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DNA-Mediated Electron Transfer in Naphthalene-Modified Oligonucleotides

Tanaka, Makiko and Elias, Benjamin and Barton, Jacqueline K. (2010) DNA-Mediated Electron Transfer in Naphthalene-Modified Oligonucleotides. Journal of Organic Chemistry, 75 (8). pp. 2423-2428. ISSN 0022-3263. PMCID PMC2879047. http://resolver.caltech.edu/CaltechAUTHORS:20100517-152102648

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Abstract

Naphthalene-modified oligonucleotides have been synthesized and characterized with respect to electron transfer chemistry. Using the Sonogashira coupling reaction, naphthalene can be covalently anchored onto a modified uridine through an ethynyl linkage. This tethering allows for effective electronic coupling with the DNA bases, resulting in a significant red shift of the absorption bands of the naphthalenic chromophore. Modification with this chromophore does not appear to affect the overall stability and structure of the DNA. Upon selective irradiation of the naphthalene moiety at 340 nm, photoreduction of a distal electron trap, 5-bromouridine, embedded in the DNA base stack occurs. This DNA-mediated reduction from a distance was found to be significantly more efficient with substitution of 5-bromouridine toward the 5′-end than toward the 3′-end. These results support a general preference for electron transfer through DNA toward the 5′-end, irrespective of the donor. In addition, differences in efficiency of photoreduction through intrastrand and interstrand pathways are observed. For DNA-mediated reduction, as with DNA-mediated oxidation, significant differences in the charge transfer reaction are apparent that depend upon subtle differences in coupling into the DNA base stack.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/jo1000862DOIArticle
http://pubs.acs.org/doi/abs/10.1021/jo1000862PublisherArticle
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC2879047/PubMed CentralArticle
ORCID:
AuthorORCID
Barton, Jacqueline K.0000-0001-9883-1600
Additional Information:© 2010 American Chemical Society. Received January 19, 2010. Publication Date (Web): March 18, 2010. We are grateful to the NIH (GM49216) for financial support. M.T. thanks the Japan Society for the Promotion of Science for a postdoctoral fellowship.
Funders:
Funding AgencyGrant Number
NIHGM49216
Japan Society for the Promotion of Science (JSPS)UNSPECIFIED
PubMed Central ID:PMC2879047
Record Number:CaltechAUTHORS:20100517-152102648
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20100517-152102648
Official Citation:DNA-Mediated Electron Transfer in Naphthalene-Modified Oligonucleotides Makiko Tanaka, Benjamin Elias, Jacqueline K. Barton The Journal of Organic Chemistry 2010 75 (8), 2423-2428
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:18330
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:19 May 2010 15:53
Last Modified:25 Jan 2016 23:20

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