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Automated Synthesis of 3‘-Metalated Oligonucleotides

Krider, Elizabeth S. and Rack, Jeffrey J. and Frank, Natia L. and Meade, Thomas J. (2001) Automated Synthesis of 3‘-Metalated Oligonucleotides. Inorganic Chemistry, 40 (16). pp. 4002-4009. ISSN 0020-1669. https://resolver.caltech.edu/CaltechAUTHORS:20170419-144840354

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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.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/ic010396vDOIArticle
http://pubs.acs.org/doi/abs/10.1021/ic010396vPublisherArticle
http://pubs.acs.org/doi/suppl/10.1021/ic010396vPublisherSupporting Information
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.
Funders:
Funding AgencyGrant Number
National Institute of Standards and Technology (NIST)70NANB5H1031
JPL67192
Caltech Beckman InstituteUNSPECIFIED
Issue or Number:16
Record Number:CaltechAUTHORS:20170419-144840354
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20170419-144840354
Official Citation:Automated Synthesis of 3‘-Metalated Oligonucleotides Elizabeth S. Krider, Jeffrey J. Rack, Natia L. Frank, and Thomas J. Meade Inorganic Chemistry 2001 40 (16), 4002-4009 DOI: 10.1021/ic010396v
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:76709
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:19 Apr 2017 22:03
Last Modified:03 Oct 2019 17:49

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