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稳态和脉冲电化学再生 1,4-NADH 的产物分布及与酶反应的集成。

Product Distribution of Steady-State and Pulsed Electrochemical Regeneration of 1,4-NADH and Integration with Enzymatic Reaction.

机构信息

Electrochemical Energy Conversion, Max Planck Institute for Dynamics of Complex Technical Systems, Sandtorstraße 1, 39106, Magdeburg, Germany.

Institute of Biochemistry, University of Greifswald, Felix-Hausdorff-Str. 4, 17487, Greifswald, Germany.

出版信息

ChemistryOpen. 2024 Aug;13(8):e202400064. doi: 10.1002/open.202400064. Epub 2024 Apr 12.

DOI:10.1002/open.202400064
PMID:38607952
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC11319214/
Abstract

The direct electrochemical reduction of nicotinamide adenine dinucleotide (NAD) results in various products, complicating the regeneration of the crucial 1,4-NADH cofactor for enzymatic reactions. Previous research primarily focused on steady-state polarization to examine potential impacts on product selectivity. However, this study explores the influence of dynamic conditions on the selectivity of NAD reduction products by comparing two dynamic profiles with steady-state conditions. Our findings reveal that the main products, including 1,4-NADH, several dimers, and ADP-ribose, remained consistent across all conditions. A minor by-product, 1,6-NADH, was also identified. The product distribution varied depending on the experimental conditions (steady state vs. dynamic) and the concentration of NAD, with higher concentrations and overpotentials promoting dimerization. The optimal yield of 1,4-NADH was achieved under steady-state conditions with low overpotential and NAD concentrations. While dynamic conditions enhanced the 1,4-NADH yield at shorter reaction times, they also resulted in a significant amount of unidentified products. Furthermore, this study assessed the potential of using pulsed electrochemical regeneration of 1,4-NADH with enoate reductase (XenB) for cyclohexenone reduction.

摘要

烟酰胺腺嘌呤二核苷酸(NAD)的直接电化学还原会产生各种产物,这使得酶反应中关键的 1,4-NADH 辅酶的再生变得复杂。以前的研究主要集中在稳态极化上,以研究其对产物选择性的潜在影响。然而,本研究通过比较两种稳态条件下的动态曲线来探究动态条件对 NAD 还原产物选择性的影响。我们的研究结果表明,包括 1,4-NADH、几种二聚体和 ADP-核糖在内的主要产物在所有条件下保持一致。还鉴定出一种次要的副产物 1,6-NADH。产物分布取决于实验条件(稳态与动态)和 NAD 浓度,较高的浓度和过电势促进二聚化。在低过电势和 NAD 浓度下,通过稳态条件可实现 1,4-NADH 的最佳产量。虽然动态条件在较短的反应时间内提高了 1,4-NADH 的产率,但也导致了大量未识别的产物。此外,本研究评估了使用烯醇还原酶(XenB)进行脉冲电化学 1,4-NADH 再生用于环己烯酮还原的潜力。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/ad01/11319214/ed10c8bde2db/OPEN-13-e202400064-g007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/ad01/11319214/99bd8aef6031/OPEN-13-e202400064-g005.jpg
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https://cdn.ncbi.nlm.nih.gov/pmc/blobs/ad01/11319214/2ac759e90878/OPEN-13-e202400064-g009.jpg
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https://cdn.ncbi.nlm.nih.gov/pmc/blobs/ad01/11319214/98d7db035edf/OPEN-13-e202400064-g004.jpg
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https://cdn.ncbi.nlm.nih.gov/pmc/blobs/ad01/11319214/433aabf7c9e5/OPEN-13-e202400064-g008.jpg
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https://cdn.ncbi.nlm.nih.gov/pmc/blobs/ad01/11319214/2ac759e90878/OPEN-13-e202400064-g009.jpg
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https://cdn.ncbi.nlm.nih.gov/pmc/blobs/ad01/11319214/ed10c8bde2db/OPEN-13-e202400064-g007.jpg

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本文引用的文献

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Pulsed electrolysis - explained.脉冲电解——解析
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