Mechanosensitive non-equilibrium supramolecular polymerization in closed chemical systems

Xianhua Lang; Yingjie Huang; Lirong He; Yixi Wang; Udayabhaskararao Thumu; Zonglin Chu; Wilhelm T S Huck; Hui Zhao

doi:10.1038/s41467-023-38948-x

Mechanosensitive non-equilibrium supramolecular polymerization in closed chemical systems

Nat Commun. 2023 May 29;14(1):3084. doi: 10.1038/s41467-023-38948-x.

Authors

Xianhua Lang^#¹, Yingjie Huang^#¹, Lirong He¹, Yixi Wang², Udayabhaskararao Thumu², Zonglin Chu³, Wilhelm T S Huck⁴, Hui Zhao⁵

Affiliations

¹ School of Chemical Engineering, State Key Lab of Polymer Materials Engineering, Sichuan University, 610065, Chengdu, China.
² Institute of Fundamental and Frontier Sciences, University of Electronic Science and Technology of China, 610054, Chengdu, China.
³ College of Chemistry and Chemical Engineering, Hunan University, 410082, Changsha, China.
⁴ Institute for Molecules and Materials, Radboud University, Nijmegen, The Netherlands.
⁵ School of Chemical Engineering, State Key Lab of Polymer Materials Engineering, Sichuan University, 610065, Chengdu, China. zhaohuichem@scu.edu.cn.

^# Contributed equally.

Abstract

Chemical fuel-driven supramolecular systems have been developed showing out-of-equilibrium functions such as transient gelation and oscillations. However, these systems suffer from undesired waste accumulation and they function only in open systems. Herein, we report non-equilibrium supramolecular polymerizations in a closed system, which is built by viologens and pyranine in the presence of hydrazine hydrate. On shaking, the viologens are quickly oxidated by air followed by self-assembly of pyranine into micrometer-sized nanotubes. The self-assembled nanotubes disassemble spontaneously over time by the reduced agent, with nitrogen as the only waste product. Our mechanosensitive dissipative system can be extended to fabricate a chiral transient supramolecular helix by introducing chiral-charged small molecules. Moreover, we show that shaking induces transient fluorescence enhancement or quenching depending on substitution of viologens. Ultrasound is introduced as a specific shaking way to generate template-free reproducible patterns. Additionally, the shake-driven transient polymerization of amphiphilic naphthalenetetracarboxylic diimide serves as further evidence of the versatility of our mechanosensitive non-equilibrium system.