Langmuir[JOURNAL]
Sun
200 papers
Ultrasensitive Visual Detection of Chitin Degradation via Surface Pitting on a Nanofibrous -Acetylchitosan Hydrogel.
Tsudome M, Tachioka M, Baba A … +6 more , Miyazaki M, Nakamura A, Nagaki K, Todaka N, Kurosawa Y, Deguchi S
Langmuir · 2026 Jun · PMID 42316438 · Publisher ↗
Microbial enzymes play a central role in biomass valorization, and their discovery and characterization are increasingly driven by data-driven molecular approaches. However, for enzymes acting on water-insoluble polymeri...
Microbial enzymes play a central role in biomass valorization, and their discovery and characterization are increasingly driven by data-driven molecular approaches. However, for enzymes acting on water-insoluble polymeric substrates, enzymatic reactions are inherently confined to solid-liquid interfaces, and interfacial properties critically govern reaction efficiency and detectability. Here, we report an interfacial sensing strategy that enables ultrasensitive visual detection of microbial chitinolytic activity by exploiting a nanofibrous -acetylchitosan hydrogel. The hydrogel consists of an entangled nanofiber network that provides a markedly increased surface area, thereby facilitating interfacial enzymatic reactions. When chitinolytic microorganisms are grown on the hydrogel surface, extracellular chitinases locally disrupt the nanofibrous network, producing nanoscale depressions that evolve into optically visible pits upon incubation. This approach enables visual detection of chitin degradation at the nanogram scale, with profilometric quantification down to ∼1 ng and naked-eye recognition at several tens of nanograms. By explicitly linking interfacial structure, surface morphology evolution, and enzymatic reaction kinetics, this work introduces a materials-based perspective that complements data-driven molecular approaches for the discovery and evaluation of microbial enzymes acting on insoluble polymeric substrates.
In Situ Deciphering Internal Electric Field-Accelerated Charge Dynamics and Stable Methanol Dehydrogenation with a 2/1 ZnInS/CdS Heterojunction.
Zhang Y, Li D, Chen G … +4 more , Yan F, Zhuang Y, Shan L, Dong L
Langmuir · 2026 Jun · PMID 42316415 · Publisher ↗
Refining interfacial charge migration routes is vital for boosting the dehydrogenation performance of liquid organic hydrogen carriers (LOHCs). Herein, the ZnInS/CdS heterostructure was effectively fabricated via a dual-...
Refining interfacial charge migration routes is vital for boosting the dehydrogenation performance of liquid organic hydrogen carriers (LOHCs). Herein, the ZnInS/CdS heterostructure was effectively fabricated via a dual-step solvothermal approach. Integrating ultraviolet photoelectron spectroscopy (UPS) with density functional theory (DFT) computations, we verified the formation of an internal electric field (IEF) pointing from ZnInS to CdS, driven by their distinct work functions. Time-resolved photoluminescence (TR-PL) measurements demonstrated that the photoinduced carrier lifetime for the 0.6ZIS/CS composite was notably extended to 2.36 ns. This delayed decay behavior signifies an improved charge transport route promoted by the IEF, thereby favoring the adsorption and transformation of reactive intermediates. Additionally, in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) confirmed the swift activation of methoxy species (*CHO) alongside the production of formaldehyde (*CHO) over the 0.6ZIS/CS surface. Aided by these refined intermediate and photoexcited carrier migration channels, the light-driven methanol dehydrogenation process is effectively propelled. The 0.6ZIS/CS sample achieves a H evolution of 0.88 mmol g·h within the methanol mixture, with H NMR identifying valuable formaldehyde as the primary oxidized product. Ultimately, this research clarifies and introduces an IEF-regulated mechanism governing the surface reaction kinetics during photocatalytic dehydrogenation.
Emergent Nontoxic N-CQDs as Functional Nanopest Repellents against Neonicotinoid Pesticides for Sustainable Agriculture.
Biswas T, De D, Jana SK … +4 more , Bhunia S, Chakraborty S, Mandal S, Sahoo P
Langmuir · 2026 Jun · PMID 42315486 · Publisher ↗
The extensive use of neonicotinoid pesticides has greatly enhanced crop yields. However, their water solubility, environmental persistence, and toxicity to nontarget species raise ecological and health concerns. In this...
