4 research outputs found

    Photolysis of parabens using medium-pressure mercury lamps: Toxicity effects in MCF7, BAlb/c 3T3 cells and Ceriodaphnia dubia

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    Degradation studies of the propylparaben (PrP), butylparaben (BuP) and of the propylparaben-butylparaben mixture (PrP-BuP) in deionized water and surface river water was investigated as a function of pH and initial concentration of the reactants using a medium-pressure mercury lamp. The photolysis of parabens (concentration ranging from 5 to 30 mg L−1) followed apparent pseudo-first-order kinetics, with rate constants (k) in deionized water and surface river water changed from 1.80 × 10−1 to 3.68 × 10−2 min−1 and 1.43 × 10−1 to 1.45 × 10−2 min−1, respectively. Degradation reaction was faster at pH 5 in comparison with pH 7 or 11. The photolysis of parabens was greater than 91%, with low mineralization (26.15%) observed in acidic medium after 95 min. Analysis by chromatography coupled to mass spectrometry (LC-MS/MS) showed that only one product was generated during the degradation reaction and has UV bands similar to 3,4-dihydroxybenzoic acid. Estrogenic activity tests showed that non-degraded parabens stimulated the growth of breast adenocarcinoma (MCF-7) cells and this effect was evaluated after the photolysis. Cytotoxicity assays using fibroblasts cells (Balb/C 3T3 clone A31) indicated that the parental compounds and degradation products were not cytotoxic. On the contrary, non-degraded parabens were toxic to Ceriodaphnia dubia, but the product of photolysis was not. Overall, the photolytic method presented was able to degrade these parabens providing safe and non-estrogenic reaction product

    Cyanate as an Active Precursor of Ethyl Carbamate Formation in Sugar Cane Spirit

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    The thermodynamic and kinetic aspects of ethyl carbamate (EC) formation through the reaction between cyanate and ethanol were investigated. The rate constant values for cyanate ion decay and EC formation are (8.0 ± 0.4) × 10<sup>–5</sup> and (8.9 ± 0.4) × 10<sup>–5</sup> s<sup>–1</sup>, respectively, at 25 °C in 48% aqueous ethanolic solution at pH 4.5. Under the investigated experimental conditions, the rate constants are independent of the ethanol and cyanate concentrations but increase as the temperature increases (Δ<i>H</i><sub>1</sub><sup>⧧</sup> = 19.4 ± 1 kcal/mol, Δ<i>S</i><sub>1</sub><sup>⧧</sup> = −12.1 ± 1 cal/K, and Δ<i>G</i><sub>1</sub><sup>⧧</sup> = 23.0 ± 1 kcal/mol) and decrease as the solution pH increases. According to molecular modeling (DFT) that was performed to analyze the reaction mechanism, the isocyanic acid (HNCO) is the active EC precursor. The calculated Δ<i>G</i><sub>1</sub><sup>⧧</sup>, Δ<i>H</i><sub>1</sub><sup>⧧</sup>, and Δ<i>S</i><sub>1</sub><sup>⧧</sup> values are in very good agreement with the experimental ones
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