Why copper is preferred over iron for oxygen activation and reduction in haem-copper oxidases. Bhagi-Damodaran, A., Michael, M. A., Zhu, Q., Reed, J., Sandoval, B. A., Mirts, E. N., Chakraborty, S., Moënne-Loccoz, P., Zhang, Y., & Lu, Y. Nature Chemistry, 9(3):257–263, 2017. doi abstract bibtex Haem-copper oxidase (HCO) catalyses the natural reduction of oxygen to water using a haem-copper centre. Despite decades of research on HCOs, the role of non-haem metal and the reason for nature's choice of copper over other metals such as iron remains unclear. Here, we use a biosynthetic model of HCO in myoglobin that selectively binds different non-haem metals to demonstrate 30-fold and 11-fold enhancements in the oxidase activity of Cu- and Fe-bound HCO mimics, respectively, as compared with Zn-bound mimics. Detailed electrochemical, kinetic and vibrational spectroscopic studies, in tandem with theoretical density functional theory calculations, demonstrate that the non-haem metal not only donates electrons to oxygen but also activates it for efficient O-O bond cleavage. Furthermore, the higher redox potential of copper and the enhanced weakening of the O-O bond from the higher electron density in the d orbital of copper are central to its higher oxidase activity over iron. This work resolves a long-standing question in bioenergetics, and renders a chemical-biological basis for the design of future oxygen-reduction catalysts.
@article{bhagi-damodaran_why_2017,
title = {Why copper is preferred over iron for oxygen activation and reduction in haem-copper oxidases},
volume = {9},
issn = {17554349},
doi = {10.1038/nchem.2643},
abstract = {Haem-copper oxidase (HCO) catalyses the natural reduction of oxygen to water using a haem-copper centre. Despite decades of research on HCOs, the role of non-haem metal and the reason for nature's choice of copper over other metals such as iron remains unclear. Here, we use a biosynthetic model of HCO in myoglobin that selectively binds different non-haem metals to demonstrate 30-fold and 11-fold enhancements in the oxidase activity of Cu- and Fe-bound HCO mimics, respectively, as compared with Zn-bound mimics. Detailed electrochemical, kinetic and vibrational spectroscopic studies, in tandem with theoretical density functional theory calculations, demonstrate that the non-haem metal not only donates electrons to oxygen but also activates it for efficient O-O bond cleavage. Furthermore, the higher redox potential of copper and the enhanced weakening of the O-O bond from the higher electron density in the d orbital of copper are central to its higher oxidase activity over iron. This work resolves a long-standing question in bioenergetics, and renders a chemical-biological basis for the design of future oxygen-reduction catalysts.},
number = {3},
journal = {Nature Chemistry},
author = {Bhagi-Damodaran, Ambika and Michael, Matthew A. and Zhu, Qianhong and Reed, Julian and Sandoval, Braddock A. and Mirts, Evan N. and Chakraborty, Saumen and Moënne-Loccoz, Pierre and Zhang, Yong and Lu, Yi},
year = {2017},
pmid = {28221360},
pages = {257--263},
}
Downloads: 0
{"_id":"G3rCbY5iJPKtGw77r","bibbaseid":"bhagidamodaran-michael-zhu-reed-sandoval-mirts-chakraborty-monneloccoz-etal-whycopperispreferredoverironforoxygenactivationandreductioninhaemcopperoxidases-2017","author_short":["Bhagi-Damodaran, A.","Michael, M. A.","Zhu, Q.","Reed, J.","Sandoval, B. A.","Mirts, E. N.","Chakraborty, S.","Moënne-Loccoz, P.","Zhang, Y.","Lu, Y."],"bibdata":{"bibtype":"article","type":"article","title":"Why copper is preferred over iron for oxygen activation and reduction in haem-copper oxidases","volume":"9","issn":"17554349","doi":"10.1038/nchem.2643","abstract":"Haem-copper oxidase (HCO) catalyses the natural reduction of oxygen to water using a haem-copper centre. Despite decades of research on HCOs, the role of non-haem metal and the reason for nature's choice of copper over other metals such as iron remains unclear. Here, we use a biosynthetic model of HCO in myoglobin that selectively binds different non-haem metals to demonstrate 30-fold and 11-fold enhancements in the oxidase activity of Cu- and Fe-bound HCO mimics, respectively, as compared with Zn-bound