化学•材料最新文献

{"title":"Investigating Magnetic, Magnetodielectric, and Structural Properties of Sc-Substituted Hexagonal LuFeO3","authors":"Dhanpal Bairwa, S. D. Kaushik, P. D. Babu, H. L. Bhat, Suja Elizabeth","doi":"10.1021/acs.jpcc.5c00079","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c00079","url":null,"abstract":"In this work, we investigated the structural, magnetodielectric, and magnetic properties of scandium-substituted hexagonal LuFeO₃. The Lu_0.33Sc_0.67FeO₃ (LSFO) compound stabilizes in a hexagonal structure (metastable) after synthesis by the sol–gel technique. The phase purity was confirmed by powder X-ray diffraction and neutron diffraction at room temperature. X-ray photoelectron spectroscopy (XPS) studies confirm the 3+ oxidation states of Lu, Sc, and Fe. The temperature-dependent magnetic data in the higher temperature range (180–300 K) fit well with the Curie–Weiss law, indicating paramagnetic behavior. Below 175 K, inverse susceptibility deviates from the fit due to magnetic ordering, which is the magnetic ordering temperature of LSFO. According to several research studies, the magnetic ordering temperature (<i>T</i>_N) in h-R(Fe/Mn)O₃ depends on the <i>c</i>/<i>a</i> ratio, with <i>T</i>_N increasing as the <i>c</i>/<i>a</i> ratio rises. In the title compound, we found the <i>c</i>/<i>a</i> ratio to be 2.008, the highest in the R(Fe/Mn)O₃ family, giving rise to the highest magnetic ordering temperature. The high negative Weiss temperature (−867 K) indicates a dominant antiferromagnetic interaction and frustration in the system. In the vicinity of 100 K, LSFO exhibits a weak ferromagnetic moment with a small loop opening in the M – H data. The dielectric constant has a little hump at the magnetic ordering temperature (175 K). The temperature versus dielectric constant data below 90 K at 0 and 7 T suggest that the dielectric constant depends on the external magnetic field, thus confirming magnetodielectric coupling in the system. We have observed up to a 1.5% magnetodielectric effect in LSFO.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"23 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143766975","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":"Satellite Remote Sensing-Implemented Nontargeted Screening of Emerging Contaminant Fingerprints in a River-to-Ocean Continuum through Interpretable Machine Learning: The Pivotal Intermediary Role of Dissolved Organic Matter","authors":"Chao Zhang, Junyu Zhu, Wenjie Mai, Zhenguo Chen, Yue Xie, Shuna Fu, Di Xia, Chun Cai, Wanbing Zheng, Jinxin Liu, Lianmiao Yang, Zhe Zhang, Mingzhi Huang, Fengchang Wu","doi":"10.1021/acs.est.4c14425","DOIUrl":"https://doi.org/10.1021/acs.est.4c14425","url":null,"abstract":"Emerging contaminants (ECs) can exert irreversible health impacts on humans, even at trace concentrations. Currently, nontargeted screening of ECs has been developed for their assessment, which requires sophisticated instrumentation. Although satellite remote sensing is a cost-effective technology for water quality assessment, accurately measuring ECs in a river-to-ocean continuum remains a significant challenge due to their trace levels. To address this challenge, we innovate a strategy utilizing satellite remote sensing to achieve high-resolution nontargeted EC screening. By employing DOM as an intermediary variable, bridging the gap between satellite remote sensing and ECs in river-to-ocean continua. DOM, including the total sum of ECs, reflects their distribution and spectral sensitivity, enabling satellite sensing to capture their unique fingerprints. In this study, this strategy has enhanced the accuracy of nontargeted EC screening from 32.2 to 95.7% using machine learning. Interpretable machine learning causal inference and SHAP models reveal that shortwave infrared (SWIR) S2-B11 is crucial for EC screening while emphasizing the importance of avoiding multicollinearity with similar SWIR band S2-B12. Additionally, the band reflectance is influenced by the proportion of polarity-related heterogeneity in the ECs. Furthermore, we developed a real-time remote sensing surveillance system featuring interactive maps for nontargeted screening of ECs and GPT-based contamination interpretation.","PeriodicalId":36,"journal":{"name":"环境科学与技术","volume":"107 1","pages":""},"PeriodicalIF":9.028,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143766852","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":"Implementation of Matrix-Matched Semiquantification of PFAS in AFFF-Contaminated Soil","authors":"Catharina Capitain, Melanie Schüßler, Boris Bugsel, Jonathan Zweigle, Christian Vogel, Peter Leube, Christian