Communications Chemistry最新文献_第2页

Functional biosynthetic stereodivergence in a gene cluster via a dihydrosydnone N-oxide

IF 5.9 2区化学

Communications Chemistry Pub Date : 2024-12-19 DOI: 10.1038/s42004-024-01372-3

Jiajun Ren, Anugraha Mathew, María Rodríguez-García, Tobias Kohler, Olivier Blacque, Anthony Linden, Leo Eberl, Simon Sieber, Karl Gademann

{"title":"Functional biosynthetic stereodivergence in a gene cluster via a dihydrosydnone N-oxide","authors":"Jiajun Ren, Anugraha Mathew, María Rodríguez-García, Tobias Kohler, Olivier Blacque, Anthony Linden, Leo Eberl, Simon Sieber, Karl Gademann","doi":"10.1038/s42004-024-01372-3","DOIUrl":"10.1038/s42004-024-01372-3","url":null,"abstract":"Chirality plays a critical role in the biochemistry of life and often only one enantiomeric series is observed (homochirality). Only a few natural products have been obtained as racemates, e.g. the signalling molecule valdiazen produced by Burkholderia cenocepacia H111. In this study, we investigated the ham biosynthetic gene cluster and discovered that both the enantiomerically pure (R)-fragin and the racemic valdiazen result from the same pathway. This stereodivergence is based on the unusual heterocyclic intermediate dihydrosydnone N-oxide, as evident from gene knockout, stable isotope feeding experiments, and mass spectrometry experiments. Both non-enzymatic racemisation via keto-enol tautomerisation and enzyme-mediated dynamic kinetic resolution were found to be crucial to this stereodivergent pathway. This novel mechanism underpins the production of configurationally and biologically distinct metabolites from a single gene cluster. Our findings highlight the intricate design of an intertwined biosynthetic pathway and provide a deeper understanding of microbial secondary metabolism related to microbial communication. The ham gene cluster in Burkholderia cenocepacia H111 produces two compounds: the signalling molecule valdiazen as racemate and the antifungal fragin in enantiopure form. Here, the authors demonstrate that the stereodivergence is based on the heterocyclic intermediate dihydrosydnone N-oxide, with both non-enzymatic racemization and enzyme-mediated dynamic kinetic resolution occurring in parallel.","PeriodicalId":10529,"journal":{"name":"Communications Chemistry","volume":" ","pages":"1-9"},"PeriodicalIF":5.9,"publicationDate":"2024-12-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.com/articles/s42004-024-01372-3.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142845196","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Rapid and scalable ruthenium catalyzed meta-C–H alkylation enabled by resonant acoustic mixing

IF 5.9 2区化学

Communications Chemistry Pub Date : 2024-12-18 DOI: 10.1038/s42004-024-01390-1

Arnab Dey, Rajesh Kancherla, Kuntal Pal, Nathan Kloszewski, Magnus Rueping

{"title":"Rapid and scalable ruthenium catalyzed meta-C–H alkylation enabled by resonant acoustic mixing","authors":"Arnab Dey, Rajesh Kancherla, Kuntal Pal, Nathan Kloszewski, Magnus Rueping","doi":"10.1038/s42004-024-01390-1","DOIUrl":"10.1038/s42004-024-01390-1","url":null,"abstract":"Synthetic chemistry approaches for direct C–H bond alkylation offers a promising alternative to traditional functional-group-centered strategies which often involve multi-step procedures and may suffer from a variety of challenges including scalability. Here, we introduce resonant mixing as an efficient method for meta-C–H alkylation of arenes using a Ru-catalyst, avoiding the need for bulk solvents, external temperature, or light. The described methodology is highly rapid, enabling multigram-scale synthesis of meta-alkylation products within a short reaction time and achieving a very high turnover frequency. The reaction operates via a radical mechanism and is characterized by its mild reaction conditions, substrate compatibility, and exceptional meta-selectivity, all while significantly reducing reaction times. Synthetic chemistry approaches for direct C–H bond alkylation offers a promising alternative to traditional functional-group-centered strategies which often involve multi-step procedures and may suffer from a variety of challenges including scalability. Here, the authors introduce resonant acoustic mixing as an efficient method for meta-C–H alkylation of arenes using a Ru-catalyst via a radical mechanism, avoiding the need for bulk solvents, external temperature, or light.","PeriodicalId":10529,"journal":{"name":"Communications Chemistry","volume":" ","pages":"1-7"},"PeriodicalIF":5.9,"publicationDate":"2024-12-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.com/articles/s42004-024-01390-1.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142845143","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Modulating self-assembly and polymorph transitions in bisdendronized squaramides

