Transient Metallo-Lipidoid Assemblies Amplify Covalent Catalysis of Aqueous and Non-Aqueous Reactions

Solra, M and Kapila, R and Das, S and Bhatt, P and Rana, S (2024) Transient Metallo-Lipidoid Assemblies Amplify Covalent Catalysis of Aqueous and Non-Aqueous Reactions. In: Angewandte Chemie - International Edition .

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Abstract

Dissipative supramolecular assemblies are hallmarks of living systems, contributing to their complex, dynamic structures and emerging functions. Living cells can spatiotemporally control diverse biochemical reactions in membrane compartments and condensates, regulating metabolite levels, signal transduction or remodeling of the cytoskeleton. Herein, we constructed membranous compartments using self-assembly of lipid-like amphiphiles (lipidoid) in aqueous medium. The new double-tailed lipidoid features Cu(II) coordinated with a tetravalent chelator that dictates the binding of two amphiphilic ligands in cis-orientation. Hydrophobic interactions between the lipidoids coupled with intermolecular hydrogen bonding led to a well-defined bilayer vesicle structure. Oil-soluble SNAr reaction is efficiently upregulated in the hydrophobic cavity, acting as a catalytic crucible. The modular system allows easy incorporation of exposed primary amine groups, which augments the catalysis of retro aldol and C�N bond formation reactions. Moreover, a higher-affinity chelator enables consumption of the Cu(II) template leveraging the differential thermodynamic stability, which allows a controllable lifetime of the vesicular assemblies. Concomitant temporal upregulation of the catalytic reactions could be tuned by the metal ion concentration. This work offers new possibilities for metal ion-mediated dynamic supramolecular systems, opening up a massive repertoire of functionally active dynamic �life-like� materials. © 2024 Wiley-VCH GmbH.

Item Type:	Journal Article
Publication:	Angewandte Chemie - International Edition
Publisher:	John Wiley and Sons Inc
Additional Information:	The copyright for this article belongs to John Wiley and Sons Inc.
Keywords:	Amines; Chelation; Copper compounds; Covalent bonds; Hydrogen bonds; Hydrophobicity; Ketones; Metabolites; Metal ions; Signal transduction; Sulfur compounds; Supramolecular chemistry, Aqueous reactions; Biochemical reactions; Complex dynamics; Dynamic structure; Lipidoid; Living cell; Living systems; Non-aqueous; Supramolecular; Supramolecular assemblies, Catalysis
Department/Centre:	Division of Chemical Sciences > Materials Research Centre
Date Deposited:	15 May 2024 04:05
Last Modified:	15 May 2024 04:05
URI:	https://eprints.iisc.ac.in/id/eprint/84467

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