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Rates of DNA-Mediated Electron Transfer Between Metallointercalators

Arkin, M. R. and Stemp, E. D. A. and Holmlin, R. E. and Barton, J. K. and Hörmann, A. and Olson, E. J. C. and Barbara, P. F. (1996) Rates of DNA-Mediated Electron Transfer Between Metallointercalators. Science, 273 (5274). pp. 475-480. ISSN 0036-8075. doi:10.1126/science.273.5274.475. https://resolver.caltech.edu/CaltechAUTHORS:20141211-093844438

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Abstract

Ultrafast emission and absorption spectroscopies were used to measure the kinetics of DNA-mediated electron transfer reactions between metal complexes intercalated into DNA. In the presence of rhodium(III) acceptor, a substantial fraction of photoexcited donor exhibits fast oxidative quenching (>3 × 10^(10) per second). Transient-absorption experiments indicate that, for a series of donors, the majority of back electron transfer is also very fast (∼10^(10) per second). This rate is independent of the loading of acceptors on the helix, but is sensitive to sequence and π stacking. The cooperative binding of donor and acceptor is considered unlikely on the basis of structural models and DNA photocleavage studies of binding. These data show that the DNA double helix differs significantly from proteins as a bridge for electron transfer.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1126/science.273.5274.475DOIArticle
http://www.sciencemag.org/content/273/5274/475PublisherArticle
http://www.jstor.org/stable/2890511JSTORArticle
ORCID:
AuthorORCID
Stemp, E. D. A.0000-0003-2098-4214
Barton, J. K.0000-0001-9883-1600
Additional Information:© 1996 American Association for the Advancement of Science. 22 November 1995; Accepted 6 May 1996. We are grateful to NIH (GM49216 to J.K.B.) and NSF (CHE-9304373 to P.F.B.) for financial support. We also thank NSF for predoctoral support of M.R.A. and R.E.H., and the American Cancer Society for postdoctoral support of E.D.A.S. We are also grateful to N. J. Turro for helpful discussions and to the reviewers for thoughtful comments.
Funders:
Funding AgencyGrant Number
NIHGM49216
NSFCHE-9304373
American Cancer SocietyUNSPECIFIED
Issue or Number:5274
DOI:10.1126/science.273.5274.475
Record Number:CaltechAUTHORS:20141211-093844438
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20141211-093844438
Official Citation:Arkin, M. R., Stemp, E. D. A., Holmlin, R. E., Barton, J. K., Hörmann, A., Olson, E. J. C., & Barbara, P. F. (1996). Rates of DNA-Mediated Electron Transfer Between Metallointercalators. Science, 273(5274), 475-480. doi: 10.1126/science.273.5274.475
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:52585
Collection:CaltechAUTHORS
Deposited By: Joanne McCole
Deposited On:11 Dec 2014 21:29
Last Modified:10 Nov 2021 19:42

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