Waste-Free Fully Electrically Fueled Dissipative Self-Assembly System

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(6), P. 3727 - 3735

Published: Feb. 6, 2023

The importance and prevalence of energy-fueled active materials in living systems have inspired the design synthetic using various fuels. However, several major limitations current designs remain to be addressed, such as accumulation chemical wastes during process, unsustainable behavior, lack precise spatiotemporal control. Here, we demonstrate a fully electrically fueled (e-fueled) self-assembly material that can overcome aforementioned limitations. Using an electrochemical setup with dual electrocatalysts, anodic oxidation one electrocatalyst (ferrocyanide, [Fe(CN)6]4-) creates positive fuel activate self-assembly, while simultaneously, cathodic reduction other (methyl viologen, [MV]2+) generates negative triggering fiber disassembly. Due catalytic nature for reaction networks, this e-fueled system does not generate any waste, sustain behavior extended period when electrical potential is maintained, provides

Language: Английский

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Supramolecular Soft Material Enabled by Metal Coordination and Hydrogen Bonding: Stretchability, Self‐Healing, Impact Resistance, 3D Printing, and Motion Monitoring

Small, Journal Year: 2023, Volume and Issue: 19(30)

Published: April 10, 2023

Abstract Metal coordination can significantly improve the macroscopic performance of many materials by enhancing their dynamic features. In this study, two supramolecular interactions, Fe 3+ –carboxylic acid coordination, and structural water‐induced hydrogen bonding, into an artificial polymer were introduced. Various attractive features, including flexibility stretchability, are achieved because bulk state bonds poly(thioctic acid‐water) (poly[ TA ‐ H ]). These unique features considerably enhanced after incorporation cations poly[ ] metal increased mobility chains. Thus, acid‐water‐metal) HM ]) copolymer exhibited better stretchability. Moreover, notable underwater/low‐temperature self‐healing capacity is obtained via synergistic effect bonding. Most impact energy quickly absorbed or effectively rapidly dissipated reversible debonding/bonding interactions between hydrogen. Macroscopic plastic deformation failure not observed during high‐speed (50–70 m s −1 ) experiments high‐altitude (90 m) falling tests. Furthermore, displayed good thermal molding properties, which enabled its processing 3D fused deposition modeling printing. Poly[ also showed considerable effectiveness for monitoring complicated, dynamic, irregular biological activities owing to highly pressure‐sensitive nature.

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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Highly robust supramolecular polymer networks crosslinked by a tiny amount of metallacycles

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

Published: April 9, 2024

Abstract Supramolecular polymeric materials have exhibited attractive features such as self-healing, reversibility, and stimuli-responsiveness. However, on account of the weak bonding nature most noncovalent interactions, it remains a great challenge to construct supramolecular with high robustness. Moreover, usage units is usually necessary promote formation robust materials, which restrains their applications. Herein, we describe construction highly polymer networks by using only tiny amount metallacycles crosslinkers. A norbornene ring-opening metathesis copolymer 120° dipyridine ligand prepared self-assembled 60° or Pt(II) acceptor fabricate metallacycle-crosslinked networks. With 0.28 mol% less pendant form metallacycle crosslinkers, mechanical properties polymers are significantly enhanced. The tensile strengths, Young’s moduli, toughness reinforced reach up more than 20 MPa, 600 150 MJ/m 3 , respectively. Controllable destruction reconstruction further demonstrated sequential addition tetrabutylammonium bromide silver triflate, indicative good stimuli-responsiveness These remarkable performances attributed thermodynamically stable, but dynamic metallacycle-based coordination complexes that offer strong linkages adaptive characteristics.

Language: Английский

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Enzymatic Reaction-Coupled, Cooperative Supramolecular Polymerization

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(21), P. 14844 - 14855

Published: May 15, 2024

Nature employs sophisticated mechanisms to precisely regulate self-assembly and functions within biological systems, exemplified by the formation of cytoskeletal filaments. Various enzymatic reactions auxiliary proteins couple with process, meticulously regulating length resulting macromolecular structures. In this context, we present a bioinspired, reaction-coupled approach for controlled supramolecular polymerization in synthetic systems. To achieve this, employ an reaction that interfaces adenosine triphosphate (ATP)-templated naphthalene diimide monomers (

Language: Английский

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Spontaneous and Selective Peptide Elongation in Water Driven by Aminoacyl Phosphate Esters and Phase Changes

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(48), P. 26086 - 26094

Published: Nov. 22, 2023

Nature chose phosphates to activate amino acids, where reactive intermediates and complex machinery drive the construction of polyamides. Outside biology, pathways mechanisms that allow spontaneous selective peptide elongation in aqueous abiotic systems remain unclear. Herein we work uncover those by following chemistry aminoacyl phosphate esters, synthetic counterparts adenylates. The esters act as solubility tags, making hydrophobic acids their oligomers soluble water enabling different emerge. Thus, up dodecamers were synthesized one flask on minute time scale, consecutive additions activated autonomous phase changes. Depending pathway, resulting phases initially carry nonpolar peptides amphiphilic containing esters. During release, shorter dominate solution, while aggregated favors presence longer due self-assembly propensity. Furthermore demonstrated solution can be isolated a new environment for continuous elongation, adding various These findings suggest selection mechanism bond formation merging synthesis self-assembly.

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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Organelle-Mediated Dissipative Self-Assembly of Peptides in Living Cells

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 146(1), P. 330 - 341

Published: Dec. 19, 2023

Implementing dissipative assembly in living systems is meaningful for creation of materials or even artificial life. However, intracellular remains scarce and significantly impeded by the challenges lying precisely operating chemical reaction cycles under complex physiological conditions. Here, we develop organelle-mediated self-assembly peptides cells fueled GSH, via design a mitochondrion-targeting redox-responsive hexapeptide. While hexapeptide undergoes efficient self-assembly, addition GSH into peptide solution presence mitochondrion-biomimetic liposomes containing hydrogen peroxide allows transient peptides. Internalization LPS-stimulated macrophages leads to driven reduction association assemblies with mitochondria. The facilitates reversible oxidation reduced mitochondrion-residing ROS thereby dissociates from mitochondria re-enter cytoplasm reduction. metastable peptide–mitochondrion complexes prevent thermodynamically equilibrated thus establishing stimulated macrophages. entire self-assembling process elimination elevated decrease pro-inflammatory cytokine expression. Creating assisted internal structures provides new avenues development medical agents future.

Language: Английский

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

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(28)

Published: April 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.

Language: Английский

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Kinetically Controlled and Nonequilibrium Assembly of Block Copolymers in Solution

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(28), P. 18781 - 18796

Published: July 5, 2024

Covalent polymers are versatile macromolecules that have found widespread use in society. Contemporary methods of polymerization made it possible to construct sequence polymers, including block copolymers, with high precision. Such copolymers assemble solution when the blocks differing solubilities. This produces nano- and microparticles various shapes sizes. While is straightforward draw an analogy between such amphiphilic phospholipids, these two classes molecules show quite different assembly characteristics. In particular, often under kinetic control, thus producing nonequilibrium structures. leads a rich variety behaviors being observed copolymer assembly, as pathway dependence (e.g., thermal history), nonergodicity responsiveness. The dynamics polymer assemblies can be readily controlled using changes environmental conditions and/or integrating functional groups situated on external chemical reactions. perspective highlights control both pervasive useful attribute mechanics assembly. Recent examples highlighted order toggling static dynamic behavior used generate, manipulate dismantle states. New kinetics will provide endless unanticipated applications materials science, biomimicry medicine.

Language: Английский

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