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Science 12 November 1993:
Vol. 262. no. 5136, pp. 1025 - 1029
DOI: 10.1126/science.7802858
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Articles
Science, Vol 262, Issue 5136, 1025-1029
Copyright © 1993 by American Association for the Advancement of Science
Long-range photoinduced electron transfer through a DNA helix
CJ Murphy,
MR Arkin,
Y Jenkins,
ND Ghatlia,
SH Bossmann,
NJ Turro,
and
JK Barton
Beckman Institute, California Institute of Technology, Pasadena 91125.
Rapid photoinduced electron transfer is demonstrated over a distance of greater than 40 angstroms between metallointercalators that are tethered to the 5' termini of a 15-base pair DNA duplex. An oligomeric assembly was synthesized in which the donor is Ru(phen)2dppz2+ (phen, phenanthroline, and dppz, dipyridophenazine) and the acceptor is Rh(phi)2phen3+ (phi, phenanthrenequinone diimine). These metal complexes are intercalated either one or two base steps in from the helix termini. Although the ruthenium-modified oligonucleotide hybridized to an unmodified complement luminesces intensely, the ruthenium-modified oligomer hybridized to the rhodium-modified oligomer shows no detectable luminescence. Time-resolved studies point to a lower limit of 10(9) per second for the quenching rate. No quenching was observed upon metallation of two complementary octamers by Ru(phen)3(2+) and Rh(phen)3(3+) under conditions where the phen complexes do not intercalate. The stacked aromatic heterocycles of the DNA duplex therefore serve as an efficient medium for coupling electron donors and acceptors over very long distances.
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