Search Results (7,853)

Developing cost-effective alternatives to platinum-based catalysts remains paramount for commercializing anion exchange membrane fuel cells (AEMFCs). We report a metal-free nitrogen-doped carbon catalyst derived from a rationally designed polyurea–polyimine copolymer that outperforms commercial 20 wt% Pt/C in superior relative durability and methanol tolerance. Strategic integration of polyurea’s pore-forming capability with polyimine’s thermal stability enabled the synthesis of a catalyst (NC-1000N) featuring ultrahigh surface area (1276.5 m² g⁻¹), optimal nitrogen speciation (20.5% pyridinic-N, 45.3% graphitic-N), and enhanced graphitization, which improves the electrical conductivity of catalysts. NC-1000N exhibited exceptional oxygen reduction performance with an onset potential of 0.96 V, almost four-electron selectivity (n = 3.87), a medium Tafel slope (105 mV dec⁻¹), and minimal charge transfer resistance (46.74 Ω). When evaluated in single-cell AEMFCs, NC-1000N delivered a peak power density of 372.1 mW cm⁻², which is 26% higher than Pt/C at equivalent loading, while demonstrating superior stability (94.8% retention after 7 h) and complete methanol tolerance. Systematic pyrolysis temperature optimization (800–1000 °C) revealed critical structure–property relationships governing catalyst evolution from disordered precursor to highly graphitic, nitrogen-enriched carbon with precisely engineered active sites. This work establishes polymer-derived carbons and provides design principles for scalable synthesis of high-performance metal-free electrocatalysts for sustainable energy conversion technologies. Full article

The morphological and structural state of rough solid electrodes usually has a complex effect on the kinetics of an electrochemical process. In order to correctly distinguish the influence of different factors on the rate of an electrode reaction, it is necessary to first separate a purely geometric current rise caused by the surface area increase. At the same time, it is necessary to take into account that surface roughness itself often not only leads to a geometric rise in the electrode area, but also contributes to a change in the kinetic parameters of the electrochemical process. As a consequence, the conclusion regarding an electrocatalytic effect will be reasonable only if the roughness effect is correctly taken into account. The most difficult problem is to establish the role of roughness when experimental electrochemical data are obtained under mixed diffusion–kinetic control of the electrode process. However, the use of appropriate theoretical approaches is required to correctly determine the kinetic characteristics of the electrochemical stage, i.e., of the charge transfer stage. This paper establishes the influence of the morphology and structure of electrodeposited copper coatings on the kinetics of the cathodic reduction of nitrate ion, which occurs in a mixed diffusion–kinetic mode, using the theoretical model of chronoamperometry of an electrochemical process on a rough electrode developed earlier by the authors. Several Cu-electrodes with roughness and structure, the parameters of which vary widely enough, were obtained by cathodic deposition from sulfate solutions of different compositions. The integral (roughness factor) and local (average roughness) characteristics of the surface morphology were determined by methods of underpotential deposition and atomic force microscopy, respectively. Structural investigation of the electrodeposited coatings was carried out by X-ray diffraction to determine their crystallographic structure and average crystallite size. The methods of voltammetry and a rotating disk electrode revealed the mixed kinetics of the electroreduction of ${\mathrm{NO}}_3^{-}$ ions. The kinetic parameters of the charge transfer stage on the copper coatings with a roughness factor of f_r ≤ 3.5 are determined for the first time in this paper by treatment of the experimental current decay curves with the non-linear theoretical equation obtained by the authors for the chronoamperogram of the process on rough electrodes. It was found that the rate constant of the charge transfer stage and the exchange current density of the nitrate ion electroreduction increase by about 50%, with an increase in the average surface roughness from 25 to 120 nm. Considering that this effect is not caused by a purely geometric increase in the true surface area of the electrode, and that the average crystallite size is approximately the same (25 ± 2 nm) for all investigated coatings, it can be concluded that the electrocatalytic activity of copper increases in the reaction of the cathodic reduction of nitrate ions during the transition to copper electrodes with the higher average surface roughness. Taking into account XRD data, the role of the structural and morphological state in the kinetics of the electroreduction of nitrate ions has been established. The smoothest polycrystalline coating was found to be the least electrocatalytically active in this reaction. On the contrary, the roughest coatings with the most prominent plane (220) show the highest activity, which increases with increasing average roughness, possibly due to the growth of defects and excess energy of such curved surfaces. Full article

