Electrosynthesis and Microanalysis in Thin Layer: An Electrochemical Pipette for Rapid Electrolysis and Mechanistic Study of Electrochemical Reactions
Electrosynthesis and Microanalysis in Thin Layer: An Electrochemical Pipette for Rapid Electrolysis and Mechanistic Study of Electrochemical Reactions
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薄层电合成和微量分析：用于快速电解和电化学反应机理研究的电化学移液器
DOI：
10.1002/anie.202312048
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发表时间：
2023
期刊：
影响因子：
--
通讯作者：
Rafiee, Mohammad
中科院分区：
文献类型：
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作者：
Punchihewa, Buwanila T.;Minda, Vidit;Gutheil, William G.;Rafiee, Mohammad
电化学代表了化学反应的促进和机理研究的独特方法，并在化学的不同领域获得了越来越多的关注。这种扩展需要增强传统的电化学电池，其本质上受到质量传输限制的约束。在此，我们提出了一种通过将反应室限制在与扩散层的厚度相当的薄层溶液来设计电化学电池的方法。这种薄层电极（TLE）提供了一个模块化平台，以绕过传统电解池的限制，并在电分析技术的时间尺度内进行电解反应。TLE在电合成应用中的实用性以NHPI介导的电化学C-H官能化为基准。通过阐明对乙酰氨基酚药物的氧化途径，展示了微尺度电解在药物代谢物研究中的应用。此外，在TLE中托管微电极，显示能够真实的实时探测这些快速电合成反应的氧化还原活性组分的分布。
Electrochemistry represents unique approaches for the promotion and mechanistic study of chemical reactions and has garnered increasing attention in different areas of chemistry. This expansion necessitates the enhancement of the traditional electrochemical cells that are intrinsically constrained by mass transport limitations. Herein, we present an approach for designing an electrochemical cell by limiting the reaction chamber to a thin layer of solution, comparable to the thickness of the diffusion layer. This thin layer electrode (TLE) provides a modular platform to bypass the constraints of traditional electrolysis cells and perform electrolysis reactions in the timescale of electroanalytical techniques. The utility of the TLE for electrosynthetic applications benchmarked using NHPI‐mediated electrochemical C−H functionalization. The application of microscale electrolysis for the study of drug metabolites was showcased by elucidating the oxidation pathways of the paracetamol drug. Moreover, hosting a microelectrode in the TLE, was shown to enable real‐time probing of the profiles of redox‐active components of these rapid electrosynthesis reactions.