The extensive use of neonicotinoid pesticides has greatly enhanced crop yields. However, their water solubility, environmental persistence, and toxicity to nontarget species raise ecological and health concerns. In this research, we present nitrogen-doped carbon quantum dots (N-CQDs) approximately 6 nm in size that serve as a multifunctional platform. They can detect neonicotinoid pesticides through a simple fluorescence turn-off method, diminish their effectiveness in water and agricultural settings, and act as nanopesticide repellents. The N-CQDs exhibit strong, stable fluorescence, numerous surface functional groups, and high biocompatibility, enabling selective interactions with compounds such as imidacloprid, thiamethoxam, clothianidin, thiacloprid, and nicotine. Characterization techniques such as TEM, PXRD, FT-IR, XPS, EDX, UV-vis, H NMR, and fluorescence spectroscopy were used to analyze the nanosensor's morphology and features. The sensor achieved a detection limit of 23 nM, indicating excellent sensitivity. Spectroscopic analyses indicate that N-CQDs form strong noncovalent associations and stable complexes with neonicotinoid pesticides, accompanied by a noticeable decrease in their biological activity as observed in functional experiments. Practical tests, including cytotoxicity assays, fruit bioassays, and ant-repellence trials, confirm that N-CQDs can effectively neutralize neonicotinoid pesticides in real-world conditions without being toxic or unsafe. This approach offers a sustainable way to address neonicotinoid pesticide pollution, promoting safer farming methods and environmental preservation. Surprisingly, the nanosensor not only detects and mitigates neonicotinoid pesticides but also serves as a nanopest repellent in real-world agricultural use.
Polythiourea-Decorated CuO Nanorod Films for Efficient Nitrophenol Hydrogenation with Reconstruction.
Cao J, Li T, Deng Z … +1 more , Li Y
Langmuir · 2026 Jun · PMID 42314150 · Publisher ↗
The development of high-performance, noble-metal-free catalytic films for wastewater remediation is fundamentally constrained by weak interfacial affinity, slow mass transfer kinetics, and inadequate structural stability...
The development of high-performance, noble-metal-free catalytic films for wastewater remediation is fundamentally constrained by weak interfacial affinity, slow mass transfer kinetics, and inadequate structural stability under harsh reducing conditions. In this study, we present a multiscale interfacial engineering strategy to successfully fabricate catalytic films based on one-dimensional (1D) CuO nanorods decorated with an ultrathin polythiourea (PTU) layer. Through sodium citrate-assisted anisotropic growth, a morphological transition of CuO from 2D nanosheets to 1D nanorods is precisely achieved. The results demonstrate that, owing to their high aspect ratio, the 1D nanorods can form an effective mechanical interlocking network with porous substrates, thereby overcoming the critical adhesion bottleneck associated with catalyst detachment in liquid-phase environments. The film modified with 10 mL of PTU exhibits an optimal reaction time of 18 min for the catalytic reduction of 4-nitrophenol. Two-dimensional correlation spectroscopy is employed to unambiguously elucidate the catalytic kinetic pathway at the molecular sequential level. The hybrid film maintains a conversion rate exceeding 95% over 14 consecutive batch cyclic tests. Postreaction characterization reveals a unique "adaptive in situ reconstruction" mechanism: although the 1D nanorods evolve into a 3D porous nanoparticle network, the robust PTU polymer chains act as flexible binders that firmly anchor the reconstructed active species, ensuring exceptional long-term durability. This study not only provides a scalable paradigm for designing ultrastable catalytic films but also establishes a transformative spectroscopic methodology for probing interfacial dynamic kinetics at the molecular level.
High-Efficiency P(VDF-HFP)-Based Nanocomposite Dielectrics: Embedding PP Chain Segments to Offset the Efficiency Penalty of Ceramic Fillers.
Ran C, Liang Y, Li B … +9 more , Xing Y, Chen X, Cai C, Guo J, Tong G, Sun J, Zheng Y, Liao H, Zhang J
Langmuir · 2026 Jun · PMID 42314120 · Publisher ↗
Poly(vinylidene fluoride) (PVDF)-based ferroelectrics are essential for film capacitors, yet their high dielectric loss and low charge/discharge efficiency caused by ferroelectric hysteresis severely limit practical appl...
Poly(vinylidene fluoride) (PVDF)-based ferroelectrics are essential for film capacitors, yet their high dielectric loss and low charge/discharge efficiency caused by ferroelectric hysteresis severely limit practical applications. Linear polypropylene (PP), in contrast, dominates the commercial capacitor market due to its high efficiency and low loss, prompting extensive efforts to combine the advantages of both polymers. However, existing approaches often rely on costly molecular design or complex film-forming processes, conflicting with the demands for low-cost and miniaturized electronic devices. Here, we report a solution-based and scalable strategy that avoids high-temperature melt processing to fabricate a hybrid dielectric film comprising a P(VDF-HFP) matrix, embedded PP chain segments, and core-shell structured BT@SiO nanoparticles. Polypropylene chain segments are embedded into the poly(vinylidene fluoride--hexafluoropropylene) [P(VDF-HFP)] matrix via solution blending, forming molecularly interpenetrating interfaces that effectively suppress ferroelectric hysteresis. Core-shell structured BT@SiO nanoparticles are simultaneously incorporated to further enhance dielectric properties. The resulting P(VDF-HFP)-PP/BT@SiO nanocomposite films exhibit a high dielectric constant of 46, a charge/discharge efficiency consistently exceeding 80%, and a maximum energy density of 3.92 J/cm. Phase-field simulations further reveal that the P(VDF-HFP)-PP/BT@SiO architecture with graded dielectric constants mitigates local electric field concentration, accounting for the excellent breakdown performance. Unlike conventional high-temperature melt processing or complex molecular design, this work offers a low-cost and scalable route that avoids high-temperature melt processing to high-performance polymer dielectrics, demonstrating that combining molecular interpenetration with core-shell filler engineering provides a promising pathway for next-generation capacitors.
