JACS Au最新文献

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Direct Deoxygenation of Free Alcohols and Ketones 游离醇和酮的直接脱氧
IF 8.5
JACS Au Pub Date : 2025-04-11 DOI: 10.1021/jacsau.5c0015410.1021/jacsau.5c00154
Haoyu Zhang, Shiyong Guan, Hanbo Chen, Genhong Zhang and Yuegang Chen*, 
{"title":"Direct Deoxygenation of Free Alcohols and Ketones","authors":"Haoyu Zhang,&nbsp;Shiyong Guan,&nbsp;Hanbo Chen,&nbsp;Genhong Zhang and Yuegang Chen*,&nbsp;","doi":"10.1021/jacsau.5c0015410.1021/jacsau.5c00154","DOIUrl":"https://doi.org/10.1021/jacsau.5c00154https://doi.org/10.1021/jacsau.5c00154","url":null,"abstract":"<p >This work presents a feasible method for the elimination of alcohol hydroxyls through the direct activation of typical alkyl alcohols using neutral boron radicals. This transformation necessitates a proficient reagent capable of swiftly activating the alcohol hydroxyl group to produce radicals, thereby circumventing numerous alternative side reactions associated with the alcohol hydroxyl group. To implement this method, we have created an innovative photocatalytic reaction system that oxidizes sodium tetraphenylboron to produce neutral boron radicals, which subsequently enable the direct homolytic conversion of alcohol hydroxyl groups. This deoxygenation technique necessitates no additional preactivation of the alcohol and yields favorable outcomes for the majority of alcohol substrates. The technique facilitates the direct methylene reduction of aldehydes and ketones. Mechanistic studies have established that the reaction likely initiates with the production of alcohols, thereafter undergoing dehydroxylation to yield methylene-reduced products.</p>","PeriodicalId":94060,"journal":{"name":"JACS Au","volume":"5 4","pages":"1932–1939 1932–1939"},"PeriodicalIF":8.5,"publicationDate":"2025-04-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/jacsau.5c00154","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143878287","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Manipulating the Interfacial Hydrophobic Microenvironment via Electrolyte Engineering Promotes Electrocatalytic Fatty Alcohol Oxidation Coupled with Hydrogen Production 通过电解液工程控制界面疏水微环境促进电催化脂肪醇氧化与制氢耦合
IF 8.5
JACS Au Pub Date : 2025-04-10 DOI: 10.1021/jacsau.5c0021510.1021/jacsau.5c00215
Ruiqi Du, Zemao Chen, Shiyan Wang, Shumao Zeng, Rui Jia, Kaizheng Zhang, Diannan Lu, Haihui Wang* and Yi Cheng*, 
{"title":"Manipulating the Interfacial Hydrophobic Microenvironment via Electrolyte Engineering Promotes Electrocatalytic Fatty Alcohol Oxidation Coupled with Hydrogen Production","authors":"Ruiqi Du,&nbsp;Zemao Chen,&nbsp;Shiyan Wang,&nbsp;Shumao Zeng,&nbsp;Rui Jia,&nbsp;Kaizheng Zhang,&nbsp;Diannan Lu,&nbsp;Haihui Wang* and Yi Cheng*,&nbsp;","doi":"10.1021/jacsau.5c0021510.1021/jacsau.5c00215","DOIUrl":"https://doi.org/10.1021/jacsau.5c00215https://doi.org/10.1021/jacsau.5c00215","url":null,"abstract":"<p >The selective oxidation of fatty alcohols to fatty acids represents a pivotal transformation in organic synthesis. Traditional methods often require harsh conditions and environmentally harmful oxidants or solvents. Electrocatalytic oxidation emerges as a promising green alternative, enabling mild oxidation in aqueous media and concurrent energy-efficient hydrogen production at the cathode. However, the poor solubility of fatty alcohols in water poses a significant challenge, reducing the reactant availability at the electrode surface, thereby hindering mass transfer and overall reaction rates. Herein, we develop an electrolyte engineering strategy that incorporates cetyltrimethylammonium hydroxide (CTAOH) as an additive. This strategy significantly enhances the oxidation current density of fatty alcohols as well as the production rate of fatty acids on a gold electrocatalyst. Through a mechanistic investigation combining experimental evidence from a quartz crystal microbalance (QCM) and in situ attenuated total reflectance surface-enhanced infrared spectroscopy (ATR-SEIRAS) with molecular dynamics (MD) simulations, we confirm that the preferential adsorption of CTAOH creates a hydrophobic interfacial microenvironment at the anode, promoting the enrichment of reactant at the electrode–electrolyte interface. This work highlights the significance of interfacial hydrophobicity modulation in boosting aqueous-phase electrocatalytic oxidation, paving the way for more efficient electrocatalytic transformations involving water-insoluble reactants.