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
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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.
KeywordsArtificial photosynthesis Photosystem II Manganese Nano-layered manganese oxide Imidazolium Guanidinium
MMN, MAT, and BH are grateful to the Institute for Advanced Studies in Basic Sciences support and the National Elite Foundation for financial support. This study was also supported by Grants from the Russian Foundation for Basic Research (nos. 11-04-01389a, 12-04-92101, 13-04-91372, 13-04-92711), by Molecular and Cell Biology Programs of the Russian Academy of Sciences, by BMBF (No: 8125) Bilateral Cooperation between Germany and Russia, to SIA.
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