IF 5.9 2区化学

Communications Chemistry Pub Date : 2024-12-18 DOI: 10.1038/s42004-024-01391-0

Sergi Bujosa, Llorenç Rubert, Carmen Rotger, Bartolome Soberats

{"title":"Modulating self-assembly and polymorph transitions in bisdendronized squaramides","authors":"Sergi Bujosa, Llorenç Rubert, Carmen Rotger, Bartolome Soberats","doi":"10.1038/s42004-024-01391-0","DOIUrl":"10.1038/s42004-024-01391-0","url":null,"abstract":"Supramolecular self-assembly is an advanced approach for constructing ordered nanoscale architectures with broad applications. While the principles of supramolecular polymerization have been thoroughly explored in artificial small molecules, polymer transformations remain barely explored, likely due to the lack of suitable reference models presenting well-defined and reversible transitions between aggregates. In this study, we introduce a series of bisdendronized squaramides (SQs) 1-3, showcasing complex self-assembly behaviours involving four distinct aggregates, three different interaction patterns, and various thermodynamically controlled polymorph transformations. Notably, SQ 3, with ethyl spacers between the SQ cores and the dendrons, exhibits a concentration and temperature-dependent equilibrium among three polymorphs: the particle-like Agg-A and fibrillar Agg-C, formed by slipped hydrogen bonds, and the fibrillar Agg-B, formed by head-to-tail hydrogen bonds. Additional solid-state experiments revealed that these SQs also form columnar liquid crystals, assembled by π–π interactions in SQ 1 and hydrogen bonding in SQ 2 and SQ 3. This work positions SQ units as valuable models for understanding polymorph equilibrium in solution and solid-state, which is crucial for developing stimuli-responsive supramolecular polymers. Squaramides are compelling self-assembly models, known for exhibiting diverse interaction patterns and supramolecular polymorphism. In this study, the authors investigate a series of bisdendronized squaramides to uncover polymorphic transformations in supramolecular polymers, linking insights from solution-phase assemblies to solid-state liquid-crystalline structures.","PeriodicalId":10529,"journal":{"name":"Communications Chemistry","volume":" ","pages":"1-11"},"PeriodicalIF":5.9,"publicationDate":"2024-12-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.com/articles/s42004-024-01391-0.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142845150","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Charting a new course with plasmon-mediated chemistry

IF 5.9 2区化学

Communications Chemistry Pub Date : 2024-12-17 DOI: 10.1038/s42004-024-01340-x

Christa L. Brosseau, Emiliano Cortés

引用次数: 0

On-surface synthesis

IF 5.9 2区化学

Communications Chemistry Pub Date : 2024-12-09 DOI: 10.1038/s42004-024-01359-0

Jennifer MacLeod, Alexander Saywell, Ping Yu

引用次数: 0

On-surface synthesis of phthalocyanines with extended π-electron systems

IF 5.9 2区化学

Communications Chemistry Pub Date : 2024-12-09 DOI: 10.1038/s42004-024-01351-8

Lukas J. Heuplick, Qitang Fan, Dmitriy A. Astvatsaturov, Tatiana V. Dubinina, J. Michael Gottfried

