Langmuir最新文献

{"title":"Fe-Doped Ni3S2/Ni0.96S on Nickel Foam: A High-Efficiency and Chlorine-Resistant Electrocatalyst for Industrial Seawater Oxygen Evolution Reaction","authors":"Longzhen Li, Shuangyan Lin, Zhikun Xu, Tianle Li, Zhifeng Zhao","doi":"10.1021/acs.langmuir.5c02010","DOIUrl":"https://doi.org/10.1021/acs.langmuir.5c02010","url":null,"abstract":"Designing effective oxygen evolution reaction (OER) electrocatalysts for seawater electrolysis necessitates the simultaneous optimization of catalytic activity and chlorine corrosion resistance. Herein, Fe-doped Ni₃S₂/Ni_0.96S on nickel foam (Fe–Ni₃S₂/Ni_0.96S/NF) was prepared through sulfurization of the Fe-doped Ni(OH)₂ precursor. The sulfurization process induces electronic structure modulation, optimizing charge transfer kinetics and generating a high density of catalytically active sites. As a result, Fe–Ni₃S₂/Ni_0.96S demonstrates exceptional OER performance, achieving an overpotential of only 320 mV at an industrial current density of 1000 mA cm^–2 in alkaline freshwater. Notably, in alkaline seawater, Fe–Ni₃S₂/Ni_0.96S maintains outstanding activity (397 mV @ 1000 mA cm^–2) and operational stability (at least 150 h at 100 mA cm^–2). Furthermore, the Fe–Ni₃S₂/Ni_0.96S/NF||Pt/C requires a low voltage of 1.73 V to deliver 100 mA cm^–2 and exhibits at least 200 h stability, demonstrating its great potential for industrial seawater electrolysis applications.","PeriodicalId":50,"journal":{"name":"Langmuir","volume":"89 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2025-06-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144320257","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":"Controllable Superlubricity of Ricinoleic Acid/Tungsten-Doped Amorphous Carbon Coating Composite System via Water Content","authors":"Pengcheng Ma, Liuqing Yang, Longfei Wu, Qiang Wang, Cuijuan Xuan, Junying Hao, Xudong Sui","doi":"10.1021/acs.langmuir.5c01492","DOIUrl":"https://doi.org/10.1021/acs.langmuir.5c01492","url":null,"abstract":"Carbon-based coatings combined with ricinoleic acid exhibit exceptional lubrication and macroscale superlubricity, yet the influence of the water content remains insufficiently explored. In this paper, a tungsten-doped amorphous carbon coating/ricinoleic acid composite system was prepared, and superlubricity was achieved by controlling the water content in ricinoleic acid. When the water content is 13.89 wt %, the friction coefficient of the solid–liquid system is approximately 0.005. This phenomenon is attributed to the formation of a −(CH₂–CH₂)_<i>n</i>– passivation layer during the sliding process. Based on this passivation layer, a hydrogen bond layer is formed from ricinoleic acid–water and the decomposition products of ricinoleic acid containing −OH groups. This hydrogen bond layer is strong enough to withstand normal loads, effectively preventing contact between solid surfaces.","PeriodicalId":50,"journal":{"name":"Langmuir","volume":"13 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2025-06-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144320312","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":"Lysozyme Amyloid Modulates Membrane Structure and Hydration and Impacts Its Fusogenicity.","authors":"Shah Imtajul Haque,Ria Saha,Vibeizonuo Rupreo,Rajib Kumar Mitra","doi":"10.1021/acs.langmuir.5c00807","DOIUrl":"https://doi.org/10.1021/acs.langmuir.5c00807","url":null,"abstract":"Lysozyme, which is abundantly found in cellular environments, can form cytotoxic amyloid fibrils under stressed conditions. While amyloid formation leads to the loss of enzymatic function of lysozyme, its effects could extend beyond this, as the fibrils could interact with lipid membranes and impair their fusion propensity, which is harmful to membrane functionality, like particle degradation and triggering of immune responses. To address this, we investigate the interaction between lysozyme fibrils and two model liposomes: an ordered raft-like mixed membrane composed of DOPC-sphingomyelin-cholesterol and a less-ordered non-raft-like membrane DOPC. Dynamic light scattering, fluorescence spectroscopy, and scanning electron microscopy studies reveal that lysozyme amyloids do interact with the lipid membranes and alter their ordering; THz-Fourier Transform Infrared Spectroscopy (FTIR) measurements show that membrane hydration also gets perturbed. The liposomes, in the presence of the amyloid, show significantly reduced fusion propensity; interestingly, the decrease in fusion propensity is found to be less pronounced in the mixed raft-like membrane compared to non-raft-like membranes. The mixed raft-like membranes, owing to their ordered structure, modify the hydration in a manner that fusogenicity is retained to a greater extent than in the non-raft-like liposomes.","PeriodicalId":50,"journal":{"name":"Langmuir","volume":"14 