Pub Date : 2024-10-03DOI: 10.1038/s41557-024-01636-4
Adam Noble
Adam Noble discusses the diverse uses of eosin Y over its 150-year history, from its origin as a dye and pigment used by post-impressionist masters to its versatile reactivity as a catalyst in visible light photochemistry.
亚当-诺贝尔（Adam Noble）讨论了曙红 Y 150 年来的多种用途，从其作为后印象派大师使用的染料和颜料的起源，到其作为可见光光化学催化剂的多功能反应性。
{"title":"From geranium lakes to catalysis with light","authors":"Adam Noble","doi":"10.1038/s41557-024-01636-4","DOIUrl":"10.1038/s41557-024-01636-4","url":null,"abstract":"Adam Noble discusses the diverse uses of eosin Y over its 150-year history, from its origin as a dye and pigment used by post-impressionist masters to its versatile reactivity as a catalyst in visible light photochemistry.","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"16 10","pages":"1734-1734"},"PeriodicalIF":19.2,"publicationDate":"2024-10-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142369436","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 : 2024-10-01DOI: 10.1038/s41557-024-01639-1
John Paul Pezacki, Eryn Lundrigan, Parrish Evers, Spencer Uguccioni
Determining the ligandability of the human proteome can provide key insights to characterize biological processes and promote drug discovery. Now, multi-tiered activity-based protein profiling provides comprehensive proteomic maps of chiral small-molecule interactions. Over 300 distinctive proteins were identified to ligand tryptoline acrylamides, including stereoselective and site-specific events.
{"title":"Charting the ligandable proteome for stereoselective interactions","authors":"John Paul Pezacki, Eryn Lundrigan, Parrish Evers, Spencer Uguccioni","doi":"10.1038/s41557-024-01639-1","DOIUrl":"10.1038/s41557-024-01639-1","url":null,"abstract":"Determining the ligandability of the human proteome can provide key insights to characterize biological processes and promote drug discovery. Now, multi-tiered activity-based protein profiling provides comprehensive proteomic maps of chiral small-molecule interactions. Over 300 distinctive proteins were identified to ligand tryptoline acrylamides, including stereoselective and site-specific events.","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"16 10","pages":"1571-1573"},"PeriodicalIF":19.2,"publicationDate":"2024-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142330464","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 : 2024-09-30DOI: 10.1038/s41557-024-01635-5
Shreya Ray Chaudhuri, Timothy H. Warren
The enzymatic conversion of NH4+ and NO2– to N2 catalysed by bacteria is critical to maintain nitrogen balance in the environment and for wastewater treatment. Now, a simple abiotic catalyst, the naturally occurring mineral, covellite, shows a remarkable mimicry for the entire reaction pathway.
{"title":"Abiotic anammox by a naturally occurring mineral","authors":"Shreya Ray Chaudhuri, Timothy H. Warren","doi":"10.1038/s41557-024-01635-5","DOIUrl":"10.1038/s41557-024-01635-5","url":null,"abstract":"The enzymatic conversion of NH4+ and NO2– to N2 catalysed by bacteria is critical to maintain nitrogen balance in the environment and for wastewater treatment. Now, a simple abiotic catalyst, the naturally occurring mineral, covellite, shows a remarkable mimicry for the entire reaction pathway.","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"16 10","pages":"1574-1575"},"PeriodicalIF":19.2,"publicationDate":"2024-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142329634","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 : 2024-09-27DOI: 10.1038/s41557-024-01643-5
Despite advances, a general olefination strategy for the direct conversion of carboxylic acids, alcohols and alkanes into alkenes remains challenging owing to their inherent differences in reactivity. Now, a one-pot photochemical method comprising a Giese addition followed by a Norrish type-II fragmentation enables the on-demand production of alkenes from diverse substrates.
