Paper-based diffusive gradients in thin films technique coupled to energy dispersive X-ray fluorescence spectrometry for the determination of labile Mn, Co, Ni, Cu, Zn and Pb in river water

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Immobilization of lipases and assay in continuous fixed bed reactor

Lipases are versatile enzymes regarding the range of reactions they catalyse and substrates on which they act. They are as well important as catalyst in organic synthesis. Their immobilization on appropriate supports confer them greater stability besides the possibility of operating in continuous reactors. In order to explore these abilities, the reactions involving hydrolysis of p-nitrophenyl acetate (PNPA) and transesterification of PNPA with n-butanol were chosen. Lipases from two different sources were assayed, namely: microbial (Candida rugosa, CRL, Sigma Type VII) and pancreatic (PPL, Sigma, Type 11). Two immobilization methods were also used, namely: 1) adsorption, using as support the following silica derivatives (150-300μm e 450μ): phenyl, epoxy, amino and without derivation, and 2) covalent binding, using glutaraldehyde as binding agent and silica amino as support. This later method led to better results. Hydrolytic activity was 6.1 U/gsupport for CRL and 0.97U/gsupport for PPL, and of transesterification, 2,8U/gsupport for CRL and 1,9U/gsupport for PPL. Stability of the immobilized enzyme as a function of temperature was evaluated for CRL at 40°C and 50°C and for PPL at 32°C and 40°C. The assays were initially carried out batchwise, both for soluble and immobilized enzymes, aiming to the obtention of parameters for the continues reactor. Lipases immobilized by covalent binding were used in the assays of operacional stability in continuos reactors. For PPL in aqueous medium, at 32°C, and CRL in organic medium at 40°C, both operating continuously, no significant loss of activity was detected along the analysis period of 17 days. In the case of CRL in aqueous medium at 40°C there was a loss of activity around 40% after 18 days. For PPL in organic medium at 40°C the loss was 33% after 20 days. Compairing both sources with each other, very different results were obtained. Higher activitiy was found for CRL, both for hydrolysis and for transesterification reactions, with higher stability in organic medium. PPL showed lower activity as well as higher stability in aqueous medium. The immobilization method by covalent binding showed to be the most appropriate. Immobilized lipases are therefore relatively stable both in aqueous and organic medium.

Microstructure of ceramics TiO2 obtained by protein consolidation

Porous ceramics can be produced by adding starch (corn, potato) and protein (animal or vegetable) to raw material as pore forming element. In this study, titanium dioxide ceramics were formed by vegetable protein consolidation. Soybean was chosen as the binding agent and pore forming. The samples, which were produced in cylindrical shape, had the following processing: material mixture, gelling, drying, pre-sintering and sintering. Heated platinum microscopy were performed by using suspensions with different compositions in order to verify protein gelling capacity and better know the temperature in which this process occurs. The samples were characterized by apparent porosity and roughness measurement. Besides, imaging by light microscopy was also performed in order to determine the sample morphology and porosity. © (2012) Trans Tech Publications, Switzerland.

Biodisponibilidade de metais na baía da Ilha Grande, RJ: avaliação pelas técnicas de bivalves transplantados (Nodipecten nodosus) e difusão de filmes finos por gradiente de concentração

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Desenvolvimento e caracterização acústica de painéis multicamadas unifibra, multifibras e mesclados, fabricados a partir de fibras vegetais

Em um tempo em que altos níveis de ruído fazem parte do cotidiano das pessoas, a necessidade de controlá-los não é somente evidente, mas providencial. Atualmente a poluição sonora, em nível mundial, só não é mais grave do que a poluição do ar e da água. No Brasil a situação não é diferente, pois se estima que mais de 15 milhões de pessoas apresentem algum grau de deficiência auditiva devido a este problema ambiental. Dispositivos acústicos como painéis, barreiras, etc., quando de alta eficiência, geralmente, são de custosa aquisição, tornando, em muitas das vezes, inviável sua utilização, principalmente, por empresas de pequeno porte e orçamento limitado. Assim, soluções alternativas, a começar por novos materiais, que sejam menos custosos e possuam desempenho satisfatório surgem como uma ótima opção caso propostas tradicionais sejam inviabilizadas devido ao custo. Algumas fibras vegetais, na forma de painéis, possuem características acústicas satisfatórias quando utilizadas para reduzir a reverberação em determinados ambientes fechados. Dessa forma, considerando as tendências ambientais globais, o uso de fibras vegetais é uma boa oportunidade para agregar valor às referidas fibras e assim contribuir com o desenvolvimento tecnológico do país, já que estes materiais são de fácil obtenção, existem em abundância, não são tóxicos e provêm de fontes renováveis. Este trabalho apresenta a metodologia de desenvolvimento de painéis fabricados a partir de fibras vegetais (açaí, coco, sisal e dendê), assim como a metodologia utilizada para sua caracterização acústica em câmara reverberante em escala reduzida, baseando-se na norma ISO 354/1999. Os dados de coeficiente de absorção dos painéis são obtidos através de um analisador de frequências utilizando-se o Método da Interrupção do Ruído. A comparação entre os resultados obtidos para os painéis artesanais e os materiais convencionais ensaiados permite concluir que o desempenho acústico demonstrado por alguns painéis de fibras vegetais são muito satisfatórios, uma vez que seus coeficientes de absorção sonora foram compatíveis, e em alguns casos superiores, àqueles apresentados pelos materiais convencionais em determinada faixa de freqüência. Finalmente, uma comparação numérico-experimental é realizada, a fim de avaliar a influência de painéis de fibras de sisal sobre as características acústicas de uma pequena sala.

