Creation of a 3Mn/1Fe Cluster in the Oxygen-Evolving Complex of Photosystem II and Investigation of its Functional Activity

Michael Seibert; B. K..Semin; L. Davletshina; A. Rubin

doi:10.1016/j.jphotobiol.2017.11.016

Creation of a 3Mn/1Fe Cluster in the Oxygen-Evolving Complex of Photosystem II and Investigation of its Functional Activity

Michael Seibert, B. K..Semin, L. Davletshina, A. Rubin

Moscow State University

Research output: Contribution to journal › Article › peer-review

13 Scopus Citations

Abstract

Extraction of Mn cations from the oxygen-evolving complex (OEC) of Ca-depleted PSII membranes (PSII[-Ca,4Mn]) by reductants like hydroquinone (H₂Q) occurs with lower efficiency at acidic pH (2Mn/reaction center [RC] are extracted at pH 5.7) than at neutral pH (3Mn/RC are extracted at pH 6.5) [Semin et al. Photosynth. Res. 125 (2015) 95]. Fe(II) also extracts Mn cations from PSII(-Ca,4Mn), but only 2Mn/RC at pH 6.5, forming a heteronuclear 2Mn/2Fe cluster [Semin and Seibert, J. Bioenerg. Biomembr. 48 (2016) 227]. Here we investigated the efficiency of Mn extraction by Fe(II) at acidic pH and found that Fe(II) cations can extract only 1Mn/RC from PSII(-Ca,4Mn) membranes at pH 5.7, forming a 3Mn/1Fe cluster. Also we found that the presence of Fe cations in a heteronuclear cluster (2Mn/2Fe) increases the resistance of the remaining Mn cations to H₂Q action, since H₂Q can extract Mn cations from homonuclear Mn clusters of PSII(-Ca,4Mn) and PSII(-Ca,2Mn) membranes but not from the heteronuclear cluster in PSII(-Ca,2Mn,2Fe) membranes. H₂Q also cannot extract Mn from PSII membranes obtained by incubation of PSII(-Ca,4Mn) membranes with Fe(II) cations at pH 5.7, which suggests the formation of a heteronuclear 3Mn/1Fe cluster in the OEC. Functional activity of PSII with a 3Mn/1Fe cluster was investigated. PSII preparations with a 3Mn/1Fe cluster in the OEC are able to photoreduce the exogenous electron acceptor 2,6-dichlorophenolindophenol, possibly due to incomplete oxidation of water molecules as is the case with PSII(-Ca,2Mn,2Fe) samples. However, in the contrast to PSII(-Ca,2Mn,2Fe) samples PSII(-Ca,3Mn,1Fe) membranes can evolve O₂ at a low rate in the presence of exogenous Ca^{2 +} (at about 27% of the rate of O₂ evolution in native PSII membranes). The explanation for this phenomenon (either water splitting and production of molecular O₂ by the 3Mn/1Fe cluster or apparent O₂ evolution due to minor contamination of PSII(3Mn,1Fe) samples with PSII(-Ca,4Mn) membranes) is discussed.

Original language	American English
Pages (from-to)	192-200
Number of pages	9
Journal	Journal of Photochemistry and Photobiology B: Biology
Volume	178
DOIs	https://doi.org/10.1016/j.jphotobiol.2017.11.016 https://doi.org/10.1016/j.jphotobiol.2017.11.016
State	Published - 2018

Bibliographical note

Publisher Copyright:
© 2017

NREL Publication Number

NREL/JA-2700-68047

Keywords

Calcium
Iron
Manganese
Oxygen-evolving complex
Photosystem II
Water-splitting

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@article{300c645a5e684e399207f9e865fbeef5,

title = "Creation of a 3Mn/1Fe Cluster in the Oxygen-Evolving Complex of Photosystem II and Investigation of its Functional Activity",

