Search Results (532)

The crystal structure of proteins is generally considered static due to the constraints imposed by crystal packing. We determined the crystal structure of rice NADP-malic enzyme 2 (OsNADP-ME2), an oxidative decarboxylase that converts malic acid to pyruvate and provides NADPH to generate reactive oxygen species. The OsNADP-ME2 is crystallized as a tetramer in the space group of P2₁. In the crystal, all the crystal packing interactions are made through the NADP-binding domain of the enzyme. Interestingly, a protomer shows a conformational change, with a 7.4° tilt in the NADP-binding domain. Basically, the crystal packing consists of a horizontal arrangement of vertically parallel P2₁ screw axes. In the vertical direction, a protomer (Mol A) is tightly sandwiched by two protomers (Mol C) of nearby tetramers and vice versa. In the horizontal direction, two protomers (Mol B and D) of a tetramer are parallelly bound to nearby tetramers, of which one protomer (Mol B) has tighter interactions than the other protomer (Mol D). The protomer Mol D, with the least interaction surface in the crystal packing, adopts an open conformation of the NADP-binding domain, which may be the flexible part of the enzyme for NADP+ cofactor binding. Crystallization can provide valuable information for protein structure. Full article

Three-dimensional (3D) scanning and printing technologies enable the production of personalized rehabilitation splints, yet challenges such as scanning artifacts in complex anatomical areas (e.g., finger webs), lengthy post-processing, long printing times, and material limitations (e.g., brittleness and poor breathability) hinder routine clinical adoption. This feasibility study developed and evaluated a clinician-accessible protocol for fabricating cock-up wrist splints using 3D scanning (Creaform GO!SCAN 50 with VXelements 4.1), modeling (Materialise Magics), and fused deposition modeling printing with polylactic acid (PLA) on a MakerBot Replicator+. Five healthy participants wore the splints for one week, with user satisfaction assessed via the Quebec User Evaluation of Satisfaction with Assistive Technology (QUEST 2.0; average total score 4.14/5, range 3.75–4.42) questionnaire. An experienced occupational therapist provided expert feedback. High satisfaction was reported for weight (4.6/5) and ease of use (4.6/5), confirming advantages over traditional thermoplastic splints in lightness and esthetics. However, lower scores for durability (3.6/5), comfort (3.6/5), and effectiveness (3.6/5) stemmed from PLA brittleness (cracking under load or overtightening), rough surfaces despite vapor polishing, inadequate ventilation causing moisture buildup, and fit issues (e.g., pressure points). Printing time averaged 9–19 h per splint. The protocol demonstrates proof-of-concept feasibility for clinicians with basic computer techniques, but material constraints and process refinements are required for reliable application in patient populations. Full article

Steel slag is a major solid waste generated by the steelmaking industry. Its characteristics, including high hardness and large specific surface area, offer the potential to replace traditional mineral fillers in asphalt mixtures. However, the high alkalinity of unmodified steel slag often leads to unbalanced rheological properties and insufficient moisture stability in asphalt mastic. In this study, a modified steel slag filler was prepared using a process involving crushing and screening, water washing for dealkalization, and surface modification with a silane coupling agent. Using limestone powder and hydrated lime as control groups, the modification effects on base asphalt mastic were systematically investigated. Rheological properties were characterized using a dynamic shear rheometer (DSR) and bending beam rheometer (BBR). Interfacial performance was evaluated through pull-off tests and water immersion dispersion tests. Furthermore, mechanisms were elucidated using X-ray Fluorescence (XRF), BET specific surface area analysis, and surface free energy (SFE) tests. The results indicate that the modified steel slag significantly enhances the high-temperature deformation resistance of the asphalt mastic. At 58 °C, the complex modulus reached 7.3 MPa, representing increases of 43.3% compared to limestone powder mastic. At −18 °C, the creep stiffness increased by only 3.0%, suggesting that low-temperature cracking resistance remained fundamentally stable. The water immersion dispersion loss rate was 2.12%, and the attenuation rate of pull-off strength after water immersion was 12.5%, indicating that its resistance to moisture damage is superior to that of limestone powder and comparable to that of hydrated lime. Mechanism analysis reveals that the large specific surface area of the modified steel slag strengthens physical adsorption, while the basic oxides undergo a weak acid–base reaction with the acidic components of the asphalt. Additionally, surface modification improves compatibility. The preparation process for modified steel slag is simple; it can be used as a standalone substitute for traditional mineral fillers, balancing both performance and environmental benefits. Full article