Determinação de Cd, Cu, Ni, Pb e Zn em águas marinhas oriundas da Bacia Potiguar utilizando a técnica de difusão em filmes finos por gradiente de concentração (DGT)

The DGT technique has been used to determine and better understand the dynamics and bioavailability of metals in the sea near to marine outfalls. In this work, the DGT was assessed for the determination of Cd, Pb, Cu, Zn and Ni in marine water samples from Potiguar Basin in its conventional aspect (binding agent, Chelex-100 and diffusive agent: Diffusive polyacrylamide gel (D) and restrictive (R)) and determination of Pb and Cd through its alternative aspect (binding agent: Saccharomyces cerevisiae immobilized in agarose gels and diffusive agent: 3MM Chromatography Paper). The deployment curves for long periods of immersion in the sample, showed a good linear correlation for the conventional aspect to Zn (D: R²=0.9586, R: R²=0.9444), Ni (D: R²=0.9789, R: R²=0.9286) and Cu (D: R²=0.764, R: R²=0.8143), and alternative to Pb (R²=0.9228) and Cd (R²=0.9673). The results of the organic and inorganic composition analysis in conventional aspect, showed that for every element there is no significant fraction of organic compounds in the sample. In addition, considering the alternative aspect, the comparison of obtained and expected masses suggests that some of the Pb is not labile and that the main retention mechanism of Pb for S. Cerevisiae occurs through ion exchange

Avaliação da membrana P81 como agente ligante da técnica de difusão em filmes finos por gradiente de concentração (DGT) para determinação de mercúrio em sistemas aquáticos

Worldwide environmental degradation is an undesirable byproduct resulting from the increasing demand for natural resources. Water sources are suffering intense contamination since they usually receive a huge amount of domestic and industrial effluents - which are mostly wasted without proper treatment - inserting a large number of pollutants in the environment, heavy metals included. Mercury holds great toxicological importance because, under some physicochemical conditions in a water environment, Hg (II) ion turns into methylated compounds stemming from this element, such as methylmercury CH3Hg, which is highly toxic for the aquatic community in which bioaccumulation occurs. Nowadays passive sampling techniques are being developed to enable the analytical procedures which are applied in environmental monitoring. Diffusive gradients in thin-films technique (DGT) has been proven an interesting tool for the determination of labile metal species due to its in situ application. The DGT technique consists of a piston-like device on which the following series of agents is disposed: a binding agent (conventionally Chelex 100 resin), a diffusive agent, usually a polyacrylamide gel, and a membrane filter. Nevertheless, the agents conventinally used for this technique don't usually show satisfactory results in mercury sampling. The main goal of this study was to evaluate the phosphate-treated cellulose membrane (Whatman P 81), an alternative material, as binding agent in the DGT to determine labile mercury fractions in aquatic systems. In this context, we conducted a study of the behavior of this material in relation with system variables, pH and ionic strength. Afterwards we performed immersions of the DGT devices in real and enriched samples and in situ aiming the determination of mercury

Determinação de vanádio em águas usando a técnica de difusão em filmes finos por gradientes de concentração

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Determination of labile barium in petroleum-produced formation water using paper-based DGT samplers

A polyacrylamide hydrogel containing the Chelex-100 resin has traditionally been used as the binding agent for the diffusion gradients in thin films (DGT) technique. The Chelex-100 resin, although important for the determination of various transition metals, is unsatisfactory for the determination of alkaline earth metals, particularly Ba. In this paper, a cellulose membrane, treated with phosphate (P81 membrane), was evaluated as a binding agent for DGT devices for the determination of Ba in produced formation water (PEW) samples. In addition, diffusive layers of filter paper (cellulose) were tested to diffuse Ba through the DGT devices. Experiments to evaluate the key variables of the technique (pH, deployment time, and ionic strength/salinity) were performed. The Ba sampled by these DGT devices was measured using inductively coupled plasma optical emission spectrometry. Aiming to generate information (related to bioavailability of Ba) on the reuse of PEW for irrigation, the determination of Ba in onshore and offshore samples was performed. The new approach was effective for determination of Ba in onshore samples. To determine Ba in offshore samples, it was necessary to use an alternative calibration procedure due to the high NaCl concentration in these samples. (C) 2012 Elsevier B.V. All rights reserved.

