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Synthesis and Properties of Novel Oligonucleotide Conjugates
註釋The driving force dependence of photoinduced electron transfer dynamics in duplex DNA has been investigated for sixteen synthetic DNA hairpins in which an acceptor chromophore serves as a linker connecting two complementary oligonucleotide arms containing a single donor nucleobase located either adjacent to the linker or separated from the linker by two unreactive base pairs. The dynamics of charge separation and charge recombination have been determined by means of sub-picosecond time-resolved transient absorption spectroscopy and the results were analyzed using quantum mechanical Marcus theory. This analysis provides intimate details about electron transfer processes in DNA including the distance dependence of the electronic coupling between the acceptor and nucleobase donor and the solvent and nuclear reorganization energies.