化学•材料最新文献

{"title":"Dietary Exposure to Imidacloprid at Environmental Doses Induces Renal Injury in Mice via P-AMPK Inhibition and Subsequent Purine Metabolism Dysregulation","authors":"Wen Xie, Yajing Zhang, Yu He, Hang Su, Jinni Zhang, Canrong Chen, Peisi Xie, Jing Chen, Zian Lin, Zongwei Cai","doi":"10.1021/acs.est.5c05893","DOIUrl":"https://doi.org/10.1021/acs.est.5c05893","url":null,"abstract":"Imidacloprid (IMI), a neonicotinoid insecticide extensively applied in agriculture, is among the most frequently detected pesticides in food. However, the long-term impact of chronic dietary exposure to environmentally relevant IMI doses on kidney health has not been fully elucidated, particularly regarding its nephrotoxic mechanisms. To address this gap, chronic exposure to IMI was administered to mice through supplementation of their feed with environmentally relevant doses (approximately 100 and 1000 μg/kg/day) for 24 weeks to investigate its nephrotoxicity and underlying mechanisms. Toxicological analysis revealed that chronic IMI exposure led to renal dysfunction, histopathological alterations, and excessive apoptosis in mice. Mechanistic investigations suggested that IMI might inhibit AMP-activated protein kinase (AMPK) activity through both direct and indirect pathways. Direct inhibition occurred through the binding of IMI and its metabolites to AMPK, reducing its phosphorylation activity. Indirect inhibition involved excessive production of reactive oxygen species, which suppressed AMPK phosphorylation, leading to sustained purine metabolism dysregulation in the renal system. Consequently, the kidneys showed an aggravated redox imbalance, heightened inflammatory states, and increased cellular apoptosis. The results of this study are intended to raise awareness of pesticide use and food safety among agricultural workers and consumers.","PeriodicalId":36,"journal":{"name":"环境科学与技术","volume":"24 1","pages":""},"PeriodicalIF":9.028,"publicationDate":"2025-09-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144931225","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 Orientation of Isocyanate Groups Determined by Combined Sum Frequency Generation Vibrational Spectroscopic Study and Ab Initio Calculation","authors":"Guangyao Wu, Shuqing Zhang, Jianing Gan, Hanning Chen, Zhan Chen","doi":"10.1021/acs.jpcc.5c04729","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c04729","url":null,"abstract":"Sum frequency generation (SFG) vibrational spectroscopy is a powerful nonlinear optical technique that provides molecular-level information about surfaces and interfaces with submonolayer sensitivity. In this study, we combined SFG experiments with ab initio calculations to investigate the surface orientations of isocyanate groups on a commercial primer containing isocyanate functionalities, polymeric diphenylmethane diisocyanate (pMDI), and 4,4′-methylene diphenyl diisocyanate (MDI). We examined the effects of surface exposure to humidity and the duration of such exposure on the orientation of surface isocyanate groups. Instead of using the widely adopted orientation determination method based on the fitted signal strength ratios of SFG spectra collected with different polarizations, we employed a spectral comparison method. We calculated orientation-dependent SFG spectra using IR transition dipole moments and Raman polarizability tensors of relevant vibrational modes obtained from ab initio calculations, and then compared these spectra with the reconstructed experimental data (after removing the nonresonant signal contribution) to deduce the most likely isocyanate orientation. We found that the isocyanate stretching normal mode involves vibrations of many atoms in the molecule, and the spectral comparison method is advantageous when dealing with multiple peaks arising from isocyanate stretching. It was found that although the SFG spectra intensity decreased after sample surfaces were exposed to humid air due to chemical reactions between surface isocyanate groups and moisture, the remaining unreacted isocyanate groups retained similar orientations, regardless of humidity exposure or duration.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"8 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-09-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144931357","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":"Ice Nucleation Regulation by Nanoscale Surface Topography","authors":"Mingxia Ren, Yi Peng, Chengwei Zhang, Bo Guan, Guoying Bai, Jianjun Wang","doi":"10.1021/acs.jpclett.5c02069","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c02069","url":null,"abstract":"Heterogeneous ice nucleation, triggered by surfaces, profoundly impacts climate systems, biological processes, and technological applications. Classical nucleation theory (CNT) predicts that with curvature radii decreasing within 1 order of magnitude of the critical nucleus radius, convex surfaces should suppress nucleation and concave surfaces should promote nucleation; however, such regularity has not been observed explicitly in experiments, and there are even conflicting results. Here, we resolve this long-standing controversy by providing the first experimental evidence about the bidirectional regulation of ice nucleation from both liquid and vapor phases through precisely engineered convex (nanosphere) and concave (nanopore) surfaces. Systematic experiments reveal size-dependent trends: as curvature radii decrease at the critical nucleus scale, ice nucleation temperatures and rates decrease on convex but increase on concave surfaces, directly linked to opposing nucleation free energy barrier variations that align with CNT predictions. This work bridges CNT’s predictions for surface topography with practical ice-control engineering.