Subwavelength resonant nanostructures have facilitated strong light–matter interactions and tunable degrees of freedom of light, such as spectrum, polarization, and direction, thus boosting photonic applications toward light emission, manipulation, and detection. For photodetection, resonant nanostructures have enabled emerging technologies, such as light detection and ranging, spectrometers, and polarimeters, within an ultracompact footprint. However, resonant nanophotonics usually relies on nanofabrication technology, which suffers from the trade-offs between precision and scalability. Here, we first realize the self-assembly of subwavelength resonant nanostructures of metal-halide perovskites for spatial object localization and tracking. By steering crystallization along capillary corner bridges localized at edges, we achieve single crystallinity, subwavelength size, and resonant coupling between perovskite nanowires, thus leading to an angle-resolved photodetector with an angular resolution of 0.523°. Furthermore, we integrate multiple pairs of coupled resonant nanowires along two orthogonal orientations to form angle-resolved photodetector arrays for spatial light localization of both static and moving objects with an error of less than 0.6 cm. These findings create a platform for self-assembled resonant nanostructures, thus paving the way for multifunctional nanophotonic and optoelectronic devices.
{"title":"Self-Assembled Subwavelength Nanophotonic Structures for Spatial Object Localization and Tracking","authors":"Jianpeng Ma, Ziguang Zhao, Yingjie Zhao, Jingyuan Zhang, Jiangang Feng, Hanfei Gao, Junchuan Yang, Meng Yuan, Zhenglian Qin, Ke He, Tenglong Li, Junli Bai, Wei Li, Xiao Wei, Zihao Huang, Fengmian Li, Lei Jiang, Yuchen Wu","doi":"10.1021/jacs.4c14899","DOIUrl":"https://doi.org/10.1021/jacs.4c14899","url":null,"abstract":"Subwavelength resonant nanostructures have facilitated strong light–matter interactions and tunable degrees of freedom of light, such as spectrum, polarization, and direction, thus boosting photonic applications toward light emission, manipulation, and detection. For photodetection, resonant nanostructures have enabled emerging technologies, such as light detection and ranging, spectrometers, and polarimeters, within an ultracompact footprint. However, resonant nanophotonics usually relies on nanofabrication technology, which suffers from the trade-offs between precision and scalability. Here, we first realize the self-assembly of subwavelength resonant nanostructures of metal-halide perovskites for spatial object localization and tracking. By steering crystallization along capillary corner bridges localized at edges, we achieve single crystallinity, subwavelength size, and resonant coupling between perovskite nanowires, thus leading to an angle-resolved photodetector with an angular resolution of 0.523°. Furthermore, we integrate multiple pairs of coupled resonant nanowires along two orthogonal orientations to form angle-resolved photodetector arrays for spatial light localization of both static and moving objects with an error of less than 0.6 cm. These findings create a platform for self-assembled resonant nanostructures, thus paving the way for multifunctional nanophotonic and optoelectronic devices.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"28 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-02-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143427328","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}
Lei Yang, Congqi Li, Na An, Jinhua Gao, Yanan Wei, Jiawei Qiao, Junpeng Dai, Na Yu, Yan Sun, Qijie Lin, Xin Zhang, Jianqi Zhang, Zheng Tang, Xiaotao Hao, Guanghao Lu, Zhixiang Wei, Ian Manners, Yongbo Kuang, Hui Huang, Antonio Facchetti, Huibin Qiu
Polymer self-assembly offers an important route to construct well-defined nanostructures. However, it remains challenging to assemble polymers into vertically oriented nanostructures. Here, we use a seed-induced confinement self-assembly strategy to construct vertically aligned semiconducting nanobrushes from polyfluorene-based polymers on conductive substrates. Mechanism studies elucidate that the immobilized seeds on the substrate initiate the vertical growth of nanobrushes, and supercritical drying as well as the rigid charged coronas collectively contribute to retaining the vertical architecture. This process enables nanobrushes with ∼40× higher charge mobilities than their bulk film counterparts. Thus, inverted organic solar cells using the nanobrushes as the electron transporting layer (ETL) exhibit a record power conversion efficiency of 18.51% as a result of increased ETL texturing and the ETL-active layer interface favoring electron extraction. Moreover, our approach also enables the uniform growth of nanobrushes on a nanoporous photoanode (bismuth vanadate) for photoelectrochemical water splitting, improving catalyst distribution and electron transfer. Our work presents a feasible approach to fabricating challenging vertical polymer nanostructures, thereby unlocking the tremendous potential of conjugated polymers in optoelectronic applications.
