Stability of the chlorinated derivatives of the DNA/RNA nucleobases, purine and pyrimidine toward radical formation via homolytic CCl bond dissociation

Laura Kaliyeva, Shingis Zhumagali, Nuriya Akhmetova, Amir Karton, Robert J. O'Reilly

Research output: Contribution to journalArticlepeer-review

6 Citations (Scopus)

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 CCl 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 CCl BDEs, using a recently reported set of 28 highly accurate CCl 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 CCl bond dissociation energies for a wide range of chlorinated isomers of the DNA/RNA nucleobases, purine and pyrimidine.

Original languageEnglish
Article numbere25319
JournalInternational Journal of Quantum Chemistry
Volume117
Issue number4
DOIs
Publication statusPublished - Feb 15 2017

Keywords

  • G3 theory
  • W1 theory
  • bond dissociation energy
  • chlorinated nucleobase
  • homolytic cleavage

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics
  • Condensed Matter Physics
  • Physical and Theoretical Chemistry

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