LangmuirPub Date : 2026-11-11DOI: 10.1021/acs.langmuir.6c05809
Puwen Fan,Jian Liu,Jiamei Hao,Rong Huang,Zefan Zhang,Dongdong He
{"title":"Bidentate Chelation-Driven Selective Depression of Pyrite: Adsorption Mechanism and Flotation Application of an N-Heterocyclic Carboxylic Acid Depressant","authors":"Puwen Fan,Jian Liu,Jiamei Hao,Rong Huang,Zefan Zhang,Dongdong He","doi":"10.1021/acs.langmuir.6c05809","DOIUrl":"https://doi.org/10.1021/acs.langmuir.6c05809","url":null,"abstract":"The selective flotation separation of chalcopyrite and pyrite constitutes a core bottleneck in the comprehensive utilization of copper–sulfur ores. Given the proneness of pyrite to copper activation and pipeline scaling defects induced by the conventional high-alkaline lime depression process, novel organic depressants with outstanding selectivity under weak alkaline media are urgently required to be developed. In this study, 3-hydroxy-2-pyridine carboxylic acid (3-HPA) was adopted as a novel eco-friendly organic depressant to realize the selective flotation separation of chalcopyrite from pyrite under weakly acidic conditions (pH = 6). The selective depression mechanism of 3-HPA against pyrite was systematically investigated via microflotation assays, multiscale surface characterizations, and first-principles theoretical computations. Flotation experimental data verified that 3-HPA is capable of selectively depressing pyrite floatability while maintaining excellent floatability of chalcopyrite, with a maximum recovery gap of 92.71% observed between the two minerals. Collectively, 3-HPA serves as an efficient and highly selective organic depressant for pyrite. On pyrite surfaces, 3-HPA undergoes bidentate chelation with surface iron active sites: the nitrogen atom on its pyridine ring and the oxygen atoms of the carboxyl group coordinate with Fe atoms to generate stable Fe–N and Fe–O bonds, which drastically reduce the surface hydrophobicity of pyrite. By comparison, only feeble intermolecular interactions take place between 3-HPA and chalcopyrite surfaces, whereby the surface hydrophobicity of chalcopyrite remains intact. The present research clarifies the selective depression mechanism of 3-HPA against pyrite and provides new theoretical guidance for the development of green and efficient pyrite depressants.","PeriodicalId":50,"journal":{"name":"Langmuir","volume":"14 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2026-11-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149374772","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}
LangmuirPub Date : 2026-11-11DOI: 10.1021/acs.langmuir.6c05005
Yanrong Zhang,J. M. Bas Klement,Hugo den Besten,Linda E. Eijsink,Ronald Hage,N. Scott Lynn, Jr.,Wesley R. Browne
{"title":"Balancing O2 Consumption and Monomer Evaporation to Tune Alkene Polymerization in Protective Coatings","authors":"Yanrong Zhang,J. M. Bas Klement,Hugo den Besten,Linda E. Eijsink,Ronald Hage,N. Scott Lynn, Jr.,Wesley R. Browne","doi":"10.1021/acs.langmuir.6c05005","DOIUrl":"https://doi.org/10.1021/acs.langmuir.6c05005","url":null,"abstract":"Alkene resins with acrylate-based cross-linkers are widely used as coatings to protect metal surfaces from corrosion. Environmental and safety concerns are stimulating the replacement of resin components. Especially, replacing volatile reactive diluents (i.e., styrene) with less volatile diluents and the cobalt(II) carboxylates that activate the alkyl peroxide initiators with benign transition-metal catalysts (e.g., Fe(II) complexes) is desirable. Polymerization of thin coatings (ca. 50–300 μm, depending on the application) involves both physical and chemical processes, including evaporation of diluent, diffusion-driven compositional gradients, and continuous ingress and consumption of O2. In this report, we deconvolute the effects of monomer evaporation and O2 uptake/consumption in air-exposed resin films and show that the final composition of the film is determined by the relative rates of catalyzed O2 depletion and O2 uptake from air and the increase in viscosity due to evaporation of the diluent. The one-dimensional diffusion-reaction model developed for O2 penetration/consumption enables rational tuning of loading of the commercially relevant catalyst Fe(II)-bispidine to provide similar performance as with the industry-standard Co(II) catalysts.","PeriodicalId":50,"journal":{"name":"Langmuir","volume":"9 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2026-11-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149374770","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}
LangmuirPub Date : 2026-11-10DOI: 10.1021/acs.langmuir.6c03037
Tong Zhang,Jia-wei Yang,Sheng-ru Long,Sui-lin Liu,Jia-cao Yang,Zhi-mei Wei,Jie Yang,Xiao-jun Wang
