The role of Kinetic Asymmetry in Chemical and Thermodynamic Coupling DOI
R. Dean Astumian

ChemSystemsChem, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 15, 2024

Abstract The input of energy can shift an isomerization reaction A⇌B away from equilibrium, but which way, in favor A or B? answer to this question lies understanding kinetic asymmetry, a concept first discussed the context how oscillating fluctuating perturbation act concert with catalyst drive equilibrium. key theoretical result is non‐equilibrium pumping equality that generalizes idea equilibrium constant steady‐state.

Language: Английский

Can Molecular Systems Learn? DOI Open Access
Kübra Kaygisiz, Rein V. Ulijn

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

Published: Jan. 24, 2025

Abstract Research across various disciplines shows the benefits of learning and memory for gaining functionality improving performance. It is increasingly clear that can be found in both physical virtual systems, from intelligent life forms to machines, simple organisms, even designed chemical systems. We are interested understanding what extent embodiments these processes synthesized engineered bottom up by using molecular components. In this perspective, we raise attempt answer conceptual questions about supramolecular systems as smallest units capable learning. define a process where complex system interacting components modifies itself response an applied stress or stimulus, resulting structural changes information gain. highlight potential chemistry networks design meet definition encoding, decoding, storing within system′s composition. Understanding basis could inform development materials autonomously acquire new properties their environment. This also provide insights next‐generation computing physical, rather than virtual,

Language: Английский

Citations

1

PSL Chemical Biology Symposia: The Increasing Impact of Chemistry in Life Sciences DOI

Romain Sastourné‐Haletou,

Sacha Marynberg, Arthur Prudêncio de Araújo Pereira

et al.

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

Published: April 7, 2025

This symposium is the 6th Paris Sciences & Lettres (PSL) Chemical Biology meeting (2015, 2016, 2019, 2023, 2024, 2025) being held at Institut Curie. initiative originally started in 2013 de Chimie des Substances Naturelles (ICSN) Gif‐sur‐Yvette and was mostly focused on organic synthesis. It then exported Curie to cover a larger scope, before becoming official French meeting. year, around 200 participants had opportunity meet world leaders chemistry biology who described their latest innovations future trends covering topics as diverse prebiotic chemistry, activity‐based protein profiling, high‐resolution cell imaging, nanotechnologies, bio‐orthogonal metal ion signaling, ferroptosis, biocatalysis.

Language: Английский

Citations

0

Abiotic Acyl Transfer Cascades Driven by Aminoacyl Phosphate Esters and Self-Assembly DOI Creative Commons
Mahesh D. Pol, Ralf Thomann, Yi Thomann

et al.

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

Citations

3

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

Mahesh Pol,

Ralf Thomann, Yi Thomann

et al.

Published: Aug. 5, 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 aqueous cascades outside biology remains challenging due need control multiple, sequential reactions in a single pot manage stability reactive intermediates. Herein, we developed abiotic 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 lead hydrolysis, bypassing elongation after thioester formation. Additionally, mixtures containing multiple substrates, achieved selective product following distinct pathway favors through self-assembly. By coupling molecules with varying timescales, reaction clocks lifetimes dynamics, thereby facilitating precise temporal regulation.

Language: Английский

Citations

1

The role of Kinetic Asymmetry in Chemical and Thermodynamic Coupling DOI
R. Dean Astumian

ChemSystemsChem, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 15, 2024

Abstract The input of energy can shift an isomerization reaction A⇌B away from equilibrium, but which way, in favor A or B? answer to this question lies understanding kinetic asymmetry, a concept first discussed the context how oscillating fluctuating perturbation act concert with catalyst drive equilibrium. key theoretical result is non‐equilibrium pumping equality that generalizes idea equilibrium constant steady‐state.

Language: Английский

Citations

1