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在 UVA 激发 6-硫代鸟嘌呤时,对水溶液中单重态氧的直接观察和定量描述。

Direct observation and quantitative characterization of singlet oxygen in aqueous solution upon UVA excitation of 6-thioguanines.

机构信息

Department of Chemistry and Biochemistry, Jackson State University, Jackson, Mississippi 39217, USA.

出版信息

J Phys Chem B. 2011 Mar 3;115(8):1889-94. doi: 10.1021/jp109590t. Epub 2011 Feb 4.

Abstract

The incorporation of 6-thioguanine (6-TG) into DNA increases the risk of (1)O(2)-initiated skin cancer. We herein provide the first report on quantitative characterization of the photoactivity of 6-thioguanines including 6-TG and 6-thioguanosine. Time-resolved singlet oxygen luminescence was observed directly for the first time after UVA irradiation of 6-thioguanines in both CHCN(3) and aqueous solutions. Their photosensitization was characterized by the quantum yield of singlet oxygen production, showing a dramatic decrease over time from the initial 0.49-0.58 to zero. Experiments performed on both 6-TG and 6-thioguanosine did not show any significant difference in the quantum yield of singlet oxygen production, indicating that there was no potential participation of 7H- and 9H-tautomers. Our findings provide a primary basis for a better understanding of molecular events of thiopurine drugs in biological systems.

摘要

6-硫代鸟嘌呤(6-TG)掺入 DNA 会增加 (1)O(2)引发皮肤癌的风险。我们在此首次报道了定量表征包括 6-TG 和 6-硫代鸟苷在内的 6-硫代鸟嘌呤光活性的情况。在 CHCN(3)和水溶液中,UVA 辐照 6-硫代鸟嘌呤后,我们首次直接观察到了时间分辨的单线态氧发光。通过单线态氧产生的量子产率来表征其敏化作用,发现其随时间从初始的 0.49-0.58 急剧下降至零。在 6-TG 和 6-硫代鸟苷上进行的实验均未显示出单线态氧产生量子产率的任何显著差异,表明不存在 7H-和 9H-互变异构体的潜在参与。我们的研究结果为更好地理解生物体系中硫嘌呤药物的分子事件提供了初步依据。

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