Where water is oxidized to dioxygen: structure of the photosynthetic Mn4Ca cluster.
The oxidation of water to dioxygen is catalyzed within photosystem II (PSII) by a Mn(4)Ca cluster, the structure of which remains elusive. Polarized extended x-ray absorption fine structure (EXAFS) measurements on PSII single crystals constrain the Mn(4)Ca cluster geometry to a set of three similar high-resolution structures. Combining polarized EXAFS and x-ray diffraction data, the cluster was placed within PSII, taking into account the overall trend of the electron density of the metal site and the putative ligands. The structure of the cluster from the present study is unlike either the 3.0 or 3.5 angstrom-resolution x-ray structures or other previously proposed models.
Yano
Junko
J
Melvin Calvin Laboratory, Physical Biosciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA 94720, USA.
Kern
Jan
J
Sauer
Kenneth
K
Latimer
Matthew J
MJ
Pushkar
Yulia
Y
Biesiadka
Jacek
J
Loll
Bernhard
B
Saenger
Wolfram
W
Messinger
Johannes
J
Zouni
Athina
A
Yachandra
Vittal K
VK
D001665:Binding Sites; D002118:Calcium / Q000737:chemistry*; D003460:Crystallization; D018360:Crystallography, X-Ray; D000458:Cyanobacteria / Q000737:chemistry* / Q000378:metabolism; D005583:Fourier Analysis; D008024:Ligands; D008345:Manganese / Q000737:chemistry*; D008958:Models, Molecular; D010084:Oxidation-Reduction; D010100:Oxygen / Q000737:chemistry* / Q000378:metabolism; D045332:Photosystem II Protein Complex / Q000737:chemistry* / Q000378:metabolism; D013057:Spectrum Analysis; D014867:Water / Q000737:chemistry* / Q000378:metabolism; D014961:X-Ray Diffraction; D014965:X-Rays
D008024:Ligands; D045332:Photosystem II Protein Complex; D014867:Water; D008345:Manganese; D010100:Oxygen; D002118:Calcium