The present work reports on the microstructural and micro-mechanical characterization of Ti-Nb-HA-based composites. The composites were prepared via a spark plasma sintering (SPS) consolidation process. The effect of two distinct levels of hydroxyapatite (HA) content (e.g., 10 and 20 wt.%) on the microstructural and micro-mechanical properties were investigated via in situ micro-pillar compression, and the results were compared against a sole Ti-Nb composite. The microstructure of the composites was composed of parent Ti and Nb grains, together with the reaction products; due to the decomposition of HA, there was a rise in different biocompatible phases. The Vickers hardness of the composite was sensitive to applied loads due to the presence of pores and voids, which was foreseen to be beneficial when the composite was used as an implant, according to the literature. The addition of 20 wt.% HA causes a decrease in hardness to 990 HV, compared to 1109 HV for 10 wt.% HA and 1275 HV for sole Ti-Nb. The addition of HA into Ti-Nb also lowers the compressive strength from 553 MPa for Ti-Nb to 189 MPa for Ti-30Nb-20HA. This was accompanied by a reduction in the elastic modulus, from 130 GPa for Ti-Nb to 29 GPa for Ti-30Nb-20HA. The deformation mechanism was ductile-dominated in all cases, with the presence of a quasi-brittle nature for HA-containing composites. Full article

Background: Actinic keratosis (AK) is a common premalignant skin disorder associated with chronic ultraviolet exposure and a recognized risk of progression to cutaneous squamous cell carcinoma. Tirbanibulin 1% ointment is an effective short-course field therapy for AK, but its efficacy in hyperkeratotic lesions (Olsen grade II–III) may be limited by reduced drug penetration through a thickened stratum corneum. Keratolytic pretreatment may represent a plausible strategy to improve topical drug delivery in these more challenging lesions. Methods: This retrospective chart review included consecutive adults with Olsen grade II–III AK treated in routine clinical practice with either a bland emollient lead-in followed by tirbanibulin (Group A) or salicylic acid 30% ointment pre-treatment (Decapan, Sanitpharma; Milan, Italy) followed by tirbanibulin (Group B). No study-driven procedures or additional visits were implemented. The 14-day bland emollient lead-in used in Group A was part of the routine clinical management applied during the relevant treatment period and was not introduced or retrospectively constructed for the purposes of the present comparative analysis. Outcomes were extracted from de-identified medical records and photographic documentation obtained as part of standard care. For the purposes of analysis, post-treatment evaluations were grouped into predefined windows of 3–6 weeks (T1), 10–14 weeks (T2), and 22–30 weeks (T3), corresponding approximately to 1, 3, and 6 months after treatment initiation. The primary efficacy endpoints were the Actinic Keratosis Area and Severity Index (AKASI) and Total Lesion Count (TLC). Secondary endpoints included quality of life assessed by the Dermatology Life Quality Index (DLQI). Results: Both treatment regimens were associated with clinically meaningful improvements in AK severity. At T3, mean AKASI was significantly lower in Group B than in Group A (0.86 ± 0.38 vs. 1.35 ± 0.27; p < 0.001), corresponding to reductions from baseline of 60.6% and 36.9%, respectively. Similarly, mean TLC at T3 was significantly lower in Group B than in Group A (4.80 ± 1.5 vs. 6.35 ± 1.6; p < 0.001), corresponding to reductions from baseline of 46.7% and 27.0%, respectively. Quality-of-life outcomes also favored the sequential approach, with lower DLQI scores at T3 in Group B compared with Group A (2.9 ± 1.6 vs. 3.8 ± 1.9; p = 0.006). Both treatments were generally well tolerated. Although the incidence of local skin reactions (LSRs) was similar between groups, Group B showed lower retrospectively documented composite LSR scores and lower patient-reported discomfort (p < 0.001) and lower patient-reported discomfort (p < 0.001). Conclusions: Sequential keratolytic pretreatment followed by tirbanibulin was associated with greater reductions in disease burden and with lower severity of treatment-related local reactions in this retrospective cohort (Olsen grade II–III). This retrospective study suggests that keratolytic pretreatment may represent a useful adjunctive strategy in hyperkeratotic AK treated with tirbanibulin. Prospective randomized studies are warranted to confirm these findings and to define standardized treatment protocols. Full article

