铕-镧-诺氟沙星-十二烷基磺酸钠稀土共发光体系的研究及分析应用

利用荧光光度法研究了铕-镧-诺氟沙星-十二烷基磺酸钠体系的稀土共发光效应,并对其作用机理进行了探讨.研究了本体系测定Eu3+的最佳条件,结果表明,体系的荧光强度与Eu3+的浓度在1.0×10-10～5.0×10-7 mol/L范围内呈良好的线性关系,其检出限为2.0×10-12 mol/L.采用标准加入法测定混合稀土样品中的Eu3+,结果令人满意.     

稀土元素共发光效应的研究——铕-钇-二苯甲酰甲烷-二苯胍-丙酮荧光体系及分析应用

本文详细研究了铕-钇-二苯甲酰甲烷(DBM)-二苯胍(DPG)-丙酮体系的共发光效应,在最佳实验条件下,Eu~(3+)在1.0×10~(-10)～5.0×10~(-8)mol/L浓度范围内与荧光强度成线性关系,检测限达5.0×10~(-13)mol/L。用多点增量标准加入法测定了合成样品中的铕结果满意。     

甲基蓝-铕为光散射探针测定美他环素的共振瑞利散射及共振非线性散射法研究

在pH=5.50的HAc-NaAc缓冲体系中,低浓度的甲基蓝(MB)-铕稀土配合物的光散射较弱,将微量的美他环素(MTC)加入后体系的共振瑞利散射(RRS)、二级散射(SOS)和倍频散射(FDS)均显著增强,且光散射信号与MTC浓度在一定范围内呈良好的线性关系,据此建立了灵敏的测定美他环素的共振瑞利散射和共振非线性散射分析法.实验以RRS法考查了甲基蓝-铕-美他环素体系形成三元离子缔合物的适宜条件、影响因素等,并初步探讨了其反应机制.     

镁-美他环素胶束体系荧光特性及美他环素的测定

研究了在金属离子存在下美他环素在胶柬体系中的荧光特性,实验结果表明：在pH 9.50～11.30的H3PO4-HAc-H3BO3-NaOH缓冲溶液中,镁离子和非离子表面活性剂曲通X-100对美他环素的荧光具有显著的协同增敏作用.据此建立了测定药物制剂中美他环素的荧光光谱法.定量线性范围为0.16～16μg/mL,检出限为0.0036μg/mL,相对标准偏差为1.9%.     

稀土混合共发光效应的研究——(铽-钆-钇)-铕-噻吩甲酰三氟丙酮-氯化甲基三烷基铵-Triton X-100荧光体系

本文研究了铽(Tb)、钇(Y)、钆(Gd)及它们的混合物对铕(Eu)-噻吩甲酰三氟丙酮(TTA)-氯化甲基三烷基铵(N_(263))-Triton X-100体系的共发光效应,发现稀土离子混合物的共发光效应具有线性加和性,用混合共发光体系不仅能保持单个稀土离子的共发光体系的增敏性,而且抗干扰能力增强,并经过实际样品分析的验证,结果令人满意。     

稀土混合共发光效应的研究—（铽—钆—钇）—铕—噻吩甲酰三氟丙酮—氯化…

本文研究了铽（Ｔｂ）、钇（Ｙ）、钆（Ｇｄ）及它们的混合物对铕（Ｅｕ）－噻吩甲酰三氟丙酮（ＴＴＡ）－氯化甲基三烷基铵（Ｎ２６３）－Ｔｒｉｔｏｎ Ｘ－１００体系的共发光效应，发现稀土离子混合物的共发光效应具有线性加和性，用混合共发光体系不仅能保持单个稀土离子的共发光体系的增敏性，并经过实际樯品分析的验证，结果令人满意。     

茜素红S-铕(Ⅲ)-米诺环素体系的共振瑞利散射光谱研究及应用

在pH=4.4的NaAc-HAc缓冲溶液中,茜素红S-铕(Ⅲ)与米诺环素形成三元配合物,导致共振瑞利散射(RRS)增强,据此建立了一种测定米诺环素的RRS分析法。在λ=370nm处,米诺环素浓度在0.073～5.493μg/mL范围内与体系RRS强度呈良好的线性关系,检出限为0.021μg/mL。该方法灵敏度高,简单、快速,具有良好的选择性和重复性,对尿样进行加标回收及用于片剂、胶囊中米诺环素的测定,结果满意。     

