Even-electron [M-H](+) ions generated by loss of AgH from argentinated peptides with N-terminal imine groups.

RATIONALE: Experiments were performed to probe the creation of apparent even-electron, [M-H](+) ions by CID of Ag-cationized peptides with N-terminal imine groups (Schiff bases). METHODS: Imine-modified peptides were prepared using condensation reactions with aldehydes. Ag(+) -cationized precursors were generated by electrospray ionization (ESI). Tandem mass spectrometry (MS(n) ) and collision-induced dissociation (CID) were performed using a linear ion trap mass spectrometer. RESULTS: Loss of AgH from peptide [M + Ag](+) ions, at the MS/MS stage, creates closed-shell [M-H](+) ions from imine-modified peptides. Isotope labeling unambiguously identifies the imine C-H group as the source of H eliminated in AgH. Subsequent CID of the [M-H](+) ions generated sequence ions that are analogous to those produced from [M + H](+) ions of the imine-modified peptides. CONCLUSIONS: Experiments show (a) formation of novel even-electron peptide cations by CID and (b) the extent to which sequence ions (conventional b, a and y ions) are generated from peptides with fixed charge site and thus lacking a conventional mobile proton.

Apparent activation of H2O and elimination of H2 from gas-phase mixed-metal complexes containing silver, calcium and deprotonated glycine.

RATIONALE: Ion trap mass spectrometry was used to study the reactivity of species derived from gas-phase, mixed-metal complexes, [Ag2 Xx(Gly-H)3 ](+) , where Xx = Ca, Mg, Sr and Ag, and in particular the apparent activation of an H2 O ligand added during an ion-molecule reaction. METHODS: Precursor [Ag2 Xx(Gly-H)3 ](+) complexes were formed by electrospray ionization (ESI) using spray solutions in which AgNO3 , XxNO3 and glycine were mixed in a 1:1:3 molar ratio. Specific species for study of ion-molecule reactions were created in a "top down" fashion using collision-induced dissociation (CID). Ion-molecule reactions were performed by selective isolation and storage in a linear ion trap, where reactions with adventitious H2 O can occur. RESULTS: Multiple stages of CID of [Ag2 Ca(Gly-H)3 ](+) resulted in the formation of [AgHCa(Gly-H)](+) . An ion-molecule reaction of this ion produced a peak 16 mass units higher which is hypothesized to be a result of addition of H2 O followed by loss of H2 . This reaction was studied further by replacing Ca with Mg, Sr and Ag; as well as by incorporating deuterium-labelled glycine into the complex. CONCLUSIONS: The experimental results showed the following pattern for the apparent rates of reaction: Mg > Sr > Ca. When silver is the only metal present there is an addition of water but no loss of H2 . DFT and MP2 calculations help identify plausible pathways for decomposition of H2 O and formation of H2.

Formation of bare UO2(2+) and NUO(+) by fragmentation of gas-phase uranyl-acetonitrile complexes.

In a prior study [Van Stipdonk; et al. J. Phys. Chem. A 2006, 110, 959-970], electrospray ionization (ESI) was used to generate doubly charged complex ions composed of the uranyl ion and acetonitrile (acn) ligands. The complexes, general formula [UO2(acn)n](2+), n = 0-5, were isolated in an 3-D quadrupole ion-trap mass spectrometer to probe intrinsic reactions with H2O. Two general reaction pathways were observed: (a) the direct addition of one or more H2O ligands to the doubly charged complexes and (b) charge-exchange reactions. For the former, the intrinsic tendency to add H2O was dependent on the number and type of nitrile ligand. For the latter, charge exchange involved primarily the formation of uranyl hydroxide, [UO2OH](+), presumably via a collision with gas-phase H2O and the elimination of a protonated nitrile ligand. Examination of general ion fragmentation patterns by collision-induced dissociation, however, was hindered by the pronounced tendency to generate hydrated species. In an update to this story, we have revisited the fragmentation of uranyl-acetonitrile complexes in a linear ion-trap (LIT) mass spectrometer. Lower partial pressures of adventitious H2O in the LIT (compared to the 3-D ion trap used in our previous study) minimized adduct formation and allowed access to lower uranyl coordination numbers than previously possible. We have now been able to investigate the fragmentation behavior of these complex ions completely, with a focus on tendency to undergo ligand elimination versus charge reduction reactions. CID can be used to drive ligand elimination to completion to furnish the bare uranyl dication, UO2(2+). In addition, fragmentation of [UO2(acn)](2+) generated [UO2(NC)](+), which subsequently fragmented to furnish NUO(+). Formation of the nitrido by transfer of N from cyanide was confirmed using precursors labeled with (15)N. The observed formation of [UO2(NC)](+) and NUO(+) was modeled by density functional theory.