A new three-step strategy for the preparation of 1,2-disubstituted 1H-benzo[d]imidazoles has been developed. The approach involved (1) S_NAr addition-elimination of alkyl- or arylamines to 1-fluoro-2-nitrobenzene to give N-alkyl- or N-aryl-2-nitroanilines, (2) acylation of these adducts with acid chlorides to afford N-alkyl- or N-aryl-N-(2-nitrophenyl) amides, and (3) reduction of the aromatic nitro with iron in acetic acid at 95–100 °C, followed by closure of the resulting amine on the amide carbonyl to produce 1,2-disubstituted benzimidazoles in high yields. The sequence gave the benzimidazole products in NMR-pure form with only one purification after Step 2. Thirty-seven derivatives were prepared, providing a broad selection of 1,2-disubstituted benzimidazoles. Interestingly, the reaction of the aniline nitrogen derived from the reduction of the nitro group afforded the final product by addition to the acyl carbonyl, followed by dehydrative aromatization with no competing rearrangement, acyl transfer, or side products. Full article

Backfilling the industrial solid waste coal gangue into deep coal mine goafs for CO₂ geological sequestration is a crucial pathway to achieve the synergistic effect of pollution reduction and carbon mitigation. However, in complex deep geological environments, the chemical evolution of multiple mineral phases of coal gangue under gas–water–rock coupling effects and the carbon-controlling mechanism of residual total organic carbon (TOC) remain unclear. In this study, coal gangue from the goaf of the Xiaobaodang Coal Mine was used as the research object. Relying on a customized high-temperature and high-pressure reaction system to simulate the deep in situ environment (45 °C, 10 MPa), and combined with X-ray diffraction (XRD), total organic carbon determination, and isothermal CO₂ adsorption experiments, the geochemical mechanism by which inorganic minerals and organic residual carbon synergistically control the ultimate CO₂ adsorption potential was systematically revealed. The results show that the modification of the CO₂ adsorption potential of coal gangue by gas–water–rock reactions exhibits strong mineral phase differentiation. Systems rich in active silicates generate a large amount of secondary clay minerals through intense carbonation alteration, achieving a significant increase in micro–nano pores and absolute adsorption capacity. Systems rich in carbonates steadily release deep primary adsorption potential by widening mass transfer channels through mineral dissolution. In contrast, systems rich in primary clay minerals face an irreversible attenuation of adsorption space due to physical clogging of pore throats caused by fluid migration. Furthermore, the initial organic carbon content exerts a significant non-linear regulatory effect on the development of the micropore network. The physical adsorption sites provided by the high relative content of layered clay minerals (>41%), coupled with the interfacial enhancement effect exerted by a moderate organic carbon content (0.12~0.16%), constitute an optimal physicochemical synergistic enhancement network, which is the core geological reason for stimulating the ultimate carbon sequestration capacity of coal gangue. The results of this study not only enrich the multiphase interfacial thermodynamic theory of complex heterogeneous geological bodies but also provide solid theoretical support for the precise optimization of target areas and the long-term evaluation of carbon sinks in goaf CO₂ sequestration engineering. Full article

