Cylindrical Zwitterionic Particles via Interpolyelectrolyte Complexation on Molecular Polymer Brushes

Abstract

The fabrication of macromolecular architectures with high aspect ratio and well‐defined internal and external morphologies remains a challenge. The combination of template chemistry and self‐assembly concepts to construct peculiar polymer architectures via a bottom‐up approach is an emerging approach. In this study, a cylindrical template—namely a core–shell molecular polymer brush—and linear diblock copolymers (DBCP) associate to produce high aspect ratio polymer particles via interpolyelectrolyte complexation. Induced, morphological changes are studied using cryogenic transmission electron and atomic force microscopy, while the complexation is further followed by isothermal titration calorimetry and ξ‐potential measurements. Depending on the nature of the complexing DBCP, distinct morphological differences can be achieved. While polymers with a non‐ionic block lead to internal compartmentalization, polymers featuring zwitterionic domains lead to a wrapping of the brush template.

Morphology Control of Multicompartment Micelles in Water through Hierarchical Self-Assembly of Amphiphilic Terpolymers

“…For instance, cascade catalysis in water is especially intriguing to overcome incompatibility issues of the catalysts and to decrease the use of harmful and expensive organic solvents, while drug delivery with multifunctional carrier systems anyway must take place under physiological conditions. 9,10 Several polymer architectures like diblock blends 11,12 and graft 13,14 or bottlebrush 15,16 copolymers were assembled to MCMs with diverse methods, but ABC triblock terpolymers (miktoarm star 17−20 or linear 21 ) remain the most common building block to form MCMs. For instance, terpolymers containing one hydrophilic block, poly(oligo(ethylene oxide) monomethyl ether acrylate) (POEGMA), and two hydrophobic blocks, poly(benzyl acrylate) (PBzA) and poly(1H,1Hperfluorobutyl acrylate), self-assembled into spherical MCMs in water by first dissolving the terpolymers in acetone followed by dropwise addition of water, evaporation of acetone, and annealing at 75 °C for 2 weeks.…”

Strong Anionic/Charge-Neutral Block Copolymers from Cu(0)-Mediated Reversible Deactivation Radical Polymerization

“…Nonetheless, the solubility of the charge-neutral PEO block enables their use for the formation and stabilization of complex coacervate core micelles (C3Ms; Figure A). Copolymers featuring a poly­(ethylene glycol)-based segment and another charged moiety have been widely studied for such purposes and have already permitted the formation of multicompartment micelles , and polymer nanowires. , Herein, we utilize a poly­(4-vinylpyridine) (P4VP) homopolymer produced through RAFT polymerization following an earlier reported procedure . The polymer was quaternized using iodomethane (P4VPq 119 ) to introduce permanent charges and ensure pH-independent solubility.…”

“…The presence of charges amidst these macromolecules can be taken advantage of not only to produce synthetic counterparts of natural polymers but also to enable the build-up of soft matter into complex structures . Polyanions are capable of intermolecular − or intramolecular , interactions, which opens up to numerous applications including the chelation of underwater adhesives, , the stabilization of inorganic nanoparticles, as well as the attachment of macrocyclic compounds, genetic materials, , or therapeutics. , Therefore, anionic/charge-neutral diblock, terblock, or star copolymers remain of high interest in soft matter science and have already demonstrated great capability as lubricants, surfactants for emulsion polymerization, , surface modification agents, − or for the fabrication of proton-exchange membrane fuel cells . However, the vast majority of these systems rely on the use of weak polyelectrolytes, which can drastically limit their range of applications, while strong polyelectrolytes suffer from limited solubility and remain far more challenging to produce and characterize.…”

Molecular Bottlebrushes Featuring Brush-on-Brush Architecture

“…However, BoB molecular bottlebrush features bulky bottlebrush side chains that allow stretch of the backbone even at a low grafting density and may offer more control over its chemistry and dimension. Unlike the molecular assemblies with BoB architectures via interpolyelectrolyte complexation reported by Mullner and co-workers, 35 the BoB bottlebrushes presented in this work are individual macromolecules with well-defined structures via covalent bonding. The skeleton of the BoB molecular bottlebrushes based on poly(ε-caprolactone) (PCL) was designed for two reasons.…”