美他环素与β-环糊精形成包合物的荧光光谱研究及其分析应用

用荧光光谱法研究了美他环素(MTC)与β-环糊精(β-CD)形成包合物的荧光光谱特性. 对美他环素与β-环糊精形成包合物的条件、作用机理进行了研究, 探讨了可能的包合方式, 测定了包合物的包合常数和热力学参数ΔH、ΔS和ΔG, 验证了包合反应驱动力. 实验结果表明: MTC与β-CD可形成1∶1的包合物, 包合物的包合常数为382.19 mol/L. 包合过程中, ΔH=-99.10 kJ/moL, ΔS=-286.42JmoL-1K-1, 常温下ΔG<0. 说明包合反应为自发反应, 且是一个焓驱动过程. 在Tris-HCl缓冲溶液中, β-CD的加入生成包结物可显著增强美他环素的荧光强度, 据此建立了测定药物制剂中美他环素的新方法. 该方法的定量线性范围为1.93×10-7～1.45×10-5 mol/L, 检出限为1.45×10-8 mol/L,相对标准偏差为1.2% (n=13). 对药物制剂中美他环素的含量进行了测定, 测定结果与标示量吻合, 平均回收率为102%.     

The fluorescence enhancement effect of Tb-Gd-adenosine triphosphate-phen system and its analytical application

It is found that the fluorescence of Tb-adenosine triphosphate (ATP)-phenanthroline (phen) system can be enhanced by Gd³⁺. The fluorescence enhancement of the Tb-Gd-ATP-phen system is considered to originate from intramolecular and intermolecular energy transfers, and the energy-insulating sheath effect of Gd-ATP-phen complex. In addition, a new energy transfer pathway in Tb-ATP-phen system is proposed. As a mediator, phen can transfer the energy absorbed by ATP to Tb³⁺ through the stacking action between aromatic ring of phen and purine ring of ATP. The proposed method has been used to determine trace amount of ATP. The detection limit is 5.4 × 10⁻⁹ mol/l, which is about 40 times lower than that of the Tb-ATP-phen system. The proposed method is one of the most sensitive fluoremetries of ATP.     

钇(Ⅲ)-莫西沙星配合物的荧光性质及分析应用

钇(Y3+)与莫西沙星(MoxifloxacinMXFX)形成的配合物能显著地增敏莫西沙星的荧光强度,据此,建立了测定莫西沙星的新方法。该方法的检出限为8.5×10-10mol/L;莫西沙星的浓度在1.0×10-8～1.0×10-6mol/L范围内与配合物体系的荧光强度呈良好的线性关系。对1.0×10-6mol/L莫西沙星平行测定12次,RSD为1.1%。该法可用于测定尿样中的莫西沙星。对荧光增强机理作了简要的探讨。     

Die Reaktionen von Europium und Yttrium mit N‐Iod‐triphenylphosphanimin. Kristallstrukturen von [EuI2(DME)3], [Eu2I(NPPh3)5(DME)] und [Y2I(NPPh3)4(THF)4]+I3–

The Reactions of Europium and Yttrium with N‐Iodinetriphenylphosphoraneimine. Crystal Structures of [EuI₂(DME)₃], [Eu₂I(NPPh₃)₅(DME)] and [Y₂I(NPPh₃)₄(THF)₄]⁺I₃^– When treated with ultrasound, the reaction of europium metal with INPPh₃ in 1,2‐dimethoxyethane (DME) leads to the complexes [EuI₂(DME)₃] ( 1 ) and [Eu₂I(NPPh₃)₅(DME)] ( 2 ) which are separated from each other by fractional crystallization. On the other hand, the reaction of yttrium metal with INPPh₃ under similar conditions in THF gives the ionic phosphoraneiminato complex [Y₂I(NPPh₃)₄(THF)₄]⁺I₃^– ( 3 ). All complexes are characterized by crystal structure determinations. 1 : Space group P2₁, Z = 2, lattice dimensions at 188 K: a = 848.9(1); b = 1059.4(1); c = 1227.9(1) pm; β = 93.793(6)°; R = 0.0246. In the molecular structure of 1 the europium atom is eightfold coordinated with a bond angle I–Eu–I of 158.51°. 2 · 2 DME: Space group P1, Z = 2, lattice dimensions at 193 K: a = 1405.5(1); b = 1652.2(2); c = 2203.7(2) pm; α = 89.404(11)°; β = 72.958(11)°; γ = 78.657(11)°; R = 0.0391. In 2 the europium atoms are linked by the μ‐N‐atoms of two (NPPh₃^–) groups to form a planar Eu₂N₂ four‐membered ring. One of the Eu atoms is terminally coordinated by the N atoms of two (NPPh₃^–) groups, thus achieving a distorted tetrahedral surrounding. The second Eu atom is coordinated by the N atom of one (NPPh₃^–) group, by the terminally bounded iodine atom and by the oxygen atoms of the DME chelate, thus achieving a distorted octahedral surrounding. 3 · 6¹/₂ THF: Space group P1, Z = 2, lattice dimensions at 103 K: a = 1739.7(2); b = 1770.1(2); c = 2153.8(3) pm; α = 74.929(15)°; β = 84.223(14)°; γ = 64.612(12)°; R = 0.0638. In the cation [Y₂I(NPPh₃)₄(THF)₄]⁺ of 3 the yttrium atoms are linked by the μ‐N atoms of two (NPPh₃^–) groups as well as by the μ‐I atom. One (NPPh₃^–) ligand and two THF molecules complete the distorted octahedral coordination at each yttrium atom.     

