PMMA-PAA交联磁性复合微球的制备及其性能研究
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摘要
本文通过滴加氨水控制Fe (II)与Fe (III)盐混合溶液的pH值,经共沉淀过程制得了Fe_3O_4磁性纳米颗粒。进而用一定量的油酸钠对Fe_3O_4纳米颗粒进行原位改性,得到了表面呈疏水性的磁纳米颗粒。用红外光谱(FTIR)、透射电子显微镜(TEM)、X射线衍射(XRD)等分别分析了亲油性Fe_3O_4纳米颗粒的结构、形态、粒径和粒径分布;用ZETA电位分析了反应介质的pH值对于亲油性Fe_3O_4纳米颗粒稳定性的影响。研究表明:油酸钠的用量对于Fe_3O_4纳米颗粒的性能、粒径和粒径分布有着重要的影响,在优化条件下,得到的Fe_3O_4纳米颗粒的平均直径为12.7nm。
在Fe_3O_4纳米颗粒和二乙烯苯(DVB)存在的条件下,以聚乙烯吡咯烷酮(PVP)为稳定剂,乙醇/水的混合体系为反应介质,由偶氮二异丁腈(AIBN)引发甲基丙烯酸甲酯(MMA)和丙烯酸(AA)进行分散共聚,制得了PMMA-PAA交联型磁性复合微球。用FTIR对复合微球的结构进行了定性表征;复合磁性微球的形态、尺寸和尺寸分布用TEM表征;用热重分析(TGA)表征了复合磁性聚合物微球的磁含量和热稳定性;用UV光谱测定了亲油性Fe_3O_4磁性纳米颗粒和磁性复合微球的耐酸性能。结果表明:磁性复合微球中的Fe_3O_4含量可控制在40–70 wt%之间,整体保存规整的球形;通过改变聚合反应条件可将复合微球的粒径控制在100 nm到2μm范围内。磁流体的表面性质,介质的极性,AIBN、DVB和PVP的用量等对磁性复合微球的尺寸和多分散性均有不同程度的影响。
通过三元分散共聚反应,制得表面带有-COOH的聚合物微球。用FTIR对聚合物微球的结构进行了表征;用扫描电子显微镜(SEM)、动态激光光散射(DLS)对聚合物微球的形态、粒径以及粒径分布进行了表征。研究发现当乙醇/水(V:V)为7:3,PVP用量占反应物总量的4.1wt%时形成的聚合物微球形态及分散性最佳。
氮气保护下,在溶解有聚合物微球的水溶液中,缓慢滴加Fe2+和Fe3+的盐溶液(摩尔比为1:2),将体系的pH调节至13,通过共沉淀形成Fe_3O_4纳米颗粒,形成表面沉积有Fe_3O_4纳米颗粒的磁性复合微球。用FTIR表征了复合磁性微球的结构;用TEM表征了磁性复合微球的形态;用热重分析(TGA)表征了磁性复合微球的磁含量和热稳定性。
Magnetic nanoparticles were synthesized by precipitation method through dropwise adding aqueous solution of ammonia to mixed solution of Fe (II) and Fe (III) salts. The surfaces of Fe_3O_4 nanoparticles were modified by using a certain amount of sodium oleate under in-situ processing, to obtain hydrophobic surface of Fe_3O_4 nanoparticles. The properties of the hydrophybic Fe_3O_4 nanoparticles, such as structures, morphologies, diameter and diameter distribution were characterized by Fourier transformation infrared (FTIR),transmission electron microscopy (TEM) and X-ray diffraction(XRD) separately. The effect of the reaction medium pH value to the hydrophybic Fe_3O_4 nanoparticles was ananysised by ZETA electric potential.
It showed that the amount of the sodium oleate has the important influence on the performance,particle size and size distribution of the Fe_3O_4 nanoparticles.
Crosslinked magnetic composite microspheres with poly(crylic acid)-co-poly(methyl methacrylate) (PAA-PMMA) as shell and Fe_3O_4 as core were obtained by dispersion copolymerization initiated with 2,2’-azobisisobutyronitrile (AIBN) in ethanol/water mixed solvent containing poly(vinylpyrrolidone) (PVP) as stabilizer in the presence of Fe_3O_4 nanoparticles and divinylbenzene (DVB). The organic functional groups of magnetic composite microspheres were characterized by FTIR. The morphologies,diameter and diameter distribution of the microspheres were characterized by Transmission Electron Microscopy. The magnetism content and the thermostability of the microspheres were characterized by thermogravimetric analysis (TGA). The acid resistance of hydrophybic Fe_3O_4 nanoparticles and magnetic composite microspheres were characterized by Ultra-violet (UV) spectroscopy. The crosslinked microspheres contained 40-70 wt % of Fe_3O_4 through TGA analysis. The average size of the microspheres can be controlled in the 100 nm to 2μm range by changing the polymerization conditions. It was found that the surface properties of Fe_3O_4 nanoparticles, ratio of ethanol to water, amount of AIBN, DVB and PVP can affect size and polydispersity of the composite microspheres.
Polymer microspheres with carboxyl group on the surface were prepared by dispersion copolymerization with three monomers. The structures of polymer microspheres were characterized by Fourier transform infrared (FTIR) .The morphologies, diameter and diameter distribution of the microspheres were characterized by Scanning Electron Microscopy (SEM) and Dynamic Laser Light Scattering (DLS).It was found that when the ratio of ethanol to water was 7:3, the concentration of stabilizer were kept at 4.1wt%, the morphologies and polydispersity of the obtained polymer microspheres were the best.
