en.Wedoany.com Reported - The team led by Hui Shen from Inner Mongolia University, China, has proposed the new concept of "iso-nanozymes" and successfully constructed two atomically precise copper nanoclusters, namely [Cu₃₂(SC₂H₅)₁₆(PPh₃)₈Cl₉]⁺ (Cu₃₂) and [Cu₃₀(SC₂H₅)₁₆(PPh₃)₆Cl₉]⁺ (Cu₃₀). These two clusters exhibited significantly different catalytic efficiencies when mimicking the catalytic reaction of natural horseradish peroxidase (HRP), with the specific activity of Cu₃₀ being 6.5 times higher than that of Cu₃₂. This research provides an ideal model system for understanding the structure-activity relationship of nanozymes at the atomic scale.
Similar to natural isoenzymes, these two synthetic clusters that catalyze the same reaction but differ in structure and efficiency are defined as "iso-nanozymes." Through atomic-level characterization techniques such as single-crystal X-ray diffraction, electrospray ionization mass spectrometry, and X-ray photoelectron spectroscopy, the researchers confirmed that both clusters adopt a half-cubic geometry, with Cu₃₀ lacking only two PPh₃Cu⁺ units compared to Cu₃₂. This minor structural difference leads to a significant change in catalytic activity.
Combining density functional theory calculations with electrochemical analysis, the research team revealed a synergistic catalytic mechanism: Cu₃₀ possesses a more open surface and a more electron-rich copper charge distribution, which facilitates substrate adsorption, thereby greatly enhancing catalytic efficiency. This work achieves the construction and performance regulation of "iso-nanozymes" for the first time, highlighting the potential of atomically precise copper nanoclusters in nanozyme design and providing a new pathway for the rational development of high-performance catalytic nanomaterials.
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