Search Results (2,140)

Metal oxide nanoparticles dispersed in water are difficult to recover because of their small size and colloidal stability. In this study, the interfacial adsorption behavior of Fe₂O₃, CoO, and CuO nanoparticles at hydrophobic ionic liquid (IL)–water interfaces was investigated and compared with that at molecular solvent–water interfaces. When CuO nanoparticle dispersions were shaken with hydrophobic ILs, bis(trifluoromethanesulfonyl)imide ([NTf₂]⁻) salts of 1-butyl-3-methylimidazolium ([BMIm]⁺) and 1-octyl-3-methylimidazolium ([OMIm]⁺), the nanoparticles were removed from the aqueous phase and accumulated at the IL–water interface, while negligible Cu was detected in the bulk IL phase. The removal efficiency decreased with increasing ionic strength below 0.05 mol/dm³ and increased with pH, indicating that electrostatic interactions between charged nanoparticles and the IL–water interface contribute to adsorption. Adsorption isotherms were empirically fitted with the Langmuir equation to estimate the maximum adsorption capacity. For negatively charged Fe₂O₃ and CuO nanoparticles, the maximum adsorption capacities at IL–water interfaces exceeded those at molecular solvent–water interfaces and the theoretical monolayer capacity estimated from nanoparticle size, suggesting multilayer adsorption or aggregation at the interfaces. These results demonstrate the potential of hydrophobic IL–water interfaces for the separation and recovery of metal oxide nanoparticles from aqueous media. Full article

The rapid translocation of pesticide and metal residues in the environment and their entry into the food chain pose a significant risk to human health. Given the high global consumption of honey, quality control emphasizes the need for continuous monitoring and risk assessment. To evaluate contamination levels in honey from northern Croatia, a region with intensive agricultural land use, 38 comb honey and 22 extracted honey samples were collected by purposive one-time sampling in June 2023. These samples were analyzed for 190 pesticides using liquid chromatography–tandem mass spectrometry (LC-MS/MS) and gas chromatography–tandem mass spectrometry (GC-MS/MS), and for 17 trace metal(loid)s using inductively coupled plasma mass spectrometry (ICP-MS). The highest detection frequencies were observed for fipronil-sulfone, trifloxystrobin, and coumaphos in comb honey, and for N-(2,4-dimethylphenyl)-formamide (DMF) and N-(2,4-dimethylphenyl)-N′-methylformamidine (DPMF) in extracted honey. Glyphosate was the only pesticide to exceed the European Union (EU) maximum residue level (MRL) of 0.05 mg/kg in three honey samples. Elemental analysis quantified most target metals, with aluminum (Al), copper (Cu), iron (Fe), manganese (Mn), nickel (Ni) and zinc (Zn) being the most abundant, while silver (Ag), arsenic (As), and selenium (Se) were not detected in this study. None of the samples contained lead (Pb) above the regulatory limit for honey established in the EU (0.1 mg/kg). To ensure food safety, further efforts are required to assess the health risks associated with exposure to these contaminants through consumption of the evaluated food. Full article

This study aimed to develop a novel fluorescent sensor based on Eu³⁺ complex-doped protein crystal (EC-PC) for the efficient detection of metal ions in blood. By meticulously controlling the crystallization and annealing conditions in the co-crystallization strategy, the crystal growth processes were optimized to obtain doped Eu³⁺ complex-co-protein crystalline (EC-PC) structures. Thus, through co-crystallization of hen egg white lysozyme (HEWL) as a model protein and Eu³⁺ complex as fluorescent center, we successfully prepared Eu³⁺ complex-doped-HEWL co-crystals (EC-HC) with excellent fluorescent properties. Further treatment with 4% glutaraldehyde cross-linking enhanced the structural stability of the co-crystals. Moreover, the characteristic of sensitive, selective quenching of EC-PC fluorescence by biologically relevant cations, such as Cu²⁺, Zn²⁺, Mg²⁺, Ca²⁺ and Fe³⁺ ions, set up a smart sensing system in blood. For example, the fluorescence intensity of the crystals at 610 nm, as measured by a UV–visible spectrophotometer, decreases dose-dependently with the concentration of copper ions, thereby validating the sensor’s high sensitivity to copper ion detection. Significantly, we also found that this hybrid protein-based sensor did not induce hemolysis, at various volume concentrations, confirming good anticoagulation in blood. This research not only provides a new perspective on the application of Eu³⁺ complex-doped protein crystals in the field of biosensing but also offers a new strategy for the detection of biologically relevant cations in blood. Future work will focus on further optimizing the sensor’s performance and exploring its potential applications in clinical sample analysis. Full article

