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Metastable decay of negatively charged oligodeoxynucleotides analyzed with ultraviolet matrix-assisted laser desorption/ionization post-source decay and deuterium exchange

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Journal of the American Society for Mass Spectrometry

Abstract

In an effort to understand the initiating step in metastable-ion decay of UV matrix-assisted laser desorption/ionization (MALDI)-produced ions, we conducted experiments in which we exchanged all active protons for deuterons of tetrameric and hexameric oligodeoxynucleotides. We wish to address the controversial proposal that in the negative-ion mode, as in the positive-ion mode, fragmentation is driven by nucleobase protonation. The results show unambiguously that proton transfer, leading to zwitterion formation, charges a nucleobase prior to its elimination. The zwitterion formation directs fragmentation of both positive and negative oligodeoxynucleotide ions. Poly-T-rich oligodeoxynucleotide tetramers show surprising differences in the negative compared to the positive-ion mode, as thymine is preferentially expelled, instead of a nucleobase with higher proton affinity. For the exceptional case of negatively charged poly-T-rich oligodeoxynucleotide tetramers generated by MALDI, we propose that zwitterion formation with positive charging of a nucleobase leads to base stabilization in the negative-ion mode through an interaction of the positive nucleobase with the excess negative charge. Moreover, backbone cleavages (accompanied by H rearrangement) of a phosophodiester bond give first-generation products that can be traced back to this tripolar complex bearing one positive and two negative charges, all of which may be interacting.

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Authors and Affiliations

  1. Institute for Medical Physics and Biophysics, University of Muenster, Muenster, Germany

    Julia Gross & Franz Hillenkamp

  2. Department of Chemistry, Washington University, St. Louis, Missouri, USA

    Katty X. Wan & Michael L. Gross

Authors
  1. Julia Gross
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  2. Franz Hillenkamp
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  3. Katty X. Wan
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  4. Michael L. Gross
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Correspondence to Franz Hillenkamp.

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Gross, J., Hillenkamp, F., Wan, K.X. et al. Metastable decay of negatively charged oligodeoxynucleotides analyzed with ultraviolet matrix-assisted laser desorption/ionization post-source decay and deuterium exchange. J Am Soc Mass Spectrom 12, 180–192 (2001). https://doi.org/10.1016/S1044-0305(00)00209-9

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  • DOI: https://doi.org/10.1016/S1044-0305(00)00209-9

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