Search Results (2,835)

The sluggish kinetics of the hydrogen oxidation reaction (HOR) in alkaline media remain a primary bottleneck for anion exchange membrane fuel cells (AEMFCs), necessitating catalysts that synergistically optimize the adsorption of hydrogen (*H) and hydroxide (*OH) intermediates. Herein, we construct a well-defined heterointerface between Pd clusters and CeO₂ on nitrogen-doped carbon (Pd-CeO₂/NC) to electronically engineer the active sites. Spectroscopic studies and theoretical calculations collectively reveal that CeO₂ acts as an electron acceptor, drawing electrons from Pd via interfacial Pd-O-Ce bridges. This charge transfer induces a downshift of the Pd d-band center, which optimally tunes the adsorption strength of both *H and *OH at the interface, thereby breaking the scaling relationship that limits HOR activity. The resulting Pd-CeO₂/NC catalyst achieves an exceptional exchange current density of 3.66 mA cm⁻², surpassing that of commercial Pt/C by a factor of two and ranking among the best reported noble metal catalysts. Furthermore, it exhibits outstanding long-term stability and remarkable CO tolerance, retaining high activity in an atmosphere containing 1000 ppm CO. This work underscores the profound efficacy of metal–oxide heterointerface engineering in regulating electronic structures for multi-intermediate optimization, offering a viable design principle for advanced alkaline HOR electrocatalysts. Full article

Achieving high selectivity in the hydrogenation of CO₂ to light olefins remains challenging because of the complex reaction network and the difficulty of regulating key intermediates. Motivated by green-hydrogen-enabled power-to-chemicals pathways, we combine density functional theory (DFT) with first-principles microkinetic simulation (FPMS) to construct a quantitatively predictive reaction-energy landscape and elucidate structure–selectivity relationships. A comprehensive reaction network is established through energy-surface fitting, and steady-state rate constants are solved to capture the microkinetic competition between elementary steps. By introducing electronic density-of-states (DOS) modulation as a design variable, we directly correlate surface structural parameters with rate-controlling steps, thereby enabling targeted regulation of C–C coupling and hydrogen transfer processes. The calculated barrier for CO₂ adsorption to COOH* is 1.35 eV, while the transition state barrier for C–C coupling is 1.50 eV, corresponding to a reaction rate of 9.7 × 10³ s⁻¹; the olefin desorption rate reaches 1.7 × 10⁷ s⁻¹. Crucially, shifting the d-band center from −2.35 eV to −1.60 eV increases the C₂–C₄ olefin selectivity from 42.6% to 68.3%, establishing an actionable electronic structure lever for catalyst optimization. These results reveal the intrinsic mechanism by which surface electronic and geometric regulation governs intermediate stabilization and rate control, providing a verifiable, mechanism-based design principle for efficient CO₂-to-olefin catalysts aligned with green hydrogen deployment. Full article

Bismuth oxychloride (BiOCl) has garnered significant research interest owing to its non-toxicity, affordability, and distinct layered structure. Although BiOCl possesses promising photocatalytic potential, its large band gap and rapid photocarrier recombination restrict its practical use. In this work, a natural tourmaline mineral was effectively integrated with BiOCl to form a composite (TBO). Comprehensive characterization and photocatalytic assessments revealed that the intrinsic electric field of tourmaline notably strengthened both the adsorption capacity and the light-driven catalytic efficiency of BiOCl. Under visible-light irradiation, ofloxacin (OFX, 10 ppm) was eliminated by approximately 98% within 60 min. The apparent reaction rate constant (k) of TBO was 0.0407 min⁻¹, which was approximately 184.8 and 2.26 times those of tourmaline alone and pristine BiOCl, respectively. Furthermore, both the visible-light absorption and the separation efficiency of photogenerated electron–hole pairs were significantly enhanced. After evaluating its behavior under various simulated natural environmental conditions, TBO displayed strong potential for practical application. Reactive species trapping and analysis identified singlet oxygen (¹O₂) and superoxide radicals (·O₂⁻) as the primary active species in photocatalysis. Moreover, the degradation route of ofloxacin and the toxicity of its intermediates were systematically examined. These findings offer meaningful guidance for improving photocatalytic materials by utilizing naturally occurring minerals. Full article

