Controlled Supramolecular Polymerization via Bioinspired, Liquid–Liquid Phase Separation of Monomers

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(18), P. 12577 - 12586

Published: April 29, 2024

Dynamic supramolecular assemblies, driven by noncovalent interactions, pervade the biological realm. In synthetic domain, their counterparts, polymers, endowed with remarkable self-repair and adaptive traits, are often realized through bioinspired designs. Recently, controlled polymerization strategies have emerged, drawing inspiration from protein self-assembly. A burgeoning area of research involves mimicking liquid–liquid phase separation (LLPS) observed in proteins to create coacervate droplets recognizing significance cellular organization diverse functions. Herein, we introduce a novel perspective on coacervates, extending beyond established role biology as dynamic, membraneless phases enable structural control polymers. Drawing parallels cooperative growth amyloid fibrils LLPS, present metastable dormant monomer for polymerization. This is achieved via π-conjugated design that combines characteristics both coacervation its terminal ionic groups one-dimensional core. leads unique temporal resulting phase, which subsequently undergoes nucleation within droplets. In-depth spectroscopic microscopic characterization provides insights into evolution disordered ordered phases. Furthermore, modulate kinetics liquid-to-solid transformation achieve precise over invoke seeding droplets, showcasing living characteristics. Our work thus opens up new avenues exciting field polymerization, offering general principles synthesis precision self-assembled structures confined environments.

Language: Английский

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Materials Inspired by Living Functions

Advanced Functional Materials, Journal Year: 2024, Volume and Issue: 34(37)

Published: March 19, 2024

Abstract Engineering or mimicking living materials found in nature has the potential to transform use of materials. Unlike classic synthetic which are typically optimized for static properties, economics, and recently also sustainability, life dynamic, feedback‐controlled, evolving, adaptive. Although do not exhibit such complicated functionalities, researchers increasingly challenging this viewpoint expanding material concepts toward dynamic systems inspired by selected life‐like functions. Herein, it is suggested that can be approached from two perspectives: through engineering biological organisms their functions provide basis new materials, producing with rudimentary life‐inspired Current advances discussed perspectives (i) features based on built‐in memory associative learning, (ii) emergent structures self‐regulated designs using non‐equilibrium systems, (iii) interfacing non‐living form cellular community control growth open routes fabrication. Strategies combining (i)–(iii) responses applications interactive autonomous devices, helping realize next‐generation sensors, soft robots, external over bioproduction self‐organizing structural

Language: Английский

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Assembly of Complex Colloidal Systems Using DNA

Annual Review of Condensed Matter Physics, Journal Year: 2025, Volume and Issue: 16(1), P. 443 - 463

Published: March 10, 2025

Nearly thirty years after its inception, the field of DNA-programmed colloidal self-assembly has begun to realize initial promise. In this review, we summarize recent developments in designing effective interactions and understanding dynamic pathways DNA-coated nanoparticles microparticles, as well how these advances have propelled tremendous progress crystal engineering. We also highlight exciting new directions showing that classes subunits combining with DNA origami can be used engineer novel multicomponent assemblies, including structures self-limiting, finite sizes. conclude by providing an outlook on theoretical focusing kinetics could usher materials-design opportunities, like possibility retrieving multiple distinct target from a single suspension or accessing materials are stabilized energy dissipation, mimicking living systems.

Language: Английский

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Carbodiimide-fueled catalytic reaction cycles to regulate supramolecular processes

Chemical Communications, Journal Year: 2021, Volume and Issue: 58(9), P. 1284 - 1297

Published: Dec. 23, 2021

A challenge in supramolecular chemistry is to control self-assembly out-of-equilibrium. Towards that goal, chemically fueled has emerged as a powerful tool. We review the progress assembly by hydration of carbodiimides.

Language: Английский

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Fuel-Driven Dynamic Combinatorial Libraries

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 143(20), P. 7719 - 7725

Published: May 12, 2021

In dynamic combinatorial libraries, molecules react with each other reversibly to form intricate networks under thermodynamic control. biological systems, chemical reaction operate kinetic control by the transduction of energy. We thus introduced notion energy transduction, via cycles, a library. library, monomers can be oligomerized, oligomers deoligomerized, and recombine. Interestingly, we found that dynamics library's components were dominated transacylation, which is an equilibrium reaction. contrast, dictated fuel-driven activation, nonequilibrium Finally, self-assembly play large role in affecting reaction's kinetics feedback mechanisms. The interplay simultaneously operating reactions mechanisms result hysteresis effects outcome competition for fuel depends on events occurred past. future work, envision diversifying library modifying building blocks catalytically active motifs information-containing monomers.

