Resumo em Inglês:

Organophosphorus compounds (OPs) are a large and diverse class of chemicals that have been synthesized, since the XIX century for several purposes like chemical weapons, flame-retardants, ectoparasiticides and investigational new drugs, but mainly as agrochemicals in agriculture and indoor. Although the amount of OP pesticides being used is declining, especially in developed countries, OPs continue being one of the most important classes of insecticides and chemical warfare agents today due to its toxic effects on the enzyme acetylcholinesterase (AChE). Existing research on the toxicological effects of OPs is extensive, however, there is a lack of knowledge on the long-term effects of low levels of OPs and their exactly pathways of toxicity. Recent data prove that other molecular targets than AChE could be targeted by OPs, triggering these effects. Here these data are reviewed and it is highlighted that the current uses of OPs are producing several neurotoxic effects. It is also shown that, to protect people from possible uses and misuses of OPs, more regulations on OPs are needed. Moreover, more mechanistic studies are needed to completely understand their toxicological interactions and mechanisms of action and to identify the whole group of enzymes that interact with them.

Resumo em Inglês:

A suitable and efficient high-performance liquid chromatography (HPLC) method was developed for the simultaneous determination of tuberculostatic isoniazid and its related impurities, isonicotinic acid and isonicotinamide, in oral solid dosage forms. We studied the influence on chromatographic separation of mobile phase parameters, such as pH, ion pairing and ionic strength, as well as column bonded phase and brands. The use of buffer solution pH 6.8:acetonitrile 96:4 (v/v) at 0.8 mL min-1, C18 column (250 × 4.6 mm, 5 µm), allowed proper separation of these ionizable analytes without the need of ion pairing agents. The limit of quantification of the method (0.1 µg mL-1) was suitable for the analysis of impurities. A drug-excipient compatibility study was carried out with the anaytical method proposed in this work and addressed frequent excipients used in isoniazid coated tablets. The dye FD&C blue 2 lake promoted the highest degradation of the tuberculostatic agent.

Resumo em Inglês:

A 23 factorial design with center point in triplicate was used to evaluate the application of different enzymes in extraction of sunflower oil, comparing its quality with the oil obtained by conventional methods (solvent and pressing) in relation to antioxidant capacity, phytosterol and tocopherol contents, and fatty acid composition. Three enzymes were used; Pectinex Ultra SPL, Celluclast 1.5 L and Alcalase 2.4 L; and three factors were evaluated: enzyme concentration, sample/water ratio and extraction time. Enzymatic aqueous extraction produced oil with better quality in relation to some of the evaluated parameters: highest antioxidant capacity against peroxyl radicals (371 µmol Trolox g-1 of oil), total phytosterols (183 mg 100 g-1 of oil) and omega-3 fatty acid content, as well the lowest content of saturated fatty acids. The application of enzymes in sunflower oil extraction represents an environmentally friendly methodology, free of toxic solvent residues and providing a final product of high quality.

Resumo em Inglês:

The proton dissociation equilibria of ascorbic acid were investigated using a combination of spectrophotometric/potentiometric techniques at constant temperature 25.0 ± 0.1 °C. The study was carried out over a wide range of ionic strengths of 0.1-3.0 mol dm-3 NaClO4 in ethanol-water mixture (1:1). The Gran's method was used for glass electrode calibration to obtain pH readings based on the concentration scale (pcH). Data process for calculation of the protonation constants was done using the STAR (stability constants by absorbance reading) computer program. The dependence on ionic strength of the constants was analyzed by means of the SIT approach (specific ion interaction theory). In addition to the specific interaction parameters of the ionic species, the protonation constants at infinite dilution (zero ionic strength) were obtained. Finally, the thermodynamic functions ΔG0 (standard Gibbs free energy change) for the protonation processes were also calculated at different ionic strengths.

Resumo em Inglês:

The electrochemical properties of montelukast sodium (MKST) at zinc oxide nanoparticles modified carbon paste electrode were investigated by cyclic voltammetry and square wave voltammetry. All studies were based on the irreversible and adsorption-controlled electrochemical reduction signal of montelukast sodium at about -0.7 vs. Ag/AgCl at pH 2.3 in methanol-Britton-Robinson buffer mixture. This adsorptive character of the molecule was used to develop a novel, validated, rapid, selective and simple square wave cathodic adsorptive stripping voltammeric method for the direct determination of montelukast sodium in pharmaceutical and biological fluids without time-consuming steps prior to drug assay. Peak current of electrochemical reduction of montelukast sodium was found to vary linearly with the concentration in the range from 1.0 × 10-8 to 1.28 × 10-6 mol L-1. In this method, limit of detection was found to be 7.7 × 10-9 mol L-1. The method was applied to determine the content of MKST tablet and spiked human serum.

