镧系、过渡金属功能配合物的构筑及荧光性质、手性传感的研究

发布时间：2018-05-04 16:22

本文选题：金属有机骨架材料 + 单相荧光粉　；参考：《山西师范大学》2017年博士论文

【摘要】：金属有机骨架材料(MOFs)具有多孔、结构和性质可调控性等特点,使其在光、电、磁、传感与分离、催化、气体吸附、药物传输等领域具有潜在的应用价值。本论文根据晶体学工程原理,以金属有机骨架材料功能为导向,重点研究了MOFs在光学和手性传感领域的应用,其中选用了镧系金属与合适的有机羧酸配体以及具有d10电子组态的过渡金属与合理设计的含有羧基和氮的手性杂化配体通过水热法或溶剂热法合成了一系列的配合物,主要分析了其结构,对其荧光或圆二色性进行了表征,并进一步探索了其应用。研究成果包括以下几个方面:1.根据发光镧系金属有机骨架材料(LnMOFs)的原理以及构筑该类材料的一些原则,我们结合理论计算,选取了合适的有机配体,设计和构筑了一系列多色的LnMOFs材料。根据三基色原理,将发蓝光的配体、发红光的Eu3+和发绿光的Tb3+构筑在同一MOFs中,经过调节激发波长,获得了两种发白光的近紫外单相MOFs材料:Eu0.045Tb0.955CPOMBA(λex=365 nm)和La0.6Eu0.1Tb0.3CPOMBA(λex=380 nm),通过研究其晶体形貌、热稳定性、热猝灭性质、荧光性质、量子产率以及荧光寿命等,我们发现它们完全具备UV LED用荧光粉的条件,将其创造性地应用在UV LED上。我们用Eu0.045Tb0.955CPOMBA作为荧光粉手工制作了一系列大功率(1W)UV WLEDs,其中激发波长为365 nm的紫外白光LED灯珠,它的相关色温较低,达到5733K,显色指数较高,Ra达到73.4,色坐标是(0.3264,0.3427),这和市场上销售的蓝光芯片和YAG:Ce3+黄光荧光粉制备的白光LED是可比较的。2.为了开发出适合在UV WLED上应用的更加高效的白光MOFs材料,在第1部分工作基础上,我们做了改进,选取了量子产率较高的LnMOFs(Ln BTPCA)。根据三基色原理,将镧系金属离子掺杂入同一个Ln MOFs中,获得了完全不同于文献报道的激发波长为380 nm的白光掺杂材料Eu0.025Tb0.975(BTPCA)。我们特别改进了实验方法,获得了粒径均匀的(8-15μm)且适合应用在LED上的晶体,经过研究其晶体形貌、热稳定性、热猝灭效应、荧光性质、量子产率以及荧光寿命等,发现该材料适合应用在LED上,用该白光材料手工制作了380 nm的n-UV WLEDs,其色坐标为(0.3281,0.3316),色温为5609 K,显色指数为78.9,在不同的驱动电流下其流明值为28-35 lm。3.食品与人类的健康、生命息息相关。对食品添加剂中具有性质不同的手性对映体的检测是至关重要的,目前对于食品添加剂的传统探测方法表现了费用较高、耗时较长等缺陷,而光学传感器已成为研究的主流。MOFs在手性传感领域表现出了优异的性能,促使我们开发了手性MOFs荧光传感器,并用来探测和识别性质不同的食品添加剂中的手性对映体。选择廉价易得的(1R,2R)-环己二甲酸作为原料设计了手性有机配体,其立体构型类似于螺旋桨的叶片,该配体和吡啶辅助配体,共同构筑的HMOF-2展示了比配体更强的荧光,且具有菱形状的二维螺旋管结构,其管道沿c轴方向较窄,只有3.567?,然而沿a轴方向管道则较宽,能达到13.152?,这种特殊的结构对进入管道内的分子有一定的选择性。HMOF-2作为荧光传感器可选择性地传感手性α-羟基羧酸有机小分子,对于体积较大的扁桃酸分子使HMOF-2的荧光猝灭率低、识别能力较差,而对酒石酸、乳酸等体积较小的分子则猝灭率较大,且对D-和L-酒石酸识别体现为KD/KL能达到1.884:1,而对D-和L-乳酸的识别体现为KD/KL能达到1:1.313,这些值是较高的,特别是对D-和L-乳酸的识别能力在已报道的荧光传感器中是最高的。4.生命体的生物和化学活动取决于其基本手性构筑单元(氨基酸等)的立体化学,对食品和有机体中不同构型氨基酸的手性识别和传感在分析营养成分和诊断疾病方面具有特别重要的意义。考虑到圆二色谱能快速、直观地展示分子的立体构型(这要优于那些传统的色谱法、毛细管电泳法识别氨基酸对映体),我们开发了一个能快速、高效以及对映选择性地识别氨基酸的新策略,通过一个类似于DNA结构的纯手性MOFs(拥有内在的CD信号)和D/L-氨基酸进行作用。运用合理设计的手性配体和Zn盐构筑了HMOF-3,它具有类似于DNA的右手双螺旋二维结构。HMOF-3乳状液显示了强的圆二色信号,通过氨基酸的诱导可引起CD强度信号有规律的变化,它能快速、方便、灵敏地识别微量的未修饰的氨基酸。最为显著的是3?10-8 mol的L-天冬氨酸和4?10-8 mol的D-天冬氨酸能完全猝灭HMOF-3水相乳状液的CD信号,对天冬氨酸的检测限为13.31ppm。在所有被探测的8对氨基酸中,其中有关对映体识别能力最高的是D-和L-脯氨酸,其识别效率分别为22.9%和65.7%。这是首次将圆二色谱引入MOFs的传感领域,开创了MOFs传感领域的先河,拓宽了MOFs的应用。
[Abstract]:The metal organic framework material (MOFs) has the potential application value in the fields of light, electricity, magnetism, sensing and separation, catalysis, gas adsorption and drug transmission in the fields of porous, structure and properties. This paper focuses on the study of MOFs in optics and in the light of the principle of crystallographic Engineering and the function of metal organic skeleton materials as the guidance. In the field of chiral sensing, a series of complexes were synthesized by hydrothermal method or solvothermal method, with the lanthanide metal and suitable organic carboxylic acid ligands, the transition metals with D10 electronic configuration and the reasonably designed chiral hybrid ligands containing carboxyl and nitrogen. The structure