Thermal dissociation of gaseous bradykinin ions

Singly, doubly, and triply charged bradykinin ions have been dissociated thermally in a quadrupole ion trap operated with a bath gas comprised principally of helium at 1 mTorr. Dissociation rates as a function of bath gas temperature were measured along with product ion spectra. Studies were conducted to show that dissociation rates were independent of ion storage conditions and bath gas pressure. These studies indicate that good approximations to true Arrhenius parameters could be determined from Arrhenius plots using the bath gas temperature as a measure of the internal energy distribution of the parent ion population, Arrhenius parameters derived in this work agree with those reported recently using blackbody-induced radiative dissociation for the singly and doubly charged ions within experimental error. The spectrum of dissociation products were also very similar, reflecting the equivalency of the two methods for deriving Arrhenius parameters. Arrhenius parameters for the triply charged ion (E-a= 0.79 +/- 0.03 eV; log A = 9.3 +/- 0.36 s(-1)) are reported for the first time. Comparison of the Arrhenius parameters for the doubly and triply charged parent ions, along with dissociation reactions of the ions formed via water loss from the two parent ions indicate that water loss reactions from doubly protonated bradykinin and from triply protonated bradykinin proceed via distinctly different mechanisms.