Fluorescence Enhancement of Rare Earths by Yttrium and its Application

Abstract

A study of the enhancement effect on the fluorescence intensity of the Eu³⁺–-thenoyltrifluoroacetone (TTA)–-cetyltri–-methylammonium bromide (CTMAB) and the Dy³⁺ pyrocatechol–-3,5-disulphonic acid (Tiron) systems by Y³⁺has been carried out. In the presence of yttrium the fluorescence intensity of the systems was enhanced by a factor of about 100 and 15, respectively. The fluorescence intensity was a linear function of the concentration of europium or dysprosium in the range 1.0 × 10^?10–-1.0 × 10^?8mol dm^?3 and 8.0 × 10^?8–-9.0 × 10^?6mol dm^?3, respectively. The detection limit was 1.0 × 10^?11mol dm^?3 and 1.0 × 10^?10mol dm^?3, respectively. The standard addition method was used for the determination of europium or dysprosium in rare earth oxides and gave satisfactory results. The mechanism of enhanced fluorescence was proposed.     

钇离子及其阳离子卟啉配合物与金黄色葡萄球菌的相互作用

用LKB-2277生物活性检测系统考察了Y~(3+)，TMP及其阳离子型钇卟啉配合物 {[Y(TMP)(H_2O)_3]Cl, TMP = 5, 10, 15, 20-四（4-甲氧基苯基）卟啉}对金黄色 葡萄球菌全程代谢作用的影响，测定了Y~(3+)，TMP和[Y(TMP)(H_2O)_3]Cl对金黄 色葡萄球菌作用的产热曲线，根据产热曲线求算了金黄色葡萄球菌在Y~(3+)，TMP ，[Y(TMP)(H_2O)_3]Cl作用下生长代谢的速率常数k_1，k_2，抑制率I_1，I_2，和 半抑制浓度IC_(50)~1，IC_(50)~2等热动力学参数。实验结果表明：Y~(3+)，[Y (TMP)(H_2O)_3]Cl对金黄色葡萄球菌的生长代谢有双向调节作用，在低浓度下表现 为刺激作用，高浓度为抑制作用，而TMP对金黄色葡萄球菌的生长代谢主要为抑制 作用，在低浓度下表现为刺激作用，高浓度为抑制作用，而TMP对金黄色葡萄球菌 的生长代谢主要为抑制作用，对金黄色葡萄球菌的抑制作用[Y(TMP)(H_2O)_3]Cl > TMP > Y~(3+)。     

钇(Ⅲ)、铽(Ⅲ)、铒(Ⅲ)对氨基苯甲酸配合物共掺杂二氧化硅的光声光谱研究

合成了Tb(p-ABA)₃·H₂O和Ln(p-ABA)₃·H₂O(p-ABA: 对氨基苯甲酸, Ln: Y或Er)配合物共掺杂的SiO₂样品. 荧光光谱测定结果表明, Y(p-ABA)₃·H₂O的引入增强了样品中Tb³⁺离子的特征发光, 而Er(p-ABA)₃·H₂O的引入使Tb³⁺的发光减弱. 光声光谱结果表明, 与Tb³⁺配合物单掺的样品相比, Tb³⁺和Y³⁺配合物共掺样品的光声强度降低; 而Tb³⁺和Er³⁺配合物共掺的样品则情况相反. 实验测定了共掺杂样品的相对量子发光效率和发光寿命, 从无辐射跃迁和辐射跃迁的角度提出共发光效应可能的机制. 结合对室温下陈化干燥样品的分析发现, 只有经适当的热处理过程才能在SiO₂凝胶中形成具有多核结构的稀土配合物.     

