Synthesis and Fluorescent Properties of New Binuclear Europiumβ-Diketone Chelates Eu_mY_(1-m)(TTA)_3phen as Red Electroluminescent Materials

A new type of binuclear europlum β-diketone chelates Eum Y1-m(TTA)3 phen (0≤m≤1) and the influence of the proportion of Y on fluorescence intensity of the Eu-complexes were studied. It was found the proportion of Y3+ could affect the fluorescence properties and the film formation seriously. only m≥0.5.Y3+ could increase the luminescent intensity and improve the film formalion. As a resull. three new binuclear europium β-diketone chelales consisted of Eu, Y1-m (TTA)3phen (m=0.9. 0.7 and 0.5) were designed and synthesized. Their structures were elucidated by IR. UV. DSC and Elementary Analysis. Their PL properties were studied. The results showed that the three binuclear europium β-diketone chelates had better PL properties and film formation than Eu(TYA)3phen. They could emit sharply red light, and fluorescenl wavelength of them was all at 613nm (half bandwidth 10nm). They can be used as red organic electroluminescent materials (OELMs) in organic electrolminescent devices (OELDS).

Synthesis,Fluorescence and Magnetic Properties of a New Europium(Ⅲ)Complex Eu(C14H9O3)2(C12H8N2)2(NO3)

A new europium(III)complex Eu(CHO)(CHN)(NO)has been synthesized with 2-benzoylbenzoic acid and 1,10-phenanthroline as ligands.Crystal data for the complex are as follows:monoclinic,space group P2/c,a=9.6733(6),b=22.9521(14),c=19.7701(12)?,β=94.9800(10)o,V=4372.8(5)?~3,D=1.557 g/cm~3,Z=4,μ(Mo Kα)=1.501 mm,F(000)=2064,the final R=0.0214 and w R=0.0510.The Eu(III)ion is coordinated by ten atoms to give a bicapped square antiprism coordination geometry.The complex shows two intense fluorescence emission bands arising from the transitions of Eu:~5D→~7F(594 nm)and ~5D→~7F(618 nm).In addition,its XT decreases from 1.29767 cm~3?mol?K at 300 K to 0.01531 cm~3?mol?K at 2 K.

Crystal Structure and Fluorescent Study of a Binuclear Europium(Ⅲ) Complex

A novel binuclear Eu（Ⅲ） complex [Eu2（dpa dioxide）2（NO3）4（bpdioxide）-（EtOH）] （dpa dioxide = di-2-pyridylamine N,N＇-dioxide, bpdioxide = 2,2＇-bipyridine N,N＇-dioxide） has been synthesized and it exhibits strong and sharp fluorescent emission at 614 nm under UV radiation of 245 nm at room temperature. X-ray structural determination indicates two independent Eu（Ⅲ） ions in the structure with different EuO8N and EuOgN environments. The compound crystallizes in the triclinic system, space group P1, with a = 10.8089（7）, b = 11.4670（8）, c = 17.1440（12） A, α = 92.834（2）, β = 93.854（3）, γ = 95.433（2）°, Z = 2, Dc = 1.876 g/cm3, V= 2107.3（2） A3, F（000） = 1168.0, the final R = 0.032 and wR = 0.086 for 6331 observed reflections with I 〉 2σ（I）.

Synthesis and Fluorescent, Magnetic and Thermal Stability Properties of a New Europium（Ⅲ） Complex Eu2(C15H11O3)6(C12H8N2)2

A new europium（Ⅲ） complex Eu2(C15H11O3)6(C12H8N2)2 has been synthesized with 2-（4-Methylbenzoyl）benzoic acid and 1,10-phenanthroline as ligands. Crystal data for the complex are as follows: monoclinic, space group P21/n, a = 15.1238（5）, b = 13.5928（4）, c = 22.9840（7） ?, β = 104.132（3）o, V = 4582.0（2） ?3, Dc = 1.522 g/cm3, Z = 4, μ（Mo Kα） = 1.433 mm-1, F（000） = 2128, the final R = 0.0447 and wR = 0.0826. The Eu（Ⅲ） ion is coordinated by eight atoms to give a distorted square antiprism coordination geometry. The complex shows two intense fluorescence emission bands arising from the transitions of Eu3+: 5 D0 → 7 F1（594 nm） and 5 D0 → 7 F2（617 nm）. The complex is an antiferromagnetism system in the range of 150～300 K. Also reported in the paper is the thermal stability property of the title complex.

