铽-N-苯基邻氨基苯甲酸的合成及荧光性质

采用共沉淀法制备了稀土铽的N-苯基邻氨基苯甲酸二元配合物,同时,采用溶胶-凝胶法制备了掺杂稀土铽的N-苯基邻氨基苯甲酸二元配合物的SiO2凝胶玻璃复合发光体,研究了合成的两种配合物的热稳定性及荧光性质。结果表明:在凝胶玻璃中合成的稀土二元配合物,其热稳定性明显提高,而其特征荧光基本保持不变。     

铽-N-苯基邻氨基苯甲酸的合成及荧光性质

采用共沉淀法制备了稀土铽的N-苯基邻氨基苯甲酸二元配合物,同时,采用溶胶-凝胶法制备了掺杂稀土铽的N-苯基邻氨基苯甲酸二元配合物的SiO2凝胶玻璃复合发光体,研究了合成的两种配合物的热稳定性及荧光性质。结果表明:在凝胶玻璃中合成的稀土二元配合物,其热稳定性明显提高,而其特征荧光基本保持不变。     

铽-N-苯基邻氨基苯甲酸的合成及荧光性质

采用共沉淀法制备了稀土铽的N-苯基邻氨基苯甲酸二元配合物.同时,采用溶胶-凝胶法制备了掺杂稀土铽的N-苯基邻氨基苯甲酸二元配合物的SiO2凝胶玻璃复合发光体,研究了合成的2种配合物的热稳定性及荧光性质.结果表明,在凝胶玻璃中合成的稀土二元配合物,其热稳定性明显提高,而其特征荧光基本保持不变.     

稀土(铽)二元和三元配合物的合成及荧光性质

分别合成了稀土铽-N-苯基邻氨基苯甲酸、铽-N-苯基邻氨基苯甲酸-邻菲罗啉两种稀土二元及三元配合物。此外,采用溶胶-凝胶湿化学制备手段在SiO2凝胶玻璃中引入了铽-N-苯基邻氨基苯甲酸-邻菲罗啉三元配合物,对合成的配合物进行了表征,在紫外光激发下,它们均能发射铽离子的特征荧光。     

表面活性剂存在下铽-镥(钆、钇)-乙酰水杨酸共发荧光体系的研究

本文研究了镥等三种稀土离子与铽－乙酰水杨酸配合物产生的共发荧光效应．在最佳条件下,Ｌｕ３＋、Ｇｄ３＋、Ｙ３＋的存在可使铽－乙酰水杨酸配合物的荧光分别增强１０８,５８和７３倍．讨论了共发光体系的形成条件和荧光特性．利用Ｔｂ－Ｌｕ－乙酰水杨酸体系和Ｔｂ－Ｌｕ－乙酰水杨酸－乙二胺四乙酸－十六烷基三甲基溴化铵体系分析了合成稀土样品和包头稀土标准氧化物中的铽,结果满意,加标回收率为９０．５～１０５．６％,并对共发光的机理和表面活性剂的作用进行了初步探讨．     

稀土铽三元有机配合物合成及荧光性能研究

合成了7种铽的稀土荧光有机材料——铽三元有机配合物,通过荧光光谱的测定,比较了第一配体的改变对配合物发光性能,尤其是发光强度的影响。实验表明,在以邻菲啉为第二配体的情况下,第一配体对铽三元配合物荧光强度影响顺序依次是:磺基水杨酸对甲基苯甲酸水杨酸苯甲酸对氨基苯甲酸乙酰丙酮,其磺基水杨酸为第一配体的铽三元有机配合物荧光强度最大,其相对强度为20000。     

表面活性剂存在下铽—镥（钆,钇）—乙酰水杨酸共发荧光体系？…

本文研究了镥等三种稀土离子与铽－乙酰水杨酸配合物产生的共发荧光效应,最佳条件下,Ｌｕ＾３＋、Ｇｄ＾３＋、Ｙ＾３＋的存在可使铽－乙酰水杨酸复合物的荧光分别增强１０８,５８和７３倍,讨论了共发光体系的形成条件和荧光特性,利用Ｔｂ－Ｌｕ乙酰水杨酸－乙二胺四乙酸－十六烷基三甲基溴化铵体系分析了合成稀土样品和包头稀土标准氧化物中的铽,结果满意,加标回收率为９０．５－１０５．６％,并对共发光的机理和表面活性剂     

