Ru（bpy）3^2＋ -DNA体系的共振光散射光谱研究及其分析应用

研究了Ru(bpy)32 与脱氧核糖核酸(DNA)作用的共振光散射光谱。基于DNA对Ru(bpy)32 共振光散射的增强效应,建立了共振光散射法测定DNA的新方法。在最佳实验条件下,Ru(bpy)32 在373nm处的共振光散射增强与DNA的质量浓度呈线性关系,线性范围为0.04~3.2μg/mL,检出限为16ng/mL。应用于合成样品及实际样品中DNA的测定。     

Ru(phen)_2dppx~(2+)-SDBS-DNA体系共振瑞利散射光谱及其分析应用研究

在水溶液中,带正电荷的Ru(phen)2dppx2+在阴离子表面活性剂十二烷基苯磺酸钠(SDBS)的表面聚集后,产生很强的共振瑞利散射.由于Ru(phen)2dppx2+与DNA之间有较大的结合常数(KB≥106 L·5mol-1),DNA的加入会使体系中"光开关"与SDBS分离,散射光强度大大降低,且体系散射光的降低程度与DNA的浓度呈线性关系.据此建立了DNA的定量测定新方法.     

乙醇/Tris-水中Cu(Ⅱ)对SDS和DNA增强[Ru(bpy)2(dppz)]2+光致发光的调控

应用荧光光谱、荧光显微镜和伏安法研究了乙醇/水体系中Cu(Ⅱ)对十二烷基硫酸钠(SDS)和鱼精DNA增强[Ru(bpy)2(dppz)]2+(bpy=2,2′-联吡啶,dppz=邻联二吡啶[3,2-a:2′,3′-c]吩嗪)光致发光的调控。结果表明,在乙醇/三羟甲基氨基甲烷(Tris)-水(V乙醇∶VTris=1∶5)体系中,DNA和阴离子表面活性剂SDS均能增强[Ru(bpy)2(dppz)]2+的光致发光,其与[Ru(bpy)2(dppz)]2+间的键合常数分别为5.5×105和4.2×102L.mol-1;Cu(Ⅱ)离子能通过DNA和SDS介导的光诱导电子转移淬灭乙醇/水溶液中[Ru(bpy)2(dppz)]2+的光致发光,DNA介导的Stern-Volmer淬灭常数为2.0×105L.mol-1,远远大于SDS介导的淬灭常数(9.0×103L.mol-1)。此外,结合SDS、DNA和Cu(Ⅱ)对[Ru(bpy)2(dppz)]2+在铟锡氧化物(ITO)电极上发生的氧化还原反应的影响,进一步探讨了乙醇/Tris-水中Cu(Ⅱ)对SDS和DNA增强[Ru(bpy)2(dppz)]2+光致发光的调控机理。该研究有助于更好地理解DNA嵌入剂的发光和淬灭机制,为生物分子光开关的构建提供新思路。     

荧光探针Ru(phen)2(dppx)2+测定H1N1禽流感病毒DNA

利用荧光探针Ru(phen)2dppx2+与ssDNA作用时不产生荧光或荧光很弱,而与dsDNA作用时荧光增强的机理,将H1N1禽流感病毒ssDNA与其完全互补ssDNA杂交形成dsDNA实现Ru(phen)2dppx2+对H1N1禽流感病毒DNA特定序列（5’-CTA CCA TGC GAA CAA TTC AAC CGA CAC TGT T-3’）的定量检测。在优化的实验条件下,测定H1N1禽流感病毒 DNA的线性范围为9.3×10-10～7.4×10-8 mol/L,线性关系：y = 3.3829x + 8.3948,R2 =0.9982,检出限为5.3×10-10 mol/L。该方法具有操作简单,检测快速,灵敏度高和选择好等优点。     

纳米银粒子对[Ru(bpy)_3]~(2+)光谱学性质的影响及电解质效应

研究了[Ru(bpy)3]2+溶液中引入纳米银粒子的光谱学性质变化规律以及[Ru(bpy)3]2+与纳米银粒子所构成的溶液体系([Ru(bpy)3]2+-Ag)的电解质效应.研究结果表明,[Ru(bpy)3]2+吸附在纳米银粒子表面使纳米银粒子相互桥连形成规则的类链状网络聚集体.纳米银粒子造成[Ru(bpy)3]2+溶液荧光猝灭,且大尺寸的纳米银粒子引起的荧光猝灭程度较大.在[Ru(bpy)3]2+-Ag体系中引入电解质造成纳米银粒子不同程度的聚集和生长.电解质对纳米银聚集影响为:CaCl2MgCl2Ca(NO3)2KClKNO3.随着[Ru(bpy)3]2+-Ag体系中引入电解质含量的增加,溶液的荧光强度先降低而后又逐渐增强,直至达到定值,表明一定量的电解质可产生荧光猝灭释放效应.电解质对荧光强度影响顺序为:Ca(NO3)2CaCl2MgCl2KClKNO3.采用透射电子显微镜、紫外-可见吸收分光光度计和荧光分光光度计等手段从分子间相互作用和能量传输等方面初步探讨了纳米银粒子对表面吸附[Ru(bpy)3]2+溶液光谱学性质的影响机制以及电解质效应.     

