Search Results (114)

Six 1,4-disubstituted pyrazoles linked to a benzenesulfonamide and a benzodioxane unit have been synthesized through a copper(I)-catalyzed formal [3+2] cycloaddition (32CA) reaction of alkynes with 3-arylsydnones. The Cu-catalyzed sydnone–alkyne cycloaddition (CuSAC) procedure has been optimized to promote the formation of the pyrazole ring and to deliver in three steps the six target compounds 5a–f, fully characterized by ¹H/¹³C-NMR and mass spectrometry (EIMS). Ten solvent conditions were evaluated. The reaction proceeded most efficiently in the presence of copper(II) sulfate pentahydrate in aqueous t-butanol in the presence sodium acetate, to reach a yield of 96%. The mechanism of the Cu(I)-catalyzed reaction has been studied within the Molecular Electron Density Theory (MEDT). This rection is a domino process that consists in a Cu(I)-catalyzed formal [3+2] cycloaddition followed of an extrusion of CO₂ yielding the final pyrazole. The capacity of heterocyclic compounds 5a–f to interact with human cyclophilin A (Cyp A), which is a host cofactor for hepatitis C virus (HCV) and human immunodeficiency virus 1 (HIV-1), and with the HIV-1 protein gp120-CD4 was evaluated using molecular docking. Compounds 5a,b,d,f showed a satisfactory protein binding capacity. The physicochemical and metabolic properties of the compounds were also evaluated in silico. These predictions provide important information to guide future design in this series of potential antiviral agents. Full article

Quaternary lavas (ankaramite, basalt, basaltic andesite, andesite, dacite) from the Kamchatka, Kurile, Ecuador and Cascade volcanic arcs contain Cl-bearing mineral microinclusions in rock-forming minerals and groundmass volcanic glass. They are represented by chlorargyrite (with a variable amount of native Ag), Cu, Ag, Sn, and Zn compounds with Cl and S, Sn- and Pb-Sb oxychlorides compositionally similar to abhurite and nadorite, as well as bismoclite and Cl-F-apatite. The Cl-bearing compounds with chalcophile metals are best approximated by mixtures of chlorargyrite with Cu sulfides, malachite, or azurite. Some Cl-bearing solid microinclusions in magmatic rock-forming minerals could have formed from Cl-rich melts exsolved from arc magmas during differentiation. Alternatively, specific magmatic microinclusions may record the decomposition of primary sulfides in the presence of Cl-bearing magmatic volatiles. Post-magmatic Cl microminerals found in fractures, pores, grain contacts, and groundmass glass are most probably precipitated from hydrothermal fluids accompanying their emplacement at the surface and post-eruption transformations in active fumarole fields. Assemblages of Cl-bearing microminerals with native metal, alloy, sulfide, oxide, and sulfate microinclusions in arc lavas potentially record late-magmatic to post-magmatic stages of formation of the epithermal and possibly porphyry mineralization beneath arc volcanoes. Full article

The synthesis of a small library of fused Cyclic Aryl Amino Carbon (f-CArAC) carbene precursors in the form of 1,1,2,4-tetraaryl-1H-isoindol-2-ium triflate (6), (7-R) (R = ^tBu, CF₃) or 3,3-dimethyl-2,8-bis-arene-substituted-3,4-dihydro-isoquinolin-2-ium hydrogen-dichloride (8) and 2,4,8-tri(substituted)-isoquinolin-2-ium tosylate salts (12) has been achieved. All of them feature an arene incorporated on the annulated benzene ring of the corresponding heterocycle, introduced at the early stages of their synthesis via the Suzuki cross-coupling reaction between 2,6-dibromo-benzaldehyde and the desired aryl boronic acid. The terphenyl-2′carbaldehyde by-products of this Suzuki reaction are useful starting points for the preparation of two new iminium iodide salts (10-R) (R = H, CF₃) as potential precursors to access ACyclic Amino Carbon (ACAC) carbenes. Compounds (6) and (7-^tBu) react readily with hydroxide either in THF or in a biphasic Et₂O/aqueous OH⁻ solution to produce the substituted isoindolinols (13) and (14), respectively. The thermal dehydration of the former generates the corresponding f-CArAC carbene in situ, which is trapped by Cu(I)Cl furnishing, a rare example of a two-coordinate Cu(I) complex (15) supported by this new ligand scaffold. Full article

