ACS Publications最新文献

{"title":"Halloysite/polyaniline Nanocomposites for Enhanced Actinide Sorption.","authors":"Valery N Bliznyuk, Yuriy V Noskov, Kamila Karniłowicz, Nikolay A Ogurtsov, Scott M Husson, Brian A Powell, Timothy A DeVol, Yuri M Lvov, Alexander A Pud","doi":"10.1021/acsami.5c08795","DOIUrl":"https://doi.org/10.1021/acsami.5c08795","url":null,"abstract":"<p><p>Extracting radionuclides from natural and anthropogenic sources addresses two challenges: remediating contaminated environments and enabling the separation of technologically important isotopes. Understanding how actinides interact and form complexes with polymer-based ligands allows the development of efficient extractants for selective remediation, supporting sustainable environmental protection and resource recovery strategies. Here, we report on the structure and actinide sorption properties of eco-friendly hybrid nanocomposite systems based on the natural mineral halloysite and multifunctional conjugated polymers. Three polyaniline (PANI)-based polymers and their nanocomposites with halloysite nanotubes (HNT) were synthesized and evaluated as sorbents for removing uranium and plutonium from aqueous solutions. The study included two PANI variants synthesized at high (60 °C) and low (1-2 °C) temperatures using different acid-dopants, H₂SO₄ and <i>p</i>-toluenesulfonic acid, and a PANI copolymer incorporating aminoterephthalic acid (PANIATA), which introduces carboxylic functional groups. X-ray photoelectron spectroscopy and electron microscopy revealed the formation of core-shell nanocomposites with HNT as the core and a polymer shell several nanometers thick. The HNT/PANI nanocomposites exhibited a synergistic enhancement in actinide retention capacity, exceeding the additive performance of the individual components. Sorption experiments with artificial groundwater and seawater confirmed the nanocomposites' selectivity for uranium. Analysis of the FTIR spectra of the polymer composites before and after uranium sorption provided detailed insight into uranyl cation-polymer complexation mechanisms responsible for high selectivity and sorption performance.</p>","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":" ","pages":""},"PeriodicalIF":8.2,"publicationDate":"2025-08-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144881635","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Engineering Nanoparticles for Gynecologic Cancer Therapy.","authors":"Amanda M Murray, Kelsey L Swingle, Michael J Mitchell","doi":"10.1021/acsnano.5c07748","DOIUrl":"https://doi.org/10.1021/acsnano.5c07748","url":null,"abstract":"<p><p>The significant morbidity and mortality of gynecologic cancers places a substantial burden on global healthcare and creates an urgent need for new treatment modalities. Here, we explore the emerging role of nanoparticles in treating gynecologic cancers, specifically ovarian, cervical, and endometrial cancers. These diseases are often diagnosed after they have metastasized, developed multidrug resistance, and formed immunosuppressive tumor microenvironments, hampering the effectiveness of traditional debulking surgery and chemotherapy. We first discuss the gynecologic cancer-specific barriers to nanoparticle drug delivery, including systemic and off-target toxicity, peritoneal fluid shear and convective forces, stromal fibrosis, and immunosuppressive tumor microenvironments. We then comprehensively analyze how various nanoparticle drug delivery platforms, such as liposomes, ionizable lipid nanoparticles, and layer-by-layer nanoparticles, have been engineered preclinically to selectively target tumor cells and increase retention within tumor lesions. Additionally, we examine the application of nanoparticles in delivering nucleic acids and immunotherapies, which can heat up immunologically cold tumors and tumor microenvironments to restore antitumor immune function. Despite promising preclinical results, additional efforts are needed to optimize nanoparticle design and ensure safe and effective translation into the clinic for all gynecologic cancers, and we conclude by discussing potential solutions to these barriers. Overall, this review explores the latest preclinical studies and emerging frontiers in nanoparticle therapies for gynecologic cancers, with a focus on efforts to overcome the disease-specific delivery challenges to effectively treat these lethal diseases.