Biodegradação bacteriana de compostos organoclorados

Due to their recalcitrant nature, organochlorides are already found in environment and the search for alternatives to eliminate these compounds such as biodegradation using native microorganisms is of great interest. A screening trial to select environmental bacteria able to degrade DDD, PCP and dieldrin was conducted. Among 14 isolates, the soil bacteria Pseudomonas aeruginosa L2-1 showed the highest tolerance to increasing concentrations of the organochlorides and was selected for further studies. Biodegradation was assessed in liquid medium, varying the concentrations of glucose and the presence of rhamnolipids (RL). The best medium for the occurrence of biodegradation of the compounds contained 0.5% glucose, giving approximately 50% yield after three days of incubation. Results showed that the biodegradation rates of the organochlorides by P. aeruginosa L2-1 were greater at low concentrations of glucose and in the presence of rhamnolipids.

Desenvolvimento de reator tipo "dip catalyst" para filmes poliméricos contendo nanopartículas de metais de transição

This article describes the development of a new catalytic reactor designed to operate with nanoparticle-embedded polymer thin films. Stabilization of metal nanoparticles in films that serve as catalysts in organic reactions is relatively new; therefore, the development of reactors to facilitate their use is necessary. We describe in detail the preparation of the GDCR reactor-type "dip catalyst" and its evaluation in the Suzuki - Miyaura cross-coupling reaction of phenylboronic acid and 4-bromoanisole catalyzed by palladium nanoparticle-embedded cellulose acetate thin film (CA/PD(0)). Compared with earlier prototypes, GDCR reactor showed excellent results when operating with CA/PD(0) thin films.

AVALIAÇÃO DE MÉTODOS DE SOLUBILIZAÇÃO PARA DETERMINAÇÃO DE METAIS EM GLICERINA PROVENIENTE DA PRODUÇÃO DE BIODIESEL POR TÉCNICAS DE ESPECTROMETRIA ATÔMICA

This paper describes the evaluation of simple and fast solubilization methods for the determination of Ca, Mg, and K in glycerin samples from biodiesel production by atomic spectrometry. The solubilization in water was compared with two other methods: solubilization in formic acid and solubilization in ethanol. Using solubilization in water, determination of the three analytes was possible; the values of limits of detection for Ca, K, Mg were 0.31, 0.06, and 0.16 mg kg−1, respectively. Because no adequate reference material was available, the accuracy was evaluated by assessing the recoveries tests with both solubilization methods; the evaluation ranged from 90% to 115%, with values of relative standard deviation >8%, indicating good accuracy of the measure. Four crude glycerin samples obtained from biodiesel plants of Rio Grande do Sul were analyzed after treatment with the different methods of solubilization, and the obtained results of Ca, Mg, and K concentration were in agreement with the values obtained from both solubilization methods. Therefore, solubilization in water is concluded to be a simpler, faster, and viable method for sample preparation of glycerin.

A VERSATILIDADE DOS COMPOSTOS DE COORDENAÇÃO NA PRODUÇÃO DE POLIETILENOS: UMA REVISÃO DOS SISTEMAS CATALÍTICOS

Taking into account the relevance of polyethylene for modern society and the role of catalysts for the production of this material, in the present work, we carried out a review of the main catalytic systems used in industry and academia. Most systems consist of coordination compounds, whose structural versatility allows the tuning of the characteristics of polyethylene for different applications. The structural aspects and chemical reactivity of such systems are discussed based on the existing literature and experimental data.

Zingiber officinale (GENGIBRE) COMO FONTE ENZIMÁTICA NA REDUÇÃO DE COMPOSTOS CARBONÍLICOS

Various vegetables as biological catalysts were evaluated in enantioselective reduction of carbonyl compounds. The stereoselectivity of the process was in agreement with Prelog's rule for twelve of the vegetables, whereas okra and green peppers formed anti-Prelog products. Zingiber officinale exhibited the best results with 30% conversion and 89% ee. The parameters of the reaction such as time, solvent and other substrates investigated, as well as the specie, showed good chemo- and enantioselectivity.

ANÁLISE EXPLORATÓRIA DAS CONCENTRAÇÕES DOS METAIS NA, CA, MG, SR E FE EM EXTRATO AQUOSO DE PETRÓLEO, DETERMINADOS POR ICP OES, APÓS OTIMIZAÇÃO EMPREGANDO PLANEJAMENTO DE EXPERIMENTOS

AbstractThe purpose of this study was to evaluate the best operating conditions of ICP OES for the determination of Na, Ca, Mg, Sr and Fe in aqueous extract of crude oil obtained after hot extraction with organic solvents (ASTM D 6470-99 modified). Thus, the full factorial design and central composite design were used to optimize the best conditions for the flow of nebulization gas, the flow of auxiliary gas, and radio frequency power. After optimization of variables, a study to obtain correct classification of the 18 samples of aqueous extract of crude oils (E1 to E18) from three production and refining fields was carried out. Exploratory analysis of these extracts was performed by principal component analysis (PCA), hierarchical cluster analysis (HCA) and linear discriminant analysis (LDA), using the original variables as the concentration of the metals Na, Ca, Mg, Sr and Fe determined by ICP OES.

