Pub Date : 2025-06-18DOI: 10.1038/s41570-025-00725-3
Arpan Das, Quentin Le Dé, Viktoria H. Gessner
Carbanionic compounds provide unique reactivity patterns resulting from the high negative partial charge at the carbon centre, making them invaluable in chemical synthesis. They are important reagents in synthesis, including for challenging metalation reactions or the formation of C–C bonds. Despite this, broader applications have long been limited by their high reactivity and sensitivity to air and moisture. However, recent studies have underscored the versatility of carbanions beyond their traditional role as strong bases and nucleophiles. Utilization of molecular design strategies has opened applications such as their use as electron-donating groups isoelectronic with amines, ambiphilic reagents and even as weakly coordinating anions. In this review article, we provide an overview of these emerging uses of carbanionic compounds, aiming to inspire a broader rethinking of their potential and to encourage the development of new applications. This Review highlights the unconventional reactivities of carbanions beyond their traditional roles as nucleophiles and strong bases. It summarizes their applications as ambiphiles, powerful electron-donating groups and even weakly coordinating anions, emphasizing novel synthetic methodologies, catalytic applications and the development of new reagents.
{"title":"Rethinking carbanion chemistry from donor substituents to weakly coordinating carbanions","authors":"Arpan Das, Quentin Le Dé, Viktoria H. Gessner","doi":"10.1038/s41570-025-00725-3","DOIUrl":"10.1038/s41570-025-00725-3","url":null,"abstract":"Carbanionic compounds provide unique reactivity patterns resulting from the high negative partial charge at the carbon centre, making them invaluable in chemical synthesis. They are important reagents in synthesis, including for challenging metalation reactions or the formation of C–C bonds. Despite this, broader applications have long been limited by their high reactivity and sensitivity to air and moisture. However, recent studies have underscored the versatility of carbanions beyond their traditional role as strong bases and nucleophiles. Utilization of molecular design strategies has opened applications such as their use as electron-donating groups isoelectronic with amines, ambiphilic reagents and even as weakly coordinating anions. In this review article, we provide an overview of these emerging uses of carbanionic compounds, aiming to inspire a broader rethinking of their potential and to encourage the development of new applications. This Review highlights the unconventional reactivities of carbanions beyond their traditional roles as nucleophiles and strong bases. It summarizes their applications as ambiphiles, powerful electron-donating groups and even weakly coordinating anions, emphasizing novel synthetic methodologies, catalytic applications and the development of new reagents.","PeriodicalId":18849,"journal":{"name":"Nature reviews. Chemistry","volume":"9 8","pages":"523-536"},"PeriodicalIF":51.7,"publicationDate":"2025-06-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144326317","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 : 2025-06-16DOI: 10.1038/s41570-025-00730-6
Chenjie Lou, Ming Liu
Fifty-two years ago, Wright and colleagues discovered that complexes of alkali metal ions with polyethylene oxide conduct ions, and that this conductivity is temperature-sensitive. This seminal work unveiled the potential application of such complexes as solid-state electrolytes. Here, we discuss the history of and advances in polymer solid-state electrolytes, and future research directions.
{"title":"Unchained power","authors":"Chenjie Lou, Ming Liu","doi":"10.1038/s41570-025-00730-6","DOIUrl":"https://doi.org/10.1038/s41570-025-00730-6","url":null,"abstract":"Fifty-two years ago, Wright and colleagues discovered that complexes of alkali metal ions with polyethylene oxide conduct ions, and that this conductivity is temperature-sensitive. This seminal work unveiled the potential application of such complexes as solid-state electrolytes. Here, we discuss the history of and advances in polymer solid-state electrolytes, and future research directions.","PeriodicalId":18849,"journal":{"name":"Nature reviews. Chemistry","volume":"13 1","pages":""},"PeriodicalIF":36.3,"publicationDate":"2025-06-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144296179","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 : 2025-06-11DOI: 10.1038/s41570-025-00728-0
I. M. Peters, C. J. Brabec
Introducing recyclability into photovoltaic design adds complexity. Recyclability depends on parameters governing material cohesion and separability, often conflicting with traditional criteria such as efficiency, stability and cost. Achieving circularity transforms solar-cell design into the art of managing intrinsic trade-offs, harmonizing the ease of material recovery with photovoltaic performance.
