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Photoinduced Electron Transfer between Anionic Corrole and DNA.

Li-Li Wang1,2, Lei Zhang1,2, Hui Wang1,2

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This study reveals ultrafast electron transfer between a Gallium(III) corrole and guanine bases in DNA. This interaction, occurring within femtoseconds, is crucial for understanding DNA-drug interactions.

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Area of Science:

  • Photochemistry
  • Biophysical Chemistry
  • Materials Science

Background:

  • Understanding the interaction between small molecules and DNA is vital for drug development.
  • Gallium(III) corroles are potential candidates for DNA-interactive agents.
  • Femtosecond spectroscopy provides insights into ultrafast molecular dynamics.

Purpose of the Study:

  • To investigate the interaction between a water-soluble anionic Ga(III) corrole, [Ga(tpfc)(SO3Na)2], and calf thymus DNA (ct-DNA).
  • To elucidate the mechanism and dynamics of electron transfer between the corrole and DNA bases.

Main Methods:

  • Femtosecond transient absorption spectroscopy was employed to monitor the interaction.
  • Control experiments used model DNA sequences ([poly(dG-dC)]2 and [poly(dA-dT)]2).
  • Molecular orbital calculations and electrochemical experiments were performed.

Main Results:

  • A significant spectral broadening was observed in the Ga(III) corrole-ct-DNA complex upon photoexcitation.
  • This broadening was attributed to electron transfer involving guanine bases.
  • Ultrafast forward electron transfer from guanine to the Ga(III) corrole occurred within 156 fs, followed by back transfer.

Conclusions:

  • The Ga(III) corrole interacts with ct-DNA via ultrafast electron transfer, primarily involving guanine bases.
  • The observed electron transfer is thermodynamically favorable and occurs on an ultrafast timescale.
  • This finding contributes to the understanding of DNA-ligand interactions and potential photodynamic applications.