Search Results (1,131)

The self-consistent field Poisson–Boltzmann framework is applied for analysis of equilibrium partitioning of ampholytic protein-like nanocolloids between buffer solution and weak (pH-sensitive) versus strong polyelectrolyte (polyanionic) brushes with the same net charge per unit area. The position-dependent nanocolloid net charge and the insertion freeenergy profiles are derived as a function of pH and ionic strength in the solution. It is demonstrated that, similar to strong polyelectrolyte brushes, pH-sensitive brushes are capable of the uptake of nanocolloids in the vicinity of the isoelectric point, that is, when the net charge of the colloid in the buffer has either the opposite or the same sign as the ionized monomer units of the brush. At $pI\ge p{K}_{brush}$ and $pH\ge pI$, the particle absorption patterns by similarly (negatively) charged brushes are qualitatively similar in the cases of strong and weak polyelectrolyte brushes, but the freeenergy barrier at the brush periphery is wider for weak than for strong polyelectrolyte brushes, which may cause stronger kinetic hindrance for the nanocolloid uptake by the brush. A decrease in $pH$ below the IEP leads to a monotonic increase in the depth of the insertion freeenergy minimum inside a strong polyelectrolyte brush, whereas for weak polyelectrolyte brushes, a more peculiar trend is predicted: due to competition between the increasing positive charge of the nanocolloid and the decreasing magnitude of the negative charge of the brush, the absorption is weakened at low $pH$. Full article

To satisfy the superior surface quality requirements in the fabrication of HBM (High-Bandwidth Memory) and 3D NAND Flash Memory, high-efficiency Si chemical mechanical planarization (CMP) is essential. In this study, a colloidal silica abrasive-based Si-wafer CMP slurry was developed to simultaneously achieve a high polishing rate (≥10 nm/min) and low surface roughness (≤0.2 nm) without inducing CMP-induced scratches. The proposed Si-wafer CMP slurry incorporates two functional components: triammonium phosphate (TAP) as a hydrolysis reaction accelerator and hydroxyethyl cellulose (HEC) as an abrasive drag force accelerator. The polishing rate enhancement mechanism of TAP was analyzed by monitoring the OH⁻ mol concentration, surface adsorption behavior, and XPS spectra. The results showed that increasing the TAP concentration raised the OH⁻ mol concentration and converted Si–Si and Si–O–Si bonds to Si–OH via a hydrolysis reaction, thereby increasing the polishing rate. However, excessive hydrolysis also led to increased surface roughness. On the other hand, HEC influenced slurry viscosity, abrasive dispersibility, and drag force. At low HEC concentrations, increased abrasive drag force improved the polishing rate. At high concentrations, however, HEC formed a hindrance layer on the Si surface via hydrogen bonding and condensation reactions, reducing the effective contact area of abrasives and thus decreasing the polishing rate. By optimizing the concentrations of TAP (0.0037 wt%) and HEC (≤0.0024 wt%), the proposed slurry formulation achieved high-performance Si-wafer CMP, satisfying both surface roughness and polishing rate targets required for advanced memory packaging applications. Full article

The oxidation behaviors of varying Cr-alloyed automotive beam steels—0.015 wt.% Cr, 0.15 wt.% Cr, and 1 wt.% Cr—were investigated using isothermal oxidation experiments. The morphologies of the oxide scale were characterized, and the formation mechanisms were analyzed to understand the change in the oxidation kinetics of the investigated steels. The results show that a small amount of Cr, up to 0.15 wt.%, can reduce oxidation kinetics; the addition of Cr at 1 wt.% causes the oxidation rate to decline at a low isothermal temperature, but the hindrance effect expires when the oxidation temperature is above 1050 °C. The oxidation scale, including the inner FeO layer, the intermediate Fe₃O₄ layer, and the outer Fe₂O₃ layer, exhibits a morphological evolution from marble-like to pore-like, then whisker-like, flocculation-like, fine oxide grains, and finally coarse oxide grains. With increasing Cr addition, the thickness of the FeO layer decreases significantly, leading to a reduction in the total thickness of the oxidation scale. During the oxidation process of the investigated steel with 0.15 wt.% Cr, a Cr-rich layer and FeO-(Cr, Fe, Mn)₃O₄ eutectic form; meanwhile, FeO-(Cr, Fe)₂O₃ eutectic and Si-rich oxides, as well as a (Cr, Si)-rich layer, occur in the oxidation scale when 1 wt.% Cr is added to the steel. The occurrence of voids in the (Cr, Si)-rich layer is responsible for the increasing oxidation kinetics of the 1 wt.% Cr steel when the isothermal temperature is above 1050 °C, and the optimal Cr concentration in automotive beam steel is 0.15 wt.%, considering both oxidation resistance and cost. Full article

