{"title":"Toward Socially Responsive Ambient Air Quality Monitoring in the Era of Distributed Sensing","authors":"Naomi Zimmerman","doi":"10.1021/acs.est.6c01858","DOIUrl":"https://doi.org/10.1021/acs.est.6c01858","url":null,"abstract":"","PeriodicalId":36,"journal":{"name":"环境科学与技术","volume":"59 1","pages":""},"PeriodicalIF":9.028,"publicationDate":"2026-02-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146138892","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}
The interface between a weakly adsorbed, solvated cation and a metal electrode is investigated by density functional theory using a hybrid implicit-explicit solvation model. The cations remain charged upon adsorption, the counter-charge resides on the metal surface. There is no diffuse double-layer in this system; experimentally this corresponds to adsorption from a low concentration of cations. The change Δϕ in electrode potential upon adsorption is determined from the change in the electrostatic potential at large distances from the electrode. The phenomenon of partial charge transfer leads to two separate operational definitions for the charge on the ions: the formal charge ze0, where z is the valency, and the partial charge remaining after adsorption, which we quantify with the Bader charge. The measurable integral capacitance is determined by ze0, and for all systems investigated it lies in a range which compares well with experimental data. The divalent ions Ca2+ and Mg2+ show a substantial partial charge transfer, which enhances the capacitance. In contrast, alkali ions K+ and Na+ keep their unit charge. Since there is no diffuse layer, the electrosorption valency equals the negative of the partial charge transfer. Interpreting our results within a simple parallel plate capacitor model allows us to calculate an effective dielectric constant, governed mainly by contributions from the polarizabilities of the metal surface and of the water molecules. Thus, our model provides important insights into the structure of the compact double-layer and its concomitant interactions.
{"title":"The Effect of Weakly Adsorbed Cations on the Helmholtz Capacitance of Metal–Water Interfaces","authors":"Fabiola Domínguez-Flores,Axel Groß,Wolfgang Schmickler","doi":"10.1021/acs.jpcc.5c08002","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c08002","url":null,"abstract":"The interface between a weakly adsorbed, solvated cation and a metal electrode is investigated by density functional theory using a hybrid implicit-explicit solvation model. The cations remain charged upon adsorption, the counter-charge resides on the metal surface. There is no diffuse double-layer in this system; experimentally this corresponds to adsorption from a low concentration of cations. The change Δϕ in electrode potential upon adsorption is determined from the change in the electrostatic potential at large distances from the electrode. The phenomenon of partial charge transfer leads to two separate operational definitions for the charge on the ions: the formal charge ze0, where z is the valency, and the partial charge remaining after adsorption, which we quantify with the Bader charge. The measurable integral capacitance is determined by ze0, and for all systems investigated it lies in a range which compares well with experimental data. The divalent ions Ca2+ and Mg2+ show a substantial partial charge transfer, which enhances the capacitance. In contrast, alkali ions K+ and Na+ keep their unit charge. Since there is no diffuse layer, the electrosorption valency equals the negative of the partial charge transfer. Interpreting our results within a simple parallel plate capacitor model allows us to calculate an effective dielectric constant, governed mainly by contributions from the polarizabilities of the metal surface and of the water molecules. Thus, our model provides important insights into the structure of the compact double-layer and its concomitant interactions.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"295 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2026-02-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146138802","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}
Pub Date : 2026-02-09DOI: 10.1021/acs.jpclett.5c03985
Tao Yang,Jiaqing Zhang,Haotian Chen,Xiaoze Yuan,Yuwei Zhou,Wenping Guo,Xingchen Liu,Xiaotong Liu,Jinjia Liu
Accurate identification of material structures is crucial for establishing reliable structure–property relationships, yet this task is often hindered by the coexistence of multiple metastable phases and their facile transformations under reaction conditions. Although spectroscopic techniques are powerful tools for probing structural motifs, the lack of comprehensive reference data remains a critical bottleneck for experimental analysis. Here, we propose a unified strategy that integrates structure prediction, thermodynamic stability calculations, machine learning models, and Mössbauer spectroscopy simulations, tailored for iron-based intermetallic compounds. By constructing quantitative relationships between local structural features and Mössbauer parameters with machine learning, and by leveraging a theoretical spectral database to interpret experimental spectra, we successfully identified candidate iron sulfide metastable phases that were previously unresolved. This data-driven framework provides a robust complement to experimental approaches, enabling more accurate and efficient identification of metastable phases in dynamically evolving systems.
