Search Results (767)

Herein, we rationally designed a molecular catalytic filter for effective micropollutants decontamination via peroxymonosulfate (PMS) activation. Specifically, iron phthalocanine (FePc) molecules with defined Fe–N₄ coordination were immobilized onto carbon nanotubes (CNTs), forming a hybrid catalyst that integrated molecular precision with heterogeneous catalytic properties. The resulting CNT-FePc filter achieved a 98.4% removal efficiency for bisphenol A (10 ppm) in a single-pass operation system, significantly outperforming the CNT/PMS system without FePc (41.6%). Additionally, the CNT-FePc/PMS system demonstrated remarkable resistance to performance inhibition by common water matrix components. Unlike typical radical-dominated PMS activation processes, mechanistic investigations confirmed that the CNT-FePc/PMS system selectively promoted singlet oxygen (¹O₂) generation as the primary oxidative pathway. Density functional theory (DFT) calculations revealed that PMS exhibited stronger adsorption on FePc (−3.05 eV) compared to CNT (−2.86 eV), and that FePc effectively facilitated O–O bond elongation in PMS, thereby facilitating ¹O₂ generation. Additionally, seed germination assays indicated a significant reduction in the biotoxicity of the treated effluents. Overall, this work presents a catalyst design strategy that merges molecular-level coordination chemistry with practical flow-through configuration, enabling rapid, selective, and environmentally benign micropollutant removal. Full article

Background/Objectives: The growing demand for biocompatible and fluoride-free alternatives in oral care has led to the development of formulations containing nano-hydroxyapatite (nanoHAP). This study aimed to evaluate the antimicrobial, antibiofilm, antioxidant, and anti-inflammatory properties of a novel mouthwash containing nanoHAP, zinc lactate, D-panthenol, licorice extract, and cetylpyridinium chloride, with particular focus on its efficacy against Staphylococcus aureus and its biofilm on various dental materials. Methods: The antimicrobial activities of the mouthwash KWT0000 and control product ELM were assessed via minimal inhibitory concentration (MIC) testing against selected Gram-positive and Gram-negative bacteria and Candida fungi. Antibiofilm activity was evaluated using fluorescence and digital microscopy following 1-h exposure to biofilms of Staphylococcus aureus, Pseudomonas aeruginosa, and Candida albicans. The efficacy was compared across multiple dental materials, including titanium, zirconia, and PMMA. Antioxidant capacity was determined using the 2,2-diphenyl-1-picrylhydrazyl radical (DPPH) assay, and anti-inflammatory potential via hyaluronidase inhibition. Results: KWT0000 exhibited strong antimicrobial activity against S. aureus and C. albicans (MICs: 0.2–1.6%) and moderate activity against Gram-negative strains. Fluorescence imaging revealed significant biofilm disruption and bacterial death after 1 h. On metallic surfaces, especially polished titanium and zirconia, KWT0000 reduced S. aureus biofilm density considerably. The formulation also demonstrated superior antioxidant (55.33 ± 3.34%) and anti-inflammatory (23.33 ± 3.67%) activity compared to a fluoride-based comparator. Conclusions: The tested nanoHAP-based mouthwash shows promising potential in antimicrobial and antibiofilm oral care, particularly for patients with dental implants. Its multifunctional effects may support not only plaque control but also soft tissue health. 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

