Langmuir最新文献

The chiral nematic phase structure, formed by the self-assembly of cellulose nanocrystals (CNCs) in an aqueous suspension and maintained in a solid film, shows great potential for optical applications. To achieve complex structures in optical devices, it is crucial to subject CNCs to specific shearing processes, such as spinning and printing. Understanding the structural and property changes of the CNC liquid crystal phase in these processes is of utmost importance. In this study, we investigated the effect of adding tannic acid (TA) on the rheological properties and cholesteric phase structures of CNCs/TA mixed suspensions. By calculating the surface site interaction points, we observed that TA can adsorb onto the surface of CNC rods in suspensions through hydrogen bonding. Through characterization techniques, such as polarized optical microscopy, rheology, and synchrotron SAXS, we examined the effects of TA addition on the microstructure and rheological properties of the CNC liquid crystal phase and clarified the change relating to the system composition. Under the same CNC concentration, the volume fraction of the anisotropic phase, the pitch, and the rod spacing of the cholesteric phase were not significantly affected by the addition of TA. However, the system viscosity was significantly reduced with the appropriate amount of TA (2 wt %), in a wide range of CNC concentrations (up to 15 wt % CNCs). The flow indexes (n) in Region I and Region III of steady-state shear curves of CNCs/TA systems (11-15 wt % CNCs) were compared. Moreover, we introduced the well-established theoretical models for liquid crystal polymers to tentatively interpret Region I of the CNCs/TA cholesteric phase and realized that increased numbers of smaller cholesteric-phase domains in the CNCs/TA system and interfacial modification by TA may contribute to the fluidity change. The feature of the domain texture of CNCs/TA systems is verified by polarized optical microscopy observations.

The accurate measurement of pH in highly alkaline environments is critical for various industrial applications but remains a complex task. This paper discusses the development of novel Fe-doped SrCoO_x-based FET sensors for the detection of extreme alkaline pH levels. Through a comprehensive investigation of the effects of Fe doping on the structure, electrical properties, and sensing performance of SrCoO_x, we have identified the optimal doping level that significantly enhances the sensor's performance in highly alkaline conditions. With a Fe doping level of 5 mol %, the sensitivity of the sensor improves to 0.86 lg(Ω)/pH while maintaining the response rate. Further increasing the Fe doping to 10 mol % results in a sensor that demonstrates favorable response time, a suitable pH range, and a linear correlation between lg(R) and pH. The combination of X-ray photoelectron spectroscopy and X-ray diffraction analysis provides insight into the regulation mechanisms of Fe doping on the crystal structure, electronic structure, and oxygen vacancy concentration of SrCoO_x. Our findings indicate that Fe doping leads to an increase in oxygen vacancy concentration and a decrease in the energy barrier for oxygen ion migration, which contributes to the improved sensing performance of the Fe-doped SrCoO_x sensors. Additionally, the study highlights the influence of oxygen vacancy concentration on the electrical properties of SrCoO_x. Precise control over the concentration of oxygen vacancies is crucial for optimizing the sensitivity and response speed of SrCoO_x FET sensors under extreme alkalinity conditions.

The huge polyoxometalate, ${Na}_{48}\left[H_x{Mo}_{256}^{VI}{Mo}_{112}^V{O}_{1032}{\left(H_{2}O\right)}_{240}{\left({\text{SO}}_4\right)}_{48}\right]$ ({Mo₃₆₈}), which can be prepared by a facile solution process and can be applied in lithium-ion storage applications as the anode. The large and open hollow nanostructure is promising to store a larger number of lithium ions and expedite the diffusion of lithium ions. A single {Mo₃₆₈} nanocluster can transfer 624 electrons, referred to as a "huge electron sponge". Pure {Mo₃₆₈} without any support materials exhibits very high capacities of 964 mA h g^-1 with hardly any decay for 100 cycles at 0.1 A g^-1 and still maintains 761 mA h g^-1 after 180 cycles at 0.5 A g^-1, indicating great cycling stability. The {Mo₃₆₈} anode provides excellent rate performance and reversibility during the lithiation/delithiation processes, which are contributed by both the diffusion-controlled process and the capacitive process. The capacitive contribution can reach 71.7% at a scan rate of 2 mV s^-1. The high D_Li⁺ value measured by GITT confirms the fast reaction kinetics of the {Mo₃₆₈} electrode. The {Mo₃₆₈}//NCM111-A full cell is practically applied to light LED lamps. These investigations indicate that {Mo₃₆₈} nanoclusters are advanced energy storage materials with high capacities, fast charge transfer, and low-cost mass production for lithium-ion storage. Moreover, {Mo₃₆₈} should be considered a clean energy material because there is no production of environmental pollution during the charge/discharge processes.

