Mapping the Oxygens in the Oxygen-Evolving Complex of Photosystem II by Their Nucleophilicity Using Quantum DescriptorsClick to copy article linkArticle link copied!
- Muhamed Amin*Muhamed Amin*Email: [email protected]Laboratory of Computational Biology, National Heart, Lung and Blood Institute, National Institutes of Health, Bethesda, Maryland 20892, United StatesDepartment of Sciences, University College Groningen, University of Groningen, 9718 BG Groningen, The NetherlandsMore by Muhamed Amin
- Divya KaurDivya KaurDepartment of Chemistry, Brock University, 500 Glenridge Avenue, St. Catharines, Ontario, Canada L2S 3A1More by Divya Kaur
- Gary W. BrudvigGary W. BrudvigDepartment of Chemistry, Yale University, New Haven, Connecticut 06520-8107, United StatesMore by Gary W. Brudvig
- Bernard R. BrooksBernard R. BrooksLaboratory of Computational Biology, National Heart, Lung and Blood Institute, National Institutes of Health, Bethesda, Maryland 20892, United StatesMore by Bernard R. Brooks
Abstract
![Abstract Image](/cms/10.1021/acs.jctc.3c00926/asset/images/medium/ct3c00926_0008.gif)
The oxygen-evolving complex (OEC) of Photosystem II catalyzes the water-splitting reaction using solar energy. Thus, understanding the reaction mechanism will inspire the design of biomimetic artificial catalysts that convert solar energy to chemical energy. Conceptual Density Functional Theory (CDFT) focuses on understanding the reactivity of molecules and the atomic contribution to the overall nucleophilicity and electrophilicity of the molecule using quantum descriptors. However, this method has not been applied to the OEC before. Here, we use Fukui functions and the dual descriptor to provide quantitative measures of the nucleophilicity and electrophilicity of oxygens in the OEC for different models in different S states. Our results show that the μ-oxo bridges connected to terminal Mn4 are nucleophilic, and those in the cube formed by Mn1, Mn2, and Mn3 are mostly electrophilic. The dual descriptors of the bridging oxygens in the OEC showed a similar reactivity to that of bridging oxygens in Mn model compounds. However, the terminal water W1, which is bound to Mn4, showed very strong reactivity in some of the S3 models. Thus, our calculations support the model that proposes the formation of the O2 molecule through nucleophilic attack by a terminal water.
Cited By
This article has not yet been cited by other publications.
Article Views
Altmetric
Citations
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.