Abstract
The design of artificially engineered chiral structures has received much attention, but the implementation of dynamic functions to modulate the chiroptical response of the systems is less explored. Here, we present a light-responsive G-quadruplex (G4)-based assembly in which chirality enrichment is induced, tuned, and fueled by molecular switches. In particular, the mirror-image dependence on photoactivated azo molecules, undergoing trans-to-cis isomerization, shows chiral recognition effects on the inherent flexibility and conformational diversity of DNA G4s having distinct handedness (right- and left-handed). Through a detailed experimental and computational analysis, we bring compelling evidence on the binding mode of the photochromes on G4s, and we rationalize the origin of the chirality effect that is associated with the complexation event.
Highlights
The design of artificially engineered chiral structures has received much attention, but the implementation of dynamic functions to modulate the chiroptical response of the systems is less explored
While many classes of photoresponsive compounds have been developed,[5] azobenzene (AB) switches have attracted the most attention in the field ofmolecular recognition.[6−8] The light-induced trans-to-cis isomerization of ABs can be achieved by using light of different wavelengths and is accompanied by the simultaneous change in geometry and polarity of the two different isomeric forms.[9,10]
Molecular strategies that target avoiding the use of short-wavelength UV light required to induce isomerization of the azo bond have led to the synthesis of red-shifted ABs that can be switched with the use of the visible light, offering possibilities to control biologically relevant targets in a noninvasive way.[11−13] Naturally occurring systems such as DNA, RNA, and proteins have been widely implemented as structural platforms to build stimuliresponsive nanostructured hybrid materials with adaptive and reversible functions.[1,8,14,15]
Summary
The design of artificially engineered chiral structures has received much attention, but the implementation of dynamic functions to modulate the chiroptical response of the systems is less explored. We report on the design, synthesis, and characterization of the G4-interactive binding properties of four novel bioinspired AB derivatives with differences in both the modification of the azobenzene ring and substitution pattern of the chiral pendant ligand’s arms
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