The dissociation chemistry of primary fragment ions from the protonated proline-containing tripeptides glycylprolylglycine,prolylglycylglycine,and prolylprolylglycine was investigated by electrospray ionization multi-stage mass spectrometry.Calcula-tions showed the a 2 ions generated from b 2 ions were cyclic,which is energetically more favorable than the linear form.The prolyl residue in the structure affected the energy hypersurface of the dissociation reaction from the b 2 ion to the a 2 ion.In the fragmen-tation of a 2 ions,the iminium-imine complex corresponding to loss of CO from the a 2 ion was suggested to be an ion-neutral com-plex (INC).The a 1 ion was generated from direct separation of this INC,and the internal iminium ion,which was absent in PGG,was generated from another INC that was formed from the first INC via proton-bridged complex-mediated intramolecular proton transfer.Although these intermediates are unstable,their existence is supported by experiments and density functional theory calculations.
In the negative ion mode of electrospray ionization tandem mass spectrometry （ES1-MS/MS） of four sulfonyl- urea herbicides, Smiles rearrangements were observed in rimsulfuron and nicosulfuron. In the case of rimsulfuron, two competitive gas-phase Smiles rearrangements initiated by nitrogen anion and oxygen anion respectively were witnessed. The ion-neutral complex was proposed as the reactive intermediate in the course of this unimoleeular dissociation reaction of the oxygen attack Smiles rearrangement route. The density functional theory （DFT） was carried out to elucidate the mechanism as well as to show the possible transition states and the intermediates.
