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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., (© 2023. The Author(s), under exclusive licence to Springer-Verlag GmbH, DE part of Springer Nature.)

Desferrioxamine (DFO) and diethylenetriaminepentaacetic acid (DTPA) conjugated with silica gel (IDFOSG and IDTPASG, respectively) were evaluated as adsorbents for chromium in aqueous solutions. Different parameters affecting adsorption such as pH, sorbent dosage, contact time, sample volume and potential of interfering ions have been optimized. The optimum pH for chromium binding was 4 for 100 mg of adsorbents at 5 min of table shaking with 5 mL sample volume of chromium solutions. Langmuir adsorption model described the removal of chromium ions. The adsorption capacity for chromium was 90% for IDFOSG and 83% for IDTPASG in single solutions, and at least 75% in multielemental solutions. Considering the removal efficacy, regeneration and stability, DFO-grafted silica gel was generally superior to its DTPA counterpart and may be applied to the removal of traces of chromium species from natural waters.

Matte photographic paper was explored as a low-cost material for metal-ion retention. The extraction was promoted by ultrasound, the mechanical waves of which forced adhesion to the photographic paper surface of an ion pair formed by DTAB (dodecyltrimethylammonium bromide) with the anionic coordination complex formed by metal ions and SPADNS (1,8-dihydroxy-2-(4-sulfophenylazo)naphthalene-3,6-disulfonic acid trisodium salt). As a proof of concept, the migration of copper ions present in aqueous solution to the solid phase and their direct measurement by laser-induced breakdown spectroscopy (LIBS) was evaluated. The main parameters that affected the extraction (paper type and sonication time) and analyte detection in the solid phase (delay, spot size and accumulated number of pulses) were optimised in a univariate way. The conditions influencing the complexation reaction and formation of the ion pair in aqueous solution (pH and copper, SPADNS and DTAB concentrations) were set according to a previous study. Under the optimised conditions, it was possible to use this extraction technology as an alternative in determining copper content in aqueous solutions by LIBS, overcoming the intrinsic difficulties of this instrumental technique in the analysis of liquid samples. The calibration curves were obtained in a linear range of 0.50-7.50 mg L -1 copper in solution, with detection and quantification limits estimated at 0.08 and 0.24 mg L -1 , respectively. The precision of the method was less than 4.3% and the accuracy was checked by spike and recovery tests on liquid samples with different chemical compositions and by comparison of LIBS results with graphite furnace atomic absorption spectrometry data. The potential of the proposed method for extraction of Al 3+ , Ag + , Fe 3+ , Mn 2+ , Ni 2+ and Zn 2+ was also evaluated and adequate extraction efficiencies were obtained. The proposed method stands out due to its low cost and ease of execution., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Mushrooms are bioaccumulating organisms commonly used in selenium (Se) enrichment studies. However, the addition of Se in the culture medium may alter the distribution of other essential elements in the mushroom fruiting body. To evaluate the effects of the Se enrichment, Ca, Mg, and K distributions in pink oyster (Pleurotus djamor) and K and Mg distributions in white oyster (Pleurotus ostreatus) mushrooms were mapped by laser-induced breakdown spectroscopy (LIBS), which can be used at room temperature and requires minimal or no sample preparation. It was verified that Se enrichment favoured the accumulation of Ca in the lower part of the pink oyster mushroom and prevented the transport of this element to the edges and tops. The Se enrichment also altered the distribution of K and Mg, decreasing the numerical correlation between the K and Mg distributions (R² = 0.5871). In the white oyster mushroom, however, despite the changes in the morphological characteristics of the fruiting bodies after enrichment, there were generally nonsignificant differences in the K and Mg distributions between the control and the Se-enriched mushrooms.

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.

Desferrioxamine (DFO) is a potent iron chelator used in the treatment of iron overload (IO) disorders. However, due to its low cell permeability and fast clearance, DFO administration is usually prolonged and of limited use for the treatment of IO in tissues such as the brain. Caffeine is a safe, rapidly absorbable molecule that can be linked to other compounds to improve their cell permeability. In this work, we successfully prepared and described DFO-caffeine, a conjugate with iron scavenging ability, antioxidant properties and enhanced permeation in the HeLa cell model.

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.

The development of methods for direct determinations of Al, Cd, and Pb in rice by SS-GF AAS is presented. Heating program optimization associated with the use of an adequate chemical modifier containing Pd + Mg allowed direct analysis against aqueous calibrations. The obtained LOD values were 114.0, 3.0, and 16.0 μg kg⁻¹ for Al, Cd, and Pb, respectively. Important parameters associated with a solid sampling analysis were investigated, such as minimum and maximum sample mass size and analyte segregation. Seventeen rice samples available in São Paulo City were analyzed, and all of them presented analyte mass fractions less than the maximum allowed by legislation. The influences of rice washing and the cooking procedure were also investigated. The washing procedure diminished the Al and Pb total mass fractions, indicating an exogenous grain contamination. The cooking procedure diminished the Cd total mass fraction. Rice cooking using an aluminum container did not cause a significant increase in the Al mass fraction in the rice, indicating no translocation of this element from container to food. In general, coarse rice presented higher levels of Al when compared to polished or parabolized rice.

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., (Copyright © 2012 Elsevier Ltd. All rights reserved.)

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., (Copyright © 2012 Elsevier Inc. All rights reserved.)

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., (Copyright © 2010 Elsevier Inc. All rights reserved.)

The physical and chemical characteristics of peat were assessed through measurement of pH, percentage of organic matter, cationic exchange capacity (CEC), elemental analysis, infrared spectroscopy and quantitative analysis of metals by ICP OES. Despite the material showed to be very acid in view of the percentage of organic matter, its CEC was significant, showing potential for retention of metal ions. This characteristic was exploited by coupling a peat mini-column to a flow system based on the multicommutation approach for the in-line copper concentration prior to flame atomic absorption spectrometric determination. Cu(II) ions were adsorbed at pH 4.5 and eluted with 0.50 molL(-1) HNO(3). The influence of chemical and hydrodynamic parameters, such as sample pH, buffer concentration, eluent type and concentration, sample flow-rate and preconcentration time were investigated. Under the optimized conditions, a linear response was observed between 16 and 100 microgL(-1), with a detection limit estimated as 3 microgL(-1) at the 99.7% confidence level and an enrichment factor of 16. The relative standard deviation was estimated as 3.3% (n=20). The mini-column was used for at least 100 sampling cycles without significant variation in the analytical response. Recoveries from copper spiked to lake water or groundwater as well as concentrates used in hemodialysis were in the 97.3-111% range. The results obtained for copper determination in these samples agreed with those achieved by graphite furnace atomic absorption spectrometry (GFAAS) at the 95% confidence level.

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.

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).