化学•材料最新文献

{"title":"Contribution of Nilaparvata lugens Nicotinic Acetylcholine Receptor Subunits Toward Triflumezopyrim and Neonicotinoid Susceptibility","authors":"Yan-Chao Zhang, Zi-Xin Zhuang, Fan Zhang, Xiao-Yan Song, Wen-Nan Ye, Shun-Fan Wu, Chris Bass, Andrias O. O’Reilly, Congfen Gao","doi":"10.1021/acs.est.5c02110","DOIUrl":"https://doi.org/10.1021/acs.est.5c02110","url":null,"abstract":"Nicotinic acetylcholine receptors (nAChRs) are the molecular targets of some important insecticides including triflumezopyrim and neonicotinoids. However, our understanding of insect nAChR pharmacology and the specific nAChR subunits targeted by these insecticides remains limited. Here, we cloned 11 nAChR subunit genes, comprising <i>Nlα1</i> to <i>Nlα8</i>, <i>Nlα10</i>, <i>Nlβ1</i> and <i>Nlβ3</i>, from <i>Nilaparvata lugens</i>, a highly damaging insect pest of rice crops worldwide. Analysis of the expression of these genes in different tissues of <i>N. lugens</i> by qPCR analysis identified the brain as the primary site of expression. Knock down of the expression of <i>Nlα1</i>, <i>Nlα2</i>, <i>Nlα8</i> and <i>Nlβ1</i> using RNAi reduced <i>N. lugens</i> sensitivity to triflumezopyrim, suggesting these genes encode potential target subunits for triflumezopyrim. Knock out of <i>Nlα2</i> and <i>Nlα8</i> nAChR subunits by CRISPR/Cas9 genome editing showed that their deletion significantly reduced the toxicity of triflumezopyrim toward <i>N. lugens</i>. Furthermore, the deletion of <i>Nlα2</i> also increased <i>N. lugens</i> resistance to imidacloprid and dinotefuran. However, numerous attempts revealed that the <i>Nlβ1</i> knockout was nonviable. <i>In vitro</i> expression of receptors composed of <i>Drosophila</i> homologous subunits showed that this all-insect nAChR was inhibited by nanomolar concentrations of triflumezopyrim. The present findings identify specific nAChR subunits that are important both as targets for monitoring resistance-associated mutations and as subjects for molecular studies aimed at developing novel insecticides targeting these essential ion channels.","PeriodicalId":36,"journal":{"name":"环境科学与技术","volume":"34 1","pages":""},"PeriodicalIF":9.028,"publicationDate":"2025-04-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143776087","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":"Discrepancies between Theory and Experiment in Determining the Ionization Energy of NF₃.","authors":"Megan R Bentley, Peter R Franke, Kaila E Weflen, David H Bross, Branko Ruscic, John F Stanton","doi":"10.1021/acs.jpca.5c00613","DOIUrl":"https://doi.org/10.1021/acs.jpca.5c00613","url":null,"abstract":"<p><p>High-accuracy <i>ab initio</i> thermochemical predictions for the ionization energy of NF₃, the barrier height (to inversion) of NF₃⁺, and the dissociative ionization threshold of NF₃ to NF₂⁺ + F are presented and incorporated into Active Thermochemical Tables. The adiabatic ionization energy of the first ionization band of NF₃, calculated at 12.647 ± 0.010 eV, is at odds with previous experimental interpretations by nearly 0.36 eV due to unfavorable Franck-Condon factors associated with this transition. The barrier (to inversion) height is calculated to be about 0.6 eV lower in energy than the prior interpretation, which instigates a discussion of the supposed vibrational structure of the first ionization band of NF₃. Updated assignments of the photoelectron spectrum are proposed, and the loss in vibrational spacing on the high-energy side of the experimental ionization band is discussed. Rudimentary anharmonic Franck-Condon simulations qualitatively reproduce the broad spectral features observed in experiment.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":""},"PeriodicalIF":2.7,"publicationDate":"2025-04-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143784379","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 Spectroscopies Unraveling the Molecular Mechanisms of H+ and Cl– on Pyridine Inhibition of Low-Carbon Steel Corrosion","authors":"Huihui Hu, Yuening Zhang, Peng Shang, Linyu Han, Rongjuan Feng, Xiaorui Ren, Dong Wang, Yuan Guo, Zhen Zhang","doi":"10.1021/acs.jpclett.5c00396","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c00396","url":null,"abstract":"This study utilized a variety of in situ spectroscopic techniques to investigate the corrosion inhibition mechanism of three pyridine-based inhibitors on carbon steel in HCl and NaCl solutions. The results demonstrated that the adsorption and orientation of the inhibitor molecules play key roles in the corrosion inhibition mechanism studied using second harmonic generation (SHG). The number density of molecules adsorbed on the substrate is