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镧系金属有机骨框架(Lanthanide metal organic frameworks,Ln-MOFs)是以镧系离子为中心,与配体有机物组合的多孔材料,具有良好的光学性质,在许多领域有广泛的应用。不同的镧系离子与相应的有机配体结合,可组成不同性能的Ln-MOFs。在众多镧系元素中,Tb3+和Eu3+是良好的发光中心,常被用于组建发光Ln-MOFs。由Tb3+/Eu3+与有机配体形成的Ln-MOFs具有独特的荧光特性、较大stokes位移以及长发光寿命等优点在荧光检测领域具有重要应用。本文综述了基于Tb3+/Eu3+的Ln-MOFs在离子检测、生物标志物检测以及小分子检测领域的研究进展,对Ln-MOFs的发展前景进行了展望。 相似文献
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利用溶剂热方法合成了一种以Tb3+离子为中心的金属有机骨架材料[Tb2(bpt)2(H2O)2]·(DMA)4.5, 并通过单晶X射线衍射(SXRD)、 粉末X射线衍射(PXRD)、 元素分析(EA)、 热重分析(TGA)、 傅里叶变换红外光谱 (FTIR)以及荧光光谱技术(FS)表征了该材料的结构与基本物理化学性质. 单晶衍射分析结果显示该材料具有包含一维直孔道的三维结构, 结构中孔道窗口尺寸约为1.23 nm×1.10 nm. 荧光分析测试结果表明该材料对Cr3+离子有荧光响应, 离子检测限低至0.22 mg/L, 同时具有良好的选择性, 在Cr3+离子的荧光检测领域具有重要的应用潜力. 相似文献
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设计了一个三羧酸柔性配体L,其可提供捕获镧系金属的亲和力及调节配体的能级,并可用于合成同时具有高稳定性和双发射特性的柔性镧系金属有机骨架(Eu-MOF)材料。利用柔性配体到金属的不完全能量转移使得材料出现350 nm和623 nm处的强双发射,构筑了比例荧光传感平台。由于柔性配体不稳定的电子构型以及Eu3+和Fe3+之间的离子交换,Eu-MOF可用于对Fe3+的比例荧光检测。Eu-MOF对Fe3+的检出限为0.592μmol/L,并分别在1.0~60.0μmol/L和60.0~90.0μmol/L范围内呈线性关系,响应时间低至3 min。Eu-MOF对Fe3+检测具有良好的选择性、抗干扰性以及可回收性,用于实际样品中Fe3+检测,加标回收率为98.4%~102.6%。 相似文献
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镧系金属配位聚合物因其独特的组成、结构和性质被广泛应用于荧光识别检测性质研究,但其功能导向构筑依然具有挑战性。本文基于双功能基团配体构筑策略构筑了一例Tb~(3+)配位聚合物[Tb(TZI)(DMF)_2(H_2O)]·(H_2O)(1)((H_3TZI=5-(1-氢-5-四唑基)间苯二甲酸,DMF=N,N-二甲基甲酰胺)),在对其进行详细结构表征的基础上研究了其金属离子识别检测性质。结果表明,基于羧酸和四唑基团与Tb~(3+)离子配位能力的不同,在确保Tb~(3+)配位聚合物成功构筑的同时可将四唑作为识别位点引入配位聚合物框架,使得配合物1可展现出基于金属离子与四唑功能位点配位导致的荧光增强,可实现对Zn~(2+)和Na~+离子的识别检测。本文所报道的结果可为镧系金属配位聚合物的荧光识别检测性质导向构筑提供有价值的参考。 相似文献
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本文通过水热法合成了含有3种不同稀土离子的层状稀土氢氧化物(Gd0.5Tb0.5-xEux)2(OH)5NO3.nH2O,并选择有机物水杨酸(HSA)作为敏化剂,通过在水热条件下的离子交换反应,成功将其以有机阴离子形式与层状稀土氢氧化物插层组装获得有机-无机杂化荧光材料(SA--LRHs∶xEu)。荧光性质测定表明,SA-通过有效的能量转移增强了Tb3+的特征绿色荧光发射,随着Eu3+含量的增加,Eu3+的特征红色荧光发射随之增强,而Tb3+的特征绿色荧光发射随之减弱。在此基础上,将发光颜色可调的有机-无机荧光材料与聚甲基丙烯酸甲酯(PMMA)复合组装出透明的荧光薄膜。 相似文献
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0 引言 稀土是一类具有特殊结构和性质的元素,稀土元素不仅大量用于工业,而且在农业和医学领域也有广泛应用 [1,2].其中,镧系离子以其独特的光、电、磁、催化和分析等性能而受到人们的广泛关注,并进行了大量的研究.镧系离子本身发光效率低,目前,设计并合成含有稀土离子La3+和Eu3+的超分子配合物,作为发光分子器件和荧光探针成为稀土配位化学,材料科学,超分子化学,分析化学和生物化学等研究领域的热点课题之一 [3~8].但对它们的热化学行为的研究鲜见文献报道. 相似文献
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应用分子力学计算得到了α-丙氨酸和L-组氨酸在溶液中的分子结构。在此基础上, 通过对镧系离子诱导位移的分析和模拟, 计算了氨基酸镧系离子配合物的13^C NMR作接触位移, 模拟了配合物的分子结构。结果表明, 在α-丙氨酸镧系离子配合物中, Ce^3+, Pr^3+, Nd^3+与丙氨酸的一个氧原子和一个氮原子形成双齿配位; Sm^3+, Eu^3+, Tb^3+, Dy^3+, Ho^3+, Er^3+, Tm^3+, Yb^3+则与两个氧原子形成双齿配位, 在L-组氨酸镧系离子配合物中, Ce^3+~Eu^3+与组氨酸的两个氧原子和α-氨基的氮原子形成三齿配位, 镧系离子Tb^3+~Yb^3+则与两个氧原子形成双齿配位, 同时, 还讨论了pH条件对氨基酸镧系离子配合物结构的影响。 相似文献
