化学•材料最新文献

{"title":"Impact of Parametrizations of the One-Body Reduced Density Matrix on the Energy Landscape","authors":"Nicolas G. Cartier, Klaas J. H. Giesbertz","doi":"10.1021/acs.jpclett.5c00308","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c00308","url":null,"abstract":"Many electronic structure methods rely on the minimization of the energy of the system with respect to the one-body reduced density matrix (1-RDM). To formulate a minimization algorithm, the 1-RDM is often expressed in terms of its eigenvectors via an orthonormal transformation and its eigenvalues. This transformation drastically alters the energy landscape. Especially in 1-RDM functional theory this means that the convexity of the energy functional is lost. We show that degeneracies in the occupation numbers can lead to additional critical points which are classified as saddle points. Using a Cayley or Householder parametrization for the orthonormal transformation, no extra critical points arise. In the case of Given’s rotations or the exponential, additional critical points can arise, which are of no concern in practical minimization. These findings provide an explanation for the success of recent minimization procedures using second-order information.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"4 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2025-04-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143798332","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":"Photophysical and Photochemical Features of Lysine Derivatives Bearing Two Triphenylaminocinnamic-Based Fluorophores.","authors":"Mario Saletti, Marco Paolino, Jacopo Venditti, Gianluca Giorgi, Claudia Bonechi, Alessandro Donati, Claudio Rossi, Germano Giuliani, Antonella Caterina Boccia, Chiara Botta, Lluís Blancafort, Andrea Cappelli","doi":"10.1021/acs.jpcb.5c01032","DOIUrl":"https://doi.org/10.1021/acs.jpcb.5c01032","url":null,"abstract":"<p><p>A Morita-Baylis-Hillman adduct (MBHA) derivative bearing a triphenylamine (TPA) moiety was previously found to react with Nα-acetyl-l<i>-</i>lysine methyl ester with the formation of the corresponding diadduct derivative as the major reaction product and a monoadduct as the minor one. The characterization of photochemical features of the diadduct bearing two triphenylaminocinnamic (TPAC) fluorophores suggested that this compound shows the tendency to undergo the [2 + 2] photocycloaddition reaction. This hypothesis was evaluated in the present study in both the diadduct derivatives obtained with Nα-acetyl-l-lysine methyl ester and Nα-acetyl-l-lysine. The hypothesis was confirmed in the case of the diadduct derivative obtained from Nα-acetyl-l-lysine methyl ester, whereas the UV-A irradiation of the diadduct derivative obtained from Nα-acetyl-l-lysine led to the formation of a strongly emissive (QY = 69%, λ_em = 460 nm) symmetric dimer.</p>","PeriodicalId":60,"journal":{"name":"The Journal of Physical Chemistry B","volume":" ","pages":""},"PeriodicalIF":2.8,"publicationDate":"2025-04-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143802134","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":"Room Temperature Operation of All-Solid-State Potassium-Ion Battery Enabled by Unconventional Ionic Solid Electrolyte K₆[Rh₄Zn₄(l-cys)₁₂O]·nH₂O.","authors":"Ryo Sakamoto, Kosuke Nakamoto, Atsushi Inoishi, Masato Ito, Nobuto Yoshinari, Takumi Konno, Yukihiro Hara, Takafumi Fujii, Shigeto Okada","doi":"10.1002/asia.202401781","DOIUrl":"https://doi.org/10.1002/asia.202401781","url":null,"abstract":"<p><p>The unconventional ionic solid, K₆[Rh₄Zn₄(L-cys)₁₂O]·nH₂O, exhibited excellent formability as well as high ionic conductivity. These features enabled a straightforward assembly of all-solid-state potassium-ion battery: A cold-pressed solid sample of K₆[Rh₄Zn₄(L-cys)₁₂O]·nH₂O, which was sandwiched by solid samples of K₂Ni[Fe(CN)₆] and chloranil as cathode, and anode, respectively, displayed an initial discharge capacity of 21.6 mAh g^-1-electrodes at 25 °C at a current density of 0.5 mA cm^-2 (∼0.34C). Energy dispersive X-ray spectroscopy analysis confirmed that K⁺ ions swiftly conduct through K₆[Rh₄Zn₄(L-cys)₁₂O]·nH₂O between the cathode and anode during charge-discharge cycles.