Paper-based diffusive gradients in thin films technique coupled to energy dispersive X-ray fluorescence spectrometry for the determination of labile Mn, Co, Ni, Cu, Zn and Pb in river water

The diffusive gradients in thin films (DGT) technique has shown enormous potential for labile metal monitoring in fresh water due to the preconcentration, time-integrated, matrix interference removal and speciation analytical features. In this work, the coupling of energy dispersive X-ray fluorescence (EDXRF) with paper-based DGT devices was evaluated for the direct determination of Mn, Co. Ni, Cu, Zn and Pb in fresh water. The DGT samplers were assembled with cellulose (Whatman 3 MM chromatography paper) as the diffusion layer and a cellulose phosphate ion exchange membrane (Whatman P 81 paper) as the binding agent. The diffusion coefficients of the analytes on 3 MM chromatography paper were calculated by deploying the DGT samplers in synthetic solutions containing 500 mu g L-1 of Mn. Co, Ni, Cu, Zn and Pb (4 L at pH 5.5 and ionic strength at 0.05 mol L-1). After retrieval, the DGT units were disassembled and the P81 papers were dried and analysed by EDXRF directly. The 3 MM chromatographic paper diffusion coefficients of the analytes ranged from 1.67 to 1.87 x 10(-6) cm(2) s(-1). The metal retention and phosphate group homogeneities on the P81 membrane was studied by a spot analysis with a diameter of 1 mm. The proposed approach (DGT-EDXRF coupling) was applied to determine the analytes at five sampling sites (48 h in situ deployment) on the Piracicaba river basin, and the results (labile fraction) were compared with 0.45 mu m dissolved fractions determined by synchrotron radiation-excited total reflection X-ray fluorescence (SR-TXRF). The limits of detection of DGT-EDXRF coupling for the analytes (from 7.5 to 26 mu g L-1) were similar to those obtained by the sensitive SR-TXRF technique (3.8 to 9.1 mu g L-1). (C) 2012 Elsevier B.V. All rights reserved.

Attenuation of skeletal muscle atrophy in cancer cachexia by d-myo-inositol 1,2,6-triphosphate

PURPOSE: To determine the effectiveness of the polyanionic, metal binding agent D-myo-inositol-1,2,6-triphosphate (alpha trinositol, AT), and its hexanoyl ester (HAT), in tissue wasting in cancer cachexia. METHODS: The anti-cachexic effect was evaluated in the MAC16 tumour model. RESULTS: Both AT and HAT attenuated the loss of body weight through an increase in the nonfat carcass mass due to an increase in protein synthesis and a decrease in protein degradation in skeletal muscle. The decrease in protein degradation was associated with a decrease in activity of the ubiquitin-proteasome proteolytic pathway and caspase-3 and -8. Protein synthesis was increased due to attenuation of the elevated autophosphorylation of double-stranded RNA-dependent protein kinase, and of eukaryotic initiation factor 2alpha together with hyperphosphorylation of eIF4E-binding protein 1 and decreased phosphorylation of eukaryotic elongation factor 2. In vitro, AT completely attenuated the protein degradation in murine myotubes induced by both proteolysis-inducing factor and angiotensin II. CONCLUSION: These results show that AT is a novel therapeutic agent with the potential to alleviate muscle wasting in cancer patients.

