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. © 2014 American Chemical Society.Financial support from the Projects MAT2012-31088 (MINECO), T-654-13 (GV) and S-PE13UN034 (GV) is acknowledged. A. S.-S. thanks the Ph.D. grant support of Basque Government. This work has been supported by the European Commission under the 7th Framework Programme through the “Research Infra-structures” action of the “Capacities” Programme, NMI3-II Grant Number 283883.Peer Reviewe