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

Angewandte Chemie, Год журнала: 2024, Номер 136(28)

Опубликована: Апрель 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.

Язык: Английский

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Molecular entanglement can strongly increase basicity

Communications Chemistry, Год журнала: 2024, Номер 7(1)

Опубликована: Май 28, 2024

Brønsted basicity is a fundamental chemical property featured by several kinds of inorganic and organic compounds. In this Review, we treat particularly high resulting from the mechanical entanglement involving two or more molecular subunits in catenanes rotaxanes. Such allows number basic sites to be close proximity with each other, highly increasing proton affinity comparison corresponding, non-entangled counterparts up obtain superbases, properly defined as mechanically interlocked superbases. following pages, development kind superbases will described historical perusal, starting initial, serendipitous findings most recent reports where strong entangled units object rational design.

Язык: Английский

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

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(43), С. 29621 - 29629

Опубликована: Окт. 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.

Язык: Английский

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Kinetic Trapping of an Out‐of‐Equilibrium Dynamic Library of Imines by Changing Solvent

Chemistry - A European Journal, Год журнала: 2024, Номер 30(37)

Опубликована: Апрель 8, 2024

A well-behaved dynamic library composed of two imines and corresponding amines was subjected to the action an activated carboxylic acid (ACA), whose decarboxylation is known be base promoted, in different solvents, namely CD

Язык: Английский

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Time‐Encoded Information Encryption with pH Clock Guided Broad‐Spectrum Emission by Dynamic Assemblies

Angewandte Chemie International Edition, Год журнала: 2024, Номер unknown

Опубликована: Авг. 22, 2024

With growing threats from counterfeiting-based security breaches, multi-level and specific stimuli-responsive anti-counterfeiting devices message encryption methods have attracted immense research interest. Fluorescence-based aggregation-induced emission (AIE)-based materials solves the problems to a considerable extent. However, development of smarter patterns with hierarchical levels alongside dynamic display is still challenging. To screen out this complication, we bring forward pH-switchable fluorescent assembly an AIEgen aliphatic acid. We later temporally direct molecular aid chemical trigger-regulated pH clock, generating transitory multicolor emission, including transient white light generation. The pH-dependent emissions were further implemented in constructing smart multi-input AND gates. Subsequently, integrate time-gated emissive system develop advanced multi-dimensionally secure data strategy. This novel approach enhances measures by introducing additional layer based on temporal characteristics.

Язык: Английский

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Time‐Encoded Information Encryption with pH Clock Guided Broad‐Spectrum Emission by Dynamic Assemblies

Angewandte Chemie, Год журнала: 2024, Номер unknown

Опубликована: Авг. 22, 2024

Abstract With growing threats from counterfeiting‐based security breaches, multi‐level and specific stimuli‐responsive anti‐counterfeiting devices message encryption methods have attracted immense research interest. Fluorescence‐based aggregation‐induced emission (AIE)‐based materials solves the problems to a considerable extent. However, development of smarter patterns with hierarchical levels alongside dynamic display is still challenging. To screen out this complication, we bring forward pH‐switchable fluorescent assembly an AIEgen aliphatic acid. We later temporally direct molecular aid chemical trigger‐regulated pH clock, generating transitory multicolor emission, including transient white light generation. The pH‐dependent emissions were further implemented in constructing smart multi‐input AND gates. Subsequently, integrate time‐gated emissive system develop advanced multi‐dimensionally secure data strategy. This novel approach enhances measures by introducing additional layer based on temporal characteristics.

Язык: Английский

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A Doubly Dissipative System Driven by Chemical and Radiative Stimuli

Chemistry - A European Journal, Год журнала: 2023, Номер 29(49)

Опубликована: Июнь 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.

Язык: Английский

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Artificial Molecular Ratchets: Tools Enabling Endergonic Processes

Angewandte Chemie, Год журнала: 2023, Номер 135(47)

Опубликована: Авг. 7, 2023

Abstract Non‐equilibrium chemical systems underpin multiple domains of contemporary interest, including supramolecular chemistry, molecular machines, prebiotic and energy transduction. Experimental chemists are now pioneering the realization artificial that can harvest away from equilibrium. In this tutorial Review, we provide an overview ratchets: mechanisms enabling absorption environment. By focusing on mechanism type—rather than application domain or source—we offer a unifying picture seemingly disparate phenomena, which hope will foster progress in fascinating science.

Язык: Английский

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Out-of-Equilibrium Assembly Based on Host–Guest Interactions

CCS Chemistry, Год журнала: 2023, Номер 6(1), С. 27 - 40

Опубликована: Авг. 10, 2023

The field of supramolecular chemistry is rapidly progressing, transitioning from the creation thermodynamically stable systems found in local or global minima on free energy landscape to development out-of-equilibrium that rely chemical reactions establish and maintain their structures.Over past decade, numerous artificial have been devised various domains chemistry, many which extensively reviewed.However, one area has received limited attention thus far use processes regulate host-guest interactions.This minireview aims address this gap by exploring construction out-ofequilibrium based complexation, likely employs similar strategies those employed analogous noncovalent interactions.The review begins with a summary these shared strategies.Subsequently, it discusses representative publications exemplify classifies them component being modulatedhost, guest, competitive molecules.Through examination, our objective shed light design relying interactions provide valuable insights into preparation for transient materials.

Язык: Английский

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Switched “On” Transient Fluorescence Output from a Pulsed-Fuel Molecular Ratchet

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(49), С. 27113 - 27119

Опубликована: Дек. 4, 2023

We report the synthesis and operation of a molecular energy ratchet that transports crown ether from solution onto thread, along axle, over fluorophore, off other end thread back into bulk solution, all in response to single pulse chemical fuel (CCl3CO2H). The fluorophore is pyrene residue whose fluorescence normally prevented by photoinduced electron transfer (PET) nearby N-methyltriazolium group. However, binding site inhibits PET, switching on under UV irradiation. Each results cycle transient (encompassing threading, transport site, then dethreading), with onset fluorescent time period determined amount each end-point concentration reagents for disulfide exchange reaction. system provides potential alternative signaling approach artificial machines read symbols sequence-encoded tapes.

Язык: Английский

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