Ru(bipy)_2(dppz)~(2+)与DNA相互作用的光谱研究

利用荧光和紫外可见吸收光谱研究了 Ru( bipy) 2 ( dppz) 2 +与 DNA之间的插入键合作用。结果表明 ,Ru( bipy) 2 ( dppz) 2 +是通过 dppz配体插入到 DNA的双螺旋结构中。而且 ,一定浓度的 Fe( CN) 4 - 6 和 Na Cl对 Ru( bipy) 2 ( dppz) 2 +- DNA复合物的荧光无猝灭作用 ,这一结果也证实了 Ru( bipy) 2 ( dppz) 2 +和 DNA之间的插入键合作用     

方波伏安法研究[Ru（bpy）2dppz]2+与DNA的相互作用

合成了含有嵌入配体二吡啶并[3,2-a:2′,3′-c]-吩嗪(dppz)的钌配合物二联吡啶二吡啶并[3,2-a;2′,3′-c]吩嗪钌([Ru(bpy)2dppz]2+),并对其结构和物理化学性质进行了表征。采用方波伏安法研究了[Ru(bpy)2dppz]2+与天然双链小牛胸腺DNA的相互作用,实验结果表明,[Ru(bpy)2dppz]2+配合物的嵌入配体会嵌入DNA的碱基对中,与DNA结合形成体积较大的"金属配合物-DNA"联合体,该联合体在电解质溶液中扩散速度较慢,导致溶液中游离的钌配合物分子减少,峰电流信号降低。计算得到[Ru(bpy)2dppz]2+与DNA的结合常数Ka=1.7×105 L/mol,结合位点n=0.84。     

钌(Ⅱ)的氮杂环配体配合物的CNDO/2理论研究

本文运用CNDO/2方法经SCF计算获得了钌(Ⅱ)配合物Ru(L)₃²⁺(其中L=bpy, bpm和bpz)，分别是2，2′-联吡啶，2，2′- 联嘧啶，2，2′- 联吡嗪)和Ru(bpy)₂(bqdi)²⁺(其中bqdi是邻二亚胺苯醌)的电子结构参数，并且从电子微观结构层次研究了它们的结构—性能关系。计算结果与实验事实相吻合。     

乙醇/Tris-水中Cu(Ⅱ)对SDS和DNA增强[Ru(bpy)2(dppz)]2+光致发光的调控

应用荧光光谱、荧光显微镜和伏安法研究了乙醇/水体系中Cu(Ⅱ)对十二烷基硫酸钠(SDS)和鱼精DNA增强[Ru(bpy)₂(dppz)]²⁺(bpy=2,2′-联吡啶, dppz=邻联二吡啶[3,2-a:2′,3′-c]吩嗪)光致发光的调控。结果表明, 在乙醇/三羟甲基氨基甲烷(Tris)-水 (V_乙醇:V_Tris=1:5)体系中, DNA和阴离子表面活性剂SDS均能增强[Ru(bpy)₂(dppz)]²⁺的光致发光, 其与[Ru(bpy)₂(dppz)]²⁺间的键合常数分别为5.5×10⁵和4.2×10² L·mol^-1;Cu(Ⅱ)离子能通过DNA和SDS介导的光诱导电子转移淬灭乙醇/水溶液中[Ru(bpy)₂(dppz)]²⁺的光致发光, DNA介导的Stern-Volmer淬灭常数为2.0×10⁵ L·mol^-1, 远远大于SDS介导的淬灭常数(9.0×10³ L·mol^-1)。此外, 结合SDS、DNA和Cu(Ⅱ)对[Ru(bpy)₂(dppz)]²⁺在铟锡氧化物(ITO)电极上发生的氧化还原反应的影响, 进一步探讨了乙醇/Tris-水中Cu(Ⅱ)对SDS和DNA增强[Ru(bpy)₂(dppz)]²⁺光致发光的调控机理。该研究有助于更好地理解DNA嵌入剂的发光和淬灭机制, 为生物分子光开关的构建提供新思路。     

