Biomimetic self-templating supramolecular structures
Biomimetic self-templating supramolecular structures
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DOI：
10.1038/nature10513
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发表时间：
2011-10-20
期刊：
影响因子：
64.8
通讯作者：
Lee, Seung-Wuk
中科院分区：
文献类型：
--
作者：
Chung, Woo-Jae;Oh, Jin-Woo;Lee, Seung-Wuk
在自然界中，螺旋大分子如胶原蛋白、几丁质和纤维素对于各种分层结构材料的形态发生和功能至关重要（1-3）。在组织形成过程中，这些手性大分子被分泌并经历自模板组装，这是一个多个动力学因素影响进入的结构单元组装以产生非平衡结构的过程（1，4）。单个大分子在不同条件下自模板化可以形成多种功能结构。例如，I型胶原蛋白由正交排列的纤维形成透明角膜组织（5），由纤维相纤维束形成独特颜色的皮肤组织（6，7），以及由分层组织的纤维形成矿化组织（8）。自然界的自模板材料超越了目前自上而下和自下而上的制造方法所能实现的功能和结构复杂性（9-12）。然而，自模板还没有被彻底探索的工程合成材料。在这里，我们展示了仿生，自模板组装的手性胶体粒子（M13噬菌体）成功能材料。一个单步过程产生长程有序，超分子膜显示多级的层次组织和螺旋扭曲。三种不同的超分子结构是通过这种方法创建：正交扭曲，螺旋带和近晶螺旋纳米纤维。手性液晶相转变和竞争的界面处的界面力被发现是决定组装过程中的模板结构的形态的关键因素。由此产生的材料显示出独特的光学和光子特性，作为手性反射器/过滤器和结构颜色矩阵。此外，M13与基因结合的生物活性肽配体一起以分级组织的方式指导软组织和硬组织的生长。我们的组装方法提供了深入了解自然界中的层次组装的复杂性，并可以扩展到其他手性分子工程师复杂的功能螺旋扭曲结构。
In nature, helical macromolecules such as collagen, chitin and cellulose are critical to the morphogenesis and functionality of various hierarchically structured materials(1-3). During tissue formation, these chiral macromolecules are secreted and undergo self-templating assembly, a process whereby multiple kinetic factors influence the assembly of the incoming building blocks to produce non-equilibrium structures(1,4). A single macromolecule can form diverse functional structures when self-templated under different conditions. Collagen type I, for instance, forms transparent corneal tissues from orthogonally aligned nematic fibres(5), distinctively coloured skin tissues from cholesteric phase fibre bundles(6,7), and mineralized tissues from hierarchically organized fibres(8). Nature's self-templated materials surpass the functional and structural complexity achievable by current top-down and bottom-up fabrication methods(9-12). However, self-templating has not been thoroughly explored for engineering synthetic materials. Here we demonstrate the biomimetic, self-templating assembly of chiral colloidal particles (M13 phage) into functional materials. A single-step process produces long-range-ordered, supramolecular films showing multiple levels of hierarchical organization and helical twist. Three distinct supramolecular structures are created by this approach: nematic orthogonal twists, cholesteric helical ribbons and smectic helicolidal nanofilaments. Both chiral liquid crystalline phase transitions and competing interfacial forces at the interface are found to be critical factors in determining the morphology of the templated structures during assembly. The resulting materials show distinctive optical and photonic properties, functioning as chiral reflector/filters and structural colour matrices. In addition, M13 phages with genetically incorporated bioactive peptide ligands direct both soft and hard tissue growth in a hierarchically organized manner. Our assembly approach provides insight into the complexities of hierarchical assembly in nature and could be expanded to other chiral molecules to engineer sophisticated functional helical-twisted structures.