{"title":"Surface-Emanated Vertical Organic Semiconducting Nanobrushes","authors":"Lei Yang, Congqi Li, Na An, Jinhua Gao, Yanan Wei, Jiawei Qiao, Junpeng Dai, Na Yu, Yan Sun, Qijie Lin, Xin Zhang, Jianqi Zhang, Zheng Tang, Xiaotao Hao, Guanghao Lu, Zhixiang Wei, Ian Manners, Yongbo Kuang, Hui Huang, Antonio Facchetti, Huibin Qiu","doi":"10.1021/jacs.4c16540","DOIUrl":"https://doi.org/10.1021/jacs.4c16540","url":null,"abstract":"Polymer self-assembly offers an important route to construct well-defined nanostructures. However, it remains challenging to assemble polymers into vertically oriented nanostructures. Here, we use a seed-induced confinement self-assembly strategy to construct vertically aligned semiconducting nanobrushes from polyfluorene-based polymers on conductive substrates. Mechanism studies elucidate that the immobilized seeds on the substrate initiate the vertical growth of nanobrushes, and supercritical drying as well as the rigid charged coronas collectively contribute to retaining the vertical architecture. This process enables nanobrushes with ∼40× higher charge mobilities than their bulk film counterparts. Thus, inverted organic solar cells using the nanobrushes as the electron transporting layer (ETL) exhibit a record power conversion efficiency of 18.51% as a result of increased ETL texturing and the ETL-active layer interface favoring electron extraction. Moreover, our approach also enables the uniform growth of nanobrushes on a nanoporous photoanode (bismuth vanadate) for photoelectrochemical water splitting, improving catalyst distribution and electron transfer. Our work presents a feasible approach to fabricating challenging vertical polymer nanostructures, thereby unlocking the tremendous potential of conjugated polymers in optoelectronic applications.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"1 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-02-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143435636","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}
Felix Pultar, Moritz Thürlemann, Igor Gordiy, Eva Doloszeski, Sereina Riniker
We present the design and implementation of a novel neural network potential (NNP) and its combination with an electrostatic embedding scheme, commonly used within the context of hybrid quantum-mechanical/molecular-mechanical (QM/MM) simulations. Substitution of a computationally expensive QM Hamiltonian by an NNP with the same accuracy largely reduces the computational cost and enables efficient sampling in prospective MD simulations, the main limitation faced by traditional QM/MM setups. The model relies on the recently introduced anisotropic message passing (AMP) formalism to compute atomic interactions and encode symmetries found in QM systems. AMP is shown to be highly efficient in terms of both data and computational costs and can be readily scaled to sample systems involving more than 350 solute and 40,000 solvent atoms for hundreds of nanoseconds using umbrella sampling. Most deviations of AMP predictions from the underlying DFT ground truth lie within chemical accuracy (4.184 kJ mol–1). The performance and broad applicability of our approach are showcased by calculating the free-energy surface of alanine dipeptide, the preferred ligation states of nickel phosphine complexes, and dissociation free energies of charged pyridine and quinoline dimers. Results with this ML/MM approach show excellent agreement with experimental data and reach chemical accuracy in most cases. In contrast, free energies calculated with static DFT calculations paired with implicit solvent models or QM/MM MD simulations using cheaper semiempirical methods show up to ten times higher deviation from the experimental ground truth and sometimes even fail to reproduce qualitative trends.
