Department of Materials Science and Engineering, Yonsei University, 50 Yonsei-ro, Seoul, 03722, Korea.
Angew Chem Int Ed Engl. 2016 Sep 19;55(39):12003-7. doi: 10.1002/anie.201605696. Epub 2016 Aug 24.
To overcome the limitations of molecular assemblies, the development of novel supramolecular building blocks and self-assembly modes is essential to create more sophisticated, complex, and controllable aggregates. The self-assembly of peptide-DNA conjugates (PDCs), in which two orthogonal self-assembly modes, that is, β-sheet formation and Watson-Crick base pairing, are covalently combined in one supramolecular system, is reported. Despite extensive research, most self-assembly studies have focused on using only one type of building block, which restricts structural and functional diversity compared to multicomponent systems. Multicomponent systems, however, suffer from poor control of self-assembly behaviors. Covalently conjugated PDC building blocks are shown to assemble into well-defined and controllable nanostructures. This controllability likely results from the decrease in entropy associated with the restriction of the molecular degrees of freedom by the covalent constraints. Using this strategy, the possibility to thermodynamically program nano-assemblies to exert gene regulation activity with low cytotoxicity is demonstrated.
为了克服分子组装的局限性，开发新型超分子构建模块和自组装模式对于创建更复杂、更精细和更可控的聚集体至关重要。本文报道了肽-DNA 缀合物（PDC）的自组装，其中两种正交的自组装模式，即β-折叠形成和 Watson-Crick 碱基配对，在一个超分子系统中通过共价键结合。尽管已经进行了广泛的研究，但大多数自组装研究都集中于仅使用一种类型的构建模块，这与多组分系统相比限制了结构和功能的多样性。然而，多组分系统在自组装行为的控制方面存在困难。实验证明，共价键合的 PDC 构建模块可以组装成具有良好定义和可控的纳米结构。这种可控性可能源于通过共价键的约束限制分子自由度所导致的熵的减少。通过使用这种策略，有可能通过热力学编程纳米组装来发挥具有低细胞毒性的基因调控活性。