Adhesion Depends on Interfacial Strength: Time and Temperature Effects.
Wang SQ, Fan Z, Pang T … +1 more , Cui Z
Langmuir · 2026 Jun · PMID 42314020 · Publisher ↗
In the conventional description, peeling of an adhesive from a solid substrate is expressed in terms of adhesion energies at adhesive-substrate interfaces. However, this energy-based perspective faced considerable diffic...
In the conventional description, peeling of an adhesive from a solid substrate is expressed in terms of adhesion energies at adhesive-substrate interfaces. However, this energy-based perspective faced considerable difficulties in explaining why the adhesion energy, also known as peel strength Γ, is many orders of magnitude greater than Dupré's thermodynamic work of adhesion, Γ. In this study, we present experimental evidence to demonstrate that polymer adhesion is governed by interfacial strength σ, defined by the pair of adhesive and substrate. A tensile adhesion test is performed to estimate σ from adhesion strength σ equal to the engineering stress at detachment. This test stretches, at various rates under different temperatures, one end of a ribbon-like specimen with the other end adhered to the same substrate used in peeling tests until adhesive detachment. The dependence of σ on applied rate and temperature is found to be the same as that of Γ from conventional peeling tests on peeling speed and temperature. Our stress perspective shows that Γ explicitly correlates with σ through a characteristic length scale instead of Γ. Here, is the distance from the peeling front, beyond which the adhesive undergoes little deformation. Since is a much larger length scale than a molecular scale and σ directly depends on polymer-substrate interfacial interactions, Γ explicitly depends on σ. As activated processes, in both peeling and tensile adhesion tests, interfacial debonding on shorter time scales and lower temperature required higher interfacial stress.
Effect of pH and Protein Flexibility on the Structure of Protein Foams: A Multi-Scale Approach.
Gräff K, Zimmer J, Soltwedel O … +5 more , Robertson H, Chiappisi L, Micciulla S, Schneck E, von Klitzing R
Langmuir · 2026 Jun · PMID 42313636 · Publisher ↗
Aqueous protein-stabilized foams are omnipresent in daily life, e.g., within food or in industrial applications. In this study, we apply a multiscale approach and investigate proteins adsorbed at the air/water interface,...
Aqueous protein-stabilized foams are omnipresent in daily life, e.g., within food or in industrial applications. In this study, we apply a multiscale approach and investigate proteins adsorbed at the air/water interface, as well as foam films and macroscopic foams stabilized by four different proteins: β-lactoglobulin (BLG), bovine serum albumin (BSA), casein (CN), and lupine protein isolate (LPI). Protein adsorption at the air/water interface was investigated using Brewster angle microscopy (BAM) and X-ray reflectivity (XRR). Adding to individual thin film studies with a thin film pressure balance (TFPB), we employed small-angle scattering (SANS), which is able to investigate Newton black films (NBFs) within macroscopic foams. The film is thinnest near the isoelectric point (IEP), while adsorption layers at the air/water interface are thickest at the IEP. Importantly, we report for the first time the properties of NBFs within protein foams, enabling a direct comparison across length scales with individual foam films.
Theranostic Activity of a Fluorescent Heterobimetallic Ir-Pd Complex toward Cancer Cells.
Das D, Bhattacharya S, Banerjee T … +6 more , Das U, Majumder A, Roy P, Morgan DJ, Maity R, Sen K
Langmuir · 2026 Jun · PMID 42313515 · Publisher ↗
Advanced and inexpensive imaging techniques need to be developed urgently to mitigate the burden of cancer globally. Compared with traditional imaging techniques, fluorescence imaging offers an immensely sensitive and se...