Zwiener","doi":"10.1021/acs.est.4c14255","DOIUrl":"https://doi.org/10.1021/acs.est.4c14255","url":null,"abstract":"This study presents a novel semiquantification approach for nontarget screening (NTS), combining matrix-matched calibration and ionization class-specific average calibration curves (ACCs) to address the lack of analytical reference standards for most per- and polyfluoroalkyl substances (PFAS). Ionization class-specific ACCs for carboxylic and sulfonic acids, sulfonamides, and cationic PFAS result in high accuracy, with median absolute accuracy quotients below 2.27×. The approach was applied to soil impacted by aqueous film-forming foam (AFFF) contamination. A total of 96 tentatively identified PFAS were semiquantified in addition to 28 quantified compounds based on available standards. Semiquantified concentrations exceeded those of target analytes, demonstrating the critical role of this method in capturing broader PFAS contamination. In this case, validation against extractable organofluorine (EOF) showed a 102% closed mass balance. The innovative approach not only enables comprehensive PFAS contamination assessment in complex matrices but also expands the scope of the NTS for environmental monitoring, remediation, and risk assessment of AFFF-contaminated sites.","PeriodicalId":36,"journal":{"name":"环境科学与技术","volume":"4 1","pages":""},"PeriodicalIF":9.028,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143766854","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":"Aluminum Nanoparticles for Photobleaching Resistance of Quantum Dots in Solution","authors":"Théo Duarte De Assuncao, Silvère Schuermans, Thomas Lerond, Jérôme Martin, Davy Gérard, Thomas Maurer, Jérôme Plain, Julien Proust","doi":"10.1021/acs.jpcc.5c00879","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c00879","url":null,"abstract":"We report on the optical properties of aluminum spherical nanoparticles exhibiting diameters ranging between 2 and 20 nm made by the reduction of aluminum ions in alkane solvents. In the UV-range, the extinction spectroscopy measurements unveiled well-defined surface plasmon resonances corresponding to the calculations performed using Mie theory. Furthermore, a photobleaching resistance effect appears for semiconductor quantum dots (QDs) in a solution containing aluminum nanoparticles. The particles allowed for a global increase in the number of photons emitted by a factor of up to 1.75 compared to QDs alone. Our investigation led us to the conclusion that the aluminum nanoparticles initially absorb a part of the emitted light and prevent the photobleaching of the QDs. Thus, these nanoparticles have the potential to be used as elementary building blocks for making more complex aluminum nanostructures for nanophotonics and also to protect emitters from photobleaching.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"19 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143766978","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":"Pterin-Thymidine Adducts: From Their Photochemical Synthesis to Their Photosensitizing Properties.","authors":"Gricelda Godoy-Ortega, Gemma M Rodríguez-Muñiz, Virginie Lhiaubet-Vallet, Carolina Lorente, Andrés H Thomas","doi":"10.1021/acs.jpcb.5c00185","DOIUrl":"10.1021/acs.jpcb.5c00185","url":null,"abstract":"<p><p>Pterin (Ptr) is the model compound of aromatic pterins, which are efficient photosensitizers present in human skin and are able to oxidize biomolecules upon UVA irradiation. Photosensitization involves chemical alteration of a biomolecule as a result of the initial absorption of radiation by another chemical species, the photosensitizer. Under anaerobic conditions, Ptr reacts with thymine (T) to form photoadducts (T-Ptr). In this work, we present a method to prepare and purify T-Ptr adducts, using 2'-deoxythymidine 5'-monophosphate (dTMP) and single stranded oligonucleotide 5'-d(TTTTT)-3' (dT₅), and investigate their photosensitizing properties. Interestingly, the Ptr moiety, when attached to T, retains its photophysical properties. The adduct dTMP-Ptr, upon excitation, forms singlet and triplet excited states, the latter being capable of transferring energy to dissolved O₂ and generating singlet oxygen, with an efficiency similar to Ptr. In air-equilibrated solutions, both dTMP-Ptr and dT₅-Ptr adducts can photosensitize the oxidation of tryptophan and 2'-deoxyguanosine 5'-monophosphate, two of the main targets of photosensitization in biological systems, with efficiencies close to that of free Ptr. The mechanisms involved in the oxidation of biomolecules can be either type I (electron transfer) or type II (singlet oxygen).