The stability of molecularly imprinted membranes (MIMs) is a critical factor influencing their reusability and detection performance. To overcome stability limitations, a robust porous imprinted hydrogel membrane (porous PVA/HS-β-CD/Ag/MIPs) was developed by grafting recognition sites onto a porous framework. The membrane was synthesized through a multistep process: (i) A porous hydrogel matrix was formed via freeze–thaw-induced cross-linking between poly(vinyl alcohol) (PVA) and thiolated β-cyclodextrin (HS-β-CD), combined with the use of a pore-forming agent; (ii) the membrane was functionalized as a surface-enhanced Raman scattering (SERS) substrate through in situ reduction of silver ions (from AgNO3); (iii) glyphosate (GLY)-imprinted polymers were anchored via precipitation polymerization, utilizing HS-β-CD as grafting sites to achieve specific recognition and detection. Morphological and stability analyses demonstrated that the SERS-imprinted porous membrane exhibits high structural integrity, retaining 94.89% of its detection capability after 12 h under continuous water flow. This study introduces a robust covalent anchoring strategy between the imprinting layer and the substrate to form chemical cross-linking, providing an effective pathway for designing high-performance, long-lifespan molecularly imprinted membranes.
{"title":"A Stable, Molecularly Imprinted Porous Hydrogel Membrane via Chemical Cross-Linking for Glyphosate Detection","authors":"Wen Xin,Yajun Ren,Xiaofeng Song,Honghui Teng,Mingyue Jin,Menghao Tian","doi":"10.1021/acs.langmuir.5c05698","DOIUrl":"https://doi.org/10.1021/acs.langmuir.5c05698","url":null,"abstract":"The stability of molecularly imprinted membranes (MIMs) is a critical factor influencing their reusability and detection performance. To overcome stability limitations, a robust porous imprinted hydrogel membrane (porous PVA/HS-β-CD/Ag/MIPs) was developed by grafting recognition sites onto a porous framework. The membrane was synthesized through a multistep process: (i) A porous hydrogel matrix was formed via freeze–thaw-induced cross-linking between poly(vinyl alcohol) (PVA) and thiolated β-cyclodextrin (HS-β-CD), combined with the use of a pore-forming agent; (ii) the membrane was functionalized as a surface-enhanced Raman scattering (SERS) substrate through in situ reduction of silver ions (from AgNO3); (iii) glyphosate (GLY)-imprinted polymers were anchored via precipitation polymerization, utilizing HS-β-CD as grafting sites to achieve specific recognition and detection. Morphological and stability analyses demonstrated that the SERS-imprinted porous membrane exhibits high structural integrity, retaining 94.89% of its detection capability after 12 h under continuous water flow. This study introduces a robust covalent anchoring strategy between the imprinting layer and the substrate to form chemical cross-linking, providing an effective pathway for designing high-performance, long-lifespan molecularly imprinted membranes.","PeriodicalId":50,"journal":{"name":"Langmuir","volume":"82 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2026-02-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146098103","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}
Pub Date : 2026-02-02DOI: 10.1021/acs.langmuir.5c06707
Zhiwu Chen,Yapei Wang
The utilization of low-grade waste heat and the demand for detecting physical signals with the presence of heat as their manifestation, have driven the refinement and advancement of thermoelectric concepts in theory, materials, devices, and applications. Ionic thermoelectric materials, characterized by low cost, flexibility, and high ionic Seebeck coefficients, are emerging as the next-generation medium for the utilization and conversion of thermal energy. The Soret effect, also known as ion thermal diffusion is broadly recognized as the primary driving force for energy conversion in ionic thermoelectric materials. Significant efforts have been dedicated to material chemistry design, theoretical modeling, and thermoelectric voltage enhancement within the theoretical framework of the Soret effect. However, tracing the evolution of ionic thermoelectric concepts, another theoretical perspective has persisted throughout. Although widely overlooked, the equally critical electrode–electrolyte interface has increasingly been proven to be central to the generation of thermoelectric voltage, and the derived asymmetric interfacial ion rearrangement effect stands as a hidden gem in this field. Given the lack of consensus in the ionic thermoelectric theory, the organization of this review is both timely and necessary. This article will comprehensively review the historical development and relevant theories of nonfaradaic ionic thermoelectric conversion, and thoroughly analyze the mechanisms and relative contributions of the Soret effect and asymmetric interfacial ion rearrangement. The new opportunities presented by the theory of asymmetric interfacial ion rearrangement for the structure and performance of thermoelectric devices will be highlighted. It will conclude by outlining the key challenges and research priorities facing this field in its future development.
