光系统II中锰复合物的结构：来自X射线光谱学的见解
Structure of the manganese complex in photosystem II: insights from X-ray spectroscopy.
作者信息
Yachandra Vittal K
机构信息
Melvin Calvin Laboratory, Physical Biosciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA 94720, USA.
出版信息
Philos Trans R Soc Lond B Biol Sci. 2002 Oct 29;357(1426):1347-57; discussion 1357-8, 1367. doi: 10.1098/rstb.2002.1133.
Abstract
We have used Mn K-edge absorption and Kbeta emission spectroscopy to determine the oxidation states of the Mn complex in the various S states. We have started exploring the new technique of resonant inelastic X-ray scattering spectroscopy; this technique can be characterized as a Raman process that uses K-edge energies (1s to 4p, ca. 6550 eV) to obtain L-edge-like spectra (2p to 3d, ca. 650 eV). The relevance of these data to the oxidation states and structure of the Mn complex is presented. We have obtained extended X-ray absorption fine structure data from the S(0) and S(3) states and observed heterogeneity in the Mn-Mn distances leading us to conclude that there may be three rather than two di-mu-oxo-bridged units present per tetranuclear Mn cluster. In addition, we have obtained data using Ca and Sr X-ray spectroscopy that provide evidence for a heteronuclear Mn-Ca cluster. The possibility of three di-mu-oxo-bridged Mn-Mn moieties and the proximity of Ca is incorporated into developing structural models for the Mn cluster. The involvement of bridging and terminal O ligands of Mn in the mechanism of oxygen evolution is discussed in the context of our X-ray spectroscopy results.
摘要
我们利用锰K边吸收光谱和Kβ发射光谱来确定锰配合物在不同S态下的氧化态。我们已开始探索共振非弹性X射线散射光谱这项新技术；该技术可被描述为一种拉曼过程，它利用K边能量（1s到4p，约6550电子伏特）来获取类L边光谱（2p到3d，约650电子伏特）。展示了这些数据与锰配合物的氧化态和结构的相关性。我们已从S(0)态和S(3)态获得了扩展X射线吸收精细结构数据，并观察到锰-锰距离存在异质性，这使我们得出结论，每个四核锰簇中可能存在三个而非两个双μ-氧桥联单元。此外，我们利用钙和锶X射线光谱获得了数据，这些数据为异核锰-钙簇提供了证据。三个双μ-氧桥联锰-锰部分的可能性以及钙的接近性被纳入到锰簇结构模型的构建中。结合我们的X射线光谱结果，讨论了锰的桥联和末端氧配体在析氧机制中的作用。
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