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Title: Artificial Metalloproteins Containing Co4O4Cubane Active Sites

Journal Article · · Journal of the American Chemical Society
DOI:https://doi.org/10.1021/jacs.7b13052· OSTI ID:1433123
 [1];  [2]; ORCiD logo [2];  [1];  [2]; ORCiD logo [3]; ORCiD logo [1]
  1. Univ. of California, Irvine, CA (United States). Dept. of Chemistry
  2. Univ. of California, Berkeley, CA (United States). Dept. of Physics
  3. Univ. of California, Berkeley, CA (United States). Dept. of Physics; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Science Division
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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 Co III-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. Finally, 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.

Research Organization:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Institutes of Health (NIH)
Grant/Contract Number:
AC02-05CH11231
OSTI ID:
1433123
Journal Information:
Journal of the American Chemical Society, Vol. 140, Issue 8; ISSN 0002-7863
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 25 works
Citation information provided by
Web of Science

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Cited By (9)

Stabilization of reactive Co 4 O 4 cubane oxygen-evolution catalysts within porous frameworks journal May 2019
Bi-Microporous Metal-Organic Frameworks with Cubane [M 4 (OH) 4 ] (M=Ni, Co) Clusters and Pore-Space Partition for Electrocatalytic Methanol Oxidation Reaction journal August 2019
Reactivity and Selectivity of Iminium Organocatalysis Improved by a Protein Host journal August 2018
Electrocatalytic water oxidation studies of a tetranuclear Cu( ii ) complex with cubane-like core Cu 4 (μ 3 -O) 4 journal January 2019
Reactivity and Selectivity of Iminium Organocatalysis Improved by a Protein Host journal August 2018
Bi‐Microporous Metal–Organic Frameworks with Cubane [M 4 (OH) 4 ] (M=Ni, Co) Clusters and Pore‐Space Partition for Electrocatalytic Methanol Oxidation Reaction journal July 2019
Strategic Isolation of a Polyoxocation Mimicking Vanadium(V) Oxide Layered-Structure by Stacking of [H2V2O8]4− Anions Bridged by (1,4,7-Triazacyclononane)Co(III) Complexes journal August 2018
Rational Design of Artificial Metalloproteins and Metalloenzymes with Metal Clusters journal July 2019
Ferritin encapsulation of artificial metalloenzymes: engineering a tertiary coordination sphere for an artificial transfer hydrogenase text January 2018

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