Among the thirty-two crystallographic point groups, 432 is the only one that lacks an inversion center but does not exhibit piezoelectricity. A gyroidal structure belongs to point group 432 and shows characteristic physical properties attributed to its distinctive strong isotropic network. Here, we investigate a gyroidal cobalt oxalate metal–organic framework (MOF) with disordered orientations of SO4 tetrahedra. Synchrotron X-ray diffraction experiments using a single crystal reveal a cubic-to-cubic structural phase transition at TS = 120 K. This transition involves a change in the point group from nonpiezoelectric 432 to piezoelectric 23. The symmetry change arises from the ordering of distorted SO4 molecules, leading to a three-dimensional helical arrangement of electric dipole moments. Furthermore, pyroelectric current measurements using polycrystalline pellet samples reveal that electric polarization emerges below TS depending on the magnitude of the pelletizing pressure, demonstrating piezoelectricity. The gyroidal MOF offers an opportunity to explore unique dielectric properties induced by the helical ordering of molecules and structural flexibility.
{"title":"Piezoelectric Transition in a Nonpyroelectric Gyroidal Metal–Organic Framework","authors":"Shunsuke Kitou, Hajime Ishikawa, Yusuke Tokunaga, Masato Ueno, Hiroshi Sawa, Yuiga Nakamura, Yuto Kinoshita, Tatsuya Miyamoto, Hiroshi Okamoto, Koichi Kindo, Taka-hisa Arima","doi":"10.1021/jacs.5c00886","DOIUrl":"https://doi.org/10.1021/jacs.5c00886","url":null,"abstract":"Among the thirty-two crystallographic point groups, 432 is the only one that lacks an inversion center but does not exhibit piezoelectricity. A gyroidal structure belongs to point group 432 and shows characteristic physical properties attributed to its distinctive strong isotropic network. Here, we investigate a gyroidal cobalt oxalate metal–organic framework (MOF) with disordered orientations of SO<sub>4</sub> tetrahedra. Synchrotron X-ray diffraction experiments using a single crystal reveal a cubic-to-cubic structural phase transition at <i>T</i><sub>S</sub> = 120 K. This transition involves a change in the point group from nonpiezoelectric 432 to piezoelectric 23. The symmetry change arises from the ordering of distorted SO<sub>4</sub> molecules, leading to a three-dimensional helical arrangement of electric dipole moments. Furthermore, pyroelectric current measurements using polycrystalline pellet samples reveal that electric polarization emerges below <i>T</i><sub>S</sub> depending on the magnitude of the pelletizing pressure, demonstrating piezoelectricity. The gyroidal MOF offers an opportunity to explore unique dielectric properties induced by the helical ordering of molecules and structural flexibility.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"40 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-03-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143677998","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}
Hongming Li, David A. Thaisrivongs, Gao Shang, Yonggang Chen, Qinghao Chen, Lushi Tan, Kai-Jiong Xiao, Reed T. Larson, Jeffrey T. Kuethe, Joshua Lee, Nicholas R. Deprez, Andrew F. Nolting, Marc Poirier, Paul G. Bulger, Erik L. Regalado, Mirlinda Biba, Fuh-Rong Tsay, Jimmy DaSilva, Chris K. Prier, Christopher A. Strulson, Kerstin Zawatzky, Zhu Liu, Justin A. Newman, Kathleen Sokolowsky, Weijuan Tang, Kari Hullen, Nimisha Thakur, Cody Welch, Smit Patel, Yu He, Jing Xu, Narayan Variankaval, Artis Klapars, Jongrock Kong, Richard Desmond, Richard Varsolona, Peter E. Maligres, Carlos A. Pons Siepermann, Lee Robison, Tiffany Piou, Clara Hartmanshenn, Anagha Chandra, Anisha Patel, Marc R. Becker, Guiquan Liu, Jianjun Duan, Baoqiang Wan, Chengqian Xiao, Yongpeng Yuan, Xiaohui Cao, Lu Chen, Ruxia Yi, Zheng Wu, Minyi Feng, Donghong Li, Zhiyan Song, Yawei Dong, Julin Sun, Biao Li, Guangxin Shao, Louis-Charles Campeau, Jingjun Yin
We report the total synthesis of enlicitide decanoate, an orally bioavailable inhibitor of proprotein convertase subtilisin/kexin type 9 that is being developed for the treatment of atherosclerotic cardiovascular disease. It is a highly complex macrocyclic peptide with a significant number of nonpeptide structural elements that presents a daunting synthetic chemistry challenge. We describe the development of a convergent, efficient, and robust manufacturing process that enables the large-scale production of enlicitide.
