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Article Dans Une Revue Angewandte Chemie International Edition Année : 2021

The pH-Induced Selectivity Between Cysteine or Histidine Coordinated Heme in an Artificial alpha-Helical Metalloprotein

Résumé

De Novo metalloprotein design assesses the relationship between metal active site architecture and catalytic reactivity. Herein, we use an alpha-helical scaffold to control the iron coordination geometry when a heme cofactor is allowed to bind to either histidine or cysteine ligands, within a single artificial protein. Consequently, we uncovered a reversible pH-induced switch of the heme axial ligation within this simplified scaffold. Characterization of the specific heme coordination modes was done by using UV-Vis and Electron Paramagnetic Resonance spectroscopies. The penta- or hexa-coordinate thiolate heme (9 ≤ pH ≤ 11) and the penta-coordinate imidazole heme (6 ≤ pH ≤ 8.5) reproduces well the heme ligation in chloroperoxidases or cyt P450 monooxygenases and peroxidases, respectively. The stability of heme coordination upon ferric/ferrous redox cycling is a crucial property of the construct. At basic pHs, the thiolate mini-heme protein can catalyze O2 reduction when adsorbed onto a pyrolytic graphite electrode.
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Dates et versions

hal-03017501 , version 1 (20-11-2020)
hal-03017501 , version 2 (16-02-2021)
hal-03017501 , version 3 (18-10-2021)

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Karl J Koebke, Toni Kühl, Elisabeth Lojou, Borries Demeler, Barbara Schoepp-Cothenet, et al.. The pH-Induced Selectivity Between Cysteine or Histidine Coordinated Heme in an Artificial alpha-Helical Metalloprotein. Angewandte Chemie International Edition, 2021, 60 (8), pp.3974-3978. ⟨10.1002/anie.202012673⟩. ⟨hal-03017501v3⟩
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