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Ethidium bromide (EB) and acridine orange (AO) in the complexes with DNA in aqueous solution were studied using variety of spectroscopy techniques: emission up-conversion, absorption pump-probe, flashphotolysis, steady-state luminescence, and circular dichroism (CD). Combination of the methods allowed to detect oxidized form of ethidium and to associate this with a fast 10 ps component observed in the upconversion experiments. Thus, a photoinduced electron transfer from a small fraction of the dyes to the DNA bases was concluded. It suggests that those DNA sites have a redox potential higher than -0.9 V (an upper limit for the excited-state oxidation potential of ethidium), while the redox potential of the most affinic DNA bases, thymine and cytosine in water, is -1.09 V. It is proposed that certain conformations of the stacked bases have low-lying electronic orbitals. The involvement of such low-lying electronic levels in the processes of electron transfer through DNA stack is suggested. The results obtained by the pump-probe experiments for the AO-DNA system and by the CD measurements for the EB-DNA complex point at a delocalization of the electronic excitation over the neighboring dyes separated by two base pairs, i.e., 10 Å, in the DNA stack.
Original language | English |
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Pages (from-to) | 535-541 |
Number of pages | 7 |
Journal | Journal of Physical Chemistry B |
Volume | 105 |
Issue number | 2 |
DOIs | |
State | Published - 18 Jan 2001 |
ID: 76775182