{"title":"Neural Network Potential with Multiresolution Approach Enables Accurate Prediction of Reaction Free Energies in Solution","authors":"Felix Pultar, Moritz Thürlemann, Igor Gordiy, Eva Doloszeski, Sereina Riniker","doi":"10.1021/jacs.4c17015","DOIUrl":"https://doi.org/10.1021/jacs.4c17015","url":null,"abstract":"We present the design and implementation of a novel neural network potential (NNP) and its combination with an electrostatic embedding scheme, commonly used within the context of hybrid quantum-mechanical/molecular-mechanical (QM/MM) simulations. Substitution of a computationally expensive QM Hamiltonian by an NNP with the same accuracy largely reduces the computational cost and enables efficient sampling in prospective MD simulations, the main limitation faced by traditional QM/MM setups. The model relies on the recently introduced anisotropic message passing (AMP) formalism to compute atomic interactions and encode symmetries found in QM systems. AMP is shown to be highly efficient in terms of both data and computational costs and can be readily scaled to sample systems involving more than 350 solute and 40,000 solvent atoms for hundreds of nanoseconds using umbrella sampling. Most deviations of AMP predictions from the underlying DFT ground truth lie within chemical accuracy (4.184 kJ mol<sup>–1</sup>). The performance and broad applicability of our approach are showcased by calculating the free-energy surface of alanine dipeptide, the preferred ligation states of nickel phosphine complexes, and dissociation free energies of charged pyridine and quinoline dimers. Results with this ML/MM approach show excellent agreement with experimental data and reach chemical accuracy in most cases. In contrast, free energies calculated with static DFT calculations paired with implicit solvent models or QM/MM MD simulations using cheaper semiempirical methods show up to ten times higher deviation from the experimental ground truth and sometimes even fail to reproduce qualitative trends.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"85 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-02-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143435637","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}
Yanyao Liu, Somanea Tranin, Yu-Che Chang, Evan B. Piper, Thomas Fessard, Ryan Van Hoveln, Christophe Salome, M. Kevin Brown
Rigid bicyclic hydrocarbons have emerged as important building blocks in the drug discovery industry. Despite progress in this general area, bicyclo[2.1.0]pentanes (housanes) are an understudied class of molecules. Herein we report an unconventional synthesis of borylated housanes. Our method features a broad scope and high diastereoselectivities in the synthesis of versatile intermediates. The route involves a strain-release diboration of bicyclo[1.1.0]butane and intramolecular deborylative alkylation. The versatility of the bridgehead boronic ester was demonstrated in several functionalizations. Lastly, the mechanism of the reaction was investigated, and an unusual stereospecific and diastereoselective ring expansion was uncovered.
{"title":"Facile Synthesis of Housanes by an Unexpected Strategy","authors":"Yanyao Liu, Somanea Tranin, Yu-Che Chang, Evan B. Piper, Thomas Fessard, Ryan Van Hoveln, Christophe Salome, M. Kevin Brown","doi":"10.1021/jacs.4c13298","DOIUrl":"https://doi.org/10.1021/jacs.4c13298","url":null,"abstract":"Rigid bicyclic hydrocarbons have emerged as important building blocks in the drug discovery industry. Despite progress in this general area, bicyclo[2.1.0]pentanes (housanes) are an understudied class of molecules. Herein we report an unconventional synthesis of borylated housanes. Our method features a broad scope and high diastereoselectivities in the synthesis of versatile intermediates. The route involves a strain-release diboration of bicyclo[1.1.0]butane and intramolecular deborylative alkylation. The versatility of the bridgehead boronic ester was demonstrated in several functionalizations. Lastly, the mechanism of the reaction was investigated, and an unusual stereospecific and diastereoselective ring expansion was uncovered.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"34 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-02-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143435611","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}
Rubriflordilactone B is a Schisandra bisnortriterpenoid with a unique 5/5/7/6/5/5-hexacyclic framework that includes a characteristic tetrasubstituted aromatic ring. Herein, we report a convergent, enantioselective total synthesis of this natural product by a bioinspired skeletal reorganization approach. Key transformations include a chelation-controlled [2,3]-Wittig–Still rearrangement to assemble the western cyclohexenyl fragment with complete diastereocontrol, a Cu(II)-catalyzed tandem acyloin acylation–Wittig olefin to build the eastern butanolide fragment, a Friedel–Crafts cyclization to construct the seven-membered ring, and an E1cB reaction/transesterification/oxa-Michael addition cascade to forge the pivotal 5/5-fused bicyclic lactone. This work vividly demonstrates that bioinspired skeletal reorganization is a useful strategy for simplifying the retrosynthetic analysis of structurally complex natural products.
