Oliver Alex M, Gwyther Jessica, Boott Charlotte E, Davis Sean, Pearce Samuel, Manners Ian
School of Chemistry , University of Bristol , Bristol , BS8 1TS , U.K.
Department of Chemistry , University of Victoria , Victoria , British Columbia, V8W 3V6 , Canada.
J Am Chem Soc. 2018 Dec 26;140(51):18104-18114. doi: 10.1021/jacs.8b10993. Epub 2018 Dec 14.
Self-assembled 1D block copolymer nanoparticles (micelles) are of interest for a range of applications. However, morphologically pure samples are often challenging to access, and precise dimensional control is not possible. Moreover, the development of synthetic protocols that operate on a commercially viable scale has been a major challenge. Herein, we describe the preparation 1D fiber-like micelles with crystalline cores at high concentrations by a one-pot process termed polymerization-induced crystallization-driven self-assembly (PI-CDSA). We also demonstrate the formation of uniform fibers by living PI-CDSA, a process in which block copolymer synthesis, self-assembly, and seeded growth are combined. We have demonstrated that the method is successful for block copolymers that possess the same composition as that of the seed (homoepitaxial growth) and also where the coronal chemistries differ to give segmented 1D fibers known as block co-micelles. We have also shown that heteroepitaxial growth allows the formation of scaled-up block co-micelles where the composition of both the core and corona was varied. These proof-of-concept experiments indicate that PI-CDSA is a promising, scalable route to a variety of polydisperse or uniform 1D nanoparticles based on block copolymers with different crystalline core chemistries and, therefore, functions.
自组装一维嵌段共聚物纳米颗粒（胶束）在一系列应用中备受关注。然而，获得形态纯净的样品往往具有挑战性，且无法进行精确的尺寸控制。此外，开发具有商业可行性规模的合成方案一直是一项重大挑战。在此，我们描述了通过一种称为聚合诱导结晶驱动自组装（PI-CDSA）的一锅法，在高浓度下制备具有结晶核的一维纤维状胶束。我们还展示了通过活性PI-CDSA形成均匀纤维，该过程将嵌段共聚物合成、自组装和种子生长结合在一起。我们已经证明，该方法对于与种子具有相同组成的嵌段共聚物（同质外延生长）以及冠层化学性质不同以形成称为嵌段共胶束的分段一维纤维的情况都是成功的。我们还表明，异质外延生长允许形成放大的嵌段共胶束，其中核和冠层的组成都有所变化。这些概念验证实验表明，PI-CDSA是一种有前途的、可扩展的途径，可用于制备基于具有不同结晶核化学性质和功能的嵌段共聚物的各种多分散或均匀的一维纳米颗粒。
