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基于明胶和聚丙烯酸通过模板聚合制备的智能核壳纳米粒子与空心球。

Intelligent core-shell nanoparticles and hollow spheres based on gelatin and PAA via template polymerization.

作者信息

Wang Yansong, Zhang Youwei, Du Weiping, Wu Chengxun, Zhao Jiongxin

机构信息

State Key Laboratory for Modification of Chemical Fibers and Polymer Materials, College of Material Science and Engineering, Donghua University, Shanghai 201620, PR China.

出版信息

J Colloid Interface Sci. 2009 Jun 15;334(2):153-60. doi: 10.1016/j.jcis.2009.02.063. Epub 2009 Apr 8.

Abstract

PAA/gelatin nanoparticles, with interpolymer complexes of gelatin and polyacrylic acid (PAA) as the cores and gelatin as the shells, were prepared via facile polymerization of AA on gelatin template. The morphology change of the nanoparticles during the reaction was traced by a combined use of dynamic light scattering (DLS) and atomic force microscopy (AFM) techniques, which revealed a discrepancy among the structure of the nanoparticles formed at different stages of the reaction: as the reaction proceeds, nanoparticles with larger compact cores and thinner shells are produced. The resultant nanoparticles are multi-responsive. Especially, they exhibit a significant temperature-dependent size change: upon raising the temperature from 25 degrees C, the nanoparticle size decreases monotonically until reaching equilibrium at about 40 degrees C. This temperature-dependence of the nanoparticle size was found to be reversible provided the nanoparticle solution was cooled at a low temperature (4 degrees C). The thermo-sensitivity of the nanoparticles is attributed to the thermo-induced sol-gel transition of the gelatin shells. In addition, the nanoparticles were further converted to hollow spheres via successive locking the shell structure by the reaction of gelatin with cross-linker glutaraldehyde, and cavitation of the cross-linked nanoparticles by switching the medium from acidic to neutral. The cavitation process was monitored by DLS, which indicated a mass decrease and size shrinkage. AFM and transmission electron microscopy (TEM) were used to trace the morphology change of the nanoparticles during the cavitation. The hollow structure was confirmed by TEM observation.

摘要

以明胶和聚丙烯酸(PAA)的聚合物间复合物为核、明胶为壳的PAA/明胶纳米粒子,是通过在明胶模板上使丙烯酸(AA)进行简便聚合反应制备而成的。通过联合使用动态光散射(DLS)和原子力显微镜(AFM)技术追踪反应过程中纳米粒子的形态变化,结果表明在反应不同阶段形成的纳米粒子结构存在差异:随着反应进行,会生成具有更大紧密核和更薄壳的纳米粒子。所得纳米粒子具有多重响应性。特别是,它们表现出显著的温度依赖性尺寸变化:从25℃升高温度时,纳米粒子尺寸单调减小,直至在约40℃达到平衡。如果将纳米粒子溶液在低温(4℃)下冷却,发现这种纳米粒子尺寸的温度依赖性是可逆的。纳米粒子的热敏感性归因于明胶壳的热致溶胶-凝胶转变。此外,通过明胶与交联剂戊二醛反应依次锁定壳结构,并通过将介质从酸性切换为中性使交联纳米粒子空化,纳米粒子进一步转变为空心球。空化过程通过DLS进行监测,结果表明质量减少和尺寸收缩。使用AFM和透射电子显微镜(TEM)追踪空化过程中纳米粒子的形态变化。通过TEM观察证实了空心结构。

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