钌(Ⅱ)多吡啶配合物与DNA相互作用的光切割与荧光性质研究

利用琼脂糖凝胶电泳法研究了钌(Ⅱ)多吡啶配位物[Ru(bpy)2(ODCIP)]2+(bpy:2,2'-联吡啶,ODCIP:含多个配位中心的多吡啶配体,3,4-二氯基-咪唑并[4,5-f][1,10]邻菲咯啉)对pBR322质粒DNA的光切割作用及其可能机理,并运用紫外可见吸收光谱、荧光光谱和琼脂糖凝胶电泳法研究了[Ru(bpy)2(ODCIP)]2+与Zn2+配位后与DNA的光谱性质和光切割作用.结果表明[Ru(bpy)2(ODCIP)]2+对DNA有较好的光切割作用,其机理可能是产生了超氧阴离子自由基和单线态氧.[Ru(bpy)2(ODCIP)]2+与Zn2+配位可能形成的双核配位物[Ru(bpy)2(ODCIP)Zn]4+与DNA也能进行插入结合,对DNA的光切割效果并没有明显增强。     

A bis(2,2′-Bipyridine) (Dipyrido[3, 2-a:2′ 3′-c]Phenazine-N4N5) Ruthenium(II)-Based Electrochemiluminescence Biosensor for Evaluation of DNA Damage

The electrochemiluminescence of bis(2, 2′-bipyridine) (dipyrido[3, 2-a:2′ 3′-c]phenazine-N₄N₅) ruthenium(II) ([Ru(bpy)₂(dppz)]²⁺) was used to monitor deoxyribonucleic acid (DNA) charge transfer with tri-n-propylamine as a coreactant. This system was used to measure damage to DNA induced by perfluorooctanoic acid. Fifteen-base pairs of double-stranded DNA with a thiol group at the 5′ end position were covalently bonded to a gold electrode. An electrochemiluminescence sensor was then constructed by incubating the modified gold electrode in [Ru(bpy)₂(dppz)]²⁺ solution for 30 min. For comparison, single-stranded DNA, well-matched double-stranded DNA, and single base-mismatched double-stranded DNA were assembled on the gold surface. The results showed that the electrochemiluminescence behavior of the DNA sensors were unique. The electrochemiluminescence decreased when the [Ru(bpy)₂(dppz)]²⁺-DNA ECL sensor was incubated in a perfluorooctanoic acid solution. The damage to DNA caused by perfluorooctanoic acid was monitored using a combination of DNA charge transfer theory and the interaction between DNA and [Ru(bpy)₂(dppz)]²⁺. The detection limit for perfluorooctanoic acid was 1 × 10^?12 mol/L. [Ru(bpy)₂(dppz)]²⁺ was shown to be a sensitive electrochemiluminescence sensor for the determination of DNA damage.     

A Novel Optical Properties of Molecular “Light Switch” and its Analytical Application

Because of the high affinity (Ka≥ 10^6 L mol^-1) between Ru(phen)2(dppz)^2 and DNA, the adding of DNA in the solution of Ru(phen)E(dppz)^2 -SDS makes the dissociation of Ru(phen)E(dppz)^2 -SDS, and results in decrease of the resonance light scattering (RLS) signals andincrease of the absorbance. Based on this, a novel method is proposed for DNA assay.     

Chemistry of ruthenium in N2P2X2 (X = Cl, Br) coordination sphere: Synthesis, characterization and reactivities

Reaction of 2-(phenylazo)pyridine (pap) with [Ru(PPh₃)₃X₂] (X = Cl, Br) in dichloromethane solution affords [Ru(PPh₃)₂(pap)X₂]. These diamagnetic complexes exhibit a weakdd transition and two intense MLCT transitions in the visible region. In dichloromethane solution they display a one-electron reduction of pap near − 0.90 V vs SCE and a reversible ruthenium(II)-ruthenium(III) oxidation near 0.70 V vs SCE. The [Ru^III(PPh₃)₂(pap)Cl₂]⁺ complex cation, generated by coulometric oxidation of [Ru(PPh₃)₂(pap)Cl₂], shows two intense LMCT transitions in the visible region. It oxidizes N,N-dimethylaniline and [Ru^II(bpy)₂Cl₂] (bpy = 2,2′-bipyridine) to produce N,N,N′,N′-tetramethylbenzidine and [Ru^III(bpy)₂Cl₂]⁺ respectively. Reaction of [Ru(PPh₃)₂(pap)X₂] with Ag⁺ in ethanol produces [Ru(PPh₃)₂(pap)(EtOH)₂]²⁺ which upon further reaction with L (L = pap, bpy, acetylacetonate ion(acac⁻) and oxalate ion (ox²⁻)) gives complexes of type [Ru(PPh₃)₂(pap)(L)]ⁿ⁺ (n = 0, 1, 2). All these diamagnetic complexes show a weakdd transition and several intense MLCT transitions in the visible region. The ruthenium(II)-ruthenium(III) oxidation potential decreases in the order (of L): pap > bpy > acac⁻ > ox²⁻. Reductions of the coordinated pap and bpy are also observed.     

