Aromatic peptides are an emerging class of building units for molecular self-assembly and creation of functional biomaterials. The strength of aromatic association plays an essential role in the self-assembly of aromatic peptides. Here, we design a series of aromatic peptides with different hydrophobic domains but the same peptide sequence. The hydrophobicity and aromaticity can be carefully regulated by the number of benzene rings and the alkyl spacer between the benzene and peptide regions. Upon the continuous enhancement of aromaticity, diverse supramolecular nanostructures, including nanotubes, nanofibers, and short helical ribbons, were clearly observed. The peptide with diphenyl groups exhibits the highest regularity of molecular packing, due to the synergy of force balance between hydrogen bonding and π–π interactions. In addition, the incorporation of a spacer in between the aromatic and peptide regions facilitates the self-assembly capability, as the interference between aromatic association and hydrogen bonding is hindered. These dramatic results demonstrate that aromaticity serves as an effective and robust parameter in the molecular arrangement, providing a new perspective into the formation and evolution of supramolecular assembly.

中文翻译：

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揭示芳香端帽对肽自组装的影响

芳香肽是一类新兴的构建单元，用于分子自组装和功能性生物材料的创建。芳香缔合的强度在芳香肽的自组装中起着至关重要的作用。在这里，我们设计了一系列具有不同疏水结构域但肽序列相同的芳香肽。疏水性和芳香性可以通过苯环的数量以及苯和肽区域之间的烷基间隔基来仔细调节。随着芳香性的不断增强，可以清晰地观察到各种超分子纳米结构，包括纳米管、纳米纤维和短螺旋带。由于氢键和π-π相互作用之间力平衡的协同作用，具有联苯基的肽表现出最高的分子堆积规律性。此外，在芳香族和肽区域之间加入间隔基有利于自组装能力，因为芳香族缔合和氢键之间的干扰受到阻碍。这些引人注目的结果表明，芳香性是分子排列中有效且稳健的参数，为超分子组装的形成和演化提供了新的视角。