The Kinetic Deuterium Isotope Effect as a Probe of a Proton Coupled Electron Transfer Mechanism in the Oxidation of Guanine by 2-Aminopurine Radicals

Vladimir Shafirovich, Alexander Dourandin, Natalia P. Luneva, Nicholas E. Geacintov

Research output: Contribution to journalArticle

Abstract

Photoexcitation of 2-aminopurine riboside (2APr, 2-amino-9-β-D-ribofuranosylpurine) and 2-aminopurine (2AP) in oxygenated aqueous buffer solutions (pH 7.0) with 308 nm XeCl excimer laser pulses (fwhm = 12 ns, ca. 70 mJ/pulse/cm2) results in the consecutive two-photon ionization of the aromatic 2APr (or 2AP) residues. In neutral solutions, the 2APr (or 2AP) radical cations rapidly deprotonate (<100 ns). The 2APr(-H)· (or 2AP(-H)· neutral radicals thus formed reversibly oxidize 2-deoxyguanosine 5′-monophosphate (dGMP) on μs time scales, resulting in the formation of dGMP(-H)· neutral radicals. Transient absorption measurements show that a remarkable solvent isotope effect is observed on the kinetics of oxidation of dGMP by 2APr(-H)· (or 2AP(-H)·) radicals in H2O and D2O solutions. In H2O, the rate constants of dGMP(-H)· formation, as well as the rate constants of the reverse reaction of the 2APr (or 2AP) oxidation by dGMP(-H)· is larger than in D2O by a factor of 1.5-2. This kinetic isotope effect indicates that the electron-transfer reaction from dGMP to 2APr(-H)· (or to 2AP(-H)·), and the reverse electron transfer from 2APr (or 2AP) to dGMP(-H)·, is coupled to a deprotonation of the primary electron-transfer radical cation products, dGMP·+ and 2APr·+ (or 2AP·+). Therefore, these reactions, involving redox equilibria between different nucleobases, can be considered in terms of proton-coupled electron-transfer reactions.

Original languageEnglish (US)
Pages (from-to)137-139
Number of pages3
JournalJournal of Physical Chemistry B
Volume104
Issue number1
StatePublished - Jan 13 2000

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Surfaces, Coatings and Films
  • Materials Chemistry

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