Dynamics of Intercalated Molecules in DNA
J. Phys. Chem. B, Vol. 107, No. 45, 2003 12517
(6.8 cm-1) of the zinc chlorin-C60 dyad with an edge-to-edge
distance (Ree) of 5.89 Å,42 which is much smaller than the V
value (230 cm-1) reported by Lewis et al.16b that is derived from
the driving force dependence of the dynamics of PET in hairpin-
forming bis(oligonucleotide) conjugates in which the acceptor
linker and donor nucleobases are located adjacent to each other.
They reported a smaller V value (17 cm-1) for π-stacked bridge-
mediated PET in which the acceptor linker and donor nucleo-
bases are separated by two base pairs.16b Harriman5 also reported
the V value (4.4 cm-1) for ET between an intercalated donor
and acceptor separated by three intervening base pairs. Thus,
the distance between Eth+ and the nearest-neighbor intercalator
in DNA may be more than twice the average stacking distance
of 3.4 Å. This estimation seems reasonable because the
intercalation of two intercalators into adjacent base pairs is
unlikely to occur because of the steric repulsion. However, the
exact geometry of two intercalated molecules in DNA has yet
to be clarified. In any case, the relatively small λ value (0.43
eV) indicates that electron transfer in DNA requires only a small
reorganization energy and thus DNA is an ideal environment
for efficient electron transfer.
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Acknowledgment. This work was partially supported by
Grants-in-Aid for Scientific Research on Priority Area (nos.
13440216 and 13031059) from the Ministry of Education,
Culture, Sports, Science and Technology, Japan.
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Supporting Information Available: Stern-Volmer plots
for the fluorescence quenching of Eth+ by p-benzoquinones,
SHACV for the reduction of p-benzoquinones, the UV-vis
spectral change of Eth+ in DNA in the presence of various
concentrations of AcrPri+, and decay time profiles of Eth•2+ in
the PET obtained by laser flash photolysis. This material is
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