Concerted One-Electron Two-Proton Transfer Processes in Models Inspired by the Tyr-His Couple of Photosystem II
Abstract
Nature employs a TyrZ-His pair as a redox relay that couples proton transfer to the redox process between P680 and the water oxidizing catalyst in photosystem II. Artificial redox relays composed of different benzimidazole- phenol dyads (benzimidazole models His and phenol models Tyr) with substituents designed to simulate the hydrogen bond network surrounding the TyrZ-His pair have been prepared. When the benzimidazole substituents are strong proton acceptors such as primary or tertiary amines, theory predicts that a concerted two proton transfer process associated with the electrochemical oxidation of the phenol will take place. Also, theory predicts a decrease in the redox potential of the phenol by ~300 mV and a small kinetic isotope effect (KIE). Indeed, electrochemical, spectroelectrochemical, and KIE experimental data are consistent with these predictions. Notably, these results were obtained by using theory to guide the rational design of artificial systems and have implications for managing proton activity to optimize efficiency at energy conversion sites involving water oxidation and reduction.
- Authors:
-
- University of Illinois at Urbana-Champaign
- Arizona State University
- Sandia National Laboratories
- Universite de Paris XI (Paris-Sud)
- University of Virginia
- University of California, San Diego
- Publication Date:
- Research Org.:
- Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
- Sponsoring Org.:
- USDOE
- OSTI Identifier:
- 1710200
- Report Number(s):
- PNNL-SA-128378
- DOE Contract Number:
- AC05-76RL01830
- Resource Type:
- Journal Article
- Journal Name:
- ACS Central Science
- Additional Journal Information:
- Journal Volume: 3; Journal Issue: 5
- Country of Publication:
- United States
- Language:
- English
Citation Formats
Huynh, Mioy T., Mora, S Jimena, Villalba, Matias, Tejeda-Ferrari, Marely E., Liddell, Paul A., Cherry, Brian R., Teillout, Anne-Lucie, Machan, Charles W., Kubiak, Cliff, Gust, Devens, Moore, Thomas A., Hammes-Schiffer, Sharon, and Moore, Ana L. Concerted One-Electron Two-Proton Transfer Processes in Models Inspired by the Tyr-His Couple of Photosystem II. United States: N. p., 2017.
Web. doi:10.1021/acscentsci.7b00125.
Huynh, Mioy T., Mora, S Jimena, Villalba, Matias, Tejeda-Ferrari, Marely E., Liddell, Paul A., Cherry, Brian R., Teillout, Anne-Lucie, Machan, Charles W., Kubiak, Cliff, Gust, Devens, Moore, Thomas A., Hammes-Schiffer, Sharon, & Moore, Ana L. Concerted One-Electron Two-Proton Transfer Processes in Models Inspired by the Tyr-His Couple of Photosystem II. United States. https://doi.org/10.1021/acscentsci.7b00125
Huynh, Mioy T., Mora, S Jimena, Villalba, Matias, Tejeda-Ferrari, Marely E., Liddell, Paul A., Cherry, Brian R., Teillout, Anne-Lucie, Machan, Charles W., Kubiak, Cliff, Gust, Devens, Moore, Thomas A., Hammes-Schiffer, Sharon, and Moore, Ana L. Wed .
"Concerted One-Electron Two-Proton Transfer Processes in Models Inspired by the Tyr-His Couple of Photosystem II". United States. https://doi.org/10.1021/acscentsci.7b00125.
@article{osti_1710200,
title = {Concerted One-Electron Two-Proton Transfer Processes in Models Inspired by the Tyr-His Couple of Photosystem II},
author = {Huynh, Mioy T. and Mora, S Jimena and Villalba, Matias and Tejeda-Ferrari, Marely E. and Liddell, Paul A. and Cherry, Brian R. and Teillout, Anne-Lucie and Machan, Charles W. and Kubiak, Cliff and Gust, Devens and Moore, Thomas A. and Hammes-Schiffer, Sharon and Moore, Ana L.},
abstractNote = {Nature employs a TyrZ-His pair as a redox relay that couples proton transfer to the redox process between P680 and the water oxidizing catalyst in photosystem II. Artificial redox relays composed of different benzimidazole- phenol dyads (benzimidazole models His and phenol models Tyr) with substituents designed to simulate the hydrogen bond network surrounding the TyrZ-His pair have been prepared. When the benzimidazole substituents are strong proton acceptors such as primary or tertiary amines, theory predicts that a concerted two proton transfer process associated with the electrochemical oxidation of the phenol will take place. Also, theory predicts a decrease in the redox potential of the phenol by ~300 mV and a small kinetic isotope effect (KIE). Indeed, electrochemical, spectroelectrochemical, and KIE experimental data are consistent with these predictions. Notably, these results were obtained by using theory to guide the rational design of artificial systems and have implications for managing proton activity to optimize efficiency at energy conversion sites involving water oxidation and reduction.},
doi = {10.1021/acscentsci.7b00125},
url = {https://www.osti.gov/biblio/1710200},
journal = {ACS Central Science},
number = 5,
volume = 3,
place = {United States},
year = {2017},
month = {5}
}
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Works referencing / citing this record:
Water Molecules Gating a Photoinduced One-Electron Two-Protons Transfer in a Tyrosine/Histidine (Tyr/His) Model of Photosystem II
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