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Artificial Metalloproteins Containing Co4O4 Cubane Active Sites

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Department of Chemistry, University of California, Irvine, Irvine, California 92697, United States
Department of Chemistry, University of California, Berkeley, Berkeley, California 94720, United States
Chemical Science Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, United States
Cite this: J. Am. Chem. Soc. 2018, 140, 8, 2739–2742
Publication Date (Web):February 5, 2018
https://doi.org/10.1021/jacs.7b13052
Copyright © 2018 American Chemical Society

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    Artificial metalloproteins (ArMs) containing Co4O4 cubane active sites were constructed via biotin–streptavidin technology. Stabilized by hydrogen bonds (H-bonds), terminal and cofacial CoIII–OH2 moieties are observed crystallographically in a series of immobilized cubane sites. Solution electrochemistry provided correlations of oxidation potential and pH. For variants containing Ser and Phe adjacent to the metallocofactor, 1e/1H+ chemistry predominates until pH 8, above which the oxidation becomes pH-independent. Installation of Tyr proximal to the Co4O4 active site provided a single H-bond to one of a set of cofacial CoIII–OH2 groups. With this variant, multi-e/multi-H+ chemistry is observed, along with a change in mechanism at pH 9.5 that is consistent with Tyr deprotonation. With structural similarities to both the oxygen-evolving complex of photosystem II (H-bonded Tyr) and to thin film water oxidation catalysts (Co4O4 core), these findings bridge synthetic and biological systems for water oxidation, highlighting the importance of secondary sphere interactions in mediating multi-e/multi-H+ reactivity.

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    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/jacs.7b13052.

    • Synthesis and characterization of biotin conjugates; primer sequences and methods for Sav gene construction, expression and purification; XRD sample preparation, data processing, refinement statistics, electron and anomalous density and omit maps; biot-β-Ala-1 ⊂ 2xm-S112F-Sav and biotin ⊂ 2xm-S112Y-Sav structures; SWV sample preparation, control experiments, CV and optical measurements over 48 h, Ep and Imax values, and binding titration data (PDF)

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