Key Laboratory of Precise Synthesis of Functional Molecules of Zhejiang Province, Department of Chemistry, School of Science, Westlake University, Institute of Natural Sciences, Westlake Institute for Advanced Study, No. 600 Dunyu Road, Hangzhou, 310024, Zhejiang Province, China.
Westlake Laboratory of Life Sciences and Biomedicine, School of Life Sciences, Westlake University, Hangzhou, 310024, Zhejiang, China.
Angew Chem Int Ed Engl. 2023 Sep 4;62(36):e202303455. doi: 10.1002/anie.202303455. Epub 2023 Jul 26.
Chirality correction, asymmetry, ring-chain tautomerism and hierarchical assemblies are fundamental phenomena in nature. They are geometrically related and may impact the biological roles of a protein or other supermolecules. It is challenging to study those behaviors within an artificial system due to the complexity of displaying these features. Herein, we design an alternating D,L peptide to recreate and validate the naturally occurring chirality inversion prior to cyclization in water. The resulting asymmetrical cyclic peptide containing a 4-imidazolidinone ring provides an excellent platform to study the ring-chain tautomerism, thermostability and dynamic assembly of the nanostructures. Different from traditional cyclic D,L peptides, the formation of 4-imidazolidinone promotes the formation of intertwined nanostructures. Analysis of the nanostructures confirmed the left-handedness, representing chirality induced self-assembly. This proves that a rationally designed peptide can mimic multiple natural phenomena and could promote the development of functional biomaterials, catalysts, antibiotics, and supermolecules.
手性校正、不对称性、环链互变异构和分级组装是自然界中的基本现象。它们在几何上是相关的，可能影响蛋白质或其他超分子的生物学作用。由于在人工系统中显示这些特征的复杂性，研究这些行为具有挑战性。在此，我们设计了一种交替的 D，L 肽，以在水中环化之前重新创建和验证自然发生的手性反转。所得含有 4-咪唑烷酮环的不对称环状肽为研究纳米结构的环链互变异构、热稳定性和动态组装提供了极好的平台。与传统的环状 D，L 肽不同，4-咪唑烷酮的形成促进了缠结纳米结构的形成。对纳米结构的分析证实了左手性，代表了手性诱导的自组装。这证明了合理设计的肽可以模拟多种自然现象，并可以促进功能生物材料、催化剂、抗生素和超分子的发展。