Resumo em Inglês:

We investigated the photoelectrochemical oxidation of the dye Reactive Blue 4 in the presence of a DSA®-type electrode of nominal composition Ti/Ru0.3Ti0.7O2 under ultraviolet radiation, aiming to enhance the degradation yields of this dye. We conducted the photoelectrocatalytic treatment under galvanostatic control, using an 80 W mercury vapor lamp as the UV source. We also compared unassisted electrooxidative processes and photocatalytic processes with photoelectrochemical oxidation, to gain better insight into the employed advanced oxidation processes and to evaluate their applicability. The photoelectrooxidative process conducted at 37.8 mA cm-2 promoted fast color removal in the tested solution. The chemical oxygen demand and total organic carbon decreased by approximately 64.7 and 42.7%, respectively. High performance liquid chromatography, gas chromatography coupled to mass spectrometry helped to identify the intermediate compounds produced along the photoelectrochemical process, namely phthalic anhydride, phthalimide, phthalide, 1,3-indanone, and benzoic acid.

Resumo em Inglês:

The extraction of copper from aqueous sulfate solution with new extractant Cupromex-3302 (active substance is the 5-nonylsalicylaldoxime) using a rotating disc contactor (RDC) was investigated. It was observed from batch experiments that the best results were obtained with the initial aqueous pH and concentration of Cupromex-3302 of 1.9 and 10% (v/v) respectively. In continuous experiments, the first critical rotor speed based on drop breakage probabilities was determined. Then the effects of rotor speed, dispersed and continuous phase flow rates on hydrodynamic parameters such as static hold-up, mean drop sizes and extraction efficiency were studied. The experimental results were compared with the ones obtained by the empirical correlations for prediction of the dispersed phase static hold-up and mean drop sizes in terms of the operating variables and the physical properties. The results of experiments proved the feasibility of operating the solvent extraction of copper from the aqueous solution using rotating disc contactor.

Resumo em Inglês:

Improper disposal of electronic waste in the environment facilitates migration of heavy metals, especially lead, into the soil and can contribute to the bioavailability of this species. Based on a simplex-centroid mixture experimental design, small-scale tests were performed for incubation of printed circuit boards (PCBs) in mixtures containing organic matter (OM), kaolinite (KA) and iron oxides (IO) to verify lead migration. Regression equations were acquired and were adjusted to the obtained responses. Results showed high total content of Pb, ranging from 400 to 4000 mg kg-1, depending on the mixture and incubation time. Mobility and/or bioavailability of lead in the mixtures were evaluated by a three-step sequential extraction. The bioavailability factor (BF) was obtained from the ratio of the sum of exchangeable fraction (F1) and the organically bound fraction (F2) by F1, F2 and the residual fraction (F3) and the values of bioavailability factor for Pb, the heavy metal considered of greatest environmental concern in this study, ranged between 0.16 and 0.52.

Resumo em Inglês:

Four sulfonamide-chalcone derivatives were prepared and their crystal structure were elucidated by single-crystal X-ray diffraction technique. They were synthesized by Claisen-Schmidt condensation reaction between N-(4-acetylphenyl)benzenesulfonamide or N-(4-acetylphenyl)-2,5-dichlorobenzenesulfonamide with benzaldehyde or p-nitrobenzaldehyde. Values of Z' > 1 are found in three compounds as a consequence of conformerism. The chalcone molecular backbones are featured by different levels of planarity in their conformers. Another conformational variability is in its benzenesulfonamide moiety. In the compound came from N-(4-acetylphenyl)benzenesulfonamide and benzaldehyde, there is a rotation of ca. 180° on the bond axis bridging the sulfonamide and chalcone motifs of one conformer if the two others are taken as references. The cytotoxic activity of all compounds synthesized here and of two other related sulfonamide chalcones was also assessed against three cancer cell lines (SF-295, HCT-8 and MDA-MB-435). The para-nitro compounds were the most active ones among all those tested, regardless of substitution pattern in benzenesulfonamide core.