Arsenopyrite (FeAsS) is an important sulfide that holds gold in orogenic systems. Its arsenic content is often used as a proxy for gold fertility. However, arsenopyrite from the Um Rus gold deposit in Egypt’s Central Eastern Desert shows a complicated gold distribution that makes simple Au-As correlations hard to make. Integrated electron microprobe analysis (EMPA), laser ablation ICP-MS, and principal component analysis (PCA) reveal three unique textural and geochemical domains. Fine-grained arsenopyrite inclusions within pyrite aggregates (28–31 at% As) are devoid of detectable gold; PCA elucidates 84% of their variance through Fe–S versus Co-As substitution (PC1: 61.8%) and Pb-decoupled variability (PC2: 22.2%), suggesting crystallization from a Co-rich, Au-poor fluid. On the other hand, coarse oscillatory-zoned arsenopyrite can hold up to 6154 ppm of invisible gold. This is because of a moderate Au-As substitution (R = 0.41063, p = 0.08074) that was overprinted by a separate Au-Ag-Sb-Te hydrothermal pulse (Au–Ag: R = 0.97762; Au–Sb: R = 0.97608). PCA finds four parts (72.8% variance): Ag-Cu-As associations (PC1: 25.1%), Te versus Bi-Au signatures (PC2: 17.8%), Fe–S stoichiometry (PC3: 17.1%), and an Au versus Pb-decoupled event (PC4: 12.9%). This shows that minerals formed in more than one stage. Irregular As-rich overgrowths, containing ≤950 ppm gold and lacking significant Au–As correlation (R = −0.14011, p = 0.56726), show PCA (74.3% variance) that highlights S-As contrasts (PC1: 25.2%), Co-Ni enrichment (PC2: 18.8%), Cu-Fe-Ni associations (PC3: 16.2%), and a late Au-decoupled event (PC4: 14.2%), indicating barren recrystallization. These results show that just adding arsenic is not a good way to tell if gold is fertile. The highest amounts of invisible gold, on the other hand, are found in oscillatory-zoned domains with Ag-Sb-Te signatures. This research highlights the importance of combining PCA, geochemistry, and microtextures to differentiate auriferous from barren arsenopyrite, thereby enhancing exploration methodologies for structurally intricate orogenic gold systems. Full article

Luminescent organic–inorganic Cu(I) halide hybrid molecular crystals exhibit remarkable structural diversity and photophysical properties, but their application in aqueous environments is often limited by insufficient stability. Herein, we report portable and reusable photoluminescent sensors based on Cu(I)–I triethylenediamine derivatives [Cu₄I₆(pr-ted)₂] and [Cu₃I₅(bz-ted)₂] (pr-ted = 1-propyl-1,4-diazabicyclo[2.2.2]octan-1-ium; bz-ted = 1-benzyl-1,4-diazabicyclo[2.2.2]octan-1-ium). Their submicrometric particles exhibit intense UV-excited emissions and high photoluminescence quantum yields but limited water stability. To address this limitation, ultrasound sonication was employed to control particle size and produce stable suspensions that can be incorporated into polymeric matrices via 3D printing with photocurable resins or polylactic acid (PLA) films by drop-casting, yielding mechanically robust composites that retain their structural and optical properties. The devices used act as selective turn-off luminescent sensors for Fe³⁺ in aqueous media, with nanomolar detection limits (1.33–1.58 nM) below regulatory thresholds for drinking water. Moreover, [Cu₃I₅(bz-ted)₂] enables tetracycline detection in river water with a limit of detection of 0.038 nM. Mechanistic studies indicate that reversible photoinduced electron transfer is the primary quenching pathway, while composites maintain sensing performance over multiple reuse cycles. Full article

