Efficient synthesis of single-chain polymer nanoparticles via amide formation

This is an open access article distributed under the Creative Commons Attribution License.Single-chain technology (SCT) allows the transformation of individual polymer chains to folded/collapsed unimolecular soft nanoparticles. In this work we contribute to the enlargement of the SCT toolbox by demonstrating the efficient synthesis of single-chain polymer nanoparticles (SCNPs) via intrachain amide formation. In particular, we exploit cross-linking between active methylene groups and isocyanate moieties as powerful >click> chemistry driving force for SCNP construction. By employing poly(methyl methacrylate)- (PMMA-) based copolymers bearing β-ketoester units distributed randomly along the copolymer chains and bifunctional isocyanate cross-linkers, SCNPs were successfully synthesized at r.t. under appropriate reaction conditions. Characterization of the resulting SCNPs was carried out by means of a combination of techniques including size exclusion chromatography (SEC), infrared (IR) spectroscopy, proton nuclear magnetic resonance (1H NMR) spectroscopy, dynamic light scattering (DLS), and elemental analysis (EA).Financial support from Projects MAT2012-31088 (MINECO), T-654-13 (GV), and S-PE13UN034 (GV) is acknowledged. Ana Sanchez-Sanchez thanks the Ph.D. grant support of Basque Government.Peer Reviewe