甲基百里酚蓝-钐(III)配合物与鲱鱼精DNA的相互作用

在pH＝7.25的Tris-HCl缓冲溶液中, 以中性红(NR)作为光谱探针, 采用UV光谱、FS光谱、粘度等方法研究了甲基百里酚蓝(MTB)与稀土金属离子钐[Sm(III)]形成的配合物Sm(III)(MTB)₂与鲱鱼精DNA的作用机制. 确定了Sm(III)(MTB)₂与鲱鱼精DNA之间有嵌插作用方式存在, 说明Sm(III)(MTB)₂金属配合物能使鲱鱼精DNA的功能产生一定影响.     

甲基百里酚蓝-钐(Ⅲ)配合物与鲱鱼精DNA的相互作用

在pH=7.25的Tris-HCl缓冲溶液中,以中性红(NR)作为光谱探针,采用UV光谱、FS光谱、粘度等方法研究了甲基百里酚蓝(MTB)与稀土金属离子钐[Sm(Ⅲ)]形成的配合物Sm(Ⅲ)(MTB)2与鲱鱼精DNA的作用机制.确定了Sm(Ⅲ)(MTB)2与鲱鱼精DNA之间有嵌插作用方式存在,说明Sm(Ⅲ)(MTB)2金属配合物能使鲱鱼精DNA的功能产生一定影响.     

Sm(Ⅲ)(MTB)2配合物与DNA作用的光谱法研究

The interaction between Sm(Ⅲ)(MTB)₂ complex and Herring Sperm DNA has been studied by UV-Vis spectral, Fluorescence spectral in buffer solution of Tris-HCl (pH=7.25) using Neutral Red (NR) as a probe. The intercalation and electrostatic manner are confirmed to be the two major modes for interaction between Sm(Ⅲ)(MTB)₂ complex and Herring Sperm DNA. The balance constant of Sm(Ⅲ)(MTB)₂ rare earth metal complex and Herring Sperm DNA is K=4.10 × 10⁴ L·mol^-1. The results indicate that biological functions of Herring Sperm DNA are changed to a certain extend due to the interaction between Sm(Ⅲ)(MTB)₂ rare earth metal complex and Herring Sperm DNA.     

TiO2纳米颗粒对钌(II)三联吡啶配合物光损伤小牛胸腺DNA能力的影响

由于极短的激发态寿命, 钌(II)三联吡啶配合物对脱氧核糖核酸(DNA)的光损伤能力低下. 设计合成了三个钌(II)三联吡啶配合物[Ru(ttp)(tpy)]^2＋ (1), [Ru(ttp-COOH)(tpy)]^2＋ (2)和[Ru(ttp-COOH)(tpy-pyr)]^2＋ (3), 其中tpy为2,2':6',2"-三联吡啶, ttp为4′-(4-甲苯基)-2,2':6',2"-三联吡啶, ttp-COOH为4′-(4-羧基苯基)-2,2':6',2"-三联吡啶, tpy-pyr为4'-(1-芘基)-2,2':6',2"-三联吡啶. 比较了TiO₂纳米颗粒对它们光损伤小牛胸腺DNA的影响. 发现TiO₂纳米颗粒在空气和氩气条件下均可显著提高配合物3光损伤DNA的能力. TiO₂纳米颗粒和配合物3间的光诱导电子转移作用及其该作用生成的钌(III)物种可能是促进配合物3对DNA光损伤的主要原因.     

TiO2纳米颗粒对钌(II)三联吡啶配合物光损伤小牛胸腺DNA能力的影响

由于极短的激发态寿命, 钌(II)三联吡啶配合物对脱氧核糖核酸(DNA)的光损伤能力低下. 设计合成了三个钌(II)三联吡啶配合物[Ru(ttp)(tpy)]^2＋ (1), [Ru(ttp-COOH)(tpy)]^2＋ (2)和[Ru(ttp-COOH)(tpy-pyr)]^2＋ (3), 其中tpy为2,2':6',2"-三联吡啶, ttp为4′-(4-甲苯基)-2,2':6',2"-三联吡啶, ttp-COOH为4′-(4-羧基苯基)-2,2':6',2"-三联吡啶, tpy-pyr为4'-(1-芘基)-2,2':6',2"-三联吡啶. 比较了TiO₂纳米颗粒对它们光损伤小牛胸腺DNA的影响. 发现TiO₂纳米颗粒在空气和氩气条件下均可显著提高配合物3光损伤DNA的能力. TiO₂纳米颗粒和配合物3间的光诱导电子转移作用及其该作用生成的钌(III)物种可能是促进配合物3对DNA光损伤的主要原因.     

