首页 > 最新文献

ACS Publications最新文献

英文 中文
IF:
Osmotic Pressure-Induced Lipid Membrane Phase Separation within Macromolecular Environments. 在大分子环境中渗透压诱导的脂膜相分离。
IF 2.9 2区 化学 Q3 CHEMISTRY, PHYSICAL Pub Date : 2026-02-07 DOI: 10.1021/acs.jpcb.5c07221
Shunsuke Yamazaki, Tomoya Fujita, Shino Mizuno, Tsutomu Hamada

Lipid membrane phase separation, which is a thermodynamic physical process, has attracted attention as a dynamic function of cellular interfaces. As membrane tension influences the phase separation of cellular membranes under isothermal conditions, it is essential to clarify the physicochemical mechanism involved. Living cells contain numerous macromolecules that can generate osmotic pressure across the membrane due to the semipermeable nature of the lipid bilayer. In this research, we examined how macromolecular surroundings and the transmembrane osmotic pressure influence membrane phase separation, utilizing model membranes like giant lipid vesicles. We generated osmotic pressure across the membrane using dextran (molecular weights 40,000 and 200,000) and polyethylene glycol (molecular weight 6,000) as model macromolecules. Microscopic observations represented the changes in the percentage of phase-separated vesicles and miscibility temperature caused by osmotic tension, indicating that macromolecular surroundings tend to suppress membrane phase separation, while macromolecular osmotic pressure across the membrane markedly induces phase separation. Lipid membrane phase separation can be regulated by the macromolecular concentration and osmotic pressure across the membrane. This finding offers new insights into the formation and regulation of membrane domains within the macromolecularly crowded environments of living cells.

{"title":"Osmotic Pressure-Induced Lipid Membrane Phase Separation within Macromolecular Environments.","authors":"Shunsuke Yamazaki, Tomoya Fujita, Shino Mizuno, Tsutomu Hamada","doi":"10.1021/acs.jpcb.5c07221","DOIUrl":"https://doi.org/10.1021/acs.jpcb.5c07221","url":null,"abstract":"<p><p>Lipid membrane phase separation, which is a thermodynamic physical process, has attracted attention as a dynamic function of cellular interfaces. As membrane tension influences the phase separation of cellular membranes under isothermal conditions, it is essential to clarify the physicochemical mechanism involved. Living cells contain numerous macromolecules that can generate osmotic pressure across the membrane due to the semipermeable nature of the lipid bilayer. In this research, we examined how macromolecular surroundings and the transmembrane osmotic pressure influence membrane phase separation, utilizing model membranes like giant lipid vesicles. We generated osmotic pressure across the membrane using dextran (molecular weights 40,000 and 200,000) and polyethylene glycol (molecular weight 6,000) as model macromolecules. Microscopic observations represented the changes in the percentage of phase-separated vesicles and miscibility temperature caused by osmotic tension, indicating that macromolecular surroundings tend to suppress membrane phase separation, while macromolecular osmotic pressure across the membrane markedly induces phase separation. Lipid membrane phase separation can be regulated by the macromolecular concentration and osmotic pressure across the membrane. This finding offers new insights into the formation and regulation of membrane domains within the macromolecularly crowded environments of living cells.</p>","PeriodicalId":60,"journal":{"name":"The Journal of Physical Chemistry B","volume":" ","pages":""},"PeriodicalIF":2.9,"publicationDate":"2026-02-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146130543","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}
引用次数: 0
Enantioselective Total Synthesis of (+)-Subincanadine F via Organo-SOMO Catalysis. 有机somo催化对映选择性合成(+)-Subincanadine F。
IF 5 1区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2026-02-07 DOI: 10.1021/acs.orglett.5c04906
Tian-Yuan Zhang, Chun-Yan Peng, Bin Liu, YuanHu Mao, Liang Ding, Hui-Min Qin, XiangKai Kong, JinGang Peng, Xiang-Zhi Luo, Yu-Die Zhang, JiaYu Huang, Ran Xu, JianTa Wang, Lei Tang

The asymmetric total synthesis of (+)-subincanadine F has been achieved in only 9 steps from commercial tryptamine. A key step involves an Organo-SOMO-catalyzed α-arylation of aldehydes to construct the azepino[4,5-b]indole core. Finally, a subsequent intramolecular aza-Michael addition process leads to the formation of the 1-azabicyclo[4.3.1]decane framework. In addition, this Organo-SOMO catalytic strategy features a broad substrate scope, with diverse functionalized products afforded in generally moderate to good yields and good to excellent enantioselectivities.

