Out‐of‐Equilibrium (Supra)molecular Systems and Materials: An Introduction

Giuseppone, Nicolas; Walther, Andreas

doi:10.1002/9783527821990.ch1

Cited by 22 publications

(28 citation statements)

References 96 publications

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“…[1][2][3][4][5][6][7][8][9][10][11] Light-driven molecular motors are fascinating molecules that can be utilised to impart motion at the nanoscale, and can drive systems out of equilibrium due to their intrinsic ability to undergo unidirectional and repetitive rotation. 12 Since the first light-driven unidirectional rotary molecular motor presented by our group in 1999, 13 a vast amount of research has been carried out on overcrowded alkene-based molecular motors. 14,15 They are now highly tuneable actuators which can be tailored to diverse purposes in a multitude of different fields, such as smart materials, [16][17][18] catalysis [19][20][21] and biomedical applications.…”

Section: Introductionmentioning

confidence: 99%

Controlling rotary motion of molecular motors based on oxindole

et al. 2022

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Section: Introductionmentioning

confidence: 99%

Controlling rotary motion of molecular motors based on oxindole

et al. 2022

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“…1 The emergent functions of such systems can only be maintained as long as energy is dissipated in the form of the consumption of highenergy molecules that stem from metabolic pathways. 2 In some cases, most notably in actin filaments 3 and microtubules, 4 chemical fuels drive the self-assembly of organic building blocks into transient supramolecular scaffolds. Over the past decade, researchers in the field of systems chemistry 5−7 have begun to mimic these natural processes, using artificial building blocks, chemical fuels, 8 and catalysts.…”

Section: ■ Introductionmentioning

confidence: 99%

A Ribonucleotide ↔ Phosphoramidate Reaction Network Optimized by Computer-Aided Design

et al. 2022

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A growing number of out-of-equilibrium systems have been created and investigated in chemical laboratories over the past decade. One way to achieve this is to create a reaction cycle, in which the forward reaction is driven by a chemical fuel and the backward reaction follows a different pathway. Such dissipative reaction networks are still relatively rare, however, and most non-enzymatic examples are based on the carbodiimidedriven generation of carboxylic acid anhydrides. In this work, we describe a dissipative reaction network that comprises the chemically fueled formation of phosphoramidates from natural ribonucleotides (e.g., GMP or AMP) and phosphoramidate hydrolysis as a mild backward reaction. Because the individual reactions are subject to a multitude of interconnected parameters, the software-assisted tool "Design of Experiments" (DoE) was a great asset for optimizing and understanding the network. One notable insight was the stark effect of the nucleophilic catalyst 1-ethylimidazole (EtIm) on the hydrolysis rate, which is reminiscent of the action of the histidine group in phosphoramidase enzymes (e.g., HINT1). We were also able to use the reaction cycle to generate transient self-assemblies, which were characterized by dynamic light scattering (DLS), confocal microscopy (CLSM), and cryogenic transmission electron microscopy (cryo-TEM). Because these compartments are based on prebiotically plausible building blocks, our findings may have relevance for origin-of-life scenarios.

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“…[1][2][3][4][5] Toward these goals, in addition to conventional static or thermodynamically controlled supramolecular polymers, the development of dynamic supramolecular materials that are responsive to external stimuli such as chemical reactions has been extensively studied. [6][7][8][9][10][11][12][13][14][15][16][17][18] To design supramolecular polymers based on p-conjugated monomers that can implement chemical reactivity, one needs to introduce a reaction site where the chemical reaction proceeds under mild conditions without byproducts or a catalyst that could have unintended effects on the supramolecular polymers. These stringent requirements for the design of p-conjugated molecules hinder the further development of dynamic supramolecular polymers, although elaborate dynamic supramolecular assemblies that incorporate efficient chemical reactions have been reported.…”

Section: Introductionmentioning

confidence: 99%