Effect of Morphology and Concentration on Crossover between Antioxidant and Pro-oxidant Activity of MgO...

The toxicity of nanomaterials can sometimes be attributed to photogenerated reactive oxygen species (ROS), but these ROS can also be scavenged by nanomaterials, yielding opportunities for crossover between the properties. The morphology of nanomaterials also influences such features due to defect-induced properties. Here we report morphology-induced crossover between pro-oxidant activity (ROS generation) and antioxidant activity (ROS scavenging) of MgO. To study this process in detail, we prepared three different nanostructures of MgO (nanoparticles, nanoplates, and nanorods) and characterized them by HRTEM. These three nanostructures effectively generate superoxide anions (O₂^•-) and hydroxyl radicals (^•OH) at higher concentrations (>500 μg/mL) but scavenge O₂^•- at lower concentrations (40 μg/mL) with successful crossover at 200 μg/mL. Nanorods of MgO generate the highest levels of O₂^•-, whereas nanoparticles scavenge O₂^•- to the highest extent (60%). Photoluminescence studies reveal that such crossover is based on the suppression of F²⁺ and the evolution of F⁺, F₂⁺, and F₂³⁺ defect centers. The evolution of these defect centers reflects the antibacterial activity of MgO nanostructures which is initiated at 200 μg/mL against Gram-positive S. aureus ATCC 29737 and among different bacterial strains including Gram-positive B. subtilis ATCC 6633 and M. luteus ATCC 10240 and Gram-negative E. coli ATCC K88 and K. pneumoniae ATCC 10031. Nanoparticles exhibited the highest antibacterial (92%) and antibiofilm activity (17%) against B. subtilis ATCC 6633 in the dark. Interestingly, the nitrogen-centered free radical DPPH is scavenged (100%) by nanoplates due to its large surface area (342.2 m²/g) and the presence of the F₂⁺ defect state. The concentration-dependent interaction with an antioxidant defense system (ascorbic acid (AA)) highlights nanoparticles as potent scavengers of O₂^•- in the dark. Thus, our findings establish guidelines for the selection of MgO nanostructures for diverse therapeutic applications.