高分子磁性微球的制备及应用
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摘要
磁性高分子微球(Magnetic Polymer Microspheres，简称MPM)是一种以Fe_3O_4纳米粒子为核，聚苯乙烯为壳的兼具磁性材料和高分了材料性能的新型功能材料，由于粒径小，比表面积大，可偶联的生物分子容量大，且能分散在体系中不易沉降，非常适合在生物体系中使用，迄今已在细胞生物学、生物医学和生物工程等诸多领域展现了广阔的应用前景，本文在总结前人的研究成果的基础上，改进了实验方法，制备出了单分散、强磁响应性的聚苯乙烯磁性高分子微球(PS-MPM)。本论文的主要内容有：
1．采用化学共沉淀法制备出了可达到纳米级分散的Fe_3O_4纳米粒子。深入探讨了沉淀剂的种类、加入方式、表面活性剂、反应温度、熟化温度等各种因素对产物的粒径及磁性能的影响，对Fe_3O_4纳米粒子进行了晶体结构、粒径、磁性能、铁含量等性能的表征。产物具有完美的晶体结构，粒径约16nm，比饱和磁化强度为55.4emu／g，磁化率为8.28×10~(-3)emu／Oe，磁响应性强，具有超顺磁性，剩磁和矫顽力均为零，粒径分布均匀，分散性良好。
2．本文采用油酸作为表面活性剂对Fe_3O_4纳米粒子进行了改性，实现了Fe_3O_4由亲水性向亲油性的转变，并利用TAM air等温微量热检测仪研究了在不同温度下，油酸与Fe_3O_4吸附过程中的热量变化情况，讨论这个过程中热量的变化，分析了两者之间的吸附机理。
3．本文采用了一种难溶助剂，用改进了的微悬浮聚合法制备出了聚苯乙烯磁性高分子微球，对产物进行了结构、粒径、磁性能的表征，分析了反应机理，并探讨了难溶助剂、分散剂、表面活性剂、引发剂用量、搅拌速度等因素对磁性高分子微球性能的影响。产物粒径约15μm，表面光滑，分散性好，磁含量可达到6.44％，比饱和磁化强度为3.928emu／g，磁化率分别为3.249×10~(-6)emu／Oe，剩磁和矫顽力均为零，具有超顺磁性。
4．本文采用免疫学方法，在聚苯乙烯磁性微球表面包覆了抗体，并与
武汉理一1几大学硕十学位论文
特定的抗原发生特异性反应，利用TAM air等温微量热检测仪测量了微球与
抗体吸附过程及与抗原发生特异性反应过程中的热量变化，探讨了微球与抗
体之间的吸附机理和与抗原之间的特异性反应，为更为深入地研究磁性微球
在生物方面的应用奠定基础。
Magnetic Polymer Microspheres (MPM) are a kind of novel functional materials, which behave properties of magnetic materials and polymer materials. MPM are quite fit for application in biological system because of their small particle size, large specific surface area, great capacity of coupling biology molecules, and good suspension in disperse system. Heretofore, MPM have exhibited extensive application prospect. In this paper, PS-MPM was prepared with monodispersity and strong magnetic responsivity on the base of others' research. The main content of this paper is such as following:
1. Fe3O4 nano-particles, which can be dispersed in nano scale, were prepared by means of chemical co-precipitation method. Such influencing factors as the type of precipitant, the feeding mode, the surfactants, the reaction temperature, the curing temperature were surveyed. Some properties such as crystal structure, particle size, magnetic properties and iron content were characterized. The particle size of the product is about 16 nm with perfect crystal structure. The product exhibits superparamagnetism and strong magnetic responsivity, the saturation magnetization being 55.4emu/g and the magnetic susceptibility being 8.28 10-3emu/Oe.The particle size distribution is homogeneous with good dispersion.
2. The Fe3O4 nano-particles were converted from hydrophilic to oleophylic by being modified by oleic acid. The heat change in the adsorption process of Fe3O4 nano-particles to oleic acid was measured and discussed by using microcalorimetry. The adsorption mechanism was analyzed.
3. PS-MPM was prepared by improved microsuspension polymerization. Product structure, particle size and magnetic properties, were characterized and the reaction mechanism was analyzed. Such influencing factors as the indissoluble assistant, the dispersant agent, the surfactants, the amount of initiator and the stirring speed were surveyed. The product 'particle size is about
15 m, with smooth surface and good dispersion. The product exhibits superparamagnetism, the saturation magnetization being 3.928 emu/g and the magnetic susceptibility being 3.249 10-3 emu/Oe. The particle size distribution is homogeneous with good dispersion. The magnetic content was 6.44%.