{"title":"Molecular Engineering of Polyimide Sizing Agents with Ether and Sulfone Groups for Tailored Interfacial Performance in CF/PASS Composites","authors":"Tong Zhang,Jia-wei Yang,Sheng-ru Long,Sui-lin Liu,Jia-cao Yang,Zhi-mei Wei,Jie Yang,Xiao-jun Wang","doi":"10.1021/acs.langmuir.6c03037","DOIUrl":"https://doi.org/10.1021/acs.langmuir.6c03037","url":null,"abstract":"The interfacial adhesion between carbon fibers and polymer matrices critically determines the mechanical performance of fiber-reinforced composites, yet achieving strong bonding remains a persistent challenge. A molecular engineering strategy is developed to tailor the fiber-matrix interphase in carbon fiber-reinforced poly(arylene sulfide sulfone) (PASS) composites by designing three sizing agents: poly(amic acid) (PAA) and its thermally imidized polyimide derivatives bearing either ether or sulfone groups. Through a combined experimental and computational approach, the influence of the chemical structure of the sizing agents─specifically, the nature of the groups (ether vs sulfone), and the postimidization state-on interfacial adhesion and failure behavior is systematically investigated. The results demonstrate that the sulfone-containing polyimide sizing agent exhibits superior interfacial reinforcement, which is attributed to its strong intermolecular interactions with the PASS matrix, including hydrogen bonding as well as π-π stacking enabled by its rigid, conjugated chain architecture. This leads to a marked enhancement in mechanical performance: tensile strength, interlaminar shear strength, and interfacial shear strength increase by 43.9%, 115.2%, and 101.5%, respectively, compared to desized CF, accompanied by a transition in failure mode from interfacial debonding to cohesive failure within the matrix and fiber fracture. Moreover, the interfacial layer thickness reaches 445 nm, and complementary simulations (finite element analysis, molecular dynamics, and density functional theory) confirm the correlation between sizing-induced adhesion and interfacial failure characteristics. This work clarifies the distinct roles of ether/sulfone architectures and PAA imidization in enhancing the CF/PASS interphase, providing theoretical and experimental guidance for engineering high-performance fiber composites.","PeriodicalId":50,"journal":{"name":"Langmuir","volume":"18 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2026-11-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149374764","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":"Silver Nanowire Composite Acrylate Humidity Sensors with Ultrafast Response and Low Hysteresis","authors":"Xu Ma,Tao Jin,Yansheng Li,Rong Chen,Chengye Liu,Zhaokun Wang,Yufang Chen","doi":"10.1021/acs.langmuir.6c04309","DOIUrl":"https://doi.org/10.1021/acs.langmuir.6c04309","url":null,"abstract":"In this study, the polyelectrolyte PDH was prepared by copolymerizing [2-(methacryloyloxy)ethyl]trimethylammonium chloride (DMC) with hydroxyethyl methacrylate (HEMA), and silver nanowires (AgNWs) were incorporated to construct a PDH/Ag composite humidity-sensitive film. A systematic comparison of the linear response, humidity hysteresis, dynamic response speed, and long-term stability between PDH and PDH/Ag devices was conducted, and the sensing mechanism was analyzed using complex impedance spectroscopy. The test results show that the composite-modified PDH/Ag sensor achieved a linear correlation coefficient as high as 0.996, with humidity hysteresis reduced from 3.15% RH to 1.39% RH and a response time shortened to less than 1 s; after 20 consecutive days of testing at 30% RH, 60% RH, and 90% RH, the PDH/Ag sensor exhibited virtually no baseline drift, demonstrating significantly improved long-term stability. Complex impedance spectroscopy confirmed that at low humidity (11% RH), both types of devices exhibited only intrinsic polymer conductivity; as humidity increased to the medium- and high-humidity ranges, Warburg ion diffusion behavior gradually emerged and continued to intensify. The interwoven silver nanowire network constructs continuous water vapor diffusion channels, enhances ion transport, and restrains polymer swelling and aging, simultaneously addressing the multiple performance shortcomings of pure polyelectrolyte humidity-sensitive materials. This work provides a feasible modification strategy for the structural design of high-performance, long-life polyelectrolyte-based humidity-sensitive membranes.","PeriodicalId":50,"journal":{"name":"Langmuir","volume":"18 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2026-11-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149374767","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":"Insights