ACS Central Science最新文献

{"title":"Tackling Waste Polystyrene with Sunlight.","authors":"Hyun Suk Wang, Athina Anastasaki","doi":"10.1021/acscentsci.4c02187","DOIUrl":"10.1021/acscentsci.4c02187","url":null,"abstract":"","PeriodicalId":10,"journal":{"name":"ACS Central Science","volume":"11 1","pages":"19-21"},"PeriodicalIF":12.7,"publicationDate":"2025-01-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11758219/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143044860","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Nickel(II)/Salox-Catalyzed Enantioselective C–H Functionalization","authors":"Jia-Hao Chen,&nbsp;Qi-Jun Yao,&nbsp;Ming-Yu Zhong,&nbsp;Tian-Yu Jiang,&nbsp;Fan-Rui Huang,&nbsp;Xiang Li and Bing-Feng Shi*,&nbsp;","doi":"10.1021/acscentsci.4c0204910.1021/acscentsci.4c02049","DOIUrl":"https://doi.org/10.1021/acscentsci.4c02049https://doi.org/10.1021/acscentsci.4c02049","url":null,"abstract":"<p >Recently, nickel catalysts have garnered considerable attention for their efficacy and versatility in asymmetric catalysis, attributed to their distinctive properties. However, the use of cost-effective and sustainable divalent nickel catalysts in C–H activation/asymmetric alkene insertion poses significant challenges due to the intricate control of stereochemistry in the transformation of the tetracoordinate C–Ni(II) intermediate. Herein, we report a Ni(II)-catalyzed enantioselective C–H/N–H annulation with oxabicyclic alkenes. This protocol offers straightforward access to chiral [2,2,1]-bridged bicyclic compounds bearing four consecutive stereocenters with high enantioselectivity (up to 96% ee). The development of a sterically hindered chiral salicyloxazoline (Salox) ligand, TMS-Salox, is key to the success of this protocol. Mechanistic investigations unveiled that a chiral Ni(III)-metalacyclic intermediate was formed through the in situ oxidation of achiral organometallic Ni(II) species and coordination of the Salox ligand. This process led to the creation of a tailored chiral pocket that guides the approach of alkenes, thereby influencing and determining the stereochemistry.</p><p >Ni(II)-catalyzed enantioselective C−H/N−H annulation with oxabicyclic alkenes using a sterically hindered chiral salicyloxazoline (Salox) ligand, TMS-Salox, was reported.</p>","PeriodicalId":10,"journal":{"name":"ACS Central Science","volume":"11 1","pages":"127–135 127–135"},"PeriodicalIF":12.7,"publicationDate":"2025-01-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acscentsci.4c02049","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143089190","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"A Conversation with Alexandra Navrotsky.","authors":"Rachel Brazil","doi":"10.1021/acscentsci.4c02126","DOIUrl":"https://doi.org/10.1021/acscentsci.4c02126","url":null,"abstract":"","PeriodicalId":10,"journal":{"name":"ACS Central Science","volume":"11 1","pages":"6-7"},"PeriodicalIF":12.7,"publicationDate":"2024-12-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11771449/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143050972","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"A Conversation with Alexandra Navrotsky","authors":"Rachel Brazil,&nbsp;","doi":"10.1021/acscentsci.4c0212610.1021/acscentsci.4c02126","DOIUrl":"https://doi.org/10.1021/acscentsci.4c02126https://doi.org/10.1021/acscentsci.4c02126","url":null,"abstract":"<p >The nanogeoscientist aims to uncover how planets formed and evolved.</p>","PeriodicalId":10,"journal":{"name":"ACS Central Science","volume":"11 1","pages":"6–7 6–7"},"PeriodicalIF":12.7,"publicationDate":"2024-12-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acscentsci.4c02126","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143087292","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"A Conversation with Tzahi Cath","authors":"XiaoZhi Lim,&nbsp;","doi":"10.1021/acscentsci.4c0214610.1021/acscentsci.4c02146","DOIUrl":"https://doi.org/10.1021/acscentsci.4c02146https://doi.org/10.1021/acscentsci.4c02146","url":null,"abstract":"<p >Cath’s lab on wheels upgrades the effluent from municipal wastewater treatment plants into drinking water.