A fast and simple FIA-chemiluminescence method for the evaluation of Roselle flowers as scavenger of the free radicals generated by UV irradiated antibiotics.

This work proposes a new method for the in vitro evaluation of the effect of UV irradiation on the production of free radicals and other reactive species during the photodecomposition of drugs. The method was based on the UV irradiation of antibiotics molecules to generate excited states that undergo to homolytic bond cleavages. These reactive species can be detected by their ability to oxidize the luminol, producing the electronically excited aminophtalate, which decays to the ground state releasing electromagnetic radiation in the visible zone of the spectrum. This method was applied to penicillin G, nafcillin, azlocillin and neomycin dissolved in water. It was found that the intensity of the luminol chemiluminescence emission (CL) was proportional to the concentration and dependent on the molecular structure of these drugs. Under the optimized conditions, it was found that penicillin and azlocillin were the most susceptible to photodegradation, while neomycin sulfate was the less affected by the UV light. It was observed that the addition to the antibiotics dissolutions of a hydro-alcoholic extract of petals of calyxes of Roselle reduced the CL intensity, indicating that the extract was able to scavenge the free radicals in the irradiated drugs. This result suggest that its addition to the antibiotics can help in the protection against the radicals formed during the exposition to solar light of patients treated with topic similar antibiotics.

Determination of Co(II) in plant tissue by microwave digestion and ion chromatography coupled with luminol/perborate or luminol/percarbonate chemiluminescence detection.

INTRODUCTION: The cobalt is an essential element for leguminous plants but may be harmful for other species; for that reason determination of Co(II) is very important for the management of polluted areas and for discover plants with capacity for the hyperaccumulation of heavy metals, which has produced a growing necessity of fast, sensitive and selective analytical techniques. OBJECTIVE: To develop an analytical procedure for the determination of cobalt in plant tissue by coupling the ionic chromatography to the luminol-based chemiluminescence detection. METHODOLOGY: The sample was digested in a mixture of concentrated nitric acid and hydrogen peroxide, using an microwave oven to dissolve the Co(II). The solution containing Co(II) ions was injected to an ionic chromatograph using oxalic acid as the eluent. The detection was based on the catalytic effect of Co(II) on the luminol chemiluminescence using perborate or percarbonate as oxidants. Experimental variables, such as concentrations, pH, flow rates and acid digestion conditions were optimised. RESULTS: Well-resolved chromatographic peaks were obtained. The height and area showed linear dependences with the Co(II) concentration, which were used to quantify the heavy metal, with recoveries up to 95%. The microwave irradiation (60 s) was sufficient for the complete mineralisation of 200 mg of sample, employing 2 mL of the acid mixture. The method was free from the interferences, requiring less than 12 minutes to complete the analysis. CONCLUSION: The method was simple and rapid for the determination of cobalt in plant tissue with detection limits comparable to those obtained with more sophisticated and expensive analytical equipment.

Evaluation of lead(II) immobilization by a vermicompost using adsorption isotherms and IR spectroscopy.

The immobilization of lead ions by a vermicompost with calcite added was evaluated by adsorption isotherms and the results were explained on basis of the pH dependent surface charge and by IR spectroscopy. The results showed maximum adsorption values between 113.6 mg g(-1) (33 degrees C) and 123.5mg g(-1) (50 degrees C). The point of zero net charge (PZC) was 7.5+/-0.1, indicating the presence of a positive surface charge at the pH of batch experiments. The differences in the IR spectra at pH 3.8 and 7.0 in the region from 1800 to 1300 cm(-1), were interpreted on the basis of the carboxyl acid ionization, that reduced the band intensity around 1725 cm(-1), producing signals at 1550 cm(-1) and 1390 cm(-1) of carboxylate groups. Similar changes were detected at pH 3.8 when Pb2+ was present suggesting that the ion complexation takes place by a cationic exchange equilibrium, between the protons and Pb2+ ions.

Evaluación de la interacción vermicompost-Pb²+ a través de isotermas de adsorción y espectroscopia FTIR / Evaluation of interaction of vermicompost-Pb²+ through adsorption isothermals and FTIR spectroscopy

La adsorción de plomo por un vermicompost comercial fue estudiada a 284, 306 y 323 K aplicando los modelos de Langmuir y Freundlich, los cuales describen adecuadamente el proceso de adsorción. Las capacidades de adsorción máximas de 116,3; 113,6 y 123,5 mg.g-¹. De acuerdo a las funciones termodinámicas, la retención de plomo involucra una reacción endotérmica (ΔHadsorción = 4,25 ± 0,92 kCal.mol-¹) con un aumento de la entropía del sistema (ΔS = 7,55 a 8,62 kCal.K-1mol-¹) asociado a la ionización de los grupos carboxílicos. La baja espontaneidad de la reacción fue determinada por los valores positivos de la Energía Libre de Gibbs (ΔG = 2,11 a 1,49 kCal.mol-¹). Las diferencias observadas en los espectros FTIR del compost en la región de 1800 a 1300 cm-¹ a diferentes condiciones de pH fueron interpretadas como el resultado de la ionización de los grupos carboxílicos, reduciendo la intensidad de las bandas alrededor de 1725 cm-¹, generándose las señales a 1550 cm-¹ y 1390 cm-¹ de los grupos carboxilato. Los mismos cambios fueron observados a pH 3,8 en presencia del ión Pb²+, lo que sugiere que el acomplejamiento con el metal pesado se produce por medio de una reacción de intercambio catiónico.

The adsorption of Pb2+ by a comercial vermicompost was studied at 284, 306 and 323 K using Langmuir and Freunldich isotherms. The maximum adsorption capacities were 116.3; 113.6 and 123.5 mg.g-¹. Thermodinamic functions showed that the retention takes place by an endothermic reaction (ΔHadsorción = 4,25 ± 0,92 KCal.mol-¹) in which entropy increases (ΔS = 7,55 to 8,62 kCal.K-1mol-¹) along with the acidity of the solutions due to the ionization of carboxylic groups. The low spontaneity was reflected by positive values of the Gibbs free energy (ΔG = 2,11 a 1,49 kCal.mol-¹). The differences in FTIR spectra of vermicompost at pH 3.8 and 7.0 in the region between 1800 to 1300 cm-¹ were interpreted on the basis of caboxylic acids ionization thet reduced the band intensity around 1725 cm-¹, producing signals at 1550 and 1390 cm-1of the carboxylate groups. Similar changes were detected at pH 3.8 when ionic lead was present which suggested that heavy metal complexation by a cationic exchange reaction.

Comparación de métodos para el análisis de mercurio en suelos procedentes de el Callao, Estado Bolívar-Venezuela / Comparison of methods for mercury analysis in soils from The Callao, Bolivar State-Venezuela

El contenido de mercurio en muestras de suelos provenientes de El Callao, Estado Bolívar, Venezuela, fue determinado por digestion en agua regia y cuantificación por el método del vapor frío-absorción atómica (CVAAS), y por determinación directa en la matriz sólida por pirólisis y preconcentración en el analizador automático de mercurio AMA-224 (AMA). Los niveles de Hg en las muestras analizadas estuvieron en los intervalos de 0,05 a 17,31 mg/kg para CVAAS y de 0,050 a 20,066mg/kg para AMA. Las mayores concentraciones de Hg se detectaron en las áreas de molinos, donde es empleado para amalgamar el oro. La exactitud de la técnica AMA fue estimada por el análisis de rocas de referencia (US Geological Survey) comprobándose que la técnica es de exactitud y precisión satisfactorias. Se comprobó que ambas técnicas producen resultados equivalentes sin que se produzcan errores sistemáticos