</p>","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":" ","pages":""},"PeriodicalIF":16.0,"publicationDate":"2025-08-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144881645","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Nanoscale Miscibility in In Situ Polymerized Hybrid Electrolytes Speeds Up Ion Dynamics and Enables Stable Cycling of Li Metal Batteries.","authors":"M Shahriar, Monojoy Goswami, Jong K Keum, Harry M Meyer Iii, Md Anisur Rahman, Ruhul Amin, Catalin Gainaru, Alexei P Sokolov, Jaswinder Sharma, Georgios Polizos","doi":"10.1021/acsnano.5c08040","DOIUrl":"https://doi.org/10.1021/acsnano.5c08040","url":null,"abstract":"<p><p>While the potential use of copolymerized electrolytes in Li metal batteries is subject to intense investigation, the fundamental understanding of the nanoscale domain formation and its effect on Li⁺ transport is still lacking. In this study, we investigated the correlation between the Li⁺ transport mechanism and the miscibility of monomers in polymer blend electrolytes derived from the in situ copolymerization of methyl methacrylate (MMA) and vinylene carbonate (VC) in the presence of polyethylene glycol dimethyl ether (PEGDME) plasticizer and bis(trifluoromethanesulfonyl)imide (LiTFSI) salt. The addition of a polar short chain plasticizer reduced the dynamic and structural heterogeneities of the electrolyte. Small-angle X-ray scattering (SAXS) measurements and coarse-grained molecular dynamics (MD) simulations were used to investigate the nanoscale structure of the electrolytes. The distribution of relaxation times corresponding to the three distinct diffusion mechanisms of the free and interfacial Li⁺ ions at the copolymer/plasticizer and electrolyte/SEI boundaries was analyzed in a broad temperature range to elucidate the Li⁺ transport mechanism. The chemical composition of the SEI and the contribution of a ceramic lithium lanthanum zirconium oxide (LLZO, Li₇La₃Zr₂O₁₂) phase on the interfacial resistance, salt degradation, and SEI stability were studied by X-ray photoelectron spectroscopy (XPS) depth profile analysis and electrochemical testing.</p>","PeriodicalId":21,"journal":{"name":"ACS Nano","volume":" ","pages":""},"PeriodicalIF":16.0,"publicationDate":"2025-08-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144881646","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Infrared Spectroscopy with Variable Decomposition Level Dual-Tree Complex Wavelet Transform for Quantification of Air Pollutants.","authors":"Yusheng Qin, Xin Han, Xangxian Li, Jianfei Yang, Jingjing Tong, Min-Guang Gao, Yujun Zhang","doi":"10.1021/acs.analchem.5c03806","DOIUrl":"https://doi.org/10.1021/acs.analchem.5c03806","url":null,"abstract":"<p><p>Open-Path Fourier Transform Infrared Spectroscopy (OP-FTIR) is a key active remote sensing technology for detecting and identifying atmospheric pollutants. However, accurately characterizing gaseous pollutants under open-path conditions presents significant challenges, primarily due to the real-time estimation of background spectra. To address this issue, a variable decomposition level dual-tree complex wavelet transform method is proposed for adaptive background spectrum estimation. The algorithm dynamically adjusts the decomposition level based on spectral band characteristics and incorporates nonlinear compression with L1 regularization for enhanced stability under variable environmental conditions. The method was evaluated through both controlled gas cell experiments and field measurements. Compared with high-order Legendre polynomial fitting, it achieved lower average root-mean-square errors for C₂H₄ and C₃H₆ by 7.04 and 19.37%, respectively, indicating improved retrieval accuracy. In addition, it reduced the relative uncertainties for key background gases such as CO₂ and CO across three distinct field sites, demonstrating enhanced robustness under variable environmental conditions. This approach provides a generalizable strategy for background estimation in complex open-path environments, supporting more accurate and scalable OP-FTIR-based gas monitoring.