Under the protection of nitrogen, a certain amount of polymer microspheres was dispersed into the water. Then Fe2+ and Fe3+ salt solution (molar ratio was 1:2) was added to the dispersed liquid, control the speed of dropping while instilling the NH4OH. To form Fe_3O_4 nanoparticles which would load on the surface of the polymer microspheres by the method of co-precipitation, just adjust pH to 13.Thus the core-shell composite magnetic microspheres were formed. The structures of magnetic microspheres were characterized by FTIR. The morphologies of magnetic microspheres were characterized by Transmission Electron Microscopy (TEM). The stability of magnetic microspheres and magnetism content were characterized by thermogravimetric analysis (TGA).
在Fe_3O_4纳米颗粒和二乙烯苯(DVB)存在的条件下,以聚乙烯吡咯烷酮(PVP)为稳定剂,乙醇/水的混合体系为反应介质,由偶氮二异丁腈(AIBN)引发甲基丙烯酸甲酯(MMA)和丙烯酸(AA)进行分散共聚,制得了PMMA-PAA交联型磁性复合微球。用FTIR对复合微球的结构进行了定性表征;复合磁性微球的形态、尺寸和尺寸分布用TEM表征;用热重分析(TGA)表征了复合磁性聚合物微球的磁含量和热稳定性;用UV光谱测定了亲油性Fe_3O_4磁性纳米颗粒和磁性复合微球的耐酸性能。结果表明:磁性复合微球中的Fe_3O_4含量可控制在40–70 wt%之间,整体保存规整的球形;通过改变聚合反应条件可将复合微球的粒径控制在100 nm到2μm范围内。磁流体的表面性质,介质的极性,AIBN、DVB和PVP的用量等对磁性复合微球的尺寸和多分散性均有不同程度的影响。
通过三元分散共聚反应,制得表面带有-COOH的聚合物微球。用FTIR对聚合物微球的结构进行了表征;用扫描电子显微镜(SEM)、动态激光光散射(DLS)对聚合物微球的形态、粒径以及粒径分布进行了表征。研究发现当乙醇/水(V:V)为7:3,PVP用量占反应物总量的4.1wt%时形成的聚合物微球形态及分散性最佳。
氮气保护下,在溶解有聚合物微球的水溶液中,缓慢滴加Fe2+和Fe3+的盐溶液(摩尔比为1:2),将体系的pH调节至13,通过共沉淀形成Fe_3O_4纳米颗粒,形成表面沉积有Fe_3O_4纳米颗粒的磁性复合微球。用FTIR表征了复合磁性微球的结构;用TEM表征了磁性复合微球的形态;用热重分析(TGA)表征了磁性复合微球的磁含量和热稳定性。
Magnetic nanoparticles were synthesized by precipitation method through dropwise adding aqueous solution of ammonia to mixed solution of Fe (II) and Fe (III) salts. The surfaces of Fe_3O_4 nanoparticles were modified by using a certain amount of sodium oleate under in-situ processing, to obtain hydrophobic surface of Fe_3O_4 nanoparticles. The properties of the hydrophybic Fe_3O_4 nanoparticles, such as structures, morphologies, diameter and diameter distribution were characterized by Fourier transformation infrared (FTIR),transmission electron microscopy (TEM) and X-ray diffraction(XRD) separately. The effect of the reaction medium pH value to the hydrophybic Fe_3O_4 nanoparticles was ananysised by ZETA electric potential.
It showed that the amount of the sodium oleate has the important influence on the performance,particle size and size distribution of the Fe_3O_4 nanoparticles.
Crosslinked magnetic composite microspheres with poly(crylic acid)-co-poly(methyl methacrylate) (PAA-PMMA) as shell and Fe_3O_4 as core were obtained by dispersion copolymerization initiated with 2,2’-azobisisobutyronitrile (AIBN) in ethanol/water mixed solvent containing poly(vinylpyrrolidone) (PVP) as stabilizer in the presence of Fe_3O_4 nanoparticles and divinylbenzene (DVB). The organic functional groups of magnetic composite microspheres were characterized by FTIR. The morphologies,diameter and diameter distribution of the microspheres were characterized by Transmission Electron Microscopy. The magnetism content and the thermostability of the microspheres were characterized by thermogravimetric analysis (TGA). The acid resistance of hydrophybic Fe_3O_4 nanoparticles and magnetic composite microspheres were characterized by Ultra-violet (UV) spectroscopy. The crosslinked microspheres contained 40-70 wt % of Fe_3O_4 through TGA analysis. The average size of the microspheres can be controlled in the 100 nm to 2μm range by changing the polymerization conditions. It was found that the surface properties of Fe_3O_4 nanoparticles, ratio of ethanol to water, amount of AIBN, DVB and PVP can affect size and polydispersity of the composite microspheres.
Polymer microspheres with carboxyl group on the surface were prepared by dispersion copolymerization with three monomers. The structures of polymer microspheres were characterized by Fourier transform infrared (FTIR) .The morphologies, diameter and diameter distribution of the microspheres were characterized by Scanning Electron Microscopy (SEM) and Dynamic Laser Light Scattering (DLS).It was found that when the ratio of ethanol to water was 7:3, the concentration of stabilizer were kept at 4.1wt%, the morphologies and polydispersity of the obtained polymer microspheres were the best.
Under the protection of nitrogen, a certain amount of polymer microspheres was dispersed into the water. Then Fe2+ and Fe3+ salt solution (molar ratio was 1:2) was added to the dispersed liquid, control the speed of dropping while instilling the NH4OH. To form Fe_3O_4 nanoparticles which would load on the surface of the polymer microspheres by the method of co-precipitation, just adjust pH to 13.Thus the core-shell composite magnetic microspheres were formed. The structures of magnetic microspheres were characterized by FTIR. The morphologies of magnetic microspheres were characterized by Transmission Electron Microscopy (TEM). The stability of magnetic microspheres and magnetism content were characterized by thermogravimetric analysis (TGA).