The osseo-ligamentous lumbopelvic complex is essential for musculoskeletal load transfer, yet location-specific material data and standardized test protocols remain scarce, which is a hindrance for comparability. Based on 91 specimen locations per cadaver (five cadavers, average age: 77.3 years), we developed detailed methods for specimen preparation and mechanical testing (bending, tensile, and compression) with defined boundary conditions. Multiple measurements were taken to assess repeatability. The proposed methods allow us to identify location-specific properties of the lumbopelvic system for the first time. Cortical bone exhibited an elastic modulus of 1750 MPa and an ultimate strength of 28.2 MPa, while those of trabecular bone were 32.7 MPa and 1.26 MPa, and soft tissues revealed values of 148 MPa and 14.3 MPa for fascial tissue and 103 MPa with 10.7 MPa for ligamentous tissue, respectively. The quantified properties for cortical and trabecular bone and soft tissues not only enhance the comparability of material properties but also support more accurate numerical simulations and implant design. Furthermore, the ease of implementation and standardization of these methods enable their widespread application, as well as the accumulation of a broad database and the setting of benchmarks for future investigations. Full article

To address the issue of drilling fluid performance drop and wellbore instability induced by desorption between treatment agents and clay in the high-temperature environment of ultra-deep drilling, this study synthesized three organosilicon polymers (ADE, ADM, ADD) with different substituents. The study confirmed that the covalent bond significantly improved the high-temperature adsorption resistance of clay, which is closely related to the interface behavior of gels. Through rolling recovery, rheology, and filtration experiments for performance evaluation, these organic silicon polymers showed excellent high-temperature performance: the shale rolling recovery rate exceeded 80% at 210 °C, and the filtration loss was reduced to 14 mL, with a reduction rate of 53.3%. The adsorption capacity of the three polymers on clay remained unchanged from 150 °C to 210 °C, among which the adsorption amount of trimethoxy groups stabilized at 8–11 mg/g after 150 °C. The adsorption capacity of ethoxy groups increased by 7.9% at 150–210 °C. The adsorption capacity of dimethoxy groups with methyl steric hindrance increased by 28.1% at 150–210 °C. These results indicate that covalent bonds effectively enhance the high-temperature adsorption of clay, allowing for polymer molecules to firmly anchor on the clay surface at high temperatures. This breakthrough overcomes the limitations of traditional inhibitors in high-temperature desorption, and provides a valuable reference for the preparation of high-temperature adsorption resistant functional materials in water-based drilling fluid gel systems. Full article

Silicone oil-based magnetic liquids containing carbon nanotubes (CNTs) were prepared using an in situ chemical coprecipitation method. The surface modification of Fe₃O₄/CNT composite particles was carried out by using three silane coupling agents: γ-aminopropyltriethoxysilane (550), γ-methacryloxypropyltrimethoxysilane (570), and phenyltrimethoxysilane (7030). Infrared Spectroscopy (IR), Transmission Electron Microscopy (TEM), and X-ray Diffraction (XRD) were used to confirm the successful doping of CNTs and the effective coating of the coupling agents. The rheological behavior of the magnetic liquids was systematically studied using an Anton Paar Rheometer. The results show that viscosity decreases exponentially with increasing temperature (fitting the Arrhenius equation), increases and tends to saturate with rising magnetic field intensity, and exhibits shear-thinning characteristics with increasing shear rate. Among the samples, Fe₃O₄@7030 has the best visco-thermal performance due to the benzene ring structure, which reduces the symmetry of the molecular chains. In contrast, Fe₃O₄@570 shows the most significant magneto-viscous effect (viscosity variation of 161.4%) as a result of the long-chain structure enhancing the steric hindrance of the magnetic dipoles. Full article

