Abstract
The chlorinated derivatives of nucleobases (and nucleosides), as well as those of purine, have well-established anticancer activity, and in some cases, are also shown to be involved in the link between chronic inflammatory conditions and the development of cancer. In this investigation, the stability of all of the isomeric forms of the chlorinated nucleobases, purine and pyrimidine are investigated from the perspective of their homolytic CCl bond dissociation energies (BDEs). The products of these reactions, namely chlorine atom and the corresponding carbon-centered radicals, may be of importance in terms of potentiating biological damage. Initially, the performance of a wide range of contemporary theoretical procedures were evaluated for their ability to afford accurate CCl BDEs, using a recently reported set of 28 highly accurate CCl BDEs obtained by means of W1w theory. Subsequent to this analysis, the G3X(MP2)-RAD procedure (which achieves a mean absolute deviation of merely 1.3 kJ mol−1, with a maximum deviation of 5.0 kJ mol−1) was employed to obtain accurate gas-phase homolytic CCl bond dissociation energies for a wide range of chlorinated isomers of the DNA/RNA nucleobases, purine and pyrimidine.
| Original language | English |
|---|---|
| Article number | e25319 |
| Journal | International Journal of Quantum Chemistry |
| Volume | 117 |
| Issue number | 4 |
| DOIs | |
| Publication status | Published - Feb 15 2017 |
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Keywords
- bond dissociation energy
- chlorinated nucleobase
- G3 theory
- homolytic cleavage
- W1 theory
ASJC Scopus subject areas
- Atomic and Molecular Physics, and Optics
- Condensed Matter Physics
- Physical and Theoretical Chemistry
Cite this
Stability of the chlorinated derivatives of the DNA/RNA nucleobases, purine and pyrimidine toward radical formation via homolytic CCl bond dissociation. / Kaliyeva, Laura; Zhumagali, Shingis; Akhmetova, Nuriya; Karton, Amir; O'Reilly, Robert J.
In: International Journal of Quantum Chemistry, Vol. 117, No. 4, e25319, 15.02.2017.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Stability of the chlorinated derivatives of the DNA/RNA nucleobases, purine and pyrimidine toward radical formation via homolytic CCl bond dissociation
AU - Kaliyeva, Laura
AU - Zhumagali, Shingis
AU - Akhmetova, Nuriya
AU - Karton, Amir
AU - O'Reilly, Robert J.
PY - 2017/2/15
Y1 - 2017/2/15
N2 - The chlorinated derivatives of nucleobases (and nucleosides), as well as those of purine, have well-established anticancer activity, and in some cases, are also shown to be involved in the link between chronic inflammatory conditions and the development of cancer. In this investigation, the stability of all of the isomeric forms of the chlorinated nucleobases, purine and pyrimidine are investigated from the perspective of their homolytic CCl bond dissociation energies (BDEs). The products of these reactions, namely chlorine atom and the corresponding carbon-centered radicals, may be of importance in terms of potentiating biological damage. Initially, the performance of a wide range of contemporary theoretical procedures were evaluated for their ability to afford accurate CCl BDEs, using a recently reported set of 28 highly accurate CCl BDEs obtained by means of W1w theory. Subsequent to this analysis, the G3X(MP2)-RAD procedure (which achieves a mean absolute deviation of merely 1.3 kJ mol−1, with a maximum deviation of 5.0 kJ mol−1) was employed to obtain accurate gas-phase homolytic CCl bond dissociation energies for a wide range of chlorinated isomers of the DNA/RNA nucleobases, purine and pyrimidine.
AB - The chlorinated derivatives of nucleobases (and nucleosides), as well as those of purine, have well-established anticancer activity, and in some cases, are also shown to be involved in the link between chronic inflammatory conditions and the development of cancer. In this investigation, the stability of all of the isomeric forms of the chlorinated nucleobases, purine and pyrimidine are investigated from the perspective of their homolytic CCl bond dissociation energies (BDEs). The products of these reactions, namely chlorine atom and the corresponding carbon-centered radicals, may be of importance in terms of potentiating biological damage. Initially, the performance of a wide range of contemporary theoretical procedures were evaluated for their ability to afford accurate CCl BDEs, using a recently reported set of 28 highly accurate CCl BDEs obtained by means of W1w theory. Subsequent to this analysis, the G3X(MP2)-RAD procedure (which achieves a mean absolute deviation of merely 1.3 kJ mol−1, with a maximum deviation of 5.0 kJ mol−1) was employed to obtain accurate gas-phase homolytic CCl bond dissociation energies for a wide range of chlorinated isomers of the DNA/RNA nucleobases, purine and pyrimidine.
KW - bond dissociation energy
KW - chlorinated nucleobase
KW - G3 theory
KW - homolytic cleavage
KW - W1 theory
UR - http://www.scopus.com/inward/record.url?scp=85003906003&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=85003906003&partnerID=8YFLogxK
U2 - 10.1002/qua.25319
DO - 10.1002/qua.25319
M3 - Article
VL - 117
JO - International Journal of Quantum Chemistry
JF - International Journal of Quantum Chemistry
SN - 0020-7608
IS - 4
M1 - e25319
ER -