Language: Английский

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Out‐of‐equilibrium supramolecular self‐assembling systems driven by chemical fuel

Aggregate, Journal Year: 2021, Volume and Issue: 2(5)

Published: Aug. 24, 2021

Abstract A rich variety of smart materials developed via supramolecular assembly strategies have been introduced in the past decades. However, most reside thermodynamic equilibrium state, opposed to those nonequilibrium structures with sophisticated functions that are observed living systems. To develop advanced synthetic systems, chemists begun focus on how use similar used biological systems for fabricating artificial out‐of‐equilibrium Heretofore, a developed. In this review, we summarized recent progress and categorized them terms chemical fuel used, including adenosine triphosphate (ATP), acid/base, carbodiimide reagents, many others. For these self‐assembling their design strategies, potential applications, as well advantageous features discussed. At end remaining challenges an outlook chemical‐fuel‐driven were also It is believed review has provided some insights could be useful who interested assembling subsequent constructing various transient materials.

Language: Английский

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The chemistry of chemically fueled droplets

Trends in Chemistry, Journal Year: 2022, Volume and Issue: 5(1), P. 45 - 60

Published: Dec. 5, 2022

Liquid compartments without a surrounding membrane control vital functions and chemistries in living cells. One subset of droplets regulated by chemical reactions is chemically fueled droplets. The phase-separating molecules that form these are activated deactivated reaction cycle consumes high-energy molecule (i.e., fuel). That means the droplet exists out equilibrium at expense energy. This review aims to demonstrate how design which types unique behaviors can be expected. We highlight experimental advances corroborated theory. close with an outlook aim bridge gap between theoreticians experimentalists build better liquid models.

Language: Английский

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Temporal Stimulus Patterns Drive Differentiation of a Synthetic Dipeptide-Based Coacervate

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(33), P. 15155 - 15164

Published: Aug. 9, 2022

The fate of living cells often depends on their processing temporally modulated information, such as the frequency and duration various signals. Synthetic stimulus-responsive systems have been intensely studied for >50 years, but it is still challenging chemists to create artificial that can decode dynamically oscillating stimuli alter systems' properties/functions because lack sophisticated reaction networks are comparable with biological signal transduction. Here, we report morphological differentiation synthetic dipeptide-based coacervates in response distinct patterns light pulse. We designed a simple cationic diphenylalanine peptide derivative enable formation coacervates. concentrated an anionic methacrylate monomer photoinitiator, which provided unique environment facilitated light-triggered radical polymerization─even air. Pulsed irradiation at 9.0 Hz (but not 0.5 Hz) afforded polymers. This dependence pulse attributable competition reactive intermediates between molecular oxygen. temporal pattern-dependent polymer enabled differentiate terms morphology internal viscosity, ultrasensitive switch-like mode. Our achievements will facilitate rational design smart supramolecular soft materials insightful regarding synthesis chemical cells.

Language: Английский

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Chemical signal regulated injectable coacervate hydrogels

Chemical Science, Journal Year: 2023, Volume and Issue: 14(6), P. 1512 - 1523

Published: Jan. 1, 2023

Incorporation of reversible Michael addition controlled coacervate crosslinks in a polymer hydrogel led to injectable gels that are responsive nucleophilic chemical signals, enabling accelerated degradation culture media after injection.

Language: Английский

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Chemically Fueled Autonomous Sol→Gel→Sol→Gel→Sol Transitions

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(23)

Published: April 4, 2023

Complex non-equilibrium phase behaviors are a hallmark of natural self-assembling systems. Here we show how intricate transitions can be achieved through chemically fueled reaction cycle to yield autonomous sol→gel→sol→gel→sol transitions. A relay chemical transformations based on thiazinane metathesis leads two consecutive transient gelations in closed system. Within seconds fuel addition deactivated monomers, an imine-based hydrogel forms that consists fibrillar microspheres. This gel quickly loses its mechanical strength and solution, from which second aldehyde-based nucleates remains stable for over one day. Overall, our gives rise re-entrant without any experimental intervention.

Language: Английский

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