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化学进展 2019, Vol. 31 Issue (1): 94-109 DOI: 10.7536/PC180506 前一篇   后一篇

• 综述 •

常压电喷雾离子化的机理及应用

李瑜玲, 赵君博, 郭寅龙**()   

  1. 金属有机国家重点实验室 上海有机质谱中心 中国科学院上海有机化学研究所 上海 200032
  • 收稿日期:2018-05-11 修回日期:2018-09-30 出版日期:2019-01-15 发布日期:2018-12-07
  • 通讯作者: 郭寅龙
  • 基金资助:
    国家自然科学基金项目(21532005); 国家自然科学基金项目(21472228); 国家自然科学基金项目(21874144); 国家科技支撑计划资助(2016YFC0800704)
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The Principles and Applications of Electrospray-Based Ambient Ionization

Yuling Li, Junbo Zhao, Yinlong Guo**()   

  1. State Key Laboratory of Organometallic Chemistry, National Center for Organic Mass Spectrometry in Shanghai, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032, China
  • Received:2018-05-11 Revised:2018-09-30 Online:2019-01-15 Published:2018-12-07
  • Contact: Yinlong Guo
  • About author:
    ** Corresponding author e-mail:
  • Supported by:
    The work was supported by the National Natural Foundation of China(21532005); The work was supported by the National Natural Foundation of China(21472228); The work was supported by the National Natural Foundation of China(21874144); The National Key Research and Development Program of China(2016YFC0800704)

作为最有前景的分析仪器之一,质谱技术已在药物、食品、环境、人类健康、国家安全及相关领域展现出广阔的应用前景。不同种类的分析物具有多种特征,这为直接离子化及质谱分析增加了难度。常压敞开式离子源是近年来新兴的一种离子源,这类离子源具有无需复杂的样品前处理、操作方便、快速、非破坏性、灵敏度及特异性好、能实现实时原位、高通量分析等特点。本文综述了基于电喷雾离子化(ESI)原理的各种离子源的电离机理、特征及应用,展望了常压敞开式离子源的发展趋势。

关键词： 质谱, 电喷雾离子化, 敞开式离子化, 离子化机理, 质谱成像

As one of the most promising analytical instruments, mass spectrometry(MS) technology has shown a broad application prospect in medicine, food, environment, human health, national security and other related fields. While the different types of analytes have diverse characteristics and largely add the difficulties of direct ionization and mass spectrometric analysis. Ambient mass spectrometry(AMS) is a kind of newly emerging technology performed under ambient conditions that allows the direct analysis of sample or sample surfaces with little or no sample pretreatment. The development and applications of ambient ionization mass spectrometry(AI-MS) that realized ionization under ambient conditions without sample pretreatment have become a frontier field in mass spectrometry and deserved much attention over the last few years. Ambient ionization has high sensitivity and specificity. It also can rapidly analysis real-time in situ and achieve high-throughput analysis without destructing the sample. As a soft ionization method, ESI offers unique advantages for proteomics by allowing the direct analysis of thermolabile compounds and forming multiply charged ions. The developments and applications of mass spectrometry imaging(MSI) have become a frontier field in mass spectrometry and molecular imaging. Some recent contributions on the development of ambient ionization can be applied to mass spectrometry imaging. This review focuses on the development of ionization mechanism, characteristics and applications of various ion sources, which are based on electrospray ionization (ESI) principle.