{"title":"Nonfaradaic Ionic Thermoelectric Conversion: The Soret Effect or Asymmetric Interfacial Ion Rearrangement?","authors":"Zhiwu Chen,Yapei Wang","doi":"10.1021/acs.langmuir.5c06707","DOIUrl":"https://doi.org/10.1021/acs.langmuir.5c06707","url":null,"abstract":"The utilization of low-grade waste heat and the demand for detecting physical signals with the presence of heat as their manifestation, have driven the refinement and advancement of thermoelectric concepts in theory, materials, devices, and applications. Ionic thermoelectric materials, characterized by low cost, flexibility, and high ionic Seebeck coefficients, are emerging as the next-generation medium for the utilization and conversion of thermal energy. The Soret effect, also known as ion thermal diffusion is broadly recognized as the primary driving force for energy conversion in ionic thermoelectric materials. Significant efforts have been dedicated to material chemistry design, theoretical modeling, and thermoelectric voltage enhancement within the theoretical framework of the Soret effect. However, tracing the evolution of ionic thermoelectric concepts, another theoretical perspective has persisted throughout. Although widely overlooked, the equally critical electrode–electrolyte interface has increasingly been proven to be central to the generation of thermoelectric voltage, and the derived asymmetric interfacial ion rearrangement effect stands as a hidden gem in this field. Given the lack of consensus in the ionic thermoelectric theory, the organization of this review is both timely and necessary. This article will comprehensively review the historical development and relevant theories of nonfaradaic ionic thermoelectric conversion, and thoroughly analyze the mechanisms and relative contributions of the Soret effect and asymmetric interfacial ion rearrangement. The new opportunities presented by the theory of asymmetric interfacial ion rearrangement for the structure and performance of thermoelectric devices will be highlighted. It will conclude by outlining the key challenges and research priorities facing this field in its future development.","PeriodicalId":50,"journal":{"name":"Langmuir","volume":"82 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2026-02-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146098096","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}
A chitosan-coated biochar sphere (BC-CG-CT) was fabricated via facile copyrolysis of municipal sewage sludge (SS) and coal gangue (CG), followed by ionic gelation encapsulation. Under optimized conditions (650 °C pyrolysis, 100 min, SS:CG = 1:1), BC-CG-CT achieved a maximum Cr(VI) adsorption capacity of 23.85 mg·g–1 and removal rates above 97% at pH 5 in aqueous systems. Kinetic and isotherm studies revealed a dominant pseudo-first-order behavior, monolayer adsorption, and energetically favorable interactions. Thermodynamic analysis indicated spontaneous, endothermic adsorption. In soil incubation tests (90 days, up to 300 g·kg–1 dosage), BC-CG-CT reduced soluble Cr(VI) by up to 57.6%, shifted Cr fractionation from labile (EX/CB) to stable (OX/RS) pools, elevated soil pH and TOC, and suppressed CaCl2-extractable Cr to below 0.1 mg·kg–1. Mechanistic investigations combining SEM-EDS, XRD, FTIR, and XPS confirmed synergistic immobilization via pore-filling, electrostatic adsorption, Cr(VI) reduction by electron-donor groups, and complexation/precipitation. The robust spherical morphology enhances recoverability and reuse. This work demonstrates a promising and sustainable strategy for simultaneous remediation of Cr(VI) in water and soil, leveraging industrial and municipal waste valorization.
