Search Results (2,246)

Metal ions, including Mg(II), Ca(II), Sr(II), Co(II), Ni(II), Cu(II), Nd(III), Eu(III), and Tb(III), were investigated in binary systems alongside ampicillin at molar ratios of 1:1 and 1:2. These investigations were carried out in aqueous solutions, and the formation of complexes was verified through meticulous computational analysis. Detailed stability constants for the formed complexes and equilibrium constants for the involved reactions were meticulously determined. Furthermore, a comprehensive examination of the impact of ligand concentration on the configuration of the central metal atom’s coordination sphere was conducted. This investigation was complemented by spectroscopic measurements, which effectively confirmed the observed changes in the coordination sphere of the metal ions. Full article

A novel centrifuge-less cloud point extraction (CL-CPE) method was developed for the spectrophotometric determination of copper(II) using 4-nitrocatechol (4NC) as the chelating agent. The extraction system utilizes a mixed micellar phase composed of the nonionic surfactant Triton X-114 and the ionic liquid (IL) Aliquat^® 336 (A336). The extracted ternary ion-association complex, identified as (A336⁺)₂[Cu(4NC)₂], exhibits a maximum absorbance at 451 nm, with a molar absorption coefficient of 8.9 × 10⁴ M⁻¹ cm⁻¹ and a Sandell’s sensitivity of 0.71 ng cm⁻². The method demonstrates a linear response in the copper(II) concentration range of 32–763 ng mL⁻¹ and a limit of detection of 9.7 ng mL⁻¹. The logarithmic extraction constant (log K_ex) was determined to be 7.9, indicating efficient extraction. Method performance, evaluated by the Blue Applicability Grade Index (BAGI) and the Click Analytical Chemistry Index (CACI), confirmed its feasibility, practicality, simplicity, convenience, cost-effectiveness, environmental friendliness, and analytical competitiveness. The proposed IL-CL-CPE method was successfully applied to the analysis of a dietary supplement, a solution for infusion, and synthetic mixtures simulating various copper alloys. Full article

Greenhouses have positively impacted plant production by allowing the cultivation of different crops per year. However, the accumulation of agricultural plastics, potentially contaminated with agrochemicals, raises environmental concerns. This work evaluates the combined effect of Bordeaux mixture and low-density polyethylene (LDPE) microplastics (<5 mm) on the growth of lettuce (Lactuca sativa L.) and soil microbial communities. Different levels of Bordeaux mixture (0, 100 and 500 mg kg⁻¹), equivalent to Cu(II) concentrations (0, 17 and 83 mg kg⁻¹), LDPE microplastics (0, 1% and 5%) and their combination were selected. After 28 days of growth, biometric and photosynthetic parameters, Cu uptake, and soil microbial responses were evaluated. Plant germination and growth were not significantly affected by the combination of Cu and plastics. However, individual Cu treatments influenced root and shoot length and biomass. Chlorophyll and carotenoid concentrations increased with Cu addition, although the differences were not statistically significant. Phospholipid fatty acid (PLFA) analysis revealed a reduction in microbial biomass at the highest Cu dose, whereas LDPE alone showed limited effects and may reduce Cu bioavailability. These results suggest that even at the highest concentration added, Cu can act as a plant nutrient, while the combination of Cu–plastics showed varying effects on plant growth and soil microbial communities. Full article

Application of organic ligand 2-(3-ethyl-pyrazin-2-yl)quinoline-4-carboxylate with N/O donor atoms enabled solvothermal synthesis of a 2D Cu(II) coordination polymer, {Cu(L)BF₄}_n (L = deprotonated 2-(3-ethyl-pyrazin-2-yl)quinoline-4-carboxylate). Both the ligand and its coordination polymer have been characterized. The condensed ring system of the applied ligand promotes the formation of coordination polymers rather than mononuclear species. The obtained 2D coordination polymer is photoluminescent with bathochromic/hypsochromic shifts in ligand absorption bands leading to a single absorption band at 465 nm. Density Functional Theory was employed to provide a theoretical description of the possible conformational changes within the ligand, with emphasis on the difference between the ligand conformation in its hydrochloride salt and in the polymer. Two models of polymer fragments were constructed to describe the electronic structure and non-covalent interactions. The Quantum Theory of Atoms in Molecules (QTAIM) was applied for this purpose. Using the obtained results, we were able to develop potential energy profiles for various conformations of the ligand. For the set of the studied systems, we detected non-covalent interactions, which are responsible for the spatial conformation. Concerning the models of polymers, electron spin density distribution has been visualized and discussed. Full article

