Preparation for the potential emergence of future human coronaviruses (HCoVs) calls for the development of versatile and effective treatment strategies. The signs and symptoms of HCoVs include an immune inflammatory response. Therefore, our study focuses on the simultaneous inhibition of HCoV infection and the alleviation of lung inflammation. Inspired by conformational epitope matching, we engineered a de novo antigen spatial-matching polyaptamer (ASM-pApt) nanostructure designed to align perfectly with multiple spike (S) proteins on severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) pseudovirus (PsV). Compared with monovalent aptamer, the dissociation constant (KD) of the ASM-pApt nanostructure decreased by over 1,000-fold, and its viral semi-inhibitory concentration (IC50) improved by over 100,000-fold to 89.7 fM (fmol/L), indicating the effectiveness of antigen spatial matching. By loading polyphenol as anti-inflammatory drug and chitosan (CS) as an excipient, the ASM-pApt nanostructure showed anti-inflammatory and long drug retention properties. Our design shows the promise of polyaptamer as an antiviral/anti-inflammatory candidate against emerging HCoVs in the future.
{"title":"Antigen spatial-matching polyaptamer nanostructure to block coronavirus infection and alleviate inflammation","authors":"Jingqi Chen, Yuqing Li, Xueliang Liu, Hongyi Li, Jiawei Zhu, Rui Ma, Linxin Tian, Lu Yu, Jiabei Li, Zhuang Liu, Weihong Tan, Yu Yang","doi":"10.1016/j.chempr.2024.10.021","DOIUrl":"https://doi.org/10.1016/j.chempr.2024.10.021","url":null,"abstract":"Preparation for the potential emergence of future human coronaviruses (HCoVs) calls for the development of versatile and effective treatment strategies. The signs and symptoms of HCoVs include an immune inflammatory response. Therefore, our study focuses on the simultaneous inhibition of HCoV infection and the alleviation of lung inflammation. Inspired by conformational epitope matching, we engineered a <em>de novo</em> antigen spatial-matching polyaptamer (ASM-pApt) nanostructure designed to align perfectly with multiple spike (S) proteins on severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) pseudovirus (PsV). Compared with monovalent aptamer, the dissociation constant (K<sub>D</sub>) of the ASM-pApt nanostructure decreased by over 1,000-fold, and its viral semi-inhibitory concentration (IC<sub>50</sub>) improved by over 100,000-fold to 89.7 fM (fmol/L), indicating the effectiveness of antigen spatial matching. By loading polyphenol as anti-inflammatory drug and chitosan (CS) as an excipient, the ASM-pApt nanostructure showed anti-inflammatory and long drug retention properties. Our design shows the promise of polyaptamer as an antiviral/anti-inflammatory candidate against emerging HCoVs in the future.","PeriodicalId":268,"journal":{"name":"Chem","volume":"2 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2024-11-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142678776","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}
Pub Date : 2024-11-21DOI: 10.1016/j.chempr.2024.10.023
Gabriel Sanchez-Cano, Pablo Cristobal-Cueto, Lydia Saez, Antonio Lastra, Ana Marti-Calvo, Juan José Gutiérrez-Sevillano, Sofía Calero, Sara Rojas, Patricia Horcajada
Water disinfection is one of the most challenging processes for public health. Nevertheless, this process can generate inorganic by-products (chlorite [ClO2−] and chlorate [ClO3−]) associated with human diseases. Recently, the European Union established a permissible maximum concentration of 0.25 mg⋅L−1 for both oxyanions in drinking water; thus, the existing technologies have to be adapted. Here, the earliest use of metal-organic frameworks (MOFs) in the elimination of the disinfection by-products ClO2− and ClO3− from fresh water is presented. Among the Fe-MOFs proposed, the robust MIL-88B-NH2 demonstrated exceptional oxyanions elimination capacities (100% and 30% of ClO2− and ClO3− in 1 and 5 min, respectively). Based on these results, a continuous-flow device based on MIL-88B-NH2 was tested under simulated realistic conditions, achieving high oxyanions elimination capacities, and the reusability of the system was demonstrated. This pioneering work opens new perspectives in the implementation of MOFs in real drinking water treatment plants (DWTPs).