{"title":"On-surface synthesis of phthalocyanines with extended π-electron systems","authors":"Lukas J. Heuplick, Qitang Fan, Dmitriy A. Astvatsaturov, Tatiana V. Dubinina, J. Michael Gottfried","doi":"10.1038/s42004-024-01351-8","DOIUrl":"10.1038/s42004-024-01351-8","url":null,"abstract":"Expanded phthalocyanines are a promising class of materials for optoelectronic applications, owing to their unique properties and versatile metal coordination reactivity. The expansion of their π-electron systems and resulting red-shifted absorption are of particular interest for achieving broader applications. Here, we report the on-surface synthesis of metallo-phthalocyanines with extended electron systems and an open-chain polycyanine from ortho-dicarbonitrile precursors on Ag(111) and Au(111), studied by scanning tunneling microscopy (STM) and X-ray photoelectron spectroscopy (XPS). The larger 6,7-di(2-naphthyl)-2,3-naphthalenedicarbonitrile (NND) undergoes spontaneous cyclotetramerization on the Ag(111) surface forming the corresponding silver naphthalocyanines (Ag-NPc), contrasting previous reports where a partially aliphatic ortho-dicarbonitrile precursor formed polycyanine chains. In contrast, monolayers of the smaller 6,7-diphenyl-2,3-naphthalenedicarbonitrile (PND) form the corresponding naphthalocyanine only in the presence of co-adsorbed iron atoms (Fe-NPc). In the absence of iron, PND multilayers form polycyanine chains and Ag-NPc. NND and PND further differ in their reactivity due to the supramolecular behavior of their products. While the larger Ag-NPc aggregates to non-covalent one-dimensional ribbons, the smaller Fe-NPc forms an extended non-covalent two-dimensional network. Our study demonstrates the versatility of on-surface dinitrile tetramerization for the synthesis of π-extended cyclic phthalocyanines and their open-chain polycyanine counterparts. Expanded phthalocyanines are a promising class of materials for optoelectronic applications. Here, the authors report the on-surface synthesis of metallo-phthalocyanines with extended π-electron systems from orthodicarbonitrile precursors on Ag(111) and Au(111), alongside an open-chain polycyanine.","PeriodicalId":10529,"journal":{"name":"Communications Chemistry","volume":" ","pages":"1-8"},"PeriodicalIF":5.9,"publicationDate":"2024-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.com/articles/s42004-024-01351-8.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142799438","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Phosphinothio(seleno)ation of alkynes/olefins and application on the late-stage functionalization of natural products

IF 5.9 2区化学

Communications Chemistry Pub Date : 2024-12-05 DOI: 10.1038/s42004-024-01326-9

Chang-Wei Shao, Pei-Feng Wan, Quan Xu, Ze-Nan Yang, Mei-Yu Geng, Yu Zhang, Xing-Hua Zhang, Xu-Wen Li

{"title":"Phosphinothio(seleno)ation of alkynes/olefins and application on the late-stage functionalization of natural products","authors":"Chang-Wei Shao, Pei-Feng Wan, Quan Xu, Ze-Nan Yang, Mei-Yu Geng, Yu Zhang, Xing-Hua Zhang, Xu-Wen Li","doi":"10.1038/s42004-024-01326-9","DOIUrl":"10.1038/s42004-024-01326-9","url":null,"abstract":"Non-metallic catalysis has been known as a remarkable development strategy for hydrofunctionalization of unsaturated hydrocarbons. Herein, we report a unique chemically active method of BF3·OEt2 promoted multi-component, highly regioselective, and chemoselective hydrothio(seleo)phosphonylation of unsaturated hydrocarbons, which exhibits high yield and good substrate universality. The reaction mechanism was further elucidated to be Markovnikov addition by controlling experiments, 31P and 19F NMR spectra tracking experiments, X-ray diffraction analysis, and DFT calculations. Furthermore, the gram-scale attempt and the application of the reaction on the derivatization of natural products have been successfully conducted, leading to the discovery of 3as with potential anti-Parkinson''s disease (PD) activities at 1 μM. This streamlined and efficient methodology has established a new platform for non-metallic Lewis acids-promoted hydrofunctionalization of unsaturated hydrocarbons and its application on new drug research. Transition metal catalysts are typically used for the hydrofunctionalization of unsaturated hydrocarbons, however, such reactions are time-consuming and may be challenging. Herein, the authors report the non-metallic BF3·OEt2-promoted multi-component, highly regioselective, and chemoselective hydrothio(seleo)phosphonylation of unsaturated hydrocarbons, which exhibits high yields and good substrate universality","PeriodicalId":10529,"journal":{"name":"Communications Chemistry","volume":" ","pages":"1-13"},"PeriodicalIF":5.9,"publicationDate":"2024-12-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.com/articles/s42004-024-01326-9.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142778665","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

