Fragmentation of Oligoribonucleotides from Gas-Phase Ion-Electron Reactions

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作者：
Yang, Jiong [1 ]
Håkansson, Kristina [1 ]
机构：
[1] Department of Chemistry, University of Michigan, Ann Arbor, MI, United States
来源：
Journal of the American Society for Mass Spectrometry | 2006年 / 17卷 / 10期
关键词：
We have recently demonstrated that both electron capture dissociation (ECD) and electron detachment dissociation (EDD) can provide complementary sequence-specific cleavage of DNA compared with collision activated dissociation (CAD) and infrared multiphoton dissociation (IRMPD). However; EDD is preferred because of more extensive fragmentation at higher sensitivity (due to its negative ion mode operation). Here; we extend the radical ion chemistry of these two gas-phase ion-electron reaction techniques to the characterization of RNA. Compared with DNA; rather limited information is currently available on the gas-phase fragmentation of RNA. We found that the ECD fragmentation patterns of the oligoribonucleotides A6; C6; and CGGGGC are nucleobase dependent; suggesting that cleavage proceeds following electron capture at the nucleobases. Only limited backbone cleavage was observed in ECD. EDD; on the other hand; provided complete sequence coverage for the RNAs A6; G6; U6; CGGGGC; and GCAUAC. The EDD fragmentation patterns were different from those observed with CAD and IRMPD in that the dominant product ions correspond to d- and w-type ions rather than c- and y-type ions. The minimum differences between oligoribonucleotides suggest that EDD proceeds following direct electron detachment from the phosphate backbone. © 2006 American Society for Mass Spectrometry;
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页码：1369 / 1375
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