Search Results (69)

Heavy metal contamination of seafood remains a critical challenge for public health and industrial processing. Emerging research demonstrates that post-mortem treatments can reduce toxic elements through distinct mechanistic pathways, including diffusion-driven leaching, ligand-specific chelation, thermal redistribution, and physicochemical separation. This article synthesizes recent evidence to evaluate innovative processing approaches through a mechanistic and technology-oriented lens. Acidified marinades promote proton-mediated desorption and diffusion of arsenic, achieving reductions approaching 90%. Chelation strategies using food-grade ligands such as sodium acetate or combined cysteine–EDTA systems show strong affinity for divalent metals, removing up to 88.6% of lead, 80% of nickel, and over 90% of mercury. In parallel, advanced green technologies, such as supercritical CO₂ extraction and electrocoagulation, enable 90–98% removal. Full article

Metal ions exemplify one of the most harmful and environmentally detrimental contaminants of water systems. This work describes the creation of an innovative chelated carbon-doped nickel and titanium oxide (C-NiTiO₂) hybrid as an adsorbent for the effective elimination of metal ions. The dominance of the TiO₂ anatase phase with a ≈ 61 nm crystallite size was verified by XRD and Raman investigation. Morphology investigations exposed polygonal nanoparticles consisting of Ti, C, Ni, and O. The nanostructure exhibited a surface area of 17 m²·g⁻¹, a pore diameter of ≈1.5 nm, and a pore volume of 0.0315 cm³·g⁻¹. The nanostructure was evaluated for the elimination of Zn (II) ions from an aqueous solution. The metal ion adsorption onto the hybrid nanomaterial was described and comprehended using adsorption kinetics and equilibrium models. The adsorption data matched well with the pseudo-second-order kinetics and Langmuir adsorption models, indicating a monolayer chemisorption mechanism and achieving a maximum Zn (II) ion elimination of 369 mg·g⁻¹. Mechanistic investigation indicated film diffusion-controlled adsorption through inner-sphere complexation. The nanosorbent could be regenerated and reused for four rounds without appreciable activity loss, thus demonstrating its potential for water cleanup applications. Full article

Copper and nickel ions play pivotal, albeit distinct, roles as essential trace elements in living systems, and primarily serve as co-factors for a range of enzymes. However, as with all trace metal ions, excessive concentrations can exert adverse toxicological properties. Interestingly, the incorporation of these in cell culture media can establish novel chemical interactions, with their speciation status markedly influencing characteristics, including cell maturation, and cellular uptake mechanisms. Thus, the primary objective of this study was to investigate and determine the speciation status (i.e., complexation) of nickel(II) and copper(II) ions by biomolecules present in RPMI 1640 mammalian cell culture medium using virtually non-invasive high-resolution proton NMR analysis, an investigation of much relevance to now routine studies of their toxicological actions towards cultured cells. Samples of the above aqueous culture medium were ¹H NMR-titrated with increasing added concentrations of 71–670 µmol/L Ni(II)(aq.), and 0.71–6.7, 7.1–67 and 71–670 µmol/L Cu(II)(aq.), in duplicate or triplicate. ¹H NMR spectra were acquired on a JEOL ECZ-600 spectrometer at 298 K. Results demonstrated that addition of increasing concentrations of Ni(II) and Cu(II) ions to the culture medium led to the selective broadening of a series of biomolecule resonances, results demonstrating their complexation by these agents. The most important complexants for Ni(II) were histidine > glutamine > acetate ≈ methionine ≈ lysine ≈ threonine ≈ branched-chain amino acids (BCAAs) > asparagine ≈ aspartate > tyrosine ≈ tryptophan, whereas for Cu(II) they were found to be histidine > glutamine > phenylalanine ≈ tyrosine ≈ nearly all remaining aliphatic metabolites (particularly the wealth of amino acids detectable) > 4-hydroxyphenylacetate (trace culture medium contaminant), in these orders. However, Cu(II) had the ability to influence the linewidths of these signals at much lower added levels (≤7 µmol/L) than that of Ni(II), the broadening effects of the latter occurring at concentrations which were approximately 10-fold greater. Virtually all of these added metal ion-induced resonance modifications were, as expected, reversible on addition of equivalent or excess levels of the chelator EDTA. From this study, changes in the co-ordination sphere of metal ions in physiological environments can give rise to marked modifications in their physicochemical properties (e.g., redox potentials, electronic charges, the potential catalytic generation of reactive oxygen species (ROS), and cell membrane passages). Moreover, given that the above metabolites may also function as potent hydroxyl radical (^●OH) scavengers, these findings suggest that generation of this aggressively reactive oxidant directly from Cu(II) and Ni(II) ions in physiologically-relevant complexes may be scavenged in a ‘site-dependent’ manner. This study is of further relevance to trace metal ion research in general since it enhances our understanding of the nature of their interactions with culture medium biomolecules, and therefore provides valuable information regarding their overall chemical and biological activities, and toxicities. Full article

