Abstract
Plants and cyanobacteria produce atmospheric dioxygen from water, powered by sunlight and catalyzed by a manganese complex in photosystem II. A classic S-cycle model for oxygen evolution involves five states, but only four have been identified. The missing S 4 state is particularly important because it is directly involved in dioxygen formation. Now progress comes from an x-ray technique that can monitor redox and structural changes in metal centers in real time with 10-microsecond resolution. We show that in the O 2 -formation step, an intermediate is formed—the enigmatic S 4 state. Its creation is identified with a deprotonation process rather than the expected electron-transfer mechanism. Subsequent electron transfer would give an additional S 4 ′ state, thus extending the fundamental S-state cycle of dioxygen formation.
References
31
Referenced
426
- Biochim. Biophys. Acta1503 Special Issue on Photosynthetic Water Oxidation (Elsevier Amsterdam 2001).
10.1016/j.bbabio.2003.10.011
10.1038/35055589
10.1073/pnas.0135651100
10.1126/science.1093087
10.1016/S0968-0004(01)01874-6
10.1111/j.1751-1097.1970.tb06017.x
10.1038/nature02676
10.1016/0076-6879(95)46028-4
10.1007/s00216-003-1982-2
10.1038/nsb889
10.1038/nsb0203-75
10.1021/bi9924258
10.1016/S0014-5793(02)02237-8
10.1021/bi048697e
10.1107/S0909049504027803
10.1126/science.258.5086.1335
10.1126/science.277.5334.1953
10.1016/0014-5793(76)81058-7
10.1021/bi9614287
10.1021/bi00170a003
10.1016/0005-2728(94)90222-4
10.1039/b407500e
10.1016/0304-4173(85)90014-X
10.1007/s11120-004-7080-2
10.1016/0005-2728(68)90190-4
10.1007/BF00046752
10.1021/bi9719152
10.1021/bi980194j
10.1021/bi990716a
- The x-ray experiments were carried out at the experimental station ID26 of the European Synchrotron Radiation Facility (ESRF) (Grenoble France). We thank T. Neisius S. Eeckhout and P. Glatzel (all of ESRF) who contributed significantly to the preparation of the x-ray experiment and P. Loja (of our research group) for her important contributions to XAS data collection. Financial support by the Deutsche Forschungsgemeinschaft (DFG) (Collaborative Research Center SFB 498 projects C6 and C8) and the Bundesministerium für Bildung und Forschung (BMBF) (grant 05KS1KEA/6) is gratefully acknowledged.
Dates
Type | When |
---|---|
Created | 19 years, 9 months ago (Nov. 10, 2005, 5:33 p.m.) |
Deposited | 1 year, 7 months ago (Jan. 9, 2024, 9:25 p.m.) |
Indexed | 1 month, 2 weeks ago (July 16, 2025, 9:28 a.m.) |
Issued | 19 years, 9 months ago (Nov. 11, 2005) |
Published | 19 years, 9 months ago (Nov. 11, 2005) |
Published Print | 19 years, 9 months ago (Nov. 11, 2005) |
@article{Haumann_2005, title={Photosynthetic O 2 Formation Tracked by Time-Resolved X-ray Experiments}, volume={310}, ISSN={1095-9203}, url={http://dx.doi.org/10.1126/science.1117551}, DOI={10.1126/science.1117551}, number={5750}, journal={Science}, publisher={American Association for the Advancement of Science (AAAS)}, author={Haumann, M. and Liebisch, P. and Müller, C. and Barra, M. and Grabolle, M. and Dau, H.}, year={2005}, month=nov, pages={1019–1021} }