{"title":"Enantioselective Total Synthesis of (+)-Subincanadine F via Organo-SOMO Catalysis.","authors":"Tian-Yuan Zhang, Chun-Yan Peng, Bin Liu, YuanHu Mao, Liang Ding, Hui-Min Qin, XiangKai Kong, JinGang Peng, Xiang-Zhi Luo, Yu-Die Zhang, JiaYu Huang, Ran Xu, JianTa Wang, Lei Tang","doi":"10.1021/acs.orglett.5c04906","DOIUrl":"https://doi.org/10.1021/acs.orglett.5c04906","url":null,"abstract":"<p><p>The asymmetric total synthesis of (+)-subincanadine F has been achieved in only 9 steps from commercial tryptamine. A key step involves an Organo-SOMO-catalyzed α-arylation of aldehydes to construct the azepino[4,5-<i>b</i>]indole core. Finally, a subsequent intramolecular aza-Michael addition process leads to the formation of the 1-azabicyclo[4.3.1]decane framework. In addition, this Organo-SOMO catalytic strategy features a broad substrate scope, with diverse functionalized products afforded in generally moderate to good yields and good to excellent enantioselectivities.</p>","PeriodicalId":54,"journal":{"name":"Organic Letters","volume":" ","pages":""},"PeriodicalIF":5.0,"publicationDate":"2026-02-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146130447","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}
引用次数: 0
Synthesis of 3,5-Disubstituted-(1H-) and (2H-) Heteroaryl-1,2,4-triazoles via an Oxidative Annulation Strategy. 氧化环化合成3,5-二取代-(1H-)和(2H-)杂芳基-1,2,4-三唑。
IF 3.6 2区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2026-02-07 DOI: 10.1021/acs.joc.5c03029
Emmanuel E Aimiuwu, Damian P Duda, Allen G Oliver, David A Dixon, Jesse D Carrick

1,2,4-Triazole is a ubiquitous heterocycle of significance for pharmaceuticals, materials, and ligand design. A convergent, atom-economical strategy for the construction of this important moiety has been developed, leveraging functionalized heteroaryl hydrazonimides and carbaldehydes via iodine-mediated oxidative annulation in an efficient, scalable, and metal-free manner, providing completely chemoselective 1H- or 2H-3,5-disubstituted-1,2,4-triazoles of relevance to separation science and medicinal chemistry. The twenty-nine-example substrate scope is highlighted by rapid access to sp2- and sp3-hybridized substituents through carbaldehyde selection. Diversely functionalized pyridyl- and heteroaryl components were incorporated through a hydrazonimide synthon with several examples having relevance to unsymmetric, soft-N-donor complexant scaffolds utilized in minor actinide extraction in support of improving the sustainability of the nuclear fuel cycle. Single-crystal X-ray diffraction experiments confirmed the presence of 1H- and 2H-tautomers. Density functional theory computations provided support of a proposed mechanistic hypothesis. Method optimization, substrate scope, scale-up experiments, and a preliminary reaction mechanism are reported herein.

{"title":"Synthesis of 3,5-Disubstituted-(1<i>H</i>-) and (2<i>H</i>-) Heteroaryl-1,2,4-triazoles via an Oxidative Annulation Strategy.","authors":"Emmanuel E Aimiuwu, Damian P Duda, Allen G Oliver, David A Dixon, Jesse D Carrick","doi":"10.1021/acs.joc.5c03029","DOIUrl":"https://doi.org/10.1021/acs.joc.5c03029","url":null,"abstract":"<p><p>1,2,4-Triazole is a ubiquitous heterocycle of significance for pharmaceuticals, materials, and ligand design. A convergent, atom-economical strategy for the construction of this important moiety has been developed, leveraging functionalized heteroaryl hydrazonimides and carbaldehydes via iodine-mediated oxidative annulation in an efficient, scalable, and metal-free manner, providing completely chemoselective 1<i>H</i>- or 2<i>H</i>-3,5-disubstituted-1,2,4-triazoles of relevance to separation science and medicinal chemistry. The twenty-nine-example substrate scope is highlighted by rapid access to sp<sup>2</sup>- and sp<sup>3</sup>-hybridized substituents through carbaldehyde selection. Diversely functionalized pyridyl- and heteroaryl components were incorporated through a hydrazonimide synthon with several examples having relevance to unsymmetric, soft-N-donor complexant scaffolds utilized in minor actinide extraction in support of improving the sustainability of the nuclear fuel cycle. Single-crystal X-ray diffraction experiments confirmed the presence of 1<i>H</i>- and 2<i>H</i>-tautomers. Density functional theory computations provided support of a proposed mechanistic hypothesis. Method optimization, substrate scope, scale-up experiments, and a preliminary reaction mechanism are reported herein.</p>","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":" ","pages":""},"PeriodicalIF":3.6,"publicationDate":"2026-02-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146130522","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}
引用次数: 0
Tracking PFAS across Environmental Media Surrounding Fluorochemical Industrial Park: Insights from Nontarget Analysis and Risk Assessment. 氟化工园区周边环境介质中PFAS的追踪:来自非目标分析和风险评估的见解
IF 11.3 1区 环境科学与生态学 Q1 ENGINEERING, ENVIRONMENTAL Pub Date : 2026-02-07 DOI: 10.1021/acs.est.5c10040
Xin Li, Minmin Hou, Xiaodong Wu, Xuwenqi Zhang, Zhengquan Ji, Pengfei Li, Yingying Zhang, Hao Ding, Yali Shi, Yaqi Cai

