Search Results (840)

This paper presents the expected and unexpected, but typically substituent-dependent, ferrocene-catalyzed DDQ-mediated oxidative transformations of a series of 5,8-bis(methylthio)-1-aryl-1,2-dihydropyridazino[4,5-d]pyridazines and 8-(3,5-dimethyl-1H-pyrazol-1-yl)-5-(methylthio)-1-aryl-1,2-dihydropyridazino[4,5-d]pyridazines. Under noncatalytic conditions the reactions were sluggish, mainly producing a substantial amount of undefined tarry materials; nevertheless, the ferrocene-catalyzed reactions of the 5,8-bis(methylthio)-substituted precursors gave the aromatic products the expected aromatic products in low yields. Their formation was accompanied by ring transformations proceeding via aryne-generating fragmentation/Diels–Alder (DA)/N₂-releasing retro Diels–Alder (rDA) sequence to construct arene-fused phthalazines. On the other hand, neither the noncatalytic nor the catalytic reactions of the 8-pyrazolyl-5-methylthio-substituted dihydroaromatics yielded the expected aromatic products. Instead, depending on their substitution pattern, the catalytic reactions of these pyrazolyl-substituted precursors also led to the formation of dearylated arene-fused phthalazines competing with an unprecedented multistep fragmentation sequence terminated by the hydrolysis of cationic intermediates to give 4-(methylthio)pyridazino[4,5-d]pyridazin-1(2H)-one and the corresponding 3,5-dimethyl-1-aryl-1H-pyrazole. When 0.6 equivalents of DDQ were applied in freshly absolutized THF, a representative pyrazolyl-substituted model underwent an oxidative coupling to give a dimer formed by the interaction of the cationic intermediate, and a part of the N-nucleophilic precursor remained intact. A systematic computational study was conducted on these intriguing reactions to support their complex mechanisms proposed on the basis of the structures of the isolated products. Full article

The (1−x)Ba_0.96Ca_0.04TiO₃−xBi(Li_1/3Zr_2/3)O₃ (x = 0.03–0.15) ceramics were fabricated via the traditional solid reaction method. Characterization results revealed that each component exhibited a pure perovskite structure, and the average grain size significantly diminishes with increasing x. The (1−x)Ba_0.96Ca_0.04TiO₃−xBi(Li_1/3Zr_2/3)O₃ ceramics exhibited prominent relaxor ferroelectric behavior, whose characteristic narrow hysteresis loops effectively enhanced the energy storage performance of the material. Most importantly, the composition with x = 0.10 demonstrated exceptional energy storage properties at 150 kV/cm, achieving a high recoverable energy storage density (W_rec = 1.91 J/cm³) and excellent energy efficiency (η = 90.87%). Under the equivalent electric field, this composition also displayed a superior pulsed discharge performance, including a high current density (871 A/cm²), a high power density (67.3 MW/cm³), an ultrafast discharge time (t_0.9 = 109 ns), and a discharged energy density of 1.47 J/cm³. These results demonstrate that the (1−x)Ba_0.96Ca_0.04TiO₃−xBi(Li_1/3Zr_2/3)O₃ ceramic system establishes a promising design paradigm for the creation and refinement of next-generation dielectrics for pulse power applications. Full article

Anion exchange membrane (AEM) water electrolysis is a potentially inexpensive and efficient source of hydrogen production as it uses effective low-cost catalysts. The catalytic activity and performance of nickel iron oxide (NiFeO_x) catalysts for hydrogen production in AEM water electrolyzers were investigated. The NiFeO_x catalysts were synthesized with various iron content weight percentages, and at the stoichiometric ratio for nickel ferrite (NiFe₂O₄). The catalytic activity of NiFeO_x catalyst was evaluated by linear sweep voltammetry (LSV) and chronoamperometry for the oxygen evolution reaction (OER). NiFe₂O₄ showed the highest activity for the OER in a three-electrode system, with 320 mA cm⁻² at 2 V in 1 M KOH solution. NiFe₂O₄ displayed strong stability over a 600 h period at 50 mA cm⁻² in a three-electrode setup, with a degradation rate of 15 μV/h. In single-cell electrolysis using a X-37 T membrane, at 2.2 V in 1 M KOH, the NiFe₂O₄ catalyst had the highest activity of 1100 mA cm⁻² at 45 °C, which increased with the temperature to 1503 mA cm⁻² at 55 °C. The performance of various membranes was examined, and the highest performance of the tested membranes was determined to be that of the Fumatech FAA-3-50 and FAS-50 membranes, implying that membrane performance is strongly correlated with membrane conductivity. The obtained Nyquist plots and equivalent circuit analysis were used to determine cell resistances. It was found that ohmic resistance decreases with an increase in temperature from 45 °C to 55 °C, implying the positive effect of temperature on AEM electrolysis. The FAA-3-50 and FAS-50 membranes were determined to have lower activation and ohmic resistances, indicative of higher conductivity and faster membrane charge transfer. NiFe₂O₄ in an AEM water electrolyzer displayed strong stability, with a voltage degradation rate of 0.833 mV/h over the 12 h durability test. Full article

