Synthesis and Characterization of Rare Earth Complexes with Phthalanilic Acids and Amino Acids

The complexes with the general formula REP3A· H2O [P = 2- (COO ) C6H4CONHC6H4X, X=2-CI, 4-Br; A=Gly, Ala, Leu; RE=Pr3+, Nd3+] were synthesized and characlerized by elemental analysis, IR and reflectance electronic spectra and TG methods. The results show that rare earth ion in each complex is coordinated by three oxygen atoms. One is from the amido and the other two from the hydroxyl in the carboxylate and the amino acid respectively, and each complex contains one coordinate water molecule. Condon parameters Fk, Lande parameters(4f), Nephelanxetic ratio(β), percentage convalency parameter(δ) and bonding parameter(b ) of the chelates were calculated from the reflectance electronic spectra, indicating certain covalent character in the metalligand bond. The apparent decompose activation energies were evaluated and the decompose mechanism were discussed.

THE CRYSTAL STRUCTURE OF RARE EARTH COMPLEX WITH AMINO ACIDS Ⅱ The Crystal Structure of Gtutamate Comptex of Erbium Perchtorate

The crystat structure of {[Er;（L—Glu）;（H;O）;]（ClO;）;·3H;O);has been studied by X-ray diffraction. The crystal is monoctinic with space group P2;and cell parameters a=19.987（3） , b=16.505（3） , c=11.040（2） , β=104.69（1）;, V=3538（1） , Z=2, Dc=2.29 g. cm;, μ=53.2 cm;, F（000）=2384. The asymmetric unit contains two complex motecules and four centre ions. Each erbium （Ⅲ） is coordinated by five oxygen donors from four different glutamates and four oxygen donors from the aqua ligand to form a nine coordination potyhedron. The mean distances of Er—0 （carboxylate） and Er—Ow are 2.439 and 2.41 respectivety. The finat R and Rw are 0.043 and 0. 058, respectivety.

Synthesis and Characterization of Rare Earth Solid Complexes with Sodium 5-Aminosalicylate

Ten new rare earth solid complexes were synthesized by the reaction of sodium 5-aminosalicyliate with rare earth chloride. The structure character, physical and chemical properties of these complexes were studied by IR, UV, ()~1H NMR spectra, TG-DTA, fluorescence, elemental analyses, molar conductance and magnetic susceptibility. The ten rare earth complexes exist in dimeric form probably and the coordination number is seven. The antibacterial activity of the ligand and six complexes was also tested against Staphylococcus aureus, Escherichia coli and Bacillus subtilis, and the effect of Yb complex at 20 mg·ml^(-1) against Staphylococcus aureus is most significant.

Effects of Lanthanum on Liquid Culture and Contents of Amino Acids ofNostoc Commune Flagelliforme Cells

The effects of La(NO3)(3) on the liquid culture and the contents of amino acids of Nostoc commune flagelliforme cells were studied. It is indicated from the experimental results that the growth of Nostoc commune flagelliforme cells can be stimulated by La(NO3)(3) at the concentrations from 1 to 200 mg.L-1, and among them the treatment of 100 mg.L-1 La(NO3)(3) has the largest A(670) and dry weight which increased by 64.9% and 61.1%, respectively as compared with the control, and La(NO3)(3) can also influence the contents of some kinds of amino acids in Nostoc commune flagelliforme cells. The contents of aspartic acid and glutamic acid decreased by 59.9% and 57.9%, respectively, and that of proline increased by 24.5% with the treatment of 200 mg.L-1 La(NO3)(3).

Synthesis and Characterization of Lanthanum Complexes with Amino Acid Schiff Base

Six new complexes of lanthanum with amino acid Schiff base ligands, A-F, were prepared in methanol-aqueous solution. The composition and properties of the title complexes were characterized by elemental analysis, molar conductance, infrared, electronic spectra, H-1 NMR, thermogravimetric and differential thermal analysis.