Resumo em Inglês:

Phenolic tert-butyldimethylsilyl (TBDMS) ethers can be deprotected to yield phenols in excellent yield using sodium cyanide (NaCN) as catalyst in ethanol. The deprotectation of various phenolic TBDMS ethers were found to be very convenient, fast, high yielding and chemoselective.

Resumo em Inglês:

The barrier and mechanical properties of polymer matrices are affected by the polymer crystallization kinetics and the incorporation of nanoparticles can modify the nucleation density as well as the rate and mechanism of crystallization. In this study, a nanocomposite of poly(lactic acid) (PLA) containing cellulose nanocrystals (CNC) was prepared in order to evaluate the effect of the CNC content on the crystallization kinetics of the polymer matrix. Dimethylformamide, a solvent of PLA, was used to replace the aqueous medium for the dispersion of the CNC, to facilitate the preparation of PLA films with dispersed CNC. Higher levels of CNC in the films induced an increase in the crystallization rate and reduced the degree of crystallinity without affecting the dimensions of the crystal lattice. In conclusion, the incorporation of CNC into PLA influences the crystallization kinetics, which significantly affects the PLA processing conditions.

Resumo em Inglês:

A simple, fast, sensitive and accurate spectrophotometric method has been developed for the quantitative determination of cephalexin monohydrate in dosage form and in commercial formulations. The method involves the addition of CeIV to cephalexin in acidic medium, followed by the determination of residual CeIV by reacting with a fixed amount of methyl orange, and the absorbance was measured at 510 nm. Beer's law was obeyed in the concentration range of 0.6-20 µg mL-1 with correlation coefficient of 0.992. The molar absorptivity was calculated and was found to be 9.8 × 104 L mol-1 cm-1. Different variables affecting the reaction conditions such as concentration and volume of CeIV, type and concentration of acids used, reaction time and temperature were carefully studied and optimized. The limit of detection (LOD) and limit of quantification (LOQ) were calculated and found to be 0.221 and 0.736 µg mL-1, respectively. The proposed method was found to have good reproducibility with a relative standard deviation of 4.4% (n = 9). The interference effects of common excipients found in pharmaceutical preparations were studied. The developed method was validated statistically by performing recoveries studies and successfully applied for the determination of cephalexin in bulk powder and pharmaceutical preparations. Percent recoveries were calculated and found to range from 90.6 to 102.9% for bulk powder and from 98.7 to 104.8% for pharmaceutical preparations.

Resumo em Inglês:

The aim of this study was to evaluate the performance of a reflux system adapted in the digestion tubes in sample preparation of xanthan gum for subsequent determination of Ca, Cu, K, Mg, Na and Zn by using spectrometric techniques. Through the proposed method, the samples were digested with HNO3 for 3 h in a digester block at 220 °C. The accuracy of the method was evaluated by comparing the results with another sample preparation method and by using recovery tests, which results vary between 83 and 103%. The efficiency of digestion was assessed and significant results were verified through residual carbon values, which were five times lower compared to conventional acid digestion in open system, with use of HNO3 and HClO4. The proposed methodology is a simple and accurate analytical strategy, which does not require the use of special equipment, neither a mixture of strong oxidizing acid in the sample preparation.

Resumo em Inglês:

This work describes an electrochemical and quantum chemical investigation of the fipronil insecticide. Cyclic voltammetry (CV) and square wave voltammetry (SWV) experiments were performed over a graphite-polyurethane (GPU) composite electrode. The fipronil molecule presents an one-electron irreversible oxidation reaction. Profiting the SWV signal a square wave stripping voltammetry (SWSV) procedure to determine the fipronil molecule in a 0.10 mol L-1 Britton-Robinson buffer solution, pH 8.0 was developed with accumulation potential and time of 0.50 V and 120 s, respectively. The limits of detection and quantification were 0.80 and 2.67 μg L-1, respectively. Recovery tests were performed in three natural waters samples with values ranging from 99.67 to 101.37%. Quantum chemical studies showed that the nitrogen atom of the pyrazole group is the most probable oxidation site of the fipronil molecule.

