Lisa A. Schlor, Maya Peußner, Silke Müller, Andreas Marx
Human RNA ligase 1 (Rlig1) calalyzes the ligation of 5’-phosphate to 3’-hydroxyl ends via a conserved three-step mechanism. Rlig1-deficient HEK293 cells exhibit reduced cell viability and RNA integrity under oxidative stress, suggesting Rlig1’s role in RNA repair maintenance. Reactive oxygen species (ROS) are linked to various diseases, including neurodegenerative disorders and cancers, where RNA damage has significant effects. This study identifies and characterizes Rlig1 inhibitors to elucidate its role in RNA metabolism. We developed a fluorescence resonance energy transfer (FRET)-based assay to monitor RNA ligation and screened a library of 13,026 bioactive small molecules. SGI-1027 emerged as a promising lead compound, and structure-activity relationship (SAR) studies revealed that the terminal residues play a key role in its inhibitory effect. In total 22 SGI-1027 derivatives were synthesized and tested, providing insights into the structural requirements for effective Rlig1 inhibition. Three derivatives showed low micromolar IC50 values and minimal cytotoxicity in HEK293 cells under physiological conditions. The combination of Rlig1 inhibition and oxidative stress led to reduced cell viability and compromised RNA integrity, reinforcing Rlig1's role in RNA maintenance. These findings provide a foundation for developing novel therapeutics aimed at targeting RNA maintenance pathways in conditions of dysregulated ROS levels.
{"title":"Potent inhibitors of the human RNA ligase Rlig1 highlights its role in RNA integrity maintenance under oxidative cellular stress","authors":"Lisa A. Schlor, Maya Peußner, Silke Müller, Andreas Marx","doi":"10.1039/d4sc06542e","DOIUrl":"https://doi.org/10.1039/d4sc06542e","url":null,"abstract":"Human RNA ligase 1 (Rlig1) calalyzes the ligation of 5’-phosphate to 3’-hydroxyl ends via a conserved three-step mechanism. Rlig1-deficient HEK293 cells exhibit reduced cell viability and RNA integrity under oxidative stress, suggesting Rlig1’s role in RNA repair maintenance. Reactive oxygen species (ROS) are linked to various diseases, including neurodegenerative disorders and cancers, where RNA damage has significant effects. This study identifies and characterizes Rlig1 inhibitors to elucidate its role in RNA metabolism. We developed a fluorescence resonance energy transfer (FRET)-based assay to monitor RNA ligation and screened a library of 13,026 bioactive small molecules. SGI-1027 emerged as a promising lead compound, and structure-activity relationship (SAR) studies revealed that the terminal residues play a key role in its inhibitory effect. In total 22 SGI-1027 derivatives were synthesized and tested, providing insights into the structural requirements for effective Rlig1 inhibition. Three derivatives showed low micromolar IC50 values and minimal cytotoxicity in HEK293 cells under physiological conditions. The combination of Rlig1 inhibition and oxidative stress led to reduced cell viability and compromised RNA integrity, reinforcing Rlig1's role in RNA maintenance. These findings provide a foundation for developing novel therapeutics aimed at targeting RNA maintenance pathways in conditions of dysregulated ROS levels.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"26 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-01-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142989468","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}
Using photoswitchable molecules to manipulate supramolecular interactions under light illumination has driven advancements in numerous fields, allowing for the strategic alteration of molecular systems. However, integrating the moiety responsible for these interactions into the photochromic scaffold can be complex and may hamper the switching efficiency. We thus explored a simple class of organic molecules, namely thiosemicarbazones, featuring both a photoisomerizable CN double bond and a thiourea moiety capable of hydrogen bonding. The scalable two-step synthesis allowed us to prepare 23 thiosemicarbazones to systematically elucidate their optical properties. Attaching various functional groups, extended π-systems, and heterocycles enabled fine-tuning of their absorption profiles. UV light illumination converts thiosemicarbazones from the stable E-isomer to the metastable Z-isomer, exhibiting both negative and positive T-type photochromism, a wide range of thermal half-lives, PSS values up to 92%, and high fatigue resistance. Substituting the CN moiety with a pyridinyl group stabilizes the Z-isomer via intramolecular hydrogen bonding, confirmed by single-crystal X-ray analysis, and transforms thiosemicarbazones into bistable P-type photoswitches. Additionally, thiosemicarbazones dimerize or form aggregates through hydrogen bonding—a process that can be turned off or on with light. Overall, thiosemicarbazones offer tunable photochromic and supramolecular properties, rendering them a promising photoswitch for creating stimuli-responsive systems.
