磷光金属铱聚合物纳米粒子的合成及其在光学成像、核磁成像和光动力学治疗上的应用

发布时间：2018-06-03 00:43

本文选题：铱配合物 + 聚合物纳米粒子　；参考：《上海师范大学》2015年硕士论文

【摘要】：金属铱配合物具有荧光寿命长、发射波长易调节、较大的斯托克位移和光稳定性强等优良的光物理性质,使其在催化、光化学传感和发光二极管等领域应用广泛。但由于铱配合物的水溶性和生物相容性较差,限制了其在生物方面的应用。本文通过两种简单的方法合成了两类铱聚合物纳米粒子,探讨了其在生物成像和光动力学治疗方面的应用。具体研究内容如下:1、磷光聚合物纳米粒子在光学成像和光动力学治疗中的研究利用三种铱二氯桥(2-苯基吡啶铱二氯桥(ppy)2Ir(μ-Cl)2(ppy)2、2-苯基喹啉铱二氯桥[(pq)2Ir(μ-Cl)2(pq)2]、2-(2,4-二氟苯基)吡啶铱二氯桥(dfppy)2Ir(μ-Cl)2(dfppy)2)分别与二嵌段聚合物聚(4-乙烯基吡啶-聚环氧乙烷)(P4VP-b-PEO)配位交联,可形成三种分散均一,稳定性和生物相容性良好的具有多色磷光发射的聚合物纳米粒子。通过细胞毒性和内吞实验,证明了制备的纳米粒子能被细胞有效地吞噬,且细胞毒性较小,具有较好的生物相容性。激光共聚焦实验证明了三种磷光聚合物纳米粒子可用于细胞标记。基于铱的重金属效应在光动力学治疗方面的应用,我们研究了纳米粒子在溶液中产生单线态氧的效率,并通过台盼蓝实验和MTT法进一步证实了制备的纳米粒子在细胞光动力学治疗方面具有较好的效果。2、配位聚合物纳米粒子在T1/光学双模式成像和光动力学治疗中的研究在聚乙烯吡咯烷酮的存在下,利用羧酸和稀土Gd离子的配位作用,以2-苯基喹啉3,3’-联吡啶二羧酸铱配合物和醋酸钆为构筑模块,通过配位自组装一步合成了水溶性的Ir-Gd配位聚合物纳米粒子。电镜和稳定性实验结果表明,合成的纳米粒子形貌均一,分散性良好,在模拟体液环境中也能稳定存在。溶液和细胞层次的核磁成像效果表明,合成的纳米粒子仍是较好的T1成像造影剂。通过激光共聚焦实验,详细研究了纳米粒子在细胞中的荧光成像效果;进一步研究了纳米粒子在溶液中产生单线态氧的效率和在光动力学治疗中杀死癌细胞的效果。
[Abstract]:The iridium complexes have many excellent photophysical properties, such as long fluorescence lifetime, easy to adjust the emission wavelength, large Stoke shift and strong photostability, which make them widely used in the fields of catalysis, photochemical sensing and light-emitting diodes. However, the poor water-solubility and biocompatibility of iridium complexes limit their biological application. In this paper, two kinds of iridium polymer nanoparticles were synthesized by two simple methods, and their applications in biological imaging and photodynamic therapy were discussed. The specific contents of the research are as follows: 1: 1, phosphorescent polymer nanoparticles in optical imaging and photodynamic therapy; use of three iridium dichlorobridged with 2-phenylpyridine iridium dichloro bridge (渭 -Cl-2ppyn 2ppyr-2PQO2-phenyl-quinoline iridium dichloro bridge [pqt2Ir2 (渭 -Cl2pq2 (渭 -Cl2pqq2)]) iridium dichloropyridine) Iridium dichloropyridyl (渭 -Cl-2PQ2) Iridium dichloropyridine Dfppy2 Ir2 Ir2 (渭 -Cl2 + Dfppy2) was crosslinked with diblock polymer P4VP-b-PEO, respectively, with a diblock polymer of 4-vinylpyridine (P4VP-b-PEO). Three kinds of polymer nanoparticles with uniform dispersion, good stability and biocompatibility can be formed with polychromatic phosphorescence emission. The results of cytotoxicity and endocytosis showed that the prepared nanoparticles could be effectively phagocytized by cells and had better biocompatibility. Laser confocal experiments show that three kinds of phosphorescent polymer nanoparticles can be used for cell labeling. Based on the application of iridium heavy metal effect in photodynamic therapy, we have studied the efficiency of nanocrystalline particles to produce singlet oxygen in solution. The results of Trypan blue experiment and MTT method further proved that the prepared nanoparticles had good effect in cell photodynamic therapy. The coordination polymer nanoparticles were used in T1 / optical dual-mode imaging and photodynamic therapy. In the presence of polyvinylpyrrolidone, Based on the coordination of carboxylic acid and rare earth Gd ions, the water-soluble Ir-Gd coordination polymer nanoparticles were synthesized by coordination self-assembly with the iridium complex of 2-phenyl-quinoline 3O3-bipyridine dicarboxylic acid and gadolinium acetate as the building blocks. The results of electron microscope and stability experiments show that the synthesized nanoparticles have uniform morphology and good dispersion, and can also exist stably in simulated humoral environment. The results of nuclear magnetic resonance imaging at the solution and cell levels show that the synthesized nanoparticles are still good contrast agents for T1 imaging. The fluorescence imaging effect of nanoparticles in cells was studied in detail by laser confocal experiments, and the efficiency of nanocrystalline particles to produce singlet oxygen in solution and the effect of killing cancer cells in photodynamic therapy were further studied.
【学位授予单位】：上海师范大学
【学位级别】：硕士
【学位授予年份】：2015
【分类号】：TB383.1;O641.4

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