Jump to main content
Jump to site search

Issue 19, 2004
Previous Article Next Article

Dissociative electron transfer to and from pyrimidine cyclobutane dimers: An electrochemical study

Author affiliations

Abstract

Cyclic voltammetry was used to study the reduction and oxidation behaviour of several pyrimidine cyclobutane dimers mimicking UV induced lesion in DNA strands in polar solvents (N,N-dimethylformamide and acetonitrile). Both electron injection and removal to and from the dimers, respectively, lead to their cleavage and reformation of the monomeric base. The influence of stereochemistry and substitution pattern at the cyclobutane motif on the reactivity has been studied. It appears that the repair process always proceeds in a sequential fashion with initial formation of a dimer ion radical intermediate, which then undergoes ring opening by homolytic cleavage of the two C–C bonds. Standard redox potentials for the formation of both radical anion and radical cation state of the dimers were determined. Quantum calculations on simplified model compounds reveal the reason for the finding that the exergonic homolytic cleavages of the carbon–carbon bonds are endowed with sizeable activation barriers. The consequences of these mechanistic studies on the natural enzymatic repair by photolyase enzyme are discussed.

Graphical abstract: Dissociative electron transfer to and from pyrimidine cyclobutane dimers: An electrochemical study

Back to tab navigation

Publication details

The article was received on 10 May 2004, accepted on 15 Jul 2004 and first published on 31 Aug 2004


Article type: Paper
DOI: 10.1039/B406923D
Citation: Org. Biomol. Chem., 2004,2, 2742-2750
  •   Request permissions

    Dissociative electron transfer to and from pyrimidine cyclobutane dimers: An electrochemical study

    F. Boussicault, O. Krüger, M. Robert and U. Wille, Org. Biomol. Chem., 2004, 2, 2742
    DOI: 10.1039/B406923D

Search articles by author

Spotlight

Advertisements