反式阿魏酸钌配合物的合成、表征、荧光光谱及其与DNA/蛋白作用

Synthesis,Characterization,Fluorescence and Interactions with DNA/BSA Properties of Ruthenium Ferulate Complexes

对天然产物反式阿魏酸进行化学修饰,设计、合成了2种单核钌配合物[Ru(cym)(L)Cl]Cl(Ru⁃1)与[Ru(bpy)2(L)]Cl2(Ru⁃2)(cym=对伞花烃,bpy=2,2′-联吡啶,L=(E)-3-(4-hydroxy-3-methoxyphenyl)-N-((4′-methyl-(2,2′-bipyridin)-4-yl)methyl)acrylamide),通过核磁共振氢谱和碳谱、电喷雾质谱对配合物进行了结构表征。利用荧光、紫外-可见光谱等方法研究了配合物的溶解性和光学性质。配合物均具有良好的亲水性。Ru⁃2有良好的荧光性能,其发射波长达到近红外的631 nm,且可以在pH值为8~10之间实现响应。Ru⁃2还具有较高的单线态氧量子产率(Φ=0.70),有望成为一类高效的光敏剂。2种配合物都与CT-DNA发生嵌入作用(Kb分别为1.210×10^4和1.233×10^3 L·mol^-1);均与BSA有一个结合位点,使其荧光发生静态淬灭(Ka值分别为1.94×10^4,2.45×10^4)。

We synthesized two novel mononuclear ruthenium complexes,[Ru(cym)(L)Cl]Cl(Ru⁃1)and[Ru(bpy)2(L)]Cl2(Ru⁃2)(cym=cymene,bpy=2,2′-bipyridine,L=(E)-3-(4-hydroxy-3-methoxyphenyl)-N-((4′-methyl-(2,2′-bipyridin)-4-yl)methyl)acrylamide),with the modified natural product trans-ferulic acid.Their structures were determined by 1H NMR,13C NMR and ESI-MS techniques.Optical properties and lipophilicity of complexes were characterized by using the fluorescence and UV-visible spectra.The results suggested that both complexes exhibited high water solubility.Ru⁃2 showed good fluorescence performance with the maximum emission wavelength at 631 nm in the near infrared area and had pH responsive ability(pH=8~10).Additionally,Ru⁃2 exhibited high singlet oxygen quantum yield(Φ=0.70),which might be expected to become an efficient photosensitizer.Both of the complexes binded to CT-DNA through intercalation mode(Kb:1.210×10^4 L·mol^-1 for Ru⁃1;1.233×10^3 L·mol^-1 for Ru⁃2)and interacted with BSA with one site,causing static quenching of their fluorescence(Ka:1.94×10^4 for Ru⁃1;2.45×10^4 for Ru^⁃2).