into the Role of Cs2CuSbCl6 and Cs2AgSbBr6 as Absorber Layers in Improving the Efficiency of Double Perovskite Solar Cells Using Density Functional Theory Integrated with Simulation Frameworks","authors":"Gagan Kumar,Babban Kumar Ravidas,Mukesh Kumar Roy,Dip Prakash Samajdar","doi":"10.1021/acs.langmuir.6c02863","DOIUrl":"https://doi.org/10.1021/acs.langmuir.6c02863","url":null,"abstract":"Double perovskites (DPs) have become significant lead (Pb)-free alternatives because of their toxic-free nature and high stability compared to Pb-based PSCs. In this work, the DPs Cs2CuSbCl6 and Cs2AgSbBr6 are thoroughly investigated as possible photovoltaic (PV) materials using DFT computation and device simulation through WIEN2K and SCAPS-1D tools, respectively. First, we investigated the optoelectronic characteristics of both Cs2CuSbCl6 and Cs2AgSbBr6 through the WIEN2k tool. The computed band gaps (Eg) of Cs2CuSbCl6 and Cs2AgSbBr6 are found to be 1.64 eV and 1.89 eV, respectively. UV absorption peaks at around 13 eV are seen in Cs2CuSbCl6 and Cs2AgSbBr6, with an increase in peak magnitudes occurring at photon energies of 2.19 eV for Cs2CuSbCl6 and 2.81 eV for Cs2AgSbBr6, respectively. These findings suggest that Cs2CuSbCl6 and Cs2AgSbBr6 have strong potential as absorbers for solar cell (SC) applications. This paper compares the modeling and optimization of three types of PSC structures, including the single-junction FTO/ZnO/Cs2CuSbCl6/Spiro/Au, FTO/ZnO/Cs2AgSb6/Spiro/Au, and graded double absorber layer-based FTO/ZnO/Cs2CuSbCl6/Cs2AgSb6/Spiro/Au architecture, using a simulation method via SCAPS-1D. The proposed graded double active layer-based PSC architecture delivered improved performance as compared to the single-layered architecture. An optimized performance of a graded double active layer-based PSC architecture with a Jsc of 21.52 mA/cm2, a Voc of 1.06 V, an FF of 84.13%, and a PCE of 19.20% has been observed, while Cs2CuSbCl6- and Cs2AgSbBr6-based single-junction PSCs demonstrated PCEs of 14.64% and 17.88%, respectively. In this work, we use the SCAPS-1D modeling tool to propose and simulate a unique lead-free dual absorber layer design. This design strategy offers a feasible path to the development of highly effective, environmentally friendly, and thermally stable perovskite (PVSK) PV systems. These results can bring about significant advancement in the field of nontoxic DP technology through careful and optimized experimental design and fabrication.","PeriodicalId":50,"journal":{"name":"Langmuir","volume":"1 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2026-11-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149374787","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":"Chain-End Carboxy Functionalization of Zwitterionic Polymethacrylate Brushes Grafted from Polymer Particles for Bioconjugation without Compromising Protein Repellency","authors":"Ryota Niwa,Shigeko Kawai-Noma,Daisuke Aoki,Atsushi Tamura,Tatsuo Taniguchi","doi":"10.1021/acs.langmuir.6c05314","DOIUrl":"https://doi.org/10.1021/acs.langmuir.6c05314","url":null,"abstract":"Combining both biomolecule immobilization and suppression of nonspecific biomolecule adsorption is a key requirement for advanced biointerfaces. In particular, polymer brush surfaces prepared via surface-initiated atom transfer radical polymerization (SI-ATRP) represent a promising approach for suppressing nonspecific adsorption while allowing the introduction of reactive groups into polymer side chains or chain ends. However, direct one-step chain-end functionalization remains challenging for polymers bearing tertiary alkyl bromide termini. Here, the terminal tertiary alkyl bromides of poly(2-methacryloyloxyethyl phosphorylcholine) (PMPC) brushes prepared by SI-ATRP were directly converted into reactive carboxy groups via thiolate-mediated substitution using 3-mercaptopropionic acid (MPA). The reaction conditions were first optimized using a low-molecular-weight model compound and free PMPC and subsequently applied to PMPC brushes on polymer particles. The density of the surface-accessible carboxy groups was determined to be 0.040 groups/nm2 by fluorescence labeling, corresponding to 32% of the total number of polymer brush chains, which was comparable to that obtained for free PMPC. Importantly, the adsorption of bovine serum albumin and lysozyme remained unchanged after carboxy functionalization, demonstrating that the protein repellency of the PMPC brushes were preserved. Furthermore, superfolder green fluorescent protein (sfGFP) was successfully immobilized through the introduced carboxy groups, as confirmed by fluorescence spectroscopy and microscopy. These results demonstrate that chain-end functionalization of