The valence-shell electronic state spectroscopy of β-butyrolactone (CH₃CHCH₂CO₂) is comprehensively investigated by employing experimental and theoretical methods. We report a novel vacuum ultraviolet (VUV) absorption spectrum in the photon wavelength range from 115 to 320 nm (3.9–10.8 eV), together with ab initio quantum chemical calculations at the time-dependent density functional (TD-DFT) level of theory. The dominant electronic excitations are assigned to mixed valence-Rydberg and Rydberg transitions. The fine structure in the CH₃CHCH₂CO₂ photoabsorption spectrum has been assigned to C=O stretching, $v_7^{\prime }\left(a\right)$, CH₂ wagging, $v_{14}^{\prime }\left(a\right)$, C–O stretching, $v_{22}^{\prime }\left(a\right)$, and C=O bending, $v_{26}^{\prime }\left(a\right)$ modes. Photolysis lifetimes in the Earth’s atmosphere from 0 km up to 50 km altitude have been estimated, showing to be a non-relevant sink mechanism compared to reactions with the ^•OH radical. The nuclear dynamics along the C=O and C–C–C coordinates have been investigated at the TD-DFT level of theory, where, upon electronic excitation, the potential energy curves show important carbonyl bond breaking and ring opening, respectively. Within such an intricate molecular landscape, the higher-lying excited electronic states may keep their original Rydberg character or may undergo Rydberg-to-valence conversion, with vibronic coupling as an important mechanism contributing to the spectrum. Full article

A novel ruthenium(II) complex, [RuCl₂(η⁶-p-cymene)(bph-κN)] (1), was synthesized and structurally characterized using FTIR and NMR spectroscopy. Density functional theory (DFT) calculations supported the proposed geometry and allowed for comparative analysis of experimental and theoretical spectroscopic data. The interaction of complex 1 with human serum albumin (HSA) and calf thymus DNA was investigated through fluorescence quenching experiments, revealing spontaneous binding driven primarily by hydrophobic interactions. The thermodynamic parameters indicated mixed quenching mechanisms in both protein and DNA systems. Ethidium bromide displacement assays and molecular docking simulations confirmed DNA intercalation as the dominant binding mode, with a Gibbs free binding energy of −34.1 kJ mol⁻¹. Antioxidant activity, assessed by EPR spectroscopy, demonstrated effective scavenging of hydroxyl and ascorbyl radicals. In vitro cytotoxicity assays against A375, MDA-MB-231, MIA PaCa-2, and SW480 cancer cell lines revealed selective activity, with pancreatic and colorectal cells showing the highest sensitivity. QTAIM analysis provided insight into metal–ligand bonding characteristics and intramolecular stabilization. These findings highlight the potential of 1 as a promising candidate for further development as an anticancer agent, particularly against multidrug-resistant tumors. Full article

Inspired by the active site of methane monooxygenase, we designed a Cu₂O cluster anchored in the six-membered nitrogen cavity of a C₂N monolayer (Cu₂O@C₂N) as a stable and efficient enzyme-like catalyst. Density functional theory (DFT) calculations reveal that the bridged Cu-O-Cu structure within C₂N exhibits strong electronic coupling, which is favorable for methanol formation. Two competing mechanisms—the concerted and radical-rebound pathways—were systematically investigated, with the former being energetically preferred due to lower energy barriers and more stable intermediate states. Furthermore, strain engineering was employed to tune the geometric and electronic structure of the Cu-O-Cu site. Biaxial strain modulates the Cu-O-Cu bond angle, adsorption properties, and d-band center alignment, thereby selectively enhancing the concerted pathway. A volcano-like trend was observed between the applied strain and the methanol formation barrier, with 1% tensile strain yielding the overall energy barrier to methanol formation (ΔG_overall) as low as 1.31 eV. N₂O effectively regenerated the active site and demonstrated strain-responsive kinetics. The electronic descriptor Δε (ε_d − ε_p) captured the structure–activity relationship, confirming the role of strain in regulating catalytic performance. This work highlights the synergy between geometric confinement and mechanical modulation, offering a rational design strategy for advanced C1 activation catalysts. Full article

