化学•材料最新文献

{"title":"Vapor-phase dehydration of 1,2-propanediol to allyl alcohol over silica-supported cesium phosphate","authors":"Masafumi Morooka ,&nbsp;Enggah Kurniawan ,&nbsp;Junji Okamura ,&nbsp;Yusei Nagamura ,&nbsp;Yasuhiro Yamada ,&nbsp;Satoshi Sato","doi":"10.1016/j.apcata.2024.120064","DOIUrl":"10.1016/j.apcata.2024.120064","url":null,"abstract":"<div><div>SiO₂-supported cesium phosphate (Cs_<em>x</em>P/SiO₂, <em>x</em> = molar ratio of Cs/P) catalysts show promising catalytic performance for the vapor-phase transformation of 1,2-propanediol (1,2-PDO) to allyl alcohol (AAL). The formation of AAL proceeded <em>via</em> propylene oxide (PO) formation. Simultaneously, 1,2-PDO was also converted to propanal (PAL). The Cs/SiO₂ without P mainly generated PO, and introducing P into Cs/SiO₂ promoted the consecutive transformation of PO to AAL with the concurrent reduction of PAL selectivity. Several reaction parameters, such as reaction temperature, contact time, and the phosphate content influenced the catalytic activity and product distribution. A Cs_1.4P/SiO₂ catalyst with a phosphate content of 20 wt% exhibited 100 % 1,2-PDO conversion with the AAL selectivity of 77 % at 400 °C and a contact time of 1.67 h. The poisoning experiment using probe molecules reveals that basic sites are essential for the PO formation, while acid-base sites are important in the isomerization of PO to AAL.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"691 ","pages":"Article 120064"},"PeriodicalIF":4.7,"publicationDate":"2025-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143135252","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Electrochemical Synthesis of 2-Amino-1,3-benzoxazines via TBAI-mediated Desulfurative Cyclization of Isothiocyanates and 2-Aminobenzyl Alcohols","authors":"Fengkai Sun, Man Miao, Yu Huang, Xiuli Wu, Wenxue Li, Xiao-Bing Lan, Jian-Qiang Yu, Jian Zhang, Zhenyu An","doi":"10.1021/acs.joc.4c02703","DOIUrl":"https://doi.org/10.1021/acs.joc.4c02703","url":null,"abstract":"An efficient one-step protocol has been developed to access a variety of 2-amino-1,3-benzoxazine derivatives via tetrabutylammonium iodide-mediated electrochemical desulfurative cyclization of isothiocyanates and 2-aminobenzyl alcohols. The reaction proceeds through a cycle involving <i>in situ</i> iodine generation, desulfurative cyclization, and iodide regeneration, efficiently forming intermolecular C–O and C–N bonds and affording 2-amino-1,3-benzoxazines in moderate to excellent yields. The practical utility of this strategy is evidenced by its broad substrate scope, good functional group compatibility, scalability to gram-scale synthesis, and metal- and oxidant-free conditions.","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"11 1","pages":""},"PeriodicalIF":4.354,"publicationDate":"2025-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143192377","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}

{"title":"Collective Total Synthesis of Aculeatin A, B, D, E, and F","authors":"Manoj Kumar, Parthasarathi Subramanian","doi":"10.1021/acs.joc.4c03024","DOIUrl":"https://doi.org/10.1021/acs.joc.4c03024","url":null,"abstract":"A collective convergent approach for the enantioselective total synthesis of aculeatins A, B, D, E, and F is presented, featuring [3 + 2]-cycloaddition, iron-mediated reductive N–O bond cleavage, and cascade spirocyclization. Moreover, this short six-step strategy is supplemented in synthesizing unnatural analogs of aculeatins such as 6-<i>epi</i>-aculeatin D, 6-<i>epi</i>-aculeatin E, and 6-<i>epi</i>-aculeatin F.","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"34 1","pages":""},"PeriodicalIF":4.354,"publicationDate":"2025-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143192380","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}

{"title":"Reactions of Thioamides with Iminoiodinanes: An Approach toward 1,2-Thiazines, Thiophenes, and Sulfonylisothiazolines","authors":"Vladimir G. Ilkin, Ilya D. Gridnev, Mikhail S. Novikov, Pavel S. Silaichev, Tetyana V. Beryozkina, Pavel A. Slepukhin, Wim Dehaen, Vasiliy A. Bakulev","doi":"10.1021/acs.joc.4c02623","DOIUrl":"https://doi.org/10.1021/acs.joc.4c02623","url":null,"abstract":"Transition metal-catalyzed and noncatalytic reactions of acrylic thioamides with <i>N</i>-sulfonyliminoiodinanes enabling the selective synthesis under mild conditions of a series of fully decorated S- and N,S-containing heterocycles are described. Fine-tuning of the thioamide structure allows selective preparation in good yields of ortho-fused thiophenes, 1,2-thiazines, and spiro-fused isothiazolines. A one-pot thermally induced rearrangement of sulfonylisothiazolines was discovered as a complementary route to thiophenes.","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"164 1","pages":""},"PeriodicalIF":4.354,"publicationDate":"2025-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143192675","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}