{"title":"The ideal recyclable solar cell","authors":"I. M. Peters, C. J. Brabec","doi":"10.1038/s41570-025-00728-0","DOIUrl":"10.1038/s41570-025-00728-0","url":null,"abstract":"Introducing recyclability into photovoltaic design adds complexity. Recyclability depends on parameters governing material cohesion and separability, often conflicting with traditional criteria such as efficiency, stability and cost. Achieving circularity transforms solar-cell design into the art of managing intrinsic trade-offs, harmonizing the ease of material recovery with photovoltaic performance.","PeriodicalId":18849,"journal":{"name":"Nature reviews. Chemistry","volume":"9 7","pages":"427-429"},"PeriodicalIF":51.7,"publicationDate":"2025-06-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144260437","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 : 2025-06-05DOI: 10.1038/s41570-025-00721-7
Enping Du, Xianhui Tang, Wenqiang Zhang, Jinqiao Dong, Yong Cui, Yan Liu
Mechanically interlocked molecules, including catenanes, rotaxanes and knots, are an intriguing class of synthetic targets with potential applications in molecular switches and machines. Although mechanically interlocked molecules are typically constructed using macrocyclic frameworks, the interlocking of two or more three-dimensional, shape-persistent cages remains relatively underexplored. Recent advances have accelerated the development of mechanically interlocked cages (MICs), which consist of interlocked three-dimensional molecular cages rather than macrocycles. Despite their potential in areas such as molecular recognition, separation and catalysis, the design and synthesis of MICs remain challenging. This Review examines the synthetic strategies used to construct MICs, along with their interlocked architecture characteristics, structural dynamics and potential applications. Special attention is given to the guest-binding properties and catalytic performance of monomeric versus catenated cages. We conclude with perspectives on the current challenges and opportunities for future development of MICs. Mechanically interlocked cages are a distinctive class of molecular architectures. This Review highlights their design strategies, structural features and potential applications, while also addressing current challenges and providing insights into future directions for mechanically interlocked cages.
{"title":"Emerging mechanically interlocked cages","authors":"Enping Du, Xianhui Tang, Wenqiang Zhang, Jinqiao Dong, Yong Cui, Yan Liu","doi":"10.1038/s41570-025-00721-7","DOIUrl":"10.1038/s41570-025-00721-7","url":null,"abstract":"Mechanically interlocked molecules, including catenanes, rotaxanes and knots, are an intriguing class of synthetic targets with potential applications in molecular switches and machines. Although mechanically interlocked molecules are typically constructed using macrocyclic frameworks, the interlocking of two or more three-dimensional, shape-persistent cages remains relatively underexplored. Recent advances have accelerated the development of mechanically interlocked cages (MICs), which consist of interlocked three-dimensional molecular cages rather than macrocycles. Despite their potential in areas such as molecular recognition, separation and catalysis, the design and synthesis of MICs remain challenging. This Review examines the synthetic strategies used to construct MICs, along with their interlocked architecture characteristics, structural dynamics and potential applications. Special attention is given to the guest-binding properties and catalytic performance of monomeric versus catenated cages. We conclude with perspectives on the current challenges and opportunities for future development of MICs. Mechanically interlocked cages are a distinctive class of molecular architectures. This Review highlights their design strategies, structural features and potential applications, while also addressing current challenges and providing insights into future directions for mechanically interlocked cages.","PeriodicalId":18849,"journal":{"name":"Nature reviews. Chemistry","volume":"9 8","pages":"506-522"},"PeriodicalIF":51.7,"publicationDate":"2025-06-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144219205","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}
