One-Step Doping of P and S Elements to Fe-ZIF-8 Derivatives for Enhanced ROS Generation and Antibacterial Application

Area of Science:

• Materials Science
• Catalysis
• Biotechnology

Background:

• Artificial enzymes are crucial for various applications, but their homogeneous active site charge distribution limits substrate affinity and catalytic efficiency.
• Developing novel strategies to modulate active sites is essential for enhancing artificial enzyme performance.

Purpose of the Study:

• To develop a dual-heteroatom doping strategy for MOF-derived carbon hybrids to improve artificial enzyme catalytic activity.
• To investigate the effect of P and S co-doping on the electronic structure and catalytic performance of ZFPS (ZnS/FeP/Fe4P6N12S).

Main Methods:

• Synthesized MOF-derived carbon hybrids using a dual-heteroatom doping strategy with P and S.
• Characterized the material's structure and electronic properties, including band gap and charge distribution.
• Employed density functional theory (DFT) calculations to understand the mechanism of P, S co-doping on Fe sites.
• Assessed peroxidase-like activity, halogen peroxidase-like activity, and glutathione depletion capability.
• Evaluated the material's efficacy in eradicating bacterial biofilms in an anti-oral-biofilm application.

Main Results:

• ZFPS exhibited asymmetric charge distribution and electron-rich active sites due to P and S doping.
• DFT calculations confirmed that P, S co-doping enhances the affinity between substrates and active sites by modulating the D-band electronic structure of Fe sites.
• ZFPS showed a 33.3-fold increase in peroxidase-like activity (Kcat/Km) compared to undoped counterparts.
• The material demonstrated superior halogen peroxidase-like activity and glutathione depletion capability.
• Synergistic catalytic activities led to rapid generation of reactive oxygen species, effectively eradicating bacterial biofilms.

Conclusions:

• The dual-heteroatom doping strategy effectively enhances the catalytic activity of artificial enzymes by optimizing active site properties.
• ZFPS exhibits significant potential as an antimicrobial biomaterial due to its enhanced catalytic functions and biofilm eradication capabilities.
• This work provides a facile strategy for designing advanced artificial enzymes with improved performance for biomedical applications.