ACS Central Science最新文献

{"title":"Divergent and Enantioselective Synthesis of Three Types of Chiral Polycyclic N‑Heterocycles via Copper-Catalyzed Dearomative Cyclization.","authors":"Wen-Feng Luo, Li-Gao Liu, Yan-Xin Zheng, Miao Sun, Xin Lu, Bo Zhou, Long-Wu Ye, Long Li","doi":"10.1021/acscentsci.5c00248","DOIUrl":"10.1021/acscentsci.5c00248","url":null,"abstract":"<p><p>Significant advancements have been made in the catalytic asymmetric dearomatization of indoles for constructing valuable chiral polycyclic N-heterocycles. However, the asymmetric dearomative cyclopropanation of indoles continues to pose a formidable challenge. Furthermore, the diverse transformations of indoline-fused cyclopropanes via strain release remain largely unexplored, potentially unveiling new chemistry. Here, we disclose a Cu-catalyzed asymmetric dearomative cyclopropanation of indole-diynes and subsequent [3 + 2] cycloaddition with oxygen, facilitating the divergent and atom-economical synthesis of enantioenriched cyclopropane- and 1,2-dioxolane-fused indolines with moderate to excellent yields and generally outstanding diastereo- and enantioselectivities with broad substrate scope. Importantly, this protocol not only represents the first asymmetric dearomative cyclopropanation of indoles utilizing alkynes as carbene precursors but also constitutes the first catalytic asymmetric construction of chiral 1,2-dioxolanes with high stereoselectivity. Interestingly, Brønsted acid-promoted ring-opening and rearrangement of cyclopropane-fused indolines display distinctive chemoselectivity to afford enantioenriched cyclohepta-[<i>b</i>]-indoles in good to excellent efficiency and enantiocontrol. In addition, both potential reaction pathways and the origins of chiral control within this Cu-catalyzed asymmetric tandem sequence are robustly supported by control experiments and theoretical calculations.</p>","PeriodicalId":10,"journal":{"name":"ACS Central Science","volume":"11 5","pages":"805-815"},"PeriodicalIF":12.7,"publicationDate":"2025-05-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12123464/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144197671","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":"The Characteristically Slow Proton Transfer Coupled to Platinum Oxidation in Alkaline Polyelectrolyte as Elucidated at the Molecular Level","authors":"Mo-Li Huang,&nbsp;Wenhui Ling,&nbsp;Zhangrui Wang,&nbsp;Yang Lu,&nbsp;Hong-Ning Shen,&nbsp;Li-Wen Wu,&nbsp;Chiyan Liu,&nbsp;Yong Han,&nbsp;Zhi Liu*,&nbsp;Bo Yang* and Yi-Fan Huang*,&nbsp;","doi":"10.1021/acscentsci.5c0012410.1021/acscentsci.5c00124","DOIUrl":"https://doi.org/10.1021/acscentsci.5c00124https://doi.org/10.1021/acscentsci.5c00124","url":null,"abstract":"<p >The proton transfer in alkaline polyelectrolyte membrane (APEM)/electrode interfaces is significantly coupled to the electrochemical reactions in energy conversion and green synthesis. The OH^– in APEM/electrode interfaces is characteristically without cations in the surroundings but ambiguous in proton-transfer-coupled electrochemical reactions at the molecular level. Here we employed <i>in situ</i> electrochemical surface-enhanced Raman spectroscopy and high-level quantum-chemical calculations to elucidate the proton transfer in the APEM/Pt interface by using electrochemical Pt oxidation as an indicator. To manifest the characters in APEM, a comparison to that in conventional NaOH solution was made. With the similar electron transfer of Pt oxidation in both APEM and NaOH, the driving force and rate of proton transfer were distinguished respectively according to the onset oxidation potential and morphology of Pt nanoparticles, which suggested the slow proton transfer in an APEM/Pt interface. The similar vibrational fingerprints of subsurface oxygenated intermediates in both APEM and NaOH solution evidenced the characteristically slow proton transfer in an APEM/Pt interface. The high-level quantum-chemical calculations combined with molecular dynamics simulation showed that the driving force of proton transfer in APEM was reduced since OH^– was coordinated by more water molecules in its hydration shell. The characteristically slow interfacial proton transfer may be universally coupled to electrochemical reactions in devices with APEMs.</p><p >The proton-transfer-coupled Pt oxidation in the alkaline polyelectrolyte membrane/Pt interface was elucidated to be characteristically slow due to the H₂O coordination number of interfacial OH⁻.