Pub Date : 2025-03-13DOI: 10.1016/j.chempr.2024.10.029
Huai Qin Fu , Tingting Yu , Jessica White , Ji Wei Sun , Yuming Wu , Wen Jing Li , Nicholas M. Bedford , Yun Wang , Thomas E. Rufford , Cheng Lian , Porun Liu , Hua Gui Yang , Huijun Zhao
The path to practical production of targeted chemicals and fuels application via carbon dioxide reduction reactions (CO2RRs) remains a significant challenge mainly due to low CO2 solubility. Aiming to tackle this key issue, herein, we used the CuSbOx cathode-catalyzed reduction of CO2 to CO as a model system to quantitatively depict CO2 demand-supply and performance relationships. We propose a cathode/electrolyte interface model consisting of a porous catalyst layer, and we combined the experimental and computational COMSOL Multiphysics finite-element studies to quantitatively unveil CO2 demand-supply relationships and determine the maximum CO2 supply capacity in both stationary H cell and gas diffusion electrode (GDE) flow cell. This work exemplifies that experimentally measured catalytic performance may not accurately reflect the maximum capacity/intrinsic electrocatalytic activity of electrocatalysts and reveals that CO2 supply capacity in the GDE flow cell can be dramatically affected by the thickness of the liquid layer between the hydrophobic gas diffusion layer and the catalyst layer.
{"title":"Amorphous CuSbOx composite-catalyzed electrocatalytic reduction of CO2 to CO: CO2 demand-supply-regulated performance","authors":"Huai Qin Fu , Tingting Yu , Jessica White , Ji Wei Sun , Yuming Wu , Wen Jing Li , Nicholas M. Bedford , Yun Wang , Thomas E. Rufford , Cheng Lian , Porun Liu , Hua Gui Yang , Huijun Zhao","doi":"10.1016/j.chempr.2024.10.029","DOIUrl":"10.1016/j.chempr.2024.10.029","url":null,"abstract":"<div><div>The path to practical production of targeted chemicals and fuels application via carbon dioxide reduction reactions (CO<sub>2</sub>RRs) remains a significant challenge mainly due to low CO<sub>2</sub> solubility. Aiming to tackle this key issue, herein, we used the CuSbO<sub>x</sub> cathode-catalyzed reduction of CO<sub>2</sub> to CO as a model system to quantitatively depict CO<sub>2</sub> demand-supply and performance relationships. We propose a cathode/electrolyte interface model consisting of a porous catalyst layer, and we combined the experimental and computational COMSOL Multiphysics finite-element studies to quantitatively unveil CO<sub>2</sub> demand-supply relationships and determine the maximum CO<sub>2</sub> supply capacity in both stationary H cell and gas diffusion electrode (GDE) flow cell. This work exemplifies that experimentally measured catalytic performance may not accurately reflect the maximum capacity/intrinsic electrocatalytic activity of electrocatalysts and reveals that CO<sub>2</sub> supply capacity in the GDE flow cell can be dramatically affected by the thickness of the liquid layer between the hydrophobic gas diffusion layer and the catalyst layer.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 3","pages":"Article 102362"},"PeriodicalIF":19.1,"publicationDate":"2025-03-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142758663","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-03-13DOI: 10.1016/j.chempr.2025.102495
Jian He , Chi-Ming Che
Using C–H substrates as limiting reagents to achieve non-directed C–H activation with high selectivity has been a long-standing challenge in organic synthesis. Recently in Nature Catalysis, Liu et al. introduce a biomimetic catalytic system that employs Cu(II)-bound tert-butoxy radicals for site-selective C–H abstraction, enabling highly efficient asymmetric C(sp3)–H oxidation.
