Peptide-Based Supramolecular Systems Chemistry

Chemical Reviews, Journal Year: 2021, Volume and Issue: 121(22), P. 13869 - 13914

Published: Sept. 14, 2021

Peptide-based supramolecular systems chemistry seeks to mimic the ability of life forms use conserved sets building blocks and chemical reactions achieve a bewildering array functions. Building on design principles for short peptide-based nanomaterials with properties, such as self-assembly, recognition, catalysis, actuation, are increasingly available. is starting address far greater challenge systems-level access complex functions that emerge when multiple interactions coordinated integrated. We discuss key features relevant design, including regulating order disorder, development active adaptive by considering kinetic thermodynamic aspects combinatorial dynamic covalent noncovalent interactions. Finally, we how structural concepts, preorganization induced fit, critical develop materials tunable photonic, electronic, catalytic properties. highlight examples where combined, resulting in display properties cannot be achieved without this level integration.

Language: Английский

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Dipeptide coacervates as artificial membraneless organelles for bioorthogonal catalysis

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

Published: Jan. 2, 2024

Abstract Artificial organelles can manipulate cellular functions and introduce non-biological processes into cells. Coacervate droplets have emerged as a close analog of membraneless organelles. Their biomimetic properties, such molecular crowding selective partitioning, make them promising components for designing cell-like materials. However, their use artificial has been limited by complex structure, control over internal microenvironment inherent colloidal instability. Here we report the design dipeptide coacervates that exhibit enhanced stability, biocompatibility, hydrophobic microenvironment. The character facilitates encapsulation species, including transition metal-based catalysts, enhancing efficiency in aqueous environments. Dipeptide carrying catalyst are incorporated active cells trigger an chemical reaction. development with opens alternative avenue field materials applications catalysis synthetic biology.

Language: Английский

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Liquid spherical shells are a non-equilibrium steady state of active droplets

Nature Communications, Journal Year: 2023, Volume and Issue: 14(1)

Published: Oct. 17, 2023

Liquid-liquid phase separation yields spherical droplets that eventually coarsen to one large, stable droplet governed by the principle of minimal free energy. In chemically fueled separation, formation phase-separating molecules is coupled a fuel-driven, non-equilibrium reaction cycle. It thus dissipative structures sustained continuous fuel conversion. Such are ubiquitous in biology but poorly understood as they thermodynamics. Here, we bridge gap between passive, close-to-equilibrium, and active, with separation. We observe spherical, active can undergo morphological transition into liquid, shell. demonstrate mechanism related gradients short-lived material. characterize how far out equilibrium shell state chemical power necessary sustain it. Our work suggests alternative avenues for assembling complex morphologies, which might already be exploited form membraneless organelles cells.

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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Sustained enzymatic activity and flow in crowded protein droplets

Nature Communications, Journal Year: 2021, Volume and Issue: 12(1)

Published: Nov. 1, 2021

Abstract Living cells harvest energy from their environments to drive the chemical processes that enable life. We introduce a minimal system operates at similar protein concentrations, metabolic densities, and length scales as living cells. This approach takes advantage of tendency phase-separated droplets strongly partition enzymes, while presenting barriers transport small molecules across interface. By dispersing these microreactors in reservoir substrate-loaded buffer, we achieve steady states densities match those hungriest microorganisms. further demonstrate formation pH gradients, capable driving microscopic flows. Our enables investigation function diverse enzymes mimic cytoplasm, provides flexible platform for studying collective behavior matter driven far equilibrium.

Language: Английский

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An Approach to the De Novo Synthesis of Life

Accounts of Chemical Research, Journal Year: 2021, Volume and Issue: 55(2), P. 145 - 155

Published: Dec. 29, 2021

ConspectusAs the remit of chemistry expands beyond molecules to systems, new synthetic targets appear on horizon. Among these, life represents perhaps ultimate challenge. Building an increasingly detailed understanding inner workings living systems and advances in organic synthesis supramolecular chemistry, de novo (i.e., construction a form based completely components) is coming within reach. This Account presents our first steps journey toward this long-term goal. The requires functional integration different subsystems that harbor characteristics are deemed essential life. most important these self-replication, metabolism, compartmentalization. Integrating features into single system, maintaining system out equilibrium, allowing it undergo Darwinian evolution should ideally result emergence Our started with serendipitous discovery mechanism self-replication. We found self-assembly mixture interconverting oligomers general way achieving where assembly process drives very assemble. Mechanically induced breakage growing replicating assemblies resulted their exponential growth, which enabler for evolution. Through mechanism, self-replication compounds containing peptides, nucleobases, fully was achieved. Several examples evolutionary dynamics have been observed including spontaneous diversification replicators them specialize food sets, history dependence replicator composition, parasitic behavior. Peptide-based were organize peptide units space manner that, inadvertently, gives rise microenvironments capable catalysis chemical reactions or binding-induced activation cofactors. can be catalyzed by ones produce precursors from grow, amounting assimilation proto-metabolism. Operating chemically fueled out-of-equilibrium replication-destruction regime promote increase molecular complexity. Fueling counteracts inherent tendency evolve lower complexity (caused fact smaller tend replicate faster). remaining road now assimilate compartmentalization achieve open-ended resulting system. Success life, once obtained, will far-reaching implications what is, search extraterrestrial how may originated earth, every-day opening up vistas technology materials.

Language: Английский

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The intertwined physics of active chemical reactions and phase separation

Current Opinion in Colloid & Interface Science, Journal Year: 2022, Volume and Issue: 61, P. 101606 - 101606

Published: Aug. 2, 2022

Language: Английский

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Phase Transitions in Chemically Fueled, Multiphase Complex Coacervate Droplets

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(46)

Published: Sept. 6, 2022

Abstract Membraneless organelles are droplets in the cytosol that regulated by chemical reactions. Increasing studies suggest they internally organized. However, how these subcompartments remains elusive. Herein, we describe a complex coacervate‐based model composed of two polyanions and short peptide. With reaction cycle, control affinity peptide for polyelectrolytes leading to distinct regimes inside phase diagram. We study transitions from one regime another identify new can only occur under kinetic control. Finally, show cycle controls liquidity offering insights into active processes cells play an important role tuning liquid state membraneless organelles. Our work demonstrates not thermodynamic properties but also kinetics should be considered organization multiple phases droplets.

Language: Английский

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Non-enzymatic oligonucleotide ligation in coacervate protocells sustains compartment-content coupling

Nature Communications, Journal Year: 2023, Volume and Issue: 14(1)

Published: May 9, 2023

Abstract Modern cells are complex chemical compartments tightly regulated by an underlying DNA-encoded program. Achieving a form of coupling between molecular content, reactions, and chassis in synthetic represents key step to the assembly evolvable protocells but remains challenging. Here, we design coacervate droplets that promote non-enzymatic oligonucleotide polymerization restructure as result reaction dynamics. More specifically, rationally exploit complexation end-reactive oligonucleotides able stack into long physical polymers cationic azobenzene photoswitch produce three different phases—soft solids, liquid crystalline or isotropic coacervates droplets—each them having impact on efficiency. Dynamical modulation dissolution via trans - cis photo-isomerization is used demonstrate cycles light-actuated ligation. Remarkably, changes population polynucleotides during induce phase transitions due length-based DNA self-sorting multiphase coacervates. Overall, combining tight reaction-structure environmental responsiveness, our reactive provide general route synthesis pave way emergence primitive compartment-content membrane-free protocells.

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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