Advanced and inexpensive imaging techniques need to be developed urgently to mitigate the burden of cancer globally. Compared with traditional imaging techniques, fluorescence imaging offers an immensely sensitive and selective tool for cancer cell imaging with the advantage of high spatial and temporal resolution. Herein, we present a fluorescent heterobimetallic complex (HBMC) of Ir(III)/Pd(II), which selectively images the nucleus of cancer cells (HeLa) over normal cells (HaCaT) at a very low concentration (12 μM), established by confocal laser scanning microscopy. HBMC has a unique property by virtue of which it is selectively taken up by cancer cells and hence allows selective imaging of cancer cells over normal cells. The cell viability of HeLa cells showed an IC50 of 18 μM for HBMC. However, the homonuclear subunits of HBMC are ineffective in imaging cancer cells. The possible reason behind its selectivity toward cancer cells is its interaction with a protein with ∼44 kDa molecular weight, which was obtained from mass spectrometric analysis. A bioinformatics study predicted the protein with ∼44 kDa molecular weight as a serotonin receptor, 5-HT, overexpressed in HeLa cells. The most interesting fact is that HBMC has a dual effect in selective fluorescence imaging and a cytotoxic effect toward HeLa cells, establishing its remarkable theranostic properties toward cancer cells in contrast to normal cells. Interactions of DNA with HBMC establish a sequential binding pattern between them. Hence, our low-cost fluorosensor may have dual applicability in the early diagnosis of patients having cancer with a therapeutic approach.
Synergistic Engineering Assembly of Twisted Mesoporous Carbon Nanorods as Potential Lithium-Ion Battery Anodes.
Li H, Huang S, Kang Z … +3 more , Zhu Y, Zhu G, Zhang H
Langmuir · 2026 Jun · PMID 42312945 · Publisher ↗
Precise engineering of geometrical structure in mesoporous carbon materials is crucial for enhancing their electrochemical storage performance. Herein, we report a tannic acid-mediated molecular-level interface assembly...
Precise engineering of geometrical structure in mesoporous carbon materials is crucial for enhancing their electrochemical storage performance. Herein, we report a tannic acid-mediated molecular-level interface assembly strategy to construct highly nitrogen-doped twisted mesoporous carbon nanorods (MCR) for the first time. Controlled experiments reveal that tannic acid and toluene act as synergistic molecular regulators, guiding the assembly of Pluronic P123 (PEOPPOPEO) into stable cylindrical micelles via hydrogen bonding and hydrophobic interactions, which subsequently evolve into a twisted rod-like morphology. The twisted architecture effectively buffers volume expansion during repeated lithiation/delithiation. Meanwhile, the large specific surface area and high nitrogen doping level (13.9 at. %) provide abundant electroactive sites for lithium-ion storage. Furthermore, the well-aligned one-dimensional mesoporous channels facilitate rapid ion diffusion and efficient electron transport. As a result, the designed MCR anode delivers a high reversible capacity of 701.9 mA h g at 100 mA g after 150 cycles and remains at 563.9 mA h g at 1000 mA g after 1500 cycles, outperforming the control mesoporous carbon spheres (only 436.6 mA h g at 100 mA g, 341.7 mA h g at 1000 mA g). This work offers valuable insights for the rational design of high-performance porous carbon electrode materials with tailored geometric architectures.
Enhanced Sr Sequestration in Fe-Modified Sodium Titanate: Adsorption Performance and Mechanisms.
Zhang Q, Qian Z, Liu X … +3 more , Wang S, Qiao Y, Liu X
Langmuir · 2026 Jun · PMID 42312890 · Publisher ↗
The sequestration of Sr remains a significant challenge in the treatment of radioactive liquid waste. In this work, we studied the synthesis and characterization of sodium titanate (NTO) and Fe-modified sodium titanate (...
The sequestration of Sr remains a significant challenge in the treatment of radioactive liquid waste. In this work, we studied the synthesis and characterization of sodium titanate (NTO) and Fe-modified sodium titanate (Fe-NTO) for the removal of Sr from complex aqueous environments. The introduction of Fe species was accompanied by an expanded interlayer spacing of the sodium titanate phase, which may improve Sr accessibility and influence adsorption behavior. Adsorption kinetics and isotherms of Fe-NTO could be described by the pseudo-second-order model and the Langmuir equation, respectively, giving an enhanced capacity of 173.92 mg g as compared to pristine NTO (151.03 mg g). In complex solution matrices, Fe-NTO maintained effective Sr uptake in simulated seawater, although the Sr/Ca discrimination was modest. In simulated waste liquid of the thorium molten salt reactor nuclear energy system (TMSR), Fe-NTO exhibited strong Sr adsorption with a high distribution coefficient of 1.47 × 10 mL g, while also showing strong uptake of other multivalent ions. Combined Raman, XPS, postadsorption XRD, and ICP-OES analyses support that Sr sequestration involves electrostatic attraction, Na/Sr ion exchange, and weak interactions with oxygen-containing sites in the titanate structure. These findings demonstrate the potential of Fe-NTO for effective Sr sequestration in complex aqueous matrices, including simulated TMSR-related waste liquid, while underscoring the need for further optimization of ion selectivity in multicomponent systems.
