2-(2-羟基苯基)苯并噻唑-十一烯酸-锌与苯乙烯共聚物制备及性能研究

采用先配合再聚合的技术路线,先以Zn2+为中心离子,2-(2-羟基苯基)苯并噻唑为第一配体、10-十一烯酸为活性配体合成了反应型锌配合物2-(2-羟基苯基)苯并噻唑-十一烯酸-锌[Zn(BTZ)(UA)];再采用溶液聚合法,将Zn(BTZ)(UA)与苯乙烯共聚制备了聚苯乙烯-2-(2-羟基苯基)苯并噻唑-十一烯酸-锌[St-co-Zn(BTZ)(UA)]。通过红外光谱、紫外光谱、荧光光谱和热重分析对配合物和聚合物的结构和发光性能进行了表征。红外和紫外光谱表明,共聚物不仅表现出了聚苯乙烯的吸收,也表现出了配合物的吸收;荧光光谱表明,配合物在395nm的激发波长下发射蓝绿光,发射峰位于471nm处;聚合物在395nm的激发波长下,发射蓝光,发射峰位于451nm处,色坐标为(0.145,0.139),位于蓝光区;热重分析显示,聚合物的热分解温度为273℃,可用于三基色白光LED荧光粉的蓝光成分。     

双齿席夫碱配基功能化的聚苯乙烯与Eu(Ⅲ)离子配合物的制备及其发光特性

通过几步大分子反应过程,将双齿席夫碱(SB)配基键合在聚苯乙烯(PS)侧链,制得了双齿席夫碱配基功能化的聚苯乙烯PS-SB。使大分子配体PS-SB与Eu(Ⅲ)离子螯合配位,制备了二元高分子-稀土发光配合物PS-(SB)3-Eu(Ⅲ),也以邻菲罗啉(Phen)为小分子第二配体,制备了三元高分子-稀土发光配合物PS-(SB)3-Eu(Ⅲ)-(Phen)1。研究结果表明,键合的双齿席夫碱(SB)配基兼具有螯合配位与传能敏化双重功能,所制备的高分子-稀土配合物均能发射出很强的Eu(Ⅲ)离子的特征荧光。大分子配体PSSB本身具有强的荧光发射,但与Eu(Ⅲ)离子配位后,其自身的荧光发射大为减弱,通过配合物分子内能量转移,可强烈地敏化Eu(Ⅲ)离子发光。     

新型配体(MRBHP)分子的制备与MRBHP-Al3+光学性能与应用研究

以罗丹明B酰肼为主体,利用马来酸酐、4-氨基苯甲醛为原料修饰主体设计合成一种功能性发光小分子配体(MRBHP)。MRBHP在乙腈与水溶液(v/v=95∶5)中与Al³⁺结合形成配合物后,溶液颜色由无色变为红色。通过核磁共振、红外光谱、紫外可见吸收光谱对配体结构以及MRBHP与Al³⁺的配位方式与性能进行了表征。结果表明,Al³⁺与MRBHP亚氨基的N原子,羰基的O原子以及马来酸酐的O原子结合以1∶1的方式形成配合物,配合物呈现特异性强光学吸收,吸收峰波长为558 nm。同时应用研究发现,这种配体对Al³⁺呈现很强的选择性,在558 nm峰位置的吸收且有较强的抗干扰能力;同时配体对Al³⁺线性检测范围为0.2~1μM时,最低检测限为0.14μM,配位常数为1.61×10^-6M^-1。     

色酮衍生席夫碱镁离子荧光探针的制备与表征

通过6-羟基-3-甲酰基色酮和烟酸酰肼的缩合反应,合成了一种新型席夫碱配体6-羟基-3-甲酰基色酮-(烟酸酰基)腙(L)并对其与镁离子配位的荧光探针的性能进行研究利用荧光光谱、核磁共振氢谱、红外光谱等方法对该荧光探针分子的结构进行表征和荧光性能进行探究。结果表明,该配体在431nm处具有较弱的荧光发射峰,镁离子的加入会使431nm处的荧光发射强度降低,而在529nm处产生一个新的很强的荧光发射峰,但该配体对其它金属离子无明显的荧光响应;经计算,其检测限可达到9.16×10~(-7) mol/L,结合常数为5.65×10~(-8) mol/L。该配体与镁离子之间形成配位比为1∶1的配合物(L-Mg)其对镁离子的识别机理是基于光诱导电子转移(PET)现象。     