4. Antibody, which was coated to PS-MPM by using immunology method, reacted to special corresponding antigen. The heat change in the adsorption process of antibody to MPM and the reaction process to antigen were measured by using microcalorimetry. The adsorption mechanism and the special reaction were analyzed, which established the primary base of profound study on the aspect of biology application for MPM.
1．采用化学共沉淀法制备出了可达到纳米级分散的Fe_3O_4纳米粒子。深入探讨了沉淀剂的种类、加入方式、表面活性剂、反应温度、熟化温度等各种因素对产物的粒径及磁性能的影响，对Fe_3O_4纳米粒子进行了晶体结构、粒径、磁性能、铁含量等性能的表征。产物具有完美的晶体结构，粒径约16nm，比饱和磁化强度为55.4emu／g，磁化率为8.28×10~(-3)emu／Oe，磁响应性强，具有超顺磁性，剩磁和矫顽力均为零，粒径分布均匀，分散性良好。
2．本文采用油酸作为表面活性剂对Fe_3O_4纳米粒子进行了改性，实现了Fe_3O_4由亲水性向亲油性的转变，并利用TAM air等温微量热检测仪研究了在不同温度下，油酸与Fe_3O_4吸附过程中的热量变化情况，讨论这个过程中热量的变化，分析了两者之间的吸附机理。
3．本文采用了一种难溶助剂，用改进了的微悬浮聚合法制备出了聚苯乙烯磁性高分子微球，对产物进行了结构、粒径、磁性能的表征，分析了反应机理，并探讨了难溶助剂、分散剂、表面活性剂、引发剂用量、搅拌速度等因素对磁性高分子微球性能的影响。产物粒径约15μm，表面光滑，分散性好，磁含量可达到6.44％，比饱和磁化强度为3.928emu／g，磁化率分别为3.249×10~(-6)emu／Oe，剩磁和矫顽力均为零，具有超顺磁性。
4．本文采用免疫学方法，在聚苯乙烯磁性微球表面包覆了抗体，并与
武汉理一1几大学硕十学位论文
特定的抗原发生特异性反应，利用TAM air等温微量热检测仪测量了微球与
抗体吸附过程及与抗原发生特异性反应过程中的热量变化，探讨了微球与抗
体之间的吸附机理和与抗原之间的特异性反应，为更为深入地研究磁性微球
在生物方面的应用奠定基础。
Magnetic Polymer Microspheres (MPM) are a kind of novel functional materials, which behave properties of magnetic materials and polymer materials. MPM are quite fit for application in biological system because of their small particle size, large specific surface area, great capacity of coupling biology molecules, and good suspension in disperse system. Heretofore, MPM have exhibited extensive application prospect. In this paper, PS-MPM was prepared with monodispersity and strong magnetic responsivity on the base of others' research. The main content of this paper is such as following:
1. Fe3O4 nano-particles, which can be dispersed in nano scale, were prepared by means of chemical co-precipitation method. Such influencing factors as the type of precipitant, the feeding mode, the surfactants, the reaction temperature, the curing temperature were surveyed. Some properties such as crystal structure, particle size, magnetic properties and iron content were characterized. The particle size of the product is about 16 nm with perfect crystal structure. The product exhibits superparamagnetism and strong magnetic responsivity, the saturation magnetization being 55.4emu/g and the magnetic susceptibility being 8.28 10-3emu/Oe.The particle size distribution is homogeneous with good dispersion.
2. The Fe3O4 nano-particles were converted from hydrophilic to oleophylic by being modified by oleic acid. The heat change in the adsorption process of Fe3O4 nano-particles to oleic acid was measured and discussed by using microcalorimetry. The adsorption mechanism was analyzed.
3. PS-MPM was prepared by improved microsuspension polymerization. Product structure, particle size and magnetic properties, were characterized and the reaction mechanism was analyzed. Such influencing factors as the indissoluble assistant, the dispersant agent, the surfactants, the amount of initiator and the stirring speed were surveyed. The product 'particle size is about
15 m, with smooth surface and good dispersion. The product exhibits superparamagnetism, the saturation magnetization being 3.928 emu/g and the magnetic susceptibility being 3.249 10-3 emu/Oe. The particle size distribution is homogeneous with good dispersion. The magnetic content was 6.44%.