A novel macrodesign for a dental implant characterized by a non-monotonic variation in core diameter and thread shape has been described to produce lower stress levels during insertion as compared to conventional tapered implants. Two finite element models resembling the lower left molar region with preformed osteotomies were created based on a cone beam computed tomography (CBCT) scan. Insertion of both the novel and the conventional, tapered implant type were simulated using Standard for the Exchange of Product model data (STEP) files of both implant types. Von Mises equivalent stress, strain development, and amount of redistributed bone were recorded. The conventional implant demonstrated a continuous increase in strain values and reaction moment throughout the insertion process, with a brief decrease observed during the final stages. Stress levels in the cortical bone gradually increased, followed by a reduction when the implant was finally positioned subcrestally. The novel implant achieved the maximum magnitude of reaction moment and cortical bone strain values when the implant’s maximum core diameter passed the cortical bone layer at around 60% of the insertion process. Following a notable decrease, both the reaction moment and stress started to rise again as the implant penetrated further. The novel implant removed more bones in the trabecular region while the conventional implant predominantly interacted with cortical bone. Overall, the novel design seems to be less traumatic to alveolar bone during the insertion process and hence may lead to reduced levels of initial peri-implant bone loss. Full article

In this study, alkali-activated coal gangue-slag material (AACGS) was prepared using coal gangue and slag as precursors, and its feasibility as conductive mortar substrate material was preliminarily investigated. Firstly, this study employed Response Surface Methodology (RSM) to develop statistical models correlating the alkali equivalent, water-to-binder ratio, and slag content with the compressive strength, flexural strength, and resistivity of AACGS, aiming to identify the optimal mix proportions. Secondly, based on the optimal ratio identified above and using carbon fibers (CF) as the conductive phase, an alkali-activated conductive mortar (CF-AACGS) was prepared, and its compressive strength, flexural strength, and resistivity were tested. Lastly, XRD and SEM-EDS were conducted to characterize the mineral composition and microstructure of CF-AACGS. The results indicate that when the alkali equivalent, water-to-binder ratio, and slag content are 13.34%, 0.54, and 57.52%, respectively, the AACGS achieves compressive strength, flexural strength, and resistivity of 72.5 MPa, 7.0 MPa, and 62.41 Ω·m at 28 days. Under the action of the alkali activator, coal gangue and slag undergo hydration reactions, forming a denser N, C-(A)-S-H gel. This effectively improves the interface transition zone between the CF and AACGS, endowing the CF-AACGS with superior mechanical properties. Furthermore, the AACGS matrix enhances the conductive contact point density by optimizing CF dispersion, which significantly reduces the resistivity of the CF-AACGS. Full article

Pyrochlore Bi_1.8Mn_0.5Ni_0.5Ta₂O_9-Δ (sp.gr. Fd-3m, a = 10.5038(9) Å) was synthesized by the solid-phase reaction method and characterized by vibrational and X-ray spectroscopy. According to scanning electron microscopy, the ceramics are characterized by a porous microstructure formed by randomly oriented oblong grains. The average crystallite size determined by X-ray diffraction is 65 nm. The charge state of transition element cations in the pyrochlore was analyzed by soft X-ray spectroscopy using synchrotron radiation. For mixed pyrochlore, a characteristic shift of Bi4f and Ta4f and Ta5p spectra to the region of lower energies by 0.25 and 0.90 eV is observed compared to the binding energy in Bi₂O₃ and Ta₂O₅ oxides. XPS Mn2p spectrum of pyrochlore has an intermediate energy position compared to the binding energy in MnO and Mn₂O₃, which indicates a mixed charge state of manganese (II, III) cations. Judging by the nature of the Ni2p spectrum of the complex oxide, nickel ions are in the charge state of +(2+ζ). The relative permittivity of the sample in a wide temperature (up to 350 °C) and frequency range (25–10⁶ Hz) does not depend on the frequency and exhibits a constant low value of 25. The minimum value of 4 × 10⁻³ dielectric loss tangent is exhibited by the sample at a frequency of 10⁶ Hz. The activation energy of conductivity is 0.7 eV. The electrical behavior of the sample is modeled by an equivalent circuit containing a Warburg diffusion element. Full article

