Search Results (368)

A simple and cost-effective graphite paste electrode modified with 5-(4-aminophenyl)-4-amino-1,2,4-triazole-3(2H)-thione was developed for the selective voltammetric determination of Cu(II) ions in environmental water samples. The N,S-donor ligand was incorporated into a graphite–polystyrene matrix without the use of nanomaterials, providing a reproducible and straightforward electrode fabrication route. Scanning electron microscopy revealed a rough, porous surface morphology with an enhanced electroactive surface area of 0.065 cm², approximately twice the geometric area. Electrochemical impedance spectroscopy confirmed diffusion-controlled mass transport, while cyclic voltammetry indicated quasi-reversible behaviour of the Cu(II)/Cu(0) redox system with a linear dependence of peak current on the square root of the scan rate. Differential pulse voltammetry under optimised conditions (0.1 mol·L⁻¹ H₂SO₄, pH 1.0–1.2) yielded a linear analytical response over the concentration range of 0.01–0.4 μmol·L⁻¹ (R² = 0.99507), with a limit of detection of 0.02 μmol·L⁻¹ and a limit of quantification of 0.06 μmol·L⁻¹—well below the WHO guideline for copper in drinking water. The sensing mechanism involves selective N,S-bidentate coordination of Cu(II) at the electrode surface, followed by electrochemical reduction, as supported by FT-IR spectroscopic evidence. The sensor demonstrated good selectivity toward Cu(II) in the presence of common interfering metal ions at up to 20-fold excess. The method was successfully validated against ICP-OES (recovery 99.8%, RSD < 0.33%) and confirmed by spike–recovery experiments (99.0–99.5%), confirming its practical applicability for trace-level environmental monitoring. The modified electrode retained approximately 93% of its initial response after 30 consecutive measurements and 91% after 14 days of storage, demonstrating good operational stability. Full article

A novel carbohydrazide-based ligand (L) and its binuclear Cu(II) complex were successfully synthesized and characterized. Structural analysis confirmed that the Cu(II) complex adopted a monoclinic crystal system with a distorted coordination configuration, in which the multidentate Schiff base ligand chelated and bridged two Cu(II) centers. The in vitro anti-tumor results revealed that the Cu(II) complex exhibited prominent cytotoxicity against five human cancer cell lines with much lower IC₅₀ values than the free ligand, copper chloride and cisplatin. Mechanistic studies demonstrated that the Cu(II) complex significantly increased intracellular ROS and MDA levels, decreased the GSH/GSSG ratio, and reduced ATP content, thereby disrupting cellular redox balance and bioenergetic metabolism. In addition, flow cytometry analysis verified that the complex effectively triggered tumor cell apoptosis. In contrast, free CuCl₂ showed almost no anticancer activity, indicating that the synergistic effect between the Schiff base ligand and copper ions contributed to the excellent anti-tumor performance. This work suggests that the prepared binuclear Cu(II) complex can serve as a promising candidate for developing metal-based anticancer agents. Full article

The present study reports the application of a gold microelectrode array to determine copper(II) ions by anodic stripping voltammetry (ASV). The microelectrode characterization of the presented working electrode was investigated. Moreover, the way of its preparation ensures its reusability and eco-friendly character, thanks to the use of environmentally benign electrode material. The procedure does not require modification of the surface of the working electrode. Main experimental parameters were optimized, including pH and a concentration of the supporting electrolyte, activation and deposition conditions, and square wave parameters. The calibration graph was linear in the range of Cu(II) concentrations from 2 × 10⁻⁹ to 2 × 10⁻⁷ mol L⁻¹ (with a deposition time of 30 s) and from 5 × 10⁻¹⁰ to 5 × 10⁻⁸ mol L⁻¹ (with a deposition time of 90 s; RSD was 4.7% (n = 3) for a 1 × 10⁻⁸ mol L⁻¹ of Cu(II)). The limit of detection was equal to 1.93 × 10⁻¹⁰ mol L⁻¹ (t_acc = 90 s). The correctness of the developed procedure was successfully checked by analysis of certified reference material and a tap water sample, confirming the possibility of its practical application. Satisfactory recovery values were also obtained during the analysis of an environmental water sample. Full article