</p>","PeriodicalId":60,"journal":{"name":"The Journal of Physical Chemistry B","volume":" ","pages":"3334-3344"},"PeriodicalIF":2.8,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143699117","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":"Application of Amber Suppression To Study the Role of Tyr M210 in Electron Transfer in <i>Rhodobacter sphaeroides</i> Photosynthetic Reaction Centers.","authors":"Khoi N Tran, Kaitlyn M Faries, Nikki Cecil Macasinag Magdaong, Irimpan I Mathews, Jared B Weaver, Jacob M Kirsh, Dewey Holten, Christine Kirmaier, Steven G Boxer","doi":"10.1021/acs.jpcb.5c00082","DOIUrl":"10.1021/acs.jpcb.5c00082","url":null,"abstract":"<p><p>The initial light-induced electron transfer (ET) steps in the bacterial photosynthetic reaction center (RC) have been extensively studied and provide a paradigm for connecting structure and function. Although RCs have local pseudo-<i>C</i>_<i>2</i> symmetry, ET only occurs along the A branch of chromophores. Tyrosine M210 is a key symmetry-breaking residue adjacent to bacteriochlorophyll B_A that bridges the primary electron donor P and the bacteriopheophytin acceptor H_A. We used amber suppression to incorporate phenylalanine variants with different electron-withdrawing/-donating capabilities at the position M210. X-ray data generally reveal no appreciable structural changes due to the mutations. P* decay and P⁺H_A^- formation are multiexponential (∼2 to 9, ∼10 to 60, and ∼100 to 300 ps) and temperature dependent. The 1020 nm transient-absorption band of P⁺B_A^- is barely resolved for a few variants at 295 K and for none at 77 K. The results indicate a change from two-step ET for wild-type RCs to the dominance of one-step superexchange ET for the mutants. Resonance Stark spectroscopy reveals that the free energy of P⁺B_A^- changes by -57 to +66 meV among the phenylalanine variants. Because P⁺B_A^- apparently lies above P* in all phenylalanine variants, the perturbations primarily affect the energy denominator for superexchange mixing. The findings deepen insight into primary ET in the bacterial RC.</p>","PeriodicalId":60,"journal":{"name":"The Journal of Physical Chemistry B","volume":" ","pages":"3317-3333"},"PeriodicalIF":2.8,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143707787","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":"Effects of Nanoplastics on Lipid Membranes and Vice Versa: Insights from All-Atom Molecular Dynamics Simulations.","authors":"Anderson D S Duraes, Elaine L Jiao, Wenlin Zhang","doi":"10.1021/acs.jpcb.4c08361","DOIUrl":"10.1021/acs.jpcb.4c08361","url":null,"abstract":"<p><p>We compute the potential of mean force (PMF) between semicrystalline polyethylene (PE) nanoplastics (NPLs) and model POPC and DPPC bilayers, which approximate in vivo membranes, using atomistic simulations. Our work shows that atomistic resolution is required to characterize the NPL and lipid interactions. By analyzing the PMF, we demonstrate that the mechanical properties of membranes, rather than NPL semicrystalline morphologies, govern NPL-membrane interactions. Resistance to NPL penetration arises from the elastic energy of the membrane deformation. The flexible POPC membranes resist NPL translocation, and the brittle DPPC membranes fracture under stress. Using an elastic free energy model, we approximate effective repulsions between lipid membranes and NPLs of various sizes. Our mean first-passage time analysis shows that even small, bare NPLs cannot easily penetrate brittle lipid membranes via passive diffusion, even at high concentrations. However, eco-coronas or other mechanisms, such as endocytosis, may still facilitate the cellular uptake of NPLs and MPLs. While semicrystalline morphologies do not directly impact NPL translocation, they do influence NPL behavior within lipid membranes upon translocation. Semicrystalline NPLs remain intact within lipid membranes, whereas amorphous NPLs can dissolve into the hydrophobic core and alter the elastic properties of the membrane.