A high-level G4(MP2) thermochemical study of the relative energies of the N-chlorinated isomers formed upon chlorination of cytosine

Dana Stambekova, Robert O Reilly John Christopher

Research output: Contribution to journalArticle

Abstract

Although the relative energies of the various tautomers of cytosine and 5-chlorocytosine have been studied in detail, little is known about the relative energies of the N-chlorinated isomers of cytosine. N-chlorination of cytosine is known to occur when cytosine is exposed to hypochlorous acid, a potent oxidant that is formed during the inflammatory process, and is presumed to have consequences concerning, for example, the structural integrity of DNA and RNA. In this study, the high-level G4(MP2) thermochemical protocol has been employed in studying the relative gas-phase free energies of thirty isomers that may be formed upon N-chlorination of cytosine. Using free energy of solvation corrections obtained by way of continuum models (CPCM and SMD), an approximation of the effect of aqueous solvation on the relative energies of the isomers has also been taken into account. In both the gas- and aqueous-phases, the lowest energy isomer is an exocyclic N-chloroimino derivative.

Original languageEnglish
Pages (from-to)220-228
Number of pages9
JournalChemical Data Collections
Volume9-10
DOIs
Publication statusPublished - Aug 1 2017

Fingerprint

Chlorination
Cytosine
Isomers
Solvation
Free energy
Gases
Hypochlorous Acid
Surface mount technology
Structural integrity
Oxidants
RNA
Derivatives
DNA

Keywords

  • DNA
  • G4(MP2)
  • Myeloperoxidase
  • N-chlorocytosine
  • Nucleobases

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

A high-level G4(MP2) thermochemical study of the relative energies of the N-chlorinated isomers formed upon chlorination of cytosine. / Stambekova, Dana; O Reilly John Christopher, Robert.

In: Chemical Data Collections, Vol. 9-10, 01.08.2017, p. 220-228.

Research output: Contribution to journalArticle

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