Photoinduced Electron Transfer Occurs between 2-Aminopurine and the DNA Nucleic Acid Monophosphates: Results from Cyclic Voltammetry and Fluorescence Quenching
journal contributionposted on 19.08.2010, 00:00 by Madhavan Narayanan, Goutham Kodali, Yangjun Xing, Robert J. Stanley
2-Aminopurine (2AP) is a fluorescent adenine analogue that is useful in part because its substantial fluorescence quantum yield is sensitive to base stacking with native bases in ss- and ds-DNA. However, the degree of quenching is sequence dependent and the mechanism of quenching is still a matter of some debate. Here we show that the most likely quenching mechanism in aqueous solution involves photoinduced electron transfer (PET), as revealed by cyclic voltammetry (CV) performed in aprotic organic solvents. These potentials were used with spectroscopic data to obtain excited-state reduction and oxidation potentials. Stern−Volmer (S−V) experiments using the native base monophosphate nucleotides (NMPs) rGMP, rAMP, rCMP, and dTMP were performed in aqueous solution to obtain quenching rate constants kq. The results suggest that 2AP* can act as either an electron donor or an electron acceptor depending on the particular NMP but that PET proceeds for all NMPs tested.
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cyclic voltammetryPhotoinduced Electron Transfer Occurssolutionphotoinduced electron transferelectron donorelectron acceptorfluorescence quantumCyclic Voltammetryadenine analoguespectroscopic dataDNA Nucleicbase monophosphate nucleotidesoxidation potentialsquenching rate constants kqPET proceedsCVNMP2 APquenching mechanism