{"title":"Enantioselective Total Synthesis of (−)-Rubriflordilactone B by a Bioinspired Skeletal Reorganization Approach","authors":"Yancheng Xie, Jiajing Bao, Yu Wang, Yi Shen, Zexuan Liang, Hailong Tian, Jinghan Gui","doi":"10.1021/jacs.4c18292","DOIUrl":"https://doi.org/10.1021/jacs.4c18292","url":null,"abstract":"Rubriflordilactone B is a <i>Schisandra</i> bisnortriterpenoid with a unique 5/5/7/6/5/5-hexacyclic framework that includes a characteristic tetrasubstituted aromatic ring. Herein, we report a convergent, enantioselective total synthesis of this natural product by a bioinspired skeletal reorganization approach. Key transformations include a chelation-controlled [2,3]-Wittig–Still rearrangement to assemble the western cyclohexenyl fragment with complete diastereocontrol, a Cu(II)-catalyzed tandem acyloin acylation–Wittig olefin to build the eastern butanolide fragment, a Friedel–Crafts cyclization to construct the seven-membered ring, and an E1cB reaction/transesterification/oxa-Michael addition cascade to forge the pivotal 5/5-fused bicyclic lactone. This work vividly demonstrates that bioinspired skeletal reorganization is a useful strategy for simplifying the retrosynthetic analysis of structurally complex natural products.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"24 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-02-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143427331","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}
Ronald T. Jerozal, Jaehwan Kim, Carolyn Ma, Tristan A. Pitt, Jung-Hoon Lee, Phillip J. Milner
Hydrofluorocarbons (HFCs) are anthropogenically produced greenhouse gases with longer atmospheric lifetimes and higher global warming potentials than those of carbon dioxide. General strategies to abate their emissions from industrial point sources, such as via adsorptive capture, remain scarce. Herein, we uncover the key structure–property relationships that lead to strong binding of HFCs such as fluoroform (CHF3) and difluoromethane (CH2F2) in metal–organic frameworks (MOFs) under the low pressures relevant to flue gas scrubbing. Extensive gas sorption and computational studies support that the Zr-based microporous framework MOF-801-Br or HHU-2-Br (HHU = Heinrich-Heine-University Düsseldorf) strongly binds HFCs due to its synergistic combination of Zr-OH sites on the nodes and bromine sites on the linkers. As such, MOF-801-Br demonstrates a record-setting performance for separating CHF3 from N2 under dilute conditions. Our work highlights that the combination of multiple hydrogen-bonding sites in microporous MOFs represents a generalizable strategy for HFC capture, enabling their selective removal from industrial waste streams.
