The pH effect on the naphthoquinone-photosensitized oxidation of 5-methylcytosine

Chemistry. 2008;14(33):10453-61. doi: 10.1002/chem.200800840.


The pH effect on the one-electron photooxidation of 5-methyl-2'-deoxycytidine (d(m)C) by sensitization with 2-methyl-1,4-naphthoquinone (NQ) was investigated. Photoirradiation of an aqueous solution containing d(m)C and NQ under slightly acidic conditions of pH 5.0 efficiently produced 5-formyl-2'-deoxycytidine, whereas similar NQ-photosensitized oxidation of d(m)C proceeded to a lesser extent under more acidic or basic conditions. Fluorescence-quenching experiments revealed that the less-efficient photooxidation at pH values below 4.5 is attributed to the decreased rate of one-electron oxidation of d(m)C owing to protonation at the N(3)-position. The NQ-photosensitized oxidation of an N(4)-dimethyl-substituted d(m)C derivative under various pH conditions also suggests that the pH change in the range of 5.0 to 8.0 may be responsible for a reversible deprotonation-protonation equilibrium at the N(4)-exocyclic amino group of the d(m)C radical cation. In accord with the photochemical reactivity of monomeric d(m)C, the 5-methylcytosine residue in oligodeoxynucleotides was oxidized efficiently by photoexcited NQ-tethered oligodeoxynucleotides under slightly acidic conditions to form an alkali-labile 5-formylcytosine residue.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • 5-Methylcytosine / chemistry*
  • Chromatography, High Pressure Liquid
  • Hydrogen-Ion Concentration
  • Molecular Structure
  • Naphthoquinones / chemistry*
  • Oxidation-Reduction
  • Photosensitizing Agents / chemistry*


  • Naphthoquinones
  • Photosensitizing Agents
  • 5-Methylcytosine