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Imidazolium or guanidinium/layered manganese (III, IV) oxide hybrid as a promising structural model for the water-oxidizing complex of Photosystem II for artificial photosynthetic systems
Authors:Mohammad Mahdi Najafpour  Mahmoud Amouzadeh Tabrizi  Behzad Haghighi  Julian J Eaton-Rye  Robert Carpentier  Suleyman I Allakhverdiev
Institution:1. Department of Chemistry, Institute for Advanced Studies in Basic Sciences (IASBS), 45137-66731, Zanjan, Iran
2. Center of Climate Change and Global Warming, Institute for Advanced Studies in Basic Sciences (IASBS), 45137-66731, Zanjan, Iran
3. Department of Biochemistry, University of Otago, P.O. Box 56, Dunedin, 9054, New Zealand
4. Groupe de Recherche En Biologie Végétale (GRBV), Université du Québec à Trois-Rivières, C.P. 500, Trois-Rivières, QC, G9A 5H7, Canada
5. Controlled Photobiosynthesis Laboratory, Institute of Plant Physiology, Russian Academy of Sciences, Botanicheskaya Street 35, Moscow, 127276, Russia
6. Institute of Basic Biological Problems, Russian Academy of Sciences, Pushchino, Moscow, 142290, Russia
Abstract:Photosystem II is responsible for the light-driven biological water-splitting system in oxygenic photosynthesis and contains a cluster of one calcium and four manganese ions at its water-oxidizing complex. This cluster may serve as a model for the design of artificial or biomimetic systems capable of splitting water into oxygen and hydrogen. In this study, we consider the ability of manganese oxide monosheets to self-assemble with organic compounds. Layered structures of manganese oxide, including guanidinium and imidazolium groups, were synthesized and characterized by scanning electron microscopy, transmission electron microscopy, X-ray diffraction spectrometry, and atomic absorption spectroscopy. The compounds can be considered as new structural models for the water-oxidizing complex of Photosystem II. The overvoltage of water oxidation for the compounds in these conditions at pH = 6.3 is ~0.6 V. These compounds may represent the first step to synthesize a hybrid of guanidinium or imidazole together with manganese as a biomimetic system for the water-oxidizing complex of Photosystem II.
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