化学•材料最新文献

{"title":"Blue-Shifting Hydridic Hydrogen Bonds in Complexes of (Me₃Si)₃SiH.","authors":"Maximilián Lamanec, Vladimír Špirko, Svatopluk Civiš, Pavel Hobza","doi":"10.1021/acs.jpca.5c05765","DOIUrl":"https://doi.org/10.1021/acs.jpca.5c05765","url":null,"abstract":"<p><p>Hydridic hydrogen bonds, formed by X-H···Y interactions with negatively charged hydrogen, expand the conventional view of H-bonding beyond elements that are more electronegative than hydrogen. Using a highly polarizable silane donor (Me₃Si)₃SiH, we systematically examined various electron acceptors (σ- and π-hole) and observed both red and blue shifts in the X-H stretching frequency. We provide the first experimental evidence of a blue-shifting hydridic bond and report the largest experimental blue shift for any hydrogen-bonded system. Thermodynamic, spectroscopic, and theoretical analyses show that the dispersion energy is crucial for stabilizing these complexes and reproducing their spectral signatures. Notably, the IR band intensity increases for red-shifting bonds and increases or decreases for blue-shifting hydridic bonds, offering a distinct spectroscopic fingerprint. Adiabatic ALMO-EDA calculations indicate that red shifts in hydridic bonds primarily arise from electrostatics and dispersion rather than charge transfer. It can be thus concluded that protonic as well as hydridic hydrogen bonds exhibit similar spectral manifestations, namely, the red or blue shift of the X-H stretching frequency connected with the intensity increase or decrease. These findings broaden hydrogen-bonding paradigms for diverse chemical applications.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":""},"PeriodicalIF":2.8,"publicationDate":"2025-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145298040","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":"Inactivation Challenges of SARS-CoV-2 on Surfaces in the Built Environment by Irradiation from Pulse Xenon, 275 nm Light-Emitting-Diode, and Far-Ultraviolet Sources.","authors":"Lukas Oudejans,Katherine Ratliff,William Richter,Michelle Sunderman,Michael Worth Calfee","doi":"10.1021/acs.est.5c06547","DOIUrl":"https://doi.org/10.1021/acs.est.5c06547","url":null,"abstract":"Motivated by the COVID-19 pandemic, laboratory tests were conducted to evaluate ultraviolet-C (UVC) radiation-emitting devices that are potentially capable of inactivating severe acute respiratory syndrome coronavirus-2 (SARS-CoV-2) on surfaces common to the built environment. In this study, we evaluated the efficacy of three UVC radiation-emitting devices: a pulsed xenon light, a 275 nm LED, and a 222 nm far-UVC light. Experiments were conducted using virus-containing droplets in either tissue culture media or simulated saliva inoculated onto the materials. UVC radiation was significantly more effective in the inactivation of SARS-CoV-2 on hard nonporous surfaces versus porous surfaces; more effective in wet droplets versus dried droplets, while the inoculum type had less of an impact. These observations are partially supported by UVC absorption measurements of the inoculum, which indicated a higher UVC absorption for simulated saliva versus tissue culture media. Absorption spectra for dried inoculum were identical between 260 and 280 nm, with higher absorbances for tissue culture media versus simulated saliva for shorter wavelengths. The observed reduction in efficacy from laboratory conditions (wet, tissue culture media in, e.g., Petri dishes) to more realistic conditions (dried, simulated saliva droplets) indicates that the implementation of UVC radiation leading to an effective risk reduction remains challenging for surface treatment.","PeriodicalId":36,"journal":{"name":"环境科学与技术","volume":"22 1","pages":""},"PeriodicalIF":9.028,"publicationDate":"2025-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145305486","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":"Discovery of Comprehensive Sets of Chemical Constituents as Markers of PFAS Sources through a Nontarget Screening and Machine Learning Approach.","authors":"Nayantara T Joseph,Boris Droz,Trever Schwichtenberg,Karl Oetjen,Sarah Sühnholz,Gerrad D Jones,Jennifer A Field,Christopher P Higgins,Damian E Helbling","doi":"10.1021/acs.est.5c07560","DOIUrl":"https://doi.org/10.1021/acs.est.5c07560","url":null,"abstract":"The objective of this study was to identify chemical constituents as markers of six per- and polyfluoroalkyl substance (PFAS) sources including aqueous film-forming foam-impacted groundwater, landfill leachate, biosolids leachate, municipal wastewater treatment plant effluent, and wastewater effluents from the pulp and paper and power generation industries. Previous chemical fingerprinting methods relying on target and suspect PFASs alone have been unable to differentiate PFAS sources containing complex target and suspect PFAS profiles. Here, we demonstrate that high-resolution mass spectral acquisitions from six distinct PFAS sources can be processed by means of an integrated nontarget analysis (NTA) and machine learning (ML) classification-based approach to improve source classification. NTA