Topology‐Induced Chiral Amplification and Inversion in Self‐Assembling Dipeptide Films

Abstract

AbstractSelf‐assembly of peptides into highly ordered chiral nanostructures has great potential applications in optics, sensing, biomedicine, and templated synthesis. However, the detailed mechanism for the chiral amplification and spontaneous ordering during the self‐assembly of peptides remains largely unexplored. Here, it is shown that by topology control of the co‐assembly of a simple dipeptide and a chiral diamine within a confined film, the supramolecular structures can be controlled precisely from hierarchically organized helical bundles to microcrystals and then parallel aligned nanohelices. The peptide and diamines can co‐assemble into aligned microcrystals when the molar ratio (χ = Cdiamine/Cpeptide) of the two components is 0.5. However, by changing the χ value, excess peptides or diamines create topological defects during the self‐assembly process. This leads to chiral amplification and the formation of long‐range‐ordered nanohelical arrays with controlled phase behaviors. Moreover, the formation of right‐ or left‐handed nanohelices can be further inversed by the topological control, without the need to change the chirality of the peptides. These findings provide new insights into the chiral self‐assembly of amyloid‐related peptides and offer a facile strategy to fabricate highly ordered functional materials.