The occurrence and accumulation of novel perfluoroalkyl and polyfluoroalkyl substances (PFAS) have emerged as a scientific concern in recent years. While numerous studies have identified elevated concentrations of certain emerging PFAS, the sources and environmental accumulation differences of many homologues remain insufficiently characterized. In this study, we employed suspect and nontarget screening to characterize both legacy and emerging PFAS across environmental matrices, including water, sediment, and soil, surrounding an industrial park with predominant perfluoroalkyl carboxylic acids (PFCAs) contamination. A total of 32 classes comprising 112 compounds were identified, including 80 emerging PFAS detected through the screening approach. In addition to PFCAs, emerging PFAS, including perfluoroalkyl ether carboxylic acids (PFECAs), perfluoroalkyl alcohols (PFAs), and PFA derivatives, were frequently detected in the study area, primarily in water and sediment samples. In contrast, the contamination profile was less complicated in soil samples, where PFCAs were the predominant homologues. The median total concentrations of target PFAS in water, sediment, and soil samples were 427 ng/L, 4.17 ng/g of dw, and 3.92 ng/g of dw, respectively. Predicted risk assessment further indicated that these emerging PFAS with high concentrations pose non-negligible risks to both ecological and human health, underscoring the need for further investigation into their potential impacts.

{"title":"Tracking PFAS across Environmental Media Surrounding Fluorochemical Industrial Park: Insights from Nontarget Analysis and Risk Assessment.","authors":"Xin Li, Minmin Hou, Xiaodong Wu, Xuwenqi Zhang, Zhengquan Ji, Pengfei Li, Yingying Zhang, Hao Ding, Yali Shi, Yaqi Cai","doi":"10.1021/acs.est.5c10040","DOIUrl":"https://doi.org/10.1021/acs.est.5c10040","url":null,"abstract":"<p><p>The occurrence and accumulation of novel perfluoroalkyl and polyfluoroalkyl substances (PFAS) have emerged as a scientific concern in recent years. While numerous studies have identified elevated concentrations of certain emerging PFAS, the sources and environmental accumulation differences of many homologues remain insufficiently characterized. In this study, we employed suspect and nontarget screening to characterize both legacy and emerging PFAS across environmental matrices, including water, sediment, and soil, surrounding an industrial park with predominant perfluoroalkyl carboxylic acids (PFCAs) contamination. A total of 32 classes comprising 112 compounds were identified, including 80 emerging PFAS detected through the screening approach. In addition to PFCAs, emerging PFAS, including perfluoroalkyl ether carboxylic acids (PFECAs), perfluoroalkyl alcohols (PFAs), and PFA derivatives, were frequently detected in the study area, primarily in water and sediment samples. In contrast, the contamination profile was less complicated in soil samples, where PFCAs were the predominant homologues. The median total concentrations of target PFAS in water, sediment, and soil samples were 427 ng/L, 4.17 ng/g of dw, and 3.92 ng/g of dw, respectively. Predicted risk assessment further indicated that these emerging PFAS with high concentrations pose non-negligible risks to both ecological and human health, underscoring the need for further investigation into their potential impacts.</p>","PeriodicalId":36,"journal":{"name":"环境科学与技术","volume":" ","pages":""},"PeriodicalIF":11.3,"publicationDate":"2026-02-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146130527","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"环境科学与生态学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Unlocking the Potential of Fluoroethylene Carbonate with Lithium Difluoro(oxalate)borate for High-Voltage and High-Rate Lithium Metal Batteries. 利用二氟(草酸)硼酸锂释放碳酸氟乙烯在高压和高倍率锂金属电池中的潜力。
IF 4.6 2区 化学 Q2 CHEMISTRY, PHYSICAL Pub Date : 2026-02-07 DOI: 10.1021/acs.jpclett.5c03897
Changquan Wu, Guangni Ding, Du Liu, Xuerui Yang, Xiaowei Huang, Naigen Zhou

Fluoroethylene carbonate (FEC), as a key electrolyte component, has been extensively employed across diverse electrolyte systems owing to its excellent compatibility with different anode materials. However, its mechanistic role on the cathode side remains under debate due to the strong electron-withdrawing nature of the fluorine incorporation. Here, we demonstrate that lithium difluoro(oxalate)borate (LiDFOB) can effectively trigger the latent cathode-side functionality of FEC through a rationally designed dual-additive electrolyte. At the LiNi0.9Co0.05Mn0.05O2 cathode, oxidative cleavage of LiDFOB generates BOF2 intermediates that activate FEC and direct its decomposition toward LiF and B-O/B-F-rich inorganic species, constructing a compact and resilient cathode-electrolyte interphase (CEI). Simultaneously, the coupled reduction of FEC and DFOB- at the lithium metal anode yields a boron-rich, LiF-enriched solid electrolyte interphase (SEI) that enhances interfacial compatibility and suppresses dendrite growth. These LiDFOB-enabled, FEC-mediated interfacial pathways significantly improve ion transport and durability, delivering 73.4% capacity retention of Li||NCM9055 full cells after 1000 cycles at 4.7 V, versus 55.1% for the base electrolyte.