In recent decades, triazine herbicides (THs), one of the most widely used agrochemicals, have been extensively applied to enhance crop yields. However, their persistent nature and high mobility have resulted in pervasive contamination of aquatic ecosystems, posing significant risks to non-target organisms and human health through bioaccumulation and endocrine disruption. Addressing THs pollution in water bodies has thus emerged as a critical environmental challenge. This study reviews the efficacy of biochar, a carbon-rich material derived from biomass pyrolysis, for TH removal due to its high surface area, hierarchical porosity, and tunable surface functionality. The maximum reported adsorption capacities are up to 260.5 mg·g⁻¹; with degradation efficiencies, they can exceed 99.5% in advanced oxidation systems. Mechanistic investigations reveal that TH removal primarily involves π–π interactions, hydrogen bonding, pore filling, and electrostatic attraction during adsorption, while degradation proceeds via radical pathways (e.g., •OH, SO₄^•−) and nonradical routes (e.g., ¹O₂, direct electron transfer) in processes such as persulfate activation, photocatalysis, and Fenton-like reactions. By analyzing degradation intermediates and pathways, this review underscores the necessity of coupling adsorption with advanced oxidation to achieve complete mineralization and mitigate secondary ecological risks. Furthermore, it emphasizes the importance of tailoring biochar’s physicochemical properties through feedstock selection, pyrolysis conditions, and chemical modifications to optimize THs’ removal performance. This work advocates for the integration of biochar-based technologies into sustainable water treatment frameworks, aligning with carbon neutrality goals and circular economy principles. Future research should prioritize scalable synthesis methods, long-term stability assessments, and field-scale validations to translate laboratory insights into practical solutions for safeguarding global water resources. However, realizing this potential requires that we overcome challenges related to matrix interference, catalyst deactivation, and incomplete mineralization, which are often overlooked in laboratory-scale studies. Full article

Textile wastewater remains one of the most challenging industrial effluents to remediate due to its intense and persistent coloration, high organic load, elevated salinity, and fluctuating pH and the presence of recalcitrant dye structures and auxiliary chemicals. Conventional physicochemical and biological treatments frequently achieve incomplete removal, generate secondary wastes, or fail under high-salt and toxic dye matrices. Advanced oxidation processes (AOPs) provide molecular-level degradation via reactive oxygen species (ROS), yet their deployment is often constrained by narrow operating windows, catalyst instability, chemical/energy demand, and scale-up limitations. In this context, metal–organic frameworks (MOFs) have emerged as tunable porous catalytic platforms that integrate adsorption and oxidation within a single architecture through controllable metal nodes, functional linkers, and engineered pore environments. This critical review reimagines textile effluent treatment through the lens of MOF-based hybrid catalysts, synthesizing progress across Fenton/photo-Fenton catalysis, photocatalytic MOFs, persulfate activation, and MOF-derived/composite systems. Mechanistic pathways are discussed by linking pollutant enrichment, cyclic redox reactions, charge-transfer processes, and ROS-driven degradation toward mineralization, with emphasis on the distinction between rapid decolorization and true organic removal. A critical comparison highlights how hybridization improves charge transport, stability, and catalyst recovery, while persistent gaps remain in hydrolytic robustness, metal leaching control, intermediate toxicity assessment, real-wastewater validation, continuous-flow reactor integration, and techno-economic feasibility. Finally, the review outlines actionable research directions, including water-stable and defect-engineered MOFs, immobilized and structured catalysts, solar-driven operation, standardized performance metrics, and life-cycle-informed design, to accelerate translation toward scalable and sustainable textile wastewater remediation. By bridging material chemistry with reactor-level feasibility and sustainability assessment, this review provides an implementation-oriented perspective for next-generation textile wastewater treatment. Full article

