Non-Coordinative Binding of O2 at the Active Center of a Copper-Dependent Enzyme

Leisinger, Florian and Miarzlou , Dzmitry A. and Seebeck, Florian P.. (2021) Non-Coordinative Binding of O2 at the Active Center of a Copper-Dependent Enzyme. Angewandte Chemie International Edition, 60 (11). pp. 6154-6159.

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Official URL: https://edoc.unibas.ch/87391/

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Molecular oxygen (O 2 ) is a sustainable oxidation reagent. O 2 is strongly oxidizing but kinetically stable and its final reaction product is water. For these reasons learning how to activate O 2 and how to steer its reactivity along desired reaction pathways is a longstanding challenge in chemical research. [1] Activation of ground-state diradical O 2 can occur either via conversion to singlet oxygen or by one-electron reduction to superoxide. Many enzymes facilitate activation of O 2 by direct fomation of a metal-oxygen coordination complex concomitant with inner sphere electron transfer. The formylglycine generating enzyme (FGE) is an unusual mononuclear copper enzyme that appears to follow a different strategy. Atomic-resolution crystal structures of the precatalytic complex of FGE demonstrate that this enzyme binds O 2 juxtaposed, but not coordinated to the catalytic Cu I . Isostructural complexes that contain Ag I instead of Cu I or nitric oxide instead of O 2 confirm that formation of the initial oxygenated complex of FGE does not depend on redox activity. A stepwise mechanism that decouples binding and activation of O 2 is unprecedented for metal-dependent oxidases, but is reminiscent of flavin-dependent enzymes.
Faculties and Departments:05 Faculty of Science > Departement Chemie > Chemie > Molecular Bionics (Seebeck)
UniBasel Contributors:Seebeck, Florian Peter
Item Type:Article, refereed
Article Subtype:Research Article
Note:Publication type according to Uni Basel Research Database: Journal article
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Last Modified:15 Feb 2022 15:36
Deposited On:15 Feb 2022 15:36

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