The specificity and efficiency of enzyme-mediated reactions have the potential to positively impact many biotechnologies; however, many enzymes are easily degraded. Immobilization on a solid support has recently been explored to improve enzyme stability. This study aims to gain insights and facilitate enzyme adsorption onto gold nanoparticles (AuNPs) to form a stable bioconjugate through the installation of thiol functional groups that alter the protein chemistry. In specific, the model enzyme, horseradish peroxidase (HRP), is thiolated via Traut's reagent to increase the robustness and enzymatic activity of the bioconjugate. This study compares HRP and its thiolated analog (THRP) to deduce the impact of thiolation and AuNP-immobilization on the enzyme activity and stability. HRP, THRP, and their corresponding bioconjugates, HRP-AuNP and THRP-AuNP, were analyzed via UV-vis spectrophotometry, circular dichroism, zeta potential, and enzyme-substrate kinetics assays. Our data show a 5-fold greater adsorption for THRP on the AuNP, in comparison to HRP, that translated to a 5-fold increase in the THRP-AuNP bioconjugate activity. The thiolated and immobilized HRP exhibited a substantial improvement in stability at elevated temperatures (50 °C) and storage times (1 month) relative to the native enzyme in solution. Moreover, HRP, THRP, and their bioconjugates were incubated with trypsin to assess the susceptibility to proteolytic digestion. Our results demonstrate that THRP-AuNP bioconjugates maintain full enzymatic activity after 18 h of incubation with trypsin, whereas free HRP, free THRP, and HRP-AuNP conjugates are rendered inactive by trypsin treatment. These results highlight the potential for protein modification and immobilization to substantially extend enzyme shelf life, resist protease digestion, and enhance biological function to realize enzyme-enabled biotechnologies.

In this study, a simultaneously decorated graphene sheet with titanium (Ti) and palladium (Pd) atoms is proposed to improve hydrogen adsorption uptake. Density functional theory (DFT) with a DFT-D3 correction dispersion study was applied. Initially, the hydrogen adsorption energy, energy band gap, partial density of state (PDOS), thermal stability, and H₂ desorption temperature for Ti-decorated, Pd-decorated, and Ti-Pd-decorated graphene sheets were investigated. Clustering formation for the Ti-decorated graphene sheet was examined in detail. Grand canonical Monte Carlo (GCMC) simulation was applied to examine the hydrogen adsorption isotherm. Simulation results showed that the hydrogen adsorption energy and desorption temperature of the Ti-decorated graphene sheet are -0.61 eV and 765.4 K, respectively, which are significantly higher than those of the Pd-decorated graphene sheet (-0.108 eV and 135.5 K). However, Ti atoms form clusters when their distances from each other are less than 6 Å. Inserting adaptable metal atoms such as Pd into the Ti-decorated graphene adjusts the hydrogen adsorption energy to -0.544 eV and the desorption temperature to 627.4 K. In addition, the values of Gibbs free energy changes (ΔG) of metal adsorption showed that the Ti-Pd graphene sheet has good stability at different temperatures. Calculated hydrogen adsorption isotherm using the GCMC method approved the suitable performance of the Ti-Pd-decorated graphene sheet for hydrogen adsorption. At the pressure of 60 bar and temperature of 298 K, the hydrogen adsorption content increases from 1.49 wt % on the Ti-decorated graphene sheet with cluster to 2.06 wt % on the Ti-Pd-decorated graphene sheet. Finally, Ti-Pd-decorated graphene sheet was proposed as a novel adsorbent in the hydrogen storage industry.

