Kinetics of surface-induced dissociation of N(CH3)4(+) and N(CD3)4(+) using silicon nanoparticle assisted laser desorption/ionization and laser desorption/ionization.

The implementation of surface-induced dissociation (SID) to study the fast dissociation kinetics (sub-microsecond dissociation) of peptides in a MALDI TOF instrument has been reported previously. Silicon nanoparticle assisted laser desorption/ionization (SPALDI) now allows the study of small molecule dissociation kinetics for ions formed with low initial source internal energy and without MALDI matrix interference. The dissociation kinetics of N(CH(3))(4)(+) and N(CD(3))(4)(+) were chosen for investigation because the dissociation mechanisms of N(CH(3))(4)(+) have been studied extensively, providing well-characterized systems to investigate by collision with a surface. With changes in laboratory collision energy, changes in fragmentation timescale and dominant fragment ions were observed, verifying that these ions dissociate via unimolecular decay. At lower collision energies, methyl radical (CH(3)) loss with a sub-microsecond dissociation rate is dominant, but consecutive H loss after CH(3) loss becomes dominant at higher collision energies. These observations are consistent with the known dissociation pathways. The dissociation rate of CH(3) loss from N(CH(3))(4)(+) formed by SPALDI and dissociated by an SID lab collision energy of 15 eV corresponds to log k = 8.1, a value achieved by laser desorption ionization (LDI) and SID at 5 eV. The results obtained with SPALDI SID and LDI SID confirm that (1) the dissociation follows unimolecular decay as predicted by RRKM calculations; (2) the SPALDI process deposits less initial energy than LDI, which has advantages for kinetics studies; and (3) fluorinated self-assembled monolayers convert about 18% of laboratory collision energy into internal energy. SID TOF experiments combined with SPALDI and peak shape analysis enable the measurement of dissociation rates for fast dissociation of small molecules.