{"title":"Unlocking the Potential of Fluoroethylene Carbonate with Lithium Difluoro(oxalate)borate for High-Voltage and High-Rate Lithium Metal Batteries.","authors":"Changquan Wu, Guangni Ding, Du Liu, Xuerui Yang, Xiaowei Huang, Naigen Zhou","doi":"10.1021/acs.jpclett.5c03897","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c03897","url":null,"abstract":"<p><p>Fluoroethylene carbonate (FEC), as a key electrolyte component, has been extensively employed across diverse electrolyte systems owing to its excellent compatibility with different anode materials. However, its mechanistic role on the cathode side remains under debate due to the strong electron-withdrawing nature of the fluorine incorporation. Here, we demonstrate that lithium difluoro(oxalate)borate (LiDFOB) can effectively trigger the latent cathode-side functionality of FEC through a rationally designed dual-additive electrolyte. At the LiNi<sub>0.9</sub>Co<sub>0.05</sub>Mn<sub>0.05</sub>O<sub>2</sub> cathode, oxidative cleavage of LiDFOB generates BOF<sub>2</sub> intermediates that activate FEC and direct its decomposition toward LiF and B-O/B-F-rich inorganic species, constructing a compact and resilient cathode-electrolyte interphase (CEI). Simultaneously, the coupled reduction of FEC and DFOB<sup>-</sup> at the lithium metal anode yields a boron-rich, LiF-enriched solid electrolyte interphase (SEI) that enhances interfacial compatibility and suppresses dendrite growth. These LiDFOB-enabled, FEC-mediated interfacial pathways significantly improve ion transport and durability, delivering 73.4% capacity retention of Li||NCM9055 full cells after 1000 cycles at 4.7 V, versus 55.1% for the base electrolyte.</p>","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":" ","pages":""},"PeriodicalIF":4.6,"publicationDate":"2026-02-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146130593","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}
引用次数: 0
Zn2+-Driven Tavaborole-Adenosine Hydrogel: A Strategy for Enhanced Solubility, Sustained Release, and Antifungal Efficacy. Zn2+驱动的他瓦波洛尔-腺苷水凝胶:一种增强溶解度、缓释和抗真菌功效的策略。
IF 4.5 2区 医学 Q2 MEDICINE, RESEARCH & EXPERIMENTAL Pub Date : 2026-02-07 DOI: 10.1021/acs.molpharmaceut.5c01541
Yehua Sun, Hanming Sha, Changyang Lei, Fangke Zhi, Nanrong Hu, Chenhao Song, Renzhong Qiao, Chao Li

Onychomycosis is a common fungal nail infection, causing nail thickening and discoloration. Tavaborole, a topical antifungal, has fewer side effects but requires long treatment periods and often results in low cure rates. In this study, we developed a Zn2+-driven tavaborole-adenosine (AT-Zn2+) hydrogel to improve its therapeutic effect. The hydrogel enhanced tavaborole's solubility, drug loading, and antifungal activity. Characterization by nuclear magnetic resonance (NMR), ultraviolet-visible (UV-vis) spectroscopy, and transmission electron microscopy (TEM) confirmed its successful synthesis and nanofiber structure. In vitro release tests showed that about 65% of tavaborole was released in PBS at pH 5.5 over 24 h, indicating pH-sensitive drug release for targeted therapy. Permeation studies using a bovine hoof model showed effective tavaborole penetration through keratinized tissues with a steady-state flux of 162 μg/cm2/h. The AT-Zn2+ hydrogel demonstrated lower minimum inhibitory concentrations (MICs) for C. albicans (0.00156 mM) and A. fumigatus (0.025 mM) compared to those of tavaborole alone. In a bovine onychomycosis model, the hydrogel showed stronger antifungal effects than the tavaborole solution. Cytotoxicity assays on RAW 264.7 cells indicated good biocompatibility with >85% cell viability. These findings suggest that the AT-Zn2+ hydrogel holds significant potential as a clinically effective antifungal agent.