{"title":"One-step synthesized Cu-containing Silicalite-1 zeolite using Cu-NTA complex for the selective ammoxidation reaction","authors":"Jialiang Ke ,&nbsp;Wenqian Fu ,&nbsp;Lei Zhang ,&nbsp;Chenglong Yuan ,&nbsp;Tiandi Tang","doi":"10.1016/j.apcata.2024.120076","DOIUrl":"10.1016/j.apcata.2024.120076","url":null,"abstract":"<div><div>A one-pot synthesis strategy for the Cu-containing Silicalite-1 (Cu@S-1-N) zeolite with Cu⁺ anchored in silanol nests was initially presented via using nitrilotriacetic acid (H₃NTA) as a ligand. Introducing H₃NTA guaranteed the formation of a copper-chelate in the form of [Cu(NTA)₂]^2- in the precursor solution, whose un-coordinated carboxylate ion may condensate with silicate during the crystallization process, leading to the innumerable highly active and stable Cu⁺ species in the final Cu@S-1-N zeolite. In the model benzaldehyde ammoxidation reaction, the highly dispersed and electron-deficient Cu⁺ species in the Cu@S-1-N catalyst was more active and stable than the Cu²⁺ species in the Cu/S-1-N catalyst prepared by the incipient wetness impregnation method. The Cu⁺ species preferentially chemisorbed benzaldehyde, activating its carbonyl carbon for nucleophilic attack by the amino group from the decomposition of ammonium carbonate and subsequent toward the benzonitrile formation.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"691 ","pages":"Article 120076"},"PeriodicalIF":4.7,"publicationDate":"2025-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143135265","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}

{"title":"Catalytic hydrogenolysis of lignin with NiO-CuO catalyst via alcohol-water coprecipitation","authors":"Fengkai Liang,&nbsp;Yanbo Yin,&nbsp;Tiantian Jiao,&nbsp;Xiangping Li,&nbsp;Haifeng Zhou,&nbsp;Peng Liang","doi":"10.1016/j.apcata.2024.120082","DOIUrl":"10.1016/j.apcata.2024.120082","url":null,"abstract":"<div><div>Using lignin to produce valuable chemicals can help reduce reliance on fossil fuels. The NiO catalyst prepared by alcohol/water co-precipitation method showed higher activity than NiO prepared by ammonia-water precipitation method in catalytic hydrogenolysis (CH) reaction of enzymatic hydrolysis lignin (EHL). The yield of lignin oil reached 85.68 % at 270 °C for 30 min. The catalytic performance was further improved by the introduction of CuO. Under the optimized conditions (290 °C, 120 min), the yield of lignin oil was up to 95.13 % using N-C (4:1) as the catalyst. The GC-MS analysis showed that the lignin oil mainly consisted of phenols, esters, hydrocarbons, and other oxygenated compounds, among which, the phenolic content was up to 57.90 %. These results indicate that the prepared catalyst can effectively break the C-O and C-C bonds in lignin and significantly promote the formation of phenolics.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"691 ","pages":"Article 120082"},"PeriodicalIF":4.7,"publicationDate":"2025-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143135266","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}

{"title":"Hormesis as a Hidden Hand in Global Environmental Change?","authors":"Matthias C. Rillig, Anika Lehmann, Mohan Bi","doi":"10.1021/acs.est.5c01101","DOIUrl":"https://doi.org/10.1021/acs.est.5c01101","url":null,"abstract":"Figure 1. (A) Hormetic responses mean a response to a negative influence is positive at very low doses. (B) If widespread, such hermetic effects could lead to ecosystem process rates being affected, leading to an overestimation or underestimation of the effect of other factors of global change. (C) When environmental drivers are exceeding the hormetic threshold, the ecosystem state can undergo a transition from a stable state to an unstable state. M.C.R. wrote the first draft of the paper, and M.B. and A.L. added additional ideas and designed the figure. Matthias C. Rillig studied biology in Germany and Scotland and obtained a Ph.D. in California, USA. After nine years of being on the faculty of the University of Montana, he joined Freie Universität Berlin, where he is now a professor of ecology. He is director of the Berlin-Brandenburg Institute of Advanced Biodiversity Research. Matthias won an Advanced Grant of the European Research Council, is a fellow of the Ecological Society of America, and is a member of the German National Academy of Sciences, Leopoldina, and Academia Europaea. His lab focuses on soil ecology, human-caused effects on soils and their biodiversity, and emerging environmental challenges. This article references 11 other publications. This article has not yet been cited by other publications.","PeriodicalId":36,"journal":{"name":"环境科学与技术","volume":"5 1","pages":""},"PeriodicalIF":9.028,"publicationDate":"2025-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143124474","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}

