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Xiaoti Yang1,2, Wenjie Wu1,2, Xiling Chen3

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Artificial metalloenzymes (ArMs) now directly catalyze electrochemical water oxidation using bacterial small laccase (SLAC) scaffolds. This breakthrough enables efficient bioelectrocatalysis for broader applications.

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Area of Science:

  • Bioinorganic Chemistry
  • Electrocatalysis
  • Protein Engineering

Background:

  • Artificial metalloenzymes (ArMs) typically use buried pockets, limiting heterogeneous catalysis.
  • Interfacial electron transfer in traditional ArMs is hindered by protein backbones.
  • A need exists for ArMs capable of direct electrochemical transformations.

Purpose of the Study:

  • To develop a novel protein scaffold for artificial metalloenzymes.
  • To enable direct electrochemical catalysis of water oxidation.
  • To explore the versatility of this new scaffold for bioelectrocatalysis.

Main Methods:

  • Utilized bacterial small laccase (SLAC) as a novel protein scaffold.
  • Employed molecular dynamics, X-ray crystallography, spectroscopy, and computation.
  • Assembled an oxo-bridged dicobalt motif on the SLAC protein surface.

Main Results:

  • Demonstrated direct electrochemical water oxidation catalyzed by the SLAC-based ArM in aqueous solution.
  • Revealed the SLAC scaffold's role in directing the four-electron water-to-oxygen transfer pathway.
  • Showcased successful bioelectrocatalysis of water electrolysis using various metal ions (Ni, Mn, Ru, Pd, Ir) with SLAC-ArMs.

Conclusions:

  • Bacterial small laccase is a viable scaffold for creating artificial metalloenzymes for direct electrocatalysis.
  • This approach overcomes limitations of traditional ArMs in heterogeneous transformations.
  • Provides a versatile platform for expanding the applications of artificial metalloenzymes in bioelectrocatalysis.