Bellan Riccardo, Attia David, van Genderen Marcel H P, Dankers Patricia Y W
Institute for Complex Molecular Systems and Department of Biomedical Engineering, Eindhoven University of Technology, 5600 MB, Eindhoven, The Netherlands.
Department of Chemical Engineering and Chemistry, Eindhoven University of Technology, 5600 MB, Eindhoven, The Netherlands.
Chemistry. 2025 Jun 12;31(33):e202500429. doi: 10.1002/chem.202500429. Epub 2025 May 15.
Supramolecular biomaterials based on 1D supramolecular polymers in water replicate the fibrous and dynamic structures of natural architectures. Peptides, valued for their biocompatibility, are commonly employed as building blocks for supramolecular biomaterials, often in combination with large aromatic or hydrogen-bonding groups at the N-terminus to improve their structural stability. Herein, the self-assembly properties of two β-sheet peptides combined with the ureido-pyrimidinone self-dimerizing motif in aqueous solution are investigated in detail. The assembly of the resulting molecules is demonstrated to be intimately dependent on the β-sheet sequence, while the incorporation of a hydrophobic spacer enhances the assembly of the monomers, irrespective of the peptide sequence employed. Furthermore, the assembly of each monomer is significantly enhanced at pH = 3.0 while being stable between pH = 5.0 and 9.0. Only at pH = 12, upon enolate formation, the transition to random coil conformation is observed for all the monomers. The supramolecular polymers developed hereby point to fundamental design principle toward the development of UPy-peptide based materials with tuneable properties and potential applications in the biomedical fields of research.
基于一维超分子聚合物在水中形成的超分子生物材料，复制了天然结构的纤维状和动态结构。肽因其生物相容性而受到重视，通常被用作超分子生物材料的构建单元，并且常在N端与大的芳香族或氢键基团结合使用，以提高其结构稳定性。在此，详细研究了两种β-折叠肽与脲基嘧啶酮自二聚基序在水溶液中的自组装性质。结果表明，所得分子的组装紧密依赖于β-折叠序列，而引入疏水间隔基则增强了单体的组装，与所采用的肽序列无关。此外，每种单体在pH = 3.0时组装显著增强，而在pH = 5.0至9.0之间保持稳定。仅在pH = 12时，烯醇盐形成后，观察到所有单体向无规卷曲构象转变。由此开发的超分子聚合物为开发具有可调性质且在生物医学研究领域具有潜在应用的基于UPy-肽的材料指明了基本设计原则。
