Xiaoding Jiang, Xu He, Jonathan Wong, Stephan Scheeff, Sam Chun Kit Hau, Tak Hin Wong, Yao Qin, Chi Hang Fan, Bowen Ma, Ngai Lam Chung, Junzhe Huang, Jiajia Zhao, Yu Yan, Min Xiao, Xueqin Song, Tony K. C. Hui, Z. Zuo, William Ka-Kei Wu, Ho Ko, Kim Hei-Man Chow, Billy Wai-Lung Ng
{"title":"Lactone-to-Lactam Editing Alters the Pharmacology of Bilobalide","authors":"Xiaoding Jiang, Xu He, Jonathan Wong, Stephan Scheeff, Sam Chun Kit Hau, Tak Hin Wong, Yao Qin, Chi Hang Fan, Bowen Ma, Ngai Lam Chung, Junzhe Huang, Jiajia Zhao, Yu Yan, Min Xiao, Xueqin Song, Tony K. C. Hui, Z. Zuo, William Ka-Kei Wu, Ho Ko, Kim Hei-Man Chow, Billy Wai-Lung Ng","doi":"10.1021/jacsau.4c00416","DOIUrl":"https://doi.org/10.1021/jacsau.4c00416","url":null,"abstract":"","PeriodicalId":14799,"journal":{"name":"JACS Au","volume":"1 4","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-07-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141640596","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Heejung Jung, Virginia Jiang, Zihang Su, Yuta Inaba, Farid F. Khoury, Scott Banta
{"title":"Overexpression of a Designed Mutant Oxyanion Binding Protein ModA/WtpA in Acidithiobacillus ferrooxidans for the Low pH Recovery of Molybdenum and Rhenium","authors":"Heejung Jung, Virginia Jiang, Zihang Su, Yuta Inaba, Farid F. Khoury, Scott Banta","doi":"10.1021/jacsau.4c00296","DOIUrl":"https://doi.org/10.1021/jacsau.4c00296","url":null,"abstract":"","PeriodicalId":14799,"journal":{"name":"JACS Au","volume":"63 35","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-07-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141651770","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Minseok Kim, Sohag Biswas, Isabel Barraza Alvarez, Phillip Christopher, Bryan M. Wong, Lorenzo Mangolini
Nonthermal plasmas provide a unique approach to electrically driven heterogeneous catalytic processes. Despite much interest from the community, fundamental activation pathways in these processes remain poorly understood. Here, we investigate how exposure to a nonthermal plasma sustained in an argon nonreactive atmosphere affects the desorption of carbon monoxide (CO) from platinum nanoparticles. Temperature-programmed desorption measurements indicate that the plasma reduces the effective binding energy (BE) of CO to Pt surfaces by as much as ∼0.3 eV, with the reduction in the BE scaling linearly with the plasma density. We find that the effective CO BE is most strongly reduced for under-coordinated sites (steps and edges) compared to well-coordinated sites (terraces). Density functional theory calculations suggest that this is due to plasma-induced charging and electric fields at the catalyst surface, which preferentially affect under-coordinated sites. This study provides direct experimental evidence of plasma-induced nonthermal activation of the adsorbate-catalyst couple.