{"title":"Drinking water purification using metal-organic frameworks: Removal of disinfection by-products","authors":"Gabriel Sanchez-Cano, Pablo Cristobal-Cueto, Lydia Saez, Antonio Lastra, Ana Marti-Calvo, Juan José Gutiérrez-Sevillano, Sofía Calero, Sara Rojas, Patricia Horcajada","doi":"10.1016/j.chempr.2024.10.023","DOIUrl":"https://doi.org/10.1016/j.chempr.2024.10.023","url":null,"abstract":"Water disinfection is one of the most challenging processes for public health. Nevertheless, this process can generate inorganic by-products (chlorite [ClO<sub>2</sub><sup>−</sup>] and chlorate [ClO<sub>3</sub><sup>−</sup>]) associated with human diseases. Recently, the European Union established a permissible maximum concentration of 0.25 mg⋅L<sup>−1</sup> for both oxyanions in drinking water; thus, the existing technologies have to be adapted. Here, the earliest use of metal-organic frameworks (MOFs) in the elimination of the disinfection by-products ClO<sub>2</sub><sup>−</sup> and ClO<sub>3</sub><sup>−</sup> from fresh water is presented. Among the Fe-MOFs proposed, the robust MIL-88B-NH<sub>2</sub> demonstrated exceptional oxyanions elimination capacities (100% and 30% of ClO<sub>2</sub><sup>−</sup> and ClO<sub>3</sub><sup>−</sup> in 1 and 5 min, respectively). Based on these results, a continuous-flow device based on MIL-88B-NH<sub>2</sub> was tested under simulated realistic conditions, achieving high oxyanions elimination capacities, and the reusability of the system was demonstrated. This pioneering work opens new perspectives in the implementation of MOFs in real drinking water treatment plants (DWTPs).","PeriodicalId":268,"journal":{"name":"Chem","volume":"14 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2024-11-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142678749","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}
Pub Date : 2024-11-20DOI: 10.1016/j.chempr.2024.10.018
Wentao Song, Xinyue Zhang, Wanrong Li, Bowen Li, Bin Liu
Constructing biotic-abiotic hybrid systems for solar energy conversion receives growing interest owing to their sustainable and eco-friendly approach to producing chemicals. The integration of intracellular biochemical pathways with semiconductor materials offers superior product selectivity and efficient light utilization in solar-driven biocatalysis. However, the complicated multidisciplinary features and limited understanding of extracellular electron transfer at the biological-material interfaces hinder the practical application of biotic-abiotic hybrid systems for converting solar energy. In this perspective, we summarize the fundamental mechanisms of biohybrid systems for solar-to-chemical conversion and highlight ongoing challenges and promising directions for future development. First, a comprehensive overview of biotic-abiotic hybrid systems is introduced together with the mechanism of extracellular electron transfer for chemical production. Then, recent achievements of biohybrid systems for H2 production, CO2 reduction, N2 fixation, and chemical synthesis are discussed in detail. Finally, the current challenges in biotic-abiotic hybrid systems and prospective research directions are explored.