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2025-06-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144311621","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":"Adhesion Enhancement of Chlorosulfonated Polyethylene via Self-Interface Roughening on Aluminum Substrate","authors":"Yusuke Nagae, Takao Ogawa, Hiroki Kuniwaki, Toshihiro Saito, Shingo Kouda, Shin Horiuchi","doi":"10.1021/acs.langmuir.5c00617","DOIUrl":"https://doi.org/10.1021/acs.langmuir.5c00617","url":null,"abstract":"The adhesion of chlorosulfonated polyethylene (CSM) to aluminum (Al) and its adhesion mechanism was investigated. The lap-shear strength between CSM and Al was nearly 3 times higher than that between chlorinated polyethylene (CPE) and Al, suggesting that the chlorosulfonyl (SO₂Cl) group enhances the adhesion strength. The CSM-Al interfaces were analyzed using electron energy loss spectroscopy with scanning transmission electron microscopy (STEM-EELS), atomic force microscopy (AFM), and X-ray photoelectron spectroscopy (XPS). The results show that the CSM creates a rough interface with a thick oxide layer containing Al(OH)₃ simultaneously in the bonding process. Such an increase in the interfacial roughness is considered to result from the electrochemical reaction of Al mediated by the interaction between the free chloride ions detached from the SO₂Cl group and the Al oxide layer. The insoluble adsorbed layers of CSM and CPE on Al were also characterized by ellipsometry. CSM is more likely to contain loosely adsorbed polymer chains. The loosely adsorbed polymer chains behave as connection points between the Al substrate and bulk polymer chains, thereby enhancing the adhesion strength. SO₂Cl-containing polymers may offer a new type of adhesive material that does not require surface pretreatment of adherent.","PeriodicalId":50,"journal":{"name":"Langmuir","volume":"2 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2025-06-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144320313","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":"First-Principles Dynamics of the Surface Fluorination of Diamond","authors":"Henry Thake, Stephen J. Jenkins","doi":"10.1021/acs.langmuir.5c01587","DOIUrl":"https://doi.org/10.1021/acs.langmuir.5c01587","url":null,"abstract":"We present first-principles dynamic simulations of molecular fluorine dissociatively adsorbing on clean C{001} and identify a range of possible outcomes depending upon the interplay of impact site, molecular orientation, and surface temperature. These include adsorption of a single fluorine atom with desorption of the other, in which case both the surface and the isolated atom gain radical character. In most scenarios, however, both fluorine atoms adsorb, either at opposite ends of a single surface dimer or on two such dimers. In the former situation the reaction end-point is closed-shell in nature, whereas in the latter the surface acquires singlet diradical character.","PeriodicalId":50,"journal":{"name":"Langmuir","volume":"24 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2025-06-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144320316","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"In-Depth Study of Captopril Adsorption on a Biosourced Adsorbent: Statistical Physics Approach and Pore Characterization, with Modeling of Adsorption Isotherms, Energetic and Steric Analysis","authors":"Amin Naifar, Kods Oueslati, Eder Claudio Lima, Fatma Aouaini, Abdelmottaleb Ben Lamine","doi":"10.1021/acs.langmuir.5c01235","DOIUrl":"https://doi.org/10.1021/acs.langmuir.5c01235","url":null,"abstract":"This current research implements statistical physics principles to microscopically elucidate and interpret the retention mechanism of Captopril onto the activated carbon derived from Butia catarinensis (ABc-600) for water decontamination. The empirical points were modeled exploiting four different statistical isotherm frameworks: the single-energy monolayer, dual-energy monolayer, trienergetic monolayer and dual-energy bilayer. Supported by an error quantification approach (<i>R</i>², Reduced Chi-Square, RSS and <i>R</i>_adj²) the single-energy monolayer was identified as the most rigorous scenario. Stereographic analysis revealed that the adsorption sites consistently capture a fraction of the adsorbed species with <i>n</i> &lt; 1 across all tested temperatures indicating a multianchorage mechanism without aggregation. The decrease in the monolayer adsorbed amount with incrementing temperature highlights the endothermic nature of the Captopril/ABc-600 retention mechanism. Moreover, the energetic assessment corroborates the predominance of physisorption (&lt;40 kJ/mol) indicating that van der Waals forces primarily govern the docking operation. PSD examination revealed a predominantly macroporous structure (0.7 μm) with a discernible shift toward smaller pore radii at elevated temperatures. The AED curves consistently