磁性、荧光、CT造影纳米微粒的制备、表征及应用
发布时间：2018-09-14 11:37
【摘要】：纳米复合微粒,尤其是功能性纳米复合微粒近年来研究广泛。其中将具有磁性的无机材料(如Fe3O4, γ-Fe2O3, Ni, Co以及Mn的氧化物等)与各种具有功能性的聚合物材料(如环境响应性,荧光,靶向治疗等)相结合制备的磁性纳米复合微粒,由于其多样的功能性,广泛应用于生物医药(如靶向载药,蛋白质、基因、细胞分离,MRI、CT、光学造影成像)和工业应用(污水处理等)等领域,均取得了很好的效果,因而其研究潜力巨大。本文通过使用配体交换法和无皂乳液聚合法分别制备了具有磁性荧光功能的纳米粒子和具有磁性、荧光、CT三重功能的高分子微球。配体交换法是用新合成的配体,在一定条件下置换原有材料表面配体的一类方法,在制备水性Fe304纳米粒子上应用广泛；无皂乳液聚合用于合成生物医用高分子微球,由于反应温和,没有乳化剂的加入,拥有明显的优势。其具体内容如下：使用3-(甲基丙烯酰氧)丙基三甲氧基硅烷(KH-570),聚乙二醇甲基丙烯酸酯(PEGMA)以及可聚合的荧光配合物Eu(AA)3Phen合成出含稀土Eu元素的两亲性聚合物,然后以其作为配体,以油酸改性的Fe3O4粒子为核,通过配体交换法,制备出水性磁性荧光微粒。通过核磁共振波谱仪、傅里叶红外光谱仪、透射电子显微镜、动态光散射粒径测试仪、X射线衍射仪、振动样品磁强计、荧光分光光度计、热重分析仪对该磁性荧光微粒的形态特征、磁性能和荧光性能等进行了测试表征。所获结果表明,制得的两亲性聚合物有效地包覆于磁性纳米粒子表面,最终产物磁性荧光微粒能够良好的分散于水相之中,且粒径均一,平均粒径仅45nm。磁性荧光微粒粉末室温下饱和磁化强度值是2.3 emu/g,荧光性能测试可得到微粒中稀土Eu3+在594 nm和619 nm位置的明显特征发射峰。实验室制备了新型含碘稀土配合物Eu(AA)2(DTA)Phen,并与Fe304磁流体、苯乙烯(St)以及甲基丙烯酸缩水甘油酯(GMA)结合起来,通过无皂乳液聚合法,制备了以Fe304为磁性中心的双层核-壳结构聚合物微球。新型含碘配合物具有优异的X射线造影和稀土荧光特性,相比于原料中的碘剂,配合物具有了更好的造影效果。结合了具有双重功能的配合物与超顺磁性Fe304纳米粒子制得的磁性功能微球可以应用于电子计算机断层扫描(CT),磁共振成像(MRI)以及光学三重功能造影成像,并表现出许多优良的特征：微球表现出良好的均匀分散性且具有很高的封装率；在体外CT试验中,当碘负载量低于4.8 mgI/ml微球仍然可以表现出明显的CT造影效果；微球的饱和磁化强度为2.16 emu/g,弛豫率为259.59 mM-1 S-1,其通过静脉注射至小鼠体内后,在肝脏和脾脏部位表达出良好的T2造影效果；在双光子共聚焦成像下,微球在肝脏和脾脏组织中表现出明显特征红色荧光。同时,新型的配合物和功能微球也显示出一种新的碘造影剂试验方法,具有潜在的研究前景。
[Abstract]:Nano-composite particles, especially functional nano-composite particles, have been widely studied in recent years. Magnetic nanoparticles were prepared by combining magnetic inorganic materials (such as Fe3O4, 纬 -Fe _ 2O _ 3, Ni, Co and Mn oxides, etc.) with various functional polymer materials (such as environmental responsiveness, fluorescence, targeted therapy, etc.). Because of its various functions, it has been widely used in biomedicine (such as targeted drug, protein, gene, cell separation MRI CTT, optical imaging) and industrial application (sewage treatment, etc.). Therefore, its research potential is huge. In this paper, nanoparticles with magnetic fluorescence function and polymer microspheres with magnetic and fluorescent CT triple function were prepared by ligand exchange method and soap-free emulsion polymerization method, respectively. Ligands exchange method is a kind of method to replace the surface ligands of the original materials with new synthesized ligands under certain conditions. It is widely used in the preparation of waterborne Fe304 nanoparticles, and soap-free emulsion polymerization is used to synthesize biomedical polymer microspheres. Due to the mild reaction, there is no emulsifier added, with obvious advantages. The main contents are as follows: using 3- (methacryloxy) propyltrimethoxysilane (KH-570), polyethylene glycol methacrylate (PEGMA) and polymerizable fluorescent complex Eu (AA) 3Phen, amphiphilic polymers containing rare earth elements Eu were synthesized and used as ligands. Waterborne magnetic fluorescent particles were prepared by ligand exchange using oleic acid modified Fe3O4 particles as nucleus. By means of nuclear magnetic resonance spectrometer, Fourier infrared spectrometer, transmission electron microscope, dynamic light scattering particle size tester and X-ray diffractometer, vibrating sample magnetometer, fluorescence spectrophotometer, The morphology, magnetic properties and fluorescence properties of the magnetic fluorescent particles were characterized by thermogravimetric analysis. The results show that the amphiphilic polymer is effectively coated on the surface of magnetic nanoparticles, and the final product magnetic fluorescent particles can be well dispersed in the aqueous phase, and the particle size is uniform, the average particle size is only 45 nm. The characteristic emission peaks of rare earth Eu3 at 594 nm and 619 nm can be obtained by measuring the saturation magnetization intensity of the powder at room temperature and measuring the fluorescence properties of the particles at 2. 3 emu/g,. A new iodized rare earth complex, Eu (AA) _ 2 (DTA) Phen, was prepared by soap-free emulsion polymerization with Fe304 magnetic fluid, styrene (St) and glycidyl methacrylate (GMA). Double layer core-shell polymer microspheres with Fe304 as magnetic center were prepared. The new iodized complexes have excellent X-ray radiography and rare earth fluorescence properties, compared with the iodine agent in raw materials, the complexes have a better contrast effect. The magnetic functional microspheres prepared by combining double functional complexes with superparamagnetic Fe304 nanoparticles can be used in (MRI) imaging of (CT), and triple function optical imaging. The microspheres showed good uniform dispersion and high encapsulation efficiency, in vitro CT test, when the iodine loading was less than 4.8 mgI/ml, the microspheres still showed obvious CT imaging effect. The saturation magnetization of the microspheres was 2.16 emu/g, and the relaxation rate was 259.59 mM-1 S-1.After intravenous injection into mice, the microspheres showed a good T 2 imaging effect in the liver and spleen. The microspheres showed obvious red fluorescence in liver and spleen. At the same time, new complexes and functional microspheres also show a new iodine contrast agent test method, which has potential research prospects.
