Valis, Linda and Wang, Qiang and Raytchev, Milen and Buchvarov, Ivan and Wagenknecht, Hans-Achim and Fiebig, Torsten (2006) Base pair motions control the rates and distance dependencies of reductive and oxidative DNA charge transfer. PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA, 103 (27). pp. 10192-10195. ISSN 0027-8424,
Full text not available from this repository. (Request a copy)Abstract
In 1999, Wan et al. [Proc. Natl. Acad. Sci. USA 96, 6014-6019] published a pioneering paper that established the entanglement between DNA base pair motions and the transfer time of the charge carrier. The DNA assemblies contained an ethidium covalently bound via a flexible alkyl chain to the 5' hydroxyl group of the DNA backbone. Although covalently attached, the loose way in which the ethidium was linked to DNA allowed for large degrees of conformational freedom and thus raised some concern with respect to conformational inhomogeneity. In this letter, we report studies on a different set of ethidium DNA conjugates. In contrast to the "Caltech systems," these conjugates contain ethidium tightly incorporated (as a base pair surrogate) into the DNA base stack, opposite to an abasic site analog. Despite the tight binding, we found that charge transfer from the photoexcited ethidium base pair surrogate across two or more base pairs is several orders of magnitude slower than in case of the DNA systems bearing the tethered ethidium. To further broaden the scope of this account, we compared (oxidative) electron hole transfer and (reductive) electron transfer using the same ethidium chromophore as a charge donor in combination with two different charge acceptors. We found that both electron and hole transfer are characterized by similar rates and distance dependencies. The results demonstrate the importance of nuclear motions and conformational flexibility and underline the presence of a base gating mechanism, which appears to be generic to electronic transfer processes through pi-stacked nucleic acids.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | PHOTOINDUCED ELECTRON-TRANSFER; ETHIDIUM-BROMIDE; INTERCALATED ETHIDIUM; FEMTOSECOND DYNAMICS; PHENANTHRIDINIUM; MOLECULES; METHYLVIOLOGEN; 5-NITROINDOLE; DERIVATIVES; MECHANISM; conformational gating; electron transfer; ultrafast spectroscopy; hole transfer |
| Subjects: | 500 Science > 540 Chemistry & allied sciences |
| Divisions: | Chemistry and Pharmacy > Institut für Organische Chemie > Alumni or Retired Professors > Arbeitskreis Prof. Dr. Hans-Achim Wagenknecht |
| Depositing User: | Dr. Gernot Deinzer |
| Date Deposited: | 10 Feb 2021 07:23 |
| Last Modified: | 10 Feb 2021 07:23 |
| URI: | https://pred.uni-regensburg.de/id/eprint/34308 |
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