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Mechanistic Studies on Cationization in MALDI-MS Employing a Split Sample Plate Set-up.

  • Metternich JB Department of Chemistry and Applied Biosciences, ETH Zurich, CH-8093, Zurich, Switzerland.
  • Czar MF Department of Chemistry and Applied Biosciences, ETH Zurich, CH-8093, Zurich, Switzerland.
  • Mirabelli MF Department of Chemistry and Applied Biosciences, ETH Zurich, CH-8093, Zurich, Switzerland.
  • Bartolomeo GL Department of Chemistry and Applied Biosciences, ETH Zurich, CH-8093, Zurich, Switzerland.
  • Zouboulis KCM Department of Chemistry and Applied Biosciences, ETH Zurich, CH-8093, Zurich, Switzerland.
  • Zenobi R Department of Chemistry and Applied Biosciences, ETH Zurich, CH-8093, Zurich, Switzerland. zenobi@org.chem.ethz.ch.
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  • 2019-08-09
Published in:
  • Journal of the American Society for Mass Spectrometry. - 2019
MALDI mechanism
Polymer cationization
English In the analysis of polymers by matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS), a commonly observed ionization pathway is cation-adduct formation, as polymers often lack easily ionizable (basic/acidic) functional groups. The mechanism of this process has been hypothesized to involve gas-phase cation attachment. In previous experiments, a split sample plate set-up has been introduced, enabling separate deposition of the components on individual MALDI plates. The plates are divided by a small gap of a few micrometers, allowing simultaneous laser irradiation from both plates, while precluding the possibility of any other interactions prior to ablation. Here, we extend on these studies by using different polymer-salt combinations to test the generalizability of a gas-phase ionization process. Clear evidence for in-plume ionization is presented for the model polymers poly (methyl methacrylate) and polystyrene. Furthermore, the contribution of in-plume processes to the overall ion formation by cationization is gauged, providing a first estimate for the importance of this pathway.
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  • English
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green
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https://sonar.ch/global/documents/185352
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