卟啉与铜Cu（II）卟啉配合物LB膜的制备及性质研究

合成了5-（间羟基苯基）-10,15,20-三对氯苯基卟啉（5-（m-hydroxyphenyl）-10,15,20—tir（P—chlorohenyl）porphyrin,m-OH—TCP）及铜卟啉配合物（m-0H—TCP—Cu（Ⅱ））,并系统地研究了其在气／液界面上的成膜性能。利用UV--vis分光光度计,原子力显微镜等方法对其膜的表面形貌及金属离子Cu（Ⅱ）对卟啉环在LB膜中的排列取向及相互作用的影响进行了详细研究。实验结果表明：在制备的单层膜中,当亚相为超纯水时,m-OH—TCP分子中卟啉环面与水平面倾角约为14．5°;当改变亚相环境时（亚相为Cu（Ⅱ）离子浓度为5×10^ -4 mol／L的水溶液）,m-OH—TCP分子中卟啉环面与水平面倾角约为51．9°;而对于合成的铜卟啉配合物（亚相条件为超纯水）,m-OH—TCP～Cu（Ⅱ）分子中卟啉环面与水平面倾角约为33．2°;证明在亚相中引入Cu（Ⅱ）,可以有效的诱导卟啉环取向,亚相中Cu（Ⅱ）的诱导机理可能是通过Cu（Ⅱ）与卟啉环面空腔形成的氢键作用,而非配位作用。这为卟啉衍生物功能纳米材料性质LB膜研究提供了理论和实验依据。     

铕配合物与苯乙烯共聚物的研究

Copolymers containing rare earth complex were prepared via copolymerizing complex Eu^3 (BA)2 (AA) (phen)) with styrene. A sort of semitransparent luminescent polymer material with high fluorescent intensity was obtained. They were characterized by means of IR and UV spectra, which show that they were copolymers, not blendings. The fluorescence spectra of copolymer indicated that it showed intense UV absorption characteristics of rare earth complex as long as only a little complex join in it. Moreover, thermal analysis showed that they had excellent heat-stability.     

5修-铕油酸长链配合物的性质研究

本文合成了以Eu3+为中心离子,芳香羧酸、邻菲咯啉和噻酚甲酰三氟丙酮为第一配体,油酸为第二配体的七种新的铕三元荧光配合物。通过红外光谱分析、紫外光谱分析、元素分析、EDTA配位滴定分析以及电导率的测定对铕三元荧光配合物的组成及结构进行表征。通过荧光光谱分析,确定了铕三元荧光配合物的最佳激发波长,在最佳激发波长下测定了它们的发射光谱。结果表明,所有铕三元荧光配合物的荧光发射光谱均相似,发出了铕离子的5D0-7F2,5D0-7F1,5D0-7F0(很弱)特征光,荧光表现为红色。在含油酸配体的铕三元荧光配合物中,各第一配体向铕离子传递光能的能力为:邻菲咯啉>噻吩甲酰三氟丙酮>大茴香酸>间氯苯甲酸>苯甲酸>对甲基苯甲酸>对羟基苯甲酸。     

铕-乙酰丙酮-丙烯酸配合物及其苯乙烯共聚物的研究

用三异丙氧基铕与乙酰丙酮、丙烯酸合成铕-乙酰丙酮-丙烯酸配合物[Eu（acac)2AA],将其与苯乙烯共聚制得共聚物（Eu-CO-PS）。用元素分析、IR、UV、DMTA和荧光光谱表征其结构与性质,表明共聚物（EU-CO-PS）是发光性较强的一类新型高分子材料。     

多元苯甲酸铕配合物的合成及其荧光性能研究

分别合成了Eu3+-苯甲酸(BA)-丙烯酸(AA)和Eu3+-苯甲酸(BA)-丙烯酸(AA)-邻菲罗啉(phen)有机稀土配合物,通过元素分析、红外光谱和紫外光谱确定了它们的结构式分别为Eu3+(BA)2(AA)和Eu3+(BA)2(AA)(phen),同时研究了样品的荧光性和热性能,荧光光谱表明样品引入邻菲罗啉后,荧光强度和荧光单色性大大提高,热分析表明该配合物具有优异的热稳定性.     

