Remote control of charge transport and chiral induction along a DNA-metallohelicate
| Autor: | Mohammad S. Askari, Hanadi F. Sleiman, Christophe Lachance-Brais, Violeta Toader, Felix J. Rizzuto |
|---|---|
| Rok vydání: | 2019 |
| Předmět: |
Guanine
chemistry.chemical_element DNA 02 engineering and technology 010402 general chemistry 021001 nanoscience & nanotechnology 01 natural sciences Redox Copper 0104 chemical sciences Ion Metal Crystallography chemistry.chemical_compound chemistry visual_art visual_art.visual_art_medium Nucleic Acid Conformation General Materials Science Chemical stability A-DNA 0210 nano-technology Chelating Agents |
| Zdroj: | Nanoscale. 11:11879-11884 |
| ISSN: | 2040-3372 2040-3364 |
| DOI: | 10.1039/c9nr03212f |
| Popis: | Herein we present a new strategy to achieve chiral induction and redox switching along the backbone of metallohelicate architectures, wherein a DNA duplex directs the handedness and charge transport properties of a metal–organic assembly more than 60 bonds away (a distance of >10 nm). The quantitative and site-specific binding of copper(I) ions to DNA-templated coordination sites imparts enhanced thermodynamic stability to the assembly, while the DNA duplex transfers its natural right-handed helicity to the proximal and distal metal centers of the helicates. When copper(II) ions are employed instead of copper(I) ions, spontaneous DNA-mediated reduction occurs, which we propose is followed by a slower change in coordination environment (from pentacoordinate CuII to tetrahedral CuI) to generate copper(I) helicates. We demonstrate that the reduction of the adjacent and distal bis-phenanthroline sites is dependent on their proximity to DNA guanine bases (which act as the electron source). The kinetics of helical charge transport can thus be tuned based on guanine-CuII separation, resulting in a sequence- and distance-dependent redox switch that transfers electronic information from DNA to multiple linearly-arranged metal centers. |
| Databáze: | OpenAIRE |
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