RESUMEN
BACKGROUND: Remediation of heavy metal-contaminated water using phytoremediation with accumulator aquatic plants is a promising low-cost emerging technology that adapts very well to the surrounding ecosystem. For the system to work efficiently, metal-saturated plants must be replaced, producing a potentially toxic amount of biomass that is usually stored dry to reduce its volume. The speciation of the high metal content in this biomass is crucial to define its final destination. This work explores the application of synchrotron-based EDIXS (Energy Dispersive Inelastic X-ray Scattering) to monitor the speciation of copper in regional aquatic plants from a laboratory-scale phytoremediation system. RESULTS: The phytofiltration system utilized Lemna minor L. and Salvinia biloba Raddi species grown under controlled conditions of light and nutrient availability. Both species are known hyperaccumulators of copper and are prevalent in lakes and rivers across South America. The validation of EDIXS was previously carried out by comparing the results of copper standard samples with those obtained by XANES. The findings revealed that both plant species retained copper in chemical complexes exhibiting octahedral coordination with a Cu valence of 2. Notably, differences emerged between the leaves and roots of Lemna minor L., suggesting a more pronounced adsorption of copper in its leaves, a trend that intensified with exposure. In opposite, for Salvinia the differences between leaves and roots suggests the presence of specific protective mechanisms to cope the copper exposure. Surprisingly, no significant dependence on copper concentration of the aqueous media was observed for either species. SIGNIFICANCE AND NOVELTY: These promising results endorse the viability of the proposed methodology in identifying the most effective fate of biomass generated in phytoremediation systems. EDIXS provides a valid tool for performing local copper speciation in aquatic plants with sufficient selectivity to identify subtle differences in various biological tissues. The simplicity of this methodology renders it a valuable tool for advancing our comprehension of metal speciation within waste biomass, thereby holding significant implications for the development of environmental remediation strategies.
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Biodegradación Ambiental , Biomasa , Cobre , Cobre/química , Cobre/metabolismo , Cobre/análisis , Contaminantes Químicos del Agua/análisis , Contaminantes Químicos del Agua/metabolismo , Contaminantes Químicos del Agua/química , Araceae/metabolismo , Araceae/química , FiltraciónRESUMEN
Selective recognition and sensing of catecholamine-based neurotransmitters by fluorescent synthetic receptors capable of operating in pure water is a central topic of modern supramolecular chemistry that impacts biological and analytical chemistry. Despite advances achieved in the recognition of some neurotransmitters such as dopamine, little effort has been invested in the optical recognition of other neurotransmitters of paramount importance in biochemistry and medicinal chemistry such as the drug L-dihydroxy-phenylalanine (levodopa). Herein, a cationic Cu(II)-terpyridine complex bearing an intramolecular fluorescent quinolinium ring covalently linked to phenylboronic acid (CuL1) was synthesized, structurally described by single-crystal X-ray diffraction and studied in-depth as a fluorescent receptor for neurotransmitters in water. The complex CuL1 was designed to act as a receptor for levodopa through two Lewis acids of different natures (Cu(II) and B atoms) as cooperative binding points. The receptor CuL1 was found to have a strongly acidified -B(OH)2 group (pKa = 6.2) and exceptionally high affinity for levodopa (K = 4.8 × 106 M-1) with selectivity over other related neurotransmitters such as dopamine, epinephrine, norepinephrine and nucleosides in the micromolar concentration range at physiological pH. Such levodopa affinity/selectivity for a boronic acid-based receptor in water is still rare. On the basis of spectroscopic tools (11B NMR, UV-vis, EPR, and fluorescence), high-resolution ESI-MS, crystal structure, and DFT calculations, the interaction mode of CuL1 with levodopa is proposed in a 1 : 1 model using two-point recognition involving a boronate-catechol esterification and a coordination bond Cu(II)-carboxylate. Furthermore, a visual sensing ensemble was constructed using CuL1 and the commercial fluorescent dye eosin Y. Levodopa is efficiently detected by the displacement of the eosin Y bound to the Cu(II)-receptor, monitoring its green emission. The use of Cu(II)-boronate complexes for fast and selective neurotransmitter sensing was unexplored until now.