</p>","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":" ","pages":""},"PeriodicalIF":6.7,"publicationDate":"2025-08-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144881653","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Internal Calibration without Internal Calibrants by Mass Difference Analysis in FT-ICR Mass Spectrometry.","authors":"Ryan P Rodgers, Christopher L Hendrickson, Christopher A Holder Montenegro, Alvaro J Tello-Rodriguez, Teja Potu, Benjohn Shung, Mason Hagan, Chad R Weisbrod, Pierre Giusti, Christopher P Rüger, Martha L Aguilera, Germain Salvato Vallverdu","doi":"10.1021/acs.analchem.5c02420","DOIUrl":"https://doi.org/10.1021/acs.analchem.5c02420","url":null,"abstract":"<p><p>We report an improved, fully automated method of mass spectral calibration that relies on mass differences instead of internal calibrants. First, we introduce the mass difference spectrum and note that confident elemental formulas can be assigned to the most abundant mass differences between 0 and 50 Daltons, even for poorly calibrated data. Second, we demonstrate recalibration to as low as 80 ppb rms error by optimizing the measured mass differences, without reference to any known masses in the spectrum. Finally, the improved global calibration facilitates a subsequent \"walking\" calibration that proceeds through simple matrix intersection calculations and ultimately yields confident molecular formula assignments. We apply the method to a variety of complex samples, including petroleum, dissolved organic matter (natural, pyrogenic, anthropogenic), biomass, biofuels, lithium-ion batteries, polymers, aerosols, and emerging environmental contaminants, and others that contain repeated series of mass differences (characteristic \"building blocks\"). Obvious for polymers, but less so for other sample types, the repeated mass spacings can arise from thermal/chemical degradation pathways, combustion/pyrolysis, molecular synthesis methodologies, and/or electrochemical reactions, which are exploited herein for mass spectral recalibration. The method is implemented in an open-source, Python-based, software platform, PyC2MC, which also enables automated batch file processing of time-resolved, complex mass spectral data.</p>","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":" ","pages":""},"PeriodicalIF":6.7,"publicationDate":"2025-08-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144881654","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Multicomponent Protection at Metal/Oxide Interfaces: Electron-Atomic Scale Mechanism of TT-LYK Inhibitor in Cobalt Chemical Mechanical Polishing.","authors":"Lianjun Hu, Qian Sun, Shuping Hou, Yang Wu, Gaoxing Fu, Junkai Shao, Yi Xu","doi":"10.1021/acs.langmuir.5c02460","DOIUrl":"https://doi.org/10.1021/acs.langmuir.5c02460","url":null,"abstract":"<p><p>In the chemical mechanical polishing (CMP) of cobalt (Co), surface planarization is critically influenced by the selective adsorption of inhibitor molecules at the metal/oxide interface. Existing studies have confirmed the presence of CoO and Co(OH)₂ on cobalt surfaces; however, there has been no investigation into the adsorption behavior of inhibitors on these oxide and hydroxide surfaces. This area remains largely unexplored in the current theoretical research landscape. To date, no studies have systematically investigated the cooperative passivation effects of the TT-LYK inhibitor at metal oxide/hydroxide interfaces, nor have they explored its corrosion inhibition mechanisms across multiple cobalt surface phases. In this study, the adsorption behavior and corrosion inhibition mechanism of the TT-LYK inhibitor at cobalt multiphase interfaces, specifically cobalt monoxide (CoO) and cobalt hydroxide (Co(OH)₂), were systematically investigated using density functional theory (DFT) and geometric optimization. Theoretical calculations reveal that TT-LYK exhibits strong chemisorption on both CoO(200) and Co(OH)₂(101) surfaces, with adsorption energies reaching -14.1185, -13.6720, -10.1941, and -10.9807 eV, respectively. Electronic structure analysis indicates that TT-LYK forms stable coordination bonds with surface Co²⁺ ions via its active functional groups, accompanied by significant orbital hybridization and changes in the density of states (DOS). DOS calculations further confirm that TT-LYK adsorption reduces surface reactivity and stabilizes the adsorption configuration. This study provides an atomic-scale explanation of how the inhibitor adsorbs onto the surface of Co oxides and hydroxides, partially isolating the chemical components in the polishing solution from the wafer surface. This helps to slow down undesirable corrosion on the wafer surface, offering a theoretical foundation for the design of high-quality cobalt polishing solutions.