School of Chemical Engineering and Technology, State Key Laboratory of Chemical Engineering, Tianjin University, Tianjin 300072, People's Republic of China.
Tianjin Key Laboratory of Membrane Science and Desalination Technology, Tianjin 300072, People's Republic of China.
ACS Nano. 2021 Jun 22;15(6):9827-9840. doi: 10.1021/acsnano.1c00746. Epub 2021 May 28.
Chiral self-assembly of peptides has attracted great interest owing to their promising applications in biomedicine, chemistry, and materials science. However, compared with the rich knowledge about their chiral self-assembly at the molecular or nanoscale, the formation of long-range-ordered hierarchical helical arrays (HHAs) from simple peptides remains a formidable challenge. Herein, we report the self-templated assembly of an amyloid-like dipeptide into long-range-ordered HHAs by their spontaneous fibrillization and hierarchical helical assembly within a confined film. The chiral interactions between the peptide and diamines result in geometry frustration and the phase transition of self-assembling peptide films from achiral spherulite structures into chiral HHAs. By changing the chirality and enantioselective interactions, we can control the phase behavior, handedness, and chiroptics of the self-assembled HHAs precisely. Moreover, the redox activity of the HHAs allows the decoration of nanoparticles with high catalytic activity. These results provide insights into the chiral self-assembly of peptides and the fabrication of highly ordered materials with complex architectures and promising applications in chiroptics and catalysis.
手性自组装肽因其在生物医学、化学和材料科学中的应用前景而受到广泛关注。然而，与在分子或纳米尺度上对手性自组装的丰富知识相比，由简单肽形成长程有序的分级螺旋阵列（HHAs）仍然是一个巨大的挑战。在此，我们报告了通过自下而上的纤维状形成和受限薄膜内的分级螺旋组装，将类似淀粉样的二肽自组装成长程有序的 HHAs。手性肽与二胺之间的相互作用导致手性组装肽膜的几何失配和相转变，从非手性球晶结构转变为手性 HHAs。通过改变手性和对映选择性相互作用，我们可以精确控制自组装 HHAs 的相行为、手性和手性光学性质。此外，HHAs 的氧化还原活性允许具有高催化活性的纳米粒子进行修饰。这些结果为手性肽的自组装以及具有复杂结构的高度有序材料的制造提供了新的见解，在手性光学和催化方面具有广阔的应用前景。