</p>","PeriodicalId":145,"journal":{"name":"Chemistry - An Asian Journal","volume":" ","pages":"e202401781"},"PeriodicalIF":3.5,"publicationDate":"2025-04-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143802135","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":"Ultrafast Dynamics in Flavocytochrome C by Using Transient Absorption and Femtosecond Fluorescence Lifetime Spectroscopy.","authors":"Krishna P Khakurel, Gustavo Fuertes, Aron Sipos, Gábor Paragi, Jakub Dostal, Miroslav Kloz, Gabriel Žoldák, Jakob Andreasson, András Tóth","doi":"10.1021/acs.jpcb.4c05496","DOIUrl":"https://doi.org/10.1021/acs.jpcb.4c05496","url":null,"abstract":"<p><p>Flavocytochrome c sulfide dehydrogenase (FCC) is an important enzyme of sulfur metabolism in sulfur-oxidizing bacteria, and its catalytic properties have been extensively studied. However, the ultrafast dynamics of FCC is not well understood. We present ultrafast transient absorption and fluorescence spectroscopy measurements to unravel the early events upon excitation of the heme and flavin chromophores embedded in the flavocytochrome c (FccAB) from the bacterium <i>Thiocapsa roseopersicina</i>. The fluorescence kinetics of FccAB suggests that the majority of the photoexcited species decay nonradiatively within the first few picoseconds. Transient absorption spectroscopy supports these findings by suggesting two major dynamic processes in FccAB, internal conversion occurring in about 400 fs and the vibrational cooling occurring in about 4 ps, mostly affecting the heme moiety.</p>","PeriodicalId":60,"journal":{"name":"The Journal of Physical Chemistry B","volume":" ","pages":""},"PeriodicalIF":2.8,"publicationDate":"2025-04-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143810177","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":"Multisite Microkinetic Models in Catalysis: Automatic Formulation and Direct Solutions of the Master Equation","authors":"Kevin Adams, Jiankai Ge, Baron Peters","doi":"10.1021/acs.jpcc.5c01655","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c01655","url":null,"abstract":"Accurate kinetic models are crucial for catalyst development efforts. Tremendous progress has been made with existing mean-field microkinetic models (MF-MKMs) and kinetic Monte Carlo (kMC) simulations. However, MF-MKMs cannot accurately describe reactions where adsorbates interact with each other or where surface diffusion is important, whereas kMC (while accurate) lacks the convenience and insight that comes from a closed-form rate expression. We introduce a master equation microkinetic modeling (ME-MKM) approach that bridges the gap between MF-MKMs and kMC simulations. We describe a generalizable way to partition a surface into linear periodic tiles, to automate the formulation of the master equation including adsorption, reaction, diffusion, and desorption steps (with adsorbate interactions of any strength), and to exactly solve the master equation. We demonstrate this method for examples that are notoriously difficult for MF-MKMs and obtain results which are essentially indistinguishable from numerically exact kMC results. We also demonstrate (using kMC data) that the analytic ME-MKM rate expression can be used “in reverse” to accurately estimate rate parameters and adsorbate interactions from data.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"31 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-04-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143798391","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":"Tungsten Donor Substitution and Oxygen Vacancy Modulation in Bismuth Titanate-Tantalate (Bi3TiTaO9) for Enhanced High-Temperature Piezoelectric Properties and Resistivity","authors":"Qian Wang, Chen-Yang Liu, Yuan-Kai Yang, Le-Le Jia, Xian Zhao, Chun-Ming Wang","doi":"10.1021/acs.jpcc.5c00697","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c00697","url":null,"abstract":"High-temperature piezoelectric ceramics with excellent piezoelectric properties and temperature stability are crucial for advancing high-temperature piezoelectric sensor applications. However, challenges such as relatively low piezoelectric responses and increased conductivity at elevated temperatures persist. In this study, we enhanced the piezoelectric and electrical properties of bismuth titanate-tantalate (Bi₃TiTaO₉) ceramics by introducing tungsten as a donor substitution. The Bi₃Ti_1–<i>x</i>W<i>_<i>x</i></i>TaO₉ (abbreviated as BTT–100<i>x</i>W) ceramics were synthesized via a conventional solid-solution method. The substitution of tungsten induces tetragonal distortion and reduces the pinning effect on the domain wall, resulting in a significant enhancement of the piezoelectric performance. Specifically, BTT–3W exhibits a high piezoelectric