新型三齿多吡啶钴(II)、钌(II)配合物的合成、表征及其与DNA的作用研究

合成了两种新型三齿多吡啶钴(II)和钌(II)的混配配合物[Co(TolylTPy)(H₂Bzimpy)]Cl₂ [TolylTPy＝4'-对甲基苯 基-2,2':6',2'-三联吡啶, H₂Bzimpy＝2,6-二(苯并咪唑-2)吡啶] (A)和Ru(TolylTPy)(Bzimpy) (B). 用元素分析, IR, ¹H NMR等对它们进行了表征, 测定了配合物B的晶体结构, 用电子吸收光谱、荧光光谱等研究了配合物与小牛胸腺DNA(CTDNA)的相互作用及其对pBR322 DNA的断裂作用. 结果表明, 配合物A和B与CTDNA的作用属静电结合, 凝胶电泳实验说明配合物A在310 nm光辐射15 min, 可使超螺旋pBR322 DNA断裂为开环缺口型和线型DNA.     

新型三齿多吡啶钴(II)、钌(II)配合物的合成、表征及其与DNA的作用研究

合成了两种新型三齿多吡啶钴(II)和钌(II)的混配配合物[Co(TolylTPy)(H₂Bzimpy)]Cl₂ [TolylTPy＝4'-对甲基苯 基-2,2':6',2'-三联吡啶, H₂Bzimpy＝2,6-二(苯并咪唑-2)吡啶] (A)和Ru(TolylTPy)(Bzimpy) (B). 用元素分析, IR, ¹H NMR等对它们进行了表征, 测定了配合物B的晶体结构, 用电子吸收光谱、荧光光谱等研究了配合物与小牛胸腺DNA(CTDNA)的相互作用及其对pBR322 DNA的断裂作用. 结果表明, 配合物A和B与CTDNA的作用属静电结合, 凝胶电泳实验说明配合物A在310 nm光辐射15 min, 可使超螺旋pBR322 DNA断裂为开环缺口型和线型DNA.     

配体形状对多吡啶铜(Ⅱ)配合物与DNA作用的影响

合成了一系列含有平面配体的Cu(Ⅱ)多吡啶配合物[Cu(IP)₂]²⁺、[Cu(PIP)₂]²⁺、[Cu(DPPZ)₂]²⁺和[Cu(HPIP)₂]²⁺，用吸收光谱、CD光谱和粘度等方法研究了这些配合物与小牛胸腺DNA的作用。结果表明配体上的取代基及配体的平面性对这些四面体配合物与DNA的结合强弱产生一定的影响。[Cu(DPPZ)₂]²⁺与DNA的结合较强，而[Cu(HPIP)₂]²⁺与DNA的结合较弱。CD光谱显示配合物[Cu(DPPZ)₂]²⁺、[Cu(PIP)₂]²⁺和[Cu(HPIP)₂]²⁺的加入会导致DNA的CD光谱减弱。而[Cu(IP)₂]²⁺的加入则会使DNA的CD光谱增强。同时，[Cu(IP)₂]²⁺与DNA结合后，还会引起一定程度的DNA构型转换，即DNA从B型转换成Z型。     

钯(Ⅱ)三元配合物稳定性及其与DNA作用研究

合成了[Pd(bipy)(DL-gly)]Cl•2H₂₂O(2)两个钯三元配合物. 配合物１和２的稳定常数对数值lgβ分别为13.81和13.71, 表征常数ΔlgK、lgX高于统计值, 表明在配合物分子内存在d-p π电子协同效应. 紫外光谱、荧光光谱结果表明, 配合物１和２与鱼精DNA主要以插入方式键合, 键合常数分别为2.37×10⁶(1)和4.57×10⁶(2). CD光谱图也显示, 配合物与DNA分子之间发生了作用. 质粒pBR322 DNA的凝胶电泳图表明, 配合物浓度在3.0０×10^-3～7.5０×10^-4 mol •L^-1范围内对DNA分子有切割作用, 配合物浓度低于3.75×10^-4 mol •L^-1时则主要以插入方式与DNA键合.     

