Abstract
Over 40 years ago, Joliot et al. (Photochem Photobiol 10:309–329, 1969) designed and employed an elegant and highly sensitive electrochemical technique capable of measuring O2 evolved by photosystem II (PSII) in response to trains of single turn-over light flashes. The measurement and analysis of flash-induced oxygen evolution patterns (FIOPs) has since proven to be a powerful method for probing the turnover efficiency of PSII. Stemler et al. (Proc Natl Acad Sci USA 71(12):4679–4683, 1974), in Govindjee’s lab, were the first to study the effect of “bicarbonate” on FIOPs by adding the competitive inhibitor acetate. Here, we extend this earlier work by performing FIOPs experiments at various, strictly controlled inorganic carbon (Ci) levels without addition of any inhibitors. For this, we placed a Joliot-type bare platinum electrode inside a N2-filled glove-box (containing 10–20 ppm CO2) and reduced the Ci concentration simply by washing the samples in Ci-depleted media. FIOPs of spinach thylakoids were recorded either at 20-times reduced levels of Ci or at ambient Ci conditions (390 ppm CO2). Numerical analysis of the FIOPs within an extended Kok model reveals that under Ci-depleted conditions the miss probability is discernibly larger (by 2–3 %) than at ambient conditions, and that the addition of 5 mM HCO3 − to the Ci-depleted thylakoids largely restores the original miss parameter. Since a “mild” Ci-depletion procedure was employed, we discuss our data with respect to a possible function of free or weakly bound HCO3 − at the water-splitting side of PSII.
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Abbreviations
- α:
-
Miss parameter
- β:
-
Double hit parameter
- Ci :
-
Inorganic carbon (HCO3 −, CO2, CO3 2−)
- C −i :
-
Inorganic carbon depleted
- C +i :
-
Containing ambient level of inorganic carbon
- FIOP:
-
Flash-induced oxygen evolution pattern
- MIMS:
-
Membrane-inlet mass spectrometry
- PSII:
-
Photosystem II
- OEC:
-
Oxygen-evolving complex
- S i states:
-
Oxidation states of the OEC, where i is the number of stored oxidizing equivalents
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Acknowledgments
This study was supported by the Knut and Alice Wallenberg Foundation, the Kempe Foundation, the Swedish Research Council (VR), the Strong Research Environment Solar Fuels (Umeå University), the Artificial Leaf Project (K&A Wallenberg Foundation) and the Max-Planck Gesellschaft. The authors would like to thank Govindjee, Vyacheslav Klimov, and Alan Stemler for fruitful discussions on the “bicarbonate effect” over the last few years and Ethel Hüttel for sample preparation.
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Shevela, D., Nöring, B., Koroidov, S. et al. Efficiency of photosynthetic water oxidation at ambient and depleted levels of inorganic carbon. Photosynth Res 117, 401–412 (2013). https://doi.org/10.1007/s11120-013-9875-5
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DOI: https://doi.org/10.1007/s11120-013-9875-5