Abstract
AbstractThe effects of internal energy upon metastable and collision‐induced dissociation (CID) processes observed in the tandem mass spectrometry of multiply protonated molecules of horse‐heart cytochrome c (Mr 12360) are described. The internal energy of the multiply protonated (15H+) molecules (at m/z 825) formed by electrospray ionization (ESI) was manipulated using electric fields in the atmospheric pressure/vacuum interface region. Highly efficient CID is obtained for molecular ions collisionally activated in the ESI interface. The dissociation efficiency at 3.8 eV to 5.8 eV (center of mass) collision energies for internally “hot” molecular ions under multiple collision conditions in a triple quadrupole mass spectrometer is shown to be much greater than for “cold” ions. The CID spectra show dramatic effects due to internal energy, with charge stripping dominating for cold ions (where CID efficiency is very low) and extensive fragmentation observed for hot ions.
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