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Electron transfer from guanosine to the lowest triplet excited state of 4-nitroindole through hydrogen-bonded complex
Journal of Photochemistry and Photobiology A: Chemistry ( IF 4.3 ) Pub Date : 2020-12-30 , DOI: 10.1016/j.jphotochem.2020.113106
Zhao Ye , Yong Du , Xinghang Pan , Xuming Zheng , Jiadan Xue

The photochemical reaction of 4-nitroindole and guanosine was studied with the transient absorption spectroscopy as guanine is an effective hole trap during the charge transfer in DNA, and 4-nitroindole is a universal base. Excitation of 4-nitroindole generates the lowest triplet excited state 4-nitroindole (3HN-NO2) within 10 ns in the quantum yield 0.41. 3HN-NO2 has increased basicity compared to its ground state. Consequently, its nitro group exhibits the hydrogen bond accepting ability. 3HN-NO2 can interact with guanosine (G) to form the hydrogen-bonded 3HN-NO2G complex with the rate constant k=(8.7 ± 0.3)×109 M−1⋅s−1. The hydrogen-bonded complex is identified based on the blue shift evolvement of the absorption maximum of 3HN-NO2 in alcoholic solutions. The reduction potential of 3HN-NO2 is Ered(3HN-NO2) = 1.23 V vs. SCE. The electron transfer occurs in the 3HN-NO2G complex and generates G+• and HN-NO2−• followed by the proton transfer from N1 and N2 of G producing radicals HN-NO2H, G(N1-H) and G(N2-H).



中文翻译:

电子通过氢键配合物从鸟苷转移到4-硝基吲哚的最低三重激发态

用鸟嘌呤是DNA电荷转移过程中的有效空穴陷阱,而4-硝基吲哚是通用碱,因此采用瞬态吸收光谱法研究了4-硝基吲哚和鸟嘌呤的光化学反应。4-硝基吲哚的激发在10 ns内产生最低的三重态激发态4-硝基吲哚(3 HN-NO 2),量子产率为0.41。3 HN-NO 2与基态相比增加了碱度。因此,其硝基具有氢键接受能力。3 HN-NO 2可以与鸟嘌呤(G)相互作用形成氢键结合的3 HN-NO 2 G络合物,速率常数k =(8.7±0.3)×109个中号-1 ⋅s -1。基于酒精溶液中3 HN-NO 2的最大吸收量的蓝移演变,确定了氢键配合物。3 HN-NO 2的还原电位为E red3 HN-NO 2)= 1.23 V vs. SCE。电子转移发生在3 HN-NO 2 G络合物中,并生成G +•和HN-NO 2- •,然后从G的N 1和N 2进行质子转移,产生自由基HN-NO 2 H ,G(N 1 -H)和G(N 2 -H)

更新日期:2020-12-30
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