Light-switchable enzyme-mimetic organocatalysis in water via supramolecular assembly
Divya Chauhan1,2, Pratheepkumar Annamalai2, Arup Sinha2
1(Organic) Materials and Engineering Laboratory, Vellore Institute of Technology (VIT), Vellore, India.
Abstract:
Light-regulated control over catalytic activity is a key step toward adaptive and programmable chemical systems. Here, we report a minimalistic supramolecular organocatalytic platform that enables reversible spatiotemporal regulation of enzyme-mimetic activity in water using light as a non-invasive trigger. An azobenzene-imidazole conjugate (Azo-Imd) integrates a photoresponsive molecular switch with a catalytically active imidazole unit. In aqueous media, Azo-Imd self-assembles into vesicular nanostructures, while light-induced trans→cis isomerization drives a vesicle→micelle transition. Supramolecular complexation with β-cyclodextrin acts as a molecular gate, suppressing catalysis in the trans ("OFF") state through host-guest complexation. Photoisomerization disrupts this interaction, releasing the catalyst that self-assembly to micelle structure and restoring activity in the cis ("ON") state, with full reversibility achieved via thermal back-isomerization. The system exhibits hydrolase-like behaviour, Michaelis-Menten kinetics, and precise light-controlled modulation of catalytic rates. This strategy provides a general framework for environmentally benign, light-gated supramolecular catalysis.
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