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"27 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2025-09-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144931406","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":"Computational Analysis of Threonine Ladders on Distinct β-Solenoid Scaffolds, with Implications for the Design of Novel Antifreeze Proteins.","authors":"Cianna N Calia, Francesco Paesani","doi":"10.1021/acs.jpcb.5c05027","DOIUrl":"https://doi.org/10.1021/acs.jpcb.5c05027","url":null,"abstract":"<p><p>Cold-adapted organisms frequently express antifreeze proteins (AFPs) that facilitate their survival at low temperatures, with some especially potent insect AFPs exhibiting β-solenoid structures with ice-binding threonine ladders. β-solenoids exist in nature in numerous forms and emerging protein design technologies may afford opportunities to diversify them further, suggesting the possibility of developing a variety of new AFPs by installing a threonine ladder on non-AFP natural or designed β-solenoids. However, early attempts at such engineering, combined with differences observed between AFPs and structurally similar ice-nucleating proteins, have raised a critical question: Will a threonine ladder show essentially the same behavior regardless of the β-solenoid scaffold that hosts it, or does the specific solenoid scaffold significantly affect a threonine ladder's structural characteristics (and thus potentially alter its suitability for ice binding)? We set out to address this question by creating distinct variants of a simplified model β-solenoid for <i>in silico</i> analysis <i>via</i> structure prediction and molecular dynamics simulations. Our findings indicate that local structural details such as the distance between the hydroxyl groups of adjacent threonines in a TXT motif can vary depending on the β-solenoid scaffold. In the most extreme example among our model solenoids, we observed in simulations that differences in only inward-facing residues of the scaffold were sufficient to influence the presence of ordered channel waters between the threonines, a noted feature of natural ice-binding threonine surfaces such as that of TmAFP. While additional studies will be necessary to expand on how such distinctions affect activity, these results emphasize that the impact of a particular β-solenoid scaffold on the local geometry of a threonine ladder may be a pertinent consideration in future efforts to design novel hyperactive AFPs to support applications ranging from biomedical cryopreservation to food science. We conclude our present investigation with a preliminary exploration of how this and other considerations manifest in a proposed workflow for generating predicted AFP-like β-solenoids using AlphaFold and ProteinMPNN.</p>","PeriodicalId":60,"journal":{"name":"The Journal of Physical Chemistry B","volume":" ","pages":""},"PeriodicalIF":2.9,"publicationDate":"2025-09-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144991071","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":"Butylparaben-Loaded Aged Polystyrene Nanoplastics Amplify Its Toxicity in Microcystis aeruginosa via Quorum Sensing Suppression and Enhanced Microcystin-LR Release","authors":"Zhong-Hong Zhang, Yi-Fan Zhu, Yu-Cheng Yang, Yuan-Zhen Xiao, Shun-Ni Zhu, Wei-Dong Yang, Hong-Ye Li, Xiang Wang","doi":"10.1021/acs.est.5c08029","DOIUrl":"https://doi.org/10.1021/acs.est.5c08029","url":null,"abstract":"Aged nanoplastics are emerging pollutants in aquatic environments, but the effects of their loaded pollutants on cyanobacteria are still poorly understood. This study evaluated the adsorption of butylparaben (BP) by pristine (PS) and aged polystyrene nanoplastics (APS) and prepared BP-loaded aged PS to analyze their effects on Microcystis aeruginosa. The results showed that APS had stronger BP adsorption and translocation capacity, with APS increasing BP adsorption by 4.34-fold and significantly enhancing its bioconcentration in M. aeruginosa. Compared with the PS–BP treatment, the 1.13 ng/g APS–BP treatment significantly inhibited algal growth, exacerbated cell membrane damage and oxidative stress, and promoted MC-LR synthesis and release. Transcriptome analyses and molecular docking showed that BP inhibited quorum sensing (QS) by binding to luxR, whereas APS further enhanced the binding affinity of BP and blocked the binding of N-acylhomoserine lactone, a natural QS signaling molecule, to its receptor, amplifying the QS inhibitory