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Ácidos Borónicos , Complejos de Coordinación , Cobre , Agua , Ácidos Borónicos/química , Agua/química , Cobre/química , Complejos de Coordinación/química , Complejos de Coordinación/síntesis química , Modelos Moleculares , Levodopa/química , Estructura Molecular , Sitios de UniónRESUMEN
An integrated chemical and mineralogical characterization approach was applied to smelter wastes collected from 50-year-old dump sites in Argentina. Characterization included pseudo-total element concentrations, acid generation/neutralization potential, sequential extractions, pH-dependent leaching kinetics, and mineralogical analysis of all residues. These analyses provided detailed information on the reactivity of the minerals in the waste material and associated metal release. Cadmium and Zn were the elements of greatest environmental concern due to their high mobility. On average, the release of Zn and Cd in pH-dependent leaching essays reached 17.6% (up to 5.24 mg g-1) and 52.7% (up to 0.02 mg g-1) of the pseudo-total content, respectively. Moreover, Cd and Zn were also the metals that showed the higher proportions of labile fractions associated to the adsorbed and exchangeable fraction (60-92% for Cd and 19-38% for Zn). Since Cd and Zn concentrations in the residue are not high enough to form their own minerals, a large proportion of these elements would be weakly adsorbed on Fe oxyhydroxides. In contrast, the low release of Cu, Pb and Fe would be associated with these elements being incorporated into the crystalline structure of insoluble or very poorly soluble minerals. Lead is incorporated into plumbojarosite and anglesite. Copper was mainly in association with Fe oxyhydroxides and may also have been incorporated into the plumbojarosite structure. The latter could act as a sink especially for Pb under the acidic conditions of the smelter residue. Despite the elevated concentrations of Pb observed in the residue, it showed a very low mobility (≈0.1%), indicating that it is mostly stabilized. Nevertheless, the smelter residue is a continuous source of metals requiring remediation.
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Cadmio , Cobre , Hierro , Plomo , Zinc , Argentina , Plomo/análisis , Plomo/química , Cadmio/análisis , Cadmio/química , Zinc/análisis , Zinc/química , Hierro/química , Hierro/análisis , Cobre/análisis , Cobre/química , Metales Pesados/análisis , Metales Pesados/química , Metalurgia , Monitoreo del Ambiente , Fraccionamiento Químico , Minerales/química , Contaminantes Químicos del Agua/análisis , Contaminantes Químicos del Agua/química , Contaminantes del Suelo/análisis , Contaminantes del Suelo/químicaRESUMEN
To ascertain the bioinorganic chemistry of metals conjugated with quinones, the complexes [Ag(ATV)(PPh3)2] (1), [Au(ATV)(PPh3)]·2H2O (2), and [Cu(ATV)(PPh3)2] (3) were synthesized by the coordination of the antimalarial naphthoquinone atovaquone (ATV) to the starting materials [Ag(PPh3)2]NO3, [Au(PPh3)Cl], and [Cu(PPh3)2NO3], respectively. These complexes were characterized by analytical and spectroscopical techniques. X-ray diffraction of single crystals precisely confirmed the coordination mode of ATV to the metals, which was monodentate or bidentate, depending on the metal center. Both coordination modes showed high stability in the solid state and in solution. All three complexes showed negative log D values at pH 5, but at pH 7.4, while complex 2 continued to have a negative log D value, complexes 1 and 3 displayed positive values, indicating a more hydrophilic character. ATV and complexes 1-3 could bind to ferriprotoporphyrin IX (FePPIX); however, only complexes 1-3 could inhibit ß-hematin crystal formation. Phenotype-based activity revealed that all three metal complexes are able to inhibit the growth of P. falciparum with potency and selectivity comparable to those of ATV, while the starting materials lack this activity. The outcomes of this chemical design may provide significant insights into structure-activity relationships for the development of new antimalarial agents.
Asunto(s)
Antimaláricos , Atovacuona , Complejos de Coordinación , Hemo , Plasmodium falciparum , Antimaláricos/farmacología , Antimaláricos/química , Antimaláricos/síntesis química , Plasmodium falciparum/efectos de los fármacos , Complejos de Coordinación/farmacología , Complejos de Coordinación/química , Complejos de Coordinación/síntesis química , Hemo/química , Atovacuona/farmacología , Atovacuona/química , Atovacuona/síntesis química , Estructura Molecular , Cobre/química , Cobre/farmacología , Plata/química , Plata/farmacología , Oro/química , Oro/farmacología , Fosfinas/química , Fosfinas/farmacología , Pruebas de Sensibilidad Parasitaria , Relación Estructura-Actividad , Modelos Moleculares , HumanosRESUMEN
OBJECTIVE: The aim of this study was to evaluate the effect of an adhesive loaded with 0.2 % copper (Cu) and 5 % zinc oxide (ZnO) nanoparticles (Nps) on its adhesive properties and enzymatic activity at the hybrid layer ex vivo in a randomized clinical model. METHODS: Fifteen patients participated in this study, and a total of 30 third molars were used. Occlusal cavities (4 × 4 × 2 mm) were made in each tooth, and randomly divided into 2 groups: (i) Experimental group: commercial adhesive loaded with 0.2wt % CuNps and 5wt % ZnONps; and (ii) Control Group: non-loaded commercial adhesive. Teeth were restored with resin composite. Thirty days later, extractions were performed. Extracted teeth were longitudinally sectioned. Nps in powder were characterized by field emission scanning electron microscope (FE-SEM) and energy dispersive X-ray (EDX) analysis. Microtensile bond strength (µTBS), degree of conversion (DC), and nanoleakeage (NL) tests were executed. In situ zymography (Zym) was performed to evaluate the gelatinolytic activity at the hybrid layer. Student's t-test (α = 0.05) was applied for all tests. RESULTS: µTBS and DC did not show significant differences (p > 0.05) between both groups. However, NL and gelatinolytic activity at the hybrid layer showed significant values (p < 0.05) for experimental group in comparison with control group. CONCLUSION: The addition of 0.2 % CuNps and 5 % ZnONps to a universal adhesive decreases NL and gelatinolytic activity at the hybrid layer, without jeopardizing its adhesive properties. SIGNIFICANCE: This randomized clinical trial with ex vivo analysis demonstrate that a commercial adhesive modified with 0.2wt % Cu and 5wt % ZnO Nps that does not affect its adhesive properties, reducing gelatinolytic activity and nanoleakage at the hybrid layer, which should contribute to an improvement of long term bonding-dentine clinical performance.