铽(镧、钆)-乙酰丙酮-邻菲啰啉配合物的合成及其在塑料中的应用

合成了铽-乙酰丙酮-邻菲啰啉配合物,发现镧、钆对铽-乙酰丙酮-邻菲啰啉配合物具有荧光增强作用,应用荧光镧、铽混合配合物制备了光致发光塑料。     

稀土金属铽配合物材料的研究与应用

本文简要介绍了稀土金属铽配合物在发光材料方面的研究进展,阐述了稀土金属铽配合物在白光用荧光材料、纳米发光纤维、荧光探针、木材修饰改性、碳量子点复合和金属功能材料等方面的最新应用成果,概述了稀土铽配合物在应用过程中出现的不足和亟待解决的问题,并对稀土铽配合物的应用前景和未来发展予以展望。     

含吡啶环稀土配合物的合成与表征

以2-氨基吡啶、3-异氰酸酯丙基三甲氧基硅烷和稀土硝酸盐为制备原料,选用溶胶-凝胶法合成含吡啶环的Gd、Er、Eu稀土配合物。探索了温度、时间等因素对产品产率的影响,通过平行实验确定了配体和配合物的最佳反应温度、时间、投料比。使用红外光谱仪、紫外分光光计等仪器对目的产物进行结构表征,并通过荧光分析后确定了最优产物是含Eu稀土配合物。     

稀土配合物及其共聚物的合成与性能研究

以丙烯酸(HAA)、甲基丙烯酸(HMA)及1,10-邻菲罗啉(Phen)为配体与氧化铕(Eu2O3)反应得到二元配合物Eu(AA)3、Eu(MA)3和三元配合物Eu(AA)3Phen、Eu(MA)3Phen。将生成的配合物与HMA和甲基丙烯酸甲酯(MMA)共聚,得到一系列三元共聚物。通过元素分析、红外光谱、荧光光谱和热分析对配合物进行了分析与表征,发现配合物具有良好的荧光强度和热稳定性。三元配合物的荧光强度相对于二元配合物有显著提高。共聚物可发射Eu3+的特征荧光,荧光强度随配合物含量的增加而增加,且未发生浓度猝灭现象。三元配合物在反应单体MMA和HMA中的溶解度低于二元配合物,从而使在最大溶解度下二元配合物与反应单体生成共聚物的荧光强度高于相应的三元配合物与反应单体生成的共聚物。     

稀土钐二元、三元配合物的合成、表征及其生物活性研究

以氯化钐、2-氨基嘧啶和钼酸钠为原料,制备了两种新型稀土钐二元、三元配合物,通过元素分析、紫外光谱、红外光谱等手段对其进行了表征,确定了二元配合物的化学组成为Sm2(AP)(H2O)2Cl3(AP=2-氨基嘧啶),三元配合物的化学组成为:Sm3(AP)(MoO4)2(CH3OH)4Cl5。抗菌结果表明,二元配合物对大肠杆菌和金黄色葡萄球菌的抑菌圈直径分别为13 mm和15 mm,三元配合物分别为13 mm和13 mm,两种配合物对大肠杆菌、金黄色葡萄球菌都有一定的抑制作用。采用MTT法对两种配合物诱导癌细胞凋亡能力做了初步研究,两种配合物的半数抑制浓度IC50在0.001~0.01 mg/mL之间,证明其具有诱导癌细胞凋亡的作用。     

Metal-5-Fluorouracil-histamine complexes: solution, structural, and antitumour studies