稀土铕高分子荧光配合物的制备及性能研究

稀土配合物作为发光材料已广泛应用于众多领域,为了使材料获得更稳定更持久的发光性能,本文以N-乙烯基甲酰胺(NVF)和丙烯酰胺(AM)为共聚单体,水为溶剂,在高温、引发剂条件下经自由基溶液聚合制备出含有氨基、羧基等多种配位官能团的水溶性高分子聚合物两性聚乙烯胺(PVAm),并以此作为高分子配体,再辅以1,10-邻菲咯啉(phen)作为第二配体,用三价稀土离子铕(Eu)的盐溶液与之配位,制备出具有优良荧光效应的稀土配合物Eu(PVAm)_3phen荧光粉。对高分子配体PVAm进行IR、NMR等分析,找出配位官能团,并对稀土配合物的外观形貌进行荧光显微镜等观察分析,对配合物的结构进行XRD等表征,并分析其紫外光谱、荧光光谱、荧光余辉亮度。配合物在220～275 nm范围内对紫外光有较强的吸收,最大吸收峰在260 nm处。配合物在580、593、614、650 nm的4处有明显的荧光发射峰。     

运用量子化学计算预测铽离子配体三重态能级的方法研究

以邻氨基苯甲酸(HL)为第一配体,邻菲啰啉(Phen)、三苯基氧膦(TPPO)为中性配体合成了3种铽配合物,测定了配合物的红外光谱,结果表明,邻氨基苯甲酸的氨基和羧基均与稀土离子发生配位,邻菲啰啉和三苯基氧膦也均与稀土离子配位;通过紫外光谱和荧光光谱对比研究了其发光性能,发光强度顺序为Tb(L)3(TPPO)2>Tb(L)3(H2O)2>Tb(L)3(Phen),通过量子化学计算出配体的最高已占分子轨道(HOMO)、最低未占分子轨道(LUMO)能级及单重态和三重态能级,对比分析了不同中性配体铽配合物的能量传递过程。     

铕(Ⅲ)-4-VP光致发光稀土配合物单体的制备

以 4 乙烯基吡啶 (4VP)、邻菲洛啉 (Phen)为配体 ,与EuCl3 在乙醇溶液中一步合成了含有双键的三元稀土配合物 ,通过紫外光谱与荧光光谱的测定 ,研究稀土配合物光致发光的机理。结果表明 ,4 乙烯基吡啶通过吡啶环上的氮原子与稀土离子可直接配位 ;邻菲洛啉配体具有协同配位效应。稀土配合物较EuCl3 的荧光发射强度提高了 12倍之多。     

铽与5-氨基间苯二甲酸配合物的合成及发光性能

稀土有机配合物荧光材料是材料、化学、信息等领域近年来的研究热点。本文在水溶液中合成了铽与5-氨基间苯二甲酸配合物,紫外灯辐照下,配合物能发出明亮的绿光。元素分析表明其组成为TbLCl.H2O(L=C6H3NH2(COO)22-),配合物的紫外吸收主要是配体的吸收,红外吸收光谱表明配合物中铽与羰基氧双齿螯合配位;荧光光谱表明配合物具有良好的荧光性能,激发谱带很宽,最佳激发波长为359nm,与配体的吸收一致,发射光谱为Tb3+离子的特征光谱,发光强度最高的是波长为545.8nm的5D4→7F5跃迁。     