引文
[1] WANG P H, PAN C Y.Polymer metal composite microspheres preparation and characterization of poly(St-co-AN)Ni microspheres[J]. Eur Polym J, 2000, 36(10):2297—2300.
[2] Nikitin L V, Stepanov G V, Mironova L S, et al. Properties of magnetoelastics synthesized in external magnetic field[J]. J of Magn and Magnetic Mater, 2003, (258-259):468—470.
[3]石可瑜,李朝兴,何炳林.磁导向阿霉素-羧甲基葡聚糖毫微粒的研究[J].生物医学工程学杂志, 2000, 17(1):21—24.
[4]任广智,李振华,何炳林.磁性壳聚糖微球用于脲激酶的固定化研究[J].离子交换与吸附,2000,16(4):304—310.
[5]钱建华,杨凯,范我等.用作磁共振造影增强剂的氧化铁溶液理化性质测定[J].核技术,2001,24(6):487—490.
[6] Rittich B, Spanova A, Ohlashennyy Y. Characterization of deoxyribonuclease I immobilized on magnetic hydrophilic polymer particles[J]. J of Chromatog B: Analy Tech in the Biomed and Life Sci, 2220,774(1):25—31.
[7] Papell S S. USP 3,215,572,1965.
[8] Neuringer J L,Rosensweig R E. Phys Fluids,1964,27:1927.
[9] Zaitsev V S, Filimonov D S,Presnyakov I A, et al. Physical and chemical properties of magnetite and magnetite-polymer nanoparticles and their colloidal dispersions[J].J of Colloid and Interface Sci,1999, 212:49-57.
[10] Shchukin D G, Sukhorukov G B.Synthesis of binary polyelectrolyte/inorganic composite capsules of micron size[J].Colloid Poym Sci, 2003,281:1201-1204.
[11]蒋新宇,周春山,张俊山等.导向药物用纳米Fe3O4磁性粒子的制备及表征[J].中南工业大学学报(自然科学版), 2003, 34(5):516—520
[12]解耸林,李宏涛,任泽胜.纳米磁粉制备工艺[J].长春工业大学学报(自然科学版),2005, 26(1):31—33
[13] Liu X Q, Xing J M, Guan Y P, et al. Colloids and Surfaces A: Physicochem Eng Aspects, 2004, 238(123):127
[14] Deng J G, Ding X B, Zhang W C, et al. Magnetic and conducting Fe3O4-cross-linked polyaniline nanoparticles with core-shell structure[J]. Polymer, 2002, 43(8):2179-2184.
[15]涂国荣,刘翔峰,杜光旭等.Fe3O4纳米材料的制备与性能测定[J]精细化工,2004,21(9):641—644
[16] Itoh H, Sugimoto T. Systematic control of size, shape, structure and magnetic properties of uniform magnetite and maghemite particles[J].J of Colloid and Interface Sci, 2003, 265(2):283-295.
[17] Thapa D, et al. Mater Lett, 2004, 58(21):2692
[18] Zhou Z H, et al. J Mater Chem, 2001, 11(6):1704
[19] Arturo M, López Q, JoséR.J Colloid Interf Sci,1993,158(2):446
[20] Si S, et al.Cryst Growth Des,2005,5(2), 391
[21]杨华,黄可龙,刘素琴.水热法制备的Fe3O4磁流体[J].磁性材料及器件,2003,34(2):4—6
[23] Rockenberger J, Scher E C,Alivisatos P A. J Am Chem Soc,1999,121:11595.
[24] Hyeon T, Lee S S, Park J, et al.J Am Chem Soc,2001,123:12798.
[25] Guo Q, Teng X, Rahman S, et al. J Am Chem Soc, 2003, 125:630.
[26] Murray C B, Sun S, Gaschler W, et al. IBMJ Res &Dev, 2004, 45:47.
[27] Sun S, Murray C B. J Appl Phys, 1999, 85:4325.
[28] Li Z, Chen H, Bao H, et al.Chem Mater,2004,16(8):1391.