{"title":"Total Synthesis of Enlicitide Decanoate","authors":"Hongming Li, David A. Thaisrivongs, Gao Shang, Yonggang Chen, Qinghao Chen, Lushi Tan, Kai-Jiong Xiao, Reed T. Larson, Jeffrey T. Kuethe, Joshua Lee, Nicholas R. Deprez, Andrew F. Nolting, Marc Poirier, Paul G. Bulger, Erik L. Regalado, Mirlinda Biba, Fuh-Rong Tsay, Jimmy DaSilva, Chris K. Prier, Christopher A. Strulson, Kerstin Zawatzky, Zhu Liu, Justin A. Newman, Kathleen Sokolowsky, Weijuan Tang, Kari Hullen, Nimisha Thakur, Cody Welch, Smit Patel, Yu He, Jing Xu, Narayan Variankaval, Artis Klapars, Jongrock Kong, Richard Desmond, Richard Varsolona, Peter E. Maligres, Carlos A. Pons Siepermann, Lee Robison, Tiffany Piou, Clara Hartmanshenn, Anagha Chandra, Anisha Patel, Marc R. Becker, Guiquan Liu, Jianjun Duan, Baoqiang Wan, Chengqian Xiao, Yongpeng Yuan, Xiaohui Cao, Lu Chen, Ruxia Yi, Zheng Wu, Minyi Feng, Donghong Li, Zhiyan Song, Yawei Dong, Julin Sun, Biao Li, Guangxin Shao, Louis-Charles Campeau, Jingjun Yin","doi":"10.1021/jacs.4c15966","DOIUrl":"https://doi.org/10.1021/jacs.4c15966","url":null,"abstract":"We report the total synthesis of enlicitide decanoate, an orally bioavailable inhibitor of proprotein convertase subtilisin/kexin type 9 that is being developed for the treatment of atherosclerotic cardiovascular disease. It is a highly complex macrocyclic peptide with a significant number of nonpeptide structural elements that presents a daunting synthetic chemistry challenge. We describe the development of a convergent, efficient, and robust manufacturing process that enables the large-scale production of enlicitide.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"296 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-03-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143677966","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}
While high-pressure phase transitions have been widely studied in inorganic compounds such as oxides and chalcogenides, relatively little attention has been given to compounds containing molecular anions, such as carbodiimides and cyanamides. This study investigates the phase transition of marcasite-type orthorhombic Ba0.9M0.1NCN carbodiimides, where a transformation to a CsCl-type tetragonal phase was observed at room temperature under hydrostatic pressure of 0.8 GPa (M = Ca) and 0.3 GPa (M = Sr). This transition, accompanied by an increase in the metal coordination under from 6 to 8, occurs at pressures significantly lower than those required for the high-pressure phase transitions of rock-salt-type metal halides and marcasite-type metal diantimonides. Remarkably, partial phase transitions were also induced by hand milling, a process that applies localized shear forces, distinct from the particle-crushing effects of high-energy ball milling. The transition mechanism, analyzed via variable-cell nudged elastic band (VCNEB) calculations, revealed that while the linear NCN2– anions remain stable, the shear-sliding of Ba2+ cations and the rotation of NCN2– anions are critical to the structural transformation. These findings underscore the potential of hand milling to effectively induce phase transitions in compounds containing linear molecular anions, offering new strategies for predicting and controlling such transitions in similar materials.
