Ionic interactions between DNA phosphates and positively charged amino acid residues in aqueous environments are ubiquitous and essential across all biological systems. Such interactions are readily disrupted by polar solvents according to Coulomb’s law, which accounts for the predominant use of non-polar or weakly polar organic solvents in chiral phosphate-mediated asymmetric organocatalysis. This intriguing discrepancy prompted us to exploit the possibility of conducting asymmetric catalysis in water with intrinsically chiral and abundant DNA phosphates. Here we experimentally and computationally demonstrate that DNA phosphates play a critical role in rate acceleration and stereoinduction through ion-pairing interactions with cationic reagents, featuring a cation-dependent dynamic and adaptive nature of the DNA catalyst rarely seen in highly specific enzymatic systems. The application of DNA phosphates to mediate asymmetric reactions is underdeveloped in synthetic chemistry. Now, DNA phosphates are designed to catalyse enantioselective fluorination, Mannich and photo-induced cross-dehydrogenative coupling reactions in water driven by ion-pairing interactions.
{"title":"DNA phosphates are effective catalysts for asymmetric ion-pairing catalysis in water","authors":"Zhaoyang Li, Yang Zheng, Qi Zhao, Yihan Li, Adon Yap, Xinglong Zhang, Ru-Yi Zhu","doi":"10.1038/s41929-025-01437-z","DOIUrl":"10.1038/s41929-025-01437-z","url":null,"abstract":"Ionic interactions between DNA phosphates and positively charged amino acid residues in aqueous environments are ubiquitous and essential across all biological systems. Such interactions are readily disrupted by polar solvents according to Coulomb’s law, which accounts for the predominant use of non-polar or weakly polar organic solvents in chiral phosphate-mediated asymmetric organocatalysis. This intriguing discrepancy prompted us to exploit the possibility of conducting asymmetric catalysis in water with intrinsically chiral and abundant DNA phosphates. Here we experimentally and computationally demonstrate that DNA phosphates play a critical role in rate acceleration and stereoinduction through ion-pairing interactions with cationic reagents, featuring a cation-dependent dynamic and adaptive nature of the DNA catalyst rarely seen in highly specific enzymatic systems. The application of DNA phosphates to mediate asymmetric reactions is underdeveloped in synthetic chemistry. Now, DNA phosphates are designed to catalyse enantioselective fluorination, Mannich and photo-induced cross-dehydrogenative coupling reactions in water driven by ion-pairing interactions.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"8 11","pages":"1220-1231"},"PeriodicalIF":44.6,"publicationDate":"2025-10-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145404976","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-10-31DOI: 10.1038/s41929-025-01434-2
Jin Zhu, Qiaoyu Zhang, Tao Gu, Binbin Chen, Mingzhe Ma, Xiaoyu Wang, Xiao Liu, Mingjie Ma, Binju Wang, Yajie Wang
Established strategies for enantioselective hydroalkylation for C(sp3)–C(sp3) bond formation usually require prefunctionalized substrates as radical precursors in both transition-metal and photoenzymatic catalysis. Here, based on a sequential proton transfer/electron transfer strategy, we show a cooperative photoenzymatic system consisting of a flavin-dependent ‘ene’-reductase and an organophotoredox catalyst fluorescein (FI) to achieve atom-economic enantiodivergent hydroalkylation of electron-deficient C(sp3)–H with olefins. Mechanistic studies revealed a pathway for radical intermediate formation via excited-state FI*-induced single-electron oxidation of carbanions under alkaline conditions. The overall catalytic efficiency is enhanced by the electron transfer between FMNox and FI−•, while the stereoselectivity is controlled by ene-reductases through enantioselective hydrogen atom transfer. We anticipate that this mode of photoenzymatic catalysis will inspire new pathways for generating free radical intermediates and foster innovative strategies for achieving photoenzymatic new-to-nature reactions. Constructing C(sp3)–C(sp3) bonds using non-prefunctionalized substrates as radical precursors is challenging. Now an ene-reductase and an organophotoredox catalyst work together to enable the enantiodivergent hydroalkylation of electron-deficient C(sp3)–H bonds via radical intermediates generated from carbanions.
