Abstract
• Multithiolated block copolymer nanoparticles (P-NPs) were synthesized by RAFT-PISA. • Monodisperse P-NPs with tunable size are formed under uncontrolled RAFT polymerization. • P-NPs with thermo-responsive core and hydrophilic shell exhibit high water stability. • Thiolated P-NPs serve as template for in situ assembly of luminescent CuNCs in water. • Fluorescent nanohybrids exhibit pH/thermo-response, photostability and oxidation resistance. The development of fluorescent water stable copper nanoclusters (CuNCs) deserves the scientific interest due to their outstanding properties and low-cost. These fluorescent CuNCs can be synthesized using natural or synthetic polymers with thiol groups. Herein, for the first time, we propose the use of novel amphiphilic block copolymer nano-objects, synthesized by polymerization induced self-assembly (PISA) via reversible-addition fragmentation chain transfer (RAFT), as templates for the synthesis and water stabilization of CuNCs. The polymeric NPs provide water-stability due to the poly(hydroxyethyl acrylate) corona and the thermos-responsive core, based on 2-(2-methoxyethoxy) ethyl methacrylate (MEO 2 MA) and 2-(acetylthio) ethyl methacrylate (AcSEMA) decorated with protected thiol groups, drive the “ in situ ” reduction of copper ions into copper nanocrystals and their assembling in high luminescent nanohybrids in water. In order to optimize the fluorescence properties a methodical study was carried out varying polymers composition and architecture, thiol content and nanoparticle size. All the polymeric nanoparticles synthesized by PISA and decorated with thiol groups induce the formation of luminescent CuNCs in their hydrophobic core. The sizes of the hydrophilic/hydrophobic block, as well as, thiol content are key factors in the emission properties of the CuNC nanohybrids that offer high colloidal stability in water, pH- and thermo-response, significance photostability and strong resistance to oxidation.
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