Selective depression of serpentine remains a major challenge in the flotation of low-grade nickel sulphide ores because serpentine slimes impair concentrate grade and recovery. In this study, four structurally related micromolecular depressants bearing amino and phosphonic functionalities were designed, synthesized and systematically evaluated. Micro-flotation screening (depressant range: 0–20 mg·L⁻¹) and bench-scale tests identified an operational optimum near pH 9 and a reagent dosage of ≈18 mg·L⁻¹; potassium butyl xanthate (PBX) was used as a collector and methyl isobutyl carbinol (MIBC) as a frother. Phosphonate-containing molecules (PMIDA and GLY) delivered the largest gains in pentlandite recovery and concentrate selectivity compared with carboxylate analogues and a benchmark depressant. Mechanistic studies (zeta potential, adsorption isotherms, FT-IR, and XPS) indicated that selective adsorption of amino and phosphonate groups on serpentine occurs via coordination with surface Mg sites and by altering the electrical double layer. The DLVO modelling showed that these reagents generate an increased repulsive barrier, mitigating slime coating and entrainment. Contact-angle measurements confirmed selective hydrophilization of serpentine while pentlandite remained hydrophobic. These findings demonstrate that incorporating targeted phosphonate chelation into small-molecule depressants is an effective strategy to control serpentine interference and to enhance flotation performance. Full article

Understanding how redox-active ligands coordinate to metal centers of different oxidation states is essential for applications ranging from metal remediation and recycling to drug discovery. In this study, coordination complexes of nickel(II), copper(II), and zinc(II) chloride salts were synthesized by mixing the salts with either arylazoformamide (AAF) or arylazothioformamide (ATF) ligands in toluene or methanol. The AAF and ATF ligands coordinate through their 1,3-heterodienes, N=N–C=O and N=N–C=S, respectively, and, due to their known strong binding, the piperidine and pyrrolidine formamide units were selected, as was the electron-donating methoxy group on the aryl ring. A total of 12 complexes were obtained, representing potential chelation events from ligand-driven oxidation of zerovalent metals and/or coordination of oxidized metal salts. The X-ray crystallography revealed a range of coordination patterns. Notably, the Cu(II)Cl₂ complexes, in the presence of ATF, produce [ATF-CuCl]₂ dimers, supporting a potential reduction event at the copper, while other metals with ATF and all metals with AAF remain in the 2+ oxidation state. Hirshfeld analysis was performed on all complexes, and it was found that most interactions across the complexes were dominated by H…H, followed by Cl…H/H…Cl, with metals showing very little to no interaction with other atoms. Spectroscopic techniques such as UV–VIS absorption, NMR (when diamagnetic), and FTIR, in addition to electrochemical studies support the metal–ligand coordination. Full article

