Communication

Direct Detection of Oxygen Ligation to the Mn4Ca Cluster of Photosystem II by X-ray Emission Spectroscopy†

  1. Yulia Pushkar Dr.2,7,
  2. Xi Long2,8,
  3. Pieter Glatzel Dr.3,
  4. Gary W. Brudvig Prof.4,
  5. G. Charles Dismukes Prof.5,
  6. Terrence J. Collins Prof.6,
  7. Vittal K. Yachandra Dr.2,
  8. Junko Yano Dr.2,
  9. Uwe Bergmann Dr.1

Article first published online: 16 DEC 2009

DOI: 10.1002/anie.200905366

Issue

Angewandte Chemie International Edition

Angewandte Chemie International Edition

Volume 49, Issue 4, pages 800–803, January 18, 2010

Additional Information

How to Cite

Pushkar, Y., Long, X., Glatzel, P., Brudvig, Gary W., Dismukes, G. Charles., Collins, Terrence J., Yachandra, Vittal K., Yano, J. and Bergmann, U. (2010), Direct Detection of Oxygen Ligation to the Mn4Ca Cluster of Photosystem II by X-ray Emission Spectroscopy. Angew. Chem. Int. Ed., 49: 800–803. doi: 10.1002/anie.200905366

Author Information

  1. 1

    SSRL, SLAC National Accelerator Laboratory, Menlo Park, CA 94025 (USA)

  2. 2

    Physical Biosciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA 94720 (USA)

  3. 3

    European Synchrotron Radiation Facility, Grenoble (France)

  4. 4

    Department of Chemistry, Yale University (USA)

  5. 5

    Department of Chemistry, Princeton University (USA)

  6. 6

    Department of Chemistry, Carnegie-Mellon University (USA)

  7. 7

    Current address: Department of Physics, Purdue University (USA)

  8. 8

    Current address: Department of Chemistry, University of California (USA)

  1. †

    This work was supported by the NIH grant (GM 55302) and the DOE, Director, Office of Science, Office of Basic Energy Sciences (OBES), Chemical Sciences, Geosciences, and Biosciences Division, under Contract DE-AC02-05CH11231. Portions of this research were carried out at SSRL, operated by Stanford University for DOE, OBES. The SSRL SMB Program is supported by the DOE, OBER and by the NIH, NCRR. We thank Prof. Steve Cramer for the use of his emission spectrometer (NIH Grant EB-001962) for some of the work and Prof. Ken Sauer for many useful discussions.

Publication History

  1. Issue published online: 13 JAN 2010
  2. Article first published online: 16 DEC 2009
  3. Manuscript Received: 25 SEP 2009

Funded by

  • NIH. Grant Number: GM 55302
  • DOE, Director, Office of Science, Office of Basic Energy Sciences (OBES), Chemical Sciences, Geosciences, and Biosciences Division. Grant Number: DE-AC02-05CH11231

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Keywords:

  • coordination modes;
  • manganese;
  • photosystem II;
  • spectroscopic methods;
  • X-ray emission spectroscopy
Thumbnail image of graphical abstract

Seeing O: Mn Kβ2,5 and Kβ′′ X-ray emission spectra arise from transitions from the ligand 2s and 2p shells of the metal complexes to the metal 1s levels. In biological systems, it is difficult to specifically probe the O and N ligands. This spectroscopic technique is used to study the O ligands of the Mn4Ca cluster that catalyzes photosynthetic water splitting and allows direct detection for the first time of the bridging oxo groups of Mn.

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