期刊
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
卷 133, 期 37, 页码 14586-14589出版社
AMER CHEMICAL SOC
DOI: 10.1021/ja2072252
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资金
- National Science Foundation [0809483]
- Vietnam Education Foundation
- Division Of Chemistry
- Direct For Mathematical & Physical Scien [0809483] Funding Source: National Science Foundation
Redox-active enzyme cofactors derived from ribonucleotides have been called fossils of the RNA world, suggesting that early catalysts employed modified nucleo-bases to facilitate redox chemistry in primitive metabolism. Here, we show that the common oxidative damage product 8-oxo-7,8-dihydroguanine (OG), when incorporated into a DNA or RNA strand in proximity to a cyclobutane pyrimidine dimer, can mimic the function of a flavin in photorepair. The OG nucleotide acts catalytically in a mechanism consistent with that of photolyase in which the photo excited state of the purine donates an electron to a pyrimidine dimer to initiate bond cleavage; subsequent back electron transfer regenerates OG. This unusual example of one form of DNA damage, oxidation, functioning to repair another, photo-dimerization, may provide insight into the origins of prebiotic redox processes.
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