Programmable Micelles from DNA-Block Copolymers: Hierarchical Assembly of Catalytically Active Nanostructures

DNA分子是现代科学的标志之一，代表了自然界中最多功能的分子结构之一。利用DNA构建2D和3D纳米结构是基于其独特的和可逆的识别特性。DNA可以单独形成这些纳米结构的骨架，或者DNA可以作为连接物或模板与其他材料形成DNA杂化纳米结构。在这项提议中，我们将探索基于DNA的纳米粒子的分级组装，即DNA嵌段共聚胶束，以及它们作为新催化系统的支架的应用。1)插层催化剂在DS-DNA嵌段共聚胶束电晕中的手性催化作用。可以预见，最近开发的基于DNA的不对称催化的高对映选择性与胶束催化中观察到的非凡的速率增强相结合，导致了将水环境中的高活性与高对映选择性相结合的催化系统。2)DNA嵌段共聚胶束电晕上的级联反应。在这项提议中，将探索不同催化部分在DNA嵌段共聚胶束的电晕中的模块化组装，以在定义明确的隔间空间内执行催化级联反应。3)通过附着在电晕上的催化剂控制胶束核心的包封化合物的释放。这可能导致在药物输送领域的重要应用，因为DNA嵌段共聚物胶束和催化的结合将允许在治疗期间的特定时间触发释放过程。这项拟议的研究处于聚合物化学、生物纳米技术和化学催化的交界处，代表了一种全新的方法，可以实现新催化系统的分级组装。因此，预计将对超分子化学和催化界产生深远的影响。

The DNA molecule, one of the icons of modern science, represents one of the most versatile molecular structures in nature. The use of DNA to build up 2D- and 3D-nanostructures is based on its unique and reversible recognition properties. DNA alone can form the skeleton of these nanostructures, alternatively DNA can serve as an interconnector or template to form DNA-hybrid-nanostructures with other materials. In this proposal we will explore the hierarchical assembly of DNA-based nanoparticles, i.e. DNA block copolymer micelles, and their application as a scaffold for new catalytic systems. The following three applications will be pursued:1) Chiral Catalysis in the corona of ds-DNA block copolymer micelles by intercalating catalysts. It is envisioned that combination of high enantioselectivity of the recently developed DNA-based asymmetric catalysis with the extraordinary rate enhancements observed in micellar catalysis, leading to catalytic systems that combine high activity in aqueous environments with high enantioselectivity.2) Cascade reactions on the corona of DNA block copolymer micelles. In this proposal the modular assembly of different catalytic moieties in the corona of DNA block copolymer micelles will be explored to perform catalytic cascade reactions in a well-defined compartmentalised space.3) Controlled release of encapsulated compounds from the core of the micelle by a catalyst attached to the corona. This could lead to important applications in the area of drug delivery, since the combination of DNA-block copolymer micelles and catalysis will allow the release process to be triggered at a specific time during treatment. This proposed research, which is at the interface of polymer chemistry, bio-nanotechnology, and chemical catalysis, represents a fundamentally new approach towards the hierarchical assembly of new catalytic systems. As such is expected to have a profound impact on both the supramolecular chemistry and catalysis community.