{"title":"Chitosan-Coated Sewage Sludge–Coal Gangue Biochar Spheres for Efficient Cr(VI) Removal from Water and Soil","authors":"Xiao Ma,Xingyu Liu,Hongtao Wu,Yuxuan Li,Junlun Mei,Qiao Xiong","doi":"10.1021/acs.langmuir.5c05407","DOIUrl":"https://doi.org/10.1021/acs.langmuir.5c05407","url":null,"abstract":"A chitosan-coated biochar sphere (BC-CG-CT) was fabricated via facile copyrolysis of municipal sewage sludge (SS) and coal gangue (CG), followed by ionic gelation encapsulation. Under optimized conditions (650 °C pyrolysis, 100 min, SS:CG = 1:1), BC-CG-CT achieved a maximum Cr(VI) adsorption capacity of 23.85 mg·g–1 and removal rates above 97% at pH 5 in aqueous systems. Kinetic and isotherm studies revealed a dominant pseudo-first-order behavior, monolayer adsorption, and energetically favorable interactions. Thermodynamic analysis indicated spontaneous, endothermic adsorption. In soil incubation tests (90 days, up to 300 g·kg–1 dosage), BC-CG-CT reduced soluble Cr(VI) by up to 57.6%, shifted Cr fractionation from labile (EX/CB) to stable (OX/RS) pools, elevated soil pH and TOC, and suppressed CaCl2-extractable Cr to below 0.1 mg·kg–1. Mechanistic investigations combining SEM-EDS, XRD, FTIR, and XPS confirmed synergistic immobilization via pore-filling, electrostatic adsorption, Cr(VI) reduction by electron-donor groups, and complexation/precipitation. The robust spherical morphology enhances recoverability and reuse. This work demonstrates a promising and sustainable strategy for simultaneous remediation of Cr(VI) in water and soil, leveraging industrial and municipal waste valorization.","PeriodicalId":50,"journal":{"name":"Langmuir","volume":"292 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2026-02-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146098140","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}
Through dual encapsulation of the insecticide lufenuron with β-cyclodextrin octadecanoate and urea-formaldehyde resin, a lufenuron@β-cyclodextrin octadecanoate/urea formaldehyde resin (LF@β-CDs/UF) nanoformulation was prepared. This dual-carrier synergy significantly prolonged the release cycle of lufenuron and enhanced environmental adaptability. Results demonstrated that under 25 °C and pH 7 conditions, its release cycle reached 324 h in 20% methanol-water, representing a 1.5-fold prolongation compared to the single-carrier lufenuron@β-cyclodextrin octadecanoate (LF@β-CDs) nanoformulation, with a pH/temperature-responsive release behavior. The photolysis half-life (t50) was extended by 1.6- and 9.3-fold compared to LF@β-CDs (51 h) and lufenuron (LF) microemulsion (8.9 h), respectively. At a low concentration of 6.25 mg/L, the mortality rate against Spodoptera litura reached 73.33%, significantly outperforming LF@β-CDs (29.33%) and LF microemulsion (5.33%). The LF@β-CDs/UF also substantially prolonged insecticidal duration and enhanced the systemic translocation of lufenuron in plants. Biosafety assessment showed that it significantly reduced ecological toxicity, increasing rice seed germination rates from 40.7% (microemulsion) to 71.3% at 400 mg/L seed-soaking concentration, while elevating the acute toxicity LC50 value in zebrafish by 4.4-fold, demonstrating substantially comparative eco-friendliness compared to conventional formulations. This dual-carrier technology, via structure-function synergy, provides an innovative solution to challenges such as low pesticide utilization efficiency and high environmental risks.