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利用烯-巯加成的方法,合成了一种带有三联吡啶基团的有机硅氧烷,该中间体用核磁共振、红外、质谱等手段进行了表征确认.以该中间体作为第二配体,加入稀土(Eu3+、Tb3+)烟酸配合物,在正硅酸乙酯的存在下用溶胶-凝胶法原位制备了稀土(Eu3+、Tb3+)烟酸配合物与二氧化硅基质以共价键相连的烟酸稀土分子杂化发光材料.通过红外光谱、紫外-可见光漫反射光谱、荧光光谱和寿命测试表征了制备的杂化发光材料.荧光光谱数据表明在杂化材料中,由于三联吡啶配体通过有效的分子内传能过程将其激发态的能量传递给稀土离子的发射能级,从而极大地提高了稀土离子的特征发射.掺铕离子的最强发射为617nm,是纯红光发射;而掺铽离子的最强发射为543nm,是典型的绿光发射.掺铕和铽的分子杂化材的荧光寿命分别为0.66ms,0.68ms,同时荧光衰减均为一级指数衰减,说明稀土离子在杂化材料中分散得很均匀. 相似文献
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废水中有机化合物的快速检测一直是一个重要的问题。采用离子交换法制备了具有荧光特性的铽基金属有机凝胶MOG(Tb)。研究表明,即使存在其他有机化合物,微量的呋喃唑酮(FZD)、甲硝唑(MDZ)、2,4-二硝基甲苯(2,4-DNT)和4-硝基苯酚(4-NP)也能有效猝灭MOG(Tb)的荧光发射,证明MOG(Tb)干凝胶作为一种化学传感器可以有效检测抗生素(FZD、MDZ)和硝基芳香族化合物(2,4-DNT、4-NP)。有趣的是,青霉素钾(PCLP)却能增强MOG(Tb)的荧光。此外,还进行了MOG(Tb)干凝胶的可回收性和水稳定性试验,并得到了较为满意的结果。 相似文献
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利用平衡析,原子吸收,荧光滴定和荧光寿命测定等方法确定了皖南尖吻蝮蛇蛇毒纤溶组分中Ca^2+含量,并利用荧光光谱研究了Tb^3+与FP中色氨酸残基之间能量转移和FP中的微区结构。 相似文献
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Wang S Liu Q Chen Z Zhang Y 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2000,56(9):1843-1849
By using equilibrium dialysis, atomic absorption spectrometry, fluorescence titration and determination of fluorescence lifetime, it can be determined that each fibrinolytic principle (FP) molecule contains one Ca2+-binding site and one Ca2+ ion, which can be substituted by a Tb3+ ion completely. The intramolecular energy transfer between Tb3+ and the tryptophan (Trp) residue in FP has been investigated through fluorescence spectroscopy. In the FP molecule, the excited energy can transfer from the Trp residue as an energy donor to the Tb3+ ion substituted as an acceptor. The distance between Tb3+ and the Trp residue, approximately 0.38 nm, has been calculated with the experimental data and Forster theory. 相似文献
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Jun‐Hua Wei Jing‐Wei Yi Min‐Le Han Bo Li Shan Liu Ya‐Pan Wu Lu‐Fang Ma Dong‐Sheng Li 《化学:亚洲杂志》2019,14(20):3694-3701
Effective detection of organic/inorganic pollutants, such as antibiotics, nitro‐compounds, excessive Fe3+ and MnO4?, is crucial for human health and environmental protection. Here, a new terbium(III)–organic framework, namely [Tb(TATAB)(H2O)]?2H2O ( Tb‐MOF , H3TATAB=4,4′,4′′‐s‐triazine‐1,3,5‐triyltri‐m‐aminobenzoic acid), was assembled and characterized. The Tb‐MOF exhibits a water‐stable 3D bnn framework. Due to the existence of competitive absorption, Tb‐MOF has a high selectivity for detecting Fe3+, MnO4?, 4‐nirophenol and nitroimidazole (ronidazole, metronidazole, dimetridazole, ornidazole) in aqueous through luminescent quenching. The results suggest that Tb‐MOF is a simple and reliable reagent with multiple sensor responses in practical applications. To the best of our knowledge, this work represents the first TbIII‐based MOF as an efficient fluorescent sensor for detecting metal ions, inorganic anions, nitro‐compounds, and antibiotics simultaneously. 相似文献