尽管取得了一些进展，但由于羧酸、醇和烷烃的固有反应性不同，将它们直接转化为烯的通用烯化策略仍具有挑战性。现在，一种由 Giese 加成和 Norrish II 型破碎组成的单锅光化学方法可以按需从不同的底物中生产烯烃。
{"title":"Integrated photochemical strategy for alkene synthesis from diverse substrates","authors":"","doi":"10.1038/s41557-024-01643-5","DOIUrl":"10.1038/s41557-024-01643-5","url":null,"abstract":"Despite advances, a general olefination strategy for the direct conversion of carboxylic acids, alcohols and alkanes into alkenes remains challenging owing to their inherent differences in reactivity. Now, a one-pot photochemical method comprising a Giese addition followed by a Norrish type-II fragmentation enables the on-demand production of alkenes from diverse substrates.","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"16 11","pages":"1751-1752"},"PeriodicalIF":19.2,"publicationDate":"2024-09-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142324973","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 : 2024-09-27DOI: 10.1038/s41557-024-01642-6
Hao Zeng, Ruize Yin, Yu Zhao, Jun-An Ma, Jie Wu
Alkenes serve as versatile building blocks in diverse organic transformations. Despite notable advancements in olefination methods, a general strategy for the direct conversion of carboxylic acids, alcohols and alkanes into alkenes remains a formidable challenge owing to their inherent reactivity disparities. Here we demonstrate an integrated photochemical strategy that facilitates a one-pot conversion of these fundamental building blocks into alkenes through a sequential C(sp3)–C(sp3) bond formation–fragmentation process, utilizing an easily accessible and recyclable phenyl vinyl ketone as the ‘olefination reagent’. This practical method not only offers an unparalleled paradigm for accessing value-added alkenes from abundant and inexpensive starting materials but also showcases its versatility through various complex scenarios, including late-stage on-demand olefination of multifunctional molecules, chain homologation of acids and concise syntheses of bioactive molecules. Moreover, initiating from carboxylic acids, alcohols and alkanes, this protocol presents a complementary approach to traditional olefination methods, making it a highly valuable addition to the research toolkit for alkene synthesis. The synthesis of alkenes from carboxylic acids, alcohols and alkanes is a formidable challenge owing to their inherent differences in reactivity. Now the one-pot conversion of these building blocks into alkenes is reported through an integrated photochemical strategy using a phenyl vinyl ketone as the olefination reagent.
{"title":"Modular alkene synthesis from carboxylic acids, alcohols and alkanes via integrated photocatalysis","authors":"Hao Zeng, Ruize Yin, Yu Zhao, Jun-An Ma, Jie Wu","doi":"10.1038/s41557-024-01642-6","DOIUrl":"10.1038/s41557-024-01642-6","url":null,"abstract":"Alkenes serve as versatile building blocks in diverse organic transformations. Despite notable advancements in olefination methods, a general strategy for the direct conversion of carboxylic acids, alcohols and alkanes into alkenes remains a formidable challenge owing to their inherent reactivity disparities. Here we demonstrate an integrated photochemical strategy that facilitates a one-pot conversion of these fundamental building blocks into alkenes through a sequential C(sp3)–C(sp3) bond formation–fragmentation process, utilizing an easily accessible and recyclable phenyl vinyl ketone as the ‘olefination reagent’. This practical method not only offers an unparalleled paradigm for accessing value-added alkenes from abundant and inexpensive starting materials but also showcases its versatility through various complex scenarios, including late-stage on-demand olefination of multifunctional molecules, chain homologation of acids and concise syntheses of bioactive molecules. Moreover, initiating from carboxylic acids, alcohols and alkanes, this protocol presents a complementary approach to traditional olefination methods, making it a highly valuable addition to the research toolkit for alkene synthesis. The synthesis of alkenes from carboxylic acids, alcohols and alkanes is a formidable challenge owing to their inherent differences in reactivity. Now the one-pot conversion of these building blocks into alkenes is reported through an integrated photochemical strategy using a phenyl vinyl ketone as the olefination reagent.","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"16 11","pages":"1822-1830"},"PeriodicalIF":19.2,"publicationDate":"2024-09-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142324976","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 : 2024-09-27DOI: 10.1038/s41557-024-01646-2
