悬浮聚合大粒径磁性高分子微球的制备及其表征
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摘要
磁性高分子微球是指由无机纳米磁性粒子与有机高分子材料结合而生成的一种复合微球,其兼具磁响应性和高分子微球的表面功能性,在生物分离工程和生物医学工程应用中已经展现出独特的优势,成为当今研究的热门课题之一。
在本文中我们详细探讨了悬浮聚合法制备大粒径磁性微球的工艺条件,研究了各种反应条件(如:悬浮分散剂的种类和用量、单体种类、单体/水比、搅拌强度、聚合温度、聚合时间等)对微球产生的影响。利用光学显微镜观察微球形貌,并进行粒径分析;通过磁铁,振动磁强计对不同反应条件下微球的磁性进行对比研究;通过红外测谱仪分析了微球的表面基团;并利用接触角分析仪对微球的表面亲水――疏水性进行了详细的研究;通过偶联山羊抗人IgG-FITC的实验分析了微球的生物相容性。
本试验中我们通过一步悬浮聚合法制备的大粒径磁性微球,显微镜下呈现出光滑规整的球形,无团聚,具有很好的单分散性和相对较窄的粒径分布;并具有超顺磁性和良好的耐腐蚀性;表面带有丰富的官能团,偶联抗体实验表明我们制备的磁性微球具有很好的生物相容性。
Magnetic microspheres are compound formed by combining inorganic magnetic nanoparticles with organic polymer, which have concurrently magnetic response and surface functionality. Magnetic microspheres have been one of the hot researches because of the unique advantages in the fields of bioseparation, biomedical engineering and so on.
In the job, we discussed the technique conditions of the preparation big-size magnetic microspheres by suspension polymerization, and investigated the influence factors to microspheres properties, such as dispersant’category and dosage, monomers’category, the volume ratio of monomer/water, stirring intensity, polymerization temperature and so on. We obtained the microspheres’morphology by the optical micrographs and analyzed the particle size; and did some compared study by VSM, FTIR and so on.
In the present work, we synthesized magnetic microspheres by one-step suspension polymerization. The resulting magnetic microspheres have good morphology and properties with uniform and spherical form, narrow size dispersion and superparamagnetism. And the products’surface has abundance functional groups. The paper also reports the magnetic microspheres can be linked well with the IgG-FITC, which indicates its potential application in the fields of biomedical diagnostics, biotechnology and bioengineering.
在本文中我们详细探讨了悬浮聚合法制备大粒径磁性微球的工艺条件,研究了各种反应条件(如:悬浮分散剂的种类和用量、单体种类、单体/水比、搅拌强度、聚合温度、聚合时间等)对微球产生的影响。利用光学显微镜观察微球形貌,并进行粒径分析;通过磁铁,振动磁强计对不同反应条件下微球的磁性进行对比研究;通过红外测谱仪分析了微球的表面基团;并利用接触角分析仪对微球的表面亲水――疏水性进行了详细的研究;通过偶联山羊抗人IgG-FITC的实验分析了微球的生物相容性。
本试验中我们通过一步悬浮聚合法制备的大粒径磁性微球,显微镜下呈现出光滑规整的球形,无团聚,具有很好的单分散性和相对较窄的粒径分布;并具有超顺磁性和良好的耐腐蚀性;表面带有丰富的官能团,偶联抗体实验表明我们制备的磁性微球具有很好的生物相容性。
Magnetic microspheres are compound formed by combining inorganic magnetic nanoparticles with organic polymer, which have concurrently magnetic response and surface functionality. Magnetic microspheres have been one of the hot researches because of the unique advantages in the fields of bioseparation, biomedical engineering and so on.
In the job, we discussed the technique conditions of the preparation big-size magnetic microspheres by suspension polymerization, and investigated the influence factors to microspheres properties, such as dispersant’category and dosage, monomers’category, the volume ratio of monomer/water, stirring intensity, polymerization temperature and so on. We obtained the microspheres’morphology by the optical micrographs and analyzed the particle size; and did some compared study by VSM, FTIR and so on.
