School of Chemistry, University of Bristol, Bristol BS8 1TS, UK.
Science. 2012 Aug 3;337(6094):559-62. doi: 10.1126/science.1221206.
Although solution self-assembly of block copolymers (BCPs) represents one of the most promising approaches to the creation of nanoparticles from soft matter, the formation of non-centrosymmetric nanostructures with shape anisotropy remains a major challenge. Through a combination of crystallization-driven self-assembly of crystalline-coil BCPs in solution and selective micelle corona cross-linking, we have created short (about 130 nanometers), monodisperse cylindrical seed micelles that grow unidirectionally. These nanostructures grow to form long, non-centrosymmetric cylindrical A-B and A-B-C block co-micelles upon the addition of further BCPs. We also illustrate the formation of amphiphilic cylindrical A-B-C block co-micelles, which spontaneously self-assemble into hierarchical star-shaped supermicelle architectures with a diameter of about 3 micrometers. The method described enables the rational creation of non-centrosymmetric, high aspect ratio, colloidally stable core-shell nanoparticles in a manner that until now has been restricted to the biological domain.
虽然嵌段共聚物（BCPs）的溶液自组装代表了一种最有前途的从软物质中创建纳米粒子的方法，但具有形状各向异性的非中心对称纳米结构的形成仍然是一个主要挑战。通过结晶诱导的溶液中晶-胶嵌段共聚物的自组装与选择性胶束冠交联的结合，我们创建了短（约 130 纳米）、单分散的圆柱形种子胶束，这些胶束能够单向生长。在加入更多的 BCP 后，这些纳米结构会生长形成长的、非中心对称的圆柱形 A-B 和 A-B-C 嵌段共聚物胶束。我们还说明了两亲性圆柱形 A-B-C 嵌段共聚物胶束的形成，这些胶束能够自发地自组装成具有约 3 微米直径的分级星形超胶束结构。所描述的方法能够以一种以前仅限于生物领域的方式合理地创建非中心对称、高纵横比、胶体稳定的核壳纳米粒子。
