铽配合物Tb(2-MBA)_3·2H_2O和Tb(2-MBA)_3 phen的荧光性能研究

以2-甲基苯甲酸(2-MBA)为第一配体、1,10-邻菲罗啉(phen)为第二配体,制备了三元铽配合物Tb(2-MBA)3phen和二元铽配合物Tb(2-MBA)3·2H2O,并利用元素分析、红外光谱、紫外光谱、荧光光谱和荧光寿命对二者的结构与性能进行分析表征。研究结果表明:三元铽配合物Tb(2-MBA)3phen的荧光发射强度要强于二元铽配合物Tb(2-MBA)3·2H2O,而二者的荧光寿命恰好相反,三元铽配合物Tb(2-MBA)3phen的荧光寿命短于二元铽配合物Tb(2-MBA)3·2H2O。热重分析表明Tb(2-MBA)3·2H2O的热分解温度要远高于Tb(2-MBA)3phen。     

稀土烟酸与8-羟基喹啉三元配合物的合成、表征及荧光光谱

合成了 4种稀土烟酸 (HL)与 8 羟基喹啉 (Hhq)的三元固体配合物 ,对它们进行元素分析 ,确定其通式为REL2 ·hq·2H2 O (RE =La ,Eu ,Tb ,Dy) ,用摩尔电导、TG DTA分析、IR、UV和荧光光谱等研究了配合物的有关性质。结果表明 ,烟酸脱掉羧酸上的质子以酸根的形式与稀土离子呈双齿配位 ,而吡啶环上的氮原子未参加配位。hq- 的羟基氧和杂氮原子与RE3+ 离子配位。配体与稀土配位后 ,配合物中稠环数目增多 ,π键共轭程度增大。配合物中所含的水可能为配位水。荧光光谱研究发现 ,La和Dy的配合物的荧光表现为配体的荧光 ,Eu配合物中心离子的特征荧光峰表现不明显 ,而Tb配合物中配体能有效地将吸收的能量传递给Tb3+ ,敏化Tb3+ 的发光 ,发射较强荧光     

一个新双氮杂冠醚及其稀土硝酸盐配合物的合成表征

合成了一个新的二十员大环双氮杂冠醚及其与稀土硝酸盐所形成的1∶2(M∶L)型配合物, 并经过红外光谱, 元素分析, 摩尔电导, 热分析及荧光光谱等方法表征. 结果表明, 配位是通过配体中的C-O-C进行的, 而Ar-O-C未参与配位, 同时含两分子配位水, 对Sm3+, Eu3+, Tb3+, Dy3+的配合物进行了荧光光谱测定, 均有较强的荧光强度, 其中Tb(Ⅲ)配合物荧光强度最高.     

对叔丁基杯[6]芳烃稀土配合物的合成及荧光性能研究

合成了以对叔丁基[6]芳烃(H6L)及DMF为配体,单一稀土RE3+(sm3+,Dy3+,Tb3+)及混合稀土Tb3+:(Ln3+(Ln3+=Gd3+,Y3+)为中心的5种稀土配合物.对其进行了元素分析、摩尔电导、红外光谱、差热分析、紫外光谱、核磁共振氢谱及荧光性能研究.荧光光谱的测试表明:Tb3+及其掺杂配合物具有较强的特征荧光,荧光惰性离子(Gd3+,Y3+)对Tb3+的荧光有增强作用,其中Y3+的敏化效果明显.     

铽-聚二甲基硅氧烷配合物的荧光特性

用多种谱学方法证明聚二甲基硅氧烷(PDMS)中的氧原子能与Tb3+键合生成Tb3+和PDMS的配合物(Tb3+-PDMS), 并发现生成配合物后, PDMS和Tb3+的荧光发射同时得到增强. 荧光强度的增强与配合物中Tb3+含量有关, 当配合物中Tb3+的含量为2.0%(w)时, 配合物的荧光强度最大, 可增强1547%左右.     