{"title":"Engineering biotic-abiotic hybrid systems for solar-to-chemical conversion","authors":"Wentao Song, Xinyue Zhang, Wanrong Li, Bowen Li, Bin Liu","doi":"10.1016/j.chempr.2024.10.018","DOIUrl":"https://doi.org/10.1016/j.chempr.2024.10.018","url":null,"abstract":"Constructing biotic-abiotic hybrid systems for solar energy conversion receives growing interest owing to their sustainable and eco-friendly approach to producing chemicals. The integration of intracellular biochemical pathways with semiconductor materials offers superior product selectivity and efficient light utilization in solar-driven biocatalysis. However, the complicated multidisciplinary features and limited understanding of extracellular electron transfer at the biological-material interfaces hinder the practical application of biotic-abiotic hybrid systems for converting solar energy. In this perspective, we summarize the fundamental mechanisms of biohybrid systems for solar-to-chemical conversion and highlight ongoing challenges and promising directions for future development. First, a comprehensive overview of biotic-abiotic hybrid systems is introduced together with the mechanism of extracellular electron transfer for chemical production. Then, recent achievements of biohybrid systems for H<sub>2</sub> production, CO<sub>2</sub> reduction, N<sub>2</sub> fixation, and chemical synthesis are discussed in detail. Finally, the current challenges in biotic-abiotic hybrid systems and prospective research directions are explored.","PeriodicalId":268,"journal":{"name":"Chem","volume":"23 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2024-11-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142673764","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}
Pub Date : 2024-11-18DOI: 10.1016/j.chempr.2024.10.019
Wenhao Ren, Huanlei Zhang, Miyeon Chang, Nanjun Chen, Wenchao Ma, Jun Gu, Meng Lin, Xile Hu
Zero-gap membrane electrode assembly (MEA) CO electrolyzer stands as a promising technology for circular carbon economy. However, current CO electrolyzers are energetically inefficient when operating at ampere-level current densities. Here, by analyzing the performance discrepancies between MEA and flow cells, we identify the depletion of K+ and water at the cathode as the main contributor to the low performance of MEA CO electrolyzers. This is attributed to the unique cathodic interface in catholyte-free MEA, where there is no aqueous electrolyte to maintain the three-phase interface. Through the development of needle-array catalysts with intensified electric fields (EFs) at their tips, we are able to concentrate the limited K+ cations onto the tips of the cathode, while simultaneously facilitating water uptake via electro-osmosis. We construct an MEA CO electrolyzer that achieves a large current density of 2,500 mA cm−2 at a voltage of only 2.7 V.
零间隙膜电极组件（MEA）一氧化碳电解槽是一种很有前途的循环碳经济技术。然而，目前的二氧化碳电解槽在安培级电流密度下运行时能量效率较低。在这里，通过分析 MEA 和流动电池之间的性能差异，我们发现阴极的 K+ 和水耗尽是导致 MEA CO 电解槽性能低下的主要原因。这归因于无阴极电解质 MEA 中独特的阴极界面，即没有水电解质来维持三相界面。通过开发针状阵列催化剂，并在其顶端加强电场 (EF)，我们能够将有限的 K+ 阳离子集中到阴极顶端，同时通过电渗透促进水的吸收。我们构建的 MEA CO 电解槽在电压仅为 2.7 V 的情况下可达到 2,500 mA cm-2 的大电流密度。
{"title":"Field-enhanced CO electroreduction in membrane electrolyzers at a dehydrated interface","authors":"Wenhao Ren, Huanlei Zhang, Miyeon Chang, Nanjun Chen, Wenchao Ma, Jun Gu, Meng Lin, Xile Hu","doi":"10.1016/j.chempr.2024.10.019","DOIUrl":"https://doi.org/10.1016/j.chempr.2024.10.019","url":null,"abstract":"Zero-gap membrane electrode assembly (MEA) CO electrolyzer stands as a promising technology for circular carbon economy. However, current CO electrolyzers are energetically inefficient when operating at ampere-level current densities. Here, by analyzing the performance discrepancies between MEA and flow cells, we identify the depletion of K<sup>+</sup> and water at the cathode as the main contributor to the low performance of MEA CO electrolyzers. This is attributed to the unique cathodic interface in catholyte-free MEA, where there is no aqueous electrolyte to maintain the three-phase interface. Through the development of needle-array catalysts with intensified electric fields (EFs) at their tips, we are able to concentrate the limited K<sup>+</sup> cations onto the tips of the cathode, while simultaneously facilitating water uptake via electro-osmosis. We construct an MEA CO electrolyzer that achieves a large current density of 2,500 mA cm<sup>−2</sup> at a voltage of only 2.7 V.","PeriodicalId":268,"journal":{"name":"Chem","volume":"36 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2024-11-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142665346","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}
Pub Date : 2024-11-14DOI: 10.1016/j.chempr.2024.07.033
Nikita Y. Gugin , Kirill V. Yusenko , Andrew King , Klas Meyer , Dominik Al-Sabbagh , Jose A. Villajos , Franziska Emmerling
Mechanochemistry is an environmentally friendly synthetic approach that enables the sustainable production of a wide range of chemicals while reducing or eliminating the need for solvents. Reactive extrusion aims to move mechanochemistry from its conventional gram-scale batch reactions, typically performed in laboratory ball mills, to a continuous, large-scale process. Meeting this challenge requires in situ monitoring techniques to gain insights into reactive extrusion and its underlying processes. While the effectiveness of in situ Raman spectroscopy in providing molecular-level information has been demonstrated, our study uses energy-dispersive X-ray diffraction to monitor reactive extrusion in real time at the crystalline level. Our results provide previously unavailable control over the reactive extrusion process, promoting its perception as an industrially feasible green alternative to traditional solvent-based syntheses.