effect. QS inhibition downregulated genes related to photosynthesis, membrane synthesis, and oxidative stress and upregulated genes related to MC-LR synthesis. These findings revealed that APS is a pollutant carrier that exacerbates cyanobacterial toxicity and MC-LR release through pollutant adsorption, posing significant ecological risks to aquatic ecosystems.","PeriodicalId":36,"journal":{"name":"环境科学与技术","volume":"38 1","pages":""},"PeriodicalIF":9.028,"publicationDate":"2025-09-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144931361","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":"Successive Spin Coating Induces an Order–Disorder Transition in a Block Copolymer Micellar Nanoarray","authors":"Yonggang Chen, Ruihao Xue, Ze Gong, Hongyuan Jiang","doi":"10.1021/acs.jpclett.5c01847","DOIUrl":"https://doi.org/10.1021/acs.jpclett.5c01847","url":null,"abstract":"Controlling the spatial arrangement of nanodots is pivotal for functional nanomaterials and biointerfaces, and the spontaneous self-assembly of block copolymer micelles has been widely used to fabricate ordered nanostructures. However, achieving tunable disorder remains a fundamental challenge. Here, we demonstrate how successive spin coating dynamically modulates both density and disorder in micellar arrays, revealing an unexpected non-monotonic evolution of structural order. By using the Voronoi tessellation and Alpha shapes filtering algorithm, we found that initial coatings produce hexagonal order (interparticle distance: 126 nm, σ_{<i>d</i>/<i>d̅</i>} = 0.12) and intermediate cycles induce maximal disorder (interparticle distance: 95 nm, σ_{<i>d</i>/<i>d̅</i>} = 0.26), while further deposition partially restores order driven by steric hindrance (interparticle distance: 73 nm, σ_{<i>d</i>/<i>d̅</i>} = 0.20). Our successive spin-coating approach achieves tunable disorder equivalent to conventional polymer-blending methods but without additives, offering a versatile strategy for engineering nanoscale surface patterns with potential applications for biomaterials and optical device design.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"161 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2025-09-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144931409","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":"Microorganisms Enhance Denitrification of Low Carbon-to-Nitrogen Ratio Municipal Wastewater and Reduce N2O Emission: Metabolites Promote Carbon Flux to Nitrate Bioreduction.","authors":"Zhiyi Qin,Qimeng Liu,Lei Dong,Xin Zhang,Chun-Jian Ding,Yinguang Chen","doi":"10.1021/acs.est.4c13005","DOIUrl":"https://doi.org/10.1021/acs.est.4c13005","url":null,"abstract":"Denitrifying carbon source is mainly used for microbial growth and proliferation, substrate transport, and nitrate bioreduction. This paper reported a new approach to dramatically promote denitrification and reduce N2O emission of low carbon-to-nitrogen ratio (C/N) municipal wastewater by introducing two microorganisms to increase carbon flux to nitrate bioreduction without increasing the external carbon source. At a C/N of 3, the total nitrogen removal efficiency of the model denitrifier (P. denitrificans) was increased from 48.1% to 87.4%, with a 63.2% reduction in N2O emission after adding S. oneidensis MR-1 and B. subtilis. Mechanism investigation revealed that the carbon flux for P. denitrificans growth and proliferation remained unchanged but decreased for substrate transport, resulting in more carbon flux to produce more NADH for nitrate bioreduction. Proteomics analysis showed that the decreased carbon flux for substrate transport was due to biosurfactants (surfactin, lichenysin, and fengycin) secreted by B. subtilis, increasing P. denitrificans cell membrane permeability and decreasing substrate uptake via active transport. Moreover, metabolites (riboflavin, heme, and cytochromes) from S. oneidensis MR-1 improved electron transfer, while lichenysin improved P. denitrificans surface hydrophilicity, which promoted the entry of metal ions associated with denitrification into the cell, increasing denitrifying enzyme activity, particularly N2O reductase, ultimately enhancing denitrification and reducing N2O emission.","PeriodicalId":36,"journal":{"name":"环境科学与技术","volume":"24 1","pages":""},"PeriodicalIF":9.028,"publicationDate":"2025-09-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144960157","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":"Supramolecular Assembly of Stimuli-Responsive Protein-Chromophore Conjugate and Triggered Protein Delivery.","authors":"Rajesh Khamrui, Krishna Dan, Suhrit Ghosh","doi":"10.1021/acs.bioconjchem.5c00340","DOIUrl":"https://doi.org/10.1021/acs.bioconjchem.5c00340","url":null,"abstract":"<p><p>Protein delivery has emerged as a powerful therapeutic tool to treat many life-threatening diseases. In this study, we report the synthesis of a protein (Lysozyme = LYS)-supramolecular-structure-directing-unit (SSDU) conjugate using a redox-responsive self-destructive linker, its spontaneous self-assembly in water, intracellular delivery, and selective killing of cancer cells. The LYS