Tb(Ⅲ)-PNVA-co-PSt纳米微球的制备及其光学性能研究

以KPS为引发剂,一定比例的水/乙醇混合物为反应介质,采用改进的无皂种子乳液聚合方法,制得了以聚苯乙烯(PSt)为核、 聚N-乙烯基乙酰胺(PNVA)为壳的单分散纳米级PNVA-co-PSt共聚微球,并使Tb3 离子与纯化后的PNVA-co-PSt微球进行配位,得到了Tb(Ⅲ)-PNVA-co-PSt配合物微球. 利用扫描电子显微镜、 Zeta-电位、红外光谱、紫外光谱及荧光光谱对微球及其配合物进行了表征. 结果表明:PNVA-co-PSt微球具有良好的球形结构;Tb3 离子与PNVA-co-PSt微球之间确实存在配位作用,大大增强了配合物微球在紫外区的吸光性能,且在PNVA-co-PSt微球和Tb3 之间发生了有效的Frster能量传递,使得位于490,545以及583 nm处的Tb3 的特征发射明显增强. 配合物微球的荧光光谱峰形尖锐,说明其单色性较好,是一种有应用潜力的发光新材料.     

邻苯二甲酸铽发光纤维的研究

在液相中合成了邻苯二甲酸铽发光配合物。通过元素分析、滴定分析、红外光谱(FTIR)分析,确定其化学组成为Tb2L3·6H2O。热分析(TG DTA)结果表明配合物在317℃以下稳定性较好。X射线衍射分析(XRD)、扫描电镜分析(SEM)结果表明配合物为块状晶体物质,晶粒大小为1～2μm。荧光光谱分析(PL)结果表明配合物在紫外光的激发下发出铽的特征荧光。将制得的发光配合物与粘胶纤维作用,在一定的条件下,采用酸浴湿法纺丝,制得稀土发光粘胶纤维。对所得的发光纤维进行荧光光谱测试。实验结果表明,在紫外光270nm的激发下,发射峰位于540nm附近。它归属于5D4→7F5跃迁,是Tb3+的特征绿色发光,与配合物的光谱极为相似。漫反射光谱实验结果表明:与粘胶纤维相比,加入发光配合物后的粘胶纤维对紫外光有明显的吸收。     

铽、镝-3-噻吩乙酸二元、三元配合物的合成及表征

合成了四种新型的铽、镝的二元、三元配合物.通过元素分析、EDTA配位滴定分析表明其通式为RETh3·2H2O,RETh3phen(RE=Dy,Tb;Th=3-噻吩乙酸根;phen=1,10邻菲啰啉);对配合物进行了紫外光谱、红外光谱、荧光光谱、热重分析.结果表明,二元配合物在100℃左右失去结晶水,三元配合物具有较好的稳定性;在TbTh3phen中,3-噻吩乙酸和邻菲啰罗啉能很好地将能量传递给Tb3+离子,Tb3+离子546nm绿色荧光发射峰最强.     

稀土(铕、铽)配合物中荧光性能相互影响

以5-磺基水杨酸、α-噻吩甲酰三氟丙酮为小分子配体,以溶液聚合制备的甲基丙烯酸甲酯和丙烯酸共聚物(PMMA-AA)为高分子配体,合成了一系列铕、铽的高分子配合物,并通过UV、IR和元素分析对其结构进行了表征。用荧光分光光度计研究了它们的荧光性能及铕、铽之间的荧光性能的互相影响规律,讨论了它们的荧光发射峰位、荧光发射强度与组成的关系。实验结果表明,在稀土(铕、铽)多核高分子荧光配合物中,Eu3 与Tb3 之间的荧光光谱有相互敏化或猝灭的作用。其中Eu3 对Tb3 的荧光有很强的荧光猝灭作用,且在n(Eu3 )∶n(Tb3 )=1∶1时,Eu3 对Tb3 的荧光猝灭作用最大;Tb3 在低浓度n(Eu3 )∶n(Tb3 )大于1∶1时,Tb3 对Eu3 的荧光有猝灭作用,Tb3 在高浓度n(Eu3 )∶n(Tb3 )小于1∶1时,Tb3 对Eu3 的荧光有很强的敏化作用。     

新型稀土Eu,Tb(Ⅲ)芳香羧酸配合物的合成及发光性能

以2-二苯胺羰基苯甲酸(L)为第一配体,咪唑并[5,6-f]邻菲罗啉(IP)为第二配体,合成出新型稀土铕、铽三元配合物。采用元素分析、红外光谱、紫外-可见光谱对配体和配合物的结构进行了表征。红外光谱分析表明配合物中的稀土离子与第一配体L中的氧原子以及第二配体IP中的氮原子进行了配位。紫外光谱表明配合物主要是由第一配体L吸收能量。通过荧光光谱、荧光量子效率和荧光寿命研究了配合物的荧光性能,结果显示:两种配合物均表现出稀土离子的特征发射,且配合物的荧光量子效率和荧光寿命与发光强度成正比,配合物Tb(L)3IP的各项荧光性能均优于Eu(L)3IP。     