Nonintrusive Dynamic Pressure Monitoring of Sloshing Liquid Using a Hierarchically Microstructured Flexible Sensor.
Thapa P, Sarma S
Langmuir · 2026 Jun · PMID 42312697 · Publisher ↗
Monitoring dynamic pressure in sloshing liquids is critical for the safety of storage, transportation, and aerospace systems, as uncontrolled sloshing can increase structural loads and cause vehicle instability or contai...
Monitoring dynamic pressure in sloshing liquids is critical for the safety of storage, transportation, and aerospace systems, as uncontrolled sloshing can increase structural loads and cause vehicle instability or containment failure. Conventionally, such measurements are done using rigid pressure transducers that are flush-mounted through drilled ports. This process disturbs the flow, limits the repositioning of sensors, and is unsuitable for curved or flexible tank surfaces. In this study, a hierarchically microstructured flexible pressure sensor (FlexiHMS) was employed to monitor slosh-induced wall pressures and benchmarked against a commercial piezoelectric (PZT) sensor. Controlled sloshing experiments were conducted in a lab-developed rectangular tank at 22%, 30%, and 70% fill volumes under base excitation from 0.8 to 1.2 times the first-mode natural frequency. Free-decay tests validated the test protocol, where dominant frequencies deviated from theoretical values by less than 5%. FlexiHMS successfully captured peak dynamic pressures ranging over (0.3-127) Pa and closely followed the expected resonant amplification behavior. Frequency-domain analysis using fast Fourier transforms and steady-state boxplots revealed pronounced nonlinear pressure characteristics near resonance, with increased dispersion and intermittency. While both sensors demonstrated repeatable cycle-to-cycle responses across multiple trials, FlexiHMS continued to exhibit a measurable pressure response under conditions where the PZT response diminished, especially at higher fill volumes. Our results highlight the potential of flexible pressure sensors like FlexiHMS for conformal, nonintrusive, dynamic pressure monitoring in fluid-structure interaction systems where conventional rigid sensor mounting is impractical.
Interfacial Redox Decoupling via Amphiphilic Carbon Dots for Highly Efficient Biphasic Photocatalytic HO Production and Selective Benzyl Alcohol Oxidation.
Wu C, Tong H, Shu F … +5 more , Wu T, Cui H, Zhu H, Wang C, Song Q
Langmuir · 2026 Jun · PMID 42312476 · Publisher ↗
Photocatalytic hydrogen peroxide (HO) production from water and molecular oxygen offers a sustainable alternative to the energy-intensive anthraquinone process; however, its practical advancement is limited by inefficien...
Photocatalytic hydrogen peroxide (HO) production from water and molecular oxygen offers a sustainable alternative to the energy-intensive anthraquinone process; however, its practical advancement is limited by inefficient charge utilization, poor selectivity, product instability, and challenging separation. Herein, we report a quasi-homogeneous phase-transfer photocatalytic system enabled by rhodamine B-derived amphiphilic carbon dots that enables interfacial redox decoupling for high-efficiency HO photosynthesis. The as-prepared carbon dots serve a trifunctional role as visible-light harvesters, interfacial stabilizers, and redox catalysts, facilitating the formation of a light-responsive water/benzyl alcohol emulsion. This biphasic architecture maximizes interfacial charge carrier flux while ensuring spontaneous phase separation postirradiation. In this configuration, the two-electron oxygen reduction reaction is localized within the aqueous phase, while the photogenerated holes drive the selective oxidation of benzyl alcohol to value-added benzaldehyde in the organic phase. Consequently, an exceptional HO production rate of 13 250 μmol g h is achieved, accompanied by a benzyl alcohol conversion of 83.7% and a benzaldehyde yield of 82.6%. This strategy not only suppresses HO decomposition through spatial segregation but also enables in situ product isolation and facile catalyst recycling. This work establishes interfacial phase-transfer photocatalysis as a robust and versatile platform for integrating solar-to-chemical energy conversion with selective organic transformations.
Laser-Patterned Oxidized Steel Mesh with Dual Wettability for Efficient Atmospheric Water Harvesting.
Omidali F, Azizian S, Sohrabi B … +2 more , Shabanlou E, Jaleh B
Langmuir · 2026 Jun · PMID 42312349 · Publisher ↗
Surface modification techniques play a vital role in improving fogwater harvesting efficiency. In this study, stainless steel mesh was modified using pulsed laser ablation and subsequently functionalized with stearyl alc...