{"title":"Enhancing Selective Hydrofluorocarbon Greenhouse Gas Capture via Halogenation of Metal–Organic Frameworks","authors":"Ronald T. Jerozal, Jaehwan Kim, Carolyn Ma, Tristan A. Pitt, Jung-Hoon Lee, Phillip J. Milner","doi":"10.1021/jacs.5c00393","DOIUrl":"https://doi.org/10.1021/jacs.5c00393","url":null,"abstract":"Hydrofluorocarbons (HFCs) are anthropogenically produced greenhouse gases with longer atmospheric lifetimes and higher global warming potentials than those of carbon dioxide. General strategies to abate their emissions from industrial point sources, such as via adsorptive capture, remain scarce. Herein, we uncover the key structure–property relationships that lead to strong binding of HFCs such as fluoroform (CHF<sub>3</sub>) and difluoromethane (CH<sub>2</sub>F<sub>2</sub>) in metal–organic frameworks (MOFs) under the low pressures relevant to flue gas scrubbing. Extensive gas sorption and computational studies support that the Zr-based microporous framework MOF-801-Br or HHU-2-Br (HHU = Heinrich-Heine-University Düsseldorf) strongly binds HFCs due to its synergistic combination of Zr-OH sites on the nodes and bromine sites on the linkers. As such, MOF-801-Br demonstrates a record-setting performance for separating CHF<sub>3</sub> from N<sub>2</sub> under dilute conditions. Our work highlights that the combination of multiple hydrogen-bonding sites in microporous MOFs represents a generalizable strategy for HFC capture, enabling their selective removal from industrial waste streams.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"23 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-02-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143427362","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}
Pablo G. Lustemberg, Chengwu Yang, Yuemin Wang, M. Veronica Ganduglia-Pirovano, Christof Wöll
The mechanisms underlying the reaction between carbon monoxide (CO) and activated dioxygen on metal oxide substrates to produce CO2 remain poorly understood, particularly regarding the role of oxygen vacancies and the nature of the activated O2 adsorbate. In this study, we present experimental findings from infrared reflection–absorption spectroscopy on a model system of bulk monocrystalline CeO2(111). Contrary to expectations, exposing the reduced surface to dioxygen (O2) at 80 K does not yield activated oxygen species, such as superoxo or peroxo. Notably, in the presence of adsorbed CO, an unexpected low-temperature oxidation reaction occurs, consuming CO while oxidizing the CeO2 substrate. Since a direct reaction between impinging O2 and adsorbed CO is unlikely at these low temperatures, a novel mechanism is proposed. Extensive spin-polarized density functional theory (DFT) calculations reveal that oxygen vacancies play a critical role in this low-temperature CO oxidation. Initially located in the subsurface region (Vss), these vacancies migrate to the surface (Vs) via a concerted interaction with coadsorbed CO and O2, leading to O2 activation and the formation of superoxo or peroxo species. Detailed analysis identifies key reaction intermediates and quantifies their adsorption energies and activation barriers. Our findings suggest that the peroxo-mediated pathway, with its lower activation barrier, is more favorable for CO oxidation at low temperatures compared to the carbonate pathway. This study provides valuable insights into the dynamic role of subsurface oxygen vacancies in the activation of gaseous O2 and CO oxidation mechanisms on CeO2.
