Monte Carlo thermodynamic and structural properties of the TIP4P water model: dependence on the computational conditions

Classical Monte Carlo simulations were carried out on the NPT ensemble at 25°C and 1 atm, aiming to investigate the ability of the TIP4P water model [Jorgensen, Chandrasekhar, Madura, Impey and Klein; J. Chem. Phys., 79 (1983) 926] to reproduce the newest structural picture of liquid water. The results were compared with recent neutron diffraction data [Soper; Bruni and Ricci; J. Chem. Phys., 106 (1997) 247]. The influence of the computational conditions on the thermodynamic and structural results obtained with this model was also analyzed. The findings were compared with the original ones from Jorgensen et al [above-cited reference plus Mol. Phys., 56 (1985) 1381]. It is notice that the thermodynamic results are dependent on the boundary conditions used, whereas the usual radial distribution functions g(O/O(r)) and g(O/H(r)) do not depend on them.

Determinação de carbaril utilizando testes ELISA (Enzyme-linked immunosorbent assay) e CLAE com detecção por arranjo de diodos

ELISAs have been applied to pesticide residue analysis due to their high sensitivity and selectivity. However, some ELISAs performance may be affected by matrix components. In this work, ELISA for carbaryl in water samples was checked for interference by naturally occurring fulvic acids. The results suggested that the high fulvic acid concentration (ž³30 mg L-1) and acidic pH conditions (pH 4.0) interfere with the signal detection decreasing the method sensitivity. A dilution of the samples and adjust to pH 8.0 are appropriate to minimize the matrix interferences in the ELISA method. Good correlation between ELISA and HPLC-DAD results was observed.

Determinação da 2,5-hexanodiona em amostras de urina submetidas à hidrólise ácida: importância da coluna cromatográfica e do pH do meio

Acidic hydrolysis of samples is frequent in urinary 2,5-hexanodione determination. This hydrolysis should be performed under proper conditions, in order to avoid interference, such as the presence of 2,5-dimethylfurane and 2-acetylfurane. The results of the present work, as well as data from the literature, show that the use of non-polar or slightly polar chromatographic columns of 30 m length is an essential condition for 2,5-HD determination in an acid hydrolysed urine sample. In the same way the pH should be kept between 0.3 and 0.5. The mean concentrations of 2,5-HD in samples submitted to hydrolysis (0.50 ± 0.28 mg/g of creatinine) was about 3 times higher than those found in the samples without acid hydrolysis (0.19 ± 0.3 mg/g of creatinine).

Influência do método de extração nos teores de metilxantinas em erva-mate (Ilex paraguariensis a. St.-Hil., aquifoliaceae)

Ilex paraguariensis A. St. -Hil. is a native species of southern South America. The caffeine content in Ilex paraguariensis leaves has been considered an important quality parameter for maté-derived products. In this work different extraction methods for the determination of these methylxantines are compared. The influence of the extraction conditions on the methylxanthine yields was evaluated. Extraction by decoction with acidic aqueous solution (H2SO4 4N) presented the higher efficiency in the theobromine extraction. The extraction in a Soxhlet with acidic aqueous solution and decoction with acidic aqueous solution showed the highest caffeine yield. For the concomitant theobromine and caffeine quantification, the decoction with acidic aqueous solution is suggested.

Reaction mixtures formed by nitrite and selected sulfa-drugs showed mutagenicity in acidic medium

Nitrite, which is present in preserved meat and can be produced in the oral cavity by reduction of nitrate taken from vegetables, could react in stomach with nitrosatable drugs, giving genotoxic-carcinogenic N-nitroso compounds (NOC). The mutagenicity of reaction mixtures formed by sodium nitrite and selected sulfa-drugs (sulfathiazole, HST; phtalylsulfathiazole, PhST; complex Co(II)-sulfathiazole, Co(II)-ST) in acidic medium was evaluated using the Salmonella typhimurium reverse mutation assay (Ames test), with TA98 and TA 100 strains. The reactions were carried out at room temperature, with a mole ratio [nitrite]/[sulfa-drug] > 1. The three reaction mixtures showed mutagenic effects in the considered range.