Surface modification techniques play a vital role in improving fogwater harvesting efficiency. In this study, stainless steel mesh was modified using pulsed laser ablation and subsequently functionalized with stearyl alcohol, an eco-friendly, low cost and fluorine-free hydrophobic agent. The fabricated surfaces were characterized by field emission scanning electron microscopy (FESEM), atomic force microscopy (AFM), energy dispersive X-ray spectroscopy (EDS), and elemental mapping to confirm their morphological and chemical features. The effects of laser patterning (0.5 and 1 cm line intervals), stearyl alcohol concentration, and immersion time were systematically investigated. Among all prepared samples, the chemically modified mesh with 0.5 cm laser patterning (m-L5) exhibited the highest performance, achieving a water harvesting rate (WHR) of 7.36 mg min cm, which is ∼2.5 times higher than the pristine stainless-steel mesh. Furthermore, tilting angle experiments revealed that horizontal positioning (0°) provides superior efficiency compared to 45° and 90°. These results highlight the potential of sustainable surface engineering strategies for effective fog collection.
Resolving Discrepancies in Disjoining Pressure Predictions for Liquid Nanofilms from Molecular Simulations.
Yang Y, Zuo Z, Wan J … +2 more , Sun S, Lau D
Langmuir · 2026 Jun · PMID 42312329 · Publisher ↗
Literature values of disjoining pressure in liquid nanofilms from different molecular simulation methods show significant discrepancies. We demonstrate that these arise from neglecting long-range dispersion interactions...
Literature values of disjoining pressure in liquid nanofilms from different molecular simulation methods show significant discrepancies. We demonstrate that these arise from neglecting long-range dispersion interactions and inconsistent definitions of film thickness in the original Peng method. A key insight is that long-range dispersion affects surface tension in a thickness-dependent manner, increasing it at large thickness but suppressing its enhancement at small thickness due to disjoining-pressure-induced normal compression and lateral expansion. This even gives rise to a crossover behavior in the surface tension of water nanofilms simulated with the flexible SPC/E potential, although the crossover is not clearly observed in the rigid SPC/E and TIP4/2005 models at the same temperature. Since disjoining pressure is obtained from the derivative of surface tension with respect to thickness, this nontrivial dependence strongly impacts its accuracy. With proper treatment of dispersion interactions and a consistent thickness definition, the revised Peng method agrees with the Bhatt method and yields more accurate Hamaker constants.
Multiscale Analysis of the Impact of the Isomerization of 4-Amine Tetraortho-Azobenzenes on the Structure and Dynamics of Tubular Micelles.
Luviano AS, Rincón-Londoño N, Ramírez-Rave S … +3 more , Gracia-Mora J, Bernad-Bernad MJ, Yatsimirsky AK
Langmuir · 2026 Jun · PMID 42311086 · Full text
A multiscale analysis of photoresponsive micellar systems based on CTAB/NaSal and 4-amine tetraortho-azobenzenes (AzoCH and AzoCl) was carried out to elucidate how molecular photoisomerization modulates micellar morpholo...
A multiscale analysis of photoresponsive micellar systems based on CTAB/NaSal and 4-amine tetraortho-azobenzenes (AzoCH and AzoCl) was carried out to elucidate how molecular photoisomerization modulates micellar morphology, mesoscopic organization, and macroscopic dynamics in the semidilute regime. Under basic conditions (pH 11), CTAB/NaSal solutions incorporating trans-AzoCH and trans-AzoCl form well-defined wormlike micelles (WLMs), as confirmed by TEM and molecular dynamics simulations, which reveal the presence of tubular structures. Dynamic light scattering (DLS) measurements indicate that these systems lie within the semidilute-entangled regime, where collective hydrodynamic behavior dominates over individual micellar dimensions, in agreement with viscosity measurements. Upon UV irradiation at 360 nm, photoisomerization of the azobenzenes induces a pronounced disruption of the WLM network, leading to partial collapse and fragmentation of tubular structures, as evidenced by HR-TEM imaging and simulations. Despite this significant structural rearrangement, DLS measurements reveal no substantial change in the hydrodynamic correlation length, indicating that the system remains in the semidilute regime, consistent with the slight decrease in viscosity while preserving shear-thinning behavior. Thermal -to- isomerization kinetics were monitored by UV-vis spectroscopy and were well described by monoexponential behavior, confirming reversible photosensitivity within the micellar environment. These results demonstrate that azobenzene photoisomerization can modulate micellar morphology without altering the overall concentration regime, highlighting a decoupling between local micellar structure and mesoscopic collective dynamics. This behavior underscores the robustness of semidilute wormlike micellar networks and their potential for applications in light-responsive soft materials.
