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- W2023446739 abstract "A DNA system consisting of pyrene-modified oligonucleotides and nitrobenzoate (Nb)-modified DNA-binding tripeptides has been applied to study electron-transfer processes through the DNA−peptide interface. 5-(Pyren-1-yl)-2‘-deoxyuridine (Py-dU) has been used as the photoinducible charge generator. Upon excitation at 350 nm, a pyrene-like excited state (Py-dU)* is formed which undergoes an electron transfer yielding the charge-separated state which is the contact ion pair Py•+−dU•-. The subsequent electron shift from dU•- into the base stack competes with charge recombination and can be probed chemically by trapping the electron at the 5-bromo-2‘-deoxyuridine (Br-dU) group leading to strand cleavage which can be quantified by HPLC analysis. Several Nb-modified DNA-binding tripeptides influence these DNA-mediated electron-transfer processes as shown by fluorescence spectroscopy experiments. Fluorescence quenching can occur primarily through a reductive electron-transfer process in which the Nb group traps the electron thermodynamically from the contact ion pair Py•+−dU•-. Moreover, our results indicate that, once the negative charge has been trapped on the peptide, oxidative processes from Py•+ take place resulting in an enhanced and nonspecific strand degradation of the Py-dU-modified duplexes. The latter type of strand cleavage can be inhibited by the presence of tryptophane or tyrosine as part of the peptides. Most remarkably, DNA-binding tripeptides, which bear both the Nb and the tryptophan/tyrosine moiety, are able to trap both the negative and the positive charge from the contact ion pair Py•+−dU•-." @default.
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- W2023446739 date "2005-08-09" @default.
- W2023446739 modified "2023-09-23" @default.
- W2023446739 title "Electron Transfer Chemistry between DNA and DNA-Binding Tripeptides" @default.
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- W2023446739 doi "https://doi.org/10.1021/bi0504557" @default.
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