{"title":"Zn<sup>2+</sup>-Driven Tavaborole-Adenosine Hydrogel: A Strategy for Enhanced Solubility, Sustained Release, and Antifungal Efficacy.","authors":"Yehua Sun, Hanming Sha, Changyang Lei, Fangke Zhi, Nanrong Hu, Chenhao Song, Renzhong Qiao, Chao Li","doi":"10.1021/acs.molpharmaceut.5c01541","DOIUrl":"https://doi.org/10.1021/acs.molpharmaceut.5c01541","url":null,"abstract":"<p><p>Onychomycosis is a common fungal nail infection, causing nail thickening and discoloration. Tavaborole, a topical antifungal, has fewer side effects but requires long treatment periods and often results in low cure rates. In this study, we developed a Zn<sup>2+</sup>-driven tavaborole-adenosine (AT-Zn<sup>2+</sup>) hydrogel to improve its therapeutic effect. The hydrogel enhanced tavaborole's solubility, drug loading, and antifungal activity. Characterization by nuclear magnetic resonance (NMR), ultraviolet-visible (UV-vis) spectroscopy, and transmission electron microscopy (TEM) confirmed its successful synthesis and nanofiber structure. In vitro release tests showed that about 65% of tavaborole was released in PBS at pH 5.5 over 24 h, indicating pH-sensitive drug release for targeted therapy. Permeation studies using a bovine hoof model showed effective tavaborole penetration through keratinized tissues with a steady-state flux of 162 μg/cm<sup>2</sup>/h. The AT-Zn<sup>2+</sup> hydrogel demonstrated lower minimum inhibitory concentrations (MICs) for <i>C. albicans</i> (0.00156 mM) and <i>A. fumigatus</i> (0.025 mM) compared to those of tavaborole alone. In a bovine onychomycosis model, the hydrogel showed stronger antifungal effects than the tavaborole solution. Cytotoxicity assays on RAW 264.7 cells indicated good biocompatibility with >85% cell viability. These findings suggest that the AT-Zn<sup>2+</sup> hydrogel holds significant potential as a clinically effective antifungal agent.</p>","PeriodicalId":52,"journal":{"name":"Molecular Pharmaceutics","volume":" ","pages":""},"PeriodicalIF":4.5,"publicationDate":"2026-02-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146130460","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"医学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Sputter-Deposited Ruthenium Nitrides for Electrochemical Nitrogen Fixation to Ammonia under Ambient Conditions. 溅射沉积氮化钌在环境条件下对氨的电化学固氮。
IF 8.2 2区 材料科学 Q1 MATERIALS SCIENCE, MULTIDISCIPLINARY Pub Date : 2026-02-07 DOI: 10.1021/acsami.5c23657
Xin Wei, Ruicheng Feng, Sa'id Albarqawi, Jacob Johny, Fan Yang, Michael Noyong, Ulrich Simon

Electrochemical nitrogen reduction reaction (eNRR) under ambient conditions offers a promising route for ammonia synthesis, although it currently suffers from slow kinetics and competing hydrogen evolution. Transition metal nitrides (TMNs) enable efficient nitrogen activation via the Mars-van Krevelen mechanism; however, effectively suppressing nitrogen leaching under electrochemical conditions remains challenging. Here, we report a nanostructured ruthenium nitride (RuN) catalyst synthesized via magnetron sputtering, demonstrating its application for eNRR for the first time. Structural characterization confirms a zincblende-like RuN phase, while surface properties (i.e., roughness and wettability) are tuned by the deposition duration. The optimal catalyst achieved an ammonia yield of 3.0 × 10-10 mol cm-2 s-1 at -0.3 V vs RHE and a Faradaic efficiency of 6.1% at -0.1 V vs RHE in a 0.1 mol L-1 KOH electrolyte, surpassing most reported ambient TMN catalysts. These findings underscore the promise of metal nitride-based electrocatalysts and provide insights into the rational design of next-generation catalysts for sustainable nitrogen fixation.

{"title":"Sputter-Deposited Ruthenium Nitrides for Electrochemical Nitrogen Fixation to Ammonia under Ambient Conditions.","authors":"Xin Wei, Ruicheng Feng, Sa'id Albarqawi, Jacob Johny, Fan Yang, Michael Noyong, Ulrich Simon","doi":"10.1021/acsami.5c23657","DOIUrl":"https://doi.org/10.1021/acsami.5c23657","url":null,"abstract":"<p><p>Electrochemical nitrogen reduction reaction (eNRR) under ambient conditions offers a promising route for ammonia synthesis, although it currently suffers from slow kinetics and competing hydrogen evolution. Transition metal nitrides (TMNs) enable efficient nitrogen activation via the Mars-van Krevelen mechanism; however, effectively suppressing nitrogen leaching under electrochemical conditions remains challenging. Here, we report a nanostructured ruthenium nitride (RuN) catalyst synthesized via magnetron sputtering, demonstrating its application for eNRR for the first time. Structural characterization confirms a zincblende-like RuN phase, while surface properties (i.e., roughness and wettability) are tuned by the deposition duration. The optimal catalyst achieved an ammonia yield of 3.0 × 10<sup>-10</sup> mol cm<sup>-2</sup> s<sup>-1</sup> at -0.3 V vs RHE and a Faradaic efficiency of 6.1% at -0.1 V vs RHE in a 0.1 mol L<sup>-1</sup> KOH electrolyte, surpassing most reported ambient TMN catalysts. These findings underscore the promise of metal nitride-based electrocatalysts and provide insights into the rational design of next-generation catalysts for sustainable nitrogen fixation.</p>","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":" ","pages":""},"PeriodicalIF":8.2,"publicationDate":"2026-02-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146130584","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}
引用次数: 0
Managing Active Hydrogen Species on Ternary Copper-Based Catalyst for Efficient Electrochemical Ammonia Synthesis from Nitrate. 三元铜基催化剂上活性氢的控制及其对硝酸盐电化学高效合成氨的影响。
IF 15.6 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-02-07 DOI: 10.1021/jacs.5c21149
Bin Lei, Bo Li, Yin Wang, Wanying Wang, Long Chen, Xinyi Wu, Bo-Hang Zhao, Weichao Wang, Jian-Gong Ma, Peng Cheng

