Biossensor enzimático para detecção de fungicidas ditiocarbamatos: estudo cinético da enzima aldeído desidrogenase e otimização do biossensor

Initially, all major factors that affect the rate of the AldH-catalyzed reaction (enzyme concentration, substrate concentration, temperature and pH) were investigated. Optimal activity was observed between pH values of 7.5 and 9.5 in the temperature range of 25 to 50 ºC. Kinetic parameters, such as Km (2.92 µmol L-1) and Vmax (1.33 10-2 µmol min-1) demonstrate a strong enzyme-substrate affinity. The sensors were based on screen-printed electrodes modified with the Meldola Blue-Reinecke salt (MBRS) combination. Operational conditions (NAD+ and substrate contents, enzyme loading and response time) were optimized. Also, two enzyme immobilization procedures were tested: entrapment in poly(vinyl alcohol) bearing styrylpyridinium groups (PVA-SbQ) and crosslinking with glutaraldehyde. Chronoamperometry was employed to observe the biosensor responses during enzymatic hydrolysis of propionaldehyde and also to construct inhibition curves with maneb and zineb fungicides. Best results were found with the following conditions: [NAD+] = 0.25 mmol L-1; [propionaldehyde] = 80 µmol L-1; enzyme loading = 0.8 U per electrode; response time = 10 min, and inhibition time = 10 min. Current intensities around 103 ± 13 nA with the sensors and good stability was obtained for both immobilization procedures. Detection limits, calculated using 10% inhibition were 31.5 µg L-1 and 35 µg L-1 for maneb and zineb, respectively. Results obtained with other MBRS-modified electrodes consisting of mono and bi-enzymic sensors were compared. The ability to catalyze NADH oxidation by MB was also highlighted.

Electrical and magnetic properties of new compounds of the conductor anion [Ni(dmit)2]- and nitronyl nitroxide magnetic radicals

Three compounds have been synthesized with formulae [3-MeRad][Ni(dmit)2] (1), [4-MeRad][Ni(dmit)2] (2) and [4-PrRad][Ni(dmit)2] (3) where [Ni(dmit)2]- is an anionic pi-radical (dmit = 1,3-dithiol-2-thione-4,5-dithiolate) and [3-MeRad]+ is 3-N-methylpyridinium alpha-nitronyl nitroxide, [4-MeRad]+ is 4-N-methylpyridinium alpha-nitronyl nitroxide and [4-PrRad]+ is 4-N-propylpyridinium alpha-nitronyl nitroxide. The temperature-dependent magnetic susceptibility of 1 revealed that an antiferromagnetic interaction operates between the 3-MeRad+ radical cations with exchange coupling constants of J1 = - 1.72 cm-1 and antiferromagnetism assigned to the spin ladder chains of the Ni(dmit)2 radical anions. Compound 1 exhibits semiconducting behavior and 3 presents capacitor behavior in the temperature range studied (4 - 300 K).

Determinação da espessura da camada polimérica de fases estacionárias imobilizadas para cromatografia líquida de alta eficiência por termogravimetria

This paper presents a simple and practical thermogravimetric method for determining the layer thickness of immobilized polymer stationary phases used in reversed-phase high-performance liquid chromatography. In this method, the weight loss of different polysiloxanes immobilized onto chromatographic supports, determined over the temperature range 150-650 ºC, demonstrated excellent agreement with the sum of carbon and hydrogen content obtained by elemental analysis. The results presented here suggest that the thermogravimetric procedure is an accurate and precise method to determine the polymeric material content on polymer-coated stationary phases.

Double-bilayer: a new phase formed by lysophospholipids and the corresponding fatty acid

The product of catalytic activity of the enzyme phospholipase A2, which resembles the core unit of animal toxins, on phospholipids is a 1:1 mixture of lysolipid and fatty acid. This mixture was studied by time-resolved simultaneous small- and wide angle x-ray diffraction over the temperature range from 23 to 53.5ºC. An unusually large lamellar structure was observed, with d = 11 nm, contradicting the complex functional dimer model between lysolipid and fatty acid. It can be explained by formation of a "double-bilayer", a new phase consisting of two different bilayers, one formed by lysophospholipid and other by fatty acid, bound together by head group interactions. Its strucutre was confirmed by simulations of the X-ray scattering pattern.

Desenvolvimento e avaliação de um porta-amostra de baixo custo para caracterização elétrica de materiais cerâmicos

Conventional sample holder cells used to the electric characterization of ceramics at high temperature consists of an alumina tube and platinum wires and plates using a complex design. The high cost materials used in the conventional sampler holder cell were replaced by stainless steel and conventional ceramics. The sample holder was validated by characterizing yttria-stabilized-zirconia in a temperature range of 25 to 700 ºC. The results do not present variations, discontinuity or unusual noise in the electric signals. Several samples were characterized without maintenance, which demonstrates that the sample holder is electric and mechanic adequate to be used to electrical characterization of ceramics up to 700 ºC.