Synthesis and Characterization of 2-Decyl-DTPA and Its Gd(Ⅲ) Chelate

The present paper covers the synthesis and the characterization of ligand 2-decyl-3,6,9-tris(carboxymethyl)-3,6,9-triazaundecan-1,11-dioic acid,H_5L,and its Gd(Ⅲ) chelate. The protonation constants for H_5L(lg K H_ i =10.90,8.50,4.55,2.92,2.20) and the stability constant for GdL 2- (lg K _ GdL 2- =22.80) were determined by means of potentiometric titration. They are similar to the corresponding values of DTPA and Gd-DTPA,respectively. The results obtained show that the basicity of the ligand and the stability constant of its Gd(Ⅲ) chelate are not obviously altered after the introduction of a linear chain decyl group into the terminal acetic acid residue of DTPA. The Gd(Ⅲ) chelate may be a potential contrast agent with liver-specificity for magnetic resonance imaging(MRI).

Synthesis,Fluorescence and Magnetic Properties of a New Europium(Ⅲ) Complex Eu(L)3(Phen)2

A new europium（III） complex Eu（L）3（Phen）2（1） with 2-benzoylbenzoic acid（HL） and 1,10-phenanthroline（Phen） as ligands has been synthesized. Crystal data for the complex are as follows： monoclinic, space group P21/c, a = 2.2577（4）, b = 1.23484（19）, c = 1.8789（3） nm, β = 94.918（3）o, V = 5.2189（14） nm^3, Dc = 1.512 g/cm^3, Z = 4, μ（Mo Kα） = 1.269 mm^-1, F（000） = 2408, the final R = 0.0433 and w R = 0.1038. The Eu（III） ion is coordinated by nine atoms to give a single-capped square antiprism coordination geometry. 1 shows two intense fluorescence emission bands arising from the transitions of Eu^3＋： ^5D0→^7F1（597 nm） and ^5D0→^7F2（615 nm） with an excitation wavelength of 396 nm. In addition, 1 displays antiferromagnetic property at low temperature.

LABELING OF PROTEIN WITH A NEW EUROPIUM CHELATE OF 5-CHLOROSULFOYL-2-THENOYLTRIFLUOROACETONE(CTTA)AND APPLICATION TO IMMUNOASSAY

We describe for the first time the synthesis and the optimal conditions for protein labeling with a new fluorescent probe,5-chlorosulfoyl-2-thenoyltrifluoroacetone(CTTA),whicb forms a highly fluorescent conplex with Eu^(3+) when conjugated to protein.The labeled proteins were characterized by absorbance and fluorescence measurements and the effect of labeling on the biological activity of sone proteins was also studied.It is shown that the new label is suitable for applications in time-resolved fluoroimmunoassay.

Synthesis, Crystal Structure and Luminescence of a New Europium(Ⅲ) Coordination Polymer with Imidazole Carboxylic Ligand

A new luminescent compound, {[Eu3（L）4（H2 O）8]·（NO3）·4 H2 O}n（1, H2 L = 2-（pyridine-3-yl）-imidazole-4,5-dicarboxylic acid） has been solvothermally synthesized and structurally characterized by elemental analyses, IR and single-crystal X-ray diffraction. 1 crystallizes in monoclinic, space group C2/c with a = 21.0183（19）, b = 9.5227（6）, c = 28.227（3） ?, β = 106.885（5）o, V = 5406.1（8） ?3, Dc = 2.038 g/cm3, μ = 3.358 mm-1, Mr = 1658.76, F（000） = 3247, Z = 4, the final R = 0.0488, wR = 0.1195 and S = 1.075. The deprotonated L ligand employs a μ4-bridge to coordinate with three Eu（Ⅲ） ion, forming a wave-like（3,4）-connected 2 D structure. The existence of π···π interaction between the pyridine rings of L ligands leads to an infinite 3 D network. Furthermore, the thermal analysis, powder diffraction and solid-state photoluminescent properties of compound 1 have also been investigated.

A FLUORESCENCE QUENCHING IMNUNOASSAY METHOD FOR DETERMINATION OF TRACE ALBUMIN USING UNLABELED EUROPIUM CHELATE

A fluoroimmunoassay method using unlabeled europium chelate is described.The principle is similar to that of fluoroimmunoassay method using lanthanide chelate as labels.The procedure is simple because labeling process is omitted.The detection limit is about 10^(10) mol/L antigen.The relative standard deviation of immunoassay is less than 10%.The recoveries of human serum albumin and estradiol protein conjugate are 96-105% and 111% respectively.

