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在生物灵感的人工光合作用中控制质子合电子转移
Emmanuel Odella1, S Jimena Mora1, Brian L Wadsworth1
1School of Molecular Sciences , Arizona State University , Tempe , Arizona 85287-1604 , United States.
Journal of the American Chemical Society
|November 1, 2018
概括
研究人员设计了生物灵感分子来模仿自然的质子合电子转移,通过化学替代人工光合作用来控制质子运动距离.
科学领域:
- 生物有机化学
- 人工光合作用
- 质子合电子转移 (PCET)
背景情况:
- 光系统II使用TyrZ-His190氧化还原继电器进行高效的质子合电子转移 (PCET).
- 模仿生物PCET机制对于开发人工光合作用系统至关重要.
- 了解质子和电子转移之间的相互作用是生物能量学的关键.
研究的目的:
- 设计和合成模仿TyrZ-His190中继器H键网络的胺-构造物.
- 研究替代剂对PCET过程中的质子转位距离的影响.
- 通过分子设计探索控制质子合电子转移的潜力.
主要方法:
- 生物启发的胺--N-胺构造物的合成.
- 红外光谱电化学 (IRSEC) 来检测质子事件.
- 密度函数理论 (DFT) 计算以建模电子和质子转移路径.
主要成果:
- 证明了电子捐赠替代剂促进了性质子转移,从而产生了两质子产物 (E2PT).
- 表明电子取代剂有利于一个质子产物 (EPT),限制质子转移.
- 建立了替代哈梅特常数,H键强度和氧化还原潜力之间的线性相关性,对于基/对观察到的高潜力.
结论:
- 分子设计,特别是N-胺替代,可以精确控制PCET中的质子转位距离 (∼1.6 Å或∼6.4 Å).
- 这些生物灵感模型作为研究基本PCET机制的有价值平台.
- 这些发现对于推进高效人工光合作用系统的开发和了解生物能量转化具有重要意义.
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