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Hydrogencarbonate is not a tightly bound constituent of the water-oxidizing complex in photosystem II
Umeå University, Faculty of Science and Technology, Department of Chemistry.
Umeå University, Faculty of Science and Technology, Department of Chemistry.
2008 (English)In: Biochimica et Biophysica Acta (BBA) - Bioenergetics, Vol. 1777, no 6, 532-9 p.Article in journal (Refereed) Published
Abstract [en]

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.

Place, publisher, year, edition, pages
2008. Vol. 1777, no 6, 532-9 p.
Keyword [en]
Membrane-inlet mass spectrometry (MIMS), Photosystem II, Water-splitting, Water oxidation, Hydrogencarbonate, Bicarbonate
URN: urn:nbn:se:umu:diva-11557DOI: 10.1016/j.bbabio.2008.03.031OAI: diva2:151228
Available from: 2009-01-15 Created: 2009-01-15 Last updated: 2012-12-17Bibliographically approved

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Shevela, DmitriyMessinger, Johannes
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