绿脓杆菌反应中心细胞色素亚基中点电位的静电控制
Electrostatic control of midpoint potentials in the cytochrome subunit of the Rhodopseudomonas viridis reaction center.
作者信息
Gunner M R, Honig B
机构信息
Department of Biochemistry and Molecular Biophysics, Columbia University, New York, NY 10032.
出版信息
Proc Natl Acad Sci U S A. 1991 Oct 15;88(20):9151-5. doi: 10.1073/pnas.88.20.9151.
Abstract
The photosynthetic reaction center of Rhodopseudomonas viridis has four hemes in a linear arrangement with alternating high- and low-potential sites. Their midpoints are -60, 20, 310, and 380 mV [Dracheva, S. M., Drachev, L. A., Konstantinov, A. A., Semenov, A. Y., Skulachev, V. P., Arutjunjan, A. M., Shuvalov, V. A. & Zaberezhnaya, S. M. (1988) Eur. J. Biochem. 171, 253-264]. Electrostatic calculations reproduce the 440-mV midpoint spread and assignments of high- and low-potential hemes. When calculations on model compounds to connect the theoretical midpoints to the standard hydrogen electrode are used, the absolute electrochemical midpoints for the reaction center hemes are also in good agreement with experiment. The free energy of oxidation is found to be dependent on pairwise interactions with charged amino acids, heme propionic acids, previously oxidized hemes, and axial ligands and on the reaction field induced by heme oxidation.
摘要
绿色红假单胞菌的光合反应中心有四个呈线性排列的血红素，其高低电位位点交替出现。它们的中点电位分别为-60、20、310和380毫伏[德拉切娃，S.M.，德拉切夫，L.A.，康斯坦丁诺夫，A.A.，谢苗诺夫，A.Y.，斯库拉乔夫，V.P.，阿鲁秋尼扬，A.M.，舒瓦洛夫，V.A.和扎贝雷日纳亚，S.M.（1988年）《欧洲生物化学杂志》171卷，253 - 264页]。静电计算重现了440毫伏的中点电位差以及高低电位血红素的归属。当使用对模型化合物进行计算以将理论中点电位与标准氢电极联系起来时，反应中心血红素的绝对电化学中点电位也与实验结果高度吻合。发现氧化自由能取决于与带电荷氨基酸、血红素丙酸、先前氧化的血红素、轴向配体的成对相互作用以及血红素氧化所诱导的反应场。
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