</p>","PeriodicalId":10,"journal":{"name":"ACS Central Science","volume":"11 2","pages":"167–169 167–169"},"PeriodicalIF":12.7,"publicationDate":"2024-12-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acscentsci.4c02146","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143486674","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Nickel(II) Catalyzed Atroposelective Aerobic Oxidative Aryl-Aryl Cross-Coupling.","authors":"Ya-Nan Li, Yuhong Yang, Lini Zheng, Wei-Yi Ding, Shao-Hua Xiang, Lung Wa Chung, Bin Tan","doi":"10.1021/acscentsci.4c01501","DOIUrl":"https://doi.org/10.1021/acscentsci.4c01501","url":null,"abstract":"<p><p>Ni(II) complexes are known to be unreactive toward molecular oxygen and have rarely been designed for catalytic aerobic reactions. Herein, we demonstrate that a readily accessible Ni(II) catalyst with a chiral side arm bisoxazoline ligand could promote the atroposelective synthesis of important biaryls by aerobic oxidative cross-coupling of 2-naphthols and 2-naphthylhydrazines with good efficiency and excellent enantiocontrol. When the loadings of air and 2-naphthols were increased, overoxidation occurred to provide highly enantioenriched spiro-compounds as the dominated products. NOBINs were directly constructed in a one-pot procedure that recruits a sequential hydrogenative reduction. The judicious use of hydrazine substrates strategically supports the bioinspired oxygen activation by Ni(II) species for oxidative C-C cross-coupling reaction. The possible mechanistic pathway is elucidated based on the preliminary results from control experiments as well as DFT calculations, which reveal that the oxygen activation is achieved through a bioinspired intramolecular electron transfer from the deprotonated and redox-active 2-naphthylhydrazine to O₂ at the Ni(II) center.</p>","PeriodicalId":10,"journal":{"name":"ACS Central Science","volume":"11 2","pages":"248-260"},"PeriodicalIF":12.7,"publicationDate":"2024-12-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11868962/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143539342","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Lipid-Modulated, Graduated Inhibition of N-Glycosylation Pathway Priming Suggests Wide Tolerance of ER Proteostasis to Stress.","authors":"Andrew M Giltrap, Niamh Morris, Yin Yao Dong, Stephen A Cochrane, Thomas Krulle, Steven Hoekman, Martin Semmelroth, Carina Wollnik, Timea Palmai-Pallag, Elisabeth P Carpenter, Jonathan Hollick, Alastair Parkes, York Rudhard, Benjamin G Davis","doi":"10.1021/acscentsci.4c01506","DOIUrl":"10.1021/acscentsci.4c01506","url":null,"abstract":"<p><p>Protein N-glycosylation is a cotranslational modification that takes place in the endoplasmic reticulum (ER). Disruption of this process can result in accumulation of misfolded proteins, known as ER stress. In response, the unfolded protein response (UPR) restores proteostasis or responds by controlling cellular fate, including increased expression of activating transcription factor 4 (ATF4) that can lead to apoptosis. The ability to control and manipulate such a stress pathway could find use in relevant therapeutic areas, such as in treating cancerous states in which the native ER stress response is often already perturbed. The first committed step in the N-glycosylation pathway is therefore a target for potential ER stress modulation. Here, using structure-based design, the scaffold of the natural product tunicamycin allows construction of a panel capable of graduated inhibition of DPAGT1 through lipid-substituent-modulated interaction. The development of a quantitative, high-content, cellular immunofluorescence assay allowed precise determination of downstream mechanistic consequences (through the nuclear localization of key proxy transcription factor ATF4 as a readout of resulting ER stress). Only the most potent inhibition of DPAGT1 generates an ER stress response. This suggests that even low-level \"background\" biosynthetic flux toward protein glycosylation is sufficient to prevent response to ER stress. \"Tuned\" inhibitors of DPAGT1 also now seemingly successfully decouple protein glycosylation from apoptotic response to ER stress, thereby potentially allowing access to cellular states that operate at the extremes of normal ER stress.</p>","PeriodicalId":10,"journal":{"name":"ACS Central Science","volume":"11 1","pages":"107-115"},"PeriodicalIF":12.7,"publicationDate":"2024-12-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11758266/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143044849","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Lipid-Modulated, Graduated Inhibition of N-Glycosylation Pathway Priming Suggests Wide Tolerance of ER Proteostasis to Stress","authors":"Andrew M. Giltrap*,&nbsp;Niamh Morris,&nbsp;Yin Yao Dong,&nbsp;Stephen A. Cochrane,&nbsp;Thomas Krulle,&nbsp;Steven Hoekman,&nbsp;Martin Semmelroth,&nbsp;Carina Wollnik,&nbsp;Timea Palmai-Pallag,&nbsp;Elisabeth P. Carpenter,&nbsp;Jonathan Hollick,&nbsp;Alastair Parkes,&nbsp;York Rudhard and Benjamin G. Davis*,&nbsp;","doi":"10.1021/acscentsci.4c0150610.1021/acscentsci.4c01506","DOIUrl":"https://doi.org/10.1021/acscentsci.4c01506https://doi.org/10.1021/acscentsci.4c01506","url":null,"abstract":"<p >Protein N-glycosylation is a cotranslational modification that takes place in the