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Title: Removal of Ca2+ from the Oxygen-Evolving Complex in Photosystem II Has Minimal Effect on the Mn4O5 Core Structure: A Polarized Mn X-ray Absorption Spectroscopy Study

Journal Article · · Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry
 [1];  [1];  [1];  [1];  [1]
  1. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Physical Biosciences Division

Ca 2+ -depleted and Ca 2+ -reconstituted spinach photosystem II was studied using polarized X-ray absorption spectroscopy of oriented PS II preparations to investigate the structural and functional role of the Ca 2+ ion in the Mn 4 O 5 Ca cluster of the oxygen-evolving complex (OEC). Samples were prepared by low pH/citrate treatment as one-dimensionally ordered membrane layers and poised in the Ca 2+ -depleted S 1 (S 1') and S 2 (S 2') states, the S 2'Y Z • state, at which point the catalytic cycle of water oxidation is inhibited, and the Ca 2+ -reconstituted S 1 state. Polarized Mn K-edge XANES and EXAFS spectra exhibit pronounced dichroism. Polarized EXAFS data of all states of Ca 2+ -depleted PS II investigated show only minor changes in distances and orientations of the Mn-Mn vectors compared to the Ca 2+ -containing OEC, which may be attributed to some loss of rigidity of the core structure. Thus, removal of the Ca 2+ ion does not lead to fundamental distortion or rearrangement of the tetranuclear Mn cluster, which indicates that the Ca 2+ ion in the OEC is not critical for structural maintenance of the cluster, at least in the S 1 and S 2 states, but fulfills a crucial catalytic function in the mechanism of the water oxidation reaction. On the basis of this structural information, reasons for the inhibitory effect of Ca 2+ removal are discussed, attributing to the Ca 2+ ion a fundamental role in organizing the surrounding (substrate) water framework and in proton-coupled electron transfer to Y Z • (D1-Tyr161).

Research Organization:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
AC02-05CH11231; GM55302
OSTI ID:
1257848
Alternate ID(s):
OSTI ID: 1378612
Journal Information:
Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry, Vol. 119, Issue 43; ISSN 1520-6106
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 17 works
Citation information provided by
Web of Science

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