displayed physisorption within the 22–29 kJ/mol energy range across all temperature conditions.","PeriodicalId":50,"journal":{"name":"Langmuir","volume":"600 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2025-06-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144320317","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 Hydrophobic Goldilocks Zone for Cyclodextrin-Lipid-Membrane Interactions: Implications of Drug Hydrophobicity on Kinetics of Cholesterol Removal from Lipid Membranes","authors":"Ethan M. Fong, J. Sebastian D. Kinzie, Aaron Christopherson, Jacob K. Al-Hussieni, Kevin Ye, Ananya Vinay, Ryan Mooney, Malkiat S. Johal","doi":"10.1021/acs.langmuir.5c00786","DOIUrl":"https://doi.org/10.1021/acs.langmuir.5c00786","url":null,"abstract":"Cyclodextrins (CDs) are cyclic oligosaccharides known for their ability to form guest–host complexes with hydrophobic molecules such as cholesterol, making them useful in various biomedical and industrial applications. However, their nonselective cholesterol extraction from cellular membranes raises concerns about cytotoxicity, necessitating a deeper understanding of their interactions with lipid bilayers. In this study, we investigate the role of CD hydrophobicity, as modulated by various substituent chemistries, on cholesterol extraction from supported lipid bilayers (SLBs) using quartz crystal microgravimetry with dissipation monitoring (QCM-D). Our results reveal a hydrophobicity-dependent “Goldilocks Zone” where intermediate hydrophobicity optimizes cholesterol removal while preserving membrane integrity. Additionally, preliminary analyses suggest that CD-membrane binding cooperativity, influenced by hydrophobicity, plays a crucial role in the efficiency and selectivity of cholesterol extraction. CDs with intermediate hydrophobicity exhibit enhanced binding cooperativity and more efficient cholesterol removal, suggesting a synergistic relationship between hydrophobicity and binding dynamics. These findings highlight the importance of CD hydrophobicity and binding cooperativity in designing cyclodextrin-based therapeutics with minimal cytotoxicity.","PeriodicalId":50,"journal":{"name":"Langmuir","volume":"240 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2025-06-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144320314","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 Review of Preparation of Low-Carbon Cementitious Materials from Chemically Activated Red Mud: Synergy, Hydration Mechanism, Rheological Properties and Applications","authors":"Wenhuan Liu, Siying Wang, Tongsheng Zhang, Huimei Zhu, Ning Chang, Lu Zhang, Zijing Hu","doi":"10.1021/acs.langmuir.5c01088","DOIUrl":"https://doi.org/10.1021/acs.langmuir.5c01088","url":null,"abstract":"Red mud, a byproduct of the alumina refining process, is generated at a rate of 1–2.5 tonnes per tonne of alumina produced. In 2022, China’s alumina production totaled 77.475 million tonnes, contributing over 4 billion tonnes of accumulated red mud, which is the third-largest industrial solid waste in the country. Red mud’s high alkalinity and presence of toxic elements pose environmental challenges, particularly in terms of disposal. This review provides a comprehensive examination of red mud-based cementitious materials, focusing on their preparation, properties, and environmental impact. By combining red mud with high-calcium and silica–aluminum solid wastes and enhancing its reactivity through mechanical grinding or thermal activation, red mud’s cementitious activity can be significantly improved. Optimized compositions, with a Ca/Si ratio of 2.05 and Al/S ratio of 0.70, have achieved compressive strengths of up to 63.9 MPa at 28 day. Durability studies highlight the material’s resistance to chloride ion penetration and sulfate attack, with reduced permeability enhancing long-term performance. Additionally, environmental assessments confirm that stabilization and solidification techniques effectively mitigate heavy metal leaching, ensuring compliance with EPA standards. Despite these advancements, challenges remain in optimizing red mud activation processes, improving rheological properties, and reducing production costs. Future research should focus on refining activation methods, enhancing hydration mechanisms, and developing scalable industrial applications. By addressing these gaps, red mud-based cementitious materials can become a sustainable solution for eco-friendly construction, supporting global efforts to repurpose industrial byproducts into low-carbon, durable building materials.","PeriodicalId":50,"journal":{"name":"Langmuir","volume":"42 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2025-06-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144320315","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":"Introducing the PARCH Scale for Quantifying the Hydropathy of Nucleic Acids and Nucleic