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Title: Structural insights into the light-driven auto-assembly process of the water-oxidizing Mn4CaO5-cluster in photosystem II

Journal Article · · eLife
DOI:https://doi.org/10.7554/eLife.26933· OSTI ID:1408448

In plants, algae and cyanobacteria, Photosystem II (PSII) catalyzes the light-driven splitting of water at a protein-bound Mn4CaO5-cluster, the water-oxidizing complex (WOC). In the photosynthetic organisms, the light-driven formation of the WOC from dissolved metal ions is a key process because it is essential in both initial activation and continuous repair of PSII. Structural information is required for understanding of this chaperone-free metal-cluster assembly. For the first time, we obtained a structure of PSII from Thermosynechococcus elongatus without the Mn4CaO5-cluster. Surprisingly, cluster-removal leaves the positions of all coordinating amino acid residues and most nearby water molecules largely unaffected, resulting in a pre-organized ligand shell for kinetically competent and error-free photo-assembly of the Mn4CaO5-cluster. First experiments initiating (i) partial disassembly and (ii) partial re-assembly after complete depletion of the Mn4CaO5-cluster agree with a specific bi-manganese cluster, likely a di-µ-oxo bridged pair of Mn(III) ions, as an assembly intermediate.

Research Organization:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
AC02-05CH11231
OSTI ID:
1408448
Journal Information:
eLife, Vol. 6; ISSN 2050-084X
Publisher:
eLife Sciences Publications, Ltd.Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 49 works
Citation information provided by
Web of Science

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Cited By (10)

Investigating the Structure and Dynamics of Apo‐Photosystem II journal June 2019
O2 evolution and recovery of the water-oxidizing enzyme journal March 2018
Calcium, conformational selection, and redox-active tyrosine YZ in the photosynthetic oxygen-evolving cluster journal May 2018
A novel chlorophyll protein complex in the repair cycle of photosystem II journal October 2019
Photosystem II oxygen-evolving complex photoassembly displays an inverse H/D solvent isotope effect under chloride-limiting conditions journal September 2019
Assessment of the manganese cluster’s oxidation state via photoactivation of photosystem II microcrystals journal December 2019
Surface-grafted lanthanoid complexes of the tungstosilicate polyanion [SiW 12 O 40 ] 4− : a synthetic, structural and computational investigation journal October 2018
Structural Changes in the Acceptor Site of Photosystem II upon Ca2+/Sr2+ Exchange in the Mn4CaO5 Cluster Site and the Possible Long-Range Interactions journal August 2019
Investigating the Structure and Dynamics of Apo‐Photosystem II text January 2019
Structural changes in the acceptor site of photosystem II upon Ca$^{2+}$/Sr$^{2+}$ exchange in the Mn$_4$CaO$_5$ Cluster Site and the Possible Long-Range Interactions text January 2019