PMID- 35693844 OWN - NLM STAT- PubMed-not-MEDLINE LR - 20220716 IS - 2155-5435 (Print) IS - 2155-5435 (Electronic) VI - 8 IP - 9 DP - 2018 Sep 7 TI - O(2) Reduction by Biosynthetic Models of Cytochrome c Oxidase: Insights into Role of Proton Transfer Residues from Perturbed Active Sites Models of CcO. PG - 8915-8924 LID - 10.1021/acscatal.8b02240 [doi] AB - Myoglobin based biosynthetic models of perturbed cytochrome c oxidase (CcO) active site are reconstituted, in situ, on electrodes where glutamate residues are systematically introduced in the distal site of the heme/Cu active site instead of a tyrosine residue. These biochemical electrodes show efficient 4e(-)/4H(+) reduction with turnover rates and numbers more than 10(7) M(-1) s(-1) and 10(4), respectively. The H(2)O/D(2)O isotope effects of these series of crystallographically characterized mutants bearing zero, one, and two glutamate residues near the heme Cu active site of these perturbed CcO mimics are 16, 4, and 2, respectively. In situ SERRS-RDE data indicate complete change in the rate-determining step as proton transfer residues are introduced near the active site. The high selectivity for 4e(-)/4H(+) O(2) reduction and systematic variation of KSIE demonstrate the dominant role of proton transfer residues on the isotope effect on rate and rate-determining step of O(2) reduction. FAU - Mukherjee, Sohini AU - Mukherjee S AD - Department of Inorganic Chemistry, Indian Association for the Cultivation of Science, Kolkata 700032, India. FAU - Mukherjee, Manjistha AU - Mukherjee M AUID- ORCID: 0000-0001-6550-6262 AD - Department of Inorganic Chemistry, Indian Association for the Cultivation of Science, Kolkata 700032, India. FAU - Mukherjee, Arnab AU - Mukherjee A AD - Department of Chemistry, University of Illinois at Urbana-Champaign, Champaign, Illinois 61801, United States. FAU - Bhagi-Damodaran, Ambika AU - Bhagi-Damodaran A AD - Department of Chemistry, University of Illinois at Urbana-Champaign, Champaign, Illinois 61801, United States. FAU - Lu, Yi AU - Lu Y AUID- ORCID: 0000-0003-1221-6709 AD - Department of Chemistry, University of Illinois at Urbana-Champaign, Champaign, Illinois 61801, United States. FAU - Dey, Abhishek AU - Dey A AUID- ORCID: 0000-0002-9166-3349 AD - Department of Inorganic Chemistry, Indian Association for the Cultivation of Science, Kolkata 700032, India. LA - eng GR - R01 GM062211/GM/NIGMS NIH HHS/United States PT - Journal Article DEP - 20180815 PL - United States TA - ACS Catal JT - ACS catalysis JID - 101562209 PMC - PMC9186439 MID - NIHMS1812113 OTO - NOTNLM OT - O2 reduction reaction OT - biosynthetic model OT - cytochrome c oxidase OT - kinetic isotope effect OT - kinetic rate constant OT - proton transfer residues COIS- The authors declare no competing financial interest. EDAT- 2018/09/07 00:00 MHDA- 2018/09/07 00:01 PMCR- 2022/06/10 CRDT- 2022/06/13 03:21 PHST- 2022/06/13 03:21 [entrez] PHST- 2018/09/07 00:00 [pubmed] PHST- 2018/09/07 00:01 [medline] PHST- 2022/06/10 00:00 [pmc-release] AID - 10.1021/acscatal.8b02240 [doi] PST - ppublish SO - ACS Catal. 2018 Sep 7;8(9):8915-8924. doi: 10.1021/acscatal.8b02240. Epub 2018 Aug 15.