Photochemical Fluorescence Enhancement of Terbuium-Fleroxacin System and Determination of Fleroxacin

ABSTRACT

The sensitized fluorescence of the terbium ion (Tb³⁺) can be observed when excited in the presence of fleroxacin (FLRX) in the aqueous solution because a Tb³⁺ -FLRX complex was formed. The sensitised fluorescence was greatly enhanced after the complex system was irradiated by 365nm ultraviolet light. The irradiation makes the complex system undergo photochemical reactions and a new terbium complex which is more favourable to the intramolecular energy transfer is formed. On this basis a new sensitive and selective photochemical fluorimetric method for the determination of FLRX was developed. Under the optimum experimental conditions, the linear range of the determination is 1.0—200×10^?7 mol 1^?1 for FLRX, and the detection limit is 1.2×10^?8mol 1^?1. Without any pre-treatment the recoveries of FLRX in human urine samples were determined with satisfaction.     

Luminescence behavior of a water soluble calix[4]arene derivative complex with terbium ion(III) in gelation solution

The complexation luminescence behavior of a water soluble calix[4]arene derivative, 5,11,17,23-tetra-sulfonate-25,26,27,28-tetra-carboxymethoxycalix[4]arene (L) with lanthanoid ion (Tb(3+)) has been investigated in gelation solution at 25 degrees C by using UV-vis and fluorescence spectra. The results obtained indicated that the water soluble calix[4]arene derivative can form an efficient energy transfer complex with terbium ion(III). The fluorescence of L x Tb(3+)complex is partially quenched by gelatin in gelation solution. The quenching intensity is related to the concentration and the hydrolysis degree of gelatin. Absorption and fluorescence spectra analysis show that the -COO(-) groups on gelatin have a definite binding ability to Tb(3+), and then, gelatin could compete binding with calix[4]arene derivative upon complexation with Tb(3+), leading to the relative fluorescence quenching of the formation complex of terbium(III) ion with calix[4]arene derivative.     

Photochemical fluorescence enhancement of the terbium-lomefloxacin complex and its application

The sensitized fluorescence intensity of the terbium ion (Tb(3+)) can be notably enhanced after the Tb(3+)-lomefloxacin(LFLX) complex system was irradiated by 365nm ultraviolet light. A photochemical reaction occurs to the irradiated Tb(3+)-LFLX complex. A new Tb(3+)system with intense fluorescence is obtained. On this basis a new sensitive and selective photochemical fluorimetry for the determination of LFLX was established. Under the optimal experimental conditions, the linear range of the determination is 2.0-500x10(-8) mol l(-1) for LFLX, and the detection limit is 6.0x10(-9) mol l(-1).Without any pre-treatment the recoveries of LFLX in human urine and serum were determined.     

Observations on photochemical fluorescence enhancement of the terbium(III)-sparfloxacin system.

Fluorescence of terbium(III) was sensitized when excited in the presence of sparfloxacin (SPFX) in the aqueous solution because a Tb(III)-SPFX complex was formed. The sensitized fluorescence was further enhanced when this system was exposed to 365 nm ultraviolet light. By the spectral properties and contrast experiments, it is proved that irradiation makes this system undergo photochemical reactions and a new terbium complex which is more favorable to the intramolecular energy transfer is formed. The mechanism of photochemical fluorescence enhancement of the Tb(III)-SPFX system is discussed and a new sensitive and selective photochemical fluorimetry for the determination of SPFX is established. Under the optimum conditions, the linear range is 1.0-50 x 10(-7) M for SPFX, the detection limit is 3.0 x 10(-9) M and the R.S.D. for 5.0 x 10(-7) M SPFX is 1.3% (n = 9). Without any pretreatment the recovery of SPFX in human urine was determined with satisfaction.     