Antonio Del Rio Flores, Rui Zhai, David W. Kastner, Kaushik Seshadri, Siyue Yang, Kyle De Matias, Yuanbo Shen, Wenlong Cai, Maanasa Narayanamoorthy, Nicholas B. Do, Zhaoqiang Xue, Dunya Al Marzooqi, Heather J. Kulik, Wenjun Zhang
Azides are energy-rich compounds with diverse representation in a broad range of scientific disciplines, including material science, synthetic chemistry, pharmaceutical science and chemical biology. Despite ubiquitous usage of the azido group, the underlying biosynthetic pathways for its formation remain largely unknown. Here we report the characterization of an enzymatic route for de novo azide construction. We demonstrate that Tri17, a promiscuous ATP- and nitrite-dependent enzyme, catalyses organic azide synthesis through sequential N-nitrosation and dehydration of aryl hydrazines. Through biochemical, structural and computational analyses, we further propose a plausible molecular mechanism for azide synthesis that sets the stage for future biocatalytic applications and biosynthetic pathway engineering. Despite widespread use of azides across material science and various areas across chemistry, the underlying biosynthetic pathways for its formation have so far been unknown. Now, a promiscuous ATP-utilizing enzyme, Tri17, capable of synthesizing various azide molecules has been identified. Biochemical, structural and computational analyses support a potential molecular mechanism for azide formation by Tri17.
叠氮化物是一种富含能量的化合物，在材料科学、合成化学、制药科学和化学生物学等广泛的科学学科中具有不同的代表性。尽管叠氮基的使用无处不在，但其形成的基本生物合成途径在很大程度上仍然未知。在这里，我们报告了从头构建叠氮基的酶学途径的特征。我们证明 Tri17 是一种依赖 ATP 和亚硝酸盐的杂合酶，它通过芳基肼的 N-亚硝基化和脱水顺序催化有机叠氮化物的合成。通过生化、结构和计算分析，我们进一步提出了叠氮化物合成的合理分子机制，为未来的生物催化应用和生物合成途径工程奠定了基础。
{"title":"Enzymatic synthesis of azide by a promiscuous N-nitrosylase","authors":"Antonio Del Rio Flores, Rui Zhai, David W. Kastner, Kaushik Seshadri, Siyue Yang, Kyle De Matias, Yuanbo Shen, Wenlong Cai, Maanasa Narayanamoorthy, Nicholas B. Do, Zhaoqiang Xue, Dunya Al Marzooqi, Heather J. Kulik, Wenjun Zhang","doi":"10.1038/s41557-024-01646-2","DOIUrl":"10.1038/s41557-024-01646-2","url":null,"abstract":"Azides are energy-rich compounds with diverse representation in a broad range of scientific disciplines, including material science, synthetic chemistry, pharmaceutical science and chemical biology. Despite ubiquitous usage of the azido group, the underlying biosynthetic pathways for its formation remain largely unknown. Here we report the characterization of an enzymatic route for de novo azide construction. We demonstrate that Tri17, a promiscuous ATP- and nitrite-dependent enzyme, catalyses organic azide synthesis through sequential N-nitrosation and dehydration of aryl hydrazines. Through biochemical, structural and computational analyses, we further propose a plausible molecular mechanism for azide synthesis that sets the stage for future biocatalytic applications and biosynthetic pathway engineering. Despite widespread use of azides across material science and various areas across chemistry, the underlying biosynthetic pathways for its formation have so far been unknown. Now, a promiscuous ATP-utilizing enzyme, Tri17, capable of synthesizing various azide molecules has been identified. Biochemical, structural and computational analyses support a potential molecular mechanism for azide formation by Tri17.","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"16 12","pages":"2066-2075"},"PeriodicalIF":19.2,"publicationDate":"2024-09-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142324974","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 : 2024-09-27DOI: 10.1038/s41557-024-01647-1
