ArticleThe Journal of biological chemistry2011
Carboxylate shifts steer interquinone electron transfer in photosynthesis.
Article in The Journal of biological chemistry, 2011. The graph could read no effect estimate from its abstract, so it casts no vote on the map. Cited by 11 papers.
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Who cites it
11 citing papers in PubMed, 35 citations in OpenAlex.
- Tracking the first electron transfer step at the donor side of oxygen-evolving photosystem II by time-resolved infrared spectroscopy.Photosynthesis research · 2024Article
- Absence of a link between stabilized charge-separated state and structural changes proposed from crystal structures of a photosynthetic reaction center.Communications chemistry · 2024Article
- Conformational Changes and H-Bond Rearrangements during Quinone Release in Photosystem II.Biochemistry · 2022Article
- Bicarbonate-controlled reduction of oxygen by the QProceedings of the National Academy of Sciences of the United States of America · 2022Article
- Proton-mediated photoprotection mechanism in photosystem II.Frontiers in plant science · 2022Article
- A single residue controls electron transfer gating in photosynthetic reaction centers.Scientific reports · 2017Article
- Bicarbonate-induced redox tuning in Photosystem II for regulation and protection.Proceedings of the National Academy of Sciences of the United States of America · 2016Article
- Structure/function/dynamics of photosystem II plastoquinone binding sites.Current protein & peptide science · 2014Review
- The nonheme iron in photosystem II.Photosynthesis research · 2013Review
- Rapid X-ray photoreduction of dimetal-oxygen cofactors in ribonucleotide reductase.The Journal of biological chemistry · 2013Article
- Mechanism of proton-coupled quinone reduction in Photosystem II.Proceedings of the National Academy of Sciences of the United States of America · 2013Article
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Authors and funding
4 authors at 1 institution in 1 country.
Funding
No grant is acknowledged in the PubMed record.
Abstract
Understanding the mechanisms of electron transfer (ET) in photosynthetic reaction centers (RCs) may inspire novel catalysts for sunlight-driven fuel production. The electron exit pathway of type II RCs comprises two quinone molecules working in series and in between a non-heme iron atom with a carboxyl ligand (bicarbonate in photosystem II (PSII), glutamate in bacterial RCs). For decades, the functional role of the iron has remained enigmatic. We tracked the iron site using microsecond-resolution x-ray absorption spectroscopy after laser-flash excitation of PSII. After formation of the reduced primary quinone, Q(A)(-), the x-ray spectral changes revealed a transition (t½ ≈ 150 μs) from a bidentate to a monodentate coordination of the bicarbonate at the Fe(II) (carboxylate shift), which reverted concomitantly with the slower ET to the secondary quinone Q(B). A redox change of the iron during the ET was excluded. Density-functional theory calculations corroborated the carboxylate shift both in PSII and bacterial RCs and disclosed underlying changes in electronic configuration. We propose that the iron-carboxyl complex facilitates the first interquinone ET by optimizing charge distribution and hydrogen bonding within the Q(A)FeQ(B) triad for high yield Q(B) reduction. Formation of a specific priming intermediate by nuclear rearrangements, setting the stage for subsequent ET, may be a common motif in reactions of biological redox cofactors.
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