Video abstract
Download: Download video (18MB)
机械化学是一种环境友好型合成方法，可实现多种化学品的可持续生产，同时减少或消除对溶剂的需求。反应挤压法旨在将机械化学从传统的克级批量反应（通常在实验室球磨机中进行）转变为连续的大规模工艺。要应对这一挑战，需要采用原位监测技术来深入了解反应挤压及其基本过程。虽然原位拉曼光谱在提供分子级信息方面的有效性已得到证实，但我们的研究利用能量色散 X 射线衍射技术在晶体级实时监测反应挤压。我们的研究结果提供了以前无法获得的对反应性挤压过程的控制，促进了人们对反应性挤压作为传统溶剂型合成的一种工业上可行的绿色替代方法的认识。视频摘要下载：下载视频 (18MB)
{"title":"Lighting up industrial mechanochemistry: Real-time in situ monitoring of reactive extrusion using energy-dispersive X-ray diffraction","authors":"Nikita Y. Gugin , Kirill V. Yusenko , Andrew King , Klas Meyer , Dominik Al-Sabbagh , Jose A. Villajos , Franziska Emmerling","doi":"10.1016/j.chempr.2024.07.033","DOIUrl":"10.1016/j.chempr.2024.07.033","url":null,"abstract":"<div><div>Mechanochemistry is an environmentally friendly synthetic approach that enables the sustainable production of a wide range of chemicals while reducing or eliminating the need for solvents. Reactive extrusion aims to move mechanochemistry from its conventional gram-scale batch reactions, typically performed in laboratory ball mills, to a continuous, large-scale process. Meeting this challenge requires <em>in situ</em> monitoring techniques to gain insights into reactive extrusion and its underlying processes. While the effectiveness of <em>in situ</em> Raman spectroscopy in providing molecular-level information has been demonstrated, our study uses energy-dispersive X-ray diffraction to monitor reactive extrusion in real time at the crystalline level. Our results provide previously unavailable control over the reactive extrusion process, promoting its perception as an industrially feasible green alternative to traditional solvent-based syntheses.</div></div><div><h3>Video abstract</h3><div><span><span><span><span><video><source></source></video></span><span><span>Download: <span>Download video (18MB)</span></span></span></span></span></span></div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"10 11","pages":"Pages 3459-3473"},"PeriodicalIF":19.1,"publicationDate":"2024-11-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142085779","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}
Pub Date : 2024-11-14DOI: 10.1016/j.chempr.2024.09.022
Da Zhao , Tobias Ritter
Late-stage deuteration is a crucial technique in the pharmaceutical industry. Direct aromatic deuteration without the use of directing groups or transition-metal catalysts presents a substantial challenge. Now, through the integration of an interrupted Birch reduction, Liang, Xia, and co-workers have developed a photochemical protocol for the efficient hydrogen isotope exchange to incorporate deuterium into the arenes of pharmaceuticals.
