化学最新文献

{"title":"The Dihydroindeno[2,1‐c]fluorene Core: from Syntheses to Properties and Potential Applications","authors":"Timothée Cadart, Martin Kotora","doi":"10.1002/ejoc.202500036","DOIUrl":"https://doi.org/10.1002/ejoc.202500036","url":null,"abstract":"In the last decade, substances possessing the dihydroindeno[2,1‐c]fluorene scaffold showed interesting photo‐physical properties and other potential applications in electronics. The afore‐mentioned compounds belong to the family of five regioisomeric dihydroindenofluorenes, but unlike other ones, they possess angular or, in the case of higher congeners, helical shape. This review is mainly focused on various synthetic approaches to compounds possessing the dihydroindeno[2,1‐c]fluorene scaffold and their conversions to other polyaromatic hydrocarbons. In addition, their physico‐chemical and photophysical properties, and current and/or potential applications are briefly described as well.","PeriodicalId":167,"journal":{"name":"European Journal of Organic Chemistry","volume":"47 1","pages":""},"PeriodicalIF":2.8,"publicationDate":"2025-05-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143915804","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":"Synergistic Catalysis for Recycling and Upcycling of Plastics","authors":"Hongshun Ran, Xinyang Sun, Mengying Zheng, Yaxuan Jing","doi":"10.1021/acscatal.5c00984","DOIUrl":"https://doi.org/10.1021/acscatal.5c00984","url":null,"abstract":"The management of waste plastics is a critical challenge due to their chemical stability, high production volume, low economic value, and short lifespan. Currently, only a small fraction of plastic waste is mechanically recycled, while most are incinerated, landfilled, or released into the environment, exacerbating pollution. Given their potential as energy-rich carbon resources, chemical valorization has gained increasing attention. A key challenge in plastic chemical recycling lies in the selective activation and cleavage of C–C, C–O, C–N, and C–Cl bonds within polymeric macromolecules. The whole cleavage process involving substrate adsorption, H₂/O₂ dissociation, bond activation-cleavage, intermediate saturation and product desorption usually requires synergistic catalysis between two or more different active sites. Understanding these cooperative catalytic mechanisms is crucial for optimizing catalyst design and reaction pathways. It integrates insights from molecular-level catalysis, active site engineering, and mechanistic studies of tandem catalysis systems, providing a comprehensive understanding of reaction networks and pathways that enable precise bond activation and cleavage using multifunctional catalysts.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"11 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-05-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143915805","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}

{"title":"Photochemical [2+2] reaction-tuned spin-crossover cooperativity in an Fe(II)-Ag(I) bimetallic Hofmann-type framework","authors":"Long-Fei Wang, Liang Wu, Guo-Zhang Huang, Si-Guo Wu, Ming-Liang Tong","doi":"10.1039/d5qi00821b","DOIUrl":"https://doi.org/10.1039/d5qi00821b","url":null,"abstract":"Photo-responsive spin-crossover (SCO) compounds are particularly appealing due to their adjustable wavelength/energy of light and the capability for remote switching. Herein, we introduce the 3-styrylpyridine (3-spy) ligand into a 2D Fe(II)-Ag(I) bimetallic Hofmann-type framework to construct a photo-responsive SCO compound [Fe(3-spy)<small>₂</small>{Ag(CN)<small>₂</small>}<small>₂</small>] (<strong>1</strong>). Upon irradiation at 365 nm, the criss-crossed C=C double bonds of 3-spy ligands in <strong>1</strong> undergo a pedal-like conformational motion and a photochemical [2+2] cycloaddition reaction, leading to the structural disorder but resulting in a more regular coordination geometry around the SCO center in the cyclobutane product [Fe(<em>hh-rctt</em>-1,2-ppcb){Ag(CN)<small>₂</small>}<small>₂</small>] (<strong>2</strong>) (<em>hh-rctt</em>-1,2-ppcb = <em>hh-rctt</em>-1,2-bis(3-pyridyl)-3,4-bis(phenyl)cyclobutane, <em>r</em> = reference group, <em>c</em> = cis and <em>t</em> = trans, <em>hh</em> = head-to-head). These structural changes exert opposite influences on SCO cooperativity and the ligand field of SCO center. Studies of SCO behavior under different irradiation times revealed that the SCO cooperative behavior gradually shifts from a two-step SCO in <strong>1</strong> to the incomplete and gradual one-step SCO in <strong>2</strong>. Notably, <em>T</em><small>_1/2</small>, which represent the intermediate spin state where <em>γ</em><small>_HS</small> = 0.5, remains almost unchanged, indicating only the SCO cooperativity is significantly modulated in this unique photochemical [2+2] reaction-integrated SCO system. Moreover, upon irradiation at 254 nm, partial stereoselective cleavage of the cyclobutane moieties in <strong>2</strong> was observed, suggesting the potential for constructing photo-switchable SCO materials.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"103 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-05-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143915822","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}

{"title":"Elucidating the role of potassium in methane steam reforming using first-principles-based kinetic Monte Carlo simulations","authors":"Sai Sharath Yadavalli, Glenn Jones, Carlos Fonte, Michail Stamatakis","doi":"10.1016/j.jcat.2025.116203","DOIUrl":"https://doi.org/10.1016/j.jcat.2025.116203","url":null,"abstract":"In the chemical industry, potassium is commonly employed as a promoter to reduce coke formation on the Ni catalyst surface and has been demonstrated to significantly improve the productivity of the methane steam reforming (MSR) reaction. Despite numerous studies, a detailed understanding of the potassium effect at steam reforming conditions is lacking. In this contribution, we have developed a first-principles-based KMC model of MSR on Ni(1 1 1) and potassium-doped Ni(1 1 1) surfaces. The cluster expansion (CE) methodology was employed to systematically capture adsorbate–adsorbate interactions between MSR species and their effects on reaction rates. We performed KMC simulations with different loadings of potassium (0.5–3 %) on Ni(1 1 1) to understand the effect on MSR net turnover rates and macroscopic coverages. At high temperatures, we found that potassium strongly promotes the oxidation of CH and carbon adsorbates. For instance, at 1273.0 K, we observe that the MSR net turnover rate on the potassium-doped Ni(1 1 1) system (K-Ni(1 1 1)-2.8 %) is around 13.6 times higher than on Ni(1 1 1). The KMC process statistics analysis reveals that key oxidation events such as the formation of CHO, CHOH, COH and CO occur significantly faster on the potassium sites compared to Ni sites. Furthermore, on K-Ni(1 1 1)-2.8 % at 1273.0 K, the CO pathway on the potassium sites, which entails complete dehydrogenation of methane to C and oxidation of the latter to CO, makes the highest contribution (around 57 %) to the MSR net turnover rate. Our KMC simulations provide a deeper mechanistic-level understanding of the role of potassium in MSR and can potentially aid in the design of next-generation Ni-based catalysts that exhibit high activity and stability at steam reforming conditions.","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"103 1","pages":""},"PeriodicalIF":7.3,"publicationDate":"2025-05-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143915827","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}

{"title":"Silylchromium-Catalyzed Selective Semihydrogenation ofUndirected Allenes by Sila-metalation and beta-Silyl Elimination","authors":"Zheng Luo, Linhong Long, Shuaiyong Zhao, Xiaoyu Zhang, Yong Peng, Meiming Luo, Hui Chen, Xiaoming Zeng","doi":"10.1002/anie.202424273","DOIUrl":"https://doi.org/10.1002/anie.202424273","url":null,"abstract":"The semihydrogenation of simple allenes remains an issue because of the difficulty in control of selectivity without coordination assistance of directing groups, wherein over-hydrogenated alkanes and E/Z-mixed stereo- and regio-isomers can be potentially formed. We report here an electron-rich cyclic (alkyl)(amino)carbene (CAAC)-phosphine-ligated chromium(III) complex serving as precatalyst in promoting the selective semihydrogenation of undirected allenes by forming active silylchromium species. The semihydrogenation allows the selective addition of H2 to the less substituted and electron-rich alkyl-substituted C=C bonds of allenes with enabling the suppression of competitive over-hydrogenation, proving general to form trisubstituted E-alkenes in high chemo-, regio- and stereoselectivity. By this CAAC-phosphine-Cr-catalyzed selective semihydrogenation, unsaturated nitro, nitrile, alkenyl and hydrogenation-sensitive bromide, chloride and fluoride were compatible with various substitution environments. The in-situ forming silylchromium as active catalyst by reaction of low-valent chromium complex with chlorosilane was established by studying the catalytic and stoichiometric reactivity of this species in the semihydrogenation. Deuterium labeling experiments, HRMS, XPS, EPR and magnetic susceptibility analysis of the related intermediates and theoretical studies support a pathway involving sila-metalation of allene and b-silyl elimination processes with silyl as non-innocent ligand, leading to the E-alkene products.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"47 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-05-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143915852","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}