Study of Complexes of Lanthanum with Amino Acids by Titration Calorimeter

The stability constants and thermodynamic functions for complexes of lanthanum with eight kind of amino acids according to 1∶1 and 1∶2 in proportion have been determined by titration calorimeter at 298.15 K. The enthalpy change makes a predominant contribution to the stability of these complexes. The ring in amino acid associated with lanthanum ion helps to enhance the stability of complexes. Steric effects between rings in complexes leads to that the equilibrium constants of reaction of the complexes (1∶2) is much less than that of the complexes (1∶1).

Studies on the Adsorption of Amino Methylene Phosphonic Acid Resin for Holmium(Ⅲ)

The adsorption behavior and mechanism of a novel chelate resin, amino methylene phosphonic acid resin (APAR) for Ho(Ⅲ) were investigated. The statically saturated adsorption capacity is 258 mg·g^(-1) resin at 298 K in HAc-NaAc medium. The Ho(Ⅲ) adsorbed on APAR can be repeatedly eluted by 3.0 mol·L^(-1) HCl and the elution percentage is as high as 95.8%. The resin can be regenerated and reused without apparent decrease in adsorption capacity. The apparent adsorption rate constant is k_(298)=1.14×10^(-5) s^(-1). The adsorption behavior of APAR for Ho(Ⅲ) obeys the Freundlich isotherm. The thermodynamic adsorption parameter, enthalpy change ΔH of APAR for Ho(Ⅲ) is 11.4 kJ·mol^(-1). The apparent activation energy is E_a=15.8 kJ·mol^(-1). The molar coordination ratio of the functional group of APAR to Ho(Ⅲ) is about 2∶1. The adsorption mechanism of APAR for Ho(Ⅲ) was examined by using chemical method and IR spectrometry.

Phase Chemistry of the Complexes of RE Amino Acids

Forty three phase diagrams of ternary system concerning rare earth salts, α amino acids and water, which were constructed by phase equilibrium methods, were expounded. The influences of the factors such as cations, anions, the structure of amino acids, temperature on the phase diagrams were discussed. Under the guidance of phase equilibrium results, over 150 new solid complexes were prepared. IR, reflecting, UV, FS, and Raman spectra for these complexes were investigated and the regularity of 'tripartite effect', 'tetrad effect', 'Nephelanxetic effect', 'Oddo Harkins' was observed. Thermal decomposition processes of the complexes were confirmed. Based on the comparison with the known crystal structures of rare earth amino acid complexes, an estimation method for predicting the crystal structure data of series complexes was founded. The constant volume combustion energies of the complexes were determined by RBC 1 type rotating bomb calorimeter. The standard enthalpies of combustion and standard enthalpies of formation were calculated for these complexes.

Synthesis，Crystal Structure and Infrared Spectrum of Lanthanum Dinuclear Coordination Compound with Alanine：〔La2（ala）4（H2O）8〕·（ClO4）6

Lanthanum coordination compound with l-alanine[La2（ala）4（H2O）8]·（ClO4）6（ala=l-alanine） was synthesized by reaction of lanthanum perchlorate with l-alanine in aqueous solution and obtained in the form of single crystals.The X-ray crystal structure has been determined and the IR spectrum has been studied.The title compound Cl6La2C12H44O40N4,Mr=1375.2,crystallizes in the triclinic,space group P1 , with parameters: a= 11.227（3）,b=11.445（2）,c=11.014（3）,α=114.46（2）,β=114.51（2）,γ=78.62（2）°,V=1171.73,Z=1,Dc=1.95 g/cm￣3,F（000）=680,μ=22.9 cm￣-1（MoKα）.The final R=0.050,Rω=0.051.In the crystal,two lanthanum ions are coordinated by four alanine molecules via four carboxylate bridges to form a dinuclear coordination compound.Four water molecules are coordinated to each lanthanum ion. There is a symmetric centre between the two lanthanum ions.The IR spectrum of the coordination compound and the relationship between the IR spectrum and the structure have been studied.The mechanism of the configuration inversion of alanine has been proposed.

