高浓度磷酸盐缓冲液中多巴胺电化学氧化过程的在线质谱分析

林嘉美, 王昊天, 李慧, 余振东, 宋丽丽, 朱玉玲, 徐加泉

林嘉美, 王昊天, 李慧, 余振东, 宋丽丽, 朱玉玲, 徐加泉. 高浓度磷酸盐缓冲液中多巴胺电化学氧化过程的在线质谱分析[J]. 质谱学报, 2024, 45(1): 103-110. DOI: 10.7538/zpxb.2023.0108
引用本文: 林嘉美, 王昊天, 李慧, 余振东, 宋丽丽, 朱玉玲, 徐加泉. 高浓度磷酸盐缓冲液中多巴胺电化学氧化过程的在线质谱分析[J]. 质谱学报, 2024, 45(1): 103-110. DOI: 10.7538/zpxb.2023.0108
LIN Jia-mei, WANG Hao-tian, LI Hui, YU Zhen-dong, SONG Li-li, ZHU Yu-ling, XU Jia-quan. On-line Analysis of the Electrochemical Oxidation of Dopamine in High Concentration Phosphate Buffer Solution by Electrochemical Mass Spectrometry[J]. Journal of Chinese Mass Spectrometry Society, 2024, 45(1): 103-110. DOI: 10.7538/zpxb.2023.0108
Citation: LIN Jia-mei, WANG Hao-tian, LI Hui, YU Zhen-dong, SONG Li-li, ZHU Yu-ling, XU Jia-quan. On-line Analysis of the Electrochemical Oxidation of Dopamine in High Concentration Phosphate Buffer Solution by Electrochemical Mass Spectrometry[J]. Journal of Chinese Mass Spectrometry Society, 2024, 45(1): 103-110. DOI: 10.7538/zpxb.2023.0108
林嘉美, 王昊天, 李慧, 余振东, 宋丽丽, 朱玉玲, 徐加泉. 高浓度磷酸盐缓冲液中多巴胺电化学氧化过程的在线质谱分析[J]. 质谱学报, 2024, 45(1): 103-110. CSTR: 32365.14.zpxb.2023.0108
引用本文: 林嘉美, 王昊天, 李慧, 余振东, 宋丽丽, 朱玉玲, 徐加泉. 高浓度磷酸盐缓冲液中多巴胺电化学氧化过程的在线质谱分析[J]. 质谱学报, 2024, 45(1): 103-110. CSTR: 32365.14.zpxb.2023.0108
LIN Jia-mei, WANG Hao-tian, LI Hui, YU Zhen-dong, SONG Li-li, ZHU Yu-ling, XU Jia-quan. On-line Analysis of the Electrochemical Oxidation of Dopamine in High Concentration Phosphate Buffer Solution by Electrochemical Mass Spectrometry[J]. Journal of Chinese Mass Spectrometry Society, 2024, 45(1): 103-110. CSTR: 32365.14.zpxb.2023.0108
Citation: LIN Jia-mei, WANG Hao-tian, LI Hui, YU Zhen-dong, SONG Li-li, ZHU Yu-ling, XU Jia-quan. On-line Analysis of the Electrochemical Oxidation of Dopamine in High Concentration Phosphate Buffer Solution by Electrochemical Mass Spectrometry[J]. Journal of Chinese Mass Spectrometry Society, 2024, 45(1): 103-110. CSTR: 32365.14.zpxb.2023.0108

高浓度磷酸盐缓冲液中多巴胺电化学氧化过程的在线质谱分析

基金项目: 

江西省重点研发计划(20232BBG70004);江西省重点研发计划一般项目(20192BBG70008)

详细信息
  • 中图分类号: O657.63

On-line Analysis of the Electrochemical Oxidation of Dopamine in High Concentration Phosphate Buffer Solution by Electrochemical Mass Spectrometry