{"title":"Synergistic Effects in Low-Temperature CO Oxidation on Cerium Oxide Surfaces","authors":"Pablo G. Lustemberg, Chengwu Yang, Yuemin Wang, M. Veronica Ganduglia-Pirovano, Christof Wöll","doi":"10.1021/jacs.4c17658","DOIUrl":"https://doi.org/10.1021/jacs.4c17658","url":null,"abstract":"The mechanisms underlying the reaction between carbon monoxide (CO) and activated dioxygen on metal oxide substrates to produce CO<sub>2</sub> remain poorly understood, particularly regarding the role of oxygen vacancies and the nature of the activated O<sub>2</sub> adsorbate. In this study, we present experimental findings from infrared reflection–absorption spectroscopy on a model system of bulk monocrystalline CeO<sub>2</sub>(111). Contrary to expectations, exposing the reduced surface to dioxygen (O<sub>2</sub>) at 80 K does not yield activated oxygen species, such as superoxo or peroxo. Notably, in the presence of adsorbed CO, an unexpected low-temperature oxidation reaction occurs, consuming CO while oxidizing the CeO<sub>2</sub> substrate. Since a direct reaction between impinging O<sub>2</sub> and adsorbed CO is unlikely at these low temperatures, a novel mechanism is proposed. Extensive spin-polarized density functional theory (DFT) calculations reveal that oxygen vacancies play a critical role in this low-temperature CO oxidation. Initially located in the subsurface region (Vss), these vacancies migrate to the surface (Vs) via a concerted interaction with coadsorbed CO and O<sub>2</sub>, leading to O<sub>2</sub> activation and the formation of superoxo or peroxo species. Detailed analysis identifies key reaction intermediates and quantifies their adsorption energies and activation barriers. Our findings suggest that the peroxo-mediated pathway, with its lower activation barrier, is more favorable for CO oxidation at low temperatures compared to the carbonate pathway. This study provides valuable insights into the dynamic role of subsurface oxygen vacancies in the activation of gaseous O<sub>2</sub> and CO oxidation mechanisms on CeO<sub>2</sub>.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"3 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-02-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143418272","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}
Alons Lends, Gaelle Lamon, Loic Delcourte, Aude Sturny-Leclere, Axelle Grélard, Estelle Morvan, Muhammed Bilal Abdul-Shukkoor, Mélanie Berbon, Alicia Vallet, Birgit Habenstein, Erick J. Dufourc, Paul Schanda, Vishukumar Aimanianda, Antoine Loquet
Pathogenic fungal and bacterial cells are enveloped within a cell wall, a molecular barrier at their cell surface, and a critical architecture that constantly evolves during pathogenesis. Understanding the molecular composition, structural organization, and mobility of polysaccharides constituting this cell envelope is crucial to correlate cell wall organization with its role in pathogenicity and to identify potential antifungal targets. For the fungal pathogen Cryptococcus neoformans, the characterization of the cell envelope has been complexified by the presence of an additional external polysaccharide capsular shell. Here, we investigate how magic-angle spinning (MAS) solid-state NMR techniques increase the analytical capabilities to characterize the structure and dynamics of this encapsulated pathogen. The versatility of proton detection experiments, dynamic-based filters, and relaxation measurements facilitate the discrimination of the highly mobile external capsular structure from the internal rigid cell wall of C. neoformans. In addition, we report the in situ detection of triglyceride molecules from lipid droplets based on NMR dynamic filters. Together, we demonstrate a nondestructive technique to study the cell wall architecture of encapsulated microbes using C. neoformans as a model, an airborne opportunistic fungal pathogen that infects mainly immunocompromised but also competent hosts.