</p>","PeriodicalId":50,"journal":{"name":"Langmuir","volume":" ","pages":""},"PeriodicalIF":3.9,"publicationDate":"2025-08-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144881706","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":"Principle and Application of Novel Negative Air (Oxygen) Ion Storage and Release Products.","authors":"Angze Li, Jun Wang, Wei Zhu, Muqing Liu, Shangfeng Liu","doi":"10.1021/acs.molpharmaceut.5c00361","DOIUrl":"https://doi.org/10.1021/acs.molpharmaceut.5c00361","url":null,"abstract":"<p><p>Negative air ions (NAI) are ions present in the air that enhance blood oxygen absorption and utilization, stimulate metabolism, and modulate mood and nervous system activity. However, the application of NAI has been limited by storage challenges and low concentrations due to the conditions under which they are produced and the nature of the ions themselves. In order to overcome these limitations and develop NAI as a viable method of treatment, we have introduced a novel, highly concentrated NAI prodrug that incorporates NAI into flaxseed oil. This innovative drug can be administered in liquid, semiliquid, and dietary forms. Additionally, we have explored various NAI-related actions and mechanisms, such as the antiaging effects of these drugs through ROS inhibition. Our research has shown that NAI agents can penetrate the brain through the skin and the blood-brain barrier, rapidly reoxygenating cells throughout the body. Particularly, NAI has demonstrated excellent antitumor and cognitive-enhancing properties. These findings have significant implications for the potential of our NAI-based prodrug as a groundbreaking approach in antiaging therapy, providing a novel strategy for enhancing endogenous oxygenation and treating respiratory compromise and beyond.</p>","PeriodicalId":52,"journal":{"name":"Molecular Pharmaceutics","volume":" ","pages":""},"PeriodicalIF":4.5,"publicationDate":"2025-08-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144881713","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"医学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Combination DFT and Molecular Dynamics Study on Noncatalytic Reduction of Nitrogen Oxide by Furan during Cocombustion with Biomass: Soot Inhibition and Nitrogen Evolution.","authors":"Shanhui Zhao, Siwen Zhang, Haiming Gu, Wanjun Xu","doi":"10.1021/acs.jpca.5c04130","DOIUrl":"https://doi.org/10.1021/acs.jpca.5c04130","url":null,"abstract":"<p><p>Using biotar as a reburning fuel is a potential method for NO reduction. Furan, a typical biomass tar compound, is used to study NO reduction during cocombustion with biomass. The combination density functional theory (DFT) and ReaxFF molecular dynamics (MD) methods were used to study the detailed mechanism at the molecular level. ReaxFF MD simulation results indicate that significant decomposition of furan occurs at temperatures above 2000 K, releasing small molecular products such as CO. At 3000 K, the decomposition process is accompanied by polymerization reactions, leading to the formation of substantial amounts of soot. The reaction results of the NO and furan mixture system indicate that the presence of NO inhibits the formation of soot during furan decomposition. Conversely, furan plays a significant role in promoting the reduction of NO. Furan undergoes significant conversion at lower temperatures, suggesting that NO can directly oxidize furan molecules. HNO is recognized as a key intermediate. DFT calculations reveal that the activation energy required for the direct oxidation of furan by NO is 228.2 kJ/mol, which is much lower than that for the direct decomposition of furan, which is 311.13 kJ/mol. The research results theoretically demonstrate the feasibility of using furan-type biomass tar as a reburning fuel for NO reduction. This holds significant importance for biomass gasification coupled with coal-fired technology.