</p>","PeriodicalId":94060,"journal":{"name":"JACS Au","volume":"5 4","pages":"1974–1982 1974–1982"},"PeriodicalIF":8.5,"publicationDate":"2025-04-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/jacsau.5c00215","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143878188","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Disentangling the Contribution of Surface and Bulk Ti3+ Defects to the Band Gap States of Rutile TiO2(011) 表面和体Ti3+缺陷对金红石型TiO2(011)带隙态的影响
IF 8.5
JACS Au Pub Date : 2025-04-10 DOI: 10.1021/jacsau.5c0007510.1021/jacsau.5c00075
Yajie Gao, Kaiping Wang, Tianjun Wang, Shucai Xia, Qunqing Hao, Zhiqiang Wang, Bo Wen*, Zefeng Ren, Xueming Yang, Annabella Selloni* and Chuanyao Zhou*, 
{"title":"Disentangling the Contribution of Surface and Bulk Ti3+ Defects to the Band Gap States of Rutile TiO2(011)","authors":"Yajie Gao,&nbsp;Kaiping Wang,&nbsp;Tianjun Wang,&nbsp;Shucai Xia,&nbsp;Qunqing Hao,&nbsp;Zhiqiang Wang,&nbsp;Bo Wen*,&nbsp;Zefeng Ren,&nbsp;Xueming Yang,&nbsp;Annabella Selloni* and Chuanyao Zhou*,&nbsp;","doi":"10.1021/jacsau.5c0007510.1021/jacsau.5c00075","DOIUrl":"https://doi.org/10.1021/jacsau.5c00075https://doi.org/10.1021/jacsau.5c00075","url":null,"abstract":"<p >Band gap states (BGS) induced by Ti<sup>3+</sup> defects play a pivotal role in the physical and chemical properties of TiO<sub>2</sub>. However, there is no consensus on the relative contributions of surface and bulk Ti<sup>3+</sup> defects to the BGS measured by ultraviolet photoelectron spectroscopy (UPS). This is mainly due to the lack of vertical spatial resolution of UPS and limitations in the preparation and quantitative characterization of bulk Ti<sup>3+</sup> defects. In this study, we create surface and bulk Ti<sup>3+</sup> defects in a controllable way by introducing surface and bulk hydroxyls into rutile TiO<sub>2</sub>(011)-(2 × 1) via atomic deuterium exposure. Utilizing UPS combined with density functional theory (DFT) calculations, we successfully disentangled the contributions of surface and bulk Ti<sup>3+</sup> defects to the BGS. The UPS data indicate that surface and bulk Ti<sup>3+</sup> defects give rise to BGS at binding energies of approximately 0.85 and 1.57 eV, respectively. DFT calculations reveal that the separation of surface and bulk BGS originates from the distinct atomic environments of surface and bulk Ti<sup>3+</sup> ions that induce characteristic 3d orbital splittings. Our finding that the surface and bulk Ti<sup>3+</sup>(OH) states are separated in energy could provide a fingerprint for the in situ monitoring of metal–support interactions and hydrogenation reactions in heterogeneous catalysis.</p>","PeriodicalId":94060,"journal":{"name":"JACS Au","volume":"5 4","pages":"1822–1832 1822–1832"},"PeriodicalIF":8.5,"publicationDate":"2025-04-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/jacsau.5c00075","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143878189","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
How the Larger Methionine-Rich Domain of CueO from Hafnia alvei Enhances Cuprous Oxidation 来自Hafnia alvei的CueO的更大的富蛋氨酸结构域如何促进铜的氧化
IF 8.5
JACS Au Pub Date : 2025-04-10 DOI: 10.1021/jacsau.5c0007610.1021/jacsau.5c00076
Umberto Contaldo*, Paolo Santucci, Alexandra Vergnes, Philippe Leone, Jérôme Becam, Frédéric Biaso, Marianne Ilbert, Benjamin Ezraty, Elisabeth Lojou* and Ievgen Mazurenko*, 