To elucidate the mechanisms by which the hydrophobic hydrocarbon chain length of emulsifiers and the surface properties of aggregates influence the adhesive performance at the emulsified asphalt–aggregate interface, this study employed molecular dynamics simulations to construct interface models. Key parameters, including relative concentration, diffusion coefficients, and interfacial adhesion work, were systematically analysed to reveal the intrinsic effects of imidazoline-type emulsifier chain length and aggregate type on interfacial behaviour. The results indicate that increasing the hydrophobic chain length of the emulsifier suppresses the adsorption of emulsified asphalt at the aggregate interface. The diffusion coefficients of both emulsifier and asphalt molecules initially increase and subsequently decrease with chain length, with the non-polar asphalt components (aromatics and saturates) exhibiting greater sensitivity to chain length variations. Moderate extension of the hydrophobic chain enhances interfacial adhesion work, whereas exceeding the optimal chain length reverses this trend, weakening adhesion. Aggregate surface properties exert a significant influence on interfacial behaviour. Compared with the acidic SiO₂ (0 0 1) surface, the basic CaCO₃ (1 0 4) surface exhibits lower peak relative concentrations of emulsified asphalt, reduced sensitivity to variations in emulsifier chain length, lower molecular diffusion coefficients, and stronger interactions with asphalt molecules, resulting in superior interfacial adhesion. This study provides a molecular-level theoretical basis for the targeted design of emulsifier structures and the efficient adaptation of emulsified asphalt to different aggregate systems. Full article

Quaternary Ni-Zn-Mg-Al metallic mixed oxide (MMO) catalysts were synthesized by co-precipitation from layered double hydroxide precursors. The effect of varying Zn content on physicochemical properties and catalytic performance was evaluated. Mg-Al and ternary Ni-Mg-Al and Zn-Mg-Al catalysts were synthetized for comparative purposes. XRD, N₂ sorption, MP-AES, CO₂-TPD, NH₃-TPD, SEM, and EDS characterized the materials’ physicochemical properties. The tested reaction was the transesterification between glycerol and dimethyl carbonate to obtain glycerol carbonate to improve the biodiesel industry. The catalyst containing both Ni and Zn showed the highest glycerol conversion among the evaluated materials. This was related to the increased number and strength of surface basic and acid active sites. Specifically, a high density of strong basic sites and acid ones in the quaternary catalysts was required for the reaction mechanism. The catalyst with 20 at% of Zn (MMO-Ni₁₅Zn₂₀) achieved the highest glycerol carbonate yield (89.6%) under mild reaction conditions and was solvent-free. MMO-Ni₁₅Zn₂₀ catalytic performance was associated with its high total basicity and predominance of strong basic sites and a moderate amount of acid sites. The differences observed between catalytic performances suggest that these results depend on the influence of structural, textural, acid, and basic properties. Reuse tests of the MMO-Ni₁₅Zn₂₀ catalyst showed moderate stability, with a progressive decrease in activity due to the loss of strong basic sites and the formation of agglomerated regions. Nevertheless, MMO-Ni₁₅Zn₂₀ maintained a GC selectivity of 100% in the successive cycles. Full article

This study focuses on the synthesis and characterization of buckwheat husk-derived activated carbon, chemically activated with potassium hydroxide (KOH) and subsequently modified with urea and Prussian Blue (PB). The obtained carbons were evaluated in terms of particle-size distribution, surface morphology, structural features, and electrokinetic properties using scanning electron microscopy coupled with energy-dispersive X-ray spectroscopy (SEM–EDS), Fourier-transform infrared spectroscopy (FTIR), Raman spectroscopy, and electrophoresis, as well as N₂ adsorption–desorption (BET surface area and porosity analysis). The results confirmed that both pyrolysis conditions and the type of modifier significantly affect the physicochemical properties of the activated carbon and its behavior in electrolyte solutions. Colloidal stability and particle size were strongly dependent on pH and the type of anions present in solution, with sodium nitrate (NaNO₃) systems showing higher stability than sodium chloride (NaCl). Modification with KOH and urea imparted a more basic surface character, whereas PB introduced more acidic properties. All samples exhibited predominantly negative surface charges and mesoporous structures, which are favorable for adsorption processes and enhance affinity for heavy-metal cations. Among the tested materials, BH-KOH-Fe (Fe-modified KOH-activated carbon) showed the most favorable performance for the targeted application, while BH-KOH (KOH-activated buckwheat husk-derived carbon) exhibited high surface area and good colloidal stability. The prepared materials show promising applicability for water purification, including the removal of organic pollutants and radionuclides (e.g., ¹³⁷Cs and ⁹⁰Sr), as well as metal cations (K⁺, Na⁺, and Li⁺). Full article