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":" ","pages":""},"PeriodicalIF":2.8,"publicationDate":"2025-08-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144881727","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":"Fully Triazine-Based Covalent Framework for Antibacterial Phototreatment with High Biosafety.","authors":"Hu Liu, Ruoyan Miao, Xiaoying Zhao, Xiaolong Du, Lizhen Liu, Wenfeng Li, Zhenhui Ma, Liang Zhang, Jianzheng He, Zhichuan J Xu","doi":"10.1021/acsami.5c07582","DOIUrl":"https://doi.org/10.1021/acsami.5c07582","url":null,"abstract":"<p><p>The application of antibacterial photocatalytic therapy remains a great challenge due to the limitations of photocatalytic efficiency and biosafety of photocatalysts. Herein, we report an organic semiconductor catalyst featuring a unique covalent triazine framework (CTF) structure, which is entirely composed of triazine-based rings. This catalyst exhibits the lowest forbidden bandgap, full spectral absorption range, and high biosafety, achieving a record-high antibacterial activity under visible light irradiation. The experimental and theoretical results confirm that the CTF structure broadens the light absorption range of carbon nitride and enhances the separation efficiency of photogenerated electron-hole pairs, which improves the photocatalytic activity. The unique CTF structure not only exhibits excellent antibacterial activity toward both <i>Escherichia coli</i> and <i>Staphylococcus aureus</i> but also eradicates <i>Staphylococcus aureus</i> in a mouse wound infection model and greatly promotes wound healing. The in vivo toxicity evaluation was conducted on the physiological activities of Drosophila, confirming the high biosafety and great potential of as-prepared CTF/poly(vinyl alcohol) hydrogel for antibacterial and wound healing applications.</p>","PeriodicalId":5,"journal":{"name":"ACS Applied Materials & Interfaces","volume":" ","pages":""},"PeriodicalIF":8.2,"publicationDate":"2025-08-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144870154","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Bias-Modulated Dual-Channel Photoelectrochemical Immunosensor Enabled by a Dual-Responsive Nanolabel.","authors":"Yujia Dong, Yong Hao, Haiyang Li, Yongxin Shi, Wenli Zhao, Huan Wang, Hongmin Ma","doi":"10.1021/acs.analchem.5c02947","DOIUrl":"https://doi.org/10.1021/acs.analchem.5c02947","url":null,"abstract":"<p><p>Photoelectrochemical (PEC) immunosensors have attracted extensive attention in biomarker detection owing to their high sensitivity, operational simplicity, and low cost. However, conventional PEC sensors are susceptible to generate false-positive results in complex biological matrices, due to nonspecific binding at the sensing interfaces. The dual-channel design can reduce the false detection rate and improve detection accuracy through mutual verification and complementation of the two signals, we demonstrate herein a novel bias-modulated dual-channel PEC immunosensor for the efficient detection of the breast cancer biomarker CA15-3. Two photoactive materials, In₄SnS₈/Bi₂O₂S and BiOBr_0.8I_0.2, are separately assembled on an indium tin oxide (ITO) electrode and act as anode and cathode sensing regions, respectively. By precisely tuning the bias of the electrode, anode and cathode PEC signals can be acquired independently. Furthermore, ZnFe₂O₄ is exploited as a dual-responsive nanolabel, which can enhance the anode signal but reduce the cathode signal when attached to the electrode by immunorecognition. The two independent noninterfering signals on one electrode were integrated to enhance both sensitivity and accuracy. This work offers a new strategy for early breast cancer screening and holds significant promise for clinical diagnostic applications.</p>","PeriodicalId":27,"journal":{"name":"Analytical Chemistry","volume":" ","pages":""},"PeriodicalIF":6.7,"publicationDate":"2025-08-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144870177","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}