Acid–Protein Complexes","authors":"Ratnakshi Mandal, Jingjing Ji, Claire Nicole Sheridan, Anna M. Baur, Andre Christophe Noel, Shikha Nangia","doi":"10.1021/acs.langmuir.5c01051","DOIUrl":"https://doi.org/10.1021/acs.langmuir.5c01051","url":null,"abstract":"Hydropathy studies have been extensively conducted for proteins, offering valuable insights into their structure and functionality. However, there is far less understanding of the hydropathy associated with the tertiary and quaternary structures of nucleic acids─such as deoxyribonucleic acid (DNA) and ribonucleic acid (RNA)─and their interactions with proteins. In this work, we extend our recently developed Protocol for Assigning a Residue’s Character on a Hydropathy (PARCH) scale to nucleic acids and nucleic acid–protein complexes. The PARCH scale quantifies the hydropathy of each nucleic acid residue based on its chemical identity and topographical features. The PARCH analysis for both DNA and RNA reveals that the backbone, consisting of phosphate and sugar atoms, is significantly more hydrophilic than the nucleotide bases; backbone PARCH values are an order of magnitude higher than those of the bases. In DNA, distortions from the organized double-helical structure, such as base flipping or altered base pairing, increase the hydropathy values. With its greater structural complexity, RNA exhibits a broader range of hydropathy values than DNA, reflecting its increased interaction with water. Thus, based on the PARCH values, RNA is more hydrophilic than DNA on average. PARCH analysis of DNA–protein and RNA–protein complexes reveals intricate binding patterns, including interactions between charged amino acid residues and the hydrophilic nucleic acid backbone, as well as hydrophobic patches on proteins engaging with the hydrophobic grooves of nucleic acid bases. These findings highlight the potential of PARCH analysis to provide valuable insights into the underlying principles of nucleic acid–protein interactions. The PARCH scale shows promise as a useful tool for advancing the development of functional RNA and DNA fragments for future therapeutic applications.","PeriodicalId":50,"journal":{"name":"Langmuir","volume":"12 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2025-06-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144312267","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":"First-Principles Prediction of Vibrational Sum Frequency Generation Features of Phenyl Groups at the 2D Interface with C∞ Symmetry","authors":"Jihyeong Ryu, Yiwen Guo, Sibing Chen, Juseok Choi, Xing Chen, Seong H. Kim","doi":"10.1021/acs.langmuir.5c01221","DOIUrl":"https://doi.org/10.1021/acs.langmuir.5c01221","url":null,"abstract":"Vibrational sum frequency generation (SFG) spectroscopy is capable of probing the orientation of the interfacial molecules. A conventional approach assumes that hyperpolarizability tensors governing the SFG signal intensity can be determined based on the point group symmetry of individual functional groups. However, vibrational coupling among neighboring groups breaks the normal mode symmetry. This makes it difficult to accurately interpret SFG spectra, particularly for phenyl (C₆H₅-) groups. In this study, we employed density functional theory (DFT) calculations to predict the SFG spectral features of C₆H₅ groups at two-dimensional interfaces with <i>C</i>_∞ symmetry. Using model compounds such as iodobenzene (C₆H₅–I) and various substituted phenyl derivatives, we systematically investigated the effect of vibrational coupling with neighboring atoms on the aromatic C–H stretching modes presented in the 3000–3100 cm^–1 region. If the substituent group lacks C–H bonds capable of coupling with the phenyl ring vibrations, the computed polarizability and dipole derivative tensors align well with the A1 and B1 symmetries expected from the <i>C</i>_2<i>v</i> point group. However, when the substituent contains C–H groups in the nearest or next-nearest positions to the phenyl ring, significant deviations from <i>C</i>_2<i>v</i> symmetry arise, leading to shifts in peak positions and intensity variations in SFG spectra. These findings underscore the limitations of conventional <i>C</i>_2<i>v</i>-based SFG analyses in determining the tilt angle of phenyl groups at polymer interfaces and emphasize the necessity of incorporating vibrational coupling effects for accurate SFG spectral interpretation. The approach presented in this work provides a more rigorous framework for accurately predicting and characterizing interfacial molecular orientations and can be extended to other complex systems, where vibrational interactions play a crucial role.","PeriodicalId":50,"journal":{"name":"Langmuir","volume":"15 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2025-06-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144312268","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}