在 H2/α-酮酸酶燃料电池中从 N2 到手性氨基酸的生物电催化转化,Journal of the American Chemical Society

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在 H2/α-酮酸酶燃料电池中从 N2 到手性氨基酸的生物电催化转化
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2020-02-04 , DOI: 10.1021/jacs.9b13968
Hui Chen ₁ , Matthew B Prater ₁ , Rong Cai ₁ , Fangyuan Dong ₁ , Hsiaonung Chen ₁ , Shelley D Minteer ₁

Affiliation

酶促电合成是一种有前途的方法，可以在需要外部电能输入的情况下生产有用的化学品。酶燃料电池 (EFC) 是通过阳极处燃料的氧化和阴极处的氧气或过氧化物的还原，将化学能转化为电能的装置。酶促电合成与 EFC 架构的集成可以同时产生自供电酶促电合成，更有价值地使用电子来生产高附加值的化学品。在这项研究中，开发了一种 H2/α-酮酸 EFC，用于将化学惰性的氮气转化为由 H2 氧化驱动的手性氨基酸。首先设计并构建了高效的阴极反应级联。由外加电压供电，阴极提供足够的还原当量以支持固氮酶和心肌黄酶催化的 NH3 生产和 NADH 循环。产生的 NH3 和 NADH 与亮氨酸脱氢酶 (LeuDH) 原位反应以生成 L-正亮氨酸，2-酮己酸作为 NH3 受体。实现了 92% 的 NH3 转化率和 87.1% 的法拉第效率。在此基础上，以超热稳定氢化酶 (SHI) 作为阳极催化剂的 H2 动力燃料电池与阴极反应级联相结合，形成 H2/α-酮酸 EFC。反应 10 小时后，L-正亮氨酸的浓度达到 0.36 mM，对映体过量 (eep) 大于 99%，法拉第效率为 82%。从广泛的底物范围和 LeuDH 的高酶对映选择性来看，

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Bioelectrocatalytic Conversion from N2 to Chiral Amino Acids in a H2/α-keto Acid Enzymatic Fuel Cell

Enzymatic electrosynthesis is a promising approach to produce useful chemicals with the requirement of external electri-cal energy input. Enzymatic fuel cells (EFCs) are devices to convert chemical energy to electrical energy via the oxidation of fuel at the anode and usually the reduction of oxygen or peroxide at the cathode. The integration of enzymatic electro-synthesis with EFC architectures can simultaneously result in the self-powered enzymatic electrosynthesis with more val-uable usage of electrons to produce high value-added chemicals. In this study, a H2/α-keto acid EFC was developed for the conversion from chemically inert nitrogen gas to chiral amino acids powered by H2 oxidation. A highly efficient ca-thodic reaction cascade was first designed and constructed. Powered by an applied voltage, the cathode supplied enough reducing equivalents to support the NH3 production and NADH recycling catalyzed by nitrogenase and diaphorase. The produced NH3 and NADH were in situ reacted with leucine dehydrogenase (LeuDH) to generate L-norleucine with 2-ketohexanoic acid as the NH3 acceptor. 92% NH3 conversion ratio and 87.1% Faradaic efficiency were achieved. On this basis, a H2 powered fuel cell with hyper thermostable hydrogenase (SHI) as the anodic catalyst was combined with the cathodic reaction cascade to form the H2/α-keto acid EFC. After 10 hours of reaction, the concentration of L-norleucine achieved 0.36 mM with > 99% enantiomeric excess (eep) and 82% Faradaic efficiency. From the broad substrate scope and the high enzymatic enantioselectivity of LeuDH, the H2/α-keto acid EFC is an energy-efficient alternative to electrochem-ically produce chiral amino acids for biotechnology applications.

更新日期：2020-02-04

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