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Synthesis and self-assembly of optically active random copolymers bearing L-alanine and L-glutamic acid moieties in aqueous medium
Reactive & Functional Polymers ( IF 4.5 ) Pub Date : 2020-11-16 , DOI: 10.1016/j.reactfunctpolym.2020.104778
Mioara Murariu , Lenuta Stroea , Violeta Melinte

This study reports the synthesis by free radical polymerization and aggregation behavior of two new optically active hydrophilic random copolymers comprising glutamic acid or alanine-derived acrylamides and N-[3-(dimethylamino)propyl] methacrylamide (DMAPMA) taken in a 3:1 M ratios. Their structures, chemical composition and optical activity are confirmed by spectral analysis (FTIR, 1H/13C NMR), thermal methods (TGA, DSC), molecular weight measurements (GPC) and specific rotation measurements. In addition, surface tension, fluorescence spectroscopy, dynamic light scattering (DLS), atomic force microscopy (AFM) and transmission electron microscopy (TEM) are utilized for the characterization of the self-assemblies in solution and/or thin films. The critical aggregation concentration (CAC) determined by surface tension and fluorescence spectroscopy shows similar values of 6 × 10−2 and 5 × 10−2 g∙L−1, respectively. Steady-state fluorescence measurements using 1-pyrene-methanol as molecular probe suggest the tendency of micro-domain formation as a result of interpolymer hydrophobic interactions, while their hydrodynamic sizes are determined by DLS technique. Moreover, the micrographs from AFM technique evidence a combination of comb and brush-shaped orderly structures for the L-glutamic acid-based copolymer, and a star-type structure with four arms, in which each arm presents in turn a brush structure for the L-alanine-based copolymer.



中文翻译:

水性介质中带有L-丙氨酸和L-谷氨酸部分的光学活性无规共聚物的合成和自组装

这项研究报告了自由基聚合法合成的两种新型旋光亲水性无规共聚物,它们由谷氨酸或丙氨酸衍生的丙烯酰胺和N- [3-(二甲基氨基)丙基]甲基丙烯酰胺(DMAPMA)制成,比例为3:1 M比率。通过光谱分析(FTIR,1 H / 13NMR),热方法(TGA,DSC),分子量测量(GPC)和比旋测量。此外,表面张力,荧光光谱,动态光散射(DLS),原子力显微镜(AFM)和透射电子显微镜(TEM)用于表征溶液和/或薄膜中的自组装体。通过表面张力和荧光光谱确定的临界聚集浓度(CAC)显示相似的值6×10 -2和5×10 -2  g∙L -1, 分别。使用1-py-甲醇作为分子探针的稳态荧光测量表明,由于互聚物疏水相互作用,微区形成的趋势,而它们的流体动力学大小是通过DLS技术确定的。此外,来自AFM技术的显微照片证明了L-谷氨酸基共聚物的梳状结构和刷子状有序结构的组合,以及具有四个臂的星形结构,其中每个臂依次为L-丙氨酸基共聚物。

更新日期:2020-11-16
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