UV-Induced Proton Transfer between DNA Strands

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• 作者：Yuyuan Zhang ; Kimberly de La Harpe ; Ashley A. Beckstead ; Roberto Improta ; Bern Kohler
• 刊名：Journal of the American Chemical Society
• 出版年：2015
• 出版时间：June 10, 2015
• 年：2015
• 卷：137
• 期：22
• 页码：7059-7062
• 全文大小：323K
• ISSN：1520-5126

文摘

UV radiation creates excited states in DNA that lead to mutagenic photoproducts. Photoexcitation of single-stranded DNA can transfer an electron between stacked bases, but the fate of excited states in the double helix has been intensely debated. Here, photoinduced interstrand proton transfer (PT) triggered by intrastrand electron transfer (ET) is detected for the first time by time-resolved vibrational spectroscopy and quantum mechanical calculations. Long-lived excited states are shown to be oppositely charged base pair radical ions. In two of the duplexes, the base pair radical anions are present as tautomers formed by interstrand PT. Charge recombination occurs on the picosecond time scale preventing the accumulation of damaging radicals or mutagenic tautomers.