KZnF3：Eu^3＋单晶生长及光谱特性

利用Ｂｒｉｄｇｍａｎ－Ｓｔｏｃｋｂａｒｇｅｒ方法在氩气气氛下生长出ＫＺｎＦ３：Ｅｕ＾３＋单晶，测定了晶体的激发光谱、荧光发射光谱和ＥＳＲ谱，讨论了Ｅｕ离子的取代格位。     

Crystal Structures of the Europium and Yttrium Hydroxychromates Eu(OH)(CrO4) and Y(OH)(CrO4); Structural Evolution as a Function of the Ln3+ Ionic Radius

The compounds Eu(OH)(CrO₄) and Y(OH)(CrO₄) were obtained under hydrothermal conditions and characterized by single‐crystal X‐ray diffraction analysis. They are isostructural and crystallize in the monoclinic system, space group P2₁/n (no. 14) with lattice parameters a = 8.278(1) Å, b = 11.400(2) Å, c = 8.393(1) Å, β = 93.76(2)°, V = 790.3(2) Å³, Z = 4, d = 4.79 g · cm^–3 for Eu(OH)(CrO₄) and a = 8.151(1) Å, b = 11.362(2) Å, c = 8.285(1) Å, β = 94.23(1)°, V = 765.2(2) Å³, Z = 4, d = 3.85 g · cm^–3 for Y(OH)(CrO₄). The [EuO₈] polyhedra form infinite double chains along the a direction, which are connected by common edges and corners. These double chains are related together in the two other directions by the [CrO₄]^2– tetrahedra to form a three‐dimensional network in which channels appear parallel to the [100] direction. We examine the structural evolution, as a function of the Ln³⁺ ionic radius, in the series Ln(OH)(CrO₄) compounds (with Ln = Nd, Eu, Gd, Tb, Er, Yb) and Y(OH)(CrO₄). To determine the best coordination number of each lanthanide and yttrium ions, different calculations of bond valence sum were realized.     

Y2O3:Eu (5 mol%) with Ag nanoparticles prepared by citrate precursor

Y₂O₃:Eu³⁺ (5 mol% Eu³⁺) and Y₂O₃:Eu³⁺ (5 mol% Eu³⁺) containing 1 mol% of Ag nanoparticles were prepared by heat treatment of a viscous resin obtained via citrate precursor. TEM and EDS analyses showed that Y₂O₃:Eu³⁺ (5 mol% Eu³⁺) is formed by nanoparticles with an average size of 12 nm, which increases to 30 nm when Ag is present because the effect of metal induced crystallization occurs. Ag nanoparticles with a size of 9 nm dispersed in Y₂O₃:Eu³⁺ (5 mol% Eu³⁺) were obtained and the surface plasmon effect on Ag nanoparticles was observed. The emission around 612 nm assigned to the Eu³⁺ (⁵D₀→⁷F₂) transition enhanced when the Ag nanoparticles were present in the Y₂O₃:Eu³⁺ luminescent material.     

溶胶-凝胶法制备(Ca-Zn)O-Al_2O_3-SiO_2:Eu~(3+),Bi~(3+)发光体

用溶胶-凝胶法合成无机玻璃、玻璃陶瓷和陶瓷已得到发展。本文报道利用此法低温合成(Ca-Zn)O-Al_2O_3-SiO_2:Eu~(3+),Bi~(3+)发光体的研究结果。所用原料为99.99％的Eu_2O_3、99.99％的金属铝、99.999％的金属铋及CaCO_3、ZnCO_3和Li_2CO_3(提纯)。上述原料用HNO_3(GR)溶解。将计算的摩尔比量的Si(OC_2H_5)_4、C_2H_5OH和CH_3COOH以及Ca(NO_3)_2、Al(NO_3)_3、Zn(NO_3)_2、LiNO_3、Bi(NO_3)_3和Eu(NO_3)_3溶液,在一定的pH值下,在75℃水浴中回流数小时,经水解,缩聚成凝胶。制得