{"title":"Manipulating alkoxy radicals for site- and enantioselective C–H oxidation","authors":"Jian He , Chi-Ming Che","doi":"10.1016/j.chempr.2025.102495","DOIUrl":"10.1016/j.chempr.2025.102495","url":null,"abstract":"<div><div>Using C–H substrates as limiting reagents to achieve non-directed C–H activation with high selectivity has been a long-standing challenge in organic synthesis. Recently in <em>Nature Catalysis</em>, Liu et al. introduce a biomimetic catalytic system that employs Cu(II)-bound <em>tert</em>-butoxy radicals for site-selective C–H abstraction, enabling highly efficient asymmetric C(sp<sup>3</sup>)–H oxidation.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 3","pages":"Article 102495"},"PeriodicalIF":19.1,"publicationDate":"2025-03-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143608679","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-03-13DOI: 10.1016/j.chempr.2025.102490
Fernando Fresno , Nicolas Keller
In this preview, we showcase Peters, Agapie, Atwater, and co-workers’ recent findings published in Device. The team developed a versatile and scalable selective-absorber-based photothermocatalytic reactor for sunlight-driven sustainable fuel synthesis. Ethylene oligomerization reactions using homogeneous and heterogeneous Ni catalysts were efficiently carried out in both batch and flow configurations.
{"title":"Versatile selective-absorber-based photothermocatalytic reactor for solar fuel synthesis","authors":"Fernando Fresno , Nicolas Keller","doi":"10.1016/j.chempr.2025.102490","DOIUrl":"10.1016/j.chempr.2025.102490","url":null,"abstract":"<div><div>In this preview, we showcase Peters, Agapie, Atwater, and co-workers’ recent findings published in <em>Device</em>. The team developed a versatile and scalable selective-absorber-based photothermocatalytic reactor for sunlight-driven sustainable fuel synthesis. Ethylene oligomerization reactions using homogeneous and heterogeneous Ni catalysts were efficiently carried out in both batch and flow configurations.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 3","pages":"Article 102490"},"PeriodicalIF":19.1,"publicationDate":"2025-03-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143608690","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-03-12DOI: 10.1016/j.chempr.2025.102481
Homan Kang, Seung Hun Park, Guliz Ersoy Ozmen, Won Hur, Jason Dinh, Haoran Wang, Vy Nguyen, Sung Ahn, Atsushi Yamashita, Wesley R. Stiles, Satoshi Kashiwagi, Kai Bao, Maged Henary, Hak Soo Choi
Early diagnosis is crucial for the effective treatment of rheumatoid arthritis because continuing inflammation can lead to irreversible joint damage. However, current diagnostic methods lack tissue-specific guidelines to monitor the progressive course of degenerative joint diseases. Here, we demonstrate that cartilage-targeting fluorophores (CARFs) exhibit a remarkable cartilage-specific affinity and offer advanced imaging capabilities in the near-infrared II (NIR-II) window, characterized by minimal tissue scattering and negligible autofluorescence. CARFs show little to no toxicity, both in vitro (up to 100 μM) and in vivo (3 μmol/kg via intravenous injection), suggesting clinical potential. Furthermore, CARFs in the NIR-II window enable the precise visualization of cartilage lining, serving as a reliable diagnostic indicator for the early detection of arthritis in preclinical mouse models. CARFs are NIR fluorescence-emitting targeted contrast agents for prognostic imaging of joint tissue, with the potential to revolutionize applications in tissue engineering, joint surgery, and drug development for inflammatory diseases.
{"title":"Cartilage-targeting fluorophores for early detection of arthritis in the NIR-II window","authors":"Homan Kang, Seung Hun Park, Guliz Ersoy Ozmen, Won Hur, Jason Dinh, Haoran Wang, Vy Nguyen, Sung Ahn, Atsushi Yamashita, Wesley R. Stiles, Satoshi Kashiwagi, Kai Bao, Maged Henary, Hak Soo Choi","doi":"10.1016/j.chempr.2025.102481","DOIUrl":"https://doi.org/10.1016/j.chempr.2025.102481","url":null,"abstract":"Early diagnosis is crucial for the effective treatment of rheumatoid arthritis because continuing inflammation can lead to irreversible joint damage. However, current diagnostic methods lack tissue-specific guidelines to monitor the progressive course of degenerative joint diseases. Here, we demonstrate that cartilage-targeting fluorophores (CARFs) exhibit a remarkable cartilage-specific affinity and offer advanced imaging capabilities in the near-infrared II (NIR-II) window, characterized by minimal tissue scattering and negligible autofluorescence. CARFs show little to no toxicity, both <em>in vitro</em> (up to 100 μM) and <em>in vivo</em> (3 μmol/kg via intravenous injection), suggesting clinical potential. Furthermore, CARFs in the NIR-II window enable the precise visualization of cartilage lining, serving as a reliable diagnostic indicator for the early detection of arthritis in preclinical mouse models. CARFs are NIR fluorescence-emitting targeted contrast agents for prognostic imaging of joint tissue, with the potential to revolutionize applications in tissue engineering, joint surgery, and drug development for inflammatory diseases.","PeriodicalId":268,"journal":{"name":"Chem","volume":"87 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2025-03-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143599571","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-03-10DOI: 10.1016/j.chempr.2025.102489