{"title":"Atom-economic enantioselective photoenzymatic radical hydroalkylation via single-electron oxidation of carbanions","authors":"Jin Zhu, Qiaoyu Zhang, Tao Gu, Binbin Chen, Mingzhe Ma, Xiaoyu Wang, Xiao Liu, Mingjie Ma, Binju Wang, Yajie Wang","doi":"10.1038/s41929-025-01434-2","DOIUrl":"10.1038/s41929-025-01434-2","url":null,"abstract":"Established strategies for enantioselective hydroalkylation for C(sp3)–C(sp3) bond formation usually require prefunctionalized substrates as radical precursors in both transition-metal and photoenzymatic catalysis. Here, based on a sequential proton transfer/electron transfer strategy, we show a cooperative photoenzymatic system consisting of a flavin-dependent ‘ene’-reductase and an organophotoredox catalyst fluorescein (FI) to achieve atom-economic enantiodivergent hydroalkylation of electron-deficient C(sp3)–H with olefins. Mechanistic studies revealed a pathway for radical intermediate formation via excited-state FI*-induced single-electron oxidation of carbanions under alkaline conditions. The overall catalytic efficiency is enhanced by the electron transfer between FMNox and FI−•, while the stereoselectivity is controlled by ene-reductases through enantioselective hydrogen atom transfer. We anticipate that this mode of photoenzymatic catalysis will inspire new pathways for generating free radical intermediates and foster innovative strategies for achieving photoenzymatic new-to-nature reactions. Constructing C(sp3)–C(sp3) bonds using non-prefunctionalized substrates as radical precursors is challenging. Now an ene-reductase and an organophotoredox catalyst work together to enable the enantiodivergent hydroalkylation of electron-deficient C(sp3)–H bonds via radical intermediates generated from carbanions.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"8 11","pages":"1188-1197"},"PeriodicalIF":44.6,"publicationDate":"2025-10-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145404977","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-10-27DOI: 10.1038/s41929-025-01429-z
Wenjie Li, Muwen Yang, Zhiheng Zhao, Ming Zhao, Rong Ye, Bing Fu, Peng Chen
Many vital electrocatalytic transformations hinge on reactive surface metal–hydrogen intermediates (M–H*), yet the low concentration and transient nature of such intermediates present formidable challenges to in-depth investigation. Here we use single-molecule super-resolution reaction imaging to directly probe surface palladium–hydrogen (Pd–H*) intermediates on individual palladium nanocubes during electrocatalytic hydrogen evolution. Our approach visualizes hydrogen spillover from palladium to the surrounding substrate surface over hundreds of nanometres away and dissects substantial inter- and intraparticle heterogeneity. Through Gaussian-broadening kinetic analysis, we reveal that ensemble-averaged measurements systematically overestimate the stability of Pd–H*. Moreover, we resolve three subpopulations of palladium nanocubes with distinct reactivity features, uncovering critical correlations between intermediate stability, hydrogenation reactivity and transition-state properties. Our findings highlight the necessity of single-particle resolution for capturing the intrinsic complexity of electrocatalysts; our approach is also broadly applicable to interrogate surface-reactive intermediates across a wide array of electrocatalytic pathways. Probing transient intermediates and deriving subsequent mechanistic and kinetic analyses is very challenging. Now, Pd–H* intermediates on palladium nanocubes are identified at the single-particle level by means of single-molecule reaction imaging, evidencing intra- and interparticle heterogeneity and hydrogen spillover events.
{"title":"Single-molecule reaction mapping uncovers diverse behaviours of electrocatalytic surface Pd–H intermediates","authors":"Wenjie Li, Muwen Yang, Zhiheng Zhao, Ming Zhao, Rong Ye, Bing Fu, Peng Chen","doi":"10.1038/s41929-025-01429-z","DOIUrl":"10.1038/s41929-025-01429-z","url":null,"abstract":"Many vital electrocatalytic transformations hinge on reactive surface metal–hydrogen intermediates (M–H*), yet the low concentration and transient nature of such intermediates present formidable challenges to in-depth investigation. Here we use single-molecule super-resolution reaction imaging to directly probe surface palladium–hydrogen (Pd–H*) intermediates on individual palladium nanocubes during electrocatalytic hydrogen evolution. Our approach visualizes hydrogen spillover from palladium to the surrounding substrate surface over hundreds of nanometres away and dissects substantial inter- and intraparticle heterogeneity. Through Gaussian-broadening kinetic analysis, we reveal that ensemble-averaged measurements systematically overestimate the stability of Pd–H*. Moreover, we resolve three subpopulations of palladium nanocubes with distinct reactivity features, uncovering critical correlations between intermediate stability, hydrogenation reactivity and transition-state properties. Our findings highlight the necessity of single-particle resolution for capturing the intrinsic complexity of electrocatalysts; our approach is also broadly applicable to interrogate surface-reactive intermediates across a wide array of electrocatalytic pathways. Probing transient intermediates and deriving subsequent mechanistic and kinetic analyses is very challenging. Now, Pd–H* intermediates on palladium nanocubes are identified at the single-particle level by means of single-molecule reaction imaging, evidencing intra- and interparticle heterogeneity and hydrogen spillover events.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"8 11","pages":"1159-1168"},"PeriodicalIF":44.6,"publicationDate":"2025-10-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145382245","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-10-24DOI: 10.1038/s41929-025-01414-6
Héctor Soria-Carrera, Job Boekhoven
A study demonstrates that fully synthetic molecules can undergo self-replication, mutation and selection — hallmarks of Darwinian evolution — without relying on DNA or proteins.
