Multifunctional polymer inorganic nanoparticle hybrid tandems as selective metal sensors

• Intrinsic versus extrinsic nanostructuration strategies. • Aqueous RAFT-PISA for catechol multifunctional block copolymers. • Catechol copolymers as templates for in situ assembly of high luminescent metal NCs. • Polymer composition dictates morphology, optics, and sensing performance. • Hybrid AgNCs exhibit selective Cu 2+ sensing. The design of multifunctional copolymers with tailored architectures is a central topic in polymer science, as macromolecular structure strongly governs self-assembly and material performance. While RAFT polymerization is widely used to synthesize well-defined copolymers, direct comparisons between statistical copolymers and nano-structured block terpolymers prepared by RAFT-mediated polymerization-induced self-assembly (RAFT-PISA) with similar compositions remain scarce. Herein we report the synthesis of novel multifunctional copolymers that combine the thermoresponsive behavior of triethylene glycol monomethyl ether methacrylate (MeO 3 MA) with the versatile functionality of catechol groups, introduced via dopamine methacrylamide (DMA) using two distinct synthetic strategies. In the first stage, statistical copolymers with tunable DMA content were synthesized to probe the effect of cathecol groups on polymer properties. Subsequently, the RAFT-PISA technique in aqueous media was employed to obtain nano-diblock terpolymers, featuring a hydrophilic block of polyglycerol methacrylate (pGMA) and a second hydrophobic block composed of MeO 3 MA with a fixed DMA content (10 mol%) enabling in situ controlled self-assembly into well-defined nanostructures (spherical and worm-like) dictated by the block size ratio. Finally, both the random and block copolymers were employed as stabilizing templates for the synthesis of luminescent silver and copper nanoclusters (AgNCs and CuNCs), which were subsequently evaluated as sensors for the detection of heavy metals in aqueous environment. This dual approach provides valuable insight into how polymer architecture and nanostructuration dictate hybrid morphology, optical response, and sensing performance.