导数分光光度法研究——(二)RE-TTA-2,6-二甲基吡啶体系二阶导数分光光度法测定混合稀土中的镨、钕、铕、钬、铒、铥

噻吩甲酰三氟丙酮(TTA)、二苯甲酰甲烷(DBM)等β-二酮类试剂与稀土元素形成络合物后,其超灵敏跃迁谱带有显著的增强。当有第二配位体参与形成的三元稀土异配位络合物,其吸收谱带的强度和形状又有新的变化。鉴于导数分光光度法对锐形谱带有较高的放大能力和分辨能力,因而用导数分光光度法有可能提高单一稀土的检测灵敏度和选择性。我们在系统探索各单一稀土与TTA和DBM以及吡啶类有机碱     

稀土配合物-PAA-g-PE膜的荧光光谱

通过紫外光接枝聚合反应 ,将丙烯酸 (AA)接枝于PE膜表面 ,在一定 pH值条件下 ,使接枝膜与Eu3+、α 噻吩甲酰三氟丙酮 (TTA)的乙醇 水溶液或Tb3+、乙酰丙酮 (AcAc)的氯仿 水溶液作用 ,制得红色或绿色荧光膜。与相应的Eu(TTA) 3·(H2 O) 2 或Tb(AcAc) 3·(H2 O) 2 固态配合物相比 ,荧光膜的激发和发射光谱都发生了明显的变化 ,可以推测 ,稀土配合物与高分子材料之间发生了化学键结合。此外 ,还对荧光膜的红外光谱进行了观察。     

2-噻吩甲酰基-2-咔唑-N-丁基三氟丙酮化合物的合成与光谱研究

在苯和 5 0 %NaOH介质中 ,温度在 70～ 80℃时 ,1 ,4 二溴丁烷与咔唑 (CZ)反应 ,生成N 溴丁基咔唑 (BCZ)。在丙酮和K2 CO3 介质中 ,温度在 5 0℃时 ,N 溴丁基咔唑与噻吩甲酰三氟丙酮 (TTA)反应 ,生成 2 噻吩甲酰基 2 咔唑 N 丁基三氟丙酮 (TCBTA)。TCBTA为浅褐色针状结晶 ,熔点 2 1 1～ 2 1 4℃。详细研究了CZ ,BCZ ,TTA和TCBTA的紫外光谱和红外光谱 ,以及TCBTA的色谱 /质谱 ,证实了TCBTA合成产物的真实性。在氯仿中TCBTA的最大吸收波长为 2 4 1 ,2 6 5和 2 95nm ,摩尔吸光系数依次为 1 88× 1 0 5,1 2 5× 1 0 5和 1 0 8×1 0 5L·mol-1 ·cm-1 。TCBTA用于Fe(Ⅲ )和Nd(Ⅲ )的萃取 ,萃取率比TTA分别高 3倍和 1 6倍 ,与Nd(Ⅲ )形成络合物的荧光强度 ,TCBTA是TTA的 6倍 ,表明TCBTA具有优良的光敏特性。     

三价铕荧光络合物与聚乙烯吡咯烷酮复合物研究

为研究稀土荧光络合物与高分子形成的复合物的结构与发光性能间的关系,利用α-噻吩甲酰三氟丙酮（TTA）和三苯基氧化膦（TPPO）与氯化铕（EuCl₃）分别制备了Eu(TTA)₃·2H₂O和Eu(TTA)₃·(TPPO)₂络合物,及其与聚乙烯吡咯烷酮（PVP）的复合物。采用荧光光谱,红外光谱和透射电镜等方法对复合物进行了表征。荧光光谱测定结果表明Eu(TTA)₃·2H₂O与PVP K30结构单元摩尔比为1∶35的PVP/Eu(TTA)₃·2H₂O复合物的612　nm发射峰的荧光强度较Eu(TTA)₃·2H₂O络合物有显著提高。红外光谱研究表明络合物的Eu3+与PVP分子的羰基之间存在着明显的配位作用,并且存在多种配位方式。透射电镜观察结果表明复合物具有微相分离结构,其中的稀土络合物为无定形结构,这进一步表明PVP与络合物分子间存在相互作用。     