STUDY OF DERIVATIZATION OF PROTEIN WITH A EUROPIUM CHELATE AND APPLICATION TO HIGH-PERFORMANCE LIQUID CHROMATOGRAPHY

A europium chelate of 5-chlorosulfoyl-2- thenoyltrifluoroacetone(CTTA)was investigated for precolumn derivatization of protein for high performance liquid chromatography.This new label was highly fluorescent and suitable for time-resolved fluorometric detection.The detective limit of protein is less than 0.3ug in sample with a volume of 100ul.Theoretically,the new label can also be used in gel electrophoresis and protein blotting.

Spectral Analysis and Crystal Structure of Tris（benzoyl－trifluoroacetonate）bis（triphenyl－phosphine oxide）Europium（Ⅲ）

C6H5COCHCOCF3)3[(C6H5)3PO]2Eu,Mr=1354.01,triclinic P1,a=11.244(3),b=12.252(3),c=23.784(1),α=79.66(2),β=76.38(3),γ=71.44(3)°,V=2999.33,Z=2,Dc=1.499g/cm3,μ(MoKα)=11.79 cm-1,final R=0.066(Rw=0.069) for 7899 observed reflections with I】3σ(Ⅰ),The europium ion(Ⅲ) is coordinated by eight oxygen atoms,of which six from C6H5COCHCOCF3 and the other two from (C6H5)3PO,to form a dodecahedral configuration with the average distance of Eu-O(C6H5COCHCOCF3) of 2.410 and that of Eu-O[(C6H5)3PO] of 2.385.The coordination of Eu(Ⅲ) with the ligands was characterized by IR and Raman spectroscopy.The molecular rigidity,which effects luminescence of the complexes,was discussed by fluorescence spectroscopy of the Eu(Ⅲ) complexes.

新的β-二酮及其Eu(Ⅲ)三元配合物的合成与发光研究

合成了一种新的β 二酮,4 甲氧基联苯甲酰三氟丙酮(1 (4′ meothoxybiphenyl 4yl ) 4,4,4, trifluoro butane 1,3 dione,MBPTFA),以元素分析和1H NMR谱确定了其组成;进而以MBPTFA作第一配体和邻菲罗啉(1,10 phenanthroline,Phen)为第二配体,与EuCl3反应,合成了一种三元配合,Eu(MBPTFA)3Phen。用元素分析、红外、紫外 可见吸收光谱和荧光光谱进行了表征。荧光分析结果表明:配体本身是一种良好的蓝色发光材料;配合物中的有机配体能够有效地的把吸收的能量传递给中心Eu3+离子,强烈敏化Eu3+发光,且发射谱线很窄,主发射峰为Eu3+的5D0-7F2发射。这对寻找新型稀土配合物发光材料和制备有机电郅发光器件具有一定的价值。

α-十四烷基-DOTA及其钆(Ⅲ)螯合物的合成与表征(英文)

Synthesis and characterization of the ligand,[10-( α -tetradecylcarboxymethyl)-1,4,7,10-tetraazacyclododecane-1,4,7-triacetic acid,H 4 L]and its Gd (Ⅲ) chelate are described.Protonation constants for H 4 L(lgK iH =10.62,9.50,4.74,4.12)and the stability constant for GdL - (lgK GdL - =24.60)were determined by potentiometric titrations.The results obtained show that the basicity of the ligand is not significantly altered and the ligand still maintains the strong chelating properties of the parent DOTA after introduction of a linear chain tetradecyl group at the acetic side chain of DOTA.

含有载流子传输功能基团咔唑和噁二唑的有机铕(Ⅲ)配合物的合成及其发光性能

合成了一种含有载流子传输功能基团咔唑和噁二唑的有机铕(Ⅲ)配合物.在研究了光致发光等性能的同时,制备了结构为ITO/NPB(40 nm)/2.5%铕(Ⅲ)配合物:CBP(30 nm)/BCP(10 nm)/Alq3(30 nm)/LiF(1 nm)/Al(100 nm)的电致发光器件,器件在612 nm处有半峰宽为4 nm的高纯度的明亮红光发射,起亮电压约为6 V,在17.3 V时达到最大亮度1778 cd/m2.