{"title":"Molecular Distinction of Cell Wall and Capsular Polysaccharides in Encapsulated Pathogens by In Situ Magic-Angle Spinning NMR Techniques","authors":"Alons Lends, Gaelle Lamon, Loic Delcourte, Aude Sturny-Leclere, Axelle Grélard, Estelle Morvan, Muhammed Bilal Abdul-Shukkoor, Mélanie Berbon, Alicia Vallet, Birgit Habenstein, Erick J. Dufourc, Paul Schanda, Vishukumar Aimanianda, Antoine Loquet","doi":"10.1021/jacs.4c16975","DOIUrl":"https://doi.org/10.1021/jacs.4c16975","url":null,"abstract":"Pathogenic fungal and bacterial cells are enveloped within a cell wall, a molecular barrier at their cell surface, and a critical architecture that constantly evolves during pathogenesis. Understanding the molecular composition, structural organization, and mobility of polysaccharides constituting this cell envelope is crucial to correlate cell wall organization with its role in pathogenicity and to identify potential antifungal targets. For the fungal pathogen <i>Cryptococcus neoformans</i>, the characterization of the cell envelope has been complexified by the presence of an additional external polysaccharide capsular shell. Here, we investigate how magic-angle spinning (MAS) solid-state NMR techniques increase the analytical capabilities to characterize the structure and dynamics of this encapsulated pathogen. The versatility of proton detection experiments, dynamic-based filters, and relaxation measurements facilitate the discrimination of the highly mobile external capsular structure from the internal rigid cell wall of <i>C. neoformans</i>. In addition, we report the <i>in situ</i> detection of triglyceride molecules from lipid droplets based on NMR dynamic filters. Together, we demonstrate a nondestructive technique to study the cell wall architecture of encapsulated microbes using <i>C. neoformans</i> as a model, an airborne opportunistic fungal pathogen that infects mainly immunocompromised but also competent hosts.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"24 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-02-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143427360","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}
Qingyun Qu, Yu Mao, Shufang Ji, Jiangwen Liao, Juncai Dong, Ligang Wang, Qichen Wang, Xiao Liang, Zedong Zhang, Jiarui Yang, Haijing Li, Yongfang Zhou, Ziyun Wang, Geoffrey I. N. Waterhouse, Dingsheng Wang, Yadong Li
Nitrogen-doped carbon-supported Fe catalysts (Fe-N-C) with Fe-N4 active sites hold great promise for the oxygen reduction reaction (ORR). However, fine-tuning the structure of Fe-N4 active sites to enhance their performance remains a grand challenge. Herein, we report an innovative design strategy to promote the ORR activity and kinetics of Fe-N4 sites by engineering their Lewis acidity, which is achieved by tuning the spatial Fe coordination geometry. Theoretical calculations indicated that Fe1-N4SO2 sites (with an axial –SO2 group bonded to Fe) offered favorable Lewis acidity for the ORR, leading to optimized adsorption energies for the key ORR intermediates. To implement this strategy, we developed a molecular-cage-encapsulated coordination strategy to synthesize a Fe single-atom site catalyst (SAC) with Fe1-N4SO2 sites. In agreement with theory, the Fe1-N4SO2/NC catalyst demonstrated outstanding ORR performance in both alkaline (E1/2 = 0.910 V in 0.1 M KOH) and acidic media (E1/2 = 0.772 V in 0.1 M HClO4), surpassing commercial Pt/C and traditional Fe SACs with Fe1-N4 sites or planar S-coordinated Fe1-N4-S sites. Moreover, this newly developed catalyst showed great application potential in quasi-solid-state Zn–air batteries, delivering superior performance across a wide temperature range.
{"title":"Engineering the Lewis Acidity of Fe Single-Atom Sites via Atomic-Level Tuning of Spatial Coordination Configuration for Enhanced Oxygen Reduction","authors":"Qingyun Qu, Yu Mao, Shufang Ji, Jiangwen Liao, Juncai Dong, Ligang Wang, Qichen Wang, Xiao Liang, Zedong Zhang, Jiarui Yang, Haijing Li, Yongfang Zhou, Ziyun Wang, Geoffrey I. N. Waterhouse, Dingsheng Wang, Yadong Li","doi":"10.1021/jacs.4c17444","DOIUrl":"https://doi.org/10.1021/jacs.4c17444","url":null,"abstract":"Nitrogen-doped carbon-supported Fe catalysts (Fe-N-C) with Fe-N<sub>4</sub> active sites hold great promise for the oxygen reduction reaction (ORR). However, fine-tuning the structure of Fe-N<sub>4</sub> active sites to enhance their performance remains a