abstract = "Extraction of Mn cations from the oxygen-evolving complex (OEC) of Ca-depleted PSII membranes (PSII[-Ca,4Mn]) by reductants like hydroquinone (H2Q) occurs with lower efficiency at acidic pH (2Mn/reaction center [RC] are extracted at pH 5.7) than at neutral pH (3Mn/RC are extracted at pH 6.5) [Semin et al. Photosynth. Res. 125 (2015) 95]. Fe(II) also extracts Mn cations from PSII(-Ca,4Mn), but only 2Mn/RC at pH 6.5, forming a heteronuclear 2Mn/2Fe cluster [Semin and Seibert, J. Bioenerg. Biomembr. 48 (2016) 227]. Here we investigated the efficiency of Mn extraction by Fe(II) at acidic pH and found that Fe(II) cations can extract only 1Mn/RC from PSII(-Ca,4Mn) membranes at pH 5.7, forming a 3Mn/1Fe cluster. Also we found that the presence of Fe cations in a heteronuclear cluster (2Mn/2Fe) increases the resistance of the remaining Mn cations to H2Q action, since H2Q can extract Mn cations from homonuclear Mn clusters of PSII(-Ca,4Mn) and PSII(-Ca,2Mn) membranes but not from the heteronuclear cluster in PSII(-Ca,2Mn,2Fe) membranes. H2Q also cannot extract Mn from PSII membranes obtained by incubation of PSII(-Ca,4Mn) membranes with Fe(II) cations at pH 5.7, which suggests the formation of a heteronuclear 3Mn/1Fe cluster in the OEC. Functional activity of PSII with a 3Mn/1Fe cluster was investigated. PSII preparations with a 3Mn/1Fe cluster in the OEC are able to photoreduce the exogenous electron acceptor 2,6-dichlorophenolindophenol, possibly due to incomplete oxidation of water molecules as is the case with PSII(-Ca,2Mn,2Fe) samples. However, in the contrast to PSII(-Ca,2Mn,2Fe) samples PSII(-Ca,3Mn,1Fe) membranes can evolve O2 at a low rate in the presence of exogenous Ca2 + (at about 27% of the rate of O2 evolution in native PSII membranes). The explanation for this phenomenon (either water splitting and production of molecular O2 by the 3Mn/1Fe cluster or apparent O2 evolution due to minor contamination of PSII(3Mn,1Fe) samples with PSII(-Ca,4Mn) membranes) is discussed.",

keywords = "Calcium, Iron, Manganese, Oxygen-evolving complex, Photosystem II, Water-splitting",

author = "Michael Seibert and B. K..Semin and L. Davletshina and A. Rubin",

note = "Publisher Copyright: {\textcopyright} 2017",

year = "2018",

doi = "10.1016/j.jphotobiol.2017.11.016",

language = "American English",

volume = "178",

pages = "192--200",

journal = "Journal of Photochemistry and Photobiology B: Biology",

issn = "1011-1344",

publisher = "Elsevier B.V.",

}

TY - JOUR

T1 - Creation of a 3Mn/1Fe Cluster in the Oxygen-Evolving Complex of Photosystem II and Investigation of its Functional Activity

AU - Seibert, Michael

AU - K..Semin, B.

AU - Davletshina, L.

AU - Rubin, A.

PY - 2018

Y1 - 2018

N2 - Extraction of Mn cations from the oxygen-evolving complex (OEC) of Ca-depleted PSII membranes (PSII[-Ca,4Mn]) by reductants like hydroquinone (H2Q) occurs with lower efficiency at acidic pH (2Mn/reaction center [RC] are extracted at pH 5.7) than at neutral pH (3Mn/RC are extracted at pH 6.5) [Semin et al. Photosynth. Res. 125 (2015) 95]. Fe(II) also extracts Mn cations from PSII(-Ca,4Mn), but only 2Mn/RC at pH 6.5, forming a heteronuclear 2Mn/2Fe cluster [Semin and Seibert, J. Bioenerg. Biomembr. 48 (2016) 227]. Here we investigated the efficiency of Mn extraction by Fe(II) at acidic pH and found that Fe(II) cations can extract only 1Mn/RC from PSII(-Ca,4Mn) membranes at pH 5.7, forming a 3Mn/1Fe cluster. Also we found that the presence of Fe cations in a heteronuclear cluster (2Mn/2Fe) increases the resistance of the remaining Mn cations to H2Q action, since H2Q can extract Mn cations from homonuclear Mn clusters of PSII(-Ca,4Mn) and PSII(-Ca,2Mn) membranes but not from the heteronuclear cluster in PSII(-Ca,2Mn,2Fe) membranes. H2Q also cannot extract Mn from PSII membranes obtained by incubation of PSII(-Ca,4Mn) membranes with Fe(II) cations at pH 5.7, which suggests the formation of a heteronuclear 3Mn/1Fe cluster in the OEC. Functional activity of PSII with a 3Mn/1Fe cluster was investigated. PSII preparations with a 3Mn/1Fe cluster in the OEC are able to photoreduce the exogenous electron acceptor 2,6-dichlorophenolindophenol, possibly due to incomplete oxidation of water molecules as is the case with PSII(-Ca,2Mn,2Fe) samples. However, in the contrast to PSII(-Ca,2Mn,2Fe) samples PSII(-Ca,3Mn,1Fe) membranes can evolve O2 at a low rate in the presence of exogenous Ca2 + (at about 27% of the rate of O2 evolution in native PSII membranes). The explanation for this phenomenon (either water splitting and production of molecular O2 by the 3Mn/1Fe cluster or apparent O2 evolution due to minor contamination of PSII(3Mn,1Fe) samples with PSII(-Ca,4Mn) membranes) is discussed.