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Resinas Compuestas , Cobre , Recubrimiento Dental Adhesivo , Microscopía Electrónica de Rastreo , Resistencia a la Tracción , Óxido de Zinc , Humanos , Óxido de Zinc/química , Cobre/química , Recubrimiento Dental Adhesivo/métodos , Resinas Compuestas/química , Nanopartículas/química , Recubrimientos Dentinarios/química , Dentina/efectos de los fármacos , Dentina/enzimología , Ensayo de Materiales , Masculino , Cementos de Resina/química , Adulto , Femenino , Propiedades de Superficie , Cementos Dentales/química , Tercer Molar , Restauración Dental Permanente/métodos , Espectrometría por Rayos XRESUMEN
The success of a classic inorganic coordination compound, Cisplatin, cis-[Pt(NH3)2Cl2], as the first anticancer metallodrug started a field of research dedicated to discovering coordination compounds with antitumor activity, encompassing various metals. Among these, copper complexes have emerged as interesting candidates to develop drugs to treat cancer. In this work, mixed ligand complexes of Cu(II) with diimines (phenanthroline or 4-methylphenanthroline) and 3-(4-hydroxyphenyl)propanoate, phenylcarboxylate or phenylacetate were synthesized. They were characterized in the solid state, including a new crystal structure of [Cu2(3-(4-hydroxyphenyl)propanoate)3(phenanthroline)2]Cl·H2O. The obtained complexes presented a variety of stoichiometries. In solution, complexes were partially dissociated in the corresponding Cu-diimine complex. The complexes bound to the DNA by partial intercalation and groove binding, as assessed by Circular Dichroism, relative viscosity change and UV-Vis titration. The cytotoxicity of the complexes was determined in vitro on MDA-MB-231, MCF-7 (human metastatic breast adenocarcinomas, the first triple negative), MCF-10A (breast nontumoral), A549 (human lung epithelial carcinoma), and MRC-5 (human nontumoral lung epithelial cells), finding an activity higher than that of Cisplatin, although with less selectivity.
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Antineoplásicos , Complejos de Coordinación , Cobre , Fenantrolinas , Humanos , Cobre/química , Fenantrolinas/química , Fenantrolinas/farmacología , Antineoplásicos/farmacología , Antineoplásicos/química , Antineoplásicos/síntesis química , Complejos de Coordinación/farmacología , Complejos de Coordinación/química , Complejos de Coordinación/síntesis química , Línea Celular Tumoral , Ligandos , ADN/química , ADN/metabolismo , Células A549 , Ácidos Carboxílicos/química , Ácidos Carboxílicos/farmacología , Neoplasias/tratamiento farmacológico , Neoplasias/metabolismo , Células MCF-7RESUMEN
Triple-negative breast cancer (TNBC), accounting for 15-20% of all breast cancers, has one of the poorest prognoses and survival rates. Metastasis, a critical process in cancer progression, causes most cancer-related deaths, underscoring the need for alternative therapeutic approaches. This study explores the anti-migratory, anti-invasive, anti-tumoral, and antimetastatic effects of copper coordination compounds Casiopeína IIIia (CasIIIia) and Casiopeína IIgly (CasIIgly) on MDA-MB-231 and 4T1 breast carcinoma cell lines in vitro and in vivo. These emerging anticancer agents, mixed chelate copper(II) compounds, induce apoptosis by generating reactive oxygen species (ROS) and causing DNA damage. Whole-transcriptome analysis via gene expression arrays indicated that subtoxic concentrations of CasIIIia upregulate genes involved in metal response mechanisms. Casiopeínas® reduced TNBC cell viability dose-dependently and more efficiently than Cisplatin. At subtoxic concentrations (IC20), they inhibited random and chemotactic migration of MDA-MB-231 and 4T1 cells by 50-60%, similar to Cisplatin, as confirmed by transcriptome analysis. In vivo, CasIIIia and Cisplatin significantly reduced tumor growth, volume, and weight in a syngeneic breast cancer model with 4T1 cells. Furthermore, both compounds significantly decreased metastatic foci in treated mice compared to controls. Thus, CasIIIia and CasIIgly are promising chemotherapeutic candidates against TNBC.