{"title":"How the Larger Methionine-Rich Domain of CueO from Hafnia alvei Enhances Cuprous Oxidation","authors":"Umberto Contaldo*,&nbsp;Paolo Santucci,&nbsp;Alexandra Vergnes,&nbsp;Philippe Leone,&nbsp;Jérôme Becam,&nbsp;Frédéric Biaso,&nbsp;Marianne Ilbert,&nbsp;Benjamin Ezraty,&nbsp;Elisabeth Lojou* and Ievgen Mazurenko*,&nbsp;","doi":"10.1021/jacsau.5c0007610.1021/jacsau.5c00076","DOIUrl":"https://doi.org/10.1021/jacsau.5c00076https://doi.org/10.1021/jacsau.5c00076","url":null,"abstract":"<p >CueOs, members of the multicopper oxidase family, play a crucial role in bacterial copper detoxification. These enzymes feature a unique methionine-rich (Met-rich) domain, which is essential for the oxidation of Cu<sup>+</sup> to Cu<sup>2+</sup>. Recent studies using CueO from <i><i>Escherichia coli</i></i> (<i>Ec</i>CueO) suggest that the Met-rich domain facilitates Cu<sup>+</sup> recruitment from highly chelated species. To further explore this hypothesis, we produced and characterized a novel CueO from the bacterium <i>Hafnia alvei</i> (<i>Ha</i>CueO). <i>Ha</i>CueO possesses a significantly larger Met-rich domain than <i>Ec</i>CueO, providing new insights into the role of this domain in cuprous oxidase activity. We first showed that <i>Ha</i>CueO was as efficient in copper detoxification as <i>Ec</i>CueO in vivo. The structures of both wild-type <i>Ha</i>CueO and a variant lacking the Met-rich domain were resolved by X-ray crystallography and simulated by molecular dynamics, offering a detailed structural basis for understanding their functions. Cuprous oxidase activity was then quantified either from free electrogenerated Cu<sup>+</sup> with CueO immobilized on an electrode or from different Cu<sup>+</sup>-complexes with CueO in solution. These methods enabled the fine-tuning of Cu<sup>+</sup> chelation strength. Consistent with findings for <i>Ec</i>CueO, it was confirmed that the Met-rich domain of <i>Ha</i>CueO is dispensable for Cu<sup>+</sup> oxidation when weakly chelated Cu<sup>+</sup> is used. However, its role becomes crucial as chelation strength increases. Comparative analyses of cuprous oxidase activity between <i>Ha</i>CueO and <i>Ec</i>CueO revealed that <i>Ha</i>CueO outperforms <i>Ec</i>CueO, demonstrating superior efficiency in oxidizing Cu<sup>+</sup> from chelated forms. This enhanced activity correlates with the higher methionine content in <i>Ha</i>CueO, which appears to play a pivotal role in facilitating Cu<sup>+</sup> oxidation under conditions of stronger chelation.</p>","PeriodicalId":94060,"journal":{"name":"JACS Au","volume":"5 4","pages":"1833–1844 1833–1844"},"PeriodicalIF":8.5,"publicationDate":"2025-04-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/jacsau.5c00076","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143878161","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Electrochemical Observation and pH Dependence of All Three Expected Redox Couples in an Extremophilic Bifurcating Electron Transfer Flavoprotein with Fused Subunits 具有融合亚基的嗜极性分叉电子转移黄蛋白中所有三种预期氧化还原对的电化学观察和pH依赖性
IF 8.5
JACS Au Pub Date : 2025-04-07 DOI: 10.1021/jacsau.4c0121910.1021/jacsau.4c01219
Debarati Das, Wassim El Housseini, Monica Brachi, Shelley D. Minteer* and Anne-Frances Miller*, 
{"title":"Electrochemical Observation and pH Dependence of All Three Expected Redox Couples in an Extremophilic Bifurcating Electron Transfer Flavoprotein with Fused Subunits","authors":"Debarati Das,&nbsp;Wassim El Housseini,&nbsp;Monica Brachi,&nbsp;Shelley D. Minteer* and Anne-Frances Miller*,&nbsp;","doi":"10.1021/jacsau.4c0121910.1021/jacsau.4c01219","DOIUrl":"https://doi.org/10.1021/jacsau.4c01219https://doi.org/10.1021/jacsau.4c01219","url":null,"abstract":"<p >Bifurcating enzymes employ energy from a favorable electron transfer to drive unfavorable transfer of a second electron, thereby generating a more reactive product. They are therefore highly desirable in catalytic systems, for example, to drive challenging reactions such as nitrogen fixation. While most bifurcating enzymes contain air-sensitive metal