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<p>Metalloenzymes play essential roles in biology. However, unraveling how outer-sphere interactions can be predictably controlled to influence their functions remains a significant challenge. Inspired by Cu enzymes, we demonstrate how variations in the primary, secondary, and outer coordination-sphere interactions of de novo designed artificial copper proteins (ArCuPs) within trimeric (3SCC) and tetrameric (4SCC) self-assemblies—featuring a trigonal Cu(His)<sub>3</sub> and a square pyramidal Cu(His)<sub>4</sub>(OH<sub>2</sub>) coordination—influence their catalytic and electron transfer properties. While 3SCC electrocatalyzes C-H oxidation, 4SCC does not. Cu<sup>I</sup>-3SCC reacts more rapidly with H<sub>2</sub>O<sub>2</sub> than O<sub>2</sub>, whereas 4SCC is less active. Electron transfer, reorganization energies, and extended H<sub>2</sub>O-mediated hydrogen bonding patterns provide insights into the observed reactivity differences. The inactivity of 4SCC is attributed to a significant solvent reorganization energy barrier mediated by a specific His---Glu hydrogen bond. When this hydrogen bond is disrupted, the solvent reorganization energy is reduced, and C-H peroxidation activity is restored.</p>

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Controlling outer-sphere solvent reorganization energy to turn on or off the function of artificial metalloenzymes

  • 期刊论文

  • 出版模式：

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  • 发表日期：

    2025年3月28日

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  • Divyansh Prakash,
  • Suchitra Mitra,
  • Simran Sony,
  • Morgan Murphy,
  • Babak Andi,
  • Landon Ashley,
  • Pallavi Prasad,
  • Saumen Chakraborty

摘要

Metalloenzymes play essential roles in biology. However, unraveling how outer-sphere interactions can be predictably controlled to influence their functions remains a significant challenge. Inspired by Cu enzymes, we demonstrate how variations in the primary, secondary, and outer coordination-sphere interactions of de novo designed artificial copper proteins (ArCuPs) within trimeric (3SCC) and tetrameric (4SCC) self-assemblies—featuring a trigonal Cu(His)3 and a square pyramidal Cu(His)4(OH2) coordination—influence their catalytic and electron transfer properties. While 3SCC electrocatalyzes C-H oxidation, 4SCC does not. CuI-3SCC reacts more rapidly with H2O2 than O2, whereas 4SCC is less active. Electron transfer, reorganization energies, and extended H2O-mediated hydrogen bonding patterns provide insights into the observed reactivity differences. The inactivity of 4SCC is attributed to a significant solvent reorganization energy barrier mediated by a specific His---Glu hydrogen bond. When this hydrogen bond is disrupted, the solvent reorganization energy is reduced, and C-H peroxidation activity is restored.