Langmuir最新文献

{"title":"Molecular Dynamics Simulation on the Conformational Change of a pH-Switchable Lipid","authors":"Hao Zhang, Xiaoyan Zhuang, Yutong Wang, Zhen Zhao, Lijuan Yan, Guangyong Li, Jun Li, Hui Yan","doi":"10.1021/acs.langmuir.4c03704","DOIUrl":"https://doi.org/10.1021/acs.langmuir.4c03704","url":null,"abstract":"pH-sensitive lipids are important components of lipid nanoparticles, which enable the targeted delivery and controlled release of drugs. Understanding the mechanism of pH-triggered drug release at the molecular level is important for the rational design of ionizable lipids. Based on a recently reported pH-switchable lipid, named SL2, molecular dynamics (MD) simulations were employed to explore the microscopic mechanism behind the membrane destabilization induced by the conformational change of pH-switchable lipids. The simulated results showed that, at neutral pH, the neutral SL2 lipids assembled with other components (helper lipids and cholesterol) to form a structurally ordered bilayer structure. At this moment, the two hydrocarbon chains of SL2 were closely aligned and inserted in an orderly manner inside of the membrane. With a decrease in pH, the protonation of the pyridinium ring caused a large degree of molecular structural change. The pyridinium ring preferred to form intramolecular H-bonds with the methoxy groups and intermolecular H-bonds with water, resulting in the flip of the pyridinium ring. Meanwhile, due to the structural flip, the two alkane chains showed a more open state, which perturbed the arrangement of molecules within the membrane. The perturbations caused local collapse of the membrane and the formation of water molecule channels, which contributed to the pH-induced drug release. Our results verified the experimentally proposed mechanism at the molecular level and provided more complementary information, which are expected to have deeper insights into the pH-triggered drug release.","PeriodicalId":50,"journal":{"name":"Langmuir","volume":"24 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2024-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142874536","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":"Functional Group Effects on the Interfacial Adsorption of Arylquinoline-3-Carbonitriles on Iron: A DFT-D3 Investigation of Surface Interaction Mechanisms","authors":"Hassane Lgaz, Savas Kaya, Dong-Eun Lee, Ali Aldalbahi, Han-seung Lee","doi":"10.1021/acs.langmuir.4c03611","DOIUrl":"https://doi.org/10.1021/acs.langmuir.4c03611","url":null,"abstract":"Reliable corrosion inhibition systems are crucial for extending the lifespan of industrial metal structures. Quinolines, with their high adsorption capacity and protective efficiency, are promising next-generation inhibitors. However, the impact of substitutions on their coordination with iron surfaces requires deeper understanding. Herein, we investigate the influence of various functional groups on the adsorption behavior of three 2-amino-4-arylquinoline-3-carbonitriles (AACs) on iron surfaces using first-principles density functional theory calculations. Results reveal that nitrophenyl and hydroxyphenyl significantly enhance the adsorption strength of AACs on the Fe(110) surface, facilitated by donor–acceptor interactions. Neutral molecules were more stable than their protonated counterparts. Key results show strong adsorption energies, with values ranging from −2.005 to −1.809 eV for the AACs, along with significant electron gains across carbon atoms as indicated by Bader charge analysis. These strong interactions result in notable charge redistribution and bond formation, as shown by projected density of states and electron density difference iso-surfaces. Furthermore, electron localization function analysis indicates that van der Waals interactions, influenced by multiple nitrogen atoms, play a crucial role in stabilizing the adsorbed molecules. Stronger adsorption through electron donation and retro-donation mechanisms suggests enhanced corrosion protection efficiency of these substituted quinolines. The conductor-like screening model for real solvents analysis provides complementary insights into the solvation characteristics. Overall, the findings demonstrate the specific role functional groups play in the coordination of arylquinoline-3-carbonitriles with iron surfaces.","PeriodicalId":50,"journal":{"name":"Langmuir","volume":"3 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2024-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142874535","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":"Tailoring DNA Surface Interactions on Single-Layer Graphene: Comparative Analysis of Pyrene, Acridine, and Fluorenyl Methyl Linkers","authors":"Telma Domingues, Chun-Da Liao, Marta Prado, M. Fátima Cerqueira, Dmitri Y. Petrovykh, Pedro Alpuim, Jérôme Borme, Joana Rafaela Guerreiro","doi":"10.1021/acs.langmuir.4c03420","DOIUrl":"https://doi.org/10.1021/acs.langmuir.4c03420","url":null,"abstract":"This study investigates the effect of