Pumping Small Molecules Selectively through an Energy-Assisted Assembling Process at Nonequilibrium States

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(5), P. 3323 - 3330

Published: Jan. 26, 2024

In living organisms, precise control over the spatial and temporal distribution of molecules, including pheromones, is crucial. This level equally important for development artificial active materials. this study, we successfully controlled small molecules in system at nonequilibrium states by actively transporting them, even against apparent concentration gradient, with high selectivity. As a demonstration, aqueous solution acid orange (AO7) TMC

Language: Английский

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Dissipative crystallization of ion-pair receptors

Chem, Journal Year: 2023, Volume and Issue: 9(3), P. 709 - 720

Published: Jan. 16, 2023

Language: Английский

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The Multifunctional Role of Templates in Chemically Fueled Dynamic Combinatorial Libraries

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

Published: Jan. 10, 2025

Abstract RNA is an information‐carrying molecule that instructs protein synthesis, but it also functions as a catalyst in so‐called ribozymes. Here, we study this multifunctional character using dynamic combinatorial library powered by chemical fuel. On the one hand, demonstrate templates oligomerization and inhibits deoligomerization. other show can be structural element formation of hydrogels. Moreover, its hydrogel, degradation nucleases accelerated. Thus, have role beyond blueprints, protectors, selectors. Template‐oligomer interactions create new (micro)environments might affect evolutionary dynamics.

Language: Английский

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Communication and Cross‐Regulation between Chemically Fueled Sender and Receiver Reaction Networks**

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 62(2)

Published: Nov. 10, 2022

Nature connects multiple fuel-driven chemical/enzymatic reaction networks (CRNs/ERNs) via cross-regulation to hierarchically control biofunctions for a tailored adaption in complex sensory landscapes. Herein, we introduce facile example of communication and among two DNA-based ERNs regulated by concatenated RNA transcription regulator. ERN1 ("sender") is designed the promoter formation T7 polymerase, which activates transcription. The produced can deactivate or activate DNA ERN2 ("receiver") toehold-mediated strand displacement, leading between ERNs. from repress promote state ERN2; turn feedbacks regulate lifetime ERN1. Furthermore, incorporation RNase H allows degradation enables autonomous recovery ERN2. We believe that concatenation CRNs/ERNs provides basis design more elaborate regulatory mechanisms systems chemistry synthetic biology.

Language: Английский

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Allosteric Control of the Catalytic Properties of Dipeptide-Based Supramolecular Assemblies

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(32), P. 22522 - 22529

Published: Aug. 1, 2024

Allostery, as seen in extant biology, governs the activity regulation of enzymes through redistribution conformational equilibria upon binding an effector. Herein, a minimal design is demonstrated where dipeptide can exploit dynamic imine linkage to condense with simple aldehydes access spherical aggregates catalytically active states, which facilitates orthogonal reaction due closer proximity catalytic residues (imidazoles). The allosteric site (amine) catalyst concomitantly bind inhibitor via exchange, leads alternation energy landscape self-assembled state, resulting downregulation activity. Further, temporal control over realized feedback-controlled autonomous network that utilizes hydrolytic (in)active state function time.

Language: Английский

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Abiotic Acyl Transfer Cascades Driven by Aminoacyl Phosphate Esters and Self-Assembly