Adsorption desulfurization of fuel oil is regarded as one of the most promising technologies for obtaining clean fuel because it can remove refractory sulfur compounds at ambient temperature and pressure. Studies indicate that HKUST-1, as an important type of metal–organic framework (MOF), is a potential candidate for adsorption desulfurization of fuel oil. In this work, we report that defective HKUST-1 can be rapidly synthesized at room temperature with the aid of NH₄F and exhibit superior adsorption desulfurization performance compared to conventional HKUST-1 by the solvothermal method. Moreover, the influence of adsorption parameters on the desulfurization performance of HKUST-1 prepared with the aid of NH₄F was investigated. We used 50 mg of HKUST-1-5 synthesized with 5 wt% added NH₄F to adsorb 5 g of model oil with a sulfur concentration of 1000 ppm at 25 °C for 1 h, and the adsorption capacity of the adsorbent reached 23.8 mgS/g, 46.8 mgS/g and 36.8 mgS/g for benzothiophene (BT), dibenzothiophene (DBT) and 4,6-dimethyldibenzothiophene (4,6-DMDBT), respectively, which are higher values than those of conventional HKUST-1. Such performance can be mainly attributed to its relatively small particle size and the presence of more unsaturated Cu sites. The results of regeneration experiments show that HKUST-1-5 still maintains excellent adsorption performance after four cycles. These findings highlight the great potential of this material as an efficient adsorbent for adsorption desulfurization of fuel oil. Full article

Brewer’s spent grain (BSG) is the main solid byproduct of the brewing industry, generated in large quantities worldwide. Its high organic content and availability make it an attractive substrate for biotechnological valorization and recycling within a circular economy framework, contributing to the recovery and reuse of agro-industrial residues. This study investigates the potential of Talaromyces stollii I05.06 to simultaneously produce laccase and release phenolic compounds through submerged fermentation (SmF) using BSG as the sole carbon source. Initial SmF trials confirmed the fungus’s capacity to metabolize BSG. Subsequent fermentations with phosphate buffer supplementation (100 mM) significantly enhanced laccase activity (1535 ± 151.6 U·L⁻¹ on day 5) and phenolic content (6.28 ± 0.07 mg GAE per 100 g on day 1 with 50 mM buffer). However, the addition of typical laccase inducers (Cu²⁺ and Mn²⁺) led to inhibitory effects. The results highlight T. stollii I05.06 as a promising microorganism for the integrated valorization of BSG, contributing to sustainable agro-industrial waste management and the development of value-added bioproducts. 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

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

To date, two-dimensional metal–organic frameworks (2D MOFs) have attracted much attention in many fields. Owing to their ultra-high porosity and specific surface area, great structural diversity and functional tunability, as well as feasible precision design at the molecular level, 2D MOFs have won rapid development in the field of energy storage. However, as a coordination compound, MOFs possess poor structural stability and are prone to structural collapse in electrochemical reactions, which seriously limits their electrochemical performance. Therefore, there is an urgent need to improve the structural stability of MOF electrode materials. In this study, a 2D MOF@Ti₃C₂T_X hybrid was constructed, in which urea pyrimidinone isocyanate (UPy-NCO) units were introduced via a condensation reaction with the active functional groups on MOFs, thus forming multiple hydrogen bonds among MOF frameworks to strengthen their structural stability. Importantly, 2,6-diaminopyridine was utilized to modulate the structure and properties. Initially, the mono-coordination model of the N atom on a pyridine ring with metal ions could create defects and form further pores. Two −NH₂ groups helped to improve the grafting reaction degree of UPy-NCO, leading to an increased ratio of forming quadruple hydrogen bonds (H-bonds), further strengthening the structure of the hybrid. As expected, the Cu-MOF@Ti₃C₂T_X-20%DAP-UPy hybrid exhibited a specific capacitance of 148 F g⁻¹ at 1 A g⁻¹, which is 45% higher than that of Cu-MOF@Ti₃C₂T_X-UPy (102 F g⁻¹). A good capacitance retention of 88% was obtained as the current density increased from 0.2 to 5 A g⁻¹. Moreover, excellent cycling stability (91.1%) was obtained at 1 A g⁻¹ after 5000 cycles. Full article

