Eu/MCM-41介孔复合体系的制备与表征

以十六烷基三甲基溴化铵(CTAB)为模板剂，正硅酸乙酯(TEOS)为无机硅源，以及1，3，5-三甲苯(TMB)为加长剂合成了有序介孔分子(MCM-41)。选择Eu(DBM)3phen为客体，纳米级介孔分子筛为主体，在氯仿中进行分子组装，制备了具有强发光性能的超分子纳米复合材料Eu(DBM)3phen-MCM-41。采用XRD，HRTEM，FTIR和荧光光谱分析等对产物的结构与性能进行了分析。结果表明，在361nm紫外光激发下，Eu配合物在613nm处有较强的荧光，归属于^5Do→^7F2跃迁峰，且在400～550nm波段有介孔基体的荧光发光。     

介孔氧化硅孔径尺寸对Eu(Ⅲ)配合物的影响

分别以十六烷基三甲基溴化铵(CTAB)和聚乙氧基-聚丙氧基-聚乙氧基三嵌段共聚物(P123)为模板剂、正硅酸乙酯(TEOS)为硅源，采用水热法合成了有序介孔分子筛MCM-41和SBA-15。选择Eu(DBM)₃phen为客体，有序介孔氧化硅MCM-41和SBA-15为载体，分别在氯仿中进行分子组装，制备出具有较强发光性能的介孔复合材料Eu(DBM)₃phen/APTES-MCM-41(EAM)和Eu(DBM)₃phen/APTES-SBA-15(EAS)。采用XRD、TEM、N₂吸附-脱附和荧光光谱等对产物的结构与性能进行了分析。结果表明，Eu(DBM)₃phen组装进有序介孔氧化硅的孔道中后，发光纯度提高。而且孔径越小，发光纯度越高。选用较大孔径的SBA-15为载体，在不显著影响发光纯度的同时，可以获得较高的发光强度。     

新型双稀土配合物掺杂的Ag@SiO_2纳米粒子的制备及表征

首先合成配合前驱体对氨基苯甲酸(PABA)-二乙烯三胺五乙酸(DTPA)-3-氨丙基三甲氧基硅烷(APTMS)及双稀土配合物Eu3+/Tb3+-PABA-DTPA-APTMS,然后采用反相微乳液法成功制备出表面带氨基的核壳型稀土配合物Eu3+/Tb3+-PABA-DTPA-APTMS掺杂的Ag@SiO2荧光纳米粒子.利用透射电子显微镜、荧光光谱、紫外-可见光谱等手段进行表征,并进行了光稳定性及氨基测定等实验,结果表明,该纳米粒子中Eu3+与Tb3+在最大发射峰处的荧光强度较Eu3+/Tb3+-PABA-DTPA-APTMS掺杂的没有银核的SiO2荧光纳米粒子分别提高了3.0和3.4倍,所制备的纳米粒子呈规则球状,具有良好的分散性和光稳定性,纳米粒子表面带有氨基,可不需要进行表面修饰而直接与生物分子反应.该纳米粒子有望作为一种新型的稀土荧光探针应用于高灵敏检测的时间分辨荧光免疫分析、生物传感器、生物芯片等.     

Eu(dbm)_3phen/SiO_2@KH570-NH_2核壳结构微球的制备及其性能表征

将由二苯甲酰甲烷、1,10-菲罗啉及氯化铕三者合成的荧光配合物Eu(dbm)3phen嵌入于用水刻蚀法制得的二氧化硅微球,得到Eu(dbm)3phen/SiO_2复合微球。为解决上述复合微球易泄漏的问题,在微球表面包覆了一层约10nm厚的γ-甲基丙烯酰氧基丙基三甲氧基硅烷,形成核-壳结构,并通过与甲基丙烯酸缩水甘油酯的聚合反应,使微球表面带上环氧基团。通过环氧基团与乙二胺的开环反应,使微球表面带有氨基,其荧光强度可保持为原强度的72%,并便于与抗体连接。通过激发粒径仪、扫描电镜等多种方法对此材料的结构及性能作了表征。结果表明该材料有条件用作荧光免疫检测中生物分子的标记。     

