Langmuir最新文献

{"title":"Mastering Syntheses of Siliceous Hierarchical Porous Self-Standing Monoliths through the Integration of the Sol-Gel Process, Complex Fluids, and a Planetary Mixer.","authors":"Antoine Vardon,Marie-Anne Dourges,Éric Laurichesse,Véronique Schmitt,Ahmed Bentaleb,Frédéric Nallet,Isabelle Ly,Rénal Backov","doi":"10.1021/acs.langmuir.5c03237","DOIUrl":"https://doi.org/10.1021/acs.langmuir.5c03237","url":null,"abstract":"Self-standing siliceous monoliths bearing hierarchical porosity have been synthesized while combining the sol-gel process, complex fluids, and a planetary mixer. The mechanically well-defined and a priori reproducible stirring procedure leads to a precise control over the final hierarchical porous characteristics of the materials: Both the macroscopic cell and interconnecting throat dimensions in the monoliths, i.e., macroporosity, can be tuned by choosing the rotation speed. The fabrication process also leads to well-defined macrocellular wall thicknesses that can be tuned in the range of 30-90 nm by stirring control. Final high internal phase emulsion-based siliceous materials, Si(HIPE), are offering around 80-90% porosity, decreasing with stirring speed, and a broadly mixing invariant BET specific surface area of about 860 ± 60 m2 g-1, where the microporous surface area is rather constant at 480 ± 20 m2 g-1, with the BJH (mesoporous) area being more spread in the range of 380 ± 80 m2 g-1.","PeriodicalId":50,"journal":{"name":"Langmuir","volume":"58 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2025-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145127396","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":"Amphiphilic Polyphosphazene-Stabilized High Internal Phase Emulsions toward Porous Polymers with Designed Hydrophilicity and Hydrophobicity for Selective Adsorption of Water and Oil.","authors":"Zhiyi Zang,Yongkang Wang,Wei Liu,Congcong Chao,Guanghui Cui,Shaojun Wu,Zhanpeng Wu","doi":"10.1021/acs.langmuir.5c02759","DOIUrl":"https://doi.org/10.1021/acs.langmuir.5c02759","url":null,"abstract":"High internal phase emulsion (HIPE) technology offers a robust approach to fabricating porous polymers with precise morphological control. However, monomers with high water solubility, such as methyl methacrylate (MMA) and hydroxyethyl methacrylate (HEMA), present significant challenges in forming stable water-in-oil HIPEs with the help of conventional surfactants. In this work, a series of amphiphilic polyphosphazenes (PPZs) with hydrophobic fluorine-containing segments and hydrophilic segments were synthesized via nucleophilic substitution reactions between poly(dichlorophosphazene) and various nucleophilic reagents. These PPZs were used to stabilize MMA and MMA-HEMA HIPEs by forming an anchoring layer at the water-oil interface. The resulting HIPEs demonstrated remarkable stability over 24 h with only 1 wt % PPZs. Porous PMMA and copolymers P(MMA-HEMA) with a controllable pore size were successfully synthesized via free radical polymerization. The porous PMMA exhibited excellent hydrophobic-oleophilic properties, achieving a maximum water contact angle of 159.8°. The porous PMMA also shows strong absorption performance to various organic solvents, with a maximum absorption capacity to dichloromethane of 3.9 g/g. Conversely, the porous P(MMA-HEMA) showed hydrophilicity with minimum water contact angles of 23° and a maximum absorption capacity to water of 1.9 g/g. Moreover, the effects of the molecular structures and the dosage of PPZs and the concentration of HEMA in the formulation on the morphologies and properties of the HIPEs and the corresponding porous polymers were comprehensively investigated. These notable performances endow the prepared porous PMMA and its copolymer P(MMA-HEMA) with exceptional potential for advanced applications in the field of adsorption. The developed material demonstrates efficacy in environmental remediation and resource recovery, particularly for capturing halogenated solvents (e.g., dichloromethane) and oxygenated residuals (e.g., ethyl acetate) in printing operations, regeneration of acetone-based semiconductor cleaning solutions, and emergency containment of marine hydrocarbon pollutants.","PeriodicalId":50,"journal":{"name":"Langmuir","volume":"84 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2025-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145127397","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":"Dual-Layer Anticorrosion Coating: Advanced Multifunctional Coating with Both Superhydrophobicity and pH-Responsive Behavior.","authors":"Lijuan Zhu,Chun Feng,Pengao Yu,Yuchi Guo,Zongxue Yu,Xiaofeng Bai,Yuji Li","doi":"10.1021/acs.langmuir.5c03577","DOIUrl":"https://doi.org/10.1021/acs.langmuir.5c03577","url":null,"abstract":"This article prepared a multifunctional anticorrosion superhydrophobic dual-layer coating with pH-response behavior. By modification of ZIF-8 with low surface energy substance stearic acid, and then loading the corrosion inhibitor 2-amino-5-mercapto-1,3,4-thiadiazole (AMT), a superhydrophobic nanocontainer encapsulating the corrosion inhibitor was prepared. The first layer of the smart coating was