Pub Date : 2024-10-25DOI: 10.1038/s41557-024-01662-2
Md Azimul Haque, Andrew Grieder, Steven P. Harvey, Roman Brunecky, Jiselle Y. Ye, Bennett Addison, Junxiang Zhang, Yifan Dong, Yi Xie, Matthew P. Hautzinger, Heshan Hewa Walpitage, Kai Zhu, Jeffrey L. Blackburn, Zeev Valy Vardeny, David B. Mitzi, Joseph J. Berry, Seth R. Marder, Yuan Ping, Matthew C. Beard, Joseph M. Luther
In hybrid metal halide perovskites, chiroptical properties typically arise from structural symmetry breaking by incorporating a chiral A-site organic cation within the structure, which may limit the compositional space. Here we demonstrate highly efficient remote chirality transfer where chirality is imposed on an otherwise achiral hybrid metal halide semiconductor by a proximal chiral molecule that is not interspersed as part of the structure yet leads to large circular dichroism dissymmetry factors (gCD) of up to 10−2. Density functional theory calculations reveal that the transfer of stereochemical information from the chiral proximal molecule to the inorganic framework is mediated by selective interaction with divalent metal cations. Anchoring of the chiral molecule induces a centro-asymmetric distortion, which is discernible up to four inorganic layers into the metal halide lattice. This concept is broadly applicable to low-dimensional hybrid metal halides with various dimensionalities (1D and 2D) allowing independent control of the composition and degree of chirality.
在混合金属卤化物包光体中，手性特性通常来自于结构对称性的破坏，即在结构上加入手性 A 位有机阳离子，这可能会限制组成空间。在这里，我们展示了高效的远程手性转移，即通过近端手性分子将手性强加给原本非手性的混合卤化金属半导体，该分子并不作为结构的一部分穿插其中，但却能产生高达 10-2 的大圆二色性不对称因子 (gCD)。密度泛函理论计算显示，立体化学信息从手性近端分子到无机框架的传递是通过与二价金属阳离子的选择性相互作用进行的。手性分子的锚定会引起中心不对称变形，这种变形在金属卤化物晶格的四个无机层中都可以看到。这一概念广泛适用于具有不同维度（一维和二维）的低维混合金属卤化物，可独立控制手性的组成和程度。
{"title":"Remote chirality transfer in low-dimensional hybrid metal halide semiconductors","authors":"Md Azimul Haque, Andrew Grieder, Steven P. Harvey, Roman Brunecky, Jiselle Y. Ye, Bennett Addison, Junxiang Zhang, Yifan Dong, Yi Xie, Matthew P. Hautzinger, Heshan Hewa Walpitage, Kai Zhu, Jeffrey L. Blackburn, Zeev Valy Vardeny, David B. Mitzi, Joseph J. Berry, Seth R. Marder, Yuan Ping, Matthew C. Beard, Joseph M. Luther","doi":"10.1038/s41557-024-01662-2","DOIUrl":"https://doi.org/10.1038/s41557-024-01662-2","url":null,"abstract":"<p>In hybrid metal halide perovskites, chiroptical properties typically arise from structural symmetry breaking by incorporating a chiral A-site organic cation within the structure, which may limit the compositional space. Here we demonstrate highly efficient remote chirality transfer where chirality is imposed on an otherwise achiral hybrid metal halide semiconductor by a proximal chiral molecule that is not interspersed as part of the structure yet leads to large circular dichroism dissymmetry factors (<i>g</i><sub>CD</sub>) of up to 10<sup>−2</sup>. Density functional theory calculations reveal that the transfer of stereochemical information from the chiral proximal molecule to the inorganic framework is mediated by selective interaction with divalent metal cations. Anchoring of the chiral molecule induces a centro-asymmetric distortion, which is discernible up to four inorganic layers into the metal halide lattice. This concept is broadly applicable to low-dimensional hybrid metal halides with various dimensionalities (1D and 2D) allowing independent control of the composition and degree of chirality.</p><figure></figure>","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"11 1","pages":""},"PeriodicalIF":21.8,"publicationDate":"2024-10-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142489266","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 : 2024-10-23DOI: 10.1038/s41557-024-01661-3
Adsorbents for efficient hydrogen storage require both a high gravimetric and volumetric storage capacity. A catenation strategy guided by hydrogen bonding is now demonstrated for the construction of supramolecular crystals with both high volumetric and large gravimetric surface areas, robustness and ideal pore diameters, which contribute to their good performance for hydrogen storage.
