Pub Date : 2025-11-25DOI: 10.1038/s41557-025-01977-8
Ya-Wei Zhou, Enric Ibáñez-Alé, Núria López, Beatriz Roldan Cuenya, Christopher S. Kley
Interfacial hydration layers critically determine energy and chemical conversion processes, notably influencing the kinetics of electrocatalytic reactions. Fundamental mechanisms of reactions such as CO 2 electroreduction and hydrogen evolution remain controversial due to the challenge of in situ deciphering of hydration structures alongside reaction intermediates and products. Here, by using vibrational and electrochemical spectroscopy paired with theory we reveal how carbonates structure interfacial water, affecting CO 2 electroreduction and hydrogen evolution reactions on gold electrocatalysts in bicarbonate electrolytes. High cathodic potentials accelerate hydrogen evolution reactions by rapid proton delivery from ordered interfacial hydration networks, induced by carbonate molecules in equilibrium with their anion radicals. These radicals can serve, in addition to CO 2 , as a carbon source for CO and aldehyde production. Moreover we show water to be the primary proton donor for CO 2 electroreduction and hydrogen evolution reactions, with bicarbonate mostly participating in the Heyrovsky step. Our molecular-level insights are relevant to rationalizing and optimizing electrochemical interfaces.
{"title":"Carbonate anions and radicals induce interfacial water ordering in CO2 electroreduction on gold","authors":"Ya-Wei Zhou, Enric Ibáñez-Alé, Núria López, Beatriz Roldan Cuenya, Christopher S. Kley","doi":"10.1038/s41557-025-01977-8","DOIUrl":"https://doi.org/10.1038/s41557-025-01977-8","url":null,"abstract":"Interfacial hydration layers critically determine energy and chemical conversion processes, notably influencing the kinetics of electrocatalytic reactions. Fundamental mechanisms of reactions such as CO <jats:sub>2</jats:sub> electroreduction and hydrogen evolution remain controversial due to the challenge of in situ deciphering of hydration structures alongside reaction intermediates and products. Here, by using vibrational and electrochemical spectroscopy paired with theory we reveal how carbonates structure interfacial water, affecting CO <jats:sub>2</jats:sub> electroreduction and hydrogen evolution reactions on gold electrocatalysts in bicarbonate electrolytes. High cathodic potentials accelerate hydrogen evolution reactions by rapid proton delivery from ordered interfacial hydration networks, induced by carbonate molecules in equilibrium with their anion radicals. These radicals can serve, in addition to CO <jats:sub>2</jats:sub> , as a carbon source for CO and aldehyde production. Moreover we show water to be the primary proton donor for CO <jats:sub>2</jats:sub> electroreduction and hydrogen evolution reactions, with bicarbonate mostly participating in the Heyrovsky step. Our molecular-level insights are relevant to rationalizing and optimizing electrochemical interfaces.","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"136 1","pages":""},"PeriodicalIF":21.8,"publicationDate":"2025-11-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145593912","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 : 2025-11-24DOI: 10.1038/s41557-025-02005-5
D. I. Ioannou, J. N. H. Reek
Electrophotocatalysis offers a promising strategy for relatively inert molecules, but designing robust systems has been challenging. Now, heterogeneous polymers, composed of perylenediimide units with flexible linkers, unlock chloroarene reduction and functionalization through closed-shell dianion generation and substrate precomplexation.
