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Related Experiment Videos

Fast photoinduced electron transfer through DNA intercalation

C J Murphy1, M R Arkin, N D Ghatlia

  • 1Division of Chemistry and Chemical Engineering, Beckman Institute, California Institute of Technology, Pasadena 91125.

Proceedings of the National Academy of Sciences of the United States of America
|June 7, 1994
PubMed
Summary

DNA helix facilitates rapid electron transfer between intercalating metal complexes. This process, crucial for DNA-mediated charge transport, was studied using ruthenium and rhodium complexes, revealing long-range electron transfer capabilities.

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Area of Science:

  • Photochemistry
  • Biophysical Chemistry
  • Molecular Biology

Background:

  • DNA's unique structure can mediate electronic processes.
  • Metal complexes are essential for studying DNA-mediated electron transfer.
  • Understanding charge transport in DNA is vital for molecular electronics and biological sensing.

Purpose of the Study:

  • To provide evidence for fast photoinduced electron transfer mediated by the DNA helix.
  • To investigate the role of avid DNA intercalators in this electron transfer process.
  • To elucidate the mechanism of long-range electron transfer through DNA.

Main Methods:

  • Utilized bis(phenanthroline)(dipyridophenazine)ruthenium(II) [Ru(phen)2dppz2+] as a donor and bis(9,10-phenanthrenequinone diimine)(phenanthroline)rhodium(III) [Rh(phi)2phen3+] as an acceptor.

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  • Performed luminescence quenching experiments with varying DNA lengths.
  • Compared results with a non-intercalative electron acceptor, Ru(NH3)3+(6), to differentiate mechanisms.

    • Main Results:

    • Both Ru(phen)2dppz2+ and Rh(phi)2phen3+ demonstrated high affinity for DNA intercalation (Kb > 10^6 M^-1).
    • Luminescence quenching experiments showed upward-curving Stern-Volmer plots, indicating complex interactions.
    • Electron transfer with intercalating complexes was significantly more efficient than with non-intercalative acceptors, supporting DNA-mediated transfer.

    Conclusions:

    • The DNA helix acts as a conduit for fast, long-range photoinduced electron transfer.
    • Metal complexes that avidly intercalate into DNA are key mediators of this charge transport.
    • These findings support a model of electron transfer occurring through the DNA helix between intercalated species.