BioDolphin as a comprehensive database of lipid–protein binding interactions

IF 5.9 2区化学

Communications Chemistry Pub Date : 2024-12-04 DOI: 10.1038/s42004-024-01384-z

Li-Yen Yang, Kaike Ping, Yunan Luo, Andrew C. McShan

{"title":"BioDolphin as a comprehensive database of lipid–protein binding interactions","authors":"Li-Yen Yang, Kaike Ping, Yunan Luo, Andrew C. McShan","doi":"10.1038/s42004-024-01384-z","DOIUrl":"10.1038/s42004-024-01384-z","url":null,"abstract":"Lipid-protein interactions are crucial for virtually all biological processes in living cells. However, existing structural databases focusing on these interactions are limited to integral membrane proteins. A systematic understanding of diverse lipid-protein interactions also encompassing lipid-anchored, peripheral membrane and soluble lipid binding proteins remains to be elucidated. To address this gap and facilitate the research of universal lipid-protein assemblies, we developed BioDolphin - a curated database with over 127,000 lipid-protein interactions. BioDolphin provides comprehensive annotations, including protein functions, protein families, lipid classifications, lipid-protein binding affinities, membrane association type, and atomic structures. Accessible via a publicly available web server ( www.biodolphin.chemistry.gatech.edu ), users can efficiently search for lipid-protein interactions using a wide range of options and download datasets of interest. Additionally, BioDolphin features interactive 3D visualization of each lipid-protein complex, facilitating the exploration of structure-function relationships. BioDolphin also includes detailed information on atomic-level intermolecular interactions between lipids and proteins that enable large scale analysis of both paired complexes and larger assemblies. As an open-source resource, BioDolphin enables global analysis of lipid-protein interactions and supports data-driven approaches for developing predictive machine learning algorithms for lipid-protein binding affinity and structures. Lipid–protein interactions are crucial for virtually all biological processes in living cells, however, systematic structural databases covering broad types of lipid–protein interaction are lacking. Here, the authors develop BioDolphin, a curated database with over 127,000 lipid–protein interactions, providing comprehensive annotations detailing lipid–protein complexes.","PeriodicalId":10529,"journal":{"name":"Communications Chemistry","volume":" ","pages":"1-11"},"PeriodicalIF":5.9,"publicationDate":"2024-12-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.com/articles/s42004-024-01384-z.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142778669","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Potential energy landscape formalism for quantum molecular liquids