{"title":"Heterogeneous polymer designs that bring electricity, light and substrates together","authors":"D. I. Ioannou, J. N. H. Reek","doi":"10.1038/s41557-025-02005-5","DOIUrl":"10.1038/s41557-025-02005-5","url":null,"abstract":"Electrophotocatalysis offers a promising strategy for relatively inert molecules, but designing robust systems has been challenging. Now, heterogeneous polymers, composed of perylenediimide units with flexible linkers, unlock chloroarene reduction and functionalization through closed-shell dianion generation and substrate precomplexation.","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"17 12","pages":"1809-1810"},"PeriodicalIF":20.2,"publicationDate":"2025-11-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145583044","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 : 2025-11-24DOI: 10.1038/s41557-025-01997-4
Zixu Wang, Chengxiang Ding, Yizhen Chen, Mengdi Huang, Dongmin Wang, Lei Xu, Sudip Pan, Shengfa Ye, Gengwen Tan
Isonitriles (R–N≡C), first discovered by Lieke in 1859, are well-established functional molecules in organic and organometallic chemistry. By contrast, the synthesis and investigation of tetrela-isonitriles (R–N≡E, E = Si, Ge, Sn or Pb), their heavier group 14 analogues, remain challenging due to their high reactivity. The characterization of such species has largely relied on spectroscopic data collected at cryogenic temperatures or under gas-phase conditions. Here we report the synthesis and characterization of a germa-isonitrile (Ar–N≡Ge) stabilized by a bulky aryl ligand. This compound, which features a terminal N≡Ge triple bond with a Ge‒N bond length of 1.6395(19) Å, has been characterized through X-ray crystallographic, solid-state ¹⁵N nuclear magnetic resonance spectroscopic and computational studies. The highly polarized N≡Ge moiety exhibits versatile reactivity towards organic substrates and transition metal precursors, underscoring its potential use in synthetic chemistry. The study of tetrela-isonitriles—the heavier group 14 analogues of isonitriles—has largely relied on the investigation of transient species under matrix isolation or gas-phase conditions. Now a germa-isonitrile featuring a terminal N≡Ge triple bond and a pseudo-monocoordinate germanium atom has been isolated in the condensed phase. Its reactivity towards selected organic substrates and transition metal complexes has also been explored.
异腈（R-N≡C）于1859年由李克首次发现，是有机和有机金属化学中公认的功能分子。相比之下，四元异腈（R-N≡E, E = Si, Ge， Sn或Pb）的合成和研究，它们较重的14族类似物，由于其高反应性仍然具有挑战性。这类物质的表征很大程度上依赖于在低温或气相条件下收集的光谱数据。在这里，我们报道了一种由庞大的芳基配体稳定的锗异腈（Ar-N≡Ge）的合成和表征。该化合物以端N≡Ge三键为特征，Ge - N键长为1.6395（19）Å，已通过x射线晶体学、固态¹5 N核磁共振光谱和计算研究对其进行了表征。高度极化的N≡Ge基团对有机底物和过渡金属前体表现出多种反应性，强调了其在合成化学中的潜在用途。四元异腈（四元异腈的重基团14类似物）的研究主要依赖于在基质分离或气相条件下对瞬态物质的研究。现在，在缩合相中分离出了一个末端为N≡Ge三键和伪单配位锗原子的锗-异腈。它对选定的有机底物和过渡金属配合物的反应性也进行了探索。
{"title":"An isolable germa-isonitrile featuring a terminal nitrogen–germanium triple bond","authors":"Zixu Wang, Chengxiang Ding, Yizhen Chen, Mengdi Huang, Dongmin Wang, Lei Xu, Sudip Pan, Shengfa Ye, Gengwen Tan","doi":"10.1038/s41557-025-01997-4","DOIUrl":"10.1038/s41557-025-01997-4","url":null,"abstract":"Isonitriles (R–N≡C), first discovered by Lieke in 1859, are well-established functional molecules in organic and organometallic chemistry. By contrast, the synthesis and investigation of tetrela-isonitriles (R–N≡E, E = Si, Ge, Sn or Pb), their heavier group 14 analogues, remain challenging due to their high reactivity. The characterization of such species has largely relied on spectroscopic data collected at cryogenic temperatures or under gas-phase conditions. Here we report the synthesis and characterization of a germa-isonitrile (Ar–N≡Ge) stabilized by a bulky aryl ligand. This compound, which features a terminal N≡Ge triple bond with a Ge‒N bond length of 1.6395(19) Å, has been characterized through X-ray crystallographic, solid-state ¹⁵N nuclear magnetic resonance spectroscopic and computational studies. The highly polarized N≡Ge moiety exhibits versatile reactivity towards organic substrates and transition metal precursors, underscoring its potential use in synthetic chemistry. The study of tetrela-isonitriles—the heavier group 14 analogues of isonitriles—has largely relied on the investigation of transient species under matrix isolation or gas-phase conditions. Now a germa-isonitrile featuring a terminal N≡Ge triple bond and a pseudo-monocoordinate germanium atom has been isolated in the condensed phase. Its reactivity towards selected organic substrates and transition metal complexes has also been explored.","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"18 2","pages":"356-363"},"PeriodicalIF":20.2,"publicationDate":"2025-11-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145582932","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 : 2025-11-21DOI: 10.1038/s41557-025-02000-w
Xianglin Zhu, Ruijie Deng
Subtle mutations in the genome play key roles in both disease progression and pathogen evolution. Now, a fluorescent aptamer-based RNA switch has been shown to enable rapid and robust detection of single nucleotide mutations.