色氨酸-镝(Ⅲ)配合物与鲱鱼精DNA的作用方式

采用UV光谱法、荧光光谱法,在pH=7.40的缓冲溶液中确定了镝(Ⅲ)与色氨酸的结合比n_Dy(Ⅲ)∶n_Trp=1∶3,Dy(Ⅲ)(Trp)₃配合物与鲱鱼精DNA的结合比n_{Dy(Ⅲ)(Trp)3}∶n_DNA=2∶1。用双倒数法确定了结合常数K_25℃=5.75×10⁴ L·mol^-1和K_37℃=3.27×10⁴ L·mol^-1。化学热力学研究显示配合物Dy(Ⅲ)(Trp)₃与hsDNA的结合为熵和焓共同驱动。结合Scatchard法和粘度法,确定了配合物Dy(Ⅲ)(Trp)₃与hsDNA之间主要为静电作用和嵌插作用。     

Synthesis,characterization, and DNA-binding of Ln(III) complexes with 2-hydroxybenzylidene-2-phenylquinoline-4-carbonylhydrazone

2-Hydroxybenzylidene-2-phenylquinoline-4-carbonylhydrazone (H₂L) and five Ln(III) complexes, [Ln(H₂L)(NO₃)₂]NO₃ [Ln = La (1), Pr (2), Sm (3), Eu (4), and Tb (5)], have been synthesized and characterized by ¹H NMR, elemental analysis, conductivity measurements, mass spectra, IR spectra, and UV spectra. The interaction of these complexes with calf thymus DNA was investigated by UV absorption spectroscopy, fluorescence spectroscopy, circular dichroism spectroscopy and viscosity measurements. Results suggest that these complexes bind to DNA via groove binding.     

苏木素与DNA相互作用的光谱研究

以吖啶橙(AO)作探针研究了苏木素(HE)与DNA的相互作用. 吸收光谱和荧光光谱研究表明, 苏木素与DNA发生作用生成了复合物. 其结合比n_HE∶n_DNA＝3∶1, 22 ℃时苏木素与DNA的结合常数K＝5.96×10⁴ L/mol. 同时研究了酸度、盐效应和温度等对苏木素与DNA相互作用的影响以及它们之间的作用方式, 确定了苏木素与鲱鱼精DNA之间为混合作用方式.     

Synthesis, characterization and DNA interaction studies of complexes of lanthanide nitrates with tris(2-[(3,4-dihydroxybenzylidene)imino]ethyl)amine

A new tripodal, hydroxyl-rich ligand, tris{2-[(3,4-dihydroxybenzylidene)imino]ethyl}amine (L), and its complexes with lanthanide nitrates were synthesized. These complexes which are stable in air with the general formula of [LnL(NO(3))(2)]NO(3).H(2)O (Ln=La, Sm, Eu, Gd, Y) were characterized by molar conductivity, elemental analysis, IR spectra and thermal analysis. The NO(3)(-) groups coordinated to lanthanide mono-dentately, and the coordination number in these complexes may be 8. The interaction of complexes with DNA were investigated by ultraviolet and fluorescent spectra, which showed that the binding mode of complexes with DNA was intercalation, and the binding affinity with DNA were La(III) complex>Sm(III) complex>Eu(III) complex>Gd(III) complex>Y(III) complex. Based on these results, it can be shown that the La(III)complex is promising candidate for therapeutic reagents and DNA probes.     

Synthesis and structure of a new ternary monocopper(II) complex containing mixed ligands of 2,2′‐diamino‐4,4′‐bithiazole and picrate: in vitro anticancer activity,molecular docking and reactivity towards DNA

A new ternary monocopper(II) complex with co‐ligands of 2,2′‐diamino‐4,4′‐bithiazole (dabt) and picrate (pic), namely [Cu(dabt)(pic)₂], has been synthesized and characterized using elemental analyses, molar conductance measurements, infrared and electronic spectral studies and single‐crystal X‐ray diffraction. The crystal structure analyses revealed that the copper(II) ion has a {CuN₂O₄} distorted octahedral coordination environment. The hydrogen bonding interactions contribute to a three‐dimensional supramolecular structure in the crystal. The reactivity towards herring sperm DNA showed that the copper(II) complex can interact with DNA in the mode of intercalation. The molecular docking of the complex with DNA sequence d(ACCGACGTCGGT)₂ demonstrated that the copper(II) complex is stabilized by hydrogen bonding interaction. The in vitro anticancer activities suggested that the copper(II) complex is active against selected tumor cell lines. The effects of the two co‐ligands in the copper(II) complex on DNA‐binding events and in vitro anticancer activity are preliminarily discussed. Copyright © 2016 John Wiley & Sons, Ltd.     

Studies on the Electrochemical Property of Dinuclear Copper(II) Complex Containing Dimethylglyoxime and Its Interaction with DNA

The electrochemical property of dinuclear copper(II) complex containing dimethylglyoxime [Cu₂(Hdmg)₄] was studied with cyclic voltammetry. Cu₂(Hdmg)₄ had an irreversible oxidation peak in pH 5.0 B–R buffer solution at the stearic acid‐modified carbon paste electrode. Cyclic voltammetry, UV‐vis absorption spectra and viscosity measurements were used to study the interaction of Cu₂(Hdmg)₄ with herring fish sperm DNA. Cu₂(Hdmg)₄ interacts with the bases of DNA to form nonelectroactive adducts. The interaction of Cu₂(Hdmg)₄ with ssDNA was stronger than that of Cu₂(Hdmg)₄ with dsDNA because of the exposed bases of ssDNA. The gene sequence related to the BAR transgene in the transgenic corn was detected using Cu₂(Hdmg)₄ as electroactive indicator.     

