稀土离子跨人血红细胞膜的荧光法研究

采用Fura-2荧光浓度指示剂对红细胞的稀土跨膜作用进行了系列研究.结果表明,稀土离子不能通过完整的红细胞膜进入细胞内.通过与离子载体实验相对照,发现细胞ATP耗竭后,低浓度的稀土离子(5×10^-6mol/L)不能跨膜进入ATP-耗竭红细胞.KCl去极化及加入电压依赖性钙通道刺激剂Bay-K8644对稀土离子的跨膜也没有促进作用.在Ca²⁺内流正常的情况下,低浓度稀土离子(5×10^-6mol/L)对钙离子内流无影响.增大稀土离子浓度到5×10^-4mol/L,用显微镜观察此时红细胞已开始溶血.在模拟胞内离子组分的缓冲液中(pH=7.05),比较了La³⁺,Eu³⁺和Ca²⁺对Fura-2的敏感程度.此条件下Fura-2对La³⁺和Eu³⁺的检测限分别为10-12和10-14mol/L,对Ca²⁺的检测限为10-8mol/L,并测得Fura-2-La³⁺(Eu³⁺)的络合比为1∶1,表观离解常数为1.7×10^-12和4.95×10^-14mol/L,表明用此法检测稀土离子跨膜行为相当灵敏有效.     

尖吻蝮蛇毒抗凝血因子Ⅱ的稀土离子荧光探针研究

尖吻蝮蛇毒抗凝血因子(ACF)分子中有两个钙离子结合位点,钙离子对ACF的内源荧光有增强作用,稀土离子(Nd³⁺,Sm³⁺,Eu³⁺,Gd³⁺和Tb³⁺)能取代ACF分子中的钙离子,并对ACF的内源荧光有不同程度的猝灭作用,其中Tb³⁺接受ACF分子中Trp残基传递的能量后,特征荧光增强.稀土离子与ACF荧光滴定表明,ACF分子中有两个稀土离子结合位点,稀土离子和钙离子在ACF分子中两个结合部位是共同的竞争结合部位.ACF与不同稀土离子之间有相近的表观结合常数K₁或K₂.Tb³⁺与RE³⁺(RE=Nd,Sm,Eu或Gd)间线性自由能关系表明,稀土离子与ACF结合时,没有明显的空间效应.ACF分子中的两个结合位点在结构上都有较大的柔性,这种结构柔性为钙离子在ACF与活化凝血因子X的结合反应中起到的促进作用提供了结构基础.     

稀土离子诱导钙调蛋白构象变化后的单克隆抗体制备

采用单克隆抗体技术研究了三价稀土离子与钙调蛋白作用后对其与靶分子识别能力的影响。牛脑钙调蛋白经2.4-二硝基氟苯修饰后再结合三价的铕离子,然后免疫Balb/c小鼠,经过3次免疫后在小鼠血清中检测到相应的抗体,抗体效价为1:12000;用杂交瘤细胞技术制备出一株抗钙调蛋白的单克隆抗体细胞株2C3;酶联免疫吸附法(ELISA)测定结果证实钙调蛋白结合稀土离子前后对该抗体的识别能力存在显着差异,表明该抗体可以用于进一步研究金属离子对钙调蛋白构象变化及其对靶分子识别的影响。     

氧化镥中杂质对铈掺杂硅酸镥多晶粉体光谱性质影响

氧化镥中杂质元素对其分离制备工艺、生产成本及镥基硅酸盐闪烁晶体的性能有很大影响,但杂质元素对晶体的性质影响研究较为有限,有待进一步完善。 本文采用高温固相法制备了Lu₂O₃分离过程中关键杂质元素Yb³⁺和Ca²⁺共掺杂Lu₂SiO₅∶Ce多晶粉体,研究了Yb³⁺或Ca²⁺含量对多晶粉体光谱性质的影响,结果表明:Yb³⁺或Ca²⁺共掺并未改变发射光谱的形状和位置,随着杂质元素摩尔分数的增加,光谱强度和荧光寿命逐渐降低。     

Study on the controllable synthesis of SH-MCM-41 mesoporous materials and their adsorption properties of the La3+, Gd3+ and Yb3+

SH-MCM-41 was examined in adsorption and desorption experiments to investigate the adsorption capacities of La³⁺, Gd³⁺ and Yb³⁺ and the reusability.     

Keggin结构稀土钼钒磷四元杂多配合物的合成、表征及苯酚羟化制苯二酚的催化活性

合成了5种通式为(NH₄)₁₅[RE(PMo₉V₂O₃₉)₂]·xH₂O(RE=La³⁺,Ce³⁺,Gd³⁺,Y³⁺,Yb³⁺)的稀土钼钒磷四元杂多配合物,并用IR,UV,XRD,ICP,TG-DTA和CV等手段对其结构和性能进行了表征.催化活性实验表明,标题化合物对苯酚过氧化氢羟化制苯二酚反应有良好的催化活性.     

