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  

Synthesis and Characterization of a Cu(I) Complex of Dipyrido[3,2-a:2',3-c]-7-aza-phenazine and Its Interaction with DNA

作　　者：高云燕[1] 曹璐[1] 欧植泽[1] 陈晨[1] 李嫕[2] 王雪松[2] 

机构地区：[1]西北工业大学理学院,空间应用物理与化学教育部重点实验室,西安710072 [2]中国科学院理化技术研究所,光化学转换与功能材料重点实验室,北京100190

出　　处：《物理化学学报》2013年第10期2162-2172,共11页Acta Physico-Chimica Sinica

基　　金：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);西北工业大学研究生创新基金资助项目~~

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]PF_6,利用核磁共振氢谱(1~H 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]PF_6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(ΔT_m=7.8°C),说明dpapz以沟槽结合的方式与CT DNA相互作用.而[Cu(dpapz)_2]PF_6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(ΔT_m=11.1°C),表明[Cu(dpapz)_2]PF_6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]PF_6与DNA的结合常数分别为2.88×105和5.32×105mol·L^(-1).光照条件下,[Cu(dpapz)_2]PF_6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]PF_6对DNA的光损伤作用.[Cu(dpapz)_2]PF_6对DNA的亲和性要高于对dpapz的,使得[Cu(dpapz)_2]PF_6对质粒DNA的光损伤效率明显强于dpapz.A 1,10-phenanthroline dipyrido[3,2-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 （tH 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 redshift 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 （△Tm=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 （△Tm=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× 10^5 and 5.32×10^5 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）=]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 th

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 

分 类 号：O641.4[理学—物理化学]