In the present work, we synthesized magnetic microspheres by one-step suspension polymerization. The resulting magnetic microspheres have good morphology and properties with uniform and spherical form, narrow size dispersion and superparamagnetism. And the products’surface has abundance functional groups. The paper also reports the magnetic microspheres can be linked well with the IgG-FITC, which indicates its potential application in the fields of biomedical diagnostics, biotechnology and bioengineering.
引文
[1] Kronick P, Gilpin RW. International Symposium on Magnetic Carriers-Biological and Clinical Applications. J Biochem Biophy Meth 1986,12,73
[2] Abudiab T, Beitle RR. Preparation and characterization of Magnetic Targeted Drag Controlled-Release. J Chromatogr A 1998, 795, 211
[3] Josephson L. Magnetic Particles for Use in Separations. U.S. Patent No. 4 672 040; 1987
[4] Yue Chang, Zhixing Su. Preparation and characterization of thermosensitive magnetic particles [J] Materials Science and Engineering, A: 2002, (333):155-159
[5] Xiaoqiao Liu, Yueping Guan, Yu Yang, Zhiya Ma, Xiaobing Wu, Huizhou Liu, Preparation of Superparamagnetic Immunomicrospheres and Application for Antibody Purification, [J] Journal of Applied Polymer Science, 2004, (94):2205-2211
[6]毕爱华.医学免疫学.同济医科大学.1986:277-282
[7] Cupta PK, Hung CT. Life Sci 1989.44: 175
[8]魏衍超,杨连生.生物高分子磁性微球的制备结构性质和应用.磁性材料及器件.1999,12(30).6:18-21
[9] Cordula Grütter, Sandra Rudershansen, Joachim Teller. Improved properties of magnetic particles by combination of different polymer materials as particle matrix [J] Journal of Magnetism and Magnetic Meterials, 2001, (225):1-7
[10] Xiaoqiao Liu, Yueping Guan, Rui Shen, Huizhou Liu, Immobilization of lipase onto micron-size magnetic beads, [J] Journal of Chromatography B, 2005, (822):91-97
[11] Guang-Ming Qiu, Bao-Ku Zhu, You-Yi Xu, a-Amylase Immobilized by Fe3O4/Poly(styrene-co-maleic anhydride) Magnetic Composite Microspheres: Preparation and Characterization, [J] Journal of Applied Polymer Science, 2005 (95):328-335
[12] Xiaoqiao Liu, Yueping Guan, Huizhou Liu, Zhiya Ma, Yu Yang, Xiaobing Wu,Preparation and characterization of magnetic polymer nanospheres with high protein binding capacity, [J] Journal of Magnetism and Magnetic Materials, 2005 (293):111-118
[13] Chengli Yang, Huizhou Liu, Yueping Guan, Preparation of magnetic poly(methylmethacrylate-divinylbenzene-glycidylmethacrylate) microspheres by spraying suspension polymerization and their use for protein adsorption, [J] Journal of Magnetism and Magnetic Materials, 2005 (293):187-192
