MECHANISM OF PHOTOSYNTHETIC MOLECULAR OXYGEN FORMATION
Abstract
This paper considers the mechanism of how molecular oxygen is formed in the process of plant photosynthesis as a result of water molecule oxidation in the structure of the oxygen-evolving complex (OEC) in chloroplast membranes. We have implemented the entire complex of investigations of the OEC starting with the development of the innovation methods for its isolation and analysis of its properties and ending with the establishment of its molecular structure and mechanism of its functioning. We have shown for the first time that the OEC consists of two monomeric pigment-lipoprotein complexes of photosystem 2 (PLPC PS-2) that are associated by the mirror symmetry rule into a dimeric structure as a result of their hydrophobic interaction. It has been ascertained that this association zone is the place of the formation of the hydrophobic boiler that stabilizes the water-oxidizing center (WOC), which is located inside this boiler. The research into the regularities of the functioning of the OEC has enabled us to advance and substantiate the concept of the two-anode organization of its WOC that is formed as a result of the opposite facing of two functional Mn cations, each of which is built into the system of photochemical electron transfer and undergoes photo-oxidation in the structure of the PLPC PS-2 of the dimeric OEC. The two-anode action of the WOC implements the possibility of the synchronous oxidation of two water molecules at once with the formation of O2. The mechanism has been proposed, according to which the stages of the four-quanta oxidation of the functional Mn cations are accompanied by their photo-hydrolysis, Ca2+-activated formation of a dihydroxide associate [Mn4+ (OH)···(HO) Mn4+], and the reaction of electron density disproportionation in this associate with O2 evolution and with reduction of manganese cations to Mn2+. The thermodynamic efficiency of the reaction is determined by the optimal conditions for the formation of a cylindrically symmetric σ-π-bond between the oxygen atoms in the formed O2 molecules. The developed mechanism has been confirmed by the quantum-chemical analysis and can find use in the design of molecular oxygen generators based on artificial structures.
About the Author
N. I. Shutilova
Institute of Fundamental Problems of Biology
Russian Federation
D. Sc. (Biol.), Leading researcher
Russian Federation
D. Sc. (Biol.), Leading researcher
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