Molecular Ratchets and Kinetic Asymmetry: Giving Chemistry Direction

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(23)

Опубликована: Апрель 3, 2024

Abstract Over the last two decades ratchet mechanisms have transformed understanding and design of stochastic molecular systems—biological, chemical physical—in a move away from mechanical macroscopic analogies that dominated thinking regarding dynamics in 1990s early 2000s (e.g. pistons, springs, etc), to more scale‐relevant concepts underpin out‐of‐equilibrium research sciences today. Ratcheting has established nanotechnology as frontier for energy transduction metabolism, enabled reverse engineering biomolecular machinery, delivering insights into how molecules ‘walk’ track‐based synthesisers operate, acceleration reactions enables be transduced by catalysts (both motor proteins synthetic catalysts), dynamic systems can driven equilibrium through catalysis. The recognition biology, their invention systems, is proving significant areas diverse supramolecular chemistry, covalent DNA nanotechnology, polymer materials science, heterogeneous catalysis, endergonic synthesis, origin life, many other branches science. Put simply, give chemistry direction. Kinetic asymmetry, key feature ratcheting, counterpart structural asymmetry (i.e. chirality). Given ubiquity processes significance behaviour function it surely just fundamentally important. This Review charts recognition, development ratchets, focussing particularly on role which they were originally envisaged elements machinery. Different kinetically asymmetric are compared, consequences discussed. These archetypal examples demonstrate inexorably equilibrium, rather than relax towards it.

Язык: Английский

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Artificial Molecular Ratchets: Tools Enabling Endergonic Processes

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(47)

Опубликована: Авг. 7, 2023

Abstract Non‐equilibrium chemical systems underpin multiple domains of contemporary interest, including supramolecular chemistry, molecular machines, prebiotic and energy transduction. Experimental chemists are now pioneering the realization artificial that can harvest away from equilibrium. In this tutorial Review, we provide an overview ratchets: mechanisms enabling absorption environment. By focusing on mechanism type—rather than application domain or source—we offer a unifying picture seemingly disparate phenomena, which hope will foster progress in fascinating science.

Язык: Английский

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Photoswitchable Imines Drive Dynamic Covalent Systems to Nonequilibrium Steady States

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(30), С. 20720 - 20727

Опубликована: Июль 18, 2024

Coupling a photochemical reaction to thermal exchange process can drive the latter nonequilibrium steady state (NESS) under photoirradiation. Typically, systems use separate motifs for photoresponse and equilibrium-related processes. Here, we show that photoswitchable imines fulfill both roles simultaneously, autonomously driving dynamic covalent system into NESS continuous light irradiation. We demonstrate this using transimination reactions, where

Язык: Английский

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Artificial Homeostasis Systems Based on Feedback Reaction Networks: Design Principles and Future Promises

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(14)

Опубликована: Янв. 16, 2024

Abstract Feedback‐controlled chemical reaction networks (FCRNs) are indispensable for various biological processes, such as cellular mechanisms, patterns, and signaling pathways. Through the intricate interplay of many feedback loops (FLs), FCRNs maintain a stable internal environment. Currently, creating minimalistic synthetic cells is long‐term objective systems chemistry, which motivated by natural integrity. The design, kinetic optimization, analysis to exhibit functions akin those cell still pose significant challenges. Indeed, reaching homeostasis essential engineering components. However, maintaining in artificial against agitations difficult task. Several events can provide us with guidelines conceptual understanding homeostasis, be further applicable designing systems. In this regard, we organize our review driven at different length scales, including homogeneous, compartmentalized, soft material First, stretch quick overview molecular supramolecular systems, toolbox nonlinear homeostatic Moreover, existing history their advanced self‐correcting, regulating properties also emphasized.

Язык: Английский

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Fuel-Driven Enzymatic Reaction Networks to Program Autonomous Thiol/Disulfide Redox Systems

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(15), С. 10281 - 10285

Опубликована: Апрель 3, 2024

Fuel-driven dissipative formation of disulfide bonds using competing oxidative activation and reductive deactivation presents a possibly very versatile avenue for autonomous materials design. However, this is challenging to realize because the direct annihilation oxidizing fuel deactivating reducing agent. We overcome challenge by introducing redox-based enzymatic reaction network (ERN), enabling molecularly dissolved thiols in fully manner. Moreover, ERN allows programming hydrogel lifetimes utilizing thiol-terminated star polymers (sPEG-SH). The can be customized operate with aliphatic aromatic should thus broadly applicable functional thiols.