The dynamic phosphorylation of the human RNA Pol II CTD establishes a code applicable to all eukaryotic transcription processes. However, the ability of these specific post-translational modifications to convey molecular signals through structural changes remains unclear. We previously explained that each gene can be modeled as a combination of n circuits connected in parallel. RNA Pol II accesses these circuits and, through a series of pulses, matches the resonance frequency of the DNA qubits, enabling it to extract genetic information and quantum teleport it. Negatively charged phosphates react under RNA Pol II catalysis, which increases the electron density on the deoxyribose acceptor carbon (2’C in the DNA sugar backbone). The phosphorylation effect on the stability of a carbon radical connects tyrosine to the nitrogenous base, while the subsequent pulses link the protein to molecular water through hydrogen bonds. The selective activation of inert C(sp³)–H bonds begins by reading the quantum information stored in the nitrogenous bases. The coupling of hydrogen proton transfer with electron transfer in water generates a supercurrent, which is explained by the correlation of pairs of the same type of fermions exchanging a boson. All these changes lead to the formation of a molecular protein–DNA–water transcriptional condensate. Full article

Anion exchange membranes (AEMs) are vital for electrochemical energy devices such as alkaline fuel cells and water electrolyzers, enabling the use of non-precious metal catalysts despite challenges from alkaline degradation. Hyperbranched polymers (hbPs) with their globular structure, high functional group density, and simple synthesis, offer a promising platform for enhancing transport and stability. In this study, multifunctional hbPs were synthesized from 4-vinylbenzyl chloride (VBC) and 2-hydroxyethyl methacrylate (HEMA) via atom transfer radical self-condensing vinyl polymerization (ATR-SCVP) and crosslinked into polyurethane-based AEMs. Characterization confirmed successful copolymerization and crosslinking, with excellent alkaline stability. Membranes crosslinked with higher molecular weight (MW) and VBC-richer hbPs (e.g., OH-hbP1-PU) exhibited high water uptake (75%) but low ion-exchange capacity (1.54 mmol/g) and conductivity (186 µS/cm), attributed to steric hindrance and insufficient ionic network connectivity. In contrast, OH-hbP2-PU exhibited optimal properties, with the highest OH⁻ conductivity (338 µS/cm) and IEC (2.64 mmol/g), highlighting a balanced structure for efficient ion transport. This work offers a tunable strategy for high-performance AEM development through tailored hbP architecture. Full article

This article provides an overview of the use of electrochemical advanced oxidation processes (EAOPs) applied to the treatment of water contaminated by pesticides. Given the global increase in the use of pesticides and the ineffectiveness of conventional treatment methods, EAOPs emerge as promising alternatives. They stand out for their efficiency in the degradation of organic compounds, minimal reliance on additional chemical reagents, and minimal generation of waste. The main methods addressed include anodic oxidation, photoelectro-oxidation, electro-Fenton and photoelectro-Fenton, which use hydroxyl radicals, a potent non-selective oxidant, to mineralize pollutants. A total of 165 studies were reviewed, with emphasis on the contributions of countries such as China, Spain, Brazil, and India. Factors such as electrode type, presence of catalysts, pH, and current density influence the effectiveness of treatments. Combined processes, especially those integrating UV light and renewable sources, have proven to be more efficient. Despite challenges related to electrode cost and durability, recent advances highlight the sustainability and scalability of EAOPs for the treatment of agricultural and industrial effluents contaminated with pesticides. Full article

Cowpea (Vigna unguiculata L.) pods are an underexploited by-product of legume production with significant antioxidant potential. Their recovery and characterization support sustainable waste valorization in agri-food systems. This study aimed to optimize the extraction of phenolic compounds (PCs) with antioxidant capacity (AOC) from cowpea pods and identify key bioactives through experimental and theoretical approaches. First, high-intensity ultrasound extraction was optimized using response surface methodology with ethanol–water mixtures. Under optimal conditions (20% amplitude, 15 min, 50% ethanol), the ethanolic extract (Eo) showed higher total phenolic content (TPC) and AOC than the aqueous extract (Wo). Subsequently, fractionation by Sephadex LH-20 chromatography yielded fractions E2 and W2 with enhanced TPC and AOC. Phytochemical profiling showed that E2 was enriched in caftaric acid, p-coumaric acid, and morin, while W2 had higher levels of caftaric, p-coumaric, and caffeic acids. Finally, density functional theory was used to assess thermodynamic parameters linked to antioxidant mechanisms (HAT, SET-PT, SPLET), revealing morin as the most effective radical scavenger, followed by caffeic and caftaric acids. These findings show that AOC depends not only on phenolic concentration but also on molecular structure and solvent interactions. Thus, cowpea pod extracts and fractions hold promise for antioxidant-rich formulations in food, nutraceutical, or cosmetic applications. Full article