The enzymatic saccharification of cellulose remains a key step in biomass conversion processes, often influenced by enzyme stability, distribution, and accessibility at solid–liquid interfaces. Immobilization of cellulolytic enzymes on nanostructured supports has been proposed as a strategy to modulate catalytic behavior; however, the relationship between enzyme loading and catalytic response remains insufficiently understood. In this study, CuO-based nanobiocatalysts were prepared through controlled cellulase immobilization and systematically evaluated under defined experimental conditions. Structural and physicochemical characterization was performed using X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), and integrated thermal analysis (TGA–DTG–DSC), enabling a comparative assessment of the analyzed systems. SEM analysis showed that the average particle diameter increased from 39.5 ± 14.8 nm (CuO nanoparticles) to 95.6 ± 21.8 nm (NPI10), 106.6 ± 27.7 nm (NPI15), and 113.5 ± 23.1 nm (NPI20), indicating progressive variations in particle organization with increasing enzyme loading. Catalytic performance was evaluated through enzymatic hydrolysis of cellulose filter paper as a model substrate, with products quantified by HPLC at a representative reaction time. The system prepared at lower enzyme loading (NPI10) exhibited product formation comparable to that of the free enzyme, with apparent average glucose formation values of 1.054 and 1.047 mg·mL⁻¹·h⁻¹, respectively. In contrast, higher immobilization levels were associated with reduced catalytic output. Across all systems, glucose was the predominant product, with negligible accumulation of intermediate oligomers under the evaluated conditions. These results indicate that increasing enzyme loading does not correspond to proportional increases in product formation and highlight the influence of enzyme distribution and accessibility within the system. The combined structural and catalytic observations provide a controlled framework for evaluating how immobilization conditions influence system behavior in nanobiocatalytic systems. Full article

Two-dimensional antimonene has recently emerged as a promising electrocatalytic platform; however, its oxygen reduction reaction (ORR) activity and modulation strategies remain largely unexplored. Herein, density functional theory (DFT) calculations are employed to systematically investigate ORR catalysis on antimonene co-doped with transition metal (TM) and nonmetal (C, P) dual atoms. The results reveal that Pd@C–Sb, Pt@C–Sb, and Pd@P–Sb exhibit remarkably enhanced ORR activity, delivering low overpotentials of 0.31 V, 0.32 V, and 0.38 V, respectively, significantly outperforming their single-atom-doped counterparts. Mechanistic analyses demonstrate that nonmetal dopants induce strong synergistic interactions with TM centers, leading to charge redistribution and effective regulation of the TM d-band center, which optimizes the adsorption energetics of key ORR intermediates. Notably, the number of d-electrons of TM atoms is identified as a reliable electronic descriptor governing intermediate binding strength and catalytic activity. Furthermore, ab initio molecular dynamics simulations confirm the excellent thermodynamic stability of the optimized dual-atom catalysts. This work elucidates the atomic-scale origin of synergistic enhancement in dual-atom-doped antimonene and provides a rational design strategy for high-performance ORR electrocatalysts based on two-dimensional main-group materials. Full article

Background: Schizophrenia in adolescence disrupts neurodevelopment and long-term functioning. While symptom reduction remains a primary treatment goal, quality of life (QoL) represents a critical, patient-centered outcome. Pharmacogenetic variability, particularly in CYP2D6 metabolism of second-generation antipsychotics, may influence tolerability and subjective well-being beyond symptom control. Materials and Methods: Forty-seven adolescents (aged 14–18 years) diagnosed with schizophrenia (DSM-5) were followed in routine clinical care. CYP2D6 genotyping classified patients as normal metabolizers (NM, n = 27) or reduced-function metabolizers (RFM, including intermediate/poor, n = 20). Symptom severity was assessed with PANSS, QoL was assessed with the Pediatric Quality of Life Enjoyment and Satisfaction Questionnaire (PQ-LES-Q), and adverse effects (hyperprolactinemia, extrapyramidal symptoms, sedation, metabolic changes) were monitored. Non-parametric tests and multiple linear regression were applied. Results: At 12 months, RFM patients showed significantly higher PANSS scores, markedly more adverse reactions (95% vs. 48.1%), and lower PQ-LES-Q total and domain scores (all p < 0.0001) compared to NM patients. A regression analysis identified the metabolizer status (β = −0.410, p = 0.001), extrapyramidal symptoms (β = −0.248, p = 0.003), sedation (β = −0.193, p = 0.029), and hyperprolactinemia (β = −0.190, p = 0.012) as independent predictors of a reduced QoL, explaining 84% of the variance. The residual symptom severity was not independently associated. Conclusions: In adolescent schizophrenia, the CYP2D6-reduced metabolizer status is the strongest independent predictor of long-term QoL impairment, associated primarily through a substantially higher burden of treatment-related adverse effects (metabolic, endocrine, neurological, and sedative) rather than through persistence of psychotic symptoms alone. These findings support early pharmacogenetic testing to guide individualized dosing and improve tolerability and patient-reported outcomes. Full article

