带有位阻基团的钌多吡啶手性配合物与DNA键合及其光断裂DNA性质的研究

DNA-Binding and Photocleavage of Polypyridyl Chiral Ruthenium(Ⅱ) Complexes Containing Steric Hinderance Group

合成了钌多吡啶手性配合物的对映异构体Δ-Ru(bpy)2DMNP](ClO4)2与Λ-[Ru(bpy)2DMNP](C1O4)2(Δ-1与Λ-1,DMNP=4-咪唑并[4,5-f](1,10)-邻菲咯啉-2-N,N二甲基苯胺),Δ-[Ru(bpy)2(BOPIP)](ClO4)2与Λ-Ru(bpy)2(BOPIP)](ClO4)2(Δ-2与Λ-2,BOPIP=2-(4-丁氧基基苯基-)咪唑并[4,5-f](1,10)-邻菲咯啉),用元素分析、核磁共振及旋光仪对手性配合物结构进行了表征,通过电子吸收光谱、荧光光谱、粘度实验对手性配合物与CT-DNA相互作用的性质进行了研究。结果表明:两对Δ-型异构体均与CT-DNA以插入模式作用。在紫外光照下,两对对映异构体均能使质粒pBR322DNA断裂,但Λ-1型异构体比Δ-1型异构体断裂DNA效率更高,说明存在立体选择性,而Δ-2与Λ-2对DNA断裂无明显区别。

Two types of chiral polypyridyl ruthenium（Ⅱ） complexes Δ-Ru（bpy）2DMNP]（ClO4）2 and Λ-[Ru（bpy）2DMNP] （ClO4）2 （Δ-1 and Λ-1, DMNP=4-（1H-imidazo [4,5-f][1,10]phenanthrolin-2-yl）-N, N-dimethyl-benzenamine）, Δ-[Ru （bpy）2（BOPIP）]（ClO4）2 and Λ-Ru（bpy）2（BOPIP）]（ClO4）2（Δ-2 and Λ-2, BOPIP=2-（4-but oxyphenyl）-1H-imidazo[4,5-f] [1,10]phenanthroline）,have been synthesized. Their structures have been ascertained with elemental analysis, nuclear magnetic resonance spectra and polarimeter.The characteristics of the interaction of the optical isomers with CT-DNA were examined by Ultra-Vis absorption spectra,fluorescent spectra, and viscosity measurements. Experimental data indicate that all the enantiomers of these complexes bound to DNA through an intercalative mode. Upon irradiation at 365 nm,all four complexes have been found to efficiently photocleave plasmid pBR322 DNA. However Λ-1 is more efficient than Δ-1,which demonstrates enantioselective interaction of the optical isomers with plasmid pBR322 DNA.No obvious difference was found between Δ-2 and Λ-2 on photocleaving plasmid pBR322 DNA.