Although amorphous calcium phosphate (ACP) has been extensively employed as a biomaterial in dental and orthopedic fields, its exploration for environmental applications—particularly in potentially toxic element remediation—remains notably limited in the scientific literature. This study reports the rational design of a multifunctional adsorbent by integrating sodium citrate-stabilized ACP (Cit-ACP) nanoparticles into calcium-crosslinked sodium alginate (SA) hydrogel beads for selective Cu²⁺ sequestration from aqueous systems. Comprehensive sorption assessments revealed that equilibrium uptake aligned with the Freundlich isotherm (indicating heterogeneous surface interactions), while kinetic profiles adhered to pseudo-second-order behavior, characteristic of chemisorption-driven processes. Under optimized operational parameters (pH 5.0, 45 °C), the Cit-ACP/SA composite attained an exceptional maximum adsorption amount of 307.76 mg/g. Thermodynamic analysis further confirmed the spontaneity (ΔG° < 0) and endothermic nature (ΔH° > 0) of the process. Multi-technique characterization (XPS, FTIR, XRD, pH trajectory) elucidated a dual-mode adsorption mechanism: (i) ion exchange between aqueous Cu²⁺ and structural Ca²⁺ within both the alginate matrix and ACP framework; and (ii) in situ surface precipitation yielding copper-substituted hydroxyapatite. Owing to its facile aqueous-phase synthesis, superior adsorption performance, biodegradability, macroscopic bead morphology enabling rapid separation, and robust selectivity in complex matrices, the Cit-ACP/SA composite presents a sustainable, scalable, and eco-compatible platform for practical remediation of copper-contaminated wastewater. Full article

Moxifloxacin-based Schiff-base ligands provide a useful platform for tuning the coordination and biological properties of fluoroquinolone derivatives. Here, a moxifloxacin–salicylaldehyde hydrazone ligand (MOX-S) was prepared and coordinated with cobalt(II), nickel(II), copper(II), oxovanadium(IV), and gadolinium(III) ions to obtain a series of metal complexes. Citrate-stabilized gold nanoparticles (AuNPs) were also prepared and functionalized with MOX-S and the Cu(II) complex to evaluate the effect of nanoformulation on biological performance. The compounds were characterized using complementary analytical, spectroscopic, magnetic, thermal, and microscopic techniques. The combined data support 1:2 metal-to-ligand formulations for the complexes and indicate coordination mainly through the azomethine nitrogen and oxygen donor sites of MOX-S. In antimicrobial screening, the activity was strongly metal- and organism-dependent. Cu–MOX-S and VO–MOX-S showed the most pronounced activity against Gram-positive bacteria, with inhibition zones of up to 30 mm, while Cu–MOX-S displayed MIC values of 19.53 and 39.06 µg mL⁻¹ against Bacillus subtilis and Staphylococcus aureus, respectively. Cytotoxicity assays showed that MOX-S was more active than moxifloxacin against MCF-7 and HepG2 cells, while Cu–MOX-S showed enhanced potency, particularly toward HepG2 cells, with an IC₅₀ of 0.98 µM and a selectivity index of 5.97. AuNP formulations further increased the apparent antiproliferative potency in the tested cancer cell lines, giving sub-micromolar IC₅₀ values. Computational analyses, including DFT-based electronic descriptors and molecular docking, provided qualitative support for the experimentally observed coordination and cytotoxicity trends. Overall, metal coordination and AuNP formulations provide complementary strategies for modulating the physicochemical and in vitro biological behavior of this moxifloxacin-derived hydrazone scaffold. Full article

