Migration and trapping of photoinjected excess electrons in double-stranded B-form DNA but not in single-stranded DNA

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

Research output: Contribution to journalArticle

Abstract

Photoexcitation of a pyrene derivative covalently bound to double-stranded calf thymus DNA with 355 nm Nd:YAG laser pulses (fwhm = 24 ps, 50 mJ/cm2/pulse) results in the efficient two-photon-induced ionization of the pyrenyl residues. By use of nanosecond transient absorption techniques, it is shown that the excess electrons injected into the DNA can reduce methylviologen cations (MV2+) that are noncovalently bound to the DNA but not MV2+ in the outer aqueous solution phase. In double-stranded DNA, this reduction of MV2+ to MV•+ occurs via two kinetic phases, a rapid one that is complete within ≤7 ns and a slower one (200-300 ns) due to the diffusive reduction of MV2+ by hydrated electrons. The appearance of the first, rapid reduction phase of MV2+ depends on the secondary structure of the DNA, since it is observed only in the double-stranded form but not in the denatured, single-stranded form. This rapid reduction phase is entirely eliminated upon the addition of magnesium ions, which displace the positively charged MV2+ cations from the double-stranded DNA molecules. By variation of the concentration of MV2+ cations at a constant distribution of covalently bound pyrenyl residues (60 base pairs per pyrenyl residue), a mean distance of migration of excess electrons in double-stranded DNA of ca. 40 Å is estimated.

Original languageEnglish (US)
Pages (from-to)5863-5868
Number of pages6
JournalJournal of Physical Chemistry B
Volume101
Issue number30
DOIs
StatePublished - Jul 24 1997

ASJC Scopus subject areas

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

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