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Antineoplásicos , Cobre , Neoplasias de la Mama Triple Negativas , Neoplasias de la Mama Triple Negativas/tratamiento farmacológico , Neoplasias de la Mama Triple Negativas/patología , Neoplasias de la Mama Triple Negativas/metabolismo , Animales , Humanos , Femenino , Cobre/química , Ratones , Antineoplásicos/farmacología , Antineoplásicos/química , Línea Celular Tumoral , Quelantes/farmacología , Apoptosis/efectos de los fármacos , Ensayos Antitumor por Modelo de Xenoinjerto , Complejos de Coordinación/farmacología , Complejos de Coordinación/química , Complejos de Coordinación/uso terapéutico , Movimiento Celular/efectos de los fármacos , Especies Reactivas de Oxígeno/metabolismo , Proliferación Celular/efectos de los fármacos , Supervivencia Celular/efectos de los fármacos , Ratones Endogámicos BALB C , Daño del ADN/efectos de los fármacosRESUMEN
This work describes determining urea in milk samples using a multicommuted approach with a urease enzyme immobilized in bacterial cellulose and solid MOF as a colorimetric reagent. The Cu(2+)-MOF was characterized by FTIR spectroscopy, XRD, and SEM. The urea quantification was based on the urea hydrolysis reaction catalyzed by urease and reacted with Cu(2+)-MOF forming [Cu(NH3)4]2+, monitored at 450 nm. Linear responses were obtained from 1.0 to 50.0 mg dL-1 urea (R = 0.9959, n = 11), detection and quantitation limits of 0.082 mg dL-1 and 0.272 mg dL-1 respectively, analytical frequency of 8 determinations per hour, 0.8 mL sample solution consumption. Potential interfering studies have shown the selectivity of the proposed method. Addition and recovery tests were performed obtaining variation from 90 to 103%. Applying the F-test and t-test, the results showed no significant difference at the 95% confidence level Comparing the proposed and the reference method.
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Celulosa , Colorimetría , Cobre , Enzimas Inmovilizadas , Leche , Urea , Ureasa , Ureasa/química , Leche/química , Animales , Colorimetría/métodos , Enzimas Inmovilizadas/química , Celulosa/química , Cobre/química , Urea/química , Urea/análisis , Estructuras Metalorgánicas/química , Bovinos , Espectrofotometría , Bacterias/enzimología , Bacterias/química , Bacterias/aislamiento & purificaciónRESUMEN
Advanced Oxidation Processes (AOPs) offer promising methods for disinfection by generating radical species like hydroxyl radicals, superoxide anion radicals, and hydroxy peroxyl, which can induce oxidative stress and deactivate bacterial cells. Photocatalysis, a subset of AOPs, activates a semiconductor using specific electromagnetic wavelengths. A novel material, Cu/Cu2O/CuO nanoparticles (NPs), was synthesized via a laser ablation protocol (using a 1064 nm wavelength laser with water as a solvent, with energy ranges of 25, 50, and 80 mJ for 10 min). The target was sintered from 100 °C to 800 °C at rates of 1.6, 1.1, and 1 °C/min. The composite phases of Cu, CuO, and Cu2O showed enhanced photocatalytic activity under visible-light excitation at 368 nm. The size of Cu/Cu2O/CuO NPs facilitates penetration into microorganisms, thereby improving the disinfection effect. This study contributes to synthesizing mixed copper oxides and exploring their activation as photocatalysts for cleaner surfaces. The electronic and electrochemical properties have potential applications in other fields, such as capacitor materials. The laser ablation method allowed for modification of the band gap absorption and enhancement of the catalytic properties in Cu/Cu2O/CuO NPs compared to precursors. The disinfection of E. coli with Cu/Cu2O/CuO systems serves as a case study demonstrating the methodology's versatility for various applications, including disinfection against different microorganisms, both Gram-positive and Gram-negative.
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Cobre , Escherichia coli , Cobre/química , Escherichia coli/efectos de los fármacos , Catálisis , Nanopartículas del Metal/química , Rayos Láser , Oxidación-Reducción , Desinfección/métodos , LuzRESUMEN
Poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) nanofibers embedded with borate glasses of 45B5 composition doped with Co2+, Cu2+, and Zn2 +(46.1 B2O326.9-X CaO24.4 Na2O2.6 P2O5, X CoO/CuO/ZnO mol % (X = 0-5)) were produced by electrospinning for wound healing applications. Prior to their addition, the glasses exhibited two broad halos typical of a vitreous borate network, which were mainly composed of ring-type metaborate structural units. The particle distribution in the PHBV nanofibers embedded with 45B5 borate bioactive glasses is present in isolated and agglomerated states, being partially coated by a polymeric layer-except for the cobalt-doped glass, which resulted in a successful encapsulation with 100% embedding efficiency. The incorporation of the glasses reduced the PHBV crystallinity degree and its decomposition temperature, as well as its mechanical properties, including Young's modulus, tensile strength, and elongation at break. The neat PHBV fibers and those containing the cobalt-doped glasses demonstrated great cytocompatibility with human keratinocytes (HaCat), as suggested by the high cell viability after 7 days of exposure. Further studies are needed to fully understand the wound healing potential of these fibers, but our results significantly contribute to the area.