The thiourea grafting method can effectively improve the ability of activated carbon to recover chloroauric acid (AuCl₄⁻). Conventional grafting strategies rely on acyl halide reactions using reagents such as SOCl₂ and CH₂Cl₂, which suffer from instability and high toxicity. Herein, we propose a green grafting strategy for thiourea by activating carboxyl groups with EDC-HCl/NHS in acetonitrile, followed by the amidation reaction to obtain thiourea-modified carbon (AC-NCS). FT-IR and XPS analyses confirm the successful grafting of thiourea onto the activated carbon surface. Compared with pristine activated carbon, the adsorption capacity of AC-NCS is 104.8 mg/g, increased by 5.76 times. Furthermore, it maintains a recovery rate of 84.2% after three cycles. XPS and FT-IR further reveal that adsorption occurs on the thiourea sulfur atoms (C=S) and protonated primary amines(-NH₃⁺), and the recovery of chloroauric acid is achieved through a synergistic “reduction–electrostatic attraction” mechanism. This method reduces the dependence on highly toxic reagents and provides a promising approach for the efficient and green recovery of gold from secondary resources. Full article

With the expansion of modern protected agriculture, the amount of post-harvest tomato biomass has increased sharply. Conventional unmanaged disposal practices disrupt carbon flows and cause substantial environmental emissions. Tomato plant residues (TPRs), which are rich in lignocellulose and selected high-value secondary metabolites, have considerable potential as feedstocks for green industrial materials. However, their complex biophysical properties, high physiological moisture content, and recalcitrant cell-wall barriers hinder large-scale processing. This review systematically examines the mechanisms and process architectures for converting TPRs into macromolecular products. First, it analyzes cross-scale anatomical heterogeneity and dynamic rheological properties of TPRs, defining their physicochemical boundaries as industrial precursors. Second, it summarizes the development of physical field-coupled equipment, ranging from anti-tangling harvest-shredding to die-roller densification. Furthermore, it examines the core mechanisms of multi-field-coupled pretreatment technologies, including steam explosion, deep eutectic solvents (DES), and mechanochemistry, in deconstructing vascular skeletons and reducing multiphase mass-transfer resistance. Finally, this review discusses reconstruction pathways for TPR-derived components in advanced polymer materials, including biodegradable nanocellulose films, bio-based composites, aerogels, and lignin-based polyurethane networks. Overall, it links microscopic reaction kinetics with macroscopic equipment engineering, proposes a closed-loop material conversion system from in-field volume reduction to cascaded biorefinery, and provides an engineering framework for future multi-machine intelligent collaboration and continuous production across the industrial chain. Full article

Reactivity of non-aromatic 2,5-dichloro-2H-pyrroles toward S-nucleophiles was investigated. It was found that these non-aromatic derivatives exhibit both oxidative and electrophilic properties. Their reaction with thiols and xanthates proceeds as redox process to form disulfides and 5-chlorinated pyrroles as a result of 2,5-dichloro-2H-pyrroles reduction. However, the reaction with ammonium thiocyanate afforded the corresponding 5-thiocyanated 1H-pyrroles. Based on these findings, a novel one-pot method for the thiocyanation of 2,3,4-trisubstituted pyrroles was developed. The protocol involves the in situ generation of highly reactive 2,5-dichloro-2H-pyrroles via dearomative chlorination of the corresponding pyrroles using trichloroisocyanuric acid (TCCA). Subsequent addition of ammonium thiocyanate leads to regioselective incorporation of a thiocyanate group at the C5 position and rearomatization of the pyrrole core. A broad scope of pyrrole-5-thiocyanates was obtained in yields up to 82%. Furthermore, these derivatives were efficiently transformed into 5-trifluoromethylthiolated pyrroles using Ruppert’s reagent in up to 94% yield. This reaction sequence provides a cost-effective way to obtain 5-trifluoromethylthiolated pyrroles, avoiding the need for high-cost electrophilic reagents. The synthetic utility of these novel sulfur-containing pyrrole derivatives was also demonstrated. Full article

