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Photoinduced Electron Transfer in DNA: Charge Shift Dynamics between 8-Oxo-Guanine Anion and Adenine (83 views)

Zhang Y, Dood J, Beckstead AA, Li X-B, Nguyen KV, Burrows CJ, Improta R, Kohler B

J Phys Chem B (ISSN: 1520-6106, 1520-5207, 1520-5207electronic), 2015; 119(24): 7491-7502.

Femtosecond time-resolved IR spectroscopy is used to investigate the excited-state dynamics of a dinucleotide containing an 8-oxoguanine anion at the 5′-end and neutral adenine at the 3′-end. UV excitation of the dinucleotide transfers an electron from deprotonated 8-oxoguanine to its γ-stacked neighbor adenine in less than 1 ps, generating a neutral 8-oxoguanine radical and an adenine radical anion. These species are identified by the excellent agreement between the experimental and calculated IR difference spectra. The quantum efficiency of this ultrafast charge shift reaction approaches unity. Back electron transfer from the adenine radical anion to the 8-oxguanine neutral radical occurs in 9 ps, or approximately 6 times faster than between the adenine radical anion and the 8-oxoguanine radical cation (Zhang, Y. et al. Proc. Natl. Acad. Sci. U.S.A. 2014, 111, 11612-11617). The large asymmetry in forward and back electron transfer rates is fully rationalized by semiclassical nonadiabatic electron transfer theory. Forward electron transfer is ultrafast because the driving force is nearly equal to the reorganization energy, which is estimated to lie between 1 and 2 eV. Back electron transfer is highly exergonic and takes place much more slowly in the Marcus inverted region. © 2015 American Chemical Society.

Affiliations ▼
*** IBB - CNR Affiliation

Department of Chemistry and Biochemistry, Montana State University, Bozeman, MT, United States

CNR-Consiglio Nazionale Delle Ricerche Istituto di Biostrutture e Bioimmagini (IBB-CNR), Via Mezzocannone 16, Napoli, Italy

School of Medicine and Biomedical Sciences, The University at Buffalo, SUNY, Buffalo, NY, United States

Details ▼
Impact factor: 3.187, 5-year impact factor: 3.265

Paper type: Journal Article,

Keywords: Electron Transitions, Excited States, Nucleotides, Adenine Radicals, Back Electron Transfer, Excited-State Dynamics, Femtosecond Time-Resolved, Non-Adiabatic Electron Transfer Theory, Photo-Induced Electron Transfer, Reorganization Energies, Free Radical Reactions,

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7 Records (6 excluding Abstracts and Conferences).
Total impact factor: 30.158 (26.992 excluding Abstracts and Conferences).
Total 5-year impact factor: 29.489 (26.347 excluding Abstracts and Conferences).

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