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Vendajes , Boratos , Cobalto , Cobre , Poliésteres , Zinc , Humanos , Cobre/química , Cobalto/química , Poliésteres/química , Boratos/química , Zinc/química , Vidrio/química , Ensayo de Materiales , Cicatrización de Heridas , Nanofibras/química , Línea Celular , PolihidroxibutiratosRESUMEN
In this work, a polyhedral silsesquioxane (POSS) was used as an engineered drug delivery system for two oxindolimine-copper(II) anticancer complexes, [Cu(isaepy)]+ and [Cu(isapn)]+. The interest in hybrid POSS comes from the necessity of developing materials that can act as adjuvants to improve the cytotoxicity of non-soluble metallodrugs. Functionalization of POSS with a triazole ligand (POSS-atzac) permitted the anchorage of such copper complexes, producing hybrid materials with efficient cytotoxic effects. Structural and morphological characterizations of these copper-POSS systems were performed by using different techniques (IR, NMR, thermogravimetric analysis). A combination of continuous-wave (CW) and pulsed EPR (HYSCORE) spectroscopies conducted at the X-band have enabled the complete characterization of the coordination environment of the copper ion in the POSS-atzac matrix. Additionally, the cytotoxic effects of the loaded materials, [Cu(isapn)]@POSS-atzac and [Cu(isaepy)]@POSS-atzac, were assessed toward melanomas (SK-MEL), in comparison to non-tumorigenic cells (fibroblast P4). Evaluation of their nuclease activity or ability to facilitate cleavage of DNA indicated concentrations as low as 0.6 µg mL-1, while complete DNA fragmentation was observed at 25 µg mL-1. By using adequate scavengers, investigations on active intermediates responsible for their cytotoxicity were performed, both in the absence and in the presence of ascorbate as a reducing agent. Based on the observed selective cytotoxicity of these materials toward melanomas, investigations on the reactivity of these complexes and corresponding POSS-materials with melanin, a molecule that contributes to melanoma resistance to chemotherapy, were carried out. Results indicated the main role of the binuclear copper species, formed at the surface of the silica matrix, in the observed reactivity and selectivity of these copper-POSS systems.
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Antineoplásicos , Complejos de Coordinación , Cobre , Melanoma , Compuestos de Organosilicio , Cobre/química , Cobre/farmacología , Antineoplásicos/farmacología , Antineoplásicos/química , Humanos , Melanoma/tratamiento farmacológico , Melanoma/patología , Compuestos de Organosilicio/química , Compuestos de Organosilicio/farmacología , Complejos de Coordinación/química , Complejos de Coordinación/farmacología , Complejos de Coordinación/síntesis química , Línea Celular Tumoral , Sistemas de Liberación de Medicamentos , Supervivencia Celular/efectos de los fármacos , Portadores de Fármacos/química , Ensayos de Selección de Medicamentos AntitumoralesRESUMEN
We report the discovery that the molecule 1-(pyridin-2-ylmethylamino)propan-2-ol (HL) can reduce oxidative stress in neuronal C6 glioma cells exposed to reactive oxygen species (O2-â¢, H2O2, and â¢OH) and metal (Cu+) stress conditions. Furthermore, its association with Cu2+ generates [Cu(HL)Cl2] (1) and [Cu(HL)2](ClO4)2 (2) complexes that also exhibit antioxidant properties. Potentiometric titration data show that HL can coordinate to Cu2+ in 1:1 and 1:2 Cu2+:ligand ratios, which was confirmed by monocrystal X-ray studies. The subsequent ultraviolet-visible, electrospray ionization mass spectrometry, and electron paramagnetic resonance experiments show that they can decompose a variety of reactive oxygen species (ROS). Kinetic studies revealed that 1 and 2 mimic the superoxide dismutase and catalase activities. Complex 1 promotes the fastest decomposition of H2O2 (kobs = 2.32 × 107 M-1 s-1), efficiently dismutases the superoxide anion (kcat = 3.08 × 107 M-1 s-1), and scavenges the hydroxyl radical (RSA50 = 25.7 × 10-6 M). Density functional theory calculations support the formation of dinuclear Cu-peroxide and mononuclear Cu-superoxide species in the reactions of [Cu(HL)Cl2] with H2O2 and O2â¢-, respectively. Furthermore, both 1 and 2 also reduce the oxidative stress of neuronal glioma C6 cells exposed to different ROS, including O2â¢- and â¢OH.