constant (<i>d</i>₃₃ = 15.3 pC/N) and an elevated Curie temperature (<i>T</i>_C = 883 °C). Furthermore, BTT–3W demonstrates excellent thermal stability of its electromechanical coupling properties up to 650 °C. The dielectric and electrical properties of BTT–100<i>x</i>W ceramics were further investigated through frequency- and temperature-dependent dielectric/impedance spectroscopy. The reduced dielectric loss and changes in the conduction mechanisms suggest that a decrease in the concentration of oxygen vacancies is primarily responsible for the reduced conductivity at high temperatures. This study highlights the role of oxygen vacancy defects in tailoring the physical properties of BTT-based ceramics, making them promising candidates for high-temperature piezoelectric applications.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"92 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-04-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143798394","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":"Synthesis and Toxicity Evaluation of p-Phenylenediamine-Quinones","authors":"Pranav Nair, Jianxian Sun, Linna Xie, Lisa Kennedy, Derek Kozakiewicz, Sonya M. Kleywegt, Chunyan Hao, Hannah Byun, Holly Barrett, Joshua Baker, Joseph Monaghan, Erik T. Krogh, Datong Song, Hui Peng","doi":"10.1021/acs.est.4c12220","DOIUrl":"https://doi.org/10.1021/acs.est.4c12220","url":null,"abstract":"<i>N</i>-(1,3-Dimethylbutyl)-<i>N′</i>-phenyl-<i>p</i>-phenylenediamine-quinone (6PPD-Q), the tire rubber-derived transformation product of 6PPD, was recently discovered to cause the acute mortality of coho salmon (<i>Oncorhynchus kisutch</i>). Aiming to identify potential replacement antiozonants for 6PPD that do not produce toxic quinones, seven PPD-quinones with distinct side chains were synthesized to investigate their structure-related toxicities <i>in vivo</i> using rainbow trout (<i>Oncorhynchus mykiss</i>). While 6PPD-Q exerted high toxicity (96 h LC₅₀ = 0.35 μg/L), toxicity was not observed for six other PPD-quinones despite their similar structures. The fish tissue concentrations of 6PPD-Q after sublethal exposure (0.29 μg/L) were comparable to the other PPD-quinones, which indicated that bioaccumulation levels were not the reason for the selective toxicity of 6PPD-Q. Hydroxylated PPD-quinones were detected as the predominant metabolites in fish tissue. Interestingly, a single major aromatic hydroxylation metabolite was detected for the alternate PPD-quinones, but two abundant OH-6PPD-Q isomers were detected for 6PPD-Q. MS² spectra confirmed that hydroxylation occurred on the alkyl side chain for one isomer. The structurally selective toxicity of 6PPD-Q was also observed in a coho salmon (CSE-119) cell line, which further supports its intrinsic toxicity. This study reported the selective toxicity of 6PPD-Q and pinpointed the possibility for other PPDs to be applied as potential substitutes of 6PPD.","PeriodicalId":36,"journal":{"name":"环境科学与技术","volume":"38 1","pages":""},"PeriodicalIF":9.028,"publicationDate":"2025-04-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143798194","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":"Neural Network Atomistic Potential for Pyrophyllite Clay Simulations.","authors":"Chloe Sanz, Abdul-Rahman Allouche, Colin Bousige, Pierre Mignon","doi":"10.1021/acs.jpca.5c00406","DOIUrl":"https://doi.org/10.1021/acs.jpca.5c00406","url":null,"abstract":"<p><p>In this study, a high-dimensional neural network potential for the smectite pyrophyllite clay has been developed from density functional theory (DFT) data, including correction for dispersion interactions. The data set has been built from the adaptive learning approach, resulting in a diverse and very concise set of selected structures comprising only representative ones. Two neural network potential (NNP) data sets have been constituted from sets of energies and forces computed at two different levels of DFT accuracy. Validation tests show very good accuracy for the computed energies and forces of various systems differing by their size and simulation conditions. The developed potentials are able to reproduce structural parameters with excellent agreement with DFT values as well as experimental data and are the first NNPS able to reproduce clay layers' properties held together via van der Waals interactions. The NNP constructed from data of higher DFT levels shows better results for extreme condition simulations. In addition, elastic properties, exfoliation energies, and vibrational density of state are also well reproduced, showing better performances than standard force fields at a fraction of DFT computation time.