Greatly Enhanced Accessibility and Reproducibility of Worm‐like Micelles by In Situ Crosslinking Polymerization‐Induced Self‐Assembly

Abstract

Worm‐like micelles have attracted great interest due to their anisotropic structures. However, the experimental conditions for obtaining worm‐like micelles are very restricted, which usually causes seriously poor reproducibility. In this work, significantly enhanced accessibility of worm‐like micelles is realized by in situ crosslinking polymerization‐induced self‐assembly (PISA). The reproducibility of worm‐like micelles is greatly improved due to the significantly enlarged experimental windows of worm‐like micelles in the morphology diagram. Moreover, the reliability of the methodology to enhance the accessibility of worm‐like micelles has been demonstrated in various in situ crosslinking PISA systems. The greatly enhanced accessibility and reproducibility of worm‐like micelles is undoubtedly cost‐effective especially in scale‐up production, which paves the way for further application of worm‐like micelles with various compositions and functionalities.

Light-Triggered Reversible Slimming of Cross-linked Nanowires Synthesized by Polymerization-Induced Hierarchical Self-assembly and Photodimerization

“…Apart from these strategies, Hong et al recently put forward a robust methodology to effectively enhance the accessibility and reproducibility of worm-like micelles by in situ cross-linking PISA. 25 These worms possessed superior resistance of perturbations and this method was reliable for various PISA formulations.…”

“…In order to enlarge the experimental windows of the cylindrical micelles, the introduction of additional driving forces such as hydrogen bonding, electrostatic interaction (polymerization-induced electrostatic self-assembly, PIESA), crystallization (polymerization-induced crystallization-driven self-assembly, PI-CDSA), , and liquid crystalline (LC) ordering (polymerization-induced hierarchical self-assembly, PIHSA) − is commonly necessary. Apart from these strategies, Hong et al recently put forward a robust methodology to effectively enhance the accessibility and reproducibility of worm-like micelles by in situ cross-linking PISA . These worms possessed superior resistance of perturbations and this method was reliable for various PISA formulations.…”

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

“…Moreover, branched polymer structures can be included in the NP design 190 . Although more challenging to reproduce and characterize, branching offers an additional handle of control, for example, by promoting morphological transitions at lower DPs compared to linear BCPs 191,192 …”

“…While PISA allows for the general accessibility of higherorder morphologies, the preparation of anisotropic particles, such as rod-or worm-like micelles or nanotubes (Figure 8A), remains challenging due to the typically narrow experimental window in which these structures are accessible. 192 Obtaining pure phases of such particles is often practically not feasible or requires tedious screening of reaction conditions. Given the potential of anisotropic particles for biomedical applications, 72,73,75,193 there is significant interest in developing strategies that make their synthesis via PISA more robust.…”

“…Covalent crosslinking can be achieved either during PISA by incorporating divinyl monomers in the core in situ 161,192,[212][213][214][215] (see Figure 8B), or via (photo-)chemical post-PISA processing. 216 In situ crosslinking can reduce experimental steps, but is prone to inhibit morphological evolution due to progressively restricted chain mobility during PISA.…”