The electrochemical nitrate reduction to ammonia (NO3RR) has garnered considerable interest as a highly promising route for value-added nitrate conversion. However, the efficiency of NO3RR is often limited by the inadequate supply of active hydrogen species (H*) and their preferential consumption via the competing hydrogen evolution reaction (HER), both of which stem from the lack of precise management of H*. Herein, we report a rationally designed ternary catalyst Pt@ZIF@Cu to achieve precise control and targeted utilization of H*. The spatially separated Pt and Cu sites serve as independent centers for H* generation and consumption, respectively. A ZIF layer is introduced as a hydrogen buffer, facilitating the efficient migration of H* from Pt sites to Cu sites with a reduced energy barrier, which ultimately enhances the NO3RR performance on the Cu surface while simultaneously suppressing HER at the Pt sites. The ternary Pt@ZIF@Cu exhibits superior NO3RR performance with an ammonia yield rate of up to 4.6 mmol h-1 mgcat-1 at -0.8 V (vs RHE) through meticulous H* management. Furthermore, it demonstrates enhanced performance (8.34 mmol h-1 mgcat-1) in a membrane electrode assembly (MEA) under ampere-level current densities, and enables the convenient preparation of high-purity solid ammonium products via Ar-stripping.

{"title":"Managing Active Hydrogen Species on Ternary Copper-Based Catalyst for Efficient Electrochemical Ammonia Synthesis from Nitrate.","authors":"Bin Lei, Bo Li, Yin Wang, Wanying Wang, Long Chen, Xinyi Wu, Bo-Hang Zhao, Weichao Wang, Jian-Gong Ma, Peng Cheng","doi":"10.1021/jacs.5c21149","DOIUrl":"https://doi.org/10.1021/jacs.5c21149","url":null,"abstract":"<p><p>The electrochemical nitrate reduction to ammonia (NO<sub>3</sub>RR) has garnered considerable interest as a highly promising route for value-added nitrate conversion. However, the efficiency of NO<sub>3</sub>RR is often limited by the inadequate supply of active hydrogen species (H*) and their preferential consumption via the competing hydrogen evolution reaction (HER), both of which stem from the lack of precise management of H*. Herein, we report a rationally designed ternary catalyst Pt@ZIF@Cu to achieve precise control and targeted utilization of H*. The spatially separated Pt and Cu sites serve as independent centers for H* generation and consumption, respectively. A ZIF layer is introduced as a hydrogen buffer, facilitating the efficient migration of H* from Pt sites to Cu sites with a reduced energy barrier, which ultimately enhances the NO<sub>3</sub>RR performance on the Cu surface while simultaneously suppressing HER at the Pt sites. The ternary Pt@ZIF@Cu exhibits superior NO<sub>3</sub>RR performance with an ammonia yield rate of up to 4.6 mmol h<sup>-1</sup> mg<sub>cat</sub><sup>-1</sup> at -0.8 V (vs RHE) through meticulous H* management. Furthermore, it demonstrates enhanced performance (8.34 mmol h<sup>-1</sup> mg<sub>cat</sub><sup>-1</sup>) in a membrane electrode assembly (MEA) under ampere-level current densities, and enables the convenient preparation of high-purity solid ammonium products via Ar-stripping.</p>","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":" ","pages":""},"PeriodicalIF":15.6,"publicationDate":"2026-02-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146130459","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}
引用次数: 0
Bilateral Nitrogen Interface Chemistry for Dendrite-Free Zinc-Iodine Batteries with Enhanced Four-Electron Redox Activity. 增强四电子氧化还原活性的无枝晶锌碘电池的双边氮界面化学。
IF 16 1区 材料科学 Q1 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-02-07 DOI: 10.1021/acsnano.5c16195
Yongshuai Liu, Wenyi Lu, Fengkai Zuo, Shaochong Cao, Pengshu Yi, Longli Ma, Zhu Liu, Shan He, Zhouhong Ren, Liang Cao, Mingxin Ye, Jianfeng Shen

Aqueous zinc-iodine (Zn-I2) batteries, owing to their compelling combination of environmental friendliness, cost-effectiveness, and enhanced safety features, are regarded as promising candidates for large-scale energy storage systems. Nevertheless, the limited I2/2I- two-electron redox chemistry and nonuniform Zn deposition critically impair the energy density and cycling stability of aqueous Zn-I2 batteries, hindering their practical deployment. Herein, multifunctional cyclohexylamine hydrochloride (CHAH) additive is introduced into the ZnSO4 electrolyte, which synergistically enables a dendrite-free Zn anode for extended cyclability and simultaneously activates a stable four-electron 2I+/I2/2I- redox chemistry at the I2 cathode. Combined experimental characterization and theoretical calculations reveal that the cyclohexylamine (CHA) reconstructs the Zn2+ solvation structure by displacing active H2O, while fostering a nitrogen-rich solid electrolyte interphase on the Zn anode at the same time. It suppresses parasitic reactions and enables excellent Zn plating/stripping cycling for 2150 h at 1 mA cm-2/1 mAh cm-2. Furthermore, nucleophilic amine groups in CHA act synergistically with Cl- to coordinate I+ by forming (2CHA)ICl, which improves four-electron 2I+/I2/2I- redox kinetics and achieves exceptional Zn-I2 battery performances (256.3 mAh g-1 at 10 A g-1). This bilateral nitrogen interface chemistry mechanism offers key insights into the development of high-performance Zn-I2 batteries.