centers, bifurcating electron transfer flavoproteins (bETFs) employ flavins. However, they have not been successfully deployed on electrodes. Herein, we demonstrate immobilization and expected thermodynamic reactivity of a bETF from a hyperthermophilic archaeon, <i>Sulfolobus acidocaldarius</i> (<i>Sa</i>ETF). <i>Sa</i>ETF differs from previously biochemically characterized bETFs in being a single protein, representing a concatenation of the two subunits of known ETFs. However, <i>Sa</i>ETF retains the chemical properties of heterodimeric bETFs, including possession of two FADs: one that undergoes sequential 1-electron (1e) reductions at high E° and forms an anionic semiquinone, and another that is amenable to lower-E° 2e reduction, including by NADH. We found homologous monomeric ETF genes in archaeal and bacterial genomes, accompanied by genes that also commonly flank heterodimeric ETFs, and <i>Sa</i>ETF’s sequence conservation is 50% higher with bETFs than with canonical ETFs. Thus, <i>Sa</i>ETF is best described as a bETF. Our direct electrochemical trials capture reversible redox couples for all three thermodynamically expected redox events. We document electrochemical activity over a range of pH values and reveal a conformational change coupled to proton acquisition that affects the electrochemical activity of the higher-E° FAD. Thus, this well-behaved monomeric bETF opens the door to bioinspired bifurcating devices or bifurcation on a chip.</p>","PeriodicalId":94060,"journal":{"name":"JACS Au","volume":"5 4","pages":"1689–1706 1689–1706"},"PeriodicalIF":8.5,"publicationDate":"2025-04-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/jacsau.4c01219","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143878282","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Amino Acid Electrosynthesis with Oxygen Vacancy-Mediated CeO2 Nanocrystals: Facet Effect and Catalytic Mechanism 氧空位介导的CeO2纳米晶体氨基酸电合成:Facet效应和催化机理
IF 8.5
JACS Au Pub Date : 2025-04-05 DOI: 10.1021/jacsau.5c0025210.1021/jacsau.5c00252
Jiang Shao, Jun-Hao Wang, Yi-Fei Zhang, Sheng-Zhi Xue, Hao Dong, Hai-Chao Liu, Chen Li* and Ya-Wen Zhang*, 
{"title":"Amino Acid Electrosynthesis with Oxygen Vacancy-Mediated CeO2 Nanocrystals: Facet Effect and Catalytic Mechanism","authors":"Jiang Shao,&nbsp;Jun-Hao Wang,&nbsp;Yi-Fei Zhang,&nbsp;Sheng-Zhi Xue,&nbsp;Hao Dong,&nbsp;Hai-Chao Liu,&nbsp;Chen Li* and Ya-Wen Zhang*,&nbsp;","doi":"10.1021/jacsau.5c0025210.1021/jacsau.5c00252","DOIUrl":"https://doi.org/10.1021/jacsau.5c00252https://doi.org/10.1021/jacsau.5c00252","url":null,"abstract":"<p >Amino acids are widely used in food, pharmaceuticals, and agrochemicals, presenting significant societal demand, and the artificial synthesis of amino acids is an important yet challenging task. Through electrocatalytic C–N coupling, the synthesis of amino acids from biomass α-keto acids and waste nitrate under mild aqueous conditions has become a green and alternative strategy. Rare-earth-based materials, due to their unique 4f orbitals and tunable crystal facets, often serve as potential resource-rich catalysts. However, their structure–performance relationship in C–N coupling for amino acids synthesis remains unclear. Therefore, eight rare-earth-based catalysts were screened in this work and CeO<sub>2</sub> was chosen as an appropriate model catalyst for the mechanism investigation on the electrosynthesis of alanine. Four CeO<sub>2</sub> nanomaterials with distinct morphologies and crystal facets were synthesized, among which CeO<sub>2</sub> nanorods (CeO<sub>2</sub>-NRs) exposing the (110) facet exhibited the highest oxygen vacancy (O<sub>v</sub>) concentration and optimal electrosynthetic performance for alanine. A series of control experiments, electrochemical characterizations, <i>in situ</i> electrochemical attenuated total reflection Fourier transform infrared spectroscopy (<i>in situ</i> ATR-FTIR), online electrochemical differential mass spectrometry (DEMS), quasi <i>in situ</i> electron paramagnetic resonance (quasi <i>in situ</i> EPR) experiments, combined with density functional theory (DFT) calculations indicated that the synthesis pathway for alanine involved the reduction of NO<sub>3</sub><sup>–</sup> to produce <sup>*</sup>NH<sub>2</sub>OH <i>in situ</i>, which nucleophilically attacked the carbonyl group of pyruvate to form the key intermediate species, oxime, then underwent further amination to generate alanine. The key step responsible for the performance difference of four CeO<sub>2</sub> nanocrystals lay in the reduction amination of pyruvate oxime (PO), confirming the (110) facet with more O<sub>v</sub> exposure facilitated the cleavage of the N–O bond in pyruvate oxime (<sup>*</sup>OOC(H<sub>3</sub>C)C═N–OH→<sup>*</sup>OOC(H<sub>3</sub>C)C═N), while also lowering the energy consumption for the hydrogenation of the C═N bond (<sup>*</sup>OOC(H<sub>3</sub>C)C═NH→<sup>*</sup>OOC(H<sub>3</sub>C)CNH<sub>2</sub>). This innovative strategy not only provides a new route for the valorization of biomass and waste nitrate but also offers valuable guidance for the design of more efficient rare-earth-based catalysts in this field.</p>","PeriodicalId":94060,"journal":{"name":"JACS Au","volume":"5 4","pages":"2015–2026 2015–2026"},"PeriodicalIF":8.5,"publicationDate":"2025-04-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/jacsau.5c00252","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143878277","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Effect of Pyridinecarboxaldehyde Functionalization on Reactivity and N-Terminal Protein Modification 吡啶甲酸功能化对反应性和n端蛋白修饰的影响
IF 8.5
JACS Au Pub Date : 2025-04-04 DOI: 10.1021/jacsau.5c0023810.1021/jacsau.5c00238
Lydia J. Barber, Ksenia S. Stankevich and Christopher D. Spicer*, 
{"title":"Effect of Pyridinecarboxaldehyde Functionalization on Reactivity and N-Terminal Protein Modification","authors":"Lydia J. Barber,&nbsp;Ksenia S. Stankevich and Christopher D. Spicer*,&nbsp;","doi":"10.1021/jacsau.5c0023810.1021/jacsau.5c00238","DOIUrl":"https://doi.org/10.1021/jacsau.5c00238https://doi.org/10.1021/jacsau.5c00238","url":null,"abstract":"<p >The site-selective modification of protein N-termini represents a powerful strategy for producing homogeneous bioconjugates. 2-Pyridinecarboxaldehydes have emerged as a leading reagent class in this area. However, these conjugations suffer from relatively slow rates and a degree of reversibility. In this work, we therefore studied the effects of pyridinecarboxaldehyde functionalization on N-terminal modification. This allowed us to provide insight into the factors governing relative contributions from competing reaction pathways and design criteria for second generation reagents for protein labeling. Importantly, 3-methoxy-2-pyridinecarboxaldehydes were identified as providing both accelerated and more stable protein labeling, enabling further applications of this powerful technology.</p>","PeriodicalId":94060,"journal":{"name":"JACS Au","volume":"5 4","pages":"1983–1991 1983–1991"},"PeriodicalIF":8.5,"publicationDate":"2025-04-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/jacsau.5c00238","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143878238","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Electrode–Electrolyte Engineering and In Situ Spectroscopy for Urea Electrosynthesis from Carbon Dioxide and Nitrate Co-Reduction 二氧化碳和硝酸盐共还原电合成尿素的电极-电解质工程和原位光谱研究
IF 8.5
JACS Au Pub Date : 2025-04-03 DOI: 10.1021/jacsau.5c0006510.1021/jacsau.5c00065
Gabriel F. Costa,  and , María Escudero-Escribano*, 
