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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Coacervates Composed of Low‐Molecular‐Weight Compounds– Molecular Design, Stimuli Responsiveness, Confined Reaction

Advanced Biology, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 12, 2025

The discovery of coacervation within living cells through liquid-liquid phase separation has inspired scientists to investigate its fundamental principles and significance. Indeed, coacervates composed low-molecular-weight compounds based on supramolecular strategy can offer valuable models for biomolecular condensates useful tools. This mini-review highlights recent findings advances in (artificial condensates), primarily compounds, with focuses their molecular design, stimuli responsiveness, controlled reactions or leading the coacervates.

Language: Английский

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Compressible Hydrogels with Stabilized Chirality from Thermoresponsive Helical Dendronized Poly(phenylacetylene)s

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(34)

Published: May 21, 2024

Fabrication of chiral hydrogels from thermoresponsive helical dendronized phenylacetylene copolymers (PPAs) carrying three-fold dendritic oligoethylene glycols (OEGs) is reported. Three different temperatures, i.e. below or above cloud point temperatures (T

Language: Английский

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Acetylation of Short Glycopeptides Enables Phase Separation

Biomacromolecules, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 4, 2025

Liquid-liquid phase separation (LLPS) of biomacromolecules is crucial for regulating cellular functions. To explore their molecular mechanisms, peptide-based coacervates mimicking natural proteins have been developed, but the role side chain modifications such as glycosylation remains underexplored. Here, we demonstrate that acetylation short glycopeptides can induce pH- and concentration-dependent separation, while removing acetyl groups abolishes this behavior. Circular dichroism spectroscopy revealed a strong link between peptide structural ordering propensity. Peptides capable forming liquid droplets displayed significant ellipticity change at 205 nm upon changing solution pH. Moreover, these interact with cells enhance antiproliferative property doxorubicin. Therefore, work highlights critical O-acetylation in LLPS provides valuable tool studying parameters its implications processes.

Language: Английский

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A minimalist design approach to simple coacervates from low-molecular-weight components

Polymer Journal, Journal Year: 2025, Volume and Issue: unknown

Published: May 8, 2025

Language: Английский

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Unveiling the Liquid‐Liquid Phase Separation of Benzene‐1,3,5‐Tricarboxamide in Water

ChemSystemsChem, Journal Year: 2024, Volume and Issue: 6(4)

Published: April 23, 2024

Abstract The intricate interplay between self‐assembly and phase separation orchestrates biomolecular organization inside cells, thereby dictating the formation of vital structures such as protein assemblies membraneless organelles (MLOs). However, in context supramolecular polymerization, these fundamental processes have traditionally been studied separately. This study reevaluates polymerization process to unveil presence phase‐separated droplet state. Utilizing well‐studied benzene‐1,3,5‐tricarboxamide (BTA) motif, we explore its thermally driven liquid‐liquid (LLPS). Thermodynamic kinetic analysis, employing temperature‐dependent spectroscopic microscopic techniques, elucidates distinct BTA states their evolution towards thermodynamic fiber research sheds light on existence hidden phases monomers, emphasizing delicate balance non‐covalent interactions among monomers with solvents governing vs. separation. is particularly important comprehending biological realm MLOs, for applications condensate‐modifying therapeutics.

Language: Английский

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Coacervate Droplets as Biomimetic Models for Designing Cell‐Like Microreactors

Macromolecular Rapid Communications, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 26, 2024

Abstract Coacervates are versatile compartments formed by liquid–liquid phase separation. Their dynamic behavior and molecularly crowded microenvironment make them ideal materials for creating cell‐like systems such as synthetic cells microreactors. Recently, combinations of natural molecules have been exploited via simple or complex coacervation to create that can be used build hierarchical chemical with life‐like properties. This review highlights recent advances in the design coacervate their application biomimetic reactors cell mimicking systems. It first explores variety influence structure on controlled behavior. Then, applications coacervates reviewed, focusing how they microreactors through ability sequester provide a distinct regulatory reactions aqueous media.

Language: Английский

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Cell‐Like Synthetic Supramolecular Soft Materials Realized in Multicomponent, Non‐/Out‐of‐Equilibrium Dynamic Systems

Advanced Science, Journal Year: 2023, Volume and Issue: 11(8)

Published: Nov. 28, 2023

Abstract Living cells are complex, nonequilibrium supramolecular systems capable of independently and/or cooperatively integrating multiple bio‐supramolecules to execute intricate physiological functions that cannot be accomplished by individual biomolecules. These biological design strategies offer valuable insights for the development synthetic with spatially controlled hierarchical structures, which, importantly, exhibit cell‐like responses and functions. The next grand challenge in chemistry is control organization types supramolecules a single system, thus these an orthogonal cooperative manner. In this perspective, recent progress constructing multicomponent soft materials through hybridization supramolecules, such as self‐assembled nanofibers/gels coacervates, other functional molecules, including polymer gels enzymes highlighted. Moreover, results show bioinspired stimuli, bidirectional rheological double‐network hydrogels, temporal stimulus pattern‐dependent 3D hydrogel patterning response reaction–diffusion processes presented. Autonomous active structures hold promise diverse applications, robotics directional motion, point‐of‐care disease diagnosis, tissue regeneration.

Language: Английский

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Two‐Photon Clusteroluminescence Enabled by Through‐Space Conjugation for In Vivo Bioimaging

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 137(1)

Published: Aug. 28, 2024

Abstract Clusteroluminescence (CL) materials without largely conjugated structures have gained significant attention due to their unique photophysical properties and potential in bioimaging. However, low luminescence efficiency short emission wavelength limit development. This work designs three luminogens with CL (CLgens) by introducing n ‐electron‐involved through‐space conjugation (TSC) into diarylmethane. Apart from single‐photon excited long‐wavelength (686 nm) high‐efficiency (29 %) CL, two‐photon clusteroluminescence (TPCL) is successfully achieved such small only two isolated heteroatomic units. TSC stabilized the aggregate state has been proven realize efficient spatial electron delocalization similar conventionally compounds. Encouraged excellent TPCL properties, imaging of blood vessels vivo biocompatibility verification utilizing CLgens are also achieved. illustrates essential role promoting nonlinear optical may facilitate further design development next generation bioprobes biocompatibility.

Language: Английский

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Bioinspired programmable coacervate droplets and self-assembled fibers through pH regulation of monomers

Journal of Materials Chemistry B, Journal Year: 2024, Volume and Issue: unknown

Published: Jan. 1, 2024

Demonstration of transient coacervate droplets and programmable fibers was achieved by temporally regulating the pH solution through biocatalytic modulation.

Language: Английский

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