{"title":"Bilateral Nitrogen Interface Chemistry for Dendrite-Free Zinc-Iodine Batteries with Enhanced Four-Electron Redox Activity.","authors":"Yongshuai Liu, Wenyi Lu, Fengkai Zuo, Shaochong Cao, Pengshu Yi, Longli Ma, Zhu Liu, Shan He, Zhouhong Ren, Liang Cao, Mingxin Ye, Jianfeng Shen","doi":"10.1021/acsnano.5c16195","DOIUrl":"https://doi.org/10.1021/acsnano.5c16195","url":null,"abstract":"<p><p>Aqueous zinc-iodine (Zn-I<sub>2</sub>) batteries, owing to their compelling combination of environmental friendliness, cost-effectiveness, and enhanced safety features, are regarded as promising candidates for large-scale energy storage systems. Nevertheless, the limited I<sub>2</sub>/2I<sup>-</sup> two-electron redox chemistry and nonuniform Zn deposition critically impair the energy density and cycling stability of aqueous Zn-I<sub>2</sub> batteries, hindering their practical deployment. Herein, multifunctional cyclohexylamine hydrochloride (CHAH) additive is introduced into the ZnSO<sub>4</sub> electrolyte, which synergistically enables a dendrite-free Zn anode for extended cyclability and simultaneously activates a stable four-electron 2I<sup>+</sup>/I<sub>2</sub>/2I<sup>-</sup> redox chemistry at the I<sub>2</sub> cathode. Combined experimental characterization and theoretical calculations reveal that the cyclohexylamine (CHA) reconstructs the Zn<sup>2+</sup> solvation structure by displacing active H<sub>2</sub>O, while fostering a nitrogen-rich solid electrolyte interphase on the Zn anode at the same time. It suppresses parasitic reactions and enables excellent Zn plating/stripping cycling for 2150 h at 1 mA cm<sup>-2</sup>/1 mAh cm<sup>-2</sup>. Furthermore, nucleophilic amine groups in CHA act synergistically with Cl<sup>-</sup> to coordinate I<sup>+</sup> by forming (2CHA)ICl, which improves four-electron 2I<sup>+</sup>/I<sub>2</sub>/2I<sup>-</sup> redox kinetics and achieves exceptional Zn-I<sub>2</sub> battery performances (256.3 mAh g<sup>-1</sup> at 10 A g<sup>-1</sup>). This bilateral nitrogen interface chemistry mechanism offers key insights into the development of high-performance Zn-I<sub>2</sub> batteries.</p>","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":" ","pages":""},"PeriodicalIF":16.0,"publicationDate":"2026-02-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146130502","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Self-Assembling Nanoparticle Enhances RNA Interference Efficiency against Hyphantria Cunea (Drury) with Minimal Risk to Nontarget Organisms. 自组装纳米颗粒增强RNA干扰对加利福尼亚棘球蚴的效率,对非靶生物的风险最小。
IF 6.2 1区 农林科学 Q1 AGRICULTURE, MULTIDISCIPLINARY Pub Date : 2026-02-07 DOI: 10.1021/acs.jafc.5c13240
Mengting Wu, Wenhui Liu, Chunmei Jiang, Yu Mao, Feng Lan, Jianyang Bai, Tianzi Gu, Binyu Wu, Jiang Zhang, Longwa Zhang, Ling Chang

RNA interference (RNAi) represents a promising approach for insect pest management; however, its application in Lepidoptera is constrained by double-stranded RNA (dsRNA) instability, limited cellular uptake, and inefficient RNAi machinery. In this study, we developed a bacteriophage MS2 virus-like particle (VLP)-based delivery platform for hairpin RNA (hpRNA) targeting the invasive pest Hyphantria cunea. When expressed in Escherichia coli, MS2 VLPs efficiently encapsulate hpRNA, markedly enhancing its resistance to nuclease activity and environmental degradation. In addition, surface display of the HIV trans-activator of transcription (TAT) peptide on MS2 VLPs significantly improved cellular internalization of hpRNA, resulting in robust RNAi-mediated gene silencing in H. cunea at low hpRNA doses. Importantly, no adverse effects were detected in three nontarget organisms: Clostera restitura, Plagiodera versicolora, and the parasitoid Chouioia cunea. Together, these results demonstrate that the MS2-hpRNA system represents a scalable, effective, and environmentally safe strategy for RNA-based pest control.