We report a Fe₃O₄@Pt@poly-LDOPA nanozyme that displays enhanced peroxidase (POD)-like activity. Polymerisation of levodopa onto the surface of Fe₃O₄@Pt yields a carboxyl-rich poly-LDOPA shell that is available for bioconjugation with antibodies and other types of receptors. Physicochemical characterisation confirmed the integrity of the Fe₃O₄ core, successful Pt modification, and formation of the polymer coating under acidic and basic conditions. Steady-state kinetic analysis using the Michaelis–Menten model revealed robust catalytic performance toward both substrates: for H₂O₂, V_max = 4.0 × 10⁻⁸ M·s⁻¹ and K_m = 25.13 mM; for TMB, V_max = 6.07 × 10⁻⁸ M·s⁻¹ and K_m = 0.229 mM, indicative of high turnover and strong apparent affinity for the chromogenic substrate. A nanozyme-linked immunosorbent assay for the SARS-CoV-2 nucleocapsid was developed. The anti-nucleocapsid antibodies were immobilised onto Fe₃O₄@Pt@poly-LDOPA via EDC/NHS. In buffer, the calibration range (1.0–100 ng·mL⁻¹) afforded an LOD of 6.95 ng·mL⁻¹. In 10% human serum, reduced background and improved nanozyme dispersion yielded a linear low-concentration response (0.1–10 ng·mL⁻¹), with an LOD of 0.0036 ng·mL⁻¹. These results establish Fe₃O₄@Pt@poly-LDOPA as a promising inorganic–organic nanozyme platform that combines catalytic effectiveness, magnetic manipulability, and facile bioconjugation for immunosensing of various disease-related biomarkers. Full article

Preventing spoilage in food products, particularly in those highly susceptible to rapid deterioration like mutton, has been a persistent challenge in the food industry. In this study, an Active Biological Film (ABF) was developed using chitosan (CS) and whey protein isolate (WPI), with the addition of 0.01 wt% titanium dioxide (TiO₂) and 0.1 wt% white pepper essential oil (WPEO). This ABF was applied to preserve fresh mutton at super-chilling temperatures of −1.7 ± 0.2 °C. The effects of ABF on myofibrillar protein (MP) oxidation and structural characteristics, as well as on the microbial status, physicochemical properties, and sensory quality of mutton, were systematically evaluated. The results demonstrated that, compared to the control group (CK), ABF treatment significantly enhanced the total sulfhydryl content, protein solubility, and zeta potential of MPs, while reducing carbonyl content, surface hydrophobicity, and particle size. MPs in the ABF group showed a higher α-helix proportion and a lower random coil content, along with a notable increase in intrinsic fluorescence intensity. Scanning electron microscopy (SEM) revealed a denser gel structure. Additionally, ABF effectively inhibited microbial growth in mutton, delayed pH increase, reduced thiobarbituric acid-reactive substances (TBARS) and total volatile basic nitrogen (TVB-N), and improved sensory scores, extending mutton shelf life by over 10 days. Therefore, the ABF effectively inhibited oxidation in MPs, maintained their structural integrity, and preserved mutton quality during super-chilling storage. Full article

Smart polymers have attracted significant scientific interest in recent years because of their capability to modify their physical and/or chemical properties in response to external stimuli, including temperature, pH, and electric or magnetic fields. Poly(2-(diethylamino)ethyl methacrylate) (PDEAEMA) is a pH-responsive polymer with significant potential for biomedical applications. Significant research has focused on the synthesis of PDEAEMA polymers given their potential in smart polymer applications. In this study, PDEAEMA thin films were synthesized via a planar inductively coupled plasma (ICP) system at 13.56 MHz in both continuous and pulsed modes. The effects of substrate temperature, plasma power, and plasma pulse off time on polymer surfaces were systematically studied. The deposited polymer films were analyzed for their chemical composition and structural properties using X-ray Photoelectron Spectroscopy (XPS) and Fourier Transform Infrared Spectroscopy (FTIR). Additionally, the plasma environment was analyzed using Optical Emission Spectroscopy (OES). Results indicated that polymers prepared under pulsed plasma conditions more closely retained the structure of the monomer. Moreover, the deposition rate increased as the plasma pulse off time decreased in pulsed mode experiments. PDEAEMA-based copolymer films were deposited to investigate their behavior under different pH conditions. The results indicate that the films exhibited distinct responses in acidic and basic environments. Full article

