Enhanced in-source fragmentation in MALDI-TOF-MS of oligonucleotides using 1,5-diaminonapthalene |
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Authors: | Hagan Nathan A Smith Christine A Antoine Miquel D Lin Jeffrey S Feldman Andrew B Demirev Plamen A |
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Institution: | (1) Johns Hopkins University Applied Physics Laboratory, Laurel, MD 20723, USA |
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Abstract: | The capability to rapidly and confidently determine or confirm the sequences of short oligonucleotides, including native and
chemically-modified DNA and RNA, is important for a number of fields. While matrix-assisted laser desorption/ionization (MALDI)
time-of-flight (TOF) mass spectrometry (MS) has been used previously to sequence short oligonucleotides, the typically low
fragmentation efficiency of in-source or post-source decay processes necessitates the accumulation of a large number of spectra,
thus limiting the throughput of these methods. Here we introduce a novel matrix, 1,5-diaminonapthalene (DAN), for facile in-source
decay (ISD) of DNA and RNA molecular anions, which allows for rapid sequence confirmation. d-, w-, and y-series ions are prominent in the spectra, complementary to the (a-B)- and w- ions that are typically produced by MALDI post-source decay (PSD). Results are shown for several model DNA and RNA oligonucleotides,
including combinations of DAN-induced fragmentation with true tandem TOF MS (MS/MS) for pseudo-MS3 and “activated-ion PSD.” |
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