Keywords :
Bioreactions; Chiral self assembly; Chiroptical spectroscopy; Delivery process; DNA-assembly; DNA-template; External stimulus; Hybridization process; Nucleobases; Photoswitch; DNA; Models, Molecular; Nucleic Acid Hybridization; Chemistry (all); Biomedical Engineering; Materials Science (all)
Abstract :
[en] 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.
Funding text :
This work was supported by the Fonds de la Recherche Scientifique – FNRS and by the French Community of Belgium within the framework of a FRIA grant for D. D. M. S. is a FNRS research director and acknowledges FNRS-FWO for EOS Grant no. 30650939. Computational resources are provided by the Consortium des Équipements de Calcul Intensif (CÉCI), funded by FNRS (Grant No. U.G.018.18) and Wallonia Region, and we acknowledge EuroCC Belgium, for awarding this project access to the LUMI supercomputer, owned by the EuroHPC Joint Undertaking, hosted by CSC (Finland) and the LUMI consortium. In addition, this research was funded by the Spanish Agencia Estatal de Investigación (AEI, project PID2020-119306GB-100) and the European Union (CLASSY project, Horizon 2020 Research and Innovation Program, Grant Agreement No. 862081).
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