Programmable Transient Supramolecular Chiral G‐quadruplex Hydrogels by a Chemically Fueled Non‐equilibrium Self‐Assembly Strategy

• Published in: Angewandte Chemie International Edition Vol. 61; no. 9; pp. e202114471 - n/a
• Main Authors: Xie, Xiao‐Qiao, Zhang, Yunfei, Liang, Yujia, Wang, Mengke, Cui, Yihan, Li, Jingjing, Liu, Chun‐Sen
• Format: Journal Article
• Language: English
• Published: Germany Wiley Subscription Services, Inc 21.02.2022
• Edition: International ed. in English
• Subjects: Assembly; Chemical fuels; Computer applications; Disaggregation; Equilibrium; Equilibrium conditions; G-quadruplexes; Hydrogels; Non-equilibrium self-assembly; Smart materials; Superstructures; Supramolecular chirality; Systems chemistry; Transient hydrogels; Systems chemistry; Transient hydrogels; Non-equilibrium self-assembly; G-quadruplexes; Supramolecular chirality
• ISSN: 1433-7851; 1521-3773
• DOI: 10.1002/anie.202114471

The temporal and spatial control of natural systems has aroused great interest for the creation of synthetic mimics. By using boronic ester based dynamic covalent chemistry and coupling it with an internal pH feedback system, we have developed a new chemically fueled reaction network for non‐equilibrium supramolecular chiral G‐quadruplex hydrogels with programmable lifetimes from minutes, to hours, to days, as well as high transparency and conductivity, excellent injectability, and rapid self‐healing properties. The system can be controlled by the kinetically controlled in situ formation and dissociation of dynamic boronic ester bonds between the cis‐diol of guanosine (G) and 5‐fluorobenzoxaborole (B) in the presence of chemical fuels (KOH and 1,3‐propanesultone), thereby leading to a precipitate‐solution‐gel‐precipitate cycle under non‐equilibrium conditions. A combined experimental‐computational approach showed the underlying mechanism of the non‐equilibrium self‐assembly involves aggregation and disaggregation of right‐handed helical G‐quadruplex superstructures. The proposed dynamic boronic ester‐based non‐equilibrium self‐assembly strategy offers a new option to design next‐generation adaptive and interactive smart materials. The temporal and spatial control of natural systems has aroused great interest for the creation of synthetic mimics. Herein, a dynamic boronic ester based non‐equilibrium self‐assembly strategy has enabled the creation of programmable and transient supramolecular chiral G‐quadruplex hydrogels with tunable lifetimes from minutes, to hours, to days, as well as high transparency and conductivity, excellent injectability, and self‐healing properties.