Sm_(1-x)Tb_x(TTA)_3phen转光剂的合成及SiO_2表面改性

为了提高稀土有机配合物的转光能力和紫外稳定性,以Sm(Ⅲ)为中心稀土离子,Tb为敏化离子,β-二酮类有机配体α-噻吩甲酰三氟丙酮(HTTA)及第二配体1,10-菲咯啉(phen)等作为主要配体,采用化学沉淀法合成了具有紫外转红光性能的转光剂Sm1-xTbx(TTA)3phen,并利用SiO2对配合物进行了表面改性.借助红外光谱、紫外-可见光吸收光谱及荧光光谱对配合物Sm1-xTbx(TTA)3phen的光学性能进行了系统分析.结果表明:Sm1-xTbx(TTA)3phen与Sm(TTA)3phen的配位结构基本一致;配合物的紫外光吸收特性主要由有机配体决定;配合物吸收紫外光后,均可产生Sm3+的特征光,其中Sm0.5Tb0.5(TTA)3phen在647nm处的荧光强度最高,达到8.0×106cps,光转换能力最强;敏化离子Tb3+的掺入可以显著提高配合物的荧光强度;配合物经二氧化硅包裹后,其紫外稳定性明显提高.     

测量非辐射能从荧光分子到介电界面的传输

我们测量了被Al2O3隔离层与Ag,In2O3和SnO2表面分隔开的噻吩甲酰三氟丙酮铕〔europium(Ⅲ)thenoytrifluoroacetonate,EuTTA〕分子的荧光强度。实验结果显示当隔离层厚度为1～10nm时,由于非辐射能从发射中心Eu3+离子传输入介电界面,荧光强度随隔离层厚度减少按指数式减弱。这与能通量模型理论结果相符合.     

Sm1－xTbx(TTA)3phen转光剂的合成及SiO2表面改性

为了提高稀土有机配合物的转光能力和紫外稳定性,以Sm(Ⅲ)为中心稀土离子,Tb为敏化离子,β-二酮类有机配体α-噻吩甲酰三氟丙酮(HTTA)及第二配体1,10-菲咯啉(phen)等作为主要配体,采用化学沉淀法合成了具有紫外转红光性能的转光剂Sm1－xTbx(TTA)3phen,并利用SiO2对配合物进行了表面改性.借助红外光谱、紫外-可见光吸收光谱及荧光光谱对配合物Sm1－xTbx(TTA)3phen的光学性能进行了系统分析.结果表明:Sm1－xTbx(TTA)3phen与Sm(TTA)3phen的配位结构基本一致|配合物的紫外光吸收特性主要由有机配体决定|配合物吸收紫外光后,均可产生Sm3+的特征光,其中Sm0.5Tb0.5(TTA)3phen在647 nm处的荧光强度最高,达到8.0×106 cps,光转换能力最强|敏化离子Tb3+的掺入可以显著提高配合物的荧光强度|配合物经二氧化硅包裹后,其紫外稳定性明显提高.     

系列新型铕—β—二酮三元及四元混配化合物发光性质研究

本文报道了五种铕－β－二酮（二苯甲酰甲烷ＤＢＭ,噻吩甲酰三氟丙酮ＴＴＡ）－丙烯酸（ＨＡＡ）三元及四元混配化合物的紫外、荧光光谱,量子产率瞬态光谱。观察到主配体、协同配体对配合物吸收及发射光谱的影响。测得配合物溶液中铕离子＾５Ｄ１能级向＾５Ｄ０能级的传能过程及荧光寿命,发现室温下溶液中以ＴＴＡ为主配体的四元或三元配合物的寿命相近且远大于以ＤＢＭ为主配体的配合物。     

含稀土铕(Ⅲ)配位聚合物的研究Ⅰ.铕(Ⅲ)-噻吩甲酰三氟丙酮-聚(苯乙烯-丙烯酸)的结构表征

研究了铕 (Ⅲ )和噻吩甲酰三氟丙酮 (HTTA)形成的有机配合物与聚 (苯乙烯 丙烯酸 )PSAA在不同pH值时发生配位反应得到配位聚合物NaEu(Ⅲ ) TTA PSAA的 3种样品 (a) ,(b) ,(c)。红外光谱、紫外光谱、X光电子能谱的测试表明了Eu3 分别与PSAA ,TTA- 发生配位。元素分析和电导率测定结果证明了配位组成和结构在不同的 pH条件下发生变化。结果表明 ,配合物试样 (a) ,(b) ,(c)中Eu3 的含量分别为11 89% ,12 5 5 % ,13 4 1%。     

