Photoinduced electron transfer quenching of excited Ru(II) polypyridyls bound to DNA: the role of the nucleic acid double helix
Abstract
In the presence of double helical polynucleotides (sodium poly(dA-dT)-poly(dA-dT) or calf thymus DNA), the efficiency of oxidative or reductive electron transfer between photoexcited ruthenium(II) chelates Ru(tap)2(hat)^(2+) or Ru(phen)^(⅔+) (where tap =1,4,5,8-tetraazaphenanthrene, hat = 1,4,5,8,9,12-hexaazatriphenylene, and phen = 1,10-phenanthroline) and appropriate cationic quenchers (ethidium, Ru(NH3)3/6^+, methyl viologen, or M(phen)3/3^+, where M = Co, Rh, Cr) increases 1–2 orders of magnitude compared to the efficiency of the same quenching in microhomogeneous aqueous medium (k_q= 0.3-1.8 × 10^9 M's^(−1)). The enhancement is more pronounced when the binding constant of the quencher (10^3 < Kh < 10^6 M^(−1)) is large. Similar trends are found when the biopolymers are replaced by sodium poly(styrenesulfonate) (PSS). The accelerated electron transfer process is proposed to be due mainly to the effect of accumulation of the reagents in the electrostatic field of the polymer; if corrections for this effect are introduced (e.g. ratioing [quencher]/[polynucleotide]), the reaction rate becomes essentially independent of the polymer concentration. Based upon a model for electron transfer reaction of the complexes within a small cylindrical interface around the DNA helix, calculations of the bimolecular electron transfer rate constants are computed to be 10′ times smaller when the reactants are bound to the double-stranded polynucleotides and decreased mobility of the cationic species is apparent. The effect is less pronounced if a simpler polyelectrolyte (PSS) is employed. Emission lifetimes of the Ru(II) polypyridyls bound to the DNA (0.32–2μs, double exponential decays) are discussed as well.
Additional Information
© 1991 Pergamon Press. (Received 16 January 1991; accepted 16 April 1991) The authors gratefully acknowledge the NATO for a Scientific Research Grant (A.K.-D.), and the Spanish Ministry of Education and Science and the U.S. Government for a Fulbright Postdoctoral Fellowship (G.O.) under which this work was performed. They are also grateful to Professor J. Nasielski, F. de Buyl, and L. Jacquet for their gift of Ru(tap)_2(hat^(+2), and thank the NIH (GM33309) for its generous support. Additional support from NSF and AFOSR is acknowledged.Additional details
- Eprint ID
- 63974
- Resolver ID
- CaltechAUTHORS:20160126-113442705
- North Atlantic Treaty Organization (NATO)
- Ministerio de Educacion y Ciencia (MEC)
- Fulbright Scholar Program
- NIH
- GM33309
- NSF
- Air Force Office of Scientific Research (AFOSR)
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2016-01-26Created from EPrint's datestamp field
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2021-11-10Created from EPrint's last_modified field