Seeded RAFT Polymerization‐Induced Self‐assembly: Recent Advances and Future Opportunities

Abstract

Over the past decade, polymerization‐induced self‐assembly (PISA) has fully proved its versatility for scale‐up production of block copolymer nanoparticles with tunable sizes and morphologies; yet, there are still some limitations. Recently, seeded PISA approaches combing PISA with heterogeneous seeded polymerizations have been greatly explored and are expected to overcome the limitations of traditional PISA. In this review, recent advances in seeded PISA that have expanded new horizons for PISA are highlighted including i) general considerations for seeded PISA (e.g., kinetics, the preparation of seeds, the selection of monomers), ii) morphological evolution induced by seeded PISA (e.g., from corona‐shell‐core nanoparticles to vesicles, vesicles‐to‐toroid, disassembly of vesicles into nanospheres), and iii) various well‐defined nanoparticles with hierarchical and sophisticated morphologies (e.g., multicompartment micelles, porous vesicles, framboidal vesicles, AXn‐type colloidal molecules). Finally, new insights into seeded PISA and future perspectives are proposed.This article is protected by copyright. All rights reserved

The Valence-Dependent Activity of Colloidal Molecules as Ice Recrystallization Inhibitors

“…In recent years, as a modified PISA technique, polymerization-induced particle-assembly (PIPA) has been developed for the preparation of CMs through the ABC-type triblock terpolymers of poly( N , N -dimethylaminoethyl methacrylate)- b -poly(benzyl methacrylate)- b -poly(2-perfluorohexylethyl methacrylate) (PDMA- b -PBzMA- b -PFHEMA), poly( N , N -dimethylaminoethyl methacrylate)- b -poly(benzyl methacrylate)- b -poly(2-hydroxypropyl methacrylate) (PDMA- b -PBzMA- b -PHPMA), and PDMA -b -PFBEMA- b -PBzMA . The method is based on the seeded RAFT-PISA using the AB-type particles as seeds, and the phase separation of the in situ propagating C-blocks resulted in a patch on the spheres serving as the linkages for AX n types of CMs. , …”

“…57 The method is based on the seeded RAFT-PISA using the AB-type particles as seeds, and the phase separation of the in situ propagating C-blocks resulted in a patch on the spheres serving as the linkages for AX n types of CMs. 58,59 In this work, we propose to use PIPA to synthesize AX n CMs (n assigned to the valence) for IRI investigation, providing a strategy to mimic the heterogeneous structure of antifreezing proteins and develop new antifreezeing materials. To increase the stability of the CMs in water and the monomer conversion considering the needs of cryopreservation, the cationic monomer of acryloxyethyl trimethylammonium chloride (ATAC) was used for building block PA to enhance the Coulombic forces, while benzyl acrylate (BzA) instead of BzMA was employed as block PB to slightly depress the hydrophobicity and diacetone acrylamide (DAAM) was used for block PC, which is water-soluble but would be insoluble after polymerization due to the strong intermolecular Hbonding that is suitable to be applied as the patchy linkages.…”

Modern Trends in Polymerization-Induced Self-Assembly

“…However, in practice, the isolation of intermediate products (i.e., the initial macro-RAFT agent or macro-aminoxyl) is applied more frequently [130]. The synthesis of dispersions of ABC-triblock copolymers is performed by seeded polymerization [11,[131][132][133].…”

“…This process, known as polymerization-induced self-assembly (PISA), has been developed recently and has attracted the attention of numerous research teams due to its ability to produce stable colloidal dispersions of block copolymer particles with tunable morphologies without the need for any surfactants or steric stabilizers [9]. The progress in the synthesis of welldefined block copolymers organized into particles with diverse morphologies has been discussed extensively in numerous research articles and reviews [10][11][12][13][14][15]. However, many of these reviews focus on a specific aspect of the PISA process, such as the specific mechanism of implementation [10,13], progress in dispersion or emulsion-based PISA [12], potential applications of PISA [16], or control of particle morphology through PISA [9,15].…”