时间分辨激光荧光光谱技术在免疫分析中的应用

本研究以时间分辨激发荧光光谱分析技术为基础 ,进行稀土离子标记的激光激发的时间分辨荧光免疫分析 (TRFIA)研究。实验以自行合成的二乙三胺五醋酸酐 (DTPAA)为双功能螯合剂。用 Eu3+标记兔抗人 (RAH) Ig G抗体 ,依据解离增强原理 (DEL FIA) ,研究了 Eu3+ -β萘甲酰三氟丙酮 (β- NTA)的荧光分辨体系 ,测定了荧光光谱和荧光寿命 ,建立了铕离子分析检出方法 ,其工作曲线范围为 1× 10 - 7～ 1× 10 - 1 1g· m L- 1 ,检测限为 1× 10 - 1 3g· m L- 1 ,相对标准偏差为 6 .4%。结合 TRFIA方法学研究 ,进行了人血清丙型肝炎病毒抗体 (Anti- HCV)检测。并同酶联免疫法 (EL ISA)对比。取得 TRFIA法阳性检测率明显高于EL ISA法的结果。     

Spectroscopic Study of the Photophysical Properties of Rare Earth Ions Encapsulated: Water Soluble Functional Calixresorcin[4]Arene

Abstract

A novel macrocyclic compound-water soluble functional calixresorcin[4]arenes—tetra para sulfo-phenylmethyl-calixresorcin[4]arenes was synthesized for the first time. the photophysical properties of terbium and europium ions encapsulated in the macrocyclic ligand were studied in detail. the triplet state energy of the calixresorcin[4]arene was determined to be 24400 cm^?1 by the low temperature phosphorescence spectrum and it was found that it can sensitize both terbium ion and europium ion. the possible energy transfer process between the functional calixresorcin[4]arene and the encapsulated Tb³⁺ and Eu³⁺ was discussed. the luminescence quantum efficiency of Tb³⁺- calixresorcin[4]arene was calculated.     

Synthesis and luminescence properties of lanthanide(III) chelates with polyacid derivatives of thienyl-substituted terpyridine analogues

Two new polyacid derivative ligands of thienyl-substituted terpyridine analogues, N,N,N¹,N¹-[4′-(2?-thienyl)-2,2′:6′,2″-terpyridine-6,6″-diyl]bis(methylenenitrilo) tetrakis(acetic acid) (TTTA) and N,N,N¹,N¹-[2,6-bis(3′-aminomethyl-1′-pyrazolyl)-4-(2″-thienyl)pyridine] tetrakis(acetic acid) (BTTA), were synthesized, and the luminescence properties of their Eu³⁺ and Tb³⁺ chelates were investigated. The Eu³⁺chelates of the two ligands are strongly luminescent having luminescence quantum yields of 0.150 (TTTA-Eu³⁺) and 0.114 (BTTA-Eu³⁺), and lifetimes of 1.284 ms (TTTA-Eu³⁺) and 1.352 ms (BTTA-Eu³⁺), whereas their Tb³⁺ chelates are weakly luminescent. The TTTA-Eu³⁺ chelate was used for streptavidin (SA) labeling, and the labeled SA was used for time-resolved fluoroimmunoassay of insulin in human sera. The method gives the detection limits of 33 pg ml⁻¹.     

Effect of water vapors on the luminescence of cation-exchange membranes modified by Pt(II) and Ru(II) complexes and Nile blue

The surface of a cation-exchange membrane was modified by the [PtEnPpy]⁺, [PtEnBt]⁺, [PtEnTpy]⁺, [RuBpy₃]⁺², and NB⁺, (En is ethylenediamine; Ppy, Bt, Tpy are α-deprotonated forms of 2-phenylpyridine, 2-phenylbenzothiazole, and 2-(2′-thienyl)pyridine, respectively; Bpy is 2,2′-bipyridyl, and NB⁺ is Nile blue) ions, which exhibit intense luminescence. It is found that the quenching of the luminescence of the modified cation-exchange membrane by water vapors depends on the nature of the excited electronic state of the immobilized cation.     

