含BODIPY的光敏型铜配合物的制备及与DNA的相互作用研究  

Preparation of photosensitive copper complex containing boron dipyrromethenes and its interaction with DNA

作　　者：熊惠娟 方霄 王宇静 王诗 周学文 王小波 XIONG Hui-juan;FANG Xiao;WANG Yu-jing;WANG Shi;ZHOU Xue-wen;WANG Xiao-bo(School of Pharmacy,Hubei University of Science and Technology,Xianning 437100,China)

机构地区：[1]湖北科技学院药学院,湖北咸宁437100

出　　处：《分子科学学报》2022年第6期513-520,共8页Journal of Molecular Science

基　　金：湖北省自然科学基金资助项目(2018CFB323);湖北科技学院药学重点学科专项资助项目(2019-20YZ21)。

摘　　要：设计合成了一个含BODIPY的化合物BA-DPA及其铜配合物BA-DPA-Cu(Ⅱ),通过质谱、核磁共振波谱对其进行了表征,并以X射线单晶衍射测定了BA的晶体结构.利用紫外-可见吸收光谱实验对比研究了BA-DPA和BA-DPA-Cu(Ⅱ)与CT-DNA的相互作用,并以琼脂糖凝胶电泳法探讨了它们对pBR322 DNA的切割活性.研究表明,BA-DPA-Cu(Ⅱ)相对于BA-DPA具有更强的CT-DNA结合能力,两者与CT-DNA作用均发生减色效应,Cu(Ⅱ)配合物的减色幅度更大.同时,BA-DPA-Cu(Ⅱ)对DNA的切割能力优于BA-DPA,在光照条件下能显著地将超螺旋pBR322切割成缺刻型和少量线型DNA.A boron dipyrromethenes(BODIPY,BA)-containing compound 2-pyridinaminel(BA-DPA) and its copper complex BA-DPA-Cu(Ⅱ) were designed and synthesized, then their structures were systematically characterized by means of mass spectroscopy(MS) and nuclear magnetic resonance(NMR). Moreover, the crystal structure of BA was determined by X-ray single crystal diffraction. It can be seen from the crystal structure that BA has a strong planar rigid structure. The planar aromatic ring of BA can be embedded in DNA base pairs when BA interacts with DNA, and the interaction between them comes from the π-π interaction between the delocalized π system of BA aromatic ring and the base π system. The interaction between BA-DPA/BA-DPA-Cu(Ⅱ) and CT-DNA was comparatively studied by UV-vis absorption spectrum method. The maximum absorption wavelength of BA-DPA is 520 nm, while the maximum absorption wavelength of BA-DPA-Cu(Ⅱ) is 498 nm when the complex is formed with Cu2+. Compared with BA-DPA, the blue shift is 22 nm. Additionally, the intensity of absorption peak increased obviously, because the heteroatom on BA-DPA enters the outer electron orbit of Cu2+metal ion, which makes the electron structure in BA-DPA recombined. The binding constants Kbwhich present the affinity of BA-DPA and BA-DPA-Cu(Ⅱ) toward CT-DNA were calculated and compared by Stern-Volmer formula. The linear equation of interaction between BA-DPA-Cu(Ⅱ) and CT-DNA is y=6.4×10-8x-2.65×10-9(R~2=0.98), the binding constant Kbis 24 L·mol-1. The linear equation of interaction between BA-DPA and CT-DNA is y=1.1×10-7x + 5.41×10-9(R~2=0.96), the binding constant Kbis 20 L·mol-1. Their cleavage activity on pBR322 DNA was investigated by agarose gel electrophoresis, the cleavage rates of BA-DPA and BA-DPA-Cu(Ⅱ) with pBR322 DNA were 10.7%, 45.5%, 56.4% and 83.1%, respectively, the cleavage efficiency of BA-DPA-Cu(Ⅱ) was better than that of BA-DPA. The results show that BA-DPA-Cu(Ⅱ) has stronger CT-DNA binding ability than BA-DPA. Both of them interact with

关 键 词：铜配合物 DNA切割 凝胶电泳 BODIPY 光敏剂 

分 类 号：O614[理学—无机化学]