Chitosan-based copper composites have attracted considerable interest for biomedical and antimicrobial uses due to their biocompatibility, adjustable dielectric characteristics, and ion-mediated antimicrobial effectiveness. In this study, chitosan films doped with Cu(NO₃)₂, containing 3, 6, and 9 wt% of copper nitrate were produced using a solution-casting method at room temperature. This was done to explore the relationship between structural interactions, dielectric relaxation, optical properties, and antimicrobial efficacy. The resulting composite has been investigated physically using FTIR, XRD, optical analysis, and dielectric spectroscopy, and biologically for its antimicrobial activity. FTIR revealed the molecular structure of Cs-Cu(NO₃)₂ and changes resulting from new bond(s) formation and/or decomposition. XRD indicated that there are no peaks assigned for CuO, which weakens the composite antimicrobial activity. Optical analysis showed an increase in the band gap with copper (II) nitrate concentration over 3%. Additionally, the electrical impedance of the resulting composite increased by approximately one decade. A detailed electrical analysis of the charge-carrier types is provided. Moreover, the antimicrobial activity of chitosan is slightly enhanced by the additive copper (II) nitrate in a dose-dependent manner. The current research offers a mechanistic understanding of the structure–property relationships that govern the behavior of Cu(NO₃)₂–chitosan composites, emphasizing the significant influence of processing conditions on adapting of their dielectric and biological properties. Full article

The causative event in transmissible spongiform encephalopathies is the misfolding of the prion protein (PrP), a process influenced, in a way that is not yet fully understood, by transition metal ions, particularly copper, which modulate folding, aggregation, and redox activity. In this study, we investigated the interaction of copper(II) ions with the prion fragment PrP(95–126), which includes the non-octarepeat high-affinity sites His96 and His111, as well as an amyloidogenic tail involved in PrP misfolding and membrane interaction. UV–vis and circular dichroism analyses revealed the predominant formation of a 1:1 Cu/PrP(95–126) complex, accompanied by modest restructuring, consistent with an increased aggregation propensity upon copper binding. The Cu/PrP(95–126) complexes exhibited limited redox activity toward catechol substrates, which was further reduced in membrane-mimetic systems such as SDS micelles and large unilamellar vesicles (LUVs). His96 appears not to play a critical role in copper coordination or redox activation. This study explores the coordination modes and reactivity of copper(II) with PrP, as well as employing a membrane mimic, aspects that are still highly controversial in the literature, providing insights for further in vitro studies. Full article

Sustainable valorization of biomass through hydrothermal carbonization (HTC) represents an environmentally benign method for producing carbon materials for water treatment applications. This research aims to optimize the production of hydrochar from waste food by focusing on parameter optimization, physicochemical characterization, and the capacity of hydrochar to act as an adsorbent for the removal of the copper (II) ion from polluted water. A design of experiments using the RSM approach was employed to evaluate and optimize the influence of carbonization temperature, ranging from 180 to 250 °C, with a residence time of 2–5 h. The predictive ability of the MINITAB-generated model was close to accurate, as demonstrated by the design application for process simulation. The maximum % hydrochar yield was 72.65% for the experimental yield and 71.53% for the predicted yield, both obtained from a sample carbonized at 166 °C for 3.5 h. Batch adsorption experiments were conducted to assess the hydrochar’s ability to remove Cu²⁺ from aqueous solutions, and the Langmuir and the Freundlich isotherms were fitted at different pH levels. A comprehensive characterization of the produced hydrochar was conducted using Fourier-transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), X-ray fluorescence (XRF), and scanning electron microscopy (SEM-EDS). The results revealed significant modifications in surface morphology, pore development, and the presence of oxygen-containing functional groups. Based on the findings in this report, it is safe to conclude that hydrochar derived from food waste could serve as a potential adsorbent. Overall, the study demonstrates that sustainable hydrochar production from biomass can simultaneously address waste management challenges and provide an efficient solution for heavy metal removal, thereby advancing circular bioeconomy and environmental protection. Full article