Pickering double emulsions exhibit higher stability and biocompatibility compared with surfactant-stabilized double emulsions. However, tailored synthesis of particle stabilizers with appropriate wettability is time consuming and complicated and usually limits their large-scale adoption. Using binary stabilizers may be a simple and scalable strategy for Pickering double emulsion formation. Herein, commercially available hydrophobic silica nanoparticles (SNPs) and sodium alginate (SA) as binary stabilizers are used to prepare O/W/O Pickering double emulsions in one-step emulsification. The influence of system composition on double emulsion preparation is identified by optical microscopy, confocal laser scanning microscopy, and interfacial tension and water contact angle analyses. The formation of the O/W/O Pickering double emulsion depends critically on the aqueous phase viscosity and occurrence of emulsion inversion. Both hydrophobic SNPs and SA adsorb at the droplet surface to provide a steric barrier, while SA also reduces interfacial tension and increases aqueous phase viscosity, giving double emulsion long-term stability. Their microstructure and stability are controlled by adjusting the SA concentration, water-oil volume ratio, concentration and wettability of the particle stabilizer, and oil type. As a demonstration, the middle layer of the as-prepared O/W/O Pickering double emulsions can be cross-linked in situ with calcium ions to produce calcium alginate porous microspheres. We believe that our strategy for double emulsion formation holds great potential for practical applications in food, cosmetics, or pharmaceuticals.

Aerogels have been widely studied in the field of thermal insulation. Herein, we reported a kind of conjugated micropolymer (CMP) aerogel synthesized by 1,3,5-triethynylbenzene and 2-amino-3,5-dibromopyridine. To enhance the flame-retardant property, we composited hydroxyapatite (HAP) nanowires with a CMP aerogel. Transmission electron microscopy (TEM) analysis revealed that HAP nanowires were encapsulated within nanosized CMP tubes. In addition, the thermal conductivity of HAP2-NCMP aerogel was 0.0251 W m^-1 K^-1, which possesses good thermal insulation property. In the micro-combustion calorimeter (MCC) test, compared with pure NCMP, the peak heat release rate (pHRR) of HAP2-NCMP decreased from 39.3 to 30.82 W g^-1, approximately 21.6% lower. Furthermore, with the increased addition of hydroxyapatite in the HAP-NCMP composite, the pHRR of HAP3-NCMP decreased by about 37.4%. Besides, NCMP possesses good mechanical properties, with a compressive strength of 117.3 kPa at a strain level of 60%. These findings suggest promising application potential for HAP-NCMP in energy-saving and flame-retardant applications.

Cartilage defects in large joints are a common occurrence in numerous degenerative diseases, especially in osteoarthritis. The hydrogel-on-metal composite has emerged as a potential candidate material, as hydrogels, to some extent, replicate the composition of human articular cartilage consisting of collagen fibers and proteoglycans. However, achieving tough bonding between the hydrogel and titanium alloy remains a significant challenge due to the swelling of the hydrogel in a liquid medium. This swelling results in reduced interfacial toughness between the hydrogel and titanium alloy, limiting its potential clinical applications. Herein, our approach aimed to achieve durable bonding between a hydrogel and a titanium alloy composite in a swollen state by modifying the surface texture of the titanium alloy. Various textures, including circular and triangular patterns, with dimple densities ranging from 10 to 40%, were created on the surface of the titanium alloy. Subsequently, poly(vinyl alcohol) (PVA) hydrogel was deposited onto the textured titanium alloy using a casting-drying method. Our findings revealed that PVA hydrogel on the textured titanium alloy with a 30% texture density exhibited the highest interfacial toughness in the swollen state, measuring at 1300 J m^-2 after reaching equilibrium swelling in deionized water, which is a more than 2-fold increase compared to the hydrogel on a smooth substrate. Furthermore, we conducted an analysis of the morphologies of the detached hydrogel from the textured titanium alloy after various swelling durations. The results indicated that interfacial toughness could be enhanced through mechanical interlocking, facilitated by the expanded volume of the hydrogel protrusions as the swelling time increased. Collectively, our study demonstrates the feasibility of achieving tough bonding between a hydrogel and a metal substrate in a liquid environment. This research opens up promising avenues for designing soft/hard heterogeneous materials with strong adhesive properties.