Samantha K. Bruffy, Anthony Meza, Jordi Soler, Tyler J. Doyon, Seth H. Young, Jooyeon Lim, Kathryn G. Huseth, Patrick H. Willoughby, Marc Garcia-Borràs, Andrew R. Buller
Enzymes are renowned for their catalytic efficiency and selectivity, but many classical transformations in organic synthesis have no biocatalytic counterpart. Aldolases are prodigious C–C bond-forming enzymes, but their reactivity has only been extended past activated carbonyl electrophiles in special cases. To probe the mechanistic origins of this limitation, we use a pair of aldolases whose activity is dependent on pyridoxal phosphate. Our results reveal how aldolases are limited by kinetically favourable proton transfer with solvent, which undermines aldol addition into ketones. We show how a transaldolase can circumvent this limitation, enabling efficient addition into unactivated ketones. The resulting products are highly sought non-canonical amino acids with side chains that contain chiral tertiary alcohols. Mechanistic analysis reveals that transaldolase activity is an intrinsic feature of pyridoxal phosphate chemistry and identifies principles for extending aldolase catalysis beyond its previous limits to enable convergent, enantioselective C–C bond formation from simple starting materials. Aldolases have been a mainstay in synthesis, but their scope has been limited to activated electrophiles. Now carbon–carbon bond formation with ketone electrophiles is enabled by transaldolases, which form a strong nucleophile that is resistant to protonation. This chemistry enables convergent synthesis of non-canonical amino acids bearing tertiary alcohol side chains.
{"title":"Biocatalytic asymmetric aldol addition into unactivated ketones","authors":"Samantha K. Bruffy, Anthony Meza, Jordi Soler, Tyler J. Doyon, Seth H. Young, Jooyeon Lim, Kathryn G. Huseth, Patrick H. Willoughby, Marc Garcia-Borràs, Andrew R. Buller","doi":"10.1038/s41557-024-01647-1","DOIUrl":"10.1038/s41557-024-01647-1","url":null,"abstract":"Enzymes are renowned for their catalytic efficiency and selectivity, but many classical transformations in organic synthesis have no biocatalytic counterpart. Aldolases are prodigious C–C bond-forming enzymes, but their reactivity has only been extended past activated carbonyl electrophiles in special cases. To probe the mechanistic origins of this limitation, we use a pair of aldolases whose activity is dependent on pyridoxal phosphate. Our results reveal how aldolases are limited by kinetically favourable proton transfer with solvent, which undermines aldol addition into ketones. We show how a transaldolase can circumvent this limitation, enabling efficient addition into unactivated ketones. The resulting products are highly sought non-canonical amino acids with side chains that contain chiral tertiary alcohols. Mechanistic analysis reveals that transaldolase activity is an intrinsic feature of pyridoxal phosphate chemistry and identifies principles for extending aldolase catalysis beyond its previous limits to enable convergent, enantioselective C–C bond formation from simple starting materials. Aldolases have been a mainstay in synthesis, but their scope has been limited to activated electrophiles. Now carbon–carbon bond formation with ketone electrophiles is enabled by transaldolases, which form a strong nucleophile that is resistant to protonation. This chemistry enables convergent synthesis of non-canonical amino acids bearing tertiary alcohol side chains.","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"16 12","pages":"2076-2083"},"PeriodicalIF":19.2,"publicationDate":"2024-09-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142324975","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 : 2024-09-26DOI: 10.1038/s41557-024-01651-5
Michelle Francl
Before the internet, chemists used references books to find necessary information. Michelle Francl takes us on a journey through the weird and wondrous world captured in the most famous reference book of them all, known to some as the ‘Rubber Bible’.