{"title":"Thiosemicarbazones as versatile photoswitches with light-controllable supramolecular activity","authors":"Bengi Sentürk, Burkhard Butschke, Fabian Eisenreich","doi":"10.1039/d4sc08530b","DOIUrl":"https://doi.org/10.1039/d4sc08530b","url":null,"abstract":"Using photoswitchable molecules to manipulate supramolecular interactions under light illumination has driven advancements in numerous fields, allowing for the strategic alteration of molecular systems. However, integrating the moiety responsible for these interactions into the photochromic scaffold can be complex and may hamper the switching efficiency. We thus explored a simple class of organic molecules, namely thiosemicarbazones, featuring both a photoisomerizable C<img alt=\"[double bond, length as m-dash]\" border=\"0\" src=\"https://www.rsc.org/images/entities/char_e001.gif\"/>N double bond and a thiourea moiety capable of hydrogen bonding. The scalable two-step synthesis allowed us to prepare 23 thiosemicarbazones to systematically elucidate their optical properties. Attaching various functional groups, extended π-systems, and heterocycles enabled fine-tuning of their absorption profiles. UV light illumination converts thiosemicarbazones from the stable <em>E</em>-isomer to the metastable <em>Z</em>-isomer, exhibiting both negative and positive T-type photochromism, a wide range of thermal half-lives, PSS values up to 92%, and high fatigue resistance. Substituting the C<img alt=\"[double bond, length as m-dash]\" border=\"0\" src=\"https://www.rsc.org/images/entities/char_e001.gif\"/>N moiety with a pyridinyl group stabilizes the <em>Z</em>-isomer <em>via</em> intramolecular hydrogen bonding, confirmed by single-crystal X-ray analysis, and transforms thiosemicarbazones into bistable P-type photoswitches. Additionally, thiosemicarbazones dimerize or form aggregates through hydrogen bonding—a process that can be turned off or on with light. Overall, thiosemicarbazones offer tunable photochromic and supramolecular properties, rendering them a promising photoswitch for creating stimuli-responsive systems.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"15 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-01-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142988377","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}
Joseph Treacy, James A. R. Tilden, Elaine Y. Chao, Zihuan Fu, Alex Spokoyny, K. N. Houk, Heather Maynard
Metal-mediated cysteine S-arylation is an emerging bioconjugation technique due to its high chemoselectivity, rapid kinetics, and aqueous compatibility. We have previously demonstrated that by altering the sterics of the ligand and aryl groups of an Au(III) oxidative addition complex, one can modulate the kinetics of the bimolecular coordination and induce rate constants up to 16,600 m−1s−1. To further enhance the rate of coordination, density functional theory (DFT) calculations were performed to investigate the steric properties of the P,N-ligated Au(III) oxidative addition complex as well as the thermodynamics of the S-arylation reaction. This allowed for the accelerated screening of 13 new Au(III) oxidative addition complexes. Three of these more sterically promising, synthetically available P,N-ligands were synthesized, incorporated into Au(I) and Au(III) complexes, and the rates studied experimentally. The comprehensive mechanistic insights from the DFT calculations led to the development of new reagents with bimolecular coordination rate constants as fast as 20,200 m−1s−1. Further experimental characterization of these reagents’ efficacy as S-arylation reagents led to a proposed switch in selectivity-determining step for the fastest reagent, which was further confirmed by profiling the reductive elimination kinetics. This work provides a concise workflow for the screening of metal-mediated cysteine S-arylation reagents and new fundamental insights into the coordination chemistry behavior of Au(III) systems.