Lithium and other alkali-metal-based batteries are promising candidates for next-generation energy-storage technologies. However, such batteries suffer from limited lifespans caused by the continuous inactivation of their electrodes during operation and even storage, creating inactivated or ‘dead’ Li, which is a combination of electrically insulated metallic Li and solid–electrolyte interphases (SEIs). Numerous efforts have been devoted to uncovering the origins of this inactivation and how it could be mitigated. Given that dead Li cannot be entirely prevented, rejuvenating it has emerged as a solution for prolonging the lifetimes of batteries and energy-storage systems. Here, we discuss the origins of dead Li and its effects on battery operations. We summarize the emerging challenges related to dead Li, such as SEI dissolution, dead Li migration and Li corrosion. We evaluate the limitations of the present strategies devoted to reducing the formation of dead Li, and how to recover and rejuvenate dead Li through redox chemistry and electrochemical protocols. We conclude with development opportunities in operando diagnoses and the rejuvenation of other inactivated electrode materials beyond Li chemistry in cells and large-scale systems already on the market. The inactivation of electrodes triggers the loss of capacity and decreases the lifetimes of batteries, especially for high-capacity systems. Here the rejuvenation chemistry for re-activating electrodes, aimed at prolonging the lifetimes of lithium-based batteries and similar energy-storage systems, is discussed. Li, lithium; Cu, copper; e–, electrons; RMred, reduced redox mediator; RMox, oxidized redox mediator.
{"title":"Inhibiting and rejuvenating dead lithium in battery materials","authors":"Chengbin Jin, Ouwei Sheng, Guoying Wei, Hongyan Li, Qingyue Han, Qiang Zhang, Xinyong Tao","doi":"10.1038/s41570-025-00722-6","DOIUrl":"10.1038/s41570-025-00722-6","url":null,"abstract":"Lithium and other alkali-metal-based batteries are promising candidates for next-generation energy-storage technologies. However, such batteries suffer from limited lifespans caused by the continuous inactivation of their electrodes during operation and even storage, creating inactivated or ‘dead’ Li, which is a combination of electrically insulated metallic Li and solid–electrolyte interphases (SEIs). Numerous efforts have been devoted to uncovering the origins of this inactivation and how it could be mitigated. Given that dead Li cannot be entirely prevented, rejuvenating it has emerged as a solution for prolonging the lifetimes of batteries and energy-storage systems. Here, we discuss the origins of dead Li and its effects on battery operations. We summarize the emerging challenges related to dead Li, such as SEI dissolution, dead Li migration and Li corrosion. We evaluate the limitations of the present strategies devoted to reducing the formation of dead Li, and how to recover and rejuvenate dead Li through redox chemistry and electrochemical protocols. We conclude with development opportunities in operando diagnoses and the rejuvenation of other inactivated electrode materials beyond Li chemistry in cells and large-scale systems already on the market. The inactivation of electrodes triggers the loss of capacity and decreases the lifetimes of batteries, especially for high-capacity systems. Here the rejuvenation chemistry for re-activating electrodes, aimed at prolonging the lifetimes of lithium-based batteries and similar energy-storage systems, is discussed. Li, lithium; Cu, copper; e–, electrons; RMred, reduced redox mediator; RMox, oxidized redox mediator.","PeriodicalId":18849,"journal":{"name":"Nature reviews. Chemistry","volume":"9 8","pages":"553-568"},"PeriodicalIF":51.7,"publicationDate":"2025-06-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144201627","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 : 2025-05-30DOI: 10.1038/s41570-025-00718-2
Zachary Mathe, Dimitrios Maganas, Frank Neese, Serena DeBeer
X-ray spectroscopy plays a pivotal role in understanding the geometric and electronic structures of countless molecules and materials, from homogeneous and heterogeneous catalysts to biological active sites. The element-selectivity of X-ray spectroscopy allows for phenomena at specific photoabsorbers to be investigated. Since the early 2000s, experimental sophistication has progressed, with increasing applications of X-ray emission spectroscopy and two-dimensional photon-in-photon-out spectroscopies, such as resonant inelastic X-ray scattering. Although advanced X-ray spectroscopic methods increase selectivity and information content, the spectra obtained present major challenges for both qualitative and quantitative interpretation. To maximize the insight gained from X-ray spectroscopy, close coupling of experiment and theory is essential. Herein, we present the theoretical and experimental aspects of X-ray spectroscopy, with an emphasis on molecular systems and how an integrated approach with a solid foundation in molecular electronic structure theory enables new modes of inquiry into (bio)chemical catalysis. X-ray spectroscopy offers element-selective probes of diverse (bio)chemical systems. Close coupling of experiment with ab initio calculations unveils the rich electronic structural information available and facilitates practical, chemical interpretation of spectra, as discussed in this Review.