Resumo em Inglês:

Bentonite is a natural clay that presents characteristics such as good capacity to exchange cations, large specific surface area, large porosity, and possibility to undergo intercalation and/or functionalization. This work reports on bentonite functionalization with organomodified alkoxides. Functionalization afforded hybrid materials displaying desirable properties for adsorption of chromium trivalent ions. Infrared absorption spectroscopy, X-ray powder diffraction, thermal analysis, specific surface area analysis, and adsorption experiments with methylene blue helped to characterize the materials and evaluate their cationic exchange capability. These techniques evidenced functionalization of the Brazilian bentonite. Kinetic and equilibrium experiments on the adsorption of chromium trivalent ions aided determination of the equilibrium time of kinetic adsorption isotherms and revealed whether the functionalized matrices adsorbed chromium trivalent ions. Chromium displayed S1 type adsorption isotherms, which confirmed that adsorption capacity originated from cooperative forces between the adsorbate and the hybrid adsorbents.

Resumo em Inglês:

The electrochemical copolymerization between selenophene and 3-chlorothiophene monomers was successfully realized. The influence of the applied polymerization potential and the monomer feed ratio on the copolymer properties were investigated, and the results revealed that the obtained polymer films strongly depended on the polymerization conditions. The obtained copolymers showed good redox stability in acetonitrile-based electrolyte solution. Band gap energy of the homo- and copolymer films was estimated and the values were between 1.95-2.11 eV. The electrical conductivity measurements of selenophene-3-chlorothiophene copolymers were successfully achieved using a four-probe technique and generally increased with increasing temperature. Fourier transform infrared (FTIR) characterization disclosed that the bands of homopolymers were retained in the spectra of copolymers with typical assignments suggesting that α-positions in the polymer chains were involved in the polymerization.

Resumo em Inglês:

We introduce a novel approach in simple and highly sensitive fluorometric determination of ammonium nitrogen. The proposed method is based on a fluorescence derivatization with benzyl chloride. The benzyl chloride was converted to a new fluorescent derivative by reaction with ammonium ion (NH4+) in the presence of sodium bicarbonate. The excitation and emission wavelengths were 258 and 284 nm, respectively. The effects of benzyl chloride concentration, sodium bicarbonate concentration, reaction temperature and time, and hydrochloric acid concentration were studied in detail. Under the optimal conditions of the experiment, the linear range for determination of ammonium nitrogen was 0.01-0.60 mg L-1, and the detection limit was 0.008 mg L-1. Relative standard deviation of eleven measurements for 0.40 mg L-1 NH4+-N was 2.6%. The method was successfully applied to the determination of ammonium nitrogen concentration in different water samples. The mechanism of the derivatization was further confirmed by Fourier transform infrared (FTIR) spectra.

Resumo em Inglês:

The support effect on the properties of iridium catalysts for C-C and C-O hydrogenolysis was investigated. Cyclohexane conversion and glycerol hydrogenolysis were used to compare the behavior of iridium catalysts in terms of C-C and C-O cleavage. The nature of the support influenced the catalyst performance in both cyclohexane conversion and glycerol hydrogenolysis. This effect was more evident on the product selectivity. Ir/SiO2 catalyst presented the highest cyclohexane hydrogenolysis activity and the highest selectivity to minor hydrocarbons formed from hexane re-adsorption. For glycerol hydrogenolysis, all catalysts displayed a higher selectivity to products formed by C-O cleavage, mainly 1,2-propanediol (1,2-PDO). Ir/ZrO2 catalyst presented the highest activity in all reaction conditions and the lowest selectivity to minor alcohols produced by C-C cleavage like methanol, ethanol and ethylene glycol. The results were explained in terms of the requirements and the structure of the catalytic sites.

Resumo em Inglês:

A new synthetic pathway to new bis-iminodihydrofurans is proposed, which involves the synthesis of N-substituted iminodihydrofurans from reaction of iminodihydrofurans with 2-cyanoacetohydrazide and their condensation with tertiary α-hydroxyketones. This sequence of reactions opens the new approach to the synthesis of novel polyheteroconjugated systems consisting from iminodihydrofuran rings. The methodology is simple, rapid and inexpensive affording high yields of the potentially bioactive products.

Resumo em Inglês:

The orientation of pterin-6-carboxylic acid on gold nanopillars was investigated by surface enhanced Raman spectroscopy and density functional theory methods. The experimentally vibrations from pterin-6-COOH free and attached to the Au surface display vibration features indicating chemical interaction of the pterin with the metal surface. The spectral feature evidenced that the pterin would adsorb on gold surface with a "lying down" configuration through the high intensity vibration of NH scissoring and rocking OH modes. The orientation study of pterins on gold nanopillars presented herein is believed to lead to new applications in biosensing field for detecting pterins of physiological importance.