Article Overview

Living systems can utilize homochiral building blocks to synchronously assemble diverse structures with opposite handedness (e.g., right-handed α-helices and left-handed polyproline type II helices), thereby maintaining the three-dimensional conformation and functionality of biological structures. However, replicating this process in artificial systems remains a significant challenge due to the difficulty in constructing precise noncovalent interaction patterns to achieve diversified chirality transfer. Professor Feng Chuan-liang's team from Shanghai Jiao Tong University has reported a strategy: by ingeniously introducing symbiotic noncovalent sites at the terminus of an L-phenylalanine derivative (LCN), helical nanofibers featuring both P-type and M-type substructural domains were prepared. Leveraging conformational matching between LCN molecules, the two symbiotic sites within the terminal cyanophenyl group (C≡N and ortho Ar─H) can cooperatively form distinct noncovalent interactions (C≡N⋯meta Ar─H; ortho Ar─H⋯N≡C) with different sites, thereby constructing a precise network of noncovalent interactions. Furthermore, these two noncovalent interactions, having opposite spatial orientations, can synchronously induce the formation of M-type and P-type substructural domains. A similar phenomenon was observed in the symbiotic sites (O, H) of the hydroxyl group at the other terminus, further evidencing a unique chirality transfer mode—homochirality at the molecular level can be transferred to opposite-handed structural domains at the supramolecular level. Notably, these helical substructural domains can further cooperatively assemble into higher-order P-type helices, with the long axis of the nanofiber aligned with the helical axis defined by the noncovalent interactions. This research deepens the understanding of diverse chirality transfer mechanisms based on homochirality in nature and opens a new avenue for utilizing homochiral building blocks to prepare helical nanostructures containing diverse sub-helical domains.

This article, titled "Conformation-Matched Symbiotic Noncovalent Sites Facilitated Supramolecular Nanotwists Featuring both P and M Sub-Helical Domains," was published in Angewandte Chemie International Edition.