烟酸和1,10-邻菲啰啉构建的Cu(Ⅱ)配合物与DNA的相互作用

采用光谱法、循环伏安法和热变性方法,研究了烟酸(NA)和1,10-邻菲啰啉(Phen)构建的三元Cu(Ⅱ)配合物([Cu(Phen)(NA)]·H2O)与鲱鱼精DNA的相互作用。结果显示:NA中羧酸根离子与Phen中两个氮原子均与Cu(Ⅱ)双齿配位,形成的配合物在0.141~0.205V出现一对灵敏的氧化还原峰,并且配合物在玻碳电极上的反应主要由扩散过程控制。加入DNA后配合物的最大吸收峰发生了明显红移和减色,且配合物的氧化还原峰电流显著降低,式量电位发生正移;配合物能猝灭中性红(NR)-DNA体系的荧光,同时配合物的加入使DNA熔点升高,表明配合物与DNA存在嵌入结合。     

2,2'-联吡啶In(Ⅲ)配合物与DNA作用的电化学研究

应用循环伏安法、微分脉冲伏安法和交流阻抗法研究了配合物In(bpy)Cl3.H2O与DNA在Tris-HCl缓冲溶液(pH=7.2)中的相互作用.结果表明:配合物中心In(Ⅲ)离子的循环伏安曲线上呈现一对准可逆的氧化还原波,DNA与配合物作用后,配位中心离子的氧化还原峰电流明显降低,扩散系数减小,电化学反应阻抗增大,式量电位负移,表明该配合物与DNA的作用方式为静电结合.     

2，2′-联吡啶In（Ⅲ）配合物与DNA作用的电化学研究

应用循环伏安法、微分脉冲伏安法和交流阻抗法研究了配合物In(bpy)Cl3·H2O与DNA在Tris-HCl缓冲溶液(pH=7.2)中的相互作用.结果表明配合物中心In(Ⅲ)离子的循环伏安曲线上呈现一对准可逆的氧化还原波,DNA与配合物作用后,配位中心离子的氧化还原峰电流明显降低,扩散系数减小,电化学反应阻抗增大,式量电位负移,表明该配合物与DNA的作用方式为静电结合.     

铬(Ⅵ)-谷胱甘肽配合物诱导小牛胸腺DNA变性的新表征方法

本文采用电化学方法对铬(Ⅵ)-谷胱甘肽(GSH)配合物诱导DNA变性进行表征,同时运用原子力显微镜(AFM)对DNA损伤变性过程进行可视化探测.结果表明:在pH=5.6的HAc-NaAc缓冲溶液中,DNA溶液中加入Cr(Ⅵ)-GSH配合物后进行循环伏安扫描,+0.20 V和0.00 V(vs SCE)处出现一对新的氧化还原峰,该氧化还原峰随Cr(Ⅵ)-GSH配合物浓度增加峰电流上升.DNA热变性和表面活性剂SDS变性实验进一步证明了该峰为DNA变性后的氧化还原峰,且变性DNA的峰信号在修饰电极上比裸金电极上更为灵敏.电化学动力学表明在30 min内配合物诱导DNA变性的程度随时间的上升而增加,并通过AFM观察了配合物作用下DNA断链的过程.     

铬(VI)-谷胱甘肽配合物诱导小牛胸腺DNA变性的新表征方法

本文采用电化学方法对铬(VI)-谷胱甘肽(GSH)配合物诱导DNA变性进行表征，同时运用原子力显微镜(AFM)对DNA损伤变性过程进行可视化探测。结果表明：在pH=5.6的HAc-NaAc缓冲溶液中，DNA溶液中加入Cr(VI)-GSH配合物后进行循环伏安扫描，+0.20 V和0.00 V(vs SCE)处出现一对新的氧化还原峰，该氧化还原峰随Cr(VI)-GSH配合物浓度增加峰电流上升。DNA热变性和表面活性剂SDS变性实验进一步证明了该峰为DNA变性后的氧化还原峰，且变性DNA的峰信号在修饰电极上比裸金电极上更为灵敏。电化学动力学表明在30 min内配合物诱导DNA变性的程度随时间的上升而增加，并通过AFM观察了配合物作用下DNA断链的过程。     

邻菲咯啉-铜(Ⅱ)-L-亮氨酸配合物与DNA的结合

应用循环伏安法、微分脉冲伏安法、电子吸收光谱和溴化乙锭(EB)荧光分析法研究了[Cu(phen)(H2O)(L-Leu)^ ](phen=1，10-邻菲咯啉，L-Leu=L-亮氨酸)与小牛胸腺DNA的相互作用。结果发现中心铜离子在循环伏安图上呈现一对明显的准可逆氧化还原波。当加入一定量的DNA时，配合物的氧化还原峰电流明显降低，配位阳离子的扩散系数减小，电子光谱的最大吸收峰明显红移，产生明显的减色效应。同时，配合物也能较大程度地猝灭EB-DNA体系的荧光，证明配合物与DNA存在插入结合。     