IF 5.9 2区化学

Communications Chemistry Pub Date : 2024-12-04 DOI: 10.1038/s42004-024-01342-9

Ali Eltareb, Yang Zhou, Gustavo E. Lopez, Nicolas Giovambattista

{"title":"Potential energy landscape formalism for quantum molecular liquids","authors":"Ali Eltareb, Yang Zhou, Gustavo E. Lopez, Nicolas Giovambattista","doi":"10.1038/s42004-024-01342-9","DOIUrl":"10.1038/s42004-024-01342-9","url":null,"abstract":"The potential energy landscape (PEL) formalism is a powerful tool within statistical mechanics to study the thermodynamic properties of classical low-temperature liquids and glasses. Recently, the PEL formalism has been extended to liquids/glasses that obey quantum mechanics, but applications have been limited to atomistic model liquids. In this work, we extend the PEL formalism to liquid/glassy water using path-integral molecular dynamics (PIMD) simulations, where nuclear quantum effects (NQE) are included. Our PIMD simulations, based on the q-TIP4P/F water model, show that the PEL of quantum water is both Gaussian and anharmonic. Importantly, the ring-polymers associated to the O/H atoms in the PIMD simulations, collapse at the local minima of the PEL (inherent structures, IS) for both liquid and glassy states. This allows us to calculate, analytically, the IS vibrational density of states (IS-VDOS) of the ring-polymer system using the IS-VDOS of classical water (obtained from classical MD simulations). The role of NQE on the structural properties of liquid/glassy water at various pressures are discussed in detail. Overall, our results demonstrate that the PEL formalism can effectively describe the behavior of molecular liquids at low temperatures and in the glass states, regardless of whether the liquid/glass obeys classical or quantum mechanics. The potential energy landscape formalism is a powerful tool within statistical mechanics to study the thermodynamic properties of classical low-temperature liquids and glasses. Here, the authors use path-integral molecular dynamics simulations to demonstrate that the formalism can also be used to describe quantum mechanical molecular liquids such as water.","PeriodicalId":10529,"journal":{"name":"Communications Chemistry","volume":" ","pages":"1-13"},"PeriodicalIF":5.9,"publicationDate":"2024-12-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.com/articles/s42004-024-01342-9.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142778643","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Electrochemical lithium extraction from hectorite ore

IF 5.9 2区化学

Communications Chemistry Pub Date : 2024-12-03 DOI: 10.1038/s42004-024-01378-x

Andrew Z. Haddad, Hyungyeon Cha, Liam McDonough, Chaochao Dun, Garrett Pohlman, Jeffrey J. Urban, Robert Kostecki

{"title":"Electrochemical lithium extraction from hectorite ore","authors":"Andrew Z. Haddad, Hyungyeon Cha, Liam McDonough, Chaochao Dun, Garrett Pohlman, Jeffrey J. Urban, Robert Kostecki","doi":"10.1038/s42004-024-01378-x","DOIUrl":"10.1038/s42004-024-01378-x","url":null,"abstract":"Electrochemical technologies add a unique dimension for ore refinement, representing tunable methods that can integrate with renewable energy sources and existing downstream process flows. However, the development of electrochemical extraction technologies has been impeded by the technological maturity of hydro- and pyro-metallurgy, as well as the electrical insulating properties of many metal oxide ores. The fabrication and use of carbon/insulating material composite electrodes has been a longstanding method to enable electrochemical activation. Here, using real hectorite ore, we employ this technical approach to fabricate hectorite-carbon black composite electrodes (HCCEs) and achieve electrochemical activation of hectorite. Anodic polarization results in lithium-ion release through a multi-step chemical and electrochemical mechanism that results in 50.7 ± 4.4% removal of lithium from HCCE, alongside other alkaline ions. This technical proof-of-concept study underscores that electrochemical activation of ores can facilitate lattice deterioration and ion removal from ores. Electrochemical technologies for ore refinement provide a unique opportunity to integrate with renewable energy sources but are impeded by the insulating properties of many ores. Here, the authors take inspiration from the lithium-ion battery field and fabricate hectorite–carbon black composite electrodes to enhance electron percolation into hectorite enabling lithium-ion release through a multi-step (electro)chemical mechanism.","PeriodicalId":10529,"journal":{"name":"Communications Chemistry","volume":" ","pages":"1-8"},"PeriodicalIF":5.9,"publicationDate":"2024-12-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.com/articles/s42004-024-01378-x.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142766992","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0