均苯三甲酸铕发光配合物的合成与表征

在乙醇和水的混合溶剂中,合成了铕(Ⅲ) 均苯三甲酸(H3L)发光配合物。通过元素分析、化学分析、热分析和红外光谱确定其化学组成为[EuL(H2O)5]·H2O。X射线衍射分析结果表明配合物为晶体物质,由扫描电镜照片可以看出配合物为棒状物质,晶粒大小10～20μm,荧光光谱分析结果表明配合物在紫外光激发下发出红色的荧光。     

铕配合物的合成及其荧光防伪油墨的制备

选用苯甲酸(BA)、噻吩甲酰三氟丙酮(TTA)、邻菲咯啉(Phen)作为配体合成了Eu(BA)3Phen三元配合物、Eu(BA)(TTA)2Phen四元配合物,将其作为荧光剂,制备了稀土荧光防伪油墨。红外光谱的分析表明配体与铕离子发生了配位。测定了配合物和荧光防伪油墨的荧光性能,发射波长为614 nm,制备的稀土荧光防伪油墨在可见光下印迹无色,在紫外灯下呈现明显红色荧光。     

稀土铕有机配合物的研究进展及其应用

目的介绍稀土铕有机配合物的原理、分类、应用及其最新研究进展,为高性能稀土铕配合物的研发提供一定的思路和依据。方法通过查阅国内外学者近年来对稀土铕有机配合物的各种研究文献,对稀土铕有机配合物的主配体种类及应用进行整理总结。结果稀土铕有机配合物的主配体有四大类,即β-二酮类、羧酸及羧酸盐类、有机高分子类与超分子大环类,该配合物主要应用于荧光材料、发光材料、磁性材料和生物等四大领域。结论铕有机配合物的荧光性能良好,且高分子类配合物易加工成型;有机高分子类铕配合物可以结合Eu³⁺和高分子的优点,在提高其与聚合物材料相容性的前提下,有望成为一种新型的功能材料。     

稀土铕四元配合物纳米微晶的制备及性能

为了得到粒径均匀的纳米稀土铕四元配合物,采用化学沉淀法,进一步优化试验条件,制备Eu(BA)(TTA)2邻菲罗林纳米微晶,采用元素分析、红外光谱、热重分析、荧光光谱和透射电镜等方法对其进行表征和分析。结果表明,稀土铕四元配合物中高效率的能量传递是通过在2种不同第一配体之间形成的"协同效应"来完成,四元配合物中3种不同的配体可以更好地取代配位水;四元稀土配合物不仅发光性能优于常见的三元配合物,而且热稳定性好,粒径较小且均匀,可进一步掺入高分子形成功能性含稀土高分子聚合物;选用合适的缓冲溶液,在调节pH时将缓冲溶液缓慢地逐滴加入,可采取往反应体系中通氨气的方法,以使体系的pH改变较为平稳,生成的沉淀粒径较小且均匀。     

一种新型的非线性光学材料—紫膜LB膜

本文研究光敏生物大分子掺杂的ＬＢ膜──紫膜ＬＢ膜的制备及其３次和高次光学非线性特性，研究紫膜ＬＢ膜中以光学非线性效应为基础的双光束耦合、多波混频和相位共轭等物理现象。研究结果表明，紫膜ＬＢ膜有可能在光学信息处理和光计算中得到应用。     

一种新型掺铕磁性生物玻璃陶瓷的制备与研究

通过溶胶．凝胶（sol-gel）工艺制备了一种掺铕磷灰石，硅灰石磁性生物玻璃陶瓷（apatite-wollastonite magnetic glass ceramic，AWMGC）。采用X射线衍射（XRD）、扫描电镜（SEM）、能谱（EDS）、振动磁强计（VSM）等方法分析材料晶相组成、显微结构、磁性、生物活性；并通过与人肝细胞L02、骨髓基质干细胞（MSC）复合培养对新制备的AWMGC的生物相容性及其对人体细胞的作用进行了实验分析。结果表明：掺有适量稀土铕（Eu）的生物玻璃陶瓷既能够保持良好的生物活性，又能表现出一定的磁性。是一类十分具有发展潜力的骨修复材料、骨组织工程支架材料。     

