Metal-organic frameworks-engineered reactive-oxygen catalytic materials: Enzyme-mimicking coordinations, structure evolutions, and biotherapeutic applications

Metal-organic frameworks (MOFs)-engineered reactive-oxygen catalytic materials (ROCMs) have offered essential contributions to boosting the biocatalytic efficiency in diverse biomedical applications. While since the varied coordination environments, abundant node-ligand pairs, and multiple or complex atom sites, precisely overviewing the mechanisms and revealing the structure–reactivity relationships of MOFs-engineered ROCMs still confront great challenges, which is essential to direct the future design and applications of ROCMs. Here, we provide a comprehensive summarization of the latest progress and future trends in MOFs-engineered ROCMs with enzyme-mimicking structures for ROS regulation and biotherapeutic applications. First, the catalytic behaviors and fundamental mechanisms of MOFs-engineered ROCMs on regulating ROS levels are outlined. Then, the enzyme-mimicking coordination environments and structure evolutions of MOFs-engineered ROCMs are discussed thoroughly, including coordination modulation, hybrid structures, carbon nanostructures, and single-atom materials. Particularly, we offer unique insights into enzyme structure mimicking, microenvironment modulation, structure evolutions, and theoretical understanding for revealing mechanisms. Thereafter, the representative biotherapeutic applications have been summarized with a unique focus on structural property-reactivity relationships. Finally, we systematically highlight the current challenges and future perspectives. Overall, this is a timely review that focuses on creating MOF structures for reactive-oxygen biocatalysis from structure-activity relationships to biological properties. We envision this cutting review will substantially stimulate the development and widespread utilization of MOFs-engineered ROCMs in biomedical applications.