AB - Extraction of Mn cations from the oxygen-evolving complex (OEC) of Ca-depleted PSII membranes (PSII[-Ca,4Mn]) by reductants like hydroquinone (H2Q) occurs with lower efficiency at acidic pH (2Mn/reaction center [RC] are extracted at pH 5.7) than at neutral pH (3Mn/RC are extracted at pH 6.5) [Semin et al. Photosynth. Res. 125 (2015) 95]. Fe(II) also extracts Mn cations from PSII(-Ca,4Mn), but only 2Mn/RC at pH 6.5, forming a heteronuclear 2Mn/2Fe cluster [Semin and Seibert, J. Bioenerg. Biomembr. 48 (2016) 227]. Here we investigated the efficiency of Mn extraction by Fe(II) at acidic pH and found that Fe(II) cations can extract only 1Mn/RC from PSII(-Ca,4Mn) membranes at pH 5.7, forming a 3Mn/1Fe cluster. Also we found that the presence of Fe cations in a heteronuclear cluster (2Mn/2Fe) increases the resistance of the remaining Mn cations to H2Q action, since H2Q can extract Mn cations from homonuclear Mn clusters of PSII(-Ca,4Mn) and PSII(-Ca,2Mn) membranes but not from the heteronuclear cluster in PSII(-Ca,2Mn,2Fe) membranes. H2Q also cannot extract Mn from PSII membranes obtained by incubation of PSII(-Ca,4Mn) membranes with Fe(II) cations at pH 5.7, which suggests the formation of a heteronuclear 3Mn/1Fe cluster in the OEC. Functional activity of PSII with a 3Mn/1Fe cluster was investigated. PSII preparations with a 3Mn/1Fe cluster in the OEC are able to photoreduce the exogenous electron acceptor 2,6-dichlorophenolindophenol, possibly due to incomplete oxidation of water molecules as is the case with PSII(-Ca,2Mn,2Fe) samples. However, in the contrast to PSII(-Ca,2Mn,2Fe) samples PSII(-Ca,3Mn,1Fe) membranes can evolve O2 at a low rate in the presence of exogenous Ca2 + (at about 27% of the rate of O2 evolution in native PSII membranes). The explanation for this phenomenon (either water splitting and production of molecular O2 by the 3Mn/1Fe cluster or apparent O2 evolution due to minor contamination of PSII(3Mn,1Fe) samples with PSII(-Ca,4Mn) membranes) is discussed.

KW - Calcium

KW - Iron

KW - Manganese

KW - Oxygen-evolving complex

KW - Photosystem II

KW - Water-splitting

UR - http://www.scopus.com/inward/record.url?scp=85034090668&partnerID=8YFLogxK

U2 - 10.1016/j.jphotobiol.2017.11.016

DO - 10.1016/j.jphotobiol.2017.11.016

M3 - Article

C2 - 29156347

AN - SCOPUS:85034090668

SN - 1011-1344

VL - 178

SP - 192

EP - 200

JO - Journal of Photochemistry and Photobiology B: Biology

JF - Journal of Photochemistry and Photobiology B: Biology

ER -

Creation of a 3Mn/1Fe Cluster in the Oxygen-Evolving Complex of Photosystem II and Investigation of its Functional Activity

Abstract

Bibliographical note

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Keywords

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