外源Cu2+与烟草CuZnSODⅢ的相互作用

In this paper， we have studied the interaction of CuZnSODⅢ and Outer-Copper， enzyme activity experiments expressed that 0.1mmol·L^-1 Cu²⁺ addition reduced the enzyme activity sharply， but this reduced action had not been found for the additions of 0.1mmol·L^-1 1∶1 Cu²⁺ and Zn²⁺， and 0.1mmol·L^-1 Zn²⁺， respectively. This was due to the Cu²⁺ exchanged the Zn²⁺ in CuZnSODⅢ，and it was proved by the experiment of determination of metal content. Meanwhile， the static fluorescence quenching mechanism revealed the exist of molecular complex of CuZnSOD with Cu²⁺. The binding constant was obtained from lineweaver-burk and double-lg plot. The distance of active site to Trp is about 2.83nm， was calculated according to F?rster theory.     

Simultaneous determination of zinc and copper(II) with 1-(2-pyridylazo)2-naphthol in micellar media by spectrophotometric H-point standard addition method

The H-point standard addition method (HPSAM) was applied to handling spectrophotometric data for simultaneous determination of Zn²⁺ and Cu²⁺ or selective determination of Zn²⁺ in the presence of Cu²⁺. The ligand 1-(2-pyridylazo)2-naphthol (PAN) and its metal complexes (Zn-PAN and Cu(II)-PAN) were made water-soluble by the neutral surfactant Triton X-100, and therefore, no extraction with organic solvents was required. The method is based on the difference in absorbance of formed complexes between Zn²⁺ and PAN, at two different wavelengths at pH = 9.2. The formation of both the complexes was complete within five minutes. Zn²⁺ can be determined in the range of 0.2–25 μg/mL with satisfactory accuracy and precision in the presence of excess of Cu²⁺ and most other metal ions. Interference effects of common anions and cations were studied. Under working conditions, the proposed method was successfully applied to the simultaneous determination of Zn²⁺ and Cu²⁺ in several real and synthetic mixtures with different concentration ratio of Zn²⁺ and Cu²⁺. The text was submitted by the authors in English.     

基于硼二吡咯亚甲基类(BODIPY)衍生物的合成,光谱及汞离子识别(英文)

The synthesis and sensing properties of a new BODIPY derivative 1 are outlined. 1 shows fluorescence “turn-on” and colorimetric responses with high selectivity toward Hg²⁺ over the other metal cations. Coordination of Hg²⁺ influences the electronic properties of the receptor at meso-position and alter the efficiency of non-radiative decay, hence increase the fluorescence intensity and red shift the absorption spectrum.     

[Ru(bpy)2tpphz]2+与Zn2+形成的双核配合物的荧光性质研究

The formation of heterobimetallic ruthenium(Ⅱ) complex was investigated by absorption and emission spectra. As an intercalator of DNA， the luminescent monometallic ruthenium(Ⅱ) complex [Ru(bpy)₂tpphz]²⁺ could coor-dinate with Zn²⁺ to form the nonluminescent heterobimetallic complex [Ru(bpy)₂(tpphz)Zn]⁴⁺. The emission in-tensity of complex decreased as increasing the amounts of Zn²⁺ and the luminescence was almost lost at the ratio of [Zn]/[Ru] of 1. After binding to DNA， the peripheral coordination site on the tpphz ligand remained accessible for Zn²⁺， the coordination occurred from the oppsite side of helix with respect to intercalated [Ru(bpy)₂tpphz]²⁺ and the nonluminescent heterobimetallic complex was formed. On the other hand， the [Ru(bpy)₂(tpphz)Zn]⁴⁺ also bound to DNA by intercalation and situated the region of the intercalated [Ru(bpy)₂tpphz]²⁺ between the base pairs of DNA. The complex looked like a molecular nut (the Zn²⁺) and bolt (the [Ru(bpy)₂tpphz]²⁺).     

