Upgrading the Bioinspired Iron-Polyporphyrin Structures by Abiological Metals Toward New-Generation Reactive Oxygen Biocatalysts.

Developing artificial enzymes based on organic molecules or polymers for reactive oxygen biocatalysis has broad applicability. Here, inspired by heme-based enzyme systems, we construct the abiological iron group metal-based polyporphyrin (Ru/Os-coordinated porphyrin-based biocatalyst, Ru/Os-PorBC) to serve as a new generation of efficient and versatile reactive oxygen species (ROS)-related biocatalyst. Due to the structural benefits, including excellent electron configuration, appropriate bandgap, and optimized adsorption and activation of reaction intermediates, Ru/Os-PorBC shows unparalleled ROS-production activities regarding maximum reaction rate and turnover numbers, which also demonstrates superior pH and temperature adaptability compared to natural enzymes. Impressively, the Os-PorBC manifests the most efficacious ROS-production capabilities, surpassing not only Ru/Fe-PorBC but also the existing state-of-the-art ROS-related biocatalyst. Our findings provide a pivotal direction for developing next-generation polyporphyrin-based biocatalysts, setting the stage for a new era of upgrading the artificial metalloenzymes by abiological metals.