Effective quenching of fragment formation in negative ion oligonucleotide matrix-assisted laser desorption/ionization mass spectrometry through sodium adduct formation.

Metastable decay of the sodium-free and the sodium adducts of the negatively charged hexameric nucleotides 5'-d(TTXYTT)-3' (X and Y are dC, dG or dA) in matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-ToF-MS) is reported. We show that the sodium adduct formation may be used to quantitatively quench dissociation channels in oligonucleotide MALDI-MS, and we argue, that by means of effective steps in the sample preparation that lead to per-sodiation of the sample, the sample preparation and the mass resolution of oligonucleotide mass spectra in MALDI may be improved substantially. The dependency of the fragment formation on the degree of sodiation is also discussed in context with the underlying fragmentation mechanisms. Copyright (c) 2006 John Wiley & Sons, Ltd.