ACS Publications最新文献

{"title":"Identification of JNJ-61803534, a RORγt Inverse Agonist for the Treatment of Psoriasis","authors":"Olaf Kinzel*,&nbsp;Steven D. Goldberg*,&nbsp;Maxwell D. Cummings,&nbsp;Christian Gege,&nbsp;Christoph Steeneck,&nbsp;Xiaohua Xue,&nbsp;Michael Albers,&nbsp;Thomas Schlüter,&nbsp;Gerald Kleymann,&nbsp;Brian Scott,&nbsp;Kia Sepassi,&nbsp;Freddy Schoetens,&nbsp;Hariharan Venkatesan,&nbsp;Virginia M. Tanis,&nbsp;Kevin Coe,&nbsp;Zachary S. Sales,&nbsp;John Spurlino,&nbsp;Cynthia Milligan,&nbsp;Anne M. Fourie,&nbsp;James P. Edwards and Thomas Hoffmann,&nbsp;","doi":"10.1021/acs.jmedchem.5c0039010.1021/acs.jmedchem.5c00390","DOIUrl":"https://doi.org/10.1021/acs.jmedchem.5c00390https://doi.org/10.1021/acs.jmedchem.5c00390","url":null,"abstract":"<p >The retinoic acid receptor-related orphan receptor gamma t (RORγt) is a nuclear transcription factor expressed in both innate and adaptive immune cells, driving Th17 cell differentiation and IL-17 production. The IL-23/IL-17 pathway is implicated in autoimmune and inflammatory diseases, and biologics that target IL-23/IL-17 signaling are efficacious in the treatment of psoriasis and psoriatic arthritis. RORγt, at the core of this pathway, represents an attractive opportunity for small-molecule intervention; however, combining high potency, nuclear receptor selectivity, and good physicochemical properties remains a challenge for RORγt inverse agonists. Recently, thiazole amides have been identified as potent RORγt inverse agonists; however, they often suffer from CYP450 autoinduction in the rat, precluding further development. Herein, we describe the discovery and development of potent and selective thiazole bisamide RORγt inverse agonists that avoid autoinduction in the rat. This effort culminated in the discovery of JNJ-61803534, which advanced into phase 1 clinical trials.</p>","PeriodicalId":46,"journal":{"name":"Journal of Medicinal Chemistry","volume":"68 8","pages":"8713–8728 8713–8728"},"PeriodicalIF":6.8,"publicationDate":"2025-04-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143863238","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"医学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Shooting an Arrow against Convulsion: Novel Triazole-Grafted Benzenesulfonamide Derivatives as Carbonic Anhydrase II and VII Inhibitors","authors":"Mohamed A. Zeidan,&nbsp;Mahmoud Abdelrahman Alkabbani,&nbsp;Simone Giovannuzzi,&nbsp;Eman F. Khaleel,&nbsp;Anwar A. El-Hamaky,&nbsp;Nourhan A. Khattab,&nbsp;Rehab Badi,&nbsp;Abdelhameed Abubakr,&nbsp;Abdallah M. Hamdy,&nbsp;Mohamed Fares,&nbsp;Haytham O. Tawfik*,&nbsp;Claudiu T. Supuran*,&nbsp;Wagdy M. Eldehna* and Moataz A. Shaldam,&nbsp;","doi":"10.1021/acs.jmedchem.5c0052610.1021/acs.jmedchem.5c00526","DOIUrl":"https://doi.org/10.1021/acs.jmedchem.5c00526https://doi.org/10.1021/acs.jmedchem.5c00526","url":null,"abstract":"<p >This study investigates new anticonvulsant substances that target the epilepsy-associated carbonic anhydrase isoforms II and VII. The 1,2,3-triazole with a benzenesulfonamide motif is present in the produced molecules. Of these, <b>5b</b> and <b>5c</b> exhibited remarkable selectivity and inhibitory efficacy toward hCA VII and hCA II over hCA I. The <i>K</i>_I values of <b>5b</b> and <b>5c</b> were 6.3 and 10.1 nM, respectively, and 21.6 and 18.9 nM, respectively. In a pilocarpine-induced paradigm, <i>in vivo</i> assessments showed decreased seizure severity and susceptibility with delayed seizure onset and diminished intensity. The quick absorption and <i>in vivo</i> stability of <b>5b</b> were demonstrated by pharmacokinetic investigations. Evaluations of toxicity showed no neurotoxic effects and a high safety margin (LD₅₀ &gt; 2000 mg/kg). Mechanistic research has shown effectiveness in maintaining neuronal integrity, reducing mTOR activation, and raising hippocampus KCC2 levels. Compound <b>5b</b>’s binding interactions with hCA II and hCA VII were clarified by docking and dynamics experiments.