Search Results (29)

Bioactive glasses remain promising candidates for enhancing osseointegration on metallic implants. However, achieving a composition that combines controlled dissolution, cytocompatibility, and antimicrobial functionality remains an ongoing challenge. Building upon the prior structural and thermal characterization of boron-substituted 6P55 phosphosilicate glasses, this study investigates the biological consequences of incorporating 0, 5, 10, and 15 mol% B₂O₃ to determine their suitability as coatings for Ti6Al4V. Glass extracts were evaluated using L-929 fibroblast cultures (MTT assay and ImageJ-based cell counting), antimicrobial assays against Escherichia coli and Staphylococcus aureus using a semi-quantitative dilution-plating method, and SBF immersion studies to assess pH evolution, surface mineralization, and Ca/P ratio development. FTIR and SEM analyses revealed composition-dependent formation of phosphate-, carbonate-, and silicate-rich surface layers, with 5B exhibiting the most consistent early-stage hydroxyapatite-like signatures, supported by Ca/P ratios approaching the stoichiometric value. The pH measurements showed rapid alkalization for 5B and moderate buffering behavior at higher boron contents, consistent with boron-dependent modifications to network connectivity. Cytocompatibility studies demonstrated a dose- and time-dependent reduction in cell number at elevated B₂O₃ levels, whereas the 0B and 5B extracts maintained higher viability and preserved cell morphology. Antibacterial assays revealed strain-dependent and sub-lethal inhibitory effects, with E. coli exhibiting stronger sensitivity than S. aureus, likely due to differences in cell wall architecture and susceptibility to ionic osmotic microenvironment changes. When considered alongside previously published computational and physicochemical results, the biological data indicate that moderate boron incorporation (5 mol%) provides the most favorable balance between dissolution kinetics, apatite formation, cytocompatibility, and antimicrobial modulation. These findings identify the 5B composition as a strong candidate for further optimization toward bioactive glass coatings on Ti6Al4V implants. Full article

First-principles density-functional theory (PBE, Quantum ESPRESSO) was employed to quantify how Fe substitution modulates the structural, elastic, electronic, and optical behaviour of cubic fluorite Fe_xZr_1−xO₂ (x = 0.00–1.00). The fluorite FeO₂ end member was treated as a hypothetical ambient-pressure limit to trace trends across the solid solution (experimental FeO₂ being stabilized in the high-pressure pyrite phase). Mechanical stability was verified via the cubic Born criteria, and composition-dependent stiffness and anisotropy were assessed through Voigt–Reuss–Hill moduli, Pugh ratio, and elastic indices. A strong band-gap narrowing was found—from 3.41 eV (x = 0) to ≈0.02 eV (x = 0.50)—which was accompanied by a visible–NIR red-shift, large absorption (α ≈ 10⁵ cm⁻¹ at higher x), and enhanced refractive index and permittivity; metallic-like response was indicated at high Fe content. Spin-polarized calculations converged to zero total and absolute magnetization, indicating a non-magnetic ground state at 0 K within PBE. The effect of oxygen vacancies (V₀)—expected under Fe³⁺ charge compensation—was explicitly considered: V₀ is anticipated to influence lattice metrics, elastic moduli (B, G, G/B), and sub-gap optical activity, potentially modifying stability and optical figures of merit. Stoichiometric (formal Fe⁴⁺) predictions were distinguished from V₀-rich scenarios. Absolute band gaps may be underestimated at the PBE level. Full article

This study evaluates the efficiency of sub-stoichiometric Ti₄O₇ titanium oxide anodes for the electrochemical degradation of glyphosate, a persistent herbicide classified as a probable carcinogen by the World Health Organization. After optimizing the process operating parameters (pH and current density), the mineralization efficiency and fate of degradation by-products of the treated solution were determined using a total organic carbon (TOC) analyzer and HPLC/MS, respectively. The results showed that at pH = 3, glyphosate degradation and mineralization are enhanced by the increased generation of hydroxyl radicals (^●OH) at the anode surface. A current density of 14 ${\mathrm{mA} \mathrm{cm}}^{-2}$ enables complete glyphosate removal with 77.8% mineralization. Compared with boron-doped diamond (BDD), ${\mathrm{Ti}}_4{\mathrm{O}}_7$ shows close performance for treatment of a concentrated glyphosate solution (0.41 mM), obtained after nanofiltration of a synthetic ionic solution (0.1 mM glyphosate), carried out using an NF-270 membrane at a conversion rate (Y) of 80%. At 10${ \mathrm{mA} \mathrm{cm}}^{-2}$ for 8 h, ${\mathrm{Ti}}_4{\mathrm{O}}_7$ achieved 81.3% mineralization with an energy consumption of 6.09 ${\mathrm{kWh} \mathrm{g}}^{-1}$ TOC, compared with 90.5% for BDD at 5.48 ${\mathrm{kWh} \mathrm{g}}^{-1}$ TOC. Despite a slight yield gap, ${\mathrm{Ti}}_4{\mathrm{O}}_7$ demonstrates notable efficiency under demanding conditions, suggesting its potential as a cost-effective alternative to BDD for glyphosate electro-oxidation. Full article