[14] Chengli Yang, Yueping Guan, Jianmin Xing, Preparation of Magnetic Polystyrene Microspheres with a Narrow Size Distribution, American Institute of Chemical Engineers, July 2005 Vol.51,No.7
[15]饶微.博士毕业论文.武汉理工大学.2001.3
[16]张爱平,张训,侯凡凡,王力,周展眉.应用原位杂交和原位聚合酶链反应技术检测肾组织中乙型肝炎病毒DNA中华儿科杂志.1996. 3
[17]赵原璧,邱俊明,王晓莹,邱祖民.抗肿瘤磁性靶向药物的研究进展江西科学.2006.5
[18]任杰,王佐,滕新,荣张鹏.磁性药物微球制备的研究进展材料导报.2006.4
[19]辛胜昌,李忠彦,吴新荣.磁性靶向药物的研究进展医药导报.2006.7
[20]单薇,廖明义,李杨,徐宏德.采用负离子原位聚合法制备聚丁二烯/二氧化硅纳米复合材料合成橡胶工业.2006.6
[21]孟征,欧育湘,刘进全,赵毅.蜜胺甲醛树脂原位聚合法包覆六硝基六氮杂异伍兹烷含能材料.2006.5
[22]王庆生,刘汉勋.用原位聚合法制备球形多孔高聚物玻璃毛细管柱及其保留行为的考察.分析化学.1993.1
[23]罗钟瑜,修玉英,万小龙.原位聚合制备高苯乙烯含量的聚合物多元醇.聚氨酯工业.1994.3
[24]张权,施用晞,李洋,黎渝.环氧树脂包埋切片研究聚合物结构的局限性中国塑料.1994.1
[25]王建龙,周定.冷冻聚丙烯酰胺法固定化黑曲霉生产柠檬酸的研究食品与发酵工业.1995.1
[26] V. Macho, M. Fabíni, M. Rusina, S. Bobula and M. Harustiak.Polymer 1994, 35, 5773
[27] D. Blondeau, M. Bigan and P. Despres. React Funct Polym 1995.27:163
[28] Jesús Alvarez, JoséAlvarez, Martín Hernández. Chem Eng Sci 1994.49:99
[29] Hora′k D. J Polym Sci Part A: Polym Chem 2001.39:3707
[30]顾尧,李春生,刘长欣.分散聚合法制备单分散聚甲基丙烯酸甲酯微球[J].山东师大学报(自然科学版). 1999,14 (4):470-473
[31] DANIEL HORAKMNATALIYA BENEDYK, Magnetic Poly(Glycidyl Methacrylate) Microspheres Prepared by Dispersion Polymerization in the Presence of Electrostatically Stabilized Ferrofluids, Journal of Polymer Science :Part A:Polymer Chemistry, 2004 (42):5827-5837
[32] MA Zhiya, GUAN Yueping, LIU Xiaoqiao, LIU Huizhou, Preparation and characterization of Non-porous Superparamagnetic Microspheres with Epoxy Groups by Dispersion Polymerization, Chinese J. Chem. Eng., 2005 (2):239-243
[33]谭海生,李克友,万涛.活性聚硅氧烷乳液聚合的研究.弹性体.1997.1
[34] Kondo,A.,Kamura,H.,Higashitahi,K.etc,“Preparation of magnetic latex particles by emulsion polymerization of styrene”Appl.Microbiol.Biotechnol.,1994, (41):99-105
[35]李建宗,张洪涛.微乳液的制备及稳定性.湖北大学学报.1996.3(18).1: 53-56
[36]勾华,张朝平.微乳液和反相微乳液法在合成和制备纳米铁系化合物上的应用.贵州大学学报.2001
[37] Z.L.Liu, X.B.Yang, K.l.Yao, J Magn Magn Mater 2006, 302, 529
[38] Z.L.Liu, Z.H.Ding, K.l.Yao, J Magn Magn Mater 2003, 265, 98
[39] Z.L.Liu, Y.J.Liu, K.L.Yao, J Mater Synth Proces 2002, 10, 83
[40] Z.L.Liu, X.Wang, J Mater Sci 2004, 39, 2633
[41] Z.L.Liu, H.B.Wang, Q.H.Lu., J Magn Magn Mater 2004, 283, 258
[42]潘祖仁.悬浮聚合.北京:化学工业出版社,1997:1-9
[43] (美)奥迪安(Odian,G).聚合反应原理.北京:科学出版社, 1987
[44]潘祖仁.悬浮聚合.北京:化学工业出版社, 1997:139-145
[45]潘祖仁.高分子化学.北京:化学工业出版社, 1996:107
[46]潘祖仁.悬浮聚合.北京:化学工业出版社, 1997:166-171
[47]潘祖仁.悬浮聚合.北京:化学工业出版社, 1997 :164-166
[48]都有为,徐明祥,吴坚.镍超微颗粒的磁性.物理学报.1992,41(1):149-154
[49] Lin C H, shin Z W, Wang M L,Yu Y C. Hydrothermal processing to produce magnetic particulates. IEEE Trans. Magn. 1990, 26(1):15-17
