Resumo em Inglês:

Thin films of multiwalled carbon nanotubes/polyaniline nanocomposites (CNT/PAni) were synthesized through the liquid/liquid (L/L) interfacial route, deposited over glass substrates, and evaluated through cyclic voltammetry and amperometry as electrochemical sensor, using L-ascorbic acid as probe. Films with three different CNT/PAni ratios have been prepared. After the spectroscopic and morphological characterization, the electrochemical sensitivity towards L-ascorbic acid was evaluated and compared with similar sensors prepared from neat multiwalled carbon nanotubes (MWCNT) or neat polyaniline (PAni). The nanocomposite film that presented the best nanotube dispersion through the polymeric matrix presented the higher sensor sensibility, 0.237 µA (µmol L−1)−1 and a limit of detection (LOD) of 7.91 µmol L−1. These results evidenced a synergistic effect among the components, and the best response depended on strict control of the polyaniline matrix distribution surrounding the nanotubes.

Resumo em Inglês:

The champignon mushroom has no antinutritional factors that can affect iron bioavailability. It is considered a functional food and can provide health benefits by presenting bioactive components. The simultaneous transfer of Na+, K+ and Fe2+ in the pre-cooked mushroom (Agaricus bisporus) was modeled and simulated by the finite element method (FEM). The Biot number, cross and main diffusion coefficients were determined by the super modified simplex optimization method by minimizing the percentage errors. The errors between experimental and simulated data were 5.66% for NaCl, 5.36% for KCl and 8.26% for Fe2+ in the static brine and 3.11% for NaCl, 3.30% for KCl and 15.34% for Fe2+ in stirred brine. With the obtained model, it was possible to verify the influence of the film formed on the surface of the mushroom during the diffusion of ions, as well as the increase of ferrous ion adsorption when using the salting system with stirring.

Resumo em Inglês:

The influence of vineyard on wines was evaluated for the first time using a broader analytical approach: sensory analyses and several analytical techniques (gas chromatography-mass spectrometry (GC-MS), GC flame ionization detection (FID), GC-olfactometry-Osme technique (GC-O-Osme), GC × GC-MS), taking into account odoriferous compounds of Cabernet Sauvignon wines. Sensory attributes were correlated to the concentration of volatiles and also to favorable climate/solar exposition, less clayey/lower organic matter soil, and lower vegetative growth of one out of five vineyards, C1. Among 30 coelutions in GC-MS, 12 involved some of the odoriferous volatiles and GC × GC-MS was required to elucidate their identities. Higher concentrations of ethyl propanoate and diacetyl (related with red fruits/aromatic intensity) and of acetoin (aroma of dry fruits, but coeluted with octanal in first dimension (1D), which presents green odor) were found in C1 wine. It was also correlated with positive appearance attributes, gustatory persistence, body, smell and taste harmony, as well as with higher concentrations of phenolic acids, anthocyanins, flavonols, stilbenes, and flavanols.

Resumo em Inglês:

The use of agricultural residues for the production of bio-oil is an important alternative to the use of fossil fuels. In this study, the Caupi bean pod (Vigna unguiculata) was characterized and used as biomass in the production of bio-oil. This biomass was evaluated in terms of physicochemical, morphological (scanning electron microscopy (SEM)), and thermal (thermogravimetric analysis (TGA), differential scanning calorimetry (DSC)) characterization, lignocellulosic composition, and pyrolysis processes. The pyrolysis was carried out in a stainless steel fixed-bed reactor (260 mm in length and 60 mm in diameter) under atmospheric nitrogen pressure. Pyrolysis was conducted at 550, 600, and 700 °C and N2 gas flow of 2, 5, and 7 mL min-1. The chemical composition of the bio-oils was studied through CHN, TGA, Fourier-transform infrared spectroscopy (FTIR), and gas chromatography-mass spectrometry (GC-MS). The results confirmed the bean pod’s potential in the thermochemical process. The thermogravimetric analyses demonstrate that there can be a relationship between the components of the principal biomass (cellulose, hemicellulose, and lignin) and the compounds present in the bio-oil. The obtained bio-oils represent bio-products that are rich in compounds of several chemical classes with relevant commercial value such as acids (palmitic, linoleic, oleic, and stearic), alcohols (ethylene glycol), sugars (levoglucosan), and phenols (guaiacol, catechol, phenol, and pyrocatechol).

