Ion Trap Collision-Induced Dissociation of Multiply Deprotonated RNA: c/y-Ions versus (a-B)/w-Ions

The dissociation of model RNA anions has been studied as a function of anion charge state and excitation amplitude using ion trap collisional activation. Similar to DNA anions, the precursor ion charge state of an RNA anion plays an important role in directing the preferred dissociation channels. Generally, the complementary c/y-ions from 5' P-O bond cleavage dominate at low to intermediate charge states, while other backbone cleavages appear to a limited extent but increase in number and relative abundance at higher excitation energies. The competition between base loss, either as a neutral or as an anion, as well as the preference for the identity of the lost base are also observed to be charge-state dependent. To gain further insight into the partitioning of the dissociation products among the various possible channels, model dinucleotide anions have been subjected to a systematic Study. In comparison to DNA, the 2'-OH group on RNA significantly facilitates the dissociation of the 5' P-O bond. However, the degree of excitation required for a 5' base loss and the subsequent 3' C-O bond cleavage are similar for the analogous RNA and DNA dinucleotides. Data collected for protonated dinucleotides, however, suggest that the 2'-OH group in RNA can stabilize the glycosidic bond of a protonated base. Therefore, base loss from low charge state oligonucleotide anions, in which protonation of one or more bases via intramolecular proton transfer call occur, may also be stabilized in RNA anions relative to corresponding DNA anions. (J Am Soc Mass Spectrom 2008, 19, 1832-1840) (c) 2008 American Society for Mass Spectrometry