Hydrogencarbonate is not a tightly bound constituent of the water-oxidizing complex in photosystem II. Shevela, D., Su, J., Klimov, V., & Messinger, J. Biochimica et Biophysica Acta (BBA) - Bioenergetics, 1777(6):532–539, June, 2008. Paper doi abstract bibtex Since the end of the 1950s hydrogencarbonate (‘bicarbonate’) is discussed as a possible cofactor of photosynthetic water-splitting, and in a recent X-ray crystallography model of photosystem II (PSII) it was displayed as a ligand of the Mn4OxCa cluster. Employing membrane-inlet mass spectrometry (MIMS) and isotope labelling we confirm the release of less than one (≈0.3) HCO3− per PSII upon addition of formate. The same amount of HCO3− release is observed upon formate addition to Mn-depleted PSII samples. This suggests that formate does not replace HCO3− from the donor side, but only from the non-heme iron at the acceptor side of PSII. The absence of a firmly bound HCO3− is corroborated by showing that a reductive destruction of the Mn4OxCa cluster inside the MIMS cell by NH2OH addition does not lead to any CO2/HCO3− release. We note that even after an essentially complete HCO3−/CO2 removal from the sample medium by extensive degassing in the MIMS cell the PSII samples retain ≥75% of their initial flash-induced O2-evolving capacity. We therefore conclude that HCO3− has only ‘indirect’ effects on water-splitting in PSII, possibly by being part of a proton relay network and/or by participating in assembly and stabilization of the water-oxidizing complex.
@article{shevela_hydrogencarbonate_2008,
title = {Hydrogencarbonate is not a tightly bound constituent of the water-oxidizing complex in photosystem {II}},
volume = {1777},
issn = {0005-2728},
url = {https://www.sciencedirect.com/science/article/pii/S0005272808000650},
doi = {10.1016/j.bbabio.2008.03.031},
abstract = {Since the end of the 1950s hydrogencarbonate (‘bicarbonate’) is discussed as a possible cofactor of photosynthetic water-splitting, and in a recent X-ray crystallography model of photosystem II (PSII) it was displayed as a ligand of the Mn4OxCa cluster. Employing membrane-inlet mass spectrometry (MIMS) and isotope labelling we confirm the release of less than one (≈0.3) HCO3− per PSII upon addition of formate. The same amount of HCO3− release is observed upon formate addition to Mn-depleted PSII samples. This suggests that formate does not replace HCO3− from the donor side, but only from the non-heme iron at the acceptor side of PSII. The absence of a firmly bound HCO3− is corroborated by showing that a reductive destruction of the Mn4OxCa cluster inside the MIMS cell by NH2OH addition does not lead to any CO2/HCO3− release. We note that even after an essentially complete HCO3−/CO2 removal from the sample medium by extensive degassing in the MIMS cell the PSII samples retain ≥75\% of their initial flash-induced O2-evolving capacity. We therefore conclude that HCO3− has only ‘indirect’ effects on water-splitting in PSII, possibly by being part of a proton relay network and/or by participating in assembly and stabilization of the water-oxidizing complex.},
number = {6},
urldate = {2024-11-29},
journal = {Biochimica et Biophysica Acta (BBA) - Bioenergetics},
author = {Shevela, Dmitriy and Su, Ji-Hu and Klimov, Vyacheslav and Messinger, Johannes},
month = jun,
year = {2008},
keywords = {Bicarbonate, Hydrogencarbonate, Membrane-inlet mass spectrometry (MIMS), Photosystem II, Water oxidation, Water-splitting},
pages = {532--539},
}
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The same amount of HCO3− release is observed upon formate addition to Mn-depleted PSII samples. This suggests that formate does not replace HCO3− from the donor side, but only from the non-heme iron at the acceptor side of PSII. The absence of a firmly bound HCO3− is corroborated by showing that a reductive destruction of the Mn4OxCa cluster inside the MIMS cell by NH2OH addition does not lead to any CO2/HCO3− release. We note that even after an essentially complete HCO3−/CO2 removal from the sample medium by extensive degassing in the MIMS cell the PSII samples retain ≥75% of their initial flash-induced O2-evolving capacity. We therefore conclude that HCO3− has only ‘indirect’ effects on water-splitting in PSII, possibly by being part of a proton relay network and/or by participating in assembly and stabilization of the water-oxidizing complex.","number":"6","urldate":"2024-11-29","journal":"Biochimica et Biophysica Acta (BBA) - Bioenergetics","author":[{"propositions":[],"lastnames":["Shevela"],"firstnames":["Dmitriy"],"suffixes":[]},{"propositions":[],"lastnames":["Su"],"firstnames":["Ji-Hu"],"suffixes":[]},{"propositions":[],"lastnames":["Klimov"],"firstnames":["Vyacheslav"],"suffixes":[]},{"propositions":[],"lastnames":["Messinger"],"firstnames":["Johannes"],"suffixes":[]}],"month":"June","year":"2008","keywords":"Bicarbonate, Hydrogencarbonate, Membrane-inlet mass spectrometry (MIMS), Photosystem II, Water oxidation, Water-splitting","pages":"532–539","bibtex":"@article{shevela_hydrogencarbonate_2008,\n\ttitle = {Hydrogencarbonate is not a tightly bound constituent of the water-oxidizing complex in photosystem {II}},\n\tvolume = {1777},\n\tissn = {0005-2728},\n\turl = {https://www.sciencedirect.com/science/article/pii/S0005272808000650},\n\tdoi = {10.1016/j.bbabio.2008.03.031},\n\tabstract = {Since the end of the 1950s hydrogencarbonate (‘bicarbonate’) is discussed as a possible cofactor of photosynthetic water-splitting, and in a recent X-ray crystallography model of photosystem II (PSII) it was displayed as a ligand of the Mn4OxCa cluster. Employing membrane-inlet mass spectrometry (MIMS) and isotope labelling we confirm the release of less than one (≈0.3) HCO3− per PSII upon addition of formate. The same amount of HCO3− release is observed upon formate addition to Mn-depleted PSII samples. This suggests that formate does not replace HCO3− from the donor side, but only from the non-heme iron at the acceptor side of PSII. The absence of a firmly bound HCO3− is corroborated by showing that a reductive destruction of the Mn4OxCa cluster inside the MIMS cell by NH2OH addition does not lead to any CO2/HCO3− release. We note that even after an essentially complete HCO3−/CO2 removal from the sample medium by extensive degassing in the MIMS cell the PSII samples retain ≥75\\% of their initial flash-induced O2-evolving capacity. 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