{"title":"In Silico Screening of P,N-Ligands Facilitates Optimization of Au(III)-Mediated S-Arylation","authors":"Joseph Treacy, James A. R. Tilden, Elaine Y. Chao, Zihuan Fu, Alex Spokoyny, K. N. Houk, Heather Maynard","doi":"10.1039/d4sc05920d","DOIUrl":"https://doi.org/10.1039/d4sc05920d","url":null,"abstract":"Metal-mediated cysteine <em>S</em>-arylation is an emerging bioconjugation technique due to its high chemoselectivity, rapid kinetics, and aqueous compatibility. We have previously demonstrated that by altering the sterics of the ligand and aryl groups of an Au(III) oxidative addition complex, one can modulate the kinetics of the bimolecular coordination and induce rate constants up to 16,600 m<small><sup>−</sup></small><small><sup>1</sup></small>s<small><sup>−</sup></small><small><sup>1</sup></small>. To further enhance the rate of coordination, density functional theory (DFT) calculations were performed to investigate the steric properties of the <em>P</em>,<em>N</em>-ligated Au(III) oxidative addition complex as well as the thermodynamics of the <em>S</em>-arylation reaction. This allowed for the accelerated screening of 13 new Au(III) oxidative addition complexes. Three of these more sterically promising, synthetically available <em>P</em>,<em>N</em>-ligands were synthesized, incorporated into Au(I) and Au(III) complexes, and the rates studied experimentally. The comprehensive mechanistic insights from the DFT calculations led to the development of new reagents with bimolecular coordination rate constants as fast as 20,200 m<small><sup>−</sup></small><small><sup>1</sup></small>s<small><sup>−</sup></small><small><sup>1</sup></small>. Further experimental characterization of these reagents’ efficacy as <em>S</em>-arylation reagents led to a proposed switch in selectivity-determining step for the fastest reagent, which was further confirmed by profiling the reductive elimination kinetics. This work provides a concise workflow for the screening of metal-mediated cysteine <em>S</em>-arylation reagents and new fundamental insights into the coordination chemistry behavior of Au(III) systems.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"54 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-01-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142986624","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}
Raising cut-off voltage increases the energy density of LiCoO2 for lithium-ion batteries, but it exacerbates the decomposition of the electrolyte and the capacity decay of LiCoO2. To address such issues, many artificial cathode-electrolyte-interphase (CEI) are constructed to stabilize the cathode interface by additive. However, it is rarely explored for the electrolyte degradation by catalytic oxidation of Co ions dissolved in the electrolytes. Herein, we report a new strategy of additive engineering towards the enhanced cycling stability of LiCoO2 at 4.6 V. We found that the Co4+ ions dissolved in the electrolyte due to interfacial failure degrades the electrolyte rapidly by homogeneous catalysis, which can be deactivated by chelation reaction of nitrilotri(methylphosphonic acid) (ATMP) additive with Co4+. Benefiting from the deactivated Co ions by ATMP, the catalytic oxidation of the electrolyte is suppressed, which is more stable to the LiCoO2 interface than the artificially constructed CEI, and thus the LiCoO2 cathode delivers a high capacity of 197.7 mAh g-1 after 200 cycles at 4.6 V with a retention rate of 91.4%. This work provides new insights into additive engineering towards stable cathode/electrolyte interfaces for next-generation batteries.