</p>","PeriodicalId":10,"journal":{"name":"ACS Central Science","volume":"11 5","pages":"791–796 791–796"},"PeriodicalIF":12.7,"publicationDate":"2025-04-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acscentsci.5c00124","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144146436","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":"The Characteristically Slow Proton Transfer Coupled to Platinum Oxidation in Alkaline Polyelectrolyte as Elucidated at the Molecular Level.","authors":"Mo-Li Huang, Wenhui Ling, Zhangrui Wang, Yang Lu, Hong-Ning Shen, Li-Wen Wu, Chiyan Liu, Yong Han, Zhi Liu, Bo Yang, Yi-Fan Huang","doi":"10.1021/acscentsci.5c00124","DOIUrl":"10.1021/acscentsci.5c00124","url":null,"abstract":"<p><p>The proton transfer in alkaline polyelectrolyte membrane (APEM)/electrode interfaces is significantly coupled to the electrochemical reactions in energy conversion and green synthesis. The OH^- in APEM/electrode interfaces is characteristically without cations in the surroundings but ambiguous in proton-transfer-coupled electrochemical reactions at the molecular level. Here we employed <i>in situ</i> electrochemical surface-enhanced Raman spectroscopy and high-level quantum-chemical calculations to elucidate the proton transfer in the APEM/Pt interface by using electrochemical Pt oxidation as an indicator. To manifest the characters in APEM, a comparison to that in conventional NaOH solution was made. With the similar electron transfer of Pt oxidation in both APEM and NaOH, the driving force and rate of proton transfer were distinguished respectively according to the onset oxidation potential and morphology of Pt nanoparticles, which suggested the slow proton transfer in an APEM/Pt interface. The similar vibrational fingerprints of subsurface oxygenated intermediates in both APEM and NaOH solution evidenced the characteristically slow proton transfer in an APEM/Pt interface. The high-level quantum-chemical calculations combined with molecular dynamics simulation showed that the driving force of proton transfer in APEM was reduced since OH^- was coordinated by more water molecules in its hydration shell. The characteristically slow interfacial proton transfer may be universally coupled to electrochemical reactions in devices with APEMs.</p>","PeriodicalId":10,"journal":{"name":"ACS Central Science","volume":"11 5","pages":"791-796"},"PeriodicalIF":12.7,"publicationDate":"2025-04-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12123459/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144197699","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":"Docking 14 Million Virtual Isoquinuclidines against the μ and κ Opioid Receptors Reveals Dual Antagonists-Inverse Agonists with Reduced Withdrawal Effects.","authors":"Seth F Vigneron, Shohei Ohno, Joao Braz, Joseph Y Kim, Oh Sang Kweon, Chase Webb, Christian B Billesbølle, Karthik Srinivasan, Karnika Bhardwaj, John J Irwin, Aashish Manglik, Allan I Basbaum, Jonathan A Ellman, Brian K Shoichet","doi":"10.1021/acscentsci.5c00052","DOIUrl":"10.1021/acscentsci.5c00052","url":null,"abstract":"<p><p>Large library docking of tangible molecules has revealed potent ligands across many targets. While make-on-demand libraries now exceed 75 billion enumerated molecules, their synthetic routes are dominated by a few reaction types, reducing diversity and inevitably leaving many interesting bioactive-like chemotypes unexplored. Here, we investigate the large-scale enumeration and targeted docking of isoquinuclidines. These \"natural-product-like\" molecules are rare in current libraries and are functionally congested, making them interesting as receptor probes. Using a modular, four-component reaction scheme, we built and docked a virtual library of over 14.6 million isoquinuclidines against both the μ- and κ-opioid receptors (MOR and KOR, respectively). Synthesis and experimental testing of 18 prioritized compounds found nine ligands with low μM affinities. Structure-based optimization revealed low- and sub-nM antagonists and inverse agonists targeting both receptors. Cryo-electron microscopy structures illuminate the origins of activity on each target. In mouse behavioral studies, a potent joint MOR-antagonist and KOR-inverse-agonist reversed morphine-induced analgesia, phenocopying the MOR-selective antioverdose agent naloxone. Encouragingly, the isoquinuclidine induced less severe opioid-withdrawal symptoms versus naloxone and did not induce conditioned-place aversion, reflecting reduced dysphoria, consistent with its KOR-inverse agonism. The strengths and weaknesses of bespoke library docking and of docking for opioid receptor polypharmacology will be considered.