Search Results (624)

Objectives: The current study focused on the kidney protection and antioxidant properties along with the potential anti-ferroptotic activity of Geranium macrorrhizum L. (G. macrorrhizum) oil to ameliorate the acute renal oxidative tissue damage and toxicity of the aminoglycoside antibiotic gentamicin (GM) in an experimental murine model. Methods: The research was carried out with mature Balb/c mice distributed into four groups (n = 6). Application of GM (200 mg kg⁻¹ intraperitoneal injection for 10 days) was performed to induce kidney injury. Only saline was administered to the controls. The remaining groups were administered G. macrorrhizum oil (50 mg kg⁻¹ per dose) either used alone or in combination with GM. To assess the renal antioxidant status, the activities of specific antioxidant enzymes, indicators of lipid and DNA peroxidation and renal functional damage were examined using standard commercial kits, ELISA and EPR spectroscopy. Results: G. macrorrhizum oil analysis revealed 20 organic components belonging to mono- and sesquiterpenoids and long-chain hydrocarbons. The antioxidant and anti-inflammatory effects of G. macrorrhizum oil were demonstrated by reduced malondialdehyde, ROS, 8-hydroxy-2′-deoxyguanosine and cytokine levels (especially interleukin-1β) compared with GM. Furthermore, increased activation of superoxide dismutase, catalase and glutathione (GSH) were observed in the kidney homogenates of the animals which received GM in combination with G. macrorrhizum oil compared with the GM group. Additional changes in the GSH/glutathione peroxidase-4 axis were detected, suggesting the possible anti-ferroptotic potential of the oil. Nephroprotection was also demonstrated by elevated PGC-1α expression (peroxisome proliferator-activated receptor γ coactivator 1-alpha) and reduced KIM-1 levels (kidney injury molecule-1) following application of the oil. Conclusions: The preserved kidney antioxidant and functional properties in the groups treated with oil suggest that Geranium macrorrhizum L. could be utilized clinically to mitigate the toxic effects of GM application. Full article

This study explores the antioxidant potential and delivery performance of five structurally distinct cannabinoids, with a particular focus on cannabinol (CBN). Comprehensive structural characterization using mass spectrometry (MS) and nuclear magnetic resonance (NMR) revealed key molecular features relevant to antioxidant function. Among the tested compounds, CBN exhibited the most potent and balanced radical scavenging activity against 2,2-diphenyl-1-picrylhydrazyl (DPPH), hydroxyl, and superoxide radicals. Based on these findings, CBN was selected for formulation into soy lecithin liposomes. The resulting CBN-loaded liposomes displayed favorable colloidal properties, with an average size of approximately 122.9 ± 0.4 nm. Results indicating increased membrane order upon CBN incorporation suggest enhanced stability of the liposomal bilayer. Antioxidant activity assays showed that CBN-loaded liposomes retain significant radical scavenging capacity, though with a moderate reduction compared to free CBN. EPR imaging further demonstrated superior diffusion of liposomal CBN through a gelatin-based semi-solid model compared to the control solution. While the current model does not replicate skin architecture, it provides a cost-effective and reproducible platform for early-stage screening of formulation mobility. These results position CBN-loaded liposomes as a promising candidate for dermal antioxidant applications, combining favorable physicochemical properties with enhanced diffusion behavior. Full article

Advanced oxidation processes (AOPs) utilizing peroxymonosulfate (PMS) have emerged as a promising technology for organic pollutant degradation due to their distinct environmental advantages. In this study, copper–iron bimetallic oxide catalysts with varying ratios were synthesized via a co-precipitation method to activate PMS for degrading simulated tetracycline hydrochloride wastewater. The catalysts were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), and X-ray photoelectron spectroscopy (XPS). The effects of key parameters—including the PMS concentration, catalyst dosage, initial pH, and tetracycline hydrochloride concentration—on the degradation efficiency were systematically investigated. The results demonstrated that the CuFe(2)/PMS system exhibited the highest degradation efficiency. Under optimal conditions (20 mg/L tetracycline hydrochloride, 0.4 mM PMS, 0.5 g/L CuFe(2) catalyst, and pH 3), this system achieved a 94.12% degradation rate of tetracycline hydrochloride within 120 min. The electron paramagnetic resonance (EPR) tests and radical quenching experiments identified sulfate radicals (SO₄·⁻) as the predominant reactive species. Furthermore, the XPS analysis elucidated the persulfate activation mechanism, while the liquid chromatography–mass spectrometry (LC-MS) identified the potential degradation pathways and intermediate products of tetracycline hydrochloride. Full article