Solution studies were performed pH-metrically to study the interaction of Co(II), Ni(II), Cu(II), Zn(II) and Cd(II) metal ions with 5-fluorouracil (5FU) and histamine (Hm) separately (binary) and in the presence of each other (ternary) at 25+/-0.1( degrees )C temperature and a constant ionic strength of 0.1 M NaNO(3) in aqueous solution. The ternary complexes have been found to be more stable than the corresponding binary complexes as shown by the positive value of DeltalogK. The species distribution curves have been obtained using the computer programme BEST. On the basis of species distribution results, efforts were also made to prepare some mixed complexes of Co(II), Ni(II), Cu(II), Zn(II) and Cd(II) ions by performing the reaction of their metal nitrates, 5FU and Hm in aqueous ethanol medium at suitable pH. The isolated solid complexes were characterized by different physico-chemical method in order to suggest the possible binding site of the ligands and the structure of the resultant complexes. All these complexes were checked for their antitumour activity by injecting in Dalton's lymphoma (DL) and Sarcoma-180 (S-180) bearing C(3)H/He mice. The results indicate that some complexes have good antitumour activity both in vivo and in vitro.     

铜(Ⅱ)-氨基葡萄糖-α-氨基酸三元配合物的稳定性

为研究铜(Ⅱ)-氨基葡萄糖-α-氨基酸三元配合物的稳定性,用pH电位滴定法测定了298±0.1 K,I=0.10 mol/L KNO3条件下铜(Ⅱ)-氨基葡萄糖-α-氨基酸三元配合物的稳定常数。结果表明,在铜(Ⅱ)-氨基葡萄糖-α-氨基酸三元体系中,生物配体氨基葡萄糖和α-氨基酸具有良好的相容性,三元配合物的稳定性与α-氨基酸的碱性及二元配合物稳定性之间存在直线自由能关系。     

Studies on preparation,structure and fluorescence emission of polymer-rare earth complexes composed of aryl carboxylic acid-functionalized polystyrene and Tb(Ⅲ) ion

4-(Chloromethyl) benzoic acid (CMBA) was first bonded onto the side chains of polystyrene (PS) via a polymer reaction, Friedel–Crafts alkylation reaction, and aryl carboxylic acid-functionalized polystyrene (PSBA) was generated. The functionalized polystyrene was used to prepare rare earth metal complexes. By using PSBA as macromolecule ligand, the binary polymer-rare earth complexes, PS-(BA)_n-Tb(Ⅲ), were prepared, and at the same time, ternary polymer-rare earth complexes, PS-(BA)_n-Tb(Ⅲ)-(Phen)_m, i.e. the mixed complexes in which both polymer-based aryl carboxylic acid and 1,10-phenanthroline as ligands were also prepared. The complexes were fully characterized using FTIR and proton NMR spectroscopy. Both ultraviolet absorption and fluorescence emission spectra for the complexes were recorded. The relationship between complex structure and the intensity of fluorescence emission was established. The experimental results show that the fluorescence emission from the central metal ion in the complex is strongly sensitized by the aryl carboxylic acid ligands chemically attached to the side chains of PSBA, and an apparent “Antenna Effect” is produced for these complexes. In the dilute solution of PSBA, the formed complex belongs to intramolecular complex. For the binary intramolecular complex, the apparent saturated coordination number of Tb³⁺ ion is 10, and here the binary complex has the structure of PS-(BA)₅-Tb(Ⅲ) and it has the strongest fluorescence emission among all of the binary complexes. When small-molecule Phen is added into the binary complex solution, the ternary complex PS-(BA)_n-Tb(Ⅲ)-(Phen)_m will be formed. As compared with the conventional ternary complexes PS-(BA)₁-Tb(Ⅲ)-Phen₂ and PS-(BA)₁-Tb(Ⅲ)-(Phen)₃ (the molar ratio of the central ion and the two ligands is conventional), the ternary complex with the structure of PS-(BA)₅-Tb(Ⅲ)-(Phen)₁ has the strongest fluorescence emission because of the complete coordination of the ligands to Tb³⁺ ion and the removal of the substituted water molecules around Tb³⁺ ion.     