applied by using a brushing technique, while the second layer of the superhydrophobic coating was achieved through a spraying method. This composite coating exhibits both pH-responsive behavior and superhydrophobic properties. An electrochemical impedance spectroscopy test was conducted by immersing the composite coating in a 3.5 wt % NaCl solution. The results indicated that the dual-layer superhydrophobic anticorrosion composite coating, designated as ZST/EP-S, maintained the highest low-frequency impedance value after 40 days of immersion, which was 4 orders of magnitude greater than that of pure EP and 1 order of magnitude higher than the smart anticorrosion coating ZST/EP. This demonstrates a significant enhancement in corrosion resistance for the dual-layer superhydrophobic anticorrosion composite coating. Scratch test and UV-vis light experiments verified the successful release of corrosion inhibitor AMT.","PeriodicalId":50,"journal":{"name":"Langmuir","volume":"179 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2025-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145127395","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":"Experimental Investigation of Borehole Sealing Efficiency in Coalbed Methane Extraction Using Controllable Slow-Release Materials","authors":"Yunfei Zuo, Bo Tan, Zixuan Jia, Hao Lu, Feng Du, Chunjing Han, Yu Wang, Qi Tang","doi":"10.1021/acs.langmuir.5c02789","DOIUrl":"https://doi.org/10.1021/acs.langmuir.5c02789","url":null,"abstract":"The inadequate sealing of extraction boreholes significantly reduces gas extraction efficiency and hinders the effective prevention of gas disasters. This study presents a novel sealing material with adjustable slow-release properties. The seepage and sealing performances of materials with different mix ratios were tested to determine the optimal formulation. The underlying mechanism was further analyzed based on the materials’ physicochemical characteristics, and field experiments were conducted to validate the leakage control effectiveness of the controllable slow-release sealing material, thereby elucidating its mechanism for enhancing borehole sealing performance. The results indicate that the controllable slow-release sealing material with a water-to-material ratio of 4:1 performs best. The material consists primarily of montmorillonite, which is rich in SiO₂ and Al₂O₃, and exhibits excellent permeability and sealing characteristics. The nano-oxides, in cooperation with the surfactant, impart the slow-release blocking properties to the material. Initially, the material exhibits low viscosity, with excellent fluidity and permeability, allowing it to infiltrate the microfractures of the coal seam. As the injection time increases, the cross-linking agent within the material progressively reacts to form a polymer gel with a defined strength. In addition, the material can obstruct newly formed fissures during the continued expansion of coal body fractures, thereby demonstrating an effective dynamic blocking performance. These findings provide reliable technological support for the continuous sealing of coal seam fractures and efficient gas extraction.","PeriodicalId":50,"journal":{"name":"Langmuir","volume":"73 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2025-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145134610","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":"Time-Resolved Small-Angle X-ray Scattering Studies of pH-Induced PMPC-PDPA Diblock Copolymer Self-Assembly.","authors":"Guoxing Liao,Daniel T W Toolan,Nicholas J Warren,Paul D Topham,Oleksandr O Mykhaylyk,Yunjie Zhang,Nicholas J Terrill,LinGe Wang","doi":"10.1021/acs.langmuir.5c03950","DOIUrl":"https://doi.org/10.1021/acs.langmuir.5c03950","url":null,"abstract":"Despite the potential of poly(2-methacryloyloxy ethyl phosphorylcholine)-poly(2-(diisopropylamino)ethyl methacrylate) (PMPC-PDPA) diblock copolymer nanoparticles for several biological applications, the exact mechanism of pH-induced self-assembly of the PMPC-PDPA chains into nanoparticles remains unclear, although it has been extensively studied by ex situ transmission electron microscopy. Here, we probe this process using time-resolved small-angle X-ray scattering (TR-SAXS) to gain an understanding of the phenomena that occur on the nanoscale. Modeling the TR-SAXS data indicated that spherical micelles and vesicles were formed at a pH as low as 3, and the spherical micelle and vesicle structures reformed at pH 5.5. At pH ∼5.5, insoluble PMPC25-PDPA70 diblock copolymer precipitation was also observed by SAXS. A huge soluble PMPC25-PDPA70 diblock copolymer reservoir might assist in PMPC25-PDPA70 vesicle construction. Additionally, a potential pathway of vesicle construction by spherical micelle fusion was supported by the SAXS evidence.","PeriodicalId":50,"journal":{"name":"Langmuir","volume":"40 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2025-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145127398","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":"Electro-Stretching and Electro-Coalescence of Sessile Drops of Conducting Polymer Solutions with and without Surfactant and Dielectric