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(43), P. 29621 - 29629

Published: Oct. 17, 2024

Biochemical acyl transfer cascades, such as those initiated by the adenylation of carboxylic acids, are central to various biological processes, including protein synthesis and fatty acid metabolism. Designing cascade reactions in aqueous media remains challenging due need control multiple, sequential a single pot manage stability reactive intermediates. Herein, we developed abiotic cascades using aminoacyl phosphate esters, synthetic counterparts adenylates, drive chemical self-assembly pot. We demonstrated that structural elements amino side chains (aromatic versus aliphatic) significantly influence reactivity half-lives ranging from hours days. This behavior, turn, affects number couplings can achieve network propensity activated intermediate structures. The constructed bifunctional peptide substrates featuring chain nucleophiles. Specifically, aromatic acids facilitate formation transient thioesters, which preorganized into spherical aggregates further couple chimeric assemblies composed esters thioesters. In contrast, aliphatic lack ability form structures, predominantly undergo hydrolysis, bypassing transformations after thioester formation. Additionally, mixtures containing multiple substrates, achieved selective product following distinct pathway favors subsequent through changes self-assembly. By coupling with molecules varying time scales, reaction clocks lifetimes dynamics, facilitating precise temporal regulation.

Language: Английский

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Dissipative Dynamic Libraries (DDLs) and Dissipative Dynamic Combinatorial Chemistry (DDCC)

ChemSystemsChem, Journal Year: 2022, Volume and Issue: 4(6)

Published: Sept. 5, 2022

Abstract This Concept is focused on the key features of dissipative dynamic combinatorial chemistry (DDCC). DDCC deals with transient libraries compounds, maintained out‐of‐equilibrium by consumption a fuel, whose composition changes upon selection pressure kinetic and/or thermodynamic processes. Concepts and definitions (“KDDL” “TDDL”), are introduced illustrated number actual cases, thus showing consistency present approach. Such concepts can help establish common language for this emerging field, which, in our view, has potential to become highly relevant supramolecular chemistry.

Language: Английский

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In Situ Inhibitor Synthesis and Screening by Fluorescence Polarization: An Efficient Approach for Accelerating Drug Discovery

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(45)

Published: Sept. 16, 2022

Target-directed dynamic combinatorial chemistry has emerged as a useful tool for hit identification, but not been widely used, in part due to challenges associated with analyses involving complex mixtures. We describe an operationally simple alternative: situ inhibitor synthesis and screening (ISISS), which links high-throughput bioorthogonal target binding by fluorescence. exemplify the ISISS method showing how coupling fluorescence polarization reaction of acyl-hydrazides aldehydes led efficient discovery potent novel acylhydrazone-based human prolyl hydroxylase 2 (PHD2), anemia treatment, equivalent vivo potency approved medicine.

Language: Английский

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A Doubly Dissipative System Driven by Chemical and Radiative Stimuli

Chemistry - A European Journal, Journal Year: 2023, Volume and Issue: 29(49)

Published: June 16, 2023

The operation of a dissipative network composed two or three different crown-ether receptors and an alkali metal cation can be temporally driven by the use (combined not) orthogonal stimuli nature. More specifically, irradiation with light at proper wavelength and/or addition activated carboxylic acid, are used to modulate binding capability above crown-ethers towards ion, allowing control over time occupancy in moiety given ligand. Thus, application either both initially equilibrated system, where is distributed among depending on affinities, causes programmable change receptor occupancies. Consequently, system induced evolve one more out-of-equilibrium states distributions receptors. When fuel exhausted or/and interrupted, reversibly autonomously goes back initial equilibrium state. Such results may contribute achievement new systems that, taking advantage multiple stimuli, featured sophisticated operating mechanisms programmability.

Language: Английский

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Tuning the Kinetic Trapping in Chemically Fueled Self‐Assembly**

ChemSystemsChem, Journal Year: 2022, Volume and Issue: 5(1)

Published: Oct. 6, 2022

Abstract Nature uses dynamic, molecular self‐assembly to create cellular architectures that adapt their environment. For example, a guanosine triphosphate (GTP)‐driven reaction cycle activates and deactivates tubulin for dynamic assembly into microtubules. Inspired by in biology, recent studies have developed synthetic analogs of assemblies regulated chemically fueled cycles. A challenge these is control the interplay between rapid disassembly kinetic trapping building blocks known as instabilities. In this work, we show how design can tune tendency molecules remain trapped assembly. We alter emerging assemblies. Our work should give rules approaching instabilities new adaptive nanotechnologies.

Language: Английский

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