Realizing Abundant Chirality Inversion of Supramolecular Nanohelices by Multiply Manipulating the Binding Sites in Molecular Blocks.

Multiple binding sites of biomolecules induced diverse chirality regulation is ubiquitous in nature and play an essential role in determining the biofunction of biosystems. However, mimicking this biological phenomenon and understand its mechanism from multiple binding sites at molecular level by establishing an artificial system still remains a challenge. Herein, the abundant chirality inversion is achieved by precisely and multiply manipulating the co-assembled binding sites of phenylalanine derivatives (D/LPPF) with different naphthalene derivatives (NA, NC, NP, NF). The amide and hydroxyl group of naphthalene derivatives prefer to bind with carboxyl of LPPF, while carboxylic and fluoride atom tend to bind with amide of LPPF. All these diverse interaction modes can precisely trigger the helicity inversion of LPPF nanofibers. In addition, synergistically manipulating the carboxyl and amide binding sites from a single LPPF molecule to simultaneously interact with different naphthalene derivatives is realized for chirality regulation. Typically, the variation of solvent may switch the interaction modes and the switched new interaction modes can be employed to further regulate the chirality of LPPF nanofibers. This study may provide a novel approach to explore the chirality diversity in artificial systems by regulating the intermolecular binding sites.