Key words: mass spectrometry, electrospray ionization, ambient ionization, ionization mechanism, mass spectrometry imaging
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图1 质谱离子源的发展历程示意图
Fig.1 Schematic diagram of the development of mass spectrometer ion source
表1 电喷雾离子化
Table 1 Electrospray-based ionization
abbreviation name ref
DESI Desorption electrospray ionization 24
PSI Paper spray ionization 41
EESI Extraction electrospray ionization 42,43
PESI Probe-electrospray ionization 44,45
WT-ESI Wooden-tip electrospray ionization 46
Pulsed-dc-ESI Pulsed direct current electrospray ionization 47
LAESI Laser ablation electrospray ionization 48
ESTASI Electrostatic-Spray Ionization 49
SAESI Solvent-assisted electrospray ionization 50
AFAI Air flow assisted ionization 51
APNR Atmospheric pressure neutral reionization 52
FEDI Fast eruption desorption ionization 53
CFI Carbon fiber ionization 54
图2 (a) 解吸电喷雾离子化示意图[24]; (b) 时间分辨解吸电喷雾离子化装置图[58]
Fig.2 (a) Schematic diagram of desorption electrospray ionization[24]; (b) Schematic showing the apparatus of time-resolved DESI-MS[58]
图3 空气动力辅助离子化装置示意图[51]
Fig.3 Schematic diagram of air flow assisted ionization[51]
图4 探针电喷雾离子化示意图
Fig.4 Schematic diagram of probe electrospray ionization
图5 大气压中性再电离质谱示意图[52]
Fig.5 Schematic showing the processes and apparatus used for APNR-MS[52]
图6 电喷雾萃取离子化示意图
Fig.6 Schematic of extraction electrospray ionization
图7 溶剂辅助电喷雾离子化示意图[50]
Fig.7 Schematic diagram of solvent-assisted electrospray ionization[50]
图8 二氯甲烷中Ph3 PAuNTf2催化的苯基炔丙基醚环化反应液的 (a) ESI-MS质谱图;(b) SAESI-MS质谱图[50]
Fig.8 (a) ESI-MS spectrum; (b) SAESI-MS spectrum of the reaction solution and Ph3 PAuNTf2 in CH2Cl2[50]
图9 基于介质阻挡放电离子源的毛细管电泳-质谱联用接口示意图[71]
Fig.9 Schematic diagram of the CE-DBDI-MS interface[71]
图10 基于实时直接分析的毛细管电泳-质谱联用接口示意图[72]
Fig.10 Interface for online coupling of CE to ambient MS using DART[72]
图11 纸基电喷雾离子化示意图[41]
Fig.11 Schematic diagram of paper spray ionization[41]
图12 木尖电喷雾离子化示意图[46]
Fig.12 Schematic diagram of wooden-tips eletrospray ionization[46]
图13 树叶电喷雾离子化示意图[77]
Fig.13 Schematic diagram of leaf spray[77]
图14 尖端碳纤维辅助的 ESI 喷雾嘴示意图[80]
Fig.14 Schematic of the electrospray ionization system with inhouse-made carbon fiber emitter[80]
图15 等离子体诱导电喷雾电离示意图[82]
Fig.15 Schematic view of the experimental setup allowing for reactions between radicals formed from a low-temperature helium plasma and peptide ions formed from nanoESI[82]
图16 脉冲直流电喷雾离子化示意图,生成脉冲喷雾分四步:溶液极化、产生正电喷雾、液体-气体表面的电化学反应和气体与电极之间的放电[47]
Fig.16 Model for the ionization behavior of pulsed-dc-ESI(positive mode). The procedure to generate one pulsed spray has four steps: solution polarization, positive electrospray, electrochemical reaction in liquid-gas surface, and discharge between gas and electrode, namely,step 1 to step 4, respectively[47]
图17 静电喷雾离子化示意图[49]
Fig.17 Schematic Representation of the Setups for Electrostatic-Spray Ionization[49]
图18 (a) 零电压纸喷雾离子化示意图[86]; (b) [Cr(H2O)4Cl2]+质谱检测图[87]
Fig.18 (a) Schematic of ZV-PSI[86]; (b) Spectrum of [Cr(H2O)4Cl2]+[87]
图19 快速喷发解吸离子化示意图[53]
Fig.19 Schematic of fast eruption desorption ionization[53]
图20 (a) 零电压碳纤维离子化示意图;(b) 敌草快质谱图
Fig.20 (a) Schematic of ZV-CFI; (b) Spectrum of diquat
图21 (a)零电压低温检测药物托拉塞米质谱图; (b)零电压碳纤维离子化装置图
Fig.21 (a) Spectrum of Torsememi; (b) Device schematic of ZV-CFI
图22 ESTASI-MSI的(a) 3D和(b) 侧视示意图[94]
Fig.22 (a) 3D and (b) side view schematic representation of the setup used for ESTASI-MSI[94]
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摘要

常压电喷雾离子化的机理及应用