化学•材料最新文献

{"title":"Donor–Acceptor-Substituted 5-Azaazulenes","authors":"Enikő Meiszter, Gábor Turczel, András Stirling, Péter Pál Fehér, Gábor London","doi":"10.1021/acs.joc.5c01663","DOIUrl":"https://doi.org/10.1021/acs.joc.5c01663","url":null,"abstract":"The synthesis of 5-azaazulenes with both donor and acceptor substituents on their seven-membered rings is reported through the ring expansion of stable azapentalene derivatives upon reaction with dimethyl acetylenedicarboxylate. Regioisomeric products were obtained and characterized. The mechanism of the transformation and the excited state energy levels of the products were studied computationally, suggesting that these structures can be entry points to chromophore design for organic photonics applications.","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"5 1","pages":""},"PeriodicalIF":4.354,"publicationDate":"2025-10-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145306323","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":"Iron-Catalyzed Selective Sulfonylation of Alkenes by Sulfonyl Fluorides.","authors":"Tong-Tong Zhao,Zi-Yu Liu,Si-Han Zheng,Shu-Han Wang,Ke-Yu Li,Qiang Bian,Da-Zhen Xu","doi":"10.1021/acs.joc.5c01566","DOIUrl":"https://doi.org/10.1021/acs.joc.5c01566","url":null,"abstract":"Herein, we report an iron-catalyzed approach for the generation of sulfonyl radicals from readily available bulk raw material sulfonyl chlorides and selective sulfonylation of alkenes for the synthesis of β-keto sulfones and vinyl sulfones depending on the reaction conditions. Under mild aerobic oxidation conditions in ethanol, β-keto sulfones were obtained via C(sp2)-C bond cleavage, while under argon protection in hexafluoroisopropanol, vinyl sulfones were formed. Mechanism studies reveal that iron salts play the role of hitting two birds with one stone, involving hydrogen atom transfer (HAT) and single-electron transfer (SET) processes.","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"32 1","pages":""},"PeriodicalIF":4.354,"publicationDate":"2025-10-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145305368","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":"Electrochemical Oxidative Dehydrogenative Thioacylation of N-Heterocycles with CS2 and Amines.","authors":"Lin Li,Yanan Li,Jinsong Hu,Chenpei Yang,Jianan Sun,Peng Qian","doi":"10.1021/acs.joc.5c01996","DOIUrl":"https://doi.org/10.1021/acs.joc.5c01996","url":null,"abstract":"An electrochemical strategy is developed for valorizing sulfur-rich carbon disulfide (CS2) through thioacylation of nitrogen-containing heterocycles including carbazole and indole derivatives. This methodology employs CS2 and amines as readily available precursors to construct dithiocarbamate structures, creating an efficient electrochemical platform for synthesizing diverse dithiocarbamate-functionalized N-heterocycles. The metal- and oxidant-free process facilitates sequential N-C and N-S bond formation, delivering target products in high yields. Significantly, the transformation exhibits remarkable regioselectivity, favoring exclusive N-S bond formation at the indole nitrogen atom while suppressing competing C-S bond generation at the C3 position. Mechanistic investigations involving controlled experiments and radical trapping studies indicate that the reaction proceeds via a radical-mediated pathway.","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"127 1","pages":""},"PeriodicalIF":4.354,"publicationDate":"2025-10-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145305369","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":"Microplastics Amplify Greenhouse Gas Emissions from Freshwater Sediments through Synergistic Interactions.","authors":"Ang Hu,Hao Wu,Tianheng Gao,Jianjun Wang","doi":"10.1021/acs.est.5c12509","DOIUrl":"https://doi.org/10.1021/acs.est.5c12509","url":null,"abstract":"Microplastic pollution is pervasive in freshwater ecosystems, yet the ecological consequences of increasingly complex microplastic mixtures remain poorly understood, particularly under climate warming. Here, we establish 1264 aquatic microcosms containing microplastics from 1 to 12 types and expose them to 15 and 20 °C to assess their effects on greenhouse gas (GHG) emissions. We find that the increased microplastic chemodiversity, quantified by type number and chemical composition, significantly amplifies GHG emissions by up to 4.69-times especially under warming. This pattern is consistent across a 450-day organic carbon degradation cascade. Compared to single-type microplastics, mixtures of multiple microplastics emit greater amounts of GHG in ∼64% of cases, with the effects strengthening at higher chemodiversity. These effects are driven by synergistic interactions, which prevail when three or more microplastic types are combined, especially in the presence of conventional microplastics. The warming-induced increase in GHG emission rates is more pronounced with increasing microplastic chemodiversity, driven directly by microplastic diversity and indirectly by shifts in the compositions of microbes and dissolved organic matter. Our findings reveal the mixing strategies and interaction patterns among diverse microplastics in regulating greenhouse gas emissions, and advance understanding of how plastic pollution affects freshwater-carbon cycling.","PeriodicalId":36,"journal":{"name":"环境科学与技术","volume":"65 