高特异性的La3+靶向多肽探针及其在细胞和斑马鱼成像中的应用

研究报道了一种新型多肽探针(TPE-Glu-Glu-Pro-Gly-Glu-Glu-NH₂),该多肽探针单独存在时没有荧光，稀土元素镧离子(La³⁺)加入后，与多肽探针特异性结合，限制了四苯乙烯(TPE)分子内的旋转，导致溶液产生强的荧光信号。该探针具有特异性，16种常见金属的存在也几乎不影响其对La³⁺的靶向检测。我们研究发现，谷氨酸在多肽探针结合La³⁺的过程中发挥重要作用，减少谷氨酸个数会影响其特异性识别。滴定和Job工作曲线结果表明，该多肽探针与La³⁺结合比为1∶2,结合常数为1.29×10¹⁰(L/mol)²。计算机模拟结果表明，La³⁺与多肽探针酰胺键的氧和谷氨酸羧基中羟基的氧结合。该探针可以高灵敏检测水溶液和唾液中的La³⁺,检测限分别为0.12μmol/L和0.32μmol/L。该高灵敏、高特异性多肽探针具有良好的生物相容性，可以用于细胞和斑马鱼中La³⁺     

镧系元素Dawson结构钨钒磷四元杂多配合物的合成、表征以及对H2O2分解的催化活性

合成了通式为K₁₅H₃[Ce(P₂W₁₆VO₆₁)₂]·61H₂O、K₁₅H₄[Ln(P₂W₁₆VO₆₁)₂]·xH₂O(Ln=La³⁺,Pr³⁺,Nd³⁺,Sm³⁺,Eu³⁺,Gd³⁺,Dy³⁺,Yb³⁺)的9种镧系元素Dawson结构的钨钒磷四元杂多配合物,并用IR、UV、NMR、ESR、XRD、TG-DTA等对其结构和性质进行了研究。该类配合物具有与K₁₆[Ce(P₂W₁₇VO₆₁)₂]·50H₂O类似的结构,对H₂O₂分解有较高的催化活性。     

锌-稀土矩形纳米簇的构筑及近红外发光性能

本文设计了一个新型含苯-甲基-苯骨架的席夫碱配体,构筑了两个具有矩形结构的锌-稀土纳米簇[Ln₂Zn₂L₂(OAc)₆] (Ln = Yb (1)和Er (2))。该席夫碱配体以“伸展型”配位模式与稀土离子进行配位,使这些锌-稀土纳米簇表现出较大的分子尺寸结构(0.7 nm × 1.1 nm × 2.2 nm)。荧光性质研究表明,由Zn/L组成的发色基团能有效敏化1和2中Yb³⁺和Er³⁺离子的近红外发光。通过对荧光量子产率及寿命进行分析发现,Zn/L对Yb³⁺离子的传能效率要高于Er³⁺离子。     

KMnF3的熔盐法合成及掺铕体系的发光性质

采用简单的熔盐法合成了KMnF₃单相样品及稀土离子铕掺杂的KMnF₃（KMnF₃：Eu）荧光样品. X射线粉末衍射（XRD）表征结果显示,KMnF₃属立方晶系,为AMF₃型钙钛矿结构氟化物. 对样品KMnF₃：Eu的发光性质进行了研究,荧光光谱分析结果表明,Mn²⁺,Eu²⁺与Eu³⁺这3个发光中心共存于KMnF₃：Eu体系中. 讨论了改变掺入Eu离子的摩尔分数对Mn²⁺,Eu²⁺以及Eu³⁺发光强度的影响.     

Probing site-specific calmodulin calcium and lanthanide affinity by grafting

Ca2+ binding is essential for the biological functions of calmodulin (CaM) as a trigger/sensor protein to regulate many biological processes in the Ca2+ -signaling cascade. A challenge in understanding the mechanism of Ca2+ signaling is to obtain site-specific information about the Ca2+ binding properties of individual Ca2+ -binding sites of EF-hand proteins, especially for CaM. In this paper, we report the first estimation of the intrinsic Ca2+ affinities of the four EF-hand loops of calmoduin (I-IV) by individually grafting into the domain 1 of CD2. Taking advantage of the Trp residues in the host protein, we first determined metal-binding affinities for Tb3+, Ca2+, and La3+ for all four grafted EF-loops using Tb3+ aromatic resonance energy transfer. EF-loop I exhibits the strongest binding affinity for Ca2+, La3+, and Tb3+, while EF-loop IV has the weakest metal-binding affinity. EF-loops I-IV of CaM have dissociation constants for Ca2+ of 34, 245, 185, and 814 microM, respectively, with the order I > III approximately equal to II > IV. These findings support a charge-ligand-balanced model in which both the number of negatively charged ligand residues and the balanced electrostatic dentate-dentate repulsion by the adjacent charged residues are two major determinants for the relative Ca2+ -binding affinities of EF-loops in CaM. Our grafting method provides a new strategy to obtain site-specific Ca2+ binding properties and a better estimation of the cooperativity and conformational change contributions of coupled EF-hand proteins.     