Background: Critical illness leads to profound metabolic, neuroendocrine and immune disorders that affect the prognosis of patients treated in intensive care units (ICUs). The ketogenic diet, a high-fat and low-carbohydrate eating model, is gaining increasing importance as a potential metabolic intervention in the ICU. Preliminary data suggest that the ketogenic diet (KD) may support the control of seizures in a super-refractive epileptic state (SRSE), stabilize glycemia, reduce insulin demand, and modulate the immune response in sepsis. The aim of this review was to present a synthetic presentation of the current state of knowledge regarding use of the KD in intensive care patients. Methods: The review was carried out in accordance with the guidelines of the Joanna Briggs Institute and PRISMA-ScR. PubMed, Scopus, EBSCO, Web of Science, Google Scholar and Cochrane Library databases were searched (10–19 April 2026) using the Population–Concept–Context model. Full-text observational studies, randomized trials and reviews of the use of KDs in ICU patients were included. Data extraction was performed independently by two reviewers. Results: Of the 42 publications identified, seven studies were included in the analysis. The KD was feasible and safe in both critically ill adults and children. In SRSE, most patients achieved stable ketosis within a few days, which often allowed for reduction or discontinuation of anesthetics. In sepsis, the KD led to glycemic stabilization, reduced insulin demand and reduced immune deregulation; in one study, “after day 4, none of the patients in the KD group required insulin treatment.” The KD also showed beneficial effects on cellular bioenergetics and mitochondrial function. The safety profile was acceptable and adverse reactions were manageable with appropriate monitoring. Conclusions: The KD represents a promising, non-pharmacological metabolic intervention in intensive care, particularly in the treatment of SRSE and in the stabilization of glucose metabolism in sepsis and other critical conditions. Despite the growing number of positive clinical observations, the available evidence remains limited due to small samples, heterogeneous protocols, and a lack of randomized trials. Further, well-designed prospective studies are needed to determine optimal KD implementation protocols and identify the patient populations that benefit most. Full article

We investigate invariant finite-dimensional linear spaces for a class of nonlinear evolution equations with second-order time dependence of the type ${\partial }_{tt}u=-{\partial }_x\left(A(x,u)u\right)+{\partial }_{xx}\left(B(x,u)u\right)+f\left(u\right),$ where the coefficients may depend nonlinearly on the solution. Using direct algebraic verification and invariant subspace reductions, we derive several exact solutions and reduce the governing equations to finite-dimensional systems of ordinary differential equations. Various examples are presented to illustrate the applicability of the method to nonlinear transport, diffusion, and reaction models. Full article

Effective abatement of nitrogen oxides (NO_x) is achieved by ammonia selective catalytic reduction (NH₃-SCR). In this paper, the effects of single WO₃ doping and WO_x-VO_x co-doping into the MnO_x/TiO₂ catalyst on NH₃-SCR of NO_x removal, sulfur and water resistance, and reaction mechanisms were systematically investigated. The 5MnO_x/TiO₂, WO₃-5MnO_x/TiO₂, and WO₃-V₂O₅-5MnO_x/TiO₂ were prepared using the incipient-wetness impregnation method. Furthermore, the monolithic WO₃-V₂O₅-5MnO_x/TiO₂-CC (cordierite support) catalyst involved a coating process. The WO₃-V₂O₅-5MnO_x/TiO₂ catalyst demonstrated superior NO conversion and maintained over 80% activity following prolonged exposure to SO₂ and H₂O. Characterization results indicated that the introduction of WO₃ regulated Mn valence through the formation of W-O-Mn bonds. The synergistic effect of V₂O₅ and WO₃ further promoted electron transfer, increased surface chemisorbed oxygen and oxygen vacancies, and strengthened reactant adsorption and activation. In situ DRIFTS analysis suggested that WO₃ modulated the reaction pathway, and while 5MnO_x/TiO₂ followed the Langmuir–Hinshelwood (L-H) mechanism, both WO₃-5MnO_x/TiO₂ and WO₃-V₂O₅-5MnO_x/TiO₂ exhibited a combined L-H and Eley–Rideal (E-R) pathway. This study confirmed that WO₃ played a crucial regulatory role in both single-metal and multi-metal systems, and the synergistic interaction between V₂O₅ and WO₃ was the key to achieving superior denitration performance and poisoning resistance. Full article

