分散聚合制备光反应活性壳交联/空心微球及生物大分子固定研究
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摘要
分散聚合两步法是一种新的，具有发展潜力的制备单分散表面含功能基团微球的方法。利用分散聚合制备出来的功能微球在后续的运用中能制备出不同微球结构及形貌的材料，所制备出的材料可应用于粘结材料，纳米装载材料，生物材料及光感材料等研究领域中。
本论文采用了分散聚合两步法及多步法制备了表面含有亲水单体DMAEMA,光引发单体BPMA, DBPMA等功能单体的核壳微球，并通过分散聚合两步法研究了提高微球表面功能基团含量的方法。通过研究微球在聚合过程中的形貌、结构的变化讨论了分散聚合两步法的核壳结构形成机理。在DBPMA即可作为交联剂又可作为光引发的基础上通过分散聚合两步法-自模板法制备出了表面层为交联结构的核壳微球，调节溶剂作用时间下得到了微球内部为网状结构及空心结构的功能微球。
通过分散聚合两步法/多步法制备出的光引发功能核壳及中空微球在UV光的照射下耦合上不同链长度的亲水单体PEG(200,4000)以改变微球表面的亲水性，同时还讨论了在不同搅拌环境下制备出的微球表面形貌的变化；或耦合上BSA、IgG等一类生物大分子，并对其做抗原-抗体匹配试验以改变微球表面的生物相容性。中空粒子具有很好的腔体结构且微球壳层微球多孔结构，在此基础上本论文还讨论了向中空微球装载磁性粒子，以实现有机/无机纳米粒子的相结合。
Dispersion polymerization is a new and potential technique for preparingmonodispersity particles with functional group in the surface. The functionalparticles were synthesized by Two-stage dispersion polymerization could beuse to prepare different materials with different structure and morphology.These materials can be applied to in the field of research such as the bindingmaterial, nano loading materials, biological materials and light sensormaterials.
We use Two-stage dispersion polymerization to prepare core-shellfunctional particles which surface contained hydrophobic monomer (BPMA orDBPMA) or hydrophilic monomer (DMAEMA) in this paper. We also usedthis method to study a way to increase the content of functional group ofparticles surface. This paper discussed core-shell structure formationmechanism through study the change of structure and morphology of pariticlesin process of two-stage dispersion polymerization. Our research uses a newfunctional monomer which contains structure of benzophenone (BP) and twodouble bonds which called DBPMA. PSt-core was prepared at first stagedispersion polymerization and poly (St-DBPMA)-shell was constructed byslowly adding St/DBPMA mixture into reactor after3h polymerization.Moreover, cross-linked hollow particles could be prepared by removing corein THF and different dissolved time could prepare different Mesh structureand hollow structure particles.
We introduced photoreactive agent into the surface of nanoparticles andcross-linked hollow nanoparticles could be further modified by photograftingpolymerization. Core-shell/Hollow particles were exposed to UV light cancouple with protein likes biological macromolecules (BSA), water-solubleoligomer (PEG) and mouse IgG, and hollow particles can be used as a carrierto load magnetic nanoparticles.
本论文采用了分散聚合两步法及多步法制备了表面含有亲水单体DMAEMA,光引发单体BPMA, DBPMA等功能单体的核壳微球，并通过分散聚合两步法研究了提高微球表面功能基团含量的方法。通过研究微球在聚合过程中的形貌、结构的变化讨论了分散聚合两步法的核壳结构形成机理。在DBPMA即可作为交联剂又可作为光引发的基础上通过分散聚合两步法-自模板法制备出了表面层为交联结构的核壳微球，调节溶剂作用时间下得到了微球内部为网状结构及空心结构的功能微球。
通过分散聚合两步法/多步法制备出的光引发功能核壳及中空微球在UV光的照射下耦合上不同链长度的亲水单体PEG(200,4000)以改变微球表面的亲水性，同时还讨论了在不同搅拌环境下制备出的微球表面形貌的变化；或耦合上BSA、IgG等一类生物大分子，并对其做抗原-抗体匹配试验以改变微球表面的生物相容性。中空粒子具有很好的腔体结构且微球壳层微球多孔结构，在此基础上本论文还讨论了向中空微球装载磁性粒子，以实现有机/无机纳米粒子的相结合。
Dispersion polymerization is a new and potential technique for preparingmonodispersity particles with functional group in the surface. The functionalparticles were synthesized by Two-stage dispersion polymerization could beuse to prepare different materials with different structure and morphology.These materials can be applied to in the field of research such as the bindingmaterial, nano loading materials, biological materials and light sensormaterials.