新型Schiff碱及金属配合物的合成、表征及性能研究

合成了未见报道的草酸双缩邻苯二胺双缩水杨醛Schiff碱(L1和L2)和金属离子[Co(Ⅱ),Cu(Ⅱ),Ni(Ⅱ)]与L1配合生成的三种Schiff碱金属配合物。并对合成的配体及配合物进行了元素分析、IR、UV和1 HNMR的表征,以及Schiff碱及其配合物热致变色性能和荧光性能的性质研究。结果表明化合物均不具有热致变色的性能,化合物均具有较强的荧光发射光谱,发射峰值波长λem在470~524nm。     

2,2-联吡啶-6,6-二羧酸与稀土配合物的合成及性能

利用2,2-联吡啶-6,6-二羧酸作为配体,合成了稀土配合物[Ln2(bpydc)3·3H2O]·H2O·3CH3OH(1,Ln=Eu,Tb,Yb,Gd;Hbpydc=2,2-联吡啶-6,6-二羧酸)。使用单晶X射线衍射仪、傅里叶红外光谱、紫外吸收光谱、荧光光谱以及磷光光谱等对其进行了表征和配体与发光中心的能级匹配程度的测定,探讨了配合物的荧光性能与能量传递效率。结果表明:配合物具有两种不同环境的配位中心,促使配合物在空间上具有层状堆积结构;Eu(Ⅲ)与Tb(Ⅲ)配合物分别在612与548nm处有强烈的红色与绿色荧光发射,特征荧光敏化效果明显;配体三重态能级26666cm-1与稀土离子Eu3+(5D0,17300cm-1)、Tb3+(5D4,20500cm-1)最低激发态能级匹配,存在明显天线效应,具有优良的能量传递效率。     

Novel hydrophilic bis(1,2,3-triazolyl)fluorenyl probe for in vitro zinc ion sensing

A hydrophilic bis(1,2,3-triazolyl)fluorene derivative was synthesized as a multi-photon-absorbing, zinc-ion-sensing fluorescent probe. The fluorescence response was approximately five-fold greater in presence of Zn(2+), resulting in a large binding constant (1 × 10(9)) for a 1:2 ligand to zinc complex. A four-fold increase in the two-photon absorption cross section was achieved upon binding Zn(2+). In vitro two-photon fluorescence microscopy imaging revealed a significant fluorescence increase upon introduction of Zn(2+) into HeLa cells and reversible Zn(2+) binding, demonstrating the potential of this probe for zinc ion sensing.     

Fluorescence quenching of the europium tetracycline hydrogen peroxide complex by copper (II) and other metal ions

The europium-tetracycline complex [Eu(Tc)] is known to show only weak fluorescence with an emission maximum at 615 nm. On addition of hydrogen peroxide (HP), the strongly fluorescent [Eu(Tc)(HP)] complex is formed, which displays a 15-fold stronger luminescence intensity. This study describes the decrease in luminescence intensity of the [Eu(Tc)(HP)] complex in aqueous solution in the presence of Cu2+, Fe3+, Ag+, Al3+, Zn2+, Co2+, Ni2+, Mn2+, Ca2+, and Mg2+. Static and dynamic quenching can be induced by Cu2+, and these processes were quantified by means of their quenching constants. Stern-Volmer plots were also derived from lifetime imaging measurements accomplished by the rapid lifetime determination (RLD) technique based on microwell plate assays, and also by the time-correlated single photon counting (TCSPC) technique. According to those data, a time-resolved fluorescent method for copper determination can be proposed that is based on dynamic quenching of the [Eu(Tc)(HP)] complex by Cu2+ ions. The response to copper concentrations is linear up to 1.6 micromol L(-1), providing a detection limit of 0.2 micromol L(-1).     

Porphyrin assembly on beta-cyclodextrin for selective sensing and detection of a zinc ion based on the dual emission fluorescence ratio