Rui-Tian Ge, Feng Xiong, Zhen-Bang Chen, Yuanjie Wang, Lin Zheng, Jia Zhou, Di Wu, Shu-Yu Zhang
Indocyanine polymethines are among the most clinically promising probes for fluorescence imaging. Longer wavelength NIR-II probes offer enhanced fluorescence imaging performance by improving the tissue penetration depth and signal-to-noise ratio (SNR), but this often results in reduced brightness. Despite multiple attempts to redshift indocyanine polymethines' wavelengths, their emission wavelengths are restricted to 1,103 nm. We report the first indocyanine polymethines, Cy15s, emitting beyond 1,200 nm, with the longest maximum peak emission at 1,287 nm while maintaining a high brightness of 117.1 M−1⋅cm−1 in dichloroethane (DCM), 6-fold of the best performance of polymethine fluorophores emitting over 1,200 nm. The low cytotoxicity and remarkable optical properties enable high-quality near-infrared II (NIR-II)b angiography and long-term orthotopic tumor imaging. In addition to the relatively mature terminal groups research of polymethines, this study introduces a novel scaffold for conjugation chains, opening new avenues for the design and synthesis of NIR-II probes for deep-tissue imaging and tumor research.
{"title":"Indocyanine polymethine fluorophores with extended π-conjugation emitting beyond 1,200 nm for enhanced NIR-II imaging","authors":"Rui-Tian Ge, Feng Xiong, Zhen-Bang Chen, Yuanjie Wang, Lin Zheng, Jia Zhou, Di Wu, Shu-Yu Zhang","doi":"10.1016/j.chempr.2025.102489","DOIUrl":"https://doi.org/10.1016/j.chempr.2025.102489","url":null,"abstract":"Indocyanine polymethines are among the most clinically promising probes for fluorescence imaging. Longer wavelength NIR-II probes offer enhanced fluorescence imaging performance by improving the tissue penetration depth and signal-to-noise ratio (SNR), but this often results in reduced brightness. Despite multiple attempts to redshift indocyanine polymethines' wavelengths, their emission wavelengths are restricted to 1,103 nm. We report the first indocyanine polymethines, Cy15s, emitting beyond 1,200 nm, with the longest maximum peak emission at 1,287 nm while maintaining a high brightness of 117.1 M<sup>−1</sup>⋅cm<sup>−1</sup> in dichloroethane (DCM), 6-fold of the best performance of polymethine fluorophores emitting over 1,200 nm. The low cytotoxicity and remarkable optical properties enable high-quality near-infrared II (NIR-II)b angiography and long-term orthotopic tumor imaging. In addition to the relatively mature terminal groups research of polymethines, this study introduces a novel scaffold for conjugation chains, opening new avenues for the design and synthesis of NIR-II probes for deep-tissue imaging and tumor research.","PeriodicalId":268,"journal":{"name":"Chem","volume":"212 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2025-03-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143582569","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-03-07DOI: 10.1016/j.chempr.2025.102462
Young Hyun Hong, Xiaofan Jia, Eleanor Stewart-Jones, Abhishek Kumar, Justin C. Wedal, Jose L. Alvarez-Hernandez, Carrie L. Donley, Albert Gang, Noah J. Gibson, Nilay Hazari, Madison Houck, Sungho Jeon, Jongbeom Kim, Hyeongjun Koh, James M. Mayer, Brandon Q. Mercado, Hannah S. Nedzbala, Nicole Piekut, Christine Quist, Eric Stach, Yihui Zhang
The reduction of carbon dioxide (CO2) to formate using molecular catalysts immobilized on high surface area porous silicon is described. Manganese complexes of the type (Rbpy)Mn(CO)3Br (bpy = 2,2′-bipyridine) were prepared with silatrane groups on the bpy ligand for attachment to oxide-coated porous silicon (SiOx-porSi). SiOx-porSi wafers were formed by heating hydrogen-terminated p-type porous silicon wafers under air, and the manganese complexes were immobilized on SiOx-porSi by heating at 80°C. The resulting hybrid photoelectrodes are photoelectrocatalysts for CO2 reduction in acetonitrile containing 2.0 M triethylamine and 2.0 M isopropanol, yielding formate with high selectivity (>96%) and current density (∼0.6 mA/cm2), excellent reproducibility, and a photovoltage of 280 mV at −1.75 V (versus ferrocenium/ferrocene) under 1 sun illumination. The applied potential is close to the equilibrium potential for CO2 reduction to formate. This work presents rare examples of immobilized molecular catalysts for CO2 reduction to formate and the first on semiconducting silicon.