</p>","PeriodicalId":46,"journal":{"name":"Journal of Medicinal Chemistry","volume":"68 8","pages":"8873–8893 8873–8893"},"PeriodicalIF":6.8,"publicationDate":"2025-04-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143863239","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"医学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"High Performance Aluminum Solid Electrolytic Capacitors Using Self-Doped Poly(3,4-ethylenedioxythiophene)","authors":"Yuxin Jing,&nbsp; and ,&nbsp;Hidenori Okuzaki*,&nbsp;","doi":"10.1021/acsapm.5c0011810.1021/acsapm.5c00118","DOIUrl":"https://doi.org/10.1021/acsapm.5c00118https://doi.org/10.1021/acsapm.5c00118","url":null,"abstract":"<p >Highly conductive fully water-soluble self-doped poly(3,4-ethylenedioxythiophene) (S-PEDOT) was first synthesized by electrochemical polymerization at different current densities between 0.5 and 5 mA cm^–2. The electrical conductivity of S-PEDOT increased in proportion to the current density and reached 427 S cm^–1 at 5 mA cm^–2, which was an order of magnitude greater than previously reported for electrochemically polymerized self-doped PEDOT. The improvement in electrical conductivity was due to increased carrier mobility resulting from improved crystallinity, while the carrier density remained constant regardless of the current density. Furthermore, the S-PEDOT was applied to the cathode material of Al solid electrolytic capacitors. The highly conductive and fully dissolved S-PEDOT was found to efficiently penetrate into the fine etching pits in the etched anodized Al foil and achieved a low equivalent series resistance and a high capacitance utilization rate of 92%, which was superior to capacitors using commercial PEDOT doped with poly(4-styrenesulfonate) (PEDOT:PSS) colloids.</p>","PeriodicalId":7,"journal":{"name":"ACS Applied Polymer Materials","volume":"7 8","pages":"4955–4962 4955–4962"},"PeriodicalIF":4.4,"publicationDate":"2025-04-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143867290","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Rod-Shaped Nanographenes as Emitters in Fluorescent OLEDs","authors":"Fabien Lucas*,&nbsp;Daniel Medina-Lopez,&nbsp;Cynthia Banga-Kpako,&nbsp;Thanh Trung Huynh,&nbsp;Jean-Sébastien Lauret and Stéphane Campidelli*,&nbsp;","doi":"10.1021/acsanm.5c0133210.1021/acsanm.5c01332","DOIUrl":"https://doi.org/10.1021/acsanm.5c01332https://doi.org/10.1021/acsanm.5c01332","url":null,"abstract":"<p >A significant challenge in the field of organic light-emitting diodes (OLEDs) technology is the development of stable, cost-effective, and sustainable emitters. Current emitters are frequently based on rare metals and heteroatom-based chromophores. Carbon-based nanomaterials, such as carbon dots (CDs) or nanographenes (NGs), offer a promising alternative due to their high photoluminescence quantum yields, the abundance of carbon materials, and the versatility of their syntheses. In this work, we fabricated green-light-emitting electroluminescent devices containing <b>C</b>_<b>60</b><b>-</b><i>t</i><b>Bu</b>_<b>8</b> nanographene acting as the emitter. This nanographene contains 60 <i>sp</i>² carbon atoms and <i>tert</i>-butyl solubilizing group on the periphery; it was synthesized via the bottom-up approach. The <b>C</b>_<b>60</b><b>-</b><i>t</i><b>Bu</b>_<b>8</b> was fully characterized, and it was incorporated into the emissive layer of a benchmark OLED stack (ITO/PEDOT:PSS/NG-containing active layer/BCP/TmPyPB/LiF/Al). The OLED devices containing the <b>C</b>_<b>60</b><b>-</b><i>t</i><b>Bu</b>_<b>8</b> exhibited current and power efficiencies (CE and PE) of 2.27 cd·A^–1, 0.28 lm·W^–1 and luminance of 164 cd·m^–2. The performance remains modest in comparison to state-of-the-art OLEDs, but it outperforms previous attempts to utilize nanographenes as active materials for fluorescent OLEDs. Following the initial results, we also tested two other NGs (<b>C</b>_<b>78</b><b>-</b><i>t</i><b>Bu</b>_<b>6</b> and <b>C</b>_<b>96</b><b>-</b><i>t</i><b>Bu</b>_<b>8</b>), which contain 78 and 96 <i>sp</i>² carbon atoms as fluorescent emitters in OLEDs. The objective was to fine-tune the electroluminescence to yellow-orange and red light.