Adjuvants are chemical substances used in vaccines to enhance immunogenicity. Among them, aluminum-based nanoparticles are some of the oldest and most widely employed adjuvants in vaccine formulations. A key function of aluminum adjuvants is thought to involve acting as an antigen depot, enabling slow antigen release and providing sufficient time for effective immune activation. Therefore, understanding antigen–adjuvant interactions is essential, as these interactions influence antigen stability, release kinetics, and overall vaccine performance. In this study, we investigated how the physicochemical properties of aluminum hydroxide nanoparticles modulate antigen–protein interactions and affect protein stability. Nanoparticles synthesized under acidic (pH ≈ 5.0) to near-neutral (pH ≈ 7.1) conditions exhibited lower crystallinity, reduced hydroxyl density, and higher interfacial hydration, whereas those prepared under basic conditions (pH ≈ 9.0) displayed increased crystallinity, enriched surface hydroxyl groups, and markedly reduced hydration. Antigen proteins bound to low-crystallinity aluminum hydroxide nanoparticles showed improved thermal stability, while those associated with highly crystalline nanoparticles exhibited reduced thermal stability. Complementary ITC study further suggests that these stability differences are accompanied by changes in their interaction behavior. These findings indicate that the structural and interfacial properties of aluminum hydroxide nanoparticles strongly influence their interactions with antigen proteins and the resulting physical stability. Together, our results demonstrate that the balance among crystallinity, hydroxyl organization, and interfacial hydration governs the thermal behavior of antigen proteins adsorbed onto aluminum hydroxide. This work provides a rational design principle for engineering aluminum-based adjuvants that optimize antigen–protein stability in vaccine formulations. Full article

In this study, inverse gas chromatography (IGC) was applied to characterize the key surface physicochemical properties of carbon–mineral composites and to clarify how these properties relate to removal efficiencies of selected antibiotics, with particular emphasis on surface energetic and acid–base characteristics rather than bulk structural parameters. The dispersive component of surface free energy and the acid–base characteristics (K_a/K_b ratio) were determined, alongside measurements of carbon content, while specific surface areas were compared with data reported previously. We found that there is no clear correlation between bulk structural characteristics and the removal efficiency of ciprofloxacin, doxycycline, sulfamethoxazole, and tetracycline. In contrast, the removal of all investigated antibiotics was found to be correlated with the dispersive component of surface free energy and the K_a/K_b ratio. The results suggest that surface energetic parameters and acid–base properties are more closely associated with antibiotic adsorption behavior than basic structural characteristics alone. These findings demonstrate that IGC provides valuable insight into adsorption processes and highlight the importance of surface physicochemical properties for interpreting and predicting the adsorption properties of carbon–mineral composites. Full article

This review examines the feasibility of electrochemical synthesis of poly-L-arginine (PArg) using repetitive cyclic voltammetry in neutral aqueous phosphate-buffered saline. Previous studies on electrochemical deposition of PArg onto different carbonaceous electrode materials are discussed with respect to the already reported mechanistic models. Some controversial interpretations are of interest, predominantly the formation of peptide bonds during the electropolymerisation of L-arginine. Several alternative anodic pathways are considered via the possibilities and limitations of ways of attaching L-arginine molecules to the electrode surface. Furthermore, the role of oxygen-containing surface groups is discussed, as this aspect has been largely overlooked in the context of L-arginine deposition, despite the O-terminating character of the electrode surface and its effect on the reactivity of the nucleophilic guanidine group in L-arginine. Also, the application of extremely high potentials around +2 V vs. Ag/AgCl/3 mol L⁻¹ KCl is considered, as it can lead to the generation of reactive oxygen species that may interfere with or even govern the entire deposition process. Thus, the absence of such considerations may raise doubts about the peptide nature of the electrochemically assisted polymerisation of this basic amino acid. Finally, it seems that the identity of the electrochemically synthesised PArg does not correspond to that of this polymer prepared by conventional methods, such as solid-phase peptide synthesis, solution-phase synthesis, or N-carboxy-anhydride polymerisation, and therefore the whole process remains unproved. Full article

