异咯嗪修饰富勒烯-聚丙烯酸的合成及其与DNA的相互作用  

Synthesis of Isoalloxazine Modified C_(60)-polypropylene Acid and Its Interaction with DNA

作　　者：王中丽[1] 高云燕[1] 欧植泽[1] 郭创龙[1] 李海霞[1] 金和林[1] 

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,陕西西安710072

出　　处：《影像科学与光化学》2011年第3期181-193,共13页Imaging Science and Photochemistry

基　　金：国家自然科学基金(21073143);教育部留学回国人员科研启动基金(N9YK0003;N9YK0005);西北工业大学基础研究基金(JC200822;JC20100239)资助项目

摘　　要：利用自由基聚合反应合成了聚丙烯酸修饰的富勒烯(C60-PAA),进一步通过酯化反应将核黄素类似物6,7-二甲基-9-(2′-羟乙基)-异咯嗪(DHIX)与C60-PAA共价连接,得到C60-PAA-DHIX.利用傅立叶红外光谱(FT-IR)、核磁共振氢谱(1HNMR)、紫外-可见吸收光谱(UV-Vis)、荧光光谱对产物的化学结构进行了表征.循环伏安法表明,C60-PAA-DHIX中富勒烯基团的第一还原电位要高于DHIX基团的第一还原电位.ESR实验表明C60-PAA-DHIX能与N,N-二甲基苯胺发生多步光诱导电子转移反应,即DHIX基团与N,N-二甲基苯胺发生光诱导电子转移生成DHIX负离子自由基(DHIX-.),DHIX-.能进一步将电子传递给富勒烯生成富勒烯负离子自由基.DNA熔解曲线、紫外-可见吸收光谱和荧光光谱结果表明,C60-PAA-DHIX通过沟槽结合与CTDNA作用,而C60-PAA与DNA的作用较弱.无氧条件下,C60-PAA-DHIX具有比C60-PAA更强的DNA光损伤能力.Poly（acrylic acid） conjugated fullerene（C60-PAA） is synthesized by free-radical polymerization.C60-PAA is covalently linked with riboflavin analogue 6,7-Dimethyl-9-（2′-hydroxyethyl）-isoalloxazine through esterification reaction,affording C60-PAA-DHIX.The products are characterized by Fourier transform infrared spectroscopy（FT-IR）,proton nuclear magnetic resonance（1HNMR）,UV-visible absorption spectroscopy（UV-Vis）,and fluorescence spectroscopy.Cyclic voltammetry results show that the first reduction potential of fullerene moiety is higher than that of DHIX moiety in C60-PAA-DHIX.ESR results indicate that multi-step photoinduced electron-transfer processes may occur between C60-PAA-DHIX and N,N-dimethyl aniline under irradiation.One-electron transfer from N,N-dimethyl aniline to excited-state DHIX induces the generation of DHIX-· radical,followed by electron transfer from the DHIX-· radical to C60,forming the corresponding anion radical of C60（C60-·）.The results obtained from DNA melting experiments,UV-Vis absorption and fluorescence spectra suggest that C60-PAA-DHIX could interact with CT DNA through groove binding mechanism.However,C60-PAA can only weakly interact with DNA.C60-PAA-DHIX exhibited stronger DNA photodamage ability on plasma DNA than C60-PAA under anaerobic condition.

关 键 词：富勒烯聚合物 异咯嗪 光诱导电子转移 沟槽结合 DNA光损伤 

分 类 号：O631.1[理学—高分子化学]