different linkers and solvents on the immobilization of DNA probes on graphene surfaces, which are crucial for developing high-performance biosensors. Quartz crystal microbalance with dissipation (QCM-D) measurements were used to characterize in situ and real-time the immobilization of ssDNA and hybridization efficiency on model graphene surfaces. The DNA probes immobilization kinetics and thermodynamics were systematically investigated for all the pairings between three bifunctional linkers─1-pyrenebutyric acid succinimidyl ester (PBSE), Fluorenylmethylsuccinimidyl carbonate (FSC), and Acridine Orange (AO) succinimidyl ester─and three organic solvents (DMF, DMSO, and 10% DMF/ethanol). The linker’s spatial orientation and effective surface modification for DNA probe attachment were also evaluated based on footprints and DNA probe surface coverage. Graphene surfaces functionalized with PBSE in DMF achieved the highest DNA probe surface density (up to 1.31 × 10¹³ molecules cm^–2) and fastest kinetic, <i>p</i> values above 4, and hybridization efficiencies of at least 70%, with 20 to 30% of ssDNA directly adsorbed nonspecifically on the functionalized graphene surface, which has significant implications for the design of sensitive biosensors. The efficiency of the ethanolamine-NHS blocking reaction was estimated to be 80%. The surface packing density of the linker was estimated at 25% of the entire surface coverage for PBSE, and about 22 and 13% for AO and FSC, respectively. Overall, the surface coverage achieved for probe DNA was in the same order of magnitude as that obtained on flat gold surfaces (≥10¹³ molecules cm^–2), typically used in biosensors. These findings highlight the importance of the selected conditions for graphene surface modification to achieve high DNA probe surface density on graphene materials. These results underscore the critical role of interface engineering in achieving target functional outcomes in biosensing technology.","PeriodicalId":50,"journal":{"name":"Langmuir","volume":"83 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2024-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142874361","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":"Alkaline-Assisted Excessive Impregnation for Enhancing Au Nanoparticle Loading on the TS-1 Zeolite","authors":"Chenyang Zhao, Yujia Liu, Yahui Li, Yupeng Tian, Haiyuan Jia, Wei Xu, Zhe Yang, Bing Sun","doi":"10.1021/acs.langmuir.4c04101","DOIUrl":"https://doi.org/10.1021/acs.langmuir.4c04101","url":null,"abstract":"Direct epoxidation of propylene (C₃H₆) with hydrogen (H₂) and oxygen (O₂) over the Au/TS-1 catalyst is known as the “Holy Grail” reaction for propylene oxide (PO) synthesis. However, Au nanoparticle loading on TS-1 was limited by traditional deposition precipitation, impregnation and could not achieve ideal catalytic results. In this report, alkaline-assisted excessive impregnation helped to remove Cl^– from the Au impregnation precursor, improve the loading efficiency of Au nanoparticles and overcome the abnormal growth of nanograins. Better hydrophobicity, surface acidity and an oxygen-containing free radical environment helped Au/TS-1-AEI achieve much better C₃H₆ conversion (8.0%), PO selectivity (96.7%) and stability (&gt;100 h).","PeriodicalId":50,"journal":{"name":"Langmuir","volume":"149 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2024-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142874538","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":"Theoretical Study on the Adsorption of Hexavalent Chromium by Metal-Modified and Nitrogen-Doped Carbon Materials","authors":"Qianqian Yin, Yuanhe Gao, Wenbo Zhang, Ruikun Wang, Xiaoxun Zhu, Xiaoxia Gao, Peng Gao, Kai Ma","doi":"10.1021/acs.langmuir.4c03727","DOIUrl":"https://doi.org/10.1021/acs.langmuir.4c03727","url":null,"abstract":"Cr(VI) can cause great harm to human beings and the environment and often exists in the form of HCrO₄̅ in aqueous environments. The adsorption characteristics of HCrO₄̅ on nitrogen-doped and iron–nickel-modified carbon substrates were systematically investigated using first principles. The properties of electron transfer and orbital hybridization of the substrates and HCrO₄̅ during the adsorption process were analyzed by electron deformation density and density of states. The electrons were donated by the metal atoms and gained by the oxygen atoms involved in the adsorption of HCrO₄^–. The binding energies of the substrates and metal atoms were larger than the cohesive energies of the metal atoms, indicating excellent structural stability. Both mono- and bimetallic modifications of the carbon materials by Fe/Ni were favorable for the adsorption of HCrO₄^–. The increased number of doped nitrogen atoms could promote the adsorption. Among them, (Fe,Ni)/N–C possesses the optimal adsorption of HCrO₄^–, with an adsorption energy of −4.64 eV. This is mainly attributed to the fact that the Fe–Ni bimetallic atoms simultaneously participate in the electron transfer and orbital