氟胞嘧啶与牛血清白蛋白结合反应研究

The binding of flucytosine to bovine serum albumin （BSA） was studied by means of fluorescence and absorption spectra under the conditions of simulant clay physiology. It showed a powerful ability to quench the fluorescence launching from BSA. After analyzing the fluorescence quenching data by Stem-Volmer equation and Lineweaver-Burk double-reciprocal equation, it was found that they matched the latter better and so they belonged to static quenching. The binding constant was calculated to be 5.710 × 10^3 L·mol^-1 at 297 K. The binding locality was a distance 2.49 nm away from tryptophan residue-212 based on Foster＇s non-radiation energy transfer mechanism. The binding power is mainly the hydrogen bond and van der Waals force according to the thermodynamic parameters. The information of BSA conformation was acquired by synchronous fluorescence spectrum and three-dimensional fluorescence spectrum.     

杂多酸盐K7[PTi2W10O40]·6H2O与牛血清白蛋白相互作用的研究

Under the imitated physiological condition of animal body, the interactions of heteropoly salt (PM-19) with bovine serum albumin (BSA) were investigated by fluorescence and absorption spectroscopy. It was shown that this compound had a quite strong ability to quench the fluorescence launching from BSA. After analyzing the fluorescence quenching data according to Stern-Volmer equation and Lineweaver-Burk double-reciprocal equation, we found that BSA had reacted with PM-19 and formed a certain new compound. The quenching belonged to static fluorescence quenching. According to Lineweaver-Burk equation, the forming constants of the compound (298 K: 2.68 × 10⁵ L·mol^-1; 304 K: 2.19 × 10⁵ L·mol^-1; 310 K: 1.82 × 105 L·mol^-1) and the thermodynamic parameters (ΔH=-24.72 kJ·mol^-1; ΔS=20.97 J·mol^-1·K^-1 / 20.92 J·mol^-1·K^-1/ 20.97 J·mol^-1·K^-1; ΔG=-30.97 kJ·mol^-1/ -31.08 kJ·mol^-1/-31.22kJ·mol^-1) at the corresponding temperatures were obtained. The latter shows that binding power between them is mainly electrostatic interaction. Based on F?rster′s non-radiation energy transfer mechanism, the binding locality (r=4.14 nm) was calculated between donor and accepter. The effect of PM-19 on the conformation of BSA was also analyzed by synchronous fluorescence spectroscopy.     

Study on the Interaction between Lanthanide Cationic Porphyrin Complex and Bovine Serum Albumin

The interaction between lanthanide cationic porphyri

n and bovine serum albumin （BSA） was studied by fluorescence and UV-Vis spectrum. The static quenching of BSA was observed in the presence of YbTMPyP. According to the thermodynamic parameters, this binding was regarded as ＂enthalpy-driven＂ reaction. Furthermore, YbTMPyP is so close to the residues of BSA that molecular resonance energy transfer occurs between them. Besides, the red drift and hypochromicity of absorption spectrum of YbTMPyP were accompanied with the binding reaction.     

meso-四(对烷氧基苯基)卟啉配合物的合成、表征和液晶性研究

The method of Adler was improved to prepare a series of 5,10,15,20-tetrakis(4-alkoxyphenyl)porphyrins and their complexes containing Fe³⁺, Mn³⁺, Pb²⁺, Co²⁺, Cu²⁺, Zn²⁺. Among them there were seven new compounds. All these compounds were identified through ¹H NMR, MS, IR, UV and Element analysis. The correlation between the structure of compounds and their ¹H NMR, MS, IR, UV spectra was discussed and their specific spectra were explained. We found nine metalloporphyrins exhibited liquid crystal behaviour through DSC and polarized-light microscope. They had one to three mesophases and certain phase transition temperature, ΔH and temperature range of L.C(ΔT).     

不同配体对钌多吡啶配合物与DNA的作用和荧光性质的影响

Two polypyridyl ligands DCHIP (2-hydro-3，5-dichlorophenyl-imidazo[4，5-f][1，10] phenanthroline)，MDHIP(2，4-dihydrophenyl-imidazo[4，5-f][1，10]phenanthroline) and their ruthenium(Ⅱ) complexes [Ru(phen)₂MDHIP]²⁺ and [Ru(phen)₂DCHIP]²⁺ were prepared. Their DNA-binding properties were studied by spectroscopic methods and viscosity measurements. The results indicated that the complexes both bound to DNA by partial intercalation mode， but [Ru(phen)₂DCHIP]²⁺ exhibited stronger binding affinity for DNA than [Ru(phen)₂MDHIP]²⁺ due to the different planarities and steric effects of ligands. On the other hand， after binding to DNA， the fluorescence intensity of [Ru(phen)₂MDHIP]²⁺ decreased， while the fluorescence intensity of [Ru(phen)₂ DCHIP]²⁺ increased.     