钯配合物[Pd(phen)(L-asp)]·3H2O的结构，DNA键合和细胞活性研究

本文用常温方法合成了钯配合物,化学式[Pd(phen)(L-asp)]•3H2O,并用元素分析和红外图谱的方法进行分析,经单晶X射线衍射对其结构表征。以顺铂为参照,研究了该配合物对三种不同癌细胞（人宫颈癌细胞,肝癌细胞,口腔癌细胞）的细胞毒素作用,结果证明该钯配合物对人宫颈癌细胞有较强的抑制作用。通过多种光谱手段同时研究了该配合物与鱼精DNA作用模式,结果说明通过插入方式阻断鱼精DNA的复制。同时,测定配合物与pBR322质粒DNA作用的凝胶电泳。     

配合物[Co(qina)2(H2O)2]•2DMSO的晶体结构及其与DNA作用研究

合成了配合物[Co(qina)₂(H₂O)₂]•2DMSO单晶(qina为喹哪啶酸). 配合物属于单斜晶系, P2(1)/n空间群, 其分子结构为规则的八面体构型, qina以氮原子和羧酸根氧原子与Co^2＋离子配位, 两个水分子为轴向配位. 配合物之间富有配位水分子分别与DMSO的氧原子、qina中未与Co(II)配位的氧之间氢键作用. 配合物与鱼精DNA作用的紫外光谱和荧光光谱表明, 两者之间有一定的相互作用, 并可能以局部插入方式为主.     

Syntheses and structural analyses of nine-coordinate protonated (Py)2[GdIII(HNta)(Nta)(H2O)] · 5H2O and eight-coordinate (NH4)3[HoIII(Nta)2] complexes

The syntheses and structural determination of Gd(III) and Ho(III) complexes with nitrilotriacetic acids (Nta) were reported in this paper. Their structures and compositions were determined and characterized by single-crystal X-ray structure analyses, elemental analyses, and IR spectra. The first protonated Nta complex was found. Structural analyses indicate that the structure greatly changes, while an alternative Nta ligand was protonated in the ((Py)₂[Gd^III(HNta)(Nta)(H₂O)] · 5H₂O complex and the(NH₄)₃[Ho^III(Nta)₂] complex crystallized as a centrosymmetric structure. By contrast, it is further confirmed that the coordination number and coordinate structure of all trivalent rare-earth metal complexes with aminopolycarboxylic acids mainly depend on the ionic radii and electronic configuration of the central metal ions and their countercations.     

Ternary complexes of neodymium(III) and samarium(III) picrate triethylene glycol: structural, spectroscopic, and photoluminescent properties

The ternary complexation of neodymium(III) and samarium(III) with triethylene glycol (EO3) and picrate anion (Pic) were characterized by elemental analyses, FTIR (Fourier-transform infrared) spectroscopy, single crystal X-ray diffraction, and photoluminescence (PL). Both the [Nd(Pic)(H₂O)₂(NO₃)(EO3)](Pic) and [Sm(Pic)(H₂O)₂(NO₃)(EO3)](Pic)·H₂O complexes were isostructural with a ten-coordination number. In both complexes, the picrate and nitrate anions were coordinated to Ln(III) in a bidentate manner, and with the the EO3 ligand in a tetradentate manner, the addition of two water molecules maintained a ten-coordination number. The lighter lanthanide-picrate complexes formed a ten-coordination number due to the lanthanide contraction effect, acyclic polyether chain length, and number of donor oxygen atoms. The acyclic EO3 ligand affected photoluminescent intensity and its conformation on the structure of the [Ln(Pic)(NO₃)(H₂O)₂(EO3)]⁺ moiety. Photoluminescent measurement showed complex Nd(III) emissions at 403, 486, and 682?nm, with the strongest emission peak at 403?nm. Formation of these peaks occurred due to the intraligand π–π transitions of the Pic anion. The Sm(III) complex exhibited the emission characteristic of the Sm(III) ion in the red spectral region at 616.7?nm (⁴G_5/2 → ⁶H_9/2 transition), even though the ligand emissions were also observed in the PL spectrum. The emission intensity of the 4f–4f transitions in the Sm complex was significantly higher than that found in its salt. We noted that the [Sm(Pic)(H₂O)₂(NO₃)(EO3)](Pic)·H₂O complex was an excellent red-light-emitter and would be considered as a candidate material for organic light emitting diodes.