[29] Lu Y, Yin Y. Nano Lett, 2002, 2(3):183
[30] Todaka Y S, Nakamura M, Hattori S, et al.[J]. Japan Institute of Metals, 2002, 66(1):34
[31] Tricot M, Danied J C.Process for the preparation of magnetic beads of vinylaromatic polymer. USP 4339337
[32] Danied J C, Schuppiser J L, Tricot M.Magnetic polymer latex and preparation process.USP 4358388
[33] Yanase N, Noguchi H, Asakura H. Preparation of magnetic latex particles by emulsion polymerization in the presence of a ferrofluid.Journal of Applied Polymer Science.1993,50:765
[34]邱广明,邱广亮.大粒径磁性高分子微球的制备[J].应用化学,1997,14(1):74—76
[35] Bahar T, Celebi S S.[J].J Appl Polym Sci,1999,72(1):69
[36] Josep Hson L.US Pat, 4672040.1987-06-09
[37]安小宁,苏致兴.高磁性壳聚糖微粒的制备与应用[J].兰州大学学报(自然科学版), 2001,37(2):100—104
[38] Menager C, Cabuil V. J Colloid Interf Sci, 1995, 169(1):251
[39] Harris L A, et al. Chem Mater, 2003, 15(6):1367
[40] Yen S P S, Rembaum A, Landel R F. US Pat, 4285819.1981-08-25
[41] Gupta P K, et al. Int J Pharm, 1988, 43(122):167
[42] Tricot M, Daniel J C.Process for the preparation of magnetic beads of vinylaromatic polymers.US Pat.4339337.1982-07-13
[43] Margel S, Beitler U.Polyacrolein type microspheres.US Pat.4783336.1988-11-03
[44] Tsuruta M.Manufacture of magnetic microspore.JP Pat.62204501.1987-09-27
[45]姜波,官月平,王靖等.聚乙二醇修饰的高分子磁性微球的合成及表征[J].过程工程学报, 2001,1(4):382—386
[46]王强斌,高峰,王胜林等.羧基磁性高分子微球的制备和表征[J].化学世界,2001,8:410—413
[47]何虹,杨梭.悬浮聚合法制备磁性微球的粒度分布特征[J].高效化学工程学报,2001,3(15):277
[48]王胜林,朱以华.微悬浮聚合法合成聚苯乙烯磁性微球[J].华东理工大学学报,2001,27(4):364—367
[49] Daniel J C, Schuppiser J L,Tricot M.Magnetic polymer latex and preparation process.US Pat,4358388.1982-11-09
[50] Charmot D, Vidil C. Magnetizable composite microspheres of hydrophobic crosslinked polymer.process for preparing then and their application in biology.US Pat,5356713,1994-10-18
[51]邓勇辉,王雷,样武利等.反相微乳液合成30~100nm磁性聚合物纳米微球[J].高等学校化学学报,2003,24(5):920—923
[52]丁明,孙虹.Fe3O4/壳聚糖核壳磁性微球的制备及特性[J].磁性材料及器件,2001,32(6):1—3
[53] Sole N, Hajna J. Colloidal size hydrophobic polymers particulate having discrete particles of an inorganic material dispersed therein[P]US Pat, 4421660.1983—12—20
[54]邱广明,杨春燕,孙宗华.单分散亚微米级磁性微球的合成[J].功能高分子学报,1996,9(4):565—571
[55]邱广明,杨春燕,孙宗华.磁性聚苯乙烯微球的合成和特性[J].高分子材料学与功能,1993,(2):38—43
[56]邓建国,贺传兰,龙新平等.磁性Fe3O4-聚吡咯纳米微球的合成与表征[J].高分子学报,2003,3:393—397
[57]邱广亮,李咏兰,邱广明等.肺靶向顺铂磁性白蛋白微球的制备及性质[J].中国医药工业杂志,2001,32(12):544—546
[58]高兰萍,邱广明.纳米级磁性复合微球的制备[J].内蒙古师大学报自然科学(汉文)版,1998,27(4):302—306
[59] Yanase N, Noguchi H, Asakura H, et al.Preparation of magnetic latex particles by emulsion polymerization of styrene the presence of ferrofluid.J Appl Polym Sci,1993,50:765
[60]景晓燕,王君,张密林等.磁性功能高分子微球的制备研究[J].应用科技,2000,27(1):16—17
[61] Dresco P A, Zaitsev V S, Gambio R J , et at . Langmuir, 1999, 15:1945.
[62]邓勇辉,王雷,样武利等.反相微乳液合成30~100nm磁性聚合物纳米微球[J].高等学校化学学报,2003,24(5):920—923
[63] Deng Y,Wang L,Yang W, et al.J Magn Magn Mater,2003,257(1):69.
[64] Gupta A K, Wells S, IEEE Transcations on Nanobioscience, 2004, 3(1):66.
[65] Wormuth KJ.Colloid Interface Sci,2001,241:366.
[66]邱广明,胡玲. Fe3O4/P(St-Al)磁性微球的制备和复合微相结构[J].电子显微学报,2000,19(4):463—464
[67]程彬,朱玉瑞,江万权等.无机-高分子磁性复合粒子的制备与表征[J].化学物理学报,2000,13(3):359—362
[68]谢钢,张和鹏.细乳液聚合法制备磁性复合微球及其表征[J].高分子学报,2003,5:626—630
[69]李孝红,孙宗华.磁性高分子微球的合成研究:带醛基磁性高分子微球的合成及表征[J].离子交换与吸附,1996,12(6):486—492
[70]李孝红,丁小斌,孙宗华.含羟基磁性高分子微球的合成及表征[J].功能高分子学报,1995,8(1):73—78
[71]丁小斌,孙宗华,万国祥等.热敏性高分子包裹的磁性微球的合成[J].高分子学报,1998,5:628—631
[72]丁小斌,孙宗华,万国祥等.热敏性高分子包裹的磁性微球的性质及表征[J].高分子学报,1999,6:674—679
[73]王艳君,刘江峰,姚兆玲等.磁性聚甲基丙烯酸甲酯微球的制备与研究[J].天津大学学报,2001,34(1):64—68
[74] Ugelstad J, et al. US Pat, 47742265.1988-09-27
[75] Winnik F M, et al. Langmuir, 1995,11(10):3660
[76]张兆斌,应圣康.原子转移自由基聚合及可控自由基聚合[J].高分子通报,1999,3:138—144.
[77] Hadjichristidis N, Pispas S, Floudas G.Block Copolymers: Synthetic Strategies, Physical Properties, and Applications. Chapter 3: Block Copolymers by Living Free Radical Popymerization [R].John Wiley &Sons, Inc., 2003, 47.
[78] Wang Y, Teng X.W, Wang J S, Yang H.[J].Nano letters.2003,3(6):789—793.
[79] Vetal C R, Zhang Z J.[J]. J, Am. Chem. Soc., 2002, 124:14312—14313.
[80] Rather B, Nuyken O. [J]. Macromol, Symp., 2002,177:25—41.
[81] Wieland P C, Raether B. [J]. Macromol. Rapid Commun., 2001,22:700—703.