Cs₃Cu₂I₅ single crystals are regarded as promising next-generation scintillators due to their large Stokes shift and low self-absorption characteristics. However, the cost-effective solution growth method faces critical challenges: the instability of colloidal precursors in solutions and the severe oxidation of Cu⁺ during crystal growth. This study innovatively introduces yttrium chloride (YCl₃) as a dual-functional additive to address both issues simultaneously. The hydrolysis of YCl₃ creates a controlled acidic environment, effectively suppressing the oxidation of Cu⁺; meanwhile, it enhances the stability of colloidal precursors by significantly increasing their surface charge and narrowing the particle size distribution. These synergistic effects enable the rapid growth (approximately 100 h) of near-centimeter-sized Cs₃Cu₂I₅ single crystals with high crystallinity, without the need for inert gas protection. The optimized crystals exhibit exceptional performance: a photoluminescence quantum yield (PLQY) of 93.22% ± 0.47%, a scintillation decay time of 210.04 ns, and a light yield of ~738.14 pe/MeV. This YCl₃-mediated growth strategy establishes an efficient approach for the solution-based synthesis of high-quality Cs₃Cu₂I₅ single crystals, holding great significance for advancing high-sensitivity, environment-stable radiation detection applications such as medical diagnostics and nuclear safety monitoring. Full article

Copper flotation tailings are produced in large quantities during ore beneficiation and smelting, yet remain underutilized and can act as persistent sources of potentially toxic elements. Here, we combined XRD-based mineralogical characterization, ICP-OES quantification, Tessier sequential extraction, and pH-dependent batch leaching to elucidate metal occurrence, mobility, and associated ecological risk in tailings from Tongling, Anhui Province. This study systematically analyzed the mineral composition, potentially toxic elements content, chemical fractions, leaching behavior, and ecological risks of copper flotation tailings from the Shuimuchong tailings reservoir in Tongling, Anhui Province. XRD and XRF analyses revealed that calcite, quartz, and garnet were dominant mineral phases in the tailings. Elevated levels of Cu, Cd, Pb, Zn, and As were detected, some of which surpassed both local background concentrations and national soil quality standards. Most potentially toxic elements primarily existed in the residual fraction, indicating low mobility. Leaching experiments revealed that Zn, Cu, and As showed enhanced release under acidic conditions, making them priority risk elements during tailings acidification. Pollution index and ecological risk assessments indicated that the tailings were heavily contaminated, with Cu and Cd as the main risk contributors. The Risk Assessment Code (RAC) evaluation showed that Cd had the highest bioavailability and ecological risk. By clarifying the behavior of pollutants, this study contributes to the effective regulation of environmental hazards and the sustainable use of tailing materials. Full article

Primary aromatic amines (PAAs), such as 4,4′-methylenedianiline (MDA) and 4-chloroaniline (4-CA), are toxic, carcinogenic, and persistent pollutants widely detected in aquatic environments. To address this issue, UiO-66 was modified through nitro functionalization, copper doping, and defect regulation, and further integrated with chitosan (CS) to construct a composite aerogel (CS@CuUiO-66-NO₂) for the removal of MDA and 4-CA from wastewater. The adsorbent demonstrated relatively fast adsorption kinetics (MDA: 6 h; 4-CA: 4 h) and high adsorption capacities (MDA: 643.74 mg·g⁻¹; 4-CA: 491.54 mg·g⁻¹), showing improved performance compared to pristine UiO-66 and many previously reported adsorbents under similar conditions. The enhanced adsorption performance is likely attributed to the synergistic effects of multiple interactions, including hydrogen bonding, π-π interactions, and possible coordination interactions between functional groups of the adsorbent and PAAs. Moreover, the adsorbent maintained good adsorption performance after five adsorption–desorption cycles, with only a slight decrease in efficiency (~8%), and exhibited limited interference from coexisting anions. Overall, this study presents a feasible strategy for designing porous composite adsorbents with favorable reusability for potential applications in aqueous pollutant remediation. Full article

