Dissipative self-assembly of a dual-responsive block copolymer driven by a chemical oscillator

Hypothesis: Coupling stimuli-responsive building blocks with an oscillating reaction is an effective strategy to realize and investigate dissipative self-assembly. More importantly, since there is usually more than one component of which concentration periodically changes in a chemical oscillator, it can be expected that this strategy has the advantage of achieving dissipative self-assembly of the building blocks with dual- or even multi-responsiveness. Experiments: We realized the dissipative self-assembly of a pH- and iodine-responsive block copolymer, poly(ethylene oxide)-b-poly(2-vinyl pyridine) (PEO-P2VP), by coupling it with the IO3--SO32--Fe(CN)62- (ISF) oscillator, and investigated its rhythmic self-assembly behavior. Furthermore, we proposed a mechanistic model to simulate the kinetics of the ISF oscillator coupling with different amounts of PEO-P2VP. Findings: Rhythmic core-shell reversal of the polymer micelles formed by PEO-P2VP was found in the ISF oscillator. The mechanistic model we proposed successfully reproduced the experimental oscillation and provided some data on the kinetics of the dual responsive self-assembly of PEO-P2VP. This line of research provided an example of realizing dissipative self-assembly of dual-responsive building blocks, which was seldom reported previously. It once again suggested that coupling with a suitable chemical oscillator is a promising strategy to have an insight into the kinetics of stimuli-responsive self-assembly. (c) 2022 Elsevier Inc. All rights reserved.