{"title":"Photoelectrocatalytic reduction of CO2 to formate using immobilized molecular manganese catalysts on oxidized porous silicon","authors":"Young Hyun Hong, Xiaofan Jia, Eleanor Stewart-Jones, Abhishek Kumar, Justin C. Wedal, Jose L. Alvarez-Hernandez, Carrie L. Donley, Albert Gang, Noah J. Gibson, Nilay Hazari, Madison Houck, Sungho Jeon, Jongbeom Kim, Hyeongjun Koh, James M. Mayer, Brandon Q. Mercado, Hannah S. Nedzbala, Nicole Piekut, Christine Quist, Eric Stach, Yihui Zhang","doi":"10.1016/j.chempr.2025.102462","DOIUrl":"https://doi.org/10.1016/j.chempr.2025.102462","url":null,"abstract":"The reduction of carbon dioxide (CO<sub>2</sub>) to formate using molecular catalysts immobilized on high surface area porous silicon is described. Manganese complexes of the type (<sup>R</sup>bpy)Mn(CO)<sub>3</sub>Br (bpy = 2,2′-bipyridine) were prepared with silatrane groups on the bpy ligand for attachment to oxide-coated porous silicon (SiO<sub>x</sub>-porSi). SiO<sub>x</sub>-porSi wafers were formed by heating hydrogen-terminated p-type porous silicon wafers under air, and the manganese complexes were immobilized on SiO<sub>x</sub>-porSi by heating at 80°C. The resulting hybrid photoelectrodes are photoelectrocatalysts for CO<sub>2</sub> reduction in acetonitrile containing 2.0 M triethylamine and 2.0 M isopropanol, yielding formate with high selectivity (>96%) and current density (∼0.6 mA/cm<sup>2</sup>), excellent reproducibility, and a photovoltage of 280 mV at −1.75 V (versus ferrocenium/ferrocene) under 1 sun illumination. The applied potential is close to the equilibrium potential for CO<sub>2</sub> reduction to formate. This work presents rare examples of immobilized molecular catalysts for CO<sub>2</sub> reduction to formate and the first on semiconducting silicon.","PeriodicalId":268,"journal":{"name":"Chem","volume":"37 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2025-03-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143569912","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-03-07DOI: 10.1016/j.chempr.2025.102480
Kelvin J.Y. Wu, Elena V. Aleksandrova, Paul J. Robinson, Amy E. Benedetto, Meiyi Yu, Ben I.C. Tresco, Dominic N.Y. See, Tong Jiang, Antonio Ramkissoon, Clémence F. Dunand, Maxim S. Svetlov, Joonho Lee, Yury S. Polikanov, Andrew G. Myers
We recently reported the conception and synthesis of cresomycin (CRM), a fully synthetic lincosamide antibiotic effective in vitro and in vivo against multidrug-resistant Gram-positive and Gram-negative bacteria. In this work, we describe the chemical synthesis and characterization of CRM sulfur atom replacement analogs C-CRM (S → CH2), O-CRM (S → O), and Se-CRM (S → Se). Comparison of high-resolution co-crystal structures showed that all four analogs adopted identical conformations when bound to the bacterial ribosome, but due to variations of ≤1 Å in the bond lengths between the anomeric carbon and the varied atoms, only the S and Se heteroatoms of CRM and Se-CRM, respectively, were positioned to interact with the π-face of nucleobase G2505. C-CRM and O-CRM did not benefit from such stabilizations, with correspondingly negative consequences in both target engagement and antibacterial activities. We therefore conclude that the sulfur atom of the lincosamides is important in ribosomal binding.
