Two-dimensional (2D) platelet structures with uniform dimensions and spatially defined diverse cores are highly sought but are still challenging to access. Living crystallization-driven self-assembly (CDSA)-seeded growth enables the creation of uniform 2D core–shell nanomaterials with diverse core compositions via sequential epitaxial crystallization of block copolymers. Nevertheless, general limitation of the growth process to strict requirements of heteroepitaxial crystallization is a major obstacle to the formation of segmented nanoparticles with extended diverse core chemistries. Herein, we introduce a strategy of using double-crystalline triblock copolymers, such as poly(ε-caprolactone)-block-poly(p-dioxanone)-block-poly(N,N-dimethyl acrylamide) (PCL-b-PPDO-b-PDMA), as bridges to create segmented platelets with compositionally distinct cores. The epitaxial crystallization of the PCL block excludes the PPDO block, forming out-of-plane PPDO crystals that seed subsequent epitaxial crystallization of the added PPDO unimer, producing flat-on quasi-square PPDO crystals. Meanwhile, the less-defined orientation of PPDO crystals has confirmed the presence of flat-on epitaxy between PCL and PPDO. For comparison, PCL-b-PHL (PHL = poly(ζ-heptalactone)) forms in-plane crystals with a strictly defined orientation via edge-on epitaxy due to the cocrystallization of PCL and PHL. Therefore, this approach provides a novel route to construct precisely controlled segmented 2D platelet structures with chemically distinct cores and tunable functionalities, an extension to expand the precise design of complex nanoparticles.

中文翻译：

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使用双结晶三嵌段共聚物创建具有不同结晶核心的分段片状片


具有统一尺寸和空间定义的不同核心的二维 （2D） 血小板结构备受追捧，但仍然难以接近。活结晶驱动的自组装 （CDSA） 种子生长能够通过嵌段共聚物的连续外延结晶创建具有不同核心成分的均匀 2D 核壳纳米材料。然而，生长过程通常受限于异质外延结晶的严格要求，这是形成具有扩展多样化核心化学成分的分段纳米颗粒的主要障碍。在此，我们介绍了一种使用双晶三嵌段共聚物的策略，例如聚（ε-己内酯）-嵌段-聚（对二恶烷酮）-嵌段-聚（N，N-二甲基丙烯酰胺）（PCL-b-PPDO-b-PDMA），作为桥梁，以创建具有成分不同核心的分段片状片状物。PCL 嵌段的外延结晶排除了 PPDO 嵌段，形成面外 PPDO 晶体，这些晶体随后为添加的 PPDO 单聚体的外延结晶接种，产生平开准方形 PPDO 晶体。同时，PPDO 晶体的取向不太明确，证实了 PCL 和 PPDO 之间存在平开外延。相比之下，由于 PCL 和 PHL 的共结晶，PCL-b-PHL （PHL = 聚（ζ-七内酯）） 通过边缘外延形成具有严格定义取向的面内晶体。因此，这种方法提供了一种新的途径来构建具有化学不同核心和可调功能的精确控制的分段 2D 血小板结构，扩展了复杂纳米颗粒的精确设计。