一种新型可溶喹吖啶酮衍生物LB膜的制备及其光谱特性

采用表面压-分子面积(π一A)等温曲线和紫外-可见吸收谱的方法研究了一种新型喹吖啶酮衍生物材料LB膜的制备及其光谱特性．实验表明,这种新型喹吖啶酮衍生物能够在水面上形成稳定的单分子膜,它与花生酸(AA)混合后不仅可以形成很好的单分子膜,而且可以较好地转移到固体基片上制备成LB膜多层膜．这种新型喹吖啶酮衍生物LB膜的紫外-可见吸收谱的吸收峰位较稀溶液发生了红移,这是由极性溶剂分子与其相互作用的结果．它在溶液和LB膜中都是以单体的形式存在．     

Luminescent micro- and nanofibers based on novel europium phthalate complex

We synthesized by wet chemical route a novel europium–potassium phthalate complex Eu³⁺K⁺[(COO)₂(C₆H₄)]₂. The compound is a white powder insoluble in water. X-ray diffraction evaluation shows that we obtained a new crystalline compound with no traces of the starting materials (potassium hydrogen phthalate and europium chloride). Scanning electron microscopy reveals that the powder consists of fiber-shaped structures with sizes larger than 250 nm in diameter. Energy dispersive X-ray analysis proves that the compound has a 1:1 europium–potassium ratio. Fourier transform infrared spectroscopy confirms the presence of the phthalate in the new compound. Photoluminescence and cathodoluminescence measurements show that the fiber-shaped structures are intensely luminescent with emission bands corresponding to the ⁵D₀ → ⁷F_J (J = 1–4) Eu (III) ion’s transitions in the region between 580 nm and 700 nm, the most intense maximum being observed around 615 nm. Up-converted luminescence with a maximum at 315 nm was recorded.     

Self-quenching of a photo-excited ruthenium complex in component-controllable mixed Langmuir-Blodgett films

The miscibility and phase behavior of the mixed monolayer of Ru(dpphen)₃²⁺ (dpphen=4,7-diphenyl-1,10-phenanthroline) (abbreviated as Ru(II)), octadecyltrichlorosilane (OTS) and stearic acid (SA) at air/water interface had been investigated in detail. Two-dimensional density of Ru(II) could be easily adjusted by changing the mixing ratio of Ru(II)/SA/OTS. The mixed monolayer of Ru(II)/SA/OTS with different molar proportions had been deposited and characterized by low angle X-ray diffraction, UV-visible absorption spectra and photo-induced emission spectra. The possible structure of its resulting LB film was proposed based on the results of the π-A isotherms and low angle X-ray diffraction. Photo-induced electron transfer and self quenching of Ru(II) in mixed LB films had been investigated in detail.     

Eu在羟基磷灰石中的掺杂及其发光性能研究

本文采用化学沉淀法制备了Eu3+掺杂的羟基磷灰石材料(HAP∶xEu),使用X射线衍射、红外光谱以及荧光光谱等对其结构及发光特性进行了研究。分析表明,制备得到的掺杂羟基磷灰石具有晶态结构,其红外谱中出现隶属于OH-、PO3-4的特征振动峰。光谱分析结果表明,在394nm波长激发下,掺杂Eu的羟基磷灰石样品的荧光发光强度和荧光寿命呈现随掺杂浓度的增加相反的变化趋势:发光强度增加6倍同时其荧光寿命却下降了约30%。此外,样品中电偶极跃迁与磁偶极跃迁强度之比(IR/IO)随Eu3+掺杂浓度增加表明Eu占据羟基磷灰石晶格中的CaⅡ不对称位点的比例大于占据CaⅠ对称位点的比例,并可受到掺杂量的影响。     

Monomolecular enzyme films stabilized by amphiphilic polyelectrolytes for biosensor devices

This paper describes the use of new amphiphilic polyelectrolytes for protein immobilization. Monomolecular films of glucose oxidase (GO) and monoamine oxidase (MAO) stabilized by amphiphilic polyelectrolytes (polyethyleneimine and poly-4-vinylpyridine derivatives modified by lauryl chains) were formed on a water surface in a Langmuir-Blodgett trough. The compressed films containing the enzymes were transferred onto the surface of a polypropylene membrane of a Clark electrode according to the Langmuir-Schaefer method. The analytical responses of the resulting biosensors were linear over the range 1–10 mM of glucose and 8–100 μM of tyramine. Furthermore, direct functional coupling of GO and ferrocenecarboxylic acid in multilayer films stabilized by amphiphilic polyelectrolytes was demonstrated. The amperometric response of such a sensor was linear over the range 1–20 mM of glucose. The dependence of the kinetic parameters of the enzymes on the amphiphilic polyelectrolyte structures is discussed.     

