Gabelica Valérie, De Pauw Edwin
Laboratoire de Spectrométrie de Masse, Université de Liège, Institut de Chimie, Liège, Belgium.
Mass Spectrom Rev. 2005 Jul-Aug;24(4):566-87. doi: 10.1002/mas.20027.
This review addresses the determination of the internal energy of ions produced by electrospray ionization (ESI) sources, and the influence of the internal energy on analyte fragmentation. A control of the analyte internal energy is crucial for several applications of electrospray mass spectrometry, like structural studies, construction of reproducible and exportable spectral libraries, analysis of non-covalent complexes. Sections II and III summarize the Electrospray mechanisms and source design considerations which are relevant to the problem of internal energy, and Section IV gives an overview of the inter-relationships between ion internal energy, reaction time scale, and analyte fragmentation. In these three sections we tried to make the most important theoretical elements understandable by all ESI users, and their understanding requires a minimal background in physical chemistry. We then present the different approaches used to experimentally determine the ion internal energy, as well as various attempts in modeling the internal energy uptake in electrospray sources. Finally, a tentative comparison between electrospray and other ionization sources is made. As the reader will see, although many reports appeared on the subject, the knowledge in the field of internal energy of ions produced by soft ionization sources is still scarce, because of the complexity of the system, and this is what makes this area of research so interesting. The last section presents some perspectives for future research.
本综述阐述了电喷雾电离（ESI）源产生的离子的内能测定，以及内能对分析物碎片化的影响。对于电喷雾质谱的多种应用而言，控制分析物的内能至关重要，例如结构研究、构建可重现且可移植的光谱库以及分析非共价复合物。第二和第三节总结了与内能问题相关的电喷雾机制和源设计考量因素，第四节概述了离子内能、反应时间尺度和分析物碎片化之间的相互关系。在这三个部分中，我们试图让所有电喷雾用户都能理解最重要的理论元素，而理解这些元素只需具备最少的物理化学背景知识。接着，我们介绍了用于实验测定离子内能的不同方法，以及在模拟电喷雾源中内能吸收方面的各种尝试。最后，对电喷雾与其他电离源进行了初步比较。正如读者将会看到的，尽管关于该主题已有许多报道，但由于系统的复杂性，软电离源产生的离子内能领域的知识仍然匮乏，而这正是该研究领域如此有趣的原因所在。最后一部分呈现了一些未来研究的展望。
