四苯乙烯超分子组装及聚集诱导荧光研究

发布时间：2018-03-22 19:38

本文选题：分子自组装　切入点：四苯乙烯分子(TPE)　出处：《新疆大学》2017年硕士论文　论文类型：学位论文

【摘要】：分子自组装一直是研究热点,通过自组装可以制备各种有序的功能材料。静电相互作用力是分子自组装中唯一的长程作用力,通过引入带电荧光分子作为构筑单元,可以得到有序的具有荧光的多功能聚集体,比如凝聚核胶束,层层组装薄膜,以及荧光囊泡。本论文对四苯乙烯超分子组装及聚集诱导荧光进行了研究,工作主要内容与结论如下:1.使用具有AIE效应的荧光分子TPE-DPA与稀土金属离子配位,由于稀土离子与荧光分子的配位比例为2:3,使得配位超分子带有一定量的负电荷,通过使用带电正电的嵌段高分子与金属配位超分子进行二级组装,得到了凝固核胶束,胶束直径为20 nm,内核半径为7 nm。金属配位超分子Tb3+-TPE-DPA在完全配位的情况下,形成了巨型网状结构,在水溶液中的溶解性降低;由于嵌段高分子PMVP41-PEO205的电中性部分是亲水的EO链,通过与金属配位超分子自组装,增强了Tb3+-TPE-DPA配位超分子的溶解性。形成配位超分子的有机配体和稀土金属离子具有不同的荧光,调节Tb3+-TPE-PMVP41-PEO205与Eu3+-L2EO4-PMVP41-PEO205的比例,当浓度比例为24:17时,得到了白色荧光溶液,溶液的CIE坐标为(0.364,0.368),接近标准白色荧光的CIE坐标,白色荧光溶液受温度和pH值影响很大,使用琼脂糖溶液固化白色荧光溶液,使得体系荧光强度进一步增强。2.由于白色荧光材料在化学传感器以及光电材料方面的优良性质,一直是研究的热点,目前为止还没有金属超分子层层组装制备白色荧光薄膜的报道。层层组装技术是以静电作为主要驱动构建LBL薄膜的方法,通过引入蓝色荧光配体TPE-DPA以及带有相同配位头基的L2EO4,稀土金属离子与配体相互作用可以得到红绿蓝三基色。通过分层组装,克服一些溶解性较差的超分子组装问题。调节荧光组分比例、组装顺序、组装层数等得到了(PEI/TPE/Tb3+)15/(PEI/Ln3+-L2EO4)5白色荧光薄膜,CIE坐标为(0.335,0.347),该荧光薄膜对温度、pH、爆炸物具有很好的稳定性,固定的高度49.5 nm以及较好的绝对量子产率11.74%,并且对Cl2具有特异的响应。(3)碱性磷酸酶是公认的识别癌细胞的蛋白酶,通过合理设计含有碱性磷酸酶受体的多肽分子,并将多肽分子修饰到APTES上,可以得到的P1-APTES分子可以作为硅源;以荧光囊泡TPE-BPA@8CTAB为模板,将P1-APTES和TEOS作为硅源,可以得到具有荧光的空心纳米粒子,直径为35 nm左右,壁厚为10 nm。当P1-APTES浓度为4 mM时,纳米粒子荧光消失。当P1-APTES:TEOS=25 mM:1 mM时,体系得到的纳米粒子对Hela细胞有成像的功能,孵育24 h后,几乎可以完全杀死Hela细胞,具有重大的生物应用潜能。
[Abstract]:Molecular self-assembly has always been a hot topic, and various ordered functional materials can be prepared by self-assembly. Electrostatic interaction force is the only long-range interaction force in molecular self-assembly, and the electrically charged fluorescent molecule is introduced as the building unit. Ordered multifunctional aggregates with fluorescence, such as condensed nuclear micelles, layers of assembled films, and fluorescent vesicles, can be obtained. In this paper, supramolecular assembly and agglomeration induced fluorescence of tetrastyrene were studied. The main contents and conclusions are as follows: 1. The coordination of rare earth metal ions with fluorescent molecule TPE-DPA with AIE effect is as follows: 1. Because the coordination ratio of rare earth ions and fluorescent molecules is 2: 3, the coordination supramolecular has a certain amount of negative charge. By the secondary assembly of charged block polymer with metal coordination supramolecular, a solidified nuclear micelle with a diameter of 20 nm and a core radius of 7 nm was obtained. The metal coordination supramolecular Tb3 TPE-DPA was completely coordinated. Because the electrically neutral part of block polymer PMVP41-PEO205 is hydrophilic EO chain, it is self-assembled by supramolecular coordination with metal. The solubility of Tb3 -TPE-DPA coordination supramolecular was enhanced. The organic ligands and rare earth metal ions forming the coordination supramolecular had different fluorescence. The ratio of Tb3 -TPE-PMVP41-PEO205 to Eu3 -L2EO4-PMVP41-PEO205 was adjusted. When the concentration ratio was 24:17, the white fluorescence solution was obtained. The CIE coordinate of the solution is 0.364U 0.368m, which is close to the standard white fluorescent CIE coordinate. The white fluorescence solution is greatly affected by temperature and pH value. The agarose solution is used to solidify the white fluorescent solution. Because of the excellent properties of white fluorescent materials in chemical sensors and optoelectronic materials, it has been a hot research topic. So far, there have been no reports of metal supramolecular layer-by-layer assembly to prepare white fluorescent thin films. The layer-by-layer assembly technique is based on static electricity as the main driving method to construct LBL thin films. By introducing blue fluorescent ligand TPE-DPA and L2EO4 with the same coordination head, the red green blue trichrome can be obtained by the interaction of rare earth metal ions with ligands. In order to overcome the problem of supramolecular assembly with poor solubility, we have obtained the white fluorescent thin film with CIE coordinate of 0.335 ~ 0.347m by adjusting the proportion of fluorescence components, the order of assembly, the number of assembly layers, and so on. The white fluorescent thin film has good stability to temperature, pH and explosives. A fixed height of 49.5 nm and a better absolute yield of 11.74%, and a specific response to Cl2, alkaline phosphatase (ALP) is recognized as a protease that recognizes cancer cells. When the polypeptide molecules were modified into APTES, the P1-APTES molecules could be used as silicon source, and then the hollow nanoparticles with the diameter of about 35 nm could be obtained by using P1-APTES and TEOS as silicon source, using fluorescent vesicle TPE-BPA@8CTAB as template. The wall thickness is 10 nm. When the P1-APTES concentration is 4 mm, the fluorescence of the nanoparticles disappears. When P1-APTES:TEOS=25 mM:1 mm, the nanoparticles have the function of imaging the Hela cells. After incubation for 24 h, the nanoparticles can almost completely kill the Hela cells. It has great potential for biological application.
【学位授予单位】：新疆大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O641.3

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