Modeling the Enzyme Specificity by Molecular Cages through Regulating Reactive Oxygen Species Evolution
Jiangpei Yuan, Zong‐Jie Guan, Hengyu Lin, Bing Yan, Kang‐Kai Liu, Hong‐Cai Zhou, Yu Fang
Abstract
Abstract Mimicking the active site and the substrate binding cavity of the enzyme to achieve specificity in catalytic reactions is an essential challenge. Herein, porous coordination cages (PCCs) with intrinsic cavities and tunable metal centers have proved the regulation of reactive oxygen species (ROS) generating pathways as evidenced by multiple photo‐induced oxidations. Remarkably, in the presence of the Zn 4 ‐μ 4 ‐O center, PCC converted dioxygen molecules from triplet to singlet excitons, whereas the Ni 4 ‐μ 4 ‐O center promoted the efficient dissociation of electrons and holes to conduct electron transfer towards substrates. Accordingly, the distinct ROS generation behavior of PCC‐6‐Zn and PCC‐6‐Ni enables the conversion of O 2 to 1 O 2 and O 2 ⋅ − , respectively. In contrast, the Co 4 ‐μ 4 ‐O center combined the 1 O 2 and O 2 ⋅ − together to generate carbonyl radicals, which in turn reacted with the oxygen molecules. Harnessing the three oxygen activation pathways, PCC‐6‐M (M=Zn/Ni/Co) display specific catalytic activities in thioanisole oxidation ( PCC‐6‐Zn ), benzylamine coupling ( PCC‐6‐Ni ), and aldehyde autoxidation ( PCC‐6‐Co ). This work not only provides fundamental insights into the regulation of ROS generation by a supramolecular catalyst but also demonstrates a rare example of achieving reaction specificity through mimicking natural enzymes by PCCs.