Free radicals in G-361 human melanoma malignum control cells and the cells cultured with simvastatin were examined by EPR spectroscopy. The proliferation of the cells was determined. The aim of this work was to examine the influence of simvastatin used at different concentrations in the G-361 cell culture on its free radicals. The concentrations of simvastatin—0.1 μM, 1 μM, 3 μM, and 5 μM—were tested. EPR spectra of free radicals were measured by an X-band (9.3 GHz) spectrometer. Amplitudes, integral intensities, linewidths, and g factors were determined. Melanin biopolymers are the main source of o-semiquinone free radicals in G-361 human melanoma malignum cells, for which the EPR lines show characteristic g values of 2.0046–2.0059, but also, free radicals occurring in other cellular structures may contribute to these signals. The amount of free radicals decreases after interactions of simvastatin with the G-361 cells, and this effect depends on the concentration of simvastatin. The highest amounts of free radicals exist in G-361 cells cultured with simvastatin at concentrations of 3 μM and 5 μM. The relatively lower amounts of free radicals occur in G-361 cells cultured with simvastatin at concentrations of 0.1 μM and 1 μM. The fast spin–lattice relaxation processes exist in the control G-361 cells and in the cells cultured with simvastatin, regardless of simvastatin concentration. Full article

The role of p-benzoquinone (BQ) as a photocatalyst in the synthesis of solketal under UV irradiation has been studied, along with the combined use of BQ/TiO₂ P25 as a photocatalytic system for the process. The presence of the O₂/O₂^−• redox couple is essential for the reaction to take place. However, experiments with p-benzoquinone as a superoxide radical scavenger failed, with the opposite effect of enhancing the reaction being observed. It was found that p-benzoquinone and oxygen compete for photogenerated electrons in the conduction band of titania. A redox equilibrium between p-benzoquinone and hydroquinone (H₂Q), mediated by the O₂/O₂^−• system, was identified as a key factor in enabling the reaction. Furthermore, EPR spin-trapping experiments confirmed the presence of the carbon-centered radical 2-hydroxypropan-2-yl, which was determined to be the main radical species involved in the process. Either acetone or 2-propanol can generate this radical, with the BQ/H₂Q redox system being pivotal in the formation of the hemiacetal intermediate. This intermediate is subsequently converted into the final acetal (solketal), with H₂Q acting as a photoacid through an excited-state proton transfer (ESPT) mechanism. The photoacid behavior of hydroquinone was confirmed using pyridine as a basic probe, as the formation of hydroquinone–pyridine adducts was detected by Raman spectroscopy. Full article

One of the advantages of the EPR spectroscopy method in assessing structural defects caused by irradiation is the fact that using this method it is possible to determine not only the concentration dependences of the defect structure but to also establish their type, which is not possible with methods such as X-ray diffraction or scanning electron microscopy. Based on the data obtained, the role of variation in the ratio of components in Li₄SiO₄–Li₂TiO₃ ceramics on the processes of softening under high-dose irradiation with protons simulating the accumulation of hydrogen in the damaged layer, as well as the concentration of structural defects in the form of oxygen vacancies and radiolysis products on the processes of high-temperature degradation of ceramics, was determined. It was found that the main changes in the defect structure during the prolonged thermal exposure of irradiated samples are associated with the accumulation of oxygen vacancies, the density of which was estimated by the change in the intensity of singlet lithium, characterizing the presence of E-centers. At the same time, it was found that the formation of interphase boundaries in the structure of Li₄SiO₄–Li₂TiO₃ ceramics leads to the inhibition of high-temperature degradation processes in the case of post-radiation thermal exposure for a long time. Also, during the conducted studies, the role of thermal effects on the structural damage accumulation rate in Li₄SiO₄–Li₂TiO₃ ceramics was determined in the case when irradiation is carried out at different temperatures. During the experiments, it was determined that the main contribution of thermal action in the process of proton irradiation at a fluence of 5 × 10¹⁷ proton/cm² is an increase in the concentration of radiolysis products, described by changes in the intensities of spectral maxima, characterized by the presence of defects such as ≡Si–O, SiO₄³⁻ and Ti³⁺ defects. Full article

