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 language | English |
|---|---|
| Pages (from-to) | 79-93 |
| Number of pages | 15 |
| Journal | Journal of Molecular Structure: THEOCHEM |
| Volume | 675 |
| Issue number | 1-3 |
| DOIs | |
| Publication status | Published - Apr 30 2004 |
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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 journal › Article
}
TY - JOUR
T1 - A computational study of the fragmentation of b3 ions derived from protonated peptides
AU - Tang, Ting Hua
AU - Fang, De Cai
AU - Harrison, Alex G.
AU - Csizmadia, I.
PY - 2004/4/30
Y1 - 2004/4/30
N2 - 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.
AB - 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.
KW - Ab initio calculations
KW - Atoms in molecule theory
KW - Cationic fragmentation of peptides
KW - Density functional theory calculations
KW - Mass-spectrometric fragmentation
UR - http://www.scopus.com/inward/record.url?scp=2342612921&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=2342612921&partnerID=8YFLogxK
U2 - 10.1016/j.theochem.2003.12.033
DO - 10.1016/j.theochem.2003.12.033
M3 - Article
VL - 675
SP - 79
EP - 93
JO - Computational and Theoretical Chemistry
JF - Computational and Theoretical Chemistry
SN - 2210-271X
IS - 1-3
ER -