化学•材料最新文献

{"title":"Fluidic Molecular Dynamics and Energy Relaxation Pathways in Solution-State Electronic Strong Coupling Using a High-Mode-Number Cavity.","authors":"Soh Kushida,Kuidong Wang,Marcus Seidel,Yohei Yamamoto,Cyriaque Genet,Thomas W Ebbesen","doi":"10.1021/acs.jpclett.5c02008","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c02008","url":null,"abstract":"Light-matter strong coupling (SC) has shown great potential for controlling the photophysical dynamics of molecules in recent years. Although various molecules have been used to study the laser-induced ultrafast dynamics under electronic strong coupling (ESC), nearly all measurements investigated solid molecular samples, while the impact of hybridized light-matter states on liquid phase molecular dynamics has been unexplored. Here, for the first time, we report the ultrafast dynamics of liquid-state molecules under ESC. Our transient absorption spectroscopy studies reveal the emergence of a fast decay component in liquid-state ESC, which cannot be observed in the same liquid system without a cavity. Furthermore, the depolarization kinetics is found to be accelerated, as revealed by resonant optical Kerr-effect (ROKE) spectroscopy, suggesting that energy migration occurs much faster than both the polariton lifetime and molecular rotational time constants. These findings offer critical insights into designing photochemical systems in the liquid state based on the photophysical properties of the strongly coupled molecules.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"277 1","pages":"8570-8579"},"PeriodicalIF":6.475,"publicationDate":"2025-08-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144825742","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":"Power quality improvement in DG based distribution systems: A review","authors":"Mitra Nabian Dehaghani ,&nbsp;Tarmo Korõtko ,&nbsp;Argo Rosin","doi":"10.1016/j.rser.2025.116184","DOIUrl":"10.1016/j.rser.2025.116184","url":null,"abstract":"<div><div>The rapid integration of distributed generation (DG) units in distribution networks, driven by the integration of renewable energy sources (RESs) such as solar and wind, has introduced significant power quality (PQ) challenges. These challenges, including voltage sags, harmonic distortions, and reactive power imbalances, pose risks to the stability, reliability, and efficiency of distribution systems. This paper provides a comprehensive review of PQ improvement techniques tailored for distribution systems, including filters, controllers, conditioners, flexible AC transmission systems (FACTS) devices, machine learning (ML) tools, and optimization methods. Special emphasis is placed on distributed artificial intelligence (DAI) frameworks, which offer decentralized, adaptive, and scalable solutions for managing the complexities of high RES penetration. A comparative analysis highlights the advantages of DAI over conventional and AI-based strategies in addressing the dynamic and real-time requirements of modern distribution systems. The paper concludes by emphasizing the need for integrating DAI-based control mechanisms to ensure sustainable, reliable, and high-quality power delivery in RES-dominated distribution networks.</div></div>","PeriodicalId":418,"journal":{"name":"Renewable and Sustainable Energy Reviews","volume":"225 ","pages":"Article 116184"},"PeriodicalIF":16.3,"publicationDate":"2025-08-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144828952","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}

{"title":"Ligand-Dependent Spin-Orbit Coupling Effects on Optical and Carrier Dynamics in M@Au₁₂ Nanoclusters.","authors":"Yu Zhou, Jixiang Zhou, Xueke Yu, Wei Pei, Si Zhou, Jijun Zhao","doi":"10.1021/acs.jpclett.5c01928","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c01928","url":null,"abstract":"<p><p>Spin-orbit coupling (SOC) plays a fundamental role in shaping the electronic structures, optical properties, and excited-state dynamics of nanoscale systems. However, in conventional quantum dots (e.g., CdSe and PbS), the observation and control of SOC effects are hindered by complex energy level structures and high densities of electronic states, which obscure the contributions of SOC and limit their tunability. In contrast, atomically precise superatomic metal nanoclusters (NCs), such as Au₁₃ and Au₂₅, offer a unique platform to isolate and systematically study SOC-driven phenomena, owing to their well-defined atomic configurations and discrete energy level distributions. In this work, we employed time-dependent density functional theory (TD-DFT) simulations to investigate the impact of SOC in ligand-protected Au₁₃ NCs. As a result, SOC lifts the degeneracy of the 1P superatomic orbitals, with the splitting patterns being strongly dependent on ligand identity. This ligand-specific SOC effect reshapes the optical absorption and magnetic circular dichroism (MCD) spectra, altering peak positions, intensities, and selection rules. Moreover, SOC significantly affects electronic transition channels, thereby influencing the relationship between electron-vibration interactions and carrier dynamics. These results provide a theoretical basis for designing metal nanoclusters with superior optoelectronic properties.