通过紫外-可见吸收光谱和荧光光谱滴定、稳态荧光猝灭以及盐效应实验研究了噻吩基钌配合物[Ru(bpy)2(Htip)]Cl2(1)、[Ru(Htip)2(dppz)]Cl2(2)、[Ru(Htip)3]Cl2(3)和[Ru2(bpy)4(H2bipt)]Cl4(4){bpy=2,2'-联吡啶;Htip=2-噻吩咪唑[4,5-f][1,10]邻菲咯啉;H2bipt=2,5-二(2-咪唑[4,5-f][1,10]邻菲咯啉)噻吩;dppz=二吡啶并[3,2-a:2',3'-c]吩嗪}与酵母RNA(yeast-RNA)的相互作用,并比较了该类配合物与yeast-RNA和小牛胸腺DNA(ct-DNA)的键合性质。结果表明,该类噻吩基钌配合物是较强的RNA嵌入试剂,其中配合物2和3的RNA键合强度大于其DNA键合强度;此系列配合物在低盐和高盐浓度时均能与RNA较强地结合,即使在100 mmol/L Na Cl条件下仍具有较大的RNA键合常数;配合物1与RNA键合时荧光强度下降,配合物2在水溶液中以及与RNA键合时几乎无荧光,而它们与DNA作用时荧光强度明显增大,显示出良好的区分RNA和DNA的荧光特性。
The interaction of thiophene-appended ruthenium complexes [Ru( bpy)2( Htip) ]Cl2( 1) [Ru( Htip)2( dppz) ]Cl2( 2),[Ru( Htip)3]Cl2( 3) and [Ru2( bpy)4( H2bipt) ]Cl4( 4) { bpy = 2,2'-bipyridine,Htip= 2-( thiophen-2-yl)-1H-imidazo[4,5-f][1,10]phenanthroline,H2 bipt = 2,5-bis[1,10]phenanthrolin[4,5-f]-imidazol-2-yl) thiophene,dppz = dipyrido[3,2-a: 2',3'-c]phenazine} with yeast-RNA had been investigated by UVVis and emission spectroscopy titrations,steady-state emission quenching and salt effect studies,and the RNA and calf thymus DNA( ct-DNA) binding properties of the complexes had also been compared. The results suggested that this kind of thiophene-containing complexes is the strong intercalators of RNA,and in particular,the RNA binding constants of complex 2 and 3 were obtained to be( 2. 48 ± 0. 02) × 10^7 L / mol and( 4. 04 ± 0. 04) × 10^7 L / mol,which are larger than their reported DNA binding constants and demonstrate the higher RNA binding affinity of the complexes than that of DNA. These complexes could bind to RNA with high strength not only at low salt concentration but also at high salt concentration,with the binding constants as large as( 1. 07 ± 0. 33) × 10^5,( 5. 62 ± 0. 19) ×10^6,( 2. 11 ± 0. 03) × 10^7 and( 3. 74 ± 0. 45) × 10^5 L / mol for complex 1,2,3 and 4 at the concentration of 100 mmol / L Na Cl,respectively. Notably,in contrast to the significant increase of emission intensities for DNA binding of the complex 1 and 2,the fluorescence intensity of 1 decreases evidently upon binding to RNA,and there is almost no fluorescence when 2 is free in aqueous solution or bound to RNA,which indicates that complex 1 and 2display favorable fluorescence recognition property between RNA and DNA.