was conducted from negative- and positive-mode acquisitions, resulting in 21,815 chemical features from 92 samples and 114,660 chemical features from 88 samples, respectively. The inclusion of non-PFAS markers such as preservatives, pesticides, pharmaceuticals, manufacturing intermediates, spectroscopy materials, fatty acids, metabolites, and plant-derived chemicals substantially enhanced the classification performance compared to PFAS-only classifiers. This study significantly advances PFAS forensic capabilities by offering a practical framework for source differentiation and providing critical tools for environmental monitoring and remediation efforts.","PeriodicalId":36,"journal":{"name":"环境科学与技术","volume":"65 1","pages":""},"PeriodicalIF":9.028,"publicationDate":"2025-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145305538","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":"Reactive Oxygen Species Production in Riparian Zones Governed by a Flow-Induced Chromatographic Separation Process.","authors":"Xiaochuang Bu,Man Tong,Cong Zhang,Heng Dai,Peng Zhang,Philippe Van Cappellen,Songhu Yuan","doi":"10.1021/acs.est.5c07921","DOIUrl":"https://doi.org/10.1021/acs.est.5c07921","url":null,"abstract":"Riparian zones are natural hotspots for reactive oxygen species (ROS) generation, yet the spatiotemporal dynamics of ROS within these zones remain poorly understood. In this study, we combine results from a flume experiment and reactive transport modeling to show that H2O2 production is governed by a \"chromatographic\" separation process in which water flow modulates the interplay of O2 and reductants. The riparian aquifer matrix acts as the stationary phase hosting various mobile and immobile reductants, while water flow serves as the mobile phase supplying oxidants, here dissolved oxygen (DO) and nitrate, during surface water inflow and flushing out of the mobile reductant species during flow reversal. The preferential consumption of DO by the reductants near the up-gradient boundary during surface water intrusion generates H2O2, whereas less reactive oxidants like nitrate are transported further into the riparian aquifer, where they consume the reductants that have not reacted with DO. Although the inflow of nitrate reduces the overall ROS production capacity, it enables deeper DO penetration, hence expanding the ROS production area. The resulting coupling between hydrodynamic solute transport and biogeochemical redox reactions regulates the spatial separation and temporal evolution of H2O2 across the simulated riparian aquifer. Overall, our study advances the mechanistic understanding of ROS dynamics in riparian zones with implications for redox-mediated contaminant attenuation and carbon cycling at the groundwater-river interface.","PeriodicalId":36,"journal":{"name":"环境科学与技术","volume":"104 1","pages":""},"PeriodicalIF":9.028,"publicationDate":"2025-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145305542","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":"Operando Raman Spectroscopic Analysis for Electrolyte/Electrode Interface Reaction in Lithium–Sulfur Batteries with Sparingly Solvating Electrolyte","authors":"Hikari Watanabe, Nana Arai, Yui Kawana, Erika Otani, Jihae Han, Yasuhiro Umebayashi","doi":"10.1021/acs.jpcc.5c04154","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c04154","url":null,"abstract":"Understanding electrolyte/electrode interface reactions during battery operation is essential for the development and optimization of next-generation secondary batteries. There have been many reports on the discharge reaction mechanism in lithium sulfur batteries, which are next-generation secondary batteries. However, most of these reports are related to the sulfur reduction reaction, which is strongly affected by the electrolyte system. Here, we investigated not only the active material sulfur but also the electrolyte near the interface during discharging using <i>operando</i> Raman spectroscopic methods to reveal the discharge behavior in a Lithium sulfur battery with sulfolane (SL)-based concentrated electrolyte and lithium-glyme solvate ionic liquid (Li-G SIL). We have succeeded in experimentally demonstrating that the concentration polarization of Li⁺ occurs significantly in the Li-G SIL system with a low Li⁺ transference number. This is consistent with the fact that the intermediate products differ: the intermediates produced in the SL-based electrolyte system contain Li⁺, whereas in the G4-based electrolyte system, the chemical species containing Li⁺ is hardly confirmed. We believe that the difference in the Li⁺ concentration at the interface affects the overvoltage of the battery.