</p>","PeriodicalId":10,"journal":{"name":"ACS Central Science","volume":"11 5","pages":"770-790"},"PeriodicalIF":12.7,"publicationDate":"2025-04-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12123460/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144197692","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":"Docking 14 Million Virtual Isoquinuclidines against the μ and κ Opioid Receptors Reveals Dual Antagonists–Inverse Agonists with Reduced Withdrawal Effects","authors":"Seth F. Vigneron,&nbsp;Shohei Ohno,&nbsp;Joao Braz,&nbsp;Joseph Y. Kim,&nbsp;Oh Sang Kweon,&nbsp;Chase Webb,&nbsp;Christian B. Billesbølle,&nbsp;Karthik Srinivasan,&nbsp;Karnika Bhardwaj,&nbsp;John J. Irwin*,&nbsp;Aashish Manglik*,&nbsp;Allan I. Basbaum*,&nbsp;Jonathan A. Ellman* and Brian K. Shoichet*,&nbsp;","doi":"10.1021/acscentsci.5c0005210.1021/acscentsci.5c00052","DOIUrl":"https://doi.org/10.1021/acscentsci.5c00052https://doi.org/10.1021/acscentsci.5c00052","url":null,"abstract":"<p >Large library docking of tangible molecules has revealed potent ligands across many targets. While make-on-demand libraries now exceed 75 billion enumerated molecules, their synthetic routes are dominated by a few reaction types, reducing diversity and inevitably leaving many interesting bioactive-like chemotypes unexplored. Here, we investigate the large-scale enumeration and targeted docking of isoquinuclidines. These “natural-product-like” molecules are rare in current libraries and are functionally congested, making them interesting as receptor probes. Using a modular, four-component reaction scheme, we built and docked a virtual library of over 14.6 million isoquinuclidines against both the μ- and κ-opioid receptors (MOR and KOR, respectively). Synthesis and experimental testing of 18 prioritized compounds found nine ligands with low μM affinities. Structure-based optimization revealed low- and sub-nM antagonists and inverse agonists targeting both receptors. Cryo-electron microscopy structures illuminate the origins of activity on each target. In mouse behavioral studies, a potent joint MOR-antagonist and KOR-inverse-agonist reversed morphine-induced analgesia, phenocopying the MOR-selective antioverdose agent naloxone. Encouragingly, the isoquinuclidine induced less severe opioid-withdrawal symptoms versus naloxone and did not induce conditioned-place aversion, reflecting reduced dysphoria, consistent with its KOR-inverse agonism. The strengths and weaknesses of bespoke library docking and of docking for opioid receptor polypharmacology will be considered.</p><p >Docking a virtual isoquinuclidine library revealed dual opioid receptor ligands. Structure-guided optimization led to potent antagonists that reverse morphine <i>in vivo</i> with reduced withdrawal effects.</p>","PeriodicalId":10,"journal":{"name":"ACS Central Science","volume":"11 5","pages":"770–790 770–790"},"PeriodicalIF":12.7,"publicationDate":"2025-04-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acscentsci.5c00052","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144146434","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":"Combustion Resistant Borohydrides and Their Chemical Interactions with Li-Metal Surfaces: An Experimental and Theoretical Study","authors":"Anton W. Tomich*,&nbsp;Stephen Proctor,&nbsp;Moon Young Yang,&nbsp;Jianjun Chen,&nbsp;Yifan Zhao,&nbsp;Edward Chen,&nbsp;Tridip Das,&nbsp;Boris V. Merinov,&nbsp;William A. Goddard III*,&nbsp;Juchen Guo* and Vincent Lavallo*,&nbsp;","doi":"10.1021/acscentsci.5c0004310.1021/acscentsci.5c00043","DOIUrl":"https://doi.org/10.1021/acscentsci.5c00043https://doi.org/10.1021/acscentsci.5c00043","url":null,"abstract":"<p >Borohydrides are important molecular entities for a myriad of applications from organic synthesis to components of functional materials and devices. All borohydrides have been thought to be susceptible to spontaneous ignition when exposed to a flame. Herein we demonstrate that this is not always true by identifying several borohydride rich materials that are resistant to combustion when contacted with a torch. One of these materials is a Li⁺ salt of a carborane anion that depending on its coordination environment exists as a unique ionic liquid that has a nearly naked Li⁺ countercation. This has provided us with the first opportunity to spectroscopically probe the interactions of such carborane anions with Li metal in a solvent free environment. We found that this carborane anion is immune to deleterious reduction at Li-metal surfaces, as evidenced by XPS, EDS and SEM analysis of the Li-Metal surface after exposure to the ionic liquid. Additionally, NMR analysis of the ionic liquid after stirring it with Li powder shows no reaction. Calculations show that the cage skeleton is reduced at the surface monolayer, but as the reduced form is removed from contact with Li-metal, the cage reverts to the <i>closo</i>-form, demonstrating reversibility.