Nature chemistry最新文献_第3页

Unconventional structural evolution of an oxide surface in water unveiled by in situ sum-frequency spectroscopy 原位和频光谱揭示水中氧化物表面的非常规结构演变

IF 21.8 1区化学

Nature chemistry Pub Date : 2024-10-14 DOI: 10.1038/s41557-024-01658-y

Xiaoqun Li, Flavio S. Brigiano, Simone Pezzotti, Xinyi Liu, Wanlin Chen, Huiling Chen, Ying Li, Hui Li, Xin Lin, Wenqi Zheng, Yuchong Wang, Yue Ron Shen, Marie-Pierre Gaigeot, Wei-Tao Liu

{"title":"Unconventional structural evolution of an oxide surface in water unveiled by in situ sum-frequency spectroscopy","authors":"Xiaoqun Li, Flavio S. Brigiano, Simone Pezzotti, Xinyi Liu, Wanlin Chen, Huiling Chen, Ying Li, Hui Li, Xin Lin, Wenqi Zheng, Yuchong Wang, Yue Ron Shen, Marie-Pierre Gaigeot, Wei-Tao Liu","doi":"10.1038/s41557-024-01658-y","DOIUrl":"https://doi.org/10.1038/s41557-024-01658-y","url":null,"abstract":"Oxide–water interfaces host a wide range of important reactions in nature and modern industrial applications; however, accurate knowledge about these interfaces is still lacking at the molecular level owing to difficulties in accessing buried oxide surfaces. Here we report an experimental scheme enabling in situ sum-frequency vibrational spectroscopy of oxide surfaces in liquid water. Application to the silica–water interface revealed the emergence of unexpected surface reaction pathways with water. With ab initio molecular dynamics and metadynamics simulations, we uncovered a surface reconstruction, triggered by deprotonation of surface hydroxylated groups, that led to unconventional five-coordinated silicon species. The results help demystify the multimodal chemistry of aqueous silica discovered decades ago, bringing in fresh information that modifies the current understanding. Our study will provide new opportunities for future in-depth physical and chemical characterizations of other oxide–water interfaces.<figure></figure>","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"27 1","pages":""},"PeriodicalIF":21.8,"publicationDate":"2024-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142430562","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}

引用次数: 0

Author Correction: Opportunities and challenges with hyperpolarized bioresponsive probes for functional imaging using magnetic resonance 作者更正：超极化生物反应探针在磁共振功能成像中的机遇与挑战

IF 21.8 1区化学

Nature chemistry Pub Date : 2024-10-14 DOI: 10.1038/s41557-024-01667-x

Goran Angelovski, Ben J. Tickner, Gaoji Wang

引用次数: 0

Author Correction: Real-time monitoring of reaction stereochemistry through single-molecule observations of chirality-induced spin selectivity 作者更正：通过单分子观察手性诱导的自旋选择性实时监测反应的立体化学过程

IF 21.8 1区化学

Nature chemistry Pub Date : 2024-10-14 DOI: 10.1038/s41557-024-01670-2

Chen Yang, Yanwei Li, Shuyao Zhou, Yilin Guo, Chuancheng Jia, Zhirong Liu, Kendall N. Houk, Yonatan Dubi, Xuefeng Guo

引用次数: 0

Looking into the future of hybrid glasses 展望混合眼镜的未来

IF 19.2 1区化学

Nature chemistry Pub Date : 2024-10-11 DOI: 10.1038/s41557-024-01616-8

Thomas D. Bennett, Satoshi Horike, John C. Mauro, Morten M. Smedskjaer, Lothar Wondraczek