{"title":"Catalyst optimization through synthetic Darwinian evolution","authors":"Héctor Soria-Carrera, Job Boekhoven","doi":"10.1038/s41929-025-01414-6","DOIUrl":"10.1038/s41929-025-01414-6","url":null,"abstract":"A study demonstrates that fully synthetic molecules can undergo self-replication, mutation and selection — hallmarks of Darwinian evolution — without relying on DNA or proteins.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"8 10","pages":"979-980"},"PeriodicalIF":44.6,"publicationDate":"2025-10-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145371937","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The Mannich reaction represents one of the most fundamental reactions for the stereoselective synthesis of β-amino-carbonyl compounds and has been broadly applied in organic synthesis. In contrast, the homologue of the Mannich reaction, the so-called the homo-Mannich reaction, which generates the homologated γ-amino-carbonyl products, remains largely underexplored despite its potential for diverse applications. We show here a copper-catalysed homo-Mannich reaction of cyclopropanols with in situ-formed imines, furnishing a variety of chiral 2,6-disubstituted piperidines in good yields with high diastereoselectivities. Critical is the use of a diketiminate-complexed copper as the catalyst, which allows this reaction to proceed efficiently under mild conditions in an air atmosphere. Using this method as the key reaction, we achieved total synthesis of four alkaloids. This study not only expands the application range of cyclopropanol as a homoenolate equivalent for the Mannich reaction, but also inspires utilization of diketiminate ligands in metal catalysis. The Mannich reaction has long been used by chemists for the synthesis of stereoselective synthesis of β-amino-carbonyl compounds. Here, the authors show a catalytic homo-Mannich reaction of cyclopropanols with in situ-formed imines, furnishing chiral 2,6-disubstituted piperidines in good yields with high diastereoselectivities due to the use of a diketiminate-complexed copper.
{"title":"Copper-catalysed homo-Mannich reaction of cyclopropanol for chiral piperidine synthesis","authors":"Yankun Zhao, Wenxuan Lin, Yulian Zhang, Guangcheng Pu, Zhuoyuan Jian, Hongya Yan, Ling He, Chengyang Wang, Qiuyuan Tan, Yu Lan, Min Zhang","doi":"10.1038/s41929-025-01432-4","DOIUrl":"10.1038/s41929-025-01432-4","url":null,"abstract":"The Mannich reaction represents one of the most fundamental reactions for the stereoselective synthesis of β-amino-carbonyl compounds and has been broadly applied in organic synthesis. In contrast, the homologue of the Mannich reaction, the so-called the homo-Mannich reaction, which generates the homologated γ-amino-carbonyl products, remains largely underexplored despite its potential for diverse applications. We show here a copper-catalysed homo-Mannich reaction of cyclopropanols with in situ-formed imines, furnishing a variety of chiral 2,6-disubstituted piperidines in good yields with high diastereoselectivities. Critical is the use of a diketiminate-complexed copper as the catalyst, which allows this reaction to proceed efficiently under mild conditions in an air atmosphere. Using this method as the key reaction, we achieved total synthesis of four alkaloids. This study not only expands the application range of cyclopropanol as a homoenolate equivalent for the Mannich reaction, but also inspires utilization of diketiminate ligands in metal catalysis. The Mannich reaction has long been used by chemists for the synthesis of stereoselective synthesis of β-amino-carbonyl compounds. Here, the authors show a catalytic homo-Mannich reaction of cyclopropanols with in situ-formed imines, furnishing chiral 2,6-disubstituted piperidines in good yields with high diastereoselectivities due to the use of a diketiminate-complexed copper.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"8 11","pages":"1169-1177"},"PeriodicalIF":44.6,"publicationDate":"2025-10-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145382247","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-10-24DOI: 10.1038/s41929-025-01420-8
Y. Koga, I. Fukumoto, K. Masui, T. Tanaka, Y. Naganawa, M. Hayashi, T. Ohshima, R. Yazaki
Deuterium-labelled compounds play a crucial role in drug discovery as both diagnostic tools and deuterated pharmaceuticals. While hydrogen isotope exchange is well established for activated substrates, the catalytic deuteration of unactivated amides and esters remains underdeveloped, particularly under mild conditions suitable for sensitive pharmaceuticals and polymers. This limitation hampers the late-stage modification of pharmaceutical molecules and functional materials. Here we report a catalytic hydrogen isotope exchange method using cooperative catalysts—a silicon Lewis acid and a tertiary amine base—functioning as a frustrated Lewis pair. This approach enables highly selective deuteration under mild conditions. Our method achieves high deuterium incorporation in various functionalized pharmaceuticals and polyesters, including those typically unstable under basic conditions, demonstrating its broad applicability. Deuterated bioactive compounds are important as diagnostic tools and pharmaceuticals, but current methods of development are limited. Here the authors report how a silicon Lewis acid and a tertiary amine base act as a frustrated Lewis pair to catalyse the hydrogen exchange reaction for the deuteration of amides and esters.