P-cresol, indole and indole-3-acetic acid (IAA) are catabolites of amino acids, formed by the gut microbiome. Most of these aromatic hydrocarbon derivatives are excreted by the colon before reentering the body to form “exogenous” protein-bound uremic toxins (PBUTs), which aggravate chronic kidney disease (CKD). Removal efficiencies of these PBUT precursors from model phosphate-buffered saline solutions by three different surface-modified nanoporous carbon adsorbents (PCs) were studied. PCs were produced by physicochemical and/or acid base activation of carbonized rice husk waste. Removal rates achieved values of 32–96% within a 3 h contact time. High micro/mesoporosity and surface chemistry of the N- and P-doped biochars were established by N₂ adsorption studies, SEM/EDS analysis, XPS and FT-IR-spectroscopy. The ammoxidized PC-N1 had the highest adsorption capacity (1.97 mmol/g for IAA, 2.43 mmol/g for p-cresol and 2.42 mmol/g for indole), followed by “urea-nitrified” PC-N2, whilst the phosphorylated PC-P demonstrated the lowest adsorption capacity for these solutes. These results do not correlate with the total pore volume values for PC-N2 (0.91 cm³/g) < PC-P (1.56 cm³/g) < PC-N1 (1.84 cm³/g), suggesting that other parameters such as the micropore volume (PC-N1 > PC-N2 > PC-P) and the interaction of surface chemical functional groups with the solutes play key roles in the adsorption mechanism. N-doped PC-N1 and PC-N2 have basic functional groups with higher affinity with acidic IAA and p-cresol. The ion-exchange mechanism of phenolic and indolic compound chemisorption by nanoporous carbon adsorbents, modified with surface N- and P-containing functional groups, has been proposed. Full article

Plastic streams dominated by polyethylene (PE) including PE HD/MD (High Density/Medium Density) and PE LD/LLD (Low Density/Linear Low Density), polypropylene (PP), and polyvinyl chloride (PVC) across Europe demand a design framework that links synthesis with end of life reactivity, supporting circular economic goals and European Union waste management targets. This work integrates polymerization derived chain architecture and depolymerization mechanisms to guide selective valorization of commercial plastic wastes in the European context. Catalytic topologies such as Bronsted or Lewis acidity, framework aluminum siting, micro and mesoporosity, initiators, and strategies for process termination are evaluated under relevant variables including temperature, heating rate, vapor residence time, and pressure as encountered in industrial practice throughout Europe. The analysis demonstrates that polymer chain architecture constrains reaction pathways and attainable product profiles, while additives, catalyst residues, and contaminants in real waste streams can shift radical populations and observed selectivity under otherwise similar operating windows. For example, strong Bronsted acidity and shape selective micropores favor the formation of C₂ to C₄ olefins and Benzene, Toluene, and Xylene (BTX) aromatics, while weaker acidity and hierarchical porosity help preserve chain length, resulting in paraffinic oils and waxes. Increasing mesopore content shortens contact times and limits undesired secondary cracking. The use of suitable initiators lowers the energy threshold and broadens processing options, whereas diffusion management and surface passivation help reduce catalyst deactivation. In the case of PVC, continuous hydrogen chloride removal and the use of basic or redox co catalysts or ionic liquids reduce the dehydrochlorination temperature and improve fraction purity. Staged dechlorination followed by subsequent residue cracking is essential to obtain high quality output and prevent the release of harmful by products within European Union approved processes. Framing process design as a sequence that connects chain architecture, degradation chemistry, and operating windows supports mechanistically informed selection of catalysts, severity, and residence time, while recognizing that reported selectivity varies strongly with reactor configuration and feed heterogeneity and that focused comparative studies are required to validate quantitative structure to selectivity links. In European post consumer sorting chains, PS and PC are frequently handled as separate fractions or appear in residues with distinct processing routes, therefore they are not included in the polymer set analyzed here. Polystyrene and polycarbonate are outside the scope of this review because they are commonly handled as separate fractions and are typically optimized toward different product slates than the gas, oil, and wax focused pathways emphasized here. Full article

Catalytic transfer hydrogenation (CTH) provides a practical and sustainable approach for reducing unsaturated compounds, serving as an alternative to high-pressure H₂ in laboratory and fine chemical contexts. This broad reaction class includes asymmetric transfer hydrogenation (ATH), a key strategy in enantioselective synthesis due to its operational simplicity, high stereocontrol, and compatibility with sensitive functional groups. A central variable governing CTH efficiency is the role of bases, which may function as essential activators, co-hydrogen donors, or be entirely absent depending on the catalytic system. This review provides a comparison of base-assisted, base-free, and base-as-co-hydrogen-donor CTH methodologies across diverse metal catalysts and substrates. We highlight how bases such as triethylamine, K₂CO₃, and NaOH facilitate catalyst activation, modulate hydride formation, and tune reactivity and selectivity. The dual function of bases in formic-acid-driven systems is examined alongside synergistic effects observed with mixed-base additives. In contrast, base-free CTH platforms demonstrate how tailored ligand frameworks, metal-ligand cooperativity, and engineered surface basicity can eliminate the need for external additives while maintaining high activity. Through mechanistic analysis and cross-system comparison, this review identifies the key structural, electronic, and environmental factors that differentiate base-assisted from base-free pathways. Emerging trends—including greener hydrogen donors, advanced catalyst architectures, and additive-minimized protocols—are discussed to guide future development of sustainable CTH processes. Full article