was mainly analyzed, and the fluorescence or circular two color properties of them were analyzed. The research results include the following aspects: 1. according to the principle of the lanthanide metal organic framework material (LnMOFs) and some principles to construct this kind of material, we combine the theoretical calculation, select the appropriate organic ligands, design and construct a series of polychromatic LnMOFs materials. Based on the principle of fundamental color, two kinds of near ultraviolet single phase MOFs materials, Eu0.045Tb0.955CPOMBA (lambda ex=365 nm) and La0.6Eu0.1Tb0.3CPOMBA ([lambda ex=380 nm), are obtained by using the ligands of blue light, the red Eu3+ and the Tb3+ of the green light in the same MOFs, and the crystal morphology, thermal stability and thermal quenching properties are studied. Fluorescence properties, quantum yields and fluorescence lifetime, we find that they fully possess the conditions of UV LED phosphor, and apply them creatively on UV LED. We have made a series of high-power (1W) UV WLEDs with Eu0.045Tb0.955CPOMBA as phosphor, in which the UV white light LED lamp with a wavelength of 365 nm, and its correlation color. Low temperature, 5733K, high color index, Ra up to 73.4, color coordinates (0.3264,0.3427), which is comparable to the white light LED made from blue light chip and YAG:Ce3+ yellow phosphor prepared on the market to develop a more efficient white light MOFs material suitable for the application on UV WLED. On the basis of the first part, we have made a change. The LnMOFs (Ln BTPCA) with high quantum yield was selected and lanthanide metal ions were doped into the same Ln MOFs according to the three color principle. The white light doped material Eu0.025Tb0.975 (BTPCA), which was completely different from the reported excitation wavelength of 380 nm, was obtained. We specially modified the experimental method and obtained the uniform particle size (8-15 u m) Qie Shi. The crystal on LED is applied to the crystal morphology, thermal stability, thermal quenching effect, fluorescence property, quantum yield and fluorescence lifetime. It is found that the material is suitable for application on LED, and the 380 nm n-UV WLEDs is made by the white light material, its color coordinates are (0.3281,0.3316), color temperature is 5609 K, and the color index is 78.9. When the driving current is driven by 28-35 lm.3., the food is closely related to human health and life. It is very important for the detection of chiral enantiomers with different properties in food additives. At present, the traditional detection methods of food additives have shown high cost and long time consuming defects, and optical sensors have been studied. The mainstream.MOFs has shown excellent performance in the field of chiral sensing, prompting us to develop chiral MOFs fluorescence sensors and to detect and identify chiral enantiomers in food additives with different properties. Select cheap and readily available (1R, 2R) - cyclohexane two formic acid as raw materials for chiral organic ligands, and their stereotyping is similar to that of snail The blade of the propeller, the ligands and the pyridine auxiliary ligands, the co - constructed HMOF-2 shows a stronger fluorescence than the ligand, and has a diamond shaped two-dimensional spiral tube structure, which is narrower in the direction of the c axis, only 3.567? But the pipe is more wide along the a axis, and can reach 13.152? This special structure has a certain number of molecules entering the pipe. Selective.HMOF-2 can be used as a fluorescence sensor to selectively sensing the small organic molecules of chiral alpha hydroxy carboxylic acid. For the large volume of mandelic acid molecules, the fluorescence quenching rate of HMOF-2 is low and the recognition ability is poor, but the quenching rate of the molecules with small volume of tartaric acid and lactic acid is larger, and the identification of D- and L- tartaric acid is 1.. 884:1, and the identification of D- and L- lactic acid is that KD/KL can reach 1:1.313, and these values are high, especially for the identification of D- and L- lactic acid in the reported fluorescent sensors, the highest biological and chemical activity of.4. life body depends on the stereochemistry of its basic chiral building units (amino acids, etc.), in food and organism The chiral recognition and sensing of different configuration amino acids is of special significance in the analysis of nutrients and diagnosis of diseases. Considering that circular two chromatography can quickly and intuitively display the stereotyping of molecules (which is superior to those traditional chromatography, capillary electrophoresis identification of amino acid enantiomers), we have developed a fast, high level. A new strategy for selectivity and enantioselective recognition of amino acids, using a pure chiral MOFs similar to the DNA structure (with intrinsic CD signals) and D/L- amino acids. Using a reasonably designed chiral ligand and Zn salt, HMOF-3 has been constructed. It has a right hand double helix two-dimensional structure.HMOF-3 emulsions that show strong circles in DNA. The two color signal, through the induction of amino acids, can cause a regular change in the CD intensity signal. It can quickly, conveniently and sensitively identify the trace unmodified amino acids. The most significant is the 3? 10-8 mol L- aspartic acid and 4? 10-8 mol D- aspartic acid can completely quench the CD signal of the HMOF-3 aqueous emulsion, and the detection limit of aspartic acid is 1 Among all 8 pairs of detected amino acids, 3.31ppm. has the highest ability to recognize enantiomers with D- and L- proline. The recognition efficiency of 22.9% and 65.7%. is the first to introduce the circular two chromatography into the sensing field of MOFs, which pioneers the field of MOFs sensing and broadens the application of MOFs.

【学位授予单位】：山西师范大学
【学位级别】：博士
【学位授予年份】：2017
【分类号】：O641.4

【参考文献】