多重响应性复合介孔二氧化硅纳米微球的制备及其在抗腐蚀涂层上的应用

以正硅酸乙酯(TEOS)为硅源,制备介孔二氧化硅纳米微球(MSNs),利用原子转移自由基聚合(ATRP)技术在MSNs表面接枝聚甲基丙烯酸二甲胺乙酯(PDMAEMA)作为缓释开关,成为智能纳米容器(PDMAEMA-MSNs),装载防腐蚀剂-苯并三唑(BTA)验证其双重刺激响应性释放性能。采用透射电子显微镜(TEM)、热重分析(TGA) 、X-射线光电子能谱(XPS)以及傅里叶红外光谱(FT-IR)分析手段表征了MSNs的结构、形貌及表面功能化过程,并使用荧光光谱仪实时监测BTA在不同PH、温度下的释放过程。实验结果表明,智能纳米容器掺杂于SiOx/ZrOy中实现了BTA的双重响应性释放,形成Cu-BTA复合膜,起到铜金属防腐蚀的作用。     

新型铕配合物二氧化硅荧光纳米粒子DPPDA-Eu~(3+)/SiO_2的制备与表征

本文首先合成配位体4,7-二苯基-1,10-菲罗啉-2,9-二羧酸(DPPDA,C_(26)H_(16)N_2O_4)及铕配合物DPPDA-Eu~(3+)((C_(26)H_(16)N_2O_4)_2Eu·15H_2O),然后采用反相微乳液法,通过正硅酸乙酯和3-氨丙基三甲氧基硅烷的共水解、聚合作用成功制备出表面带氨基的二氧化硅包裹铕配合物DPPDA-Eu~(3+)的核壳型荧光纳米颗粒DPPDA-Eu~(3+)/SiO_2。利用透射电子显微镜、荧光光谱、紫外-可见光谱等手段进行表征,并进行了光稳定性、荧光泄露与氨基测定等实验,结果表明所制备的纳米粒子呈规则球状,大小均匀,粒径为80±8nm,具有良好的单分散性和光稳定性,不易发生荧光分子从二氧化硅壳层中泄露,纳米粒子表面带有氨基,可不需要进行表面修饰而直接与生物分子反应。该纳米粒子可望作为一种新型的稀土荧光探针应用于时间分辨荧光免疫分析、生物芯片及生物传感器等。     

纳米Ag@SiO_2核壳结构的表面等离子体共振效应对铕配合物的荧光增强作用(英文)

分别制备了二氧化硅壳层厚度为10、25和80 nm的三种Ag@S O2纳米粒子,合成了铕与不同比例苯甲酸根(BA)的配合物、铕与1,10-邻菲罗啉(phen)及2,2′-联吡啶(bpy)的配合物,并对其进行表征.表征结果推测配合物的组成为Eu(BA)nCl3-n·2H2O(n=1,2,3)、Eu(phen)Cl3·2H2O和Eu(bpy)Cl3·2H2O.配合物的荧光光谱显示,在加入Ag@Si O2纳米粒子后,复合物的荧光强度有不同程度的增加,这可能是由于表面等离子体共振造成的.不同硅壳厚度的Ag@Si O2纳米粒子的荧光增强顺序是25 nm80 nm10 nm,这表明二氧化硅核壳厚度约25 nm时有较强的表面等离子体共振效应.此外,在这些复合物中,Eu(phen)Cl3·2H2O复合物的增强效果是最强的,而Eu(BA)nCl3-n·2H2O的增强效果是最弱的.在三个苯甲酸铕配合物中,Eu(BA)3·2H2O的增强效果最弱,其他两个苯甲酸铕复合物增强效果相对较好.原因可能是含氮配合物(Eu(phen)Cl3·2H2O和Eu(bpy)Cl3·2H2O)可以和Ag@SiO2更好地成键,而苯甲酸铕配合物和Ag@Si O2纳米粒子的作用相对较弱.Ag@SiO2纳米粒子有望应用于增强稀土材料的发光.     

