced in size, down to a few tens of nanometers, when part of the copper dopant was replaced by zinc. All materials were magnetic due to the presence of the cubic spinel phase, being ferrimagnetic, measured with external fields up to 6000 Oe, showing a narrow hysteresis of 89 Oe for the largest particle size copper ferrite material of 15 nm. Superparamagnetic behavior was observed for the smallest size, e.g., 11 nm, Cu-doped and the zinc-doped, 9-10 nm average particle size ferrites. The redox activity of the materials was studied in free-radical oxidation reactions (pH 7.4, physiological and pH 8.5, optimal) by the chemiluminescent method with (i) Fenton's reagent (^·OH, ^·OOH); (ii) H₂O₂; and (iii) O₂^·- radicals. All materials presented extremely strong inhibitory activities (converted to prooxidant only at pH 7.4 in system iii, excluding the largest isolated copper-particle-containing material, which remained inhibitory). The materials' antimicrobial potential was checked on Gram-positive and Gram-negative bacteria, Escherichia coli ATCC 25922, and Staphylococcus aureus ATCC 25923 via two classical methods, namely the spot and well diffusion tests in agar medium. The above tests included a nanocrystalline CuO, tenorite, as a reference material too. The Daphnia magna ecotoxicity test showed that all of the investigated materials are rather toxic, and since daphnia is a key component in freshwater ecosystems, the toxicity even at low concentrations may have significant consequences for the ecological balance. This requires careful monitoring and assessment of the possible use or disposal of these nanomaterials in the environment.