{"title":"Data-Driven Deciphering Structure–Mössbauer Spectroscopy Relationships in Iron-Based Compounds","authors":"Tao Yang,Jiaqing Zhang,Haotian Chen,Xiaoze Yuan,Yuwei Zhou,Wenping Guo,Xingchen Liu,Xiaotong Liu,Jinjia Liu","doi":"10.1021/acs.jpclett.5c03985","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c03985","url":null,"abstract":"Accurate identification of material structures is crucial for establishing reliable structure–property relationships, yet this task is often hindered by the coexistence of multiple metastable phases and their facile transformations under reaction conditions. Although spectroscopic techniques are powerful tools for probing structural motifs, the lack of comprehensive reference data remains a critical bottleneck for experimental analysis. Here, we propose a unified strategy that integrates structure prediction, thermodynamic stability calculations, machine learning models, and Mössbauer spectroscopy simulations, tailored for iron-based intermetallic compounds. By constructing quantitative relationships between local structural features and Mössbauer parameters with machine learning, and by leveraging a theoretical spectral database to interpret experimental spectra, we successfully identified candidate iron sulfide metastable phases that were previously unresolved. This data-driven framework provides a robust complement to experimental approaches, enabling more accurate and efficient identification of metastable phases in dynamically evolving systems.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"278 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2026-02-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146138744","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}
Xinyuan Wu,Zining Zou,Yaoyin Zhang,Yu Liu,Yunhang Wang,Xinghang Jiang,Qiong Li,Xiaofei Wang,Kan Huang,Ganesh S. Chelluboyina,Rajan K. Chakrabarty,Alexander Laskin,Hongbo Fu
Aromatic compounds (ACs) are key brown carbon constituents, yet their radiative forcing (RF) in high-elevation regions remains poorly constrained. Here, we report year-round characterization of ACs (nitrated phenols (NPs), polycyclic aromatic hydrocarbons (PAHs), and nitrated PAHs (NPAHs)) in PM2.5 at Mt. Gongga, Tibetan Plateau (TP). AC concentrations were higher in the dry season (1.38 vs 0.94 ng m–3), but mass absorption coefficients at 365 nm (MAC365) peaked in the wet season from higher aerosol liquid water content and elevated pH. Clear-sky direct RF (DRF) was positive in the wet season (5.7 × 10–4 W m–2) driven by NPs (single scattering albedo (SSA) = 0.81; imaginary part (k) = 0.055 at 365 nm) and stronger in the dry season (6.8 × 10–3 W m–2) due to higher AC concentrations and solar radiation. Under all-sky conditions, multiple scattering further amplifies DRF, highlighting the cloud modulation of BrC climatic effects. Dry-season biomass-burning transport from South and Central Asia enhanced AC deposition, elevating median snow RF ∼19-fold (4.6 × 10–4 vs 8.6 × 10–3 W m–2) through snow darkening and aging. Overall, trace ACs over the TP exert dual radiative impacts through atmospheric heating and cryospheric forcing via long-range transport and deposition.