[82] Matsuno R, Yamamoto K, Otsuka H, et al. [J]. Chem.Mater., 2003,15:3—5.
[83] Kato K, Radbruch A. Cytometry, 1993, 14(4):384
[84] Lauva M, Auzans E, Levickis V. J of Magn and Magn Mater, 1990, 85:295
[85]张梅,王补森,张玉格等.化学转化法制备磁性阳离子交换树脂的研究[J].离子交换与吸附, 1995, 11(4):302
[86] Young Kyun Kim, Kun J ai Lee. Nuclear Science and Technology, 2001, 38(9):785
[87]吴雪辉,郭祀远,李琳.磁性离子交换树脂连续化运行条件的研究[J].离子交换与吸附, 2001, 17(4):345—349
[88] Martin C, Cuellar J1 Indu & Eng Chem Res, 2004, 43(2):475
[89] Jürgen Oster, J eff rey Parker, et al. J Magnetism and Mater, 2001, 225:145
[90] Rusetski A N, Ruuge E K.Magnetic fluid as a possible drug carrier for thrombosis treatment[J].J of Magn and Magn Mater,1990,85:299—302
[91]任广智,李振华,何炳林.磁性高分子微球用于固定化酶的研究进展[J].离子交换与吸附,2000,16(1):83—87
[92] Munko P A, Dunill P, Lilly M D.Biotech Bioen, 1997, 19:101
[93] Yoshimoto T.Biochem.Biophy Res Comm, 1987, 145(2):908
[94] Sinan A, Yasemin. Food Chemistry, 2001, 74:281
[95] Anshits A G, Kondratenko E V, Catalysis Today, 2001, 64:59
[96]张密林,王君,景晓燕等.21世纪生物与化工学术研讨会论文集,云南,云南科技出版社, 2000. 1. 6
[97]吴雪辉,郭祀远,李琳等.磁性阴离子变换树脂的化学转化制备及其特性研究[J].广西大学学报(自然科学版) ,1999,24(2):163—166
[98]张梅,王补森,张玉格等.化学转化法制备磁性阳离子交换树脂的研究[J].离子交换与吸附, 1995, 11(4):302—308
[99]许乙凯.磁共振造影剂及临床应用[M].北京:人民卫生出版社,2003. 8251.
[100] Ming Y, Hu L L. Talanta, 2001, 55:479
[101] Yang M, Hu L L. Determination of trace hydrazine by differential pulse voltammetry using magnetic microspheres[J]. Talanta, 2001, 55(3):479—484.
[102] Günther A, Bilitewski U. Anal Chim Acta, 1995, 300:117
[103] SoléS, Doctoral Thesis. Autonomous University of Barcelona, 2000,2(3):123-126
[104] Yu H, Bruno J G. Appl Environ Microbiol, 1996,62(2):587
[105] Witherspoon L R, Shuler S E, Glbert S S. Clin Chem, 1985, 31:415
[106] SoléS, Alegret S, Cespedes F, et al. Anal Chem, 1998, 70:1462
[107] Mosbach K, Kriz D. Ansell R J. PCT. WO97/22366, 1997
[108] Sun Y, Wang B, Hui C, et al.[J].J Macromol Sci Phys,2006,45,653.
[109] Ma Z Y, Guan Y P, Liu H Z. Affinity adsorption of albumin on Cibacron Blue F3GA-coupled non-porous micrometer-sized magnetic polymer microspheres[J]. React Funct Polym, 2006, 66:618.
[110] Ugelstad J, Berge A, Ellingsen T, et al. Preparation and application of new monosized polymer particles[J]. Prog Polym Sci, 1992, 17(1): 87—90.
[111] Ugelstad J, Stenstad P, Kilaas L, et al. Berge A and Hornes E [J]. Blood Purif,1993 11(6): 349—69.
[112] Lea T, Vartdal F, Nustad K, et al. Monosized, magnetic polymer particles: Their use in separation of cells and subcellular components, and in the study of lymphocyte function in vitro [J]. Journal of Molecular Recognition, 1988, 1(1): 9—18.
[113] Bahar T, Celibi S S. Immobilization of glucoamylase on magnetic poly(styrene) particles[J]. J Appl Polym Sci, 1999, 72: 69.
[114] Uhlen M. Magnetic separation of DNA[J]. Nature, 1989, 34: 733.
[115] Levison P R, Badger S E, Dennis J, et al. Recent developments of magnetic beads for use in nucleic acid purification[J]. Journal of Chromatography A, 1998, 81:107.
[116]张和鹏,张秋禹,王巍等.可控制自由基聚合DPE法制备P(AA-MMA-ST)/Fe3O4磁性复合微球[J].化学学报,2006,64,(17):1831—1836
[117] Horák D, Shapoval P. J Polym Sci Part A: Polym Chem, 2000, 38, 3855.
[118]王丽娟,刘峥.磁性高分子微球的制备及在分析化学中的应用发展[J].材料导报,2006,20,(6)36—40
[119]毕如意,钟国伦,孙建中.功能化高分子磁性微球制备技术研究进展[J].科学通报,2008,24(2):246—251.
[120]景晓燕,王君,李茹民等.磁性功能高分子微球的制备研究.[J].应用科技,2000, 27(1):16—17
[121] Doina B, Vekas L, Rasa R. Preparation and magnetic properties of concentrated magnetic fluids on alcohol and water carrier liquids[J]. Magn Magn Mater, 2002, 252:10
[122] Hong-ting Pu, Feng-jing Jiang, Zheng-long Yang.Preparation and properties of soft magnetic particles based on Fe3O4 and hollow polystyrene microsphere composite[J].Materials Chemistry and Physics, 2006, (100):10—14
[123] Ahmetli G, Tarlan E. Fe (II/III) adsorption onto styrene/dicinyl benzene based polymers[J].published online 27 February 2007 in wiley InterScience(www.interscience.wiley.com)
[2] Nikitin L V, Stepanov G V, Mironova L S, et al. Properties of magnetoelastics synthesized in external magnetic field[J]. J of Magn and Magnetic Mater, 2003, (258-259):468—470.