In our previous work, we fabricated Ni single-atoms within Beta zeolite (Ni₁@Beta-NO₃⁻) using NiNO₃·6H₂O as a metal precursor without any chelating agents, which exhibited exceptional performance in the selective hydrogenation of furfural. Owing to the confinement effect, the as-encapsulated nickel species appears in the form of Ni⁰ and Ni^δ+, which implies its feasibility in metal catalysis and coordination catalysis. In the study reported herein, we further explored the hydrogen production and olefin oligomerization performance of Ni₁@Beta-NO₃⁻. It was found that Ni₁@Beta-NO₃⁻ demonstrated a high H₂ generation turnover frequency (TOF) and low activation energy (E_a) in a sodium borohydride (NaBH₄) hydrolysis reaction, with values of 331 min⁻¹ and 30.1 kJ/mol, respectively. In ethylene dimerization, it exhibited a high butylene selectivity of 99.4% and a TOF as high as 5804 h⁻¹. In propylene oligomerization, Ni₁@Beta-NO₃⁻ demonstrated high selectivity (75.21%) of long-chain olefins (≥C₆⁺), overcoming the problem of cracking reactions that occur during oligomerization using H-Beta. Additionally, as a comparison, the influence of the metal precursor (NiCl₂) on the performance of the encapsulated Ni catalyst was also examined. This research expands the application scenarios of non-noble metal single-atom catalysts and provides significant assistance and potential for the production of H₂ from hydrogen storage materials and the production of valuable chemicals. Full article

Poly(acrylic acid) (PAA) and hydroxypropylcellulose (HPC) hydrogels were synthesized in the absence of a crosslinker. Chemical crosslinking between PAA and HPC was demonstrated through free radical polymerization by a precipitation reaction in acetone as the solvent. These hydrogels exhibited smaller swelling ratios (1 to 5 g H₂O/g) than homo PAA hydrogels synthesized in water as the solvent. They were swollen in a 0.1 M NaOH solution and subsequently used to remove Ni²⁺ ions from aqueous solutions with concentrations ranging from 1000 to 4000 ppm. The absorption capacity of these hydrogels ranged from 91 to 340 mg of Ni²⁺/g in a rapid 1 h process, and from 122 to 435 mg of Ni²⁺/g in a 24 h process, demonstrating an improvement in Ni²⁺ absorption compared to previously reported hydrogels. The colored 1000 and 2000 ppm Ni²⁺ solutions became clear after treatment, while the PAA-HPC hydrogels turned green due to the uptake of Ni²⁺ ions, which were partially chelated by carboxylate groups as nickel polyacrylate and partially precipitated as Ni(OH)₂, resulting in an average absorption efficiency of 80%. The hydrogel was able to release the absorbed Ni²⁺ upon immersion in an HCl solution, with an average release percentage of 76.4%, indicating its potential for reuse. These findings support the use of PAA-HPC hydrogels for cleaning Ni²⁺-polluted water. The cost of producing 1 g of these hydrogels in laboratory conditions is approximately 0.2 USD. Full article

Polyphenolic compounds, such as flavonoids, possess important structural and physico-chemical characteristics that in combination with their biological properties render them an important class of natural compounds with medicinal prospects. Chrysin is a well-known flavone with antioxidant activity and a multitude of other beneficial properties. The potential of flavonoids to coordinate with metal ions leads to derivatives with enhanced biological profile. Within this framework, four novel heteroleptic complexes of cobalt and nickel with chrysin and the aromatic bidentate chelating agents 2,2′-bipyridine and 1,10-phenanthroline were synthesized, as well as physico-chemically and structurally characterized. The in vitro antioxidant efficiency of the synthesized complexes was examined via the 2,2-diphenyl-1-picrylhydrazyl (DPPH) assay. All complexes showed notable radical scavenging capacity comparable to that of ascorbic acid, providing the incentive for further investigation of their therapeutic potential. Full article

