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Tunable fragmentation of organic molecules in laser ablation glow discharge time-of-flight mass spectrometry

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Abstract

A DC-pulsed glow discharge (GD) has distinct temporal regimes which are characterized by “softer” or “harder” ionization of analytes introduced into the discharge. It is thus possible to obtain both molecular weight and structural fragment information from the same spectra. In order to extend the capabilities of this technique a laser ablation (LA) sampling system was coupled to a DC-pulsed GD and to a time-of-flight (TOF) mass spectrometer (MS) for characterizing organic samples such as oleic acid, reserpine, two different peptides, and a polymer. Both hard and soft ionization regimes were studied. These LAGD-TOFMS results were compared to matrix-assisted laser desorption ionization (MALDI) spectra using the same compounds (i.e., analytes, concentration, and matrix). It was found that LAGD offers tunable ionization and provides a reduced matrix dependence. However, the sensitivity achieved by the prototype LAGD-TOFMS was significantly lower when compared with commercially available MALDI-TOFMS instrumentation. Since LAGD-TOFMS is rather new, some technical details to increase its sensitivity are discussed.

Schematics of molecular and structural information of oleic acid molecule during the different temporal regimes of a pulsed GD.

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Acknowledgments

The authors would like to thank the European Community for financial support through GLADNET, a Marie Curie-RTN within the FP 6, and TOFWERK AG for providing the TOF instrument. The authors also would like to thank Dr. R. Knochenmuss for the discussion of the results, and L. Bertschi (MS service, D-CHAB) for the MALDI measurements. We also like to thank H. Longerich and two anonymous reviewers for critical and constructive comments which helped to improve the manuscript.

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Authors and Affiliations

  1. Laboratory of Inorganic Chemistry, ETH Zurich, 8093, Zurich, Switzerland

    G. Lotito & D. Günther

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  1. G. Lotito
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  2. D. Günther
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Correspondence to D. Günther.

Additional information

Published in the special issue Analytical Sciences in Switzerland with guest editors P. Dittrich, D. Günther, G. Hopfgartner, and R. Zenobi.

Appendix A

Appendix A

A.1 Chemical structures of the compounds

Here below (Fig. 12) are the chemical structures of the organic molecules used in this study. These structure’s formulas were produced using Symyx Draw 4.0.

Fig. 12
figure 12

Structural formulas of the analytes measured

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A.2 MALDI spectrum of CHCA and oleic acid

A mass spectrum measured with MALDI concerning CHCA alone and mixed with oleic acid is in Fig. 13.

Fig. 13
figure 13

Full mass spectra of oleic acid in CHCA (oleic acid and CHCA) and of the matrix alone (CHCA pure)

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Lotito, G., Günther, D. Tunable fragmentation of organic molecules in laser ablation glow discharge time-of-flight mass spectrometry. Anal Bioanal Chem 402, 2565–2576 (2012). https://doi.org/10.1007/s00216-011-5498-x

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  • DOI: https://doi.org/10.1007/s00216-011-5498-x

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