{"title":"Illuminating aromatic deuteration","authors":"Da Zhao , Tobias Ritter","doi":"10.1016/j.chempr.2024.09.022","DOIUrl":"10.1016/j.chempr.2024.09.022","url":null,"abstract":"<div><div>Late-stage deuteration is a crucial technique in the pharmaceutical industry. Direct aromatic deuteration without the use of directing groups or transition-metal catalysts presents a substantial challenge. Now, through the integration of an interrupted Birch reduction, Liang, Xia, and co-workers have developed a photochemical protocol for the efficient hydrogen isotope exchange to incorporate deuterium into the arenes of pharmaceuticals.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"10 11","pages":"Pages 3266-3267"},"PeriodicalIF":19.1,"publicationDate":"2024-11-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142487534","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}
Pub Date : 2024-11-14DOI: 10.1016/j.chempr.2024.10.014
Wenbin Huang , Zhe Dong
In this issue of Chem, Popescu and Paton report a new method to predict triplet energy sensitization of small molecules by sampling the instantaneous vertical energy gaps over molecular vibrational motions. This approach has reduced the mean absolute error of predicting ET from 9.5 to 1.7 kcal/mol compared with previous state-of-the-art methods.
在本期《化学》杂志上，Popescu 和 Paton 报告了一种通过对分子振动运动的瞬时垂直能隙采样来预测小分子三重能敏化的新方法。与以前最先进的方法相比，这种方法将预测 ET 的平均绝对误差从 9.5 千卡/摩尔减少到 1.7 千卡/摩尔。
{"title":"Accurate triplet energies prediction method based on the hot-band model","authors":"Wenbin Huang , Zhe Dong","doi":"10.1016/j.chempr.2024.10.014","DOIUrl":"10.1016/j.chempr.2024.10.014","url":null,"abstract":"<div><div>In this issue of <em>Chem</em>, Popescu and Paton report a new method to predict triplet energy sensitization of small molecules by sampling the instantaneous vertical energy gaps over molecular vibrational motions. This approach has reduced the mean absolute error of predicting E<sub>T</sub> from 9.5 to 1.7 kcal/mol compared with previous state-of-the-art methods.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"10 11","pages":"Pages 3270-3272"},"PeriodicalIF":19.1,"publicationDate":"2024-11-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142556260","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}
Pub Date : 2024-11-14DOI: 10.1016/j.chempr.2024.08.001
Liangxuan Xu , Du Chen , Peng Zhang , Chungu Xia , Chao Liu
Alkynes have played pivotal roles in numerous synthetic transformations and materials science. Here, by developing nitrogen-deletion coupling, we describe a modular synthesis of alkynes from widely accessible nitriles by swapping the N atom to a C atom in cyano groups, where lithiated gem-diborylalkanes and tert-butyl nitrite are applied sequentially. NMR analysis and crystal structure show the nature of an intermediary α-boryl lithium enamine. A diverse range of nitriles are converted into various internal and terminal alkynes within a short reaction time, including alkynes bearing bulky secondary and tertiary alkyl substituents on both sides.