A novel cellulose-degrading bacterial strain, D3-1, capable of degrading cellulose under medium- to high-temperature conditions, was isolated from soil samples and identified as Staphylococcus caprae through 16SrRNA gene sequencing. The strain’s cellulase production was optimized by controlling different factors, such as pH, temperature, incubation period, substrate concentration, nitrogen and carbon sources, and response surface methods. The results indicated that the optimal conditions for maximum cellulase activity were an incubation time of 91.7 h, a temperature of 41.8 °C, and a pH of 4.9, which resulted in a maximum cellulase activity of 16.67 U/mL, representing a 165% increase compared to pre-optimization levels. The above experiment showed that, when maize straw flour was utilized as a natural carbon source, strain D3-1 exhibited relatively high cellulase production. Furthermore, gas chromatography–mass spectrometry (GC-MS) analysis of products in the degradation liquid revealed the presence of primary sugars. The results indicated that, in the denitrification of simulated sewage, supplying maize straw flour degradation liquid (MSFDL) as the carbon source resulted in a carbon/nitrogen (C/N) ratio of 6:1 after a 24 h reaction with the denitrifying strain WH-01. The total nitrogen (TN) reduction was approximately 70 mg/L, which is equivalent to the removal efficiency observed in the glucose-fed denitrification process. Meanwhile, during a 4 h denitrification reaction in urban sewage without any denitrifying bacteria, but with MSFDL supplied as the carbon source, the TN removal efficiency reached 11 mg/L, which is approximately 70% of the efficiency of the glucose-fed denitrification process. Furthermore, experimental results revealed that strain D3-1 exhibits some capacity for nitrogen removal; when the cellulose-degrading strain D3-1 is combined with the denitrifying strain WH-01, the resulting TN removal rate surpasses that of a single denitrifying bacterium. In conclusion, as a carbon source in municipal sewage treatment, the degraded maize straw flour produced by strain D3-1 holds potential as a substitute for the glucose carbon source, and strain D3-1 has a synergistic effect with the denitrifying strain WH-01 on TN elimination. Thus, this research offers new insights and directions for advancement in environmental sewage treatment. Full article

Background: Transition metal complexes incorporating fluorinated counter anions represent a significant class of compounds with broad applications in industry, pharmaceuticals, and biomedicine. These fluorinated anions are known to enhance the solubility, stability, and reactivity of the complexes, thereby expanding their functional utility in various chemical and biological contexts. Methods: A set of metal(II) complexes of the general formula [MPy₆][B(C₆F₅)₄]₂ where (Py = pyridine, M = Mn (1), Fe (2), Co (3), Ni (4), Cu (5), Zn (6)) have been synthesized by direct reaction of metal halides and pyridine in the presence of Ag[B(C₆F₅)₄]. The complexes were characterized using different techniques to assure their purity, such as elemental analysis (EA), electron paramagnetic resonance (EPR) spectroscopy, thermogravimetric analysis (TGA), ultraviolet–visible (UV–Vis) spectroscopy, ¹¹B-NMR, ¹H-NMR, and FT-IR spectroscopy. The antimicrobial and antifungal properties against different types of bacteria and fungi were studied for all prepared complexes. Results: The synthesized complexes exhibited broad-spectrum antimicrobial activity, demonstrating variable efficacy compared to the reference antibiotic, oxytetracycline (positive control). Notably, complex 6 displayed exceptional antibacterial activity against Streptococcus pyogenes, with a minimum inhibitory concentration (MIC) of 4 µg/mL, outperforming the control (MIC = 8 µg/mL). Complexes 1, 2, and 4 showed promising activity against Shigella flexneri, Klebsiella pneumoniae, and Streptococcus pyogenes, each with MIC values of 8 µg/mL. Conversely, the lowest activity (MIC = 512 µg/mL) was observed for complexes 3, 5, and 6 against Pseudomonas aeruginosa, Escherichia coli, and Klebsiella pneumoniae, respectively. Regarding antifungal properties, complexes 5 and 6 demonstrated the highest activity against Candida albicans, with MIC values of 8 µg/mL, equivalent to that of the positive control, fluconazole. Density functional theory (DFT) calculations confirmed an overall octahedral coordination geometry for all complexes, with tetragonal distortions identified in complexes 3, 4, and 5. Full article

