Electron Detachment Dissociation,and Collision-Induced Dissociation of Polyamidoamine (PAMAM) Dendrimer Ions with Amino, Amidoethanol, and Sodium Carboxylate Surface Groups

Here, we investigate the effect of the structure (generation) and nature of the surface groups of different polyamidoamine (PAMAM) dendrimers on electron-mediated dissociation, either electron capture dissociation (ECD) or electron detachment dissociation (EDD), and compare the fragmentation with that observed in collision-induced dissociation (CID). ECD and EDD of the PAMAM dendrimers esulted in simple mass spectra, which are straightforward to interpret, whereas CID produced complex mass spectra. The results show that electron-mediated dissociation (ECD and EDD) of PAMAM dendrimers does not depend on the nature of the surface group but tends to occur within the innermost generations. CID of the PAMAM dendrimers showed a strong dependence on the nature of the surface group and occurred mostly in the outer generation. The results demonstrate the potential utility of ECD and EDD as a tool for the structural analysis of PAMAM dendrimers

Electron Capture Dissociation Mass Spectrometry of Metallo-Supramolecular Complexes

The electron capture dissociation (ECD) of metallo-supramolecular dinuclear triple-stranded helicate Fe2L3 4 ions was determined by Fourier transform ion cyclotron resonance mass spectrometry. Initial electron capture by the di-iron(II) triple helicate ions produces dinuclear double-stranded complexes analogous to those seen in solution with the monocationic metal centers CuI or AgI. The gas-phase fragmentation behavior [ECD, collision-induced dissociation (CID), and infrared multiphoton dissociation (IRMPD)] of the di-iron double-stranded complexes, (i.e., MS3 of the ECD product) was compared with the ECD, CID, and IRMPD of the CuI and AgI complexes generated from solution. The results suggest that iron-bound dimers may be of the formFeI 2L2 2 and that ECD by metallo-complexes allows access, in the gas phase,to oxidation states and coordination chemistry that cannot be accessed in solution

Electron Capture Dissociation and Collision-Induced Dissociation of Metal Ion (Ag+, Cu2+, Zn2+, Fe2+, and Fe3+) Complexes of Polyamidoamine (PAMAM) Dendrimers

The electron capture dissociation (ECD) and collision-induced dissociation (CID) of complexes of polyamidoamine (PAMAM) dendrimers with metal ions Ag+, Cu2+, Zn2+, Fe2+, and Fe3+ were determined by Fourier transform ion cyclotron resonance mass spectrometry. Complexes were of the form [PD + M + mH]5+ where PD = generation two PAMAM dendrimer with amidoethanol surface groups, M = metal ion, m = 2–4. Complementary information regarding the site and coordination chemistry of the metal ions can be obtained from the two techniques. The results suggest that complexes of Fe3+ and Cu2+ are coordinated via both core tertiary amines, whereas coordination of Ag+ involves a single core tertiary amine. The Zn2+ and Fe2+ complexes do not appear to involve coordination by the dendrimer core

Synthesis and Photophysical Properties of Novel Donor-Acceptor N-(Pyridin-2-yl)-Substituted Benzo(thio)amides and Their Difluoroboranyl Derivatives

quantum yield than its oxygen counterpart. The fluorescence quantum yield is much higher upon formation of theThe unprecedented N-pyridin-2-yl substituted benzo(thio)amides were prepared and subsequently converted into the cyclic difluoroboranyl (BF2) derivatives. Mass spectrometry, multinuclear NMR, IR, and elemental analysis confirmed the structure of these compounds. UV/vis and fluorescence spectroscopy as well as first-principle calculations were used to study their properties. For the first time, the influence of both the O/S replacement and presence/absence of the BF2 moiety on the photophysical properties of compounds exhibiting charge transfer properties were examined experimentally and theoretically. We show that the sulfur-containing compound has a much smaller emission difluoroboranyl complex