</p><p >Among a series of combustion resistant borohydrides, we describe the synthesis of a carboranyl ionic liquid whose chemical compatibility against Li metal is investigated through experiment and theory.</p>","PeriodicalId":10,"journal":{"name":"ACS Central Science","volume":"11 5","pages":"734–741 734–741"},"PeriodicalIF":12.7,"publicationDate":"2025-04-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acscentsci.5c00043","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144146404","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":"Facile Access to Hindered Ethers via Photoinduced O–H Bond Insertions","authors":"Yu Zhang,&nbsp;Xinyu Han,&nbsp;Dong Li,&nbsp;Dinggang Wang,&nbsp;Jinxin Wang,&nbsp;Xin Luan,&nbsp;Shao-Fei Ni*,&nbsp;Shoubhik Das* and Wei-Dong Zhang*,&nbsp;","doi":"10.1021/acscentsci.5c0009910.1021/acscentsci.5c00099","DOIUrl":"https://doi.org/10.1021/acscentsci.5c00099https://doi.org/10.1021/acscentsci.5c00099","url":null,"abstract":"<p >The synthesis of the hindered and polyfluorinated dialkyl ethers poses challenges owing to the bulkiness of tertiary alcohols and the low nucleophilicity of polyfluorinated alcohols. Additionally, associated competitive side reactions always provide poor reactivities. Although certain strategies, such as electrocatalytic decarboxylation and hydroalkoxylation, have been explored, a straightforward method for obtaining ethers with structural diversity remains elusive. In this study, we have exploited the photoinduced approach that involves the <i>in situ</i> formation of singlet carbenes followed by O–H insertions to access the hindered and polyfluorinated ethers with congested or polyfluorinated alcohols. Moreover, other nucleophiles such as phenols, H₂O, thiols, silanols, tributyltin hydride, <i>etc</i>., are also tolerable to obtain valuable products. The gram-scale synthesis of marketed drugs and the modification of complex molecules demonstrate the practicality of this approach. The detailed mechanistic studies have elucidated the key intermediates and reaction mechanism, which were distinct from traditional metal-carbenoid O–H insertions.</p><p >In this study, a photoinduced approach to access the hindered and polyfluorinated ethers are exploited through the <i>in situ</i> formation of singlet carbenes and subsequent O−H insertions.</p>","PeriodicalId":10,"journal":{"name":"ACS Central Science","volume":"11 5","pages":"742–752 742–752"},"PeriodicalIF":12.7,"publicationDate":"2025-04-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acscentsci.5c00099","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144146408","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":"Facile Access to Hindered Ethers via Photoinduced O-H Bond Insertions.","authors":"Yu Zhang, Xinyu Han, Dong Li, Dinggang Wang, Jinxin Wang, Xin Luan, Shao-Fei Ni, Shoubhik Das, Wei-Dong Zhang","doi":"10.1021/acscentsci.5c00099","DOIUrl":"10.1021/acscentsci.5c00099","url":null,"abstract":"<p><p>The synthesis of the hindered and polyfluorinated dialkyl ethers poses challenges owing to the bulkiness of tertiary alcohols and the low nucleophilicity of polyfluorinated alcohols. Additionally, associated competitive side reactions always provide poor reactivities. Although certain strategies, such as electrocatalytic decarboxylation and hydroalkoxylation, have been explored, a straightforward method for obtaining ethers with structural diversity remains elusive. In this study, we have exploited the photoinduced approach that involves the <i>in situ</i> formation of singlet carbenes followed by O-H insertions to access the hindered and polyfluorinated ethers with congested or polyfluorinated alcohols. Moreover, other nucleophiles such as phenols, H₂O, thiols, silanols, tributyltin hydride, <i>etc</i>., are also tolerable to obtain valuable products. The gram-scale synthesis of marketed drugs and the modification of complex molecules demonstrate the practicality of this approach. The detailed mechanistic studies have elucidated the key intermediates and reaction mechanism, which were distinct from traditional metal-carbenoid O-H insertions.