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Antioxidantes , Complejos de Coordinación , Cobre , Estrés Oxidativo , Cobre/química , Cobre/farmacología , Estrés Oxidativo/efectos de los fármacos , Complejos de Coordinación/química , Complejos de Coordinación/farmacología , Complejos de Coordinación/síntesis química , Antioxidantes/farmacología , Antioxidantes/química , Antioxidantes/síntesis química , Teoría Funcional de la Densidad , Especies Reactivas de Oxígeno/metabolismo , Catálisis , Animales , Estructura Molecular , Línea Celular Tumoral , Ratas , HumanosRESUMEN
Printed circuit boards, which make up part of waste from electrical and electronic equipment, contain elements that can be economically reused, such as copper, silver, gold, and nickel, as well as metals that are harmful to the environment and health, such as lead, mercury, and cadmium. Thus, through recycling this scrap, materials that would otherwise be discarded can be reinserted as secondary raw materials to produce new consumer goods through urban mining. In this context, the synthesis of nanoparticles shows promise as it allows the reinsertion of these materials in the manufacture of new products. Therefore, this study used obsolete computer motherboards as a secondary material to obtain copper to produce nanoparticles of this metal. From a solution based on the leach liquor of this scrap, a purification route using solvent extraction was defined and applied to the real leach liquor. Applying the hydroxyoxime extractant at a dilution of 20% (v/v) in kerosene, A/O of 1/1, 298 K, and 0.25 h of contact during extraction, and stripping in H2SO4 (2 M), 298 K, 0.25 h, W/O ratio of 3/1, and two theoretical countercurrent stages, a solution containing more than 95% of the copper in the leach liquor could be obtained with less than 1% of contaminants. From this purified liquor, nanoparticles containing copper and metallic copper oxides and hydroxides were produced, with an average size of 84 nm, at pH 11, 3 h of hot stirring, volume of 0.015 L of ascorbic acid (0.50 M) and 0.015 L of precursor solution (0.03 M Cu), and temperature (343 K).
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Cobre , Solventes , Cobre/química , Solventes/química , Reciclaje , Nanopartículas del Metal/química , Residuos Electrónicos , Nanopartículas/químicaRESUMEN
Industrialization has brought many environmental problems since its expansion, including heavy metal contamination in water used for agricultural irrigation. This research uses microbial fuel cell technology to generate bioelectricity and remove arsenic, copper, and iron, using contaminated agricultural water as a substrate and Bacillus marisflavi as a biocatalyst. The results obtained for electrical potential and current were 0.798 V and 3.519 mA, respectively, on the sixth day of operation and the pH value was 6.54 with an EC equal to 198.72 mS/cm, with a removal of 99.08, 56.08, and 91.39% of the concentrations of As, Cu, and Fe, respectively, obtained in 72 h. Likewise, total nitrogen concentrations, organic carbon, loss on ignition, dissolved organic carbon, and chemical oxygen demand were reduced by 69.047, 86.922, 85.378, 88.458, and 90.771%, respectively. At the same time, the PDMAX shown was 376.20 ± 15.478 mW/cm2, with a calculated internal resistance of 42.550 ± 12.353 Ω. This technique presents an essential advance in overcoming existing technical barriers because the engineered microbial fuel cells are accessible and scalable. It will generate important value by naturally reducing toxic metals and electrical energy, producing electric currents in a sustainable and affordable way.
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Bacillus , Fuentes de Energía Bioeléctrica , Fuentes de Energía Bioeléctrica/microbiología , Bacillus/metabolismo , Metales Pesados , Contaminantes Químicos del Agua/metabolismo , Cobre/química , Cobre/metabolismo , Concentración de Iones de Hidrógeno , Biodegradación Ambiental , Arsénico/metabolismoRESUMEN
This study presents fibers based on methacrylic acid-methyl methacrylate (Eudragit L100) as Cu(II) adsorbents, resulting in antimicrobial complexes. Eudragit L100, an anionic copolymer synthesized by radical polymerization, was electrospun in dimethylformamide (DMF) and ethanol (EtOH). The electrospinning process was optimized through a 22-factorial design, with independent variables (copolymer concentration and EtOH/DMF volume ratio) and three repetitions at the central point. The smallest average fiber diameter (259 ± 53 nm) was obtained at 14% w/v Eudragit L100 and 80/20 EtOH/DMF volume ratio. The fibers were characterized using scanning electron microscopy (SEM), infrared spectroscopy in attenuated total reflectance mode (FTIR-ATR), and differential scanning calorimetry (DSC). The pseudo-second-order mechanism explained the kinetic adsorption toward Cu(II). The fibers exhibited a maximum adsorption capacity (qe) of 43.70 mg/g. The DSC analysis confirmed the Cu(II) absorption, indicating complexation between metallic ions and copolymer networks. The complexed fibers showed a lower degree of swelling than the non-complexed fibers. The complexed fibers exhibited bacteriostatic activity against Gram-negative (Pseudomonas aeruginosa) and Gram-positive (Staphylococcus aureus) bacteria. This study successfully optimized the electrospinning process to produce thin fibers based on Eudragit L100 for potential applications as adsorbents for Cu(II) ions in aqueous media and for controlling bacterial growth.