Effects of Divalent Metal Ions on Electrochemiluminescence Sensor with Ru(bpy)32+ Immobilized in Eastman‐AQ Membrane

Different effects of divalent metal ions on electrochemiluminescence (ECL) sensor with Ru(bpy)₃²⁺ immobilized in Eastman‐AQ membrane were investigated. Mg²⁺, Ca²⁺ and Fe²⁺ can elevate the ECL of Ru(bpy)₃²⁺/proline; while metal ions that underwent redox reactions on the electrode such as Mn²⁺ and Co²⁺ presented intensive quenching effects on Ru(bpy)₃²⁺ ECL. Also, the quenching effect of Mn²⁺ on the ECL sensor with Ru(bpy)₃²⁺ immobilized in Eastman‐AQ membrane enhanced to about 30‐folds compared with the case that Ru(bpy)₃²⁺ was dissolved in phosphate buffer, and the enhanced quenching effects of Mn²⁺ were studied.     

DNA intercalating studies of [Ru(bpy)<Subscript>2</Subscript>HPIP]<Superscript>2+</Superscript> with intramolecular hydrogen bond ligand based on introduction of copper ion

The effects of copper ion on the interaction of [Ru(bpy)₂HPIP]²⁺(bpy = 2,2′-bipyridine, HPIP = 2-(2-hydroxyphenyl) imidazo [4,5-f] [1, 10] phenanthroline) with DNA have been investigated by electronic absorption spectroscopy and fluorescence spectroscopy. HPIP ligand of the complex with an intramolecular hydrogen bond can bind Cu²⁺ in the absence of DNA, as revealed by the absorbance and fluorescence decrease for [Ru(bpy)₂HPIP]²⁺. The resultant heterometallic complex binds to DNA via intercalation of HPIP into the DNA base pairs and its DNA-binding ability is stronger than [Ru(bpy)₂HPIP]²⁺ itself. The DNA bound [Ru(bpy)₂HPIP]²⁺ cannot bind Cu²⁺ at low Cu²⁺ concentration and the intramolecular hydrogen bond in HPIP is located inside the DNA helix. While the Cu²⁺ concentration is relative high, Cu²⁺ can quench the fluorescence of DNA bound [Ru(bpy)₂HPIP]²⁺. The quenching reason is proposed.     

双核钌(II)多吡啶配合物与酵母RNA的相互作用研究

用紫外-可见吸收光谱和荧光光谱滴定、稳态荧光淬灭和反向盐滴定实验研究了双核钌(II)配合物[(bpy)₂Ru(ebipcH₂)Ru(bpy)₂](ClO₄)₄ {bpy＝2,2'-联吡啶; ebipcH₂＝N-乙基-4,7-二(咪唑-[4,5-f]-(1,10-邻菲啰啉)-2-基)咔唑}与酵母RNA的相互作用. 结果表明该双核配合物以插入方式与酵母RNA作用, 在生理盐浓度下(≈150 mmol/L NaCl)该配合物与RNA的相互作用明显强于DNA.     

Chemistry of Ruthenium Polypyridine Complexes: IX. Nitro-Nitrosyl Equilibrium in cis-[Ru(2,2'-bpy)2(L)NO2]+ Complexes

Ruthenium(II) bisbipyridyl complexes cis-[Ru(bpy)₂(L)NO₂](BF₄) (bpy is 2,2'-bipyridyl) with 4-substituted pyridine ligands L = 4-(Y)py (Y = NH₂, Me, Ph, and CN) were obtained. The equilibrium constants of the reversible nitro-nitrosyl transition [Ru(bpy)₂(L)NO₂]⁺ + 2H⁺ [Ru(bpy)₂(L)NO]^{3 +} + H₂O were measured in solutions with pH 1.5-8.5 (ionic strength 0.4). The constants correlate with the protonation constants of free ligands 4-(Y)py.     

一种含吲哚咪唑基Ru(II)配合物的酸碱性质和与DNA相互作用的研究

合成了一个新的Ru(II)配合物[Ru(bpy)₂(H₂iip)](ClO₄)₂•5H₂O [bpy＝2,2'-联吡啶, H₂iip＝2-吲哚基-咪唑并[4,5-ƒ][1,10]-邻菲罗啉]. 通过酸碱滴定发射光谱测定了该配合物的表观电离常数; 用紫外可见光谱、荧光光谱、稳态荧光淬灭、溴化乙锭竞争键合、粘度测量和DNA裂解实验研究了配合物与DNA的相互作用性质. 结果表明配合物以经典的插入模式与DNA键合, 键合常数K_b＝(5.97±0.27)×10⁵ mol^－1•L (50 mmol/L NaCl).