This review explores CO₂ methanation and steam methane reforming (SMR) as two key thermochemical processes governed by reversible reactions, each offering distinct contributions to carbon-neutral energy systems. The objective is to provide a comparative assessment of both processes, highlighting how reaction reversibility can be strategically leveraged for decarbonization. The study addresses methane production via CO₂ methanation and hydrogen production via SMR, focusing on their thermodynamic behaviors, catalytic systems, environmental impacts, and economic viability. CO₂ methanation, when powered by renewable hydrogen, can result in emissions ranging from −471 to 1076 kg CO₂-equivalent per MWh of methane produced, while hydrogen produced from SMR ranges from 90.9 to 750.75 kg CO₂-equivalent per MWh. Despite SMR’s lower production costs (USD 21–69/MWh), its environmental footprint is considerably higher. In contrast, methanation offers environmental benefits but remains economically uncompetitive (EUR 93.53–204.62/MWh). Both processes rely primarily on Ni-based catalysts, though recent developments in Ru-based and bimetallic systems have demonstrated improved performance. The review also examines operational challenges such as carbon deposition and catalyst deactivation. By framing these technologies through the shared lens of reversibility, this work outlines pathways toward integrated, efficient, and circular energy systems aligned with long-term sustainability and climate neutrality goals. Full article

Assays of total antioxidant capacity (TAC) of complex materials bring no information on the composition of antioxidants present in a sample. As the thermodynamic condition for a redox reaction is that redox potential of the oxidant must be higher than that of a reductant (antioxidants), it seemed to be of interest whether it is possible to estimate the content of antioxidants of various ranges of redox potentials using a set of assays employing oxidants/indicators of different values of redox potentials. Antioxidant activities of nine antioxidants and TAC of an aqueous garlic extract were estimated using nine assays of E_o′ of oxidants/indicators ranging from 0.11 to 1.15 V. The antioxidant activities were expressed in mol Trolox equivalents/mol compound. The thermodynamic conditions made some antioxidants unreactive with indicators of sufficiently low E_o′, but otherwise, no dependence between the antioxidant activities and redox potentials of oxidants/indicators and reactivities of antioxidants was observed. TAC of the garlic extract did not show any regular dependence on the redox potential of the oxidant/indicator, being the highest in the test of 2,2′-azinobis-(3-ethylbenzothiazoline-6-sulfonate) radical (ABTS^•) decolorization. These results indicate that kinetic factors play a primary role in determining the antioxidant activities of antioxidants and TAC in various assays. Full article

The cationic chloro-P-{[4-(diphenylphosphanyl)phenyl]-N,N-dimethylmethanammonio(norbornadiene)rhodium(I) complex was encapsulated inside a self-assembled hexameric capsule. This capsule was obtained through a reaction involving 2,8,14,20-tetra-undecyl-resorcin[4]arene and water in chloroform. The formation of an inclusion complex was deduced from a combination of spectral measurements (UV-visible spectroscopy, ¹H, ³¹P{¹H} NMR and DOSY). The rhodium complex was evaluated in the [2+2+2] cycloaddition between N,N-dipropargyl-p-toluenesulfonamide and arylacetylene derivatives. In the presence of two equivalents of arylacetylenes in water-saturated chloroform at 60 °C for 24 h, the 4-methyl-N-(prop-2-yn-1-yl)-N-((2-tosylisoindolin-5-yl)methyl)benzenesulfonamide, the homocycloaddition product of 1,6-diyne is predominantly formed. In the presence of the supramolecular capsule, a selectivity inversion in favor of 5-aryl-2-tosylisoindoline is observed, with heterocycloaddition products formed in proportions between 53 and 69%. Full article

