Graduate Thesis Or Dissertation

 

Gas-phase fragmentation chemistry of protonated peptide ions 公开 Deposited

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https://ir.library.oregonstate.edu/concern/graduate_thesis_or_dissertations/v405sc58g

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  • The fragmentation characteristics of protonated peptides have been investigated using tandem mass spectrometry (MS/MS) under various fragmentation regimes and detailed density functional theory (DFT) reaction pathway calculations. The DFT calculations predict novel salt-bridge stabilized transition structures as well as consecutive reactions occurring in proton-bound dimers for some of the ions detected in the MS/MS experiments. Four previously unknown protonated peptide fragmentation mechanisms are described in this thesis based on the theoretical and experimental results. These results have been evaluated using the mobile proton model and the more recently introduced pathways in competition (PIC) protonated peptide fragmentation model. The mobile proton model cannot adequately explain these experimental findings. The PIC model on the other hand, considers post-cleavage as well as pre-cleavage and bond-cleavage events, which enable these complicated protonated peptide fragmentation pathways to be rationalized.
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