{"title":"Harnessing C–H acetoxylation: a gateway to oxygen-enriched organic frameworks","authors":"Jagrit Grover, Bishal Dutta, Devika Ghosh, Prakash Kumar Shee, Siddhartha Maiti, Daniel B. Werz, Debabrata Maiti","doi":"10.1039/d5sc00449g","DOIUrl":"https://doi.org/10.1039/d5sc00449g","url":null,"abstract":"Transition metal catalyzed C-H functionalization has emerged as a robust tool in organic synthesis, as it utilizes the most abundant functional group of an organic compound i.e. C-H bonds, omitting the need for pre-functionalization. Selectively functionalizing a particular C-H bond out of numerous C-H bonds present in the molecular skeleton is a fascinating and difficult task to perform. To differentiate between almost identical CH bonds, various strategies have evolved. Directing group (DG) assistance, non-directed functionalizations, and non-covalent interactions have significantly contributed to address the challalenge of regioselectivity in taregting distinct C-H bonds. However, further advancements are still required. Among various C-H functionalizations, C-H acetoxylation is a pivotal organic transformation which enables direct functionalization of otherwise inert C-H bonds into versatile acetoxy groups. In this review, various strategies for C-H acetoxylation, i.e. directed and non-directed C-H acetoxylation, electrochemical C-H acetoxylation, photo-induced C-H acetoxylation, are covered. A comprehensive coverage provided by this review will be extremely useful to chemists in both academia and industry, who are striving to incorporate oxygen into organic molecular skeletons.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"11 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-05-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143915865","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}

{"title":"ACA-25-200 Rev Clean version Automatised online SPE-LC-MS/MS method for the enantioselective determination of chiral β-blockers and antidepressants in wastewater","authors":"Marina Arenas, Julia Martín, Juan Luis Santos, Irene Aparicio, Esteban Alonso","doi":"10.1016/j.aca.2025.344152","DOIUrl":"https://doi.org/10.1016/j.aca.2025.344152","url":null,"abstract":"<h3>Background</h3>Pharmacologically active compounds are emerging pollutants of greatest concern because of their continuous release to the aquatic media and potential effects on non-target organisms. Nevertheless, in spite that many pharmaceuticals are chiral compounds which enantiomers may have different environmental behaviour and effects, their enantiomeric determination has been scarcely evaluated. This fact can be explained by the great challenge to overcome when developing an analytical method for the individual determination of compounds with the same physical-chemical properties, as it is the case of enantiomers.<h3>Results</h3>In this work, an automatised method based on online solid phase extraction (SPE) coupled to liquid chromatography-tandem mass spectrometry (LC-MS/MS) was optimised and validated for the enantiomeric determination of highly prescribed (β-blockers (atenolol, metoprolol and propranolol), antidepressants (citalopram, fluoxetine, sertraline, duloxetine and venlafaxine) and two of their metabolites in influent and effluent wastewater. Three of them (metoprolol, citalopram and venlafaxine) have been recently included in the European Union Directive 2024/3019 as substances that should be measured in wastewater. Method quantification limits in the range from 0.1 to 50 ng L^-1 for most compounds. Accuracy ranged from 60.8 to 114 % and precision, expressed as relative standard deviation, was lower than 12.5 % for all the compounds. Method application to wastewater samples revealed the presence of the target compounds at concentrations between 1.06 and 1213 ng L^-1 and a preferential degradation of some enantiomers: <em>S</em>-(-)-atenolol, metoprolol-E1, venlafaxine-E1 and O-desmethylvenlafaxine-E1.<h3>Significance and novelty</h3>This method is the first one for online SPE-chiral-LC-MS/MS determination of two therapeutic groups of chiral pharmaceuticals in wastewater. The method allows their automatised enantiomeric determination, including sample treatment, SPE column wash and conditioning, and LC-MS/MS determination, in 40 min with enantioresolution from 0.51 to 1.24. The online SPE method developed provides a fast way to obtain information about chiral compounds in wastewater reducing labour intensity, exposure to organic solvents, analyte loss and plastic waste","PeriodicalId":240,"journal":{"name":"Analytica Chimica Acta","volume":"37 1","pages":""},"PeriodicalIF":6.2,"publicationDate":"2025-05-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143915896","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":"Identification of plasticizers using thermal desorption dielectric barrier discharge ionization mass spectrometry","authors":"Xiaokang Guan, Xue You, Renato Zenobi, Qiao Lu","doi":"10.1039/d5an00327j","DOIUrl":"https://doi.org/10.1039/d5an00327j","url":null,"abstract":"Plasticizers, which are extensively utilized in the manufacturing of plastic products, have garnered significant attention due to their potential toxicity and the consequent health and environmental risks they pose. Traditional methods for detecting plasticizers, such as gas chromatography-mass spectrometry (GC-MS) and liquid chromatography-mass spectrometry (LC-MS), are often time-consuming and require complex sample preparation. In response to these challenges, this study introduces an innovative approach for the rapid and sensitive identification of seven common plasticizers using thermal desorption dielectric barrier discharge ionization mass spectrometry (TD-DBDI-MS). The proposed technique significantly reduces background interference by employing nitrogen as the discharge gas, thereby enabling the detection of characteristic quasi-molecular ions ([M+H]+) and their fragments, which are crucial for structural elucidation. The method exhibits remarkable sensitivity, with a limit of detection as low as 0.1 ppm for diethyl phthalate and a linear dynamic range of orders of magnitude. Furthermore, it allows for expedited screening of various plastic products, including cling wrap, package bags, and centrifuge tubes, with each sample analyzed in less than 30 seconds. This study underscores the efficacy of TD-DBDI-MS as a rapid, sensitive, and user-friendly methodology for the preliminary screening of plasticizers in a wide range of materials.","PeriodicalId":63,"journal":{"name":"Analyst","volume":"2 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2025-05-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143915923","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":"Recent Advances in Solid-State Batteries","authors":"Kelsey B. Hatzell*,&nbsp; and ,&nbsp;Linda F. Nazar*,&nbsp;","doi":"10.1021/jacs.5c0605810.1021/jacs.5c06058","DOIUrl":"https://doi.org/10.1021/jacs.5c06058https://doi.org/10.1021/jacs.5c06058","url":null,"abstract":"","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"147 18","pages":"14881–14883 14881–14883"},"PeriodicalIF":14.4,"publicationDate":"2025-05-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143911173","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}