Particles.","authors":"Rafael Granda,Jevon Plog,Vitaliy R Yurkiv,Farzad Mashayek,Alexander L Yarin","doi":"10.1021/acs.langmuir.5c03475","DOIUrl":"https://doi.org/10.1021/acs.langmuir.5c03475","url":null,"abstract":"The present study explores electrically driven stretching of individual conducting polymer drops and electro-coalescence of drop pairs on a dielectric surface under a strong electric field of 10 kV. Conducting PEDOT:PSS and PEDOT:PSS-PEO [poly(3,4-ethylenedioxythiophene):polystyrenesulfonate-poly(ethylene oxide)] drops were tested with and without a nonionic surfactant (Silwet L-77) and dispersed titanium dioxide (TiO2) particles. The surfactant dramatically reduced the solution's surface tension from ∼70 to ∼20 mN/m, and PEO doping increased viscosity and imparted shear-thinning behavior. Under the applied field, drops stretched between the electrodes and spread much wider than without voltage. This pronounced stretching is driven by electrostatic Maxwell stress overcoming capillarity (the electric capillary number CaE ∼ 0.9-2.3). The surfactant further enhanced deformation by lowering surface tension, and polarizable TiO2 particles introduced dielectrophoretic forces that also eased stretching. Furthermore, in surfactant-free cases, two initially separate drops underwent rapid electro-coalescence: upon field activation, finger-like protrusions formed within ∼2-5 ms from each drop to meet and create a narrow liquid bridge, which then expanded to merge the drops into one over a few seconds. However, drops containing surfactant (and TiO2) failed to coalesce, as strong Marangoni flow from surfactant-induced surface tension gradients dominated the Maxwell stress-driven attraction. Such surfactant-laden drops instead developed dendrite-like patterns at their trailing edges, with only a brief (∼millisecond) \"handshake\" contact and no full merging. These findings clarify how solution composition and interfacial and electrohydrodynamic mechanisms govern drop deformation and merging, providing insights for controlling drop behavior in coating processes. Moreover, the present experiments with drops of solutions of the conducting polymer with a surfactant (a superspreader SILWET L-77) and particles added reveal a novel phenomenon─a competition of the concentration-gradient Marangoni flow with electro-coalescence driven by the electric Maxwell stresses, which causes a noncoalescence even at a very high applied voltage.","PeriodicalId":50,"journal":{"name":"Langmuir","volume":"2 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2025-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145127401","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":"Host-Guest-Mediated Modulation of Pyrimidine Charge-Transfer Probes by Cyclodextrin Nanosponges for Aqueous-phase Cyanide Detection.","authors":"Sourav Mondal,Suvendu Paul,Nilanjan Dey","doi":"10.1021/acs.langmuir.5c03444","DOIUrl":"https://doi.org/10.1021/acs.langmuir.5c03444","url":null,"abstract":"We report the design and synthesis of two pyrimidine-functionalized charge transfer probes and their host-guest interactions with cyclodextrins (CDs), focusing on β-CD and its nanosponge (NS) derivative. One probe, featuring extended conjugation, exhibited aggregation-induced quenching in water but showed ∼2.3-fold fluorescence enhancement with a ∼3 nm blue shift upon β-CD complexation, indicating effective encapsulation and consequent disaggregation. Time-dependent studies revealed a ∼15-18 min kinetic window for effective complexation, whereas fluorescence anisotropy increased from 0.14 to 0.32, confirming the restriction of the overall molecular reorientation. Job's plot and a binding constant of 6866 M-1 supported a 1:1 inclusion complex. The β-CD NS (nanosponge) further enhanced the emission (∼8.9-fold after incubation), outperforming native β-CD. In contrast, the other probe, with a shorter conjugation length, displayed poor binding interactions with β-CD. Computational and docking studies supported the experimental findings, revealing favorable cavity-compatible binding interactions in the case of the longer-conjugated system. The probe also exhibited a selective turn-on fluorescence response to the cyanide anion (-CN) (∼4.1-fold) in the β-CD complex. The presence of β-CD enhanced the binding affinity for -CN through multiple polar contacts and additional hydrogen bonding interactions. This work offers a promising strategy for the aqueous-phase sensing of toxic anions by using supramolecular assemblies.","PeriodicalId":50,"journal":{"name":"Langmuir","volume":"95 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2025-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145134508","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":"Degradation of Rhodamine B by Peroxymonosulfate Activated with a NiFe-LDH@CoFe-PBA Composite.","authors":"Chunmiao Fan,Dengjie Zhong,Yunlan Xu","doi":"10.1021/acs.langmuir.5c03875","DOIUrl":"https://doi.org/10.1021/acs.langmuir.5c03875","url":null,"abstract":"In this study, CoFe-PBA-loaded NiFe-LDH (NiFe-LDH@CoFe-PBA) was synthesized and employed to catalyze peroxymonosulfate (PMS) to degrade rhodamine B (RhB). That the