Polymerization‐Induced Self‐Assembly: An Emerging Tool for Generating Polymer‐Based Biohybrid Nanostructures

Abstract

The combination of biomolecules and synthetic polymers provides an easy access to utilize advantages from both the synthetic world and nature. This is not only important for the development of novel innovative materials, but also promotes the application of biomolecules in various fields including medicine, catalysis, and water treatment, etc. Due to the rapid progress in synthesis strategies for polymer nanomaterials and deepened understanding of biomolecules’ structures and functions, the construction of advanced polymer‐based biohybrid nanostructures (PBBNs) becomes prospective and attainable. Polymerization‐induced self‐assembly (PISA), as an efficient and versatile technique in obtaining polymeric nano‐objects at high concentrations, has demonstrated to be an attractive alternative to existing self‐assembly procedures. Those advantages induce the focus on the fabrication of PBBNs via the PISA technique. In this review, current preparation strategies are illustrated based on the PISA technique for achieving various PBBNs, including grafting‐from and grafting‐through methods, as well as encapsulation of biomolecules during and subsequent to the PISA process. Finally, advantages and drawbacks are discussed in the fabrication of PBBNs via the PISA technique and obstacles are identified that need to be overcome to enable commercial application.

Preparation of PFPE-Based Polymeric Nanoparticles via Polymerization-Induced Self-Assembly as Contrast Agents for 19F MRI

“…The prepared nanoparticles have the advantages of controllable selfassembly morphology and high solid content, which make the large-scale production and application of polymer nano-selfassemblies possible and is a popular technology for the preparation of block copolymer nano-self-assemblies. 29 Panakkal et al used the water-soluble monomer N-(2,2,2trifluoroethyl) acrylamide (TFEAM) to synthesize nanoparticles by PISA in aqueous medium, with PEG as the hydrophilic shell. However, as the core-forming TFEAM block provides the 19 F signal source, the mobility of the fluorinated chain was severely inhibited.…”

“…Unlike small molecules that are easily removed from the body by renal filtration, polymeric nanoparticles typically have longer circulation times and can enter and concentrate in certain types of solid tumors through enhanced permeation and retention (EPR) effects. , Among the many methods of preparing nanoparticles, the polymerization-induced self-assembly (PISA) technology is easy to operate, with the features of polymerization and assembly at the same time. The prepared nanoparticles have the advantages of controllable self-assembly morphology and high solid content, which make the large-scale production and application of polymer nano-self-assemblies possible and is a popular technology for the preparation of block copolymer nano-self-assemblies . Panakkal et al used the water-soluble monomer N -(2,2,2-trifluoroethyl) acrylamide (TFEAM) to synthesize nanoparticles by PISA in aqueous medium, with PEG as the hydrophilic shell.…”

Temperature-Dependent Ring-Opening Polymerization-Induced Self-Assembly Using Crystallizable Polylactones as Core-Forming Blocks

“…Alternatively, the recently developed polymerization-induced self-assembly (PISA) technique can be used for easily synthesizing a wide variety of micellar morphologies at relatively high solids (up to 50% w/w). − Additionally, PISA has been extensively used for multiple applications. − However, core-forming blocks are noncrystallizable in the most-studied PISA system, in which the driving force for self-assembly is the solubility change of the core-forming blocks. When a crystallizable block is introduced to PISA, crystallization functions as an alternative driving force, which dominates the formation of different micellar morphologies. , Thus, ring-opening polymerization-induced self-assembly (ROPISA) was investigated for lactone monomers.…”

Polymerization‐induced self‐assembly for drug delivery: A critical appraisal

“…Given this versatility, PISA has the potential of being a synthetic workhorse for biomedical and pharmaceutical applications, such as bioimaging, 45–47 biocatalysis, 48 tissue culture, 49 and cell preservation 50,51 . One of the most envisioned applications of PISA is, however, the preparation of polymeric NPs for drug delivery 43,52–55 . Incorporating therapeutic agents, such as small (hydrophobic) drug molecules, peptides, proteins, and nucleic acids, as cargo in BCP‐based NPs may improve their solubility and stability in biological media, as well as prolong their in vivo circulation.…”

“…We do not aim to provide an exhaustive overview of publications that address PISA and cargo encapsulation, but focus on the most important developments reported from 2019 to 2023. For previous developments, we refer to preceding reviews covering the field 34,52–54 . Considering the bottlenecks in the development of PISA‐derived DDS suitable for in vivo application, we discuss the potential of various other concepts in the general PISA field to improve NP performance and expand the range of cargo types that can be encapsulated via PISA.…”