磷光金屬銥聚合物納米粒子的合成及其在光學成像、核磁成像和光動力學治療上的應用
發(fā)布時間:2018-06-03 00:43
本文選題:銥配合物 + 聚合物納米粒子; 參考:《上海師范大學》2015年碩士論文
【摘要】:金屬銥配合物具有熒光壽命長、發(fā)射波長易調(diào)節(jié)、較大的斯托克位移和光穩(wěn)定性強等優(yōu)良的光物理性質(zhì),使其在催化、光化學傳感和發(fā)光二極管等領域應用廣泛。但由于銥配合物的水溶性和生物相容性較差,限制了其在生物方面的應用。本文通過兩種簡單的方法合成了兩類銥聚合物納米粒子,探討了其在生物成像和光動力學治療方面的應用。具體研究內(nèi)容如下:1、磷光聚合物納米粒子在光學成像和光動力學治療中的研究利用三種銥二氯橋(2-苯基吡啶銥二氯橋(ppy)2Ir(μ-Cl)2(ppy)2、2-苯基喹啉銥二氯橋[(pq)2Ir(μ-Cl)2(pq)2]、2-(2,4-二氟苯基)吡啶銥二氯橋(dfppy)2Ir(μ-Cl)2(dfppy)2)分別與二嵌段聚合物聚(4-乙烯基吡啶-聚環(huán)氧乙烷)(P4VP-b-PEO)配位交聯(lián),可形成三種分散均一,穩(wěn)定性和生物相容性良好的具有多色磷光發(fā)射的聚合物納米粒子。通過細胞毒性和內(nèi)吞實驗,證明了制備的納米粒子能被細胞有效地吞噬,且細胞毒性較小,具有較好的生物相容性。激光共聚焦實驗證明了三種磷光聚合物納米粒子可用于細胞標記;阢灥闹亟饘傩诠鈩恿W治療方面的應用,我們研究了納米粒子在溶液中產(chǎn)生單線態(tài)氧的效率,并通過臺盼藍實驗和MTT法進一步證實了制備的納米粒子在細胞光動力學治療方面具有較好的效果。2、配位聚合物納米粒子在T1/光學雙模式成像和光動力學治療中的研究在聚乙烯吡咯烷酮的存在下,利用羧酸和稀土Gd離子的配位作用,以2-苯基喹啉3,3’-聯(lián)吡啶二羧酸銥配合物和醋酸釓為構筑模塊,通過配位自組裝一步合成了水溶性的Ir-Gd配位聚合物納米粒子。電鏡和穩(wěn)定性實驗結(jié)果表明,合成的納米粒子形貌均一,分散性良好,在模擬體液環(huán)境中也能穩(wěn)定存在。溶液和細胞層次的核磁成像效果表明,合成的納米粒子仍是較好的T1成像造影劑。通過激光共聚焦實驗,詳細研究了納米粒子在細胞中的熒光成像效果;進一步研究了納米粒子在溶液中產(chǎn)生單線態(tài)氧的效率和在光動力學治療中殺死癌細胞的效果。
[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.
【學位授予單位】:上海師范大學
【學位級別】:碩士
【學位授予年份】:2015
【分類號】:TB383.1;O641.4
【參考文獻】
相關碩士學位論文 前1條
1 秦麗潔;金屬銥配合物納米材料的合成及其應用探索[D];上海師范大學;2013年
,本文編號:1970803
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