Synthetic model of the asymmetric [Mn3CaO4] cubane core of the oxygen-evolving complex of photosystem II

被引:235
作者
Mukherjee, Shreya [1 ]
Stull, Jamie A. [2 ]
Yano, Junko [3 ]
Stamatatos, Theocharis C. [1 ]
Pringouri, Konstantina [1 ]
Stich, Troy A. [2 ]
Abboud, Khalil A. [1 ]
Britt, R. David [2 ]
Yachandra, Vittal K. [3 ]
Christou, George [1 ]
机构
[1] Univ Florida, Dept Chem, Gainesville, FL 32611 USA
[2] Univ Calif Davis, Dept Chem, Davis, CA 95616 USA
[3] Univ Calif Berkeley, Lawrence Berkeley Natl Lab, Phys Biosci Div, Berkeley, CA 94720 USA
基金
美国国家卫生研究院;
关键词
crystal structure; magnetic properties; spectroscopic properties; PHOTOSYNTHETIC MN4CA CLUSTER; MANGANESE-CALCIUM CLUSTER; CRYSTAL-STRUCTURE; WATER-OXIDATION; MN-CLUSTER; RESOLUTION; EPR; EXAFS; CRYSTALLOGRAPHY; SPECTROSCOPY;
D O I
10.1073/pnas.1115290109
中图分类号
O [数理科学和化学]; P [天文学、地球科学]; Q [生物科学]; N [自然科学总论];
学科分类号
07 ; 0710 ; 09 ;
摘要
The laboratory synthesis of the oxygen-evolving complex (OEC) of photosystem II has been the objective of synthetic chemists since the early 1970s. However, the absence of structural information on the OEC has hampered these efforts. Crystallographic reports on photosystem II that have been appearing at ever-improving resolution over the past ten years have finally provided invaluable structural information on the OEC and show that it comprises a [Mn3CaO4] distorted cubane, to which is attached a fourth, external Mn atom, and the whole unit attached to polypeptides primarily by aspartate and glutamate carboxylate groups. Such a heterometallic Mn/Ca cubane with an additional metal attached to it has been unknown in the literature. This paper reports the laboratory synthesis of such an asymmetric cubane-containing compound with a bound external metal atom, [Mn-IV 3Ca2O4(O2CBut)(8) ((BuCO2H)-C-t)(4)(1)]. All peripheral ligands are carboxylate or carboxylic acid groups. Variable-temperature magnetic susceptibility data have established 1 to possess an S 9/2 ground state. EPR spectroscopy confirms this, and the Davies electron nuclear double resonance data reveal similar hyperfine couplings to those of other Mn-IV species, including the OEC S-2 state. Comparison of the X-ray absorption data with those for the OEC reveal 1 to possess structural parameters that make it a close structural model of the asymmetric-cubane OEC unit. This geometric and electronic structural correspondence opens up a new front in the multidisciplinary study of the properties and function of this important biological unit.
引用
收藏
页码:2257 / 2262
页数:6
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