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Energetics and kinetics of photosynthetic water oxidation studied by photothermal beam deflection (PBD) experiments

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Abstract

Determination of thermodynamic parameters of water oxidation at the photosystem II (PSII) manganese complex is a major challenge. Photothermal beam deflection (PBD) spectroscopy determines enthalpy changes (ΔH) and apparent volume changes which are coupled with electron transfer in the S-state cycle (Krivanek R, Dau H, Haumann M (2008) Biophys J 94: 1890–1903). Recent PBD results on formation of the Q −A /Y •+Z radical pair suggest a value of ΔH similar to the free energy change, ΔG, of −540 ± 40 meV previously determined by the analysis of recombination fluorescence, but presently the uncertainty range of ΔH values determined by PBD is still high (±250 meV). In the oxygen-evolving transition, S3 → S0, the enthalpy change may be close to zero. A prominent non-thermal signal is associated with both Q −A /Y •+Z formation (<1 μs) and the S3 → S0 transition (~1 ms). The observed (apparent) volume expansion (ΔV of about +40 Å3 per PSII unit) in the S3 → S0 transition seems to revert, at least partially, the contractions on lower S-transitions and may also comprise contributions from O2 and proton release. The observed volume changes show that the S3 → S0 transition is accompanied by significant nuclear movements, which likely are of importance with respect to energetics and mechanism of photosynthetic water oxidation. Detailed PBD studies on all S-transitions will contribute to the progress in PSII research by providing insights not accessible by other spectroscopic methods.

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Abbreviations

BCP:

Bromocresol-purple (5′,5″-dibromo-o-cresolsulfophthalein)

Chl:

Chlorophyll

cw:

continuous wave

DCBQ:

2,6-Dichloro-p-benzoquinone

DCMU:

3-(3,4-Dichlorophenyl)-1,1-dimethyl-urea

ET:

Electron transfer

FWHM:

Full width at half-maximum

PBD:

Photothermal beam deflection

PSII:

Photosystem II

S i :

Oxidation states in the S-state cycle of PSII

YZ :

Tyr-161 of the D1 subunit of PSII

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Acknowledgment

Financial support by the Volkswagen-Foundation (grant I/77-575) and the European Union (SOLAR-H2 consortium, FP7 contract 212508) is gratefully acknowledged. We thank Monika Fünning for skillful preparation of PSII membrane particles.

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Authors and Affiliations

  1. FB Physik, Institut für Experimentalphysik, Freie Universität Berlin, Arnimallee 14, 14195, Berlin, Germany

    André Klauss, Roland Krivanek, Holger Dau & Michael Haumann

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  1. André Klauss
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  2. Roland Krivanek
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  3. Holger Dau
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  4. Michael Haumann
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Correspondence to Holger Dau or Michael Haumann.

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Klauss, A., Krivanek, R., Dau, H. et al. Energetics and kinetics of photosynthetic water oxidation studied by photothermal beam deflection (PBD) experiments. Photosynth Res 102, 499–509 (2009). https://doi.org/10.1007/s11120-009-9417-3

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