1","pages":""},"PeriodicalIF":9.028,"publicationDate":"2025-10-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145305479","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":"Unveiling the Role of Four-Phonon Scattering in Thermal Transport of Penta-XN2 (X = Pd, Pt) Monolayers: Insights from First-Principles Calculations","authors":"Yang-Shun Lan, Chuan-Fu Li, Ping Wang, Hong-Gang Zhang, Yang-Jun Yan, Xiao-Ting Zha, Yu-Zhi Li, Yun-Jun Gu, Qi-Feng Chen","doi":"10.1021/acs.jpcc.5c05887","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c05887","url":null,"abstract":"Understanding, accurately predicting, and controlling thermal transport in penta-2D materials are crucial for optimizing their applications in nanoelectronics and energy devices. To this end, we systematically elucidate the thermal conductivity modulation in penta-XN₂ (X = Pd, Pt) monolayers via first-principles calculations and four-phonon (4ph) scattering mechanisms. Penta-PtN₂ exhibits faster acoustic phonon velocities, weaker anharmonicity, and higher intrinsic thermal conductivity compared to penta-PdN₂. The inclusion of 4ph scattering significantly reduces thermal conductivity across the entire temperature range, as exemplified by reductions of 82% and 71% for penta-PdN₂ and penta-PtN₂, respectively, at 300 K. This reduction is primarily attributed to the redistribution channel of the normal process, which disrupts phonon transport by altering phonon populations, breaking transport directionality, and reducing coherence. This study unambiguously identifies the 4ph scattering under momentum conservation as the key factor limiting thermal conductivity in penta-XN₂, providing theoretical guidance for optimizing strong anharmonic penta-2D materials in nanoelectronics and energy devices.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"70 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-10-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145314829","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":"One-Pot Assembly of Dihydrofluoren-3-ones via Intramolecular Annulation of Alkynyl-Alkynones: A Way to Functionalized Fluorenes.","authors":"Chada Raji Reddy,Ankita Kumari,Adla Vijender,Shiva Kumar Kota Balaji,René Grée","doi":"10.1021/acs.joc.5c01964","DOIUrl":"https://doi.org/10.1021/acs.joc.5c01964","url":null,"abstract":"Herein, we reveal an approach for the synthesis of a unique structural framework, dihydrofluoren-3-one, from the reaction of propargylic alcohol with alkynyl silyl enol ether. The transformation proceeds through acid-catalyzed propargylation of silyl enol ether leading to alkynyl-alkynones and subsequent intramolecular annulation (3+2 cycloaddition) in the presence of PPh3AuNTf2 (2 mol %). This novel dihydrofluoren-3-one motif was found to be a versatile precursor to provide diverse functionalized fluorenes.","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"41 1","pages":""},"PeriodicalIF":4.354,"publicationDate":"2025-10-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145311672","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":"Structural Estimation of High-Molecular-Weight and Ultra-hydrophilic Trichloroacetic Acid Precursors Originated from Raphidophytes.","authors":"Yuto Tada,Katsunari Hori,Koji Kosaka,Shinya Echigo,Sadahiko Itoh","doi":"10.1021/acs.est.5c05108","DOIUrl":"https://doi.org/10.1021/acs.est.5c05108","url":null,"abstract":"Raphidophytes, algae that grow in lakes and ponds, can proliferate in drinking water sources and increase the level of trichloroacetic acid (TCAA) formation during chlorination. Raphidophytes lack cell walls, making them highly susceptible to disruption by minor physical effects, which in turn necessitates the removal of dissolved TCAA precursors during water treatment. TCAA precursors are presumably nonprotein biopolymers with ultrahydrophilic properties that pose challenges for their removal through conventional treatment. In this study, we estimated the substructures of TCAA precursors from lab-cultured raphidophytes (Gonyostomum semen) and wild raphidophytes (Gonyostomum spp.), using nuclear magnetic resonance (NMR), infrared (IR) spectroscopy, and high-resolution mass spectrometry (HRMS). 1H and 13C NMR and IR spectra revealed the presence of phenolic substructures within the TCAA precursors. Additionally, the presence of glycan substructures is confirmed. Predicted molecular formulas obtained by HRMS supported the existence of glycans. Further evaluation of the TCAA formation potentials of the model substances indicated that the glycan substructures did not contribute to TCAA formation; instead, TCAA was derived solely from the phenolic functional groups. Additionally, the phenolic substructure may be substituted with electron-donating functionalities, which enhances TCAA formation. This study pioneers the elucidation of the detailed structures of these novel and unique TCAA precursors.","PeriodicalId":36,"journal":{"name":"环境科学与技术","volume":"40 1","pages":""},"PeriodicalIF":9.028,"publicationDate":"2025-10-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145305481","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":"Experimental and Theoretical Investigations on the Structural, Electronic, and Vibrational Properties of β-Bi2Mo2O9 Dibismuth Dimolybdenum","authors":"Raí F. Jucá, José Gadelha da Silva Filho, Lindemberg S. Oliveira, Antônio Joel Ramiro de Castro, Marcelo A. S. Silva, Antonio Sérgio B. Sombra, Pierre Basílio Almeida Fechine, João Maria Soares, Antônio César Honorato Barreto, Paulo