Poly(lactic acid)/ß-cyclodextrin based nanoparticles bearing ruthenium(II)-arene naproxen complex: preparation and characterisation. Analytical validation for metal determination by microwave-induced plasma optical emission spectrometry.

The objectives of this work are to develop nanocarrier systems for the Ru(II)-p-cymene naproxen antitumor metallodrug, [Ru(η6-p-cymene)(npx)Cl] or Rupcy, based on polymeric nanoparticles (NPs) composed by the biodegradable poly(lactic acid) (PLA) and the hydrophilic polymerised ß-cyclodextrin (PolyCD); to validate an analytical method for determination of Ru incorporated into the metallodrug loaded-NPs. The PolyCD was prepared by single step condensation and polymerisation reaction and incorporated as a polymer blend during the fabrication of PLA/PolyCD blends NPs and also as a core/shell structure built by adsorption of the PolyCD onto the surface of PLA NPs to give PLA(core)/PolyCD(shell) NPs. Three different loaded-systems incorporating the metallodrug (Rupcy-PLA NPs (1), Rupcy-PLA/PolyCD blends (2), and Rupcy-PLA(core)/PolyCD(shell) NPs (3)) were prepared by nanoprecipitation. The characterisation was performed by Proton Nuclear Magnetic Resonance, Matrix Assisted Laser Desorption/Ionization Time-of-Flight, Fourier-Transform Infra-red and UV-VIS Electronic Absorption Spectroscopies, Thermogravimetric Analysis, Differential Scanning Calorimetry, Dynamic Light Scattering, and Electrophoretic Light Scattering. Ru was determined by Microwave Induced Plasma Optical Emission Spectrometry (MIP-OES) with validation of the method. The metallodrug entrapment efficiency was around 90% (w/w) and drug loading was at 3-4% (w/w). The characterised metallodrug-loaded systems exhibited monomodal size distributions and appropriate hydrodynamic diameters [218.3 ± 13.5 (1), 205.4 ± 14.4 (2), 231.5 ± 22.0 (3) nm] and zeta potential values [-31.5 ± 2.2 (1), -26.1 ± 4.5 (2), -28.8 ± 6.1 (3) mV]. The validation of the MIP-OES method by evaluating selectivity, linearity, precision, accuracy, and limits of detection and quantification succeeded. The NPs parameters are compatible with colloidally stable systems. The MIP-OES method showed to be simple, reliable, and feasible to quantify indirectly the amount of the metallodrug-loaded into the PLA NPs.

Uranium transfer in grasses grown on mining waste and natural soil.

The transfer of radionuclides from soil to the food chain often begins with uptake by plant root system. The roots of most angiosperms showed symbiosis with arbuscular mycorrhizal fungi (AMF) and to understand the transfer process of these toxic elements it is important to consider different physical, chemical and biological factors in soils. In the present study, three grass species (Poaceae), Zea mays, Chrysopogon zizanioides and Aristida setifolia were cultivated with and without organic fertilization in experimental blocks on natural soils, at Fazenda Vargem Formosa (VF) with low uranium (U) contents in the soil, and in the leached ore deposit at the Uranium Concentrate Unit Mine (URA) in Caetité (Uraniferous Province of Lagoa Real - Brazil). In the present study, the biomass production of plants, their rate of root colonization by AMF, the levels of U in soils, roots and leaves, as well as different physico-chemical parameters related to soil fertility were evaluated. The data analysis was performed using Artificial Neural Networks (ANNs), specifically Self-Organizing Maps (SOMs). The levels of available uranium in the soil ranges from 0.33 to 1.11 mg kg-1 in VF and from 177.5 to 475.8 mg kg-1 in URA. The results revealed high percentage of root AMF colonization, even in soils with high U contents. There was an inverse relationship between soil U content and its transfer to the plant organs, with U transfer rates being influenced by plant species and not by soil parameters. C. zizanioides had the lowest transfer factor to the shoot and the highest mass productivity under conditions of high U content in soil. The results indicate that C. zizanioides is an important species for use in the recovery of U mining areas.

Multivariate optimization of an ultrasound-assisted extraction procedure for the determination of Cu, Fe, Mn, and Zn in plant samples by flame atomic absorption spectrometry.