</p>","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":" ","pages":"8613-8620"},"PeriodicalIF":4.6,"publicationDate":"2025-08-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144843812","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":"Metal-Free Carbamoylation/Annulation Cascade of Aryl Alkynoates: Synthesis of Carbamoylated Coumarins, Coumarin-Decorated Unnatural Amino Acids, and Peptides","authors":"Ashish Kumar, Himadri Saha, Chandra Shekhar Nishad, Shashikant Tiwari, Biplab Banerjee","doi":"10.1021/acs.joc.5c01301","DOIUrl":"https://doi.org/10.1021/acs.joc.5c01301","url":null,"abstract":"An efficient and sustainable approach for the synthesis of pharmaceutically important carbamoylated coumarins has been developed via a metal-free radical cascade cyclization of aryl alkynoates. Readily available, inexpensive, and nontoxic oxamic acids are used as a carbamoyl radical source. Additionally, wide substrate scope, tolerance to air and water, operational simplicity, good to excellent yields, and scalability enhance the practicality of the current method. The synthetic utility of this mild and environmentally friendly method is further demonstrated by the assembly of structurally diverse unnatural amino acids with a bioactive coumarin scaffold and late-stage modification of tyrosine-containing peptides and a drug molecule. Mechanistic studies reveal that cascade cyclization is triggered by a carbamoyl radical generated from oxamic acids using cheap and environmentally friendly ammonium persulfate as a radical initiator.","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"31 1","pages":""},"PeriodicalIF":4.354,"publicationDate":"2025-08-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144840081","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":"To Bend or Not to Bend: Revealing the Stereoelectronic Origin of the Distorted <i>sp</i> Carbon in Isocyanates.","authors":"Lucas Araujo, Felipe Fantuzzi, Thiago M Cardozo, Lars V Schäfer","doi":"10.1021/acs.jpca.5c02484","DOIUrl":"https://doi.org/10.1021/acs.jpca.5c02484","url":null,"abstract":"<p><p>Isocyanates, conventionally depicted as R-N═C═O, exhibit a puzzling deviation from the expected linear geometry of <i>sp</i>-hybridized carbon centers─a structural bending that significantly influences their reactivity. In this work, we present a comprehensive theoretical investigation into the structural, electronic, and vibrational properties of isocyanates using density functional theory (DFT) and wave function-based methods. The chemical structure of isocyanates is explored through intrinsic bond orbitals (IBOs), spin-coupled generalized valence bond (SCGVB) theory, and interference energy analysis (IEA) based on SCGVB calculations. Within the valence bond framework, we show that the N═C and C═O bonds in HNCO are best described as bent (or \"banana\") bonds, as the conventional representation using orthogonal σ and π components leads to physically unreasonable results. The IEA further reveals that the two bent bonds in C═O are not equivalent. This difference originates from the asymmetric electronic environment induced by the neighboring nitrogen lone pair, which weakens one of the bonds in C═O and induces observed NCO bending. By reasoning in terms of the two dominant resonance structures, we show that different substituents can favor one form or the other, depending on their nature. These results provide a clear rationale for the distinctive electrophilic behavior of isocyanates and also contribute to a deeper understanding of the so-called \"bent <i>sp</i> carbon.