具有高比表面的介孔Co-SiO2微球的合成与表征

在碱性条件下,利用十六烷基三甲基溴化铵(CTAB)为结构导向剂,以含氨基有机硅烷与过渡金属离子Co(Ⅱ)形成的配合物Co(Ⅲ)-APTMOS为金属离子前驱体,合成了含金属元素钴的介孔Co-SiO₂微球.运用XRD,TEM以及N₂-吸附等技术对所制备的产物进行了表征.结果表明,产物为具有高比表面、孔道无序的介孔微球.同时阐述了金属离子以配合物Co-APTMOS形式加入反应体系的优越性.     

中空纳米二氧化硅微球的制备及表征

本文介绍了一种制备中空纳米二氧化硅微球的新方法。利用模板首先合成介孔纳米二氧化硅微球,再用水热反应法,成功制备了非功能化和巯基、氨基功能化中空纳米二氧化硅微球。利用透射电子显微镜,热重分析等手段对其形貌进行了表征。另外,对中空介孔纳米二氧化硅微球的形成机制进行了探讨。     

双模板法制备介孔二氧化硅纳米蚕茧

用十八烷基三甲基溴化铵(STAB)作模板剂,左旋香茅醇(CN)为结构助剂,利用溶胶-凝胶法,在CN/STAB摩尔比1∶1条件下制备了介孔二氧化硅纳米蚕茧;采用扫描电镜和透射电镜分析了产物的结构,并对其进行了氮气吸附-脱附测试.结果表明,所制备的介孔二氧化硅纳米蚕茧的孔道与蚕茧表面平行;搅拌速度对介孔二氧化硅纳米蚕茧的长度有较大的影响,随着搅拌速度的增加,其长度减小.     

以手性两亲小分子为模板剂制备介孔二氧化硅纳米空心球

以L-亮氨酸为手性源合成了手性阳离子两亲性小分子化合物L-18Leu6NEtBr,用其自组装体作为模板,氢氧化钠为催化剂,经溶胶-凝胶过程制备出介孔二氧化硅纳米空心球;分析了介孔二氧化硅纳米空心球的尺寸和孔径.结果表明,所制备的二氧化硅空心球直径约100nm;其介孔孔道平行于壳表面,孔径为3.1nm.     

Tb(DBM)3phen/APTES-SBA-15介孔复合体系的制备与表征

以三嵌段化合物P123为模板剂、正硅酸乙酯(TEOS)为无机硅源合成了有序介孔分子筛SBA-15. 选择Tb(DBM)₃phen为客体, 纳米级介孔分子筛为主体, 在氯仿中进行分子组装, 制备具有强发光性能的超分子纳米复合材料Tb(DBM)₃phen/APTES-SBA-15. 采用XRD, HRTEM, N₂吸附/脱附, FTIR和荧光光谱分析等对复合材料的结构与性能进行了研究.     

Bright red electroluminescent devices based on a soluble lanthanide complex Eu(DBM)_3(phen)

Electroluminescent devices with PVK film doped with Eu(DBM)3(phen) and PBD were fabricated. The device structure of glass substrate/indium-tin-oxide/PPV/PVK:Eu(DBM)3-(phen):PBD/Alq3/Al was employed. The emissive layer was formed by spin-casting method. A sharply red electroluminescence with a maximum luminance of 114.4 cd/m2 was achieved at 42 V.     