We use Two-stage dispersion polymerization to prepare core-shellfunctional particles which surface contained hydrophobic monomer (BPMA orDBPMA) or hydrophilic monomer (DMAEMA) in this paper. We also usedthis method to study a way to increase the content of functional group ofparticles surface. This paper discussed core-shell structure formationmechanism through study the change of structure and morphology of pariticlesin process of two-stage dispersion polymerization. Our research uses a newfunctional monomer which contains structure of benzophenone (BP) and twodouble bonds which called DBPMA. PSt-core was prepared at first stagedispersion polymerization and poly (St-DBPMA)-shell was constructed byslowly adding St/DBPMA mixture into reactor after3h polymerization.Moreover, cross-linked hollow particles could be prepared by removing corein THF and different dissolved time could prepare different Mesh structureand hollow structure particles.
We introduced photoreactive agent into the surface of nanoparticles andcross-linked hollow nanoparticles could be further modified by photograftingpolymerization. Core-shell/Hollow particles were exposed to UV light cancouple with protein likes biological macromolecules (BSA), water-solubleoligomer (PEG) and mouse IgG, and hollow particles can be used as a carrierto load magnetic nanoparticles.
引文
[1]张芬.电荷稳定分散聚合体系制备聚合物微球的研究[D].北京化工大学,2010.
[2]崔亨利.单分散交联聚苯乙烯微球的合成及性能研究[D].鲁东大学,2008.
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[27] Wang L.P., Zhao L.M., Li W.Z. Fabrication of polymer-hollow sphereoptical-functional hybrid material via raft polymerization [J]. Reactive and FunctionalPolymers,2010,70(1):35-40.
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[32] Lv H., Lin Q., Zhang K., et al. Facile fabrication of monodisperse polymer hollowspheres [J]. Langmuir,2008,24(23):13736-13741.
[33] Tiarks F., Landfester K., Antonietti M. Preparation of polymeric nanocapsules byminiemulsion polymerization [J]. Langmuir,2001,17(3):908-918.
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[37] Huang J., Kim K.H., Choi N., et al. Preparation of silica-encapsulated hollow goldnanosphere tags using layer-by-layer method for multiplex surface-enhanced ramanscattering detection [J]. Langmuir,2011.
[38] Manju S., Sreenivasan K. Hollow microcapsules built by layer by layer assembly forthe encapsulation and sustained release of curcumin [J]. Colloids and Surfaces B:Biointerfaces,2011,82(2):588-593.
[39] Gauczinski J., Liu Z., Zhang X., et al. Surface molecular imprinting in layer-by-layerfilms on silica particles [J]. Langmuir,2012.
[40] Sun Z., Bai F., Wu H., et al. Hydrogen-bonding-assisted self-assembly: Monodispersehollow nanoparticles made easy [J]. Journal of the American Chemical Society,2009,131(38):13594-13595.
[41] Yin W., Yates MZ. Effect of interfacial free energy on the formation of polymermicrocapsules by emulsification/freeze-drying [J]. Langmuir,2008,24(3):701-708.
[42] Liu J., Xue D. Thermal oxidation strategy towards porous metal oxide hollowarchitectures [J]. Advanced Materials,2008,20(13):2622-2627.
[43] Chen J., Wang D., Xi J., et al. Immuno gold nanocages with tailored optical propertiesfor targeted photothermal destruction of cancer cells [J]. Nano letters,2007,7(5):1318-1322.
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[2]崔亨利.单分散交联聚苯乙烯微球的合成及性能研究[D].鲁东大学,2008.
