title: Energetics and kinetics of photosynthetic water oxidation studied by photothermal beam deflection (PBD) experiments.
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.
authors.affiliation: FB Physik, Institut für Experimentalphysik, Freie Universität Berlin, Arnimallee 14, 14195 Berlin, Germany.
authors.forename: André
authors.initials: A
authors.lastname: Klauss
authors.forename: Roland
authors.initials: R
authors.lastname: Krivanek
authors.forename: Holger
authors.initials: H
authors.lastname: Dau
authors.forename: Michael
authors.initials: M
authors.lastname: Haumann