双重磁响应复合微球的制备及吸附性能研究
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摘要
采用种子乳液聚合法制备了Fe3O4@P(NIPAM-co-St)温敏复合微球。利用透射电镜、红外光谱仪、Zeta粒度分析仪、热重分析仪和振动样品磁力计对微球结构进行了表征,通过紫外-可见光分光光度法研究了微球对模型有机物罗丹明B(Rh B)的吸附和磁感应脱附再生行为。结果表明,复合微球呈现多核壳结构,增加聚合体系疏水单体苯乙烯(St)用量,微球中Fe3O4含量和饱和磁感应强度降低;微球中引入适量疏水聚苯乙烯(PS)链段可以提高其对Rh B的吸附量,且酸性条件有利于微球对Rh B的吸附,吸附量可达13.31 mg/g;吸附Rh B的微球在交变磁场作用下的脱附量相对于室温条件明显提高,且微球经过5次使用后,其吸附量仍然可达8.82 mg/g,说明该微球具有良好的双重磁响应特性(磁分离响应和磁感应脱附再生)。
Seed emulsion polymerization was carried out to fabricate a novel class of thermo-sensitive Fe3O4@ poly( N-isopropylacrylamide-co-styrene) composite microspheres( Fe3O4@ P( NIPAM-co-St)).The structures of the as-prepared composite microspheres were characterized by TEM,FTIR,DLS,TGA and VSM. UV-Vis was employed to investigate the adsorption and magnetic-induced desorption behaviors using Rhodamine B( Rh B) as a model molecule. The results indicated that the composite microspheres possessed a unique multi-core-shell structure. The magnetic nanoparticle content and saturation magneticinduction intensity of microspheres decreased with an increase of the St content during polymerization.Rh B adsorption performance was improved when a proper amount of hydrophobic St comonomer was introduced into microspheres. The composite microspheres showed a high Rh B adsorption capacity of up to13. 31 mg / g under an acid condition. As compared with the free desorption under room temperature,much more Rh B on the composite microspheres could be desorbed under alternating magnetic field. The adsorption capacity of composite microsphere still achieved 8. 82 mg / g after five adsorption / desorption cycles,indicating good dual-magnetic responses( magnetic separation and magnetic-induced desorption).
Seed emulsion polymerization was carried out to fabricate a novel class of thermo-sensitive Fe3O4@ poly( N-isopropylacrylamide-co-styrene) composite microspheres( Fe3O4@ P( NIPAM-co-St)).The structures of the as-prepared composite microspheres were characterized by TEM,FTIR,DLS,TGA and VSM. UV-Vis was employed to investigate the adsorption and magnetic-induced desorption behaviors using Rhodamine B( Rh B) as a model molecule. The results indicated that the composite microspheres possessed a unique multi-core-shell structure. The magnetic nanoparticle content and saturation magneticinduction intensity of microspheres decreased with an increase of the St content during polymerization.Rh B adsorption performance was improved when a proper amount of hydrophobic St comonomer was introduced into microspheres. The composite microspheres showed a high Rh B adsorption capacity of up to13. 31 mg / g under an acid condition. As compared with the free desorption under room temperature,much more Rh B on the composite microspheres could be desorbed under alternating magnetic field. The adsorption capacity of composite microsphere still achieved 8. 82 mg / g after five adsorption / desorption cycles,indicating good dual-magnetic responses( magnetic separation and magnetic-induced desorption).
引文
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[3]DAVID D,ABDELHAMID E,FRANCOIS M,et al.Adsorption of modified HIV-1 capsid p24 protein onto thermosensitive and cationic core-shell poly(styrene)-poly(N-isopropylacrylamide)particles[J].Langmuir,2000,16(23):9002-9008.
[4]ALVAREZ-LORENZO C,CONCHEIRO A.Reversible adsorption by a p H-and temperature-sensitive acrylic hydrogel[J].Journal of Controlled Release,2002,80(1):247-257.
[5]YAMASHITA K,NISHIMURA T,NANGO M.Preparation of IPN-type stimuli-responsive heavy-metal-ion adsorbent gel[J].Polymers for Advanced Technologies,2003,14(3/4/5):189-194.
[6]YILDIZ U,KEMIK O F,HAZER B.The removal of heavy metal ions from aqueous solutions by novel p H-sensitive hydrogels[J].Journal of Hazardous Materials,2010,183(1/2/3):521-532.
[7]蔡力锋,温裕乾,林志勇,等.磁性热敏聚合物微球的制备及磁感应控制释放行为[J].高分子学报,2012,8:846-851.
[8]BYEON J H B,KIN J W.Aerosol-processed thermosensitive nanocomposites for controlled drug release[J].ACS Macro Letters,2014,3(4):369-373.
[9]PENG Z,FANG E,WANG C,et al.Construction of novel thermosensitive magnetic cationic liposomes as a drug and gene co-delivery system[J].Journal of Nanoscience and Nanotechnology,2015,15(5):3823-3833.
[10]唐恢同.有机化合物的光谱鉴定[M].北京:北京大学出版社,1994:127-153.
[11]IVAYLO D,BARBARA T,ANDRZEJ D,et a1.Thermosensitive water-soluble copolymers with doubly responsive reversibly interacting entities[J].Progress in Polymer Science,2007,32(11):1275-1343.
[12]DANIEL H,NATALIYA S,FRANTISEK L.Effect of the reaction parameters on the particle size in the dispersion polymerization of 2-hydroxyethyl and glycidyl methacrylate in the presence of a ferrofluid[J].Polymer Science Part A:Polymer Chemistry,2003,41:1848-1863.
[13]XU S,MA W F,YOU L J,et al.Toward designer magnetite/polystyrene colloidal composite microspheres with controllable nanostructures and desirable surface functionalities[J].Langmuir,2012,28(6):3271-3278.
[14]CHEN L B,ZHANG F,WANG C C.Rational synthesis of magnetic thermosensitive microcontainers as targeting drug carriers[J].Small,2009,5(5):621-628.
[15]武承林,贺欢,高红军,等.Fe3O4@Si O2@polymer复合粒子的制备及在药物控制释放中的应用[J].中国科学:化学,2010,40(3):269-275.
[16]李晓东,沈家骢.胶束增强型聚电解质胶囊对罗丹明B的包埋和释放[J].高等学校化学学报,2007,28(10):2000-2005.
[17]温裕乾,蔡力锋,林志勇.双重磁响应温敏复合微球的制备及表征[J].高分子材料科学与工程,2012,28(7):120-123.