Modulating Electron Transfer in Vanadium-Based Artificial Enzymes for Enhanced ROS-Catalysis and Disinfection

Area of Science:

• Materials Science
• Catalysis
• Biochemistry

Background:

• Nanomaterials-based artificial enzymes (AEs) show promise but face challenges in enhancing catalytic performance.
• Tuning the electronic structures of active centers remains a key limitation in AE design.

Purpose of the Study:

• To develop a new strategy for de novo design of artificial enzymes by modulating electron transfer.
• To enhance the reactive oxygen species (ROS) catalytic activity of vanadium-based AEs (VOx-AE).

Main Methods:

• Designed vanadium-based AEs (VOx-AE) incorporating a unique Zn-O-V bridge to modulate electron transfer.
• Investigated the electronic structure changes at the vanadium active site.
• Evaluated the catalytic performance in H2O2 decomposition and bacterial eradication.

Main Results:

• The Zn-O-V bridge facilitated electron transfer from Zn to V, lowering the V valence state.
• This modulation resulted in a charge-filled V-dyz orbital, enhancing H2O2 catalysis with twofold Vmax and threefold turnover number compared to V2O5.
• VOx-AE demonstrated effective eradication of drug-resistant bacteria, comparable to vancomycin.

Conclusions:

• Modulating the charge-filling of d electrons offers a novel approach for designing advanced nanomaterials-based AEs.
• The findings deepen the understanding of ROS catalysis mechanisms.
• This strategy holds potential for developing new therapeutic agents and catalysts.