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Cobre , Ácidos Polimetacrílicos , Cobre/química , Ácidos Polimetacrílicos/química , Antiinfecciosos/farmacología , Antiinfecciosos/química , Adsorción , Espectroscopía Infrarroja por Transformada de Fourier , Staphylococcus aureus/efectos de los fármacos , Metacrilatos/química , Cinética , Rastreo Diferencial de Calorimetría , Pruebas de Sensibilidad MicrobianaRESUMEN
This study explored the photocatalytic hydrogen evolution reaction (HER) using novel biohydrogel composites comprising chitosan, and a photocatalyst consisting in TiO2 P25 decorated with Au and/or Cu mono- and bimetallic nanoparticles (NPs) to boost its optical and catalytic properties. Low loads of Cu and Au (1 mol%) were incorporated onto TiO2 via a green photodeposition methodology. Characterization techniques confirmed the incorporation of decoration metals as well as improvements in the light absorption properties in the visible light interval (λ > 390 nm) and electron transfer capability of the semiconductors. Thereafter, Au and/or Cu NP-supported TiO2 were incorporated into chitosan-based physically crosslinked hydrogels revealing significant interactions between chitosan functional groups (hydroxyls, amines and amides) with the NPs to ensure its encapsulation. These materials were evaluated as photocatalysts for the HER using water and methanol mixtures under simulated sunlight and visible light irradiation. Sample CuAuTiO2/ChTPP exhibited a maximum hydrogen generation of 1790 µmol g-1 h-1 under simulated sunlight irradiation, almost 12-folds higher compared with TiO2/ChTPP. Also, the nanocomposites revealed a similar tendency under visible light with a maximum hydrogen production of 590 µmol g-1 h-1. These results agree with the efficiency of photoinduced charge separation revealed by transient photocurrent and EIS.
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Quitosano , Cobre , Hidrogeles , Hidrógeno , Luz Solar , Titanio , Quitosano/química , Titanio/química , Catálisis , Hidrógeno/química , Cobre/química , Hidrogeles/química , Oro/química , Procesos Fotoquímicos , Nanocompuestos/química , Nanopartículas del Metal/químicaRESUMEN
Candida species undeniably rank as the most prevalent opportunistic human fungal pathogens worldwide, with Candida albicans as the predominant representative. However, the emergence of non-albicans Candida species (NACs) has marked a significant shift, accompanied by rising incidence rates and concerning trends of antifungal resistance. The search for new strategies to combat antifungal-resistant Candida strains is of paramount importance. Recently, our research group reported the anti-Candida activity of a coordination compound containing copper(II) complexed with theophylline (theo) and 1,10-phenanthroline (phen), known as "CTP" - Cu(theo)2phen(H2O).5H2O. In the present work, we investigated the mechanisms of action of CTP against six medically relevant, antifungal-resistant NACs, including C. auris, C. glabrata, C. haemulonii, C. krusei, C. parapsilosis and C. tropicalis. CTP demonstrated significant efficacy in inhibiting mitochondrial dehydrogenases, leading to heightened intracellular reactive oxygen species production. CTP treatment resulted in substantial damage to the plasma membrane, as evidenced by the passive incorporation of propidium iodide, and induced DNA fragmentation as revealed by the TUNEL assay. Scanning electron microscopy images of post-CTP treatment NACs further illustrated profound alterations in the fungal surface morphology, including invaginations, cavitations and lysis. These surface modifications significantly impacted the ability of Candida cells to adhere to a polystyrene surface and to form robust biofilm structures. Moreover, CTP was effective in disassembling mature biofilms formed by these NACs. In conclusion, CTP represents a promising avenue for the development of novel antifungals with innovative mechanisms of action against clinically relevant NACs that are resistant to antifungals commonly used in clinical settings.
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Antifúngicos , Candida , Complejos de Coordinación , Cobre , Farmacorresistencia Fúngica , Pruebas de Sensibilidad Microbiana , Fenantrolinas , Teofilina , Antifúngicos/farmacología , Antifúngicos/química , Antifúngicos/síntesis química , Fenantrolinas/farmacología , Fenantrolinas/química , Candida/efectos de los fármacos , Cobre/química , Cobre/farmacología , Farmacorresistencia Fúngica/efectos de los fármacos , Complejos de Coordinación/farmacología , Complejos de Coordinación/química , Complejos de Coordinación/síntesis química , Teofilina/farmacología , Teofilina/química , Especies Reactivas de Oxígeno/metabolismo , HumanosRESUMEN
The contamination of water bodies by synthetic organic compounds coupled with climate change and the growing demand for water supply calls for new approaches to water management and treatment. To tackle the decontamination issue, the activation of peroxymonosulfate (PMS) using copper magnetic ferrite (CuMF) nanoparticles prepared under distinct synthesis conditions was assessed to oxidize imidacloprid (IMD) insecticide. After optimization of some operational variables, such as CuMF load (62.5-250 mg L-1), PMS concentration (250-1000 µM), and solution pH (3-10), IMD was completely oxidized in 2 h without interferences from leached metal ions. Such performance was also achieved when using tap water but was inhibited by a simulated municipal wastewater due to scavenging effects promoted by inorganic and organic species. Although there was evidence of the presence of sulfate radicals and singlet oxygen oxidizing species, only four intermediate compounds were detected by liquid chromatography coupled to mass spectrometry analysis, mainly due to hydroxyl addition reactions. Concerning the changes in surface properties of CuMF after use, no morphological or structural changes were observed except a small increase in the charge transfer resistance. Based on the changes of terminal surface groups, PMS activation occurred on Fe sites.
