亲水性单体分布对pH响应性共聚物自组装的影响：单一共聚物组成形成的球体、蠕虫状和囊泡状结构

Effect of Hydrophilic Monomer Distribution on Self-Assembly of a pH-Responsive Copolymer: Spheres, Worms and Vesicles from a Single Copolymer Composition.

作者信息

Zhang Junliang, Farias-Mancilla Barbara, Kulai Ihor, Hoeppener Stephanie, Lonetti Barbara, Prévost Sylvain, Ulbrich Jens, Destarac Mathias, Colombani Olivier, Schubert Ulrich S, Guerrero-Sanchez Carlos, Harrisson Simon

机构信息

Shaanxi Key Laboratory of Macromolecular Science and Technology, School of Chemistry and Chemical Engineering, Northwestern Polytechnical University, Xi'an, Shaanxi, 710072, P. R. China.

Laboratory of Organic and Macromolecular Chemistry (IOMC) and Jena Center for Soft Matter (JCSM), Friedrich Schiller University of Jena, Humboldtstrasse 10 (IOMC) and Philosophenweg 7 (JCSM), 07743, Jena, Germany.

出版信息

Angew Chem Int Ed Engl. 2021 Feb 23;60(9):4925-4930. doi: 10.1002/anie.202010501. Epub 2020 Nov 9.

A series of copolymers containing 50 mol % acrylic acid (AA) and 50 mol % butyl acrylate (BA) but with differing composition profiles ranging from an AA-BA diblock copolymer to a linear gradient poly(AA-grad-BA) copolymer were synthesized and their pH-responsive self-assembly behavior was investigated. While assemblies of the AA-BA diblock copolymer were kinetically frozen, the gradient-like compositions underwent reversible changes in size and morphology in response to changes in pH. In particular, a diblock copolymer consisting of two random copolymer segments of equal length (16 mol % and 84 mol % AA content, respectively) formed spherical micelles at pH >5, a mix of spherical and wormlike micelles at pH 5 and vesicles at pH 4. These assemblies were characterized by dynamic light scattering, cryo-transmission electron microscopy and small angle neutron scattering.

合成了一系列含有50摩尔%丙烯酸（AA）和50摩尔%丙烯酸丁酯（BA）的共聚物，但其组成分布不同，范围从AA - BA二嵌段共聚物到线性梯度聚（AA - grad - BA）共聚物，并研究了它们的pH响应自组装行为。虽然AA - BA二嵌段共聚物的组装在动力学上是冻结的，但梯度状组成会随着pH值的变化而在尺寸和形态上发生可逆变化。特别地，由两个等长的无规共聚物链段（AA含量分别为16摩尔%和84摩尔%）组成的二嵌段共聚物在pH >5时形成球形胶束，在pH为5时形成球形和蠕虫状胶束的混合物，在pH为4时形成囊泡。这些组装体通过动态光散射、冷冻透射电子显微镜和小角中子散射进行了表征。