{"title":"Silicon frustrated Lewis pairs catalyse α-deuteration of amides and esters","authors":"Y. Koga, I. Fukumoto, K. Masui, T. Tanaka, Y. Naganawa, M. Hayashi, T. Ohshima, R. Yazaki","doi":"10.1038/s41929-025-01420-8","DOIUrl":"10.1038/s41929-025-01420-8","url":null,"abstract":"Deuterium-labelled compounds play a crucial role in drug discovery as both diagnostic tools and deuterated pharmaceuticals. While hydrogen isotope exchange is well established for activated substrates, the catalytic deuteration of unactivated amides and esters remains underdeveloped, particularly under mild conditions suitable for sensitive pharmaceuticals and polymers. This limitation hampers the late-stage modification of pharmaceutical molecules and functional materials. Here we report a catalytic hydrogen isotope exchange method using cooperative catalysts—a silicon Lewis acid and a tertiary amine base—functioning as a frustrated Lewis pair. This approach enables highly selective deuteration under mild conditions. Our method achieves high deuterium incorporation in various functionalized pharmaceuticals and polyesters, including those typically unstable under basic conditions, demonstrating its broad applicability. Deuterated bioactive compounds are important as diagnostic tools and pharmaceuticals, but current methods of development are limited. Here the authors report how a silicon Lewis acid and a tertiary amine base act as a frustrated Lewis pair to catalyse the hydrogen exchange reaction for the deuteration of amides and esters.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"8 10","pages":"1062-1071"},"PeriodicalIF":44.6,"publicationDate":"2025-10-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145371980","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-10-24DOI: 10.1038/s41929-025-01433-3
Xinjie Yang, Juan Guo, Junyi Qian, Jianjian Huang, Juan Shi, Miao Jiang, Junshuai Zhang, Tengfei Pang, Ningning Sun, Yu Fu, Weining Zhao, Guojiao Wu, Xi Chen, Yuzhou Wu, Fangrui Zhong
Enzyme compartmentalization is a ubiquitous biochemical mechanism that nature uses to perform simultaneous but chemically incompatible metabolic processes in physically separated environments. However, it is a substantial challenge in homogeneous catalysis to spatially confine specific reaction components to prevent undesired pathways. Here we exploit the concept of compartmentalized enantioselective energy transfer catalysis by integrating artificial triplet photoenzymes and tailored triplet quenchers. The confined protein cavity was genetically encoded with a photosensitizer for enantioselective [2 + 2] photocycloaddition of 1-naphthol derivatives, while the outer bulk solution was modified with strategically introduced quenchers to inhibit the racemic background reaction induced by direct excitation, a fundamental challenge in asymmetric photocatalysis. This study not only expands the repertoire of artificial photoenzymes but also introduces a distinctive biocatalytic approach for precisely controlling reaction processes with spatial resolution, a capability that is usually unattainable in traditional chemocatalysis. Artificial photobiocatalytic reactions are appealing but sometimes suffer from non-enzymatic side reactions. Now a photoenzyme for enantioselective [2 + 2] photocycloaddition of 2-naphthyl derivatives is reported and combined with designed quenchers that shut down the competing enzyme-free racemic reaction.
