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使用Methyl Viologen作为电子媒介的Ene-Reductase进行生物电催化烯还原
Zheng Wei1, Tanja Knaus1, Matteo Damian1
1HIMS-Biocat, Van't Hoff Institute for Molecular Sciences, University of Amsterdam, 1098 XH, Amsterdam, The Netherlands.
使用甲基生物的电化学循环回收恩降解酶 (EReds) 为性分子合成提供了一种可持续的方法. 这种生物电催化方法克服了在不对称化中大规模应用的辅因子限制.
科学领域:
- 生物催化和绿色化学
- 电化学合成 电化学合成
- 不对称的化
背景情况:
- 不对称的化对于性合成至关重要,但传统方法在立体选择性和辅因子依赖性方面面临挑战.
- 恩降解酶 (EReds) 提供生物催化途径,但它们对尼古丁胺胺氨基二核酸 (酸盐) (NAD) 的依赖阻碍了可扩展性.
- 开发独立于辅助因子的酶系统对于高效和可持续的性分子生产至关重要.
研究的目的:
- 建立一种电化学方法,用于在现场再生含有黄素的恩降解酶 (EReds) 的辅因子.
- 调查甲基维奥基因在生物电催化系统中作为中间体的使用,以进行不对称化.
- 评估在开发的系统中不同ERED和基板的性能,以优化合合成.
主要方法:
- 使用H型玻璃电池,质子交换膜和碳布电极建造生物电催化反应堆.
- 甲基生物介质的电化学还原及其随后的由EReds的酶性氧化.
- 测试了两种ERED,五乙二酸还原酶 (PETNR) 和热稳定的旧黄色酶 (TOYE),与各种基质.
- 优化反应时间,以提高产品度和可重复性.
主要成果:
- 证实了成功的电化学降解甲基维奥基因及其由EReds的酶利用.
- 优化反应条件导致产品度增加,并在4-6小时内提高可重复性.
- 玩具在降低2-环素-1-one,2-甲基-2-环素-1-one和2-甲基-2-醇方面表现出高生产率,其反体过量高达99%.
- 在PETNR中,对2-甲基-2-醇的降解表现出优异的反抗选择性 (59% ee ± 7%).
- 玩具实现了对具有挑战性的基质化的有前途的反选择性,与依赖NADH的系统相比.
结论:
- 开发的生物电催化系统有效地回收了不需要外部NAD的黄素依赖ERED.
- 这种方法为不对称的化提供了一个可扩展和可持续的替代方案,克服了辅因子的限制.
- 该系统的效率和酶性能突出显示了其在合合成中的工业应用潜力.
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