A novel S = 1/2 paramagnetic chelating ligand tert-butyl 5-(p-biphenylyl)-2-pyridyl nitroxide (bppyNO) and its S = 1 nickel(II) ion complex [Ni(bppyNO)₂Br₂] were synthesized. X-ray crystallography revealed a 2p–3d–2p heterospin triad, with half of the molecule being crystallographically independent. A relatively planar chelate geometry with the torsion angle ϕ(Ni-O-N-C_2py) = −10.6(5)° at 300 K becomes significantly out-of-plane distorted with ϕ = −46.9(8) and 26.1(11)° at 90 K accompanied by disorder at the oxygen site. The torsion angle changes, Δϕ = 36° and 37°, are among the largest reported for related compounds. Magnetic measurements indicate gradual and incomplete spin transition-like behavior around 143(2) K. A three-state model involving an intermediate-spin (S_total = 1) state is proposed to explain non-zero χ_mT plateau in a low-temperature region. Density functional theory calculations using the determined structures support the proposed mechanism. Furthermore, geometry optimizations assuming S_total = 0, 1, and 2 are in good agreement with the present model. Full article

Pathogenic bacteria of the genus Leptospira are the etiological agents of leptospirosis, a disease that affects humans and animals worldwide. Despite the increasing number of studies, the mechanisms of leptospiral pathogenesis remain poorly comprehended. In this study, we report various interactions of the LigA7’-13’ and LigB1’-7’ domains with host components. The LigA7’-13’ and LigB1’-7’ were cloned into the pET28a vector, and the recombinant proteins were expressed in E. coli C43 (DE3) and E. coli BL21 (DE3), respectively. Both recombinant protein domains were expressed in soluble form and purified using nickel-chelating chromatography. The rLigA7’-13’ and rLigB1’-7’ domains exhibited binding to several types of integrins, with most interactions occurring in a dose-dependent and saturable manner, consistent with the characteristics of typical receptor-ligand interactions. The recombinant domain LigA7’-13’ demonstrated affinity for the glycosaminoglycans (GAGs) chondroitin-4-sulfate, chondroitin sulfate, heparin, chondroitin sulfate B, and heparan sulfate, while no binding was detected for LigB1’-7’ with these molecules. Both rLigA7’-13’ and rLigB1’-7’ interacted with components of the terminal complement pathway and were capable of recruiting C9 from normal human serum (NHS). These interactions may inhibit the formation of polyC9, ultimately preventing the assembly of the membrane attack complex (MAC). Collectively, our data expand the repertoire of host components that interact with rLigA7’-13’ and rLigB1’-7’, opening new avenues for understanding leptospiral immune evasion and broadening the roles of these domains in bacterial virulence. Full article

This study explores the use of a deep eutectic solvent (DES) composed of choline chloride and pyrogallol (1:1 molar ratio) for the recovery of lithium, cobalt, and nickel from spent lithium-ion battery cathodes based on LiNi_0.33Co_0.33Mn_0.33O₂ (NMC111). The DES exhibits moderate viscosity, intrinsic redox activity, and strong complexation ability, enabling efficient metal dissolution under mild conditions. The effects of both temperature (50–80 °C) and time (up to 12 h) on leaching efficiency were systematically investigated. Optimal leaching parameters—80 °C, 8 h, and a liquid-to-solid ratio of 50—yielded extraction efficiencies of 92% for Li, 85% for Co, and 88% for Ni. Kinetic modeling indicated pseudo-first-order behavior with activation energies of 26.6, 22.1, and 25.2 kJ/mol for Li, Co, and Ni, respectively. Mechanistic analysis confirmed the dual role of pyrogallol as both reducing agent (facilitating Co³⁺ to Co²⁺ conversion) and chelating ligand. Full article

In this study, catalytically active coatings on titanium were synthesized by plasma electrolytic oxidation (PEO) in aqueous electrolytes based on sodium tungstate with the addition of sodium phosphate or sodium borate and chelate complexes of iron, cobalt or nickel. Taking into account the EDX, XPS and XRD data, the oxide–phosphate coatings (PWFe, PWCo, PWNi) contained crystalline titanium oxide and amorphous tungstates and/or phosphates of iron triad metals. Amorphization was facilitated by high phosphorus concentrations (up to 6 at.%). Replacing phosphate with borate in the electrolyte with Ni(II)-EDTA complexes led to the crystallization of WO₃ and NiWO₄ in the PEO coatings (BWNi). All formed PEO coatings were active in reactions of the oxidative desulfurization (ODS) of thiophene and dibenzothiophene and oxidative denitrogenation (ODN) of pyridine, as well as in the simultaneous removal of S- and N-containing substrates from their mixture. The stability of samples with MWO₄ increased in the following series: PWNi < PWCo < PW < PWFe < BWNi. Replacing phosphate with borate in the electrolyte resulted in the preparation of catalysts with enhanced stability and activity. In contrast to PWM catalysts, the BWNi catalyst had selectivity toward the oxidation of pyridine in its mixture with thiophene. Full article