PMPC brushes enables the introduction of reactive sites for biomolecule conjugation without compromising protein repellency. The strategy developed in this study provides a versatile route to end-functionalized polymethacrylate brushes and offers a useful platform for the design of biofunctional and low-fouling polymer interfaces.","PeriodicalId":50,"journal":{"name":"Langmuir","volume":"19 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2026-11-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149374765","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":"Synergistic Stabilization of Anionic-Cationic Dual Frameworks via Mg Doping and O2-Type Structure Construction in Lithium-Rich Cathodes","authors":"Linze Huang,Zihao Zheng,Yanmin Zhang,Lanxin Zhang,Zhiyuan Ma,Jiaxue Lin,Liang Yang,Honghua Huang,Lidong Che,Fengli Bei","doi":"10.1021/acs.langmuir.6c04710","DOIUrl":"https://doi.org/10.1021/acs.langmuir.6c04710","url":null,"abstract":"Lithium-rich manganese-based cathode materials (LRMOs) have high specific capacity (>250 mAh g–1) and low cost. However, their commercial viability is plagued by irreversible oxygen release, transition metal migration, and structural degradation (layered-to-spinel/rock-salt phase transitions) during cycling, leading to rapid capacity fading and severe voltage decay. Herein, departing from conventional single-modification routes, we propose a strategy of synergistically regulating O2-type layered structure and Mg doping, to enhance structural stability by constructing a robust anion–cation dual framework. Specifically, the ABAC stacking in the O2-type structure stabilizes the anionic framework by suppressing lattice oxygen release, while Mg doping stabilizes the local transition metal environment and mitigates cation migration and lattice distortion, achieving synergistic stabilization of both frameworks. Structural characterizations confirm that Mg introduction optimizes particle morphology and valence state distribution. The optimized O2–Mg–NCM delivers an initial Coulombic efficiency of 98.51%, a capacity retention of 86.6% after 200 cycles, and a mere voltage decay of 0.178 V after 100 cycles. It exhibits superior reaction kinetics, with a charge transfer resistance of 39.08 Ω and Li+ diffusion coefficient of 2.94 × 10–15 cm2 s–1. CV, dQ/dV, and EIS analyses further demonstrate that the synergy between the O2 structure and Mg doping enhances anionic redox reversibility and alleviates structural degradation, improving cycling stability and voltage retention of LRMOs. This study elucidates the dual-framework synergistic stabilization mechanism, providing new insights into designing highly stable, high-energy-density LRMOs.","PeriodicalId":50,"journal":{"name":"Langmuir","volume":"20 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2026-11-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149374789","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}
LangmuirPub Date : 2026-11-10DOI: 10.1021/acs.langmuir.6c04717
Hongda Li,Mengyun Liu,Zhengxue Ge,Juanling Zhang,Boyue Zheng,Fangbin Fan,Hongmei Liu
{"title":"Rational Design of pH-Tunable Magnetic Microspheres for Dual-Selective Dye Extraction","authors":"Hongda Li,Mengyun Liu,Zhengxue Ge,Juanling Zhang,Boyue Zheng,Fangbin Fan,Hongmei Liu","doi":"10.1021/acs.langmuir.6c04717","DOIUrl":"https://doi.org/10.1021/acs.langmuir.6c04717","url":null,"abstract":"The development of adsorbents with precise recognition and reversible switching remains a long-standing challenge in solid-phase extraction (SPE), particularly for the sensitive monitoring of illegal additives in complex food matrices. Herein, a pH-tunable amphoteric magnetic microsphere, M-PEI@HESP, was rationally fabricated and integrated with HPLC for high-selectivity dye detection. Unlike pristine M-HESP, which exhibits inherent single-selectivity toward cationic dyes (e.g., Rhodamine B), M-PEI@HESP employs protonatable/deprotonatable amine groups from PEI to achieve pH-dependent charge inversion: efficiently capturing anionic dyes (e.g., amaranth, acid Red 73) under acidic conditions, while specifically retaining banned cationic dyes (e.g., Rhodamine B) under alkaline conditions. A combination of pH-dependent adsorption, zeta potential, FT-IR, XPS, and DFT simulations reveals that electrostatic interaction is the dominant driving force, synergistically reinforced by hydrogen bonding, π–π stacking, and H+/OH– interactions. Notably, the adsorbent enables reversible selectivity switching and accurate quantification of anionic (amaranth) and cationic (rhodamine B) dyes within the same complex matrix simply by pH modulation. The resultant MSPE–HPLC method delivers a low LOD (0.1–1.0 μg L–1), a broad linearity (1.0–1500.0 μg L–1), high recoveries (90.58–105.64%), and satisfactory resistance to matrix effects. This work not only provides a versatile platform for the precise screening of illegal food additives but also establishes a new paradigm for designing intelligent, stimuli-responsive adsorbents.","PeriodicalId":50,"journal":{"name":"Langmuir","volume":"20 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2026-11-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149374768","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}