Preparation and Characterization of Ternary Europium ComplexDoped Thin SolGel Hybrid Film by Fluorescence Spectroscopy*

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Preparation and Characterization of Layered Compound Zirconium Bis(monohydrogenphosphate) Intercalated with Rare Earth Complex

Rare earth organic complexes usually exhibit intense narrow band emission via anenergy transfer from the ligands to the central rare earth ions under UV excitation.Although rare earth complexes, especially for the complex with 0-diketone, have strongluminescence, their photostability and thermal stability are not very good enough for thephosphor. Therefore, the key problem related to rare earth complex is to try to find asuitable matrix material to trap them. Inorganic solid matrixes are prom…     

Photophysical Properties of a Novel Organic–Inorganic Hybrid Material: Eu(III)-β-Diketone Complex Covalently Bonded to SiO2/ZnO Composite Matrix

In this article, dibenzoylmethane (DBM) was first grafted with the coupling reagent 3-(triethoxysilyl)-propyl isocyanate (TESPIC) to form precursor DBM–Si, and ZnO quantum dot was modified with 3-mercaptopropyltrimethoxysilane (MPS) to form SiO₂/ZnO nanocomposite particle. Then the precursor DBM–Si and the terminal ligand 1,10-phenthroline (phen) were coordinated to Eu³⁺ion to obtain ternary hybrid material phen–Eu–DBM–SiO₂/ZnO after hydrolysis and copolycondensation between the tetraethoxysilane (TEOS), water molecules and the SiO₂/ZnO network via the sol–gel process. In addition, for comparison, the binary hybrid material with SiO₂/ZnO network and ternary hybrid material with pure Si–O network were also synthesized, denoted as Eu–DBM–SiO₂/ZnO and phen–Eu–DBM–Si, respectively. The results reveal that hybrid material with SiO₂/ZnO network phen–Eu–DBM–SiO₂/ZnO exhibits the stronger red light, the longer lifetimes and higher quantum efficiency than hybrid material with pure Si–O network phen–Eu–DBM–Si, suggesting that SiO₂/ZnO is a favorable host matrix for the luminescence of rare earth complexes.     

Synthesis and characterization of fluorescent Europium (III) complex based on D-dextrose composite for latent fingerprint detection

A europium salt-Na[Eu(5,5′-DMBP)(phen)₃]·Cl₃ (Eu(III)-CPLx) was prepared by using various precursors such as 5,5′-Dimethyl-2,2′-bipyridyl (5,5′-DMBP), 1,10-phenanthroline (phen) and europium chloride hexahydrate (EuCl₃·6H₂O) by a complexation method. The red emission fluorescent Na[Eu(5,5′-DMBP)(phen)₃]·Cl₃/D-Dextrose (Eu(III)-CPLx/D-Dex) composite was synthesized by using an adsorption method with Eu(III)-CPLx and D-Dextrose (D-Dex). The Eu(III)-CPLx and fluorescent (Eu(III)-CPLx/D-Dex) composites were characterized by numerous techniques. The fluorescent (Eu(III)-CPLx/D-Dex) composite demonstrated a strong red emission and controlled fluorescence quenching in the solid state and was consequently used in latent fingerprint (LFP) detection. The LFPs were developed by using a powder dusting method (PDM) with Eu(III)-CPLx and fluorescent Eu(III)-CPLx/D-Dex composites on different substrates under daylight and UV-light irradiation at 365 nm. The fluorescent Eu(III)-CPLx/D-Dex composite was effectively explored for developing LFP images on various substrates and also acts as a better labeling agent for LFP detection in forensic science crime scene investigations.     

Synthesis, characterization and luminescent properties of new highly luminescent organic ligand and complexes of trivalent rare earth

A novel ligand with two carboxylic groups has been synthesized. The composition and structure of the ligand were characterized by IR, (1)H NMR and MS spectrometry. The highly luminescent intensity complexes were prepared with the ligand and phen. The IR, solid state (13)C NMR and fluorescent spectra of the complex were studied. IR absorption spectra indicate that the ligand is coordinated to the Eu(3+) ion, and chemical bonds are formed between Eu(3+) ion and nitrogen atoms of phen. The fluorescent spectra illustrate that the complex has an excellent luminescence, indicating the ligand favors energy transfer to the emitting energy level of Eu(3+). The influences of pH and reaction solvent on the fluorescence intensity of the complex were also discussed.