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与铜离子结合的氧和氧分子:电子转移平衡与小的重组能量
Rui Cao1, Claudio Saracini1,2, Jake W Ginsbach3
1Department of Chemistry, Johns Hopkins University , Baltimore, Maryland 21218, United States.
Journal of the American Chemical Society
|May 27, 2016
概括
这项研究详细介绍了二铜复合物的氧化,形成可逆降解为过氧的超氧物种. 这项研究阐明了这些铜氧物种的电子转移机制和氧化还原潜力.
科学领域:
- 无机化学
- 生物有机化学
- 协调化学
背景情况:
- 双铜复合物在生物系统中至关重要,通常涉及氧气激活.
- 了解铜氧物种的氧化还原行为是模仿酶过程的关键.
研究的目的:
- 从混合价值的Cu (II) Cu (I) 前体合成和描述一个超氧二铜 (II) 种.
- 研究超氧物种的可逆降解为氧物种.
- 确定这些铜氧中间体的氧化还原潜力和电子转移动力学.
主要方法:
- 二铜复合物的合成和结构特征.
- 氧化反应和动力学研究 (停止流动).
- 使用铁素/铁试剂进行可逆氧化还原定位.
- 光谱分析 (共振拉曼) 和密度功能理论 (DFT) 的计算.
主要成果:
- 通过氧化形成超氧二铜 ([Cu2(UN-O(-)) ((O2(•-)) ((2+)) 的物种.
- 可逆降解为二铜 (II) 种 ([Cu2(UN-O(-)) ((O2(2-))))
- 确定超氧-氧还氧潜力 (E° = +130 mV与SCE),可与生物还氧剂相比较.
- 快速平衡的μ-1,2-和μ-1,1-超氧异构体的识别,其中电子转移仅涉及μ-1,2-异构体.
- 动力学研究显示外层电子转移过程的总重组能量为1.1 eV.
结论:
- 这项研究提供了关于二铜-超氧和-氧物种的形成,结构和氧化还原化学的见解.
- 确定的氧化还原潜力与生物电子转移系统有关.
- 电子转移机制遵循马库斯理论,涉及特定的同位素和外层相互作用.
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