[3]石可瑜,李朝兴,何炳林.磁导向阿霉素-羧甲基葡聚糖毫微粒的研究[J].生物医学工程学杂志, 2000, 17(1):21—24.
[4]任广智,李振华,何炳林.磁性壳聚糖微球用于脲激酶的固定化研究[J].离子交换与吸附,2000,16(4):304—310.
[5]钱建华,杨凯,范我等.用作磁共振造影增强剂的氧化铁溶液理化性质测定[J].核技术,2001,24(6):487—490.
[6] Rittich B, Spanova A, Ohlashennyy Y. Characterization of deoxyribonuclease I immobilized on magnetic hydrophilic polymer particles[J]. J of Chromatog B: Analy Tech in the Biomed and Life Sci, 2220,774(1):25—31.
[7] Papell S S. USP 3,215,572,1965.
[8] Neuringer J L,Rosensweig R E. Phys Fluids,1964,27:1927.
[9] Zaitsev V S, Filimonov D S,Presnyakov I A, et al. Physical and chemical properties of magnetite and magnetite-polymer nanoparticles and their colloidal dispersions[J].J of Colloid and Interface Sci,1999, 212:49-57.
[10] Shchukin D G, Sukhorukov G B.Synthesis of binary polyelectrolyte/inorganic composite capsules of micron size[J].Colloid Poym Sci, 2003,281:1201-1204.
[11]蒋新宇,周春山,张俊山等.导向药物用纳米Fe3O4磁性粒子的制备及表征[J].中南工业大学学报(自然科学版), 2003, 34(5):516—520
[12]解耸林,李宏涛,任泽胜.纳米磁粉制备工艺[J].长春工业大学学报(自然科学版),2005, 26(1):31—33
[13] Liu X Q, Xing J M, Guan Y P, et al. Colloids and Surfaces A: Physicochem Eng Aspects, 2004, 238(123):127
[14] Deng J G, Ding X B, Zhang W C, et al. Magnetic and conducting Fe3O4-cross-linked polyaniline nanoparticles with core-shell structure[J]. Polymer, 2002, 43(8):2179-2184.
[15]涂国荣,刘翔峰,杜光旭等.Fe3O4纳米材料的制备与性能测定[J]精细化工,2004,21(9):641—644
[16] Itoh H, Sugimoto T. Systematic control of size, shape, structure and magnetic properties of uniform magnetite and maghemite particles[J].J of Colloid and Interface Sci, 2003, 265(2):283-295.
[17] Thapa D, et al. Mater Lett, 2004, 58(21):2692
[18] Zhou Z H, et al. J Mater Chem, 2001, 11(6):1704
[19] Arturo M, López Q, JoséR.J Colloid Interf Sci,1993,158(2):446
[20] Si S, et al.Cryst Growth Des,2005,5(2), 391
[21]杨华,黄可龙,刘素琴.水热法制备的Fe3O4磁流体[J].磁性材料及器件,2003,34(2):4—6
[23] Rockenberger J, Scher E C,Alivisatos P A. J Am Chem Soc,1999,121:11595.
[24] Hyeon T, Lee S S, Park J, et al.J Am Chem Soc,2001,123:12798.
[25] Guo Q, Teng X, Rahman S, et al. J Am Chem Soc, 2003, 125:630.
[26] Murray C B, Sun S, Gaschler W, et al. IBMJ Res &Dev, 2004, 45:47.
[27] Sun S, Murray C B. J Appl Phys, 1999, 85:4325.
[28] Li Z, Chen H, Bao H, et al.Chem Mater,2004,16(8):1391.
