Reversible bridge-mediated excited-state symmetry breaking in stilbene-linked DNA dumbbells

Frederick D. Lewis, Pierre Daublain, Ligang Zhang, Boiko Cohen, Josh Vura-Weis, Michael R Wasielewski, Vladimir Shafirovich, Qiang Wang, Milen Raytchev, Torsten Fiebig

Research output: Contribution to journalArticle

18 Citations (Scopus)

Abstract

The excited-state behavior of synthetic DNA dumbbells possessing stilbenedicarboxamide (Sa) linkers separated by short A-tracts or alternating A-T base-pair sequences has been investigated by means of fluorescence and transient absorption spectroscopy. Electronic excitation of the Sa chromophores results in conversion of a locally excited state to a charge-separated state in which one Sa is reduced and the other is oxidized. This symmetry-breaking process occurs exclusively via a multistep mechanism-hole injection followed by hole transport and hole trapping-even at short distances. Rate constants for charge separation are strongly distance-dependent at short distances but become less so at longer distances. Disruption of the A-tract by inversion of a single A-T base pair results in a pronounced decrease in both the rate constant and efficiency of charge separation. Hole trapping by Sa is highly reversible, resulting in rapid charge recombination that occurs via the reverse of the charge separation process: hole detrapping, hole transport, and charge return to regenerate the locally excited Sa singlet state. These results differ in several significant respects from those previously reported for guanine or stilbenediether as hole traps. Neither charge separation nor charge recombination occur via a single-step superexchange mechanism, and hole trapping is slower and detrapping faster when Sa serves as the electron donor. Both the occurrence of symmetry breaking and reversible hole trapping by a shallow trap in a DNA-based system are without precedent.

Original languageEnglish
Pages (from-to)3838-3843
Number of pages6
JournalJournal of Physical Chemistry B
Volume112
Issue number12
DOIs
Publication statusPublished - Mar 27 2008

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Stilbenes
stilbene
Crystal symmetry
Excited states
broken symmetry
DNA
deoxyribonucleic acid
polarization (charge separation)
excitation
Rate constants
Hole traps
trapping
Guanine
Chromophores
Absorption spectroscopy
Fluorescence
traps
Electrons
guanines
chromophores

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Reversible bridge-mediated excited-state symmetry breaking in stilbene-linked DNA dumbbells. / Lewis, Frederick D.; Daublain, Pierre; Zhang, Ligang; Cohen, Boiko; Vura-Weis, Josh; Wasielewski, Michael R; Shafirovich, Vladimir; Wang, Qiang; Raytchev, Milen; Fiebig, Torsten.

In: Journal of Physical Chemistry B, Vol. 112, No. 12, 27.03.2008, p. 3838-3843.

Research output: Contribution to journalArticle

Lewis, FD, Daublain, P, Zhang, L, Cohen, B, Vura-Weis, J, Wasielewski, MR, Shafirovich, V, Wang, Q, Raytchev, M & Fiebig, T 2008, 'Reversible bridge-mediated excited-state symmetry breaking in stilbene-linked DNA dumbbells', Journal of Physical Chemistry B, vol. 112, no. 12, pp. 3838-3843. https://doi.org/10.1021/jp710718p
Lewis, Frederick D. ; Daublain, Pierre ; Zhang, Ligang ; Cohen, Boiko ; Vura-Weis, Josh ; Wasielewski, Michael R ; Shafirovich, Vladimir ; Wang, Qiang ; Raytchev, Milen ; Fiebig, Torsten. / Reversible bridge-mediated excited-state symmetry breaking in stilbene-linked DNA dumbbells. In: Journal of Physical Chemistry B. 2008 ; Vol. 112, No. 12. pp. 3838-3843.
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