{"title":"Supramolecular crystals for hydrogen storage","authors":"","doi":"10.1038/s41557-024-01661-3","DOIUrl":"https://doi.org/10.1038/s41557-024-01661-3","url":null,"abstract":"Adsorbents for efficient hydrogen storage require both a high gravimetric and volumetric storage capacity. A catenation strategy guided by hydrogen bonding is now demonstrated for the construction of supramolecular crystals with both high volumetric and large gravimetric surface areas, robustness and ideal pore diameters, which contribute to their good performance for hydrogen storage.","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"60 1","pages":""},"PeriodicalIF":21.8,"publicationDate":"2024-10-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142487139","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 : 2024-10-23DOI: 10.1038/s41557-024-01657-z
Bruce C. Gibb
About two thirds of western society are extroverts, but the contemplative nature of science means that this is not true of the academic population. Bruce Gibb discusses extraversion and introversion in science and asks whether the movement towards larger projects involving teams of scientists is making it harder for introverts and for disruptive discoveries.
{"title":"The chemical sciences need introverts too","authors":"Bruce C. Gibb","doi":"10.1038/s41557-024-01657-z","DOIUrl":"10.1038/s41557-024-01657-z","url":null,"abstract":"About two thirds of western society are extroverts, but the contemplative nature of science means that this is not true of the academic population. Bruce Gibb discusses extraversion and introversion in science and asks whether the movement towards larger projects involving teams of scientists is making it harder for introverts and for disruptive discoveries.","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"16 11","pages":"1737-1738"},"PeriodicalIF":19.2,"publicationDate":"2024-10-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142487152","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 : 2024-10-22DOI: 10.1038/s41557-024-01659-x
Khalyd J. Clay, Ryan A. Shenvi
Much natural-product-based drug discovery has depended on the practices of Indigenous Peoples, who have sometimes invested centuries of care into the cultivation and use of plant or fungal matter. However, the contributions of the original discoverers can be lost as the natural products are developed into pharmaceutical products.
{"title":"The original caretakers of salvinorin A and recognizing Indigenous contributions to science","authors":"Khalyd J. Clay, Ryan A. Shenvi","doi":"10.1038/s41557-024-01659-x","DOIUrl":"10.1038/s41557-024-01659-x","url":null,"abstract":"Much natural-product-based drug discovery has depended on the practices of Indigenous Peoples, who have sometimes invested centuries of care into the cultivation and use of plant or fungal matter. However, the contributions of the original discoverers can be lost as the natural products are developed into pharmaceutical products.","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"16 11","pages":"1735-1736"},"PeriodicalIF":19.2,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142452441","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 : 2024-10-22DOI: 10.1038/s41557-024-01655-1
Bappaditya Chandra, Swarnendu Tripathi, Richard Kriwacki
Membraneless cellular assemblies termed biomolecular condensates — into which diverse biopolymers partition — mediate myriad biological processes. A study now reveals that physicochemical features, not specific stereochemistry, influence whether small molecules are enriched within or excluded from a diverse panel of condensates.
{"title":"Properties governing small-molecule partitioning into biomolecular condensates","authors":"Bappaditya Chandra, Swarnendu Tripathi, Richard Kriwacki","doi":"10.1038/s41557-024-01655-1","DOIUrl":"10.1038/s41557-024-01655-1","url":null,"abstract":"Membraneless cellular assemblies termed biomolecular condensates — into which diverse biopolymers partition — mediate myriad biological processes. A study now reveals that physicochemical features, not specific stereochemistry, influence whether small molecules are enriched within or excluded from a diverse panel of condensates.","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"16 11","pages":"1743-1745"},"PeriodicalIF":19.2,"publicationDate":"2024-10-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142452457","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 : 2024-10-15DOI: 10.1038/s41557-024-01652-4
David A. Rusling, Karen M. Vasquez
A method has been developed based on proximity labelling that detects the interaction of specific proteins with endogenous triplex DNA sequences formed in live cells — significantly expanding the catalogue of putative proteins that interact with these DNA structures.