In the present paper, a new cyclodextrin/porphyrin supramolecular sensitizer for zinc ion has been proposed based on the porphyrin dual fluorescence emission ratio. In aqueous solution, meso-tetraphenylporphyrin shows weak fluorescence, while in the presence of alkylated beta-cyclodextrin, it exhibits significant fluorescence enhancement by forming a cyclodextrin/porphyrin inclusion complex. Furthermore, the formation of a supramolecular complex causes a remarkable increase of the porphyrin metalation rate following the porphyrin fluorescence emission changes at two different emission wavelengths. The fluorescence emission of tetraphenylporphyrin at 656-nm bands decreases while that at 606 nm increases upon zinc ion interaction. Thus, the inclusion complex can behave as a ratiometric fluorescent sensor. Theoretically derivative equations for fluorescent ratiometry have been proposed for the first time. The feasibility of the proposed method is demonstrated by the performance of fluorometric detection of zinc ion. With the optimum conditions described, zinc ion in aqueous solution can be determined from 5.0 x 10(-7) to 2.5 x 10(-4) M. As the porphyrin electronic absorption and fluorescence emission are located in the visible range, and the fluorescence changes upon zinc ion interaction show high selectivity over biologically relevant cations, the inclusion complex could be used for biomedical application.     

Synthesis and characterization of [Eu(DBM)3phen]Cl3 @ SiO2-NH2 composite nanoparticles

Fluorescent rare earth complex Eu(DBM)3(phen)]Cl3@SiO2-NH2 nanoparticles were synthesized by combination of solvent precipitation method and St?ber method. The morphologies, structure, surface and optical properties of the samples were characterized by field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), fourier transform infrared (FTIR) spectroscopy, thermal gravimetric analysis (TGA), differential scanning calorimetry (DSC), and fluorescence spectrophotometer (FS). The observation from FE-SEM images indicate that the obtained samples are spherical and uniform nanoparticles with a tunable average sizes from 140 nm to 300 nm. TEM results verify a core-shell structure of the nanoparticles. The FTIR spectrum confirms the characteristic vibration absorption peaks of the complex [Eu(DBM)3(phen)]Cl3@SiO2-NH2. TGA result indicates that the complex is stable below 200 degrees C. The photoluminescence analysis shows that the complex has Eu3+ characteristic red luminescence and broader excitation peak from 200 nm to 450 nm that can meet the demands of fluorescent confocal imaging. The amino groups are directly introduced to the [Eu(DBM)3(phen)]Cl3@SiO2-NH2 nanoparticles surface by using APS (3-aminopropyl triethoxysilane). This makes the surface modification and bioconjugation of the nanoparticles easier. The nano-sized spheres could be provided a basis for further expansion of its application in biomedical imaging, biological detection and fluorescent nanoprobes.     

Pyrophosphate sensing by a fluorescent Zn2+ bound triazole linked imino-thiophenyl conjugate of calix[4]arene in HEPES buffer medium: spectroscopy, microscopy, and cellular studies

An in situ prepared Zn(2+) complex of triazole linked imino-thiophenyl conjugate of calix[4]arene, [ZnL], was demonstrated to be highly fluorescent in HEPES buffer solution. [ZnL] has been used as a chemo-sensing ensemble for the recognition of phosphates in general and pyrophosphates in particular among the eighteen different anions studied. The chemo-sensing behavior of the [ZnL] has been demonstrated through fluorescence, absorption, visual fluorescent color changes, ESI MS, and (1)H NMR titrations. Variations in the microstructural features of L, its zinc complex and the complex upon addition of PPi have been demonstrated through atomic force microscopy and transmission electron microscopy. Such studies have been extended to see the permeability of the conjugate into the HeLa cells by fluorescence microscopy. In accession, a reversible "write-read-erase-read" logic gate property of L has been demonstrated through a feedback loop in the presence of Zn(2+) and PPi.     

罗丹明B的荧光猝灭法测定钢铁中微量钨

本文研究了在酸介质中,NaCl存在的条件下,罗丹明B与钨酸根WO_4~_(2-)络合生成三元络合物使罗丹明B试剂荧光猝灭。以365 nm为最大激发波长,测定594 nm最大发射荧光强度。用钠型Dowex50W—X4离子交换树脂胶柱交换分离溶液中共存的磷酸根、重铬酸根、Cr~(3+)、Fe~(3+)等干扰离子,利用罗丹明B荧光强度减弱的程度和钨含量呈线性关系,测定钢样中微量钨。     

用双波长缔合光度法测定镀锌废水中的微量Zn2+

在阿拉伯树胶存在下,在pH=5.5的NH4Ac～HAc缓冲溶液中,Zn2+与硫氰化钾和中性红(NR)反应生成稳定的离子缔合物[NR]4[Zn(SCN)6],使NR褪色,在462 nm处出现正吸收峰,575 nm处出现负吸收峰.选定测定波长为462 nm和575 nm,建立了一种测定微量Zn2+的新的双波长光度法.结果表...     

