在光合作用氧演化复合体中提出的S4状态的合成结构模型中的活性悬挂
Shivaiah Vaddypally1, Sandeep K Kondaveeti1, Santosh Karki1
1Department of Chemistry, Temple University , 1901 North 13th Street, Philadelphia, Pennsylvania 19122, United States.
Journal of the American Chemical Society
|March 15, 2017
概括
研究人员开发了一种合成古巴集群模型. 该模型模仿光系统II的氧气演变中心,在原子转移反应中显示其悬挂氧部分的优先反应.
科学领域:
- 无机化学
- 生物有机化学
- 摄影化学
背景情况:
- 光系统II中氧气进化中心 (OEC) 的分子机制仍然是一个长期的争论.
- 一种拟议的机制涉及水氧化物对悬挂MnO部分的核友性攻击,但在基团中缺乏实验性化学证据.
研究的目的:
- 合成和表征一种具有悬挂氧部分的新古巴集群.
- 调查这种合成模型化合物的反应性,特别是与OEC机制相关的原子转移反应.
主要方法:
- 一个合成古巴集群的合成和特征.
- 涉及集群和有机基质 () 的反应性研究.
- 使用18O和2H来追踪原子转移途径的同位素标记研究.
主要成果:
- 合成古巴集群与吊MnO部分已成功准备和表征.
- 与的反应导致氧和原子的转移,形成酒精和产物.
- 悬挂的MnO部分表现出优先反应性,核心古巴结构保持完整.
- O和H同位素标记证实了集群和有机基质之间的原子转移.
- 无机产品,一个吊MnO被抽取的气所取代的集群,被量化分离出来.
结论:
- 合成基集群作为一个有价值的模型来研究OEC的反应性.
- 悬挂的氧部分是主要的反应点,经历原子转移反应.
- 这些发现为参与-团中的悬挂氧基机制提供了实验支持.
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