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Efficient Production of Multiply Charged MALDI Ions

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Book cover Advances in MALDI and Laser-Induced Soft Ionization Mass Spectrometry

Abstract

This chapter details a newly developed MALDI method which allows the generation of multiply charged ions of peptides and proteins similar to those produced by electrospray ionization (ESI) with high sensitivity and low sample consumption. A straightforward modification of a commercially available mass spectrometer with an atmospheric pressure (AP) ion source, and the necessary MALDI sample preparation protocol are described. This new method allows the combination of MALDI with mass analyzers of limited m/z range (e.g., quadrupoles, ion traps) for MS analysis of large biomolecules and ETD/ECD fragmentation for enhanced MS/MS analyses. In combination with ion mobility spectrometry (IMS) the signal-to-noise ratio of the multiply charged analyte ions can be significantly increased by filtering out the singly charged MALDI chemical noise ions.

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Notes

  1. 1.

    Note that any instrument modification and development work (including defeating interlocks and setting up lasers) will have Health and Safety implications and can invalidate the warranty and certain service/maintenance contracts for commercial instrumentation. For the former, please consult your local Health and Safety officer and the pertinent local rules and regulations.

  2. 2.

    Note that other UV lasers have been successfully used (e.g., Cramer et al. 2013).

  3. 3.

    The sample remains liquid under ambient conditions for weeks using this sample preparation protocol. For the DHB-based sample preparation, it was observed that for relatively high amounts of analyte (e.g., 5 pmol on target) the deposited sample may be used for at least 2 weeks, providing good analyte signal.

  4. 4.

    For this the MALDI target plate was coated with a saturated solution of CHCA in acetone, which immediately dries, leaving a thin layer of CHCA crystals behind. The thin film was then irradiated by the laser at the maximum energy for a sufficiently long period of time, making sure that the matrix on this spot was completely ablated. The size of the ablation spot was then measured under a microscope.

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Acknowledgement

This work is supported by the EPSRC through grant EP/L006227/1.

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Authors and Affiliations

  1. Department of Chemistry, University of Reading, Whiteknights, Reading, RG6 6AD, UK

    Pavel Ryumin & Rainer Cramer

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  1. Pavel Ryumin
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  2. Rainer Cramer
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Correspondence to Rainer Cramer .

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Editors and Affiliations

  1. Department of Chemistry, University of Reading, Reading, Berkshire, United Kingdom

    Rainer Cramer

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Ryumin, P., Cramer, R. (2016). Efficient Production of Multiply Charged MALDI Ions. In: Cramer, R. (eds) Advances in MALDI and Laser-Induced Soft Ionization Mass Spectrometry. Springer, Cham. https://doi.org/10.1007/978-3-319-04819-2_2

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