{"title":"Self-Assembling Nanoparticle Enhances RNA Interference Efficiency against <i>Hyphantria Cunea</i> (Drury) with Minimal Risk to Nontarget Organisms.","authors":"Mengting Wu, Wenhui Liu, Chunmei Jiang, Yu Mao, Feng Lan, Jianyang Bai, Tianzi Gu, Binyu Wu, Jiang Zhang, Longwa Zhang, Ling Chang","doi":"10.1021/acs.jafc.5c13240","DOIUrl":"https://doi.org/10.1021/acs.jafc.5c13240","url":null,"abstract":"<p><p>RNA interference (RNAi) represents a promising approach for insect pest management; however, its application in Lepidoptera is constrained by double-stranded RNA (dsRNA) instability, limited cellular uptake, and inefficient RNAi machinery. In this study, we developed a bacteriophage MS2 virus-like particle (VLP)-based delivery platform for hairpin RNA (hpRNA) targeting the invasive pest <i>Hyphantria cunea</i>. When expressed in <i>Escherichia coli</i>, MS2 VLPs efficiently encapsulate hpRNA, markedly enhancing its resistance to nuclease activity and environmental degradation. In addition, surface display of the HIV trans-activator of transcription (TAT) peptide on MS2 VLPs significantly improved cellular internalization of hpRNA, resulting in robust RNAi-mediated gene silencing in <i>H. cunea</i> at low hpRNA doses. Importantly, no adverse effects were detected in three nontarget organisms: <i>Clostera restitura</i>, <i>Plagiodera versicolora</i>, and the parasitoid <i>Chouioia cunea</i>. Together, these results demonstrate that the MS2-hpRNA system represents a scalable, effective, and environmentally safe strategy for RNA-based pest control.</p>","PeriodicalId":41,"journal":{"name":"Journal of Agricultural and Food Chemistry","volume":" ","pages":""},"PeriodicalIF":6.2,"publicationDate":"2026-02-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146130534","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"农林科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
期刊
全部 Acc. Chem. Res. ACS Applied Bio Materials ACS Appl. Electron. Mater. ACS Appl. Energy Mater. ACS Appl. Mater. Interfaces ACS Appl. Nano Mater. ACS Appl. Polym. Mater. ACS BIOMATER-SCI ENG ACS Catal. ACS Cent. Sci. ACS Chem. Biol. ACS Chemical Health & Safety ACS Chem. Neurosci. ACS Comb. Sci. ACS Earth Space Chem. ACS Energy Lett. ACS Infect. Dis. ACS Macro Lett. ACS Mater. Lett. ACS Med. Chem. Lett. ACS Nano ACS Omega ACS Photonics ACS Sens. ACS Sustainable Chem. Eng. ACS Synth. Biol. Anal. Chem. BIOCHEMISTRY-US Bioconjugate Chem. BIOMACROMOLECULES Chem. Res. Toxicol. Chem. Rev. Chem. Mater. CRYST GROWTH DES ENERG FUEL Environ. Sci. Technol. Environ. Sci. Technol. Lett. Eur. J. Inorg. Chem. IND ENG CHEM RES Inorg. Chem. J. Agric. Food. Chem. J. Chem. Eng. Data J. Chem. Educ. J. Chem. Inf. Model. J. Chem. Theory Comput. J. Med. Chem. J. Nat. Prod. J PROTEOME RES J. Am. Chem. Soc. LANGMUIR MACROMOLECULES Mol. Pharmaceutics Nano Lett. Org. Lett. ORG PROCESS RES DEV ORGANOMETALLICS J. Org. Chem. J. Phys. Chem. J. Phys. Chem. A J. Phys. Chem. B J. Phys. Chem. C J. Phys. Chem. Lett. Analyst Anal. Methods Biomater. Sci. Catal. Sci. Technol. Chem. Commun. Chem. Soc. Rev. CHEM EDUC RES PRACT CRYSTENGCOMM Dalton Trans. Energy Environ. Sci. ENVIRON SCI-NANO ENVIRON SCI-PROC IMP ENVIRON SCI-WAT RES Faraday Discuss. Food Funct. Green Chem. Inorg. Chem. Front. Integr. Biol. J. Anal. At. Spectrom. J. Mater. Chem. A J. Mater. Chem. B J. Mater. Chem. C Lab Chip Mater. Chem. Front. Mater. Horiz. MEDCHEMCOMM Metallomics Mol. Biosyst. Mol. Syst. Des. Eng. Nanoscale Nanoscale Horiz. Nat. Prod. Rep. New J. Chem. Org. Biomol. Chem. Org. Chem. Front. PHOTOCH PHOTOBIO SCI PCCP Polym. Chem.
×
引用
GB/T 7714-2015
复制
MLA
复制
APA
复制
导出至
BibTeX EndNote RefMan NoteFirst NoteExpress
×
0
微信
客服QQ
Book学术公众号 扫码关注我们
反馈
×
意见反馈
请填写您的意见或建议
请填写您的手机或邮箱
×
提示
您的信息不完整,为了账户安全,请先补充。
现在去补充
×
提示
您因"违规操作"
具体请查看互助需知
我知道了
×
提示
现在去查看 取消
×
提示
确定
Book学术官方微信
Book学术文献互助
Book学术文献互助群
群 号:604180095
Book学术
文献互助 智能选刊 最新文献 互助须知 联系我们:info@booksci.cn
Book学术提供免费学术资源搜索服务,方便国内外学者检索中英文文献。致力于提供最便捷和优质的服务体验。
Copyright © 2023 Book学术 All rights reserved.
ghs 京公网安备 11010802042870号 京ICP备2023020795号-1