The lipids located in the outermost layer of the skin, the stratum corneum (SC), play a crucial role in maintaining the skin barrier function. The primary components of the SC lipid matrix are ceramides (CERs), cholesterol (CHOL), and free fatty acids (FFAs). They form two crystalline lamellar phases: the long periodicity phase (LPP) and the short periodicity phase (SPP). In inflammatory skin conditions like atopic dermatitis and psoriasis, there are changes in the SC CER composition, such as an increased concentration of a sphingosine-based CER (CER NS) and a reduced concentration of a phytosphingosine-based CER (CER NP). In the present study, a lipid model was created exclusively forming the SPP, to examine whether alterations in the CER NS:CER NP molar ratio would affect the lipid organization. Experimental data were combined with molecular dynamics simulations of lipid models containing CER NS:CER NP at ratios of 1:2 (mimicking a healthy SC ratio) and 2:1 (observed in inflammatory skin diseases), mixed with CHOL and lignoceric acid as the FFA. The experimental findings show that the acyl chains of CER NS and CER NP and the FFA are in close proximity within the SPP unit cell, indicating that CER NS and CER NP adopt a linear conformation, similarly as observed for the LPP. Both the experiments and simulations indicate that the lamellar organization is the same for the two CER NS:CER NP ratios while the SPP NS:NP 1:2 model had a slightly denser hydrogen bonding network than the SPP NS:NP 2:1 model. The simulations show that this might be attributed to intermolecular hydrogen bonding with the additional hydroxide group on the headgroup of CER NP compared with CER NS.

Polymer-based functional surface coatings are extensively used in advanced technologies, including optics, energy, and environmental applications. Surface thermodynamic properties profoundly impact the molecular interactions that control interfacial behaviors, such as adhesion and wettability, which in turn dictate coating processes and performance. Conventionally, contact angle measurements are used to assess the surface energy of polymer films and coatings, where the wettability of a surface is assessed using probe fluids (liquid drops). However, contact angle measurement oftentimes can be nontrivial due to the roughness or chemical heterogeneity of the solid surface, as well as the potential for the liquid drop to swell or even dissolve the material being measured. Alternatively, inverse gas chromatography (iGC) is a versatile technique to measure surface thermodynamics and Lewis acid-base properties while also providing environmental control such as temperature and humidity. Despite these benefits, the application of iGC has been limited to powders or fibers, while the direct measurement of supported thin films or coatings is still a nascent area of research. This creates a challenge when using iGC as a comprehensive platform for measuring the physicochemical properties of solid surfaces. Here, we demonstrate how to effectively use iGC to characterize the surface energy of supported polymer thin films by using a two-dimensional (2D) film holder and modifying operational controls, such as the concentration range of the injected gas probe molecules. This enables the precise control of surface coverage required for analyzing samples having minimal surface area, such as thin films. Poly(methyl methacrylate) (PMMA) was employed as a benchmark to determine suitable iGC parameters and to validate our approach on polymer thin films. The seminal work presented here expands the capability of state-of-the-art iGC to embrace supported thin films (2D iGC) that could either be smooth or display texture/roughness (patterned films) as well as coatings with heterogeneous chemical/structural composition.