The transition to clean and renewable energy sources is critically dependent on efficient hydrogen production technologies. This review surveys recent advances in photocatalytic water splitting, focusing on MNb₂O₆ nanomaterials, which have emerged as promising photocatalysts due to their tunable band structures, chemical robustness, and tailored morphologies. The objectives of this work are to (i) encompass the current synthesis strategies for MNb₂O₆ compounds; (ii) assess their structural, electronic, and optical properties in relation to photocatalytic performance; and (iii) elucidate the mechanisms underpinning enhanced hydrogen evolution. Main data collection methods include a literature review of experimental studies reporting bandgap measurements, structural analyses, and hydrogen production metrics for various MNb₂O₆ compositions—especially those incorporating transition metals such as Mn, Cu, Ni, and Co. Novelty stems from systematically detailing the relationships between synthesis routes (hydrothermal, solvothermal, electrospinning, etc.), crystallographic features, conductivity type, and bandgap tuning in these materials, as well as by benchmarking their performance against more conventional photocatalyst systems. Key findings indicate that MnNb₂O₆, CuNb₂O₆, and certain engineered heterostructures (e.g., with g-C₃N₄ or TiO₂) display significant visible-light-driven hydrogen evolution, achieving hydrogen production rates up to 146 mmol h⁻¹ g⁻¹ in composite systems. The review spotlights trends in heterojunction design, defect engineering, co-catalyst integration, and the extension of light absorption into the visible range, all contributing to improved charge separation and catalytic longevity. However, significant challenges remain in realizing the full potential of the broader MNb₂O₆ family, particularly regarding efficiency, scalability, and long-term stability. The insights synthesized here serve as a guide for future experimental investigations and materials design, advancing the deployment of MNb₂O₆-based photocatalysts for large-scale, sustainable hydrogen production. 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 12-membered pyridinophane scaffold containing two pyridine and two tertiary amine residues is examined as a prototype ligand (^tBuN4) for supporting nitrene transfer to olefins. The known [(^tBuN4)M^II(MeCN)₂]²⁺ (M = Mn, Fe, Co, and Ni) and [(^tBuN4)Cu^I(MeCN)]⁺ cations are synthesized with the hexafluorophosphate counteranion. The aziridination of para-substituted styrenes with PhI=NTs (Ts = tosyl) in various solvents proved to be high yielding for the Cu(I) and Cu(II) reagents, in contrast to the modest efficacy of all other metals. For α-substituted styrenes, aziridination is accompanied by products of aziridine ring opening, especially in chlorinated solvents. Bulkier β-substituted styrenes reduce product yields, largely for the Cu(II) reagent. Aromatic olefins are more reactive than aliphatic congeners by a significant margin. Mechanistic studies (Hammett plots, KIE, and stereochemical scrambling) suggest that both copper reagents operate via sequential formation of two N–C bonds during the aziridination of styrene, but with differential mechanistic parameters, pointing towards two distinct catalytic manifolds. Computational studies indicate that the putative copper nitrenes derived from Cu(I) and Cu(II) are each associated with closely spaced dual spin states, featuring high spin densities on the nitrene N atom. The computed electrophilicity of the Cu(I)-derived nitrene reflects the faster operation of the Cu(I) manifold. Full article

Two-component dental materials are commonly used by the dentist for various applications (cementation of indirect restorations, filling of a cavity without layering, etc.). These materials are cured by redox polymerization. The (hydro)peroxide/thiourea/copper salt redox initiator system is well established and can be found in a wide range of commercially available dental materials. The thiourea is a key component of the initiator system. This study explores the influence of the nature of the thiourea reducing agent on the reactivity and efficiency of redox initiator systems. In this work, six different thiourea structures were investigated, in combination with copper(II) acetylacetonate and cumene hydroperoxide (CHP), to understand their impact on polymerization kinetics and mechanical properties of methacrylate-based materials. Various experimental techniques, including mass spectrometry (MS) and spectroscopic analyses, were employed to elucidate the underlying mechanisms governing these redox systems. The results highlight that thiourea plays a dual role, acting both as a reducing agent and as a ligand in copper complexes, affecting radical generation and polymerization efficiency. Structural modifications of thiourea significantly influence the initiation process, demonstrating that reactivity is governed by a combination of factors rather than a single property. Self-cure dental flowable composites exhibiting excellent flexural strength (>100 MPa) and modulus (>6000 MPa) were obtained using hexanoyl thiourea, N-benzoylthiourea, or 1-(pyridin-2-yl)thiourea as a reducing agent. The adjustment of the Cu(acac)₂ enables to properly set the working time in the range of 100 to 200 s. These findings provide valuable insights into the design of the next generation of redox initiating systems for mild and safe polymerization conditions. Full article

