Ding Xiangmin, Liu Dandan, Jiang Xi, Chen Xuesi, Zuckermann Ronald N, Sun Jing
State Key Laboratory of Supramolecular Structure and Materials, College of Chemistry, Jilin University, Changchun 130012, China.
Key Laboratory of Biobased Polymer Materials, College of Polymer Science and Engineering, Qingdao University of Science and Technology, Qingdao 266042, China.
ACS Nano. 2022 Jul 26;16(7):10470-10481. doi: 10.1021/acsnano.2c01171. Epub 2022 May 31.
The interplay of crystalline packing, which governs atomic length-scale order, and hierarchical assembly, which governs longer length scales, is essential to fabricate complex superstructures from polymers for many applications. Here, we demonstrate that a diblock copolymer containing an -octylglycine peptoid block, which has a propensity to crystallize, can form distinct hierarchical superstructures including a star-like morphology, a superbrush, or a nanosheet by tuning the balance between surface energy arising from the solubility of the copolymers and crystallization energy of the solvophobic polypeptoid blocks. We show that partially ordered micellar aggregates (clusters) are key intermediates that form early in the assembly process and template the formation of superstructures via the oriented fusion of individual micelles as the growth materials. Notably, the fiber-like branch of the superstructures is driven by crystallization and exhibits growth in a living linear manner. The superstructures can be internalized by mammalian cells and hold promise for biomedical applications.
控制原子长度尺度有序性的晶体堆积与控制更长长度尺度的分级组装之间的相互作用，对于从聚合物制造用于许多应用的复杂超结构至关重要。在此，我们证明，含有易于结晶的辛基甘氨酸类肽嵌段的二嵌段共聚物，可通过调节共聚物溶解度产生的表面能与疏溶剂性类肽嵌段的结晶能之间的平衡，形成包括星状形态、超刷或纳米片在内的不同分级超结构。我们表明，部分有序的胶束聚集体（簇）是在组装过程早期形成的关键中间体，并通过作为生长材料的单个胶束的定向融合来模板化超结构的形成。值得注意的是，超结构中纤维状分支由结晶驱动，并以活性线性方式生长。这些超结构可被哺乳动物细胞内化，并在生物医学应用方面具有前景。