{"title":"Ultraspecific RNA switches for robust mutation detection","authors":"Xianglin Zhu, Ruijie Deng","doi":"10.1038/s41557-025-02000-w","DOIUrl":"10.1038/s41557-025-02000-w","url":null,"abstract":"Subtle mutations in the genome play key roles in both disease progression and pathogen evolution. Now, a fluorescent aptamer-based RNA switch has been shown to enable rapid and robust detection of single nucleotide mutations.","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"17 12","pages":"1803-1805"},"PeriodicalIF":20.2,"publicationDate":"2025-11-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145560435","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 : 2025-11-21DOI: 10.1038/s41557-025-01987-6
Electrifying nonaqueous thermocatalytic reactions is challenging. Now, a multiphase approach that uses aqueous electrochemistry to drive a nonaqueous reaction through aqueous–nonaqueous interfacial proton-coupled electron transfer is developed for the production of hydrogen peroxide.
{"title":"Bridging aqueous electrochemistry and non-aqueous chemistry for chemical production","authors":"","doi":"10.1038/s41557-025-01987-6","DOIUrl":"10.1038/s41557-025-01987-6","url":null,"abstract":"Electrifying nonaqueous thermocatalytic reactions is challenging. Now, a multiphase approach that uses aqueous electrochemistry to drive a nonaqueous reaction through aqueous–nonaqueous interfacial proton-coupled electron transfer is developed for the production of hydrogen peroxide.","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"17 12","pages":"1815-1816"},"PeriodicalIF":20.2,"publicationDate":"2025-11-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145573920","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 : 2025-11-21DOI: 10.1038/s41557-025-02006-4
Lukas Palatinus
Determining the enantiomorphic excess in chiral solids remains a difficult task, yet it is crucial for the characterization of materials such as chiral catalysts. Now, a combination of 3D electron diffraction, dynamical diffraction calculations, and automated processing enables the quantification of enantiomorphs in a fast and reliable manner.
{"title":"Determining chirality in crystalline powders through 3D electron diffraction","authors":"Lukas Palatinus","doi":"10.1038/s41557-025-02006-4","DOIUrl":"10.1038/s41557-025-02006-4","url":null,"abstract":"Determining the enantiomorphic excess in chiral solids remains a difficult task, yet it is crucial for the characterization of materials such as chiral catalysts. Now, a combination of 3D electron diffraction, dynamical diffraction calculations, and automated processing enables the quantification of enantiomorphs in a fast and reliable manner.","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"17 12","pages":"1813-1814"},"PeriodicalIF":20.2,"publicationDate":"2025-11-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145560427","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 : 2025-11-21DOI: 10.1038/s41557-025-01995-6
Zhaoqing Yan, Yudan Li, Amit Eshed, Kaiyue Wu, Zachary M. Ticktin, Vel Murugan, Efrem S. Lim, Fan Hong, Alexander A. Green
The ability to detect single nucleotide polymorphisms (SNPs) is critical for identifying genetic disorders, assessing pathogen drug resistance and preventing infection transmission. Achieving a delicate balance across sequence-specific recognition, RNA structural stability and functional efficacy based on SNP-induced changes is crucial for precise genotyping using RNA-based probes. Here we report on in silico-designed aptamer-based RNA switches, referred to as ‘fast aptamer-based reporters for single-nucleotide-specific identification and genotyping through hybridization’ (FARSIGHTs), that enable rapid, low-leakage and multiplexed identification of virtually any target sequence with single-nucleotide specificity. Activation of the FARSIGHT probe can occur in as little as 5 min, separate from upstream amplification. Coupling FARSIGHTs with isothermal amplification enables the robust detection of single nucleotide mutations at attomolar concentrations through strong fluorescence output. We have demonstrated this by distinguishing the SARS-CoV-2 Omicron variant from Alpha, Beta and Gamma with 100% accuracy in RNA from clinical saliva samples. FARSIGHTs can be easily reprogrammed for genotyping emerging pathogens, with potential uses in point-of-care infectious disease monitoring and personalized healthcare applications. The robust detection of single nucleotide variants (SNVs) remains a key challenge for rapid and multiplexed diagnostics. Now it is shown that FARSIGHT, a computationally designed aptamer-based RNA switch, achieves rapid, enzyme-free genotyping via domino-like coupled strand-displacement reactions. These systems provide attomolar sensitivity when coupled with isothermal amplification, multiplexed SNV discrimination and lateral flow readout.
