Selectivity in the chiral self-assembly of nucleobase-arylazopyrazole photoswitches along DNA templates

Abstract

The control of supramolecular DNA assembly through external stimuli such as light represents a promising approach to control bioreactions, and modulate hybridization or delivery processes. Here, we report on the design of nucleobase-containing arylazopyrazole photoswitches that undergo chiral organization upon self-assembly along short DNA templates. Chiroptical spectroscopy shows that the specific nucleobases allow selectivity in the resulting supramolecular DNA complexes, and UV light irradiation triggers partial desorption of the arylazopyrazole photoswitches. Molecular modeling studies reveal the differences of binding modes between the two configurations in the templated assembly. Remarkably, our results show that the photoswitching behaviour controls the self-assembly process along DNA, opening the way to potential applications as nano- and biomaterials.