{"title":"Lufenuron Dual-Carrier Nanoformulation: Controlled Release and Systemic Translocation viaβ-Cyclodextrin Octadecanoate and Urea-Formaldehyde Resin.","authors":"Zhiping Liu, Jiansheng Li, Yanmin Huang, Weiguo Li, Chunrui Cai, Qiang Hu, Yanlin Chen, Jianguo Cui","doi":"10.1021/acs.langmuir.5c05447","DOIUrl":"https://doi.org/10.1021/acs.langmuir.5c05447","url":null,"abstract":"<p><p>Through dual encapsulation of the insecticide lufenuron with β-cyclodextrin octadecanoate and urea-formaldehyde resin, a lufenuron@β-cyclodextrin octadecanoate/urea formaldehyde resin (LF@β-CDs/UF) nanoformulation was prepared. This dual-carrier synergy significantly prolonged the release cycle of lufenuron and enhanced environmental adaptability. Results demonstrated that under 25 °C and pH 7 conditions, its release cycle reached 324 h in 20% methanol-water, representing a 1.5-fold prolongation compared to the single-carrier lufenuron@β-cyclodextrin octadecanoate (LF@β-CDs) nanoformulation, with a pH/temperature-responsive release behavior. The photolysis half-life (<i>t</i><sub>50</sub>) was extended by 1.6- and 9.3-fold compared to LF@β-CDs (51 h) and lufenuron (LF) microemulsion (8.9 h), respectively. At a low concentration of 6.25 mg/L, the mortality rate against <i>Spodoptera litura</i> reached 73.33%, significantly outperforming LF@β-CDs (29.33%) and LF microemulsion (5.33%). The LF@β-CDs/UF also substantially prolonged insecticidal duration and enhanced the systemic translocation of lufenuron in plants. Biosafety assessment showed that it significantly reduced ecological toxicity, increasing rice seed germination rates from 40.7% (microemulsion) to 71.3% at 400 mg/L seed-soaking concentration, while elevating the acute toxicity LC<sub>50</sub> value in zebrafish by 4.4-fold, demonstrating substantially comparative eco-friendliness compared to conventional formulations. This dual-carrier technology, via structure-function synergy, provides an innovative solution to challenges such as low pesticide utilization efficiency and high environmental risks.</p>","PeriodicalId":50,"journal":{"name":"Langmuir","volume":" ","pages":""},"PeriodicalIF":3.9,"publicationDate":"2026-02-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146103059","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}
Solid–liquid interfacial energy critically governs microstructural evolution and the functional properties of materials during phase transition. Here, we quantitatively characterize the anisotropy of solid–liquid interfacial energy in an Al-30 wt % Zn hypoeutectic alloy using the improved equilibrium shape method, X-ray microcomputed tomography (CT), and digital image analysis. We obtained the two-dimensional (ε4) and three-dimensional (ξ1, ξ2) anisotropy parameters by fitting droplet shapes with Fourier series and cubic harmonics. The interfacial energy is largest along the ⟨100⟩ and ⟨110⟩ directions, while the interfacial stiffness is smallest along the same directions. The near equivalence of stiffness between the ⟨100⟩ and ⟨110⟩ directions suppresses stable tip selection, destabilizes the growth front, and promotes hyperbranched, seaweed-like morphologies. This study provides quantitative evidence linking interfacial anisotropy to dendrite pattern formation and offers mechanistic insight into the morphological instability of Al–Zn alloys.
