@article{573b33a327584296853e173f42a8bd28,
title = "HYSCORE and DFT Studies of Proton-Coupled Electron Transfer in a Bioinspired Artificial Photosynthetic Reaction Center",
abstract = "The photosynthetic water-oxidation reaction is catalyzed by the oxygen-evolving complex in photosystem II (PSII) that comprises the Mn4CaO5 cluster, with participation of the redox-active tyrosine residue (YZ) and a hydrogen-bonded network of amino acids and water molecules. It has been proposed that the strong hydrogen bond between YZ and D1-His190 likely renders YZ kinetically and thermodynamically competent leading to highly efficient water oxidation. However, a detailed understanding of the proton-coupled electron transfer (PCET) at YZ remains elusive owing to the transient nature of its intermediate states involving YZ⋅. Herein, we employ a combination of high-resolution two-dimensional 14N hyperfine sublevel correlation spectroscopy and density functional theory methods to investigate a bioinspired artificial photosynthetic reaction center that mimics the PCET process involving the YZ residue of PSII. Our results underscore the importance of proximal water molecules and charge delocalization on the electronic structure of the artificial reaction center.",
keywords = "Computational Chemistry, Organic Reaction, Spectroscopy",
author = "M{\'e}ndez-Hern{\'a}ndez, {Dalvin D.} and Amgalanbaatar Baldansuren and Vidmantas Kalendra and Philip Charles and Brian Mark and William Marshall and Brian Molnar and Moore, {Thomas A.} and Lakshmi, {K. V.} and Moore, {Ana L.}",
note = "Funding Information: This study was supported by the Department of Energy , Office of Science, Office of Basic Energy Sciences, under Awards DE-FG02-07ER15903 (K.V.L., Photosynthetic Systems Program), and DE-FG02-03ER15393 (A.L.M and T.A.M.). The computational resources at Rensselaer were provided by the Center for Computational Innovations (CCI). D.D.M.-H was supported by the Start-Up funds and the “Fondo Institucional para el Desarrollo de la Investigaci{\'o}n (FIDI)” of the University of Puerto Rico at Cayey. Computational resources were provided in part by the High-Performance Computing Facility at the University of Puerto Rico supported by the Institutional Development Award (IDeA) INBRE Grant Number P20GM103475 from the National Institute of General Medical Sciences (NIGMS), a component of the National Institutes of Health (NIH) and the Bioinformatics Research Core of INBRE. Its contents are solely the responsibility of the authors and do not necessarily represent the official view of NIGMS or NIH. The authors would like to thank Oleg G. Poluektov (ANL) for helpful discussions. Funding Information: This study was supported by the Department of Energy, Office of Science, Office of Basic Energy Sciences, under Awards DE-FG02-07ER15903 (K.V.L. Photosynthetic Systems Program), and DE-FG02-03ER15393 (A.L.M and T.A.M.). The computational resources at Rensselaer were provided by the Center for Computational Innovations (CCI). D.D.M.-H was supported by the Start-Up funds and the ?Fondo Institucional para el Desarrollo de la Investigaci?n (FIDI)? of the University of Puerto Rico at Cayey. Computational resources were provided in part by the High-Performance Computing Facility at the University of Puerto Rico supported by the Institutional Development Award (IDeA) INBRE Grant Number P20GM103475 from the National Institute of General Medical Sciences (NIGMS), a component of the National Institutes of Health (NIH) and the Bioinformatics Research Core of INBRE. Its contents are solely the responsibility of the authors and do not necessarily represent the official view of NIGMS or NIH. The authors would like to thank Oleg G. Poluektov (ANL) for helpful discussions. D.D.M.-H. A.B. V.K. P.C. B. Mark, W.M. and B. Molnar conducted experiments, analyzed the data, and performed calculations; D.D.M.-H. K.V.L. A.L.M. and T.A.M. designed the experiments and wrote the paper. The authors declare no competing interests. Publisher Copyright: {\textcopyright} 2020 The Author(s)",
year = "2020",
month = aug,
day = "21",
doi = "10.1016/j.isci.2020.101366",
language = "English (US)",
volume = "23",
journal = "iScience",
issn = "2589-0042",
publisher = "Elsevier Inc.",
number = "8",
}