{"title":"Why sulfur is important in lincosamide antibiotics","authors":"Kelvin J.Y. Wu, Elena V. Aleksandrova, Paul J. Robinson, Amy E. Benedetto, Meiyi Yu, Ben I.C. Tresco, Dominic N.Y. See, Tong Jiang, Antonio Ramkissoon, Clémence F. Dunand, Maxim S. Svetlov, Joonho Lee, Yury S. Polikanov, Andrew G. Myers","doi":"10.1016/j.chempr.2025.102480","DOIUrl":"https://doi.org/10.1016/j.chempr.2025.102480","url":null,"abstract":"We recently reported the conception and synthesis of cresomycin (CRM), a fully synthetic lincosamide antibiotic effective <em>in vitro</em> and <em>in vivo</em> against multidrug-resistant Gram-positive and Gram-negative bacteria. In this work, we describe the chemical synthesis and characterization of CRM sulfur atom replacement analogs C-CRM (S → CH<sub>2</sub>), O-CRM (S → O), and Se-CRM (S → Se). Comparison of high-resolution co-crystal structures showed that all four analogs adopted identical conformations when bound to the bacterial ribosome, but due to variations of ≤1 Å in the bond lengths between the anomeric carbon and the varied atoms, only the S and Se heteroatoms of CRM and Se-CRM, respectively, were positioned to interact with the π-face of nucleobase G2505. C-CRM and O-CRM did not benefit from such stabilizations, with correspondingly negative consequences in both target engagement and antibacterial activities. We therefore conclude that the sulfur atom of the lincosamides is important in ribosomal binding.","PeriodicalId":268,"journal":{"name":"Chem","volume":"195 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2025-03-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143569907","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-03-07DOI: 10.1016/j.chempr.2025.102456
Andrew W. Heard, Samuel E. Clark, Charlie T. McTernan, Tanya K. Ronson, Petr Rozhin, Barbara Rossi, Silvia Marchesan, Jonathan R. Nitschke
Here, we report two (AgI3I)4L4 metal-organic cages that each contain a previously unobserved trisilver(I) iodide cluster at their vertices. Clusters containing fewer than 10 AgI ions are challenging to synthesize in an atomically precise manner. Previous work has demonstrated the potential of the approach of generating such clusters during the formation of higher-order metal-organic cage superstructures, but too few examples were known for design principles to be deciphered. Through analysis of the set of such cages reported herein and previously, we elaborate a set of design principles for their synthesis.
{"title":"Two (AgI3I)4L4 cages elucidate the rules for silver-cluster vertex design","authors":"Andrew W. Heard, Samuel E. Clark, Charlie T. McTernan, Tanya K. Ronson, Petr Rozhin, Barbara Rossi, Silvia Marchesan, Jonathan R. Nitschke","doi":"10.1016/j.chempr.2025.102456","DOIUrl":"https://doi.org/10.1016/j.chempr.2025.102456","url":null,"abstract":"Here, we report two (Ag<sup>I</sup><sub>3</sub>I)<sub>4</sub>L<sub>4</sub> metal-organic cages that each contain a previously unobserved trisilver(I) iodide cluster at their vertices. Clusters containing fewer than 10 Ag<sup>I</sup> ions are challenging to synthesize in an atomically precise manner. Previous work has demonstrated the potential of the approach of generating such clusters during the formation of higher-order metal-organic cage superstructures, but too few examples were known for design principles to be deciphered. Through analysis of the set of such cages reported herein and previously, we elaborate a set of design principles for their synthesis.","PeriodicalId":268,"journal":{"name":"Chem","volume":"15 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2025-03-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143569911","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-03-06DOI: 10.1016/j.chempr.2025.102487
Hoai T.B. Pham, Xiaoyu Fang, Ji Yong Choi, Shaofeng Huang, Jihye Park
Integrating metallic charge transport with high porosity in a single material can unlock significant advancements in energy storage, electrocatalysis, and chemiresistive sensing. However, these properties rarely coexist due to the conflicting need for a high charge carrier density and the presence of voids. Herein, we report a new macrocyclic ligand, 2,3,8,9,14,15-hexaaminotribenzocyclyne (HATC) and its electrically conductive metal-organic framework (EC-MOF), coordinated with nickel nodes to render Ni-HATC as nanoporous synthetic metal. HATC provides intrinsic pockets for extra porosity, while its six amino and three alkyne groups significantly enhance electron density for realizing metallic behaviors in Ni-HATC. Consequently, Ni-HATC achieves exceptional conductivities of 20 S/cm in thin films and 3 S/cm in bulk, with a high surface area of 1,000 m2/g. Our findings showcase a unique material combining metallic charge transport and high porosity, opening new possibilities for future synthetically nanoporous metallic materials.