This work systematically analyses the electrical and structural properties of a bilayer gate dielectric composed of Sm₂O₃ and ZrO₂ on a 4H-SiC substrate. The bilayer thin film was fabricated using a sputtering process, followed by a dry oxidation step with an adjusted oxygen-to-nitrogen (O₂:N₂) gas concentration ratio. XRD analysis validated formation of an amorphous structure with a monoclinic phase for both Sm₂O₃ and ZrO₂ dielectric thin films. High-resolution transmission emission (HRTEM) analysis verified the cross-section of fabricated stacking layers, confirmed physical oxide thickness around 12.08–13.35 nm, and validated the amorphous structure. Meanwhile, XPS confirmed the presence of more stoichiometric dielectric oxide formation for oxidized/nitrided O₂:N₂-incorporated samples, and more sub-stochiometric thin films for samples only oxidized in ambient O₂. The oxidation/nitridation processes with N₂ incorporation influenced the band offsets and revealed conduction band offsets (CBOs) ranging from 2.24 to 2.79 eV. The affected charge movement and influenced electrical performance where optimized samples with gas concentration ratio of 90% O₂:10% N₂ achieved the highest electrical breakdown field of 10.1 MV cm⁻¹ at a leakage current density of 10⁻⁶ A cm⁻². This gate stack also improved key parameters such as the effective dielectric constant ($k_{eff}$) up to 29.75, effective oxide charge ($Q_{eff}$), average interface trap density ($D_{it}$), and slow trap density (STD). The bilayer gate stack of Sm₂O₃ and ZrO₂ revealed potential attractive characteristics as a candidate for high-k gate dielectric applications in metal-oxide-semiconductor (MOS)-based devices. Full article

This study investigated Rhodamine B (RhB) degradation by electro-Fenton (EF), anodic oxidation (AO), and their combination (EF/AO), using a carbon felt cathode coupled to a sub-stoichiometric titanium dioxide Magnéli phase (Ti₄O₇) anode or a platinized titanium (Ti/Pt) anode. The results indicated that operational parameters influenced the kinetics of electrochemical reactions. An increase in current density from 10 to 50 mA cm⁻² significantly enhanced the RhB degradation rate; 30 mA cm⁻² was the optimal current density, balancing both energy efficiency and degradation performance. Moreover, higher RhB concentrations required longer treatment. The Microtox^® bioluminescence inhibition test revealed a significant toxicity decrease of the dye solution during electrochemical degradation, which was highest with EF/AO. Similarly, total organic carbon removal was highest with EF/AO (90% at pH 3), suggesting more efficient mineralization of RhB and its by-products than with EF or AO. Energy consumption remained relatively stable with all oxidation processes throughout the 480 min electrolysis period. High-resolution mass spectrometry elucidated RhB degradation pathways, highlighting chain oxidation reactions leading to the formation of intermediates and mineralization to CO₂ and H₂O. This study underscores the potential of EF, AO, and EF/AO as effective methods for RhB mineralization to develop sustainable and environmentally friendly wastewater treatment strategies. Full article