Microstructural and electrical studies on diamond films

X-ray diffraction, atomic force microscopy and electrical studies were performed on 2-3 μm thick diamond films on silicon substrates. The films were produced by the microwave plasma chemical vapour deposition method. The films were polycrystalline having a grain size of 32.1 nm. From room temperature current-voltage measurements, it was found that the charge transport mechanism was due to the thermionic emission over the potential barrier of 1.3 eV.     

New optical material europium EDTA complex in polyvinyl pyrrolidone films with fluorescence enhanced by silver plasmons

In our search for efficient Luminescent Solar Concentrators (LSC) we have prepared polyvinyl pyrrolidone (PVP) films incorporated by ethylenediamine tetraacetic acid (EDTA) complex of europium and co-doped with silver nanoparticles (NPs). Steady state fluorescence was studied under weak and strong excitation. Dynamical study was performed by second harmonic of Nd laser. Under weak excitation the fluorescence of europium co-doped with silver plasmons increased by a factor of three and excited by continuous laser by a factor of 50. The lifetimes of films doped by the complex were 755 μs and co-doped with silver nanoparticles 946 μs. This is the first finding that the photon density accumulates the number of plasmons interacting with electronic states of europium increasing its transition probability resulting in the strong intensification of fluorescence. In dynamical measurements of lifetimes a single pulse does not provide enough energy to create such number of plasmons.     

Studies on the formation of Langmuir monolayer and Langmuir–Blodgett films of octadecyl amine-bromocresol purple dye complex

Properties of the monolayer of octadecyl amine (ODA) molecules on aqueous solution of bromocresol purple (Bcp) dye have been studied over a wide range of pH by measuring the surface pressure-area isotherms. A strong interaction of ODA molecule was observed with the dye molecule in the pH range of 4–9. Under the present study, the dye molecules were adsorbed on the ODA monolayer at the water surface and subsequently a Langmuir–Blodgett (LB) film of ODA–dye complex was transferred from the air–water interface onto a solid substrate. Alternatively, dye molecules were incorporated into LB film by immersing the predeposited LB film of pure ODA into the dye solution, i.e. by adsorption of dye molecule at the solid–liquid interface. The adsorption behavior of ODA–Bcp dye complexes obtained through these two different routes was characterised with the help of UV–Visible spectroscopy. The nature of the ODA–dye complex deposited from air–water interface using the LB technique was found to be quite different from that of the complex formed by the adsorption of the dye into the pure ODA LB film. The adsorption spectra of the ODA–dye complex obtained from the air–water interface did not change with pH, while those of the ODA–dye complex formed from the solid–liquid interface showed pH dependence.     

Microstructure, crystallinity, and properties of low-pressure MOCVD-grown europium oxide films

A study of growth, structure, and properties of Eu₂O₃ thin films were carried out. Films were grown at 500–600 °C temperature range on Si(1 0 0) and fused quartz from the complex of Eu(acac)₃·Phen by low pressure metalorganic chemical vapor deposition technique which has been rarely used for Eu₂O₃ deposition. These films were polycrystalline. Depending on growth conditions and substrates employed, these films had also possessed a parasitic phase. This phase can be removed by post-deposition annealing in oxidizing ambient. Morphology of the films was characterized by well-packed spherical mounds. Optical measurements exhibited that the bandgap of pure Eu₂O₃ phase was 4.4 eV. High frequency 1 MHz capacitance–voltage (C–V) measurements showed that the dielectric constant of pure Eu₂O₃ film was about 12. Possible effects of cation and oxygen deficiency and parasitic phase on the optical and electrical properties of Eu₂O₃ films have been briefly discussed.