</p>","PeriodicalId":6,"journal":{"name":"ACS Applied Nano Materials","volume":"8 16","pages":"8473–8479 8473–8479"},"PeriodicalIF":5.3,"publicationDate":"2025-04-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143867291","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Enantioselective and Regiodivergent Skeletal Transformations of 1,2,3-Thiadiazoles to Alkylidene Dihydrothiophenes","authors":"Cunzhi Chen,&nbsp;Youwei Chen,&nbsp;Hongguang Du,&nbsp;Jiaxi Xu and Zhanhui Yang*,&nbsp;","doi":"10.1021/acs.orglett.5c0106710.1021/acs.orglett.5c01067","DOIUrl":"https://doi.org/10.1021/acs.orglett.5c01067https://doi.org/10.1021/acs.orglett.5c01067","url":null,"abstract":"<p >By leveraging the Rh-catalyzed asymmetric skeletal editing of 1,2,3-thiadiazoles, we successfully achieve the ligand-controlled enantioselective and regiodivergent synthesis of structurally diverse 2- and 3-alkylidene 2,3-dihydrothiophenes. Late-stage structural editing of complex natural and drug molecules is also enabled.</p>","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":"27 16","pages":"4337–4342 4337–4342"},"PeriodicalIF":4.9,"publicationDate":"2025-04-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143867286","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}

{"title":"Bioactive Gold Nanoparticles Synthesized by Lactobacillus acidophilus for Catalytic and Antibacterial Applications","authors":"Saima Hameed,&nbsp;Ruiyun Zhou,&nbsp;Sumaira Sharif,&nbsp;Bhushan Dharmadhikari,&nbsp;Peiqiao Wu,&nbsp;Prabir Patra,&nbsp;Lijuan Xie* and Yibin Ying,&nbsp;","doi":"10.1021/acsanm.5c0007310.1021/acsanm.5c00073","DOIUrl":"https://doi.org/10.1021/acsanm.5c00073https://doi.org/10.1021/acsanm.5c00073","url":null,"abstract":"<p >The biological synthesis of nanoparticles can potentially widen the possibilities for their applications by avoiding the involvement of hazardous chemicals. In this study, we used<i>Lactobacillus acidophilus</i>in an environmentally friendly way to produce gold nanoparticles (AuNPs) via extracellular means, which were confirmed by various physicochemical techniques. The surface-bound proteins and major carbon functional groups (C–H, C–C, and C–N) formed and stabilized the AuNPs. These AuNPs exhibited strong catalytic activity by reducing various dyes, including methylene blue, Congo red, methyl orange, and malachite green. Methylene blue and Congo red were reduced within 5 min, while methyl orange was reduced within 10 min, and malachite green showed a complete reduction reaction in 3 min in the presence of AuNPs with respective catalytic performance of 64.4, 5, 49.4, and 26.8% in the first cycle. These AuNPs were proven to be a moderate antioxidant agent by oxidizing 1, 1-diphenyl-2-picrylhydrazyl compound within 40 min. A thin layer of AuNPs on the disposable carbon electrode showed their electrochemical sensitivity, which can provide an excellent platform for gold nanoparticle-based biosensors. The bactericidal effect of these AuNPs was tested against<i>Escherichia coli</i>and<i>Listeria monocytogenes</i>, and their antibacterial properties were exposed by compromising cellular integrity, shown as damaged membranes and demolished cells. The distinguishable antibacterial effect of AuNPs was detected using metamaterial-based terahertz spectroscopy in our study, demonstrating its potential for rapid, noninvasive detection of microbial contamination on eggshells and crab shells, ensuring improved food safety and quality control. The synthesis approach used in this study is environmentally friendly and can produce biochemically active metal nanoparticles without involving environmental hazards.</p>","PeriodicalId":6,"journal":{"name":"ACS Applied Nano Materials","volume":"8 16","pages":"7952–7966 7952–7966"},"PeriodicalIF":5.3,"publicationDate":"2025-04-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143867292","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Calcium Impregnated Silica Gel in the Domino Reaction Involving Irreversible Aldol Addition, Dehydration, and Michael Addition","authors":"Jih Ru Hwu*,&nbsp;Khagendra Prasad Bohara,&nbsp;Animesh Roy,&nbsp;Wen-Chieh Huang,&nbsp;Kuo-Chu Hwang,&nbsp;Chun-Cheng Lin,&nbsp;Kao Shu Chuang,&nbsp;Shu-Yu Lin and Shwu-Chen Tsay,&nbsp;","doi":"10.1021/acs.joc.4c0234010.1021/acs.joc.4c02340","DOIUrl":"https://doi.org/10.1021/acs.joc.4c02340https://doi.org/10.1021/acs.joc.4c02340","url":null,"abstract":"<p >An innovative method was developed for the performance of aldol additions in an irreversible fashion by the use of calcium metal impregnated silica gel (Ca@SiO₂) as a remarkable reducing reagent. In this approach, Ca@SiO₂ drove the reaction forward, prevented reversibility, and ensured the formation of the desired products. Thus, in the presence of Ca@SiO₂ (3.0 equiv), aldehydes (1.0 equiv) condensed with ketones (1.0 equiv) in 2-MeTHF to yield α,β-unsaturated enones in 71–90% yields at 25 °C. Additionally, a domino reaction involving successive aldol addition, dehydration, and Michael addition was developed for the preparation of 1,5-diketones. Accordingly, when aldehydes (1.0 equiv) were allowed to react with ketones (2.2 equiv) and Ca@SiO₂(4.0 equiv), 1,5-diketones were produced in 67–88% yields. These reactions involved radical processes, where Ca@SiO₂ abstracted two α hydrogen atoms from ketones and the oxygen atom from aldehydes to form CaH₂@SiO₂ and CaO@SiO₂, respectively. These species were confirmed by powder X-ray diffraction analysis. The resultant impregnated silica gel species were solid and insoluble in the reaction mixtures, which made the addition reactions irreversible. This method represents a significant advancement in aldol condensation reactions and offers the advantages of both atom economy and atom efficiency.</p>","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"90 16","pages":"5343–5348 5343–5348"},"PeriodicalIF":3.3,"publicationDate":"2025-04-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.joc.4c02340","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143867563","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Assessing the Impact of the Off-Stoichiometric Epoxy/Amine Ratio on the Curing Kinetics and Properties of Space-Grade Disulfide-Based Vitrimer Resins","authors":"Joséphine de Calbiac,&nbsp;Philippe Olivier*,&nbsp;Rima Sfar Zbed,&nbsp;Marina Torres,&nbsp;Marion Broutelle,&nbsp;Mathias Destarac and Marc Guerre*,&nbsp;","doi":"10.1021/acsapm.5c0063710.1021/acsapm.5c00637","DOIUrl":"https://doi.org/10.1021/acsapm.5c00637https://doi.org/10.1021/acsapm.5c00637","url":null,"abstract":"<p >Carbon fiber-reinforced polymer composites are widely used in space structures due to their lightweight nature and excellent thermal stability. However, repairing manufacturing defects in cross-linked thermosets remains a significant challenge. In this regard, vitrimers offer a promising alternative by combining the mechanical strength of thermosets with the reprocessability of glass. These materials feature a dynamic network structure, allowing them to behave like traditional thermosets at operational temperatures while exhibiting fluid-like properties at elevated temperatures. In this study, a space-grade epoxy thermoset matrix was transformed into a high-<i>T</i>_g vitrimer (<i>T</i>_g ≈ 200 °C) for potential use in composite applications. The vitrimer chemistry relies on disulfide exchange reactions facilitated by an industrially available reagent (4-AFD). Rheological and reactivity characterization tests were performed to ensure that the cross-linking kinetics in the presence of dynamic bonds remain compatible with existing composite manufacturing processes. These measurements enabled the development of time–temperature transformation diagrams, providing precise insights into the polymerization process. To enhance repairability, off-stoichiometric formulations (epoxy/amine = 1/1.2) were explored to optimize both the curing process and the vitrimeric properties. The applicability of kinetic models to off-stoichiometric systems was also assessed. Notably, even under off-stoichiometric conditions, the resin maintained a high <i>T</i>_g of 175 °C while exhibiting excellent mechanical properties and improved reprocessability. Additionally, the outgassing properties remained identical to those of the stoichiometric reference. These findings highlight the potential of off-stoichiometric epoxy/4-AFD formulations as viable matrix materials for composite applications. By offering improved reprocessability without compromising thermal or mechanical performance, these materials present a compelling alternative to traditional thermosets for high-performance aerospace applications.