ATP‐Driven Synthetic Supramolecular Assemblies: From ATP as a Template to Fuel

Abstract

Adenosine triphosphate (ATP) is a molecular unit of energy that drives various processes in the cellular environment. In this Minireview, we discuss the potential of physical and chemical properties of ATP for the development of bio‐inspired, synthetic ATP‐induced supramolecular systems with dynamic, stimuli‐responsive and active assembly characteristics. Molecular design rules for ATP‐induced assemblies with various architectures and their stimuli‐responsive structural and functional response are categorized. Special attention is given to the immense potential of ATP‐fuelled designs in the nascent field of transient/non‐equilibrium supramolecular polymerization for the synthesis of lifelike temporally programmable soft materials. Finally, the existing dearth and fate of ATP‐driven systems for future challenges are discussed.

The Transient Covalent Bond in Abiotic Nonequilibrium Systems

“…Several rotaxane-based systems have been reported, demonstrating temporal control of fluorescence by Schmittel, [36] magnetic properties by Di Stefano and Lucarini, [37] and catalysis by Leigh. [38] Tr ansient crystallization of acucurbit [8]uril-based host-guest complex has been reported by Mukhopadhyay,Baek, and Kim. [39] Schmittel has recently shown that the chemistry can be coupled to more complex reaction networks,u sing it to trigger Li + pulses through at hree-component host-guest cascade.…”

“…[2][3][4] Often, the energy is provided by chemical fuels such as ATP; while light is the ultimate energy source in nature,chemical fuels provide specificity that enables greater system complexity. [5] Recently,there has been substantial effort to design nonbiological systems that operate out-of-equilibrium through analogous processes.One approach is to repurpose biochemical components in new contexts,s uch as cells, [6] enzymes, [7] and other biomolecules (i.e., ATP [8] and DNA [9] ). While these systems offer remarkable demonstrations of new chemical reaction networks,t he focus of this Minireview is nonequilibrium systems that take only very high level inspiration from biology,s ystems that are designed fully from the bottom up using only simple," artificial" organic reactions.S pecifically, we focus on chemical fuels that operate autonomously through the formation of covalent bonds of finite lifetime (as opposed to,f or example,o scillating reaction networks operating far from equilibrium [10,11] ).…”

Regulating the Supramolecular Polymerization of Fibrous Crystalline Structures in Aqueous Solution

“…[ 17,18 ] Establishing a similar regulation mechanism in synthetic platforms should improve our abilities in the creation of supramolecular polymers with dynamic and tunable properties, and eventually approaching the level of sophistication found in nature's self‐organized, “active” supramolecular materials. [ 19–28 ]…”

Tweaking a BODIPY Spherical Self‐Assembly to 2D Supramolecular Polymers Facilitates Excited‐State Cascade Energy Transfer

“…[3][4][5] Living supramolecular polymerization, [3,5a] crystallization-driven self-assembly [6] and seeded supramolecular polymerization [7] are examples that control the length and dimension of supramolecular structures through kinetic and thermodynamic control of self-assembly.W hile living supramolecular polymerization is undoubtedly apowerful tool for the precise control of molecular self-assembly,i tc annot be applied as ag eneral strategy.T herefore,d ifferent kinds of external stimuli such as light, [8] pH, [9] redox, [10] enzyme, [11] ultrasound, [12] and solvents, [13] have been exploited for controlled supramolecular polymerization of functional p-systems. [14] Cascade energy transfer in supramolecular architectures is af undamentally important process applicable to the biological and materials world. [15] Fore xample,t he phycobilisomes,w hich is the major light-harvesting complex in cyanobacteria and red algae,i sc onsidered one of the most efficient light-harvesting systems with more than 95 % efficiency due to the cascade energy transfer.…”