A Library of ROS‐Catalytic Metalloenzyme Mimics with Atomic Metal Centers
作者：Sujiao Cao, Zhenyang Zhao, Yijuan Zheng, Zihe Wu, Tian Ma, Bihui Zhu, Chengdong Yang, Xi Xiang, Lang Ma, Xianglong Han, Yi Wang, Quanyi Guo, Li Qiu, Chong Cheng · 发表于：Advanced Materials · 年份：2022 · DOI：10.1002/adma.202200255 · 被引用次数：153 · 研究领域：Advanced Nanomaterials in Catalysis、Electrochemical sensors and biosensors、Advanced biosensing and bioanalysis techniques
Abstract MetalN‐coordinated centers supported by carbonaceous substrates have emerged as promising artificial metalloenzymes (AMEs) to mimic the biocatalytic effects of their natural counterparts. However, the synthesis of well‐defined AMEs that contain different atomic metalN centers but present similar physicochemical and coordination structures remains a substantial challenge. Here, 20 different types of AMEs with similar geometries and well‐defined atomic metalN‐coordinated centers are synthesized to compare and disclose the catalytic activities, substrate selectivities, kinetics, and reactive oxygen species (ROS) products. Their oxidase (OXD)‐, peroxidase (POD)‐, and halogen peroxidase (HPO)‐mimetic catalytic behaviors are systematically explored. The Fe‐AME shows the highest OXD‐ and HPO‐mimetic activities compared to the other AMEs due to its high v max (0.927 × 10 −6 m s −1 ) and low K m (1.070 × 10 −3 m ), while the Cu‐AME displays the best POD‐like performance. Furthermore, theoretical calculation reveals that the ROS‐catalytic paths and activities are highly related to the electronic structures of the metal centers. Benefiting from its facile adsorption of H 2 O 2 molecule and lower energy barrier to generating •O 2 − , the Fe‐AME displays higher ROS‐catalytic performances than the Mn‐AME. The engineered AMEs show not only remarkably high ROS‐catalytic performances but also provide new guidance toward developing metalN‐coordinated biocatalysts for broad applica...