A computational study of the fragmentation of b3 ions derived from protonated peptides

Ting Hua Tang, De Cai Fang, Alex G. Harrison, I. Csizmadia

Research output: Contribution to journalArticle

9 Citations (Scopus)

Abstract

Ab initio Hartree-Fock (HF/6-31G(d,p)) and density functional theory (B3LYP/6-31G(d,p)) methods have been used to study the cationic fragmentation of b3 ions in order to deepen our mechanistic understanding of the process. The calculated results show that some b3 ions (both the oxazolone ions formed by cyclization of the nominal acylium ions CH 3CONHCH2CONHCH2CO+ and H 2NCH2CONHCH2CONHCH2CO+) can be fragmented into b2 ion only indirectly. In other words, these two decompositions of cationic b3 ions into b2 ions proceed via a multi-step mechanism. The electron density distributions of the main stationary points of the reactions have been analyzed by the theory of atoms in molecules, in addition to the energetics of the fragmentation.

Original languageEnglish
Pages (from-to)79-93
Number of pages15
JournalJournal of Molecular Structure: THEOCHEM
Volume675
Issue number1-3
DOIs
Publication statusPublished - Apr 30 2004

Fingerprint

Peptides
peptides
fragmentation
Ions
ions
Oxazolone
Electronic density of states
Cyclization
Density functional theory
density distribution
Electrons
methylidyne
density functional theory
Decomposition
decomposition
Atoms
Molecules
atoms
molecules

Keywords

  • Ab initio calculations
  • Atoms in molecule theory
  • Cationic fragmentation of peptides
  • Density functional theory calculations
  • Mass-spectrometric fragmentation

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Computational Theory and Mathematics
  • Atomic and Molecular Physics, and Optics

Cite this

A computational study of the fragmentation of b3 ions derived from protonated peptides. / Tang, Ting Hua; Fang, De Cai; Harrison, Alex G.; Csizmadia, I.

In: Journal of Molecular Structure: THEOCHEM, Vol. 675, No. 1-3, 30.04.2004, p. 79-93.

Research output: Contribution to journalArticle

Tang, Ting Hua ; Fang, De Cai ; Harrison, Alex G. ; Csizmadia, I. / A computational study of the fragmentation of b3 ions derived from protonated peptides. In: Journal of Molecular Structure: THEOCHEM. 2004 ; Vol. 675, No. 1-3. pp. 79-93.
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