Some of the popular and successful atmospheric pressure fuel/air plasma-assisted combustion methods use repetitive ns pulsed discharges and dielectric-barrier discharges. The transient phase in such discharges is dominated by transport under strong space charge from ionization fronts, which is best characterized by the streamer model. The role of the nonthermal plasma in such discharges is to produce radicals, which accelerates the chemical conversion reaction leading to temperature rise and ignition. Therefore, the characterization of the streamer and its energy partitioning is essential to develop a predictive model. We examine the important characteristics of streamers that influence combustion and develop some macroscopic parameters. Our results show that the radicals’ production efficiency at an applied field is nearly independent of time and the radical density generated depends only on the electrical energy density coupled to the plasma. We compare the results of the streamer model to the zero-dimensional uniform field Townsend-like discharge, and our results show a significant difference. The results concerning the influence of energy density and repetition rate on the ignition of a hydrogen/air fuel mixture are presented. Full article

This study aimed to investigate the effect of the type of sweetener used (xylitol, stevia, cane sugar) on the quality of liqueurs made from Vaccinium myrtillus L. and Vaccinium corymbosum L. fruits. The quality assessment was performed based on selected organoleptic and physicochemical features, with particular emphasis on the health-promoting potential of the produced beverages. The liqueurs were assessed in terms of their physicochemical parameters: pH, total acidity, density, total soluble solids, color, ethanol and polyphenol contents, and redox potential. Antioxidant capacities were determined by a 2,2-diphenyl-1-picrylhydrazyl (DPPH) and 2,2′-azinobis (3-ethylbenzothiazoline-6-sulfonic acid) (ABTS) radical scavenging capacity assay and ferric reducing antioxidant power (FRAP). The Qualitative Descriptive Analysis method was employed for their sensory assessment. The sensory profiling method was used to determine the intensity of the flavor sensations. The study results showed that the type of sweetener did not affect the antioxidative properties of the liqueur. The ABTS test yielded values from 1081.88 to 1238.13 μmol Tx/100 mL, the DPPH test from 348.8 to 367.88 μmol Tx/100 mL, and the FRAP test from 594.20 to 653.20 μmol FeSO₄/100 mL. However, the sweetening substrate affected the content of polyphenolic compounds in the resulting products, but by no more than 15%. The liqueur sweetened with xylitol had a comparable extract content to that sweetened with cane sugar. All three variants of liqueurs were accepted by the evaluation panel, and their overall qualities were comparable in the sensory assessment. It is, therefore, possible to produce a high-quality liqueur with a reduced caloric value, which will potentially increase its attractiveness for consumers. Full article

Gas sensors can provide early warning of fires by detecting pyrolysis gas components in the sheaths of high-voltage cables. However, air humidity significantly affects the thermal decomposition gas production characteristics of the outer sheath of high-voltage cables, which in turn affects the accuracy of this warning method. In this paper, the thermal decomposition and gas production characteristics of the polyethylene (PE) outer jacket of high-voltage cables under different air humidities (20–100%) are studied, and the corresponding density functional theory (DFT) simulation calculations are performed using Gaussian 09W software. The results show that with the increase in humidity, the thermal decomposition gas yield of the PE outer jacket of high-voltage cables exhibits a decreasing trend. Under high-humidity conditions (≥68.28%RH), the generation of certain thermal decomposition gases is significantly reduced or even ceases. Meanwhile, the influence of moisture on the thermal decomposition characteristics of PE was analyzed at the micro level through simulation, indicating that the H-free radicals generated by moisture promote the initial decomposition of PE, but the subsequent combination of hydroxyl groups with terminal chain C forms a relatively stable alkoxy structure, increasing the activation energy of the reaction (by up to 44.7 kJ/mol) and thus inhibiting the generation of small-molecule gases. An experimental foundation is laid for the final construction of a fire warning method for high-voltage cables based on the information of thermal decomposition gas of the outer sheath. Full article