Remoção de íons Pb2+ de solução de bateria automotiva por caulinita modificada com óxido de manganês

Nine absorbents were prepared using a mixture of Amazonian kaolinite and MnO2 at three temperatures (600, 700 and 900 ºC) in order to retain Pb2+ ions contained in the battery solutions. The batch experiments carried out with the batteries used water for 3 h and the kinetic isotherm was fitted with the pseudo-second order Lagergren equation. Findings show that synthesized adsorbents AD4, AD5 and AD7 performed well in reducing the Pb2+ ion content from 0.36 to 0.00 mg g-1. The better performance for removing the Pb2+ ions occurred for adsorbents synthesized in the temperature range from 600 to 700 ºC.

KINETIC STUDY OF SELECTIVE GAS-PHASE OXIDATION OF ISOPROPANOL TO ACETONE USING MONOCLINIC ZRO2 AS A CATALYST

Zirconia was prepared by a precipitation method and calcined at 723 K, 1023 K, and 1253 K in order to obtain monoclinic zirconia. The prepared zirconia was characterized by XRD, SEM, EDX, surface area and pore size analyzer, and particle size analyzer. Monoclinic ZrO2 as a catalyst was used for the gas-phase oxidation of isopropanol to acetone in a Pyrex-glass-flow-type reactor with a temperature range of 443 K - 473 K. It was found that monoclinic ZrO2 shows remarkable catalytic activity (68%) and selectivity (100%) for the oxidation of isopropanol to acetone. This kinetic study reveals that the oxidation of isopropanol to acetone follows the L-H mechanism.

Electrochemical and physical characterization of Ni-Cu-Fe alloy for chlor-alkali hydrogen cathodes

This work describes the development of an alternative acetate bath for the electrochemical codeposition of Ni-Cu-Fe electrodes at low pH that is stable for several weeks and produces electrodes with good performance for chlor-alkali electrolysis. Physical characterization of the electrode surface was made using X ray absorption spectroscopy (XAS), scanning electron microscopy (SEM) and energy dispersive analysis (EDX). The evaluation of the material as electrocatalyst for the hydrogen evolution reaction (her) was carried out in brine solution (160 g L-1 NaCl + 150 g L-1 NaOH) at different temperatures through steady-state polarization curves. The Ni-Cu-Fe electrodes obtained with this bath have shown low overpotentials for the her, around 0.150 V at 353 K, and good stability under continuous long-term operation for 260 hours. One positive aspect of this cathode is that the polarization behavior of the material shows only one Tafel slope over the temperature range of 298 - 353 K.

Magnetic, thermal and spectral characterization of 2,6-dimethoxybenzoates of Co(II), Ni(II) and Cu(II)

The complexes of 2,6-dimethoxybenzoic acid anion with ions of Co(II), Ni(II), and Cu(II) have been synthesized as polycrystalline solids, and characterized by elemental analysis, spectroscopy, magnetic studies, and also by X-ray diffraction and thermogravimetric measurements. The analysed complexes have following colours: pink for Co(II), green for Ni(II), and blue for Cu(II) compounds. The carboxylate group binds as monodentate, and bidentate bridging and chelating ligands. On heating in air to 1173 K the complexes decompose in four, three or two steps. At first, they dehydrate in one or two steps to anhydrous salts, that next decompose to oxides of the respective metals. The solubility of the investigated dimethoxybenzoates in water at 293 K is of the order of 10-2 mol/dm3. Their magnetic moments were determined in the temperature range of 76-303 K. The results reveal the compounds of Co(II) and Ni(II) to be high-spin complexes and that of Cu(II) to form dimer.

Comparison of some properties of Cu(II) 2,3- , 3,5- and 2,6-dimethoxybenzoates

The physico-chemical properties and thermal stability in air of Cu(II) 2,3- , 3,5- and 2,6-dimethoxybenzoates were compared and the influence of the position of -OCH3 substituent on their thermal stability was investigated. The complexes are crystalline, hydrated salts with blue colour. The carboxylate ion is a bidentate chelating or bridging group. The thermal stability of analysed Cu(II) dimethoxybenzoates was studied in the temperature range of 293-1173 K. The positions of methoxy- groups in benzene ring influence the thermal properties of studied complexes. Their different thermal properties are markedly connected with the various influence of inductive, mesomeric and steric effects of -OCH3 substituent on the electron density in benzene ring. The magnetic susceptibilities of the complexes were measured over the range of 76-300 K and the magnetic moments were calculated. The results show that they form dimers.