To address the engineering challenges associated with Guilin red clay, such as its potentially low strength and unfavorable mechanical behavior, this study investigated the effectiveness of lignin and lime as modifiers. Consolidation undrained triaxial tests and scanning electron microscopy (SEM) were employed to evaluate the strength characteristics and microstructural changes in modified clay specimens with varying dosages. The results demonstrate distinct strengthening mechanisms: Lignin exhibits an optimal dosage (6%), significantly increasing cohesion and internal friction angle through physical reinforcement (“soil fiber” formation), but higher dosages (8%) lead to particle separation and strength reduction. In contrast, lime provides continuous and substantial strength enhancement with increasing dosage (up to 8%), primarily through chemical reactions producing cementitious compounds (e.g., C-S-H, C-A-H) that densify the structure. Consequently, lime-modified clay shows significantly higher cohesion and internal friction angle compared to lignin-modified clay at equivalent or higher dosages, with corresponding stress–strain curves shifting from enhanced (strain-hardening) to softening behavior. These findings provide practical insights into red clay improvement in geotechnical engineering applications. Full article

Grief reactions among relatives of palliative care patients are often overlooked, with most interventions targeting Prolonged Grief Disorder (PGD) rather than its prevention. Few interventions have been developed for individuals at risk. This study aimed to evaluate the efficacy of Empower-Grief, a selective intervention designed to address early problematic grief reactions and to explore predictors of its effectiveness. This exploratory randomized controlled trial (RCT) compared Empower-Grief with Treatment as Usual (TAU) among relatives or caregivers of palliative and oncological patients at risk of developing PGD. A total of 46 participants were assessed at baseline, post-intervention, and six months later. The primary outcome was PGD symptoms, with additional measures including anxiety, depression, coping strategies, attachment style, psychological flexibility, post-traumatic growth, social support, and therapeutic alliance. The final analyses indicate equivalence between Empower-Grief and TAU, suggesting that both interventions yielded comparable outcomes in reducing PGD symptoms and associated psychological distress. The initial symptoms and therapeutic alliance were predictors of the results in both post- and follow-up moments. This study contributes to the evidence on grief interventions in palliative care, highlighting the importance of structured support for bereaved caregivers. While Empower-Grief demonstrated comparable effectiveness to TAU, its lower intensity, ease of training, and application make it a promising treatment option. Full article

The deflagration-to-detonation transition (DDT) is a critical process for achieving reliable ignition in detonation-based propulsion systems, such as Rotating Detonation Engines (RDEs). This study experimentally investigates the effect of spatial variations in blockage ratio (BR) on flame acceleration and detonation onset within a modular pre-detonator. Three DDT device configurations (converging, constant, and diverging) were designed to have an identical average BR of 0.5 and were tested over equivalence ratios ranging from 0.64 to 1.6. High-speed imaging, pressure transducers, and schlieren visualization were employed to characterize flame propagation velocity, pressure evolution, and exit wave structures. The converging configuration consistently promoted earlier detonation onset and higher success rates, especially under fuel-rich conditions (ϕ = 1.6), while the diverging configuration failed to initiate detonation in all cases. Enhanced flame compression in the converging layout led to strong coupling between the shock and reaction fronts, facilitating robust detonation formation. These findings indicate that the spatial distribution of BR, rather than average BR alone, plays a decisive role in DDT performance. This work offers validated design insights for optimizing pre-detonator in RDE applications. Full article

Benzoic acid and benzyl alcohol are the most used raw materials in cosmetics and pharmaceutical industries as preservative ingredients. Cinnamon cassia oil is an important natural starting material to synthesize organic compounds because it contains a high amount of cinnamaldehyde and benzaldehyde. Thanks to green chemistry techniques using mild solvents such as water and ethanol, as well as low-cost and safe reagents such as potassium permanganate, and sodium borohydride, this natural starting material was used to synthesize high yields of benzoic acid, benzyl alcohol, cinnamyl alcohol, phenylpropanol, and cinnamic acid; these products are used in cosmetics, pharmaceutical, and food industries. Various reaction conditions were applied to find convenient green chemistry procedures. Equivalents (molar) of catalysts to starting materials were optimized. The highest yields (60–90%) were achieved using water as a solvent, potassium permanganate as an oxidation catalyst, and sodium borohydride as a reduction catalyst. Water was used as a solvent in all reactions except phenylpropanol. The uses of a single natural starting material, water as a solvent, and mild reagents to synthesize five important organic compounds are all in line with green chemistry techniques. Full article