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Getting to guanine: mechanism and dynamics of charge separation and charge recombination in DNA revisited

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Abstract

The mechanism and dynamics of charge separation and charge recombination in synthetic DNA hairpins possessing a stilbenedicarboxamide linker and a single guanine-cytosine base pair have been reinvestigated. The combination of femtosecond broad-band pump probe spectroscopy, nanosecond transient absorption experiments, and picosecond fluorescence decay measurements permits analysis of the formation and decay of the stilbene anion radical. Reversible hole injection resulting in the formation of the stilbene-adenine contact radical ion pair is found to occur on the picosecond time scale. The mechanism for charge separation across two or more base pairs is revised from single step superexchange to a multi-step process: hole injection followed by hole transport and hole trapping. The mechanism of charge recombination remains assigned to a superexchange process.

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Author information

Authors and Affiliations

  1. Departments of Chemistry, Northwestern University, Evanston, IL, 60201, USA

    Frederick D. Lewis, Huihe Zhu, Pierre Daublain & Karsten Sigmund

  2. Boston College, Chestnut Hill, MA, 02467, USA

    Torsten Fiebig, Milen Raytchev & Qiang Wang

  3. New York University, New York, NY, 10003, USA

    Vladimir Shafirovich

Authors
  1. Frederick D. Lewis
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  2. Huihe Zhu
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  3. Pierre Daublain
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  4. Karsten Sigmund
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  5. Torsten Fiebig
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  6. Milen Raytchev
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  7. Qiang Wang
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  8. Vladimir Shafirovich
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Corresponding authors

Correspondence to Frederick D. Lewis, Torsten Fiebig or Vladimir Shafirovich.

Additional information

This paper was published as part of the themed issue in honour of Jakob Wirz.

Electronic supplementary information (ESI) available: Pump-probe spectra and time-dependent 525/575 nm band intensity ratios for TG and T2G (Fig. S1 and S2). See DOI: 10.1039/b719715b

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Lewis, F.D., Zhu, H., Daublain, P. et al. Getting to guanine: mechanism and dynamics of charge separation and charge recombination in DNA revisited. Photochem Photobiol Sci 7, 534–539 (2008). https://doi.org/10.1039/b719715b

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  • DOI: https://doi.org/10.1039/b719715b

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