以稀土为连接单元基于Anderson型[Al(OH)_6Mo_6O_(18)]^(3-)的一维拓展结构的合成及性质研究

在常规条件下合成4个新型的稀土-Anderson型多金属氧酸盐拓展结构化合物(C5H9NO2)2[Ln(H2O)7AlMo6H6O24].11H2O(Ln=La(1),Ce(2),Pr(3),Gd(4);C5H9NO2=脯氨酸),并通过元素分析、红外光谱、紫外可见光谱、热重分析和X射线单晶衍射等方法对化合物晶体结构进行了表征。结构分析表明:以上4个化合物是同构的,均结晶在单斜C2/c空间群。在这些结构中,[Al(OH)6Mo6O18]3-首先通过稀土离子连接形成一维链,相邻的链再进一步通过脯氨酸和结晶水分子的氢键作用形成三维超分子结构化合物。我们以化合物1为代表研究了这类化合物的光催化性能,在紫外光照射下表现出很好的降解RhB(罗丹明B)的光催化性质。

Fluorescence Properties of Eu^(3+)/Gd^(3+)/Citric Acid Mixed Complexes Doping in Silicon Rubber Matrix

Series of doped rare earth complexes-EuxGd(1-x)(CA)3·nH2O (CA=citric acid) were synthesized. Some characterizations were taken for these complexes. The experimental results shows that the doped rare earth complexes have the best fluorescence property when the ratio of Eu and Gd is from 0.7 to 0.3. Silicon rubber-based composites were prepared by mechanical blending the EuxGd(1-x)(CA)3·nH2O and silicon rubber. Then, the fluorescent property of the composites was studied. It is found that the fluorescence intensity of the composites increase linearly with the contents of the rare earth complexes increasing.

Rare earth oxides doped NiO/γ-Al_2O_3 catalyst for oxidative dehydrogenation of cyclohexane

The effect of rare earth oxides （RE=Ce, La, Gd, and Dy） doping of alumina support in NiO/7-A1203 system was investi- gated on its catalytic performance in oxidative dehydrogenation （ODH） of cyclohexane. The physicochemical properties of various samples were followed up through N2 physisorption, temperature programmed reduction （H2-TPR）, X-ray diffraction （XRD）, X-ray photoelectron spectroscopy （XPS） and potentiometric acid-base titration techniques. In the parent NiO/y-A1203 catalyst, Ni species were found to be strongly interacted with alumina surface. Addition of rare earth dopants to ）＇-A1203 in the catalyst system affected the nickel-alumina interaction and resulted in significant modifications in the catalytic performances in the ODH reaction. The results re- vealed the beneficial role of both La203 and Gd2Os doping in enhancing the ODH catalytic activity and selectivity to cyclohexene. H2-TPR and XPS results indicated that majority of Ni species in NiO/La203 modified T-A1203 were more weakly interacted with La203 and alumina whereas both NiO like species and nickel aluminate were present on the surface. Doping with cerium or dyspro- sium increased the nickel-support interaction and led to a decrease in surface nickel concentration. In case of doping with Ce, surface concentration of cerium oxide was higher than those of the other RE oxides; the doped catalyst reached its steady state activity faster than the other catalysts. The acid-base results suggested that RE metals were interacted most likely with acidic surface hydroxyl groups. The degree of nickel-alumina interaction decreased in the following order： LaAI〉GdAI〉CeAI〉DyA1.

Synthesis and luminescent properties of terbium complex with 2-amino-4-chlorobenzoic acid

A novel complex [Tb（L）_2（H_2O）_3·H_2O]（where L=2-amino-4-chlorobenzoic acid） was synthesized and characterized by a series of analysis. The molecular formula of complex was confirmed by Fourier transform infrared（FT-IR） spectroscopy and thermogravimetric/differential thermogravimetric（TG-DTG） measurements. The optical properties of complex was measured by ultraviolet spectroscopy（UV） and fluorescence spectroscopy（FS）. The results indicated that Tb^（3＋） in the complex was coordinated by ligand, and the complex emitted bright yellow-green luminescence with main peak at 548.8 nm with excitation at 369.4 nm.