mimics. Detailed electrochemical, kinetic and vibrational spectroscopic studies, in tandem with theoretical density functional theory calculations, demonstrate that the non-haem metal not only donates electrons to oxygen but also activates it for efficient O-O bond cleavage. Furthermore, the higher redox potential of copper and the enhanced weakening of the O-O bond from the higher electron density in the d orbital of copper are central to its higher oxidase activity over iron. This work resolves a long-standing question in bioenergetics, and renders a chemical-biological basis for the design of future oxygen-reduction catalysts.","number":"3","journal":"Nature Chemistry","author":[{"propositions":[],"lastnames":["Bhagi-Damodaran"],"firstnames":["Ambika"],"suffixes":[]},{"propositions":[],"lastnames":["Michael"],"firstnames":["Matthew","A."],"suffixes":[]},{"propositions":[],"lastnames":["Zhu"],"firstnames":["Qianhong"],"suffixes":[]},{"propositions":[],"lastnames":["Reed"],"firstnames":["Julian"],"suffixes":[]},{"propositions":[],"lastnames":["Sandoval"],"firstnames":["Braddock","A."],"suffixes":[]},{"propositions":[],"lastnames":["Mirts"],"firstnames":["Evan","N."],"suffixes":[]},{"propositions":[],"lastnames":["Chakraborty"],"firstnames":["Saumen"],"suffixes":[]},{"propositions":[],"lastnames":["Moënne-Loccoz"],"firstnames":["Pierre"],"suffixes":[]},{"propositions":[],"lastnames":["Zhang"],"firstnames":["Yong"],"suffixes":[]},{"propositions":[],"lastnames":["Lu"],"firstnames":["Yi"],"suffixes":[]}],"year":"2017","pmid":"28221360","pages":"257–263","bibtex":"@article{bhagi-damodaran_why_2017,\n\ttitle = {Why copper is preferred over iron for oxygen activation and reduction in haem-copper oxidases},\n\tvolume = {9},\n\tissn = {17554349},\n\tdoi = {10.1038/nchem.2643},\n\tabstract = {Haem-copper oxidase (HCO) catalyses the natural reduction of oxygen to water using a haem-copper centre. Despite decades of research on HCOs, the role of non-haem metal and the reason for nature's choice of copper over other metals such as iron remains unclear. Here, we use a biosynthetic model of HCO in myoglobin that selectively binds different non-haem metals to demonstrate 30-fold and 11-fold enhancements in the oxidase activity of Cu- and Fe-bound HCO mimics, respectively, as compared with Zn-bound mimics. Detailed electrochemical, kinetic and vibrational spectroscopic studies, in tandem with theoretical density functional theory calculations, demonstrate that the non-haem metal not only donates electrons to oxygen but also activates it for efficient O-O bond cleavage. Furthermore, the higher redox potential of copper and the enhanced weakening of the O-O bond from the higher electron density in the d orbital of copper are central to its higher oxidase activity over iron. This work resolves a long-standing question in bioenergetics, and renders a chemical-biological basis for the design of future oxygen-reduction catalysts.},\n\tnumber = {3},\n\tjournal = {Nature Chemistry},\n\tauthor = {Bhagi-Damodaran, Ambika and Michael, Matthew A. and Zhu, Qianhong and Reed, Julian and Sandoval, Braddock A. and Mirts, Evan N. and Chakraborty, Saumen and Moënne-Loccoz, Pierre and Zhang, Yong and Lu, Yi},\n\tyear = {2017},\n\tpmid = {28221360},\n\tpages = {257--263},\n}\n\n\n\n","author_short":["Bhagi-Damodaran, A.","Michael, M. A.","Zhu, Q.","Reed, J.","Sandoval, B. A.","Mirts, E. N.","Chakraborty, S.","Moënne-Loccoz, P.","Zhang, Y.","Lu, Y."],"key":"bhagi-damodaran_why_2017-1","id":"bhagi-damodaran_why_2017-1","bibbaseid":"bhagidamodaran-michael-zhu-reed-sandoval-mirts-chakraborty-monneloccoz-etal-whycopperispreferredoverironforoxygenactivationandreductioninhaemcopperoxidases-2017","role":"author","urls":{},"metadata":{"authorlinks":{}},"html":""},"bibtype":"article","biburl":"https://bibbase.org/zotero/FRGBergamini","dataSources":["o2mL7kG99iAQPpNRJ"],"keywords":[],"search_terms":["copper","preferred","over","iron","oxygen","activation","reduction","haem","copper","oxidases","bhagi-damodaran","michael","zhu","reed","sandoval","mirts","chakraborty","moënne-loccoz","zhang","lu"],"title":"Why copper is preferred over iron for oxygen activation and reduction in haem-copper oxidases","year":2017}