(294a) Computational Electrochemistry of DNA: Effect of Lithium

The general electrochemistry of deoxyribose nucleic acid (DNA) is studied using first-principles computational methods. For developing a systematic approach for analysis of its electrochemical capabilities, DNA is divided into three structural units of interest: the nucleobase, the deoxyribose sugar, and the phosphate group. Through this parted approach, in studying nucleobases, nucleosides, and nucleotides as separate species, it was possible to elucidate each contributive effect. As one of the key insights into electrochemistry, reduction potentials were pursued, via density functional theory (DFT) modeling with PBE0/6-31G**+ calculations. Furthermore, given that solvents are often involved in electrochemical applications, the effect of solvation on the reduction potential of DNA is characterized using implicit solvent model. From this study, we find that the reduction potential is affected by the solvation through conformational change. From this study, new insights are offered on the relationship between chemical structures and redox properties in DNA, promoting fundamental understanding of the electrochemistry for biological molecular materials.