a crucial factor affecting the inhibition efficiency. A two-step physical model elucidates the SHG signal time evolution, revealing initial rapid inhibitor adsorption and subsequent slow dynamic adsorption optimization. Our research indicated that, in HCl solution, H⁺ protonates the pyridine inhibitors, and the protonated species adsorb onto the positively charged substrate bridging, forming a compact chemisorbed layer that effectively blocks corrosive ion access. In contrast, in NaCl solution, Cl^– promotes the formation of a porous corrosion product film, which synergizes with adsorbed inhibitors to mitigate metal degradation. This finding offers insights into molecular-level interfacial inhibition mechanisms in environments with H⁺ and/or Cl^– ions.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"18 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2025-04-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143775881","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":"Solvent Regulating Ni–O Bond Improves the Cyclability of High-Voltage Ni-Rich Cathodes in Nonflammable Electrolytes","authors":"Xiaomei He, Rong Xu, Zhijie Wang","doi":"10.1021/acs.jpcc.4c07314","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c07314","url":null,"abstract":"The adoption of nickel (Ni)-rich cathodes in lithium (Li) batteries is well suited for electric vehicles and portable electronic devices due to their high energy density and potential for longevity. However, the intense interactions between the cathode and electrolyte compromise electrochemical stability and safety, particularly under elevated voltage conditions. In this study, a nonflammable electrolyte with a low salt concentration of 0.75 M, incorporating fluoroethylene carbonate (FEC) and trimethyl phosphate (TMP) solvents, is developed to improve the cyclability at high state of charge. The combination of theoretical calculations and experimental characterizations demonstrates that the covalency of nickel (Ni) and oxygen bond is alleviated, thereby effectively mitigating the catalytic activity of highly delithiated cathodes and suppressing oxidative decomposition of the electrolyte and rock-salt phase formation. Moreover, this electrolyte facilitates the formation of an inorganic-rich solid-electrolyte interphase (SEI) on the Li metal anode, thus enhancing its reversibility. Consequently, the electrolyte markedly enhances the cyclability, stability, and safety of NCM811-Li batteries. The findings provide a promising solution for addressing the pivotal challenges associated with high-voltage Ni-rich Li batteries.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"37 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-04-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143775889","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":"Enhanced Solar CO2 Reduction Using Single Cobalt Sites on Carbon Nitride Modified with a Dianhydride","authors":"Allison St. John, Shuting Xiang, Hannah Flayhart, Eduardo Ortega, Qian Qian, N. Aaron Deskins, Beatriz Roldan Cuenya, Jonathan Rochford, Anatoly I. Frenkel, Gonghu Li","doi":"10.1021/acs.jpcc.4c08562","DOIUrl":"https://doi.org/10.1021/acs.jpcc.4c08562","url":null,"abstract":"Photoactive single-atom catalysts (SACs) are among the most exciting catalytic materials for solar fuel production. Different SACs, including our own Co SACs, have been prepared on graphitic carbon nitride (C₃N₄) for use in photocatalysis. Building on our prior success, we report here doped C₃N₄ using various supplemental carbon dopants as the support for Co SACs. The Co SAC on a dianhydride-doped C₃N₄ showed the highest activity in photocatalytic CO₂ reduction. Catalyst characterization was carried out to explore the origin of the enhanced activity of this particular Co SAC. The dianhydride-doped C₃N₄ possesses unique microstructural features, including a large interlayer space and fibrous morphology, that could contribute to enhanced photocatalytic activity. Our results further indicate that dianhydride is the most effective dopant to incorporate aromatic moieties in C₃N₄, which resulted in improved charge separation and enhanced activity in photocatalysis.