Recently, essential rose oils and rose products have gained increasing importance in both the cosmetic and food industries, as well as in the composition of medicinal products. We investigated the in vitro antiviral activity of essential oil and floral water from Rosa damascena Mill against herpes simplex virus type 1 (HSV-1) infection in rabbit retinal cells (RRCs). The composition of the main chemical components in the rose essential oil was determined by means of gas chromatographic analysis. The effect on the viral replication cycle was determined using the cytopathic effect (CPE) inhibition assay. The virucidal activity, the effect on the adsorption stage of the virus to the host cell, and the protective effect on healthy cells were evaluated using the endpoint dilution method. The effects were determined as deviation in the viral titer, Δlg, for the treated cells from the one for the untreated viral control. The identified main active components of rose oil are geraniol (28.73%), citronellol (21.50%), nonadecane (13.13%), nerol (5.51%), heneicosane (4.87%), nonadecene (3.93), heptadecane (2.29), farnesol (2.11%), tricosane (1.29%), eicosane (1.01%), and eugenol (0.85%). The results demonstrated that both rose products do not have a significant effect on the virus replication but directly affect the viral particles and reduce the viral titer by Δlg = 3.25 for floral water and by Δlg = 3.0 for essential oil. Significant inhibition of the viral adsorption stage was also observed, leading to a decrease in the viral titers by Δlg = 2.25 for floral water and by Δlg = 2.0 for essential oil. When pretreating healthy cells with rose products, both samples significantly protected them from subsequent infection with HSV-1. This protective effect was more pronounced for the oil (Δlg = 2.5) compared to the one for the floral water (Δlg = 2.0). We used the in silico molecular docking method to gain insight into the mechanism of hindrance of viral adsorption by the main rose oil compounds (geraniol, citronellol, nerol). These components targeted the HSV-1 gD interaction surface with nectin-1 and HVEM (Herpesvirus Entry Mediator) host cell receptors, at N-, C-ends, and N-end, respectively. These findings could provide a structural framework for further development of anti-HSV-1 therapeutics. Full article

Freshwater surimi typically exhibits poor gel-forming capability and is prone to gel deterioration, limiting its applications in food products. This study successfully prepared silver carp surimi gels with improved gel strength and water-holding capacity (WHC) using carboxymethyl konjac glucomannan (CKGM) as a functional modifier. Furthermore, the regulatory mechanism of CKGM with different degrees of substitution (DS) on the gel properties of silver carp surimi was systematically investigated. Results demonstrated that DS significantly influenced gel strength, WHC, and microstructure. CKGM (DS = 0.21%) substantially enhanced the gel strength and WHC through strengthened hydrophobic interactions and hydrogen-bond networks. However, CKGM with a higher DS (0.41%) induced a steric hindrance effect, decreasing elastic modulus and WHC and resulting in a more porous gel network. Raman spectroscopy analysis revealed that CKGM facilitated the conformational transition of myofibrillar proteins from α-helix to β-sheet, thereby improving the density of the gel network. The study provides theoretical foundations and technical guidance for the quality improvement of surimi products. Full article

A new series of 6-arylaminoflavones was synthesized via the Buchwald–Hartwig cross-coupling reaction, aiming to functionalize the flavone core efficiently. Reaction optimization revealed that Pd₂(dba)₃/XantPhos with Cs₂CO₃ in toluene provided the best yields, with isolated yields ranging from 8% to 95%, depending on the arylamine structure. Steric hindrance and electron-withdrawing groups at the arylamine ring impacted the reaction outcomes. Cytotoxicity assays in different human cancer cell lines indicated that substitution patterns at both the arylamine and B-rings strongly impacted biological activity. In particular, compounds bearing a 3,4-dimethoxy substitution at the B-ring and a trifluoromethyl (13c) or chlorine (13g) group at the aniline moiety exhibited enhanced cytotoxicity. These findings provide insights into the structure–activity relationship of 6-arylaminoflavones while contributing to the development of synthetic methodologies for functionalized flavones. Full article