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Beavers CM Zuo T Duchamp JC Harich K Dorn HC Olmstead MM Balch AL 《Journal of the American Chemical Society》2006,128(35):11352-11353
The structure of isomer 2 of Tb3N@C84 has been determined through single-crystal X-ray diffraction on Tb3N@C84.NiII(OEP).2(C6H6). The carbon cage has a distinct egg shape due to the presence of a single pair of fused pentagons at one apex of the molecule. Thus, although 24 IPR structures are available to the C84 cage, Nature utilizes one of the 51 568 isomeric structures that do not conform to the IPR for this unusual molecule. The Tb3N portion of isomer 2 of Tb3N@C84 is strictly planar. One Tb atom is nestled within the fold of the fused pentagons, while the other Tb atoms are disordered over four pairs of sites. 相似文献
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Selective Sensing of Fe3+ and Al3+ Ions and Detection of 2,4,6‐Trinitrophenol by a Water‐Stable Terbium‐Based Metal–Organic Framework
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Li‐Hui Cao Fang Shi Wen‐Min Zhang Prof. Shuang‐Quan Zang Prof. Thomas C. W. Mak 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(44):15705-15712
A water‐stable luminescent terbium‐based metal–organic framework (MOF), {[Tb(L1)1.5(H2O)] ? 3 H2O}n (Tb‐MOF), with rod‐shaped secondary building units (SBUs) and honeycomb‐type tubular channels has been synthesized and structurally characterized by single‐crystal X‐ray diffraction. The high green emission intensity and the microporous nature of the Tb‐MOF indicate that it can potentially be used as a luminescent sensor. In this work, we show that Tb‐MOF can selectively sense Fe3+ and Al3+ ions from mixed metal ions in water through different detection mechanisms. In addition, it also exhibits high sensitivity for 2,4,6‐trinitrophenol (TNP) in the presence of other nitro aromatic compounds in aqueous solution by luminescence quenching experiments. 相似文献
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稀土离子(Er3+)可与荧光石墨烯量子点(GQDs)表面的含氧基团发生配位,在Er3+介导下形成高配位数的GQDs/Er3+配合物,引起GQDs聚集而使其荧光减弱.凝血酶(Tb)中的氮和氧等原子可与Er3+发生配位作用,从而与GQDs竞争结合Er3+,减弱了GQDs与Er3+的作用而使其荧光恢复.通过检测GQDs的荧光即可实现对Tb活性的高灵敏分析,构建了基于Er3+介导GQDs荧光开关的Tb传感方法,采用透射电镜、原子力显微镜、红外吸收光谱以及荧光光谱等对传感机理进行了研究.本方法对Tb的检出限低至0.049 nmol/L,其它蛋白质对Tb检测无明显干扰,实际样品中Tb加标回收率为98.0%~105.3%,相对标准偏差为0.6%~4.2%. 相似文献