\"</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":""},"PeriodicalIF":2.8,"publicationDate":"2025-08-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144843865","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":"Chloroform-Driven Excited-State Protonation of Pyrene-Dialkylaniline Derivatives Under Visible Light.","authors":"Kumar Dineshkumar, Muniappan Kalipriyadharshini, Masiyappan Karuppusamy, Chellappan Selvaraju, Kanagasabai Balamurugan, Chinnusamy Saravanan, Shanmugam Easwaramoorthi","doi":"10.1002/asia.202500553","DOIUrl":"https://doi.org/10.1002/asia.202500553","url":null,"abstract":"<p><p>The photophysical and photochemical properties of the organic chromophores are predominantly governed by the aromatic core, electron-donating/withdrawing groups, and inter- and intramolecular electrostatic interactions, while alkyl chains contribute marginally due to their weaker inductive effect. To investigate alkyl chain effects, we synthesized 1-pyrene substituted with N,N-dialkylanilines (C2, C6, C10) via Suzuki coupling. Solvatofluorochromic studies revealed a red-shifted fluorescence with increasing solvent polarity, except in chloroform and methanol, attributed to solute-solvent interaction between solvent proton and the nitrogen atom of N,N-dialkylamine. In chloroform, blue LED irradiation induced light-sensitive transformation, characterized by decreased longer wavelength absorption and emergence of shorter wavelength bands. The resulting photoproduct was identified as a protonated N,N-dialkylaniline, with chloroform serving as a proton source. This process is exclusive to chloroform among the tested chlorinated solvents. Mechanistically, photoexcitation induces single-electron transfer from N,N-dialkylaniline to pyrene, generating radical ions that abstract hydrogen from chloroform. Nanosecond transient absorption spectroscopy confirmed the presence of N,N-dialkylaniline cation and pyrene anion radicals in chloroform but not in THF, highlighting the solvent role in charge separation and stabilizing radical intermediates. The reaction kinetics vary with alkyl chain length, with C6 being the optimal chain length.</p>","PeriodicalId":145,"journal":{"name":"Chemistry - An Asian Journal","volume":" ","pages":"e00553"},"PeriodicalIF":3.3,"publicationDate":"2025-08-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144843913","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":"Three-Phase Emulsions during Cross-Coupling Reactions in Water.","authors":"Yiqing Zhang, Suzanne A Blum","doi":"10.1021/acs.joc.5c01297","DOIUrl":"https://doi.org/10.1021/acs.joc.5c01297","url":null,"abstract":"<p><p>Fluorescence lifetime imaging microscopy (FLIM) enabled identification of three-phase emulsions during a cross-coupling reaction in water, offering insight into their features and factors driving their formation. Droplet morphology was influenced by surfactant choice, ionic strength through phosphate concentration, and evolution of the reaction medium composition. Spatially resolved, subdroplet imaging characterized two organic phases, with one exhibiting preferential localization of the palladium catalyst. Anisotropy and solvatochromic polarity measurements indicated that the palladium-catalyst-containing organic-droplet core exhibited higher viscosity than the organic shell, whereas the polarity of the two organic phases was indistinguishable within the solvatochromic detection capability. The presence of three-phase emulsions correlated with overall formulation and with faster rates of product generation. These findings provide insight for composition-droplet structure relationships toward optimizing aqueous-phase organic reactions and advancing synthetic organic chemistry in water.</p>","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":" ","pages":""},"PeriodicalIF":3.6,"publicationDate":"2025-08-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144833498","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":"A wearable and wireless electrochemical device based on Cu-BTC MOF for pyocyanin detection and wound healing","authors":"Jingwen Zhang ,&nbsp;Mei Wen ,&nbsp;Danqi Wang ,&nbsp;Bin Wang ,&nbsp;Siyu Jiang ,&nbsp;Xiao Liu ,&nbsp;Yuqing Li ,&nbsp;Wansong Chen ,&nbsp;Ping Ding ,&nbsp;Tianhan Kai","doi":"10.1016/j.bios.2025.117869","DOIUrl":"10.1016/j.bios.2025.117869","url":null,"abstract":"<div><div>The prevalent and serious antimicrobial resistance in <em>Pseudomonas aeruginosa</em> (PA) infections has emerged as a critical public health challenge worldwide. Pyocyanin (PYO), an important virulence component produced by PA, is considered as an ideal indicator for identifying infections linked to this pathogen. This study evaluated ten metal-organic frameworks (MOFs) as signal amplifiers for the sensitive detection of PYO. The findings reveal that electrodes modified with Cu-MOFs exhibited a notable enhancement in current for PYO reduction. Particularly, Cu-1,3,5-benzene tricarboxylic acid (Cu-BTC) demonstrated superior enhancement for PYO reduction, primarily due to its smaller particle size and larger availability of active copper sites. Building on these findings, an innovative wearable device using Cu-BTC was developed to facilitate the wireless electrochemical evaluation of PYO in wounds artificially produced in Sprague–Dawley rat models. The findings indicate that this biocompatible device not only possesses exceptional sensitivity for detecting PYO with a limit of detection (LOD) of 93.5 pM with remarkable stability and selectivity but also shows antimicrobial properties that aid in the wound healing process.