【学位授予单位】：湖北大学
【学位级别】：硕士
【学位授予年份】：2015
【分类号】：TB383.1
本文编号：2242601
[Abstract]:Nano-composite particles, especially functional nano-composite particles, have been widely studied in recent years. Magnetic nanoparticles were prepared by combining magnetic inorganic materials (such as Fe3O4, 纬 -Fe _ 2O _ 3, Ni, Co and Mn oxides, etc.) with various functional polymer materials (such as environmental responsiveness, fluorescence, targeted therapy, etc.). Because of its various functions, it has been widely used in biomedicine (such as targeted drug, protein, gene, cell separation MRI CTT, optical imaging) and industrial application (sewage treatment, etc.). Therefore, its research potential is huge. In this paper, nanoparticles with magnetic fluorescence function and polymer microspheres with magnetic and fluorescent CT triple function were prepared by ligand exchange method and soap-free emulsion polymerization method, respectively. Ligands exchange method is a kind of method to replace the surface ligands of the original materials with new synthesized ligands under certain conditions. It is widely used in the preparation of waterborne Fe304 nanoparticles, and soap-free emulsion polymerization is used to synthesize biomedical polymer microspheres. Due to the mild reaction, there is no emulsifier added, with obvious advantages. The main contents are as follows: using 3- (methacryloxy) propyltrimethoxysilane (KH-570), polyethylene glycol methacrylate (PEGMA) and polymerizable fluorescent complex Eu (AA) 3Phen, amphiphilic polymers containing rare earth elements Eu were synthesized and used as ligands. Waterborne magnetic fluorescent particles were prepared by ligand exchange using oleic acid modified Fe3O4 particles as nucleus. By means of nuclear magnetic resonance spectrometer, Fourier infrared spectrometer, transmission electron microscope, dynamic light scattering particle size tester and X-ray diffractometer, vibrating sample magnetometer, fluorescence spectrophotometer, The morphology, magnetic properties and fluorescence properties of the magnetic fluorescent particles were characterized by thermogravimetric analysis. The results show that the amphiphilic polymer is effectively coated on the surface of magnetic nanoparticles, and the final product magnetic fluorescent particles can be well dispersed in the aqueous phase, and the particle size is uniform, the average particle size is only 45 nm. The characteristic emission peaks of rare earth Eu3 at 594 nm and 619 nm can be obtained by measuring the saturation magnetization intensity of the powder at room temperature and measuring the fluorescence properties of the particles at 2. 3 emu/g,. A new iodized rare earth complex, Eu (AA) _ 2 (DTA) Phen, was prepared by soap-free emulsion polymerization with Fe304 magnetic fluid, styrene (St) and glycidyl methacrylate (GMA). Double layer core-shell polymer microspheres with Fe304 as magnetic center were prepared. The new iodized complexes have excellent X-ray radiography and rare earth fluorescence properties, compared with the iodine agent in raw materials, the complexes have a better contrast effect. The magnetic functional microspheres prepared by combining double functional complexes with superparamagnetic Fe304 nanoparticles can be used in (MRI) imaging of (CT), and triple function optical imaging. The microspheres showed good uniform dispersion and high encapsulation efficiency, in vitro CT test, when the iodine loading was less than 4.8 mgI/ml, the microspheres still showed obvious CT imaging effect. The saturation magnetization of the microspheres was 2.16 emu/g, and the relaxation rate was 259.59 mM-1 S-1.After intravenous injection into mice, the microspheres showed a good T 2 imaging effect in the liver and spleen. The microspheres showed obvious red fluorescence in liver and spleen. At the same time, new complexes and functional microspheres also show a new iodine contrast agent test method, which has potential research prospects.
【学位授予单位】：湖北大学
【学位级别】：硕士
【学位授予年份】：2015
【分类号】：TB383.1
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