{"title":"Coupling experiment and theory to push the state-of-the-art in X-ray spectroscopy","authors":"Zachary Mathe, Dimitrios Maganas, Frank Neese, Serena DeBeer","doi":"10.1038/s41570-025-00718-2","DOIUrl":"10.1038/s41570-025-00718-2","url":null,"abstract":"X-ray spectroscopy plays a pivotal role in understanding the geometric and electronic structures of countless molecules and materials, from homogeneous and heterogeneous catalysts to biological active sites. The element-selectivity of X-ray spectroscopy allows for phenomena at specific photoabsorbers to be investigated. Since the early 2000s, experimental sophistication has progressed, with increasing applications of X-ray emission spectroscopy and two-dimensional photon-in-photon-out spectroscopies, such as resonant inelastic X-ray scattering. Although advanced X-ray spectroscopic methods increase selectivity and information content, the spectra obtained present major challenges for both qualitative and quantitative interpretation. To maximize the insight gained from X-ray spectroscopy, close coupling of experiment and theory is essential. Herein, we present the theoretical and experimental aspects of X-ray spectroscopy, with an emphasis on molecular systems and how an integrated approach with a solid foundation in molecular electronic structure theory enables new modes of inquiry into (bio)chemical catalysis. X-ray spectroscopy offers element-selective probes of diverse (bio)chemical systems. Close coupling of experiment with ab initio calculations unveils the rich electronic structural information available and facilitates practical, chemical interpretation of spectra, as discussed in this Review.","PeriodicalId":18849,"journal":{"name":"Nature reviews. Chemistry","volume":"9 7","pages":"436-453"},"PeriodicalIF":51.7,"publicationDate":"2025-05-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144177284","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 : 2025-05-29DOI: 10.1038/s41570-025-00726-2
Chuanliu Wu (, )
In 1961, it was demonstrated that the enzyme ribonuclease can correctly fold upon oxidation in air from a fully reduced and denatured polypeptide chain. Since then, the principles that govern the oxidative folding of polypeptide chains have been elucidated, and our ability to control this process has advanced significantly.