{"title":"Role of Water in the Stability and Efficiency of Ionic Liquid-Based Perovskite Solar Cells","authors":"Yuqian Xie, Shenmiao Chen, Zihan Gu, Kui Xu, Lingfeng Chao, Yingdong Xia","doi":"10.1021/acs.jpclett.4c03629","DOIUrl":"https://doi.org/10.1021/acs.jpclett.4c03629","url":null,"abstract":"The fabrication of perovskite solar cells (PSCs) in ambient air can accelerate their industrialization. However, moisture causes severe decomposition of the perovskite materials, limiting device efficiency. Here, we demonstrate that, compared to traditional <i>N</i>,<i>N</i>-dimethylformamide-based precursor solutions, the ionic liquid methylammonium acetate (MAAc) system forms a protective layer on the perovskite surface due to the C═O···Pb and N–H···I interactions between MAAc and PbI₆^4–, which effectively prevents direct contact between the perovskite components and water. Moreover, we show that a certain level of humidity weakens the interactions between MAAc and PbI₆^4–, promoting the crystallization process and resulting in films with fewer defects. PSCs based on MAAc achieved a power conversion efficiency of 20.73% under optimal water content conditions, and the unencapsulated devices maintained &gt;83% of their initial efficiency after &gt;1300 h in ambient air.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"9 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2025-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143124682","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}

{"title":"Investigating the Pump Fluence and Mn Doping Dependence in Biexciton Generation in CdTe QDs and Their Dynamics through Transient Absorption Spectroscopy","authors":"Thankappan Thrupthika, Devaraj Nataraj, Subramaniam Ramya, Kanagaraj Reivanth, T. Daniel Thangadurai","doi":"10.1021/acs.jpcc.4c06845","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c06845","url":null,"abstract":"Water-soluble CdTe quantum dots (QDs) are systematically synthesized to study the influence of Mn dopant on charge-carrier dynamics under different pump excitation fluences. Herein, we have introduced Mn dopant to manipulate the defect states in CdTe QDs and analyzed its effect on biexciton as well as hot electron dynamics. The optical studies evidently support the presence of Mn dopant energy states above the conduction band edge of the CdTe QDs. From the transient absorption analysis, the band edge bleach growth time and the early time band edge bleach position in the high-energy region to the absorption band edge portion, under higher exciton occupancy per QD, reveal the biexciton generation processes and the hot electron relaxation process in Mn-CdTe QDs. The kinetics at the band edge bleach along with the positive transient absorption spectral slice in QDs further explain the relaxation mechanism of hot charge carriers to the lower energy level. Interestingly, we obtained increases in biexciton binding energy and a suppressed hot electron cooling time in the presence of Mn dopant in CdTe QDs at fluence excitation.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"165 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143124733","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Intricacies of Carbon Dot Photoluminescence for Emerging Applications: A Review.","authors":"Nilanjana Nandi, Priyanka Sarkar, Neha Barnwal, Kalyanasis Sahu","doi":"10.1002/asia.202401470","DOIUrl":"https://doi.org/10.1002/asia.202401470","url":null,"abstract":"<p><p>Discovered in 2004, carbon dots (CDs) have already traversed a long journey, generating many promising research directions. Its cheapness, ease of synthesis, high water-solubility, tunable emission, and excellent biocompatibility make it a single-point solution to many problems, and tremendous efforts were invested into understanding the structure-property-function relationship, which eases the engineering of the CD properties suitable for a desired application. From the usual random choice of precursors or carbon materials as a starting point in the early days, more systematic approaches are now available for choosing proper starting materials and appropriate experimental conditions (solvent medium, reaction temperature, reaction duration, pH, etc) to customize its photoluminescence. The presence of impurities has a crucial role in the outcome and applicability of photoluminescence. Recently, a significant focus has been on the long-wavelength emissive CDs, particularly in the red to near-infrared (NIR) regions, for better penetration into live cells and to circumvent autofluorescence problems. Proper design can harvest phosphorescence from CDs. Many excellent reviews are available, focusing on different facets of CD prospects. Hence, we will only highlight the importance of the optical properties of CDs. We will mention some of the new works that have appeared in the last five years.</p>","PeriodicalId":145,"journal":{"name":"Chemistry - An Asian Journal","volume":" ","pages":"e202401470"},"PeriodicalIF":3.5,"publicationDate":"2025-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143187622","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}