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Herein, we reported a novel tri-block copolymer synthesized by segmented ring-opening polymerization of temperature-sensitive 5-(pyrrolidine-1-carbonyl) oxepan-2-one monomer (VPyCL) and redox-sensitive macrocyclic disulfide-substituted carbonate monomer (MSS). The structure of the copolymers was confirmed by GPC,  1 H NMR and  13 C NMR. The obtained tri-block copolymers could self-assemble in aqueous solution to form well-structured micelles, with the mPEG- b -PVPyCL block acting as the hydrophilic coronal and the PSS block acting as the hydrophobic core. Dynamic light scattering (DLS) studies confirmed that micelles formed by these tri-block copolymers with different block ratios could respond to different temperature ranges during the heating/cooling process and respond to reducing agent glutathione (GSH). In addition, transmission electron microscopy (TEM) results further confirmed the polymeric micelles’ dual-stimuli responsiveness. The potential application of this type of dual-stimuli responsive micelles in drug delivery systems was evaluated using doxorubicin (DOX) as the model molecule. The stimulus-dependent responsive behaviors of obtained micelles can be applied to the construction of smart materials capable of performing multiple functions under the appropriate conditions.

Preparation and characterization of novel functional tri-block copolymer for constructing temperature/redox dual-stimuli responsive micelles