Polyelectrolyte Surfactant Aggregates for Stabilizing and Transporting Hydrophobic Species across Oil/Water Interfaces.
Roguski M, Walker LM
Langmuir · 2026 Jun · PMID 42310893 · Publisher ↗
The delivery of hydrophobic species dispersed in aqueous media to a nonpolar phase often involves crossing an oil/water interface. Here, we demonstrate the potential of using water-dispersible polyelectrolyte surfactant...
The delivery of hydrophobic species dispersed in aqueous media to a nonpolar phase often involves crossing an oil/water interface. Here, we demonstrate the potential of using water-dispersible polyelectrolyte surfactant aggregates (PES) to solubilize hydrophobic moieties in an aqueous environment and deliver them to an oil phase. Central to the success of this approach is that these aggregates have the additional advantage of stabilizing fluid/fluid interfaces through interfacial elasticity, providing time for transport across the interface. The PES used is poly(cetyltrimethylammonium vinyl benzoate) (pCTVB), which forms rodlike aggregates (4 nm diameter, 120-150 nm in length) in solution that consist of a hydrophobic backbone of poly(vinyl benzoate) (pVB) and a stoichiometric, based on the charge, number of positively charged surfactant cetyltrimethylammonium (CTA). The interfacial properties of PES aggregates adsorbed at the oil/water interfaces are compared with those at the air/water interface. These aggregates previously showed complex adsorption behavior and high dilatational elasticity at air/water interfaces. At the oil/water interface, the PES aggregates reach a higher interfacial pressure (42.2 mN/m versus 30.8 mN/m), are more persistent, and still result in a highly elastic interface (|*| ∼ 100 mN/m). This PES system allows for the efficient transport of hydrophobic active species from aqueous solutions across an oil/water interface and stabilization of the interface by increasing the dilatational modulus and decreasing the interfacial tension.
Ion-Track-Etched Membranes as Nanoionic Platforms: Fabrication, Nanoscale Ion Transport, and Device Applications─A Review.
Ali Haider MH, Ali M, Ensinger W … +3 more , Farooq MO, Shahzad MW, Akhtar FH
Langmuir · 2026 Jun · PMID 42309980 · Publisher ↗
Ion-track-etched membranes (ITEMs) have emerged as a distinct class of nanostructured materials and represent a versatile platform that offers precise control over pore shape, size, and areal density. These membranes off...
Ion-track-etched membranes (ITEMs) have emerged as a distinct class of nanostructured materials and represent a versatile platform that offers precise control over pore shape, size, and areal density. These membranes offer considerable mechanical and chemical stability, making them valuable for a variety of applications, including nanoionic rectifiers, sensors, nanoiontronics devices, and energy harvesting systems. The chemical etching process of ITEMs introduces carboxylic acid groups on the surface, which serve as the sites for functionalization. Functionalization is crucial for using the ITEMs in sensor applications. ITEM-based sensors provide considerable sensitivity and selectivity. Moreover, the sensors have a low limit of detection compared to other traditional sensors. ITEMs also exhibit memristive behavior (hysteresis loop) and can perform logic gate functions. These attributes are crucial for nanoionic fluidic-based neuromorphic computing. Moreover, ITEMs can serve as efficient platforms for osmotic energy harvesting (OEH) as well as membrane-assisted cooling and dehumidification applications. This review article articulates the fundamentals of ITEMs, fabrication strategies, the origins of surface-charge-dominated ion-transport mechanisms under nanoconfinement, and chemical functionalization approaches. In addition to that, concepts of ionic rectification, hysteresis, and nonlinear functionalities related to the memristor and neuromorphic computing are also discussed. Moreover, special attention was paid to OEH systems, and power densities obtained with different membranes were also discussed and compared. The review article also provides insights into next-generation nanoionic systems by combining the concepts of nanofluidics and electrochemistry. In addition, a comprehensive analysis of the current challenges and future opportunities in developing multifunctional, scalable, and sustainable ITEM technologies is also presented.
NaCl-Assisted Pyrolysis of Zn (II) Complexes with BTC and PDC to Synthesize Cl, N-Codoped Carbon Highly Efficient for Oxygen Reduction.
Teng JQ, Ding XB, Cao QC … +2 more , Xiong J, Qin YH
Langmuir · 2026 Jun · PMID 42309508 · Publisher ↗
The design of high-performance, cost-effective, and durable electrocatalysts for the oxygen reduction reaction (ORR) is essential for the widespread deployment of clean energy technologies, including fuel cells and metal...