Titanium-based Metal Matrix Composites (MMCs) manufactured by additive manufacturing offer tremendous lightweighting opportunities. However, processing the high reinforcement contents needed to substantially improve elastic modulus while conserving significant ductility remains a challenge. Ti-TiC MMCs fabricated in this study reported fracture strains in tension up to 1.7% for a Young’s modulus of 149 GPa. This fracture strain is 30% higher than the previously reported values for Ti-based MMCs produced by Laser Powder Bed Fusion (LPBF) displaying similar Young’s moduli. The heat treatment used after the LPBF process leads to the doubling of the fracture strain thanks to the conversion of TiC_x dendrites into equiaxed TiC_x grains. The as-built microstructure shows both un-dissolved TiC particles and sub-stoichiometric TiC dendrites resulting from the partial dissolution of TiC particles. The reduction of the C/Ti ratio in TiC during the process results in an increase in the reinforcement content, from a nominal 12 vol% to an effective 21.5 vol%. The variation of the TiC lattice constant with its stoichiometry is measured, and an empirical expression is proposed for its effect on TiC’s Young’s modulus. The lower TiC powder size distribution displayed higher mechanical properties thanks to a reduced number of intrinsic flaws. Full article

Typical metal–organic frameworks (MOFs) usually suffer from a limited visible light-trapping ability and easy recombination of charge carriers, hindering their photocatalytic applications. Acetylacetone (AA), leveraging its exceptional coordination capabilities, serves as a versatile and effective modifier for enhancing the photocatalytic activity of MOFs via a post-synthesis approach. The synthesis of diketone-anchored MOFs with AA can be achieved by first diazotizing the amino groups on the ligands of MOFs, followed by a condensation reaction between AA and the resulting azide. Gradient AA loadings ranging from 17% to 98% were obtained, showcasing the tunability of this approach. Interestingly, a sub-stoichiometric effect was exhibited between the AA loading and the visible photocatalytic performance of the modified photocatalyst. The singlet oxygen yields of MIL-125-AA-37% and MIL-125-AA-54% were about 1.3 times that of MIL-125-AA-17% and 3.0 times that of MIL-125-AA-98%. The improved photocatalytic activity could be attributed to the fact that the AA modification altered the electron density of the Ti metal center, leading to the creation of a significant amount of oxygen defects. This alteration resulted in a reduction in the recombination of charge carriers and thus a better charge separation. In short, AA modification provides a new strategy to maximize the visible photocatalytic performance of MOFs. Full article

In the exploration of chiral solvating agents (CSAs) for nuclear magnetic resonance (NMR) spectroscopy designed for the chiral analysis of amino acid derivatives, notable advancements have been made with thiourea–CSAs. 1-TU, derived from 2-[(1R)-1-aminoethyl]phenol and benzoyl isothiocyanate, is effective in the enantiodifferentiation of N-3,5-dinitrobenzoyl (N-DNB) amino acids. In order to broaden the application of 1-TU for configurational assignment, enantiomerically enriched N-DNB amino acids were analyzed via NMR. A robust correlation was established between the relative position of specific ¹H and ¹³C NMR resonances of the enantiomers in the presence of 1-TU. 1,4-Diazabicyclo[2.2.2]octane (DABCO) was selected for the complete solubilization of amino acid substrates. Notably, the para and ortho protons of the N-DNB moiety displayed higher frequency shifts for the (R)-enantiomers as opposed to the (S)-enantiomers. This trend was consistently observed in the ¹³C NMR spectra for quaternary carbons bonded to NO₂ groups. Conversely, an inverse correlation was noted for quaternary carbon resonances of the carboxyl moiety, amide carbonyl, and methine carbon at the chiral center. This observed trend aligns with the interaction mechanism previously reported for the same chiral auxiliary. The configurational correlation can be effectively exploited under conditions of high dilution or, significantly, under sub-stoichiometric conditions. Full article

A one-pot, two-step process was developed for the preparation of pyrrole compounds from 2,5-dimethylfuran. The first step was the acid-catalyzed ring-opening reaction of 2,5-dimethylfuran (DF), leading to the formation of 2,5-hexanedione (HD). A stoichiometric amount of water and a sub-stoichiometric amount of sulfuric acid were used by heating at 50 °C for 24 h. Chemically pure HD was isolated, with a quantitative yield (up to 95%), as revealed by ¹H-NMR, ¹³C-NMR, and GC-MS analyses. In the second step, HD was used as the starting material for the synthesis of pyrrole compounds via the Paal–Knorr reaction. Various primary amines were used in stoichiometric amounts. ¹H-NMR, ¹³C-NMR, ESI-Mass, and GC-Mass analyses confirmed that pyrrole compounds were prepared with very good/excellent yields (80–95%), with water as the only co-product. A further purification step was not necessary. The process was characterized by a very high carbon efficiency, up to 80%, and an E-factor down to 0.128, whereas the typical E-factor for fine chemicals is between 5 and 50. Water, a co-product of the second step, can trigger the first step and therefore make the whole process circular. Thus, this synthetic pathway appears to be in line with the requirements of a sustainable chemical process. A pyrrole compound bearing an SH group (SHP) was used for the functionalization of a furnace carbon black (CB). The functionalized CB (CB/SHP) was utilized in place of silica, resulting in a 15% mass reduction of reinforcing filler, in an elastomeric composite based on poly(styrene-co-butadiene) from solution anionic polymerization and poly(1,4-cis-isoprene) from Hevea Brasiliensis. Compared to the silica-based composite, a reduction in the Payne effect of about 25% and an increase in the dynamic rigidity (E’ at 70 °C) of about 25% were obtained with CB/SHP. Full article