{"title":"Chemistry to hand","authors":"Michelle Francl","doi":"10.1038/s41557-024-01651-5","DOIUrl":"10.1038/s41557-024-01651-5","url":null,"abstract":"Before the internet, chemists used references books to find necessary information. Michelle Francl takes us on a journey through the weird and wondrous world captured in the most famous reference book of them all, known to some as the ‘Rubber Bible’.","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"16 10","pages":"1567-1568"},"PeriodicalIF":19.2,"publicationDate":"2024-09-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142321349","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 : 2024-09-25DOI: 10.1038/s41557-024-01624-8
Tongliang Zhou, Pengcheng Gao, Roger Lalancette, Roman Szostak, Michal Szostak
Amines are the most pivotal class of organic motifs in pharmaceutical compounds. Here we provide a blueprint for a general synthesis of amines by catalyst differentiation enabled by triple Au–H/Au+/Au–H relay catalysis. The parent catalyst is differentiated into a set of catalytically active species to enable triple cascade catalysis, where each catalytic species is specifically tuned for one catalytic cycle. This strategy enables the synthesis of biorelevant amine motifs by reductive hydroamination of alkynes with nitroarenes. Using this triple cascade approach, we have achieved exceptional functional group tolerance, enabling the use of bulk chemical feedstocks as coupling partners for the amination of both simple and complex alkynes (>100 examples), including those derived from pharmaceuticals, peptides and natural products (>30 examples). The isolation and full crystallographic characterization of gold hydride and hydride-bridged gold complexes has garnered insights into the catalyst differentiation process of fundamental organometallic gold hydride complexes. Amines are predominant motifs in pharmaceuticals, but complex amines are challenging to generate. Now, enabled by triple Au–H/Au+/Au–H relay catalysis, the synthesis of complex and structurally diverse amines by a direct reductive hydroamination of alkynes with nitroarenes is reported. Catalytic intermediates were isolated to elucidate the mechanism.
{"title":"Gold-catalysed amine synthesis by reductive hydroamination of alkynes with nitroarenes","authors":"Tongliang Zhou, Pengcheng Gao, Roger Lalancette, Roman Szostak, Michal Szostak","doi":"10.1038/s41557-024-01624-8","DOIUrl":"10.1038/s41557-024-01624-8","url":null,"abstract":"Amines are the most pivotal class of organic motifs in pharmaceutical compounds. Here we provide a blueprint for a general synthesis of amines by catalyst differentiation enabled by triple Au–H/Au+/Au–H relay catalysis. The parent catalyst is differentiated into a set of catalytically active species to enable triple cascade catalysis, where each catalytic species is specifically tuned for one catalytic cycle. This strategy enables the synthesis of biorelevant amine motifs by reductive hydroamination of alkynes with nitroarenes. Using this triple cascade approach, we have achieved exceptional functional group tolerance, enabling the use of bulk chemical feedstocks as coupling partners for the amination of both simple and complex alkynes (>100 examples), including those derived from pharmaceuticals, peptides and natural products (>30 examples). The isolation and full crystallographic characterization of gold hydride and hydride-bridged gold complexes has garnered insights into the catalyst differentiation process of fundamental organometallic gold hydride complexes. Amines are predominant motifs in pharmaceuticals, but complex amines are challenging to generate. Now, enabled by triple Au–H/Au+/Au–H relay catalysis, the synthesis of complex and structurally diverse amines by a direct reductive hydroamination of alkynes with nitroarenes is reported. Catalytic intermediates were isolated to elucidate the mechanism.","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"16 12","pages":"2025-2035"},"PeriodicalIF":19.2,"publicationDate":"2024-09-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142321923","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 : 2024-09-25DOI: 10.1038/s41557-024-01620-y
