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UVC induced oxidation of chloropurines: excited singlet and triplet pathways for the photoreaction

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Abstract

The phototransformation of 2-chloro, 6-chloro and 2,6-dichloropurines under UVC excitation (254 nm) has been studied and the major photoproducts have been identified using absorption spectroscopy, HPLC and mass spectrometry. It was shown that hydroxypurines were formed as the main products for all three investigated compounds both in the presence and absence of oxygen. In the case of 6-chloro- and 2,6-dichloropurine, a photodimer is also formed as a minor photoproduct in the absence of oxygen but is efficiently quenched in the presence of oxygen. Nanosecond photolysis experiments also revealed significant intersystem crossing to the triplet state of the chloropurines which has been characterized (transient absorption spectra, triplet formation quantum yields and rate constants of quenching by oxygen, Mn2+ ions and ground state). Experimental evidence allows to conclude that the triplet state is involved in photodimer formation whereas the hydroxypurine is formed from the reaction of the excited singlet state of chloropurines with the solvent (water addition) through heterolytic C-Cl bond rupture.Mass spectrometry and 1H NMR results allowed to propose a chemical pathway for dimer formation in the case of 2,6-dichloropurine in a two-step process: first a homolytic rupture of C-Cl bond in the triplet state of the molecule with the formation of purinyl radicals, which subsequently react with an excess of ground state molecules and/or hydroxypurine primarily formed.

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Authors and Affiliations

  1. Department of Biophysics, University of Warsaw, 02-089, Warsaw, Poland

    Elżbieta Bojarska & Marie-Pierre Fontaine-Aupart

  2. Medical Research Center, Laboratory of Experimental Pharmacology, Polish Academy of Sciences, 02-124, Warsaw, Poland

    Zygmunt Kazimierczuk

  3. Laboratory of Molecular Photophysics, CNRS UPR 3361, University Paris-Sud, 91405, Orsay Cedex, France

    Claire Mouchard & Francis Tfibel

Authors
  1. Elżbieta Bojarska
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  2. Zygmunt Kazimierczuk
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  5. Marie-Pierre Fontaine-Aupart
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Correspondence to Marie-Pierre Fontaine-Aupart.

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Bojarska, E., Kazimierczuk, Z., Mouchard, C. et al. UVC induced oxidation of chloropurines: excited singlet and triplet pathways for the photoreaction. Photochem Photobiol Sci 7, 1054–1062 (2008). https://doi.org/10.1039/b805149f

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