Bright white light through up-conversion of a single NIR source from sol-gel-derived thin film made with Ln3+-doped LaF3 nanoparticles

White light was generated from a single silica thin film made with Yb0.75La0.2Eu0.05F3, La0.45Yb0.5Er0.05F3, and La0.75Yb0.2Tm0.05F3 nanoparticles by exciting with a single source near-infrared light (980 nm CW diode laser). Eu3+ and Tm3+ ions are responsible for red and blue emission, respectively. Er3+ ion is responsible for green as well as red emission. The Commission Internationale de l'Eclairage (CIE) coordinates of the resulting light were easily adjusted by controlling the concentration of Ln3+ (Eu3+, Er3+, Tm3+) ions in the nanoparticles as well as the concentration of Ln3+-doped nanoparticles in the sol-gel thin layer.     

Na~+/Ca~(2+) Exchange-mediated La~(3+) Entry in Human Lymphocytes

With extensive applications the rare earth elements to agriculture, medicine and animal husbandry, whether rare earth ions can cross cell membranes and participate in the metabolism of animals and plants is not clear until now. Otherwise, rare earth ions have different interaction fashions to different kinds of cells, therefore, in this study we determined whether La3+ enter human peripheral blood lymphocytes via Na+/Ca2+ exchanger (measured with fura-2).Relative sensitivity of fura-2 to Ca2+…     

1,2-邻苯二氧基二乙酸铕及掺杂L(L=La,Y,Yb,Nd)配合物的合成及荧光性质研究

在乙醇体系中,以氯化铕与1,2邻苯二氧基二乙酸和二苯甲酰甲烷反应合成了三元配合物Eu-BDDA-DBM以及弱荧光离子La3+,Y3-,Yb3-和Nd3+掺杂的铕配合物.通过红外、紫外-可见、热重、荧光光谱对配合物进行了表征.红外光谱表明,单一配合物和掺杂配合物具有相似的配位结构.荧光光谱表明,La3+和Nd3+离子掺杂可以大幅度提高的铕配合物的荧光强度,其中La3+掺杂荧光强度增强最明显.     

四氮杂大环与镧系金属配合物的热力学研究

The stability constants of the 1:1 complexes of H4L2 (5,12-dipheny1-7, 14-dimethyl-1,4,8,11-tetraazamasrocyclotetradecane-N', N", N"',N""-tetraacetic acid) with Ln3+ (Ln=La, Nd, Pr, Sm, Eu, Gd, Dy, Yb) were determined by potemtiometric titrations in 0.5mol•L-1 KCl at 40±0.1℃, 50±0.1℃ and 60±0.1℃ respectively. The △H, △S and △G of the coordination reactions of H4L2 with Ln3+ were given. Influences of the steric effect and temperature changes on the stability lanthanide complexes were discussed thermodynamically.     

水溶液中新型四氮杂二乙酸基取代大环及其镧系配合物的热力学研究

The protonation constants of the macrocycle H₂L¹ (c-meso-2,4,4,11,13,13-hexamethyl-1,5,10,14-tetraazacyclooctadecane-N,N＂-diacetic acids)were determined potentiometricly and by computer fitting in 0.5 mol·L^-1 KNO₃ solution at 25±0.1℃, 30±0.1℃ and 40±0.1℃. The stability constants of the 1∶1 complexes of H₂L¹ with La³⁺, Nd³⁺, Sm³⁺, Eu³⁺, Gd³⁺, Dy³⁺, Yb³⁺ were determined by the same method at 40±0.1℃. The ΔH、 ΔS and ΔG of the coodination reaction of H₂L¹ with H⁺ in the aqueous solution were found.     

