Structural fluctuations and excitation transfer between adenine and 2-aminopurine in single-stranded deoxytrinucleotides.
Steady-state fluorescence measurements on the deoxytrinucleotides (5')dTp2APpA(3') and (5')dAp2APpA(3') show a temperature-dependence and a viscosity-dependence for energy transfer that qualitatively differ from those seen in our previous study of charge transfer (CT) in these systems. Time-resolved anisotropy studies and molecular dynamics simulations are presented that provide a detailed characterization of the structural dynamics of these systems and how these fluctuations modulate the electronic interaction between 2AP and its neighbors. To gain quantitative insight into the interplay of conformational fluctuations and stacking-induced energy transfer, we present results from a new hybrid quantum-classical simulation method for computing the A --> 2AP energy transfer rate that makes use of the full three-dimensional nature of the donor and acceptor transition densities. Analysis of the results shows that the standard transition dipole-transition dipole approximation for the Coulombic coupling substantially overestimates the transfer rate and that the nearest neighbor energy transfer from adenine to 2AP occurs on a much faster time scale than that for CT. This suggests that, unlike the CT dynamics where conformational "gating" plays a critical role, the large amplitude fluctuations that modulate the process are largely "frozen" out on the energy transfer time scale.
Jean
John M
JM
Department of Biochemistry and Molecular Biophysics, Washington University School of Medicine, St. Louis, Missouri 63108, USA. jjean@wanda.wustl.edu
Krueger
Brent P
BP
D015075:2-Aminopurine / Q000737:chemistry*; D000225:Adenine / Q000737:chemistry*; D004277:DNA, Single-Stranded / Q000737:chemistry*; D004735:Energy Transfer; D008956:Models, Chemical; D015394:Molecular Structure; D013696:Temperature; D013997:Time Factors
D004277:DNA, Single-Stranded; D015075:2-Aminopurine; D000225:Adenine