The dissociation chemistry of primary fragment ions from the protonated proline-containing tripeptides glycylprolylglycine,prolylglycylglycine,and prolylprolylglycine was investigated by electrospray ionization multi-...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.展开更多
基金supported by China National Funds for Distinguished Young scientists(21025207)the National Natural Science Foundation of China(20975092)the Zhejiang Provincial Natural Science Foundation of China(Y4100020)
文摘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.