Biochar has emerged as a promising soil amendment for mitigating heavy metal contamination in agricultural systems. This study investigates the effects of biochar on cadmium (Cd) and copper (Cu) uptake, plant growth, oxidative stress, and physiological responses in lettuce (Lactuca sativa L.) plants exposed to different metal concentrations. Results indicate that biochar significantly influenced Cd bioavailability, reducing its accumulation in plant tissues by up to 31.9% and alleviating oxidative stress, with malondialdehyde and proline levels decreasing by up to 51.0% and 60.2%, particularly at higher application rates (5%). Cd-exposed plants treated with biochar exhibited an improved fresh weight (+22.6%), lower malondialdehyde and proline levels, and enhanced the chlorophyll content (+14.9% to 24.1%) compared to untreated plants. The bioaccumulation factor for Cd decreased (up to 31.8%) while the immobilization index (II) increased, confirming the role of biochar in limiting Cd mobility in soil. In contrast, Cu uptake remained consistently low across all treatments, with a significant reduction observed only at higher contamination levels (up to −34.2%). Biochar contributed to Cu immobilization, reflected in increased II values, and enhanced the plant biomass and chlorophyll content under Cu exposure (+15.4% and up to +24.1%, respectively), suggesting a partial alleviation of Cu toxicity. These findings highlight biochar’s potential in heavy metal remediation, particularly for Cd, by reducing bioavailability and improving plant resilience. However, its role in Cu-contaminated soils is mainly through immobilization rather than uptake reduction. Full article

The eight new copper(II), nickel(II), zinc(II), and iron(III) coordination compounds [Cu(L)Cl]₂ (1), [Cu(L)Br]₂ (2), [Cu(L)(NO₃)]₂ (3), [Cu(phen)(L)]NO₃ (4), [Ni(HL)₂](NO₃)₂·H₂O (5), [Ni(HL)₂]Cl₂ (6), [Zn(L)₂]·0.125H₂O (7), and [Fe(L)₂]Cl (8), where HL stands for 2-benzoylpyridine 4-allylthiosemicarbazone, were synthesized and characterized. ¹H, ¹³C NMR, and FTIR spectroscopies were used for characterization of the HL thiosemicarbazone. The elemental analysis, the FTIR spectroscopy, and the study of molar electrical conductivity were used for characterization of the coordination compounds 1–8. Also, the crystal structures of HL, its salts ([H₂L]Cl; [H₂L]NO₃), and complexes 1, 3, 5, 7, and 8 were determined using single-crystal X-ray diffraction analysis. Complexes 5, 7, 8 have mononuclear structures, while copper(II) complexes 1 and 3 have a dimeric structure with the sulfur atoms of the thiosemicarbazone ligand bridging two copper atoms together. Thiosemicarbazone HL and the complexes manifest antibacterial and antifungal activities. The studied substances are more active towards Gram-negative bacteria than towards Gram-positive bacteria and fungi. Complex 1 is the most active one towards Gram-positive bacteria and C. albicans, while the introduction of 1,10-phenanthroline into the inner sphere enhances the activity towards Gram-negative bacteria. Thiosemicarbazone and complexes 6 and 7 manifest antiradical activity that exceeds the activity of Trolox. HL and complex 1 manifest antiproliferative activity towards HL-60 cancer cells which exceeds the activity of their analogs with 2-formyl-/2-acetylpyridine 4-allylthiosemicarbazone. Full article

Mining and analyzing information from multiple sources—such as geophysics and geochemistry—is a key aspect of big data-driven mineral prediction. Clustering, which groups large datasets based on distance metrics, is an essential method in multidimensional data analysis. The Two-Step Clustering (TSC) approach offers advantages by handling both categorical and continuous variables and automatically determining the optimal number of clusters. In this study, we applied the TSC method to mineral prediction in the northeastern margin of the Jiaolai Basin by: (i) converting residual gravity and magnetic anomalies into categorical variables using Ward clustering; and (ii) transforming 13 stream sediment elements into independent continuous variables through factor analysis. The results showed that clustering is sensitive to categorical variables and performs better with fewer categories. When variables share similar distribution characteristics, consistency between geophysical discretization and geochemical boundaries also influences clustering results. In this study, the (3 × 4) and (4 × 4) combinations yielded optimal clustering results. Cluster 3 was identified as a favorable zone for gold deposits due to its moderate gravity, low magnetism, and the enrichment in F1 (Ni–Cu–Zn), F2 (W–Mo–Bi), and F3 (As–Sb), indicating a multi-stage, shallow, hydrothermal mineralization process. This study demonstrates the effectiveness of combining Ward clustering for variable transformation with TSC for the integrated analysis of categorical and numerical data, confirming its value in multi-source data research and its potential for further application. Full article