[3] Ha S.T., Park O.O., Im S.H. Size control of highly monodisperse polystyrene particlesby modified dispersion polymerization [J]. Macromolecular Research,2010,18(10):935-943.
[4] Sugihara S., Armes S.P., Blanazs A., et al. Non-spherical morphologies fromcross-linked biomimetic diblock copolymers using raft aqueous dispersionpolymerization [J]. Soft Matter,2011,7(22):10787-10793.
[5] Peng B., van der Wee E., Imhof A., et al. Facile synthesis of monodisperse highlycross-linked fluorescent pmma particles by dispersion polymerization [J].2012.
[6]党高飞,付志峰.分散聚合技术及其研究进展[J].高分子通报,2008,(10):41-46.
[7] Song J.S., Winnik M.A. Monodisperse, micron-sized reactive low molar masspolymer microspheres by two-stage living radical dispersion polymerization ofstyrene [J]. Macromolecules,2006,39(24):8318-8325.
[8] Song J.S., Tronc F., Winnik M.A. Monodisperse, controlled micron-size dye-labeledpolystyrene particles by two-stage dispersion polymerization [J]. Polymer,2006,47(3):817-825.
[9] Emoto K., Iijima M., Nagasaki Y., et al. Functionality of polymeric micelle hydrogelswith organized three-dimensional architecture on surfaces [J]. Journal of theAmerican Chemical Society,2000,122(11):2653-2654.
[10] Li W.H., St ver H.D.H. Monodisperse cross-linked core-shell polymer microspheresby precipitation polymerization [J]. Macromolecules,2000,33(12):4354-4360.
[11]张凯,曾敏.核壳高分子微球的制备[J].材料导报,2002,16(006):74-75.
[12] Wen F., Zhang W., Zheng P., et al. One‐stage synthesis of narrowly dispersedpolymeric core‐shell microspheres [J]. Journal of Polymer Science Part A: PolymerChemistry,2008,46(4):1192-1202.
[13] Lee J.M., Lee D.G., Lee S.J., et al. One-step synthetic route for conducting coreshell poly (styrene/pyrrole) nanoparticles [J]. Macromolecules,2009,42(13):4511-4519.
[14] Kobayashi M., Terada M., Terayama Y., et al. Direct controlled polymerization ofionic monomers by surface‐initiated atrp using a fluoroalcohol and ionic liquids [J].Israel Journal of Chemistry,2012.
[15] Taniguchi T., Obi S., Kamata Y., et al. Preparation of organic/inorganic hybrid andhollow particles by catalytic deposition of silica onto core/shell heterocoagulatesmodified with poly [2-(N,N-dimethylamino) ethyl methacrylate][J]. Journal ofColloid and Interface Science,2011.
[16] Yin M., Kang N., Cui G., et al. Synthesis, electrochemical properties and self‐assembly of a proton‐conducting core–shell macromolecule [J]. Chemistry-AEuropean Journal,2012,18(8):2239-2243.
[17] Ghosh C.R., Paria S. Core/shell nanoparticles: Classes, properties, synthesismechanisms, characterization, and applications [J]. Chemical reviews,2011.
[18] Li J., Hitchcock A.P., Sto ver H.D.H. Pickering emulsion templated interfacial atomtransfer radical polymerization for microencapsulation [J]. Langmuir,2010.
[19]王政,高原,王佳瑜, et al.结合表面引发的原子转移自由基聚合和气/固反应制备cds纳米微粒/聚苯乙烯核壳微球[J].高等学校化学学报,2008,29(7):1452-1455.
[20] Fu GD, Zhao JP, Sun YM, et al. Conductive hollow nanospheres of polyaniline viasurface-initiated atom transfer radical polymerization of4-vinylaniline and oxidativegraft copolymerization of aniline [J]. Macromolecules,2007,40(6):2271-2275.
[21] Liu J., He W., Zhang L., et al. Bifunctional nanoparticles with fluorescence andmagnetism via surface-initiated aget atrp mediated by iron catalyst [J]. Langmuir,2011.