Observation of manganese coating and encrustation in different environments of the North-Western Atlantic ocean

The major topographic features, or provinces, beyond the continental slope off the Atlantic coast of the United States are (1) Sohm Plain, (2) Hatteras Plain, (3) Nares Plain, (4) Blake Basin, (5) Blake Plateau-Bahama Banks, and (6) Bermuda Rise. The whole of the described area is commonly referred to as the North American Basin. This basin is bounded on the north by Newfoundland Ridge and on the south by Puerto Rico Trench. Topographic features of note within the basin are the divide and the area of depressions between Sohm and Hatteras Plains, the sharply crested Blake Ridge, and the Puerto Rico Ridge. Recently accumulated data on deep-sea oores has given good evidence that the silt and sand covering the abyssal plains are displaced continental sediments in a virtually quartz-free oceanic environment. These sediments were deposited on a primary volcanic bottom. The primary or volcanic bottom is characterized by abyssal hills and seamounts, and the sediment bottom is characterized by abyssal plains, which extend seaward from the continental margins. On the Blake Plateau, bottom photographs and dredge hauls in the axis of the stream show that locally sediment has been removed and the bottom is paved with crusts and nodules of manganese. Photographs and dredged samples from the outer part of the New England Seamount, Chain and Caryn Peak also indicate extensive encrustations of manganese oxide which acts as a binding agent in areas of ooze or other organic debris and thus helps to stabilize the bottom.

Uso de diferentes agentes ligantes no desenvolvimento de barra de cereal salgada adicionada de chia (Salvia hispânica L.)

The objective of this study was to evaluate different binders when preparing salt cereal bars and to characterize them as physical, physico-chemical and sensory parameters. Four formulations of different cereal bars using binders have been developed. The evaluated binders were collagen, guar gum, xanthan gum and psyllium. The developed cereal bars were evaluated according to their physical characteristics (color and texture), physicochemical (pH, moisture, ash, protein, lipids, Aw, crude fiber) beyond their calorie, fatty acid composition and concentration of the main minerals. Among the four binding agents evaluated, psyllium stood out due to its physicochemical characteristics. A cereal bar high in protein and fiber; low in carbohydrates and water activity. The binding agent guar gum and xanthan showed characteristics similar to psyllium, especially regarding to fiber content. Collagen as binder gave the final product a high level in protein and lipid. The color and texture analyzes showed that the salt cereal bars had the color and crispness characteristics for this type of product. Regarding to the composition in the fatty acid, the developed bars offer a good supply of essential fatty acids to the human body. The same was observed regarding to mineral contents. Sensory, salt cereal bars made with chia showed good acceptability, highlighting the elaborate bar with psyllium binder. Different binders demonstrated technological efficiency in the preparation of salt cereal bars. The binder psyllium agent over others showed better physical-chemical and sensory characteristics. However, in general the product has healthy and nutritional characteristics it may be indicated for a protein diet with high fiber content and free sugars.

Screening of wheat Landraces from Madeira Island for iron tolerance

Since the fifteen century, the rainfed-cultivation of wheat for grain is traditionally performed on the Island of Madeira. Under several microclimatic conditions and along very sloppy mountains, the landraces are grown on isolated terraces of Andosols with high amounts of iron. Iron oxides are the main inorganic binding agent contributing to the stability of aggregates and to soil fertility in long-term sustainable agriculture in acid and iron-rich soils. After a two day period of seedling initial growth, a screening test of sixty traditional wheat (Triticum spp.) landraces from the ISOPlexis Genebank at the University of Madeira, Funchal, was performed using nutrient solutions containing 10 or 600 mM Fe, during five days, under controlled laboratory conditions. The elongation of the longest primary root was measured for each genotype and the mean root increment relative to control (as, % relative root increment or RRI; n=28) calculated. This parameter appeared to be a sensitive indicator of Fe tolerance in wheat. Over 85% of wheat germplasm showed the RRI higher than 50%, while the RRI of seven accessions exceeded 70%. This indicates that those landraces are Fe tolerant and might be of particular interest for cultivation under acid rich iron soils of tropical and subtropical areas.

Screening of wheat Landraces from Madeira Island for iron tolerance

Since the fifteen century, the rainfed-cultivation of wheat for grain is traditionally performed on the Island of Madeira. Under several microclimatic conditions and along very sloppy mountains, the landraces are grown on isolated terraces of Andosols with high amounts of iron. Iron oxides are the main inorganic binding agent contributing to the stability of aggregates and to soil fertility in long-term sustainable agriculture in acid and iron-rich soils. After a two day period of seedling initial growth, a screening test of sixty traditional wheat (Triticum spp.) landraces from the ISOPlexis Genebank at the University of Madeira, Funchal, was performed using nutrient solutions containing 10 or 600 mM Fe, during five days, under controlled laboratory conditions. The elongation of the longest primary root was measured for each genotype and the mean root increment relative to control (as, % relative root increment or RRI; n=28) calculated. This parameter appeared to be a sensitive indicator of Fe tolerance in wheat. Over 85% of wheat germplasm showed the RRI higher than 50%, while the RRI of seven accessions exceeded 70%. This indicates that those landraces are Fe tolerant and might be of particular interest for cultivation under acid rich iron soils of tropical and subtropical areas.