Insights into Chemically Fueled Supramolecular Polymers

Chemical Reviews, Journal Year: 2022, Volume and Issue: 122(13), P. 11759 - 11777

Published: June 8, 2022

Supramolecular polymerization can be controlled in space and time by chemical fuels. A nonassembled monomer is activated the fuel subsequently self-assembles into a polymer. Deactivation of molecule either solution or inside polymer leads to disassembly. Whereas biology has already mastered this approach, fully artificial examples have only appeared past decade. Here, we map available literature four distinct regimes depending on their activation/deactivation rates equivalents deactivating fuel. We present increasingly complex mathematical models, first considering (i.e., transient activation) later including full details isodesmic cooperative supramolecular processes self-assembly). finish showing that sustained oscillations are possible chemically fueled provide mechanistic insights. hope our models encourage quantification activation, deactivation, assembly, disassembly kinetics future studies.

Language: Английский

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Chemically Fueled Supramolecular Materials

Accounts of Materials Research, Journal Year: 2023, Volume and Issue: 4(5), P. 416 - 426

Published: April 14, 2023

In biology, the function of many molecules is regulated through nonequilibrium chemical reaction cycles. The prototypical example phosphorylation an amino acid in enzyme which induces a functional change, e.g., it folds or unfolds, assembles disassembles, binds substrate. Such does not occur spontaneously but requires phosphorylating agent with high potential (for example, adenosine triphosphate (ATP)) to be converted into molecule lower (adenosine diphosphate (ADP)). When this energy used regulate assembly, we speak chemically fueled assemblies; i.e., potential, fuel, self-assembly process. For binding guanosine (GTP) tubulin self-assembly. bound GTP hydrolyzed (GDP) upon disassembly. result dynamic assembly endowed unique characteristics, such as time-dependent behavior and ability self-heal. These intriguing, properties have inspired supramolecular chemists create similar molecular assemblies from bottom up. While examples been designed, they remain scarce partly because cycles are rare often complex. Thus, recently developed carbodiimide-driven cycle that versatile easy use, quantitatively understood, suffer side reactions. cycle, carboxylate precursor reacts carbodiimide form activated species like anhydride ester. state water thereby reverts its state; deactivated. Effectively, catalyzes carbodiimides' conversion waste forms transient state. We designed building blocks range materials at expense fuel. simplicity versatility democratized popularized field assemblies. Account, describe what "learned" on our way. introduce exemplified by biological design cycle. Using group others, offer rules for block's structure strategies desired morphology materials. discussed morphologies include fibers, colloids, crystals, oil- coacervate-based droplets. then demonstrate how these material Besides, discuss concept reciprocal coupling exerts feedback also mechanisms. Finally, close Account discussion outlook field. This aims provide fundamental understanding facilitate further progress toward conceptually new

Language: Английский

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Suppressing catalyst poisoning in the carbodiimide-fueled reaction cycle

Chemical Science, Journal Year: 2023, Volume and Issue: 14(44), P. 12653 - 12660

Published: Jan. 1, 2023

In biology, cells regulate the function of molecules using catalytic reaction cycles that convert reagents with high chemical potential (fuel) to waste molecules. Inspired by synthetic analogs such have been devised, and a widely used cycle uses carboxylates as catalysts accelerate hydration carbodiimides. The is versatile easy use, so it applied motors, pumps, self-assembly, phase separation. However, suffers from side reactions, especially formation N-acylurea. cycles, reactions are disastrous they decrease fuel's efficiency and, more importantly, destroy molecular machinery or assembling Therefore, this work tested how suppress N-acylurea screening precursor concentration, its structure, carbodiimide additives, temperature, pH. It turned out combination low pH, 10% pyridine fraction fuel could significantly product keep highly effective successful assembly. We anticipate our will provide guidelines for carbodiimide-fueled choose optimal conditions.

Language: Английский

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Template-based copying in chemically fuelled dynamic combinatorial libraries

Nature Chemistry, Journal Year: 2024, Volume and Issue: 16(8), P. 1240 - 1249

Published: July 16, 2024

Abstract One of science’s greatest challenges is determining how life can spontaneously emerge from a mixture molecules. A complicating factor that and its molecules are inherently unstable—RNA proteins prone to hydrolysis denaturation. For the de novo synthesis or better understand emergence at origin, selection mechanisms needed for unstable Here we present chemically fuelled dynamic combinatorial library model RNA oligomerization deoligomerization shine new light on purification under kinetic control. In experiments, oligomers only be sustained by continuous production. Hybridization powerful tool selecting molecules, offering feedback rates. Moreover, find templation used purify libraries oligomers. addition, template-assisted formation within coacervate-based protocells changes compartment’s physical properties, such as their ability fuse. Such reciprocal coupling between oligomer production properties key step towards synthetic life.

