Dual light control of a catalytically-driven chemical reaction cycle DOI Creative Commons
Jorge S. Valera, Álvaro López‐Acosta, Thomas M. Hermans

et al.

Published: Sept. 7, 2023

Chemically-fueled chemical reaction networks (CRNs) are key in controlling dissipative self-assembly. Having catalysts gating fuel consumption for both the activation and deactivation chemistry of (assembly-prone) monomers catalytic activity with an external stimulus would provide better control over where, when, how long self-assembled structures can form. Here we achieve light two different that govern monomer assembly into supramolecular fibers, as well fiber disassembly. Activation proceeds via photoredox catalysis under visible light, whereas is achieved by organometallic relies on a photocaged pre-fuel activated ultraviolet light. Overall, show fibers be formed destroyed using

Language: Английский

A roadmap toward the synthesis of life DOI Creative Commons
Christine M. E. Kriebisch, Olga Bantysh, Lorena Baranda Pellejero

et al.

Chem, Journal Year: 2025, Volume and Issue: unknown, P. 102399 - 102399

Published: Feb. 1, 2025

Language: Английский

Citations

3
Alkyl Chloride-Functionalized Polymers Mediate Oxidation of Thioethers Initiated by Ionizing Radiation DOI Creative Commons
Juncheng Liu, Irene Piergentili, Bing Xu

et al.

ACS Applied Polymer Materials, Journal Year: 2025, Volume and Issue: 7(6), P. 3835 - 3841

Published: March 19, 2025

Irradiation of aqueous solutions containing alkyl chlorides generates peroxyl radicals by reactions chlorides, electrons, and dissolved oxygen. The radical can oxidize thioethers to sulfoxides, a transformation that has relevance for targeted or triggered drug delivery. However, small-molecule induce liver damage, which limits their potential application in anticancer therapy. Here, we show bound hydrophilic random copolymer chain behave similar chlorides. Our work shows using polymeric be an alternative provided the chloride functionalities are easily accessible electrons.

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
Photoinitiated Transient Self‐Assembly in a Catalytically Driven Chemical Reaction Cycle DOI Creative Commons
Jorge S. Valera, Álvaro López‐Acosta, Thomas M. Hermans

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: unknown

Published: May 21, 2024

Abstract Chemically fueled chemical reaction networks (CRNs) are essential in controlling dissipative self‐assembly. A key challenge the field is to store fuel‐precursors or “pre‐fuels” system that converted into activating deactivating fuels a catalytically controlled CRN. In addition, real‐time control over catalysis CRN by light highly desirable, but so far not yet achieved. Here we show driven photoinitiated with 450 nm light, producing activated monomers go on perform transient Monomer activation proceeds via photoredox catalysis, converting monomer alcohol groups corresponding aldehydes self‐assemble large supramolecular fibers. deactivation achieved organometallic relies pre‐fuel hydrolysis release formate (i.e. fuel). Additionally, irradiation 305 accelerates of photo‐uncaging pre‐fuel, leading factor ca. 2 faster monomer. Overall, self‐assembly upon visible photoactivation, and tunable life‐times ultraviolet light.

Language: Английский

Citations

2
Towards dual light control of a catalytically-driven chemical reaction cycle DOI Creative Commons
Jorge S. Valera, Álvaro López‐Acosta, Thomas M. Hermans

et al.

Published: Jan. 31, 2024

Chemically-fueled chemical reaction networks (CRNs) are key in controlling dissipative self-assembly. Having catalysts gating fuel consumption for both the activation and deactivation chemistry of (assembly-prone) monomers catalytic activity with an external stimulus would provide better control over where, when, how long self-assembled structures can form. Here we achieve light monomer subsequent assembly into supramolecular fibers, partial fiber disassembly. Activation proceeds via photoredox catalysis under visible light, whereas is achieved by organometallic that relies on a photocaged pre-fuel activated ultraviolet light. Overall, show fibers be formed their destruction accelerated

Language: Английский

Citations

1
Chemoselective Synthesis and Anti-Kinetoplastidal Properties of 2,6-Diaryl-4H-tetrahydro-thiopyran-4-one S-Oxides: Their Interplay in a Cascade of Redox Reactions from Diarylideneacetones DOI Creative Commons
Thibault Gendron,

Don Antoine Lanfranchi,

Nicole Wenzel

et al.