{"title":"Hand Milling Induced Phase Transition for Marcasite-type Carbodiimide","authors":"Yuzuki Yamamoto, Kazuki Kume, Suzuka Miyazaki, Ayako Shinozaki, Peng Song, Sayed Sahriar Hasan, Kenta Hongo, Ryo Maezono, Hiroki Ubukata, Hiroshi Kageyama, Mikio Higuchi, Yuji Masubuchi","doi":"10.1021/jacs.5c00962","DOIUrl":"https://doi.org/10.1021/jacs.5c00962","url":null,"abstract":"While high-pressure phase transitions have been widely studied in inorganic compounds such as oxides and chalcogenides, relatively little attention has been given to compounds containing molecular anions, such as carbodiimides and cyanamides. This study investigates the phase transition of marcasite-type orthorhombic Ba<sub>0.9</sub>M<sub>0.1</sub>NCN carbodiimides, where a transformation to a CsCl-type tetragonal phase was observed at room temperature under hydrostatic pressure of 0.8 GPa (M = Ca) and 0.3 GPa (M = Sr). This transition, accompanied by an increase in the metal coordination under from 6 to 8, occurs at pressures significantly lower than those required for the high-pressure phase transitions of rock-salt-type metal halides and marcasite-type metal diantimonides. Remarkably, partial phase transitions were also induced by hand milling, a process that applies localized shear forces, distinct from the particle-crushing effects of high-energy ball milling. The transition mechanism, analyzed via variable-cell nudged elastic band (VCNEB) calculations, revealed that while the linear NCN<sup>2–</sup> anions remain stable, the shear-sliding of Ba<sup>2+</sup> cations and the rotation of NCN<sup>2–</sup> anions are critical to the structural transformation. These findings underscore the potential of hand milling to effectively induce phase transitions in compounds containing linear molecular anions, offering new strategies for predicting and controlling such transitions in similar materials.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"71 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-03-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143677999","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}
In view of the frequent occurrence of carbon–nitrogen bonds in organic compounds, the development of powerful new methods for the construction of such bonds is expected to greatly impact many of the fields that utilize organic molecules. While the substitution of an alkyl electrophile by a nitrogen nucleophile is a seemingly straightforward approach to generating a carbon–nitrogen bond, in practice classical substitution pathways have very substantial limitations in the case of unactivated secondary and tertiary alkyl electrophiles. Recent reports that transition metals can catalyze certain substitution reactions of such electrophiles are therefore of considerable significance; however, virtually no methods have been developed wherein absolute stereochemistry is controlled together with carbon–nitrogen bond formation. Herein, we address this dual challenge of reactivity and enantioselectivity, describing a photoinduced, copper-catalyzed enantioconvergent synthesis of β-aminoalcohol derivatives via the coupling of anilines with racemic, unactivated β-haloethers. We apply this method to a catalytic asymmetric synthesis of metolachlor, and we report an array of mechanistic studies that are consistent with the reaction pathway that we propose.
{"title":"Photoinduced, Copper-Catalyzed Enantioconvergent Synthesis of β-Aminoalcohol Derivatives","authors":"Arup Mondal, Gregory C. Fu","doi":"10.1021/jacs.5c02417","DOIUrl":"https://doi.org/10.1021/jacs.5c02417","url":null,"abstract":"In view of the frequent occurrence of carbon–nitrogen bonds in organic compounds, the development of powerful new methods for the construction of such bonds is expected to greatly impact many of the fields that utilize organic molecules. While the substitution of an alkyl electrophile by a nitrogen nucleophile is a seemingly straightforward approach to generating a carbon–nitrogen bond, in practice classical substitution pathways have very substantial limitations in the case of unactivated secondary and tertiary alkyl electrophiles. Recent reports that transition metals can catalyze certain substitution reactions of such electrophiles are therefore of considerable significance; however, virtually no methods have been developed wherein absolute stereochemistry is controlled together with carbon–nitrogen bond formation. Herein, we address this dual challenge of reactivity and enantioselectivity, describing a photoinduced, copper-catalyzed enantioconvergent synthesis of β-aminoalcohol derivatives via the coupling of anilines with racemic, unactivated β-haloethers. We apply this method to a catalytic asymmetric synthesis of metolachlor, and we report an array of mechanistic studies that are consistent with the reaction pathway that we propose.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"25 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-03-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143678000","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}
Jian Zhou, Qing Wang, Gongkui Cheng, Wei Shen, Richard N. Zare, Xiaoyan Sun
The cleavage of dioxygen (O2) into its atomic constituents typically requires harsh conditions and metal catalysts. We present a remarkable discovery demonstrating that dioxygen can be activated, dissociated, and subsequently transformed into the ozone anion (O3–) without any catalyst at the air–water interface in charged microdroplet sprays. Using online mass spectrometry, we directly detected the dioxygen splitting products O3– and H2O·O3– in microdroplets. The high electric field at the air–water interface, along with microlightning between oppositely charged water microdroplets, induces an electrical discharge responsible for the O–O bond cleavage, leading to the formation of reactive oxygen species (ROS). Isotope labeling experiments further reveal that various ROS, i.e., ·OH, CO3–, and HCO4–, can be generated through the reaction of dioxygen splitting products with water or CO2. This study introduces a sustainable pathway for molecular oxygen utilization and offers new insights into ROS generation in microdroplets.