[50] F. E. Spada, E. J. McNiff Jr. , S. Foner, Anomalous properties of magnetic nanoparticles, J. Magn. Magn. Mater. 1999, (196):591-594
[51] Y. Jin, C. L. Dennis, S. A. Majetich, Nanoscale characterization of magnetic nanoparticles, NanoStructured Materials, 1999, (12):763-768
[52]高家武.高分子材料近代测试技术.北京:北京航空航天大学出版社, 1994:172
[53]毕爱华.医学免疫学.同济医科大学.1986:258-277
[2] Abudiab T, Beitle RR. Preparation and characterization of Magnetic Targeted Drag Controlled-Release. J Chromatogr A 1998, 795, 211
[3] Josephson L. Magnetic Particles for Use in Separations. U.S. Patent No. 4 672 040; 1987
[4] Yue Chang, Zhixing Su. Preparation and characterization of thermosensitive magnetic particles [J] Materials Science and Engineering, A: 2002, (333):155-159
[5] Xiaoqiao Liu, Yueping Guan, Yu Yang, Zhiya Ma, Xiaobing Wu, Huizhou Liu, Preparation of Superparamagnetic Immunomicrospheres and Application for Antibody Purification, [J] Journal of Applied Polymer Science, 2004, (94):2205-2211
[6]毕爱华.医学免疫学.同济医科大学.1986:277-282
[7] Cupta PK, Hung CT. Life Sci 1989.44: 175
[8]魏衍超,杨连生.生物高分子磁性微球的制备结构性质和应用.磁性材料及器件.1999,12(30).6:18-21
[9] Cordula Grütter, Sandra Rudershansen, Joachim Teller. Improved properties of magnetic particles by combination of different polymer materials as particle matrix [J] Journal of Magnetism and Magnetic Meterials, 2001, (225):1-7
[10] Xiaoqiao Liu, Yueping Guan, Rui Shen, Huizhou Liu, Immobilization of lipase onto micron-size magnetic beads, [J] Journal of Chromatography B, 2005, (822):91-97
[11] Guang-Ming Qiu, Bao-Ku Zhu, You-Yi Xu, a-Amylase Immobilized by Fe3O4/Poly(styrene-co-maleic anhydride) Magnetic Composite Microspheres: Preparation and Characterization, [J] Journal of Applied Polymer Science, 2005 (95):328-335
[12] Xiaoqiao Liu, Yueping Guan, Huizhou Liu, Zhiya Ma, Yu Yang, Xiaobing Wu,Preparation and characterization of magnetic polymer nanospheres with high protein binding capacity, [J] Journal of Magnetism and Magnetic Materials, 2005 (293):111-118
[13] Chengli Yang, Huizhou Liu, Yueping Guan, Preparation of magnetic poly(methylmethacrylate-divinylbenzene-glycidylmethacrylate) microspheres by spraying suspension polymerization and their use for protein adsorption, [J] Journal of Magnetism and Magnetic Materials, 2005 (293):187-192
[14] Chengli Yang, Yueping Guan, Jianmin Xing, Preparation of Magnetic Polystyrene Microspheres with a Narrow Size Distribution, American Institute of Chemical Engineers, July 2005 Vol.51,No.7
[15]饶微.博士毕业论文.武汉理工大学.2001.3
[16]张爱平,张训,侯凡凡,王力,周展眉.应用原位杂交和原位聚合酶链反应技术检测肾组织中乙型肝炎病毒DNA中华儿科杂志.1996. 3
[17]赵原璧,邱俊明,王晓莹,邱祖民.抗肿瘤磁性靶向药物的研究进展江西科学.2006.5
[18]任杰,王佐,滕新,荣张鹏.磁性药物微球制备的研究进展材料导报.2006.4
