Summary
Mechanistic aspects of photosynthetic water oxidation were analysed in dark-adapted PS II fragments from cyanobacteria (Synechococcus vulcanus Copeland) and higher plants (spinach) by detecting flash-induced absorption changes at 830 nm, at 350 nm and at 562 or 580 nm, reflecting the turnover of the photoactive chlorophyll a, P680, of the PS II reaction centre, of the univalent redox transitions Si → Si+1, at the catalytic site of water oxidation and of external indicator dye response due to protolytic reactions, respectively. The possible role of hydrogen bonds for the structural integrity of the oxygen-evolving complex was investigated by measurements of the average oxygen yield per flash in thylakoids after heat treatment of suspensions in H2O or D2O.
The results obtained led to the following conclusions: (a) regardless of the redox state of the catalytic site of water oxidation, Si, P680+ reduction is almost temperature- independent in the physiological range above ‒1.5°C, (b) in contrast to that, the activation parameters of the univalent oxidation steps Si → Si+1 markedly depend on the redox state Si. A characteristic break point is observed in cyanobacteria at about 16°C for S3 oxidation leading to dioxygen formation, (c) about 6–7 hydrogen bonds play an important role for the structural integrity of the oxygen-evolving complex, and (d) the stoichiometry and kinetics of proton release exhibit a complex reaction pattern, depending on pH of the suspension.
Based on these results and data taken from the literature a model is proposed for the mechanism of photosynthetic water oxidation to dioxygen.
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Renger, G., Eckert, HJ., Hagemann, R., Hanssum, B., Koike, H., Wacker, U. (1989). New Results on the Mechanism of Photosynthetic Water Oxidation. In: Singhal, G.S., Barber, J., Dilley, R.A., Govindjee, Haselkorn, R., Mohanty, P. (eds) Photosynthesis. Springer, Berlin, Heidelberg. https://doi.org/10.1007/978-3-642-74221-7_28
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