{"title":"Charged Water Microdroplets Enable Dissociation of Surrounding Dioxygen","authors":"Jian Zhou, Qing Wang, Gongkui Cheng, Wei Shen, Richard N. Zare, Xiaoyan Sun","doi":"10.1021/jacs.4c12740","DOIUrl":"https://doi.org/10.1021/jacs.4c12740","url":null,"abstract":"The cleavage of dioxygen (O<sub>2</sub>) into its atomic constituents typically requires harsh conditions and metal catalysts. We present a remarkable discovery demonstrating that dioxygen can be activated, dissociated, and subsequently transformed into the ozone anion (O<sub>3</sub><sup>–</sup>) without any catalyst at the air–water interface in charged microdroplet sprays. Using online mass spectrometry, we directly detected the dioxygen splitting products O<sub>3</sub><sup>–</sup> and H<sub>2</sub>O·O<sub>3</sub><sup>–</sup> in microdroplets. The high electric field at the air–water interface, along with microlightning between oppositely charged water microdroplets, induces an electrical discharge responsible for the O–O bond cleavage, leading to the formation of reactive oxygen species (ROS). Isotope labeling experiments further reveal that various ROS, i.e., ·OH, CO<sub>3</sub><sup>–</sup>, and HCO<sub>4</sub><sup>–</sup>, can be generated through the reaction of dioxygen splitting products with water or CO<sub>2</sub>. This study introduces a sustainable pathway for molecular oxygen utilization and offers new insights into ROS generation in microdroplets.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"28 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-03-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143677965","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}
Evgeniy Salnikov, Morgane Adélaïde, Francisco Ramos-Martín, Ahmad Saad, Jennifer Schauer, Martina Cremanns, Mariam Rima, Christopher Aisenbrey, Saoussen Oueslati, Thierry Naas, Niels Pfennigwerth, Söeren Gatermann, Catherine Sarazin, Burkhard Bechinger, Nicola D’Amelio
Cathelicidin-BF (CatBF) is a LL-37 homologous antimicrobial peptide (AMP) isolated from Bungarus fasciatus with an exceptional portfolio of antimicrobial, antiviral, antifungal, and anticancer activities. Contrary to many AMPs, it showed a good pharmacological profile with a half-life of at least 1 h in serum and efficacy against bacterial infections in mice. To evaluate its potential against resistant nosocomial infections, we assessed its activity against 81 clinically relevant resistant bacterial isolates. CatBF exhibited minimum inhibitory concentrations (MICs) as low as 0.5 μM against carbapenem-resistant Acinetobacter baumannii, Klebsiella pneumoniae, and Escherichia coli. Its wide-ranging activity, unaffected by resistance mechanisms or Gram phenotype, prompted us to investigate its molecular mode of action. NMR spectroscopy, paramagnetic probes, and molecular dynamics (MD) simulations were employed to define its structure, penetration depth, and orientation in various membrane models, including micelles, bicelles, oriented bilayers, and vesicles. We found that CatBF’s potent activity relies on its strong charge, allowing membrane neutralization at low peptide/lipid ratios and selective recruitment of charged phospholipids. At higher concentrations, a change in peptide orientation reveals membrane invagination and the formation of transient pores possibly leading to bacterial death. Our findings highlight the potential of CatBF as a model for developing resistance-independent agents to combat multidrug-resistant (MDR) bacterial infections.
