Modulating Charge Transfer Kinetics along Poly Adenine: Chemical Modifications, Temperature, and Conformational Effects.

The charge transfer (CT) reactions in nucleic acids are crucial for genome damage and repair and nanoelectronics using DNA as a molecular conductor. Previous experimental and theoretical works underlined the significance of nucleic acid structural dynamics on CT kinetics, requiring models that incorporate the dynamics of the nucleic acid, solvents, and counterions. Here, we investigated hole transfer kinetics in poly adenine single and double strands at various temperatures and the rate enhancement due to adenine-to-7-deazaadenine mutation by means of a QM/MM approach. We found that the hole transfer rate in poly adenine double strands increases with temperature while the helix conformation is retained, whereas single strands exhibit the opposite thermal response. Additionally, the positive charge migrates more efficiently in poly-7-deazaadenine double strands. Our results, consistent with experimental data, suggest that a thermally induced hopping model can accurately describe CT kinetics in these sequences. The approach is transferable for studying CT reactions in other nucleic acid strands.