Quantitative study on La~(3+) influx mediated by sodium-calcium exchanger in human lymphocytes

Whether La3+ can enter human peripheral blood lymphocytes by the Na+/Ca2+ exchanger or not and the effect of La3+on the Na+/Ca2+ exchanger activity are examined by fura-2 technique. And that whether La3+ is sequestered by intracellular organelles (mainly endoplasmic reticulum and mitochondria) is studied by this method. La3+uptake is obviously stimulated by pre-treating the cells with ouabain and by removing extracellular Na+, and intracellular La3+concentration ([La3+]i) is directly proportional to its extracellular concentration ([La3+]o). But when [La3+]o exceeds 0.4 mmol/L, the 340/380 nm ratio of fluorescence is no longer varied and the maximum [La3+], is 1.5×10-12 mol · L-1. The higher concentration of La3+ (0.1 mmol/L) increases Na+/Ca2+ exchange-mediated calcium influx, but lower concentration (10 μmol/L) appears to block calcium influx. The results also suggest that cytosolic La3+ is transported by the ATP-dependent Ca2+ pump. Intracellular Ca2+ stores are depleted by ionomycin, and then ion     

Coordination chemistry of trivalent lanthanide and actinide ions in dilute and concentrated chloride solutions

We have used EXAFS spectroscopy to investigate the inner sphere coordination of trivalent lanthanide (Ln) and actinide (An) ions in aqueous solutions as a function of increasing chloride concentration. At low chloride concentration, the hydration numbers and corresponding Ln,An-O bond lengths are as follows: La3+, N = 9.2, R = 2.54 A; Ce3+, N = 9.3, R = 2.52 A; Nd3+, N = 9.5, R = 2.49 A; Eu3+, N = 9.3, R = 2.43 A; Yb3+, N = 8.7, R = 2.32 A; Y3+, N = 9.7, R = 2.36 A; Am3+, N = 10.3, R = 2.48 A; Cm3+, N = 10.2, R = 2.45 A. In ca. 14 M LiCl, the early Ln3+ ions (La, Ce, Nd, and Eu) show inner sphere Cl- complexation along with a loss of H2O. The average chloride coordination numbers and Ln-Cl bond lengths are as follows: La3+, N = 2.1, R = 2.92 A; Ce3+, N = 1.8, R = 2.89 A; Nd3+, N = 1.9, R = 2.85 A; Eu3+, N = 1.1, R = 2.81 A. The extent of Cl- ion complexation decreases going across the Ln3+ series to the point where Yb3+ shows no Cl- complexation and no loss of coordinated water molecules. The actinide ions, Am3+ and Cm3+, show the same structural effects as the early Ln3+ ions, i.e., Cl- ion replacement of the H2O at high chloride thermodynamic activities. The Clion coordination numbers and An-Cl bond lengths are: Am3+, N = 1.8, R = 2.81 A; Cm3+, N = 2.4, R = 2.76 A. When combined with results reported previously for Pu3+ which showed no significant chloride complexation in 12 M LiCl, these results suggest that the extent of chloride complexation is increasing across the An3+ series. The origin of the differences in chloride complex formation between the Ln3+ and An3+ ions and the relevance to earlier work is discussed.     

The Different Fluorescent Response of Quin 2 to the Binding of Ca^2＋ and La^3＋ and its Application

The fluorescence spectra of Quin 2, (2-[(2-bis-[carboxymethyl] amino-5-methylphenoxy)methyl]-6-methoxy-8-bis [carboxymethyl] aminoquiniline), a Ca^2 probe, were investigated upon incubation with Ca^2 or La^3 . The results showed that binding of La^3 to Quin 2 resulted in different fluorescent spectrum from that of Ca^2 . Based on this observation, a fluorescent method was developed for simultaneously determination of the dissociation rates of Ca^2 and La^3 from a Ca-La- calmodulin complex (Ca2La2CaM).     

Synthesis and rare earth metal ion-sensing properties of aza-crown derivative incorporating with diaryl-1,3,4-oxadiazole

A new fluorescent chemosensor (A18C6-Ox) in which a monoaza-18-crown-6 is linked to a diaryl-1,3,4-oxadiazole fluorophore by a methylene spacer has been synthesized to evaluate binding interaction with the rare earth ions by means of absorption and emission spectrophotometry. Absorption spectra of A18C6-Ox showed a broad band at 289nm and there was no significant change in the presence of Sc3+, La3+, Pr3+, Sm3+, Gd3+, Tb3+, Yb3+ and Lu3+ except for Ce3+ and Eu3+. From the emission spectral change of A18C6-Ox, interaction of the rare earth ions with A18C6-Ox is very strong. The formation of A18C6-Ox complexing with Sc3+, La3+, Pr3+, Sm3+, Gd3+, Tb3+, Yb3+ and Lu3+ leads to an increase in fluorescence intensity of A18C6-Ox, while Ce3+ and Eu3+ ions interact strongly causing fluorescence quenching of A18C6-Ox. In addition, the optimal complexation stoichiometry of the rare earth ions with A18C6-Ox was investigated by the fluorescent titration.