{"title":"Cathelicidin-BF: A Potent Antimicrobial Peptide Leveraging Charge and Phospholipid Recruitment against Multidrug-Resistant Clinical Bacterial Isolates","authors":"Evgeniy Salnikov, Morgane Adélaïde, Francisco Ramos-Martín, Ahmad Saad, Jennifer Schauer, Martina Cremanns, Mariam Rima, Christopher Aisenbrey, Saoussen Oueslati, Thierry Naas, Niels Pfennigwerth, Söeren Gatermann, Catherine Sarazin, Burkhard Bechinger, Nicola D’Amelio","doi":"10.1021/jacs.4c17821","DOIUrl":"https://doi.org/10.1021/jacs.4c17821","url":null,"abstract":"Cathelicidin-BF (CatBF) is a LL-37 homologous antimicrobial peptide (AMP) isolated from <i>Bungarus fasciatus</i> with an exceptional portfolio of antimicrobial, antiviral, antifungal, and anticancer activities. Contrary to many AMPs, it showed a good pharmacological profile with a half-life of at least 1 h in serum and efficacy against bacterial infections in mice. To evaluate its potential against resistant nosocomial infections, we assessed its activity against 81 clinically relevant resistant bacterial isolates. CatBF exhibited minimum inhibitory concentrations (MICs) as low as 0.5 μM against carbapenem-resistant <i>Acinetobacter baumannii</i>, <i>Klebsiella pneumoniae</i>, and <i>Escherichia coli</i>. Its wide-ranging activity, unaffected by resistance mechanisms or Gram phenotype, prompted us to investigate its molecular mode of action. NMR spectroscopy, paramagnetic probes, and molecular dynamics (MD) simulations were employed to define its structure, penetration depth, and orientation in various membrane models, including micelles, bicelles, oriented bilayers, and vesicles. We found that CatBF’s potent activity relies on its strong charge, allowing membrane neutralization at low peptide/lipid ratios and selective recruitment of charged phospholipids. At higher concentrations, a change in peptide orientation reveals membrane invagination and the formation of transient pores possibly leading to bacterial death. Our findings highlight the potential of CatBF as a model for developing resistance-independent agents to combat multidrug-resistant (MDR) bacterial infections.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"93 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-03-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143677967","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}
Hong Li, Xiao-Rui Ren, Yan Wang, Daliang Zhang, Zitao Wang, Lan-Ting Wei, Xin-Lan Wang, Dong Wang
Reticular chemistry has greatly stimulated the development of framework materials, yet covalent organic frameworks (COFs) featuring irregular tiling are rare, because of the strict constraints on irregular tile lengths and angles. Guided by reticular chemistry, we deconstructed type III irregular hexagonal tiling into a combination of D2h + D2h monomers and achieved the first successful synthesis of 2D COFs featuring such tiling with hit topology. By tuning the crystal growth conditions, we obtained a set of reticular isomers, COF-hit and COF-bex, with distinct reticular structures. Powder X-ray diffraction and high-resolution transmission electron microscopy were employed to precisely characterize their topology structures. COF-hit demonstrates outstanding water absorption capabilities under high humidity conditions. This rational design of COFs using irregular tiling opens a new avenue to diversify the structural types and topological varieties of COFs and promote the development of reticular chemistry.