</div></div>","PeriodicalId":259,"journal":{"name":"Biosensors and Bioelectronics","volume":"289 ","pages":"Article 117869"},"PeriodicalIF":10.5,"publicationDate":"2025-08-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144852285","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"生物学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Critical Size Transitions in Silicon Nanowires: Amorphization, Phonon Hydrodynamics, and Thermal Conductivity.","authors":"Ke Xu,Yuan Li,Dongliang Ding,Ting Liang,Jianyang Wu,Jianbin Xu","doi":"10.1021/acs.jpclett.5c01802","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c01802","url":null,"abstract":"Understanding the intrinsic thermal transport properties of ultrathin semiconductor nanowires with varying diameters is crucial for the efficient thermal management of next-generation nanoelectronic devices. Here, we developed high-fidelity machine-learning potential (MLP) within the fourth-generation neuroevolution potential framework to elucidate the interplay between structural evolution, amorphous transition behavior, and thermal transport in silicon nanowires (SiNWs), resolving long-standing discrepancies between simulations and experiments. The structure of SiNWs below 1.1 nm in diameter undergoes a complete amorphous transformation, which originates from an amorphous surface structure of 5-6 atomic layers. We identify a nonmonotonic dependence of thermal conductivity on nanowire diameter due to competition between N (Normal) and U (Umklapp) phonon scattering processes. At frequencies <1 THz, N-process scattering rates exceed U-process rates by 3 orders of magnitude in ultrafine SiNWs, enabling fluid-like phonon transport. This study underscores the transformative potential of high-fidelity MLP in unraveling complex nanoscale material behaviors.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"27 1","pages":"8580-8587"},"PeriodicalIF":6.475,"publicationDate":"2025-08-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144825741","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":"Research status and future development of the medium-deep geothermal heat pump heating system - A comprehensive review","authors":"Wei Xu,&nbsp;Ji Li,&nbsp;Guangqiu Zhang,&nbsp;Zongyu Sun,&nbsp;Jintang Li","doi":"10.1016/j.rser.2025.116141","DOIUrl":"10.1016/j.rser.2025.116141","url":null,"abstract":"<div><div>As a significant innovation in ground source heat pump technology, the medium-deep geothermal heat pump system (MD-GHPs) is designed to overcome the limitations like low-temperature inefficiencies of air source heat pumps, low heat exchange efficiency and large land use of shallow ground source heat pumps, and recharge issues of groundwater source heat pumps. Despite extensive global research on MD-GHPs' mathematical models, design optimization, and operational control, the lack of comprehensive review has obscured the developmental context of this technology. This paper constructs a systematic research framework covering five core modules. Firstly, it clarifies the applicable scenarios and technical characteristics of different borehole forms through technical classification. Secondly, the commonly used numerical and analytical models for the heat transfer process of underground buried pipes are described in detail, and key design methods for MD-GHPs are proposed. Then, from the perspective of energy efficiency improvement, the key parameters affecting the system operation are analyzed, and a system configuration scheme for multi-objective optimization and an intelligent control strategy are proposed. Subsequently, it analyzes constraining factors such as policies and systems, economic investment, technology, and social environmental challenges. Finally, three innovative directions are proposed, namely the collaboration of borehole cluster, the complementarity of composite energy systems, and the interaction with the power grid. Through systematically sorting out the technological evolution path and key breakthroughs, this study provides support for the theoretical improvement and engineering practice of MD-GHPs, thereby facilitating the large-scale application of this technology in building heating.</div></div>","PeriodicalId":418,"journal":{"name":"Renewable and Sustainable Energy Reviews","volume":"225 ","pages":"Article 116141"},"PeriodicalIF":16.3,"publicationDate":"2025-08-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144828949","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}