Increasing evidence suggests that the calcium-binding and proinflammatory protein S100A9 is an important player in neuroinflammation-mediated Alzheimer’s disease (AD). The amyloid co-aggregation of S100A9 with amyloid-β (Aβ) is an important hallmark of this pathology. Apolipoprotein E (ApoE) is also known to be one of the important genetic risk factors of AD. ApoE primarily exists in three isoforms, ApoE2 (Cys112/Cys158), ApoE3 (Cys112/Arg158), and ApoE4 (Arg112/Arg158). Even though the difference lies in just two amino acid residues, ApoE isoforms produce differential effects on the neuroinflammation and activation of the microglial state in AD. Here, we aim to understand the effect of the ApoE isoforms on the amyloid aggregation of S100A9. We found that both ApoE3 and ApoE4 suppress the aggregation of S100A9 in a concentration-dependent manner, even at sub-stoichiometric ratios compared to S100A9. These interactions lead to a reduction in the quantity and length of S100A9 fibrils. The inhibitory effect is more pronounced if ApoE isoforms are added in the lipid-free state versus lipidated ApoE. We found that, upon prolonged incubation, S100A9 and ApoE form low molecular weight complexes with stochiometric ratios of 1:1 and 2:1, which remain stable under SDS-gel conditions. These complexes self-assemble also under the native conditions; however, their interactions are transient, as revealed by glutaraldehyde cross-linking experiments and molecular dynamics (MD) simulation. MD simulation demonstrated that the lipid-binding C-terminal domain of ApoE and the second EF-hand calcium-binding motif of S100A9 are involved in these interactions. We found that amyloids of S100A9 are cytotoxic to neuroblastoma cells, and the presence of either ApoE isoforms does not change the level of their cytotoxicity. A significant inhibitory effect produced by both ApoE isoforms on S100A9 amyloid aggregation can modulate the amyloid-neuroinflammatory cascade in AD. Full article

Heterologous interactions between different amyloid-forming proteins, also called cross-interactions, may have a critical impact on disease-related amyloid formation. β-hairpin conformers of amyloid-forming proteins have been shown to affect homologous interactions in the amyloid self-assembly process. Here, we applied two β-hairpin-forming peptides derived from immunoglobulin light chains as models to test how heterologous β-hairpins modulate the fibril formation of Parkinson’s disease-associated protein α-synuclein (αSyn). The peptides SMAhp and LENhp comprise β-strands C and C′ of the κ4 antibodies SMA and LEN, which are associated with light chain amyloidosis and multiple myeloma, respectively. SMAhp and LENhp bind with high affinity to the β-hairpin-binding protein β-wrapin AS10 according to isothermal titration calorimetry and NMR spectroscopy. The addition of SMAhp and LENhp affects the kinetics of αSyn aggregation monitored by Thioflavin T (ThT) fluorescence, with the effect depending on assay conditions, salt concentration, and the applied β-hairpin peptide. In the absence of agitation, substoichiometric concentrations of the hairpin peptides strongly reduce the lag time of αSyn aggregation, suggesting that they support the nucleation of αSyn amyloid fibrils. The effect is also observed for the aggregation of αSyn fragments lacking the N-terminus or the C-terminus, indicating that the promotion of nucleation involves the interaction of hairpin peptides with the hydrophobic non-amyloid-β component (NAC) region. Full article