4. Antibody, which was coated to PS-MPM by using immunology method, reacted to special corresponding antigen. The heat change in the adsorption process of antibody to MPM and the reaction process to antigen were measured by using microcalorimetry. The adsorption mechanism and the special reaction were analyzed, which established the primary base of profound study on the aspect of biology application for MPM.
引文
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[3] 李学忠．国外纳米材料制备及应用领域评述．《首届纳米技术应用研讨会论文集》．厦门：中国电子学会，1997．1～6
[4] 吴颉，王君，景小燕等．磁性高分子微球的制备及应用．化工新型材料，2002．30(8)：23～26
[5] 谢钢，张秋禹，李铁虎．磁性高分子微球．高分子通报，2001．12：38-43
[6] 丁小斌，孙宗华，万国祥．磁性高分子微球的制备和应用研究进展．化学通报，1997．1：1-5
[7] P Friedl, PB Noble, KS Zanker. T lymphocyte locomotion in a three-dimensional collagen matrix. Expression and function of cell adhesion molecules. Journal of Immunology, 1995.154:4973～4985
[8] Poynton C H. Biological magnetic colloids.USP 4,920,061,1990-04-24
[9] Josephson. Magnetic particles for use in separations.USP 4,672,040.1987-06-09
[10] Bjerke T, Nagashima K,Anzai C, Ontogeny of human mannan-binding protein.Colloid polym. 1994.272:1104～1109
[11] Ugelstad J. Isolation of pure functionally active CD~(8+) T cells positive selection with monoclonal antibodies directly conjugated to monosized magnetic microspheres.J.Immunol.Meth., 1993.157:49～57
[12] Testa J E. Reversal of misfortune: TIMP-2 inhibits tumor cell invasion.J Nat Cancer Inst,1991.83:740～742
[13] IC Anderson, EJ Shpall, DS Leslie,etc. Elimination of malignant clonogenic breast cancer cells from human bone marrow.Cancer Rea, 1989.49:4659～4664
[14] Rusetski A N,Ruuge E K. Magnetic fluid as a possible drug cartier for thrombosis treatment. J of Magn and Magn Mater,1990.85 (4):299～302
[15] Munko P A,Dunill P, Lilly M D. A mechanical pretreatment of waste-activated sludge for HS decrease on anaerobic digestion. Biotech Bioen,1997.19 (2):101～104
[16] Yoshimoto T. Angiotensin Converting Enzyme Inhibitor But Not Calcium Blocker Down-Regulates Gene Expression of Vascular Natriuretic Peptide Receptor in Hypertensive Rats.Biochem.Biophy Res Comm, 1994.205(12): 1595～1600
[17] Skjerve E,Olsvik O, Immunomagnetic separation of Salmonella from food, Int J
Food Microbiol,1991.14:11～17
[18] Bruno J.G., Yu H., Immunomagneti-ECL detection of Bacillus anthracis spores in soil matrices, Appl.Environ.Microbiol. 1996.62(9):3474～3480
[19] Yu H, Use of an immunomagnetic separation-fluorescent immunoassay (IMS-FIA) for rapid and high throughput analysis of environmental water samples.Anal.Chem.Acta, 1998.376:77～81
[20] Hallier-Soulier, Sylvie; Guillot, Emmanuelle. An immunomagneic separation polymerase chain reation assay for rapid and ultra-sensitive detection of Cryptonsporidium parvum in drinking water, FEMS Microbiology Letters,1999.176(2):285～289
[21] 彭洪修，朱以华，郑志凤等．磁性高分子微球的研究进展．材料导报，2001．15(5)：46-48
[22] 王延梅，封耀先．磁性高分子微球的研究进展．高分子材料科学与工程，1998．5：6-8
[23] 任广志，李振华，何炳林．磁性高分子微球用于固定化酶的研究进展．离子交换与吸附，2000．16(1)：83-87
[24] 刘颖，王建华，高伟．平均粒径大小及磁性能不同的Fe_3O_4超细微粒的制取．功能材料，1993．24(1)：20-25
[25] 丁明，曾恒兴．中和沉淀法Fe_3O_4的生成研究．无机材料学报，1998，13(4)：619-621
[26] 李学慧，吴业，刘宗明．磁流体的研制．化学世界，1998．1：15-16
[27] 张茂润．工艺参数的控制对液体磁性材料—铁磁流体性能的影响．功能材料，1996．27(4)：328-330
[28] 康鸿业，王允军，施展等．影响Fe_3O_4超微粒子性能因素的研究．高等学校化学学报．1991．12(5)：684-685
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