REAÇÃO DE CONDENSAÇÃO DO GLICEROL COM COMPOSTOS CARBONÍLICOS. SÍNTESE, CARACTERIZAÇÃO E APLICAÇÃO EM CRISTAIS LÍQUIDOS

Condensation reactions of glycerol with aldehydes and ketones were performed under thermal heating and microwave irradiation regimes. Homogeneous and heterogeneous catalysts were tested in both conditions. A silica sulfated (SiO2-SO3H) heterogeneous catalyst demonstrated the best performance relative to a selectivity of >95% in favor of 5-membered ketals. For acetals, preference in favor of 5-membered or 6-membered functional groups depends on the nature of the catalyst. Homogenous catalysts favor the more stable 6-membered acetals, whereas heterogeneous catalysts favor the less stable 5-membered acetals. However, the isomer ratios in the acetalization reaction are too low, and hence the reaction cannot be used in a synthetic plan for functional materials. Ketalization processes mediated by SiO2-SO3H show a high selectivity in favor of a 5-membered ring (1,3-dioxolane). The scope of condensation was tested with different ketones. A mechanism for heterogeneous catalysis related to the selectivity in the cyclization process is presented herein. Solketal, a commercial product, was also obtained by a condensation reaction of glycerol and propanone, and showed a high selectivity in favor of 1,3-dioxolane. It was transformed to potential allylic and chiral intermediates. A mesogenic core was connected to the organic framework of glycerol to produce a monomer liquid crystal material with a stable smectic-C mesophase.

INFLUÊNCIA DO CATALISADOR EM SOLUÇÕES POLIMÉRICAS PARA O PREPARO DE GÉIS ORGÂNICOS DE RESORCINOL-FORMALDEÍDO

Resorcinol-formaldehyde (RF) organic gels have been extensively used to produce carbon aerogels. The organic gel synthesis parameters greatly affect the structure of the resulting aerogel. In this study, the influence of the catalyst quantity on the polymeric solution sol-gel process was investigated. Sodium carbonate was used as a basic catalyst. RF gels were synthesized with a resorcinol to formaldehyde molar ratio of 0.5, a resorcinol to catalyst (R/C) molar ratio equal to 50 or 300, and a resorcinol to solvent ratio of 0.1 g mL-1. The sol-gel process was evaluated in situ by Fourier transform infrared spectroscopy using a universal attenuated total reflectance sensor and measurements of the kinematic viscosity. The techniques showed the evolution of the sol-gel process, and the results showed that the lower catalyst quantity induced a higher gel point, with a lower viscosity at the gel point. Differential scanning calorimetry was used to investigate the thermal behavior of the RF dried gel, and results showed that the exothermic event related to the curing process was shifted to higher temperatures for solutions containing higher R/C ratios.

AVALIAÇÃO DA BIOACUMULAÇÃO DE METAIS EM Cyprinus carpio PELA INTERAÇÃO COM SEDIMENTO E ÁGUA DE RESERVATÓRIO

Bioaccumulation of Ag, Al, Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb and Zn was determined in the gills and liver of Cyprinus carpio and related to concentrations in the sediment and water of the Alagados Reservoir, Ponta Grossa/Paraná. Cd and Fe exceeded the legal limit for water. Fe was the most abundant metal in the reservoir's water and sediment. The metals in the sediment were below the level of probable adverse effects on biota. There were no significant differences between sampling sites for water and sediment. Liver and gills had higher concentrations of Al, Fe and Zn, with a significant increase in Al (P > 0.05) compared to the increase in weight and size of the specimens. Statistically, gills showed higher concentrations of Al, Cd, Co, Cr, Mn and Zn and liver higher concentrations of Cu and Fe. Co, Cu, Fe, Mn and Zn showed significant differences (P < 0.01) between the organs. The bioaccumulation factors (BAF) showed that the interaction of water with gills promotes greater accumulation of metals in this organ. Despite the low concentrations in the reservoir, bioaccumulation of metals in gills and liver of C. carpio occurs by its interaction with contaminated water and sediment, respectively.