</p>","PeriodicalId":10,"journal":{"name":"ACS Central Science","volume":"11 5","pages":"742-752"},"PeriodicalIF":12.7,"publicationDate":"2025-04-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12123463/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144197693","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":"Novel Click Coupling Chemistry to Explore Glycan Recognition.","authors":"Tianwei Jia, Akul Y Mehta, Catherine A Tilton, Ea Kristine Clarisse Tulin, Lauren E Pepi, Lukas Muerner, Stephan von Gunten, Jamie Heimburg-Molinaro, Sean R Stowell, Richard D Cummings","doi":"10.1021/acscentsci.4c02124","DOIUrl":"10.1021/acscentsci.4c02124","url":null,"abstract":"<p><p>Specific recognition of glycans by proteins is important in many biological processes and immune responses. Here we present a general approach for derivatizing free glycans with a novel linker MTZ (3-(methoxyamino)-propylamine added to a bioorthogonal-functional tetrazine tag) that exploits click chemistry to generate multiple platforms of glycan coupling. This derivatization preserves glycan integrity, is reversible and quantifiable, and incorporates a bioorthogonal tetrazine tag for click coupling. A library of ABO-(H) blood group MTZ-glycans was efficiently conjugated to avidin Luminex beads through a Biotin-PEG11-TCO (<i>trans</i>-cyclooctene) spacer, generating a multiplex array that was reproducibly interrogated in a high-throughput Luminex approach with multiple lectins and antibodies. We also rapidly profiled antiglycan IgG, IgM, and IgA antibodies in multiple, serially diluted human serum samples, revealing unique repertoires of antiglycan responses in each sera. Glycans were efficiently coupled to bovine serum albumin (BSA) at a high density (∼19-24 glycans/BSA) to generate a neoglycoprotein library that was useful in microarray formats that provided results equivalent to those obtained from the Luminex approach. Neoglycoproteins have many uses, including serving as acceptors for glycosyltransferases, as we demonstrate for assays of ST6Gal1 sialyltransferase. These facile and efficient technologies significantly expand the toolbox available to explore glycan-GBP interactions.</p>","PeriodicalId":10,"journal":{"name":"ACS Central Science","volume":"11 5","pages":"753-769"},"PeriodicalIF":12.7,"publicationDate":"2025-04-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12123462/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144197695","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":"Unexpected Damage on Metal Artifacts Triggered by the Hazardous Interfacial Interaction from Aging of Polymer Coatings.","authors":"Ying An, Pei Hu, Kaitao Li, Yu Kang, Gang Hu, Rui Tian, Chao Lu, Xue Duan","doi":"10.1021/acscentsci.5c00067","DOIUrl":"10.1021/acscentsci.5c00067","url":null,"abstract":"<p><p>Polymer coatings are currently being employed for preservation of metal artifacts. However, there is insufficient awareness that inevitable aging of polymer coatings is bound to damage metal artifacts due to the lack of a direct and sensitive methodology to study the aging behaviors of polymers coated on the artifacts. Herein, we have developed an in situ and three-dimensional strategy to visualize the early stage aging behaviors of polymers coated on metal artifacts by lighting carboxyl groups generated from polymer aging. It is disclosed that polymer aging occurred simultaneously at the surface and the interface with metal artifacts, generating carboxyl groups and hydroxyl radicals to induce the corrosion and oxidation of metallic artifacts. In turn, the generated metallic ions could further aggravate the aging of polymer coatings, manifested as the larger volume of the aged sites at the interface with metal artifacts in comparison with that at the surface of polymer coatings. Such a circular reaction is validated using real metal artifact samples. These findings raised a timely alarm for the conservation ability and potential threat of polymer coatings on metal artifacts. It is anticipated that the proposed strategy could provide solid supports for the implementation of advanced conservation strategies for metal artifacts.</p>","PeriodicalId":10,"journal":{"name":"ACS Central Science","volume":"11 5","pages":"694-703"},"PeriodicalIF":12.7,"publicationDate":"2025-04-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12123457/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144197700","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}