γ-Glutamyl transpeptidase (GGT) is overexpressed in a variety of diseases, making it an important diagnostic criterion for diseases. Herein, a new fluorescence probe based on naphthalimide (Glu-MDA) was developed and employed for the rapid detection of GGT in tumor cells or samples. Alkynylated naphthalimide is the fluorescent core for excellent fluorescence response. The covalent bridging of self-immolative short linkers reduces the steric hindrance between probes and enzyme cleavage sites, which leads to improved enzymatic reaction kinetics. Glu-MDA shows a rapid response and excellent selectivity with a detection limit of 0.044 U/L. This allows the efficient detection of GGT levels in solution and cells. Simultaneously, the construction of Glu-MDA pre-stained test strips provided an innovative strategy for the qualitative detection of GGT activity, helping to detect GGT faster, more portably, and cost-effectively in various scenarios. Full article

The development of ceria (CeO_2−x)-based nanoantioxidants requires fine-tuning of structural and surface properties for enhancing antioxidant behavior in biological environments. In this contest, here ultrasmall water-dispersible CeO_2−x nanoparticles (NPs), characterized by a high Ce³⁺/Ce⁴⁺ ratio, were synthesized in a non-polar solvent and phase-transfer to an aqueous environment through ligand-exchange reactions using citric acid (CeO_2−x@Cit) and post-treatment with dopamine hydrochloride (CeO_2−x@Dopa). The concept behind this work is to enhance via surface engineering the intrinsic antioxidant properties of CeO_2−x NPs. For this purpose, thanks to electron transfer reactions between dopamine and CeO_2−x, the CeO_2−x@Dopa was obtained, characterized by increased surface Ce³⁺ sites and surface functionalized with polydopamine bearing o-quinone structures as demonstrated by complementary spectroscopic (UV–vis, FT-IR, and XPS) characterizations. To test the antioxidant properties of CeO_2−x NPs, the scavenging activity before and after dopamine treatment against artificial radical 1,1-diphenyl-2-picrylhydrazyl (DPPH^·) and the ability to reduce the reactive oxygen species in Diencephalic Immortalized Type Neural Cell line 1 were evaluated. CeO_2−x@Dopa demonstrated less efficiency in DPPH^· scavenging (%radical scavenging activity 13% versus 42% for CeO_2−x@Cit before dopamine treatment at 33 μM DPPH^· and 0.13 mg/mL loading of NPs), while it markedly reduced intracellular ROS levels (ROS production 35% compared to 66% of CeO_2−x@Cit before dopamine treatment with respect to control—p < 0.001 and p < 0.01, respectively). While steric hindrance from the dopamine-derived polymer layer limited direct electron transfer from CeO_2−x NP surface to DPPH^·, within cells the presence of o-quinone groups contributed with CeO_2−x NPs to break the autoxidation chain of organic substrates, enhancing the antioxidant activity. The functionalization of NPs with o-quinone structures represents a valuable approach to increase the inherent antioxidant properties of CeO_2−x NPs, enhancing their effectiveness in biological systems by promoting additional redox pathways. Full article

Memory is a fundamental neurological function, essential for animal survival. Over the course of vertebrate evolution, elaborations in the forebrain telencephalon create new memory mechanisms, meaning basal vertebrates such as amphibians must have a less sophisticated system of memory acquisition, storage, and retrieval than the well-known hippocampal-based circuitry of mammals. Personality also appears to be a fundamental vertebrate trait and is generally defined as consistent individual behavior over time and across life history stages. In anuran amphibians (frogs), personality studies generally ask whether adult frogs retain the personality of their tadpole stage or whether personality shifts with metamorphosis, an idea behavioral ecologists term adaptive decoupling. Using a multidisciplinary perspective and recognizing there are ~7843 species of frogs, each with some molecular, morphological, physiological, or behavioral feature that makes it unique, we review, clarify, and provide perspective on what we collectively know about memory and personality and their mechanisms in anuran amphibians. We propose four working hypotheses: (1) as tadpoles grow, new telencephalic neurons become integrated into functional networks, producing behaviors that become more sophisticated with age; (2) since carnivores tend to be more bold/aggressive than herbivores, carnivorous anuran adults will be more aggressive than herbivorous tadpoles; (3) each amphibian species, and perhaps life history stage, will have a set point on the Shy–Bold Continuum; and (4) around this set point there will be a range of individual responses. We also suggest that several factors are slowing our understanding of the variety and depth of memory and personality possibilities in anurans. These include the scala natura approach to comparative studies (i.e., the idea that one frog represents all frogs); the assumption that amphibians are no more than simple reflex machines; that study species tend to be chosen more for convenience than taxonomic representation; and that studies are designed to prove or disprove a construct. This latter factor is a particular hindrance because what we are really seeking as scientists is not the confirmation or refutation of ideas, but rather what those ideas are intended to produce, which is understanding. Full article