We studied the adsorption thermodynamics and mechanism behind the binding of nitric oxide (NO) in the interior surfaces and structural fragments of the high metal center density microporous Metal-Organic Framework (MOF) CPO-27-Cu, by gas sorption, at a series of temperatures. For the purpose of comparison, we also measured the corresponding CO₂ adsorption isotherms, and as a result, the isosteric heats of adsorption for the two studied adsorptives were derived, being in the range of 12–15 kJ/mol for NO at loadings up to 0.5 NO molecules per formula unit (f.u.) of the bare compound (C₄O₃HCu), and 23–25 kJ/mol CO₂ in the range 0–1 CO₂ per f.u. Microscopically, the mode of NO binding near the square pyramid Cu(II) centers was directly accessed with the use of in situ NO gas adsorption X-ray Absorption Spectroscopy (XAS). Additionally, during the vacuum/temperature activation of the material and consequent NO adsorption, the electronic state of the Cu-species was monitored by observing the corresponding X-ray Near Edge Spectra (XANES). Contrary to the previously anticipated chemisorption mechanism for NO binding at Cu(II) species, we found that at slightly elevated temperatures, under ambient, but also cryogenic conditions, only relatively weak physisorption takes place, with no evidence for a particular adsorption preference to the coordinatively unsaturated Cu-centers of the material. Full article

Background and Objectives: The efficacy of newly synthesized water-soluble octa-mercaptopyridine-substituted oxotitanium (IV) phthalocyanine (oxo-TiPc) and copper (II) phthalocyanine (CuPc) compounds in photodynamic therapy (PDT) was investigated using human tongue squamous cell cancer cell line (SCC-9, ATCC) cultures. Materials and Methods: A laser light source with a wavelength of 635 nm was used for this study. The cytotoxic values of the cancerous (SCC-9) and healthy (L-929) cell samples to which different Pc concentrations were applied under laser light were evaluated spectroscopically with the XTT method. Results: The oxo-TiPc compound exhibited a significantly lower IC50 value (46.8 µM) for SCC-9 cells compared to the CuPc compound (286.2 µM), indicating higher anticancer activity. This cytotoxicity may be due to decreased aggregation and enhanced reactive oxygen species (ROS) formation. Double-staining tests confirmed that oxo-TiPc-induced cell death included both apoptosis and necrosis. Conclusions: The findings show that the oxo-TiPc compound, unlike the CuPc compound, exhibited more selective toxicity to the SCC-9 cell line and has a higher phototoxic effect. Full article

The oxidative degradation of anthocyanins in red wine was investigated under controlled conditions using hydroxyl radicals generated in the presence of Cu (II) as a catalyst. A full factorial experimental design with 23 replicates was used to evaluate the effects of hydrogen peroxide concentration, catalyst dosage, and reaction temperature on anthocyanin degradation over a fixed time. Statistical analysis (ANOVA and multiple regression) showed that all three variables and the main interactions significantly affected anthocyanin loss, with temperature identified as the most influential factor. The combined effects were described by a first-order polynomial model. The activation energies for degradation ranged from 56.62 kJ/mol (cyanidin-3-O-glucoside) to 40.58 kJ/mol (peonidin-3-O-glucoside acetate). Increasing the temperature from 30 °C to 40 °C accelerated the degradation kinetics, almost doubled the rate constants and shortened the half-life of the pigments. At 40 °C, the half-lives ranged from 62.3 min to 154.0 min, depending on the anthocyanin structure. These results contribute to a deeper understanding of the stability of anthocyanins in red wine under oxidative stress and provide insights into the chemical behavior of derived pigments. The results are of practical importance for both oenology and viticulture and support efforts to improve the color stability of wine and extend the shelf life of grape-based products. Full article

Annually, more than 10,000 synthetic dyes are produced worldwide, generating around 280,000 tons of waste, posing risks to human and aquatic life, and potentially creating even more toxic products than the dyes themselves. This study aims to immobilize organic dyes, forming hybrid pigments using ZnO as support obtained through starch combustion. ZnO was obtained by starch (sago) combustion and characterized by XRD, SEM and the BET method. It was then used for the adsorption of orange and green textile dyes, evaluating the adsorbent dosage, initial dye concentration, contact time, and selectivity with copper ions. The removal studies indicated up to 100% removal of both dyes at low concentrations. The co-adsorption system showed excellent performance, with removal percentages exceeding 90% for both textile dyes and Cu (II) ions. Hybrid pigments were assessed for solvent resistance and durability under extended white light exposure. ZnO immobilized the dyes, showing resistance to organic solvents and good stability under prolonged white light exposure. Full article