surface has a few (on average 6) free amine groups, which were used to attach with the SSDU consisting of a hydrazide-functionalized naphthalene-diimide (NDI) chromophore through a urethane linkage, producing a LYS-NDI conjugate having 3 NDI chromophores on average per protein. LYS-NDI was further labeled with green-emitting FITC to produce LYS-NDI-FITC, which showed spontaneous self-assembly in water, producing near-spherical aggregates of ∼90 nm in size. In such an aggregated state, LYS remained in a dormant state and was protected from enzymatic degradation to a significant extent. In the presence of glutathione (GSH), cleavage of the disulfide bond in the linker produced free thiol, which initiated a cascade reaction through intramolecular nucleophilic attack on the adjacent carbamate linkage, releasing LYS in its active form. The LYS-NDI conjugate showed significantly higher cellular uptake selectively in cancer cells, which produced reactive oxygen species (ROS) leading to cell death. Neither LYS nor NDI showed such prominent cellular uptake or cell killing.</p>","PeriodicalId":29,"journal":{"name":"Bioconjugate Chemistry","volume":" ","pages":""},"PeriodicalIF":3.9,"publicationDate":"2025-09-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144935671","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":"An Atomistic Study of Reactivity in Solid-State Electrolyte Interphase Formation for Li/Li7P3S11","authors":"Bryant Y. Li, Vir Karan, Aaron D. Kaplan, Mingjian Wen, Kristin A. Persson","doi":"10.1021/acs.jpcc.5c03589","DOIUrl":"https://doi.org/10.1021/acs.jpcc.5c03589","url":null,"abstract":"Lithium metal batteries offer superior volumetric and gravimetric specific capacities compared to those based on traditional graphite anodes. Although advancements in solid-state electrolytes address safety concerns, challenges remain, particularly regarding interphase formation in lithium metal anodes. This work presents a computational framework based on high-throughput first-principles density functional theory and machine-learning interatomic potentials (MLIPs) including automated iterative, active learning to enable robust computational exploration of interphase formation between lithium metal anodes and an inorganic solid-state electrolyte. As a demonstration, we apply the framework to a Li/Li₇P₃S₁₁ interface and find that it accurately identifies the experimentally observed, thermodynamically stable interphase products as well as their overall spatial arrangement within a heterogeneous, amorphous layered structure, with Li₂S domains of nanocrystallinity. Our simulations show two stages, a fast and slow diffusion reaction regime, that corroborate the relative phase formation rate of Li_<i>x</i>P, Li₂S, and Li₃P. Using the Onsager transport theory, we capture time-dependent ionic diffusion within the reacting interface, including cross-correlation effects. We found that cross-correlation effects between Li–P and P–S ionic motion significantly influence P-ion diffusion, making it highly sensitive to the local environment and potentially leading to “kinetic trapping” of Li–P phases. The passivation of the interface is shown as the ionic fluxes all approach zero, effectively halting interphase growth.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"43 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2025-09-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144931358","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":"Computational Study of a Copper-Catalyzed Synthesis of Fluoroalcohols from Alkylboranes and Ketones","authors":"Francisco A. Gómez-Mudarra, Gabriel Aullón, Jesús Jover","doi":"10.1021/acs.joc.5c01174","DOIUrl":"https://doi.org/10.1021/acs.joc.5c01174","url":null,"abstract":"Fluoroalcohols are a class of organic compounds containing one or more fluorine atoms together with an alcohol group in their molecular structure. These fluorinated species have a wide range of applications due to their unique properties and are used in medicine and electronics. Herein, we propose a new synthetic procedure, promoted by a copper(I) catalyst, for preparing fluoroalcohols from alkylboranes and symmetric ketones. The reaction has been computationally explored to propose a plausible mechanism, which allows identifying the rate-limiting step and quantitatively evaluating the electronic effects of each substrate on the overall reactivity. These DFT calculations suggest that the combination of electron-poor ketones with electron-rich alkylboranes produces the most efficient catalytic systems for preparing fluoroalcohols. Microkinetic modeling of the studied systems allows the prediction of the activation barrier limit to achieve fully functional reactions, and multilinear regression techniques provide a methodology to estimate the overall reaction barriers in a simple manner, opening the way for proposing new catalytic systems.","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"31 1","pages":""},"PeriodicalIF":4.354,"publicationDate":"2025-09-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144931408","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}