炔烃在众多合成转化和材料科学中发挥着关键作用。在这里，通过开发缺氮偶联，我们描述了一种通过将氰基中的 N 原子换成 C 原子，从广泛可得的腈中模块化合成炔烃的方法。核磁共振分析和晶体结构显示了中间体 α-硼烷基烯胺锂的性质。在很短的反应时间内，各种腈类都能转化为各种内部和末端炔烃，包括两侧都带有笨重的仲烷基和叔烷基取代基的炔烃。
{"title":"Atom swap in triple bonds via nitrogen-deletion coupling with gem-diborylalkanes","authors":"Liangxuan Xu , Du Chen , Peng Zhang , Chungu Xia , Chao Liu","doi":"10.1016/j.chempr.2024.08.001","DOIUrl":"10.1016/j.chempr.2024.08.001","url":null,"abstract":"<div><div>Alkynes have played pivotal roles in numerous synthetic transformations and materials science. Here, by developing nitrogen-deletion coupling, we describe a modular synthesis of alkynes from widely accessible nitriles by swapping the N atom to a C atom in cyano groups, where lithiated <em>gem</em>-diborylalkanes and <em>tert</em>-butyl nitrite are applied sequentially. NMR analysis and crystal structure show the nature of an intermediary α-boryl lithium enamine. A diverse range of nitriles are converted into various internal and terminal alkynes within a short reaction time, including alkynes bearing bulky secondary and tertiary alkyl substituents on both sides.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"10 11","pages":"Pages 3474-3487"},"PeriodicalIF":19.1,"publicationDate":"2024-11-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142138192","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}
Pub Date : 2024-11-14DOI: 10.1016/j.chempr.2024.06.015
Yi Zhao , Qingqing Gu , Xue Sun , Dong Wang , Xueqing Gong , Bing Yang , Jing Xu , Bo Peng , Ying Zhang , Chengsi Pan , Yongfa Zhu , Yang Lou
Developing a new tactic for directionally regulating a specific functional group of feedstock molecules at the molecular level is highly desired to synthesize high-value products but remains challenging. We design and construct the two-dimensional molybdenum disulfide (2D MoS2) nanosheets edge-anchored dual Rh atoms (Rh2/MoS2 dual-atom catalyst [DAC]) to boost the ethanol yield in dimethyl oxalate (DMO) selective hydrogenation by precisely manipulating the DMO adsorption configuration. Comprehensive experimental and theoretical results reveal that the pocket-like active center of Rh2 atoms, with a precise metal-metal distance (3.5 Å), realizes the spatially matched bidentate DMO adsorption via two C=O groups (distance of 3.1 Å), which remarkably enhances the DMO activation and drives the production of ethanol via a unilateral activation mechanism. The turnover frequency (TOF) and H2/DMO molar ratio of Rh2/MoS2 DAC are around 19 times higher and 17 times lower, respectively, than those of the best reported catalysts under comparable conditions. Our results offer practical opportunities for updating the industrial syngas-DMO-ethanol route.
{"title":"Steric-confinement Rh2/MoS2 dual-atom catalyst directionally modulating adsorption configuration of ester group to boost ethanol synthesis","authors":"Yi Zhao , Qingqing Gu , Xue Sun , Dong Wang , Xueqing Gong , Bing Yang , Jing Xu , Bo Peng , Ying Zhang , Chengsi Pan , Yongfa Zhu , Yang Lou","doi":"10.1016/j.chempr.2024.06.015","DOIUrl":"10.1016/j.chempr.2024.06.015","url":null,"abstract":"<div><div><span><span>Developing a new tactic for directionally regulating a specific functional group of feedstock molecules at the molecular level is highly desired to synthesize high-value products but remains challenging. We design and construct the two-dimensional </span>molybdenum disulfide (2D MoS</span><sub>2</sub><span>) nanosheets edge-anchored dual Rh atoms (Rh</span><sub>2</sub>/MoS<sub>2</sub><span> dual-atom catalyst [DAC]) to boost the ethanol yield in dimethyl oxalate (DMO) selective hydrogenation by precisely manipulating the DMO adsorption configuration. Comprehensive experimental and theoretical results reveal that the pocket-like active center of Rh</span><sub>2</sub><span> atoms, with a precise metal-metal distance (3.5 Å), realizes the spatially matched bidentate DMO adsorption via two C=O groups (distance of 3.1 Å), which remarkably enhances the DMO activation and drives the production of ethanol via a unilateral activation mechanism. The turnover frequency (TOF) and H</span><sub>2</sub>/DMO molar ratio of Rh<sub>2</sub>/MoS<sub>2</sub> DAC are around 19 times higher and 17 times lower, respectively, than those of the best reported catalysts under comparable conditions. Our results offer practical opportunities for updating the industrial syngas-DMO-ethanol route.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"10 11","pages":"Pages 3342-3363"},"PeriodicalIF":19.1,"publicationDate":"2024-11-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141578005","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}