{"title":"Inhibiting Homogeneous Catalysis of Cobalt Ions towards Stable Battery Cycling of LiCoO2 at 4.6 V","authors":"Chao Sun, Bing Zhao, Qing Wen, Xiang-tao Chen, Ningyun Hong, Jinbo Zeng, Jiafeng Zhang, Lingjun Li, Jiexi Wang, Xiahui Zhang, Junchao Zheng","doi":"10.1039/d4sc07831d","DOIUrl":"https://doi.org/10.1039/d4sc07831d","url":null,"abstract":"Raising cut-off voltage increases the energy density of LiCoO2 for lithium-ion batteries, but it exacerbates the decomposition of the electrolyte and the capacity decay of LiCoO2. To address such issues, many artificial cathode-electrolyte-interphase (CEI) are constructed to stabilize the cathode interface by additive. However, it is rarely explored for the electrolyte degradation by catalytic oxidation of Co ions dissolved in the electrolytes. Herein, we report a new strategy of additive engineering towards the enhanced cycling stability of LiCoO2 at 4.6 V. We found that the Co4+ ions dissolved in the electrolyte due to interfacial failure degrades the electrolyte rapidly by homogeneous catalysis, which can be deactivated by chelation reaction of nitrilotri(methylphosphonic acid) (ATMP) additive with Co4+. Benefiting from the deactivated Co ions by ATMP, the catalytic oxidation of the electrolyte is suppressed, which is more stable to the LiCoO2 interface than the artificially constructed CEI, and thus the LiCoO2 cathode delivers a high capacity of 197.7 mAh g-1 after 200 cycles at 4.6 V with a retention rate of 91.4%. This work provides new insights into additive engineering towards stable cathode/electrolyte interfaces for next-generation batteries.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"54 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-01-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142986848","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 overcoming the barrier of rapid Li+ transfer in lithium-ion batteries under extreme temperatures, the desolvation process and interfacial charge transport play critical roles. However, tunning the solvation structure and designing kinetically-stable electrode-electrolyte interface to achieve high-rate charging and discharging remains challenges. Here, a lithium nonafluoro-1-butanesulfonate (NFSALi) additive is introduced to optimize a stability and robust solid electrolyte interface film (SEI), realizing the rapid Li+ transfer process and the structural integrity of electrode materials. The NFSALi-derived thinner, fluorine-rich, and sulfur-containing SEI in nitrile-assistant carbonate electrolytes effectively suppresses decomposition of valeronitrile solvent during high-rate cycling and wide-temperature operation (−40~55 ℃). More importantly, the graphiteǁLiNi0.5Co0.2Mn0.3O2 pouch cell demonstrates a capacity retention of 66.88% after 200 high-rate cycles with 3 C charging and 5 C discharging at a high-temperature condition of 55 °C. This work provides significant guidance to develop inorganic-rich interfacial chemistry for lithium-ion batteries under extreme operating conditions.
{"title":"Engineering the Solid Electrolyte Interphase for Enhancing High-Rate Cycling and Temperature Adaptability of Lithium-Ion Batteries","authors":"Zhongming Wang, Zhiyuan He, Zhongsheng Wang, Kecheng Long, Jixu Yang, Shaozhen Huang, Zhibin Wu, Lin Mei, Libao Chen","doi":"10.1039/d4sc07916g","DOIUrl":"https://doi.org/10.1039/d4sc07916g","url":null,"abstract":"In overcoming the barrier of rapid Li+ transfer in lithium-ion batteries under extreme temperatures, the desolvation process and interfacial charge transport play critical roles. However, tunning the solvation structure and designing kinetically-stable electrode-electrolyte interface to achieve high-rate charging and discharging remains challenges. Here, a lithium nonafluoro-1-butanesulfonate (NFSALi) additive is introduced to optimize a stability and robust solid electrolyte interface film (SEI), realizing the rapid Li+ transfer process and the structural integrity of electrode materials. The NFSALi-derived thinner, fluorine-rich, and sulfur-containing SEI in nitrile-assistant carbonate electrolytes effectively suppresses decomposition of valeronitrile solvent during high-rate cycling and wide-temperature operation (−40~55 ℃). More importantly, the graphiteǁLiNi0.5Co0.2Mn0.3O2 pouch cell demonstrates a capacity retention of 66.88% after 200 high-rate cycles with 3 C charging and 5 C discharging at a high-temperature condition of 55 °C. This work provides significant guidance to develop inorganic-rich interfacial chemistry for lithium-ion batteries under extreme operating conditions.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"96 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-01-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142986622","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}
Junxiang Liu, Kangmin Wang, Liqiu Wan, Xianhui Yang, Bijin Li
Reported herein is the first example of a ruthenium-catalyzed C–H activation/annulation of phenothiazine-3-carbaldehydes to construct structurally diverse pyrido[3,4-c]phenothiazin-3-iums with dual-emission characteristics. Novel organic single-molecule white-light materials based on pyrido[3,4-c]phenothiazin-3-iums with dual-emission and thermally activated delayed fluorescence (TADF) characteristics have been developed for the first time herein. Furthermore, the dual-emission molecule could be fabricated as water-dispersed NPs, which could be applied in two-channel emission intensity ratio imaging to observe the intercellular structure and can specifically target the cell membrane.
