Artificial Molecular Ratchets: Tools Enabling Endergonic Processes

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(47)

Published: Aug. 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.

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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Endergonic synthesis driven by chemical fuelling

Nature Synthesis, Journal Year: 2024, Volume and Issue: 3(6), P. 707 - 714

Published: March 11, 2024

Abstract Spontaneous chemical reactions proceed energetically downhill to either a local or global minimum, limiting possible transformations those that are exergonic. Endergonic do not spontaneously and require an input of energy. Light has been used drive number deracemizations thermodynamically unfavourable bond-forming reactions, but is restricted substrates can absorb, directly indirectly, energy provided by photons. In contrast, anabolism involves uphill powered fuels. Here we report on the transduction from artificial fuel Diels–Alder reaction. Carboxylic acid catalysed carbodiimide-to-urea formation chemically orthogonal reaction diene dienophile, transiently brings functional groups into close proximity, causing otherwise prohibited cycloaddition in modest yield (15% after two fuelling cycles) with high levels regio- (>99%) stereoselectivity (92:8 exo : endo ). Kinetic asymmetry cycle ratchets away equilibrium distribution Diels–Alder:retro-Diels–Alder products. The driving endergonic occurs through ratchet mechanism (an information ratchet, depending synthetic protocol), reminiscent how molecular machines directionally bias motion. Ratcheting synthesis potential expand chemistry toolbox terms reactivity, complexity control.

Language: Английский

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Active droplets through enzyme-free, dynamic phosphorylation

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: May 17, 2024

Abstract Life continuously transduces energy to perform critical functions using stored in reactive molecules like ATP or NADH. dynamically phosphorylates active sites on proteins and thereby regulates their function. Inspired by such machinery, regulating supramolecular has gained traction. Enzyme-free, synthetic systems that use dynamic phosphorylation regulate processes have not yet been reported, our knowledge. Here, we show an enzyme-free reaction cycle consumes the phosphorylating agent monoamidophosphate transiently histidine histidine-containing peptides. The phosphorylated species are labile deactivate through hydrolysis. exhibits versatility tunability, allowing for of multiple precursors with a tunable half-life. Notably, resulting products can peptide’s phase separation, leading droplets require continuous conversion fuel sustain. will be valuable as model biological but also offer insights into protocell formation.

Language: Английский

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Supramolecular dissipative self‐assembly systems: Approaches and applications

Deleted Journal, Journal Year: 2023, Volume and Issue: 1(2)

Published: Oct. 18, 2023

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

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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Peptide-Based Biomimetic Condensates via Liquid–Liquid Phase Separation as Biomedical Delivery Vehicles

Biomacromolecules, Journal Year: 2024, Volume and Issue: 25(9), P. 5468 - 5488

Published: Aug. 23, 2024

Biomolecular condensates are dynamic liquid droplets through intracellular liquid-liquid phase separation that function as membraneless organelles, which highly involved in various complex cellular processes and functions. Artificial analogs formed via similar pathways can be integrated with biological complexity advanced functions have received tremendous research interest the field of synthetic biology. The coacervate droplet-based compartments partition concentrate a wide range solutes, regarded attractive candidates for mimicking phase-separation behaviors biophysical features biomolecular condensates. use peptide-based materials phase-separating components has advantages such diversity amino acid residues customized sequence design, allows programming their physicochemical properties resulting compartments. In this Perspective, we highlight recent advancements design construction biomimicry from peptides relevant to protein, specific reference molecular self-assembly separation, biorelated applications, envisage emerging biomedical delivery vehicles.

Language: Английский

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Carbodiimide‐Driven Toughening of Interpenetrated Polymer Networks

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(20)

Published: March 22, 2024

Abstract Recent work has demonstrated that temporary crosslinks in polymer networks generated by chemical “fuels” afford materials with large, transient changes their mechanical properties. This can be accomplished carboxylic‐acid‐functionalized hydrogels using carbodiimides, which generate anhydride lifetimes on the order of minutes to hours. Here, impact network architecture properties transiently crosslinked was explored. Single (SNs) were compared interpenetrated (IPNs). Notably, semi‐IPN precursors give IPNs treatment carbodiimide much higher fracture energies (i.e., resistance fracture) and superior compressive strain other architectures. A precursor material featuring acrylic acid only free chains yields, carbodiimide, an IPN a energy 2400 J/m 2 , fourfold increase analogous yields SN. enables formation macroscopic complex cut patterns, even at high strain, underscoring pivotal role performance.

Language: Английский

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Programmable Enzymatic Reaction Network in Artificial Cell‐Like Polymersomes

Advanced Science, Journal Year: 2024, Volume and Issue: 11(24)

Published: April 16, 2024

Abstract The ability to precisely control in vitro enzymatic reactions synthetic cells plays a crucial role the bottom‐up design of artificial cell models that can recapitulate key cellular features and functions such as metabolism. However, integration has been limited bulk or microfluidic emulsions without membrane, lacking more sophisticated higher‐order communities for reconstituting spatiotemporal biological information at multiple length scales. Herein, droplet microfluidics is utilized synthesize cell‐like polymersomes with distinct molecular permeability driven by external signals fuels. presence competing reverse reaction depletes active substrates shown enable demonstration fuel‐driven formation sub‐microcompartments within well realization out‐of‐equilibrium systems. In addition, different characteristics polymersome membranes are exploited successfully construct programmable network mimics communication heterogeneous community through selective transport.

Language: Английский

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Reactive Brownian Dynamics of Chemically Fueled Droplets: Roles of Attraction and Deactivation Modes

The Journal of Physical Chemistry B, Journal Year: 2025, Volume and Issue: 129(2), P. 626 - 636

Published: Jan. 6, 2025

The self-assembly of biological membraneless organelles can be mimicked by active droplets resulting from chemically fueled microphase separation. However, how the nonequilibrium, transient structure these controlled through physicochemical input parameters is not yet well understood. In our work, a two-state chemical reaction and subsequent droplet growth decay are modeled with reactive Brownian dynamics simulation in two spatial dimensions. model, particles that activated via consumption fuel become attractive accumulate into droplets. A local-density-dependent distinction droplet's 'internal' 'external' allows for structural feedback giving further control over deactivation process. shows only external slows down stabilizes droplets, whereas internal lead to temporary encapsulation deactivated (in nonequilibrium 'core–shell' structures) where serve as an outer shell. Additionally, role hydrophobicity resembled attraction energy ε dependency formation on various investigated. For example, high finite-size crystalline while other parameter choices indicate bimodal size distributions at specific times. Similarities differences related experiments discussed.

Language: Английский

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