[22] Vestal C.R., Zhang Z.J. Atom transfer radical polymerization synthesis and magneticcharacterization of mnfe2o4/polystyrene core/shell nanoparticles [J]. Journal of theAmerican Chemical Society,2002,124(48):14312-14313.
[23] Scott C., Wu D., Ho C.C., et al. Liquid-core capsules via interfacial polymerization: Afree-radical analogy of the nylon rope trick [J]. Journal of the American ChemicalSociety,2005,127(12):4160-4161.
[24] Dowding P.J., Atkin R., Vincent B., et al. Oil core-polymer shell microcapsulesprepared by internal phase separation from emulsion droplets. I. Characterization andrelease rates for microcapsules with polystyrene shells [J]. Langmuir,2004,20(26):11374-11379.
[25] Atkin R., Davies P., Hardy J., et al. Preparation of aqueous core/polymer shellmicrocapsules by internal phase separation [J]. Macromolecules,2004,37(21):7979-7985.
[26] Wang L.P., Li W.Z., Zhao L.M., et al. Preparation and characterization ofoptical-functional diblock copolymer brushes on hollow sphere surface via atomtransfer radical polymerization [J]. Materials Research Bulletin,2010,45(9):1314-1318.
[27] Wang L.P., Zhao L.M., Li W.Z. Fabrication of polymer-hollow sphereoptical-functional hybrid material via raft polymerization [J]. Reactive and FunctionalPolymers,2010,70(1):35-40.
[28] Xu X., Asher S.A. Synthesis and utilization of monodisperse hollow polymericparticles in photonic crystals [J]. Journal of the American Chemical Society,2004,126(25):7940-7945.
[29] Mangeney C., Bousalem S., Connan C., et al. Latex and hollow particles of reactivepolypyrrole: Preparation, properties, and decoration by gold nanospheres [J].Langmuir,2006,22(24):10163-10169.
[30] Yang M., Ma J., Zhang C., et al. General synthetic route toward functional hollowspheres with double‐shelled structures [J]. Angewandte Chemie InternationalEdition,2005,44(41):6727-6730.
[31] Fujii S., Matsuzawa S., Nakamura Y., et al. Synthesis and characterization ofpolypyrrole palladium nanocomposite-coated latex particles and their use as acatalyst for suzuki coupling reaction in aqueous media [J]. Langmuir,2010,26(9):6230-6239.
[32] Lv H., Lin Q., Zhang K., et al. Facile fabrication of monodisperse polymer hollowspheres [J]. Langmuir,2008,24(23):13736-13741.
[33] Tiarks F., Landfester K., Antonietti M. Preparation of polymeric nanocapsules byminiemulsion polymerization [J]. Langmuir,2001,17(3):908-918.
[34] Park M.K., Onishi K., Locklin J., et al. Self-assembly and characterization ofpolyaniline and sulfonated polystyrene multilayer-coated colloidal particles andhollow shells [J]. Langmuir,2003,19(20):8550-8554.
[35]任平,官建国,甘治平, et al.空心微球的制备和研究进展[J].材料导报,2004,18(F04):200-203.
[36]魏斌.空心微球研究进展[J].科技咨询导报,2007,(025):6-6.
[37] Huang J., Kim K.H., Choi N., et al. Preparation of silica-encapsulated hollow goldnanosphere tags using layer-by-layer method for multiplex surface-enhanced ramanscattering detection [J]. Langmuir,2011.
[38] Manju S., Sreenivasan K. Hollow microcapsules built by layer by layer assembly forthe encapsulation and sustained release of curcumin [J]. Colloids and Surfaces B:Biointerfaces,2011,82(2):588-593.
[39] Gauczinski J., Liu Z., Zhang X., et al. Surface molecular imprinting in layer-by-layerfilms on silica particles [J]. Langmuir,2012.
[40] Sun Z., Bai F., Wu H., et al. Hydrogen-bonding-assisted self-assembly: Monodispersehollow nanoparticles made easy [J]. Journal of the American Chemical Society,2009,131(38):13594-13595.
[41] Yin W., Yates MZ. Effect of interfacial free energy on the formation of polymermicrocapsules by emulsification/freeze-drying [J]. Langmuir,2008,24(3):701-708.
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