</p>","PeriodicalId":7,"journal":{"name":"ACS Applied Polymer Materials","volume":"7 8","pages":"5271–5279 5271–5279"},"PeriodicalIF":4.4,"publicationDate":"2025-04-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143867289","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Antibody-Functionalized Plasmonic Biofiber Sensors with Layered Nanomaterials for Sensitive Listeria monocytogenes Detection","authors":"Guiwei Zhang,&nbsp;Ragini Singh,&nbsp;Bingyuan Zhang,&nbsp;Santosh Kumar* and Guoru Li*,&nbsp;","doi":"10.1021/acsanm.5c0072110.1021/acsanm.5c00721","DOIUrl":"https://doi.org/10.1021/acsanm.5c00721https://doi.org/10.1021/acsanm.5c00721","url":null,"abstract":"<p ><i>Listeria monocytogenes</i> (<i>L. monocytogenes</i>) is one of the pathogenic bacteria threatening human health. Upon infection, it causes symptoms such as sepsis and meningitis in immunocompromised individuals. This work introduces a biofiber sensor that utilizes the plasmonic principle for detecting <i>L. monocytogenes</i>. The fiber structure consists of multimode fiber (MMF) and seven-core fiber (SCF). The core-mismatch configuration between MMF and SCF, along with the W-shaped architecture of the seven-core fiber, amplifies the evanescent field on the fiber surface. Gold nanoparticles are affixed to the sensor region’s surface to elicit the plasmonic effect. Additionally, the layered structure of bismuthene and antimonene functionalizes the fiber, improving the biocompatibility and durability of the fiber sensing region. Moreover, the layered nanostructured bismuthene and antimonene provide a high specific surface area, offering additional reference sites for antibody functionalization. To enhance the specificity of the sensor, an anti-<i>Listeria monocytogenes</i> functional fiber is used. The results show that the sensitivity of the sensor is 0.45 nm/log₁₀(CFU/mL), and the detection limit is 0.89 CFU/mL when the concentration of <i>L. monocytogenes</i> is between 10⁰ and 10⁸ CFU/mL. In addition, the actual test performance of the sensor is evaluated by using real samples. The recovery rates of milk, cheese, tomato, and ice-cream range from 133–91.5, 133–67, 133–67, and 100–74.9%, demonstrating its effectiveness in detecting <i>L. monocytogenes</i>.</p>","PeriodicalId":6,"journal":{"name":"ACS Applied Nano Materials","volume":"8 16","pages":"8250–8259 8250–8259"},"PeriodicalIF":5.3,"publicationDate":"2025-04-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143867633","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Catalytic Site Dynamics in Sn-β Zeolites: A Time-Dependent Study of the Site Structure","authors":"Leah Ford,&nbsp;Ryan Burrows,&nbsp;Nicolas Raffaele and Nicholas A. Brunelli*,&nbsp;","doi":"10.1021/acs.jpcc.5c0096810.1021/acs.jpcc.5c00968","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c00968https://doi.org/10.1021/acs.jpcc.5c00968","url":null,"abstract":"<p >Advancing the catalytic capabilities of zeolites like Sn-β requires a detailed understanding of the synthesis-structure–reactivity relationships. Sn-β is intriguingly complex, as it contains different types of catalytic sites that have been identified as the prominent active sites for different reactions. Previous work has indicated that the catalytic sites in Sn-β are affected by the composition and conditions during hydrothermal crystallization, forming a distribution of catalytic sites that are stable postsynthesis. However, our work reveals that postsynthetic transformations can occur at the catalytic sites, increasing activity in epoxide ring opening (ERO) of epichlorohydrin with methanol by a factor of 3. Specifically, when the calcination step is delayed, the catalytic sites transform. Standard characterization techniques demonstrate that bulk properties of the Sn-β are consistent for the batches calcined at different times, but ³¹P NMR measurements of materials dosed with trimethyl phosphine oxide reveal that the site distribution changes when calcination is delayed. After delaying calcination 14 or 21 days, Sn-β is determined to have 80% open-defect sites, a significant increase from the 50% observed for conventional materials. Sn-β with elevated quantities of open-defect sites then show an improvement in ERO activity over postcalcination time, suggesting a second transformation after calcination. Overall, the results demonstrate that Sn-β undergoes a dynamic process postsynthesis, and this work strengthens the connection between open-defect sites and ERO activity.</p>","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"129 16","pages":"7787–7794 7787–7794"},"PeriodicalIF":3.3,"publicationDate":"2025-04-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143863219","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}