USO DO PLANEJAMENTO EXPERIMENTAL PARA OTIMIZAÇÃO DE UM PROCEDIMENTO VOLTAMÉTRICO PARA DETERMINAÇÃO SIMULTÂNEA DAS CONCENTRAÇÕES DOS METAIS Zn, Cd, Pb E Cu LIVRES EM ÁGUA DE COCO

Optimization of the main parameters of SWASV using boron-doped diamond electrode was described for the simultaneous determination of Zn, Cd, Pb and Cu free in coconut water. The values of electroanalytical parameters studied were optimized with the factorial design and center composite design. The optimized parameters for the preconcentration of metals were -1.50 V for potential, and 240 s for deposition time. For SWV, the optimized value was 11.56 mV for step potential. In addition, frequency and pulse height were defined at 100 Hz and 55 mV, respectively. Furthermore, the concentration of the supporting electrolyte (acetate buffer, pH 4.7) was optimized in 0.206 mol L-1. The optimized procedure was applied in two samples of coconut water: natural and processed. The limits of detection (LOD) obtained for Zn, Cd, Pb and Cu were 7.2; 4.4; 3.3 and 1.5 µg L-1, respectively. The concentrations of Cd and Pb were not detected. On the other hand, the values found for the concentrations of Zn and Cu were: < LOD (29 µg L-1) and (6.8 ± 0.9) µg L-1 for the natural sample; and (85.8 ± 4.2) µg L-1 and (7.7 ± 0.6) µg L-1 for the processed sample, respectively.

Efeito de solventes orgânicos usados como veículos de fungicidas no controle in vitro e in vivo da incidência e da transmissão de Bipolaris sorokiniana em sementes de cevada

O objetivo deste trabalho foi comparar e avaliar, in vitro e in vivo, o efeito de solventes orgânicos utilizados como veículos de fungicidas na erradicação do fungo em sementes de cevada. Foram empregados o monoetilenoglicol (MEG) e o propilenoglicol (PPG), ambos a 0,5, 1 e 2%. Os fungicidas testados foram a iminoctadina, a iprodiona, o triadimenol, o triticonazol, o flutriafol e o difenoconazol. A incidência foi determinada pela ocorrência de B. sorokiniana em sementes plaquadas em meio seletivo. A erradicação foi obtida nos tratamentos com iminoctadina + MEG; iminoctadina + PPG (a 1 e 2%) e iprodiona + PPG (2%). A eficiência dos demais fungicidas foi melhorada com o emprego dos solventes orgânicos, mas sem alcançar a erradicação do fungo. In vivo na testemunha foram registrados níveis de transmissão de 89,7% para o coleóptilo e de 12,3% para a plúmula. Diferentemente dos dados obtidos in vitro, o emprego do PPG influenciou muito pouco no controle da transmissão, pois os fungicidas comportaram-se satisfatoriamente quando misturados com água. Os fungicidas iminoctadina e difenoconazol foram 100% efetivos em evitar a transmissão do fungo das sementes para os coleóptilos. Os solventes orgânicos mostraram potencialidade para melhorar a eficiência da maioria dos fungicidas testados in vitro, aspecto que não foi corroborado in vivo.

Avaliação de produtos alternativos no controle da ferrugem do cafeeiro

Objetivou-se neste trabalho avaliar produtos orgânicos quanto ao efeito protetor e indutor de resistência à ferrugem do cafeeiro (Hemileia vastatrix), comparando-se com fungicidas sistêmicos. O trabalho foi desenvolvido em casa-de-vegetação, utilizando-se mudas de cafeeiro cv. Catuaí Vermelho 144. Foram avalidados como indutores de resistência extratos foliares, suspensões de conídios fúngicos e de células bacterianas, fertilizantes foliares, hipocloritos e acibenzolar-S-methyl (ASM). O delineamento experimental utilizado foi em blocos casualizados com três repetições, sendo que cada parcela experimental foi constituída de cinco mudas de café perfazendo um total de 15 mudas por tratamento. Os experimentos foram repetidos duas vezes com resultados semelhantes. Quando avaliado o efeito protetor, a maioria dos compostos reduziu o número de pústulas e a área foliar com ferrugem em comparação à testemunha 1 (água). Extratos de folhas de café, obtidos pelo processo aquoso e extratos de sementes de Azadirachta indica ('neem") obtidos pelo processo de extração com metanol apresentaram proteção similar, mas nunca superior a epoxiconazole + piraclostrobin. Extratos aquosos de folhas de café, ASM, Bacillus subtilis e Pseudomonas putida reduziram a infecção causada por H. vastatrix em mais de 77 %.

Compostos heterometálicos. Interação do tricarbonil com ligação W-Hg, [WCl(CO)3(bipy)(HgCl)], com tiouréias

Foram efetuadas reações entre o heterometálico [WCl(CO)3(bipy)(HgCl)], (bipy = 2,2'-bipiridina) e tiouréias que levaram à formação de compostos do tipo [WCl(CO)3(bipy)(HgCl)L] [L = tiouréia (tu); N-metiltiouréia (mtu); N,N-dimetiltiouréia (dmtu)]. Os espectros de absorção no infravermelho mostram que a esfera de coordenação do tungstênio mantêm-se inalterada e que as tiouréias encontram-se ligadas ao átomo de mercúrio através do átomo de enxofre.