Gas-phase fragmentation of half- and first-generation polyamidoamine dendrimers by electrospray mass spectrometry using a quadrupole ion trap.

Polyamidoamine (PAMAM) dendrimers are nanopolymers that can bind with biomolecules such as DNA, drugs or proteins. In order to study these complexes, we first fragmented half- and first-generation PAMAM, G0.5 and G1, respectively, using a quadrupole ion trap (QIT) equipped with an electrospray ionisation source. For both G0.5 and G1 we observed a series of impurities that only can stem from synthesis defects and that are principally due to missing branches and intramolecular cyclisations. Fragmentations of G1 showed regularity in the product ions. These ions result from the loss of 60 Da, obtained by an intramolecular cyclisation, and from the loss of 114 Da, obtained by a four-centred hydrogen transfer or a retro-Michael reaction. The fragmentations stemmed either from competitive or from consecutive reactions, even though resonant fragmentation QIT was used. It is shown that the principal fragmentation reaction is a retro-Michael rearrangement for both G1 and G0.5. In addition, by fragmenting totally deuterated [G1-d28]Na+ we were able to establish fragmentation pathways. Copyright (c) 2008 John Wiley & Sons, Ltd.