In this study, we present new data about the cytotoxic activity of metal complexes of salinomycin with Co(II), Cu(II) and Zn(II) against human cervical cancer (HeLa) and melanoma (A375, SH-4) cell lines. The effect of the compounds on cell viability and proliferation was evaluated in short-term experiments (up to 72 h) with monolayer cultures using the 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) test, neutral red uptake (NR), crystal violet staining (CV) and double staining with acridine orange (AO) and propidium iodide (PI). The cytotoxic effect of the metal complexes of salinomycin was found to be comparable and even superior to that of the commercial antitumor agents cisplatin and oxaliplatin. Long-term experiments revealed the ability of the compounds to completely suppress 3D cell growth when applied at concentrations ≥ 3.1 μM (for HeLa cells) and ≥6.2 µM (for A375 cells). Embryonic Lep-3 cells are highly sensitive to the influence of the complexes investigated, whereas non-tumor HaCaT human keratinocytes exhibit relatively higher resistance to their cytotoxic effect compared to tumor cell lines. The Zn(II) disalinomycinate exerted the highest selectivity index among the tested compounds against melanoma cells, whereas the non-coordinated antibiotic showed pronounced selectivity toward HeLa cells. Full article

Chitosan, owing to its abundant amino and hydroxyl functional groups, serves as an effective biosorbent for the removal of toxic metal(loid) ions from water. This review summarizes recent advances in chitosan-based adsorbents specifically for arsenate (As(V)) and copper ions (Cu(II)), with an emphasis on adsorption mechanisms and electrospun nanofiber technologies. A conceptual “charge adaptation–structure synergy” model is proposed to elucidate the distinct adsorption behaviors of chitosan toward anionic and cationic substances: under acidic conditions, As(V) adsorption is dominated by electrostatic attraction to protonated amino groups, whereas at pH values near or above the pKa, Cu(II) removal proceeds via synergistic chelation involving deprotonated amino and hydroxyl groups. Competitive and synergistic interactions in binary systems, particularly between As(V) and coexisting anions such as phosphate, are also discussed. Notably, the kinetic advantages of electrospun chitosan nanofibers are highlighted, with equilibrium times shortened from several hours to approximately 0.5–2.6 h. Key challenges and future research directions are further discussed, including scalable manufacturing and the treatment of complex wastewater matrices. Full article

The spontaneous reduction of one Cu(II) center to Cu(I) in a series of three dinuclear copper complexes in acetonitrile is described. These complexes feature ligands that include nitrogen donors from a diazecine ring and imidazole, designated as promeim, thiopromeim, and thioenmeim; the latter two incorporate a thioether as a third donor component. The mechanism of metal reduction was elucidated through spectroscopic and spectrometric techniques (UV-vis, EPR, XANES, ESI-MS) and electrochemical tools, in combination with DFT electronic structure calculations. Based on these and on spectroelectrochemical results, a mechanism is proposed in which the one-electron reduction of one of the copper ions is achieved by a one-electron oxidation in the adjacent imidazole group, while the other copper ion remains as Cu(II). The persistent detection of superoxide and peroxide over long periods suggests a mechanism in which a catalytic cycle involving electron transfer occurs between copper, ligand, and dioxygen. Full article

Ion-imprinting technology based on biosorbents via sorption demonstrates potential for the selective removal of metal ions from water and wastewater. This offers both high sorption capacity and selectivity for specific metals. Current research trends are toward the development of sorbents with minimal environmental impact. Among the most rapidly evolving classes of sorbents are those derived from biopolymers, such as chitosan—a natural derivative of chitin that can be readily functionalized. Due to the growing interest in this topic, it is necessary to summarize the current knowledge. In this article, we provide a comprehensive overview of the latest advances in ion-imprinted chitosan-based materials designed for the purification of metal-contaminated aqueous systems. We conduct a bibliographic analysis and describe a variety of chitosan-based materials exhibiting selectivity toward heavy metals, including chromium Cr(III/VI), cobalt Co(II), nickel Ni(II), copper Cu(II), zinc Zn(II), arsenic As(III/V), cadmium Cd(II), mercury Hg(II), and lead Pb(II). Finally, we discuss future prospects and highlight current research gaps, aiming to guide further scientific exploration and innovation in this promising field. Full article

