本文選題：金屬有機(jī)骨架材料 + 單相熒光粉��； 參考：《山西師范大學(xué)》2017年博士論文

【摘要】：金屬有機(jī)骨架材料(MOFs)具有多孔、結(jié)構(gòu)和性質(zhì)可調(diào)控性等特點(diǎn),使其在光、電、磁、傳感與分離、催化、氣體吸附、藥物傳輸?shù)阮I(lǐng)域具有潛在的應(yīng)用價(jià)值。本論文根據(jù)晶體學(xué)工程原理,以金屬有機(jī)骨架材料功能為導(dǎo)向,重點(diǎn)研究了MOFs在光學(xué)和手性傳感領(lǐng)域的應(yīng)用,其中選用了鑭系金屬與合適的有機(jī)羧酸配體以及具有d10電子組態(tài)的過渡金屬與合理設(shè)計(jì)的含有羧基和氮的手性雜化配體通過水熱法或溶劑熱法合成了一系列的配合物,主要分析了其結(jié)構(gòu),對其熒光或圓二色性進(jìn)行了表征,并進(jìn)一步探索了其應(yīng)用。研究成果包括以下幾個(gè)方面:1.根據(jù)發(fā)光鑭系金屬有機(jī)骨架材料(LnMOFs)的原理以及構(gòu)筑該類材料的一些原則,我們結(jié)合理論計(jì)算,選取了合適的有機(jī)配體,設(shè)計(jì)和構(gòu)筑了一系列多色的LnMOFs材料。根據(jù)三基色原理,將發(fā)藍(lán)光的配體、發(fā)紅光的Eu3+和發(fā)綠光的Tb3+構(gòu)筑在同一MOFs中,經(jīng)過調(diào)節(jié)激發(fā)波長,獲得了兩種發(fā)白光的近紫外單相MOFs材料:Eu0.045Tb0.955CPOMBA(λex=365 nm)和La0.6Eu0.1Tb0.3CPOMBA(λex=380 nm),通過研究其晶體形貌、熱穩(wěn)定性、熱猝滅性質(zhì)、熒光性質(zhì)、量子產(chǎn)率以及熒光壽命等,我們發(fā)現(xiàn)它們完全具備UV LED用熒光粉的條件,將其創(chuàng)造性地應(yīng)用在UV LED上。我們用Eu0.045Tb0.955CPOMBA作為熒光粉手工制作了一系列大功率(1W)UV WLEDs,其中激發(fā)波長為365 nm的紫外白光LED燈珠,它的相關(guān)色溫較低,達(dá)到5733K,顯色指數(shù)較高,Ra達(dá)到73.4,色坐標(biāo)是(0.3264,0.3427),這和市場上銷售的藍(lán)光芯片和YAG:Ce3+黃光熒光粉制備的白光LED是可比較的。2.為了開發(fā)出適合在UV WLED上應(yīng)用的更加高效的白光MOFs材料,在第1部分工作基礎(chǔ)上,我們做了改進(jìn),選取了量子產(chǎn)率較高的LnMOFs(Ln BTPCA)。根據(jù)三基色原理,將鑭系金屬離子摻雜入同一個(gè)Ln MOFs中,獲得了完全不同于文獻(xiàn)報(bào)道的激發(fā)波長為380 nm的白光摻雜材料Eu0.025Tb0.975(BTPCA)。我們特別改進(jìn)了實(shí)驗(yàn)方法,獲得了粒徑均勻的(8-15μm)且適合應(yīng)用在LED上的晶體,經(jīng)過研究其晶體形貌、熱穩(wěn)定性、熱猝滅效應(yīng)、熒光性質(zhì)、量子產(chǎn)率以及熒光壽命等,發(fā)現(xiàn)該材料適合應(yīng)用在LED上,用該白光材料手工制作了380 nm的n-UV WLEDs,其色坐標(biāo)為(0.3281,0.3316),色溫為5609 K,顯色指數(shù)為78.9,在不同的驅(qū)動電流下其流明值為28-35 lm。