{"title":"Reticular Design and Synthesis of Covalent Organic Frameworks with Irregular Hexagonal Tiling","authors":"Hong Li, Xiao-Rui Ren, Yan Wang, Daliang Zhang, Zitao Wang, Lan-Ting Wei, Xin-Lan Wang, Dong Wang","doi":"10.1021/jacs.5c00494","DOIUrl":"https://doi.org/10.1021/jacs.5c00494","url":null,"abstract":"Reticular chemistry has greatly stimulated the development of framework materials, yet covalent organic frameworks (COFs) featuring irregular tiling are rare, because of the strict constraints on irregular tile lengths and angles. Guided by reticular chemistry, we deconstructed type III irregular hexagonal tiling into a combination of <i>D</i><sub>2<i>h</i></sub> + <i>D</i><sub>2<i>h</i></sub> monomers and achieved the first successful synthesis of 2D COFs featuring such tiling with <b>hit</b> topology. By tuning the crystal growth conditions, we obtained a set of reticular isomers, COF-hit and COF-bex, with distinct reticular structures. Powder X-ray diffraction and high-resolution transmission electron microscopy were employed to precisely characterize their topology structures. COF-hit demonstrates outstanding water absorption capabilities under high humidity conditions. This rational design of COFs using irregular tiling opens a new avenue to diversify the structural types and topological varieties of COFs and promote the development of reticular chemistry.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"1 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-03-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143677997","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}
Theodore C. Warner, Victoria M. Marando, Omar A. Santiago-Reyes, Elizabeth M. Hart, Stephanie R. Smelyansky, Alan W. Carter, Thomas G. Bernhardt, Bryan D. Bryson, Daria E. Kim, Laura L. Kiessling
The mycobacterial cell envelope plays both infectious and protective roles. Understanding its structure is crucial for unlocking the molecular basis underlying these functions. Studying glycans, the primary components of the cell envelope, is challenging due to their limited native functional handles for chemoselective modification. New labeling methods exploit biorthogonal chemistry, using small molecule mimics that intercept cellular metabolism or late-stage glycan biosynthesis. However, these strategies can have practical limitations, including probe delivery and effectiveness. An ideal small molecule probe should be easily deployed and exploit the critical enzyme–substrate relationships of natural substrates. To this end, we developed a “probegenic” strategy to label mycobacteria. Our approach eliminates the need for explicit substrate mimicry, as the relevant functionality is revealed by a target enzyme. Specifically, we synthesized an azide-substituted trans-β-lactone probe (AzLac), which adopts a substrate-like structure upon covalent enzyme labeling. This probe is incorporated by mycolyltransferases into a core mycobacterial cell envelope glycan, including in the pathogen Mycobacterium tuberculosis. Unlike other probes of the cell envelope, AzLac facilitates selective covalent labeling of the inner leaflet of the mycomembrane. Using Corynebacterium glutamicum mycolyltransferase deletion strains, we implicated Cmt2 as the primary mycolyltransferase target. We leveraged the ability to modify the cell envelope by demonstrating that AzLac could be used to attach a DNA barcode to mycobacteria, which would help track infection dynamics. Thus, we expect AzLac will be a valuable means of monitoring and tracking the mycobacterial cell envelope. Moreover, we anticipate masking and revealing recognition motifs in probes can be applied to diverse cellular targets.
{"title":"Intercepting a Mycobacterial Biosynthetic Pathway with Covalent Labeling","authors":"Theodore C. Warner, Victoria M. Marando, Omar A. Santiago-Reyes, Elizabeth M. Hart, Stephanie R. Smelyansky, Alan W. Carter, Thomas G. Bernhardt, Bryan D. Bryson, Daria E. Kim, Laura L. Kiessling","doi":"10.1021/jacs.4c17913","DOIUrl":"https://doi.org/10.1021/jacs.4c17913","url":null,"abstract":"The mycobacterial cell envelope plays both infectious and protective roles. Understanding its structure is crucial for unlocking the molecular basis underlying these functions. Studying glycans, the primary components of the cell envelope, is challenging due to their limited native functional handles for chemoselective modification. New labeling methods exploit biorthogonal chemistry, using