[29] Lu Y, Yin Y. Nano Lett, 2002, 2(3):183
[30] Todaka Y S, Nakamura M, Hattori S, et al.[J]. Japan Institute of Metals, 2002, 66(1):34
[31] Tricot M, Danied J C.Process for the preparation of magnetic beads of vinylaromatic polymer. USP 4339337
[32] Danied J C, Schuppiser J L, Tricot M.Magnetic polymer latex and preparation process.USP 4358388
[33] Yanase N, Noguchi H, Asakura H. Preparation of magnetic latex particles by emulsion polymerization in the presence of a ferrofluid.Journal of Applied Polymer Science.1993,50:765
[34]邱广明,邱广亮.大粒径磁性高分子微球的制备[J].应用化学,1997,14(1):74—76
[35] Bahar T, Celebi S S.[J].J Appl Polym Sci,1999,72(1):69
[36] Josep Hson L.US Pat, 4672040.1987-06-09
[37]安小宁,苏致兴.高磁性壳聚糖微粒的制备与应用[J].兰州大学学报(自然科学版), 2001,37(2):100—104
[38] Menager C, Cabuil V. J Colloid Interf Sci, 1995, 169(1):251
[39] Harris L A, et al. Chem Mater, 2003, 15(6):1367
[40] Yen S P S, Rembaum A, Landel R F. US Pat, 4285819.1981-08-25
[41] Gupta P K, et al. Int J Pharm, 1988, 43(122):167
[42] Tricot M, Daniel J C.Process for the preparation of magnetic beads of vinylaromatic polymers.US Pat.4339337.1982-07-13
[43] Margel S, Beitler U.Polyacrolein type microspheres.US Pat.4783336.1988-11-03
[44] Tsuruta M.Manufacture of magnetic microspore.JP Pat.62204501.1987-09-27
[45]姜波,官月平,王靖等.聚乙二醇修饰的高分子磁性微球的合成及表征[J].过程工程学报, 2001,1(4):382—386
[46]王强斌,高峰,王胜林等.羧基磁性高分子微球的制备和表征[J].化学世界,2001,8:410—413
[47]何虹,杨梭.悬浮聚合法制备磁性微球的粒度分布特征[J].高效化学工程学报,2001,3(15):277
[48]王胜林,朱以华.微悬浮聚合法合成聚苯乙烯磁性微球[J].华东理工大学学报,2001,27(4):364—367
[49] Daniel J C, Schuppiser J L,Tricot M.Magnetic polymer latex and preparation process.US Pat,4358388.1982-11-09
[50] Charmot D, Vidil C. Magnetizable composite microspheres of hydrophobic crosslinked polymer.process for preparing then and their application in biology.US Pat,5356713,1994-10-18
[51]邓勇辉,王雷,样武利等.反相微乳液合成30~100nm磁性聚合物纳米微球[J].高等学校化学学报,2003,24(5):920—923
[52]丁明,孙虹.Fe3O4/壳聚糖核壳磁性微球的制备及特性[J].磁性材料及器件,2001,32(6):1—3
[53] Sole N, Hajna J. Colloidal size hydrophobic polymers particulate having discrete particles of an inorganic material dispersed therein[P]US Pat, 4421660.1983—12—20
[54]邱广明,杨春燕,孙宗华.单分散亚微米级磁性微球的合成[J].功能高分子学报,1996,9(4):565—571
[55]邱广明,杨春燕,孙宗华.磁性聚苯乙烯微球的合成和特性[J].高分子材料学与功能,1993,(2):38—43
[56]邓建国,贺传兰,龙新平等.磁性Fe3O4-聚吡咯纳米微球的合成与表征[J].高分子学报,2003,3:393—397
[57]邱广亮,李咏兰,邱广明等.肺靶向顺铂磁性白蛋白微球的制备及性质[J].中国医药工业杂志,2001,32(12):544—546
[58]高兰萍,邱广明.纳米级磁性复合微球的制备[J].内蒙古师大学报自然科学(汉文)版,1998,27(4):302—306
[59] Yanase N, Noguchi H, Asakura H, et al.Preparation of magnetic latex particles by emulsion polymerization of styrene the presence of ferrofluid.J Appl Polym Sci,1993,50:765
[60]景晓燕,王君,张密林等.磁性功能高分子微球的制备研究[J].应用科技,2000,27(1):16—17
[61] Dresco P A, Zaitsev V S, Gambio R J , et at . Langmuir, 1999, 15:1945.
[62]邓勇辉,王雷,样武利等.反相微乳液合成30~100nm磁性聚合物纳米微球[J].高等学校化学学报,2003,24(5):920—923
[63] Deng Y,Wang L,Yang W, et al.J Magn Magn Mater,2003,257(1):69.
[64] Gupta A K, Wells S, IEEE Transcations on Nanobioscience, 2004, 3(1):66.
[65] Wormuth KJ.Colloid Interface Sci,2001,241:366.
[66]邱广明,胡玲. Fe3O4/P(St-Al)磁性微球的制备和复合微相结构[J].电子显微学报,2000,19(4):463—464
[67]程彬,朱玉瑞,江万权等.无机-高分子磁性复合粒子的制备与表征[J].化学物理学报,2000,13(3):359—362
[68]谢钢,张和鹏.细乳液聚合法制备磁性复合微球及其表征[J].高分子学报,2003,5:626—630
[69]李孝红,孙宗华.磁性高分子微球的合成研究:带醛基磁性高分子微球的合成及表征[J].离子交换与吸附,1996,12(6):486—492
[70]李孝红,丁小斌,孙宗华.含羟基磁性高分子微球的合成及表征[J].功能高分子学报,1995,8(1):73—78
[71]丁小斌,孙宗华,万国祥等.热敏性高分子包裹的磁性微球的合成[J].高分子学报,1998,5:628—631
[72]丁小斌,孙宗华,万国祥等.热敏性高分子包裹的磁性微球的性质及表征[J].高分子学报,1999,6:674—679
[73]王艳君,刘江峰,姚兆玲等.磁性聚甲基丙烯酸甲酯微球的制备与研究[J].天津大学学报,2001,34(1):64—68
[74] Ugelstad J, et al. US Pat, 47742265.1988-09-27
[75] Winnik F M, et al. Langmuir, 1995,11(10):3660
[76]张兆斌,应圣康.原子转移自由基聚合及可控自由基聚合[J].高分子通报,1999,3:138—144.
[77] Hadjichristidis N, Pispas S, Floudas G.Block Copolymers: Synthetic Strategies, Physical Properties, and Applications. Chapter 3: Block Copolymers by Living Free Radical Popymerization [R].John Wiley &Sons, Inc., 2003, 47.
[78] Wang Y, Teng X.W, Wang J S, Yang H.[J].Nano letters.2003,3(6):789—793.
[79] Vetal C R, Zhang Z J.[J]. J, Am. Chem. Soc., 2002, 124:14312—14313.
[80] Rather B, Nuyken O. [J]. Macromol, Symp., 2002,177:25—41.
[81] Wieland P C, Raether B. [J]. Macromol. Rapid Commun., 2001,22:700—703.
[82] Matsuno R, Yamamoto K, Otsuka H, et al. [J]. Chem.Mater., 2003,15:3—5.