Resumo em Inglês:

Formaldehyde (FA) and acetaldehyde (AA) were determined in the ambient air of five gas stations (GS) in the city of Salvador, Bahia State, Brazil, using three passive samplers exposed simultaneously for 8 h and analysis by high-performance liquid chromatography-ultraviolet detection (HPLC-UV). The concentration ranges found were 3.31-5.78 µg m−3 for FA and 10.5-28.2 µg m−3 for AA. These values were below the exposure limits recommended by national and international agencies for occupational environments, however, FA concentrations were above the more restrictive limit (3.30 µg m−3) stablished by Texas Commission on Environmental Quality (TCEQ) for long-term outdoor exposure. The lifetime cancer risks (LCR) found associated with the exposure of GS employees to these aldehydes over the 30-year period varied between 4.51 × 10−6-8.00 × 10−6 for FA and 2.46 × 10−6-6.60 × 10−6 for AA. These values are above the acceptable limit set by the USEPA (1.0 × 10−6), reinforcing the need for actions to minimize the occupational exposure, mainly to FA, which is associated with nasopharyngeal cancer.

Resumo em Inglês:

This study is the first to propose the simultaneous quantification of 10 elements in fruits of Casearia fasciculata by inductively coupled plasma optical emission spectrometry (ICP OES). A method of digestion using dilute nitric acid was optimized by mixture design for extraction of elements in the seed, peel, and pulp of Casearia fasciculata cultivated in the Bahia State, Northeastern Brazil. Four different approaches were used to evaluate the digestion procedure ((i) desirability; (ii) multiple response; (iii) residual carbon content and (iv) residual acidity). The accuracy of the method of digestion was applied for the extraction of the studied elements in two certified reference materials (RM-Agro E1001a Brachiaria brizantha and NIST 1515 apple leaves). The limits of quantification of the method (µg g−1) were: Cr, 0.42; Cu, 0.69; Fe, 1.5; Mn, 0.14; Zn, 1.8; Ca, 29.0; K, 3.5; Mg, 1.9; P, 6.4; and S, 17. Two multivariate tools, principal component analysis (PCA) and hierarchical cluster analysis (HCA), were efficient in the formation of groups, corresponding to the fruit parts. Thus, the peel and seed of Casearia fasciculata present potential to be used as mineral supplements in human nutrition.

Resumo em Inglês:

The degradation of a pharmaceutical mixture (gemfibrozil, hydrochlorothiazide and naproxen) by TiO2/UV-A in different aqueous matrices was evaluated. The matrix components affected the operational conditions, rate constants, and removal efficiency of the pharmaceuticals, as well as toxicity. For sewage treatment plant effluent, a TiO2 concentration three-fold higher (450 mg L−1) and an irradiation time 1.5-3 times longer were required to reach the same efficiency of degradation as the pharmaceuticals in deionized water and surface water matrices. An improvement in the rate constants and the removal efficiency of the pharmaceuticals was achieved by adding 6 mg L−1 of H2O2 and 150 mg L−1 of TiO2 in deionized water and surface water, but not in the sewage treatment plant effluent, due to the coupling of 450 mg L−1 of TiO2 and 50-200 mg L−1 of H2O2. Overall, TiO2/UV-A efficiently degraded all compounds, but an additional step is needed for the removal of residual toxicity.

Resumo em Inglês:

A series of novel 1-(substituted-phenyl)-3-(4,5-dihydro-1,3-oxazol-2-yl)-9H-β-carboline (8a-8i) and 1-(substituted-phenyl)-3-(5,6-dihydro-4H-1,3-oxazin-2-yl)-9H-β-carboline (9a-9h) derivatives, as well as their respective N-(chloroalkyl)-1-(substituted-phenyl)-9H-β-carboline-3-carboxamide precursors (6a-6i and 7a-7h), were synthesized and evaluated for their in vitro antileishmanial activity against promastigote and intracellular amastigote forms of Leishmania amazonensis. Compounds 8d, 8i, 9e and 9h exhibited significant activity for both promastigote and amastigote forms, with IC50 (50% inhibitory concentration) values ranging from 2.9 to 23.0 µM. In addition, spin label electron paramagnetic resonance (EPR) spectroscopy studies were carried out for the most active compounds against L. amazonensis promastigotes. The studies indicated that the tested compounds cause strong stiffness in the parasite plasma membrane and are capable of inducing internal metalloproteins oxidation of the parasite, resulting in their cross-linking to skeletal proteins. Compounds 8d and 8i produced the largest effect, showing that the presence of oxazoline group at C-3 of β-carboline nucleus is important for antileishmanial activity.