氨基酸配合物的性质及应用

本文概述了近年来国内外对稀土与过渡金属的氨基酸配合物的研究 ,主要介绍了它们的性质及其应用等。

优化迭代目标转换因子分析法

本文采用一系列步骤,如优化波长集合与优化标准浓度阵的选择,其目的是为了尽量发掘组份间的内在差异且在计算过程中予以保持,降低组份间相关性来改善迭代目标转换因子分析法的分辨混合体系的性能。应用该优化迭代目标转换因子分析法,对二元稀土和三元氨基酸体系进行光度法多组份同时测定,结果满意。

稀土氨基酸配合物的研究情况分析

系统分析了 1991～ 2 0 0 1年间发表的近百篇有关稀土与氨基酸配合物的文献 ,主要讨论作者国籍、刊物、机构、内容和方向等方面的问题。中国的科研人员对稀土氨基酸二元配合物的合成、性质、结构进行了系统的研究。从 90年代末开始 ,研究朝着稀土 氨基酸 过渡金属异核配合物和以氨基酸为配体的高pH值下镧系

稀土氨基酸配合物的相化学及新相的研究

详细研究了使用相平衡法完成的 43个稀土盐 α 氨基酸 水三元体系相图 ,讨论了盐的阳离子、抗衡阴离子、氨基酸结构及温度诸因素对相图的影响。在相平衡结果指导下制备了 15 0余种新型固态配合物 ,研究了它们的IR光谱、反射光谱、UV光谱、FS光谱和拉曼光谱 ,发现了其中存在的“三分组效应”、“四分组效应”、“电子云扩大效应” (Nephelanxeticeffect)、“Oddo Harkins规律”。分析了配合物的热分解机制。在详细比较已有稀土氨基酸配合物晶体结构的基础上 ,提出了预测系列配合物晶体结构数据的方法。使用RBC 1型转动弹量热计测定了几个系列配合物的恒容燃烧能 ,计算了它们的标准燃烧焓和标准生成焓 ,同时发现了其中的“三分组效应”和“四分组效应”

稀土对蚯蚓体内氨基酸含量的影响

采用滤纸接触染毒法,分别进行了氯化稀土、氯化镧与土居动物蚯蚓接触染毒不同时间和不同浓度的试验,研究其对蚯蚓体内氨基酸含量的影响变化.结果表明,Re、La对蚯蚓体内的氨基酸含量影响较显著,在低浓度时总体表现为促进蚯蚓体内氨基酸的形成,而在高浓度状态下则使蚯蚓体内氨基酸含量下降,产生抑制作用.两种稀土在400 mg·L-1浓度时,蚯蚓体内氨基酸含量除脯氨酸外开始上升,随着作用时间延长,氨基酸含量逐渐下降.在100～1200 mg·L-1浓度范围,两种稀土均引起蚯蚓体内脯氨酸含量的下降,产生抑制作用.

稀土氨基酸固体络合物的合成及结构分析进展

本文综述了稀土氨基酸络合物的合成,以及应用红外、核磁、X-射线衍射、热分析等方法进行结构分析研究的进展情况。

不同肥料对冬枣果实品质发育的影响

在冬枣生长期施用氨基酸肥、矿物质肥和稀土肥等3种肥料,研究了3种肥料对果实品质发育的影响。结果表明：3种肥料处理都促进了冬枣果实的横向生长及单果质量的增加,稀土肥和矿物质肥的效果更明显;3种肥料处理都提高了冬枣果实的总糖含量,含糖量上升主要集中在花后70-90 d,以双糖积累为主,其中矿物质肥的效果最明显;在花后90-110 d,冬枣果实的果糖和葡萄糖快速增加,氨基酸肥和稀土肥明显地提高了这2种单糖的含量,氨基酸肥和矿物质肥都提高了冬枣果实生长后期维生素C含量,而稀土肥使果实维生素C下降;矿物质肥和氨基酸肥处理后的冬枣果皮比对照薄,稀土肥加厚了冬枣果皮厚度。3种肥料的肥效为：矿物质肥〉氨基酸肥〉稀土肥。