{"title":"Parallel assembly of dual-electrochemical cell: a novel approach for simultaneous multiplexed sensing analysis","authors":"Pedro V. V. Romanholo,&nbsp;Larissa M. Andrade,&nbsp;Marcelo Giglioti,&nbsp;Guilherme Z. A. Luccas,&nbsp;Sergio A. S. Machado,&nbsp;Livia F. Sgobbi","doi":"10.1007/s00604-025-07194-x","DOIUrl":"10.1007/s00604-025-07194-x","url":null,"abstract":"<div><p>In the field of biosensing and chemical sensing, there is a growing demand for multiplexed detection and quantification of multiple targets within complex matrices. In electrochemical sensing, simultaneous multiplexed analysis is typically performed with multiple electrodes connected to a multichannel potentiostat. An alternative strategy involves using a single electrode capable of discriminating and detecting several analytes in a single measurement, which is, however, unfortunately limited to a selective group of molecules. Herein, we report a novel electrochemical method based on the parallel assembly of a dual-electrochemical cell (PADEC), which enables the simultaneous detection and quantification of solvent-incompatible analytes, prepared separately in two distinct electrochemical cells, using a single-channel potentiostat—thus achieving multichannel-like performance. This approach relies on connecting two electrochemical cells in parallel, allowing the concurrent measurement of distinct electrochemical responses from analytes that otherwise could not be simultaneously determined  due to solvent incompatibility. As a proof of concept, the water-soluble vitamin C, and the lipid-soluble vitamin D3 were simultaneously determined, each in its respective optimized medium. The PADEC approach demonstrated performance comparable to individual detection methods, achieving limits of detection of 27 μM for vitamin C and 32 μM for vitamin D3 over a linear range of 20–400 μM. This strategy establishes a new approach for simultaneous, multiplexed electrochemical determination  of analytes in different media. Moreover, this innovation may extend applications in electrochemistry beyond (bio)sensing to include areas such as electrocatalysis, energy and corrosion, potentially reducing dependence on multichannel potentiostats.</p><h3>Graphical Abstract</h3>\u0000<div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":705,"journal":{"name":"Microchimica Acta","volume":"192 6","pages":""},"PeriodicalIF":5.3,"publicationDate":"2025-05-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143913937","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}