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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Fuel-Driven Enzymatic Reaction Networks to Program Autonomous Thiol/Disulfide Redox Systems

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(15), P. 10281 - 10285

Published: April 3, 2024

Fuel-driven dissipative formation of disulfide bonds using competing oxidative activation and reductive deactivation presents a possibly very versatile avenue for autonomous materials design. However, this is challenging to realize because the direct annihilation oxidizing fuel deactivating reducing agent. We overcome challenge by introducing redox-based enzymatic reaction network (ERN), enabling molecularly dissolved thiols in fully manner. Moreover, ERN allows programming hydrogel lifetimes utilizing thiol-terminated star polymers (sPEG-SH). The can be customized operate with aliphatic aromatic should thus broadly applicable functional thiols.

Language: Английский

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Analysis of kinetic asymmetry in a multi-cycle reaction network establishes the principles for autonomous compartmentalized molecular ratchets

Chem, Journal Year: 2024, Volume and Issue: 10(12), P. 3644 - 3655

Published: Sept. 13, 2024

Language: Английский

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Functionalization of Supramolecular Polymers by Dynamic Covalent Boroxine Chemistry

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(24)

Published: May 8, 2024

Abstract Molecular scaffolds that enable the combinatorial synthesis of new supramolecular building blocks are promising targets for construction functional molecular systems. Here, we report a scaffold based on boroxine enables formation chiral and ordered 1D polymers, which can be easily functionalized circularly polarized luminescence. The monomers quantitatively synthesized in situ, both bulk solution, from boronic acid precursors cooperatively polymerize into helical aggregates stabilized by threefold hydrogen‐bonding π–π stacking. We then demonstrate amplification asymmetry co‐assembly chiral/achiral co‐condensation classical situ sergeant‐and‐soldiers experiments, respectively, showing fast exchange reactions occurring system. Remarkably, pyrene with results aggregation excimer emission g ‐values order 10 −3 . Yet, electron deficiency boron makes them chemically addressable nucleophiles, but also sensitive to hydrolysis. With this sensitivity mind, provide first insights prospects offered boroxine‐based polymers make addressable, functional, adaptive

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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Non‐Equilibrium Assembly of Atomically‐Precise Copper Nanoclusters

Advanced Materials, Journal Year: 2024, Volume and Issue: 36(28)

Published: Jan. 31, 2024

Abstract Accurate structure control in dissipative assemblies (DSAs) is vital for precise biological functions. However, accuracy and functionality of artificial DSAs are far from this objective. Herein, a novel approach introduced by harnessing complex chemical reaction networks rooted coordination chemistry to create atomically‐precise copper nanoclusters (CuNCs), specifically Cu 11 (µ 9 ‐Cl)(µ 3 ‐Cl) L 6 Cl (L = 4‐methyl‐piperazine‐1‐carbodithioate). Cu(I)–ligand ratio change dynamic Cu(I)–Cu(I) metallophilic/coordination interactions enable the reorganization CuNCs into metastable CuL 2 , finally converting equilibrium [CuL·Y]Cl (Y MeCN/H O) via Cu(I) oxidation/reorganization ligand exchange process. Upon adding ascorbic acid (AA), system goes further cycles. It observed that encapsulated/bridging halide ions exert subtle influence on optical properties topological changes polymeric when integrating as crosslink sites. duration/switch period could be controlled varying ions, AA concentration, O pressure pH. Cu(I)‐Cu(I) metallophilic provide versatile toolbox designing delicate life‐like materials, paving way with structures functionalities. Furthermore, can employed modular units within polymers materials mechanics or functionalization studies.

Language: Английский

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Cysteine‐Based Dynamic Self‐Assembly and Their Importance in the Origins of Life

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

Published: April 12, 2024

Abstract The knowledge regarding the origins of life from inanimate materials is still elusive. It was proposed that biological building blocks evolved inorganic substances present in early earth conditions. However, process by which chemistry can be converted into biology has not yet been achieved laboratory. artificial system out‐of‐equilibrium state must maintain a few critical features life, like compartmentalization, metabolism, and replication, to considered alive. In this direction, working with cysteine (Cys)‐based molecules strategic understand evolution process. presence sulphydryl (−SH) group Cys‐residue build dynamic equilibrium through disulfide redox under proper guidance oxidizing reducing agents. review article, our primary focus discuss Cys‐containing short‐peptide‐based self‐assembly disassembly processes. formation bonds sometimes helps gelation, but reverse also true some cases. later part we cover fact these sulphydryl‐based systems have shown their adaptability mimic different life‐essential criteria participate Darwinian evolution.

Language: Английский

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Ionic fuel-powered hydrogel actuators for soft robotics

Journal of Colloid and Interface Science, Journal Year: 2024, Volume and Issue: 677, P. 739 - 749

Published: Aug. 5, 2024

Language: Английский

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Analysis of kinetic asymmetry in a multi-cycle chemical reaction network establishes the principles for autonomous compartmentalized molecular ratchets

Published: Feb. 21, 2024

Kinetic asymmetry is a key parameter describing non-equilibrium chemical systems: it indicates the directionality of reaction network under steady-state, conditions. So far, kinetic has been evaluated only in networks featuring single cycle. Here, we have investigated multi-cycle system using combined theoretical and numerical approach. Inspired by latest experimental developments, selected com-partmentalized redox-controlled as model system. We report general analytical expression for networks, specify present system, which allows anticipating how parameters influence directionality. establish that compartmentalization can enable autonomous energy ratchet mechanisms, with dictated system's thermodynamics. simulations confirm findings illustrate interplay between diffusion, chemical, electrochemical processes. The presented treatment general, same procedure be used to assess other facilitating realization en-dergonic processes across domains.

Language: Английский

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