The study on the effect and mechanism of the second ligands on the luminescence properties of terbium complexes

The binary complex of Tb(III) with N-phenylanthranilic acid (N-HPA) was synthesized, and the ternary complexes were synthesized by introducing 1,10-phenanthroline (Phen), 2,2'-dipyridyl (Bipy), trioctylphosphine oxide (TPPO) as the second ligand, respectively. These complexes were characterized by infrared spectra, UV spectra and fluorescence spectra. The effect and mechanism of different second ligands on the fluorescent intensity of the terbium N-phenylanthranilic acid complexes was discussed. It showed that all the complexes exhibited ligand-sensitized green emission. The luminescence intensity increased in the sequence of Tb(N-PA)(3)Phen相似文献   

掺铽聚丙烯薄膜的研究

合成了化学组成为Ｙ１－ｘＴｂｘＬ３和Ｌａ１－ｘＴｂｘＬ３（Ｌ＝Ｃ８Ｈ７Ｏ２）的两种荧光粉，将其掺杂到聚丙烯中，制得两种聚丙烯荧光薄膜，通过测试机械性能，微分扫描式量热法分析，紫外分光光谱和荧光光谱测定，研究膜的物理和荧光性能。结果表明：这两种掺铽聚丙烯膜在３６５或２５４ｎｍ紫外光激发下，都能发出黄绿色荧光。掺入Ｙ１－ｘＴｂｘＬ３的聚丙烯膜的荧光强度大于掺Ｌａ１－ｘＴｂｘＬ３的聚丙烯膜。     

铽配合物Tb(PMIP)3(PhCA)的合成及阴离子识别研究

本文设计合成了稀土铽配合物Tb(PMW)3(PhCA)作为阴离子试剂,利用荧光光谱考察了其与F-、Cl-、Br-、I-、ClO4-、NO3-、AcO-和H2PO-4等阴离子的作用.研究结果表明:不同阴离子的加入能够调控,Tb(PMIP)3(PhCA)的发光行为,当一定量的氟离子(醋酸根离子、磷酸二氢根离子)加入到Tb(PMIP)3(PhCA)的乙腈溶液中后,荧光发射增强;过量的氟离子(醋酸根离子、磷酸二氢根离子)加入后则使其荧光淬灭.而在乙腈和水混合溶液中,Tb(PMIP)3(PhCA)则能选择性识别氟离子和磷酸二氢根离子.     

Spectrofluorometric determination of trace amounts of coenzyme II using norfioxacin-terbium complex as a fluorescent probe.

When terbium ion (Tb3+)-norfloxacin (NFLX) complex is issued a fluorescent probe, in a buffer solution of pH = 7.6, NADP can remarkably enhance the fluorescence intensity of the Tb3+ -NFLX complex at lambda = 545 nm. The enhanced fluorescence intensity of Tb3+ is in proportion to the concentration of NADP. The dynamic range for the determination of NADP is 1.11 x 10(-7) - 6.16 x 10(-5) mol l(-1), with a detection limit of 4.31 x 10(-8) mol l(-1). This method is simple, practical and relatively free of interference from coexisting substances, so it can be successfully applied to determination of NADP in synthetic water samples.     

Tunability of Fluorescence Property of a Terbium‐Complex‐Containing Polymer via Incorporation of a Transition‐Metal Complex

Summary: In this study, a terbium‐complex monomer and transition‐metal‐complex monomers (Fe^III, Mn^II, and Ni^II complex monomers) are synthesized, and novel acrylate copolymers are then obtained through covalent attachment of the terbium complex and the transition‐metal complex onto the macromolecular chain simultaneously. The copolymers developed herein present the characteristic fluorescence properties of the terbium(III ) ion, The incorporation of an Mn^II complex into a Tb^III‐containing polymer leads to greater fluorescence enhancement compared with the Ni^II complex, while the incorporation of the Fe^III complex results in fluorescence quenching, thus the incorporation of different transition‐metal complexes into the copolymers ensures tunability of the copolymer's fluorescence property.

Fluorescence emission spectra of the copolymer solid films. Solid: P‐Tb; dash‐dot: P‐Tb‐Mn^II; dash: P‐Tb‐Ni^II; and dot: P‐Tb‐Fe^III.     

Interaction of Tb(III) and hydrolyzed polyacrylamides in solution as a gel and in the solid state

Formation of the HPAM-Tb³ complex in solution was observed in the intensification of Tb(III) fluorescence, viscosity, and light scattering. The interaction is dependent on the degree of hydrolysis of the copolymer and the pH of the solution. As the pH value increases, an intensification of the interaction and formation of a gel is observed. The latter was associated with the appearance of crosslinks in which terbium, or one of its hydrolysis products, works as a binding agent between chains. After drying, the characterization of the residues of the gels was effected by analytical determination (C, H, N, Cl, Tb), fluorescence, and infrared spectrophotometry. The analysis and fluorescence revealed the existence of particles of terbium hydroxide; the infrared spectrophotometry showed the binding of terbium (III) to carboxylate of the copolymer.