{"title":"Electrode–Electrolyte Engineering and In Situ Spectroscopy for Urea Electrosynthesis from Carbon Dioxide and Nitrate Co-Reduction","authors":"Gabriel F. Costa,&nbsp; and ,&nbsp;María Escudero-Escribano*,&nbsp;","doi":"10.1021/jacsau.5c0006510.1021/jacsau.5c00065","DOIUrl":"https://doi.org/10.1021/jacsau.5c00065https://doi.org/10.1021/jacsau.5c00065","url":null,"abstract":"<p >The biogeochemical cycles of carbon and nitrogen are globally disturbed due to the intensive use of fossil fuels and fertilizers, which is reflected by the accumulation of carbon dioxide in the atmosphere and nitrate in water streams. The co-electroreduction of carbon dioxide and nitrate is a promising low-carbon alternative for urea synthesis that would help to reestablish both carbon and nitrogen cycles. This Perspective highlights the importance of rational catalyst and electrolyte engineering to enable electrochemical urea synthesis. Although the field has gained significant attention over the past few years, fundamental research under well-defined conditions remains underexplored. We highlight the importance of investigating structure-sensitivity and electrolyte effects on electrochemical C–N coupling through complementary in situ spectroscopy and online techniques. Model studies, including in situ surface-sensitive investigations, will be crucial to understand the molecular mechanisms and thus to rationally design more efficient systems for urea electrosynthesis, paving the way for their scalable and industrial applications.</p>","PeriodicalId":94060,"journal":{"name":"JACS Au","volume":"5 4","pages":"1538–1548 1538–1548"},"PeriodicalIF":8.5,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/jacsau.5c00065","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143878233","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Organocatalyzed Enantioselective C–N Bond-Forming SNAr Reactions for Synthesizing Stereogenic-at-Boron BODIPYs 有机催化对映选择性C-N成键SNAr反应合成立体硼体
IF 8.5
JACS Au Pub Date : 2025-04-02 DOI: 10.1021/jacsau.5c0019610.1021/jacsau.5c00196
Yan-Dong Meng, Wei Fang, Zheng-Hao Pei, Wen-Hao Chen, Shu-Ying Ding, Meng-Lan Shen, Yingcui Bu*, Chuan-Zhi Yao, Qiankun Li, Jie Yu* and Hua-Jie Jiang*, 
{"title":"Organocatalyzed Enantioselective C–N Bond-Forming SNAr Reactions for Synthesizing Stereogenic-at-Boron BODIPYs","authors":"Yan-Dong Meng,&nbsp;Wei Fang,&nbsp;Zheng-Hao Pei,&nbsp;Wen-Hao Chen,&nbsp;Shu-Ying Ding,&nbsp;Meng-Lan Shen,&nbsp;Yingcui Bu*,&nbsp;Chuan-Zhi Yao,&nbsp;Qiankun Li,&nbsp;Jie Yu* and Hua-Jie Jiang*,&nbsp;","doi":"10.1021/jacsau.5c0019610.1021/jacsau.5c00196","DOIUrl":"https://doi.org/10.1021/jacsau.5c00196https://doi.org/10.1021/jacsau.5c00196","url":null,"abstract":"<p >The precise construction of boron stereogenic centers represents a significant, yet challenging frontier in asymmetric catalysis, garnering growing attention in recent years. However, feasible catalysis has primarily been limited to transition-metal-catalyzed desymmetrization of pro-chiral BODIPY molecules, while enantioselective synthesis via organocatalysis remains unexplored. Herein, we achieve an organocatalyzed C–N bond-forming SNAr reaction of 3,5-dihalogen BODIPYs via phase-transfer catalysis, enabling the efficient synthesis of a broad range of boron-stereogenic BODIPYs with excellent enantioselectivities (&gt;40 examples, up to 99% ee). The significance and potential of this catalytic approach are further underscored by the versatile applications of enantioenriched 3-amide BODIPYs in asymmetric synthesis, optical activity regulation, bioimaging, and sensing, promoting the development of boron-stereogenic fluorophores.</p>","PeriodicalId":94060,"journal":{"name":"JACS Au","volume":"5 4","pages":"1965–1973 1965–1973"},"PeriodicalIF":8.5,"publicationDate":"2025-04-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/jacsau.5c00196","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143878196","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Deciphering the Diffusion-Improved Selectivity of Ethylene Mediated by the Mesoscale Spatial Pattern of Aromatics in Zeolite-Catalyzed Methanol-to-Olefin Processes 沸石催化甲醇制烯烃过程中芳烃中尺度空间格局对乙烯扩散选择性的影响
IF 8.5
JACS Au Pub Date : 2025-04-01 DOI: 10.1021/jacsau.5c0004510.1021/jacsau.5c00045
Qingteng Chen, Jian Liu and Bo Yang*, 
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