These are preliminary reports that have not been peer-reviewed. They should not be regarded as conclusive, guide clinical practice/health-related behavior, or be reported in news media as established information. For more information, please see our FAQs.
3 files

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

submitted on 17.05.2020, 19:36 and posted on 19.05.2020, 13:19 by 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

Light-driven water oxidation in algae, cyanobacteria, and higher plants generates dioxygen that supports life on Earth. The water-oxidation reaction is catalyzed by the oxygen-evolving complex (OEC) in photosystem II (PSII) that is comprised of the tetranuclear manganese calcium-oxo (Mn4CaO5) cluster, with participation of the redox-active tyrosine residue (YZ) and a hydrogen-bonded network of amino acids and water molecules. YZ mediates successive proton-coupled electron transfer (PCET) reactions that are essential for the oxidation of water to dioxygen at the Mn4CaO5 cluster. It has been proposed that the strong hydrogen bond between YZ and and its conjugate base, D1-His190, likely renders YZ kinetically and thermodynamically competent leading to highly efficient water oxidation.1 However, a detailed understanding of PCET at YZ remains elusive due to the transient nature of its intermediate states. In this study, we utilize a combination of high-resolution two-dimensional (2D) 14N hyperfine sublevel correlation (HYSCORE) spectroscopy and density functional theory (DFT) methods to investigate the electronic structure of a bioinspired artificial photosynthetic reaction center, benzimidazole-phenol porphyrin (BiP–PF10), that mimics the PCET process at the YZ residue of PSII. The results of these studies underscore the importance of proximal water molecules and charge delocalization on the electronic structure of the artificial reaction center.


Elucidating the Principles that Control Proton-Coupled Electron Transfer Reactions in the Photosynthetic Protein, Photosystem II. A Model for Design of Bio-Inspired Photocatalytic Water-splitting.

Basic Energy Sciences

Find out more...

Supramolecular Structures for Photochemical Energy Conversion

Basic Energy Sciences

Find out more...

“Fondo Institucional para el Desarrollo de la Investigación (FIDI)” of the University of Puerto Rico at Cayey.

Advancing Competitive Biomedical Research in Puerto Rico

National Institute of General Medical Sciences

Find out more...


Email Address of Submitting Author


University of Puerto Rico at Cayey


Puerto Rico

ORCID For Submitting Author


Declaration of Conflict of Interest

No conflict of interest.

Version Notes

First public version of the MS.