The internal energies of the emitted ions can be modulated in an electrospray source through different experimental conditions. However, the fragmentation pattern depends also on conditions that cannot be controlled by the operator, e.g. the geometry of the source or the mode of transfer of the ions
Internal energy and fragmentation of ions produced in electrospray sources
✍ Scribed by Valérie Gabelica; Edwin De Pauw
- Publisher
- John Wiley and Sons
- Year
- 2005
- Tongue
- English
- Weight
- 354 KB
- Volume
- 24
- Category
- Article
- ISSN
- 0277-7037
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✦ Synopsis
Abstract
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. © 2004 Wiley Periodicals, Inc., Mass Spec Rev 24:566–587, 2005
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The internal energy deposited in the ions in the source of a mass spectrometer governs their fragmentation and therefore the content of the spectra. When the ionization conditions are well defined and reproducible, e.g. in electron impact, the elaboration of databases benefits the use of the method.
## Abstract The internal energy distribution __P__(__E__~int~) of ions emitted in an electrospray (ESI) source interfaced with a sector mass spectrometer is evaluated by using the experimental survival yield (SY) method including the kinetic shift. This method is based on the relationship between t