{"title":"Ruthenium-catalyzed C–H bond activation and annulation of phenothiazine-3-carbaldehydes: facile access to dual-emission materials","authors":"Junxiang Liu, Kangmin Wang, Liqiu Wan, Xianhui Yang, Bijin Li","doi":"10.1039/d4sc07825j","DOIUrl":"https://doi.org/10.1039/d4sc07825j","url":null,"abstract":"Reported herein is the first example of a ruthenium-catalyzed C–H activation/annulation of phenothiazine-3-carbaldehydes to construct structurally diverse pyrido[3,4-<em>c</em>]phenothiazin-3-iums with dual-emission characteristics. Novel organic single-molecule white-light materials based on pyrido[3,4-<em>c</em>]phenothiazin-3-iums with dual-emission and thermally activated delayed fluorescence (TADF) characteristics have been developed for the first time herein. Furthermore, the dual-emission molecule could be fabricated as water-dispersed NPs, which could be applied in two-channel emission intensity ratio imaging to observe the intercellular structure and can specifically target the cell membrane.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"42 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-01-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142986623","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}
Xiaoyu Fang, Ji Yong Choi, Chenwei Lu, Elizabeth Reichert, Hoai T. B. Pham, Jihye Park
Morphology control of electrically conductive metal-organic frameworks (EC-MOFs) can be a powerful means to tune their surface area and carrier transport pathways, particularly beneficial for energy conversion and storage. However, controlling EC-MOFs’ morphology is underexplored due to the uncontrollable crystal nucleation and rapid growth kinetics. This work introduces a microwave-assisted strategy to readily synthesize Cu-HHTP (HHTP = 2,3,6,7,10,11-hexahydroxytriphenylene) with controlled morphologies. We employed modulators to facilitate particles’ directional growth to 1D and 2D crystals. Meanwhile, we found that ultrasonication can manipulate crystal seeding, yielding 0D spherical Cu-HHTP crystals. Electronic conductivity measurements suggest that the isotropic nature of the 0D crystals allows a conductivity of 7.34 × 10-1 S cm-1, much higher than 1D and 2D counterparts’. Additionally, the controlled 0D morphology enhanced the material’s capacitance and effective surface area and significantly improved its photocurrent response. These findings underscore the pivotal impact of controlled morphology in optimizing EC-MOFs’ physicochemical properties.
{"title":"From 0D to 2D: Microwave-assisted Synthesis of Electrically Conductive Metal-Organic Frameworks with Controlled Morphologies","authors":"Xiaoyu Fang, Ji Yong Choi, Chenwei Lu, Elizabeth Reichert, Hoai T. B. Pham, Jihye Park","doi":"10.1039/d4sc07025a","DOIUrl":"https://doi.org/10.1039/d4sc07025a","url":null,"abstract":"Morphology control of electrically conductive metal-organic frameworks (EC-MOFs) can be a powerful means to tune their surface area and carrier transport pathways, particularly beneficial for energy conversion and storage. However, controlling EC-MOFs’ morphology is underexplored due to the uncontrollable crystal nucleation and rapid growth kinetics. This work introduces a microwave-assisted strategy to readily synthesize Cu-HHTP (HHTP = 2,3,6,7,10,11-hexahydroxytriphenylene) with controlled morphologies. We employed modulators to facilitate particles’ directional growth to 1D and 2D crystals. Meanwhile, we found that ultrasonication can manipulate crystal seeding, yielding 0D spherical Cu-HHTP crystals. Electronic conductivity measurements suggest that the isotropic nature of the 0D crystals allows a conductivity of 7.34 × 10<small><sup>-1</sup></small> S cm<small><sup>-1</sup></small>, much higher than <strong>1D and 2D counterparts’</strong>. Additionally, the controlled 0D morphology enhanced the material’s capacitance and effective surface area and significantly improved its photocurrent response. These findings underscore the pivotal impact of controlled morphology in optimizing EC-MOFs’ physicochemical properties.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"96 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-01-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142986851","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}
Sara Bonfante, Theo Tanner, Christian Lorber, Jason Martin Lynam, Antoine Simonneau, John M. Slattery
Polarity reversal, or “umpolung”, is a widely acknowledged strategy to allow organic functional groups amenable to react in alternative ways to the usual preference set by their electronic features. In this article, we demonstrate that cyclohexyne umpolung, realized through complexation to zirconocene, makes the small strained cycloalkyne amenable to C–F bond functionalisation. Such strong bond activation chemistry is unprecedented in “free” aryne and strained alkyne chemistry. Our study also reveals that the reactivity of the Zr-cyclohexyne complex is highly sensitive to the degree of fluorination of the heteroarene. In addition, parasitic reactions of the ancillary ligand PMe3 were observed when pentafluoropyridine was the substrate.