邻菲罗啉-铜(II)-水杨酰胺配合物与DNA相互作用的研究及分析应用

采用紫外吸收光谱法、循环伏安法和微分脉冲伏安法研究了一种水杨酰胺多吡啶铜配合物[Cu(phen)(sa)](phen=1,10-邻菲罗啉,sa=水杨酰胺)与DNA的相互作用。紫外光谱法显示DNA的加入能引起配合物特征吸收峰的减色效应,表明了二者之间的相互作用。循环伏安实验表明配合物在玻碳电极上呈现一对准可逆的氧化还原峰;加入DNA后,配合物的峰电流减小,峰电位正移,表明二者可能通过嵌插方式发生作用。微分脉冲伏安法进一步表明[Cu(phen)(sa)]作为电化学探针,能在1.3×10-5～6.7×10-5moL/L DNA浓度范围内对DNA进行定量检测。将该铜配合物作为杂交指示剂应用于DNA传感器中对花椰菜花叶病毒的35S启动子基因(CaMV35S)相关DNA片段进行检测,结果显示该传感器对互补序列和非互补序列具有很好的识别能力。     

铜(Ⅱ)邻菲咯啉蛋氨酸配合物与DNA相互作用的研究

在pH=6．86磷酸盐缓冲溶液中，采用电化学(循环伏安法、微分脉冲伏安法和 交流阻抗及数据拟合技术)、粘度测定、电子吸收光谱和溴化乙锭(EB)荧光分析法 研究了[Cu(phen)(H2O)(L—Met)]^+(phen＝1，10-邻菲咯琳，L—Met=L-蛋氨酸)与 小牛胸腺DNA的相互作用。结果发现中心铜离子在循环伏安图上呈现1对明显的准可 逆氧化还原波。当加入一定量的DNA时，配合物的氧化还原峰电流明显降低，扩散 系数减小，电化学反应电阻增大，电子光谱的最大吸收峰明显红移，产生明显的减 色效应，同时，配合物也能较大程度地猝灭EB-DNA体系的荧光，说明[Cu(phen) (H2O)(L—Met)]^+与DNA的作用较强，作用模式为部分插入作用。     

一类新型冠醚稀土配合物的合成、表征及与DNA作用研究

合成了四种双(N,N′-乙基,苯基)-2,3-萘-二(氧杂乙酰胺)(L=C30H30N2O4)稀土配合物。通过元素分析、红外光谱、差热-热重及摩尔电导值的分析,确定配合物的组成为[RE(pic)3L],RE=Eu(Ⅲ),Tb(Ⅲ),Ce(Ⅲ),Y(Ⅲ)。电化学实验表明:配体无电化学活性,配合物则呈现出一准可逆的氧化还原过程,在10～1000 mV.s-1扫速范围内配合物的氧化还原峰电流与扫描速度的平方根(ν1/2)呈良好的线性关系,表明其在玻碳电极(GCE)上的伏安行为受扩散控制。另外,通过循环伏安法、光谱法及粘度法研究了配合物与DNA的作用方式,结果表明:配合物均以插入方式与DNA作用,并且作用大小次序是Ce(pic)3L>Tb(pic)3L>Y(pic)3L>Eu(pic)3L。在pH=3.0适宜酸度条件下,建立了以Ce(pic)3L为探针定量测定DNA的分析方法。     

2-氯苯甲醛缩 L-天冬氨酸合铜的合成及与DNA相互作用研究

本文合成了配体2-氯苯甲醛缩L-天冬氨酸钾和2-氯苯甲醛缩L-天冬氨酸合铜金属配合物,对化合物进行了元素分析,红外光谱、热重分析、质谱等测试;在pH=7.2的Tris-HCl缓冲溶液中,采用循环伏安法、紫外吸收光谱法研究了2-氯苯甲醛缩L-天冬氨酸合铜配合物与DNA相互作用的电子吸收光谱。结果发现铜离子在循环伏安图上呈现一对准可逆氧化还原峰。当加入DNA后,配合物的氧化峰电流明显降低,电子光谱的最大吸收峰明显红移,产生明显的减色效应,说明配合物与DNA的作用较强,作用模式为插入作用。     

Copolymers of tetrafluoroethene with chlorotrifluoroethene and with bromotrifluoroethene

Tetrafluoroethene (TFE)–chlorotrifluoroethene (CTFE) and TFE–bromotrifluoroethene (BTFE) copolymers have been synthesized by solution copolymerization over the entire range of comonomer composition. Crystallinity data are reported and first- and second-order transitions have been investigated by DSC. Glass transition temperatures of TFE-CTFE copolymers vary in a nonlinear fashion in the range defined by the homopolymers conforming best to the Johnston equation; the behavior in the TFE-BTFE system is more linear. Whereas TFE-BTFE copolymers show a steep decrease of melting temperature at higher BTFE content, due to the amorphous character of the polymers, more regular behavior was found for TFE-CTFE copolymers. Enthalpies of fusion are also reported. The results are discussed in relation to copolymer composition and structure and are compared with data on tetrafluoroethene–hexafluoropropene (FEP) fluorocarbon resins.     