芳香族化合物（ACs）是主要的棕碳成分，但其在高海拔地区的辐射强迫（RF）仍未得到很好的约束。本文报道了青藏高原贡嘎山（TP） PM2.5中硝化苯酚（NPs）、多环芳烃（PAHs）和硝化多环芳烃（NPAHs）的全年特征。干季AC浓度较高（1.38 vs 0.94 ng m-3），但由于气溶胶液水含量和ph升高，365 nm处的质量吸收系数（MAC365）在湿季达到峰值。在NPs驱动下，晴空直接RF （DRF）在湿季为正值（5.7 × 10-4 W m-2）(单散射反照率(SSA) = 0.81；虚数部(k)在365 nm处= 0.055)，由于较高的AC浓度和太阳辐射，在旱季更强（6.8 × 10-3 W m-2）。在全天条件下，多次散射进一步放大了DRF，突出了BrC气候效应的云调制。来自南亚和中亚的旱季生物质燃烧运输增强了AC沉积，通过雪变暗和老化将中位雪RF提高了19倍（4.6 × 10-4 vs 8.6 × 10-3 W m-2）。总的来说，TP上的痕量ac通过大气加热和冰冻圈强迫的远程传输和沉积产生双重辐射影响。
{"title":"Molecular-Specific Aromatic Compounds Absorption Drives Divergent Radiative Forcing in High-Altitude Air and Snow over the Tibetan Plateau","authors":"Xinyuan Wu,Zining Zou,Yaoyin Zhang,Yu Liu,Yunhang Wang,Xinghang Jiang,Qiong Li,Xiaofei Wang,Kan Huang,Ganesh S. Chelluboyina,Rajan K. Chakrabarty,Alexander Laskin,Hongbo Fu","doi":"10.1021/acs.est.5c16974","DOIUrl":"https://doi.org/10.1021/acs.est.5c16974","url":null,"abstract":"Aromatic compounds (ACs) are key brown carbon constituents, yet their radiative forcing (RF) in high-elevation regions remains poorly constrained. Here, we report year-round characterization of ACs (nitrated phenols (NPs), polycyclic aromatic hydrocarbons (PAHs), and nitrated PAHs (NPAHs)) in PM2.5 at Mt. Gongga, Tibetan Plateau (TP). AC concentrations were higher in the dry season (1.38 vs 0.94 ng m–3), but mass absorption coefficients at 365 nm (MAC365) peaked in the wet season from higher aerosol liquid water content and elevated pH. Clear-sky direct RF (DRF) was positive in the wet season (5.7 × 10–4 W m–2) driven by NPs (single scattering albedo (SSA) = 0.81; imaginary part (k) = 0.055 at 365 nm) and stronger in the dry season (6.8 × 10–3 W m–2) due to higher AC concentrations and solar radiation. Under all-sky conditions, multiple scattering further amplifies DRF, highlighting the cloud modulation of BrC climatic effects. Dry-season biomass-burning transport from South and Central Asia enhanced AC deposition, elevating median snow RF ∼19-fold (4.6 × 10–4 vs 8.6 × 10–3 W m–2) through snow darkening and aging. Overall, trace ACs over the TP exert dual radiative impacts through atmospheric heating and cryospheric forcing via long-range transport and deposition.","PeriodicalId":36,"journal":{"name":"环境科学与技术","volume":"241 1","pages":""},"PeriodicalIF":9.028,"publicationDate":"2026-02-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146138849","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}
Siqi Sun,Yingying Sun,Andrew S. Kinsela,Yunyi Zhu,Nikky LaBranche,Sheng Chen,T. David Waite
Exposure to respirable and inhalable dust from engineered stone is linked to lung diseases such as silicosis and COPD, yet the physicochemical properties affecting epithelial-to-mesenchymal transition (EMT) remain unclear. Here, 41 physicochemical properties were characterized across 30 dust samples and evaluated for associations with EMT progression in A549 lung epithelial cells after 24-h exposure. EMT was assessed using three hallmarks: E-cadherin downregulation, vimentin upregulation, and α-SMA upregulation. A hybrid feature selection strategy combining correlation filtering with LassoLarsCV reduced feature redundancy and improved model robustness. The selected features were modeled using optimized regressors (Extreme Gradient Boosting regressor for E-cadherin and Vimentin; Support Vector Machine for α-SMA), and SHAP analysis quantified each property’s contribution. Crystalline silica emerged as the most influential factor, showing negative associations with E-cadherin and positive associations with Vimentin and α-SMA. In contrast, sodium-, aluminum-, and rutile-bearing components were associated with lower EMT progression, likely reflecting their occurrence within less reactive mineral phases than crystalline silica. Specific surface area and absolute ζ potential were positively associated with the EMT, indicating enhanced particle-cell interactions and surface-related signaling. These findings establish a framework for linking dust physicochemical characteristics to marker-specific EMT responses and demonstrate the effectiveness of interpretable machine learning for particulate toxicity assessment.
