Modulating Electron Transfer in Vanadium‐Based Artificial Enzymes for Enhanced ROS‐Catalysis and Disinfection. Issue 17 (20th March 2022)

• Record Type: Journal Article
• Authors: Li, Ling; Cao, Sujiao; Wu, Zihe; Guo, Ruiqian; Xie, Lan; Wang, Liyun; Tang, Yuanjiao; Li, Qi; Luo, Xianglin; Ma, Lang; Cheng, Chong; Qiu, Li
• Is Part Of: Advanced materials. Volume 34:Issue 17(2022)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2022-03-20
• Subjects: antibacterial and wound healing -- artificial enzymes -- electron modulation -- inorganic nanomaterials -- ROS‐based biocatalysis; Materials -- Periodicals; Chemical vapor deposition -- Periodicals; 620.11
• DOI: 10.1002/adma.202108646
• Languages: English
• ISSNs: 0935-9648

Abstract

Abstract: Nanomaterials‐based artificial enzymes (AEs) have flourished for more than a decade. However, it is still challenging to further enhance their biocatalytic performances due to the limited strategies to tune the electronic structures of active centers. Here, a new path is reported for the de novo design of the d electrons of active centers by modulating the electron transfer in vanadium‐based AEs (VO x ‐AE) via a unique Zn–O–V bridge for efficient reactive oxygen species (ROS)‐catalysis. Benefiting from the electron transfer from Zn to V, the V site in VO x ‐AE exhibits a lower valence state than that in V2 O5, which results in charge‐filled V‐d yz orbital near the Fermi level to interfere with the formation of sigma bonds between the V‐ d z 2 and O‐p z orbitals in H2 O2 . The VO x ‐AE exhibits a twofold V max and threefold turnover number than V2 O5 when catalyzing H2 O2 . Meanwhile, the VO x ‐AE shows enhanced catalytic eradication of drug‐resistant bacteria and achieves comparable wound‐treatment indexes to vancomycin. This modulating charge‐filling of d electrons provides a new direction for the de novo design of nanomaterials‐based AEs and deepens the understanding of ROS‐catalysis. Abstract : A new vanadium‐based artificial enzyme (VO x ‐AE) for efficient reactive oxygen species (ROS)‐catalysis is synthesized by modulating the d electrons in the active centers via a unique Zn–O–V bridge structure. Experimental and theoretical results demonstrate that the VO x ‐AE exhibits optimal adsorption/dissociation of oxygen‐intermediates, thus showing enhanced ROS catalytic activity and augmented eradication of drug‐resistant bacteria and comparable wound‐treatment indexes to antibiotics.