高等学校化学学报 ›› 2019, Vol. 40 ›› Issue (1): 30-40.doi: 10.7503/cjcu20180370

• 无机化学 • 上一篇    下一篇

1,10-邻菲啰啉衍生物钌配合物的合成、 表征及与DNA和BSA的相互作用

赵雅晨1, 李季1, 张培培1, 刘姝娴1, 魏代娜1, 苏志1, 钱勇1, 王飞利2(), PeterJohnSadler3, 刘红科1()   

  1. 1. 南京师范大学化学与材料科学学院, 南京 210023
    2. 西北大学化工学院, 西安 710069
    3. Department of Chemistry, University of Warwick, Coventry CV47AL, UK
  • 收稿日期:2018-05-21 出版日期:2019-01-10 发布日期:2018-12-20
  • 作者简介:

    联系人简介:刘红科, 男, 博士, 教授, 博士生导师, 主要从事新型芳基钌、 锇抗癌配合物合成、 抗癌活性及抗癌机理方面的研究. E-mail: liuhongke@njnu.edu.cn;王飞利, 女, 副教授, 主要从事金属配合物的合成、 结构与生物活性方面的研究. E-mail:hgwfli@nwu.edu.cn

  • 基金资助:
    国家自然科学基金重点国际合作项目(批准号: 21420102002)、 国家自然科学基金(批准号: 21601088, 21771109, 21778033)、 江苏省自然科学基金(批准号: BE2013716, BK20171472)和江苏省六大人才高峰项目资助.

Synthesis, Characterization and DNA, BSA Interactions of Mononuclear Ruthenium Complexes with Modified 1,10-Phenanthrolines Ligands

ZHAO Yachen1, LI Ji1, ZHANG Peipei1, LIU Shuxian1, WEI Daina1, SU Zhi1, QIAN Yong1, WANG Feili2,*(), Peter John Sadler3, LIU Hongke1,*()   

  1. 1. School of Chemistry and Materials Science, Nanjing Normal University, Nanjing 210023, China
    2. School of Chemical Engineering, Northwestern University, Xi’an 710068, China;
    3. Department of Chemistry, University of Warwick, Coventry CV4 7AL, UK
  • Received:2018-05-21 Online:2019-01-10 Published:2018-12-20
  • Contact: WANG Feili,LIU Hongke E-mail:hgwfli@nwu.edu.cn;liuhongke@njnu.edu.cn
  • Supported by:
    † Supported by the Key International(Regional) Joint Research Program of National Natural Science Foundation of China(No. 21420102002), the National Natural Science Foundation of China(Nos. 21601088, 21771109, 21778033), the Natural

摘要:

通过2-(4-吡啶)-咪唑[4,5-f]-1,10-邻菲啰啉(L1)与[Ru(η6-cymene)(μ-Cl)Cl]2反应合成了3种新型芳基钌配合物, 并利用新配体2-(4-咪唑基苯基)咪唑[4,5-f]-1,10-邻菲啰啉(L2)与RuCl3反应合成了配合物4. 利用核磁共振波谱、 质谱等对配合物进行了表征. 通过紫外光谱和圆二色谱研究了配合物在缓冲溶液中的稳定性及与CT-DNA的相互作用, 利用荧光光谱研究了配合物与牛血清蛋白的作用, 用乌氏黏度计测试了配合物对DNA黏度的影响, 并通过荧光光谱、 凝胶电泳研究了配合物4在不同pH条件下的荧光响应及与pBR322 DNA的作用. 结果表明, 配合物通过嵌入的方式与DNA作用, 并对DNA的二级结构产生影响; 配合物1~4均可与牛血清蛋白的一个位点发生相互作用并使其发生静态荧光猝灭. 配合物4在光照条件下有活性氧生成, 可以使pBR322 DNA断裂并在酸性溶液中荧光增强.

关键词: 芳基钌配合物, 1,10-邻菲啰啉, DNA作用, BSA作用, 光断裂

Abstract:

Three novel arene-ruthenium complexes(1—3) were synthesized from 2-(4-pyridinyl)imidazo[4,5-f]-1,10-phenanthroline(L1) and [(η6-cymene)Ru(μ-Cl)Cl]2. A polypyridine-ruthenium complex(4) was synthesized from RuCl3 and 2-(4-(1H-imidazol-1-yl)phenyl)-1H-imidazo[4,5-f]-1,10-phenanthroline(L2). All the complexes were characterized by 1H NMR, elemental analysis and ESI-MS. UV-Vis, circular dichroism and fluorescence techniques were used to study the interactions between complexes 1—4 and calf thymus DNA(CT-DNA) or BSA, respectively. Viscosity measurements were carried out to clarify further the interaction mode of complexes 1—4 with DNA. In addition, the interactions of complex 4 with pBR322 DNA were studied by gel electrophoresis, and the pH-related fluorescence spectra of complex 4 were recorded in various pH solutions. The results show that these complexes could interact with DNA via intercalation and disturbing the secondary structure of DNA. The static quenching for complexes 1—4 were observed when these complexes were titrated with BSA protein. Only one binding site was observed between these complexes and BSA and the binding constants were calculated. Under the UV light(365 nm), complex 4 could generate 1O2 and cleave pBR322-DNA efficiently and its fluorescencewere enhanced more than 56% when the solution pH was changed from 11.37 to 1.74.

Key words: Ruthenium-arene complex, ,10-Phenanthroline, Interaction with DNA, Interaction with BSA, Photocleavage

中图分类号: