Curvature Engineering Enhances Biocatalytic Performance of Active Sites on Nanocarbon for Effective Enzyme Mimicking

Optimizing the biocatalytic performance of active sites is necessary for the development of highly effective nanozymes. Herein, curvature engineering is proposed as a strategy to enhance the biocatalytic performance of nanozyme active sites, using a carbon nanozyme as a model system. The effect of curvature on the peroxidase (POD)-mimicking activity of nanocarbons is investigated by constructing oxygenated carbon nanotube nanozymes (o-CNTs) with similar distributions of oxygenated groups as catalytically active sites but differing diameters. Both theoretical calculations and experimental results indicate that curvature in o-CNTs can significantly reduce the activation energy of biocatalytic reactions. Compared to o-CNTs with a larger diameter (>50 nm), o-CNTs with a smaller diameter (8-15 nm) exhibit a significant increase in POD-like activity by more than one order of magnitude. In a nanozyme-mediated bacterial clearance model, curvature in o-CNTs nanozymes can considerably enhance the antibacterial activity against drug-resistant bacteria. This study provides a method for developing high-efficacy nanozymes through curvature engineering for diverse biomedical applications.