This review article aims to cover the most recent advances regarding the synthesis of linear ABC-type triblock terpolymers and star-shaped polymers by RAFT polymerization, as well as their self-assembly properties in aqueous solutions. RAFT polymerization has received extensive attention, as it is a versatile technique, compatible with a great variety of functional monomers and reaction conditions, while providing exceptional and precise control over the final structure, with well-defined side-groups and post-polymerization engineering potential. Linear triblock terpolymers synthesis can lead to very interesting novel ideas, since there are countless combinations of stimuli/non-stimuli and hydrophilic/hydrophobic monomers that someone can use. One of their most interesting features is their ubiquitous ability to self-assemble in different nanostructures depending on their degree of polymerization (DP), block composition, solubilization protocol, internal and external stimuli. On the other hand, star-shaped polymers exhibit a more stable nanostructure, with a distinct crosslinked core and arm blocks that can also incorporate stimuli-responsive blocks for “smart” applications.

In this work, the synthesis, selective chemical modifications, and self-assembly behavior in aqueous media of a novel poly(2-(dimethylamino)ethyl acrylate)₂₀-b-poly(N-isopropylacrylamide)₁₁-b-poly(oligo ethylene glycol methyl ether acrylate)₁₈ (PDMAEA₂₀-b-PNIPAM₁₁-b-POEGA₁₈) dual-responsive (pH and temperature) and triply hydrophilic amino-based triblock terpolymer are reported. The amine functional triblock terpolymer was synthesized by sequential reversible addition fragmentation chain transfer polymerization (RAFT) polymerization and molecularly characterized by size exclusion chromatography (SEC) and ¹H-NMR spectroscopy that evidenced the success of the three-step polymerization scheme. The tertiary amine pendant groups of the PDMAEA block were chemically modified in order to produce the Q₁PDMAEA₂₀-b-PNIPAM₁₁-b-POEGA₁₈ as well as the Q₆PDMAEA₂₀-b-PNIPAM₁₁-b-POEGA₁₈ quaternized triblock terpolymers (Q₁ and Q₆ prefixes show the number of carbon atoms (C1 and C6) attached on the PDMAEA groups) using methyl iodide (CH₃I) and 1-iodohexane (C₆H₁₃I) as the quaternizing agents and the SPDMAEA₂₀-b-PNIPAM₁₁-b-POEGA₁₈ sulfobetainized triblock terpolymer using 1,3 propanesultone (C₃H₆O₃S) as the sulfobetainization agent. The self-assembly properties of the triblock terpolymers in aqueous solutions upon varying temperature and solution pH were studied by light scattering and fluorescence spectroscopy experiments. The novel triblock terpolymers self-assemble into nanosized aggregates upon solution temperature rise above the nominal lower critical solution temperature (LCST) of the temperature-responsive PNIPAM block. The remarkable stimuli-responsive self-assembly behavior of the novel triblock terpolymers in aqueous media make them interesting candidates for biomedical applications in the fields of drug and gene delivery.