Tuning of the Supramolecular Helicity of Peptide-Based Gel Nanofibers

Helical supramolecular architectures play important structural and functional roles in biological systems. The helicity of synthetic molecules can be tuned mainly by the chiral manipulation of the system. However, tuning of helicity by the achiral unit of the molecules is less studied. In this work, the helicity of naphthalimide-capped peptide-based gel nanofibers is tuned by the alteration of methylene units present in the achiral amino acid. The inversion of supramolecular helicity has been extensively studied by CD spectroscopy and morphological analysis. The density functional theory (DFT) study indicates that methylene spacers influence the orientation of π–π stacking interactions of naphthalimide units in the self-assembled structure that regulates the helicity. This work illustrates a new approach to tuning the supramolecular chirality of self-assembled biomaterials.