Intramolecular electrocatalysis of 8-oxo-guanine oxidation: secondary structure control of electron transfer in osmium-labeled oligonucleotides
| Autor: | Rebecca C. Holmberg, Patricia A. Ropp, H. Holden Thorp, Eric E Berg, Mark W. Grinstaff, Mark T. Tierney |
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| Rok vydání: | 2003 |
| Předmět: |
Phosphoramidite
Guanine Analytical chemistry Oligonucleotides Electrons Osmium Redox Catalysis Nucleobase Inorganic Chemistry Electron transfer Bipyridine chemistry.chemical_compound Crystallography chemistry Intramolecular force Electrochemistry Nucleic Acid Conformation Physical and Theoretical Chemistry Cyclic voltammetry Linker Chromatography High Pressure Liquid DNA Primers |
| Zdroj: | Inorganic chemistry. 42(20) |
| ISSN: | 0020-1669 |
| Popis: | A phosphoramidite containing Os(bpy)(3)(2+) (Os; bpy, 2,2'-bipyridine) with a three-carbon linker was synthesized and used to prepare oligonucleotides with the Os redox catalyst appended to the 5'-end. The electrogenerated Os(III) is capable of oxidizing 7,8-dihydro-8-oxo-guanine (8G), but 8G is not electrochemically reactive at indium tin oxide electrodes because of poor electrode kinetics for the direct reaction. The hairpin-forming oligonucleotide Os-5'-ATG TCA GAT TAG CAG GCC TGA CAT 8G was synthesized and characterized by thermal denaturation and native gel electrophoresis both in the hairpin form and when hybridized to its Watson-Crick complement. The redox potential in both forms of the appended Os(III/II) couple was 0.63 V (all potentials vs Ag/AgCl), which is identical to that for the free complex. The diffusion coefficients of the hairpin form (10.2 x 10(-)(7) cm(2)/s) and the duplex form (8.7 x 10(-)(7) cm(2)/s) were consistent with values expected from studies of noncovalently bound redox labels, which suggest that the measured diffusion coefficient should be that of the appended DNA molecule. The oligonucleotide was designed such that in the duplex form, the 8G is far from the Os(III/II) couple, but in the hairpin form, the 8G is situated close to the redox center. For the duplex form, cyclic voltammetry studies showed that mediated oxidation of the 8G nucleobase occurred only through bimolecular reaction of the electrogenerated Os(III) of one duplex with the 8G of another duplex. However, in the hairpin form, intramolecular electron transfer from 8G to Os(III) in the same molecule was apparent in both chronoamperometry and cyclic voltammetry. |
| Databáze: | OpenAIRE |
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