RESUMO
Nanoparticle (NP) applications aiming to boost plant biomass production and enhance the nutritional quality of crops hae proven to be a valuable ally in enhancing agricultural output. They contribute to greater food accessibility for a growing and vulnerable population. These nanoscale particles are commonly used in agriculture as fertilizers, pesticides, plant growth promoters, seed treatments, opportune plant disease detection, monitoring soil and water quality, identification and detection of toxic agrochemicals, and soil and water remediation. In addition to the countless NP applications in food and agriculture, it is possible to highlight many others, such as medicine and electronics. However, it is crucial to emphasize the imperative need for thorough NP characterization beyond these applications. Therefore, analytical methods are proposed to determine NPs' physicochemical properties, such as composition, crystal structure, size, shape, surface charge, morphology, and specific surface area, detaching the inductively coupled plasma mass spectrometry (ICP-MS) that allows the reliable elemental composition quantification mainly in metallic NPs. As a result, this review highlights studies involving NPs in agriculture and their consequential effects on plants, with a specific focus on analyses conducted through ICP-MS. Given the numerous applications of NPs in this field, it is essential to address their presence and increase in the environment and humans since biomagnification and biotransformation effects are studies that should be further developed. In light of this, the demand for rapid, innovative, and sensitive analytical methods for the characterization of NPs remains paramount.
Assuntos
Nanopartículas Metálicas , Nanopartículas , Humanos , Espectrometria de Massas/métodos , Plantas Comestíveis , Nanopartículas/química , Produtos Agrícolas , Solo , Nanopartículas Metálicas/químicaRESUMO
Deferasirox (DFX), an orally active and clinically approved iron chelator, is being used extensively for the treatment of iron overload. However, its water insolubility makes it cumbersome for practical use. In addition to this, the low efficacy of DFX to remove brain iron prompted us to synthesize and evaluate a DFX-TAT(47-57) peptide conjugate for its iron chelation properties and permeability across RBE4 cell line, an in vitro model of the blood-brain barrier. The water-soluble conjugate was able to remove labile iron from buffered solution as well as from iron overloaded sera, and the permeability of DFX-TAT(47-57) conjugate into RBE4 cells was not affected compared to parent deferasirox. The iron bound conjugate was also able to translocate through the cell membrane.
Assuntos
Benzoatos/química , Quelantes de Ferro/química , Sobrecarga de Ferro/tratamento farmacológico , Fragmentos de Peptídeos/química , Triazóis/química , Produtos do Gene tat do Vírus da Imunodeficiência Humana/química , Animais , Benzoatos/administração & dosagem , Benzoatos/síntese química , Barreira Hematoencefálica/efeitos dos fármacos , Linhagem Celular , Membrana Celular/química , Membrana Celular/efeitos dos fármacos , Deferasirox , Humanos , Quelantes de Ferro/administração & dosagem , Quelantes de Ferro/síntese química , Sobrecarga de Ferro/patologia , Fragmentos de Peptídeos/administração & dosagem , Fragmentos de Peptídeos/síntese química , Ratos , Solubilidade , Triazóis/administração & dosagem , Triazóis/síntese química , Água/química , Produtos do Gene tat do Vírus da Imunodeficiência Humana/administração & dosagem , Produtos do Gene tat do Vírus da Imunodeficiência Humana/síntese químicaRESUMO
Iron overload causes progressive and sometimes irreversible damage due to accelerated production of reactive oxygen species. Desferrioxamine (DFO), a siderophore, has been used clinically to remove excess iron. However, the applications of DFO are limited because of its inability to access intracellular labile iron. Cell penetrating peptides (CPPs) have become an efficient delivery vector for the enhanced internalization of drugs into the cytosol. We describe, herein, an efficient method for covalently conjugating DFO to the CPPs TAT(47-57) and Penetratin. Both conjugates suppressed the redox activity of labile plasma iron in buffered solutions and in iron-overloaded sera. Enhanced access to intracellular labile iron compared to the parent siderophore was achieved in HeLa and RBE4 (a model of blood-brain-barrier) cell lines. Iron complexes of both conjugates also had better permeability in both cell models. DFO antioxidant and iron binding properties were preserved and its bioavailability was increased upon CPP conjugation, which opens new therapeutic possibilities for neurodegenerative processes associated with brain iron overload.
