Skip to main content
PMC home page
Proceedings of the National Academy of Sciences of the United States of America logoLink to Proceedings of the National Academy of Sciences of the United States of America
. 1996 Apr 16;93(8):3335–3340. doi: 10.1073/pnas.93.8.3335

Oxidation states of the manganese cluster during the flash-induced S-state cycle of the photosynthetic oxygen-evolving complex.

T A Roelofs 1, W Liang 1, M J Latimer 1, R M Cinco 1, A Rompel 1, J C Andrews 1, K Sauer 1, V K Yachandra 1, M P Klein 1
PMCID: PMC39608  PMID: 11607649

Abstract

The Mn K-edge x-ray absorption spectra for the pure S states of the tetranuclear Mn cluster of the oxygen-evolving complex of photosystem II during flash-induced S-state cycling have been determined. The relative S-state populations in samples given 0, 1, 2, 3, 4, or 5 flashes were determined from fitting the flash-induced electron paramagnetic resonance (EPR) multiline signal oscillation pattern to the Kok model. The edge spectra of samples given 0, 1, 2, or 3 flashes were combined with EPR information to calculate the pure S-state edge spectra. The edge positions (defined as the zero-crossing of the second derivatives) are 6550.1, 6551.7, 6553.5, and 6553.8 eV for S0, S1, S2, and S3, respectively. In addition to the shift in edge position, the S0--> S1 and S1--> S2 transitions are accompanied by characteristic changes in the shape of the edge, both indicative of Mn oxidation. The edge position shifts very little (0.3 eV) for the S2--> S3 transition, and the edge shape shows only subtle changes. We conclude that probably no direct Mn oxidation is involved in this transition. The proposed Mn oxidation state assignments are as follows: S0 (II, III, IV, IV) or (III, III, III, IV), S1 (III, III, IV, IV), S2 (III, IV, IV, IV), S3 (III, IV, IV, IV).

Full text

PDF
3336

Selected References

These references are in PubMed. This may not be the complete list of references from this article.

  1. Debus R. J. The manganese and calcium ions of photosynthetic oxygen evolution. Biochim Biophys Acta. 1992 Oct 16;1102(3):269–352. doi: 10.1016/0005-2728(92)90133-m. [DOI] [PubMed] [Google Scholar]
  2. Dismukes G. C., Siderer Y. Intermediates of a polynuclear manganese center involved in photosynthetic oxidation of water. Proc Natl Acad Sci U S A. 1981 Jan;78(1):274–278. doi: 10.1073/pnas.78.1.274. [DOI] [PMC free article] [PubMed] [Google Scholar]
  3. Guiles R. D., Yachandra V. K., McDermott A. E., Cole J. L., Dexheimer S. L., Britt R. D., Sauer K., Klein M. P. The S0 state of photosystem II induced by hydroxylamine: differences between the structure of the manganese complex in the S0 and S1 states determined by X-ray absorption spectroscopy. Biochemistry. 1990 Jan 16;29(2):486–496. doi: 10.1021/bi00454a024. [DOI] [PubMed] [Google Scholar]
  4. Guiles R. D., Zimmermann J. L., McDermott A. E., Yachandra V. K., Cole J. L., Dexheimer S. L., Britt R. D., Wieghardt K., Bossek U., Sauer K. The S3 state of photosystem II: differences between the structure of the manganese complex in the S2 and S3 states determined by X-ray absorption spectroscopy. Biochemistry. 1990 Jan 16;29(2):471–485. doi: 10.1021/bi00454a023. [DOI] [PubMed] [Google Scholar]
  5. Kok B., Forbush B., McGloin M. Cooperation of charges in photosynthetic O2 evolution-I. A linear four step mechanism. Photochem Photobiol. 1970 Jun;11(6):457–475. doi: 10.1111/j.1751-1097.1970.tb06017.x. [DOI] [PubMed] [Google Scholar]
  6. Liang W., Latimer M. J., Dau H., Roelofs T. A., Yachandra V. K., Sauer K., Klein M. P. Correlation between structure and magnetic spin state of the manganese cluster in the oxygen-evolving complex of photosystem II in the S2 state: determination by X-ray absorption spectroscopy. Biochemistry. 1994 Apr 26;33(16):4923–4932. doi: 10.1021/bi00182a022. [DOI] [PubMed] [Google Scholar]
  7. Ono T. A., Noguchi T., Inoue Y., Kusunoki M., Matsushita T., Oyanagi H. X-ray Detection of the Period-Four Cycling of the Manganese Cluster in Photosynthetic Water Oxidizing Enzyme. Science. 1992 Nov 20;258(5086):1335–1337. doi: 10.1126/science.258.5086.1335. [DOI] [PubMed] [Google Scholar]
  8. Ono T., Noguchi T., Inoue Y., Kusunoki M., Yamaguchi H., Oyanagi H. Study of the intermediate S-states for water oxidation in the normal and Ca-depleted photosynthetic oxygen-evolving enzyme by means of flash-induced X-ray absorption near edge structure spectroscopy. Biochem Soc Trans. 1994 May;22(2):331–335. doi: 10.1042/bst0220331. [DOI] [PubMed] [Google Scholar]
  9. Vass I., Styring S. pH-dependent charge equilibria between tyrosine-D and the S states in photosystem II. Estimation of relative midpoint redox potentials. Biochemistry. 1991 Jan 22;30(3):830–839. doi: 10.1021/bi00217a037. [DOI] [PubMed] [Google Scholar]
  10. Yachandra V. K., DeRose V. J., Latimer M. J., Mukerji I., Sauer K., Klein M. P. Where plants make oxygen: a structural model for the photosynthetic oxygen-evolving manganese cluster. Science. 1993 Apr 30;260(5108):675–679. doi: 10.1126/science.8480177. [DOI] [PubMed] [Google Scholar]
  11. Yachandra V. K., Guiles R. D., McDermott A. E., Cole J. L., Britt R. D., Dexheimer S. L., Sauer K., Klein M. P. Comparison of the structure of the manganese complex in the S1 and S2 states of the photosynthetic O2-evolving complex: an x-ray absorption spectroscopy study. Biochemistry. 1987 Sep 22;26(19):5974–5981. doi: 10.1021/bi00393a005. [DOI] [PubMed] [Google Scholar]

Articles from Proceedings of the National Academy of Sciences of the United States of America are provided here courtesy of National Academy of Sciences

RESOURCES