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Ca K-Edge XAS as a Probe of Calcium Centers in Complex Systems

[Image: see text] Herein, Ca K-edge X-ray absorption spectroscopy (XAS) is developed as a means to characterize the local environment of calcium centers. The spectra for six, seven, and eight coordinate inorganic and molecular calcium complexes were analyzed and determined to be primarily influenced...

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Autores principales: Martin-Diaconescu, Vlad, Gennari, Marcello, Gerey, Bertrand, Tsui, Emily, Kanady, Jacob, Tran, Rosalie, Pécaut, Jacques, Maganas, Dimitrios, Krewald, Vera, Gouré, Eric, Duboc, Carole, Yano, Junko, Agapie, Theodor, Collomb, Marie-Noelle, DeBeer, Serena
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2014
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4331723/
https://www.ncbi.nlm.nih.gov/pubmed/25492398
http://dx.doi.org/10.1021/ic501991e
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author Martin-Diaconescu, Vlad
Gennari, Marcello
Gerey, Bertrand
Tsui, Emily
Kanady, Jacob
Tran, Rosalie
Pécaut, Jacques
Maganas, Dimitrios
Krewald, Vera
Gouré, Eric
Duboc, Carole
Yano, Junko
Agapie, Theodor
Collomb, Marie-Noelle
DeBeer, Serena
author_facet Martin-Diaconescu, Vlad
Gennari, Marcello
Gerey, Bertrand
Tsui, Emily
Kanady, Jacob
Tran, Rosalie
Pécaut, Jacques
Maganas, Dimitrios
Krewald, Vera
Gouré, Eric
Duboc, Carole
Yano, Junko
Agapie, Theodor
Collomb, Marie-Noelle
DeBeer, Serena
author_sort Martin-Diaconescu, Vlad
collection PubMed
description [Image: see text] Herein, Ca K-edge X-ray absorption spectroscopy (XAS) is developed as a means to characterize the local environment of calcium centers. The spectra for six, seven, and eight coordinate inorganic and molecular calcium complexes were analyzed and determined to be primarily influenced by the coordination environment and site symmetry at the calcium center. The experimental results are closely correlated to time-dependent density functional theory (TD-DFT) calculations of the XAS spectra. The applicability of this methodology to complex systems was investigated using structural mimics of the oxygen-evolving complex (OEC) of PSII. It was found that Ca K-edge XAS is a sensitive probe for structural changes occurring in the cubane heterometallic cluster due to Mn oxidation. Future applications to the OEC are discussed.
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spelling pubmed-43317232015-02-19 Ca K-Edge XAS as a Probe of Calcium Centers in Complex Systems Martin-Diaconescu, Vlad Gennari, Marcello Gerey, Bertrand Tsui, Emily Kanady, Jacob Tran, Rosalie Pécaut, Jacques Maganas, Dimitrios Krewald, Vera Gouré, Eric Duboc, Carole Yano, Junko Agapie, Theodor Collomb, Marie-Noelle DeBeer, Serena Inorg Chem [Image: see text] Herein, Ca K-edge X-ray absorption spectroscopy (XAS) is developed as a means to characterize the local environment of calcium centers. The spectra for six, seven, and eight coordinate inorganic and molecular calcium complexes were analyzed and determined to be primarily influenced by the coordination environment and site symmetry at the calcium center. The experimental results are closely correlated to time-dependent density functional theory (TD-DFT) calculations of the XAS spectra. The applicability of this methodology to complex systems was investigated using structural mimics of the oxygen-evolving complex (OEC) of PSII. It was found that Ca K-edge XAS is a sensitive probe for structural changes occurring in the cubane heterometallic cluster due to Mn oxidation. Future applications to the OEC are discussed. American Chemical Society 2014-12-10 2015-02-16 /pmc/articles/PMC4331723/ /pubmed/25492398 http://dx.doi.org/10.1021/ic501991e Text en Copyright © 2014 American Chemical Society This is an open access article published under an ACS AuthorChoice License (http://pubs.acs.org/page/policy/authorchoice_termsofuse.html) , which permits copying and redistribution of the article or any adaptations for non-commercial purposes.
spellingShingle Martin-Diaconescu, Vlad
Gennari, Marcello
Gerey, Bertrand
Tsui, Emily
Kanady, Jacob
Tran, Rosalie
Pécaut, Jacques
Maganas, Dimitrios
Krewald, Vera
Gouré, Eric
Duboc, Carole
Yano, Junko
Agapie, Theodor
Collomb, Marie-Noelle
DeBeer, Serena
Ca K-Edge XAS as a Probe of Calcium Centers in Complex Systems
title Ca K-Edge XAS as a Probe of Calcium Centers in Complex Systems
title_full Ca K-Edge XAS as a Probe of Calcium Centers in Complex Systems
title_fullStr Ca K-Edge XAS as a Probe of Calcium Centers in Complex Systems
title_full_unstemmed Ca K-Edge XAS as a Probe of Calcium Centers in Complex Systems
title_short Ca K-Edge XAS as a Probe of Calcium Centers in Complex Systems
title_sort ca k-edge xas as a probe of calcium centers in complex systems
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4331723/
https://www.ncbi.nlm.nih.gov/pubmed/25492398
http://dx.doi.org/10.1021/ic501991e
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