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Cationization Mass Spectrometry for Condensed-Phase Samples

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Ion/Molecule Attachment Reactions: Mass Spectrometry

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Abstract

Chapter 7 Electron ionization (EI) is the gold standard in analyte ionization by mass spectrometry (MS). As an alternative to EI, a wide variety of alternative ionization techniques have been developed. A characteristic feature of these ionization techniques is that often even-electron ions are generated as a result of ion attachment processes. In these ion attachment processes, generally only very little energy transfer is involved. As a result, ions related to the intact analyte molecule are generated with little fragment ions (soft ionization techniques). Next to the generation of protonated molecules ([M+H]+) by attachment of a proton, attachment of other cations, e.g., Alkali+-ions as well as other metal ions, may also be observed. This chapter discusses condensed-phase ionization techniques from the perspective of Alkali+-ion attachment mass spectrometry. Thus, attention is paid to liquid-phase ionization techniques, i.e., thermospray ionization (TSI) and electrospray ionization (ESI), and solid-phase ionization or desorption/ionization techniques, including field desorption (FDI), fast-atom bombardment (FAB), and matrix-assisted laser desorption ionization (MALDI). Application of Alkali+-cationization in these condensed-phase ionization techniques are discussed in the areas of small molecule analysis as well as tin the analysis of glycosides, sugars, glycans and oligosaccharides, lipids and phospholipids, peptides and proteins, oligonucleotides, and synthetic polymers. Differences in fragmentation between protonated and Alkali+- cationized molecules are highlighted.

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    W. M. A. Niessen

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Niessen, W. (2015). Cationization Mass Spectrometry for Condensed-Phase Samples. In: Fujii, T. (eds) Ion/Molecule Attachment Reactions: Mass Spectrometry. Springer, Boston, MA. https://doi.org/10.1007/978-1-4899-7588-1_7

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