Biological and Soft Systems, Cavendish Laboratory , University of Cambridge , Cambridge CB3 0HE , United Kingdom.
Department of Chemistry , Imperial College London , London SW7 2AZ , United Kingdom.
J Am Chem Soc. 2018 Nov 14;140(45):15384-15392. doi: 10.1021/jacs.8b09143. Epub 2018 Nov 2.
The reliable preparation of functional, ordered, nanostructured frameworks would be a game changer for many emerging technologies, from energy storage to nanomedicine. Underpinned by the excellent molecular recognition of nucleic acids, along with their facile synthesis and breadth of available functionalizations, DNA nanotechnology is widely acknowledged as a prime route for the rational design of nanostructured materials. Yet, the preparation of crystalline DNA frameworks with programmable structure and functionality remains a challenge. Here we demonstrate the potential of simple amphiphilic DNA motifs, dubbed "C-stars", as a versatile platform for the design of programmable DNA crystals. In contrast to all-DNA materials, in which structure depends on the precise molecular details of individual building blocks, the self-assembly of C-stars is controlled uniquely by their topology and symmetry. Exploiting this robust self-assembly principle, we design a range of topologically identical, but structurally and chemically distinct C-stars that following a one-pot reaction self-assemble into highly porous, functional, crystalline frameworks. Simple design variations allow us to fine-tune the lattice parameter and thus control the partitioning of macromolecules within the frameworks, embed responsive motifs that can induce isothermal disassembly, and include chemical moieties to capture target proteins specifically and reversibly.
功能有序纳米结构框架的可靠制备将成为许多新兴技术的游戏规则改变者，从能源存储到纳米医学。核酸具有出色的分子识别能力，易于合成，并且具有广泛的可用功能化，因此基于核酸的纳米技术被广泛认为是合理设计纳米结构材料的主要途径。然而，具有可编程结构和功能的结晶 DNA 框架的制备仍然是一个挑战。在这里，我们展示了简单的两亲 DNA 基序（称为“C-星”）作为可编程 DNA 晶体设计的通用平台的潜力。与完全由 DNA 组成的材料不同，后者的结构取决于单个构建块的精确分子细节，而 C-星的自组装仅由其拓扑和对称性控制。利用这一强大的自组装原理，我们设计了一系列拓扑相同但结构和化学性质不同的 C-星，它们在一锅反应中自组装成具有高比表面积、功能和结晶性的框架。简单的设计变化允许我们微调晶格参数，从而控制大分子在框架内的分配，嵌入可以诱导等温拆卸的响应性结构域，并包含化学部分以特异性和可逆地捕获靶蛋白。
