Dynamic multistimuli-responsive reversible chiral transformation in supramolecular helices

Abstract

Abstract The design of new chiral chromophores that allow tunable assembly of higher order helical structures by using natural stimuli offers promising avenue in understanding various biological processes. In particular, access to dynamic multistimuli-responsive systems can provide real-time monitoring of chiral transformation in chemical and biological systems. We report on the synthesis of naphthalenediimide appended L-glutamate (NDI-L-Glu) that self-assembles into chiral supramolecular structures under physiological conditions. Specifically, NDI-L-Glu shows a mixture of left- and right-handed helices under physiological conditions, and any deviation from the ambient biochemical environment has a remarkable influence on the chirality of these structures. For instance, acidic environments shift the helicity to left-handedness while the alkaline conditions reversed the helical structures to right-handedness, thereby mimicking the molecular virulence mechanism of tobacco mosaic virus (TMV). The chirality of these supramolecular assemblies can also be controllably tuned by using temperature as an external stimulus, allowing reversible flip of helicity.