DNA-mediated exciton coupling and electron transfer between donor and acceptor stilbenes separated by a variable number of base pairs

Frederick D. Lewis, Yansheng Wu, Ligang Zhang, Xiaobing Zuo, Ryan T. Hayes, Michael R Wasielewski

Research output: Contribution to journalArticle

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Abstract

The synthesis, steady-state spectroscopy, and transient absorption spectroscopy of DNA conjugates possessing both stilbene electron donor and electron acceptor chromophores are described. These conjugates are proposed to form nicked DNA dumbbell structures in which a stilbenedicarboxamide acceptor and stilbenediether donor are separated by variable numbers of A-T or G-C base pairs. The nick is located either adjacent to one of the chromophores or between two of the bases. Thermal dissociation profiles indicate that stable structures are formed possessing as few as two A-T base pairs. Circular dichroism (CD) spectra in the base pair region are characteristic of B-DNA duplex structures, whereas CD spectra at longer wavelengths display two bands attributed to exciton coupling between the two stilbenes. The sign and intensity of these bands are dependent upon both the distance between the chromophores and the dihedral angle between their transition dipoles [Δε ≈ Rda -2 sin(2θ)]. Pulsed laser excitation of the stilbenediamide results in creation of the acceptor-donor radical ion pair, which decays via charge recombination. The dynamics of charge separation and charge recombination display an exponential distance dependence, similar to that observed previously for systems in which guanine serves as the electron donor. Unlike exciton coupling between the stilbenes, there is no apparent dependence of the charge-transfer rates upon the dihedral angle between donor and acceptor stilbenes. The introduction of a single G-C base pair between the donor and acceptor results in a change in the mechanism for charge separation from single step superexchange to hole hopping.

Original languageEnglish
Pages (from-to)8206-8215
Number of pages10
JournalJournal of the American Chemical Society
Volume126
Issue number26
DOIs
Publication statusPublished - Jul 7 2004

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Stilbenes
Chromophores
Base Pairing
Excitons
DNA
Dichroism
Dihedral angle
Electrons
Circular Dichroism
Genetic Recombination
Spectrum Analysis
Laser excitation
B-Form DNA
Pulsed lasers
Absorption spectroscopy
Charge transfer
Guanine
Spectroscopy
Wavelength
Lasers

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

DNA-mediated exciton coupling and electron transfer between donor and acceptor stilbenes separated by a variable number of base pairs. / Lewis, Frederick D.; Wu, Yansheng; Zhang, Ligang; Zuo, Xiaobing; Hayes, Ryan T.; Wasielewski, Michael R.

In: Journal of the American Chemical Society, Vol. 126, No. 26, 07.07.2004, p. 8206-8215.

Research output: Contribution to journalArticle

Lewis, Frederick D. ; Wu, Yansheng ; Zhang, Ligang ; Zuo, Xiaobing ; Hayes, Ryan T. ; Wasielewski, Michael R. / DNA-mediated exciton coupling and electron transfer between donor and acceptor stilbenes separated by a variable number of base pairs. In: Journal of the American Chemical Society. 2004 ; Vol. 126, No. 26. pp. 8206-8215.
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N2 - The synthesis, steady-state spectroscopy, and transient absorption spectroscopy of DNA conjugates possessing both stilbene electron donor and electron acceptor chromophores are described. These conjugates are proposed to form nicked DNA dumbbell structures in which a stilbenedicarboxamide acceptor and stilbenediether donor are separated by variable numbers of A-T or G-C base pairs. The nick is located either adjacent to one of the chromophores or between two of the bases. Thermal dissociation profiles indicate that stable structures are formed possessing as few as two A-T base pairs. Circular dichroism (CD) spectra in the base pair region are characteristic of B-DNA duplex structures, whereas CD spectra at longer wavelengths display two bands attributed to exciton coupling between the two stilbenes. The sign and intensity of these bands are dependent upon both the distance between the chromophores and the dihedral angle between their transition dipoles [Δε ≈ Rda -2 sin(2θ)]. Pulsed laser excitation of the stilbenediamide results in creation of the acceptor-donor radical ion pair, which decays via charge recombination. The dynamics of charge separation and charge recombination display an exponential distance dependence, similar to that observed previously for systems in which guanine serves as the electron donor. Unlike exciton coupling between the stilbenes, there is no apparent dependence of the charge-transfer rates upon the dihedral angle between donor and acceptor stilbenes. The introduction of a single G-C base pair between the donor and acceptor results in a change in the mechanism for charge separation from single step superexchange to hole hopping.

AB - The synthesis, steady-state spectroscopy, and transient absorption spectroscopy of DNA conjugates possessing both stilbene electron donor and electron acceptor chromophores are described. These conjugates are proposed to form nicked DNA dumbbell structures in which a stilbenedicarboxamide acceptor and stilbenediether donor are separated by variable numbers of A-T or G-C base pairs. The nick is located either adjacent to one of the chromophores or between two of the bases. Thermal dissociation profiles indicate that stable structures are formed possessing as few as two A-T base pairs. Circular dichroism (CD) spectra in the base pair region are characteristic of B-DNA duplex structures, whereas CD spectra at longer wavelengths display two bands attributed to exciton coupling between the two stilbenes. The sign and intensity of these bands are dependent upon both the distance between the chromophores and the dihedral angle between their transition dipoles [Δε ≈ Rda -2 sin(2θ)]. Pulsed laser excitation of the stilbenediamide results in creation of the acceptor-donor radical ion pair, which decays via charge recombination. The dynamics of charge separation and charge recombination display an exponential distance dependence, similar to that observed previously for systems in which guanine serves as the electron donor. Unlike exciton coupling between the stilbenes, there is no apparent dependence of the charge-transfer rates upon the dihedral angle between donor and acceptor stilbenes. The introduction of a single G-C base pair between the donor and acceptor results in a change in the mechanism for charge separation from single step superexchange to hole hopping.

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