small molecule mimics that intercept cellular metabolism or late-stage glycan biosynthesis. However, these strategies can have practical limitations, including probe delivery and effectiveness. An ideal small molecule probe should be easily deployed and exploit the critical enzyme–substrate relationships of natural substrates. To this end, we developed a “probegenic” strategy to label mycobacteria. Our approach eliminates the need for explicit substrate mimicry, as the relevant functionality is revealed by a target enzyme. Specifically, we synthesized an azide-substituted <i>trans-</i>β-lactone probe (AzLac), which adopts a substrate-like structure upon covalent enzyme labeling. This probe is incorporated by mycolyltransferases into a core mycobacterial cell envelope glycan, including in the pathogen <i>Mycobacterium tuberculosis</i>. Unlike other probes of the cell envelope, AzLac facilitates selective covalent labeling of the inner leaflet of the mycomembrane. Using <i>Corynebacterium glutamicum</i> mycolyltransferase deletion strains, we implicated Cmt2 as the primary mycolyltransferase target. We leveraged the ability to modify the cell envelope by demonstrating that AzLac could be used to attach a DNA barcode to mycobacteria, which would help track infection dynamics. Thus, we expect AzLac will be a valuable means of monitoring and tracking the mycobacterial cell envelope. Moreover, we anticipate masking and revealing recognition motifs in probes can be applied to diverse cellular targets.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"37 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-03-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143677996","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}
Andriy Stelmakh, Georgios Marnieros, Erik Schrader, Georgian Nedelcu, Oleh Hordiichuk, Eduard Rusanov, Ihor Cherniukh, Daniel Zindel, Hansjörg Grützmacher, Maksym V. Kovalenko
InP-based quantum dots (QDs) represent the major commercial success of colloidal semiconductor nanocrystals (NCs). A combination of the robust, mostly covalent, structure and nontoxic nature of the constituent elements makes them a QD material of choice for display and LED technologies. Despite successful commercial realization, InP NCs still lack synthetic versatility and robustness, seen, for instance, as a continued quest to substitute a commonly used pyrophoric and expensive tris(trimethylsilyl)phosphine precursor. Herein, we propose solid-state, nonpyrophoric, and synthetically readily accessible acylphosphines as convenient phosphorus precursors for the synthesis of InP NCs. When combined with suitable anionic nucleophiles, such as arylthiolates, both tris(acyl)phosphines and indium complexes of bis(acyl)phosphines act as efficient sources of the P3– anion, as corroborated by NMR spectroscopy and powder X-ray diffraction studies. This type of reactivity is utilized in colloidal synthesis of uniform InP QDs with well-defined excitonic features in their optical absorption spectra, spanning 460–600 nm. The conversion kinetics and therefore the final NC size are controlled by the nature of acyl substituents and by the use of either indium or zinc long-chain carboxylates as ligands. The proposed acylpnictide route is anticipated to foster the development of other metal phosphide and metal arsenide NCs.
{"title":"Acylphosphine Route to Colloidal InP Quantum Dots","authors":"Andriy Stelmakh, Georgios Marnieros, Erik Schrader, Georgian Nedelcu, Oleh Hordiichuk, Eduard Rusanov, Ihor Cherniukh, Daniel Zindel, Hansjörg Grützmacher, Maksym V. Kovalenko","doi":"10.1021/jacs.5c01305","DOIUrl":"https://doi.org/10.1021/jacs.5c01305","url":null,"abstract":"InP-based quantum dots (QDs) represent the major commercial success of colloidal semiconductor nanocrystals (NCs). A combination of the robust, mostly covalent, structure and nontoxic nature of the constituent elements makes them a QD material of choice for display and LED technologies. Despite successful commercial realization, InP NCs still lack synthetic versatility and robustness, seen, for instance, as a continued quest to substitute a commonly used pyrophoric and expensive tris(trimethylsilyl)phosphine precursor. Herein, we propose solid-state, nonpyrophoric, and synthetically readily accessible acylphosphines as convenient phosphorus precursors for the synthesis of InP NCs. When combined with suitable anionic nucleophiles, such as arylthiolates, both tris(acyl)phosphines and indium complexes of bis(acyl)phosphines act as efficient sources of the P<sup>3–</sup> anion, as corroborated by NMR spectroscopy and powder X-ray diffraction studies. This type of reactivity is utilized in colloidal synthesis of uniform InP QDs with well-defined excitonic features in their optical absorption spectra, spanning 460–600 nm. The conversion kinetics and therefore the final NC size are controlled by the nature of acyl substituents and by the use of either indium or zinc long-chain carboxylates as ligands. The proposed acylpnictide route is anticipated to foster the development of other metal phosphide and metal arsenide NCs.