Advertisement

The Manganese Complex of Photosystem II: Extended-Range EXAFS Data and Specific Structural Models for Four S-States

  • Alexander Grundmeier
  • Paola Loja
  • Michael Haumann
  • Holger Dau
Conference paper

Abstract

The water-oxidizing manganese complex bound to the proteins of photosystem II (PSII) was studied by X-ray absorption spectroscopy on PSII membrane particles. An extended range for collection of EXAFS data was used (up to 16.6 Å−1). The EXAFS suggests the presence of two Mn-Mn distances close to 2.7 Å (per Mn4Ca complex); the existence of a third Mn-Mn distance below 2.9 Å is not indicated by the EXAFS data. A distance of 3.7 Å is clearly resolved in the extended-range data and tentatively assigned to a Mn-Mn distance. Taking into account the above EXAFS results (inter alia), we present a model for the structure of the PSII manganese complex, which differs from previous atomic-resolution models. Emphasizing the hypothetical character, we propose for all semi-stable S-states (i) a structure of the Mn4Ca(μ-O)n core, (ii) a model of the amino-acid environment, and (iii) assignments of distinct Mn oxidation states to the individual Mn ions. This specific working model may permit discussion, verification, and invalidation of its various features by comparison with experimental and theoretical findings.

Keywords

EXAFS manganese complex oxygen evolution Photosystem II S-states X-ray absorption spectroscopy 

Preview

Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.

References

  1. Dau H, Haumann M (2006) Reaction cycle of photosynthetic water oxidation in plants and cyanobacteria. Science 312:1471-1472.Google Scholar
  2. Dau H, Haumann M (2007) Eight steps preceding O-O bond formation in oxygenic photosynthesis - a basic reaction cycle of the Photosystem II manganese complex. Biochim Biophys Acta 1767:472-483.PubMedCrossRefGoogle Scholar
  3. Dau H, Iuzzolino L, Dittmer J (2001) The tetra-manganese complex of photosystem II during its redox cycle: X-ray absorption results and mechanistic implications. Biochim Biophys Acta 1503:24-39.PubMedCrossRefGoogle Scholar
  4. Dau H, Liebisch P, Haumann M (2003) X-ray absorption spectroscopy to analyze nuclear geometry and electronic structure of biological metal centers - potential and questions examined with special focus on the tetranuclear manganese complex of oxygenic photosynthesis. Anal Bioanal Chem 376:562-583.PubMedCrossRefGoogle Scholar
  5. Dau H, Liebisch P, Haumann M (2004) The structure of the manganese complex of photosystem II in its dark-stable S1-state: EXAFS results in relation to recent crystallographic data. Phys Chem Chem Phys 6:4781-4792.CrossRefGoogle Scholar
  6. Dau H, Grundmeier A, Loja P, Haumann M (2007) On the structure of the manganese complex of photosystem II - extended-range EXAFS data an specific atomic resolution models for four S-states. Phil Trans R Soc B 363 (doi:10.1098/rstb.2007.2220).Google Scholar
  7. Grabolle M, Haumann M, Muller C, Liebisch P, Dau H (2006) Rapid loss of structural motifs in the manganese complex of oxygenic photosynthesis by X-ray irradiation at 10-300 K. J Biol Chem 281: 4580-4588.PubMedCrossRefGoogle Scholar
  8. Gu W, Jacquamet L, Patil DS, Wang H-X, Evans DJ, Smith MC, Millar M, Koch S, Eichhorn DM, Latimer M, Cramer SP (2003) Refinement of the nickel site structure in Desulfovibrio gigas hydrogenase using range-extended EXAFS spectroscopy. J Inorg Biochem 93: 41-51.PubMedCrossRefGoogle Scholar
  9. Haumann M, Muller C, Liebisch P, Iuzzolino L, Dittmer J, Grabolle M, Neisius T, Meyer-Klaucke W, Dau H (2005) Structural and oxidation state changes of the photosystem II manganese complex in four transitions of the water oxidation cycle (S0 → S1, S1 → S2, S2 → S3, and S3,4 → S0) characterized by X-ray absorption spectroscopy at 20 K and room temperature. Biochemistry 44:1894-1908.PubMedCrossRefGoogle Scholar
  10. Loll B, Kern J, Saenger W, Zouni A, Biesiadka J (2005) Towards complete cofactor arrangement in the 3.0 Å resolution structure of photosystem II. Nature 438:1040-1044.PubMedCrossRefGoogle Scholar
  11. Yano J, Kern J, Irrgang K-D, Latimer MJ, Bergmann U, Glatzel P, Pushkar Y, Biesiadka J, Loll B, Sauer K, Messinger J, Zouni A, Yachandra VK (2005a) X-ray damage to the Mn4Ca complex in single crystals of photosystem II: A case study for metalloprotein crystal-lography. Proc Natl Acad Sci USA 102:12047-12052.PubMedCrossRefGoogle Scholar
  12. Yano J, Pushkar Y, Glatzel P, Lewis A, Sauer K, Messinger J, Bergmann U, Yachandra V (2005b) High-resolution Mn EXAFS of the oxygen-evolving complex in photosystem II: Structural implications for the Mn4Ca cluster. J Am Chem Soc 127:14974-14975.PubMedCrossRefGoogle Scholar

Copyright information

© Springer Science + Business Media, B.V. 2008

Authors and Affiliations

  • Alexander Grundmeier
    • 1
  • Paola Loja
    • 1
  • Michael Haumann
    • 1
  • Holger Dau
    • 1
  1. 1.Freie Universität BerlinBerlinGermany

Personalised recommendations