{"title":"Programmable fluorescent aptamer-based RNA switches for rapid identification of point mutations","authors":"Zhaoqing Yan, Yudan Li, Amit Eshed, Kaiyue Wu, Zachary M. Ticktin, Vel Murugan, Efrem S. Lim, Fan Hong, Alexander A. Green","doi":"10.1038/s41557-025-01995-6","DOIUrl":"10.1038/s41557-025-01995-6","url":null,"abstract":"The ability to detect single nucleotide polymorphisms (SNPs) is critical for identifying genetic disorders, assessing pathogen drug resistance and preventing infection transmission. Achieving a delicate balance across sequence-specific recognition, RNA structural stability and functional efficacy based on SNP-induced changes is crucial for precise genotyping using RNA-based probes. Here we report on in silico-designed aptamer-based RNA switches, referred to as ‘fast aptamer-based reporters for single-nucleotide-specific identification and genotyping through hybridization’ (FARSIGHTs), that enable rapid, low-leakage and multiplexed identification of virtually any target sequence with single-nucleotide specificity. Activation of the FARSIGHT probe can occur in as little as 5 min, separate from upstream amplification. Coupling FARSIGHTs with isothermal amplification enables the robust detection of single nucleotide mutations at attomolar concentrations through strong fluorescence output. We have demonstrated this by distinguishing the SARS-CoV-2 Omicron variant from Alpha, Beta and Gamma with 100% accuracy in RNA from clinical saliva samples. FARSIGHTs can be easily reprogrammed for genotyping emerging pathogens, with potential uses in point-of-care infectious disease monitoring and personalized healthcare applications. The robust detection of single nucleotide variants (SNVs) remains a key challenge for rapid and multiplexed diagnostics. Now it is shown that FARSIGHT, a computationally designed aptamer-based RNA switch, achieves rapid, enzyme-free genotyping via domino-like coupled strand-displacement reactions. These systems provide attomolar sensitivity when coupled with isothermal amplification, multiplexed SNV discrimination and lateral flow readout.","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"17 12","pages":"1826-1838"},"PeriodicalIF":20.2,"publicationDate":"2025-11-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145560430","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}
Hydrogen bonds are fundamental chemical interactions that stabilize protein structures, particularly in β sheets, enabling resistance to mechanical stress and environmental extremes. Here, inspired by natural mechanostable proteins with shearing hydrogen bonds, such as titin and silk fibroin, we de novo designed superstable proteins by maximizing hydrogen-bond networks within force-bearing β strands. Using a computational framework combining artificial intelligence-guided structure and sequence design with all-atom molecular dynamics MD simulations, we systematically expanded protein architecture, increasing the number of backbone hydrogen bonds from 4 to 33. The resulting proteins exhibited unfolding forces exceeding 1,000 pN, about 400% stronger than the natural titin immunoglobulin domain, and retained structural integrity after exposure to 150 °C. This molecular-level stability translated directly to macroscopic properties, as demonstrated by the formation of thermally stable hydrogels. Our work introduces a scalable and efficient computational strategy for engineering robust proteins, offering a generalizable approach for the rational design of resilient protein systems for extreme environments. Nature contains a variety of mechanostable proteins, which all bear extensive hydrogen-bond networks within their β-sheet architectures to sustain high stability under stress. Now through integrating AI-guided design alongside MD simulations and by maximizing hydrogen bonds in β strands, SuperMyo proteins with nanonewton mechanical stability and thermal resilience up to 150 °C were created.