{"title":"Formation of the Pattern of Al–Zn Dendrites Driven by Solid–Liquid Interfacial Energy","authors":"Lele Chen,Chenglin Huang,Fang Luo,Sansan Shuai,Lei Wang,Tao Hu,Yang Yang,Jiang Wang,Zhongming Ren","doi":"10.1021/acs.langmuir.5c06494","DOIUrl":"https://doi.org/10.1021/acs.langmuir.5c06494","url":null,"abstract":"Solid–liquid interfacial energy critically governs microstructural evolution and the functional properties of materials during phase transition. Here, we quantitatively characterize the anisotropy of solid–liquid interfacial energy in an Al-30 wt % Zn hypoeutectic alloy using the improved equilibrium shape method, X-ray microcomputed tomography (CT), and digital image analysis. We obtained the two-dimensional (ε4) and three-dimensional (ξ1, ξ2) anisotropy parameters by fitting droplet shapes with Fourier series and cubic harmonics. The interfacial energy is largest along the ⟨100⟩ and ⟨110⟩ directions, while the interfacial stiffness is smallest along the same directions. The near equivalence of stiffness between the ⟨100⟩ and ⟨110⟩ directions suppresses stable tip selection, destabilizes the growth front, and promotes hyperbranched, seaweed-like morphologies. This study provides quantitative evidence linking interfacial anisotropy to dendrite pattern formation and offers mechanistic insight into the morphological instability of Al–Zn alloys.","PeriodicalId":50,"journal":{"name":"Langmuir","volume":"117 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2026-02-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146098097","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}
Pub Date : 2026-02-02DOI: 10.1021/acs.langmuir.5c05232
Chenying Wang,Sangyeon Lee,Vidhya Chakrapani
Spontaneous generation of reactive oxygen species (ROS), such as H2O2, OH*, and O2–*, is known to occur at aqueous aerosol microdroplets or gas microbubbles in bulk water. However, the suggested mechanisms of their formation remain contentious because they posit the breaking of highly stable water bonds. In addition, the primary ROS that is the source for other ROS has also not been established. Herein, we evaluate ROS generation in much simpler macroscopic gas bubbles in the bulk electrolyte. Through in situ studies with electrolytes containing different anions (CO32–, HCO3–, SO42–, H2PO4–, and Cl–), cations (Na+, K+, and Li+), and pH and sparged with gases (O2, CH4, N2, and CO2), we show that ROS generation occurs through the hitherto unrecognized activation of CO2/HCO3–/CO32– that is present inadvertently in all air-exposed aqueous system. In addition, ROS-specific scavenging studies show that H2O2 is the primary ROS produced that serves as the source for OH*, O2–*, and 1O2 generation. The combined evidence suggests that the underlying mechanism may be much more complex than simple bond breakage; rather, it may be electrochemical in origin, with coupled sets of reduction/oxidation reactions occurring at the bubble/water interface.
{"title":"Bicarbonate-Mediated Generation of H2O2, 1O2, and OH* at the Hydrophobic Gas–Water Interface and Its Underlying Mechanism","authors":"Chenying Wang,Sangyeon Lee,Vidhya Chakrapani","doi":"10.1021/acs.langmuir.5c05232","DOIUrl":"https://doi.org/10.1021/acs.langmuir.5c05232","url":null,"abstract":"Spontaneous generation of reactive oxygen species (ROS), such as H2O2, OH*, and O2–*, is known to occur at aqueous aerosol microdroplets or gas microbubbles in bulk water. However, the suggested mechanisms of their formation remain contentious because they posit the breaking of highly stable water bonds. In addition, the primary ROS that is the source for other ROS has also not been established. Herein, we evaluate ROS generation in much simpler macroscopic gas bubbles in the bulk electrolyte. Through in situ studies with electrolytes containing different anions (CO32–, HCO3–, SO42–, H2PO4–, and Cl–), cations (Na+, K+, and Li+), and pH and sparged with gases (O2, CH4, N2, and CO2), we show that ROS generation occurs through the hitherto unrecognized activation of CO2/HCO3–/CO32– that is present inadvertently in all air-exposed aqueous system. In addition, ROS-specific scavenging studies show that H2O2 is the primary ROS produced that serves as the source for OH*, O2–*, and 1O2 generation. The combined evidence suggests that the underlying mechanism may be much more complex than simple bond breakage; rather, it may be electrochemical in origin, with coupled sets of reduction/oxidation reactions occurring at the bubble/water interface.","PeriodicalId":50,"journal":{"name":"Langmuir","volume":"29 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2026-02-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146098142","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}
Pub Date : 2026-02-01DOI: 10.1021/acs.langmuir.5c06766
Min Seok Kang,Yejun Ham,Won Cheol Yoo
Graphite offers attractive properties for lithium-metal hosting, including high electrical conductivity, chemical stability, and mechanical robustness, but its dense structure, low porosity, and basal-plane lithiophobicity hinder uniform Li plating. These limitations cause high nucleation barriers and uneven ion transport, rendering conventional graphite ineffective as a practical Li-metal host. Here, we introduce a molten NaCl─assisted low-temperature (650–950 °C) magnesiothermic reduction strategy that reconstructs polymer spheres into flake-like porous multilayered graphene (FMG) with highly aligned graphitic layers, hierarchical meso–macroporosity, and low tortuosity (∼3). The molten salt acts as both a thermal reservoir and structure-directing medium, moderating the exothermic Mg–oxygen reaction, suppressing Mg volatilization, and enabling facet-selective graphitic reorganization inaccessible through conventional reduction routes. As a Li host, FMG achieves uniform Li nucleation with an ultralow overpotential (20 mV), long-term symmetric cycling over 3000 h, and high Coulombic efficiency (98.2% over 400 cycles). LFP||FMG@Li full cells further demonstrate stable capacity retention, underscoring how molten-salt-driven structural engineering transforms graphite from an intrinsically incompatible material into an architecturally optimized host for high-energy lithium-metal batteries.