Acetaminophen, more commonly known as paracetamol (APAP), is one of the most widely used analgesics and antipyretic drugs worldwide. Its presence in the environment poses a risk to the organisms it comes into contact with, which is why it has been classified as an emerging contaminant. Given its adverse effects and continuous discharge into water bodies, it is necessary to study efficient, environmentally sustainable processes for its complete removal. Denitrification is a biological process that has been studied for the biodegradation of recalcitrant compounds and certain pharmaceuticals such as 17β-estradiol and ampicillin, transforming them into harmless products such as N₂ and HCO₃⁻. In the present study, the biodegradation of 6 mg L⁻¹ of APAP-C was evaluated through a denitrifying process. Batch experiments were conducted, achieving acetaminophen (APAP) removal efficiencies (E_APAP-C) of 83.3 ± 0.86% and nitrate removal efficiencies (E_N-NO3⁻) of 100%. The substrates were predominantly converted into HCO₃⁻ and N₂, with yields greater than 0.9, while intermediates such as NO₂⁻ were observed only transiently during the reaction. At the end of the experimental period, no secondary metabolites were detected, indicating that intermediates did not accumulate to quantifiable levels. Full article

Pyrrolo[2,3-d]pyrimidine is a privileged fused heterocyclic scaffold that has attracted considerable attention in medicinal chemistry due to its diverse biological activities. Herein, we report an efficient synthesis strategy for the preparation of the pyrrolo[2,3-d]pyrimidine-based natural toyocamycin aglycone and pyrrolo[2,3-d]pyrimidine derivatives. The synthesis of toyocamycin aglycone features a key benzylamine nucleophilic substitution followed by a palladium-catalyzed cyanation reaction. From a key intermediate derived from this route, nineteen new pyrrolo[2,3-d]pyrimidine derivatives were rapidly synthesized via key Suzuki–Miyaura coupling and amine nucleophilic substitution reactions. Their cytotoxic activities were evaluated against Huh-7 and HepG liver cancer cell lines. Most derivatives were inactive after 24 h. However, 28a–28c, 28e and 28f exhibited moderate cytotoxicity with IC₅₀ values ranging from 5.7 to 62.6 μM. Among them, compound 28e displayed the highest potency against HepG cells, with IC₅₀ values of 5.7 μM. Compared with normal HEK293 cells, it showed a selectivity index (SI) of 3.60 against HepG cells. Preliminary structure-activity relationship analysis suggested that incorporation of a cyclopropyl group further improves antitumor activity. Full article

The aim of this study was to evaluate the feasibility of inducing non-enzymatic browning using enzymatic collagen hydrolysates from turkey knee cartilage and chondroitin sulfate disaccharides derived from turkey and shark cartilage. Glycation was carried out in aqueous solutions at 60–120 °C for 3 h. After glycation, furosine content and browning intensity were determined as indicators of intermediate and final Maillard reaction products. FTIR spectra, color parameters, and antioxidant properties were also analyzed. The results showed that chondroitin sulfate disaccharides were more reactive with collagen hydrolysates than glucose and produced glycation products with higher antioxidant activity. The sulfation site on the N-acetylgalactosamine residue linked to glucuronic acid influenced the characteristics of the Maillard reaction products, including higher antioxidant activity and increased redness in products derived from turkey chondroitin sulfate disaccharides compared with those derived from shark cartilage, despite very similar FTIR spectral characteristics. Full article