  • 摘要: 研究高浓度缓冲盐体系中物质的电化学氧化还原过程,对于准确理解电化学反应机理具有重要意义。本研究研制了一款体积小、性能稳定、结构简单、制作方便的流动电解池,将其与大气压化学电离质谱联用,构建了一种可在线分析高浓度缓冲盐溶液中电化学过程的电化学-质谱分析装置,用于在线、实时研究缓冲盐溶液中多巴胺的电化学氧化过程。结果表明,通过热沉积方式可高效地在线去除缓冲溶液中的无机盐组分,有机组分可经大气压化学电离方式进行离子化,随后进入质谱检测。多巴胺电化学氧化质谱分析结果表明:在0 V氧化电位下,多巴胺不发生氧化,主要获得多巴胺的质子化信号m/z 154[M+H]+;当氧化电位为+0.3 V时,除多巴胺的质子化信号外,还可获得多巴胺失去4个e-的氧化产物多巴色素(dopachrome)质子化峰m/z 150[M+H]+,以及多巴色素与多巴胺通过分子间氢键形成的加合物信号m/z 303[M+H]+;当氧化电位升高至+0.6 V时,氧化产物m/z 150和303的丰度进一步提高。
    Abstract: Electrochemical mass spectrometry is an important technique for studying the mechanism of electrochemical reactions. Mass spectrometry has the advantages of high detection sensitivity, high detection throughput and high specificity, which enables simultaneous acquisition of qualitative and quantitative informations for multiple components, making it highly valuable in the monitoring of electrochemical reaction products and the identification of intermediates. In general, electrolyte is necessary for electrochemical reaction. However, these electrolyte salts are detrimental to mass spectrometry analysis as they not only cause condensation in the mass spectrometry inlet, leading to blockage, but also impede the signal of the target analyte or form adduct ions with target analyte, resulting in a complex mass spectrum and increased analytical challenges. It is of great significance to develop a mass spectrometry method to real-time obtain trace organic components in high concentration buffer salt solutions. Therefore, a novel atmospheric pressure chemical ionization mass spectrometry (APCI-MS) method was developed for online analysis of trace organic components in high concentration buffer salt solutions, and a small volume flow electrolytic cell, stable performance, and simple structure were fabricated for on-line electrochemical reaction, which employed Pt, Pt and Ag/AgCl as working electrode, counter electrode and reference electrode, respectively. After combination of the APCI-MS and flow electrolytic cell, an electrochemical mass spectrometry device and method for on-line analysis of the electrochemical process in high concentration buffer salt solutions were constructed. As a proof of concept application, the device and method were used to on-line and real-time study the electrochemical oxidation process of dopamine in phosphate buffer salt solutions. The experimental results showed that the APCI-MS method can efficiently remove the inorganic salts in solutions on-line by on-line thermal deposition, while the organic components can be ionized by APCI for mass spectrometry detection. The results of dopamine electrochemical oxidation analysis showed that dopamine was not oxidized under the oxidation potential at 0 V, and only the protonated dopamine m/z 154 [M+H]+ was obtained. When the oxidation potential was +0.3 V, in addition to the protonated dopamine, the protonated peak m/z 150 [M+H]+ of dopachrome was generated by losing 4e- from dopamine, and the protonated peak m/z 303 [M+H]+ of the adduct dopachrome and dopamine formed by the intermolecular hydrogen bonding were also obtained. When the oxidation potential increased to +0.6 V, the contents of oxidation products m/z 150 and m/z 303 were further increased. The results demonstrated that this method has great application potential in studying the electrochemical reaction.
  • [1]

    LIU P, ZHENG Q, DEWALD H D, ZHOU R, CHEN H. The study of electrochemistry with ambient mass spectrometry[J]. TrAC Trends in Analytical Chemistry, 2015, 70:20-30.

    [2]

    CLARK E L, BELL A T. Direct observation of the local reaction environment during the electrochemical reduction of CO2[J]. Journal of the American Chemical Society, 2018, 140(22):7012-7020.

    [3]

    AMIN H M A, KÖNIGSHOVEN P, HEGEMANN M, BALTRUSCHAT H. Role of lattice oxygen in the oxygen evolution reaction on Co3O4:isotope exchange determined using a small-volume differential electrochemical mass spectrometry cell design[J]. Analytical Chemistry, 2019, 91(20):12653-12660.

    [4]

    XU J, ZHU T, CHINGIN K, LIU Y, ZHANG H, CHEN H. Sequential formation of analyte ions originated from bulk alloys for ambient mass spectrometry analysis[J]. Analytical Chemistry, 2018, 90(23):13832-13836.