{"title":"Enantioselective energy transfer catalysis compartmentalized by triplet photoenzymes","authors":"Xinjie Yang, Juan Guo, Junyi Qian, Jianjian Huang, Juan Shi, Miao Jiang, Junshuai Zhang, Tengfei Pang, Ningning Sun, Yu Fu, Weining Zhao, Guojiao Wu, Xi Chen, Yuzhou Wu, Fangrui Zhong","doi":"10.1038/s41929-025-01433-3","DOIUrl":"10.1038/s41929-025-01433-3","url":null,"abstract":"Enzyme compartmentalization is a ubiquitous biochemical mechanism that nature uses to perform simultaneous but chemically incompatible metabolic processes in physically separated environments. However, it is a substantial challenge in homogeneous catalysis to spatially confine specific reaction components to prevent undesired pathways. Here we exploit the concept of compartmentalized enantioselective energy transfer catalysis by integrating artificial triplet photoenzymes and tailored triplet quenchers. The confined protein cavity was genetically encoded with a photosensitizer for enantioselective [2 + 2] photocycloaddition of 1-naphthol derivatives, while the outer bulk solution was modified with strategically introduced quenchers to inhibit the racemic background reaction induced by direct excitation, a fundamental challenge in asymmetric photocatalysis. This study not only expands the repertoire of artificial photoenzymes but also introduces a distinctive biocatalytic approach for precisely controlling reaction processes with spatial resolution, a capability that is usually unattainable in traditional chemocatalysis. Artificial photobiocatalytic reactions are appealing but sometimes suffer from non-enzymatic side reactions. Now a photoenzyme for enantioselective [2 + 2] photocycloaddition of 2-naphthyl derivatives is reported and combined with designed quenchers that shut down the competing enzyme-free racemic reaction.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"8 11","pages":"1178-1187"},"PeriodicalIF":44.6,"publicationDate":"2025-10-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145382002","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-10-24DOI: 10.1038/s41929-025-01409-3
Kai Liu, Omer Markovitch, Chris van Ewijk, Yari Katar Knelissen, Armin Kiani, Marcel Eleveld, Wouter H. Roos, Sijbren Otto
The onset of Darwinian evolution represents a key step in the transition of chemical systems into living ones. Furthermore, Darwinian evolution is a tremendously powerful engine of invention, but one that has remained underdeveloped in synthetic chemical systems. Here we show the emergence of Darwinian evolution in two systems of self-replicating molecules in which natural selection favours replicator mutants best capable of catalysing the production of the precursors required for their own replication. Selection occurs based on the ability of the mutants to activate a photocatalyst as a cofactor that produces singlet oxygen which, in turn, enhances the rate by which peptide-based dithiol building blocks are converted into disulfide-based replicator precursors. Selection is based on a functional trait (catalytic activity), opening up Darwinian evolution as a tool for catalyst development. This work functionally integrates self-replication with protometabolism and Darwinian evolution, marking a further advance in the de novo synthesis of life. Darwinian evolution has shaped life on our planet through natural selection. Here, the authors report on the combination of self-replication, mutation and protometabolism in an out-of-equilibrium abiotic chemical system that can lead to natural selection for protometabolic activity.
{"title":"Selection for photocatalytic function through Darwinian evolution of synthetic self-replicators","authors":"Kai Liu, Omer Markovitch, Chris van Ewijk, Yari Katar Knelissen, Armin Kiani, Marcel Eleveld, Wouter H. Roos, Sijbren Otto","doi":"10.1038/s41929-025-01409-3","DOIUrl":"10.1038/s41929-025-01409-3","url":null,"abstract":"The onset of Darwinian evolution represents a key step in the transition of chemical systems into living ones. Furthermore, Darwinian evolution is a tremendously powerful engine of invention, but one that has remained underdeveloped in synthetic chemical systems. Here we show the emergence of Darwinian evolution in two systems of self-replicating molecules in which natural selection favours replicator mutants best capable of catalysing the production of the precursors required for their own replication. Selection occurs based on the ability of the mutants to activate a photocatalyst as a cofactor that produces singlet oxygen which, in turn, enhances the rate by which peptide-based dithiol building blocks are converted into disulfide-based replicator precursors. Selection is based on a functional trait (catalytic activity), opening up Darwinian evolution as a tool for catalyst development. This work functionally integrates self-replication with protometabolism and Darwinian evolution, marking a further advance in the de novo synthesis of life. Darwinian evolution has shaped life on our planet through natural selection. Here, the authors report on the combination of self-replication, mutation and protometabolism in an out-of-equilibrium abiotic chemical system that can lead to natural selection for protometabolic activity.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"8 10","pages":"1000-1009"},"PeriodicalIF":44.6,"publicationDate":"2025-10-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145371983","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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