Direct measurement of hole transport dynamics in DNA

• Published in: Nature (London) 2000-07, Vol.406 (6791), p.51-53
• Main Authors: Lewis, Frederick D, Liu, Xiaoyang, Liu, Jianqin, Miller, Scott E, Hayes, Ryan T, Wasielewski, Michael R
• Format: Article
• Language: English
• Subjects: Base Pairing; Biological and medical sciences; Chemistry; Deoxyribonucleic acid; DNA; DNA - chemical synthesis; DNA - chemistry; Electrons; Fundamental and applied biological sciences. Psychology; Guanine - chemistry; Humanities and Social Sciences; letter; Mechanisms. Catalysis. Electron transfer. Models; Molecular biophysics; multidisciplinary; Nucleic Acid Conformation; Oxidation; Photochemicals; Photochemistry; Physical chemistry in biology; Science; Science (multidisciplinary); Spectrum Analysis; Stilbenes - chemistry; Transport processes
• ISSN: 0028-0836; 1476-4687
• DOI: 10.1038/35017524

Our understanding of oxidative damage to double helical DNA and the design of DNA-based devices for molecular electronics is crucially dependent upon elucidation of the mechanism and dynamics of electron and hole transport in DNA. Electrons and holes can migrate from the locus of formation to trap sites, and such migration can occur through either a single-step "superexchange" mechanism or a multistep charge transport "hopping" mechanism. The rates of single-step charge separation and charge recombination processes are found to decrease rapidly with increasing transfer distances, whereas multistep hole transport processes are only weakly distance dependent. However, the dynamics of hole transport has not yet been directly determined. Here we report spectroscopic measurements of photoinduced electron transfer in synthetic DNA that yield rate constants of ∼ 5 × 10 7 s-1 and 5 × 10 6 s-1, respectively, for the forward and return hole transport from a single guanine base to a double guanine base step across a single adenine. These rates are faster than processes leading to strand cleavage, such as the reaction of guanine cation radical with water, thus permitting holes to migrate over long distances in DNA. However, they are too slow to compete with charge recombination in contact ion pairs, a process which protects DNA from photochemical damage.