{"title":"Nanoporous synthetic metal: A nickel MOF with an amino-functionalized macrocyclic ligand","authors":"Hoai T.B. Pham, Xiaoyu Fang, Ji Yong Choi, Shaofeng Huang, Jihye Park","doi":"10.1016/j.chempr.2025.102487","DOIUrl":"https://doi.org/10.1016/j.chempr.2025.102487","url":null,"abstract":"Integrating metallic charge transport with high porosity in a single material can unlock significant advancements in energy storage, electrocatalysis, and chemiresistive sensing. However, these properties rarely coexist due to the conflicting need for a high charge carrier density and the presence of voids. Herein, we report a new macrocyclic ligand, 2,3,8,9,14,15-hexaaminotribenzocyclyne (HATC) and its electrically conductive metal-organic framework (EC-MOF), coordinated with nickel nodes to render Ni-HATC as nanoporous synthetic metal. HATC provides intrinsic pockets for extra porosity, while its six amino and three alkyne groups significantly enhance electron density for realizing metallic behaviors in Ni-HATC. Consequently, Ni-HATC achieves exceptional conductivities of 20 S/cm in thin films and 3 S/cm in bulk, with a high surface area of 1,000 m<sup>2</sup>/g. Our findings showcase a unique material combining metallic charge transport and high porosity, opening new possibilities for future synthetically nanoporous metallic materials.","PeriodicalId":268,"journal":{"name":"Chem","volume":"16 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2025-03-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143561044","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-03-06DOI: 10.1016/j.chempr.2025.102488
Wang Wang, Bodi Zhao, Xiaotian Qi, M. Kevin Brown
Tetrahydroisoquinolines (THIQ) are prevalent scaffolds found in natural products and pharmaceutical agents. Therefore, new methods for the synthesis of this motif, especially with unique stereochemistry or substitution patterns, are highly desirable. Herein, a new disconnection is demonstrated that combines sulfonylimines and alkenes. The convergent process operates by photoinduced energy transfer. High selectivities for the formation of the anti-isomer were observed. In addition, through the use of highly substituted alkenes, the synthesis of quaternary carbon containing tetrahydroisoquinolines can be achieved. Finally, mechanistic studies are included, revealing that the high selectivity observed is due to subtle variation of the highest occupied molecular orbital (HOMO) energies.
{"title":"An unconventional photochemical tetrahydroisoquinoline synthesis from sulfonylimines and alkenes","authors":"Wang Wang, Bodi Zhao, Xiaotian Qi, M. Kevin Brown","doi":"10.1016/j.chempr.2025.102488","DOIUrl":"https://doi.org/10.1016/j.chempr.2025.102488","url":null,"abstract":"Tetrahydroisoquinolines (THIQ) are prevalent scaffolds found in natural products and pharmaceutical agents. Therefore, new methods for the synthesis of this motif, especially with unique stereochemistry or substitution patterns, are highly desirable. Herein, a new disconnection is demonstrated that combines sulfonylimines and alkenes. The convergent process operates by photoinduced energy transfer. High selectivities for the formation of the anti-isomer were observed. In addition, through the use of highly substituted alkenes, the synthesis of quaternary carbon containing tetrahydroisoquinolines can be achieved. Finally, mechanistic studies are included, revealing that the high selectivity observed is due to subtle variation of the highest occupied molecular orbital (HOMO) energies.","PeriodicalId":268,"journal":{"name":"Chem","volume":"12 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2025-03-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143561043","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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