PMID- 26455726 OWN - NLM STAT- MEDLINE DCOM- 20160520 LR - 20240324 IS - 2041-1723 (Electronic) IS - 2041-1723 (Linking) VI - 6 DP - 2015 Oct 12 TI - A biosynthetic model of cytochrome c oxidase as an electrocatalyst for oxygen reduction. PG - 8467 LID - 10.1038/ncomms9467 [doi] LID - 8467 AB - Creating an artificial functional mimic of the mitochondrial enzyme cytochrome c oxidase (CcO) has been a long-term goal of the scientific community as such a mimic will not only add to our fundamental understanding of how CcO works but may also pave the way for efficient electrocatalysts for oxygen reduction in hydrogen/oxygen fuel cells. Here we develop an electrocatalyst for reducing oxygen to water under ambient conditions. We use site-directed mutants of myoglobin, where both the distal Cu and the redox-active tyrosine residue present in CcO are modelled. In situ Raman spectroscopy shows that this catalyst features very fast electron transfer rates, facile oxygen binding and O-O bond lysis. An electron transfer shunt from the electrode circumvents the slow dissociation of a ferric hydroxide species, which slows down native CcO (bovine 500 s(-1)), allowing electrocatalytic oxygen reduction rates of 5,000 s(-1) for these biosynthetic models. FAU - Mukherjee, Sohini AU - Mukherjee S AD - Department of Inorganic Chemistry, Indian Association for the Cultivation of Science, 2A&2B Raja SC Mullick Road, Jadavpur Kolkata 700032, India. FAU - Mukherjee, Arnab AU - Mukherjee A AD - Department of Chemistry, University of Illinois at Urbana-Champaign, Champaign, Illinois 61801, USA. FAU - Bhagi-Damodaran, Ambika AU - Bhagi-Damodaran A AD - Department of Chemistry, University of Illinois at Urbana-Champaign, Champaign, Illinois 61801, USA. FAU - Mukherjee, Manjistha AU - Mukherjee M AD - Department of Inorganic Chemistry, Indian Association for the Cultivation of Science, 2A&2B Raja SC Mullick Road, Jadavpur Kolkata 700032, India. FAU - Lu, Yi AU - Lu Y AD - Department of Chemistry, University of Illinois at Urbana-Champaign, Champaign, Illinois 61801, USA. FAU - Dey, Abhishek AU - Dey A AUID- ORCID: 0000-0002-9166-3349 AD - Department of Inorganic Chemistry, Indian Association for the Cultivation of Science, 2A&2B Raja SC Mullick Road, Jadavpur Kolkata 700032, India. LA - eng GR - R01 GM062211/GM/NIGMS NIH HHS/United States GR - GM062211/GM/NIGMS NIH HHS/United States PT - Journal Article PT - Research Support, N.I.H., Extramural PT - Research Support, Non-U.S. Gov't DEP - 20151012 PL - England TA - Nat Commun JT - Nature communications JID - 101528555 RN - 7440-57-5 (Gold) RN - EC 1.9.3.1 (Electron Transport Complex IV) RN - S88TT14065 (Oxygen) SB - IM MH - Catalysis MH - Electrodes MH - Electron Transport Complex IV/*chemistry MH - Gold MH - Oxidation-Reduction MH - Oxygen/*chemistry MH - Photoelectron Spectroscopy MH - Spectrum Analysis, Raman PMC - PMC4633646 EDAT- 2015/10/13 06:00 MHDA- 2016/05/21 06:00 PMCR- 2015/11/05 CRDT- 2015/10/13 06:00 PHST- 2014/12/15 00:00 [received] PHST- 2015/08/24 00:00 [accepted] PHST- 2015/10/13 06:00 [entrez] PHST- 2015/10/13 06:00 [pubmed] PHST- 2016/05/21 06:00 [medline] PHST- 2015/11/05 00:00 [pmc-release] AID - ncomms9467 [pii] AID - 10.1038/ncomms9467 [doi] PST - epublish SO - Nat Commun. 2015 Oct 12;6:8467. doi: 10.1038/ncomms9467.