Molecules, Journal Year: 2024, Volume and Issue: 29(7), P. 1620 - 1620

Published: April 4, 2024

2,6-Diaryl-4H-tetrahydro-thiopyran-4-ones and corresponding sulfoxide sulfone derivatives were designed to lower the major toxicity of their parent anti-kinetoplatidal diarylideneacetones through a prodrug effect. Novel diastereoselective methodologies developed generalized from 2,6-diaryl-4H-tetrahydro-thiopyran-4-ones allow introduction wide substitution profile prepare related S-oxides. The in vitro biological activity selectivity diarylideneacetones, 2,6-diaryl-4H-tetrahydro-thiopyran-4-ones, S-sulfoxide metabolites evaluated against Trypanosoma brucei brucei, cruzi, various Leishmania species comparison with cytotoxicity human fibroblasts hMRC-5. data revealed that sulfides, sulfoxides, sulfones, which Michael acceptor sites are temporarily masked, less toxic mammal cells while anti-trypanosomal potency was maintained T. b. L. infantum, donovani, thus confirming validity strategy. mechanism action is proposed be due involvement cascades redox reactions involving trypanothione system. After addition dithiol double bonds, resulting an elongated polymer, latter—upon S-oxidation, followed by syn-eliminations—fragments, under continuous release reactive oxygen sulfenic/sulfonic species, causing death trypanosomal parasites micromolar or submicromolar range high indexes.

Language: Английский

Citations

1
Acyl Phosphates as Chemically Fueled Building Blocks for Self‐Sustaining Protocells DOI Creative Commons
Oleksii Zozulia, Christine M. E. Kriebisch, Brigitte A. K. Kriebisch

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(30)

Published: May 14, 2024

Abstract Lipids spontaneously assemble into vesicle‐forming membranes. Such vesicles serve as compartments for even the simplest living systems. Vesicles have been extensively studied constructing synthetic cells or models protocells—the hypothesized to existed before life. These exist almost always close equilibrium. Life, however, exists out of In this work, we vesicle‐based regulated by a non‐equilibrium chemical reaction network that converts activating agents. way, require constant periodic supply agents sustain themselves. Specifically, use condense carboxylates and phosphate esters acyl phosphate‐based lipids form vesicles. can only be sustained when condensing are present; without them, they decay. We demonstrate operate on prebiotic agents, opening door prebiotically plausible, self‐sustainable protocells compete resources. future such should endowed with genotype, e.g., self‐replicating RNA structures, alter protocell's behavior. could enable Darwinian evolution in plausible system.

Language: Английский

Citations

1
Acyl Phosphates as Chemically Fueled Building Blocks for Self‐Sustaining Protocells DOI Creative Commons
Oleksii Zozulia, Christine M. E. Kriebisch, Brigitte A. K. Kriebisch

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(30)

Published: May 14, 2024

Abstract Lipids spontaneously assemble into vesicle‐forming membranes. Such vesicles serve as compartments for even the simplest living systems. Vesicles have been extensively studied constructing synthetic cells or models protocells—the hypothesized to existed before life. These exist almost always close equilibrium. Life, however, exists out of In this work, we vesicle‐based regulated by a non‐equilibrium chemical reaction network that converts activating agents. way, require constant periodic supply agents sustain themselves. Specifically, use condense carboxylates and phosphate esters acyl phosphate‐based lipids form vesicles. can only be sustained when condensing are present; without them, they decay. We demonstrate operate on prebiotic agents, opening door prebiotically plausible, self‐sustainable protocells compete resources. future such should endowed with genotype, e.g., self‐replicating RNA structures, alter protocell's behavior. could enable Darwinian evolution in plausible system.

Language: Английский

Citations

1
Photoinitiated Transient Self‐Assembly in a Catalytically Driven Chemical Reaction Cycle DOI Creative Commons
Jorge S. Valera, Álvaro López‐Acosta, Thomas M. Hermans

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: unknown

Published: May 21, 2024

Abstract Chemically fueled chemical reaction networks (CRNs) are essential in controlling dissipative self‐assembly. A key challenge the field is to store fuel‐precursors or “pre‐fuels” system that converted into activating deactivating fuels a catalytically controlled CRN. In addition, real‐time control over catalysis CRN by light highly desirable, but so far not yet achieved. Here we show driven photoinitiated with 450 nm light, producing activated monomers go on perform transient Monomer activation proceeds via photoredox catalysis, converting monomer alcohol groups corresponding aldehydes self‐assemble large supramolecular fibers. deactivation achieved organometallic relies pre‐fuel hydrolysis release formate (i.e. fuel). Additionally, irradiation 305 accelerates of photo‐uncaging pre‐fuel, leading factor ca. 2 faster monomer. Overall, self‐assembly upon visible photoactivation, and tunable life‐times ultraviolet light.

Language: Английский

Citations

1
Chemical reaction networks based on conjugate additions on β′-substituted Michael acceptors DOI Creative Commons
Benjamin Spitzbarth, Rienk Eelkema

Chemical Communications, Journal Year: 2023, Volume and Issue: 59(75), P. 11174 - 11187

Published: Jan. 1, 2023

The diverse reactivity of β′-substituted Michael acceptors make them a perfect fit for the application in Chemical Reaction Networks (CRNs). We show how these CRNs can find use material science, signal amplification, and beyond.

Language: Английский

Citations

3