{"title":"Decoupling sequence and structure","authors":"Chuanliu Wu \u0000 (, )","doi":"10.1038/s41570-025-00726-2","DOIUrl":"10.1038/s41570-025-00726-2","url":null,"abstract":"In 1961, it was demonstrated that the enzyme ribonuclease can correctly fold upon oxidation in air from a fully reduced and denatured polypeptide chain. Since then, the principles that govern the oxidative folding of polypeptide chains have been elucidated, and our ability to control this process has advanced significantly.","PeriodicalId":18849,"journal":{"name":"Nature reviews. Chemistry","volume":"9 6","pages":"363-364"},"PeriodicalIF":51.7,"publicationDate":"2025-05-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144165177","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 : 2025-05-29DOI: 10.1038/s41570-025-00719-1
Jonas Warneke, Hugo Y. Samayoa-Oviedo, Markus Rohdenburg, Xilai Li, Harald Knorke, Julia Laskin
Chemists often treat gaseous fragment ions as esoteric chemical species of interest to only analytical mass spectrometry and gas-phase ion chemistry. However, their potential as building blocks for designing new compounds in the condensed phase is largely unexplored. Developments in preparative mass spectrometry instrumentation have opened up a new research field focused on understanding the chemistry of well-defined gaseous fragment ions on surfaces. In this Review, we highlight the preparative potential of gaseous fragment ions for synthesizing new compounds in the condensed phase. We discuss factors affecting the selectivity of the observed reactivity of fragment ions, examine the effect of charge on reaction mechanisms, and introduce the unexpected reactivity of ions of the same polarity on surfaces in the absence of solvent molecules. These developments hold the potential to transform preparative mass spectrometry into a valuable method for small-scale chemical synthesis in almost all fields of molecular sciences. Understanding the reactivity of gaseous fragment ions of known composition and charge on surfaces provides access to new compounds in the condensed phase and leads to the precisely controlled design of functional interfaces for a broad range of applications.
{"title":"Molecular synthesis with gaseous fragment ions on surfaces","authors":"Jonas Warneke, Hugo Y. Samayoa-Oviedo, Markus Rohdenburg, Xilai Li, Harald Knorke, Julia Laskin","doi":"10.1038/s41570-025-00719-1","DOIUrl":"10.1038/s41570-025-00719-1","url":null,"abstract":"Chemists often treat gaseous fragment ions as esoteric chemical species of interest to only analytical mass spectrometry and gas-phase ion chemistry. However, their potential as building blocks for designing new compounds in the condensed phase is largely unexplored. Developments in preparative mass spectrometry instrumentation have opened up a new research field focused on understanding the chemistry of well-defined gaseous fragment ions on surfaces. In this Review, we highlight the preparative potential of gaseous fragment ions for synthesizing new compounds in the condensed phase. We discuss factors affecting the selectivity of the observed reactivity of fragment ions, examine the effect of charge on reaction mechanisms, and introduce the unexpected reactivity of ions of the same polarity on surfaces in the absence of solvent molecules. These developments hold the potential to transform preparative mass spectrometry into a valuable method for small-scale chemical synthesis in almost all fields of molecular sciences. Understanding the reactivity of gaseous fragment ions of known composition and charge on surfaces provides access to new compounds in the condensed phase and leads to the precisely controlled design of functional interfaces for a broad range of applications.","PeriodicalId":18849,"journal":{"name":"Nature reviews. Chemistry","volume":"9 7","pages":"470-480"},"PeriodicalIF":51.7,"publicationDate":"2025-05-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144165178","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 : 2025-05-29DOI: 10.1038/s41570-025-00731-5
Brian Kobilka, Stephanie Greed
Ahead of his 70th birthday, Brian Kobilka, Professor of Molecular and Cellular Physiology at Stanford University, discusses his life from growing up as a baker’s son in a small town to receiving a call from Stockholm having been awarded the Nobel Prize in Chemistry, as well as his continuing work around G protein-coupled receptors (GPCRs).
{"title":"The story of a structural sage","authors":"Brian Kobilka, Stephanie Greed","doi":"10.1038/s41570-025-00731-5","DOIUrl":"10.1038/s41570-025-00731-5","url":null,"abstract":"Ahead of his 70th birthday, Brian Kobilka, Professor of Molecular and Cellular Physiology at Stanford University, discusses his life from growing up as a baker’s son in a small town to receiving a call from Stockholm having been awarded the Nobel Prize in Chemistry, as well as his continuing work around G protein-coupled receptors (GPCRs).","PeriodicalId":18849,"journal":{"name":"Nature reviews. Chemistry","volume":"9 6","pages":"359-360"},"PeriodicalIF":51.7,"publicationDate":"2025-05-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144165174","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}
京公网安备 11010802042870号
京ICP备2023020795号-1
扫码关注我们
求助内容：
应助结果提醒方式：