{"title":"Engineering Low-Tortuosity Flake-Like Graphitic Carbon via Molten-Salt-Mediated Magnesiothermic Reduction for Lithium Metal Anodes","authors":"Min Seok Kang,Yejun Ham,Won Cheol Yoo","doi":"10.1021/acs.langmuir.5c06766","DOIUrl":"https://doi.org/10.1021/acs.langmuir.5c06766","url":null,"abstract":"Graphite offers attractive properties for lithium-metal hosting, including high electrical conductivity, chemical stability, and mechanical robustness, but its dense structure, low porosity, and basal-plane lithiophobicity hinder uniform Li plating. These limitations cause high nucleation barriers and uneven ion transport, rendering conventional graphite ineffective as a practical Li-metal host. Here, we introduce a molten NaCl─assisted low-temperature (650–950 °C) magnesiothermic reduction strategy that reconstructs polymer spheres into flake-like porous multilayered graphene (FMG) with highly aligned graphitic layers, hierarchical meso–macroporosity, and low tortuosity (∼3). The molten salt acts as both a thermal reservoir and structure-directing medium, moderating the exothermic Mg–oxygen reaction, suppressing Mg volatilization, and enabling facet-selective graphitic reorganization inaccessible through conventional reduction routes. As a Li host, FMG achieves uniform Li nucleation with an ultralow overpotential (20 mV), long-term symmetric cycling over 3000 h, and high Coulombic efficiency (98.2% over 400 cycles). LFP||FMG@Li full cells further demonstrate stable capacity retention, underscoring how molten-salt-driven structural engineering transforms graphite from an intrinsically incompatible material into an architecturally optimized host for high-energy lithium-metal batteries.","PeriodicalId":50,"journal":{"name":"Langmuir","volume":"95 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2026-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146097879","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}
Pub Date : 2026-02-01DOI: 10.1021/acs.langmuir.5c05572
Matija Popović, Tea Frey, Mladen Borovina, Ivan Kodrin, Ivana Biljan
The increased concentration of atmospheric CO2 and its impact on the environment drive the search for new materials that can capture and store this greenhouse gas effectively. Porous organic polymers (POPs) are very promising materials for this task because of their stability and the tunability of their pore structure and chemistry. In this study, we synthesized a series of azo-linked porphyrin-based porous organic polymers (APPs) using either heteroatom-containing linkers (hydroxylated biphenyl in APP-BP-OH and carbonyl-bearing anthraquinone in APP-AQ) or sterically hindered linkers (methylated biphenyl and phenyl in APP-BP-Me and APP-Ph-Me, respectively). Structural characterization confirmed the formation of azo linkages and the amorphous nature of the frameworks, while thermal analysis showed that APPs are stable up to at least 200 °C. Gas sorption studies revealed notable differences in porosity and CO2 uptake. APP-Ph-Me exhibited the largest surface area (673 m2 g–1), whereas APP-BP-OH had a smaller surface area (488 m2 g–1) but adsorbed more CO2 (49 mg g–1) compared to APP-Ph-Me (41 mg g–1). These results illustrate that CO2 adsorption in APPs is governed by not only the surface area but also the chemical environment. Nitrogen-rich porphyrin and azo moieties play a dominant role, while polar hydroxyl groups and biphenyl linkers provide additional contributions. Computational results supported these findings, indicating that hydroxyl and carbonyl groups create favorable binding sites, while methyl groups limit accessibility to porphyrin and azo regions. Overall, our results highlight how linker design and functionalization directly influence porosity and adsorption performance and offer useful guidelines for the development of new POPs for CO2 capture.