composite material was successfully synthesized was confirmed through complementary characterization techniques including energy-dispersive spectrometry, Fourier transform infrared spectroscopy, and X-ray diffraction analyses. The elimination efficiency of RhB reached 98.99% within 15 min under the conditions of an initial RhB concentration of 50 mg L-1, a catalyst concentration of 0.2 g L-1, a PMS concentration of 0.2 g L-1, and an initial pH of 6.36. The characterization results revealed that CoFe-PBA improved the dispersibility of NiFe-LDH and exposed more active sites, which made NiFe-LDH@CoFe-PBA have higher current density and electron transfer ability. In the composite, Co, Fe, and Ni were the catalytic centers to activate PMS, and the redox between Co3+/Co2+, Fe3+/Fe2+, and Ni3+/Ni2+ enhanced the production of reactive oxygen species (ROS: 1O2, O2•-, •OH, and SO4•-). Among them, 1O2 was determined to be the predominant reactive species responsible for RhB degradation. This study proposes a novel methodology for designing and synthesizing simple, efficient, stable, and environmentally friendly heterogeneous metal-based catalysts.","PeriodicalId":50,"journal":{"name":"Langmuir","volume":"11 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2025-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145127394","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":"A General Strategy for Engineering Robust Core-Shell Surface-Enhanced Raman Scattering Interfaces of Metal-Organic Framework@Plasmonic Nanoparticles.","authors":"Peng Sun,Jie Zhao,Xiaowu Liu,Lijuan Chen,Ming Wang,Renyong Liu","doi":"10.1021/acs.langmuir.5c03937","DOIUrl":"https://doi.org/10.1021/acs.langmuir.5c03937","url":null,"abstract":"The unique physicochemical properties of core-shell interface structures make them attractive for technological applications in sensing, catalysis, and hydrogen storage. In this work, we present a general strategy based on mussel-inspired polydopamine (PDA) chemistry to engineer a robust surface-enhanced Raman scattering (SERS) interface in core-shell metal-organic framework@plasmonic nanoparticles (MOF@PNPs). The ability of PDA to adhere to host materials of any chemical composition and to induce localized reduction of metal precursors made it robust for the integration of diverse MOFs and PNPs. The PDA-based method allowed for the deposition of common PNPs on the three classical MOFs with controlled plasmon properties, leading to the formation of core-shell MOF@PNPs with SERS-active interfaces. The simulation results revealed that the heterostructures provided a hot spot field larger than that of the standard aggregated PNPs. With a Raman internal standard of MOFs, the representative substrates have been successfully applied to the quantitative and sensitive detection of nerve agent simulation. Such core-shell interfaces are of great potential for SERS applications and may provide new insights into the mechanism of SERS.","PeriodicalId":50,"journal":{"name":"Langmuir","volume":"11 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2025-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145127400","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":"Complexation of siRNA with Galactose-Functionalized Dendrimers: PAMAM vs PETIM","authors":"Tarun Maity, Yogendra Kumar, Prabal K. Maiti","doi":"10.1021/acs.langmuir.5c03613","DOIUrl":"https://doi.org/10.1021/acs.langmuir.5c03613","url":null,"abstract":"siRNA-based therapies show potential for treating various diseases, but achieving efficient and targeted delivery remains a challenge. In this study, we investigated the potential of galactose-functionalized poly(amidoamine) (Gal-PAMAM) and poly(propyl ether imine) (Gal-PETIM) dendrimers as carriers for gene delivery, specifically, small interfering RNA (siRNA), using all-atom molecular dynamics simulations. We demonstrated the complexation behavior for both systems at two distinct pH conditions, i.e., 7 and 10, by analyzing the 500 ns long trajectories. The results show that electrostatic interactions are crucial for complex formation, with PMF profiles (center-of-mass, i.e., COM distance, was used as a reaction coordinate to calculate the potential of mean force, i.e., PMF) indicating a stronger binding affinity for Gal-PAMAM/siRNA at pH 7. In the Gal-PAMAM/siRNA complex at pH 7, the siRNA shows higher structural fluctuations compared with the Gal-PETIM/siRNA complex. However, in polar solvents, Gal-PETIM exhibits hydrophobic behavior, enabling rapid gene delivery at physiological pH conditions. These findings indicate that Gal-PETIM dendrimers are promising for effective siRNA delivery at physiological pH. This is due to their superior stability in forming complexes, strong interaction capabilities, and ability to rapidly release genes. Our results significantly improve the understanding of the applications of galactose-functionalized dendrimers under two different pH conditions.","PeriodicalId":50,"journal":{"name":"Langmuir","volume":"87 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2025-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145134611","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}