3.食品與人類的健康、生命息息相關(guān)。對食品添加劑中具有性質(zhì)不同的手性對映體的檢測是至關(guān)重要的,目前對于食品添加劑的傳統(tǒng)探測方法表現(xiàn)了費(fèi)用較高、耗時(shí)較長等缺陷,而光學(xué)傳感器已成為研究的主流。MOFs在手性傳感領(lǐng)域表現(xiàn)出了優(yōu)異的性能,促使我們開發(fā)了手性MOFs熒光傳感器,并用來探測和識別性質(zhì)不同的食品添加劑中的手性對映體。選擇廉價(jià)易得的(1R,2R)-環(huán)己二甲酸作為原料設(shè)計(jì)了手性有機(jī)配體,其立體構(gòu)型類似于螺旋槳的葉片,該配體和吡啶輔助配體,共同構(gòu)筑的HMOF-2展示了比配體更強(qiáng)的熒光,且具有菱形狀的二維螺旋管結(jié)構(gòu),其管道沿c軸方向較窄,只有3.567?,然而沿a軸方向管道則較寬,能達(dá)到13.152?,這種特殊的結(jié)構(gòu)對進(jìn)入管道內(nèi)的分子有一定的選擇性。HMOF-2作為熒光傳感器可選擇性地傳感手性α-羥基羧酸有機(jī)小分子,對于體積較大的扁桃酸分子使HMOF-2的熒光猝滅率低、識別能力較差,而對酒石酸、乳酸等體積較小的分子則猝滅率較大,且對D-和L-酒石酸識別體現(xiàn)為KD/KL能達(dá)到1.884:1,而對D-和L-乳酸的識別體現(xiàn)為KD/KL能達(dá)到1:1.313,這些值是較高的,特別是對D-和L-乳酸的識別能力在已報(bào)道的熒光傳感器中是最高的。4.生命體的生物和化學(xué)活動取決于其基本手性構(gòu)筑單元(氨基酸等)的立體化學(xué),對食品和有機(jī)體中不同構(gòu)型氨基酸的手性識別和傳感在分析營養(yǎng)成分和診斷疾病方面具有特別重要的意義�？紤]到圓二色譜能快速、直觀地展示分子的立體構(gòu)型(這要優(yōu)于那些傳統(tǒng)的色譜法、毛細(xì)管電泳法識別氨基酸對映體),我們開發(fā)了一個(gè)能快速、高效以及對映選擇性地識別氨基酸的新策略,通過一個(gè)類似于DNA結(jié)構(gòu)的純手性MOFs(擁有內(nèi)在的CD信號)和D/L-氨基酸進(jìn)行作用。運(yùn)用合理設(shè)計(jì)的手性配體和Zn鹽構(gòu)筑了HMOF-3,它具有類似于DNA的右手雙螺旋二維結(jié)構(gòu)。HMOF-3乳狀液顯示了強(qiáng)的圓二色信號,通過氨基酸的誘導(dǎo)可引起CD強(qiáng)度信號有規(guī)律的變化,它能快速、方便、靈敏地識別微量的未修飾的氨基酸。最為顯著的是3?10-8 mol的L-天冬氨酸和4?10-8 mol的D-天冬氨酸能完全猝滅HMOF-3水相乳狀液的CD信號,對天冬氨酸的檢測限為13.31ppm。在所有被探測的8對氨基酸中,其中有關(guān)對映體識別能力最高的是D-和L-脯氨酸,其識別效率分別為22.9%和65.7%。這是首次將圓二色譜引入MOFs的傳感領(lǐng)域,開創(chuàng)了MOFs傳感領(lǐng)域的先河,拓寬了MOFs的應(yīng)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.

【學(xué)位授予單位】：山西師范大學(xué)
【學(xué)位級別】：博士
【學(xué)位授予年份】：2017
【分類號】：O641.4

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