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"215 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-03-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143678002","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}
Tengteng Gu, Yunqi Jia, Linjie Zhang, Linwei Zhao, Jiadong Shen, Liuzhang Ouyang, Min Zhu, Jun Liu
Quasi-solid-state Zn–air batteries typically exhibit limited rate capability (<10 mA cm–2), primarily due to sluggish oxygen electrocatalysis and unstable electrochemical interfaces. Herein, we report a realistic quasi-solid-state Zn–air battery featuring multiactive sites' MnFeCoNiRu high-entropy alloys uniformly anchored in carbon nanofibers (MnFeCoNiRu/CNF) as the air cathode and a poly(acrylamide-co-acrylic acid) organohydrogel as an antifreezing conductor electrolyte. The proposed (MnFeCoNiRu/CNF) exhibits superb bifunctional activity (ΔE = 0.64 V) and stability (>10,000 cycles) toward a reversible oxygen reaction, outperforming commercial Pt/C and RuO2, which is mainly due to MnFeCoNiRu/CNF possessing different active sites in oxygen reactions, as evidenced by in situ Raman spectroscopy and density functional theory. Furthermore, a poly(acrylamide-co-acrylic acid) organohydrogel with its multiple intermolecular hydrogen bond network modified by the addition of dimethyl sulfoxide reveals strength at a freezing temperature (−50 °C) with high chemical/mechanical robustness. A high capacity of 7.15 Ah and an energy density of 110 Wh kgcell–1 are normally measured in a quasi-solid-state Zn–air battery with a cycle test under 500 mA and 250/500 mAh conditions. Quasi-solid-state Zn–air batteries operate effectively at rates of 5–2000 mA over a wide temperature range from −50 to 60 °C.
{"title":"Ampere-Hour-Scale Quasi-Solid-State Zinc–Air Batteries with a Wide Operating Temperature Range (−50 to 60 °C)","authors":"Tengteng Gu, Yunqi Jia, Linjie Zhang, Linwei Zhao, Jiadong Shen, Liuzhang Ouyang, Min Zhu, Jun Liu","doi":"10.1021/jacs.4c16807","DOIUrl":"https://doi.org/10.1021/jacs.4c16807","url":null,"abstract":"Quasi-solid-state Zn–air batteries typically exhibit limited rate capability (<10 mA cm<sup>–2</sup>), primarily due to sluggish oxygen electrocatalysis and unstable electrochemical interfaces. Herein, we report a realistic quasi-solid-state Zn–air battery featuring multiactive sites' MnFeCoNiRu high-entropy alloys uniformly anchored in carbon nanofibers (MnFeCoNiRu/CNF) as the air cathode and a poly(acrylamide-<i>co</i>-acrylic acid) organohydrogel as an antifreezing conductor electrolyte. The proposed (MnFeCoNiRu/CNF) exhibits superb bifunctional activity (Δ<i>E</i> = 0.64 V) and stability (>10,000 cycles) toward a reversible oxygen reaction, outperforming commercial Pt/C and RuO<sub>2</sub>, which is mainly due to MnFeCoNiRu/CNF possessing different active sites in oxygen reactions, as evidenced by in situ Raman spectroscopy and density functional theory. Furthermore, a poly(acrylamide-<i>co</i>-acrylic acid) organohydrogel with its multiple intermolecular hydrogen bond network modified by the addition of dimethyl sulfoxide reveals strength at a freezing temperature (−50 °C) with high chemical/mechanical robustness. A high capacity of 7.15 Ah and an energy density of 110 Wh kg<sub>cell</sub><sup>–1</sup> are normally measured in a quasi-solid-state Zn–air battery with a cycle test under 500 mA and 250/500 mAh conditions. Quasi-solid-state Zn–air batteries operate effectively at rates of 5–2000 mA over a wide temperature range from −50 to 60 °C.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"29 1","pages":""},"PeriodicalIF":15.0,"publicationDate":"2025-03-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143678001","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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