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Angew Chem Int Ed Engl. 2018 Jul 16;57(29):9013-9017. doi: 10.1002/anie.201804498. Epub 2018 Jun 19.

Water Molecules Gating a Photoinduced One-Electron Two-Protons Transfer in a Tyrosine/Histidine (Tyr/His) Model of Photosystem II.

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Laboratory of Bioinorganic Chemistry, Chemistry Department, University of Crete, PO Box 2208, 71003, Heraklion, Crete, Greece.
Institut des Sciences du vivant Frédéric Joliot/Institut de Biologie Intégrative de la Cellule, UMR 9198, CEA, CNRS, Université Paris Sud, Université Paris-Saclay, 91191, Gif-sur-Yvette, France.
Aix Marseille Univ, iSm2, CNRS, Cent Marseille, 13397, Marseille, France.
Institut de Chimie Moléculaire et des Matériaux d'Orsay, UMR 8182 CNRS, Université Paris Sud, Université Paris-Saclay, 91405, Orsay, France.
Synchrotron SOLEIL, BP 48, L'Orme des Merisiers, Saint Aubin, 91192, Gif-sur-Yvette Cedex, France.


We investigate a biomimetic model of a TyrZ /His190 pair, a hydrogen-bonded phenol/imidazole covalently attached to a porphyrin sensitizer. Laser flash photolysis in the presence of an external electron acceptor reveals the need for water molecules to unlock the light-induced oxidation of the phenol through an intramolecular pathway. Kinetics monitoring encompasses two fast phases with distinct spectral properties. The first phase is related to a one-electron transfer from the phenol to the porphyrin radical cation coupled with a domino two-proton transfer leading to the ejection of a proton from the imidazole-phenol pair. The second phase concerns conveying the released proton to the porphyrin N4 coordinating cavity. Our study provides an unprecedented example of a light-induced electron-transfer process in a TyrZ /His190 model of photosystem II, evidencing the movement of both the phenol and imidazole protons along an isoenergetic pathway.


TyrZ-His190 model; artificial photosynthesis; photophysics; porphyrin; proton-coupled electron transfer


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