The mechanism and the distance dependence of the photoinduced oxidation of guanine in DNA duplexes containing a covalently attached, selectively intercalated acridine derivative as a hole injecting chromophore have been investigated by means of femtosecond time-resolved absorption spectroscopy. The observed steep distance dependence is caused not solely by a decrease in electronic coupling, but also by a concomitant increase in reorganization energy with increasing distance. Additional experiments were performed on the complex between an engineered ligand-binding protein and fluorescein. The results underline the value of time-resolved spectroscopy for the elucidation of excited-state quenching mechanisms in complex biological systems.
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The mechanism and the distance dependence of the photoinduced oxidation of guanine in DNA duplexes containing a covalently attached, selectively intercalated acridine derivative as a hole injecting chromophore have been investigated by means of femtosecond time-resolved absorption spectroscopy. The observed steep distance dependence is caused not solely by a decrease in electronic coupling, but also by a concomitant increase in reorganization energy with increasing distance. Additional experimen...
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