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"1 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-04-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143775890","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":"Effect of tert-Butyl Substitution on the Interactions of Cobalt Phthalocyanine with a Carbon Monoxide-Functionalized Tip","authors":"Xinzhe Wang, Percy Zahl, Miguel Wiche, Hailiang Wang, Eric I. Altman, Udo D. Schwarz","doi":"10.1021/acs.jpclett.5c00414","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c00414","url":null,"abstract":"Supported cobalt phthalocyanines (CoPc) are promising catalysts for CO₂ reduction, a critical process for mitigating greenhouse gas emissions. Enhancing the catalytic performance of CoPc involves modifying the interaction between the cobalt center and intermediate species. This study focuses on the effects of <i>tert</i>-butyl substitution on CoPc using (<i>tert</i>-butyl)₄CoPc, where the substitution can both directly alter the molecule’s intramolecular electronic structure and indirectly alter it by the bulky group weakening the interaction with the support. Toward this end, we investigated the structural and chemical properties of (<i>tert</i>-butyl)₄CoPc on a Ag(111) surface at the single-molecule level using three-dimensional atomic force microscopy (AFM) with a CO-terminated tip and discussed them in comparison with data for unmodified CoPc and amino-substituted CoPc. Notably, distance-dependent force measurements revealed anomalies in the <i>tert</i>-butyl groups’ force curves, attributed to their rotational flexibility. The <i>tert</i>-butyl (<i>t</i>-butyl) groups were also observed to increase the attraction of the central Co atom to CO, but this effect was attributed largely to enhanced interactions of the back of the tip with the peripheral <i>t</i>-butyl groups. While this longer-range interaction would not be expected to impact the interaction of small molecules with the catalytic center, the results reveal the ability of AFM to characterize longer range environmental interactions that can enhance adsorption and subsequent reactions of larger molecules, as well as the role side chains that offer configurational adaptability may play in these interactions.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"4 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2025-04-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143775882","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":"Regulating the Electronic Metal–Support Interaction of Single-Atom Ruthenium Catalysts for Boosting Chlorobenzene Oxidation","authors":"Xiaoxiao Duan, Ben Niu, Yiwen Wang, Zhenwen Yang, Hongna Ren, Ganggang Li, Zheng Wei, Jie Cheng, Zhongshen Zhang, Zhengping Hao","doi":"10.1021/acs.est.5c00299","DOIUrl":"https://doi.org/10.1021/acs.est.5c00299","url":null,"abstract":"Developing highly active single-atom catalysts (SACs) with excellent chlorine resistance for efficient oxidation of harmful chlorinated volatile organic compounds (CVOCs) is a great challenge. Tuning the electronic metal–support interaction (EMSI) is viable for promoting catalytic performances of SACs. Herein, an effective strategy of modulating the EMSI in Ru₁/CeO₂ SACs by thermal treatment control is proposed, which distinctly enhances the activities of the catalyst for chlorobenzene (CB) oxidation and chlorine conversion, accomplishing total CB degradation at nearly 260 °C. Detailed characterization and theoretical calculations reveal that the EMSI induces electron transfer from Ru to CeO₂, optimizing the coordination and electronic structure of single-atom Ru and accordingly facilitating the adsorption and activation of CB. Moreover, the surface lattice oxygen (O_latt) at the Ru–O–Ce interface is demonstrated as the critical reactive oxygen species, the mobility and reactivity of which are also prompted by the EMSI, leading to the boosted conversion of reaction intermediates. This work sheds light on the effect of EMSI regulation on CVOC catalytic oxidation and provides guidance on fabricating high-efficiency SACs for environmental catalysis.","PeriodicalId":36,"journal":{"name":"环境科学与技术","volume":"108 1","pages":""},"PeriodicalIF":9.028,"publicationDate":"2025-04-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143776086","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":"Surface Structure Dependence of Electrochemical Processes at Monocrystalline Nickel Electrodes. Part 2: The Hydrogen Oxidation Reaction","authors":"K. Liam Varvaris, Derek Esau, Gregory Jerkiewicz","doi":"10.1021/acs.jpcc.5c00311","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c00311","url":null,"abstract":"Nickel single crystals grown with the innovative Controlled Atmosphere Flame Fusion (CAFF) technique are used to study the hydrogen oxidation reaction (HOR) on high-quality Ni(111), Ni(100), and Ni(110) electrodes. Cyclic voltammetry (CV) profiles are acquired in both N₂-saturated and H₂-saturated 0.10 M aqueous NaOH solution and compared. Linear sweep voltammetry (LSV) measurements conducted at a very low potential scan rate (<i>s</i> = 0.10 mV s^–1), which ensures steady-state conditions, are performed