{"title":"Zirconium-Mediated Carbon-Fluorine Bond Functionalisation Through Cyclohexyne “Umpolung”","authors":"Sara Bonfante, Theo Tanner, Christian Lorber, Jason Martin Lynam, Antoine Simonneau, John M. Slattery","doi":"10.1039/d4sc08522a","DOIUrl":"https://doi.org/10.1039/d4sc08522a","url":null,"abstract":"Polarity reversal, or “umpolung”, is a widely acknowledged strategy to allow organic functional groups amenable to react in alternative ways to the usual preference set by their electronic features. In this article, we demonstrate that cyclohexyne umpolung, realized through complexation to zirconocene, makes the small strained cycloalkyne amenable to C–F bond functionalisation. Such strong bond activation chemistry is unprecedented in “free” aryne and strained alkyne chemistry. Our study also reveals that the reactivity of the Zr-cyclohexyne complex is highly sensitive to the degree of fluorination of the heteroarene. In addition, parasitic reactions of the ancillary ligand PMe<small><sub>3</sub></small> were observed when pentafluoropyridine was the substrate.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"109 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-01-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142986846","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}
Zi-Jun Liang, Fang-Di Dong, Le Ye, Kai Zheng, Ding-Yi Hu, Xi Feng, Wen-Yu Su, Zhi-Shuo Wang, Mu-Yang Zhou, Zi-Luo Fang, Dong-Dong Zhou, Jie-Peng Zhang, Xiao-Ming Chen
The separation of C6 cyclic hydrocarbons (benzene, cyclohexene, and cyclohexane) is one of the most challenging chemical separations in the petrochemical industries. Herein, we design and synthesize a new SOD-topology metal azolate framework (MAF) with aperture gating behaviour controlled by C‒Br‧‧‧N halogen bonds, which exhibits distinct temperature- and guest-dependent adsorption behaviours for benzene/cyclohexene/cyclohexane. More importantly, the MAF enables the efficient purification of benzene from its binary and ternary mixtures (selectivity up to 113±2; purity up to 98%+), which is the highest record for benzene/cyclohexane/cyclohexene separation to date. Single-crystal diffraction analyses and computational simulations revealed that halogen bonds play a critical role in the gating and diffusion process, which is the first example of halogen-bonding controlled gating for highly effective adsorptive separation.