{"title":"Nonthermal Plasma Activation of Adsorbates: The Case of CO on Pt","authors":"Minseok Kim, Sohag Biswas, Isabel Barraza Alvarez, Phillip Christopher, Bryan M. Wong, Lorenzo Mangolini","doi":"10.1021/jacsau.4c00309","DOIUrl":"https://doi.org/10.1021/jacsau.4c00309","url":null,"abstract":"Nonthermal plasmas provide a unique approach to electrically driven heterogeneous catalytic processes. Despite much interest from the community, fundamental activation pathways in these processes remain poorly understood. Here, we investigate how exposure to a nonthermal plasma sustained in an argon nonreactive atmosphere affects the desorption of carbon monoxide (CO) from platinum nanoparticles. Temperature-programmed desorption measurements indicate that the plasma reduces the effective binding energy (BE) of CO to Pt surfaces by as much as ∼0.3 eV, with the reduction in the BE scaling linearly with the plasma density. We find that the effective CO BE is most strongly reduced for under-coordinated sites (steps and edges) compared to well-coordinated sites (terraces). Density functional theory calculations suggest that this is due to plasma-induced charging and electric fields at the catalyst surface, which preferentially affect under-coordinated sites. This study provides direct experimental evidence of plasma-induced nonthermal activation of the adsorbate-catalyst couple.","PeriodicalId":14799,"journal":{"name":"JACS Au","volume":"41 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-07-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141613216","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Jared A. Nettles, Saleh Alfarhan, Cameron A. Pascoe, Clarissa Westover, Margaret D. Madsen, Jose I. Sintas, Aadhi Subbiah, Timothy E. Long, Kailong Jin
{"title":"Functional Upcycling of Polyurethane Thermosets into Value-Added Thermoplastics via Small-Molecule Carbamate-Assisted Decross-Linking Extrusion","authors":"Jared A. Nettles, Saleh Alfarhan, Cameron A. Pascoe, Clarissa Westover, Margaret D. Madsen, Jose I. Sintas, Aadhi Subbiah, Timothy E. Long, Kailong Jin","doi":"10.1021/jacsau.4c00403","DOIUrl":"https://doi.org/10.1021/jacsau.4c00403","url":null,"abstract":"","PeriodicalId":14799,"journal":{"name":"JACS Au","volume":"1 14","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-07-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141652301","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Daniele Mazzarella, Jelena Stanić, Miguel Bernús, Arad Seyed Mehdi, Cassandra J. Henderson, Omar Boutureira, Timothy Noël
{"title":"In-Flow Generation of Thionyl Fluoride (SOF2) Enables the Rapid and Efficient Synthesis of Acyl Fluorides from Carboxylic Acids","authors":"Daniele Mazzarella, Jelena Stanić, Miguel Bernús, Arad Seyed Mehdi, Cassandra J. Henderson, Omar Boutureira, Timothy Noël","doi":"10.1021/jacsau.4c00318","DOIUrl":"https://doi.org/10.1021/jacsau.4c00318","url":null,"abstract":"","PeriodicalId":14799,"journal":{"name":"JACS Au","volume":"96 6","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-07-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141652847","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
PROTAC (Proteolysis TArgeting Chimeras) is a promising therapeutic approach for targeted protein degradation that recruits an E3 ubiquitin ligase to a specific protein of interest (POI), leading to its degradation by the proteasome. Recently, we developed a novel split-and-mix PROTAC system based on liposome self-assembly (LipoSM-PROTAC) which could achieve target protein degradation at comparable concentrations comparable to small molecules. In this study, we expanded protein targets based on the LipoSM-PROTAC platform and further examined its therapeutic effects in vivo. Notably, this platform could efficiently degrade the protein level of MEK1/2 in A375 cells or Alk in NCI-H2228 cells and display obvious tumor inhibition (60–70% inhibition rate) with negligible toxicity. This study further proved the LipoSM-PROTAC’s application potentials.
{"title":"Versatile Split-and-Mix Liposome PROTAC Platform for Efficient Degradation of Target Protein In Vivo","authors":"Chunli Song, Zijun Jiao, Zhanfeng Hou, Yun Xing, Xinrui Sha, Yuechen Wang, Jiaxin Chen, Susheng Liu, Zigang Li, Feng Yin","doi":"10.1021/jacsau.4c00278","DOIUrl":"https://doi.org/10.1021/jacsau.4c00278","url":null,"abstract":"PROTAC (Proteolysis TArgeting Chimeras) is a promising therapeutic approach for targeted protein degradation that recruits an E3 ubiquitin ligase to a specific protein of interest (POI), leading to its degradation by the proteasome. Recently, we developed a novel split-and-mix PROTAC system based on liposome self-assembly (LipoSM-PROTAC) which could achieve target protein degradation at comparable concentrations comparable to small molecules. In this study, we expanded protein targets based on the LipoSM-PROTAC platform and further examined its therapeutic effects <i>in vivo</i>. Notably, this platform could efficiently degrade the protein level of MEK1/2 in A375 cells or Alk in NCI-H2228 cells and display obvious tumor inhibition (60–70% inhibition rate) with negligible toxicity. This study further proved the LipoSM-PROTAC’s application potentials.","PeriodicalId":14799,"journal":{"name":"JACS Au","volume":"20 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-07-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141613218","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Jaeha Lee, Peter Tieu, Jordan Finzel, Wenjie Zang, Xingxu Yan, Chaitanya A. Gadre, George Graham, Xiaoqing Pan, Phillip Christopher
The author list for this paper should appear as it does in this Addition/Correction. The affiliations for the authors are as indicated under Author Information. J.L. and P.T. contributed equally to this work. This article has not yet been cited by other publications.