</p>","PeriodicalId":60,"journal":{"name":"The Journal of Physical Chemistry B","volume":" ","pages":"3385-3395"},"PeriodicalIF":2.8,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143404922","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":"New Sources of Very Persistent and Very Mobile (vPvM) Substances: A Case Study of the Fluorinated Herbicide Pyroxasulfone","authors":"Xingwang Hou, Jeremy R. Gauthier, Pranav Nair, William D. Fahy, Hui Peng, Scott A. Mabury","doi":"10.1021/acs.est.4c13346","DOIUrl":"https://doi.org/10.1021/acs.est.4c13346","url":null,"abstract":"With the increasing use of fluorinated agrochemicals, more fluorinated compounds enter into the environment. Pyroxasulfone (PYS), a broad-spectrum herbicide containing an aromatic CF₃ (Ar–CF₃), is expected to grow significantly in application. Although several transformation products (TPs) of PYS have been reported, their distribution and contribution to transformation processes remain largely unknown. This study combined laboratory simulations and a field study. In soil incubation and soil surface photolysis experiments, (5-(difluoromethoxy)-1-methyl-3-(trifluoromethyl)-1<i>H</i>-pyrazol-4-yl)methanesulfonic acid (TFPSA) was identified as the main TP of PYS in soil, accounting for over 90% of all TPs. Field study results showed that PYS and TFPSA were the main species in soil (6.48 ± 1.82 and 1.54 ± 0.90 ng g^–1 wet weight) and corn plants (2.55 ± 2.61 and 31.1 ± 39.6 ng g^–1 dry weight in roots) before harvest. Surface water photolysis experiments showed that TFPSA and TP₂₄₆ were the major TPs of PYS and no significant photodegradation of TFPSA was observed. Persistent (P) and mobile (M) property assessment indicated TFPSA, TP₂₄₆, and other Ar–CF₃ containing TPs of various fluorinated agrochemicals could be potential very P and very M (vPvM) substances. More attention should be paid to Ar–CF₃ containing agrochemicals and their TPs.","PeriodicalId":36,"journal":{"name":"环境科学与技术","volume":"216 1","pages":""},"PeriodicalIF":9.028,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143766819","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":"Ru-CNP Complex-Catalyzed Hydrogen Transfer/Annulation Reaction of 2-Nitrobenzylalcohol via an Outer-Sphere Mechanism","authors":"Ling Zhao, Yinyin Chen, Chunchun Zhang, Hua Chen, Xueli Zheng, Weichao Xue, Jiaqi Xu, Haiyan Fu, Ruixiang Li","doi":"10.1021/acs.joc.5c00157","DOIUrl":"https://doi.org/10.1021/acs.joc.5c00157","url":null,"abstract":"The development of efficient catalysts plays a central role in advancing chemical reactions. In this study, a ruthenium complex modified with a <i>N</i>-heterocyclic carbene-imine-phosphine ligand <b>(CNP)</b> was employed to enhance the hydrogen transfer/annulation process of 2-nitrobenzyl alcohols with various primary or secondary alcohols. The NMR and HRMS analyses of the reaction solution revealed the in situ formation of [fac-RuH(CO)(PPh₃)(κ³-CN(H)P)]Cl through the transfer hydrogenation of the imine moiety within the <b>CNP</b> ligand under the reaction conditions. This species, a bifunctional Noyori-type ruthenium complex featuring facial coordination with a <b>CN(H)P</b> ligand, served as a key catalytic intermediate. By leveraging the outer-sphere mechanism facilitated by [fac-RuH(CO)(PPh₃)(κ³-CN(H)P)]Cl, the synthesis of 75 quinolines from 2-nitrobenzyl alcohols and a wide range of alcohols has been achieved with yields as high as 95%.","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"60 1","pages":""},"PeriodicalIF":4.354,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143766880","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":"Operando Characterization of Porous Nickel Foam Water Splitting Electrodes Using Near-Ambient Pressure X-ray Photoelectron Spectroscopy","authors":"Ramadan Chalil Oglou, Morten Linding Frederiksen, Zhaozong Sun, Marcel Ceccato, Andrey Shavorskiy, Jeppe Vang Lauritsen","doi":"10.1021/acs.jpclett.4c03362","DOIUrl":"https://doi.org/10.1021/acs.jpclett.4c03362","url":null,"abstract":"This study presents a practical approach for characterizing industrial water-splitting nickel foam electrodes under both cathodic and anodic conditions by employing synchrotron radiation near-ambient pressure X-ray photoelectron spectroscopy (NAP-XPS). The in situ studies reveal quantitatively reduced and oxidized Ni species on the electrode surface by recording the Ni 2p_3/2 signals after cycling the potential in cathodic and anodic regions, respectively. Operando studies demonstrate that a stable electrolyte film forms, allowing the probing of the solid/liquid interface under applied potentials. We attribute this stability to capillary forces within the porous structure of the foam, which enables the monitoring of surface deprotonation under anodic potentials and surface protonation under cathodic potentials. Given that the most common industrial alkaline water electrolyzer electrodes are based on nickel foams similar to the samples measured in this study, the demonstrated method offers a valuable approach for fundamental NAP-XPS examination directly on industrially employed electrodes.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"95 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143766936","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}