Assuntos
Peptídeos Penetradores de Células/química , Peptídeos Penetradores de Células/síntese química , Desferroxamina/química , Desferroxamina/farmacologia , Portadores de Fármacos/química , Portadores de Fármacos/síntese química , Fármacos Neuroprotetores/química , Sequência de Aminoácidos , Antioxidantes/química , Antioxidantes/metabolismo , Antioxidantes/farmacologia , Apoproteínas/metabolismo , Ligação Competitiva , Peptídeos Penetradores de Células/metabolismo , Técnicas de Química Sintética , Desferroxamina/metabolismo , Portadores de Fármacos/metabolismo , Fluoresceína/metabolismo , Fluoresceínas/metabolismo , Produtos do Gene tat/química , Células HeLa , Humanos , Ferro/metabolismo , Dados de Sequência Molecular , Fármacos Neuroprotetores/metabolismo , Fármacos Neuroprotetores/farmacologia , Permeabilidade , Transferrina/metabolismoRESUMO
Dithiocarbamates are nitrogen- and sulfur-containing compounds commonly used in pharmacology, medicine and agriculture. The molecular effects of dithiocarbamates on neuronal cell systems are not fully understood, especially in terms of their ability to accumulate copper ions inside the cell. In this work, the molecular effects of N,N-diethyldithiocarbamate (DEDTC) were studied in human SH-SY5Y neuroblastoma cells to determine the role of copper in the DEDTC toxicity and the pathway trigged in cell by the complex Cu-DEDTC. From concentration-dependent studies, we found that 5 µM of this compound induced a drastic decrease in viable cells with a concomitant accumulation in intracellular copper resulted from complexation with DEDTC, measured by atomic absorption spectroscopy. The mechanism of DEDTC-induced apoptosis in neuronal model cells is thought to occur through the death receptor signaling triggered by DEDTC-copper complex in low concentration that is associated with the activation of caspase 8. Our results indicated that the mechanism of cell death involves cytochrome c release forming the apoptosome together with Apaf-1 and caspase 9, converting the caspase 9 into its active form, allowing it to activate caspase 3 as observed by immunofluorescence. This pathway is induced by the cytotoxic effects that occur when DEDTC forms a complex with the copper ions present in the culture medium and transports them into the cell, suggesting that the DEDTC by itself was not able to cause cell death and the major effect is from its copper-complex in neuroblastoma cells. The present study suggests a role for the influence of copper by low concentrations of DEDTC in the extracellular media, the absorption and accumulation of copper in the cell and apoptotic events, induced by the cytotoxic effects that occur when DEDTC forms a complex with the copper ions.
Assuntos
Caspases/metabolismo , Cobre/metabolismo , Citocromos c/metabolismo , Ditiocarb/toxicidade , Apoptose/efeitos dos fármacos , Linhagem Celular Tumoral , Sobrevivência Celular/efeitos dos fármacos , Ativação Enzimática/efeitos dos fármacos , Humanos , Neuroblastoma/metabolismo , Proteínas Proto-Oncogênicas c-bcl-2/metabolismo , Proteína Supressora de Tumor p53/metabolismoRESUMO
Elevated levels of copper have been detected in various types of human cancer cells, such as breast cancer cells, and a number of mechanisms have been proposed to explain the action and influence of copper on tumor progress. In this work, we found that stimulating the proliferation of mammary epithelial MCF7 cells with the high-redox-potential copper complex Cu (GlyGlyHis) is associated with the copper-induced intracellular generation of reactive oxygen species (ROS) that induces lipid peroxidation and causes increased roughness of external cell membranes, which leads to the formation of larger cell domes. The results presented herein provide new insights into the molecular link between copper and the proliferation of breast cancer cells and, consequently, into the mechanism by which changes in redox balance and ROS accumulation regulates cell membrane roughness.
