Fragmentation of deprotonated D-ribose and D-fructose in MALDI-Comparison with dissociative electron attachment

We present a detailed, collaborative Study on the fragmentation of deprotonated native D-ribose and D-fructose and the isotopically labelled 1-(13)C-D-ribose, 5-(13)C-D-ribose and C-1-D-D-ribose. The fragmentation is studied in a matrix assisted laser desorption/ionization time of flight mass spectrometer (MALDI ToF MS), both in in-source decay (ISD) and post-source decay (PSD) mode and compared with fragmentation through dissociative electron attachment (DEA). Fragmentation of deprotonated monosaccharides formed in the MALDI process, as well as their transient molecular anions formed upon electron attachment are characterized by loss of different numbers of H(2)O and CH(2)O units. Two different fragmentation pathways leading to cross-ring cleavage are identified. Metastable decay of deprotonated D-ribose proceeds either via an X-type cleavage yielding fragment anions at m/z = 119, 100 and 89, or via an A-type cleavage resulting in m/z = 89, 77 and 71. A fast and early metastable cross-ring cleavage of deprotonated D-ribose observed in in-source decay is dominated by X-type cleavage leading mainly to m/z = 100 and 71. For dissociative electron attachment to D-ribose a sequential dissociation was identified that includes metastable decay of the dehydrogenated molecular anion leading to m/z = 89. All other fragmentation reactions in DEA to D-ribose are likely to proceed directly and on a faster timescale (below 400 ns). (C) 2008 Elsevier B.V. All rights reserved.