Catalytic Oxygen Evolution by a Bioinorganic Model of the Photosystem II Oxygen-Evolving ComplexClick to copy article linkArticle link copied!
Abstract
Bioinorganic chemistry is a discipline that few undergraduates experience within a laboratory setting. This article details a series of experiments suitable for advanced undergraduates that will introduce them to the preparation and characterization of a bioinorganic model complex. Techniques and concepts emphasized include inorganic synthesis, UVandNdash;visible spectroscopy, titrations, catalytic mechanisms, oxidationandNdash;reduction reactions, and kinetics. The experiments are relevant to photosynthetic water oxidation, a process catalyzed by photosystem II (PSII) at an active site that contains a tetrameric μ-oxo-bridged manganese (Mn4) cluster. Bioinorganic models of the Mn4 cluster are invaluable in understanding the mechanism of water oxidation by PSII and possibly in developing artificial water-oxidation catalysts. In this laboratory, students explore the chemistry of a dimeric μ-oxo-bridged manganese complex that is a functional model for the Mn4 cluster. They synthesize the complex [(terpy)(H2O)MnIII(O)2MnIV(OH2)(terpy)]3- (terpy = 2,2':6',2"-terpyridine) and characterize the oxidation of terpy by one-electron using UV–visible spectroscopy. The terpy complex catalytically oxidizes H2O to O2 when peroxymonosulfate (oxone, HSO5-) is used as the primary oxidant. Students will measure the rate of O2 production and calculate the deuterium kinetic isotope effect when D2O is used in place of H2O as a substrate.
Cited By
This article is cited by 5 publications.
- Steven M. Malinak, Jerald E. Hertzog, Julia E. Pacilio, Deborah A. Polvani. Bioinorganic Laboratory Experiment: Synthesis and Catalytic Activity of a Vanadium Haloperoxidase Model Complex. Journal of Chemical Education 2019, 96
(3)
, 582-585. https://doi.org/10.1021/acs.jchemed.8b00543
- Evan M. W. Rumberger, Hyun S. Ahn, Alexis T. Bell, T. Don Tilley. Water oxidation catalysis via immobilization of the dimanganese complex [Mn2(μ-O)2Cl(μ-O2CCH3)(bpy)2(H2O)](NO3)2 onto silica. Dalton Transactions 2013, 42
(34)
, 12238. https://doi.org/10.1039/c3dt51472b
- Todd P. Silverstein. Photosynthetic water oxidation vs. mitochondrial oxygen reduction: distinct mechanistic parallels. Journal of Bioenergetics and Biomembranes 2011, 43
(4)
, 437-446. https://doi.org/10.1007/s10863-011-9370-7
- Juergen Clausen, Wolfgang Junge. The terminal reaction cascade of water oxidation: Proton and oxygen release. Biochimica et Biophysica Acta (BBA) - Bioenergetics 2008, 1777
(10)
, 1311-1318. https://doi.org/10.1016/j.bbabio.2008.06.009
- Maria L. Ghirardi, Pin Ching Maness, Michael Seibert. Photobiological Methods of Renewable Hydrogen Production. , 229-271. https://doi.org/10.1007/978-0-387-72810-0_8
Article Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.
Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.
The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated.