ACS Central SciencePub Date : 2024-11-26DOI: 10.1021/acscentsci.4c0124910.1021/acscentsci.4c01249
Ferran Nadal-Bufi, Raj V. Nithun, Fabio de Moliner, Xiaoxi Lin, Shaimaa Habiballah, Muhammad Jbara* and Marc Vendrell*,
{"title":"Late-Stage Minimal Labeling of Peptides and Proteins for Real-Time Imaging of Cellular Trafficking","authors":"Ferran Nadal-Bufi, Raj V. Nithun, Fabio de Moliner, Xiaoxi Lin, Shaimaa Habiballah, Muhammad Jbara* and Marc Vendrell*, ","doi":"10.1021/acscentsci.4c0124910.1021/acscentsci.4c01249","DOIUrl":"https://doi.org/10.1021/acscentsci.4c01249https://doi.org/10.1021/acscentsci.4c01249","url":null,"abstract":"<p >The cellular uptake routes of peptides and proteins are complex and diverse, often handicapping therapeutic success. Understanding their mechanisms of internalization requires chemical derivatization with approaches that are compatible with wash-free and real-time imaging. In this work, we developed a new late-stage labeling strategy for unprotected peptides and proteins, which retains their biological activity while enabling live-cell imaging of uptake and intracellular trafficking. Benzo-2,1,3-thiadiazoles were selectively incorporated into Cys residues of both linear and cyclic peptides via Pd-mediated arylation with good yields and high purities. The resulting labeled peptides are chemically stable under physiological conditions and display strong fluorogenic character for wash-free imaging studies. We utilized this approach to prepare native-like analogues of cell-penetrating peptides and performed time-course analysis of their internalization routes in live cells by fluorescence lifetime imaging. Furthermore, we applied our strategy to label the chemokine protein mCCL2 and monitor its internalization via receptor-mediated endocytosis in live macrophages. This study provides a straightforward strategy for late-stage fluorogenic labeling of intact peptides and small proteins and direct visualization of dynamic intracellular events.</p><p >Late-stage labeling to prepare unprotected fluorogenic peptides/proteins via Cys arylation with minimal bioactivity perturbation and suitable optical properties for wash-free imaging in live cells.</p>","PeriodicalId":10,"journal":{"name":"ACS Central Science","volume":"11 1","pages":"66–75 66–75"},"PeriodicalIF":12.7,"publicationDate":"2024-11-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acscentsci.4c01249","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143091714","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}
ACS Central SciencePub Date : 2024-11-26eCollection Date: 2025-01-22DOI: 10.1021/acscentsci.4c01249
Ferran Nadal-Bufi, Raj V Nithun, Fabio de Moliner, Xiaoxi Lin, Shaimaa Habiballah, Muhammad Jbara, Marc Vendrell
{"title":"Late-Stage Minimal Labeling of Peptides and Proteins for Real-Time Imaging of Cellular Trafficking.","authors":"Ferran Nadal-Bufi, Raj V Nithun, Fabio de Moliner, Xiaoxi Lin, Shaimaa Habiballah, Muhammad Jbara, Marc Vendrell","doi":"10.1021/acscentsci.4c01249","DOIUrl":"10.1021/acscentsci.4c01249","url":null,"abstract":"<p><p>The cellular uptake routes of peptides and proteins are complex and diverse, often handicapping therapeutic success. Understanding their mechanisms of internalization requires chemical derivatization with approaches that are compatible with wash-free and real-time imaging. In this work, we developed a new late-stage labeling strategy for unprotected peptides and proteins, which retains their biological activity while enabling live-cell imaging of uptake and intracellular trafficking. Benzo-2,1,3-thiadiazoles were selectively incorporated into Cys residues of both linear and cyclic peptides via Pd-mediated arylation with good yields and high purities. The resulting labeled peptides are chemically stable under physiological conditions and display strong fluorogenic character for wash-free imaging studies. We utilized this approach to prepare native-like analogues of cell-penetrating peptides and performed time-course analysis of their internalization routes in live cells by fluorescence lifetime imaging. Furthermore, we applied our strategy to label the chemokine protein mCCL2 and monitor its internalization via receptor-mediated endocytosis in live macrophages. This study provides a straightforward strategy for late-stage fluorogenic labeling of intact peptides and small proteins and direct visualization of dynamic intracellular events.</p>","PeriodicalId":10,"journal":{"name":"ACS Central Science","volume":"11 1","pages":"66-75"},"PeriodicalIF":12.7,"publicationDate":"2024-11-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11758221/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143044847","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}
ACS Central SciencePub Date : 2024-11-25DOI: 10.1021/acscentsci.4c0131710.1021/acscentsci.4c01317
Sewon Oh, Hanning Jiang, Liat H. Kugelmass and Erin E. Stache*,
{"title":"Recycling of Post-Consumer Waste Polystyrene Using Commercial Plastic Additives","authors":"Sewon Oh, Hanning Jiang, Liat H. Kugelmass and Erin E. Stache*, ","doi":"10.1021/acscentsci.4c0131710.1021/acscentsci.4c01317","DOIUrl":"https://doi.org/10.1021/acscentsci.4c01317https://doi.org/10.1021/acscentsci.4c01317","url":null,"abstract":"<p >Photothermal conversion can promote plastic depolymerization (chemical recycling to a monomer) through light-to-heat conversion. The highly localized temperature gradient near the photothermal agent surface allows selective heating with spatial control not observed with bulk pyrolysis. However, identifying and incorporating practical photothermal agents into plastics for end-of-life depolymerization have not been realized. Interestingly, plastics containing carbon black as a pigment present an ideal opportunity for photothermal conversion recycling. Herein, we use visible light to depolymerize polystyrene plastics into styrene monomers by using the dye in commercial black plastics. A model system is evaluated by synthesizing polystyrene–carbon black composites and depolymerizing under white LED light irradiation, producing styrene monomer in up to 60% yield. Excitingly, unmodified postconsumer black polystyrene samples are successfully depolymerized to a styrene monomer without adding catalysts or solvents. Using focused solar irradiation, yields up to 80% are observed in just 5 min. Furthermore, combining multiple types of polystyrene plastics with a small percentage of black polystyrene plastic enables full depolymerization of the mixture. This simple method leverages existing plastic additives to actualize a closed-loop economy of all-colored plastics.</p><p >Simple light irradiation transforms postconsumer polystyrene products to a styrene monomer, using heat from the additives already found in many commercial products.</p>","PeriodicalId":10,"journal":{"name":"ACS Central Science","volume":"11 1","pages":"57–65 57–65"},"PeriodicalIF":12.7,"publicationDate":"2024-11-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acscentsci.4c01317","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143091864","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}
ACS Central SciencePub Date : 2024-11-25DOI: 10.1021/acscentsci.4c0183610.1021/acscentsci.4c01836
Joshua M. Kofsky, and , Chantelle J. Capicciotti*,
{"title":"Zooming in on the Glycome: Visualizing Glycans at the Nanoscale Level through Expansion Microscopy","authors":"Joshua M. Kofsky, and , Chantelle J. Capicciotti*, ","doi":"10.1021/acscentsci.4c0183610.1021/acscentsci.4c01836","DOIUrl":"https://doi.org/10.1021/acscentsci.4c01836https://doi.org/10.1021/acscentsci.4c01836","url":null,"abstract":"<p >A nanoscale picture of glycans in cells, tissues, and whole organisms becomes clearer with expansion microscopy.</p>","PeriodicalId":10,"journal":{"name":"ACS Central Science","volume":"11 2","pages":"177–179 177–179"},"PeriodicalIF":12.7,"publicationDate":"2024-11-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acscentsci.4c01836","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143486882","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}
ACS Central SciencePub Date : 2024-11-25eCollection Date: 2025-01-22DOI: 10.1021/acscentsci.4c01317
Sewon Oh, Hanning Jiang, Liat H Kugelmass, Erin E Stache
{"title":"Recycling of Post-Consumer Waste Polystyrene Using Commercial Plastic Additives.","authors":"Sewon Oh, Hanning Jiang, Liat H Kugelmass, Erin E Stache","doi":"10.1021/acscentsci.4c01317","DOIUrl":"10.1021/acscentsci.4c01317","url":null,"abstract":"<p><p>Photothermal conversion can promote plastic depolymerization (chemical recycling to a monomer) through light-to-heat conversion. The highly localized temperature gradient near the photothermal agent surface allows selective heating with spatial control not observed with bulk pyrolysis. However, identifying and incorporating practical photothermal agents into plastics for end-of-life depolymerization have not been realized. Interestingly, plastics containing carbon black as a pigment present an ideal opportunity for photothermal conversion recycling. Herein, we use visible light to depolymerize polystyrene plastics into styrene monomers by using the dye in commercial black plastics. A model system is evaluated by synthesizing polystyrene-carbon black composites and depolymerizing under white LED light irradiation, producing styrene monomer in up to 60% yield. Excitingly, unmodified postconsumer black polystyrene samples are successfully depolymerized to a styrene monomer without adding catalysts or solvents. Using focused solar irradiation, yields up to 80% are observed in just 5 min. Furthermore, combining multiple types of polystyrene plastics with a small percentage of black polystyrene plastic enables full depolymerization of the mixture. This simple method leverages existing plastic additives to actualize a closed-loop economy of all-colored plastics.</p>","PeriodicalId":10,"journal":{"name":"ACS Central Science","volume":"11 1","pages":"57-65"},"PeriodicalIF":12.7,"publicationDate":"2024-11-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11758496/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143044857","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}
ACS Central SciencePub Date : 2024-11-23DOI: 10.1021/acscentsci.4c0106110.1021/acscentsci.4c01061
Joe Chin-Hun Kuo, Marshall J. Colville, Michelle R. Sorkin, Jacky Lok Ka Kuo, Ling Ting Huang, Dana N. Thornlow, Gwendolyn M. Beacham, Gunther Hollopeter, Matthew P. DeLisa, Christopher A. Alabi* and Matthew J. Paszek*,
{"title":"Bio-orthogonal Glycan Imaging of Cultured Cells and Whole Animal C. elegans with Expansion Microscopy","authors":"Joe Chin-Hun Kuo, Marshall J. Colville, Michelle R. Sorkin, Jacky Lok Ka Kuo, Ling Ting Huang, Dana N. Thornlow, Gwendolyn M. Beacham, Gunther Hollopeter, Matthew P. DeLisa, Christopher A. Alabi* and Matthew J. Paszek*, ","doi":"10.1021/acscentsci.4c0106110.1021/acscentsci.4c01061","DOIUrl":"https://doi.org/10.1021/acscentsci.4c01061https://doi.org/10.1021/acscentsci.4c01061","url":null,"abstract":"<p >Complex carbohydrates called glycans play crucial roles in regulating cell and tissue physiology, but how they map to nanoscale anatomical features must still be resolved. Here, we present the first nanoscale map of mucin-type <i>O</i>-glycans throughout the entirety of the <i>Caenorhabditis elegans</i> model organism. We constructed a library of multifunctional linkers to probe and anchor metabolically labeled glycans in expansion microscopy (ExM). A flexible strategy was demonstrated for the chemical synthesis of linkers with a broad inventory of bio-orthogonal functional groups, fluorophores, anchorage chemistries, and linker arms. Employing <i>C. elegans</i> as a test bed, metabolically labeled <i>O</i>-glycans were resolved on the gut microvilli and other nanoscale anatomical features. Transmission electron microscopy images of <i>C. elegans</i> nanoanatomy validated the fidelity and isotropy of gel expansion. Whole organism maps of <i>C. elegans O</i>-glycosylation in the first larval stage revealed <i>O</i>-glycan “hotspots” in unexpected anatomical locations, including the body wall furrows. Beyond <i>C. elegans</i>, we validated ExM protocols for nanoscale imaging of metabolically labeled glycans on cultured mammalian cells. Together, our results suggest the broad applicability of the multifunctional reagents for imaging glycans and other metabolically labeled biomolecules at enhanced resolutions with ExM.</p><p >Specialized chemical linkers embed molecules mimicking natural metabolites into an expandable gel, including cell surface sugars known as glycans, and light up nanostructures across entire nematodes.</p>","PeriodicalId":10,"journal":{"name":"ACS Central Science","volume":"11 2","pages":"193–207 193–207"},"PeriodicalIF":12.7,"publicationDate":"2024-11-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acscentsci.4c01061","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143486881","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}
ACS Central SciencePub Date : 2024-11-22eCollection Date: 2024-12-25DOI: 10.1021/acscentsci.4c01074
Noreen E Gentry, Noah J Gibson, Justin L Lee, Jennifer L Peper, James M Mayer
{"title":"Trap States in Reduced Colloidal Titanium Dioxide Nanoparticles Have Different Proton Stoichiometries.","authors":"Noreen E Gentry, Noah J Gibson, Justin L Lee, Jennifer L Peper, James M Mayer","doi":"10.1021/acscentsci.4c01074","DOIUrl":"10.1021/acscentsci.4c01074","url":null,"abstract":"<p><p>Added electrons and holes in semiconducting (nano)materials typically occupy \"trap states,\" which often determine their photophysical properties and chemical reactivity. However, trap states are usually ill-defined, with few insights into their stoichiometry or structure. Our laboratory previously reported that aqueous colloidal TiO<sub>2</sub> nanoparticles prepared from TiCl<sub>4</sub> + H<sub>2</sub>O have two classes of electron trap states, termed <b>Blue</b> and <b>Red</b>. Herein, we show that the formation of <b>Red</b> from oxidized TiO<sub>2</sub> requires 1<i>e</i> <sup>-</sup> + 1H<sup>+</sup>, while <b>Blue</b> requires 1<i>e</i> <sup>-</sup> + 2H<sup>+</sup>. The two states are in a protic equilibrium, <b>Blue</b> ⇌ <b>Red</b> + H<sup>+</sup>, with <i>K</i> <sub>eq</sub> = 2.65 mM. The <b>Blue</b> states in the TiO<sub>2</sub> NPs behave just like a soluble molecular acid with this <i>K</i> <sub>eq</sub> as their <i>K</i> <sub>a</sub>, as supported by solvent isotope studies. Because the trap states have different compositions, their population and depopulation occur with the making and breaking of chemical bonds and not (as commonly assumed) just by the movement of electrons. In addition, the direct observation of a 2H<sup>+</sup>/1<i>e</i> <sup>-</sup> trap state contradicts the emerging H atom transfer (1H<sup>+</sup>/1<i>e</i> <sup>-</sup>) paradigm for oxide/solution interfaces. Finally, this work emphasizes the importance of chemical stoichiometries, not just electronic energies, in understanding and directing the reactivity at solid/solution interfaces.</p>","PeriodicalId":10,"journal":{"name":"ACS Central Science","volume":"10 12","pages":"2266-2273"},"PeriodicalIF":12.7,"publicationDate":"2024-11-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11672544/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142902422","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}
ACS Central SciencePub Date : 2024-11-22DOI: 10.1021/acscentsci.4c0107410.1021/acscentsci.4c01074
Noreen E. Gentry, Noah J. Gibson, Justin L. Lee, Jennifer L. Peper and James M. Mayer*,
{"title":"Trap States in Reduced Colloidal Titanium Dioxide Nanoparticles Have Different Proton Stoichiometries","authors":"Noreen E. Gentry, Noah J. Gibson, Justin L. Lee, Jennifer L. Peper and James M. Mayer*, ","doi":"10.1021/acscentsci.4c0107410.1021/acscentsci.4c01074","DOIUrl":"https://doi.org/10.1021/acscentsci.4c01074https://doi.org/10.1021/acscentsci.4c01074","url":null,"abstract":"<p >Added electrons and holes in semiconducting (nano)materials typically occupy “trap states,” which often determine their photophysical properties and chemical reactivity. However, trap states are usually ill-defined, with few insights into their stoichiometry or structure. Our laboratory previously reported that aqueous colloidal TiO<sub>2</sub> nanoparticles prepared from TiCl<sub>4</sub> + H<sub>2</sub>O have two classes of electron trap states, termed <b>Blue</b> and <b>Red</b>. Herein, we show that the formation of <b>Red</b> from oxidized TiO<sub>2</sub> requires 1<i>e</i><sup>–</sup> + 1H<sup>+</sup>, while <b>Blue</b> requires 1<i>e</i><sup>–</sup> + <u>2</u>H<sup>+</sup>. The two states are in a protic equilibrium, <b>Blue</b> ⇌ <b>Red</b> + H<sup>+</sup>, with <i>K</i><sub>eq</sub> = 2.65 mM. The <b>Blue</b> states in the TiO<sub>2</sub> NPs behave just like a soluble molecular acid with this <i>K</i><sub>eq</sub> as their <i>K</i><sub>a</sub>, as supported by solvent isotope studies. Because the trap states have different compositions, their population and depopulation occur with the making and breaking of chemical bonds and not (as commonly assumed) just by the movement of electrons. In addition, the direct observation of a <u>2</u>H<sup>+</sup>/1<i>e</i><sup>–</sup> trap state contradicts the emerging H atom transfer (1H<sup>+</sup>/1<i>e</i><sup>–</sup>) paradigm for oxide/solution interfaces. Finally, this work emphasizes the importance of chemical stoichiometries, not just electronic energies, in understanding and directing the reactivity at solid/solution interfaces.</p><p >The two classes of trap states formed on reduction of colloidal TiO<sub>2</sub> nanoparticles contain 1<i>e</i><sup>−</sup>/1H<sup>+</sup> and 1<i>e</i><sup>−</sup>/2H<sup>+</sup>, differing by a proton, providing a chemical view of trap states in oxide materials.</p>","PeriodicalId":10,"journal":{"name":"ACS Central Science","volume":"10 12","pages":"2266–2273 2266–2273"},"PeriodicalIF":12.7,"publicationDate":"2024-11-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acscentsci.4c01074","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143127662","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 Regiospecific Co-Assembly Method to Functionalize Ordered Mesoporous Metal Oxides with Customizable Noble Metal Nanocrystals.","authors":"Jichun Li, Lingxiao Xue, Yu Deng, Xiaowei Cheng, Junhao Ma, Wenhe Xie, Meihua Chen, Yonghui Deng","doi":"10.1021/acscentsci.4c01592","DOIUrl":"10.1021/acscentsci.4c01592","url":null,"abstract":"<p><p>An efficient regiospecific co-assembly (RSCA) strategy is developed for general synthesis of mesoporous metal oxides with pore walls precisely decorated by highly dispersed noble metal nanocrystals with customized parameters (diameter and composition). It features the rational utilization of the specific interactions between hydrophilic molecular precursors, hydrophobic noble metal nanocrystals, and amphiphilic block copolymers, to achieve regiospecific co-assembly as confirmed by molecular dynamics simulations. Through this RSCA strategy, we achieved a controllable synthesis of a variety of functional mesoporous metal oxide composites (e.g., WO<sub>3</sub>, ZrO<sub>2</sub>, TiO<sub>2</sub>) with in-pore walls precisely decorated by various noble metal nanocrystals of tailored components (Au, Ag, Pt, Pd and their nanoalloys) and sizes (3.0-8.5 nm). As an example, the obtained mesoporous 0.5-Ag/WO<sub>3</sub> material has a highly interconnected mesoporous structure and uniform 6.5 nm Ag nanocrystals confined in the mesopores, showing superior NO sensing performances with high sensitivity, good selectivity, and stability at low working temperature (127 °C). <i>In situ</i> spectroscopy study indicates that the NO sensing process involves a unique gas-solid reaction, where NO molecules are converted into chemisorbed NO <sub><i>x</i></sub> species over the sensitive materials, inducing a remarkable change of resistance and outputting a dramatic response signal.</p>","PeriodicalId":10,"journal":{"name":"ACS Central Science","volume":"10 12","pages":"2274-2284"},"PeriodicalIF":12.7,"publicationDate":"2024-11-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11672546/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142902386","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 Regiospecific Co-Assembly Method to Functionalize Ordered Mesoporous Metal Oxides with Customizable Noble Metal Nanocrystals","authors":"Jichun Li, Lingxiao Xue, Yu Deng, Xiaowei Cheng, Junhao Ma*, Wenhe Xie*, Meihua Chen* and Yonghui Deng*, ","doi":"10.1021/acscentsci.4c0159210.1021/acscentsci.4c01592","DOIUrl":"https://doi.org/10.1021/acscentsci.4c01592https://doi.org/10.1021/acscentsci.4c01592","url":null,"abstract":"<p >An efficient regiospecific co-assembly (RSCA) strategy is developed for general synthesis of mesoporous metal oxides with pore walls precisely decorated by highly dispersed noble metal nanocrystals with customized parameters (diameter and composition). It features the rational utilization of the specific interactions between hydrophilic molecular precursors, hydrophobic noble metal nanocrystals, and amphiphilic block copolymers, to achieve regiospecific co-assembly as confirmed by molecular dynamics simulations. Through this RSCA strategy, we achieved a controllable synthesis of a variety of functional mesoporous metal oxide composites (e.g., WO<sub>3</sub>, ZrO<sub>2</sub>, TiO<sub>2</sub>) with in-pore walls precisely decorated by various noble metal nanocrystals of tailored components (Au, Ag, Pt, Pd and their nanoalloys) and sizes (3.0–8.5 nm). As an example, the obtained mesoporous 0.5-Ag/WO<sub>3</sub> material has a highly interconnected mesoporous structure and uniform 6.5 nm Ag nanocrystals confined in the mesopores, showing superior NO sensing performances with high sensitivity, good selectivity, and stability at low working temperature (127 °C). <i>In situ</i> spectroscopy study indicates that the NO sensing process involves a unique gas–solid reaction, where NO molecules are converted into chemisorbed NO<sub><i>x</i></sub> species over the sensitive materials, inducing a remarkable change of resistance and outputting a dramatic response signal.</p><p >A facile regiospecific co-assembly strategy enables the obtained mesoporous WO<sub>3</sub> materials with precisely decorated Ag nanocrystals and rich oxygen vacancies to show superior NO sensitivity.</p>","PeriodicalId":10,"journal":{"name":"ACS Central Science","volume":"10 12","pages":"2274–2284 2274–2284"},"PeriodicalIF":12.7,"publicationDate":"2024-11-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acscentsci.4c01592","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143127515","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}