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Updated: Jun 3, 2026

Sheathless Capillary Electrophoresis–Mass Spectrometry for Metabolic Profiling of Biological Samples
Published on: October 1, 2016
Ionization techniques in capillary electrophoresis-mass spectrometry: principles, design, and application
Paul Hommerson1, Amjad M Khan, Gerhardus J de Jong
1Department of Biomedical Analysis, Utrecht University, PO Box 80082, 3508 TB Utrecht, The Netherlands. p.hommerson@uu.nl
This review explores soft ionization techniques for capillary electrophoresis-mass spectrometry (CE-MS). It details alternative methods beyond electrospray ionization (ESI), highlighting their principles and applications in CE-MS.
Area of Science:
- Analytical Chemistry
- Separation Science
- Mass Spectrometry
Background:
- Capillary electrophoresis-mass spectrometry (CE-MS) coupling, particularly with electrospray ionization (ESI), revolutionized analytical capabilities since its 1987 inception.
- While ESI remains dominant, ongoing research explores diverse soft ionization techniques to enhance CE-MS performance and applicability.
Purpose of the Study:
- To present a comprehensive review of the state-of-the-art in soft ionization techniques employed with CE-MS.
- To outline the fundamental challenges and principles of hyphenating CE and microchip electrophoresis with MS.
Main Methods:
- Detailed review of established and emerging soft ionization techniques for CE-MS.
- Discussion includes sonic spray ionization (SSI), thermospray ionization (TSI), atmospheric pressure chemical ionization (APCI), atmospheric pressure photoionization (APPI), matrix-assisted laser desorption ionization (MALDI), and continuous-flow fast atom bombardment (CF-FAB).
- Description of experimental setups for CE-MS couplings and principles of each ionization method.
Main Results:
- Comprehensive overview of alternative soft ionization techniques for CE-MS.
- Analysis of the strengths and limitations of each technique in the context of CE-MS.
- Illustrative examples demonstrating the applicability of various CE-MS systems.
Conclusions:
- The evolution of CE-MS has been significantly advanced by the integration of various soft ionization techniques.
- Alternative ionization methods offer distinct advantages and address specific challenges, expanding the utility of CE-MS in diverse analytical applications.
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