Key Laboratory of Forest Plant Ecology, Ministry of Education, Engineering Research Center of Forest Bio-Preparation, College of Chemistry, Chemical Engineering and Resource Utilization, Northeast Forestry University, Harbin 150040 PR China.
Key Laboratory of Micro-systems and Micro-structures Manufacturing, Ministry of Education, Harbin Institute of Technology, Harbin 150080, PR China.
J Colloid Interface Sci. 2022 Jun;615:732-739. doi: 10.1016/j.jcis.2022.01.183. Epub 2022 Feb 7.
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.
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 IO-SO-Fe(CN) (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.
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.
将响应刺激的构建块与振荡反应相结合是实现和研究耗散自组装的有效策略。更重要的是，由于化学振荡器中通常有不止一个浓度周期性变化的组件，因此可以预期这种策略具有实现具有双重甚至多重响应性的构建块的耗散自组装的优势。
我们通过将 pH 和碘响应嵌段共聚物聚（氧化乙烯）-b-聚（2-乙烯基吡啶）（PEO-P2VP）与 IO-SO-Fe（CN）（ISF）振荡器耦合，实现了其耗散自组装，并研究了其有节奏的自组装行为。此外，我们提出了一个机械模型来模拟 ISF 振荡器与不同量的 PEO-P2VP 耦合的动力学。
在 ISF 振荡器中发现了由 PEO-P2VP 形成的聚合物胶束的周期性核壳反转。我们提出的机械模型成功地再现了实验振荡，并提供了有关 PEO-P2VP 双重响应自组装动力学的一些数据。这一系列研究为实现双重响应构建块的耗散自组装提供了一个范例，这在以前很少有报道。它再次表明，与合适的化学振荡器耦合是深入了解刺激响应自组装动力学的一种很有前途的策略。