{"title":"Identification of Key Physicochemical Characteristics Which Influence Epithelial-to-Mesenchymal Transition of Lung Cells after Exposure to Engineered and Natural Stone Dusts via a Hybrid Machine Learning Approach","authors":"Siqi Sun,Yingying Sun,Andrew S. Kinsela,Yunyi Zhu,Nikky LaBranche,Sheng Chen,T. David Waite","doi":"10.1021/acs.est.5c14999","DOIUrl":"https://doi.org/10.1021/acs.est.5c14999","url":null,"abstract":"Exposure to respirable and inhalable dust from engineered stone is linked to lung diseases such as silicosis and COPD, yet the physicochemical properties affecting epithelial-to-mesenchymal transition (EMT) remain unclear. Here, 41 physicochemical properties were characterized across 30 dust samples and evaluated for associations with EMT progression in A549 lung epithelial cells after 24-h exposure. EMT was assessed using three hallmarks: E-cadherin downregulation, vimentin upregulation, and α-SMA upregulation. A hybrid feature selection strategy combining correlation filtering with LassoLarsCV reduced feature redundancy and improved model robustness. The selected features were modeled using optimized regressors (Extreme Gradient Boosting regressor for E-cadherin and Vimentin; Support Vector Machine for α-SMA), and SHAP analysis quantified each property’s contribution. Crystalline silica emerged as the most influential factor, showing negative associations with E-cadherin and positive associations with Vimentin and α-SMA. In contrast, sodium-, aluminum-, and rutile-bearing components were associated with lower EMT progression, likely reflecting their occurrence within less reactive mineral phases than crystalline silica. Specific surface area and absolute ζ potential were positively associated with the EMT, indicating enhanced particle-cell interactions and surface-related signaling. These findings establish a framework for linking dust physicochemical characteristics to marker-specific EMT responses and demonstrate the effectiveness of interpretable machine learning for particulate toxicity assessment.","PeriodicalId":36,"journal":{"name":"环境科学与技术","volume":"92 1","pages":""},"PeriodicalIF":9.028,"publicationDate":"2026-02-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146138889","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}
Jarod C. Kelly,Amgad Elgowainy,Ram Vijayagopal,Matteo Muratori,Ian Sutherland,Hoseinali Borhan,Hyung Chul Kim,Marcus Alexander
This study presents a cradle-to-grave lifecycle analysis of energy use and greenhouse gas (GHG) emissions for U.S. medium- and heavy-duty vehicles across current (2021) and future (2035) technologies using the Greenhouse gas, Regulated Emissions, and Energy use in Technologies (GREET) model with industry-vetted assumptions. Results vary across vehicle classes but point to common trends: today, battery electric vehicles (BEVs) offer significant (10–60%) GHG emissions reduction compared to diesel internal combustion engine vehicles and are the lowest emissions option per ton-mile of cargo movement, followed by hydrogen fuel cell electric vehicles (FCEVs) (5–50% emissions reduction). Emissions savings depend largely on the duty cycle and fuel economy of the vehicle type. Future vehicle technology advancements result in comparable emission reductions associated with BEVs and hydrogen FCEVs. Weight-limited BEV trucks see less per-ton-mile emissions reduction due to the impact of battery weight on increased vehicle weight and reduced payload capacity. By 2035, improvements in vehicle efficiency can reduce emissions across all powertrains. However, very low levels of emissions require switching vehicles’ use-phase fuel/energy to low-carbon fuels and electricity. Renewable diesel, e-fuels, hydrogen produced from natural gas with carbon capture and storage or renewables, and use of low-carbon electricity can all achieve over 70% reduction in GHG emissions from the current day diesel-based internal combustion engine vehicle.