Language: Английский

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Bioinspired Self-Resettable Hydrogel Actuators Powered by a Chemical Fuel

ACS Applied Materials & Interfaces, Journal Year: 2022, Volume and Issue: 14(38), P. 43825 - 43832

Published: Sept. 14, 2022

The movements of soft living tissues, such as muscle, have sparked a strong interest in the design hydrogel actuators; however, so far, typical manmade examples still lag behind their biological counterparts, which usually function under nonequilibrium conditions through consumption high-energy biomolecules and show highly autonomous behaviors. Here, we report on self-resettable actuators that are powered by chemical fuel can spontaneously return to original states over time once fuels depleted. Self-resettable actuation originates from fuel-mediated transient change hydrophilicity networks. extent duration be programmed levels, process is recyclable refueling. Furthermore, various proof-of-concept robots created, resembling soft-bodied creatures nature. This work may serve starting point for development lifelike with

Language: Английский

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Dissipative Dynamic Covalent Chemistry (DDCvC) Based on the Transimination Reaction

Chemistry - A European Journal, Journal Year: 2022, Volume and Issue: 28(26)

Published: March 8, 2022

This work reports that the composition of a dynamic library (DL) interconverting imines can be controlled over time in dissipative fashion by addition an activated carboxylic acid used as chemical fuel. When fuel is added to DL, which initially under thermodynamic equilibrium, mixture dramatically changes and new, (out equilibrium) state reached persists until exhaustion. Thus, transient (DDL) generated that, eventually, reverts back initial DL when consumed, closing DL→DDL→DL cycle. The larger amount fuel, longer spent system DDL state. transimination reaction shown optimal candidate for realization covalent chemistry (DDCvC).

Language: Английский

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Acylphosphates as versatile transient species in reaction networks and optical catalyst screenings

Chem, Journal Year: 2023, Volume and Issue: 10(3), P. 910 - 923

Published: Dec. 28, 2023

Chemically driven reaction cycles are prevalent in nature; yet, artificial examples still rare and often lack robustness or versatility. In this study, we introduce acylphosphate steady states that can be accessed from a wide range of organophosphates using either carboxylic anhydride carbodiimide fuels. The combination fuel pyridine catalysis makes chemistry sufficiently robust to allow for 25 fueling without generation observable quantities detrimental side products such as pyrophosphates. We demonstrate the acylation gives rise transient aggregates, harness fluorescence acylphosphate-bridged excimers rapid screenings more than 50 catalysts single well plate experiment. Due its versatility robustness, anticipate organophosphate/acylphosphate cycle will prove useful creation chemically molecular machines self-assemblies.

Language: Английский

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Progressive Endergonic Synthesis of Diels–Alder Adducts Driven by Chemical Energy

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(45)

Published: July 17, 2024

The overwhelming majority of artificial chemical reaction networks respond to stimuli by relaxing towards an equilibrium state. opposite response-moving away from equilibrium-can afford the endergonic synthesis molecules, which only rare examples have been reported. Here, we report six Diels-Alder adducts formed in process and use this strategy realize their stepwise accumulation. Indeed, systems repeated occurrences same stimulus increasing amount adduct formed, with final network distribution depending on number received. Our findings indicate how processes can contribute transition responsive adaptive systems.

Language: Английский

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Dissipative Formation of Covalent Basket Cages

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(33)

Published: June 20, 2022

Abstract Living systems use chemical fuels to transiently assemble functional structures. As a step toward constructing abiotic mimics of such structures, we herein describe dissipative formation covalent basket cage CBC 5 by reversible imine condensation cup‐shaped aldehyde 2 (i.e., basket) with trivalent aromatic amine 4 . This nanosized [4+4] ( V =5 nm 3 , M w =6150 Da) has shape truncated tetrahedron four baskets at its vertices and amines forming the faces. Importantly, tris ‐aldehyde aliphatic ‐amine 7 undergo give small [1+1] 6 The metathesis into was optimized bias equilibrium favouring Addition tribromoacetic acid (TBA) as fuel perturbs this result in transient subsequent consumption TBA via decarboxylation driving system back starting state.

Language: Английский

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In situ Synthesis of Supramolecular Polymers: Finding the Right Conditions when Combining Covalent and Non‐Covalent Synthesis

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(34)

Published: June 28, 2022

The combination of covalent and non-covalent synthesis is omnipresent in nature potentially enables access to new materials. Yet, the fundamental principles that govern such a are barely understood. Here, we demonstrate how even simple reaction mixtures behave surprisingly complex when reactions coupled self-assembly processes. Specifically, study behavior system which situ formation discotic benzene-1,3,5-tricarboxamide (BTA) monomers linked an intertwined network including into helical BTA polymers. This shows unexpected phase-separation interplay reactant/product concentrations, side-products solvent purity determines composition. We envision these insights can bring us one step closer design systems combined covalent/non-covalent fashion.

Language: Английский

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