我们开发了一种基于近距离标记的方法，可以检测特定蛋白质与活细胞中形成的内源性三重 DNA 序列的相互作用，从而大大扩展了与这些 DNA 结构相互作用的假定蛋白质的目录。
{"title":"A third strand for protein–DNA interactions","authors":"David A. Rusling, Karen M. Vasquez","doi":"10.1038/s41557-024-01652-4","DOIUrl":"10.1038/s41557-024-01652-4","url":null,"abstract":"A method has been developed based on proximity labelling that detects the interaction of specific proteins with endogenous triplex DNA sequences formed in live cells — significantly expanding the catalogue of putative proteins that interact with these DNA structures.","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"16 11","pages":"1748-1750"},"PeriodicalIF":19.2,"publicationDate":"2024-10-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142436086","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 : 2024-10-15DOI: 10.1038/s41557-024-01641-7
A. Daisley, J. S. J. Hargreaves
Although supported metal catalysts are active for ammonia synthesis, there is a need for catalysts that are active under milder reaction conditions. Now, fullerenes are shown to be convenient and multifunctional promoters for ammonia production that also eliminate hydrogen poisoning.
{"title":"Fullerenes promote transition-metal-catalysed ammonia synthesis","authors":"A. Daisley, J. S. J. Hargreaves","doi":"10.1038/s41557-024-01641-7","DOIUrl":"10.1038/s41557-024-01641-7","url":null,"abstract":"Although supported metal catalysts are active for ammonia synthesis, there is a need for catalysts that are active under milder reaction conditions. Now, fullerenes are shown to be convenient and multifunctional promoters for ammonia production that also eliminate hydrogen poisoning.","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"16 11","pages":"1739-1740"},"PeriodicalIF":19.2,"publicationDate":"2024-10-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142436009","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 : 2024-10-14DOI: 10.1038/s41557-024-01656-0
Peter J. Dahl, Nikhil S. Malvankar
Hydrogen bonds get a bad rap in electronic materials because their weak, transient structure often results in poor performance. Now, this dogma has been turned on its head by intercalating molecules into two-dimensional superlattices to generate hydrogen-bonded organic–inorganic structures that feature significantly enhanced electrical conductivity.
{"title":"The Jekyll-and-Hyde electron transfer chemistry of hydrogen bonds","authors":"Peter J. Dahl, Nikhil S. Malvankar","doi":"10.1038/s41557-024-01656-0","DOIUrl":"10.1038/s41557-024-01656-0","url":null,"abstract":"Hydrogen bonds get a bad rap in electronic materials because their weak, transient structure often results in poor performance. Now, this dogma has been turned on its head by intercalating molecules into two-dimensional superlattices to generate hydrogen-bonded organic–inorganic structures that feature significantly enhanced electrical conductivity.","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"16 11","pages":"1746-1747"},"PeriodicalIF":19.2,"publicationDate":"2024-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142430560","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 : 2024-10-14DOI: 10.1038/s41557-024-01654-2
Jiahao Rao, Liang Deng
Open-shell carbenes, which feature two unpaired electrons on a carbene carbon centre, are highly unstable compounds and are usually observed as excited-state species. Now, two triplet metallocarbenes have been stabilized by transition-metal and silyl substituents; the compounds have been characterized by various techniques including single-crystal X-ray diffraction, spectroscopy and quantum-chemical analyses.
开壳碳烯的特点是碳烯碳中心有两个未成对电子，是一种极不稳定的化合物，通常以激发态形式出现。现在，两种三重金属碳烯已通过过渡金属和硅基取代基得到稳定；这些化合物已通过单晶 X 射线衍射、光谱和量子化学分析等多种技术进行了表征。
{"title":"Triplet metallocarbenes featuring carbon-centred spin localization","authors":"Jiahao Rao, Liang Deng","doi":"10.1038/s41557-024-01654-2","DOIUrl":"10.1038/s41557-024-01654-2","url":null,"abstract":"Open-shell carbenes, which feature two unpaired electrons on a carbene carbon centre, are highly unstable compounds and are usually observed as excited-state species. Now, two triplet metallocarbenes have been stabilized by transition-metal and silyl substituents; the compounds have been characterized by various techniques including single-crystal X-ray diffraction, spectroscopy and quantum-chemical analyses.","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"16 11","pages":"1741-1742"},"PeriodicalIF":19.2,"publicationDate":"2024-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142430561","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 : 2024-10-14DOI: 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
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.
{"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":"<p>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.</p><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}
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