Templated PISA: Driving Polymerization‐Induced Self‐Assembly towards Fibre Morphology

Abstract

Dispersions of block-copolymer fibres in water have many potential applications and can be obtained by polymerization-induced self-assembly (PISA), but only in very restricted experimental conditions. In order to enlarge this experimental window, we introduced a supramolecular moiety, a hydrogen-bonded bis-urea sticker, in the macromolecular reversible addition-fragmentation chain transfer agent to drive the morphology of the nano-objects produced by RAFT-mediated PISA towards the fibre morphology. This novel concept is tested in the synthesis of a series of poly(N,Ndimethylacrylamide)-b-poly(2-methoxyethyl acrylate) (PDMAc-b-PMEA) diblock copolymers prepared by dispersion polymerization in water. The results prove that the introduction of the templating bisurea stickers into PISA greatly promotes the formation of fibres in a large experimental window.

Poly(ethylene glycol)-b-poly(vinyl acetate) block copolymer particles with various morphologies via RAFT/MADIX aqueous emulsion PISA

“…The narrowness of this DP window is consistent with the PISA literature reports concerning the formation of worm/fibre particles. 42 To the best of our knowledge, these experiments are the first depicting the obtention of non-spherical morphologies by VAc PISA in emulsion. Indeed, as mentioned above, the morphologies obtained in emulsion are most of the time restrained to kinetically trapped spheres, and the number of reports of higher-order morphologies remain limited.…”

Bifunctional Peptide–Polymer Conjugate-Based Fibers via a One-Pot Tandem Disulfide Reduction Coupled to a Thio-Bromo “Click” Reaction

“… 5 − 8 Rieger and Stoffelbach et al recently documented an amphiphilic supramolecular-system for the direct access to polymer decorated fiber morphologies by polymerization-induced self-assembly in water. 9 Amphiphilic peptide systems in particular have been found to be advantageous in controlling, directing, and using artificial fibers for biomedical purposes, and have been earlier reviewed by several groups. 10 − 12 Stupp and co-workers pioneered the field by demonstrating that various peptide-amphiphile allowed their supramolecular arrangement via induced self-assembly into one-dimensional nanofibers, 10 , 13 , 14 and investigated pathway-dependent morphology and internal dynamics of such nanostructures to hold significant promise as advanced hybrid materials for biofunctions.…”

Controllable Vesicular Size and Shape in Polymerization-Induced Self-assembly Aided by Aromatic Interactions

“…In addition to solvophobic effects, some other non-covalent interactions can also drive/in uence self-assembly of block copolymers. [46][47][48] PISA aided by hydrogen bonding, 49 static electricity, 50 host-guest complexation, 51 crystallization, 52 and liquid crystal ordering, 53 obviously improve the accessibility of anisotropic nanoobjects. Applying cooperativity of multiple non-covalent interactions generates abundant structures and even functional optimization of the cells and organelles in nature.…”