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.
Highlights
Chirality is one of the most fascinating natural phenomena, leading to a specific handedness of biological structures, and directing the biochemistry to choose a specific homochirality in life processes[1,2,3]
Our current work demonstrates that akin to the biological systems, the NDI-L-Glu complex is able to self-assemble into chiral supramolecular helices under physiological conditions; and the deviation from the physiological environment leads to reversible chiral transformation in the structure of NDI-L-Glu super-helices
We present a supramolecular helical assembly that can be tuned to the opposite helicity by controlling pH and temperature with a small N-substituted NDI molecule for the first time (Fig. 1)
Summary
Chirality is one of the most fascinating natural phenomena, leading to a specific handedness of biological structures, and directing the biochemistry to choose a specific homochirality in life processes[1,2,3]. In particular, multiple glutamate (Glu) residues play an important role in disrupting the chirality of the TMV capsid superstructure[5]. There is no doubt that the control of the helicity in man-made supramolecular ensembles is of utmost significance, as it is closely connected with the topic of chirality transmission[11] This has important mechanistic implications in life sciences. Another well-known example in the human body is sickle cell anaemia that is caused by the replacement of glutamate with valine in the β-globin chain of haemoglobin, leading to protein aggregation[42]. Our current work demonstrates that akin to the biological systems, the NDI-L-Glu complex is able to self-assemble into chiral supramolecular helices under physiological conditions; and the deviation from the physiological environment leads to reversible chiral transformation in the structure of NDI-L-Glu super-helices
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