hybridization, providing a new perspective for the adsorption of Cr(VI) on bimetallic-modified substrates.","PeriodicalId":50,"journal":{"name":"Langmuir","volume":"32 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2024-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142874363","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 Marine Antifouling Coatings Based on Zwitterion-Modified Silicone Polymers","authors":"Shu Tian, Yi Li, Hao Zhang, Guangming Lu, Ruiqi Li, Junyu Yu, Chao Zhao, Jing Yang, Lei Zhang","doi":"10.1021/acs.langmuir.4c04332","DOIUrl":"https://doi.org/10.1021/acs.langmuir.4c04332","url":null,"abstract":"Silicone coatings are widely employed in marine antifouling applications due to their low surface energy. However, in static marine environments, pure silicone coatings are ineffective in preventing the adhesion of marine biofilms, which consist of proteins, marine bacteria, and extracellular matrices, ultimately promoting the attachment of macrofouling organisms. To address the limitations in antifouling performance under static conditions, this study introduces a silicone-based antifouling coating modified with zwitterionic polymers. Sulfobetaine (SB) zwitterionic segments were grafted onto the side chains of poly(dimethylsiloxane) (PDMS) to synthesize the amphiphilic polymer P(DMS-SB), which was incorporated into the PDMS network to create an interpenetrating network-structured silicone coating. The zwitterionic segments effectively inhibited the adhesion of proteins, bacteria, and algae through hydration effects. Compared to pure PDMS coatings, the adhesion of proteins, bacteria, and algae was reduced by 88%, 98.9%, and 99.3%, respectively. Additionally, the coating demonstrated excellent fouling-release properties, achieving a 91.3% removal rate for settled algae under water flow conditions and reducing the simulated barnacle adhesion strength by 68.4%. This coating presents a promising antifouling solution for ships, offshore structures, and aquaculture facilities in static marine environments with significant potential for widespread application.","PeriodicalId":50,"journal":{"name":"Langmuir","volume":"61 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2024-12-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142874540","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":"Excellent Electrochemical Performance and Air Storage Stability of Na-Ion Layered Oxide Cathodes Benefiting from Enhanced Ce–O Binding Energy","authors":"Xiangnan Li, Xinyu Tang, Mengdan Zhang, Xiaojian Liu, Yiwei Xu, Zhenpu Shi, Huishuang Zhang, Yanhong Yin, Shu-Ting Yang","doi":"10.1021/acs.langmuir.4c03801","DOIUrl":"https://doi.org/10.1021/acs.langmuir.4c03801","url":null,"abstract":"The widespread application of layered oxides is constrained by their low electrochemical performance and complex irreversible phase transition. The high entropy oxide NaNi_0.25Fe_0.15Mn_0.3Ti_0.1Sn_0.05Co_0.05Li_0.1O₂ (HEO) is synthesized by leveraging the entropy stabilization effect, which offers a partial solution to this issue, but electrochemical performance and air stability imperative to be improved. On the high entropy oxide HEO, due to the strong bond energy of Ce–O, the introduction of Ce⁴⁺ improves the specific discharge capacity and reduces the battery gas production problem. It also improves the air stability. NaNi_0.25Fe_0.15Mn_0.3Ti_0.1Sn_0.03Ce_0.02Co_0.05Li_0.1O₂ (HEO-Ce2) demonstrated a specific discharge capacity of 160 mA h g^–1 at 0.1 C. The discharge-specific capacity retention rate of the material is 86%, after air exposure for 10 days. The high entropy effect and introduction of Ce⁴⁺ provide a viewpoint for a layered oxide of sodium-ion batteries.","PeriodicalId":50,"journal":{"name":"Langmuir","volume":"20 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2024-12-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142874539","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":"Jute–Copper Nanocomposite Embedded PSf Membrane for Sustainable and Efficient Heavy Metal Removal from Water Sources","authors":"Harsh Prajapati, Jeny Gosai, Nitin Chaudhari, Balanagulu Busupalli","doi":"10.1021/acs.langmuir.4c03847","DOIUrl":"https://doi.org/10.1021/acs.langmuir.4c03847","url":null,"abstract":"Numerous corporations have overlooked environmental regulations concerning wastewater treatment, leading to a worldwide issue regarding hazardous pollutant discharge, particularly dyes and heavy metal ions, into river sources. Various industries, with water, energy, and biological sectors, actively employ membranes. Membranes capable of showing flux, metal and dye sorption, and catalysis have been developed and are extensively used by functionalizing the pores of ultrafiltration, microfiltration, and nanofiltration membranes with responsive properties. The enhancement of synthetic membrane performance can be achieved by developing new polymers or modifying the surface of existing polymers. In this study, high porosity and large internal pore volume