In this study, we systematically investigated the adsorption behavior of a titanium-based metal–organic framework (MOF) sensing layer on five primary alcohol homologs using the quartz crystal microbalance (QCM) technique. Unexpectedly, response signals were significantly enhanced for molecules exceeding the framework’s pore dimensions, contradicting conventional molecular sieving models. Further investigations revealed that the adsorption time constant (${\tau }_a$) is linearly proportional to the molecular diameter ($R^2=0.952$) and the integral response (AUC) increases almost exponentially with the molecular weight ($R^2=0.891$). Although the effective diffusion coefficient ($D_{\mathrm{eff}}$) decreases with increasing molecular size ($D_{\mathrm{eff}}\propto d^{-5.96}$, $R^2=0.981$), the normalized diffusion hindrance ratio ($D_{\mathrm{eff}}/D_{\mathrm{gas}}$) decreases logarithmically with an increasing diameter. Larger responses result from stronger host–guest interactions with the framework despite significant diffusion limitations for larger molecules. These findings demonstrate the synergistic regulation of adsorption and diffusion in MOF-QCM systems. Our investigation experimentally elucidates the ’size-selectivity paradox’ in microporous sensing interfaces and establishes a quantitative framework for optimizing sensor performance through balanced control of diffusion kinetics and interfacial interactions in similar materials. Full article

Electrocatalytic CO₂ reduction reaction (CO₂RR) is a crucial technology for achieving carbon cycling and renewable energy conversion, yet it faces challenges such as complex reaction pathways, competition for intermediate adsorption, and low product selectivity. In recent years, molecular modification has emerged as a promising strategy. By adjusting the surface properties of catalysts, molecular modification alters the electronic structure, steric hindrance, promotes the adsorption of reactants, stabilizes intermediates, modifies the hydrophilic–hydrophobic environment, and regulates pH, thereby significantly enhancing the conversion efficiency and selectivity of CO₂RR. This paper systematically reviews the modification strategies and mechanisms of molecularly modified materials in CO₂RR. By summarizing and analyzing the existing literature, this review provides new perspectives and insights for future research on molecularly modified materials in electrocatalytic CO₂ reduction. Full article

Series of pyrene-labeled diols (Py₂-DOs) and polyols (Py-POs) were synthesized by coupling a number (n_PyBA) of 1-pyrenebutyric acids to diols and polyols to yield series of end-labeled linear (n_PyBA = 2) and branched (n_PyBA > 2) oligomers, respectively. Pyrene excimer formation (PEF) between an excited and a ground-state pyrene was studied for the Py₂-DO and Py-PO samples by analyzing their fluorescence spectra and decays in tetrahydrofuran, dioxane, N,N-dimethylformamide, and dimethyl sulfoxide. Global model-free analysis (MFA) of the pyrene monomer and excimer fluorescence decays yielded the average rate constant (<k>) for PEF. After the calculation of the local pyrene concentration ([Py]_loc) for the Py₂-DO and Py-PO samples, the <k>-vs.-[Py]_loc plots were linear in each solvent, with larger and smaller slopes for the Py₂-DO and Py-PO samples, respectively, resulting in a clear kink in the middle of the plot. The difference in slope was attributed to a bias for PEF between pyrenes close to one another on the densely branched Py-PO constructs resulting in lower apparent [Py]_loc and <k> values. This study illustrated the ability of PEF to probe how steric hindrance along a main chain affects the dynamic encounters between substituents in multifunctional oligomers such as diols and polyols. Full article