Assuntos
Cobre/farmacologia , Oligopeptídeos/química , Espécies Reativas de Oxigênio/metabolismo , Western Blotting , Cobre/química , Cobre/metabolismo , Humanos , Peroxidação de Lipídeos/efeitos dos fármacos , Células MCF-7 , Microscopia de Força Atômica , Espectrofotometria AtômicaRESUMO
The presence of the bicarbonate/carbon dioxide pair is known to accelerate the transition metal ion-catalysed oxidation of various biotargets. It has been shown that stable Cu(II) complexes formed with imine ligands that allow redox cycling between Cu(I) and Cu(II) display diverse apoptotic effects on cell cultures. It is also reported that Cu(II)-tetraglycine can form a stable Cu(III) complex. In the present study, radical generation from H(2)O(2) and H(2)O(2)/HCO(3)(-) in the presence of these two different classes of Cu(II) complexes was evaluated by monitoring the oxidation of dihydrorhodamine 123 and NADH and by the quantitative determination of thiobarbituric acid reactive substances (TBARs method). Cu(II)-imine complexes produced low levels of reactive species whereas Cu(II)-Gly-derived complexes, as well as the free Cu(II) ion, produced oxygen-derived radicals in significantly larger amounts. The effects of these two classes of complexes on mammalian tumour cell viability were equally distinct, in that Cu(II)-imine complexes caused apoptosis, entered in cell and remained almost unaffected in high levels whilst, at the same concentrations, Cu(II)-Gly peptide complexes and Cu(II) sulphate stimulated cell proliferation, with the cell managing copper efficiently. Taken together, these results highlight the different biological effects of Cu(II) complexes, some of which have been recently studied as anti-tumour drugs and radical system generators, and also update the effects of reactive oxygen species generation on cell cycle control.
Assuntos
Antineoplásicos/farmacologia , Bicarbonatos/química , Dióxido de Carbono/química , Complexos de Coordenação/farmacologia , Cobre , Radicais Livres/metabolismo , Peróxido de Hidrogênio/química , Iminas/farmacologia , Antineoplásicos/química , Antineoplásicos/metabolismo , Linhagem Celular Tumoral , Proliferação de Células/efeitos dos fármacos , Sobrevivência Celular/efeitos dos fármacos , Complexos de Coordenação/química , Complexos de Coordenação/metabolismo , Cobre/metabolismo , Ensaios de Seleção de Medicamentos Antitumorais , Humanos , Iminas/química , Iminas/metabolismo , Ligantes , Oxirredução , Relação Estrutura-AtividadeRESUMO
An approach was developed for the preparation of cryogenic ground spiked filter papers with Cu and Zn for use as synthetic calibrating standards for direct solid microanalysis. Solid sampling graphite furnace atomic absorption spectrometry was used to evaluate the microhomogeneity and to check the applicability of the synthetic calibrating standards for the direct determination of Cu and Zn in vegetable certified reference materials. The found concentrations presented no statistical differences at the 95% confidence level. The homogeneity factors ranged from 2.7 to 4.2 for Cu and from 6.4 to 11.5 for Zn.
RESUMO
A method for the multielement determination of cadmium and lead in urine is proposed by simultaneous electrothermal atomic absorption spectrometry (SIMAAS) with an end-capped transversely heated graphite atomizer (EC-THGA). The best conditions for cadmium and lead determination were obtained in the presence of NH4H2PO4 as a chemical modifier, using 500 degrees C and 1800 degrees C as the pyrolysis and atomization temperatures, respectively. Urine samples were diluted 1 + 4 directly in autosampler cups with a mixture of 0.125% (w/v) Triton X-100 + 2.5% (v/v) HNO3 + 0.31% (w/v) NH4H2PO4. The optimized heating program was carried out in 57 s, and the instrument calibration was done with aqueous reference solutions. The use of EC-THGA increased the sensitivity of cadmium and lead by 14% and 25%, respectively. The detection limits (n = 20, 3delta) were 0.03 microg L(-1) (0.36 pg) for cadmium and 0.57 microg L(-1) (6.8 pg) for lead. The performance of EC-THGA was acceptable up to 500 heating cycles. The reliability of the entire procedure was checked with the analysis of a lyophilized urine certified reference material. The found concentrations were in agreement with the recommended values (95% confidence level).