Thermal and spectral properties of di-and trimethoxybenzoates of silver (I)

The complexes of silver(I) with 2,3-, 2,4-, 2,6-, 3,4-, 3,5-dimethoxy-, and 2,3,4- and 3,4,5-trimethoxybenzoic acid anions have been synthesized and characterized by elemental analysis, IR spectroscopy, thermogravimetric and X-ray studies. Their solubility in water has been also determined at 293K. All analysed complexes were found to be crystalline, anhydrous compounds with low symmetry. The carboxylate groups act as bidentate or monodentate ligands. The thermal stability of compounds has been examined in air in temperature range of 293-1173K. The analysed complexes were found to be stable at room temperature and their solubilities in water at 293K to be in the order of 10-4 mol.dm-3.

Complexes of 4-chlorophenoxyacetates of Nd(III), Gd(III) and Ho(III)

The complexes of 4-chlorophenoxyacetates of Nd(III), Gd(III) and Ho(III) have been synthesized as polycrystalline hydrated solids, and characterized by elemental analysis, spectroscopy, magnetic studies and also by X-ray diffraction and thermogravimetric measurements. The analysed complexes have the following colours: violet for Nd(III), white for Gd(III) and cream for Ho(III) compounds. The carboxylate groups bind as bidentate chelating (Ho) or bridging ligands (Nd, Gd). On heating to 1173K in air the complexes decompose in several steps. At first, they dehydrate in one step to form anhydrous salts, that next decompose to the oxides of respective metals. The gaseous products of their thermal decomposition in nitrogen were also determined and the magnetic susceptibilites were measured over the temperature range of 76-303K and the magnetic moments were calculated. The results show that 4-chlorophenoxyacetates of Nd(III), Gd(III) and Ho(III) are high-spin complexes with weak ligand fields. The solubility value in water at 293K for analysed 4-chlorophenoxyacetates is in the order of 10-4mol/dm³.

Environment in poultry production covered with thermal and aluminum roofing tiles

Brazil is a country of tropical climate, a fact that hinders the poultry production in the aspect of thermal comfort. Thus, we aimed to evaluate the thermal environment in commercial poultry houses with different covers during the months of December 2012 to May 2013, in the municipality of Rio Verde, Goiás. The experimental design was completely randomized in split plots with factorial arrangement of treatments 2x3, being two shed models (thermal and aluminum roof tiles) and three sections within each shed (initial, central and final) for 182 days, having the days as replicates. The thermal environment was assessed through thermal comfort indices: Temperature and Humidity Index, Black Globe Temperature and Humidity Index, Radiant Heat Load and Enthalpy. The data was analyzed by SISVAR 5.1., through the analysis of variance, the Scott Knott test used to compare the means, considering a significance level of 1%. The results showed a significant statistical difference between the sheds and the points assessed (P < 0.05). The thermal shed had the lowest values for the environmental variables (Dbt and Bgt) and thermal indices studied, but larger values for the RH compared to the shed with aluminum covering. The use of thermal covers minimizes the difference in temperature range throughout various times of the day, being at 14:00 o'clock the prominence time to others.

Spatialization of climate, physical and socioeconomic factors that affect the dairy goat production in Brazil and their impact on animal breeding decisions

Brazil has high climate, soil and environmental diversity, as well as distinct socioeconomic and political realities, what results in differences among the political administrative regions of the country. The objective of this study was to determine spatial distribution of the physical, climatic and socioeconomic aspects that best characterize the production of dairy goats in Brazil. Production indices of milk per goat, goat production, milk production, as well as temperature range, mean temperature, precipitation, normalized difference vegetation index, relative humidity, altitude, agricultural farms; farms with native pasture, farms with good quality pasture, farms with water resources, farms that receive technical guidance, family farming properties, non-familiar farms and the human development index were evaluated. The multivariate analyses were carried out to spatialize climatic, physical and socioeconomic variables and so differenciate the Brazilian States and Regions. The highest yields of milk and goat production were observed in the Northeast. The Southeast Region had the second highest production of milk, followed by the South, Midwest and North. Multivariate analysis revealed distinctions between clusters of political-administrative regions of Brazil. The climatic variables were most important to discriminate between regions of Brazil. Therefore, it is necessary to implement animal breeding programs to meet the needs of each region.

Physiological, morphological and biochemical characteristics of the sexual propagation of Piper aduncum (Piperaceae)

In this work we attempted to characterize the diaspores and the germination process of Piper aduncum L., as well as to verify the influence of the interaction between presence and absence of light (photoperiod of 12 hours and dark) and temperature (25 °C, 30 °C and 20-30 °C) and also of gibberellin (0, 50, 100, 200 and 400 mg L-1) on the root protrusion and normal seedlings formation. The diaspores are very small with a thousand seed weight of 0.3645 g, 13% moisture and protein reserve. Diaspores are strict positively photoblastic in the tested temperature range and the optimum temperature for root protrusion was 30 °C, while for normal seedlings was 25 °C. The previous permanence in the dark led to an increase in the speed of root protrusion and percentage and speed of seedling formation. The application of gibberellic acid negatively interfered with the protrusion and growth of the radicle while favoring the elongation of hypocotyls.