{"title":"Computational design of superstable proteins through maximized hydrogen bonding","authors":"Bin Zheng, Zhuojian Lu, Shangchen Wang, Lichao Liu, Mingjun Ao, Yurui Zhou, Guojing Tang, Ruishi Wang, Yuanhao Liu, Hantian Zhang, Yinying Meng, Jun Qiu, Tianfu Feng, Ziyi Wang, Renming Liu, Yuelong Xiao, Yutong Liu, Ziling Wang, Yifen Huang, Yajun Jiang, Peng Zheng","doi":"10.1038/s41557-025-01998-3","DOIUrl":"10.1038/s41557-025-01998-3","url":null,"abstract":"Hydrogen bonds are fundamental chemical interactions that stabilize protein structures, particularly in β sheets, enabling resistance to mechanical stress and environmental extremes. Here, inspired by natural mechanostable proteins with shearing hydrogen bonds, such as titin and silk fibroin, we de novo designed superstable proteins by maximizing hydrogen-bond networks within force-bearing β strands. Using a computational framework combining artificial intelligence-guided structure and sequence design with all-atom molecular dynamics MD simulations, we systematically expanded protein architecture, increasing the number of backbone hydrogen bonds from 4 to 33. The resulting proteins exhibited unfolding forces exceeding 1,000 pN, about 400% stronger than the natural titin immunoglobulin domain, and retained structural integrity after exposure to 150 °C. This molecular-level stability translated directly to macroscopic properties, as demonstrated by the formation of thermally stable hydrogels. Our work introduces a scalable and efficient computational strategy for engineering robust proteins, offering a generalizable approach for the rational design of resilient protein systems for extreme environments. Nature contains a variety of mechanostable proteins, which all bear extensive hydrogen-bond networks within their β-sheet architectures to sustain high stability under stress. Now through integrating AI-guided design alongside MD simulations and by maximizing hydrogen bonds in β strands, SuperMyo proteins with nanonewton mechanical stability and thermal resilience up to 150 °C were created.","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"18 2","pages":"364-373"},"PeriodicalIF":20.2,"publicationDate":"2025-11-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145550153","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}
Conceptual frameworks that describe the electronic structure of molecules are an integral part of understanding chemical structures and reaction mechanisms and designing organic compounds. Here we develop a preliminary set of design guidelines for controlling the electronic structure of DNA. Recent work indicates that charge delocalization occurs over several bases and results in coherence lengths greater than a single base pair. To examine the interactions between bases and their effects on delocalization, this study investigates the influence of nearest-neighbour base pair interactions on the charge transport properties of DNA duplexes that are predominantly composed of guanine-cytosine base pairs. Results show that, by manipulating the sequence, the conductance can be substantially modified without altering the molecular composition. The electronic density of states are then analysed to deduce a set of design guidelines aimed at maintaining high conductance values in long duplexes. Utilizing these rules, we demonstrate that 20-base-pair DNA sequences can exhibit conductance values surpassing 1 × 10-3G0.