Phenylephrine is a widely used α₁-adrenergic agonist employed as a decongestant and vasoconstrictor in numerous pharmaceutical formulations. Considering its widespread use and its relevance in biological monitoring and anti-doping control, the development of rapid, sensitive, and reliable analytical methods for its determination has attracted significant attention. A paper-based colorimetric sensor based on Prussian blue nanoparticles was developed for the determination of phenylephrine. Prussian blue nanoparticles were synthesized by the precipitation method, and their structural, morphological, and surface properties were systematically characterized using complementary analytical techniques. The sensing mechanism is based on the reduction in Prussian blue to its colorless form in the presence of phenylephrine, resulting in a decrease in absorbance intensity. Under optimized conditions (pH 6.5 and 5 min incubation time), the colorimetric sensor exhibited a linear response toward phenylephrine over the concentration range of 5–150 µg mL⁻¹, with a limit of detection of 1.56 µg mL⁻¹ (R² = 0.9986). The sensing system was further integrated into a paper-based platform, enabling visual detection of phenylephrine. Digital image analysis using ImageJ showed a linear response over 5–150 µg mL⁻¹ (R² = 0.9884) and a detection limit of 5.37 µg mL⁻¹. The sensor’s practical applicability was validated using artificial urine samples, yielding recovery values of 95.87–97.5% and relative standard deviations of 1.15–2.13%. Unlike conventional methods requiring multi-step reactions, this study introduces, for the first time, a simple paper-based colorimetric sensor for phenylephrine detection based on the direct Prussian blue–Prussian white redox transition integrated with digital image analysis. Full article

The use of water as a nucleophile in catalytic asymmetric reactions remains a significant challenge, primarily due to its intrinsically low nucleophilicity and small size, which make precise control over both reactivity and stereoselectivity particularly difficult. To address this issue, we developed a CPA-catalyzed asymmetric hydrolysis system, successfully achieving the efficient and highly stereoselective transformation of 4H-oxazines with water. Under this catalytic system, the initial formation of chiral α-bromo ketones is followed by their in situ conversion through reduction and intramolecular S_N2 reactions, directly affording valuable chiral bromo alcohols and chiral oxazolone derivatives in high yields with excellent enantioselectivity. Full article

The development of highly efficient, stable, and cost-effective non-precious metal electrocatalysts to replace conventional platinum-based materials holds profound significance for accelerating the commercialization of advanced energy conversion devices, such as zinc–air batteries (ZABs). Herein, we propose a facile and highly efficient strategy to prepare a defect-rich, highly active nitrogen-doped porous carbon-based electrocatalyst (denoted U-Fe-N-C, urea-assisted iron–nitrogen–carbon material), via high-temperature co-pyrolysis of heme with urea. Our results demonstrate that urea not only serves as an excellent nitrogen source during pyrolysis, introducing abundant topological defects and heteroatom doping sites, but also induces the carbon substrate to form a hierarchical sponge-like porous structure with a high specific surface area. This unique microenvironment effectively prevents the agglomeration of iron species at high temperatures, achieving enhanced dispersion of iron species stabilized within the nitrogen-rich carbon matrix. Electrochemical evaluations reveal that under the optimal synthesis conditions (a precursor mass ratio of 1:3, calcination at 900 °C), U-Fe-N-C exhibits excellent oxygen reduction reaction (ORR) catalytic performance, delivering a half-wave potential of 0.731 V vs. RHE, and shows long-term operational durability that significantly surpasses that of commercial Pt/C. Furthermore, liquid rechargeable zinc–air batteries assembled with U-Fe-N-C as the air cathode deliver remarkable cycling stability, operating for up to 270 h of charge–discharge cycling without noticeable performance degradation. This study not only provides useful insights into the mechanisms of pore formation and assistance but also offers a practical perspective for the rational design and scalable synthesis of high-performance metal–nitrogen–carbon (M-N-C) electrocatalysts. Full article