Sulfurization-assisted flotation is a key process that uses sulfur compounds to modify mineral surfaces, enhancing hydrophobicity and flotation efficiency, especially for copper oxide minerals. This study introduced the preliminary activation of malachite utilizing a combination of Pb²⁺ and NH₄⁺ ions in sulfurization systems, significantly improving flotation recovery. Flotation tests and surface analysis techniques were employed to examine the effects of Pb²⁺ and NH₄⁺ ions on malachite’s flotation behavior and the stability of its sulfurized surface layer. The results showed that, after activation with Pb²⁺ and NH₄⁺ at optimal reagent concentrations, malachite’s flotation recovery reached 94.6%, compared to 68.13% with traditional sulfurization. Atomic force microscopy (AFM) revealed significant changes in malachite’s surface morphology, with a dense, cloud-like sulfide film forming that contained more sulfur than in direct sulfurization, enhancing the durability of the sulfurized surface. Time-of-Flight Secondary Ion Mass Spectrometry (ToF-SIMS) analysis confirmed increased sulfide ion adsorption on the surface compared to traditional sulfurization. The Pb²⁺ + (NH₄)₂S + Na₂S system generated numerous active sites from copper-sulfide species, promoting the growth of sulfurized phases. FT-IR analysis showed stable Cu-S species on the malachite surface, improving SBX adsorption and flotation performance. Contact angle measurements indicated that the activation systems significantly improved surface hydrophobicity, with the copper-sulfide film achieving a contact angle of 95.29°, demonstrating superior durability and mineral recovery compared to traditional sulfurization. Thus, the activation of Pb²⁺ and NH₄⁺ ions offers a promising solution for sulfurization-assisted flotation, enabling more efficient and sustainable recovery of malachite ore, with improved sulfide layer durability and enhanced hydrophobicity. Full article

Familial amyotrophic lateral sclerosis (ALS) is a progressive neurodegenerative disease characterized by the selective degeneration of motor neurons. Among the main genetic causes of ALS, over 200 mutations have been identified in the Cu/Zn superoxide dismutase (SOD1) protein, a dimeric metalloenzyme essential for converting superoxides from cellular respiration into less toxic products. Point mutations in SOD1 monomers can induce protein misfolding, which spreads to wild-type monomers through a prion-like mechanism, leading to dysfunctions that contribute to the development of the disease. Understanding the structural and functional differences between the wild-type protein and its mutated variants, as well as developing drugs capable of inhibiting the propagation of misfolding, is crucial for identifying new therapeutic strategies. In this work, seven SOD1 mutations (A4V, G41D, G41S, D76V, G85R, G93A, and I104F) were selected, and three-dimensional models of SOD1 dimers composed of one wild-type monomer and one mutated monomer were generated, along with a control dimer consisting solely of wild-type monomers. Molecular dynamics simulations were conducted to investigate conformational differences between the dimers. Additionally, molecular docking was performed using a library of ligands to identify compounds with high affinity for the mutated dimers. The study reveals some differences in the mutated dimers following molecular dynamics simulations and in the docking of the selected ligands with the various dimers. Full article

Two new cage-structured compounds—NbCu₂Zn₂₀ and HfCu₂Zn₂₀—belonging to the MM’₂X₂₀ (M, M’ = transition or rare earth metals, and X = Al, Zn, or Cd) family of structures have been synthesized via the self-flux method. The new compounds crystallize in the space group $Fd\overline{3}m$ with lattice parameter 13.9013(2) Å for NbCu₂Zn₂₀ and 13.9856(2) Å for HfCu₂Zn₂₀. The structures follow the expected metallic radii trend in MM’₂₀Zn₂₀ (M = Nb or Hf, M’ = Mn, Fe, Co, Ni, and Cu). While NbCu₂Zn₂₀ is stoichiometric, HfCu₂Zn₂₀ exhibits Cu/Zn site mixing and Hf-site underoccupancy, resulting in a final stoichiometry of Hf_0.96Cu_1.67Zn_20.33 (Hf_1–δCu_2–xZn_20+x, δ = 0.04, x = 0.33). Full article

This manuscript highlights the behavior of biodegradable polymers (PLA and HD PLA Green) coated with two distinct bronze alloy powders, Metco 51F-NS (Cu 9.5Al 1.2Fe) and Metco 445 (Cu 9.5Al). The coating was realized on printed samples by using the Atmospheric Plasma Spray (APS) technique. The current investigation will explain the results related to the surface quality, micro-structure, morphology, and thermal and tribological properties. Thus, from a structural point of view, the most uniform deposition was obtained in the case of composite powder Metco 51F-NS. The thermal behavior of the samples coated with copper-based powder achieved stability up to temperatures slightly above 200 °C, with carbonization of the matrix structure taking place around 350 °C. The micro-indentation and scratch analysis responses were significantly influenced by the semicrystalline structure of the samples and the presence of the powder compounds. Based on the increased characteristics of the coated samples, the authors of the present paper consider that parts made of biodegradable polymers and coated with copper microparticles are appropriate for some applications which take place in adverse operating conditions. Full article

