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Luminescence quenching by DNA-bound viologens: effect of reactant identity on efficiency and dynamics of electron transfer in DNA

Kelley, Shana O. and Orellana, Guillermo and Barton, Jacqueline K. (2000) Luminescence quenching by DNA-bound viologens: effect of reactant identity on efficiency and dynamics of electron transfer in DNA. Journal of Photochemistry and Photobiology B: Biology, 58 (2-3). pp. 72-79. ISSN 1011-1344. http://resolver.caltech.edu/CaltechAUTHORS:20160125-195239389

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Abstract

Photoinduced electron transfer from two intercalating photoactive donors, Ru(phen)_2dppz^(2+) and ethidium, to intercalating viologen acceptors of the N,N′-dialkyl-6-(2′-pyridiniumyl)phenanthridinium family has been investigated through steady-state and time-resolved luminescence quenching measurements. Efficient quenching of the emission from these donors bound to DNA is observed at low concentrations of acceptor (1–10 eq.), and in time-resolved emission experiments it is determined that electron transfer occurs on the nanosecond time scale. Furthermore, transient absorption measurements confirm that the quenching is the result of a charge-transfer process; upon photoreaction of intercalated Ru(phen)_2dppz^(2+) with a viologen acceptor, an intermediate with spectral properties resembling the expected charge-separated pair is observed. The quenching yields and kinetics obtained with this quencher are in marked contrast to those observed with these same donors paired with Rh(phi)_2bpy^(3+) as an acceptor. The differing efficiencies of electron transfer for these donor/acceptor pairs bound to DNA as compared to others previously described are discussed qualitatively in terms of the structural and electronic properties of the different reactants.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1016/S1011-1344(00)00106-8DOIArticle
http://www.sciencedirect.com/science/article/pii/S1011134400001068PublisherArticle
ORCID:
AuthorORCID
Kelley, Shana O.0000-0003-3360-5359
Barton, Jacqueline K.0000-0001-9883-1600
Additional Information:© 2000 Elsevier. Received 3 January 2000; accepted 25 August 2000. We are grateful to NIH (GM49216 to JKB, predoctoral traineeship to SOK) and DGICYT (PB95-0406 to GO) for financial support of this research. We also thank M.C. Gutierrez-Alonso for preparation of the viologen compounds.
Funders:
Funding AgencyGrant Number
NIHGM49216
NIH Predoctoral FellowshipUNSPECIFIED
Direction General de Investigacion Cientifica y Tecnica (DGICYT)UNSPECIFIED
Subject Keywords:Luminescence quenching; Viologens; Electron transfer; DNA
Record Number:CaltechAUTHORS:20160125-195239389
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20160125-195239389
Official Citation:Shana O Kelley, Guillermo Orellana, Jacqueline K Barton, Luminescence quenching by DNA-bound viologens: effect of reactant identity on efficiency and dynamics of electron transfer in DNA, Journal of Photochemistry and Photobiology B: Biology, Volume 58, Issues 2–3, November 2000, Pages 72-79, ISSN 1011-1344, http://dx.doi.org/10.1016/S1011-1344(00)00106-8. (http://www.sciencedirect.com/science/article/pii/S1011134400001068)
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:63953
Collection:CaltechAUTHORS
Deposited By: George Porter
Deposited On:26 Jan 2016 23:47
Last Modified:27 Apr 2017 22:55

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