Dynamics and energetics of single-step hole transport in DNA hairpins

Frederick D. Lewis, Jianqin Liu, Xiaobing Zuo, Ryan T. Hayes, Michael R Wasielewski

Research output: Contribution to journalArticle

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Abstract

The dynamics of single-step hole transport processes have been investigated in a number of DNA conjugates possessing a stilbenedicarboxamide electron acceptor, a guanine primary donor, and several secondary donors. Rate constants for both forward and return hole transport between the primary and secondary donor are obtained from kinetic modeling of the nanosecond transient absorption decay profiles of the stilbene anion radical. The kinetic model requires that the hole be localized on either the primary or the secondary donor and not delocalized over both the primary and the secondary donor. Rate constants for hole transport are found to be dependent upon the identity of the secondary donor, the intervening bases, and the location of the secondary donor in the same strand as the primary donor or in the complementary strand. Rate constants for hole transport are much slower than those for the superexchange process used to inject the hole on the primary donor. This difference is attributed to the larger solvent reorganization energy for charge transport versus charge separation. The hole transport rate constants obtained in these experiments are consistent with experimental data for single-step hole transport from other transient absorption studies. Their relevance to long-distance hole migration over tens of base pairs remains to be determined. The forward and return hole transport rate constants provide equilibrium constants and free energies for hole transport equilibria. Secondary GG and GGG donors are found to form very shallow hole traps, whereas the nucleobase deazaguanine forms a relatively deep hole trap. This conclusion is in accord with selected strand cleavage data and thus appears to be representative of the behavior of holes in duplex DNA. Our results are discussed in the context of current theoretical models of hole transport in DNA.

Original languageEnglish
Pages (from-to)4850-4861
Number of pages12
JournalJournal of the American Chemical Society
Volume125
Issue number16
DOIs
Publication statusPublished - Apr 23 2003

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Rate constants
DNA
Hole traps
Stilbenes
Guanine
Base Pairing
Anions
Theoretical Models
Kinetics
Electrons
Equilibrium constants
Free energy
Charge transfer
Negative ions
Experiments

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Dynamics and energetics of single-step hole transport in DNA hairpins. / Lewis, Frederick D.; Liu, Jianqin; Zuo, Xiaobing; Hayes, Ryan T.; Wasielewski, Michael R.

In: Journal of the American Chemical Society, Vol. 125, No. 16, 23.04.2003, p. 4850-4861.

Research output: Contribution to journalArticle

Lewis, Frederick D. ; Liu, Jianqin ; Zuo, Xiaobing ; Hayes, Ryan T. ; Wasielewski, Michael R. / Dynamics and energetics of single-step hole transport in DNA hairpins. In: Journal of the American Chemical Society. 2003 ; Vol. 125, No. 16. pp. 4850-4861.
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