* Bioinformatics, MSc Level
* Structural Biochemistry, MSc Level
* Experimental Chemical Methods, BSc Level
* Molecular Structure and Statistical Thermodynamics, BSc Level
* Mathematical Methods in Chemistry, BSc Level

Mechanisms of Proton-Coupled Electron Transfer in Photosynthetic Energy Conversion

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• Bicarbonate-controlled reduction of oxygen by the Q_A semiquinone in Photosystem II in membranes

  2022. Andrea Fantuzzi (et al.). Proceedings of the National Academy of Sciences of the United States of America 119 (6)

  Artikel

  Photosystem II (PSII), the water/plastoquinone photo-oxidoreductase, plays a key energy input role in the biosphere. , the reduced semiquinone form of the nonexchangeable quinone, is often considered capable of a side reaction with O2, forming superoxide, but this reaction has not yet been demonstrated experimentally. Here, using chlorophyll fluorescence in plant PSII membranes, we show that O₂ does oxidize at physiological O₂ concentrations with a t_1/2 of 10 s. Superoxide is formed stoichiometrically, and the reaction kinetics are controlled by the accessibility of O₂ to a binding site near , with an apparent dissociation constant of 70 ± 20 µM. Unexpectedly, could only reduce O₂ when bicarbonate was absent from its binding site on the nonheme iron (Fe²⁺) and the addition of bicarbonate or formate blocked the O₂-dependant decay of . These results, together with molecular dynamics simulations and hybrid quantum mechanics/molecular mechanics calculations, indicate that electron transfer from to O₂ occurs when the O₂ is bound to the empty bicarbonate site on Fe2+. A protective role for bicarbonate in PSII was recently reported, involving long-lived triggering bicarbonate dissociation from Fe2+ [Brinkert et al., Proc. Natl. Acad. Sci. U.S.A. 113, 12144–12149 (2016)]. The present findings extend this mechanism by showing that bicarbonate release allows O₂ to bind to Fe²⁺ and to oxidize . This could be beneficial by oxidizing and by producing superoxide, a chemical signal for the overreduced state of the electron transfer chain.

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• Molecular Principles of Redox-Coupled Protonation Dynamics in Photosystem II

  2022. Friederike Allgöwer (et al.). Journal of the American Chemical Society 144 (16), 7171-7180

  Artikel

  Photosystem II (PSII) catalyzes light-driven water oxidization, releasing O₂ into the atmosphere and transferring the electrons for the synthesis of biomass. However, despite decades of structural and functional studies, the water oxidation mechanism of PSII has remained puzzling and a major challenge for modern chemical research. Here, we show that PSII catalyzes redox-triggered proton transfer between its oxygen-evolving Mn₄O₅Ca cluster and a nearby cluster of conserved buried ion-pairs, which are connected to the bulk solvent via a proton pathway. By using multi-scale quantum and classical simulations, we find that oxidation of a redox-active Tyr_z (Tyr161) lowers the reaction barrier for the water-mediated proton transfer from a Ca²⁺-bound water molecule (W3) to Asp61 via conformational changes in a nearby ion-pair (Asp61/Lys317). Deprotonation of this W3 substrate water triggers its migration toward Mn1 to a position identified in recent X-ray free-electron laser (XFEL) experiments [Ibrahim et al. Proc. Natl. Acad. Sci. USA 2020, 117, 12,624–12,635]. Further oxidation of the Mn₄O₅Ca cluster lowers the proton transfer barrier through the water ligand sphere of the Mn₄O₅Ca cluster to Asp61 via a similar ion-pair dissociation process, while the resulting Mn-bound oxo/oxyl species leads to O₂ formation by a radical coupling mechanism. The proposed redox-coupled protonation mechanism shows a striking resemblance to functional motifs in other enzymes involved in biological energy conversion, with an interplay between hydration changes, ion-pair dynamics, and electric fields that modulate the catalytic barriers. 

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