热重分析法测定乳液共沉法天然橡胶复合材料的组分含量

通过乳液共沉法制备了天然橡胶(NR)/白炭黑、NR/木粉和NR/木粉/白炭黑3种复合材料。采用热重(TG)分析法分别研究各组分及其复合材料的热质量变化过程,并根据单一组分在特定温度下的质量损失,基于残余物含量一定的方法计算出3种NR复合材料中各组分的实际含量。结果表明,复合材料各组分实际含量与其理论含量有一定偏差,证实乳液共沉工艺会造成复合材料中组分质量损失,在使用乳液共沉工艺制备复合材料时需注意调控工艺条件和原材料配比。通过TG分析仪结合理论计算方式测定用乳液共沉法制备的NR复合材料的组分含量具有很好的可操作性,可为乳液共沉工艺研究提供参考。     

Equilibrium studies of ternary systems containing some selected transition metal ions, triazoles and aromatic carboxylic acids

Solution equilibria of the binary and ternary complex systems of the divalent transition metal ions Cu²⁺, Ni²⁺, Zn²⁺, and Co²⁺ with 1,2,4-triazole (TRZ), 3-mercapto-1,2,4-triazole (TRZSH), and 3-amino-1,2,4-triazole (TRZAM) and aromatic carboxylic acids (phthalic, anthranilic, salicylic, and 5-sulfosalicylic acid) have been studied pH-metrically at (25.0±0.1) °C, and a constant ionic strength I=1×10^?1 mol L^?1 NaNO₃ in an aqueous medium. The potentiometric titration curves show that binary and ternary complexes of these ligands are formed in solution. The stability constants of the different binary and ternary complexes formed were calculated on the basis of computer analysis of the titration data. The relative stability of the different ternary complex species is expressed in terms of Δ log K values, log X and R. S.% parameters. The effect of temperature of the medium on both the proton-ligand equilibria for TRZAM and phthalic acid and their metal-ligand equilibria with Cu²⁺, Ni²⁺, and Co²⁺ has been studied along with the corresponding thermodynamic parameters. The complexation behavior of ternary complexes is ascertained using conductivity measurements. In addition, the formation of ternary complexes in solution has been confirmed by using UV-visible spectrophotometry.     

Studies on Synthetic Inorganic Ion Exchangers. IV. Electrophoretic Behavior of Metal Ions on Thorium Phosphate Papers

Abstract

The electrophoretic behavior of 19 metal ions on thorium phosphate papers is described. Seven background electrolytes were used for these studies to allow different time intervals. On the basis of the differential mobilities of the metal ions, which depend on the ion exchange properties of thorium phosphate and the nature of the complexes formed with the electrolyte, some important binary, ternary, and quaternary separations have been achieved.     

Free radical terpolymerization of three non-homopolymerizable monomers. Part IV. Terpolymerization of maleic anhydride, trans-anethole and vinyl-iso-butylether

This paper describes the free radical terpolymerization of maleic anhydride (MSA), trans-anethole (ANE) and vinyl-iso-butylether (VIBE) in chloroform, acetonitrile and tetrachloromethane at 60 °C with α,α′-azoisobutyronitrile as initiator. All these monomers are non-homopolymerizable under the used conditions, and the binary copolymerizations take place only between MSA and one of the donor-monomers but not between the two donor-monomers ANE and VIBE. Their reactivity ratios in the binary copolymerizations are all close to zero. The terpolymerizations result in polymers with always about 50 mol% donor- and 50 mol% acceptor monomer units. Against the common MSA-macroradical, VIBE is a little more reactive than ANE in acetonitrile and in chloroform; but in tetrachloromethane ANE is incorporated into the polymers 1.4 times faster than VIBE at the same concentration. The charge transfer complexes between MSA and two donor monomers have only small equilibrium constants and therefore low concentrations in the monomer feeds. But these complexes are more reactive than the free monomers. Their contribution to the total polymerization rate was kinetically determined for the two binary copolymerizations between MSA and one of the two donor monomers in chloroform. At low monomer concentrations the free monomers dominate the overall polymerization rate. At high monomer concentrations the charge transfer complex participates more to the polymerization process.