高度支化聚芳酰胺/稀土铕(Ⅲ)发光材料的合成及表征

通过溶液聚合的方法以氮三乙酸(NTA),4,4′-二氨基二苯醚(ODA)为原料合成了高度支化聚芳酰胺(PNOA),并以PNOA为配体与EuCl3配位制备出Eu/PNOA高分子发光材料。采用红外光谱分析了PNOA和Eu/PNOA的结构,用热重(TG)分析了Eu/PNOA的热稳定性,用紫外及荧光光谱法表征了它们的光学性能。结果表明,PNOA与稀土离子Eu3+发生了配位作用,Eu/PNOA在被350nm的紫外光激发后发出616nm的红色荧光,是一种具有潜力的高分子功能材料。

稀土Eu(Ⅲ)双酞菁衍生物LB膜的荧光性(英文)

合成了八 4 (四氢糠氧基 )酞菁铕 ? ,通过元素分析、红外光谱、质谱和紫外可见光谱加以确认。测定了配合物的 Π A曲线，证明它有有的成膜性， Z型沉积形成的 LB膜材料有很强的荧光响应，随着 LB膜厚度的增加，荧光性增强。掺杂邻菲咯啉形成的混合 LB膜，其荧光性比纯膜强。但不是邻菲咯啉加入的量越多荧光性越强。配合物∶邻菲咯啉 =1∶ 10时（摩尔比），有最好的荧光行为。用电子光谱对 LB膜的结构进行了表征。

聚苯乙烯基硫脲螯合树脂的制备及对Au(Ⅲ)吸附性能的研究

以氯甲基化聚苯乙烯树脂微球为原料,经胺化、接酯反应,合成了侧链上含有硫脲功能基的新型螯合树脂,研究了该树脂对Au(Ⅲ)的吸附性能。结果表明,树脂对Au(Ⅲ)吸附容量为1.84mmol.g-1,吸附过程符合G.E.Boyd液膜扩散方程,液膜扩散为吸附主控步骤;等温吸附可由Langmuir模型描述,为单分子层吸附。

Al(Ⅲ)-槲皮素配合物的光谱分析

采用UV和IR分析手段,研究在甲醇溶剂酸性和中性条件下,槲皮素(3,3,′4,′5,7-五羟基黄酮)与A l(Ⅲ)形成配合物的构型、反应配比及在配位反应过程中配体分子中各个配位点的配位能力大小及优先配位的顺序。实验结果表明:在酸性介质中,槲皮素与A l(Ⅲ)所形成配合物的反应配比为A l(Ⅲ)∶Q=1∶1,其配位点为3-羟基-4-酮,配位构型中心为A l(Ⅲ)与一个槲皮素分子形成五元环四配位的配合物。在中性介质中发生两步配位反应,第一步配位反应发生在3-羟基-4-酮配位点其反应配比为1∶2,配位构型为中心A l(Ⅲ)与两个槲皮素分子形成两个五元环之间四配位的配合物;第二步配位反应发生在3,′4′-二羟基配位点其反应配比为2∶1,两个A l(Ⅲ)离子分别在上述两个配位点与一个槲皮素分子形成五元环四配位构型的配合物。

荧光光度法研究修饰β-环糊精与Eu(Ⅲ)-金霉素体系的相互作用及其应用

在pH=6.00的NH4Ac-HAc缓冲条件下,金霉素(CTC)能显著增强Eu(Ⅲ)位于波长618nm处的特征荧光强度。加入修饰的β-环糊精后,体系的荧光强度进一步显著增强,据此建立了荧光分光光度法测量金霉素的方法。实验表明,修饰β-环糊精时,金霉素的线性范围为3.99×10-7～1.05×10-5 mol/L,检出限为1.99×10-7mol/L。该方法用于人血清、尿液及牛奶中金霉素的测定,结果满意。

2,6-二乙氧基-β-环糊精对铕(Ⅲ)-强力霉素络合物包合作用的研究及其分析应用

在pH=9.4的NH4Cl-NH3·H2O的缓冲溶液条件下,强力霉素能与铕(Ⅲ)生成二元络合物并发射出铕(Ⅲ)位于612 nm处的特征荧光,加入2,6-二乙氧基-β-环糊精后,体系的荧光强度显著增强,且增强的荧光强度与强力霉素的浓度呈线性关系,据此建立了荧光分光光度法测量强力霉素的方法。在最佳实验条件下,测量的线性范围和检出限分别为6.2×10-8~1.3×10-5mol/L和1.4×10-8mol/L。本方法曾用于血样和尿样中强力霉素的测定。本研究讨论了荧光增强的机理。