Water Molecules Gating a Photoinduced One-Electron Two-Protons Transfer in a Tyrosine/Histidine (Tyr/His) Model of Photosystem II
Dr. Georgios Chararalambidis
Laboratory of Bioinorganic Chemistry, Chemistry Department, University of Crete, PO Box 2208, 71003 Heraklion, Crete, Greece
Search for more papers by this authorDr. Shyamal Das
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
Search for more papers by this authorAdelais Trapali
Laboratory of Bioinorganic Chemistry, Chemistry Department, University of Crete, PO Box 2208, 71003 Heraklion, Crete, Greece
Search for more papers by this authorDr. Annamaria Quaranta
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
Search for more papers by this authorDr. Maylis Orio
Aix Marseille Univ, iSm2, CNRS, Cent Marseille, 13397 Marseille, France
Search for more papers by this authorDr. Zakaria Halime
Institut de Chimie Moléculaire et des Matériaux d'Orsay, UMR 8182 CNRS, Université Paris Sud, Université Paris-Saclay, 91405 Orsay, France
Search for more papers by this authorDr. Pierre Fertey
Synchrotron SOLEIL, BP 48, L'Orme des Merisiers, Saint Aubin, 91192 Gif-sur-Yvette Cedex, France
Search for more papers by this authorDr. Régis Guillot
Institut de Chimie Moléculaire et des Matériaux d'Orsay, UMR 8182 CNRS, Université Paris Sud, Université Paris-Saclay, 91405 Orsay, France
Search for more papers by this authorCorresponding Author
Prof. Athanassios Coutsolelos
Laboratory of Bioinorganic Chemistry, Chemistry Department, University of Crete, PO Box 2208, 71003 Heraklion, Crete, Greece
Search for more papers by this authorCorresponding Author
Dr. Winfried Leibl
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
Search for more papers by this authorCorresponding Author
Prof. Ally Aukauloo
Institut de Chimie Moléculaire et des Matériaux d'Orsay, UMR 8182 CNRS, Université Paris Sud, Université Paris-Saclay, 91405 Orsay, France
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
Search for more papers by this authorCorresponding Author
Dr. Marie Sircoglou
Institut de Chimie Moléculaire et des Matériaux d'Orsay, UMR 8182 CNRS, Université Paris Sud, Université Paris-Saclay, 91405 Orsay, France
Search for more papers by this authorDr. Georgios Chararalambidis
Laboratory of Bioinorganic Chemistry, Chemistry Department, University of Crete, PO Box 2208, 71003 Heraklion, Crete, Greece
Search for more papers by this authorDr. Shyamal Das
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
Search for more papers by this authorAdelais Trapali
Laboratory of Bioinorganic Chemistry, Chemistry Department, University of Crete, PO Box 2208, 71003 Heraklion, Crete, Greece
Search for more papers by this authorDr. Annamaria Quaranta
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
Search for more papers by this authorDr. Maylis Orio
Aix Marseille Univ, iSm2, CNRS, Cent Marseille, 13397 Marseille, France
Search for more papers by this authorDr. Zakaria Halime
Institut de Chimie Moléculaire et des Matériaux d'Orsay, UMR 8182 CNRS, Université Paris Sud, Université Paris-Saclay, 91405 Orsay, France
Search for more papers by this authorDr. Pierre Fertey
Synchrotron SOLEIL, BP 48, L'Orme des Merisiers, Saint Aubin, 91192 Gif-sur-Yvette Cedex, France
Search for more papers by this authorDr. Régis Guillot
Institut de Chimie Moléculaire et des Matériaux d'Orsay, UMR 8182 CNRS, Université Paris Sud, Université Paris-Saclay, 91405 Orsay, France
Search for more papers by this authorCorresponding Author
Prof. Athanassios Coutsolelos
Laboratory of Bioinorganic Chemistry, Chemistry Department, University of Crete, PO Box 2208, 71003 Heraklion, Crete, Greece
Search for more papers by this authorCorresponding Author
Dr. Winfried Leibl
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
Search for more papers by this authorCorresponding Author
Prof. Ally Aukauloo
Institut de Chimie Moléculaire et des Matériaux d'Orsay, UMR 8182 CNRS, Université Paris Sud, Université Paris-Saclay, 91405 Orsay, France
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
Search for more papers by this authorCorresponding Author
Dr. Marie Sircoglou
Institut de Chimie Moléculaire et des Matériaux d'Orsay, UMR 8182 CNRS, Université Paris Sud, Université Paris-Saclay, 91405 Orsay, France
Search for more papers by this authorAbstract
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.
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