In this work, a simple, easy, and fast ultrasound-assisted extraction procedure for the determination of Cu, Fe, Mn, and Zn in plant samples was developed. Sample preparation conditions were optimized in a multivariate manner using mixture design and Box-Behnken. The extraction conditions adequate to obtain the maximum response were 90% power, 10 minutes, 40 °C temperature, and using an extraction solution composed of HNO3 and HCl at a concentration of 0.5 and 1.1 mol L-1, respectively, for a volume of 10 mL and 250 mg of samples. Accuracy was verified from the analysis of a certified reference material (Apple leaves, NIST 1515) yielding recoveries between 89 and 98% for the procedure. Precision was evaluated in a repeatability study (n = 10), yielding RSDs less than 6.7%, and the limits of quantification (mg kg-1) were 0.95, 2.42, 1.31, and 1.18 for Cu, Fe, Mn, and Zn, respectively. The concentrations determined in the stem and leaf of the mangrove species varied according to the collection point and the tissue, being consistent with other studies. The proposed procedure was efficient and reliable for elemental determination in plant samples, with the advantages of low cost and reagent consumption besides short analysis time as a valid alternative to the conventional sample preparation procedure.

Artificial neural network employment for element determination in Mugil cephalus by ICP OES in Pontal Bay, Brazil.

Fish are important sources of protein, making them very significant in the human diet. Although the consumption of this food is beneficial for health, it is essential that the product does not contain inorganic components above the limits recommended by the current legislation. Therefore, a method for determination of elements in fish (Mugil cephalus) samples was optimized. A simplex centroid mixture design with restriction was applied for optimization of the acid digestion of samples in an open system under reflux in order to evaluate the best ratio between the reagents HNO3, H2O2 and H2O. The results indicated that more intense analyte signals were obtained when a mixture containing 3.6 mL of HNO3 (65% v/v), 0.4 mL of H2O2 (30% v/v) and 6.0 mL of H2O was used. The accuracy of the method was assessed with a CRM of oyster tissue (NIST 1566b). The method presented relative standard deviations (RSDs) of 3.54%; 3.82%; 4.81% and 3.50% for Zn, Fe, Cu and S, respectively. The detection limits were 0.002 mg kg-1 for Cu and Zn and 0.02 mg kg-1 for Fe and S. The proposed method was applied for the determination of Zn, Fe, Cu and S in fish samples. A Kohonen Self-Organizing Map (KSOM) with K-means implementation was applied to better delimit the boundary between groups and the spatial and temporal influence on how concentrations of the chemical elements were perceived. To verify the separation, the Davies-Bouldin and Silhouette indices were used, obtaining 0.5374 and 0.8541, respectively, indicating satisfactory separation.

Development of procedure for sample preparation of cashew nuts using mixture design and evaluation of nutrient profiles by Kohonen neural network.

A procedure using ICP OES for sample preparation for the determination of copper, iron and manganese in cashew nuts was developed. Constrained simplex-centroid design was applied in the optimization of the digestion in microwave oven procedure, and the results evaluated from topological maps of the Kohonen network. The best proportion evaluated for the digestion of the sample with HNO3, H2O2 and H2O was 10:45:45 (%). With optimized conditions, the detection limits were 0.63, 4.3 and 0.37 mg kg-1, and quantification 2.1, 14 and 1.2 mg kg-1 for Cu, Fe and Mg, respectively. The precision (% RSD) was 1.84, 2.31 and 2.73, for Cu, Fe and Mg, respectively. The procedure proposed had the accuracy confirmed using NIST 1568b (at 95% reliability) and was applied in the samples obtaining concentrations in the range of 10.7-19.4, 44.3-67.2 and 11.0-21.4 mg kg-1 for Cu, Fe and Mg, respectively.

Chromotropic acid-functionalized polyurethane foam: A new sorbent for on-line preconcentration and determination of cobalt and nickel in lettuce samples.

A chromotropic acid-functionalized polyurethane foam has been developed for use in an on-line preconcentration system for cobalt and nickel determination. The packing material was prepared by covalent coupling of chromotropic acid with the polyurethane foam through an azo group. Co and Ni ions were sorbed in the mini-column, from which they could be eluted directly to the nebulizer-burner system of a flame atomic absorption spectrometer. Elution of cobalt and nickel from the mini-column can be accomplished with 0.50 and 0.75 M HCl solutions, respectively. The enrichment factors obtained were 22 (Co) and 27 (Ni), for 60 s preconcentration time, and 57 (Co) and 59 (Ni), if a preconcentration time of 180 s was used. Under the optimum conditions, the proposed procedure allowed the determination of metals with detection limits of 0.43 (cobalt) and 0.52 microg/L (nickel), respectively, on using preconcentration periods of 180 s. The accuracy of the developed procedure was evaluated by analysis of the certified reference materials NIST 1515 Apple Leaves and NIST 1570a Spinach Leaves. The method was applied to the analysis of lettuce samples. The contents of cobalt in the samples analyzed varied from 0.75 to 0.98 microg/g. Nickel was not detected in the lettuce samples.