{"title":"Cradle-to-Grave Lifecycle Analysis of U.S. Medium- and Heavy-Duty Vehicle-Fuel Pathways: A Greenhouse Gas Emissions Assessment of Current (2021) and Future (2035) Technologies","authors":"Jarod C. Kelly,Amgad Elgowainy,Ram Vijayagopal,Matteo Muratori,Ian Sutherland,Hoseinali Borhan,Hyung Chul Kim,Marcus Alexander","doi":"10.1021/acs.est.5c10480","DOIUrl":"https://doi.org/10.1021/acs.est.5c10480","url":null,"abstract":"This study presents a cradle-to-grave lifecycle analysis of energy use and greenhouse gas (GHG) emissions for U.S. medium- and heavy-duty vehicles across current (2021) and future (2035) technologies using the Greenhouse gas, Regulated Emissions, and Energy use in Technologies (GREET) model with industry-vetted assumptions. Results vary across vehicle classes but point to common trends: today, battery electric vehicles (BEVs) offer significant (10–60%) GHG emissions reduction compared to diesel internal combustion engine vehicles and are the lowest emissions option per ton-mile of cargo movement, followed by hydrogen fuel cell electric vehicles (FCEVs) (5–50% emissions reduction). Emissions savings depend largely on the duty cycle and fuel economy of the vehicle type. Future vehicle technology advancements result in comparable emission reductions associated with BEVs and hydrogen FCEVs. Weight-limited BEV trucks see less per-ton-mile emissions reduction due to the impact of battery weight on increased vehicle weight and reduced payload capacity. By 2035, improvements in vehicle efficiency can reduce emissions across all powertrains. However, very low levels of emissions require switching vehicles’ use-phase fuel/energy to low-carbon fuels and electricity. Renewable diesel, e-fuels, hydrogen produced from natural gas with carbon capture and storage or renewables, and use of low-carbon electricity can all achieve over 70% reduction in GHG emissions from the current day diesel-based internal combustion engine vehicle.","PeriodicalId":36,"journal":{"name":"环境科学与技术","volume":"33 1","pages":""},"PeriodicalIF":9.028,"publicationDate":"2026-02-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146138893","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}
Tao Zhang,Henglin Zhang,Tianhui Zhao,Shiming Song,Jiye Zhang,Luhan Yang,Fengchang Wu
Neonicotinoid insecticides (NEOs) are globally prevalent environmental contaminants. However, their biological half-lives in humans remain poorly characterized. This study employed a controlled mouse pharmacokinetic experiment with human biomonitoring data to elucidate key parameters for selected NEOs. Human biomonitoring provided renal clearance (CLrenal), while controlled mice experiment provided the volume of distribution (Vd); these were combined to estimate the biological half-life. Analysis of 172 paired human urine and blood samples revealed that CLrenal varied substantially among parent NEOs (median: 9.04 to 158 mL/day/kg) and exhibited a distinct structure-dependency. The CLrenal of fused, bicyclic NEOs (i.e., imidacloprid (IMI), thiacloprid (THD), and thiamethoxam (THM)) was governed by water solubility, while that of their nonfused, monocyclic systems (i.e., acetamiprid (ACE), clothianidin (CLO), and dinotefuran (DIN)) was determined by lipophilicity. A one-compartment log–linear regression analysis of intravenous mice data provided robust estimates of Vd, which ranged from 306 to 700 mL/kg body weight for ACE, IMI, and DIN. By combining Vd with human CLrenal, the extrapolated median biological half-life for ACE, IMI, and DIN were 15.5, 24.8, and 53.7 days, respectively, indicating significant potential for bioaccumulation in humans. Uncertainty analysis and sensitivity analyses confirmed the robustness of these prolonged estimates, yielding 95% confidence intervals of 5.53 (ACE) to 157 (DIN) days, with even the most conservative scenario giving a range of 5.17 (ACE) to 17.9 (DIN) days. The prolonged half-life of NEOs indicates a significant potential for bioaccumulation in humans upon continuous exposure, which warrants further investigation regarding its implications for human health risk assessment.
