Multi‐Stimuli‐Responsive Network of Multicatalytic Reactions using a Single Palladium/Platinum Catalyst DOI Creative Commons
Gracjan Kurpik,

Anna Walczak,

Paweł Dydio

и другие.

Angewandte Chemie, Год журнала: 2024, Номер 136(37)

Опубликована: Июнь 15, 2024

Abstract Given her unrivalled proficiency in the synthesis of all molecules life, nature has been an endless source inspiration for developing new strategies organic chemistry and catalysis. However, one feature that remains thus far beyond chemists’ grasp is unique ability to adapt productivity metabolic processes response triggers indicate temporary need specific metabolites. To demonstrate remarkable potential such stimuli‐responsive systems, we present a metabolism‐inspired network multicatalytic capable selectively synthesising range products from simple starting materials. Specifically, built four classes distinct catalytic reactions—cross‐couplings, substitutions, additions, reductions, involving three materials—terminal alkyne, aryl iodide, hydrosilane. All materials are either introduced sequentially or added system at same time, with no continuous influx reagents efflux products. catalysed by multifunctional heteronuclear Pd II /Pt complex, whose performance can be controlled additives external stimuli. The reaction exhibits substantial degree orthogonality between different pathways, enabling controllable ten high efficiency selectivity through simultaneous triggering suppression mechanisms.

Язык: Английский

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

и другие.

Chem, Год журнала: 2025, Номер unknown, С. 102399 - 102399

Опубликована: Фев. 1, 2025

Язык: Английский

Процитировано

4
Abiotic Acyl Transfer Cascades Driven by Aminoacyl Phosphate Esters and Self-Assembly DOI Creative Commons
Mahesh D. Pol, Ralf Thomann, Yi Thomann

и другие.

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

Процитировано

4
Alkyl Chloride-Functionalized Polymers Mediate Oxidation of Thioethers Initiated by Ionizing Radiation DOI Creative Commons
Juncheng Liu, Irene Piergentili, Bing Xu

и другие.

ACS Applied Polymer Materials, Год журнала: 2025, Номер 7(6), С. 3835 - 3841

Опубликована: Март 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.

Язык: Английский

Процитировано

0
Photoinitiated Transient Self‐Assembly in a Catalytically Driven Chemical Reaction Cycle DOI Creative Commons
Jorge S. Valera, Álvaro López‐Acosta, Thomas M. Hermans

и другие.

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

Опубликована: Май 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.

Язык: Английский

Процитировано

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

и другие.

Опубликована: Янв. 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

Язык: Английский

Процитировано

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

и другие.

Molecules, Год журнала: 2024, Номер 29(7), С. 1620 - 1620

Опубликована: Апрель 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.

Язык: Английский

Процитировано

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

и другие.

Angewandte Chemie, Год журнала: 2024, Номер 136(30)

Опубликована: Май 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.

Язык: Английский

Процитировано

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

и другие.

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(30)

Опубликована: Май 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.

Язык: Английский

Процитировано

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

и другие.

Angewandte Chemie, Год журнала: 2024, Номер unknown

Опубликована: Май 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.

Язык: Английский

Процитировано

1
Multi‐Stimuli‐Responsive Network of Multicatalytic Reactions using a Single Palladium/Platinum Catalyst DOI Creative Commons
Gracjan Kurpik, Anna Walczak, Paweł Dydio

и другие.

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(37)

Опубликована: Июнь 15, 2024

Given her unrivalled proficiency in the synthesis of all molecules life, nature has been an endless source inspiration for developing new strategies organic chemistry and catalysis. However, one feature that remains thus far beyond chemists' grasp is unique ability to adapt productivity metabolic processes response triggers indicate temporary need specific metabolites. To demonstrate remarkable potential such stimuli-responsive systems, we present a metabolism-inspired network multicatalytic capable selectively synthesising range products from simple starting materials. Specifically, built four classes distinct catalytic reactions-cross-couplings, substitutions, additions, reductions, involving three materials-terminal alkyne, aryl iodide, hydrosilane. All materials are either introduced sequentially or added system at same time, with no continuous influx reagents efflux products. catalysed by multifunctional heteronuclear Pd

Язык: Английский

Процитировано

1