Steel pickling sludge serves as a valuable iron source for synthesizing Fe-based catalysts in heterogeneous advanced oxidation processes (AOPs). Here, MoS₂@CoFe₂O₄ catalyst derived from steel pickling sludge was prepared via a facile solvothermal approach and utilized to activate peroxymonosulfate (PMS) for tetracycline hydrochloride (TCH) degradation. Comprehensive characterization using scanning electron microscopy (SEM)-energy dispersive spectrometer (EDS), X-ray photoelectron spectroscopy (XPS), and X-ray diffraction (XRD) confirmed the supported microstructure, composition, and crystalline structure of the catalyst. Key operational parameters—including catalyst dosage, PMS concentration, and initial solution pH—were systematically optimized, achieving 81% degradation efficiency within 30 min. Quenching experiments and electron paramagnetic resonance (EPR) analysis revealed SO₄^∙− as the primary oxidative species, while the catalyst maintained high stability and reusability across cycles. TCH degradation primarily occurs through hydroxylation, decarbonylation, ring-opening, and oxidation reactions. This study presents a cost-effective strategy for transforming steel pickling sludge into a high-performance Fe-based catalyst, demonstrating its potential for practical AOP applications. 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

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

The rapid recombination of photoinduced charge carriers in semiconductors remains a significant challenge for their practical application in photocatalysis. This study presents the design of a step-scheme (S-scheme) heterojunction composed of carbon nitride (g-C₃N₄) and nickel-based metal–organic framework (Ni-MOF) to achieve enhanced charge separation. The establishment of an S-scheme charge transfer configuration at the interface of the Ni-MOF/g-C₃N₄ heterostructure plays a pivotal role in enabling efficient charge carrier separation, and hence, high CO₂ photoreduction efficiency with a CO evolution rate of 1014.6 µmol g⁻¹ h⁻¹ and selectivity of 95% under simulated solar illumination. CO evolution represents an approximately 3.7-fold enhancement compared to pristine Ni-MOF. Density functional theory (DFT) calculations, supported by in situ irradiated X-ray photoelectron spectroscopy (XPS) and electron paramagnetic resonance (EPR) experimental results, confirmed the establishment of a well-defined and strongly bonded interface, which improves the charge transfer and separation following the S-scheme mechanism. This study sheds light on MOF-based S-scheme heterojunctions as fruitful and selective alternatives for practical CO₂ photoreduction. Full article

Copper is an essential micronutrient for plants, but excessive levels can induce toxicity and impair physiological functions. This study evaluates the toxic effects of copper sulfate (CuSO₄) on the germination of common wheat (Triticum aestivum), with emphasis on the gas emission dynamics and oxidative stress biomarkers. Seeds were germinated in agar and exposed to CuSO₄ at concentrations of 1 µM, 100 µM, 1 mM, and 10 mM; distilled water served as the control. Ethylene and ammonia emissions were quantified using CO₂ laser photoacoustic spectroscopy, while electron paramagnetic resonance (EPR) spectroscopy was employed to detect free radicals and Cu²⁺ complexes. Exposure to Cu concentrations ≥ 1 mM significantly inhibited germination and biomass accumulation. Enhanced ethylene and ammonia emissions, particularly at 10 mM, indicated stress-related metabolic responses. The EPR spectra confirmed the presence of semiquinone radicals and Cu²⁺ complexes under higher Cu levels. These results demonstrate that photoacoustic and EPR techniques are effective tools for the early detection of metal-induced phytotoxicity and offer a non-invasive approach to environmental toxicity screening and plant stress assessment. Full article

Environmental persistent free radicals (EPFRs) represent a class of long-lived, redox-active species with half lives spanning minutes to months. Emerging as critical environmental pollutants, EPFRs pose significant risks due to their persistence, potential for bioaccumulation, and adverse effects on ecosystems and human health. This review critically synthesizes recent advancements in understanding EPFR formation mechanisms, analytical detection methodologies, environmental distribution patterns, and toxicological impacts. While progress has been made in characterization techniques, challenges persist—particularly in overcoming limitations of electron paramagnetic resonance (EPR) spectroscopy and spin-trapping methods in complex environmental matrices. Key knowledge gaps remain, including molecular-level dynamics of EPFR formation, long-term environmental fate under varying geochemical conditions, and quantitative relationships between chronic EPFR exposure and health outcomes. Future research priorities could focus on: (1) atomic-scale mechanistic investigations using advanced computational modeling to resolve formation pathways; (2) development of next-generation detection tools to improve sensitivity and spatial resolution; and (3) integration of EPFR data into region-specific air-quality indices to enhance risk assessment and inform mitigation strategies. Addressing these gaps will advance our capacity to mitigate EPFR persistence and safeguard environmental and public health. Full article

