Guided hierarchical co-assembly of soft patchy nanoparticles
Guided hierarchical co-assembly of soft patchy nanoparticles
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DOI：
10.1038/nature12610
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发表时间：
2013-11-14
期刊：
影响因子：
64.8
通讯作者：
Mueller, Axel H. E.
中科院分区：
文献类型：
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作者：
Groeschel, Andre H.;Walther, Andreas;Mueller, Axel H. E.
天然材料中通常遇到的层次自下而上结构的概念为具有先进功能的复杂人造材料设计提供了灵感（1,2）。自然过程已经在许多长度尺度上实现了多组分系统的编排（3,4），但是人造的自组装仍然面临着实现明确定义明确的层次结构（5-11）的障碍。在基于粒子的自组装中，挑战是通过提供合适的形状各向异性或各向异性相互作用模式（'patches'）的单分散构件来编程上层建筑的对称性和周期。粒子体系结构中的不规则性是无法忍受的，因为它们会产生在整个层次级别扩增的缺陷。对于斑点的微观硬胶胶体，通过使用自上而下的方法（例如金属阴影或微接合印刷）来应对这一挑战，从而在聚集过程中实现了分子样方向性（12-16）。但是，基于分子组装的自上而下的程序和颗粒系统都难以在所需的尺寸状态（10-100 nm）中控制斑块颗粒。在这里，我们介绍了动态斑块纳米颗粒的共同组装，即柔软的斑块纳米颗粒，它们本质上是自我组装和单分散的 - 作为一种模块化方法，是一种生产有序的二进制和三元二进制和三元上的上部层层。我们通过引导三嵌段的培训（长度尺度10 nm）来形成柔软的片状纳米颗粒（20-50 nm），从而桥接三个层次级别的水平，这些纳米颗粒（20-50 nm）的不同对称性结合结合在一起，共同组合成潜在的，分裂的材料（> 10 mu m）具有可预测且可调的纳米级周期性。我们确定了分子对聚合物组成的控制程序如何编程构建块对称并调节粒子定位，从而提供了有序的高复杂性混合介质结构的途径。
The concept of hierarchical bottom-up structuring commonly encountered in naturalmaterials provides inspiration for the design of complex artificial materials with advanced functionalities(1,2). Natural processes have achieved the orchestration of multicomponent systems across many length scales with very high precision(3,4), but man-made self-assemblies still face obstacles in realizing well-defined hierarchical structures(5-11). In particle-based self-assembly, the challenge is to program symmetries and periodicities of superstructures by providing monodisperse building blocks with suitable shape anisotropy or anisotropic interaction patterns ('patches'). Irregularities in particle architecture are intolerable because they generate defects that amplify throughout the hierarchical levels. For patchy microscopic hard colloids, this challenge has been approached by using top-down methods (such as metal shading or microcontact printing), enabling molecule-like directionality during aggregation(12-16). However, both top-down procedures and particulate systems based on molecular assembly struggle to fabricate patchy particles controllably in the desired size regime (10-100 nm). Here we introduce the co-assembly of dynamic patchy nanoparticles-that is, soft patchy nanoparticles that are intrinsically self-assembled and monodisperse-as a modular approach for producing well-ordered binary and ternary supracolloidal hierarchical assemblies. We bridge up to three hierarchical levels by guiding triblock terpolymers (length scale 10 nm) to form soft patchy nanoparticles (20-50 nm) of different symmetries that, in combination, co-assemble into substructured, compartmentalized materials (>10 mu m) with predictable and tunable nanoscale periodicities. We establish how molecular control over polymer composition programs the building block symmetries and regulates particle positioning, offering a route to well-ordered mixed mesostructures of high complexity.