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Investigations of the metastable decay of DNA under ultraviolet matrix-assisted laser desorption/ionization conditions with post-source-decay analysis and hydrogen/deuterium exchange |
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| Authors: | Julia Gross Arne Leisner Franz Hillenkamp Stephanie Hahner Michael Karas Jürgen Schäfer Frank Lützenkirchen Eckhard Nordhoff |
| Institution: | 1. Institute for Medical Physics and Biophysics, University of Münster, Robert-Koch-Str. 31, D-48149, Münster, Germany 2. Zentrum für Umweltforschung und Technologie, Genom Analytik GmbH, Bremen, Germany 3. Abteilung für Instrumentelle Analytik, Universitaet Frankfurt, Frankfurt/Main, Germany 4. Institut fuer Lasermedizin, Universitaet Duesseldorf, Duesseldorf, Germany 5. Institute for Molecular Biology, Odense University, Odense M, Denmark |
| Abstract: | The fragmentation of positive ions of DNA under the conditions of matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) was investigated by post-source decay (PSD) analysis and hydrogen/deuterium (H/D) exchange. Spectra of five different synthetic 4mer oligonucleotides were recorded. As a main result the hypothesis was confirmed that for these ions all fragment ions result from processes, initiated by protonation/deuteration of a suitable base followed by a loss of this base as a neutral or ion and further backbone cleavages. The three bases adenine, guanine, and cytosine all exhibit comparable lability for fragmentation. The spectra show evidence for an interaction of the adenine base with the phosphate backbone. Signals of fragments containing TT- and CT-cycloadducts were observed in the spectra. |
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