{"title":"Developing design guidelines for controlling charge transport in DNA.","authors":"Zahra Aminiranjbar, Caglanaz Akin Gultakti, Amy Zhang, Ersin Emre Oren, Joshua Hihath","doi":"10.1038/s41557-025-01999-2","DOIUrl":"10.1038/s41557-025-01999-2","url":null,"abstract":"<p><p>Conceptual frameworks that describe the electronic structure of molecules are an integral part of understanding chemical structures and reaction mechanisms and designing organic compounds. Here we develop a preliminary set of design guidelines for controlling the electronic structure of DNA. Recent work indicates that charge delocalization occurs over several bases and results in coherence lengths greater than a single base pair. To examine the interactions between bases and their effects on delocalization, this study investigates the influence of nearest-neighbour base pair interactions on the charge transport properties of DNA duplexes that are predominantly composed of guanine-cytosine base pairs. Results show that, by manipulating the sequence, the conductance can be substantially modified without altering the molecular composition. The electronic density of states are then analysed to deduce a set of design guidelines aimed at maintaining high conductance values in long duplexes. Utilizing these rules, we demonstrate that 20-base-pair DNA sequences can exhibit conductance values surpassing 1 × 10<sup>-3</sup>G<sub>0</sub>.</p>","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":" ","pages":""},"PeriodicalIF":20.2,"publicationDate":"2025-11-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145550223","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 : 2025-11-17DOI: 10.1038/s41557-025-02001-9
Chao Wan, Chao Yang, Magnus Rueping, Chen Zhu, Lin Guo, Wujiong Xia
Dearomative functionalization of arenes represents a powerful synthetic strategy for the rapid assembly of complex chemical architectures. A significant challenge in this process is overcoming the inherent aromaticity of arenes. Here, leveraging the potential of organic electrolysis, we show the development of a dearomative syn-1,4-hydroalkylation reaction targeting electron-deficient arenes and heteroarenes. This electrochemical approach, conducted under mild, operationally straightforward and scalable conditions, facilitates the synthesis of alkylated syn-1,4-cyclohexadienes with high chemoselectivity, regioselectivity and stereoselectivity. In addition, this alkylation protocol is controllable and switchable. By employing a niobium plate as the anode and nBu4NBr as the supporting electrolyte, our method enables the para-selective C(sp2)–H alkylation of (hetero)arenes via electrolysis. Both reactions exhibit broad substrate scope and demonstrate excellent compatibility with various electron-deficient arenes and alkyl bromides. Furthermore, preliminary mechanistic studies and density functional theory calculations have been performed to elucidate the reaction mechanism and to rationalize the observed chemoselectivity, regioselectivity and stereoselectivity. Dearomative functionalization is an extraordinary approach for transforming inert, two-dimensional arenes into three-dimensional architectures. Now it has been shown that electrolysis could facilitate dearomative syn-1,4-hydroalkylation and para-selective C(sp2)–H alkylation of electron-deficient (hetero)arenes. Mechanistic studies indicate that the chemoselectivity is primarily governed by the choice of supporting electrolyte and electrode.
{"title":"Dearomative syn-1,4-hydroalkylation and C(sp2)−H alkylation of arenes controlled by chemoselective electrolysis","authors":"Chao Wan, Chao Yang, Magnus Rueping, Chen Zhu, Lin Guo, Wujiong Xia","doi":"10.1038/s41557-025-02001-9","DOIUrl":"10.1038/s41557-025-02001-9","url":null,"abstract":"Dearomative functionalization of arenes represents a powerful synthetic strategy for the rapid assembly of complex chemical architectures. A significant challenge in this process is overcoming the inherent aromaticity of arenes. Here, leveraging the potential of organic electrolysis, we show the development of a dearomative syn-1,4-hydroalkylation reaction targeting electron-deficient arenes and heteroarenes. This electrochemical approach, conducted under mild, operationally straightforward and scalable conditions, facilitates the synthesis of alkylated syn-1,4-cyclohexadienes with high chemoselectivity, regioselectivity and stereoselectivity. In addition, this alkylation protocol is controllable and switchable. By employing a niobium plate as the anode and nBu4NBr as the supporting electrolyte, our method enables the para-selective C(sp2)–H alkylation of (hetero)arenes via electrolysis. Both reactions exhibit broad substrate scope and demonstrate excellent compatibility with various electron-deficient arenes and alkyl bromides. Furthermore, preliminary mechanistic studies and density functional theory calculations have been performed to elucidate the reaction mechanism and to rationalize the observed chemoselectivity, regioselectivity and stereoselectivity. Dearomative functionalization is an extraordinary approach for transforming inert, two-dimensional arenes into three-dimensional architectures. Now it has been shown that electrolysis could facilitate dearomative syn-1,4-hydroalkylation and para-selective C(sp2)–H alkylation of electron-deficient (hetero)arenes. Mechanistic studies indicate that the chemoselectivity is primarily governed by the choice of supporting electrolyte and electrode.","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"18 2","pages":"386-397"},"PeriodicalIF":20.2,"publicationDate":"2025-11-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145541343","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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