LangmuirPub Date : 2026-11-10DOI: 10.1021/acs.langmuir.6c01265
Luís M. S. Loura,Margarida M. Cordeiro,Alexandre C. Oliveira,Maria João Moreno
{"title":"Dual Nature of Molecules: Amphiphilicity as a Missing Descriptor in Drug Design","authors":"Luís M. S. Loura,Margarida M. Cordeiro,Alexandre C. Oliveira,Maria João Moreno","doi":"10.1021/acs.langmuir.6c01265","DOIUrl":"https://doi.org/10.1021/acs.langmuir.6c01265","url":null,"abstract":"Current drug-design approaches rely heavily on global molecular descriptors, including lipophilicity, hydrogen-bonding capacity, molecular weight, and polar surface area. Although valuable, these descriptors provide limited insights into drug behavior at biomembrane interfaces, where steep polarity gradients occur. We propose molecular amphiphilicity as a complementary descriptor relevant to pharmacokinetics and pharmacodynamics. Arising from the spatial segregation of hydrophilic and hydrophobic regions, amphiphilicity influences drug–membrane association, orientation, and permeation. We introduce a molecular-dynamics-based methodology to quantify the magnitude and orientation of the amphiphilic moment in membrane environments. Applied to selected amphiphilic molecules, this approach provides insights into membrane interactions and motivates broader evaluation of the amphiphilic moment as a complementary molecular descriptor in drug design.","PeriodicalId":50,"journal":{"name":"Langmuir","volume":"64 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2026-11-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149374766","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}
LangmuirPub Date : 2026-11-10DOI: 10.1021/acs.langmuir.6c00929
Deborah S. Nicdao,Andrea Ramnath,Thomas J. Adams,L. Marcus Wilhelmsson,Elin K. Esbjörner,Margaret N. Holme
{"title":"The Role of Membrane Asymmetry in Vesicle-Mediated In Vitro Delivery of Nucleic Acid Cargo","authors":"Deborah S. Nicdao,Andrea Ramnath,Thomas J. Adams,L. Marcus Wilhelmsson,Elin K. Esbjörner,Margaret N. Holme","doi":"10.1021/acs.langmuir.6c00929","DOIUrl":"https://doi.org/10.1021/acs.langmuir.6c00929","url":null,"abstract":"Nucleic acid therapeutics typically require a delivery vector, such as lipid-based nanoparticles. However, limitations in e.g. specific targeting and biodistribution, pose challenges to their clinical applications, and alternative lipid-based delivery vectors are therefore highly desirable. Here, we investigated the effect of introducing membrane asymmetry to lipid vesicles (i.e., the inner and outer leaflets have different lipid compositions), which has previously been shown to alter their biophysical properties. In this study, we prepared asymmetric large unilamellar vesicles (aLUVs) composed of 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC) on the inner leaflet and either 1,2-dioleoyl-sn-glycero-3-phosphatidic acid (DOPA) or sphingomyelin (SM) on the outer leaflet, with the addition of cholesterol (Chol), using methyl-β-cyclodextrin-catalyzed lipid exchange. The extent of outer leaflet exchange was found to be lipid-dependent. Further, we probed intracellular uptake and nucleic acid cargo delivery of DOPC:SM:Chol aLUVs. Widefield fluorescence imaging using HeLa_Luc705 cells and confocal imaging using SH-SY5Y-miRFP670 cells revealed cellular internalization and nuclear localization of aLUVs as early as 4 h, with analogous symmetric vesicles showing lower uptake and notable localization in the perinuclear region. However, HeLa_Luc705 cells treated with aLUVs and symmetric LUVs loaded with a splice-switching oligonucleotide showed similar levels of luciferase production after 24 h, indicating similar levels of functional oligonucleotide cargo delivery. Overall, the data presented indicates that asymmetric vesicles are able to deliver nucleic acid cargo and that the asymmetric distribution of lipids across membrane leaflets can influence the cellular uptake and intracellular distribution of vesicle nanocarriers.","PeriodicalId":50,"journal":{"name":"Langmuir","volume":"14 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2026-11-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149374769","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}