Electron spin-lattice relaxation of the so state of the oxygen-evolving complex in photosystem II and of dinuclear manganese model complexes

Kulik LV; Lubitz W; Messinger J

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Electron spin-lattice relaxation of the so state of the oxygen-evolving complex in photosystem II and of dinuclear manganese model complexes

机译：电子旋转晶格放松SO状态的光照系统II和Darcar锰模型复合物中的氧不变复合物

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摘要

The temperature dependence of the electron spin-lattice relaxation time T, was measured for the So state of the oxygen-evolving complex (OEC) in photosystem II and for two dinuclear manganese model complexes by pulse EPR using the inversion-recovery method. For [Mn(III)Mn(IV)(mu-O)(2)bipy(4)]ClO4, the Raman relaxation process dominates at temperatures below 50 K. In contrast, Orbach type relaxation was found for [Mn(II)Mn(III)(mu-OH)(mu-piv)(2)(Me(3)tacn)(2)](ClO4)(2) between 4.3 and 9 K. For the latter complex, an energy separation of 24.7-28.0 cm(-1) between the ground and the first excited electronic state was determined. In the So state of photosystem II, the T-1 relaxation times were measured in the range of 4.3-6.5 K. A comparison with the relaxation data (rate and pre-exponential factor) of the two model complexes and of the S-2 state of photosystem II indicates that the Orbach relaxation process is dominant for the So state and that its first excited state lies 21.7 +/- 0.4 cm(-1) above its ground state. The results are discussed with respect to the structure of the OEC in photosystem II.

机译：电子旋转晶格弛豫时间T的温度依赖性测量了光照型氧化复合物（OEC）的所在状态，并使用反转回收方法对脉冲EPR进行两种二核锰模型复合物。对于[Mn（III）Mn（IV）（MU-O）（2）Bipy（4）] ClO4，拉曼弛豫工艺在低于50k的温度下占主导地位。相反，发现了[Mn（II） Mn（III）（MU-OH）（MU-PIV）（2）（ME（3）TACN）（2）]（2）]（CLO 4）（2）在4.3和9K之间。对于后者复合物，能量分离24.7确定地和第一激励电子状态之间的-28.0cm（-1）。在SO SEDSTEM II状态下，在4.3-6.5k的范围内测量T-1弛豫时间。与两个模型复合物和S-2的弛豫数据（速率和预指数因子）进行比较照相状态II表示orbach松弛过程为SO状态占主导地位，并且其第一个激励状态在其地上呈现21.7 +/- 0.4cm（-1）。结果是关于在照相系统II中的OEC的结构讨论的。

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《Biochemistry》 |2005年第26期|共7页
作者
Kulik LV; Lubitz W; Messinger J;
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Max Planck Inst Bioinorgan Chem D-45470 Mulheim Germany;

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正文语种 eng
中图分类生物化学;
关键词
PHOTOSYNTHETIC WATER OXIDATION; MIXED-VALENCE INTERACTIONS; EPR MULTILINE SIGNAL; RARE-EARTH SALTS; PARAMAGNETIC-RESONANCE; S-0 STATE; PULSED EPR; MN-CLUSTER; MECHANISM; MEMBRANES;

机译：光合水氧化;混合价相互作用;epr多线信号;稀土盐;顺磁共振;S-0状态;脉冲EPR;MN簇;机制;膜;

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1. PSⅡ系统放氧复合物中的锰簇模型物 [J] . 陈昌能, 朱红平, 黄德光, 植物学报（英文版） . 2000,第012期
2. 光系统Ⅱ（PSⅡ）放氧复合物中钙结合状态的研究 [J] . 袁生, 李功藩植物学报：英文版 . 1991,第011期
3. Electron spin-lattice relaxation of the so state of the oxygen-evolving complex in photosystem II and of dinuclear manganese model complexes [J] . Kulik LV, Lubitz W, Messinger J Biochemistry . 2005,第26期

机译：电子旋转晶格放松SO状态的光照系统II和Darcar锰模型复合物中的氧不变复合物
4. Modeling the oxygen-evolving complex of photosystem II. Synthesis, redox properties, and core interconversion studies of dimanganese complexes having {Mn-2(III)(mu-O)(mu-OAc)(2)}(2+), {(MnMnIV)-Mn-III(mu-O)(2)(mu-OAc)}(2+), and {Mn-2(IV)(mu-O)(2)(mu- [J] . Lal TK., Mukherjee R. Inorganic Chemistry: A Research Journal that Includes Bioinorganic, Catalytic, Organometallic, Solid-State, and Synthetic Chemistry and Reaction Dynamics . 1998,第10期

机译：模拟光系统II的析氧复合物。具有{Mn-2（III）（mu-O）（mu-OAc）（2）}（2 +），{（MnMnIV）-Mn-III（mu--）的二锰配合物的合成，氧化还原性质和核互变研究O）（2）（mu-OAc）}（2+）和{Mn-2（IV）（mu-O）（2）（mu-
5. Modeling the oxygen-evolving complex of photosystem II. Synthesis, redox properties, and core interconversion studies of dimanganese complexes having {Mn-2(III)(mu-O)(mu-OAc)(2)}(2+), {(MnMnIV)-Mn-III(mu-O)(2)(mu-OAc)}(2+), and {Mn-2(IV)(mu-O)(2)(mu- [J] . Lal TK., Mukherjee R. Inorganic Chemistry: A Research Journal that Includes Bioinorganic, Catalytic, Organometallic, Solid-State, and Synthetic Chemistry and Reaction Dynamics . 1998,第10期

机译：模拟光系统II的析氧复合物。具有{Mn-2（III）（mu-O）（mu-OAc）（2）}（2 +），{（MnMnIV）-Mn-III（mu--）的二锰配合物的合成，氧化还原性质和核互变研究O）（2）（mu-OAc）}（2+）和{Mn-2（IV）（mu-O）（2）（mu-
6. Pulse EPR and Spin-Lattice Relaxation Study of the Oxygen-Evolving Complex of Photosystem II [C] . Leonid V. Kulik, J. Messinger, B. Epel Asia-Pacific EPR/ESR Symposium . 2006

机译：脉冲EPR和旋转晶格松弛研究光系统II的氧化复合物
7. Properties and reactivity of model manganese complexes for the oxygen-evolving complex of photosystem II [D] . Law, Neil A. 1999

机译：模型锰配合物对光系统II析氧配合物的性质和反应性
8. Electrostatic Effects on Proton-Coupled Electron Transfer in Oxomanganese Complexes Inspired by the Oxygen-Evolving Complex of Photosystem II [O] . Muhamed Amin, Leslie Vogt, Serguei Vassiliev, -1

机译：静电对光系统II释氧配合物激发的氧锰配合物中质子耦合电子转移的影响
9. The Electronic Structure of Mn in Oxides, Coordination Complexes, and the Oxygen-Evolving Complex of Photosystem II Studied by Resonant Inelastic X-ray Scattering [O] . Pieter Glatzel, Uwe Bergmann, Junko Yano, 2004

机译：通过谐振非弹性X射线散射研究的氧化物，配合复合物中Mn的电子结构和光系统II的氧不变络合物

Electron spin-lattice relaxation of the so state of the oxygen-evolving complex in photosystem II and of dinuclear manganese model complexes

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