Resumo em Inglês:

Cloud point extraction (CPE) in association with graphite furnace atomic absorption spectrometry (GF AAS) was proposed for preconcentration and quantification of trace amounts of copper and cadmium in samples of saline produced formation water from petroleum exploration. The procedure was based on the formation of hydrophobic complexes of the analytes with 1,5-diphenylthiocarbazone (dithizone) in a micellar media of the surfactant (1,1,3,3-tetramethyl butyl) phenyl-polyethylene glycol (Triton X-114). Constrained mixture design was performed for the optimization of the proportions of the three solutions employed in the CPE: Triton X-114, dithizone, and buffer solution. Under the recommended conditions, the CPE GF AAS procedure allowed to obtain enrichment factors of 18 and 11 times, limits of quantification of 0.030 and 0.12 µg L-1 and precision, expressed as relative standard deviation (RSD, n = 8, 2.0 µg L-1), of 1.1 and 4.3% for copper and cadmium, respectively. The CPE GF AAS method was applied to the determination of copper and cadmium in samples of saline produced formation water from petroleum exploration, and its accuracy was accessed by analyzing certified reference material CASS-5 (Nearshore Seawater Reference Material for Trace Metals) from National Research Council (Canada).

Resumo em Inglês:

Currently, treatment of Chagas disease is restricted to the use of benznidazole and nifurtimox; however, nifurtimox was temporarily suspended in some countries. Based on the limitations in pharmacological treatments, it is essential to guarantee the quality of benznidazole. Therefore, this work aimed to identify the degradation products of benznidazole and to validate a stability indicating method. The stability test was performed through a forced degradation study, exposing benznidazole under a range of conditions. Benznidazole proved to be unstable under acidic and alkaline conditions, and three products were identified by liquid chromatography coupled to a hybrid quadrupole time-of-flight mass spectrometer (UPLC-QTOF-MS). Furthermore, a stability indicating method by high performance liquid chromatography with a diode array detector (HPLC-DAD) for benznidazole was developed and validated according to ICH (International Conference on Harmonisation) and ANVISA (Agência Nacional de Vigilância Sanitária) guidelines. The method was linear (180-420 µg mL-1 range), selective in the presence of degradation products, precise (relative standard deviation (RSD) < 0.6%), accurate (recovery > 99.2%), robust, and free of matrix effects. The method was successfully able to quantify the benznidazole in pharmaceutical formulations.

Resumo em Inglês:

In the present study, the elemental content of the particulate matter PM2.5 (particulate matter with diameters lower than 2.5 µm) and PM10 (particulate matter with diameters lower than 10 µm) of the Brazilian city of Rio Claro (SP) were analyzed by synchrotron radiation X-ray fluorescence (SR-XRF) in the Brazilian Synchrotron Light Laboratory (LNLS). A fractional sampling of particulate matter (PM) was carried out in two climatic periods (dry and rainy season). The elemental determination of PM2.5 and PM10 included the following elements: Si, S, Ca, K, Ti, Cr, Mn, Fe, Cu, and Zn. Elemental correlation studies, cluster analysis, principal component analysis and enrichment factor determination were performed in order to allow the distinction of the main sources of the emission of PM. The mean elementary contents, especially in PM10, were statistically different to each other between the sampling seasons and higher in dry than in rainy season. The cluster analysis indicated two groups as being the main constituting element groups for the composition of PM in Rio Claro. A major group originated by the resuspension of soil composed by the elements Si, Fe, Ca and K, and a second, minor group composed of S, Ti, Mn, Cu, Cr, and Zn, presumably influenced by vehicular emissions and the regions adjacent ceramic industries.

Resumo em Inglês:

The detection of vitamin D in complex samples is challenging because of the instability of vitamin D in sample preparation. To resolve this problem, packed-fiber solid-phase extraction (PFSPE) has been successfully developed for the pre-treatment of samples containing vitamin D2 (D2) and vitamin D3 (D3) in dairy products. Based on PFSPE, vitamin D could avoid oxidation because of the shorter extraction time. The adsorbent materials, polystyrene/polypyrrole (PS/PPy) nanofibers, were prepared by electrospinning of PS and in situ polymerization of PPy on the surface of PS nanofibers. The linearity was within the range of 1-2000 ng mL−1 in dairy solution, and the recoveries were 91.9-109.1% with a relative standard deviation (RSD) < 13.6%. Therefore, the prepared method could be used for the detection of D2 and D3 in dairy products.