Federico Vismarra, Francisco Fernández-Villoria, Daniele Mocci, Jesús González-Vázquez, Yingxuan Wu, Lorenzo Colaizzi, Fabian Holzmeier, Jorge Delgado, José Santos, Luis Bañares, Laura Carlini, Mattea Carmen Castrovilli, Paola Bolognesi, Robert Richter, Lorenzo Avaldi, Alicia Palacios, Matteo Lucchini, Maurizio Reduzzi, Rocío Borrego-Varillas, Nazario Martín, Fernando Martín, Mauro Nisoli
The exposure of molecules to attosecond extreme-ultraviolet (XUV) pulses offers a unique opportunity to study the early stages of coupled electron–nuclear dynamics in which the role played by the different degrees of freedom is beyond standard chemical intuition. We investigate, both experimentally and theoretically, the first steps of charge-transfer processes initiated by prompt ionization in prototype donor–π–acceptor molecules, namely nitroanilines. Time-resolved measurement of this process is performed by combining attosecond XUV-pump/few-femtosecond infrared-probe spectroscopy with advanced many-body quantum chemistry calculations. We show that a concerted nuclear and electronic motion drives electron transfer from the donor group on a sub-10-fs timescale. This is followed by a sub-30-fs relaxation process due to the probing of the continuously spreading nuclear wave packet in the excited electronic states of the molecular cation. These findings shed light on the role played by electron–nuclear coupling in donor–π–acceptor systems in response to photoionization. The first steps of charge transfer in molecules after their interaction with light occur on an ultrafast timescale. Now, by combining attosecond pump/few-femtosecond probe spectroscopy with quantum chemistry calculations, it has been shown that a concerted nuclear and electronic motion drives electron transfer in donor–π–acceptor molecules on a sub-10-fs timescale.
{"title":"Few-femtosecond electron transfer dynamics in photoionized donor–π–acceptor molecules","authors":"Federico Vismarra, Francisco Fernández-Villoria, Daniele Mocci, Jesús González-Vázquez, Yingxuan Wu, Lorenzo Colaizzi, Fabian Holzmeier, Jorge Delgado, José Santos, Luis Bañares, Laura Carlini, Mattea Carmen Castrovilli, Paola Bolognesi, Robert Richter, Lorenzo Avaldi, Alicia Palacios, Matteo Lucchini, Maurizio Reduzzi, Rocío Borrego-Varillas, Nazario Martín, Fernando Martín, Mauro Nisoli","doi":"10.1038/s41557-024-01620-y","DOIUrl":"10.1038/s41557-024-01620-y","url":null,"abstract":"The exposure of molecules to attosecond extreme-ultraviolet (XUV) pulses offers a unique opportunity to study the early stages of coupled electron–nuclear dynamics in which the role played by the different degrees of freedom is beyond standard chemical intuition. We investigate, both experimentally and theoretically, the first steps of charge-transfer processes initiated by prompt ionization in prototype donor–π–acceptor molecules, namely nitroanilines. Time-resolved measurement of this process is performed by combining attosecond XUV-pump/few-femtosecond infrared-probe spectroscopy with advanced many-body quantum chemistry calculations. We show that a concerted nuclear and electronic motion drives electron transfer from the donor group on a sub-10-fs timescale. This is followed by a sub-30-fs relaxation process due to the probing of the continuously spreading nuclear wave packet in the excited electronic states of the molecular cation. These findings shed light on the role played by electron–nuclear coupling in donor–π–acceptor systems in response to photoionization. The first steps of charge transfer in molecules after their interaction with light occur on an ultrafast timescale. Now, by combining attosecond pump/few-femtosecond probe spectroscopy with quantum chemistry calculations, it has been shown that a concerted nuclear and electronic motion drives electron transfer in donor–π–acceptor molecules on a sub-10-fs timescale.","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"16 12","pages":"2017-2024"},"PeriodicalIF":19.2,"publicationDate":"2024-09-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.com/articles/s41557-024-01620-y.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142321924","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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