Waveform Optimization for the In Vitro Detection of Caffeic Acid by Fast-Scan Cyclic Voltammetry

IF 4.6 Q1 CHEMISTRY, ANALYTICAL ACS Measurement Science Au Pub Date : 2024-07-31 DOI:10.1021/acsmeasuresciau.4c00029
Joseph N. Tonn, Richard B. Keithley
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Abstract

Caffeic acid is a polyphenol of critical importance in plants, involved in a variety of physiological processes including lignin formation, cellular growth, stress response, and external signaling. This small molecule also acts as a powerful antioxidant and thus has therapeutic potential for a variety of health conditions. Traditional methods of detecting caffeic acid lack appropriate temporal resolution to monitor real time concentration changes on a subsecond time scale with nM detection limits. Here we report on the first usage of fast-scan cyclic voltammetry with carbon fiber microelectrodes for the detection of caffeic acid. Through the use of flow injection analysis, the optimal waveform for its detection under acidic conditions at a scan rate of 400 V/s was determined to be sawtooth-shaped, from 0 to 1.4 to −0.4 to 0 V. Signal was linear with concentration up to 1 μM with a sensitivity of 44.8 ± 1.3 nA/μM and a detection limit of 2.3 ± 0.2 nM. The stability of its detection was exceptional, with an average of 0.96% relative standard deviation across 32 consecutive injections. This waveform was also successful in detecting other catechol-based plant antioxidants including 5-chlorogenic acid, oleuropein, rosmarinic acid, chicoric acid, and caffeic acid phenethyl ester. Finally, we show the successful use of fast-scan cyclic voltammetry in monitoring the degradation of caffeic acid by polyphenol oxidase on a subsecond time scale via a novel modification of a Ramsson cell. This work demonstrates that fast-scan cyclic voltammetry can be used to successfully monitor real-time dynamic changes in the concentrations of catechol-containing plant polyphenols.

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快速扫描循环伏安法体外检测咖啡酸的波形优化
咖啡酸是一种对植物至关重要的多酚,参与木质素形成、细胞生长、应激反应和外部信号传递等多种生理过程。这种小分子还具有强大的抗氧化作用,因此对多种健康状况具有治疗潜力。传统的咖啡酸检测方法缺乏适当的时间分辨率,无法监测亚秒级的实时浓度变化,检测极限为 nM。在此,我们报告了首次使用碳纤维微电极快速扫描循环伏安法检测咖啡酸的情况。通过使用流动注射分析法,确定了在酸性条件下以 400 V/s 的扫描速率检测咖啡酸的最佳波形为锯齿形,从 0 到 1.4 到 -0.4 到 0 V。其检测稳定性极佳,连续 32 次注射的平均相对标准偏差为 0.96%。该波形还能成功检测其他儿茶酚类植物抗氧化剂,包括 5-氯原酸、油菜素、迷迭香酸、菊苣酸和咖啡酸苯乙酯。最后,我们展示了快速扫描循环伏安法的成功应用,通过对拉姆森电池的新颖改造,在亚秒级时间内监测多酚氧化酶对咖啡酸的降解。这项工作表明,快速扫描循环伏安法可用于成功监测含儿茶酚植物多酚浓度的实时动态变化。
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来源期刊
ACS Measurement Science Au
ACS Measurement Science Au 化学计量学-
CiteScore
5.20
自引率
0.00%
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0
期刊介绍: ACS Measurement Science Au is an open access journal that publishes experimental computational or theoretical research in all areas of chemical measurement science. Short letters comprehensive articles reviews and perspectives are welcome on topics that report on any phase of analytical operations including sampling measurement and data analysis. This includes:Chemical Reactions and SelectivityChemometrics and Data ProcessingElectrochemistryElemental and Molecular CharacterizationImagingInstrumentationMass SpectrometryMicroscale and Nanoscale systemsOmics (Genomics Proteomics Metabonomics Metabolomics and Bioinformatics)Sensors and Sensing (Biosensors Chemical Sensors Gas Sensors Intracellular Sensors Single-Molecule Sensors Cell Chips Arrays Microfluidic Devices)SeparationsSpectroscopySurface analysisPapers dealing with established methods need to offer a significantly improved original application of the method.
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