Degradable Block Copolymer Nanoparticles Synthesized by Polymerization‐Induced Self‐Assembly

Abstract

Polymerization‐induced self‐assembly (PISA) combines polymerization and in situ self‐assembly of block copolymers in one system and has become a widely used method to prepare block copolymer nanoparticles at high concentrations. The persistence of polymers in the environment poses a huge threat to the ecosystem and represents a significant waste of resources. There is an urgent need to develop novel chemical approaches to synthesize degradable polymers. To meet with this demand, it is crucial to install degradability into PISA nanoparticles. Most recently, degradable PISA nanoparticles have been synthesized by introducing degradation mechanisms into either shell‐forming or core‐forming blocks. This minireview summarizes the development in degradable block copolymer nanoparticles synthesized by PISA, including shell‐degradable, core‐degradable and all‐degradable nanoparticles. Future development will benefit from expansion of polymerization techniques with new degradation mechanisms and adaptation of high‐throughput approaches for both PISA syntheses and degradation studies.

Modern Trends in Polymerization-Induced Self-Assembly

“…Summarizing, PISA has enriched conventional emulsion and dispersion polymerizations with the ability to prepare nano-objects with different morphologies at relatively high polymer concentrations. It may be performed in various media, over a wide range of temperatures, and using different polymerization mechanisms [170,[201][202][203][204]206,407,408].…”

“…These include thermo-responsive properties of core-forming blocks (PITSA), simultaneous growth of block copolymers and homopolymers (PICA), formation of interpolyelectrolyte complexes by oppositely charged polyelectrolytes (PIESA), ordered structures formed by liquid crystal polymers (PIHSA), use of seeded particles (PIPA), and modified surfaces (PISSA). Additionally, degradable PISA nanoparticles can be produced, which may include shelldegradable blocks composed of peptide-, protein-, DNA-, or polysaccharide-stabilizing blocks or core-degradable hetero-chain blocks typically obtained through ring-opening polymerization [408].…”

Morphological Transformation and Surface Engineering of Glycovesicles Driven by Bioinspired Hydrogen Bonds of Nucleobases

“…These results indicate that the complementary hydrogen bonds between PGal 30 - b -PTAm 249 and PEA 40 - b -PAAm 20 are saturated, leading to the formation of spherical micelles. Notably, the morphological transformation (Figure m) is highly similar to the reverse shape transition (from spherical micelle to worm-like micelle to vesicle) during polymerization-induced self-assembly (PISA). − This is attributed to the constant incorporation of PEA 40 - b -PAAm 20 via the multiple hydrogen bonding interaction between complementary adenines and thymine moieties, altering the whole hydrophilic–hydrophobic balance.…”

Polymerization-induced self-assembly for the construction of nanostructured hydrogels

“…13–17 Especially, the emergence of polymerization-induced self-assembly (PISA) provided a powerful platform for the effective preparation of polymer assemblies with high concentration. 18–24 PISA allows for the simultaneous synthesis and self-assembly of BCPs in a single step using reversible deactivation radical dispersion polymerization or emulsion polymerization. 25–27 In a typical PISA system, a solvophilic corona-forming block is chain-extended by a solvophobic block, generating amphiphilic BCPs that undergo in situ self-assembly into primary spherical micelles.…”