{"title":"Combining Biomonitoring Data and a Pharmacokinetic Model to Estimate the Extended Half-Life of Neonicotinoid Insecticides in Humans","authors":"Tao Zhang,Henglin Zhang,Tianhui Zhao,Shiming Song,Jiye Zhang,Luhan Yang,Fengchang Wu","doi":"10.1021/acs.est.5c18046","DOIUrl":"https://doi.org/10.1021/acs.est.5c18046","url":null,"abstract":"Neonicotinoid insecticides (NEOs) are globally prevalent environmental contaminants. However, their biological half-lives in humans remain poorly characterized. This study employed a controlled mouse pharmacokinetic experiment with human biomonitoring data to elucidate key parameters for selected NEOs. Human biomonitoring provided renal clearance (CLrenal), while controlled mice experiment provided the volume of distribution (Vd); these were combined to estimate the biological half-life. Analysis of 172 paired human urine and blood samples revealed that CLrenal varied substantially among parent NEOs (median: 9.04 to 158 mL/day/kg) and exhibited a distinct structure-dependency. The CLrenal of fused, bicyclic NEOs (i.e., imidacloprid (IMI), thiacloprid (THD), and thiamethoxam (THM)) was governed by water solubility, while that of their nonfused, monocyclic systems (i.e., acetamiprid (ACE), clothianidin (CLO), and dinotefuran (DIN)) was determined by lipophilicity. A one-compartment log–linear regression analysis of intravenous mice data provided robust estimates of Vd, which ranged from 306 to 700 mL/kg body weight for ACE, IMI, and DIN. By combining Vd with human CLrenal, the extrapolated median biological half-life for ACE, IMI, and DIN were 15.5, 24.8, and 53.7 days, respectively, indicating significant potential for bioaccumulation in humans. Uncertainty analysis and sensitivity analyses confirmed the robustness of these prolonged estimates, yielding 95% confidence intervals of 5.53 (ACE) to 157 (DIN) days, with even the most conservative scenario giving a range of 5.17 (ACE) to 17.9 (DIN) days. The prolonged half-life of NEOs indicates a significant potential for bioaccumulation in humans upon continuous exposure, which warrants further investigation regarding its implications for human health risk assessment.","PeriodicalId":36,"journal":{"name":"环境科学与技术","volume":"90 1","pages":""},"PeriodicalIF":9.028,"publicationDate":"2026-02-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146138929","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}
A green and mild palladium-catalyzed solvent-free α-arylation reaction of ketones was disclosed for the first time. Using the robust N-heterocyclic carbene–palladium complex (SIPr)Ph2Pd(cin)Cl, (hetero)aryl chlorides and ketones were able to generate monoarylation products in excellent yields under solvent-free conditions, with a total of 41 examples. Furthermore, the protocol has been demonstrated to be suitable for multigram-scale preparation with a high yield.