Recovery of manganese and zinc from spent Zn-C and alkaline batteries in acidic medium

The anode and the internal paste of spent Zn-C and alkaline batteries were leached with 2 mol L-1 H2SO4 at 80 ºC for 2 h. Solid/liquid ratio was 1/10 (g mL-1). The leachate was treated with Na2S in order to precipitate Hg, Cd and Pb. Zn was quantitatively isolated at pH 1,5-2 by adding Na2S. Mn can be precipitated at pH close to 7. Na2S may be replaced by oxalic acid. Zn precipitated at pH around 0, whereas Mn was quantitatively recovered at pH > 4. Acidity control is a critical parameter. Na2SO4 and carbon are the end products.

Simple and sensitive spectrophotometric methods for the analysis of mesalamine in bulk and tablet dosage forms

Three simple, sensitive, economical and reproducible spectrophotometric methods (A, B and C) are described for determination of mesalamine in pure drug as well as in tablet dosage forms. Method A is based on the reduction of tungstate and/or molybdate in Folin Ciocalteu's reagent; method B describes the reaction between the diazotized drug and α-naphthol and method C is based on the reaction of the drug with vanillin, in acidic medium. Under optimum conditions, mesalamine could be quantified in the concentration ranges, 1-30, 1-15 and 2-30 µg mL-1 by method A, B and C, respectively. All the methods have been applied to the determination of mesalamine in tablet dosage forms. Results of analysis are validated statistically.

Descoloração e degradação do azo corante Vermelho GRLX-220 por ozonização

The discoloration and degradation of the textile dye RED GRLX-220 using the electrochemically generated ozone was investigated. Total discoloration was rapidly achieved in both acid and basic conditions. A pseudo-first order kinetics was observed for discoloration, influenced by pH and ozonation time. A considerable degree of mineralization (60%) was obtained after 30 min of ozonation in alkaline medium. The feasibility of organic matter oxidation during the ozonation process increased in both acidic and alkaline media. The toxicity decreased after the ozonation process, suggesting that the byproducts are less toxic than the parental compound.

Determination of cinnamic acid in human urine by flow injection chemiluminescence

It was found that cinnamic acid can react with potassium permanganate in the acidic medium and produce chemiluminescence, which was greatly enhanced by glyoxal. Under the optimum conditions, the linear range for the determination of cinnamic acid was 1.0×10-8 to 1.0×10-4 mol L-1 with a detection limit of 8.0×10-9 mol L-1, the relative standard deviation was 1.7% for 2.0×10-6 mol L-1 cinnamic acid solution in nine repeated measurements. This method was found to be novel0simple0fast and sensitive, it was successfully applied to the determination of cinnamic acid in human urine. Furthermore, the possible reaction mechanism was also discussed.

Obtenção de biodiesel por transesterificação em dois estágios e sua caracterização por cromatografia gasosa: óleos e gorduras em laboratório de química orgânica

Methanolic transesterification of oils and fats was carried out in a two steps procedure, under basic and acidic catalysis. Palm, soybean, canola, corn, rice, grapeseed, sunflower, peanut, pequi and olive oils, besides tallow and lard were used as feedstock. Specific gravity, relative viscosity, thin layer chromatography and gas chromatography were used to characterize the biodiesel. Biodiesel was obtained in high yield and purity. Results were used to discuss the following key-concepts: 1 - triglycerides, composition and properties; 2 - nucleophilic acyl substitution under basic and acid conditions, 3 - thin layer chromatography, 4 - gas chromatography and its quantitative methods.

Labile copper and zinc fractions under different salinity conditions in a shipyard area in the patos lagoon estuary, south of Brazil

Copper and zinc are common elements in paint residues and can be toxic to estuarine organisms. This study aims to determine the labile dissolved and labile particulate fractions (LPFs) of copper and zinc in the estuarine waters of a shipyard in southern Brazil under different salinity levels and in different seasons. The labile dissolved fraction was determined using the diffusive gradient in thin-film (DGT) technique. The variations in DGT-Cu (0.22-1.05 µg L-1), DGT-Zn (0.54-18.39 µg L-1), LPF-Cu (1.22-3.77 µg g-1), and LPF-Zn (4.29-19.12 µg g-1) concentration were related to changes in their physico-chemical parameters and as a result of boat maintenance activities.