    [5]

    van den BRINK F T G, BVTER L, ODIJK M, OLTHUIS W, KARST U, van den BERG A. Mass spectrometric detection of short-lived drug metabolites generated in an electrochemical microfluidic chip[J]. Analytical Chemistry, 2015, 87(3):1527-1535.

    [6]

    BROWN T A, CHEN H, ZARE R N. Identification of fleeting electrochemical reaction intermediates using desorption electrospray ionization mass spectrometry[J]. Journal of the American Chemical Society, 2015, 137(23):7274-7277.

    [7]

    CHENG H, TANG S, YANG T, XU S, YAN X. Accelerating electrochemical reactions in a voltage-controlled interfacial microreactor[J]. Angewandte Chemie International Edition, 2020, 59(45):19862-19867.

    [8]

    van den BRINK F T G, OLTHUIS W, van den BERG A, ODIJK M. Miniaturization of electrochemical cells for mass spectrometry[J]. TrAC Trends in Analytical Chemistry, 2015, 70:40-49.

    [9] 卢威风,张雪萌,闵乾昊. 电化学过程原位质谱分析研究进展[J]. 分析测试学报,2022,41(1):11-21. LU Weifeng, ZHANG Xuemeng, MIN Qianhao. Research progress of in situ mass spectrometry for electrochemical processes[J]. Journal of Instrumental Analysis, 2022, 41(1):11-21(in Chinese).
    [10]

    BRUINS A P. An overview of electrochemistry combined with mass spectrometry[J]. TrAC Trends in Analytical Chemistry, 2015, 70:14-19.

    [11]

    JURVA J U. Electrochemistry on-line with mass spectrometry:instrumental methods for in vitro generation and detection of drug metabolites[J]. Analytical Chemistry, 2004, 64(1):21A-33A.

    [12]

    HUANG G, LI G, COOKS R G. Induced nanoelectrospray ionization for matrix-tolerant and high-throughput mass spectrometry[J]. Angewandte Chemie International Edition, 2011, 50(42):9907-9910.

    [13]

    HU J, GUAN Q Y, WANG J, JIANG X, WU Z, XIA X, XU J, CHEN H. Effect of nanoemitters on suppressing the formation of metal adduct ions in electrospray ionization mass spectrometry[J]. Analytical Chemistry, 2017, 89(3):1838-1845.

    [14]

    CHEN H, VENTER A, COOKS R G. Extractive electrospray ionization for direct analysis of undiluted urine, milk and other complex mixtures without sample preparation[J]. Chemical Communications, 2006(19):2042-2044.

    [15]

    XU S, XUE J, BAI Y, LIU H. High-throughput single-cell immunoassay in the cellular native environment using online desalting dual-spray mass spectrometry[J]. Analytical Chemistry, 2020, 92(24):15854-15861.

    [16]

    CHEN W, GAO Z, CHU F, HE Q, GAO Y, LIU Y, FENG H, PAN Y. Heat-assisted dual neutral spray ionization for high-performance online desalting in mass spectrometric analysis[J]. Analytical Chemistry, 2022, 94(43):15002-15009.

    [17]

    IVANOVA M N, GRAYFER E D, PLOTNIKOVA E E, KIBIS L S, DARABDHARA G, BORUAH P K, DAS M R, FEDOROV V E. Pt-decorated boron nitride nanosheets as artificial nanozyme for detection of dopamine[J]. ACS Applied Materials & Interfaces, 2019, 11(25):22102-22112.

    [18]

    HAWLEY M D, TATAWAWADI S V, PIEKARSKI S, ADAMS R N. Electrochemical studies of the oxidation pathways of catecholamines[J]. Journal of the American Chemical Society, 1967, 89(2):447-450.

    [19]

    YANG X, KIRSCH J, FERGUS J, SIMONIAN A. Modeling analysis of electrode fouling during electrolysis of phenolic compounds[J]. Electrochimica Acta, 2013, 94(1):259-268.

    [20]

    QIU R, ZHANG X, LUO H, SHAO Y. Mass spectrometric snapshots for electrochemical reactions[J]. Chemical Science, 2016, 7(11):6684-6688.

计量
  • 文章访问数:  793
  • HTML全文浏览量:  12
  • PDF下载量:  30
  • 被引次数: 0
出版历程
  • 收稿日期:  2023-09-11
  • 修回日期:  2023-11-12
  • 网络出版日期:  2024-01-22

目录

    /

    返回文章
    返回