in the anodic and cathodic directions, from which Tafel plots are constructed and the exchange current density (<i>j</i>₀) and Tafel slope (<i>b</i>) are determined. The resulting Tafel plots are unique to each monocrystalline electrode and also depend on the scan direction; thus, the surface arrangement of atoms and the pretreatment of the electrode influence the values of <i>j</i>₀ and <i>b</i>. CV measurements are used to analyze the surface of the Ni(hkl) electrodes after the HOR and to determine if the process brings about any surface-structural changes. An analysis of the CV profiles leads to the conclusion that the long-range atomic order of the Ni(hkl) electrodes becomes disturbed. This study marks the first ever comprehensive investigation of the HOR on Ni(hkl) electrodes, hence its originality and importance.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"33 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-04-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143775891","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":"Optical Properties of Macrocyclic Chiral Molecules: The Limitations of Ring Size Increase","authors":"Gjergji Sini, Qi Sun, Eunkyung Cho, Jean-Luc Brédas, Veaceslav Coropceanu","doi":"10.1021/acs.jpclett.5c00690","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c00690","url":null,"abstract":"Chiral macrocyclic molecules are extensively investigated as potential candidates to develop organic emitters exhibiting circularly polarized luminescence (CPL) with large dissymmetry factors (<i>g</i>). Here, based on time-dependent density functional theory calculations, we investigate the relationship between macrocycle size and chiral properties. Our results underline that the rotatory strength (<i>R</i>) of the transition to the first excited state (S₀ → S₁) increases linearly with the macrocycle loop area. While this evolution could promote high <i>g</i> values in the case of very large rings, it is found that the increase in system size can lead to energetic quasi-degeneracy of several low-lying transitions. In large macrocycles, among those transitions, it is the slightly higher-energy transitions possessing large oscillator strengths but small <i>g</i> values that come to dominate over the S₀ → S₁ transition. Also, the corresponding decrease in energy spacing among these lowest excited states can trigger a broken symmetry of the S₁-state geometry via a pseudo Jahn–Teller effect. Overall, our results highlight that in large macrocycles the CPL can gain in intensity but this occurs at the expense of the <i>g</i> value. Thus, it is critical that the interaction of the S₀ → S₁ transition with higher-energy states be carefully considered when designing large-size CPL emitters.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"73 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2025-04-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143782886","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":"Revealing the inhibitory reduction effect of Zr species on CoO to enhance the stability for furfural hydrogenolysis to 2-methylfuran","authors":"Jun He ,&nbsp;Shuang Xiang ,&nbsp;Xiaohui Liu ,&nbsp;Yanqin Wang","doi":"10.1016/j.apcata.2025.120267","DOIUrl":"10.1016/j.apcata.2025.120267","url":null,"abstract":"<div><div>High selective hydrogenolysis of furfural to 2-methylfuran over a metal oxide-based catalyst is promising and challenging. In this paper, a Zr-modified CoO_x (Zr₁Co₆-325) catalyst was prepared via a simple co-precipitation/reduction and exhibited superior initial activity and remarkable circular stability during the hydrogenolysis of furfural (FUR) to 2-methylfuran (2-MF). As high as 71.2 % yield of 2-MF was achieved at 170 °C for 2 h and nearly no deactivation was found after five cycles, much better than those of reduced Co₃O₄ catalyst (Co₃O₄-250). Comprehensive studies demonstrated that the over-reduction of the CoO species during the reaction process was the main cause of catalyst deactivation. The introduction of Zr species, on the one hand, inhibited the over-reduction of CoO species during reaction processes, thereby enhancing the circular stability. On the other hand, the introduction of Zr species promoted the activation and dissociation of H₂ and therefore improved the activity. This research unveiled the stabilizing effect of Zr species on CoO, providing guidance for the design of high-stable CoO-based catalysts.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"699 ","pages":"Article 120267"},"PeriodicalIF":4.7,"publicationDate":"2025-04-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143783881","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}