Automated Synthesis of 3'-Metalated Oligonucleotides
Abstract
We report the first synthesis of a metallonucleoside bound to a solid support and subsequent oligonucleotide synthesis with this precursor. Large-scale syntheses of metal-containing oligonucleotides are achieved using a solid support modified with [Ru(bpy)_2(impy')]^(2+) (bpy is 2,2'-bipyridine; impy' is 2'-iminomethylpyridyl-2'-deoxyuridine). A duplex formed with the metal-containing oligonucleotide exhibits superior thermal stability when compared to the corresponding unmetalated duplex (Tm = 50 °C vs T_m = 48 °C). Electrochemical (E_(1/2) = 1.3 V vs NHE), absorption (λ_(max) = 480 nm), and emission (λ_(max) = 720 nm, τ = 44 ns, Φ = 0.11 × 10^(-3)) data for the ruthenium-modified oligonucleotides indicate that the presence of the oligonucleotide does not perturb the electronic properties of the ruthenium complex. The absence of any change in the emission properties upon duplex formation suggests that the [Ru(bpy)_2(impy)]^(2+) chromophore will be a valuable probe for DNA-mediated electron-transfer studies. Despite the relatively high Ru(III/II) reduction potential, oxidative quenching of photoexcited [Ru(bpy)_2(impy)]^(2+) does not lead to oxidative damage of guanine or other DNA bases.
Additional Information
© 2001 American Chemical Society. Received April 13, 2001. Publication Date (Web): June 30, 2001. We thank Harry B. Gray and Jay R. Winkler for helpful discussions. E.S.K. thanks Timothy Hubin and Pratip Bhattacharya for technical assistance. This work was supported by NIST (ATP) Award 70NANB5H1031, the Jet Propulsion Laboratory (JPL 67192), and the Beckman Institute Biological Imaging Center.Attached Files
Supplemental Material - ic010396v_s.pdf
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Additional details
- Eprint ID
- 76709
- Resolver ID
- CaltechAUTHORS:20170419-144840354
- National Institute of Standards and Technology (NIST)
- 70NANB5H1031
- JPL
- 67192
- Caltech Beckman Institute
- Created
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2017-04-19Created from EPrint's datestamp field
- Updated
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2021-11-15Created from EPrint's last_modified field