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"1 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145306271","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":"Correction to “Stereoselective Synthesis of Nucleotide Analog Prodrugs (ProTides) via an Oxazaphospholidine Method”","authors":"Monta Nakamura, Kiyoshi Kakuta, Kazuki Sato, Takeshi Wada","doi":"10.1021/acs.joc.5c02213","DOIUrl":"https://doi.org/10.1021/acs.joc.5c02213","url":null,"abstract":"Entries 1–3 and Entry 4 were conducted on 0.03 and 0.18 mmol scales, respectively. Entry 1: Determined from the ³¹P NMR spectrum of crude mixture. Entries 2 and 3: Determined from the ³¹P NMR spectra after purification. Entry 4 was determined from RP-HPLC after deprotection of the DMTr group of the model compound. All reagents were added as CH₃CN solution. <b>(</b><i><b>S</b></i><b>p)-4b</b> and <b>(</b><i><b>R</b></i><b>p)-4b</b> were used in Entries 1–3 and Entry 4, respectively. Determined from the ³¹P NMR spectra of crude mixtures. Determined from the ³¹P NMR spectra of crude mixtures. Extraction in 0.2 M citric acid aqueous solution. Determined from the ³¹P NMR spectra after purification. Determined from the ³¹P NMR spectra of crude mixtures. Determined from the ³¹P NMR spectra after purification. The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.joc.5c02213. Experimental details, HPLC profiles, copies of ¹H, ¹³C, and ³¹P NMR spectra of new compounds and final products (corrected) (PDF) Correction to “Stereoselective\u0000Synthesis of\u0000Nucleotide Analog Prodrugs (ProTides) via an Oxazaphospholidine Method” <span> 3 </span><span> views </span> <span> 0 </span><span> shares </span> <span> 0 </span><span> downloads </span> Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system: http://pubs.acs.org/page/copyright/permissions.html. This article has not yet been cited by other publications.","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"198 1","pages":""},"PeriodicalIF":4.354,"publicationDate":"2025-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145306325","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":"Voltage-Induced Degradation of PTB7 with Atmospheric Exposure and the Contributions of Simultaneous Exposure to Light","authors":"Thomas J. Blackburn, Sarah M. Tyler, Jeanne E. Pemberton","doi":"10.1021/acs.jpcc.5c05633","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c05633","url":null,"abstract":"Previous studies of organic semiconductor (OSC) degradation have focused primarily on photochemical processes, which are thought to be the main cause of shortened device lifetimes. However, OSC optoelectronic devices operate through charge generation, charge mobility through the active layer material, and/or charge recombination that require the presence of an electric field across the device for charge harvesting or injection. The presence of moving charges in these devices implies the presence of polaron forms in the OSC that may have vastly different chemical reactivity than the neutral OSC. Despite the critical role of the electric field in generating, collecting, and mobilizing charge carriers in OSC active layers, the contributions that these charges make to OSC degradation is not well understood. The role of device voltage as a contributor to OSC degradation is studied here for films of poly[[4,8-bis[(2-ethylhexyl)oxy] benzo[1,2-<i>b</i>:4,5-<i>b</i>′]dithiophene-2,6-diyl][3-fluoro-2-[(2-ethylhexyl)carbonyl]thieno[3,4-<i>b</i>]thiophenediyl]] (PTB7) using infrared reflectance–absorbance spectroscopy and X-ray photoelectron spectroscopy. It is proposed that the application of voltage across thin film OSCs under dark ambient atmosphere conditions, in combination with doping by atmospheric O₂, leads to the generation of superoxide anions that degrade the film through pathways different from those of purely photodegradative processes in which singlet oxygen is proposed to be the predominant player. PBT7 films exposed simultaneously to (light + voltage) host both reactive oxygen species with initial degradation pathways apparently directed to the more reactive polaron sites generated by the applied voltage. These results demonstrate that the effects of applied voltage must be considered when understanding degradation processes in OPVs.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"89 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145295542","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":"Alternate Wetting and Drying Limits Arsenic in Porewater and Rice Grain under Severe Future Climate Conditions","authors":"Aria H. Duncan, Natalia Armenta, Frida Garcia-Ledezma, Celine A. Heck, Sylvia Hafner, Britta Planer-Friedrich, Scott Fendorf","doi":"10.1021/acs.est.5c03552","DOIUrl":"https://doi.org/10.1021/acs.est.5c03552","url":null,"abstract":"Climate change, coupled with widespread soil arsenic (As) contamination, is expected to decrease rice yields and increase grain As, threatening food security. One promising mitigation strategy is alternate wetting and drying (AWD) irrigation. However, AWD has not previously been tested under potential future climate conditions. Using rhizoboxes to visualize the rhizosphere, we evaluated the efficacy of AWD for limiting porewater and grain As under both current (daily high of 33 °C and 420 ppmv CO₂) and severe warming conditions (daily high of 38 °C and 850 ppmv CO₂). Compared to continuous flooding, AWD decreased cumulative As exposure 10 cm below the surface by 8.2× under a 33 °C climate and by 15.9× under a 38 °C climate. Grain total As concentrations