T. C. Freire, Gilberto Dantas Saraiva","doi":"10.1021/acs.jpcc.5c04920","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c04920","url":null,"abstract":"This study presents a comprehensive structural, vibrational, and electronic investigation of the monoclinic β-Bi₂Mo₂O₉ compound, employing experimental and first-principles approaches. X-ray diffraction combined with Rietveld refinement confirms the crystallization of Bi₂Mo₂O₉ in the P2₁/n space group. Density functional theory calculations within the LDA-D framework reveal a slight underestimation of the lattice parameters and unit cell volume, while preserving local geometries. The vibrational properties were examined through Raman and infrared spectroscopy, supported by group-theory analysis, indicating a rich phonon activity consistent with the complex symmetry and multiatom basis of the monoclinic lattice. Electronic structure calculations identify BMO as an indirect band gap semiconductor with a computed band gap of 2.23 eV, closely matching experimental optical data. Bader charge and electron localization function (ELF) analyses highlight a mixed ionic–covalent bonding character, particularly pronounced in the Mo–O sublattice. Low-temperature Raman spectra (12–300 K) revealed systematic redshifts, peak broadenings, and intensity reductions across low- and high-wavenumber phonon modes, indicative of pronounced anharmonic effects and thermal expansion of the lattice. On the contrary, high-pressure Raman spectra collected up to 9.08 GPa showed a general phonon hardening trend with increasing pressure, attributable to lattice compression. Several Raman modes exhibited anomalous behavior, such as mode appearance, disappearance, and slope changes, pointing to pressure-induced phase transitions and potential symmetry changes.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"58 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-10-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145306267","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":"Fully Analytic Nuclear Gradients for the Bethe-Salpeter Equation.","authors":"Johannes Tölle, Marios-Petros Kitsaras, Pierre-François Loos","doi":"10.1021/acs.jpclett.5c02219","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c02219","url":null,"abstract":"<p><p>The Bethe-Salpeter equation (BSE) formalism, combined with the <i>GW</i> approximation for ionization energies and electron affinities, is emerging as an efficient and accurate method for predicting optical excitations in molecules. In this Letter, we present the first derivation and implementation of fully analytic nuclear gradients for the BSE@<i>G</i>₀<i>W</i>₀ method. Building on recent developments for <i>G</i>₀<i>W</i>₀ nuclear gradients, we derive analytic nuclear gradients for several BSE@<i>G</i>₀<i>W</i>₀ variants. We validate our implementation against numerical gradients and compare excited-state geometries and adiabatic excitation energies obtained from different BSE@<i>G</i>₀<i>W</i>₀ variants with those from state-of-the-art wave function methods.</p>","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":" ","pages":"11134-11143"},"PeriodicalIF":4.6,"publicationDate":"2025-10-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145311975","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":"Overview of advancements in overtopping breakwater for wave energy conversion (OBREC): Harnessing coastal power for renewable energy and enhanced coastal protection","authors":"Yeddid Yonatan Eka Darma ,&nbsp;Shade Rahmawati ,&nbsp;Daniel M. Rosyid ,&nbsp;Raditya Hendra Pratama ,&nbsp;Andhi Indira Kusuma","doi":"10.1016/j.rser.2025.116399","DOIUrl":"10.1016/j.rser.2025.116399","url":null,"abstract":"<div><div>Coastal engineering is increasingly moving toward multifunctional systems that integrate shoreline protection with renewable energy generation. Among these innovations, the Overtopping Breakwater for Wave Energy Conversion (OBREC) stands out as a promising technology that converts wave energy into electricity while enhancing coastal resilience. This paper presents a systematic review of OBREC research conducted between 2014 and 2024, synthesizing global developments across experimental, numerical, and prototype studies. The analysis identifies distinct national approaches, including Italy’s full-scale implementation, Malaysia’s CFD-based ramp optimization, China’s multi-level MOBREC configuration, and Thailand and South Korea’s hydraulic sensitivity investigations. Each contributes valuable methodological insights into OBREC performance and design evolution. Comparative assessment reveals persistent research gaps, particularly regarding turbine integration and the adaptation of low- and very-low-head technologies to OBREC’s intermittent flow regime. The review also examines power prediction models, capacity factors, and economic indicators, highlighting inconsistencies in performance assessment. By integrating findings on hydrodynamics, turbine technology, and environmental implications, this study provides a comprehensive foundation for advancing OBREC toward practical, efficient, and sustainable coastal energy applications.</div></div>","PeriodicalId":418,"journal":{"name":"Renewable and Sustainable Energy Reviews","volume":"226 ","pages":"Article 116399"},"PeriodicalIF":16.3,"publicationDate":"2025-10-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145324256","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}