Design and synthesis of Mg2+-selective fluoroionophores based on a coumarin derivative and application for Mg2+ measurement in a living cell

Novel Mg2+ fluorescent molecular probes (KMG-20-AM and KMG-27-AM; where AM is an acetoxymethyl group) based on a coumarin possessing a charged beta-diketone structure were designed and synthesized. These fluorescent probes produced a red shift from 425 to 445 nm in the absorption spectra after formation of a complex with Mg2+. The fluorescence spectra of these probes also showed a red shift from 485 to 495 nm and an increasing fluorescence intensity after formation of a complex with Mg2+. The optimum experimental conditions were excitation wavelength of 445 nm and a monitored wavelength of 500 nm, where these probes functioned as an indicator showing an image of increasing fluorescence in the presence of Mg2+. These probes showed a "seesaw-type" fluorescent spectral change with the isosbestic point at 480 nm due to the light excitation at 445 nm, which indicates that ratiometry can be used for the measurement. The molecular probes formed a 1:1 complex with Mg2+ and the dissociation constant (Kd) was 10.0 mM for KMG-20. The association constants of the probes with Mg2- were approximately 3 times higher than that with Ca2+, which showed that the selectivity of Mg2+ versus Ca2+ for these probes was over 200 times higher than that for commercially available Mg2+ fluorescent molecular probes such as mag-fura-2, Magnesium Green. As an application of these probes, intracellular fluorescent imaging of Mg2+ was demonstrated using a fluorescent microscope. After the addition of KMG-20-AM and KMG-27-AM into PC12 cells, a strong fluorescence was observed in the cytoplasm and a weak fluorescence in the nuclei region. After treatment with a high-K+ medium, the fluorescence intensity increased due to increasing intracellular Mg2+. The real image of Mg2+ release from the magnesium store was successfully observed with these Mg2+ fluorescent probes.     

Development of a terbium complex-based luminescent probe for imaging endogenous hydrogen peroxide generation in plant tissues

A highly sensitive Tb(3+) complex-based luminescent probe, N,N,N(1),N(1)-[2,6-(3'-aminomethyl-1'-pyrazolyl)-4-(3',4'-diaminophenoxy)methylene-pyridine] tetrakis(acetate)-Tb(3+) (BMTA-Tb(3+)), has been designed and synthesized for the recognition and detection of hydrogen peroxide (H(2)O(2)) in aqueous solutions. This probe is almost nonluminescent because the Tb(3+) luminescence is effectively quenched by the electron-rich moiety, diaminophenyl, on the basis of the photoinduced electron transfer (PET) mechanism. In the presence of peroxidase, the probe can react with H(2)O(2) to cause the cleavage of the diaminophenyl ether, which affords a highly luminescent Tb(3+) complex, N,N,N(1),N(1)-[2,6-bis(3'-aminomethyl-1'-pyrazolyl)-4-hydroxymethyl-pyridine] tetrakis(acetate)-Tb(3+) (BHTA-Tb(3+)), accompanied by a 39-fold increase in luminescence quantum yield with the increase of luminescence lifetime from 1.95 to 2.76 ms. The dose-dependent luminescence enhancement of the probe shows a good linearity with a detection limit of 3.7 nM for H(2)O(2), which is approximately 14-fold lower than those of the commonly used fluorescent probes. The probe was used for the time-resolved luminescence imaging detection of the oligosaccharide-induced H(2)O(2) generation in tobacco leaf epidermal tissues. On the basis of the probe, a background-free time-resolved luminescence imaging method for detecting H(2)O(2) in complicated biological systems was successfully established.