Oxygen-bearing platinum group minerals (O-bearing PGMs) are intergrown with base metal sulfides (BMS, e.g., pentlandite–[NiFe]₉S₈) within fractures in chromite grains from chromitite bodies on Ouen Island, New Caledonia. These PGMs are hosted in chlorite and serpentine, which formed during serpentinization of olivine and pyroxene. The O-bearing PGM grains are polygonal, show microfracturing (indicating volume loss), and contain Pt-Pd-rich sulfide remnants, suggesting pseudomorphic replacement of primary (magmatic) sulfides. They display chemical zonation, with Pt(-Pd-Ni-Fe) relict sulfide cores replaced by Pt-Fe-Ni oxidized alloy mantles and Pt-Cu-Fe(-Pd) alloy rims (tulameenite), indicating desulfurization. The core and mantle show a nanoporous structure, interpreted as the result of coupled dissolution–reprecipitation reactions between magmatic sulfides and low fO₂–fS₂ serpentinite-related fluids, probably formed during olivine transformation to serpentine + magnetite (early stages of serpentinization). This fluid infiltrated magmatic sulfides (PGE-rich and BMS), degrading them to secondary products and releasing S and metals that were accommodated in the mantle and rim of O-bearing PGMs. Upon olivine exhaustion, an increase in fO₂ might have stabilized Pt-Fe-O compounds (likely Pt⁰/Pt-Fe + Fe oxyhydroxides) alongside Ni-Fe alloys. Our results show that post-magmatic desulfurization of primary sulfides produces complex nano-scale intergrowths, mainly driven by changes in the fluid’s physicochemical properties during serpentinization. Full article

Kale (Brassica napus) and collard (Brassica oleracea) are two leafy greens in the family Brassicaceae. The leaves are rich sources of numerous health-beneficial compounds and are commonly used either fresh or cooked. This study aimed to optimize the nutrient management of kale and collard in hydroponic production for greater yield and crop quality. ‘Red Russian’ kale and ‘Flash F1’ collard were grown for 4 weeks after transplanting in a double polyethylene-plastic-covered greenhouse using a nutrient film technique (NFT) system with 18 channels. Kale and collard were alternately grown in each channel at four different electrical conductivity (EC) levels (1.2, 1.5, 1.8, and 2.1 mS·cm⁻¹). Fresh and dry yields of kale increased linearly with increasing EC levels, while those of collard did not increase when EC was higher than 1.8 mS·cm⁻¹. Kale leaves had significantly higher P, K, Mn, Zn, Cu, and B than the collard at all EC levels. Additionally, mineral nutrients (except N and Zn) in leaf tissue were highest at EC 1.5 and EC 1.8 in both the kale and collard. However, the changing trend of the total N and NO3- of the leaves showed a linear trend; these levels were highest under EC 2.1, followed by EC 1.8 and EC 1.5. EC levels also affected phytochemical accumulation in leaf tissue. In general, the kale leaves had significantly higher total anthocyanin, vitamin C, phenolic compounds, and glucosinolates but lower total chlorophylls and carotenoids than the collard. In addition, although EC levels affected neither the total chlorophyll or carotenoid content in kale nor glucosinolate content in either kale or collard, other important health-beneficial compounds (especially vitamin C, anthocyanin, and phenolic compounds) in kale and collard leaves reduced with the increasing EC levels. In conclusion, the kale leaf had more nutritional and phytochemical compounds than the collard. An EC level of 1.8 mS·cm⁻¹ was the optimum EC level for the collard, while the kale yielded more at 2.1 mS·cm⁻¹. Further investigations are needed to optimize nitrogen nutrition for hydroponically grown kale. Full article

Two new organo-inorganic hybrids, (C₂N₂H₁₀)[Cu(H₂O)₄](BeF₄)₂ (1) and (C₂N₂H₁₀)[Cu(H₂O)₄](SeO₄)₂ (2), were prepared via the interaction of ethylenediamine, copper fluoroberyllate or selenate, and H₂[BeF₄]/H₂SeO₄ in aqueous solutions. The structures of 1 and 2 are similar to each other and the previously reported (C₂N₂H₁₀)[Cu(H₂O)₄](SO₄)₂: monoclinic, P2₁/c, a = 5.1044(2) Å, b = 11.6171(4) Å, c = 10.1178(3) Å, and β = 94.431(3)° for 1; and a = 5.25020(10), b = 11.7500(2), c = 10.4434(2), and β = 94.5464(17)° for 2. All structures contain a square planar [Cu(H₂O)₄]²⁺ species, which coordinates, at rather long distances, two TX₄²⁻ tetrahedral dianions in κ¹ mode, forming relatively weak [Cu(H₂O)₄(TX₄)₂]²⁻ complexes. These are linked together via hydrogen bonding into pseudo-chains; the ethylenediammonium cations link them into a 3D architecture. Compound 1 is, to the best of our knowledge, the first—though expected—representative of a hybrid organo-inorganic fluoroberyllate. The crystal chemical relations within the structural family (enH₂)[Cu(H₂O)₄](TX₄)₂ are discussed. Full article