{"title":"Correction to How Pt Influences H2 Reactions on High Surface-Area Pt/CeO2 Powder Catalyst Surfaces","authors":"Jaeha Lee, Peter Tieu, Jordan Finzel, Wenjie Zang, Xingxu Yan, Chaitanya A. Gadre, George Graham, Xiaoqing Pan, Phillip Christopher","doi":"10.1021/jacsau.4c00541","DOIUrl":"https://doi.org/10.1021/jacsau.4c00541","url":null,"abstract":"The author list for this paper should appear as it does in this Addition/Correction. The affiliations for the authors are as indicated under Author Information. J.L. and P.T. contributed equally to this work. This article has not yet been cited by other publications.","PeriodicalId":14799,"journal":{"name":"JACS Au","volume":"44 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-07-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141587225","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
David S. Potts, Jessica K. Komar, Matthew A. Jacobson, Huston Locht, David W. Flaherty
The structure of solvent molecules within zeolite pores influences the rates and selectivities of catalytic reactions by altering the free energies of reactive species. Here, we examine the consequences of these effects on the kinetics and thermodynamics of 1,2-epoxybutane (C4H8O) ring-opening with methanol (CH3OH) in acetonitrile (CH3CN) cosolvent over Lewis acidic (Zr-BEA) and Brønsted acidic (Al-BEA) zeolites of varying (SiOH)x density. Despite ostensibly identical reaction mechanisms across materials, turnover rates depend differently on (SiOH)x density between acid types. (SiOH)x-rich Zr-BEA (Zr-BEA-OH) provides ∼10 times greater rates than a (SiOH)x-poor material (Zr-BEA-F), while Al-BEA-OH and Al-BEA-F give turnover rates within a factor of 2. Zr-BEA-OH shows more positive activation enthalpies and entropies than Zr-BEA-F across the range of [CH3OH], which reflect the displacement of solvent molecules and lead to greater rates in Zr-BEA-OH due to the dominant role of entropic gains. Measurements of the density and composition of solvent within the pores show that the (SiOH)x nests within Zr-BEA-OH promote hydrogen-bonded solvent structures distinct from Zr-BEA-F, while the Brønsted acid sites confer interactions similar to (SiOH)x nests and give solvent structures within Al-BEA-F that resemble those within Al-BEA-OH. Correlations between apparent activation enthalpies and C4H8O adsorption enthalpies show that interactions with solvent molecules give proportional changes to both C4H8O adsorption and ring-opening transition state formation. The differences in intrapore environment carry consequences for both rates and regioselectivities of epoxide ring-opening, as demonstrated by product regioselectivities that increase by a factor of 3 in response to changes in solvent composition and the type of acid site in the *BEA structure (i.e., Lewis or Brønsted). These results demonstrate the ability to control rates, regioselectivities, and adsorption thermodynamics relevant for industrially relevant liquid-phase reactions through the design of noncovalent interactions among solvating molecules, reactive species, and (SiOH)x functions.
{"title":"Consequences of Pore Polarity and Solvent Structure on Epoxide Ring-Opening in Lewis and Brønsted Acid Zeolites","authors":"David S. Potts, Jessica K. Komar, Matthew A. Jacobson, Huston Locht, David W. Flaherty","doi":"10.1021/jacsau.4c00398","DOIUrl":"https://doi.org/10.1021/jacsau.4c00398","url":null,"abstract":"The structure of solvent molecules within zeolite pores influences the rates and selectivities of catalytic reactions by altering the free energies of reactive species. Here, we examine the consequences of these effects on the kinetics and thermodynamics of 1,2-epoxybutane (C<sub>4</sub>H<sub>8</sub>O) ring-opening with methanol (CH<sub>3</sub>OH) in acetonitrile (CH<sub>3</sub>CN) cosolvent over Lewis acidic (Zr-BEA) and Brønsted acidic (Al-BEA) zeolites of varying (SiOH)<sub><i>x</i></sub> density. Despite ostensibly identical reaction mechanisms across materials, turnover rates depend differently on (SiOH)<sub><i>x</i></sub> density between acid types. (SiOH)<sub><i>x</i></sub>-rich Zr-BEA (Zr-BEA-OH) provides ∼10 times greater rates than a (SiOH)<sub><i>x</i></sub>-poor material (Zr-BEA-F), while Al-BEA-OH and Al-BEA-F give turnover rates within a factor of 2. Zr-BEA-OH shows more positive activation enthalpies and entropies than Zr-BEA-F across the range of [CH<sub>3</sub>OH], which reflect the displacement of solvent molecules and lead to greater rates in Zr-BEA-OH due to the dominant role of entropic gains. Measurements of the density and composition