Asymmetric sorbents with N-carboxymethyl-L-valine and with N-carboxymethyl-L-aspartic acid

Conclusions The asymmetric sorbents with N-carboxymethyl-L-valine with N-carboxymethyl-L-aspartic acid can be used to resolve racemates by the ligand-exchange chromatography method. Institute of Heteroorganic Compounds, Academy of Sciences of the USSR, Moscow. Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 10, pp. 2378–2380, October, 1976.     

Erbium and ytterbium complexes with the phtalocyanines with aryloxy and chlorine substituents

By nucleophilic substitution of chlorine atoms in tetrachlorophthalonitrile by phenoxy- or 1-naphthyloxy groups aryloxychlorophthalonitriles were synthesized and on this basis respective substituted erbium and ytterbium phthalocyanines with chloro-, acetate- or acetylacetonate anions as extra ligands. The compounds obtained were characterized by elemental analysis, chromato-mass spectrometry, IR, ¹³C NMR, and electronic spectroscopy.     

High-temperature reactions of trichloroethylene with toluene and with methanol

Conclusions The reactions of trichloroethylene with toluene and with methanol, conducted 560–570°, leads to the formation of a mixture of the isomers R-CH=CCl₂ and cis- and trans-R-CCl=CHCl (R=CH₂C₆H₅ and CH₂OH).Translated from Izvestiya Akademii Nauk SSSR. Seriya Khimicheskaya, No. 12, pp. 2777–2778, December, 1967.We thank E. D. Lubuzh and A. V. Kessenikh for determining and interpreting the IR and NMR spectra.     

Treatment of Wool with Laccase and Dyeing with Madder

This research has explored the effect of laccase (Denilite ІІ S) on the physical properties of the wool fabric and confirms the anti-felting of wool. In the experiment, laccase was applied to a wool fabric and different characteristics including weight loss, strength, alkali solubility, felting shrinkage, water drop absorption, and dye ability with madder were studied. The surface morphology of the wool fabrics was also observed by scanning electron microscope. The results indicated that the wool fabric treated with laccase has a higher water drop absorption, lower felting shrinkage, and lower values of a ^* and b ^*. Treatment of a wool fabric with 10% or lower percentage of laccase reduced the fabric weight but increased the tensile strength. However, using higher concentration of laccase reduced fabric weight and tensile strength. The dyeing of laccase pre-treated wool fabric with madder indicated a lower lightness.     

Fluorescence chemosensors with pyrene and their interaction with nucleotide phosphate

A group of fluorescence chemosensor with pyrene, compounds (Ⅰ), (Ⅱ) and (Ⅲ), were synthesized The fluorescence spectra and the lifetime of these compounds were carefully measured. The fluorescence quenching spec tra of pyrenyl butyric acid, compounds (Ⅰ), (Ⅱ) and (Ⅲ) by different nucleotide phosphates, AMP ADP, ATP dTTP, were also recorded and studied. The quenching and the stability constants were calculated by Stern-Volmer equa tion and eq. (2), respectively. The mechanism of interaction between fluorescence chemosensor and nucleotide phos phate was didscussed based on the comparison of the results obtained with the CPK model of free molecules of these com pounds in the ground state.     

Discrete and infinite cage-like frameworks with inclusion of anionic and neutral species and with interpenetration phenomena

Complex [Ag(tpba)N(3)] (1) was obtained by reaction of novel tripodal ligand N,N',N"-tris(pyrid-3-ylmethyl)-1,3,5-benzenetricarboxamide (TPBA) with [Ag(NH(3))(2)]N(3). While the reactions between 1,3,5-tris(imidazol-1-ylmethyl)-2,4,6-trimethylbenzene (TITMB) and silver(I) salts with different anions and solvent systems give six complexes: [Ag(3)(titmb)(2)](N(3))(3).CH(3)OH.4 H(2)O (2), [Ag(3)(titmb)(2)](CF(3)SO(3))(2)(OH).5 H(2)O (3), [Ag(3)(titmb)(2)][Ag(NO(3))(3)]NO(3).H(2)O (4), [Ag(3)(titmb)(2)(py)](NO(3))(3).H(2)O (py=pyridine) (5), [Ag(3)(titmb)(2)(py)](ClO(4))(3) (6), and [Ag(3)(titmb)(2)](ClO(4))(3).CHCl(3) (7). The structures of these complexes were determined by X-ray crystallography. The results of structural analysis of complexes 1 and 2, with the same azide anion but different ligands, revealed that 1 is a twofold interpenetrated 3D framework with interlocked cage-like moieties, while 2 is a M(3)L(2) type cage-like complex with a methanol molecule inside the cage. Entirely different structure and topology between 1 and 2 indicates that the nature of organic ligands affected the structures of assemblies greatly. While in the cases of complexes 2-7 with flexible tripodal ligand TITMB, they are all discrete M(3)L(2) type cages. The results indicate that the framework of these complexes is predominated by the nature of the organic ligand and geometric need of the metal ions, but not influenced greatly by the anions and solvents. It is interesting that there is a divalent anion [Ag(NO(3))(3)](2-) inside the cage 4 and an anion of ClO(4)(-) or NO(3)(-) spontaneously encapsulated within the cage of complexes 5, 6 and 7.