{"title":"Tuning Linkers in Azo-Linked Porphyrin-Based Porous Organic Polymers for Enhanced CO2 Capture","authors":"Matija Popović, Tea Frey, Mladen Borovina, Ivan Kodrin, Ivana Biljan","doi":"10.1021/acs.langmuir.5c05572","DOIUrl":"https://doi.org/10.1021/acs.langmuir.5c05572","url":null,"abstract":"The increased concentration of atmospheric CO<sub>2</sub> and its impact on the environment drive the search for new materials that can capture and store this greenhouse gas effectively. Porous organic polymers (POPs) are very promising materials for this task because of their stability and the tunability of their pore structure and chemistry. In this study, we synthesized a series of azo-linked porphyrin-based porous organic polymers (APPs) using either heteroatom-containing linkers (hydroxylated biphenyl in APP-BP-OH and carbonyl-bearing anthraquinone in APP-AQ) or sterically hindered linkers (methylated biphenyl and phenyl in APP-BP-Me and APP-Ph-Me, respectively). Structural characterization confirmed the formation of azo linkages and the amorphous nature of the frameworks, while thermal analysis showed that APPs are stable up to at least 200 °C. Gas sorption studies revealed notable differences in porosity and CO<sub>2</sub> uptake. APP-Ph-Me exhibited the largest surface area (673 m<sup>2</sup> g<sup>–1</sup>), whereas APP-BP-OH had a smaller surface area (488 m<sup>2</sup> g<sup>–1</sup>) but adsorbed more CO<sub>2</sub> (49 mg g<sup>–1</sup>) compared to APP-Ph-Me (41 mg g<sup>–1</sup>). These results illustrate that CO<sub>2</sub> adsorption in APPs is governed by not only the surface area but also the chemical environment. Nitrogen-rich porphyrin and azo moieties play a dominant role, while polar hydroxyl groups and biphenyl linkers provide additional contributions. Computational results supported these findings, indicating that hydroxyl and carbonyl groups create favorable binding sites, while methyl groups limit accessibility to porphyrin and azo regions. Overall, our results highlight how linker design and functionalization directly influence porosity and adsorption performance and offer useful guidelines for the development of new POPs for CO<sub>2</sub> capture.","PeriodicalId":50,"journal":{"name":"Langmuir","volume":"8 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2026-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146095665","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}
Pores are common processing defects, yet their effects on the mechanical and tribological properties of high-entropy alloys (HEAs) remain unclear. In this study, molecular dynamics simulations were conducted to systematically explore the influence of pore size on mechanical behavior and deformation mechanisms of a single-crystal FCC CoNiCrFeMn HEA during nanoindentation and scratch processes. Introducing pores leads to a noticeable decrease in hardness and a rise in potential energy, ultimately promoting greater deformability. During scratch, porous models exhibit lower friction forces and fewer wear atoms, exhibiting beneficial wear reduction properties. Compared to dense counterparts, porous structures induce localized shear concentrations around pores. Larger pores offer more space for accommodating plastic deformation and are correlated with a reduced dislocation density near the contact region. Furthermore, pores act as efficient dislocation barriers, restricting their propagation within the alloy matrix. By varying the simulation temperature and scratch speed, we further analyze their effects on deformation behavior in porous HEAs. Elevated temperatures intensify atomic rearrangements, causing pronounced material softening and reduced dislocation density. Conversely, higher scratch speeds increase frictional force and indentation load and weaken crystal plasticity.
