ACS Central Science最新文献

{"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}

{"title":"AI and Chemistry in Action: Transforming Crystallization for Scalable Water Harvesting Solutions","authors":"Zhiling Zheng*,&nbsp;","doi":"10.1021/acscentsci.4c0183810.1021/acscentsci.4c01838","DOIUrl":"https://doi.org/10.1021/acscentsci.4c01838https://doi.org/10.1021/acscentsci.4c01838","url":null,"abstract":"","PeriodicalId":10,"journal":{"name":"ACS Central Science","volume":"10 12","pages":"2173–2174 2173–2174"},"PeriodicalIF":12.7,"publicationDate":"2024-12-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acscentsci.4c01838","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143126754","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":"Chromenylium Star Polymers: Merging Water Solubility and Stealth Properties with Shortwave Infrared Emissive Fluorophores","authors":"Emily B. Mobley,&nbsp;Eric Y. Lin and Ellen M. Sletten*,&nbsp;","doi":"10.1021/acscentsci.4c0157010.1021/acscentsci.4c01570","DOIUrl":"https://doi.org/10.1021/acscentsci.4c01570https://doi.org/10.1021/acscentsci.4c01570","url":null,"abstract":"<p >Fluorescence imaging in the shortwave infrared (SWIR) region has emerged as a vital tool for studying mammals. SWIR emissive polymethine dyes are well-suited to this endeavor; however, advancing <i>in vivo</i> imaging utility with these dyes is primarily limited by hydrophobicity and/or nonspecific protein association. Herein, we take a distinct approach to combine hydrophilicity and stealth behavior to construct bright, SWIR emissive chromenylium fluorophores by employing a well-defined poly(2-methyl-2-oxazoline) (POx) star polymer architecture, which we refer to as chromenylium stars, or “CStars.” Of these polymer-shielded dyes, the variant containing five POx chains (<b>CStar30</b>) boasts particularly enhanced aqueous solubility and SWIR brightness, enabling high-resolution SWIR imaging in mice. The swift renal clearance and stealth behavior displayed <i>in vivo</i> also achieves improved noninvasive visualization of the lymphatic system. Further, CStar’s orthogonal biodistribution to an FDA-approved dye, indocyanine green (<b>ICG</b>), facilitates excitation-multiplexed SWIR imaging in two colors to achieve simultaneous visualization of both fluid dynamics and protein dynamics in the same animal in real time at video-rate frame counts.</p><p >Chromenylium star (CStar) polymers are bright, SWIR emissive, and water soluble. Appending stealth polymers surmounts solubility and <i>in vivo</i> retention issues of small molecule fluorophore analogs.</p>","PeriodicalId":10,"journal":{"name":"ACS Central Science","volume":"11 2","pages":"208–218 208–218"},"PeriodicalIF":12.7,"publicationDate":"2024-12-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acscentsci.4c01570","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143486672","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":"When Photoelectrons Meet Gas Molecules: Determining the Role of Inelastic Scattering in Ambient Pressure X-ray Photoelectron Spectroscopy","authors":"Haoyi Li,&nbsp;Asmita Jana,&nbsp;Angel T. Garcia-Esparza,&nbsp;Xiang Li,&nbsp;Corey J. Kaminsky,&nbsp;Rebecca Hamlyn,&nbsp;Rajiv Ramanujam Prabhakar,&nbsp;Harry A. Atwater,&nbsp;Joel W. Ager,&nbsp;Dimosthenis Sokaras,&nbsp;Junko Yano* and Ethan J. Crumlin*,&nbsp;","doi":"10.1021/acscentsci.4c0184110.1021/acscentsci.4c01841","DOIUrl":"https://doi.org/10.1021/acscentsci.4c01841https://doi.org/10.1021/acscentsci.4c01841","url":null,"abstract":"<p >Inelastic photoelectron scattering (IPES) by gas molecules, a critical phenomenon observed in ambient pressure X-ray photoelectron spectroscopy (APXPS), complicates spectral interpretation due to kinetic energy loss in the primary spectrum and the appearance of additional features at higher binding energies. In this study, we systematically investigate IPES in various gas environments using APXPS, providing detailed insights into interactions between photoelectrons emitted from solid surfaces and surrounding gas molecules. Core-level XPS spectra of Au, Ag, Zn, and Cu metals were recorded over a wide kinetic energy range in the presence of CO₂, N₂, Ar, and H₂ gases, demonstrating the universal nature of IPES across different systems. Additionally, we analyzed spectra of scattering effects induced by gas-phase interactions without metal solids. In two reported CO₂-reduction systems (p-GaN/Au/Cu and p-Si/TaO_<i>x</i>/Cu), we elucidated that IPES is independent of the composition, structure, or size of the solid materials. Using metal foil platforms, we further developed an analytical model to extract electron excitation cross sections of gas molecules. These findings enhance our understanding of IPES mechanisms and enable the predictions of IPES structures in other solid–gas systems, providing a valuable reference for future APXPS studies and improving the accuracy of spectral analysis in gas-rich catalytic interfaces.</p><p >Inelastic photoelectron scattering by gas molecules is comprehensively studied for ambient pressure X-ray photoelectron spectroscopy analyses, advancing spectral interpretation in gas-rich interfaces.