Supramolecular dissipative self‐assembly systems: Approaches and applications

Abstract

Dissipative self‐assembly (DSA) system requires a continuous supply of fuels to maintain the far‐from‐equilibrium assembled state. Living organisms exist and operate far from the thermodynamic equilibrium by continuous consumption of energy taken from the surroundings, so how to realize the construction of the artificial DSA system has attracted much attention by researchers all over the world. Owing to dynamic controllable noncovalent interactions, artificial supramolecular DSA systems have achieved higher functions fueled by various types of energy, such as chemical fuels, light, electric energy, acoustic energy, and mechanical energy. Upon the input of external fuels, nonactive precursors can be activated to form building blocks at higher energy levels and then self‐assemble into transient supramolecular structures. As the proceeding of deactivation reaction, the building blocks with higher energy level dissipate back to the initial precursors, resulting in the disassembly process, to complete a full cycle. In this review, we summarize the recent advances of artificial supramolecular DSA systems on its construction strategies and energy‐fueled regulation approaches. The applications of supramolecular DSA systems in luminescence modulating, information encryption, self‐regulating gels, drug delivery, and catalysis are also discussed. We hope that this review article will facilitate further understanding and development of DSA systems.

Stimuli‐responsive fluorescent hydrogels: Strategies and applications

“… In recent decades, the explosive development of dynamic chemistry, for example, supramolecular chemistry, [5‐8] dynamic covalent chemistry, [9–13] molecular machines, [14–16] and molecular switches, [17–20] give rise to a variety of stimuli‐responsive dynamic soft materials, [21–24] including stimuli‐responsive hydrogels, which undergo macroscopic changes in response to certain external stimulistim. Schematic representation of (a) fluorescent organic hydrogel P(DMA‐DEAN)/P(SMA‐9‐ANA) and its (b) information coding/decoding process; (c) information‐coding, dual‐encryption, and dynamic fluorescent decryption procedures; (d) shape memorizing/recovering process [110] .…”

“…Hydrogels are highly hydrated, functional materials with a three‐dimensional (3D) network structure formed by cross‐linking hydrophilic gelators, [1–3] with mechanical flexibility, biocompatibility, and hydrophilicity [4] . In recent decades, the explosive development of dynamic chemistry, for example, supramolecular chemistry, [5–8] dynamic covalent chemistry, [9–13] molecular machines, [14–16] and molecular switches, [17–20] give rise to a variety of dynamic soft materials, [21–24] including stimuli‐responsive hydrogels, that can undergo macroscopic changes in response to certain external stimuli (e.g., light, heating/cooling, acid/base, mechanical forces, and one or more conditions in parallel). Some of them can mimic the adaptation of organisms to the environment in nature and have artificially controllable properties [25–27] .…”

Enzymatic Dissociation of DNA-Histone Condensates in an Electrophoretic Setting: Modulating DNA Patterning and Hydrogel Viscoelasticity

“…Until now, this strategy mostly focused on controlling the lifetime and nature of the transient assembly or kinetically trapped intermediates without adding any external energy forces. − Performing an inherently dissociative assembly process in the presence of an external physical energy source can bring further complexity in the outcome. − In this paper, we report on dissipative self-assembly and the corresponding spatiotemporally nonequilibrium patterning behavior in the presence of an external electric field. Herein, we use histone as the chemical fuel, which interacts with DNA (building block) and results in assembly of DNA-histone to generate chromatin-like condensates (coacervate in nature) (Figure ).…”