{"title":"Solvent-Free α-Arylation Reaction of Ketones with (Hetero)aryl Chlorides by N-Heterocyclic Carbene–Palladium Complex (SIPr)Ph2Pd(cin)Cl","authors":"Jia-Sheng Ouyang,Xiaoling Wang,Huizhen Jiang,Ruiyong Luo,Liqun Hu,Yaqi Zhang,Liqin Qiu","doi":"10.1021/acs.joc.5c02510","DOIUrl":"https://doi.org/10.1021/acs.joc.5c02510","url":null,"abstract":"A green and mild palladium-catalyzed solvent-free α-arylation reaction of ketones was disclosed for the first time. Using the robust N-heterocyclic carbene–palladium complex (SIPr)Ph2Pd(cin)Cl, (hetero)aryl chlorides and ketones were able to generate monoarylation products in excellent yields under solvent-free conditions, with a total of 41 examples. Furthermore, the protocol has been demonstrated to be suitable for multigram-scale preparation with a high yield.","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"83 1","pages":""},"PeriodicalIF":4.354,"publicationDate":"2026-02-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146139055","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}
Abhishek Pareek, Maja Morawiak, Emran Masoumifeshani, Przemysław Gaweł
A one-pot oxygen-annulation couples chloroquinones with aromatic alcohols to efficiently construct π-expanded furans in yields up to 91%. Subsequent TIPS-acetylene functionalization and reductive aromatization enhance solubility and furnish bench-stable chromophores that absorb in the blue and exhibit strong fluorescence. Time-dependent density functional theory (TD-DFT) reveals low-energy, charge-transfer excitations in the quinone intermediates, which shift to higher-energy, localized π–π* transitions upon aromatization. Remarkably, these π-expanded furans withstand UV irradiation over 10-fold longer than TIPS-pentacene, highlighting their exceptional photostability.
{"title":"Photostable π-Expanded Furans via Base-Mediated Quinone Oxygen-Annulation","authors":"Abhishek Pareek, Maja Morawiak, Emran Masoumifeshani, Przemysław Gaweł","doi":"10.1021/acs.joc.5c02906","DOIUrl":"https://doi.org/10.1021/acs.joc.5c02906","url":null,"abstract":"A one-pot oxygen-annulation couples chloroquinones with aromatic alcohols to efficiently construct π-expanded furans in yields up to 91%. Subsequent TIPS-acetylene functionalization and reductive aromatization enhance solubility and furnish bench-stable chromophores that absorb in the blue and exhibit strong fluorescence. Time-dependent density functional theory (TD-DFT) reveals low-energy, charge-transfer excitations in the quinone intermediates, which shift to higher-energy, localized π–π* transitions upon aromatization. Remarkably, these π-expanded furans withstand UV irradiation over 10-fold longer than TIPS-pentacene, highlighting their exceptional photostability.","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"93 1","pages":""},"PeriodicalIF":4.354,"publicationDate":"2026-02-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146146337","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}
Pub Date : 2026-02-09DOI: 10.1021/acs.jpclett.5c03981
Jong-Kwon Ha, Seong Ho Kim, Seung Kyu Min
We propose mixed quantum–classical equations of motion that unify electronic coherence and phase evolution simultaneously within the exact factorization framework. Our derivation shows that incorporating the second-order electron–nuclear correlation terms from the exact coupled time-dependent Schrödinger equations is essential to recover both correct phase dynamics and complete electronic (de)coherence, including their effect on nuclear forces. Benchmark calculations on one- and two-dimensional model systems confirm that the approach accurately captures key nonadiabatic features. The equations therefore provide a rigorous first-principles foundation for mixed quantum–classical description of coupled electron–nuclear dynamics, bringing electronic coherence and phase evolution─long treated through separate heuristic corrections─into a single unified and systematically derived framework.
{"title":"Unifying Decoherence and Phase Evolution in Mixed Quantum–Classical Dynamics through Exact Factorization","authors":"Jong-Kwon Ha, Seong Ho Kim, Seung Kyu Min","doi":"10.1021/acs.jpclett.5c03981","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c03981","url":null,"abstract":"We propose mixed quantum–classical equations of motion that unify electronic coherence and phase evolution simultaneously within the exact factorization framework. Our derivation shows that incorporating the second-order electron–nuclear correlation terms from the exact coupled time-dependent Schrödinger equations is essential to recover both correct phase dynamics and complete electronic (de)coherence, including their effect on nuclear forces. Benchmark calculations on one- and two-dimensional model systems confirm that the approach accurately captures key nonadiabatic features. The equations therefore provide a rigorous first-principles foundation for mixed quantum–classical description of coupled electron–nuclear dynamics, bringing electronic coherence and phase evolution─long treated through separate heuristic corrections─into a single unified and systematically derived framework.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"59 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2026-02-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146146477","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}
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