Optimization of chromatographic conditions and comparison of extraction efficiencies of four different methods for determination and quantification of pesticide content in bovine milk by UFLC-MS/MS

This paper describes the optimization of a multiresidue chromatographic analysis for the identification and quantification of 20 pesticides in bovine milk, including three carbamates, a carbamate oxime, six organophosphates, two strobilurins, a pyrethroid, an oxazolidinedione, an aryloxyphenoxypropionate acid/ester, a neonicotinoid, a dicarboximide, and three triazoles. The influences of different chromatographic columns and gradients were evaluated. Furthermore, four different extraction methods were evaluated; each utilized both different solvents, including ethyl acetate, methanol, and acetonitrile, and different workup steps. The best results were obtained by a modified QuEChERS method that lacked a workup step, and that included freezing the sample for 2 hours at -20 ºC. The results were satisfactory, yielding coefficients of variation of less than 20%, with the exception of the 50 µg L-1 sample of famoxadone, and recoveries between 70 and 120%, with the exception of acephate and bifenthrin; however, both analytes exhibited coefficients of variation of less than 20%.

PYROLIGNEOUS LIQUOR PRODUCED FROM ACACIA MEARNSII DE WILD WOOD UNDER CONTROLLED CONDITIONS AS A RENEWABLE SOURCE OF CHEMICALS

Acacia mearnsii de Wild (black wattle) is one of the most important trees planted in Southern Brazil for tannin extraction and charcoal production. The pyrolysis of the black wattle wood used for obtaining charcoal is performed in brick ovens, with the gas fraction being sent directly into the environment. The present study examines the condensable compounds present in the liquor produced from black wattle wood at different thermal degradation conditions, using gas chromatography coupled with mass spectrometry (GC/MS). Branches of black wattle were thermally degraded at controlled ambient and temperature conditions. Overall, a higher variety of compounds were obtained under atmospheric air pressure than under synthetic air pressure. Most of the tentatively identified compounds, such as carboxylic acids, phenols, aldehydes, and low molecular mass lignin fragments, such as guayacol, syringol, and eugenol, were products of lignin thermoconversion. Substituted aromatic compounds, such as vanillin, ethyl vanillin, and 2-methoxy-4-propeny-phenol, were also identified. At temperatures above 200 ºC, furan, 2-acetylfuran, methyl-2-furoate, and furfural, amongst others, were identified as polysaccharide derivatives from cellulose and hemicellulose depolymerization. This study evidences the need for adequate management of the condensable by-products of charcoal production, both for economic reasons and for controlling their potential environmental impact.

DESENVOLVIMENTO DE EXPERIMENTO DIDÁTICO DE ELETROGRAVIMETRIA DE BAIXO CUSTO UTILIZANDO PRINCÍPIOS DA QUÍMICA VERDE

In this paper, we describe the development of low-cost teaching experiments of electrogravimetry for undergraduate students using principles of green chemistry. Copper was electrochemically deposited on brass under an electrical current density of 50 mA cm−2 from acidic solutions containing nitrate anions. Color changes at the brass electrode and of the solution were observed, indicating that the reduction of copper ions had occurred. The deposition efficiency values were between 92.8% and 93.8%, and the electrochemical efficiency values were between 85.6% and 86.5%. There was no significant contribution from parallel reactions. These experimental conditions facilitated the didactic exploration of gravimetric and electrochemical concepts. Following the principles of green chemistry, the experiments produced no toxic substances, all the materials could be recycled, and the energy consumption was the lowest. For this reason, this experiment was considered to be very interesting for didactical purposes.

OTIMIZAÇÃO DO PROCESSO DE TRANSESTERIFICAÇÃO EM DUAS ETAPAS PARA PRODUÇÃO DE BIODIESEL ATRAVÉS DO PLANEJAMENTO EXPERIMENTAL DOEHLERT

In this work, Doehlert experimental design was used to optimize the Transesterification Double Step Process (TDSP) method of methyl soybean oil biodiesel production which starts with a basic catalysis followed by an acidic catalysis. The conversion values were calculated from NMR spectra. Response surface was used to show the results of the interactions between the variables. This experimental design evaluated variables like catalyst and alcohol amount for the basic catalysis and time and temperature for the acidic catalysis. According to results obtained after Doehlert design application the alcohol amount was the main factor that influenced on the basic catalysis but for the acidic catalysis both time and temperature are important and their effects are opposite. It resulted on excellent conversions for both steps obtaining for the basic catalysis about 100% when was used like optimal conditions catalyst amount equal to 0.40 g and volume of methanol equal to 60 mL and for the acidic catalysis about 99% when was used like optimal conditions temperature of 65 °C and 90 minutes for reaction time.