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

Xuewei Li; Guangtong Wang; Qianqian Zhang; Yang Liu; Tiedong Sun; Shaoqin Liu

doi:10.1016/j.jcis.2022.01.183

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

J Colloid Interface Sci. 2022 Jun:615:732-739. doi: 10.1016/j.jcis.2022.01.183. Epub 2022 Feb 7.

Authors

Xuewei Li¹, Guangtong Wang², Qianqian Zhang³, Yang Liu⁴, Tiedong Sun⁵, Shaoqin Liu⁶

Affiliations

¹ 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.
² Key Laboratory of Micro-systems and Micro-structures Manufacturing, Ministry of Education, Harbin Institute of Technology, Harbin 150080, PR China. Electronic address: wgt@hit.edu.cn.
³ School of Life Science and Technology, Harbin Institute of Technology, Harbin 150080, PR China.
⁴ College of Chemistry, Chemical Engineering and Materials Science, Zaozhuang University, Zaozhuang 277160, PR China. Electronic address: chemliuyang@uzz.edu.cn.
⁵ 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. Electronic address: tiedongsun@nefu.edu.cn.
⁶ Key Laboratory of Micro-systems and Micro-structures Manufacturing, Ministry of Education, Harbin Institute of Technology, Harbin 150080, PR China. Electronic address: shaoqinliu@hit.edu.cn.

PMID: 35168022
DOI: 10.1016/j.jcis.2022.01.183

Abstract

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^--SO₃^2--Fe(CN)₆^2- (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.

Keywords: Chemical oscillator; Dissipative self-assembly; Dual-responsiveness; Non-equilibrium chemistry; Polymeric micelle.

MeSH terms

Kinetics
Micelles*
Polyethylene Glycols
Polymers*

Substances

Micelles
Polymers
Polyethylene Glycols