Background: Cholangiocarcinoma (CCA) of the liver is a highly aggressive cancer that arises from malignant cells in the bile ducts. Radical surgery remains the only curative option, but major liver resection carries high perioperative risks. This study investigates the predictive value of preoperative bone mineral density (BMD), measured via CT, for perioperative complications, mortality, and long-term outcomes. Methods: The analysis included 202 patients who underwent curative-intent surgery for intrahepatic cholangiocarcinoma (iCCA; n = 97) or perihilar cholangiocarcinoma (pCCA; n = 105) between 2010 and 2019. Preoperative bone mineral density (BMD) was assessed using computed tomography segmentation at the level of the 12th thoracic vertebra. Osteopenia was defined according to established cutoffs. Results: Osteopenia was highly prevalent in both iCCA (53/97, 54%) and pCCA (54/105, 51%) subcohorts. Patients suffering from osteopenia were significantly older than those without (71.1 [62–76.6] years vs. 61.3 [52.9–69.2] years; p < 0.001). Alteration in BMD did not demonstrate a significant prognostic effect in terms of perioperative morbidity (Mann–Whitney U; comprehensive complication index—CCI: 34 [9–56] vs. 40 [21–72] p = 0.185; iCCA: p = 0.803; pCCA: p = 0.165). The median overall survival in our cohort was 19 [14–25] months. Patients with osteopenia did not exhibit a significantly different overall survival compared to those with normal bone mineral density (log-rank p = 0.234). Conclusions: In contrast to our previous observations in other oncological patient cohorts, osteopenia alone had no significant negative impact on clinical outcomes in our large European cohort of patients undergoing curative-intent surgery for CCA. To validate these findings, further prospective studies are warranted. Full article

The development of high-impact denture base formulations that are suitable for digital light processing (DLP) 3D printing is demanding. Indeed, a combination of high flexural strength/modulus and high fracture toughness is required. In this contribution, eight urethane macromonomers (UMs1-8) were synthesized in a one-pot, two-step procedure. Several rigid diols were first reacted with two equivalents of trimethylhexamethylene diisocyanate. The resulting diisocyanates were subsequently end-capped with a free-radically polymerizable monomer bearing a hydroxy group. UMs1-8 were combined with the monofunctional monomer (octahydro-4,7-methano-1H-indenyl)methyl acrylate and a poly(ε-caprolactone)-polydimethylsiloxane-poly(ε-caprolactone) (PCL-PDMS-PCL) triblock copolymer (BCP1) as a toughening agent. The double-bond conversion, glass transition temperature (T_g), and mechanical properties (flexural strength/modulus, fracture toughness) of corresponding light-cured materials were measured (cured in a mold using a light-curing unit). The results showed that the incorporation of BCP1 was highly efficient at significantly increasing the fracture toughness, as long as the obtained networks exhibited a low crosslink density. The structure of the urethane macromonomer (nature of the rigid group in the spacer; nature and number of polymerizable groups) was demonstrated to be crucial to reach the desired properties (balance between flexural strength/modulus and fracture toughness). Amongst the evaluated macromonomers, UM1 and UM2 were particularly promising. By correctly adjusting the BCP1 content, light-cured formulations based on those two urethane dimethacrylates were able to fulfill ISO20795-1:2013 standard requirements regarding high-impact materials. These formulations are therefore suitable for the development of 3D printable high-impact denture bases. Full article