This study evaluates the impact of recirculating aquaponic cultivation on the biochemical, mineral, and antioxidant profiles of Swiss chard (Beta vulgaris var. cicla) integrated with Nile tilapia (Oreochromis niloticus), which serves as a source of nutrients through metabolic waste transformation within the system. Water quality parameters and microbiological testing confirmed efficient nitrification and system safety, with no Escherichia coli detected. Results showed that aquaponic cultivation yields a high nutritional value of Swiss chard, yielding high crude protein (31.4% DW) and mineral-rich biomass (ash 22.8% DW). Substantial concentrations of essential elements were recorded, including Ca, Mg, Fe (253.7 mg/kg DW), Zn, and Cu, suggesting high ionic bioavailability in the recirculating system. Physiological stability was reflected by a chlorophyll a content of 4.74 mg/g DW. Furthermore, the plants exhibited a robust phytochemical profile, with total phenolics (4.13 mg GAE/g DW) and flavonoids (5.18 mg QE/g DW) driving strong antioxidant activity (93.1% ABTS inhibition). These findings demonstrate that integrated aquaponic systems function as effective nutrient bioreactors, supporting high plant functional quality while supporting sustainable food production. The results validate aquaponics as a viable, climate-smart strategy for high-quality leafy vegetable cultivation within a circular bioeconomy framework. Full article

Continental remobilization is a crucial driver of metallogenesis and the formation of ore deposits. Some of the world’s largest mineral deposits of the economically valuable elements tin (Sn), tungsten (W), gold (Au), copper (Cu), lead (Pb), and zinc (Zn) formed during the Mesozoic Era. Additionally, the chemistry and distribution of the elements Sn and W have been investigated in previous studies to understand planetary formation and differentiation processes. These two elements are largely co-located during certain South China Mesozoic metallogenic events but are not co-located during other time periods in the same regions. Here, we investigated the mineral chemistry network similarities and dissimilarities of Sn and W to understand their mineral formation and distribution during the Mesozoic Era and throughout Earth history. Mineral chemistry network community detection analysis and electronegativity associations among mineral constituent elements of Sn minerals and W minerals indicate that the elements have similar chemistry among their oxide minerals. However, Sn forms a much wider range of minerals that also contain S compared to W, which occurs in a limited number of S-containing minerals. The divergent constituent element interactions among S-containing Sn minerals and W minerals reflect the redox sensitivity and importance of oxygen (O) fugacity in Sn mineral formation. Conversely, extensive W mineral deposits are known to form at both high and low O fugacities. The similarities and differences between the mineral chemistry networks of Sn and W reflect the mineral distribution of the two elements in the Sn-W mineralization event from 160 to 139 Ma vs. the Sn–uranium (U) mineralization event from 125 to 98 million years ago (Ma). The mineral chemistry and distribution of Mesozoic Sn and W deposits illustrate the contrasting importance of redox and O fugacity on the mineral formation of different elements, and the dynamic crustal evolution that took place during this period of Earth history. Full article

Laccase plays an important role in the detection and degradation of phenolic compounds, but it is limited by its cost and stability. In this study, the laccase-like property of copper peptide (GHK-Cu) has been revealed. In terms of enzymatic reaction kinetics, GHK-Cu has a V_max of 1.735 × 10⁻⁴ mM·s⁻¹ and a K_m of 0.061 mM, demonstrating good substrate affinity and excellent catalytic efficiency. Then, a colorimetry was developed for rapid detection of epinephrine (EP) and 2-aminophenol (2-AP). The linear response range of EP is 20–240 μM, with a limit of detection (LOD) of 9.5 μM. The linear response ranges of 2-AP are 14–100 μM (in ultrapure water) and 2–120 μM (in seawater), with LODs of 2.56 μM and 1.65 μM. In addition, combined with a smartphone platform, a cotton-based sensor has been developed for the detection of 2-AP in seawater. The linear response ranges are 0–0.2 mM and 0.2–1 mM, with LOD of 0.033 mM. The structure of GHK-Cu provides a reference for the development of novel laccase mimetic enzymes. The constructed colorimetry offers an option for the rapid detection of phenolic compounds, and the developed cotton-based sensor enabled rapid and portable detection of 2-AP. 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

