Tuning iron spin states in single-atom nanozymes enables efficient peroxidase mimicking

作者：Wei, Xiaoqian; Song, Shaojia; Song, Weiyu; Wen, Yating; Xu, Weiqing; Chen, Yifeng; Wu, Zhichao; Qin, Ying; Jiao, Lei; Wu, Yu; Sha, Meng; Huang, Jiajia; Cai, Xiaoli; Zheng, Lirong; Hu, Liuyong; Gu, Wenling; Eguchi, Miharu; Asahi, Toru; Yamauchi, Yusuke^*; Zhu, Chengzhou^*

来源：Chemical Science, 2022, 13(45): 13574-13581.

DOI：10.1039/d2sc05679h

• OXYGEN REDUCTION
• COORDINATION
• EPR
• DNA

The large-scale application of nanozymes remains a significant challenge owing to their unsatisfactory catalytic performances. Featuring a unique electronic structure and coordination environment, single-atom nanozymes provide great opportunities to vividly mimic the specific metal catalytic center of natural enzymes and achieve superior enzyme-like activity. In this study, the spin state engineering of Fe single-atom nanozymes (FeNC) is employed to enhance their peroxidase-like activity. Pd nanoclusters (Pd-NC) are introduced into FeNC, whose electron-withdrawing properties rearrange the spin electron occupation in Fe(ii) of FeNC-Pd-NC from low spin to medium spin, facilitating the heterolysis of H2O2 and timely desorption of H2O. The spin-rearranged FeNC-Pd-NC exhibits greater H2O2 activation activity and rapid reaction kinetics compared to those of FeNC. As a proof of concept, FeNC-Pd-NC is used in the immunosorbent assay for the colorimetric detection of prostate-specific antigen and achieves an ultralow detection limit of 0.38 pg mL(-1). Our spin-state engineering strategy provides a fundamental understanding of the catalytic mechanism of nanozymes and facilitates the design of advanced enzyme mimics.

• 单位
  1; 中国科学院; 武汉工程大学; y