{"title":"Looking into the future of hybrid glasses","authors":"Thomas D. Bennett, Satoshi Horike, John C. Mauro, Morten M. Smedskjaer, Lothar Wondraczek","doi":"10.1038/s41557-024-01616-8","DOIUrl":"10.1038/s41557-024-01616-8","url":null,"abstract":"Glasses are typically formed by melt-quenching, that is, cooling of a liquid on a timescale fast enough to avoid ordering to a crystalline state, and formerly thought to comprise three categories: inorganic (non-metallic), organic and metallic. Their impact is huge, providing safe containers, allowing comfortable and bright living spaces and even underlying the foundations of modern telecommunication. This impact is tempered by the inability to chemically design glasses with precise, well-defined and tunable structures: the literal quest for order in disorder. However, metal–organic or hybrid glasses are now considered to belong to a fourth category of glass chemistry. They have recently been demonstrated upon melt-quenching of coordination polymer, metal–organic framework and hybrid perovskite framework solids. In this Review, we discuss hybrid glasses through the lens of both crystalline metal–organic framework and glass chemistry, physics and engineering, to provide a vision for the future of this class of materials. Hybrid glasses are considered the fourth category of glass, and they exhibit different structures and properties to inorganic, organic or metallic glasses. This Review discusses hybrid glasses through the lens of crystalline metal–organic frameworks and glass chemistry, physics and engineering, providing a vision for the future of this class of materials.","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"16 11","pages":"1755-1766"},"PeriodicalIF":19.2,"publicationDate":"2024-10-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142404940","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}

引用次数: 0

Triazenolysis of alkenes as an aza version of ozonolysis 烯烃的三唑烯分解是臭氧分解的氮杂环版本

IF 21.8 1区化学

Nature chemistry Pub Date : 2024-10-11 DOI: 10.1038/s41557-024-01653-3

Aleksandr Koronatov, Pavel Sakharov, Deepak Ranolia, Alexander Kaushansky, Natalia Fridman, Mark Gandelman

{"title":"Triazenolysis of alkenes as an aza version of ozonolysis","authors":"Aleksandr Koronatov, Pavel Sakharov, Deepak Ranolia, Alexander Kaushansky, Natalia Fridman, Mark Gandelman","doi":"10.1038/s41557-024-01653-3","DOIUrl":"https://doi.org/10.1038/s41557-024-01653-3","url":null,"abstract":"Alkenes are broadly used in synthetic applications, thanks to their abundance and versatility. Ozonolysis is one of the most canonical transformations that converts alkenes into molecules bearing carbon–oxygen motifs via C=C bond cleavage. Despite its extensive use in both industrial and laboratory settings, the aza version—cleavage of alkenes to form carbon–nitrogen bonds—remains elusive. Here we report the conversion of alkenes into valuable amines via complete C=C bond disconnection. This process, which we have termed ‘triazenolysis’, is initiated by a (3 + 2) cycloaddition of triazadienium cation to an alkene. The triazolinium salt formed accepts hydride from borohydride anion and spontaneously decomposes to create new C–N motifs upon further reduction. The developed reaction is applicable to a broad range of cyclic alkenes to produce diamines, while various acyclic C=C bonds may be broken to generate two separate amine units. Computational analysis provides insights into the mechanism, including identification of the key step and elucidating the significance of Lewis acid catalysis.<figure></figure>","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"2 1","pages":""},"PeriodicalIF":21.8,"publicationDate":"2024-10-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142404941","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}

引用次数: 0

Multi-stage and multi-colour liquid crystal reflections using a chiral triptycene photoswitchable dopant 利用手性三庚烯光开关掺杂剂实现多级多色液晶反射

IF 21.8 1区化学

Nature chemistry Pub Date : 2024-10-04 DOI: 10.1038/s41557-024-01648-0

Indu Bala, Joshua T. Plank, Brandon Balamut, Drake Henry, Alexander R. Lippert, Ivan Aprahamian

引用次数: 0

Cobalt-catalysed desymmetrization of malononitriles via enantioselective borohydride reduction 钴催化的丙二腈对映体选择性硼氢化还原脱对称反应