Pub Date : 2024-11-14DOI: 10.1016/j.chempr.2024.06.020
Pengfei Hu , Haosen Yang , Rutong Si , Bin Wei , Xiaotian Wang , Ziyan Xu , Xiuyi Yang , Tianqi Guo , Ralph Gebauer , Gilberto Teobaldi , Li-Min Liu , Zhongchang Wang , Lin Guo
Despite the exceptional properties and advanced functionalities of two-dimensional (2D) nanomaterials, the fabrication of freestanding, atomically thin metal nanosheets poses a considerable challenge due to the inherently omnidirectional nature of typical metallic bonds. Herein, we introduce a novel ligand-confinement strategy to prepare the atomically thin Ag nanosheets. The ultrathin 2D structure is stabilized by manipulating the coordinate ligands to construct confined spaces and lower the inherent high surface energy, thus avoiding agglomeration. The atomically thin 2D structure exhibits a distinct quantum confinement effect, inducing energy level splitting conducive to uniform hot spots on planar Ag surfaces and extraordinary surface-enhanced Raman spectroscopy (SERS) properties. Leveraging the synergistic effects of electromagnetic and chemical enhancement, our approach achieves single-molecule-level SERS detection at concentrations as low as 10−17 M of bisphenol F (BPF). The atomically thin noble metal-based SERS technology possesses superb merits of ultra-high sensitivity, extraordinary uniformity, and reproducibility.
尽管二维（2D）纳米材料具有非凡的特性和先进的功能，但由于典型金属键固有的全向性，独立的原子级薄金属纳米片的制备仍面临相当大的挑战。在此，我们介绍了一种制备原子级薄银纳米片的新型配体融合策略。通过操纵配位体构建密闭空间，降低固有的高表面能，从而避免团聚，稳定超薄二维结构。原子级薄二维结构表现出明显的量子约束效应，诱导能级分裂，有利于在平面银表面形成均匀的热点和非凡的表面增强拉曼光谱（SERS）特性。利用电磁和化学增强的协同效应，我们的方法实现了单分子级 SERS 检测，检测浓度低至 10-17 M 的双酚 F (BPF)。这种基于贵金属的原子超薄 SERS 技术具有超高灵敏度、超常均匀性和可重复性等优点。
{"title":"Atomically thin Ag nanosheets for single-molecule SERS detection of BPF","authors":"Pengfei Hu , Haosen Yang , Rutong Si , Bin Wei , Xiaotian Wang , Ziyan Xu , Xiuyi Yang , Tianqi Guo , Ralph Gebauer , Gilberto Teobaldi , Li-Min Liu , Zhongchang Wang , Lin Guo","doi":"10.1016/j.chempr.2024.06.020","DOIUrl":"10.1016/j.chempr.2024.06.020","url":null,"abstract":"<div><div><span>Despite the exceptional properties and advanced functionalities of two-dimensional (2D) nanomaterials<span><span>, the fabrication of freestanding, atomically thin metal nanosheets poses a considerable challenge due to the inherently omnidirectional nature of typical </span>metallic bonds<span><span>. Herein, we introduce a novel ligand-confinement strategy to prepare the atomically thin Ag nanosheets. The ultrathin 2D structure is stabilized by manipulating the coordinate ligands to construct confined spaces and lower the inherent high surface energy, thus avoiding agglomeration. The atomically thin 2D structure exhibits a distinct quantum confinement effect, inducing </span>energy level splitting<span><span> conducive to uniform hot spots on planar Ag surfaces and extraordinary surface-enhanced Raman spectroscopy (SERS) properties. Leveraging the synergistic effects of </span>electromagnetic and chemical enhancement, our approach achieves single-molecule-level SERS detection at concentrations as low as 10</span></span></span></span><sup>−17</sup><span> M of bisphenol F (BPF). The atomically thin noble metal-based SERS technology possesses superb merits of ultra-high sensitivity, extraordinary uniformity, and reproducibility.</span></div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"10 11","pages":"Pages 3364-3373"},"PeriodicalIF":19.1,"publicationDate":"2024-11-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141578128","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}
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：