Anodes based on substoichiometric titanium oxide (Ti₄O₇) are among the most effective for the anodic oxidation of organic pollutants in aqueous solutions. Such electrodes can be made in the form of semipermeable porous structures called reactive electrochemical membranes (REMs). Recent work has shown that REMs with large pore sizes (0.5–2 mm) are highly efficient (comparable or superior to boron-doped diamond (BDD) anodes) and can be used to oxidize a wide range of contaminants. In this work, for the first time, a Ti₄O₇ particle anode (with a granule size of 1–3 mm and forming pores of 0.2–1 mm) was used for the oxidation of benzoic, maleic and oxalic acids and hydroquinone in aqueous solutions with an initial COD of 600 mg/L. The results demonstrated that a high instantaneous current efficiency (ICE) of about 40% and a high removal degree of more than 99% can be achieved. The Ti₄O₇ anode showed good stability after 108 operating hours at 36 mA/cm². Full article

Deposits of calcium sulfate scale on the surfaces of industrial equipment in distillation facilities, reverse osmosis desalination plants, in oil and gas industries lead to significant clogging of pipes and membranes and to a serious increase in production costs. For the mitigation of scale formation, the wide spectrum of antiscalants is applied. The present work is dedicated to the study of calcium sulfate deposition from supersaturated aqueous solutions in the presence of polyacrylic antiscalant with fluorescent marker (naphthalimide fragment) PAA-F1, which provides traceability of the scale inhibitor and a better understanding of its efficacy. A paradoxical phenomenon is being described here. Antiscalant causes a change in the crystal phase from bassanite to gypsum, significantly reduces the amount of deposit, but does not reveal the presence of its molecules either at the kink, step, or at selected edge sites of deposited crystals. Contrary to the predictions of the theory, it either stays in the aqueous phase, or forms its own separate phase Ca-PAA-F1. It is demonstrated that the antiscalant does not block the surfaces of calcium sulfate nuclei or crystal surfaces, but rather the foreign particles of nanodust with particle sizes around 1 nm, naturally occurring in any aqueous solution. As a result, the number of calcium nucleation sites is reduced, and the rate of scale formation decreases without any apparent antiscalant–scale interaction. On the grounds of the current experiment, the substoichiometric effect of scale inhibition obtained an alternative, quite stoichiometric explanation. Full article

Although there are numerous studies that aim to reveal the source of student failure in problem solving in STEM fields, there is a lack of attention on testing different methods to identify what works best in improving students’ problem-solving performance. In this study, the authors examined the influence of the type of problem construction intervention and compared it to the effect of traditional practice on 38 general chemistry students’ comprehension of problem-solving process as well as overall success with given stoichiometric problems. To determine students’ success with each subtopic involved in stoichiometric problems and to better understand the source of difficulty at a finer level rather than focusing on the end product as practiced in most studies, students’ solutions were examined using the COSINE (Coding System for Investigating Sub-problems and Network) method. The findings revealed that students who practiced the problem-construction method outperformed their counterparts in the control group who followed a traditional approach during their study session. An in-depth analysis also showed that the experimental group improved their success with seven out of nine subtopics while three topics observed an increase in the control group. The practical implication of the problem-construction method was discussed for a wider adoption by textbook publishers and educators across different disciplines. Full article

Gelsolin amyloidosis (AGel) is characterized by multiple systemic and ophthalmic features resulting from pathological tissue deposition of the gelsolin (GSN) protein. To date, no cure is available for the treatment of any form of AGel. More than ten single-point substitutions in the GSN gene are responsible for the occurrence of the disease and, among them, D187N/Y is the most widespread variant. These substitutions undergo an aberrant proteolytic cascade, producing aggregation-prone peptides of 5 and 8 kDa, containing the Gelsolin Amyloidogenic Core, spanning residues 182–192 (GAC_182–192). Following a structure-based approach, we designed and synthesized three novel sequence-specific peptidomimetics (LB-5, LB-6, and LB-7) built on a piperidine-pyrrolidine unnatural amino acid. LB-5 and LB-6, but not LB-7, efficiently inhibit the aggregation of the GAC_182–192 amyloidogenic peptides at sub-stoichiometric concentrations. These peptidomimetics resulted also effective in vivo, in a C. elegans-based assay, in counteracting the proteotoxicity of aggregated GAC_182–192. These data pave the way to a novel pharmacological strategy against AGel and also validate a toolbox exploitable in other amyloidogenic diseases. Full article