{"title":"Introducing halogen-bonded gates in zeolitic frameworks for efficient benzene/cyclohexene/cyclohexane separation","authors":"Zi-Jun Liang, Fang-Di Dong, Le Ye, Kai Zheng, Ding-Yi Hu, Xi Feng, Wen-Yu Su, Zhi-Shuo Wang, Mu-Yang Zhou, Zi-Luo Fang, Dong-Dong Zhou, Jie-Peng Zhang, Xiao-Ming Chen","doi":"10.1039/d4sc06624c","DOIUrl":"https://doi.org/10.1039/d4sc06624c","url":null,"abstract":"The separation of C<small><sub>6</sub></small> cyclic hydrocarbons (benzene, cyclohexene, and cyclohexane) is one of the most challenging chemical separations in the petrochemical industries. Herein, we design and synthesize a new SOD-topology metal azolate framework (MAF) with aperture gating behaviour controlled by C‒Br‧‧‧N halogen bonds, which exhibits distinct temperature- and guest-dependent adsorption behaviours for benzene/cyclohexene/cyclohexane. More importantly, the MAF enables the efficient purification of benzene from its binary and ternary mixtures (selectivity up to 113±2; purity up to 98%+), which is the highest record for benzene/cyclohexane/cyclohexene separation to date. Single-crystal diffraction analyses and computational simulations revealed that halogen bonds play a critical role in the gating and diffusion process, which is the first example of halogen-bonding controlled gating for highly effective adsorptive separation.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"24 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-01-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142981317","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}
Acentric crystalline materials are the cornerstone of numerous cutting-edge technologies and have been highly sought-after, but they are difficult to construct controllably. Herein, by introducing a new p-block element to break the symmetrical environment of the d0 transition metal in the centric matrix TiTe3O8, a novel acentric tellurite sulfate, namely Ti(TeO3)(SO4), was successfully constructed. In its structure, two types of p-block element-centered oxo-anionic groups, i.e. [TeO3] and [SO4], induce [TiO6] an out-of-center distortion along the local C3[111] direction, which is rare in titanium oxides containing lone-pair cation. The synergy of distorted [TiO6] octahedron, lone-pair [TeO3] pyramid and rigid [SO4] tetrahedron within its structure induces a strong second harmonic generation (SHG) response of 11.6×KDP (KH2PO4), the largest value among mercury-free sulfates. Additionally, Ti(TeO3)(SO4) also shows the largest birefringence (0.145) among sulfates possessing SHG response of more than ten times of KDP, showing huge potential as a nonlinear optical material. The successful implementation of the strategy of inducing intra-octahedral distortion in d0 transition metal by different p-block elements provides new opportunities for constructing acentric structures and exploiting outstanding nonlinear optically active sulfates.
{"title":"Different p-Block Elements Induce C3[111] Octahedral Distortion on Titanium to Generate Intense Nonlinear Effect","authors":"Zhenhua Li, Zhengli Liang, Jiahao Wan, Lehui Liu, Chunxiang Wu, Ping Wang, Xing-Xing Jiang, Zheshuai Lin, Hongming Liu","doi":"10.1039/d4sc06620k","DOIUrl":"https://doi.org/10.1039/d4sc06620k","url":null,"abstract":"Acentric crystalline materials are the cornerstone of numerous cutting-edge technologies and have been highly sought-after, but they are difficult to construct controllably. Herein, by introducing a new p-block element to break the symmetrical environment of the d0 transition metal in the centric matrix TiTe3O8, a novel acentric tellurite sulfate, namely Ti(TeO3)(SO4), was successfully constructed. In its structure, two types of p-block element-centered oxo-anionic groups, i.e. [TeO3] and [SO4], induce [TiO6] an out-of-center distortion along the local C3[111] direction, which is rare in titanium oxides containing lone-pair cation. The synergy of distorted [TiO6] octahedron, lone-pair [TeO3] pyramid and rigid [SO4] tetrahedron within its structure induces a strong second harmonic generation (SHG) response of 11.6×KDP (KH2PO4), the largest value among mercury-free sulfates. Additionally, Ti(TeO3)(SO4) also shows the largest birefringence (0.145) among sulfates possessing SHG response of more than ten times of KDP, showing huge potential as a nonlinear optical material. The successful implementation of the strategy of inducing intra-octahedral distortion in d0 transition metal by different p-block elements provides new opportunities for constructing acentric structures and exploiting outstanding nonlinear optically active sulfates.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"4 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-01-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142981318","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}
![[double bond, length as m-dash]](https://www.rsc.org/images/entities/char_e001.gif)
N double bond and a thiourea moiety capable of hydrogen bonding. The scalable two-step synthesis allowed us to prepare 23 thiosemicarbazones to systematically elucidate their optical properties. Attaching various functional groups, extended π-systems, and heterocycles enabled fine-tuning of their absorption profiles. UV light illumination converts thiosemicarbazones from the stable E-isomer to the metastable Z-isomer, exhibiting both negative and positive T-type photochromism, a wide range of thermal half-lives, PSS values up to 92%, and high fatigue resistance. Substituting the C
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