HYSCORE and DFT Studies of Proton-Coupled Electron Transfer in a Bioinspired Artificial Photosynthetic Reaction Center

Dalvin D. Méndez-Hernández, Amgalanbaatar Baldansuren, Vidmantas Kalendra, Philip Charles, Brian Mark, William Marshall, Brian Molnar, Thomas A. Moore, K. V. Lakshmi, Ana L. Moore

Research output: Contribution to journalArticle

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.

Original languageEnglish (US)
Article number101366
JournaliScience
Volume23
Issue number8
DOIs
StatePublished - Aug 21 2020

Keywords

  • Computational Chemistry
  • Organic Reaction
  • Spectroscopy

ASJC Scopus subject areas

  • General

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    Méndez-Hernández, D. D., Baldansuren, A., Kalendra, V., Charles, P., Mark, B., Marshall, W., Molnar, B., Moore, T. A., Lakshmi, K. V., & Moore, A. L. (2020). HYSCORE and DFT Studies of Proton-Coupled Electron Transfer in a Bioinspired Artificial Photosynthetic Reaction Center. iScience, 23(8), [101366]. https://doi.org/10.1016/j.isci.2020.101366