Protein glycation is a nonenzymatic modification that links sugar chemistry to molecular aging and chronic disease. Sequential reactions involving Schiff bases, Amadori products, and reactive α dicarbonyl intermediates generate advanced glycation end products (AGEs) that irreversibly alter protein structure and function. AGEs also act as ligands for the receptor for advanced glycation end products (RAGE), initiating oxidative stress, inflammation, and tissue remodeling. This review synthesizes the molecular pathways of AGE formation, their structural diversity, and the biological factors influencing glycation kinetics. Advances in analytical detection methods—including fluorescence spectroscopy, LC–MS/MS, and immunochemical approaches—are highlighted for their role in monitoring AGE accumulation. Particular attention is given to the contribution of glycation to diabetes, cardiovascular disease, neurodegeneration, and cancer, alongside emerging therapeutic strategies to limit AGE formation or block AGE–RAGE signaling. Glycation thus represents a central mechanism in human disease pathogenesis and an emerging therapeutic frontier. Full article

The rational design of cost-effective and highly active electrocatalysts for overall water splitting remains a critical challenge for sustainable hydrogen production. Herein, we report a two-dimensional reduced graphene oxide (rGO)-supported Mo₂S₃ nanohybrid catalyst with a tunable electronic structure engineered through interfacial coupling. The intimate integration of Mo₂S₃ nanoflakes with conductive rGO nanosheet facilitates rapid electron transport, enhanced active site exposure, and optimized adsorption energetics for reaction intermediates. Structural and spectroscopic analyses confirm strong electronic interaction between Mo₂S₃ and rGO, leading to modulated charge density distribution and improved intrinsic catalytic activity. Electrochemical evaluations reveal significantly reduced overpotentials for oxygen evolution reaction (OER) with 166 mV overpotential at 10 mA cm⁻² current density, along with favorable Tafel kinetics with 38.1 mV dec⁻¹ and long-term operational stability in alkaline electrolyte. The rGO-Mo₂S₃-2||Pt-C cell delivers 10 mA cm⁻² at 1.64 V, indicating efficient alkaline water splitting. The enhanced performance is attributed to synergistic effects arising from electronic modulation, enhanced active sites, and accelerated interfacial charge transfer. Full article

The formylation of mercaptans using CO₂ as a C1 source represents a sustainable and efficient strategy for converting CO₂ into value-added chemicals. However, to date, S-formylation still remains scarcely explored with CO₂ as the starting material, despite its important role in various biological processes. In this work, the S-formylation reaction between CO₂ and mercaptans was successfully carried out to construct C-S bonds using an inexpensive and commercially available carboxylate salt (sodium edetate) as the catalyst under mild conditions (25 °C and 0.1 MPa). Further investigations demonstrated that the present catalytic system applies to a broad substrate scope, affording moderate to excellent yields in the S-formylation of both aliphatic and aromatic thiols with CO₂. To clarify the excellent catalytic performance of carboxylates in these S-formylation reactions, reaction intermediates as well as the activating effects of carboxylates on carbon dioxide and phenylsilanes were identified through control experiments and spectroscopic analysis. Based on these findings, the reaction pathway of the S-formylation process was determined, and a corresponding reaction mechanism is proposed. Full article

An environmentally friendly synthesis of polysubstituted pyrroles in ionic liquid was achieved via a gold-catalyzed propargylic substitution/hydration/amination/cycloisomerization sequence. Treatment of propargylic alcohols, 1,3-dicarbonyl compounds, and arylamines in the presence of AuBr₃ (5 mol%) and AgOTf (15 mol%) in [EMIM][NTf₂] afforded polysubstituted pyrroles in good to high yield. This reaction involves reacting arylamine with the hydrated propargylic substitution product formed as an intermediate to yield polysubstituted pyrroles. Full article