We report a versatile and efficient strategy for the synthesis of dual thermo- and pH-responsive polymeric nano-objects with rich morphological diversity, achieved via RAFT-mediated aqueous emulsion polymerization-induced self-assembly (PISA). Using a thermoresponsive poly(triethylene glycol methyl ether methacrylate) (PTEGMA) macro-chain transfer agent and a pH-sensitive diisopropylaminoethyl methacrylate (DPA) monomer, we generated PTEGMA-b-PDPA diblock copolymer nano-objects under conditions both below and above the LCST of PTEGMA. By systematically varying the length of the PDPA block, we accessed a wide array of morphologies-including micelles, worms, vesicles, and intricate "octopus"-like structures-simply by adjusting the polymerization temperature and hydrophobic block length. These nanostructures displayed clear dual responsiveness: thermally triggered aggregation around ∼40 °C and reversible disassembly in acidic environments. Our findings highlight the precise morphological control achievable through aqueous RAFT-PISA and underscore its potential for designing smart nanomaterials tailored for biomedical and stimuli-responsive applications.

Institute of Macromolecular Chemistry v v i Academy of Sciences of the Czech Republic Heyrovsky Sq 2 162 06 Prague 6 Czech Republic

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