grand challenge. Herein, we report an innovative design strategy to promote the ORR activity and kinetics of Fe-N<sub>4</sub> sites by engineering their Lewis acidity, which is achieved by tuning the spatial Fe coordination geometry. Theoretical calculations indicated that Fe<sub>1</sub>-N<sub>4</sub>SO<sub>2</sub> sites (with an axial –SO<sub>2</sub> group bonded to Fe) offered favorable Lewis acidity for the ORR, leading to optimized adsorption energies for the key ORR intermediates. To implement this strategy, we developed a molecular-cage-encapsulated coordination strategy to synthesize a Fe single-atom site catalyst (SAC) with Fe<sub>1</sub>-N<sub>4</sub>SO<sub>2</sub> sites. In agreement with theory, the Fe<sub>1</sub>-N<sub>4</sub>SO<sub>2</sub>/NC catalyst demonstrated outstanding ORR performance in both alkaline (<i>E</i><sub>1/2</sub> = 0.910 V in 0.1 M KOH) and acidic media (<i>E</i><sub>1/2</sub> = 0.772 V in 0.1 M HClO<sub>4</sub>), surpassing commercial Pt/C and traditional Fe SACs with Fe<sub>1</sub>-N<sub>4</sub> sites or planar S-coordinated Fe<sub>1</sub>-N<sub>4</sub>-S sites. Moreover, this newly developed catalyst showed great application potential in quasi-solid-state Zn–air batteries, delivering superior performance across a wide temperature range.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"51 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-02-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143427359","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}
Mingming Yan, Rong Yang, Cuibo Liu, Ying Gao, Bin Zhang
The electric double layer (EDL), which is directly related to ions, influences the electrocatalytic performance. However, the effects of anions on the anodic EDL and reaction kinetics are unclear, especially in water-mediated electrosynthesis. Here, ClO4– anions are discovered to widen the anodic EDL to inhibit the competitive oxygen evolution reaction (OER) for the gram-scale electrosynthesis of 2-chlorocyclohexanol with a 90% Faradaic efficiency (FE) at 100 mA cm–2. The combined results of molecular dynamics simulations and in situ spectroscopies provide solid evidence for the widened EDL that originates from the repulsion of water molecules from the interface by ClO4–. The addition of ClO4– has a negligible effect on chlorination kinetics because of the electrostatic interaction between the anode and Cl– but obviously suppresses the interaction between water and the anode, leading to high FEs of anodic electrosynthesis by increasing the energy barrier of the undesirable OER. In addition, this method is suitable for other chlorination reactions with enhanced FEs at 100 mA cm–2.
{"title":"In Situ Probing the Anion-Widened Anodic Electric Double Layer for Enhanced Faradaic Efficiency of Chlorine-Involved Reactions","authors":"Mingming Yan, Rong Yang, Cuibo Liu, Ying Gao, Bin Zhang","doi":"10.1021/jacs.4c16173","DOIUrl":"https://doi.org/10.1021/jacs.4c16173","url":null,"abstract":"The electric double layer (EDL), which is directly related to ions, influences the electrocatalytic performance. However, the effects of anions on the anodic EDL and reaction kinetics are unclear, especially in water-mediated electrosynthesis. Here, ClO<sub>4</sub><sup>–</sup> anions are discovered to widen the anodic EDL to inhibit the competitive oxygen evolution reaction (OER) for the gram-scale electrosynthesis of 2-chlorocyclohexanol with a 90% Faradaic efficiency (FE) at 100 mA cm<sup>–2</sup>. The combined results of molecular dynamics simulations and in situ spectroscopies provide solid evidence for the widened EDL that originates from the repulsion of water molecules from the interface by ClO<sub>4</sub><sup>–</sup>. The addition of ClO<sub>4</sub><sup>–</sup> has a negligible effect on chlorination kinetics because of the electrostatic interaction between the anode and Cl<sup>–</sup> but obviously suppresses the interaction between water and the anode, leading to high FEs of anodic electrosynthesis by increasing the energy barrier of the undesirable OER. In addition, this method is suitable for other chlorination reactions with enhanced FEs at 100 mA cm<sup>–2</sup>.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"30 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-02-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143418274","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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