Blue LED Excitable Temperature Sensors Based on a New Europium(III) Chelate

A new europium(III) chelate is synthesized and characterized. The wavelength of sensitization of Eu³⁺ luminescence is shifted further into visible so that efficient excitation with 425, 435 and 450-nm LEDs becomes possible. Photophysical properties and temperature dependence of luminescence are investigated in toluene solution and various polymer matrixes. The sensor materials are also characterized in terms of cross-sensitivity to oxygen and photostability. The sensor material based on the europium complex immobilized into poly(vinylidene chloride-co-acrylonitrile) shows negligible cross-sensitivity to oxygen and is particularly attractive for applications at physiological conditions. Other materials can be applied for sensing and imaging purposes at room temperatures. The new materials can also be used for compensating optical (oxygen, CO₂ etc.) sensors for temperature effects.     

铕螯合物的制备及光谱性质研究

稀土螯合物的制备是均相时间分辨荧光免疫分析中的关键部分,为了合成理想的稀土螯合物,以2,6-二(溴甲基)吡啶-3,5-二甲酸二乙酯为原料,首先优化合成了Li+⊂2,6-{N,N’,N,N’-[二(2,2’-联吡啶-6,6’-二甲基)]二(氨甲基)}-吡啶-二羧酸乙酯,使其产率明显提高。进一步选择乙腈和甲醇两种反应体系合成铕螯合物,并比较了不同反应体系下合成的铕螯合物的光谱性质。研究表明,乙腈和甲醇两种反应体系所得铕螯合物的激发光谱(最大激发波长为310 nm)、发射光谱(最大发射波长为616 nm)、量子产率基本相同,荧光强度在10-8～10-5 mol·L-1范围内与Eu3+浓度均成线性,相关系数分别为0.993 73和0.986 65,两种铕螯合物(c=2.5×10-5 mol·L-1)的荧光强度略有差异,荧光寿命分别为825和830 μs。因此,两种反应体系所得铕螯合物具有斯托克斯位移大、荧光强度强以及荧光寿命长等优点,并且此种穴状螯合剂结构中的吡啶-2,2-联吡啶可保护铕离子免受其他物质的干扰,是理想的稀土螯合物,可用于蛋白质、核酸等生物分子的标记。本研究不仅拓展了合成新型稀土螯合物的方法,而且为进一步建立均相时间分辨荧光免疫分析奠定了基础。     

4,4,4-三氟-1-(4'-间三联苯基)-1,3-丁二酮邻菲咯啉铕(Ⅲ)配合物的合成与发光

合成了新的配合物EuL3phen,[HL=4,4,4-三氟-1-(4’-间三联苯基)-1,3-丁二酮,phen=邻菲咯啉]。采用元素分析,红外光谱,质谱对该配合物的结构进行了表征。该化合物在半导体InGaN芯片发出的近紫外光激发下,发出铕(Ⅲ)离子5D0—7FJ(J=0~4)跃迁特征红光,最大发射峰位于613 nm,发光量子效率为13%。配合物寿命为470μs,寿命曲线很好地和单指数衰减拟合曲线相吻合。配合物热稳定性达到220℃,满足制备LED器件的要求。将配合物EuL3phen和半导体395 nm发射InGaN芯片组合,成功地制备了红色发光二极管。发光二极管的色坐标、发光效率、配合物和硅胶质量比相关,在配合物和硅胶质量比为1∶25时,器件色坐标为x=0.64,y=0.35,光效为0.89 lm.W-1。该配合物是充当制作白光LED用的潜在的红色发光组分。     

Luminescence quenching of cyclometalated Pt(II) complexes by halogenide ions

The luminescence quenching of [Pt(CΛN)En]ClO₄ complexes ((CΛN)^? = ppy^?, tpy^?, and bt^? are deprotonated forms of 2-phenylpyridine, 2(2′-thienyl(pyridine), and 2-phenylbenzothiazole, respectively; En is ethylenediamine) by halogenide ions (Hal^? = Cl^?, Br^?, I^?) in ethanol solutions is studied. It is shown that the quenching has a dynamic character and its bimolecular rate constants are consistent with the enhancement of nonradiative deactivation of the excited state of {[Pt(CΛN)En]*...Hal} collision complexes with increasing spin-orbit interaction constant of the halogen.     