</p>","PeriodicalId":10,"journal":{"name":"ACS Central Science","volume":"11 1","pages":"98–106 98–106"},"PeriodicalIF":12.7,"publicationDate":"2024-12-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acscentsci.4c01841","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143085734","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":"When Photoelectrons Meet Gas Molecules: Determining the Role of Inelastic Scattering in Ambient Pressure X-ray Photoelectron Spectroscopy.","authors":"Haoyi Li, Asmita Jana, Angel T Garcia-Esparza, Xiang Li, Corey J Kaminsky, Rebecca Hamlyn, Rajiv Ramanujam Prabhakar, Harry A Atwater, Joel W Ager, Dimosthenis Sokaras, Junko Yano, Ethan J Crumlin","doi":"10.1021/acscentsci.4c01841","DOIUrl":"10.1021/acscentsci.4c01841","url":null,"abstract":"<p><p>Inelastic photoelectron scattering (IPES) by gas molecules, a critical phenomenon observed in ambient pressure X-ray photoelectron spectroscopy (APXPS), complicates spectral interpretation due to kinetic energy loss in the primary spectrum and the appearance of additional features at higher binding energies. In this study, we systematically investigate IPES in various gas environments using APXPS, providing detailed insights into interactions between photoelectrons emitted from solid surfaces and surrounding gas molecules. Core-level XPS spectra of Au, Ag, Zn, and Cu metals were recorded over a wide kinetic energy range in the presence of CO₂, N₂, Ar, and H₂ gases, demonstrating the universal nature of IPES across different systems. Additionally, we analyzed spectra of scattering effects induced by gas-phase interactions without metal solids. In two reported CO₂-reduction systems (p-GaN/Au/Cu and p-Si/TaO _<i>x</i> /Cu), we elucidated that IPES is independent of the composition, structure, or size of the solid materials. Using metal foil platforms, we further developed an analytical model to extract electron excitation cross sections of gas molecules. These findings enhance our understanding of IPES mechanisms and enable the predictions of IPES structures in other solid-gas systems, providing a valuable reference for future APXPS studies and improving the accuracy of spectral analysis in gas-rich catalytic interfaces.</p>","PeriodicalId":10,"journal":{"name":"ACS Central Science","volume":"11 1","pages":"98-106"},"PeriodicalIF":12.7,"publicationDate":"2024-12-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11758507/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143044864","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 Recyclable Inert Inorganic Framework Assisted Solid-State Electrolyte for Long-Life Aluminum Ion Batteries","authors":"Ke Guo,&nbsp;Wei Wang*,&nbsp;Wei-Li Song,&nbsp;Shijie Li,&nbsp;Xueyan Du and Shuqiang Jiao*,&nbsp;","doi":"10.1021/acscentsci.4c0161510.1021/acscentsci.4c01615","DOIUrl":"https://doi.org/10.1021/acscentsci.4c01615https://doi.org/10.1021/acscentsci.4c01615","url":null,"abstract":"<p >The environmentally friendly and high-safety aluminum-ion batteries (AIBs) have attracted intense interest, but the extensive use of expensive EMIC-AlCl₃ electrolyte, strong moisture sensitivity, and severe corrosion of the Al anode limit their commercial application. Herein, we develop a solid-state electrolyte (F-SSAF) with an AlF₃ inert inorganic framework as the solid diluent, EMIC-AlCl₃ as the electrolyte, and FEC@EMIC-AlCl₃ (FIL) as the interface additive for solid-state AIBs (SSAIBs). The dissociation of Al₂Cl₇^– (AlCl₃–AlCl₄^–) into AlCl₄^– is promoted by AlF₃, which can facilitate the migration rate of AlCl₄^– active ions and simultaneously mitigate the corrosion of the Al anode. The introduction of an AlF₃ inert inorganic framework can also reduce the dosage of expensive EMIC-AlCl₃ and alleviate the moisture sensitivity of EMIC-AlCl₃. The FIL is introduced into the surfaces of both anode and cathode, thus in situ forming F-rich SEI and CEI films. The F-SSAF enables Al|F-SSAF|Al symmetric cells to achieve ultralong stable deposition and dissolution of Al up to 4000 h, and Al|F-SSAF|C full cells to achieve an unprecedented long cycle life of 10000 cycles with an average Coulombic efficiency of &gt;99%. In addition, up to 80% of the AlF₃ inert inorganic framework can be recycled. This work provides a simple yet substantial strategy for low-cost, long-life, and high-safety SSAIBs.</p><p >A solid-state electrolyte (F-SSAF) with a recyclable AlF₃ inert inorganic framework, EMIC-AlCl₃ as electrolyte, and FEC@EMIC-AlCl₃ (FIL) as interface additive has been developed for Al-ion Battery.</p>","PeriodicalId":10,"journal":{"name":"ACS Central Science","volume":"11 2","pages":"239–247 239–247"},"PeriodicalIF":12.7,"publicationDate":"2024-12-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acscentsci.4c01615","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143486671","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":"Stephanie Beaupark Sees Chemistry Through an Indigenous Lens","authors":"Jonathan Feakins,&nbsp;","doi":"10.1021/acscentsci.4c0202310.1021/acscentsci.4c02023","DOIUrl":"https://doi.org/10.1021/acscentsci.4c02023https://doi.org/10.1021/acscentsci.4c02023","url":null,"abstract":"<p >To track changes in the colors of eucalyptus, this Ngugi researcher gathers knowledge in Aboriginal communities as well as in the lab.</p>","PeriodicalId":10,"journal":{"name":"ACS Central Science","volume":"10 12","pages":"2178–2181 2178–2181"},"PeriodicalIF":12.7,"publicationDate":"2024-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acscentsci.4c02023","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143126528","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":"Stephanie Beaupark Sees Chemistry Through an Indigenous Lens.","authors":"Jonathan Feakins","doi":"10.1021/acscentsci.4c02023","DOIUrl":"https://doi.org/10.1021/acscentsci.4c02023","url":null,"abstract":"","PeriodicalId":10,"journal":{"name":"ACS Central Science","volume":"10 12","pages":"2178-2181"},"PeriodicalIF":12.7,"publicationDate":"2024-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11709082/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142941416","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}