This study presents a quantitative investigation of substituent effects on the stability of 1:2 complexes formed between para-substituted 2-phenylbenzimidazole ligands and Cu(II) or Co(II) ions. The ligands, featuring hydroxyl (–OH), chloro (–Cl), and nitro (–NO₂) substituents, were synthesized via copper acetate-mediated oxidative cyclization. Stability constants (log K) were determined spectrophotometrically using both the Benesi–Hildebrand and Job methods, which yielded perfectly consistent results and confirmed ML₂ stoichiometry. For both metal series, the stability decreases in the order –OH > –Cl > –NO₂. Excellent linear correlations were obtained between log K and Hammett σ constants, yielding reaction constants of ρ = −0.79 for Cu(II) and ρ = −1.00 for Co(II). These negative ρ values confirm that electron-donating substituents enhance complex stability by increasing electron density on the donor nitrogen. Furthermore, the stability constants for Cu(II) complexes are approximately two orders of magnitude higher than those for Co(II), in agreement with the Irving–Williams series. This work establishes a clear, predictive structure–stability relationship and validates the combined methodological approach for quantifying metal–ligand interactions in tunable benzimidazole systems. Full article

1,4-Disubstituted 1,2,3-triazoles are readily obtained by copper(I)-catalyzed azide–alkyne 1,3-dipolar cycloaddition (CuAAC)—the most widespread illustration of click chemistry to date. 1,2,3-Triazoles form a vast and easily accessible library of precursors for synthesizing 1,2,3-triazolium ionic liquids (TILs). A series of four 1,3,4-trisubstituted TILs with N-1-n-octyl, N-3-methyl and different C-4 substituents (i.e., aromatic, aliphatic, PEGylated and perfluorinated groups) is synthesized in two steps involving: (i) CuAAC to generate 1,2,3-triazole precursors and (ii) N-alkylation of the 1,2,3-triazole groups with methyl iodide to afford the corresponding 1,2,3-triazolium salts with iodide counter-anions. A thorough investigation of the correlations between structure and properties is carried out using NMR spectroscopy, high-resolution mass spectrometry, differential scanning calorimetry, thermogravimetric analysis and broadband dielectric spectroscopy. The PEGylated TIL has also undergone ion metathesis to produce the TIL analogue with a bis(trifluoromethylsulfonyl)imide counter-anion. Of all the synthesized TILs, this derivative exhibits the lowest glass transition temperature (T_g = −76 °C), the highest thermal stability (T_d10 = 345 °C) and the greatest ionic conductivity (σ_DC = 6.5 × 10⁻⁴ S cm⁻¹ at 30 °C under anhydrous conditions). Full article

Protein phosphorylation and dephosphorylation reactions of intracellular molecules catalyzed by enzymes such as kinases and phosphatases are essential reactions in a lot of cellular functions such as intracellular signal transduction in living systems. The design and synthesis of artificial enzyme mimics are important research topics in bioorganic and bioinorganic chemistry. In this paper, we report on the construction of artificial phosphatases via the supramolecular self-assembly of compounds such as an amphiphilic bis(Zn²⁺-cyclen) (cyclen = 1,4,7,10-tetraazacyclododecane) complex, barbital derivatives modified with benzocrown ethers and boronophenyl groups, and a copper(II) ion in a two-phase solvent system. We have developed a hypothesis whereby a mono(4-nitrophenyl)phosphate (MNP) substrate coordinates to the Cu₂(µ-OH)₂ core in supramolecular complexes and is activated either by Lewis acidic units such as alkali metal (Li⁺, Na⁺ and K⁺)-benzocrown ether complexes or by boronophenyl moieties. The findings suggest that supramolecular phosphatase functionalized with a benzo-12-crown-4-Li⁺ complex shows a higher level of activity in the MNP hydrolysis of a two-phase solvent system compared with that of our previous supramolecular phosphatases in terms of hydrolysis activity and catalytic turnover. Full article