Spectrofluorimetric Determination of Cu2＋ Using New Fluorogenic Reagent

A new synthesized fluorogenic reagent,8-[(2-pyridine)methylideneamino] quinoline (PMAQ), was utilized for spectrofluorimetric determination of Cu(II) at trace levels. PMAQ, a good fluorogenic reagent, though insoluble in water, but is soluble in ethanol and 20% ethanol-water. The excitation and the fluorescence wavelengths of PMAQ were 310 and 434 nm respectively. When the reagent was complexed with Cu(II), the fluorescence intensity decreased proportionally with the concentration of Cu(II) at pH 4.5 by a static quenching effect. The highest sensitivity to Cu^2＋ determination was shown to be at PMAQ concentration of 1.0×10^－5mol•L^－1. In order to enhance the quenching effect, the Cu(II)-PMAQ complex solution was kept at 22 ℃ for 20 min. Though the interferences by Co(II) and Fe(III) were very serious, they were however, completely eliminated by being masked with oxalate and ascorbate ions respectively. The linear dynamic range for Cu(II) determination was between 25—441 µg•L^－1 with the detection limit of 18 µg•L^－1 (RSD＝3.7%, n＝6). The proposed method was successfully applied to the determination of Cu(II) in real samples including human blood serum, commercial tea and wheat flour.     

化学共沉淀法制备气敏材料Cd2+XSb2O6.8

采用化学共沉淀法,以可溶性的镉盐和三价锑盐为源物质、氢氧化物作共沉淀剂,在较宽的Cd/Sb摩尔配比范围内,制备出了具有缺陷烧绿石结构的镉锑复合氧化物Cd₂Sb₂O_6.8及其固溶体。研究了烧成条件对产物的影响,在较低温度(600℃)下得到了纯相Cd₂Sb₂O_6.8的超微粉,并对其高温反应机理进行了探讨。所得微粉产物制成的厚膜元件经气敏测试,发现n(Cd)/n(Sb)=1.10、 900 ℃、3 h烧成的间隙型固溶体Cd_2+XSb₂O_6.8,对乙炔气体具有非常优秀的气敏性能。     

量子顺电体La1/2Na1/2TiO3纳米晶的制备与谱学表征

用改进硬脂酸溶胶－凝胶法制备了量子顺电体Ｌａ１／２Ｎａ１／２ＴｉＯ３纳米晶,用差热－热重分析和Ｘ射线衍射测试了样品的晶化过程相结构,用ＦＴＩＲ和Ｒａｍａｎ光谱表征了其光谱特性。     

锌(Ⅱ)存在下灯盏花素与BSA相互作用的光谱分析

运用荧光光谱、吸收光谱研究了灯盏花素(Breviscapinun,BR)与牛血清白蛋白(Bovine Serum Albumin,BSA)的相互作用.BR对BSA的荧光光谱具有猝灭作用,其猝灭机制为静态-动态联合猝灭,BSA发射峰蓝移.Zn2+的存在使得BSA发射峰蓝移程度降低,猝灭常数、结合常数、结合位点数减小.在较大浓度Zn2+存在下,BR与BSA作用的相关系数增大,猝灭机制变为静态猝灭.从Zn2+与BR的竞争作用,热力学参数的变化、配位化合物的形成3个方面分析了影响BR与BSA作用的因素.     