This is the first systematic review evaluating Black Sea plankton as biosensor organisms for Biological Early Warning Systems (BEWS)—real-time monitoring approaches that detect sublethal behavioral or physiological responses to pollutants before irreversible ecosystem damage occurs. The systematic literature review was guided by the PRISMA (Preferred Reporting Items for Systematic Reviews and Meta-Analyses) approach, ensuring methodological transparency and applicability. A total of 140 publications from databases (Web of Science Core Collection, Scopus, PubMed, and Google Scholar databases) were included in the final analysis. We assess nine native planktonic taxa as candidates for automated video-based water quality monitoring, using a multi-criteria framework encompassing biological sensitivity, technical detectability, and practical feasibility. Three species emerge as the most suitable candidates: Aurelia aurita as a universal indicator (sensitive to copper, surfactants, petroleum, and microplastics; its large size enables standard video detection); Acartia tonsa for trace contamination (reproductive toxicity at metal concentrations 4–33× below regulatory standards); and Mnemiopsis leidyi for metal-specific discrimination (bioluminescent responses: 650% Zn, 430% Cu, and 350% Hg at 0.001 mg/L). Analysis of 140 publications reveals critical gaps: 33% of species lack toxicological data, 95% of studies test single toxicants despite natural mixture exposure, and microplastic methodology varies 1000-fold in particle size. Threshold analysis suggests planktonic sublethal stress at “safe” concentrations under current standards, suggesting inadequate protection of marine food webs. A complementary monitoring approach integrating these species with computer vision algorithms offers autonomous early-warning capability for Black Sea environmental management. Full article

The dose–response relationship for fluoride (F⁻) exposure remains largely unexplored. Hence, the current study assessed the hepatotoxic and nephrotoxic effects of subacute exposure (28 days) to increasing F⁻ concentrations in Wistar rats via the benchmark dose (BMD5) method. Thirty male rats were assigned to six groups (n = 5): a control group (tap water) along with five groups that received F⁻ via drinking water at increasing concentrations (10, 25, 50, 100, and 150 mg/L). F⁻ toxicity was determined via water intake, weight gain, histological analyses, redox status, and essential element levels. PROASTweb 70.1 software was utilized to investigate the external and internal F⁻ dose–response relationships. Specified major cytoarchitecture damage and superoxide anion (O₂·⁻), total oxidative status (TOS), superoxide dismutase (SOD) activity, total thiol groups (SH), and advanced oxidation protein product (AOPP) level alterations were detected in both sets of tissues. Moreover, F⁻ caused an imbalance in copper (Cu), zinc (Zn), iron (Fe), and manganese (Mn). The most sensitive parameters were O₂·⁻ (0.06 mg F⁻/kg) in the liver and AOPP (6.5 × 10⁻⁶ mg F⁻/L) in the kidneys. These findings contribute to the limited risk assessment of fluorides and highlight the dose-dependent relationship between redox status parameters and bioelements in the liver and kidneys. Full article

Owing to the high stability and low cost of nanozymes, they have been extensively investigated and reported. In this work, highly active CeO₂ nanoflowers were first prepared and then different metal elements were doped into the CeO₂ nanoflower matrix via a novel synthesis method to fabricate M-CeO₂ (M = Cu, Fe, Co, Mn, La) nanomaterials. Mn-CeO₂ with the highest peroxidase-like activity was selected via systematic screening, the as-prepared Mn-CeO₂ nanocomposites exhibited enhanced enzyme-like activity due to the strong metal-support interaction. This article explored the effects of doping ratio, pH, temperature, reaction time, and material concentration on its activity. A simple sensitive and selective colorimetric method was established and successfully used to detect hydrogen peroxide and ascorbic acid sensitively. When the hydrogen peroxide (H₂O₂) concentration is within the 2.0–120.0 μM range, the UV-visible absorbance at 652 nm was associated linearly with the H₂O₂ concentration, R² = 0.9959, LOD = 1.7 μM (S/N = 3). The absorbance of the reaction system showed a good linear relationship with the ascorbic acid (AA) concentration (1.0–40.0 μM, R² = 0.992), LOD = 0.98 μM (S/N = 3). This study provides an effective way to construct efficient nanozymes and their potential applications in sensing and detection. Full article