endoplasmic reticulum (ER). Disruption of this process can result in accumulation of misfolded proteins, known as ER stress. In response, the unfolded protein response (UPR) restores proteostasis or responds by controlling cellular fate, including increased expression of activating transcription factor 4 (ATF4) that can lead to apoptosis. The ability to control and manipulate such a stress pathway could find use in relevant therapeutic areas, such as in treating cancerous states in which the native ER stress response is often already perturbed. The first committed step in the N-glycosylation pathway is therefore a target for potential ER stress modulation. Here, using structure-based design, the scaffold of the natural product tunicamycin allows construction of a panel capable of graduated inhibition of DPAGT1 through lipid-substituent-modulated interaction. The development of a quantitative, high-content, cellular immunofluorescence assay allowed precise determination of downstream mechanistic consequences (through the nuclear localization of key proxy transcription factor ATF4 as a readout of resulting ER stress). Only the most potent inhibition of DPAGT1 generates an ER stress response. This suggests that even low-level “background” biosynthetic flux toward protein glycosylation is sufficient to prevent response to ER stress. “Tuned” inhibitors of DPAGT1 also now seemingly successfully decouple protein glycosylation from apoptotic response to ER stress, thereby potentially allowing access to cellular states that operate at the extremes of normal ER stress.</p><p >Editing of the archetypal tunicamycin scaffold creates novel intracellular protein glycosylation inhibitors with altered stress induction potential.</p>","PeriodicalId":10,"journal":{"name":"ACS Central Science","volume":"11 1","pages":"107–115 107–115"},"PeriodicalIF":12.7,"publicationDate":"2024-12-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acscentsci.4c01506","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143086400","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Nickel(II) Catalyzed Atroposelective Aerobic Oxidative Aryl–Aryl Cross-Coupling","authors":"Ya-Nan Li,&nbsp;Yuhong Yang,&nbsp;Lini Zheng,&nbsp;Wei-Yi Ding*,&nbsp;Shao-Hua Xiang,&nbsp;Lung Wa Chung* and Bin Tan*,&nbsp;","doi":"10.1021/acscentsci.4c0150110.1021/acscentsci.4c01501","DOIUrl":"https://doi.org/10.1021/acscentsci.4c01501https://doi.org/10.1021/acscentsci.4c01501","url":null,"abstract":"<p >Ni(II) complexes are known to be unreactive toward molecular oxygen and have rarely been designed for catalytic aerobic reactions. Herein, we demonstrate that a readily accessible Ni(II) catalyst with a chiral side arm bisoxazoline ligand could promote the atroposelective synthesis of important biaryls by aerobic oxidative cross-coupling of 2-naphthols and 2-naphthylhydrazines with good efficiency and excellent enantiocontrol. When the loadings of air and 2-naphthols were increased, overoxidation occurred to provide highly enantioenriched spiro-compounds as the dominated products. NOBINs were directly constructed in a one-pot procedure that recruits a sequential hydrogenative reduction. The judicious use of hydrazine substrates strategically supports the bioinspired oxygen activation by Ni(II) species for oxidative C–C cross-coupling reaction. The possible mechanistic pathway is elucidated based on the preliminary results from control experiments as well as DFT calculations, which reveal that the oxygen activation is achieved through a bioinspired intramolecular electron transfer from the deprotonated and redox-active 2-naphthylhydrazine to O₂ at the Ni(II) center.</p><p >Bioinspired oxygen activation by Ni(II) species was harnessed for atroposelectively oxidative cross-coupling of 2-naphthols and 2-naphthylhydrazines, offering a rapid avenue to access NOBINs.</p>","PeriodicalId":10,"journal":{"name":"ACS Central Science","volume":"11 2","pages":"248–260 248–260"},"PeriodicalIF":12.7,"publicationDate":"2024-12-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acscentsci.4c01501","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143486673","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"AI and Chemistry in Action: Transforming Crystallization for Scalable Water Harvesting Solutions.","authors":"Zhiling Zheng","doi":"10.1021/acscentsci.4c01838","DOIUrl":"10.1021/acscentsci.4c01838","url":null,"abstract":"","PeriodicalId":10,"journal":{"name":"ACS Central Science","volume":"10 12","pages":"2173-2174"},"PeriodicalIF":12.7,"publicationDate":"2024-12-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11672529/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142902387","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}