Ultrafine fibers from poly(3-hydroxybutyrate) (PHB) and polyvinylpyrrolidone (PVP) and their blends with different component ratios in the range of 0/100 to 100/0 wt.% were obtained, and their structure and dynamic properties were studied. The polymers were obtained via electrospinning in solution mode. The structure, morphology, and segmental dynamic behavior of the fibers were determined using optical microscopy, SEM, EPR, DSC, and IR spectroscopy. The low-temperature maximum on the DSC endotherms provided information on the state of the PVP hydrogen bond network, which made it possible to determine the enthalpies of thermal destruction of these bonds. The PHB/PVP fiber blend ratio significantly affected the structural and dynamic parameters of the system. Thus, at low concentrations of PVP (up to 9%) in the structure of ultra-fine fibers, the distribution of this polymer occurs in the form of tiny particles, which are crystallization centers, which causes a significant increase in the degree of crystallinity (χ) activation energy (E_act) and slowing down of molecular dynamics (τ). At higher concentrations of PVP, loose interphase layers were formed in the system, which caused a decrease in these parameters. The strongest changes in the concentration of hydrogen bonds occurred when PVP was added to the composition from 17 to 50%, which was due to the formation of intermolecular hydrogen bonds both in PVP and during the interaction of PVP and PHB. The diffusion coefficient of water vapor in the studied systems (D) decreased as the concentration of glassy PVP in the composition increased. The concentration of the radical decreased with an increase in the proportion of PVP, which can be explained by the glassy state of this polymer at room temperature. A characteristic point of the 50/50% mixture component ratio was found in the region where an inversion transition of PHB from a dispersion material to a dispersed medium was assumed. The conducted studies made it possible for the first time to conduct a comprehensive analysis of the effect of the component ratio on the structural and dynamic characteristics of the PHB/PVP fibrous material at the molecular scale. Full article

The study of the processes of low-temperature synthesis of one-dimensional particles, which are the basis for two- and three-dimensional structures, is relevant for materials science. The modified metal-stimulated electrochemical etching method made it possible to synthesize silicon nanowires with an average thickness of about 292.6 nm. Scanning electron microscopy has shown the formation of nanowires, flower-like structures, and clusters of matter after the deposition of zinc oxide on the porous surface. The hexagonal structure of ZnO crystallites was determined by X-ray diffraction spectroscopy. Studies of the initial sample by electron paramagnetic resonance (EPR) spectroscopy revealed a narrow signal in the center of the spectrum. The subtraction of the EPR spectra with a sequential increase in microwave power up to 8 mW shows the absence of saturation of the signal. This indicates an almost free flow of charges through the surface nanostructures under the influence of an external field. Heat treatment in an air atmosphere at 300 °C caused a significant increase in the intensity of the EPR spectrum. This led to an increase in the intensity of charge transfer through paramagnetic centers. Full article

Synthesized Ln₂O₃ (Ln = La, Nd or Gd) nanoparticles with sizes of 1–3 nm, 5–6 nm and 10–15 nm were stabilized by carbon nanoflakes (CNFs). The weight content of Ln₂O₃ in the Ln₂O₃/CNF composites was 20–50 wt. %, which makes these composites potentially suitable for practical use as computed tomography and magnetic resonance imaging contrast agents. The structure of CNFs and Ln₂O₃/CNF composites was investigated by X-ray diffraction data, X-ray photoelectron spectroscopy (XPS) and electron paramagnetic resonance (EPR). The EPR spectra of raw CNFs were silent. The oxidation of the CNF surface resulted in the appearance of paramagnetic centers associated with two types of unpaired electrons in the carbon support. After impregnation of the CNFs with the Ln³⁺ ion solution, the number of unpaired electrons was reduced, presumably due to the formation of C–O–Ln bonds. All Ln³⁺ ions changed the composites’ EPR spectra by reducing the number of unpaired electrons in the CNF structure. Full article