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氨基喹啉/乙苯胺共聚物半导体纳米颗粒的简易合成

Simple synthesis of aminoquinoline/ethylaniline copolymer semiconducting nanoparticles.

作者信息

Li Xin-Gui, Hua Yi-Min, Huang Mei-Rong

机构信息

Department of Chemistry and Chemical Biology, Harvard University, Cambridge, MA 02138, USA.

出版信息

Chemistry. 2005 Jul 4;11(14):4247-56. doi: 10.1002/chem.200401140.

Abstract

Pure copolymer nanoparticles from 8-aminoquinoline (AQ) and 2-ethylaniline (EA) were easily synthesized by a chemically oxidative polymerization in three different aqueous media. The potential and temperature of polymerization solution were used to successfully follow the polymerization progress. The molecular and morphological structures of the resulting AQ/EA copolymer particles were systematically characterized by IR, UV/Vis, NMR, gel permeation chromatography, laser particle-size analysis, atomic force and transmission electron microscopy. The oxidation potential of the monomers as well as the polymerization yield, structure, and properties of the particles were found to significantly depend on AQ/EA ratio, polymerization temperature and medium. It is surprisingly found that AQ homopolymerization and AQ/EA (50:50) copolymerization at 5 degrees C in HCl simply afford nano-ellipsoids with the major/minor axis diameters of 24/14 nm and 80/67 nm, respectively. A simple method of synthesizing semiconducting pure nanoparticles by introducing the AQ units with positively charged quaternary ammonium groups but in the absence of adscititious stabilizer or sulfonic substituent on the monomers is established first. Both the molecular weight and bulk electroconductivity of the copolymers exhibit a maximum at AQ content of 10 mol %. The solubility and film formability of the copolymers are good in highly polar solvents and reach the optimal at the AQ content of 20 and 10 mol %, respectively.

摘要

通过在三种不同的水性介质中进行化学氧化聚合反应,可轻松合成由8-氨基喹啉(AQ)和2-乙苯胺(EA)组成的纯共聚物纳米颗粒。利用聚合溶液的电位和温度成功跟踪聚合反应进程。通过红外光谱(IR)、紫外可见光谱(UV/Vis)、核磁共振(NMR)、凝胶渗透色谱法、激光粒度分析、原子力显微镜和透射电子显微镜对所得AQ/EA共聚物颗粒的分子和形态结构进行了系统表征。发现单体的氧化电位以及颗粒的聚合产率、结构和性能显著取决于AQ/EA比例、聚合温度和介质。令人惊讶的是,在5℃的HCl中,AQ均聚反应以及AQ/EA(50:50)共聚反应分别简单地得到了长径/短径直径为24/14nm和80/67nm的纳米椭球体。首次建立了一种在单体上引入带正电荷季铵基团的AQ单元,但不存在外加稳定剂或磺酸取代基的情况下合成半导体纯纳米颗粒的简单方法。共聚物的分子量和体电导率在AQ含量为10mol%时均达到最大值。共聚物在高极性溶剂中的溶解性和成膜性良好,分别在AQ含量为20mol%和10mol%时达到最佳。

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