| 联吡啶[3,2-a：2’,3-c]-7-氮杂-吩嗪铜(I)配合物的合成、表征及其与DNA的相互作用 |
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| 引用本文： | 高云燕,曹璐,欧植泽,陈晨,李嫕,王雪松.联吡啶[3,2-a：2’,3-c]-7-氮杂-吩嗪铜(I)配合物的合成、表征及其与DNA的相互作用[J].物理化学学报,2013,29(10):2162-2172. |
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| 作者姓名： | 高云燕 曹璐 欧植泽 陈晨 李嫕 王雪松 |
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| 作者单位： | 1.Key Laboratory of Space Applied Physics and Chemistry of the Ministry of Education, School of Science, Northwestern Polytechnical University, Xi'an 710072, P. R. China;2.Key Laboratory of Photochemical Conversion and Optoelectronic Materials, Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Beijing 100190, P. R. China |
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| 基金项目： | 国家自然科学基金(21073143);教育部“春晖计划”基金(Z2009-1-71002, Z2009-1-71006);西北工业大学基础研究基金(JC200822, JC20100239)及西北工业大学研究生创新基金资助项目 |
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| 摘 要： | 合成了邻菲罗啉衍生物联吡啶3,2-a:2',3'-c]-7-氮杂-吩嗪(dpapz)及其铜(I)配合物Cu(dpapz)2]PF6, 利用核磁共振氢谱(1H NMR), 傅里叶变换红外(FTIR)光谱, 高分辨质谱(HR ESI-MS)等对合成的化合物进行了表征.采用紫外-可见吸收光谱,荧光光谱, DNA熔解温度实验和循环伏安方法研究了dpapz和Cu(dpapz)2]PF6与小牛胸腺DNA(CT DNA)的相互作用. 配体dpapz与小牛胸腺DNA(CT DNA)作用时未观察到吸收峰红移并且减色效应较小(<30%), 且DNA熔解温度也上升较小(ΔTm=7.8 ℃), 说明dpapz以沟槽结合的方式与CT DNA相互作用. 而Cu(dpapz)2]PF6与CT DNA作用时, 可观测到较小的吸收峰红移(2-3 nm)和较大的减色效应(>50%), 同时DNA熔解温度上升较大(ΔTm=11.1 ℃), 表明Cu(dpapz)2]PF6以静电相互作用和部分扦插的方式与DNA结合. 溴乙锭(EB)荧光竞争实验和循环伏安实验进一步证实了这一结论. 配体dpapz和Cu(dpapz)2]PF6与DNA的结合常数分别为2.88×105和5.32×105 mol·L-1. 光照条件下, Cu(dpapz)2]PF6产生单重态氧的能力与dpapz相当, 但产生超氧负离子自由基的能力要弱于dpapz. 活性氧猝灭实验表明, 超氧负离子自由基、单重态氧和羟基自由基均参与了dpapz和Cu(dpapz)2]PF6对DNA的光损伤作用. Cu(dpapz)2]PF6对DNA的亲和性要高于对dpapz的, 使得Cu(dpapz)2]PF6对质粒DNA的光损伤效率明显强于dpapz.
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| 关 键 词： | 邻菲罗啉衍生物 Cu(I)配合物 DNA光损伤 活性氧 DNA作用模式 |
| 收稿时间： | 2013-06-20 |
| 修稿时间： | 2013-08-15 |
Synthesis and Characterization of a Cu(I) Complex of Dipyrido[3,2-a：2’,3’-c]-7-aza-phenazine and Its Interaction with DNA |
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| GAO Yun-Yan,CAO Lu,OU Zhi-Ze,CHEN Chen,LI Yi,WANG Xue-Song.Synthesis and Characterization of a Cu(I) Complex of Dipyrido[3,2-a：2’,3’-c]-7-aza-phenazine and Its Interaction with DNA[J].Acta Physico-Chimica Sinica,2013,29(10):2162-2172. |
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| Authors: | GAO Yun-Yan CAO Lu OU Zhi-Ze CHEN Chen LI Yi WANG Xue-Song |
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| Institution: | 1.Key Laboratory of Space Applied Physics and Chemistry of the Ministry of Education, School of Science, Northwestern Polytechnical University, Xi'an 710072, P. R. China;2.Key Laboratory of Photochemical Conversion and Optoelectronic Materials, Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Beijing 100190, P. R. China |
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| Abstract: | A 1,10-phenanthroline dipyrido3,2-a:2',3'-c]-7-aza-phenazine derivative (dpapz) and its Cu(I) complex Cu(dpapz)2]PF6 are prepared and characterized by proton nuclear magnetic resonance spectroscopy (1H NMR), Fourier transform infrared spectroscopy (FTIR), and high resolution electrospray ionization mass spectrometry (HR ESI-MS). The interactions of dpapz and Cu(dpapz)2]PF6 with calf thymus DNA (CT DNA) are studied by ultraviolet-visible spectroscopy (UV-Vis), fluorescence spectroscopy, DNA melting temperature, and cyclic voltammetry. When the ligand dpapz interacts with DNA, there is no red shift of the absorption peak and only a small hypochromic (<30%) effect on the absorption spectra. In addition, the interaction leads to a slight increase in the melting temperature of DNA (ΔTm=7.8 ℃). All the results indicate that groove binding is the primary interaction of dpapz with CT DNA. However, when Cu(dpapz)2]PF6 interacts with DNA, there is a red shift of the absorption peak (2-3 nm), a large hypochromic effect on the absorption spectrum (>50%), and a significant increase in the melting temperature of DNA (ΔTm=11.1 ℃), indicating that Cu(dpapz)2]PF6 electrostatically associates with DNA in a partial intercalation manner. The complexes of dpapz and Cu(dpapz)2]PF6 with DNA are further confirmed by ethidium bromide (EB) fluorescence assays and cyclic voltammetry. The association constants for dpapz and Cu(dpapz)2]PF6 with CT DNA are 2.88×105 and 5.32×105 mol·L-1, respectively. The yield of singlet oxygen produced by Cu(dpapz)2]PF6 is similar to that of dpapz, while the yield of superoxide anion radical for Cu(dpapz)2]PF6 is lower than that of dpapz. Active oxygen quencher experiments indicate that singlet oxygen, superoxide anion radicals, and hydrogen radicals all take part in the photocleavage of DNA by Cu(dpapz)2]PF6 and dpapz. However, Cu(dpapz)2]PF6 causes more photodamage of plasmid DNA than does dpapz, most likely because of its higher affinity for DNA. |
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| Keywords: | Phenanthroline derivative Cu(I) complex Photocleavage of DNA Active oxygen Mode of DNAinteraction |
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