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Cobre , Insecticidas , Neonicotinoides , Nitrocompuestos , Oxidación-Reducción , Peróxidos , Contaminantes Químicos del Agua , Insecticidas/química , Neonicotinoides/química , Nitrocompuestos/química , Contaminantes Químicos del Agua/química , Cobre/química , Peróxidos/química , Compuestos Férricos/química , Aguas Residuales/química , Purificación del Agua/métodos , Nanopartículas/química , Compuestos FerrososRESUMEN
Four new copper(II) complexes were synthesized and characterized with the general formula [Cu(N-N)(Th)(NO3)], where N-N corresponds to the N-heterocyclic ligands 1,10-phenanthroline (phen), 2,2'-bipyridine (bipy), 4,7-diphenyl-1,10-phenanthroline (dpp), and 4,4-dimethyl-2,2'-bipyridine (dmbp) and Th represents the N,N-dibenzyl-N'-benzoylthiourea. Cytotoxic activities of the complexes against HCT116 (human colon carcinoma), HepG2 (human hepatocellular carcinoma), and non-tumor MRC-5 (human lung fibroblast) cells were investigated. The copper(II) complexes 1-4 were characterized by spectroscopic techniques while complexes 1 and 2 were studied using single-crystal X-ray diffraction as well. The complexes possessed a five-coordinated structure with one nitrate ligand as a monodentate at the axial position and two bidentate ligands N-heterocyclic and N,N-dibenzyl-N'-benzoylthiourea. The complexes showed promising IC50 values, ranging from 0.3 to 9.0 µM. Furthermore, interaction studies with biomolecules such as calf thymus DNA (ct-DNA) and Bovine Serum Albumin (BSA), which can act as possible biological targets of the complexes, were carried out. The studies suggested that the compounds interact moderately with ct-DNA and BSA. Complexes 1, 2, and 4 did not lead to cell accumulation at any stage of the cell cycle but caused a significant increase in internucleosomal DNA fragmentation. Whereas, compound 3 caused cell cycle arrest in the S phase while doxorubicin caused cell cycle arrest in the G2/M phase. The effect of structural modifications on the metal compounds was correlated with their biological properties and it was concluded that an increase in biological activity occurred with increasing the extension of the diimine ligands. Thus, complex 3 was the most promising one.
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Antineoplásicos , Ciclo Celular , Complejos de Coordinación , Cobre , ADN , Albúmina Sérica Bovina , Tiourea , Cobre/química , Cobre/farmacología , Humanos , Albúmina Sérica Bovina/química , Albúmina Sérica Bovina/metabolismo , ADN/metabolismo , ADN/química , Antineoplásicos/farmacología , Antineoplásicos/química , Antineoplásicos/síntesis química , Complejos de Coordinación/farmacología , Complejos de Coordinación/química , Complejos de Coordinación/síntesis química , Bovinos , Tiourea/química , Tiourea/farmacología , Ciclo Celular/efectos de los fármacos , Animales , Iminas/química , Iminas/farmacología , Ensayos de Selección de Medicamentos Antitumorales , Proliferación Celular/efectos de los fármacos , Estructura MolecularRESUMEN
Assessing membrane protein stability is among the major challenges in protein science due to their inherent complexity, which complicates the application of conventional biophysical tools. In this work, sodium dodecyl sulfate-induced denaturation of AfCopA, a Cu(I)-transport ATPase from Archaeoglobus fulgidus, was explored using a combined model-free spectral phasor analysis and a model-dependent thermodynamic analysis. Decrease in tryptophan and 1-anilino-naphthalene-8-sulfonate fluorescence intensity, displacements in the spectral phasor space, and the loss of ATPase activity were reversibly induced by this detergent. Refolding from the SDS-induced denatured state yields an active enzyme that is functionally and spectroscopically indistinguishable from the native state of the protein. Phasor analysis of Trp spectra allowed us to identify two intermediate states in the SDS-induced denaturation of AfCopA, a result further supported by principal component analysis. In contrast, traditional thermodynamic analysis detected only one intermediate state, and including the second one led to overparameterization. Additionally, ANS fluorescence spectral analysis detected one more intermediate and a gradual change at the level of the hydrophobic transmembrane surface of the protein. Based on this evidence, a model for acquiring the native structure of AfCopA in a membrane-like environment is proposed.