| Autor: |
Chino, Marco, Leone, Linda, Maglio, Ornella, D'Alonzo, Daniele, Pirro, Fabio, Pavone, Vincenzo, Nastri, Flavia, Lombardi, Angela |
| Předmět: |
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| Zdroj: |
Angewandte Chemie International Edition; 12/4/2017, Vol. 56 Issue 49, p15580-15583, 4p |
| Abstrakt: |
Metalloproteins utilize O2 as an oxidant, and they often achieve a 4-electron reduction without H2O2 or oxygen radical release. Several proteins have been designed to catalyze one or two-electron oxidative chemistry, but the de novo design of a protein that catalyzes the net 4-electron reduction of O2 has not been reported yet. We report the construction of a diiron-binding four-helix bundle, made up of two different covalently linked α2 monomers, through click chemistry. Surprisingly, the prototype protein, DF-C1, showed a large divergence in its reactivity from earlier DFs (DF: due ferri, two iron). DFs release the quinone imine and free H2O2 in the oxidation of 4-aminophenol in the presence of O2, whereas FeIII-DF-C1 sequesters the quinone imine into the active site, and catalyzes inside the scaffold an oxidative coupling between oxidized and reduced 4-aminophenol. The asymmetry of the scaffold allowed a fine-engineering of the substrate binding pocket, that ensures selectivity. [ABSTRACT FROM AUTHOR] |
| Databáze: |
Complementary Index |
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