title: Acceleration of Long-Range Photoinduced Electron Transfer through DNA by Hydroxyquinolines as Artificial Base Pairs.
abstract: The C-nucleoside based on the hydroxyquinoline ligand (Hq) is complementary to itself and forms stable Hq-Hq pairs in double-stranded DNA. These artificial Hq-Hq pairs may serve as artificial electron carriers for long-range photoinduced electron transfer in DNA, as elucidated by a combination of gel electrophoretic analysis of irradiated samples and time-resolved transient absorption spectroscopy. For this study, the Hq-Hq pair was combined with a DNA-based donor-acceptor system consisting of 6-N,N-dimethylaminopyrene conjugated to 2'-deoxyuridine as photoinducible electron donor, and methyl viologen attached to the 2'-position of uridine as electron acceptor. The Hq radical anion was identified in the time-resolved measurements and strand cleavage products support its role as an intermediate charge carrier. Hence, the Hq-Hq pair significantly enhances the electron hopping capability of DNA compared to natural DNA bases over long distances while keeping the self-assembly properties as the most attractive feature of DNA as a supramolecular architecture.
authors.affiliation: Institute of Organic Chemistry, Karlsruhe Institute of Technology (KIT), Fritz-Haber-Weg 6, 76131 Karlsruhe (Germany).
authors.forename: Effi
authors.initials: E
authors.lastname: Bätzner
authors.affiliation: Institute of Physical Chemistry, Karlsruhe Institute of Technology (KIT), Fritz-Haber-Weg 2, 76131 Karlsruhe (Germany).
authors.forename: Yu
authors.initials: Y
authors.lastname: Liang
authors.affiliation: Institute of Physical Chemistry, Karlsruhe Institute of Technology (KIT), Fritz-Haber-Weg 2, 76131 Karlsruhe (Germany).
authors.forename: Caroline
authors.initials: C
authors.lastname: Schweigert
authors.affiliation: Institute of Physical Chemistry, Karlsruhe Institute of Technology (KIT), Fritz-Haber-Weg 2, 76131 Karlsruhe (Germany). andreas.unterreiner@kit.edu.
authors.forename: Andreas-Neil
authors.initials: AN
authors.lastname: Unterreiner
authors.affiliation: Institute of Organic Chemistry, Karlsruhe Institute of Technology (KIT), Fritz-Haber-Weg 6, 76131 Karlsruhe (Germany). Wagenknecht@kit.edu.
authors.forename: Hans-Achim
authors.initials: HA
authors.lastname: Wagenknecht
mesh_terms: D020029:Base Pairing; D001483:Base Sequence; D004247:DNA / Q000737:chemistry*; D004583:Electrons; D006912:Hydroxyquinolines / Q000737:chemistry*; D008969:Molecular Sequence Data; D015394:Molecular Structure
chemical_list: D006912:Hydroxyquinolines; D004247:DNA
keywords: base pairs; electron transfer; oligonucleotides; photochemistry; transient absorption spectroscopy