of solvent within the pores show that the (SiOH)<sub><i>x</i></sub> nests within Zr-BEA-OH promote hydrogen-bonded solvent structures distinct from Zr-BEA-F, while the Brønsted acid sites confer interactions similar to (SiOH)<sub><i>x</i></sub> nests and give solvent structures within Al-BEA-F that resemble those within Al-BEA-OH. Correlations between apparent activation enthalpies and C<sub>4</sub>H<sub>8</sub>O adsorption enthalpies show that interactions with solvent molecules give proportional changes to both C<sub>4</sub>H<sub>8</sub>O adsorption and ring-opening transition state formation. The differences in intrapore environment carry consequences for both rates and regioselectivities of epoxide ring-opening, as demonstrated by product regioselectivities that increase by a factor of 3 in response to changes in solvent composition and the type of acid site in the *BEA structure (i.e., Lewis or Brønsted). These results demonstrate the ability to control rates, regioselectivities, and adsorption thermodynamics relevant for industrially relevant liquid-phase reactions through the design of noncovalent interactions among solvating molecules, reactive species, and (SiOH)<sub><i>x</i></sub> functions.","PeriodicalId":14799,"journal":{"name":"JACS Au","volume":"25 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-07-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141614942","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Zezhao Xu, Weiwei Yang, Huiyu Liu, Shan Jiang, Andrew C.-H. Sue
In pursuit of environmental sustainability and energy efficiency, assorted macrocyclic compounds have recently emerged as crystalline adsorbents for the efficient molecular sieving of various chemical commodities. Herein, we delve into the conformational characteristics and solid-state packing modes of tiara[5]arenes (T[5]), a rim-differentiated pillar[5]arene derivative. By meticulously exploring the conformational space, we have successfully identified a multitude of distinct T[5] conformers within a relatively narrow energy range of 22 kJ/mol. This finding underscores the inherent conformational flexibility of this macrocyclic scaffold, enabling T[5] to adapt diverse packing arrangements in the solid state. While solvent-free T[5] crystals do not exhibit permanent porosity, they undergo solvomorphic interconversions when exposed to various guest compounds. Our study demonstrates that T[5]-based crystalline materials exhibit a notable preference for selectively capturing aromatic and olefinic solvents, such as benzene, toluene, chlorobenzene, and cyclohexene, over their aliphatic hydrocarbon counterparts from equivalent volume liquid mixtures, achieving up to 10:1 selectivity between benzene and cyclohexane.
{"title":"Guest-Induced Conformational Transformations in Tiara[5]arene Crystals: A Pathway for Molecular Sieving⊥","authors":"Zezhao Xu, Weiwei Yang, Huiyu Liu, Shan Jiang, Andrew C.-H. Sue","doi":"10.1021/jacsau.4c00310","DOIUrl":"https://doi.org/10.1021/jacsau.4c00310","url":null,"abstract":"In pursuit of environmental sustainability and energy efficiency, assorted macrocyclic compounds have recently emerged as crystalline adsorbents for the efficient molecular sieving of various chemical commodities. Herein, we delve into the conformational characteristics and solid-state packing modes of tiara[5]arenes (<b>T[5]</b>), a rim-differentiated pillar[5]arene derivative. By meticulously exploring the conformational space, we have successfully identified a multitude of distinct <b>T[5]</b> conformers within a relatively narrow energy range of 22 kJ/mol. This finding underscores the inherent conformational flexibility of this macrocyclic scaffold, enabling <b>T[5]</b> to adapt diverse packing arrangements in the solid state. While solvent-free <b>T[5]</b> crystals do not exhibit permanent porosity, they undergo solvomorphic interconversions when exposed to various guest compounds. Our study demonstrates that <b>T[5]</b>-based crystalline materials exhibit a notable preference for selectively capturing aromatic and olefinic solvents, such as benzene, toluene, chlorobenzene, and cyclohexene, over their aliphatic hydrocarbon counterparts from equivalent volume liquid mixtures, achieving up to 10:1 selectivity between benzene and cyclohexane.","PeriodicalId":14799,"journal":{"name":"JACS Au","volume":"23 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-07-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141587245","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
京公网安备 11010802042870号
京ICP备2023020795号-1
扫码关注我们
求助内容：
应助结果提醒方式：