IF 19.2 1区化学

Nature chemistry Pub Date : 2024-10-04 DOI: 10.1038/s41557-024-01592-z

Yin Zheng, Tilong Yang, Ka Fai Chan, Zhenyang Lin, Zhongxing Huang

{"title":"Cobalt-catalysed desymmetrization of malononitriles via enantioselective borohydride reduction","authors":"Yin Zheng, Tilong Yang, Ka Fai Chan, Zhenyang Lin, Zhongxing Huang","doi":"10.1038/s41557-024-01592-z","DOIUrl":"10.1038/s41557-024-01592-z","url":null,"abstract":"The high nitrogen content and diverse reactivity of malononitrile are widely harnessed to access nitrogen-rich fine chemicals. Although the facile substitutions of malononitrile can give structurally diverse quaternary carbons, their access to enantioenriched molecules, particularly chiral amines that are prevalent in bioactive compounds, remains rare. Here we report a cobalt-catalysed desymmetric reduction of disubstituted malononitriles to give highly functionalized β-quaternary amines. The pair of cobalt salt and sodium borohydride is proposed to generate a cobalt-hydride intermediate and initiate the reduction. Meanwhile, the enantiocontrol of the dinitrile is achieved through a tailored bisoxazoline ligand with two large flanks that create a narrow gap to host the bystanding nitrile and thus restrict the C(ipso)−C(α) bond rotation of the complexed one. Combined with the extensive derivatization possibilities of all substituents on the quaternary carbon, this asymmetric reduction unlocks pathways from malononitrile as a bulk chemical feedstock to intricate, chiral nitrogen-containing molecules. Malononitriles are widely used precursors for the synthesis of diverse enantioenriched nitrogen-containing molecules, but controlling the stereochemistry of their asymmetric transformations is challenging. Now, the desymmetric reduction of disubstituted malononitriles to chiral amines has been achieved, enabled by a bidentate ligand with extended flanks that can differentiate between the precursor’s nitrile groups through tailored steric pairings.","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"16 11","pages":"1845-1854"},"PeriodicalIF":19.2,"publicationDate":"2024-10-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142370108","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}

引用次数: 0

Hydrophobic assembly of molecular catalysts at the gas–liquid–solid interface drives highly selective CO2 electromethanation 气-液-固界面上分子催化剂的疏水装配推动了高选择性二氧化碳电甲烷化

IF 21.8 1区化学

Nature chemistry Pub Date : 2024-10-04 DOI: 10.1038/s41557-024-01650-6

Morgan McKee, Maximilian Kutter, Yue Wu, Hannah Williams, Marc-Antoine Vaudreuil, Mariolino Carta, Ashok Kumar Yadav, Harishchandra Singh, Jean-François Masson, Dieter Lentz, Moritz F. Kühnel, Nikolay Kornienko

{"title":"Hydrophobic assembly of molecular catalysts at the gas–liquid–solid interface drives highly selective CO2 electromethanation","authors":"Morgan McKee, Maximilian Kutter, Yue Wu, Hannah Williams, Marc-Antoine Vaudreuil, Mariolino Carta, Ashok Kumar Yadav, Harishchandra Singh, Jean-François Masson, Dieter Lentz, Moritz F. Kühnel, Nikolay Kornienko","doi":"10.1038/s41557-024-01650-6","DOIUrl":"https://doi.org/10.1038/s41557-024-01650-6","url":null,"abstract":"Molecular catalysts offer tunable active and peripheral sites, rendering them ideal model systems to explore fundamental concepts in catalysis. However, hydrophobic designs are often regarded as detrimental for dissolution in aqueous electrolytes. Here we show that established cobalt terpyridine catalysts modified with hydrophobic perfluorinated alkyl side chains can assemble at the gas–liquid–solid interfaces on a gas diffusion electrode. We find that the self-assembly of these perfluorinated units on the electrode surface results in a catalytic system selective for electrochemical CO2 reduction to CH4, whereas every other cobalt terpyridine catalyst reported previously was only selective for CO or formate. Mechanistic investigations suggest that the pyridine units function as proton shuttles that deliver protons to the dynamic hydrophobic pocket in which CO2 reduction takes place. Finally, integration with fluorinated carbon nanotubes as a hydrophobic conductive scaffold leads to a Faradaic efficiency for CH4 production above 80% at rates above 10 mA cm−2—impressive activities for a molecular electrocatalytic system.<figure></figure>","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"23 1","pages":""},"PeriodicalIF":21.8,"publicationDate":"2024-10-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142370121","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}

引用次数: 0

From geranium lakes to catalysis with light 从天竺葵湖到光催化

IF 19.2 1区化学

Nature chemistry Pub Date : 2024-10-03 DOI: 10.1038/s41557-024-01636-4

Adam Noble

引用次数: 0

Charting the ligandable proteome for stereoselective interactions 绘制立体选择性相互作用的可配体蛋白质组图

IF 19.2 1区化学

Nature chemistry Pub Date : 2024-10-01 DOI: 10.1038/s41557-024-01639-1

John Paul Pezacki, Eryn Lundrigan, Parrish Evers, Spencer Uguccioni

引用次数: 0