{"title":"Interfacial Wear Reduction of Porous CoNiCrFeMn High-Entropy Alloys: An Atomic-Scale Study","authors":"Shaocong Zhou, Yongchao Liang, Yuanwei Pu, Yu Zhou, Xiuzhen Tang, Lili Zhou, Qian Chen, Zean Tian, Tinghong Gao","doi":"10.1021/acs.langmuir.5c06190","DOIUrl":"https://doi.org/10.1021/acs.langmuir.5c06190","url":null,"abstract":"Pores are common processing defects, yet their effects on the mechanical and tribological properties of high-entropy alloys (HEAs) remain unclear. In this study, molecular dynamics simulations were conducted to systematically explore the influence of pore size on mechanical behavior and deformation mechanisms of a single-crystal FCC CoNiCrFeMn HEA during nanoindentation and scratch processes. Introducing pores leads to a noticeable decrease in hardness and a rise in potential energy, ultimately promoting greater deformability. During scratch, porous models exhibit lower friction forces and fewer wear atoms, exhibiting beneficial wear reduction properties. Compared to dense counterparts, porous structures induce localized shear concentrations around pores. Larger pores offer more space for accommodating plastic deformation and are correlated with a reduced dislocation density near the contact region. Furthermore, pores act as efficient dislocation barriers, restricting their propagation within the alloy matrix. By varying the simulation temperature and scratch speed, we further analyze their effects on deformation behavior in porous HEAs. Elevated temperatures intensify atomic rearrangements, causing pronounced material softening and reduced dislocation density. Conversely, higher scratch speeds increase frictional force and indentation load and weaken crystal plasticity.","PeriodicalId":50,"journal":{"name":"Langmuir","volume":"42 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2026-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146095748","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}
Interleukin-6 (IL-6) is a crucial biomarker for monitoring inflammatory responses and chronic diseases, including cancer. In this work, we present a novel label-free aptasensor that combines copper nanoparticles (CuNPs) with a light-addressable potentiometric sensor (LAPS) platform, enabling the highly-sensitive detection of IL-6. The presence of CuNPs significantly enhances electron transfer dynamics and potentiometric signal amplification, while IL-6-specific Aptamers offer high molecular recognition and binding affinity. The sensor transduces IL-6 binding events into detectable potential shifts, enabling quantitative analysis. The device exhibited exceptional selectivity in the presence of potential interfering substances, maintained high stability over multiple measurement cycles, and showed strong reproducibility. Under optimized parameters, the sensor achieved a wide linear detection range from 5 to 200 ng/mL, with a remarkably low detection limit of 2.1 pg/mL. Additionally, its successful performance in spiked human serum samples highlights its practicality and robustness for clinical diagnostic applications.
{"title":"Aptamer-Functionalized CuNPs for Label-Free and Highly-Sensitive Detection of Interleukin-6 Using a Light-Addressable Potentiometric Sensor","authors":"Beenish Noureen,Miaomiao Wang,Yating Chen,Wei Chen,Liping Du,Chunsheng Wu","doi":"10.1021/acs.langmuir.5c05621","DOIUrl":"https://doi.org/10.1021/acs.langmuir.5c05621","url":null,"abstract":"Interleukin-6 (IL-6) is a crucial biomarker for monitoring inflammatory responses and chronic diseases, including cancer. In this work, we present a novel label-free aptasensor that combines copper nanoparticles (CuNPs) with a light-addressable potentiometric sensor (LAPS) platform, enabling the highly-sensitive detection of IL-6. The presence of CuNPs significantly enhances electron transfer dynamics and potentiometric signal amplification, while IL-6-specific Aptamers offer high molecular recognition and binding affinity. The sensor transduces IL-6 binding events into detectable potential shifts, enabling quantitative analysis. The device exhibited exceptional selectivity in the presence of potential interfering substances, maintained high stability over multiple measurement cycles, and showed strong reproducibility. Under optimized parameters, the sensor achieved a wide linear detection range from 5 to 200 ng/mL, with a remarkably low detection limit of 2.1 pg/mL. Additionally, its successful performance in spiked human serum samples highlights its practicality and robustness for clinical diagnostic applications.","PeriodicalId":50,"journal":{"name":"Langmuir","volume":"17 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2026-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146097880","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}