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":""},"PeriodicalIF":2.7,"publicationDate":"2025-04-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143801965","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":"In Situ Electrochemical Reduction of Imidacloprid involving a Nitroso-Intermediate-Trapped DWCNT and Its Biomimetic Cellular Oxidative Stress-Related Mediated Oxidation of Thiols.","authors":"Kandavel Preethika Andal, Annamalai Senthil Kumar","doi":"10.1002/asia.202401779","DOIUrl":"https://doi.org/10.1002/asia.202401779","url":null,"abstract":"<p><p>Imidacloprid (IMP) is a widely used pesticide and insecticide known for its effectiveness in controlling pests and increasing crop yields. Exposure of the compound to water bodies has led to environmental pollution and adverse effects on human health. One major concern is the generation of oxidative-stress in the cellular system, which is often a result of IMP exposure. Although the exact mechanism of toxicity is not fully understood, it is believed that the nitroso-intermediate of IMP (IMP-NO) binds to acetylcholine receptors, disrupting neural function. Thiol pools in the blood serum act as antioxidants to mitigate the toxicity. This study presents an in situ electrochemical conversion of IMP into its key intermediate, IMP-NO, and its subsequent entrapment on a double-walled carbon nanotube-modified glassy carbon electrode (GCE/DWCNT@IMP-NO) as a surface confined redox-peak in a physiological solution. It was characterized by SEM, FTIR, Raman, SECM, and LC-MS techniques. The system exhibited excellent mediated oxidation of the thiol group, using cysteine as a model. The findings presented in this work correlate with observations related to cellular oxidative-stress and its thiol-assisted mitigation. Employing a Michaelis-Menten-type enzyme-substrate reaction mechanism and estimated the kinetic parameters. Chronoamperometric techniques were used to demonstrate the oxidative detection of thiol.</p>","PeriodicalId":145,"journal":{"name":"Chemistry - An Asian Journal","volume":" ","pages":"e202401779"},"PeriodicalIF":3.5,"publicationDate":"2025-04-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143802104","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":"Weathering Process and Characteristics of Microplastics in Coastal Wetlands: A 24-Month In Situ Study","authors":"Teng Wang, Dongxiang Liu, Rongze Liu, Feng Yuan, Yongcheng Ding, Jianguo Tao, Yaping Wang, Wenwen Yu, Yining Fang, Baojie Li","doi":"10.1021/acs.est.4c12140","DOIUrl":"https://doi.org/10.1021/acs.est.4c12140","url":null,"abstract":"Coastal wetlands function as critical retention zones for environmental microplastics, potentially accelerating their degradation through unique hydrological conditions. This study conducted a comprehensive 24-month in situ experiment at the Chongming Dongtan National Nature Reserve, examining the weathering processes of five morphologically distinct polyethylene (PE), polypropylene (PP), and polystyrene (PS) microplastics. Quarterly analyses revealed progressive surface deterioration in all microplastics after initial exposure, followed by polymer-specific fragmentation patterns and environmental pollutant adherence. Surface elemental analysis showed rising O/C ratios, with intertidal zones exhibiting higher variance (0.0014–0.0096 vs 0.0006–0.0028 supratidal). Carbonyl index (CI) displayed fluctuating increases, with PS showing the highest CI rise (75.75%/year intertidal vs 61.77%/year supratidal). Systematic comparisons identified three weathering determinants: enhanced intertidal degradation from mechanical-photochemical synergy; spherical particles degrading faster than films via larger surface area; and polymer vulnerabilities dictating PS &gt; PP &gt; PE degradation rates. These findings demonstrate that microplastic weathering in coastal wetlands is collectively governed by hydrological conditions, particle morphology, and polymer composition, providing crucial quantitative parameters for assessing environmental persistence and ecological risks in these sensitive transition ecosystems.","PeriodicalId":36,"journal":{"name":"环境科学与技术","volume":"13 1","pages":""},"PeriodicalIF":9.028,"publicationDate":"2025-04-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143806046","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}