Understanding soil properties that govern physicochemical and biological processes is essential for achieving high crop quality and yield. Organic matter is an important element of soil fertility and fertility in vegetable cultivation. In the process of decomposition of organic matter in the soil, humus of various quality is formed. The quality of humus depends on the content of individual acids (fulvic, humic and hymatomalanic acids) in it, which can affect the binding–chelation of heavy metals, limiting their availability to plants. The conducted studies determined the effect of adding organic matter (high peat, brown coal and wheat straw) to mineral soil on nickel detoxification in radish, its yield, nitrogen management and chloroplast pigments. The studies were conducted for three years in a greenhouse in a container system. The tested substrates were contaminated with nickel in the amount of 50, 75 and 100 mg dm⁻³. It was found that introducing organic matter into mineral soil can affect the reduction as well as the increase in nickel content in edible parts of radish. The type of organic material introduced into mineral soil as a source of organic matter has a significant impact on nickel content in radish. It was shown that nitrate reductase activity (NR) depends to a large extent on the substrate in which the plants are grown as well as on the applied dose of nickel. A similar relationship was demonstrated in the case of changes in the level of chloroplast pigments (chlorophyll a, chlorophyll b and carotenoids). Full article

Recycling of spent lithium-ion batteries is important due to the increasing demand for electric vehicles and efforts to realize a circular economy. There is a need to develop environmentally friendly processes for the refining of nickel, cobalt, and other metals contained in the batteries. Electrodialysis is an appealing method for recycling of battery metals with selective separation and low chemical input. In this study, sodium sulfate was used in an electrodialysis metathesis procedure to sequentially separate EDTA-chelated nickel and cobalt. Replacing hitherto used sulfuric acid with sodium sulfate mitigates membrane fouling caused by precipitation of EDTA. It was possible to separate up to 97.9% of nickel and 96.6% of cobalt at 0.10 M, a 30-times higher concentration than previously reported for electrodialysis of similar solutions. Through the thermally activated persulfate method, new to this application, 99.7% of nickel and 87.0% of cobalt could be precipitated from their EDTA chelates. Impurity behavior during electrodialysis of battery leachates has not previously been described in the literature. It is paramount to remove copper, iron, and phosphorous prior to electrodialysis since they contaminate the nickel product. Aluminum was difficult to remove in the solution purification step and ended up in all electrodialysis products. Full article

Cosmetic products contain numerous metals used as pigments, UV filters, preservatives, antiperspirants and antimicrobial agents, which are responsible for allergic skin reactions, with the most common being nickel. To reduce skin penetration of Ni, innovative pharmaceutical formulations such as lipogels with chelating action against the metal ions themselves can be used. Chelation therapy allows a chelating agent to combine with metal ions to form a stable ring structure called a chelate. The chelate structure is more soluble in water than the toxic metal, which facilitates removal of the toxic metal from the tissue and its excretion by the kidneys. The aim of the following work was to evaluate the chelating properties against nickel ions of different types of lipogels containing flavonoids such as resveratrol and epigallocatechin gallate with chelating activities largely dependent on the number and position of their hydroxyl groups. The results obtained showed that lipogels based on epigallocatechin gallate show high chelating action against nickel, especially at low concentrations. In addition, rheological studies showed an ideal profile to ensure viscoelasticity and swelling of the lipogel within 48 h, confirming reports of 75% epigallocatechin release from the lipogel after 48 h. Tests have shown that lipogels based on epigallocatechin gallate have high chelating action against nickel, especially at low concentrations. Full article