过渡金属席夫碱配合物的稳定性及其杀菌活性

在25±0.1℃,I=0.1 mol·L^-1 KNO₃条件下,应用pH法测定了甲酰基甲酸缩氨基硫脲(A配体,缩写H₂FFTSC),甘氨酰甘氨酸(B配体,缩写HGG)的质子化常数,它们与锰(Ⅱ)、钴(Ⅱ)、镍(Ⅱ)、铜(Ⅱ)和锌(Ⅱ)的二元配合物以及过渡金属(Ⅱ)-甲酰基甲酸缩氨基硫脲-甘氨酰甘氨酸三元配合物稳定常数,讨论了过渡金属席夫碱配合物的杀菌活性与其稳定性之间的关系,对杀菌机理提出了一些看法。     

微孔多酸CsxH5-xPW10V2O40/SiO2的制备及氧化催化作用

Keggin结构杂多酸在固相体系中的催化作用引起了人们的极大兴趣[1～3].性能稳定的杂多酸铯盐催化剂在非均相催化体系中已有广泛的应用,然而由于其在液固体系中通常呈现牛奶状,难以分离和重新使用,尽管化学家们以各种材料作为这些催化剂的载体进行了许多固载化尝试[4～6],但至今尚未从根本上解决这一难题.因此,开发高比表面的耐水微孔固体杂多酸催化剂是多酸催化化学领域中具有理论和实际意义的课题.本文采用Sol-Gel技术,以正硅酸乙酯(TEOS)为硅源,水解产生的具有网络结构的SiO2凝胶为载体,在钒取代型Keggin结构杂多酸CsxH5-xPW10V2O40存在下,制得通式为CsxH5-xPW10V2O40/SiO2的固体双功能微孔杂多酸; 以30%H2O2为氧化剂,以苯甲醇氧化为模型反应,研究其液-固体系中的催化作用.     

Er2O3的光致发光光谱,吸收光谱和Raman光谱

在可见激光的激发下,Ｅｒ２Ｏ３粉晶样品的Ｒａｍａｎ光谱易受Ｅｒ＾３＋光致发光光谱的干扰。本文利用同一Ｒａｍａｎ光谱仪测得Ｅｒ２Ｏ３的高分辨可见光吸收光谱和激发光谱。     

SnCl4催化丙酮与过氧化氢反应制取大环过氧化物

Ｈ２Ｏ２与过渡金属构成的催化体系可选择性地氧化烃类化合物,如芳烃的羟基化和烯烃的环氧化等［１～３］,且Ｈ２Ｏ２在应用中无环境污染,是一种颇有前途的氧化剂．有关金属催化Ｈ２Ｏ２与酮类化合物反应的报道很少．已知在无机酸催化下环酮（环己酮或环戊酮）与Ｈ２Ｏ...     

三头季铵盐表面活性剂导向合成新型立方相介孔二氧化硅

介孔分子筛因具有大而均一的孔道、高比表面积及相对良好的热稳定性而在精细化学品催化剂[1,2 ] 、生物大分子分离 [3] 和功能材料的主体 [4 ] 等领域有十分广阔的应用前景 .自 1 992年 Mobil公司合成 M41 S[5,6 ] 系列介孔材料以来 ,HMS[7] ,MSU[8] 和 SBA[9～ 12 ] 系列以及 FDU- 1 [13] 等不同结构的介孔分子筛材料相继被合成 .立方相介孔分子筛因具有三维网状结构和可通性较高的孔道而在反应中不易堵塞 ,相对于一维孔道结构的六角相 MCM- 41和 SBA- 1 5 ,其应用前途更加广阔 .迄今 ,人们已经合成了 MCM- 48[14～ 16 ]( Ia3d) …     

二(μ-2-(2-吡啶基)乙氧基)·四乙基合二铟(Ⅲ)的合成及晶体结构

本文报道通过1-(2-吡啶基)-2-丙醇与三乙基铟作用制备得到了一个新的配合物二(μ-2-(2-吡啶基)乙氧基)·四乙基合二铟(Ⅲ)(C₁₂H₂₀NOIn)₂。测定了化合物的晶体结构。化合物具有中心对称结构,属单斜晶系,空间群P2₁/n, 晶胞参数为：a=10.609(2)?, b=10.680(3)?, c=12.012(8)?, β=95.57(5)°, V=1354.5(10)?³, Z=2, F(000)=624, Dc=1.516 g/cm³, μ=1.722 mm^-1;铟以五配位形式存在,两个In-O的键长分别为2.129?和2.249?, ∠InOIn=106.66°, ∠OInO=73.34°。