[83] Kato K, Radbruch A. Cytometry, 1993, 14(4):384
[84] Lauva M, Auzans E, Levickis V. J of Magn and Magn Mater, 1990, 85:295
[85]张梅,王补森,张玉格等.化学转化法制备磁性阳离子交换树脂的研究[J].离子交换与吸附, 1995, 11(4):302
[86] Young Kyun Kim, Kun J ai Lee. Nuclear Science and Technology, 2001, 38(9):785
[87]吴雪辉,郭祀远,李琳.磁性离子交换树脂连续化运行条件的研究[J].离子交换与吸附, 2001, 17(4):345—349
[88] Martin C, Cuellar J1 Indu & Eng Chem Res, 2004, 43(2):475
[89] Jürgen Oster, J eff rey Parker, et al. J Magnetism and Mater, 2001, 225:145
[90] Rusetski A N, Ruuge E K.Magnetic fluid as a possible drug carrier for thrombosis treatment[J].J of Magn and Magn Mater,1990,85:299—302
[91]任广智,李振华,何炳林.磁性高分子微球用于固定化酶的研究进展[J].离子交换与吸附,2000,16(1):83—87
[92] Munko P A, Dunill P, Lilly M D.Biotech Bioen, 1997, 19:101
[93] Yoshimoto T.Biochem.Biophy Res Comm, 1987, 145(2):908
[94] Sinan A, Yasemin. Food Chemistry, 2001, 74:281
[95] Anshits A G, Kondratenko E V, Catalysis Today, 2001, 64:59
[96]张密林,王君,景晓燕等.21世纪生物与化工学术研讨会论文集,云南,云南科技出版社, 2000. 1. 6
[97]吴雪辉,郭祀远,李琳等.磁性阴离子变换树脂的化学转化制备及其特性研究[J].广西大学学报(自然科学版) ,1999,24(2):163—166
[98]张梅,王补森,张玉格等.化学转化法制备磁性阳离子交换树脂的研究[J].离子交换与吸附, 1995, 11(4):302—308
[99]许乙凯.磁共振造影剂及临床应用[M].北京:人民卫生出版社,2003. 8251.
[100] Ming Y, Hu L L. Talanta, 2001, 55:479
[101] Yang M, Hu L L. Determination of trace hydrazine by differential pulse voltammetry using magnetic microspheres[J]. Talanta, 2001, 55(3):479—484.
[102] Günther A, Bilitewski U. Anal Chim Acta, 1995, 300:117
[103] SoléS, Doctoral Thesis. Autonomous University of Barcelona, 2000,2(3):123-126
[104] Yu H, Bruno J G. Appl Environ Microbiol, 1996,62(2):587
[105] Witherspoon L R, Shuler S E, Glbert S S. Clin Chem, 1985, 31:415
[106] SoléS, Alegret S, Cespedes F, et al. Anal Chem, 1998, 70:1462
[107] Mosbach K, Kriz D. Ansell R J. PCT. WO97/22366, 1997
[108] Sun Y, Wang B, Hui C, et al.[J].J Macromol Sci Phys,2006,45,653.
[109] Ma Z Y, Guan Y P, Liu H Z. Affinity adsorption of albumin on Cibacron Blue F3GA-coupled non-porous micrometer-sized magnetic polymer microspheres[J]. React Funct Polym, 2006, 66:618.
[110] Ugelstad J, Berge A, Ellingsen T, et al. Preparation and application of new monosized polymer particles[J]. Prog Polym Sci, 1992, 17(1): 87—90.
[111] Ugelstad J, Stenstad P, Kilaas L, et al. Berge A and Hornes E [J]. Blood Purif,1993 11(6): 349—69.
[112] Lea T, Vartdal F, Nustad K, et al. Monosized, magnetic polymer particles: Their use in separation of cells and subcellular components, and in the study of lymphocyte function in vitro [J]. Journal of Molecular Recognition, 1988, 1(1): 9—18.
[113] Bahar T, Celibi S S. Immobilization of glucoamylase on magnetic poly(styrene) particles[J]. J Appl Polym Sci, 1999, 72: 69.
[114] Uhlen M. Magnetic separation of DNA[J]. Nature, 1989, 34: 733.
[115] Levison P R, Badger S E, Dennis J, et al. Recent developments of magnetic beads for use in nucleic acid purification[J]. Journal of Chromatography A, 1998, 81:107.
[116]张和鹏,张秋禹,王巍等.可控制自由基聚合DPE法制备P(AA-MMA-ST)/Fe3O4磁性复合微球[J].化学学报,2006,64,(17):1831—1836
[117] Horák D, Shapoval P. J Polym Sci Part A: Polym Chem, 2000, 38, 3855.
[118]王丽娟,刘峥.磁性高分子微球的制备及在分析化学中的应用发展[J].材料导报,2006,20,(6)36—40
[119]毕如意,钟国伦,孙建中.功能化高分子磁性微球制备技术研究进展[J].科学通报,2008,24(2):246—251.
[120]景晓燕,王君,李茹民等.磁性功能高分子微球的制备研究.[J].应用科技,2000, 27(1):16—17
[121] Doina B, Vekas L, Rasa R. Preparation and magnetic properties of concentrated magnetic fluids on alcohol and water carrier liquids[J]. Magn Magn Mater, 2002, 252:10
[122] Hong-ting Pu, Feng-jing Jiang, Zheng-long Yang.Preparation and properties of soft magnetic particles based on Fe3O4 and hollow polystyrene microsphere composite[J].Materials Chemistry and Physics, 2006, (100):10—14
[123] Ahmetli G, Tarlan E. Fe (II/III) adsorption onto styrene/dicinyl benzene based polymers[J].published online 27 February 2007 in wiley InterScience(www.interscience.wiley.com)