Hypersensitivity in the Luminescence and 4f?C4f Absorption Properties of Mono- and Dinuclear EuIII and ErIII Complexes Based on Fluorinated ??-Diketone and Diimine/ Bis-Diimine Ligands

The results of our investigation on the sensitized luminescence properties of three Eu(III) ??-diketonate complexes of the form [Eu₂(fod)₆(??-bpm)], [Eu(fod)₃(phen)] and [Eu(fod)₃(bpy)] and 4f?C4f absorption properties of their Er(III) analogues ( fod = anion of 6,6,7,7,8,8,8- heptafluoro-2,2-dimethyl-3,5-octanedione, bpm = 2,2??-bipyrimidine, phen = 1,10-phenanthroline and bpy = 2,2??-bipyridyl) in a series of non-aqueous solvents are presented. The Eu(III) complexes are highly luminescent and their luminescence properties (intensity and band shape) are sensitive to the changes in the inner coordination sphere of the Eu(III) ion. The luminescence intensity of the mononuclear complexes in pyridine is drastically decreased. The coordination structure of the complexes in pyridine is transformed into a more symmetrical one which results into a slow radiative rate of the emission from the complexes. The ancillary ligands, phen and bpy are found better co-sensitizers as compared to the bpm to sensitize Eu(III)-luminescence. The 4f?C4f absorption properties (oscillator strength and band shape) of the Er(III) complexes demonstrate that ⁴G_11/2 ?? ⁴I_11/2 and ²H_11/2 ?? ⁴I_15/2 hypersensitive transitions of Er(III) are very sensitive in some coordinating solvents which reflects complex?Csolvent interaction in solution. The hypersensitive transitions of [Er(fod)₃(phen)] remain unaffected in any of the solvents and this complex retains its bulk composition in solution. The erbium complexes as well as the Er(fod)₃ chelate are invaded by DMSO. This solvent enters the inner coordination sphere by replacing heterocyclic ligand and the complexes acquire similar structure [Er(fod)₃(DMSO)₂] in this solvent. The results reveal that the luminescence and absorption properties of lanthanide complexes in solution can be controlled by tuning the coordination structure through ancillary ligands and donor solvents. This work shall prove useful in designing new biological applications with such probes.     

铕(Ⅲ)-呋喃甲酸配合物的光谱表征

以硝酸铕 ,呋喃甲酸和邻菲咯啉 (phen)合成了配合物 [Eu(FA) 3·2H2 O]·NO3(4 ,4’ Hbpy) ,[Eu(FA) 3·phen]H2 O和Eu(FA) 2 ·NO3·phen。用元素分析、红外吸收光谱、紫外吸收光谱和溶液荧光光谱对配合物进行了组成确定和表征。溶液荧光光谱表明 ,配合物 [Eu(FA) 3·2H2 O]·NO3(4 ,4’ Hbpy)的发光强度比混配配合物Eu(FA) 2 ·NO3·phen和 [Eu(FA) 3·phen]H2 O的发光强度小很多 ,而且发光寿命较短 ,三元配合物 [Eu(FA) 3·phen]H2 O的发光强度比四元配合物Eu(FA) 2 ·NO3·phen的发光强度略大     

4,4'-双 间位联苯基苯双核铕配合物的合成与发光

合成了一个新的双核铕配合物Eu₂(bdb)₃·4H₂O 。元素分析、红外光谱、质谱证实其配位方式是三个配体同时和两个铕离子绞合配位。该配合物发出铕离子特征红光,发射峰值位于614 nm,其激发光谱的激发峰值位于370 nm。配合物的发光寿命为336 μs,寿命曲线很好地和单指数衰减拟合曲线相吻合,进一步证实配合物只有一个对称中心铕离子存在。配合物热稳定性达到230 ℃,满足制备LED器件的要求。将该配合物与370 nm 发射的InGaN芯片组合 成功地制备了红色发光二极管,当配合物和硅树脂的质量比为1 : 30时,红色发光二极管的色坐标为x=0.635 3, y=0.334 0,发光效率为 1.36 lm/W。结果表明:该配合物是制备半导体高显色指数白光LED潜在的红色有机发光材料。