Metallo-Folded Single-Chain Nanoparticles with Catalytic Selectivity.

Mimicking the substrate specificity and catalytic activity of enzymes is of great interest for different fields (e.g., chemistry, biology, nanomedicine). Enhanced reaction rates using artificial, enzyme-mimic catalysts based on a variety of molecular structures and nanoentities (e.g., macrocyclic compounds, star and helical polymers, dendrimers) have been previously reported. However, examples of enzyme-sized soft entities displaying substrate specificity are certainly scarce. Herein, we report the synthesis and characterization of single-chain nanoparticles based on metallo-folded polymer chains containing complexed Cu(II) ions showing catalytic specificity during the oxidative coupling of mixtures of chemically related terminal acetylene substrates. This work paves the way for the easy and efficient construction of other Pd-, Ni-, Co-, Fe-, Mn-, or Mo-containing soft nanoentities approaching the substrate specificity of natural enzymes for a variety of organic reactions.