Resumo em Inglês:

The present work studied aqueous extracts of castor beans as a natural inhibitor of the corrosion of mild steel in 1 M HCl using gravimetric tests, potentiodynamic polarization curves, linear polarization method, electrochemical impedance measurements, surface analysis by scanning electron microscopy (SEM) and chemical characterization by Fourier transform infrared spectroscopy (FTIR). Gravimetric tests showed that inhibition efficiency (IE) increased with immersion time and concentration of the extract, reaching 97.8% in the presence of 800 mg L−1 inhibitor after 24 h immersion time. For the gravimetric tests varying the temperature, a decrease of the activation energy (Ea) was observed, suggesting chemical adsorption of extract components on the metal surface. The extracts from the castor beans acted as a good corrosion inhibitor, and the macromolecules present in the high molecular weight fraction (HMWF) have a fundamental participation in this process since it presented 93.7% of IE for 200 mg L−1.

Resumo em Inglês:

This study describes a single step, high yield and purity, ecofriendly and scalable procedure to prepare a selenium derivative (diethyl selenodiglycolate). Diethyl selenodiglycolate rapidly reduces hypochlorous acid (HOCl, second-order rate constant of 7 × 107 M−1 s−1) to generate its corresponding selenoxide. In activated HL-60 cells, diethyl selenodiglycolate selectively reacted with HOCl (half maximal inhibitory concentration (IC50) = 23.07 µM) but not with superoxide anion radical or hydrogen peroxide without any cytotoxicity. These results show that this synthetically simple selenide reacts in a very efficient and specific way with the harmful pro-oxidant HOCl being a promising compound to be applied in oxidative inflammatory-related conditions.

Resumo em Inglês:

Biodiesel contains esters in its composition which make it susceptible to oxidation. Among the factors that cause this reaction is the contamination with metal ions. In the present work, it was analyzed biodiesel samples obtained from a mixture containing 39.0% m/m soybean oil, 22.0% m/m beef tallow and 39.0% m/m poultry fat using a methyl route. Copper ions were added to the biodiesel to evaluate its catalytic action in the oxidation reaction, in the presence and absence of rosemary extract. During 192 h of assay, samples containing copper, without extract, showed shorter induction periods, higher rate constants and lower activation energy, when compared to samples containing extract, at the same assay temperature. Copper ions presented a strong catalytic action causing linearity deviations showing a super-Arrhenius behavior, while rosemary extract delayed the oxidative process and showed no linearity deviations.

Resumo em Inglês:

Two series of new compounds containing 1,2,3-triazole moiety were designed as putative GlyT1 inhibitors aiming the discovery of new hits with activity in cognitive disorders. 1,4-Disubstituted α-hydroxy-1,2,3-triazoles were obtained as racemates in moderate to good yields by the copper-catalyzed azide-alkyne cycloaddition (CuAAC) reaction (click chemistry) as the key step between propargyl alcohols and aryl azides, previously prepared from anilines or boronic acids. Benzo[c]chromene-triazoles were planned to be obtained by palladium-catalyzed C−H activation using [bis(trifluoroacetoxy)iodobenzene] (PhI(TFA)2) of some α-hydroxy-1,2,3-triazoles, since benzo[c]chromenes are also privileged groups with several biological activities, including to the central nervous system. Unexpectedly, 9H-fluorenes-1,2,3-triazoles, instead of benzo[c]chromene-triazoles, were obtained by Friedel-Crafts alkylation reaction. The two series of compounds were tested for inhibition of the glycine transporter (rat GlyT1 isoform) but only the α-hydroxy-1,2,3-triazole 9b was active (half maximal inhibitory concentration (IC50) = 8.0 µM).

Resumo em Inglês:

The present study evaluated the main factors that influence the photocatalytic activity of titanium dioxide (TiO2) films grown by metalorganic chemical vapor deposition (MOCVD) at 400 and 500 °C, in different growth times. The photocatalytic behavior was analyzed by measuring the methyl orange dye degradation at different pH values. Structural and morphological characteristics, and the recyclability of the catalysts for several cycles were also investigated. Anatase phase was identified in all films. The higher photodegradation performances were obtained at acidic pH. The results demonstrated that the photocatalyst thickness is an important parameter in heterogenous photocatalysis. The best photocatalytic result occurred for the 395 nm-thick TiO2 film grown at 400 °C, which presented 65.3% of the dye degradation under UV light. The recyclability experiments demonstrated that the TiO2 films grown by MOCVD present a great stability after several photocatalytic cycles, which allows their practical application for water treatment with high efficiency.

Resumo em Inglês:

In this work, it is described the design of twenty-four heterocyclic amine-azachalcones compounds through molecular hybridization of chalcone scaffold and fragments of isoniazid, fluoroquinolones, and linezolid with antituberculosis potential. The new compounds were synthesized via Claisen-Schmidt condensation, providing yields of 36-95%. Fifteen compounds showed antituberculosis activity against Mycobacterium tuberculosis H37Rv strain. Two amine-azachalcones 15 and 17 showed relevant biological activity with minimum inhibitory concentration (MIC) values of 6.62 and 4.85 µM, respectively. Compound 12 showed the best profile of antitubercular activity with MIC = 9.54 µM and selectivity index (SI) = 9.33. It was found that morpholine group is important to increase potency of antimycobacterial activity but also to add some toxicity to the chalcone molecular framework. The results described herein would be a guide in the designing of novel and optimized antitubercular derivatives based on the chalcone scaffold.