[19]辛胜昌,李忠彦,吴新荣.磁性靶向药物的研究进展医药导报.2006.7
[20]单薇,廖明义,李杨,徐宏德.采用负离子原位聚合法制备聚丁二烯/二氧化硅纳米复合材料合成橡胶工业.2006.6
[21]孟征,欧育湘,刘进全,赵毅.蜜胺甲醛树脂原位聚合法包覆六硝基六氮杂异伍兹烷含能材料.2006.5
[22]王庆生,刘汉勋.用原位聚合法制备球形多孔高聚物玻璃毛细管柱及其保留行为的考察.分析化学.1993.1
[23]罗钟瑜,修玉英,万小龙.原位聚合制备高苯乙烯含量的聚合物多元醇.聚氨酯工业.1994.3
[24]张权,施用晞,李洋,黎渝.环氧树脂包埋切片研究聚合物结构的局限性中国塑料.1994.1
[25]王建龙,周定.冷冻聚丙烯酰胺法固定化黑曲霉生产柠檬酸的研究食品与发酵工业.1995.1
[26] V. Macho, M. Fabíni, M. Rusina, S. Bobula and M. Harustiak.Polymer 1994, 35, 5773
[27] D. Blondeau, M. Bigan and P. Despres. React Funct Polym 1995.27:163
[28] Jesús Alvarez, JoséAlvarez, Martín Hernández. Chem Eng Sci 1994.49:99
[29] Hora′k D. J Polym Sci Part A: Polym Chem 2001.39:3707
[30]顾尧,李春生,刘长欣.分散聚合法制备单分散聚甲基丙烯酸甲酯微球[J].山东师大学报(自然科学版). 1999,14 (4):470-473
[31] DANIEL HORAKMNATALIYA BENEDYK, Magnetic Poly(Glycidyl Methacrylate) Microspheres Prepared by Dispersion Polymerization in the Presence of Electrostatically Stabilized Ferrofluids, Journal of Polymer Science :Part A:Polymer Chemistry, 2004 (42):5827-5837
[32] MA Zhiya, GUAN Yueping, LIU Xiaoqiao, LIU Huizhou, Preparation and characterization of Non-porous Superparamagnetic Microspheres with Epoxy Groups by Dispersion Polymerization, Chinese J. Chem. Eng., 2005 (2):239-243
[33]谭海生,李克友,万涛.活性聚硅氧烷乳液聚合的研究.弹性体.1997.1
[34] Kondo,A.,Kamura,H.,Higashitahi,K.etc,“Preparation of magnetic latex particles by emulsion polymerization of styrene”Appl.Microbiol.Biotechnol.,1994, (41):99-105
[35]李建宗,张洪涛.微乳液的制备及稳定性.湖北大学学报.1996.3(18).1: 53-56
[36]勾华,张朝平.微乳液和反相微乳液法在合成和制备纳米铁系化合物上的应用.贵州大学学报.2001
[37] Z.L.Liu, X.B.Yang, K.l.Yao, J Magn Magn Mater 2006, 302, 529
[38] Z.L.Liu, Z.H.Ding, K.l.Yao, J Magn Magn Mater 2003, 265, 98
[39] Z.L.Liu, Y.J.Liu, K.L.Yao, J Mater Synth Proces 2002, 10, 83
[40] Z.L.Liu, X.Wang, J Mater Sci 2004, 39, 2633
[41] Z.L.Liu, H.B.Wang, Q.H.Lu., J Magn Magn Mater 2004, 283, 258
[42]潘祖仁.悬浮聚合.北京:化学工业出版社,1997:1-9
[43] (美)奥迪安(Odian,G).聚合反应原理.北京:科学出版社, 1987
[44]潘祖仁.悬浮聚合.北京:化学工业出版社, 1997:139-145
[45]潘祖仁.高分子化学.北京:化学工业出版社, 1996:107
[46]潘祖仁.悬浮聚合.北京:化学工业出版社, 1997:166-171
[47]潘祖仁.悬浮聚合.北京:化学工业出版社, 1997 :164-166
[48]都有为,徐明祥,吴坚.镍超微颗粒的磁性.物理学报.1992,41(1):149-154
[49] Lin C H, shin Z W, Wang M L,Yu Y C. Hydrothermal processing to produce magnetic particulates. IEEE Trans. Magn. 1990, 26(1):15-17
[50] F. E. Spada, E. J. McNiff Jr. , S. Foner, Anomalous properties of magnetic nanoparticles, J. Magn. Magn. Mater. 1999, (196):591-594
[51] Y. Jin, C. L. Dennis, S. A. Majetich, Nanoscale characterization of magnetic nanoparticles, NanoStructured Materials, 1999, (12):763-768
[52]高家武.高分子材料近代测试技术.北京:北京航空航天大学出版社, 1994:172
[53]毕爱华.医学免疫学.同济医科大学.1986:258-277