Язык: Английский

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Guiding Transient Peptide Assemblies with Structural Elements Embedded in Abiotic Phosphate Fuels

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(28)

Опубликована: Апрель 27, 2024

Abstract Despite great progress in the construction of non‐equilibrium systems, most approaches do not consider structure fuel as a critical element to control processes. Herein, we show that amino acid side chains (A, F, Nal) abiotic phosphates can direct assembly and reactivity during transient formation. The fuels bind covalently substrates subsequently influence structures process. We focus on ways which phosphate esters guide formation how cross regulate when constructing assemblies. Through chemical functionalization energy‐rich aminoacyl esters, are able yield thioesters upon adding dipeptides containing tyrosine or cysteine residues. structural elements around lifetime formed their supramolecular These properties be further influenced by peptide sequence substrates, incorporating anionic, aliphatic aromatic Furthermore, illustrate oligomerization initiated from single ester residue (Y). findings suggest activated acids with varying energy contents pave way for designing fabricating structured fuels.

Язык: Английский

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Triply Adaptive Libraries of Dynamic Covalent Macrocycles: Switching between Sorted and Unsorted States

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(22), С. 15438 - 15445

Опубликована: Май 27, 2024

Dynamic noncovalent and covalent chemistries have enabled the constitutional modulation of chemical entities within dynamic systems. The switching between order disorder, i.e., self-sorted unsorted states libraries, remains challenging. Herein, we study adaptive behaviors a library imine macrocycles generated from dialdehydes diamines, seeking ways to exert control over sorting unsorting processes. distribution constituents in present is modulated response internal external effectors (e.g., time, metal cations, fuels), resulting transient amplification out-of-equilibrium states. showcases higher complexity systems subject multiple adaptation through interconversion singularity/order diversity/disorder.

Язык: Английский

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

Chem, Год журнала: 2023, Номер 10(3), С. 910 - 923

Опубликована: Дек. 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.

Язык: Английский

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ATP‐Regulated Formation of Transient Peptide Amphiphiles Superstructures

Small, Год журнала: 2025, Номер unknown

Опубликована: Фев. 25, 2025

Abstract Self‐assembly of biotic systems serves as inspiration for the preparation synthetic supramolecular assemblies to mimic structural, temporal, and functional aspects living systems. Despite peptide amphiphiles (PAs) being widely studied in context biomimetic bioactive nanomaterials, very little is currently known about reversible spatiotemporal control their hierarchical self‐assemblies. Here, it shown that PA‐based nanofibers can transiently form superstructures, through binding with oppositely charged adenosine triphosphate (ATP), leading charge screening stabilization bundled nanofibers. Enzymatic hydrolysis ATP monophosphate phosphates causes disassembly superstructures recovery individual The lifetime be controlled by adjusting concentration either or enzyme. role formation PA has on chemical reactivity catalysis also evaluated. It observed superstructuration responsible downregulation activity, which then recovered gradual bundles. These results demonstrate potential self‐assembly modulate nanostructures.

Язык: Английский

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Imine-Based Transient Supramolecular Polymers

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Март 19, 2025

Systems that change properties upon exposure to chemical stimuli offer the interesting prospect of (partially) mimicking functions living systems. Over past decade, numerous supramolecular systems whose composition and are regulated by dissipation fuels have been reported. These typically based on transient transformation a "dormant" species into an active, self-assembling monomer. The process is powered fuel consumption terminates depletion, restoring initial dormant state. Previously reported out-of-equilibrium polymerizations relied activation adding or removing small structural units enable polymerization. Here, we present approach combines reversibility dynamic covalent chemistry trigger "recycling" components combinatorial library (DCL). Treatment equilibrated DCL aliphatic imines aromatic amines with activated carboxylic acid (ACA) generates dissipative protonated amines. acidic conditions creation polymer held together interactions between crown ether moieties embedded in scaffold imines. Thus, reshuffles connectivity enables temporary purely (polymeric) system polymer. We demonstrate strategy using two different feedstocks consisting diimine macrocycle involving calix[4]arene distribution imine (cyclo)oligomers derived from isophthalaldehyde skeleton.

Язык: Английский

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