decreased by 1.5× with AWD under a 33 °C climate and by 1.3× under a 38 °C climate. Porewater cadmium (Cd) concentrations often increased following drainage but never exceeded 1 μg L^–1, and grain Cd concentrations were 14.7× to 119.7× lower than grain As concentrations. Both AWD and the 38 °C and 850 ppmv CO₂ climate conditions enhanced root growth. Our findings indicate that AWD may still be an effective As mitigation strategy under severe future climate conditions.","PeriodicalId":36,"journal":{"name":"环境科学与技术","volume":"11 1","pages":""},"PeriodicalIF":9.028,"publicationDate":"2025-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145295908","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":"A Large Language Model-based Framework to Retrieve Life Cycle Inventory and Environmental Impact Data from Scientific Literature","authors":"Avan Kumar, Farshid Nazemi, Hariprasad Kodamana, Manojkumar Ramteke, Bhavik R. Bakshi","doi":"10.1021/acs.est.5c05955","DOIUrl":"https://doi.org/10.1021/acs.est.5c05955","url":null,"abstract":"Life cycle assessment (LCA) quantifies environmental impacts from raw material extraction to end-of-life (EoL) treatment, yet its accuracy depends on reliable life cycle inventory (LCI) data. However, obtaining such data is time-consuming and requires an extensive literature review or access to databases that are often behind paywalls that hinder transparent research. This study introduces a systematic framework leveraging a retrained large language model (LLM) to assist LCA practitioners in retrieving LCI data and insightful information about their environmental impact. The framework follows a three-stage process: (i) a fine-tuned classification model identifies relevant documents, (ii) the LLaMA-2-7B model is pretrained on selected texts to inject domain knowledge into its database, and (iii) a fine-tuned Q&amp;A model extracts LCI and environmental impact data from the scientific literature. The resulting LLM is termed as “Sustain-LLaMA”. We implement this framework in two cases: methanol production and plastic packaging EoL treatment. After retraining, the classification models achieve high accuracies (0.850 for methanol, 0.952 for plastic packaging) for unseen data, which means effectively distinguishing relevant studies. The Q&amp;A models with Retrieval Augmentated Generation (RAG) yield F1 scores of 0.823 for methanol and 0.855 for plastic studies. The Q&amp;A models’ performances are validated against the version of LLaMA-2-7B without retraining, ChatGPT-4o, and the USLCI database, demonstrating comparable or superior accuracy and efficiency. This framework enhances scalability and precision by automating LCI data retrieval, offering a promising tool for guiding the chemical and plastic industries toward sustainability.","PeriodicalId":36,"journal":{"name":"环境科学与技术","volume":"75 1","pages":""},"PeriodicalIF":9.028,"publicationDate":"2025-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145295910","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":"Crystallization Behavior of Ambient-Air-Processed CsPbBr3 Thin Films on Various Electron Transport Layers and Its Impact on Solar Cell Performance","authors":"Annisa Nandhita Kurniawati, Xorell Ivanov Monov, Bening Tirta Muhammad, Prima Fitri Rusliani, Phutri Milana, Roni Adi Wijaya, Ahmad Ibrahim, Shobih, Natalita Maulani Nursam, Gunawan, Nandang Mufti, Veinardi Suendo, Lydia Helena Wong, Kartika Sari, Brian Yuliarto, Wilman Septina","doi":"10.1021/acs.jpcc.5c03182","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c03182","url":null,"abstract":"CsPbBr₃ perovskite is a promising wide-bandgap semiconductor for photovoltaic applications, but its crystallization dynamics and charge transport properties are highly dependent on interfacial interactions with electron transport layers (ETLs). This study systematically investigates the influence of ETLs: SnO₂, TiO₂, and In₂S₃, on the crystallization, morphology, and photovoltaic performance of CsPbBr₃ thin films processed under ambient-air conditions. The choice of ETL is found to significantly affect the structural evolution of the PbBr₂ precursor and the final CsPbBr₃ film, impacting the device efficiency. Among the studied ETLs, SnO₂ promotes the formation of compact and uniform CsPbBr₃ films, leading to the highest power conversion efficiency (PCE) of 5.05%. In comparison, TiO₂-based devices exhibit a moderate efficiency of 3.44% due to suboptimal film flatness, whereas In₂S₃ results in small-grained films with high defect densities, limiting the efficiency to 0.70%. Photoluminescence and impedance spectroscopy analyses further confirm that SnO₂ effectively suppresses defect-mediated recombination, enhancing charge transport and extraction. These findings underscore the crucial role of ETL selection in optimizing CsPbBr₃ crystallization and provide valuable insights for developing efficient wide-bandgap perovskite solar cells under ambient conditions.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"19 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145314831","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}