由铜人工酶催化的光驱动的进化反应
Raphaël J Labidi1, Bruno Faivre1, Philippe Carpentier2
1Laboratoire de Chimie des Processus Biologiques, UMR 8229, Collège de France/CNRS/Sorbonne Université, 11 place Marcellin-Berthelot, 75231 Paris, France.
Journal of the American Chemical Society
|June 12, 2023
概括
色蛋白质 (Orp) 具有独特的/铜集群,可催化从质子产生. 经过修改的Orp变体,特别是Mo/Fe-Orp,在可见光下显示了创纪录的效率.
科学领域:
- 生物化学
- 生物有机化学
- 光催化
背景情况:
- 色蛋白 (Orp) 是一种细菌金属蛋白,具有独特的异金属,功能不明.
- 由于其复杂的活性位点,金属蛋白具有新型催化应用的潜力.
研究的目的:
- 研究蛋白 (Orp) 对进化的光催化活性.
- 描述Orp中的/铜 (Mo/Cu) 异金属集群,并探索其催化机制.
- 设计和评估改进的Orp变种以提高的生产.
主要方法:
- 生物化学和光谱特征的全方位.
- 进行对接和分子动力学模拟以确定活动部位.
- 使用酸盐和光敏感剂进行光催化进化实验.
- 密度函数理论 (DFT) 计算以阐明反应机制.
- 在Orp支架内组装和测试各种双核金属集群 (M/M'-Orp).
主要成果:
- 含有[S2MoS2CuS2MoS2]3-集群的Holo-Orp显示出对进化的显著光催化活性.
- 在4个小时的照射后,用全光Orp实现了890的最大周转率.
- DFT计算提出了一种涉及H2形成的终端硫原子的机制.
- 设计的Mo/Fe-Orp变种表现出了1150的显着和800小时的初始旋转频率 (TOF°),创下了人工化物的新纪录.
结论:
- 色蛋白 (Orp) 是一个有效的光催化剂.
- Orp中独特的Mo/Cu集群和特定的氨基酸残留对其催化活性至关重要.
- 工程Orp变种,特别是Mo/Fe-Orp,代表高效的人工化,具有可持续生产的潜力.
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