Resumo em Inglês:

A method for quantification of arsenic, cadmium, mercury, and lead in pineapple using inductively coupled plasma-mass spectrometry (ICP-MS) was developed, validated, and used to test the homogeneity and stability of in-house reference materials. The method was tested at the regulation levels given by the Food and Agriculture Organization of the United Nations (FAO, 100 µg kg−1). The mineralization conditions of the samples, in a microwave oven, were improved throughout the study of HNO3 and H2O2 concentrations, sample weight, time, and temperatures. The calibration was made by a gravimetric standard addition method with internal standard correction. The validation parameters were accuracy (trueness as recovery, between 97-112%, and precision as repeatability, below 12%), limits of detection (As 14.2, Cd 1.5, Hg 21.9, and Pb 5.4 µg kg−1 measured in pineapple), linearity and selectivity. The in-house material was lyophilized or dried in an oven. The best way to dry it was by the oven process because it has the lowest uncertainty.

Resumo em Inglês:

In this work, we report the synthesis and characterization of new amorphous graphene-like TiO2/chitosan carbon microspheres and its performance as photocatalyst. Four different carbon chitosan microspheres materials were obtained based on the distinctive procedure to incorporate TiO2 and TiOSO4 to chitosan structure by pyrolysis at 600 °C. Detailed characterizations were carried out using many different techniques, as thermogravimetric analysis/differential scanning calorimetry (TGA/DSC), scanning electron miscroscopy/energy dispersive X-ray spectroscopy (SEM/EDS), Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), N2 adsorption-desorption, and the obtained materials show an amorphous and a graphene-like structure, which improve the photocatalytic activity. The synthesized materials promoted a fast degradation of three micropollutants under UV-A radiation and, in all cases the degradation rate was approximately 98% at 30 min of reaction, being superior to the P-25 TiO2 efficiency. Due to the amorphous graphene-like structure, all the materials present low adsorption capacity, the high photocatalytic efficiency can be attributed to the material structure that promotes the effective charge separation which reduces the recombination electron/hole, enhancing the photocatalytic efficiency.

Resumo em Inglês:

Since the 1950s, pesticides have been used in agriculture. The increase in their consumption has been observed in recent years. In this work, it was determined the concentration of pesticides in the atmosphere of São Paulo and Piracicaba cities (sugarcane plantation site) and the hazard quotients and cancer risk caused by inhalation of these compounds were calculated. Twenty-three samples were analyzed and 34 pesticides associated to atmospheric particulate matter (with diameter equal to or less than 2.5 (PM2.5) and 10 µm (PM10)) were investigated by gas chromatograpy-mass spectrometry (GC-MS). Fourteen compounds including organochlorines, organophosphorus, and pyrethroids pesticides, were determined in these samples. The concentrations in the particulate matter ranged from 17 pg m−3 (tebuconazole) in Piracicaba, to 166 pg m−3 (endrin aldehyde) in São Paulo. The highest values of daily inhalation exposure for heptachlor were 9.0 × 10−5mg kg−1 day−1 at Piracicaba, and 6.5 × 10−5 mg kg−1 day−1 at São Paulo, in both cases registered in infants. The values of the hazard quotients are lower than 1.0, indicating that there is no danger to the exposed population, it is health protective. On the other hand, the cancer risk calculations for heptachlor resulted in values above those recommended by US Environmental Protection Agecy (EPA).

Resumo em Inglês:

Fingerprints are unique to each individual, contributing to human identification in forensic cases. The powder technique being widely used is considered one of the most important in latent fingermarks analysis. In this sense, the present work aimed to synthesize 1-thiocarbamoyl-4,5-dihydro-1H-pyrazoles and apply them as powder agents to develop latent fingermarks. The compounds were prepared from an effective and green synthesis via the condensation of chalcones with thiosemicarbazide in ethanol under microwave irradiation. Pyrazoles were tested and compared with a standard white powder (Sirchie®) on glass surfaces using sebaceous and natural fingermarks so that molecule 2c has been shown to be more promising providing image clarity. The derivatives of pyrazoles were promising as an alternative latent fingermark, presenting high quality images for fingermarks, proving to be a great tool for forensic sciences.