The design of high-performance, cost-effective, and durable electrocatalysts for the oxygen reduction reaction (ORR) is essential for the widespread deployment of clean energy technologies, including fuel cells and metal-air batteries. Carbon-based metal-free catalysts (CMFCs) have emerged as promising alternatives to Pt-based materials, with their ORR performance tunable through heteroatom doping and defect engineering. In this study, we report a novel Cl, N-codoped porous carbon catalyst (Cl, N-C) enriched with structural defects, synthesized via a modified metal-organic framework (MOF) strategy. Zinc-1,3,5-benzenetricarboxylate (Zn-BTC) was employed as the MOF precursor, with partial substitution of BTC by pyridine-3,5-dicarboxylate (PDC) to introduce nitrogen and defect sites. During Zn-BTC-PDC pyrolysis, NaCl was added to enable Cl doping and promote further defect formation. Structural characterization reveals that the optimized catalyst (Cl, N-C-2) possesses abundant mesopores, high defect density, and a favorable distribution of pyridinic and graphitic nitrogen species. As a result, Cl, N-C-2 exhibits outstanding ORR activity in alkaline media, achieving a half-wave potential of 0.891 V vs RHE, which ranks among the highest reported to date for CMFCs. Electrochemical analyses demonstrate enhanced electrochemically active surface area, faster kinetics, and excellent durability. In situ ATR-SEIRAS measurements further reveal that Cl doping promotes the formation and stabilization of key OOH intermediates, facilitating a dominant four-electron ORR pathway. When applied as an air cathode in Zn-air batteries, Cl, N-C-2 delivers higher discharge voltage and power density than Pt/C. This work provides an effective strategy for designing high-performance metal-free carbon electrocatalysts through synergistic heteroatom doping and defect engineering.
Asymmetric Bias Effects of Polyelectrolyte Brushes: A Systematic Electrochemical Impedance Spectroscopy Study.
Smook LA, Diepenbroek E, de Beer S
Langmuir · 2026 Jun · PMID 42307581 · Publisher ↗
Polyelectrolyte brushes are promising surface modifications, and it is known that their properties are affected by environmental conditions. For electrical applications, it is crucial to know the effect of these environm...
Polyelectrolyte brushes are promising surface modifications, and it is known that their properties are affected by environmental conditions. For electrical applications, it is crucial to know the effect of these environmental conditions on the electrical properties of the brushes. Here, we systematically evaluate the role of the ion concentration and bias voltage on the electrical properties of negatively charged polyelectrolyte brushes through probe-free electrochemical impedance spectroscopy. We interpret the response using an equivalent electrical circuit and find that the values of the equivalent circuit elements are affected by environmental conditions. We attribute these effects to structural and compositional changes in the brush layers. Because of the charged nature of the brush, the response displays an asymmetry between positive and negative biases, which inverts if the charge of the brush is inverted. These results reveal that brush charge and environmental conditions deserve critical consideration when charged polymer brushes are used in electronic or iontronic applications.
Generalized Statistical Isotherm for Modeling Adsorption Equilibria in Stimuli-Responsive Framework Materials.
Azzan H, Danaci D, Petit C … +1 more , Pini R
Langmuir · 2026 Jun · PMID 42307122 · Full text
Designing large-scale adsorption-based separation units requires a multiscale understanding of material behavior, from molecular interactions to process-level performance. An underpinning challenge is the development of...
Designing large-scale adsorption-based separation units requires a multiscale understanding of material behavior, from molecular interactions to process-level performance. An underpinning challenge is the development of predictive multicomponent adsorption equilibrium models for systems departing from the classic type I isotherm for microporous adsorbents. Adsorbents that undergo adsorption-induced transitions (flexible adsorbents) belong to this category and are a class of framework materials that exhibit unique features such as sigmoidal equilibrium isotherms and intrinsic thermal management capabilities. Despite their promise for practical applications, flexible adsorbents remain underexplored at the process scale due to the lack of a suitable equilibrium isotherm model that mechanistically captures their adsorption-induced structural transitions. Here, we present a simplified statistical isotherm model for transition materials (SSI-T) as a generalized approach to parametrize─using a combination of sorbate-dependent and -independent physical parameters─the adsorption equilibria in flexible adsorbents that exhibit a broad range of structural and configurational transitions upon adsorption. We have validated the model using unary and binary equilibrium data for gate-opening, breathing, and configurational transitions in multiple adsorbent-adsorbate systems. Our formulation represents the first continuous, differentiable, and explicit isotherm model in the literature capable of accurately describing unary adsorption and desorption isotherms in flexible adsorbents, and predicting binary equilibria for multiple types of adsorption-induced transitions without any additional parameters. Because SSI-T is an explicit function of state variables, it can be seamlessly integrated into process-scale simulators, enabling the design and optimization of adsorption-based technologies that use flexible adsorbents.
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