polysulfone (PSf) membrane composites were produced on a laboratory scale by adjusting the polymer coagulation conditions during the phase inversion process, incorporating copper nanoparticles for antifouling properties, and utilizing pretreated natural jute fibers. A comprehensive characterization of the composites was conducted by using FTIR, XRD, XPS, ICP-MS, and SEM techniques. To calculate their possible uses in separation and purification methods, the performance of PSf-based membrane composites was evaluated in terms of heavy metal rejection rates (%) in water.","PeriodicalId":50,"journal":{"name":"Langmuir","volume":"11 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2024-12-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142867346","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":"Advanced Liquid-Entrapped Nanosurfaces for Optimized Atmospheric Water Harvesting","authors":"Ghulam Mohd, Saswati Priyadarshini, Abhigith Nair, Versha Chauhan, Irfan Majeed Bhat, Ahmad Illahie Tantry, Shafeer Kalathil, Kowsar Majid, Saifullah Lone","doi":"10.1021/acs.langmuir.4c03851","DOIUrl":"https://doi.org/10.1021/acs.langmuir.4c03851","url":null,"abstract":"Our study addresses the pressing global freshwater scarcity crisis by engineering advanced liquid-entrapped nanosurfaces optimized for highly efficient atmospheric water harvesting (AWH). Through a synergistic approach integrating carbon fiber paper (CFP), hydrothermally synthesized nanoneedles (NNs), and silicone oil liquid entrapment (LE) within NNs, we achieved remarkable improvements in water collection efficiency. While CFP captures fog effectively during AWH, it faces challenges with water-pinning effects, mitigated by NNs’ improved droplet-spreading properties, leading to a notable 50% increase in harvesting efficiency. Further enhancements are observed upon silicone oil entrapment within CFP-bearing NNs, resulting in exceptional performance compared to noninfused surfaces. The resultant liquid entrapped nanoneedles (LE-NNs) and liquid entrapped oxidized (LE-ONNs) surfaces exhibit significant fog harvesting capability, achieving an impressive water collection rate of 21.643 ± 0.538 L/m²/h, which represents a 4-fold increase compared to CFP alone. This experiment was conducted with a sample area of 0.5 cm². The samples were tilted at different angles to optimize mist contact with the surface, and the humidifier nozzle was positioned approximately 5 cm from the test surface to ensure a minimal fog velocity. Comprehensive analysis of morphological and compositional attributes is conducted by using techniques such as field emission scanning electron microscopy (FESEM), X-ray photoelectron spectroscopy (XPS), energy dispersive X-ray spectroscopy (EDS), and Fourier transform infrared (FTIR) spectroscopy. Leveraging CFP, NNs, or ONNs with LE presents a straightforward and highly effective surface engineering method. This approach holds promise for advancing water collection technologies and addressing global water crises sustainably.","PeriodicalId":50,"journal":{"name":"Langmuir","volume":"84 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2024-12-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142857893","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 Structure Enabling Electrocatalytic Hydrogen Evolution Performance by POM@TM-BDC Composites","authors":"Binghe Yang, Lige Gong, Hongtao Cui, Jihua Wang, Limin Dong, Yunhao Gu, Hui Li, Meijia Wang","doi":"10.1021/acs.langmuir.4c03855","DOIUrl":"https://doi.org/10.1021/acs.langmuir.4c03855","url":null,"abstract":"Developing economical, efficient, and earth-rich electrocatalysts for hydrogen evolution reaction (HER) is quite challenging and ideal. We propose that [P₂W₁₈O₆₂]^6– as the guest, due to its excellent reversible 18 electron-transfer capacity and redox properties, and then TM-BDC (TM = Ni, Co, Fe, BDC = 1,4-benzene-dicarboxylate) as the host make [P₂W₁₈O₆₂]^6– packaged and not escape due to its porous structure. Benefiting from strong redox-competent interactions between [P₂W₁₈O₆₂]^6– and porous structures of TM-BDC and full exposure of abundant active sites, three {P₂W₁₈}@TM-BDC composites exhibited excellent HER activity, with {P₂W₁₈}@Ni-BDC requiring 198 mV (overpotentials) and 104 mV/dec (Tafel slope) for HER. More importantly, three {P₂W₁₈}@TM-BDC composites show excellent stability, with the voltage remaining nearly constant for 24 h. Meanwhile, the linear sweep voltammetry (LSV) and electrochemical impedance spectroscopy (EIS) curves of three {P₂W₁₈}@TM-BDC overlap well with the initial curve after the stability test. Our work offers a promising strategy for synthesizing high-performance electrocatalysts and broadens the scope of nonprecious metal composite material preparation.","PeriodicalId":50,"journal":{"name":"Langmuir","volume":"71 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2024-12-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142857894","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}