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Zinc sulfide (ZnS) quantum dot is modified with 3-mercaptopropyltrimethoxysilane (MPTMS) to obtain MPTMS functionalized SiO(2)/ZnS nanocomposite. Novel rare earth/inorganic/organic hybrid materials are prepared by using 3-(triethoxysilyl)-propyl isocyanate (TESPIC) as an organic bridge molecule that can both coordinate to rare earth ions (Eu(3+), Tb(3+), Sm(3+) and Dy(3+)) and form an inorganic Si-O-Si network with SiO(2) ZnS nanocomposite after cohydrolysis and copolycondensation through a sol-gel process. These multicomponent hybrids with double cross-linking siloxane (TESPIC-MPTMS) covalently bonding SiO(2)/ZnS and assistant ligands (Phen = 1,10-phenanthroline, Bipy = 2,2'-bipyridyl) are characterized and especially the photoluminescence properties of them are studied in detail. The luminescent spectra of the hybrids show the dominant excitation of TESPIC-MPTMS-SiO(2)/ZnS unit and the unique emission of rare earth ions, suggesting that TESPIC-MPTMS-SiO(2)/ZnS unit behaves as the main energy donor and effective energy transfer take place between it and rare earth ions. Besides, the luminescent performance of Bipy-RE-TESPIC-MPTM-SiO(2)/ZnS hybrids are superior to that of Phen-RE-TESPIC-MPTMS-SiO(2)/ZnS ones (RE=Eu, Tb, Sm, Dy), which reveals that Bipy or Phen only act as structural ligand within the hybrid systems. 相似文献
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M. Schreurs C. Gooijer N. H. Velthorst 《Fresenius' Journal of Analytical Chemistry》1991,339(7):499-503
Summary Quenched and sensitized lanthanide luminescence as detection in liquid chromatography has been investigated. An important advantage in comparison with phosphorescence is that the long-lived luminescence as applied does not require deoxygenation of the samples. In order to obtain a high luminescence intensity Tb(III) complexes with acetylacetonate have been formed, after which indirect excitation of Tb(III) can be realized via the ligands. The potential of Tb(III) luminescence as a detection method in ion chromatography has been shown for chromate, which is an efficient quencher. Sensitizing of the Tb(III) luminescence has been applied for thiol-containing analytes. These compounds are derivatized with maleimidyl salicylic acid to complexes that sensitize the Tb(III) luminescence. From a comparison of the results obtained with normal fluorescence detection and time-resolved sensitized Tb(III) luminescence detection it has become clear that the last method has a higher sensitivity, but in particular a higher selectivity. 相似文献