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树枝状聚(酰胺胺)固定化磁性聚合物复合微球的制备与功能化

Fabrication and functionalization of dendritic poly(amidoamine)-immobilized magnetic polymer composite microspheres.

作者信息

Liu Hongbo, Guo Jia, Jin Lan, Yang Wuli, Wang Changchun

机构信息

Key Laboratory of Molecular Engineering of Polymers (Ministry of Education) and Department of Macromolecular Science and Advanced Materials Laboratory, Fudan University, Shanghai, China 200433.

出版信息

J Phys Chem B. 2008 Mar 20;112(11):3315-21. doi: 10.1021/jp077465x. Epub 2008 Feb 19.

Abstract

The synthesis of functionalized magnetic polymer microspheres was described by a process involving (1) preparation of the monodisperse magnetic seeds according to a two-step procedure including the preparation of bilayer-oleic acid-coated Fe3O4 nanoparticles followed by soap-free emulsion polymerization with methyl methacrylate (MMA) and divinyl benzene (a cross-linking agent, DVB); (2) seeded emulsion polymerization proceeding under the continuous addition of glycidyl methacrylate (GMA) monomers in the presence of the magnetic PMMA seeds; and (3) chemical modification of the PGMA shells with ethylenediamine (EDA) to yield amino groups. As such, the magnetic poly(MMA-DVB-GMA) microspheres were prepared possessing monodispersity, uniform magnetic properties, and abundant surface amino groups. Then, the dendritic poly(amidoamine) (PAMAM) shells were coated on the magnetic particles on the basis of the Michael addition of methyl acrylate and the amidation of the resulting ester with a large excess of EDA, which could achieve generational growth under such uniform stepwise reactions. For improving the luminescence properties of the composite particles, fluorescein isothiocyanate, which is a popular organic dye, was reacted with the terminal -NH2 groups from the dendritic PAMAM shells, resulting in the formation of multifunctional microspheres with excellent photoluminescence, superparamagnetic, and pH-sensitive properties. In this case, it can be expected that an extension of the functionalization of these microspheres is to immobilize other target molecules onto the PAMAM shells to introduce other desired functions for potential chemical and biological applications.

摘要

功能化磁性聚合物微球的合成过程如下

(1)通过两步法制备单分散磁性种子,第一步制备双层油酸包覆的Fe3O4纳米粒子,第二步用甲基丙烯酸甲酯(MMA)和二乙烯基苯(交联剂,DVB)进行无皂乳液聚合;(2)在磁性PMMA种子存在下,连续加入甲基丙烯酸缩水甘油酯(GMA)单体进行种子乳液聚合;(3)用乙二胺(EDA)对PGMA壳层进行化学改性以产生氨基。通过这种方式,制备出了具有单分散性、均匀磁性和丰富表面氨基的磁性聚(MMA-DVB-GMA)微球。然后,基于丙烯酸甲酯的迈克尔加成反应以及所得酯与大量EDA的酰胺化反应,在磁性颗粒上包覆树枝状聚(酰胺胺)(PAMAM)壳层,在这种均匀的逐步反应下可实现代数增长。为了改善复合粒子的发光性能,将一种常用的有机染料异硫氰酸荧光素与树枝状PAMAM壳层的末端-NH2基团反应,从而形成具有优异光致发光、超顺磁性和pH敏感性能的多功能微球。在这种情况下,可以预期这些微球功能化的扩展是将其他目标分子固定在PAMAM壳层上,以引入其他所需功能用于潜在的化学和生物应用。

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