Syntheses, characterization and antifungal activity of tris(1,10-phenanthroline)iron(ii) bis(n-r-sulfonyldithiocarbimate)zincate(ii)

Four new compounds with the general formula [Fe(phen)3][Zn(RSO2N=CS2)2], where phen = 1,10-phenanthroline, R = 4-FC6H4 (1), 4-ClC6H4 (2), 4-BrC6H4 (3) and 4-IC6H4 (4), respectively, were obtained by the reaction of the appropriate potassium N-R-sulfonyldithiocarbimate (RSO2N=CS2K2) and tris(1,10-phenanthroline)iron(II) sulfate, with zinc(II) acetate dihydrate in dimethylformamide. The elemental analyses and the IR data were consistent with the formation of the expected complexes salts. The ¹H and 13C NMR spectra showed the signals for the cationic iron(II) complex and dithiocarbimate moieties. The molar conductance data were consistent with the 1:1 cation:anion complexes in 1-4. The antifungal activities of the compounds were tested in vitro against Candida albicans, Candida tropicalis and Colletotrichum gloeosporioides.

Inertization of small-scale chemical wastes using iron phosphate glass

The viability of small-scale heavy-metal waste immobilization into iron phosphate glasses was investigated. Several waste forms containing different amounts of heavy-ion wastes were evaluated (5%, 10%, 15%, 20%, 26%, 33%, 40% and 50% by mass) and their X-ray diffraction patterns revealed that no crystallization occurred in glasses with waste concentrations up to 26%. The dissolution rates for all of the reported glass compositions (ca. 10-8 g cm-2 min-1) are similar to those reported for the materials most commonly used for waste vitrification. Iron phosphate glasses thus proved to be very useful for the immobilization of heavy-metal wastes, exhibiting good contention and chemical durability comparable to that of borosilicate glasses.

DIRECT INFUSION ESI-MS APPLIED IN THE DETECTION OF BYPRODUCTS DUE TO REDUCTIVE DEGRADATION OF ACETAMIPRID BY ZERO-VALENT IRON

This study investigated the reductive degradation of acetamiprid (5 mg L-1) in aqueous medium (at pH 2.0) induced by zero-valent iron (50 mg). The process was monitored using high-performance liquid chromatography (HPLC) to determine the degradation rate as a function of reaction time, and direct infusion electrospray ionization mass spectrometry (DI-ESI-MS) to search for (and potentially characterize) any possible byproducts formed during degradation. The results obtained via HPLC showed that after 60 min, the degradation of the substrate reached nearly 100% in an acidic medium, whereas the mineralization rate (as determined by total organic carbon measurements) was as low as 3%. Data obtained by DI-ESI-MS showed that byproducts were formed mainly by insertions of hydrogen atoms into the nitrile, imine, and pyridine ring moieties, in addition to the observation of chlorine substitution by hydrogen replacement (hydrodechlorination) reactions.

Determination of Copper, Iron, Nickel and Zinc in fuel kerosene by FAAS after adsorption and pre-concentration on 2-aminothiazole-modified silica gel

Silica gel chemically modified with 2-Aminotiazole groups, abbreviated as SiAT, was used for preconcentration of copper, zinc, nickel and iron from kerosene, normally used as a engine fuel for airplanes. Surface characteristics and surface area of the silica gel were obtained before and after chemical modification using FT-IR, Kjeldhal and surface area analysis (B.E.T.). The retention and recovery of the analyte elements were studied by applying batch and column techniques. The experimental parameters, such as shaking time in batch technique, flow rate and concentration of the eluent (HCl- 0.25-2.00 mol L-1) and the amount of silica, on retention and elution, have been investigated. Detection limits of the method for copper, iron, nickel and zinc are 0.77, 2.92, 1.73 and 0.097 mg L-1, respectively. The sorption-desorption of the studied metal ions made possible the development of a preconcentration method for metal ions at trace level in kerosene using flame AAS for their quantification.

Spectrophotometric study of iron oxidation in the iron(II)/thiocyanate/acetone system and some analytical applications

The possibility of using thiocyanate to determine iron(II) and/or iron(III) in water-acetone mixture has been re-examined as part of a systematic and comparative study involving metallic complexes of pseudohalide ligands. Some parameters that affect the complete oxidation of the ferrous cations, their subsequent complexation and the system stability have been studied to optimize the experimental conditions. Our results show the viability and potentiality of this simply methodology as an alternative analytical procedure to determine iron cations with high sensitivity, precision and accuracy. Studies on the calibration, stability, precision, and effect of various different ions have been carried out by using absorbance values measured at 480 nm. The analytical curve for the total iron determination obeys Beer's law (r = 0.9993), showing a higher sensitivity (molar absorptivity of 2.10x10(4) L cm-1 mol-1) when compared with other traditional systems (ligands) or even with the "similar" azide ion [1.53x10(4) L cm-1 mol-1, for iron-III/azide complexes, in 70% (v/v) tetrahydrofuran/water, at 396 nm]. Under such optimized experimental conditions, it is possible to determine iron in the concentration range from 0.5 to 2 ppm (15-65% T for older equipments, quartz cells of 1.00 cm). Analytical applications have been tested for some different materials (iron ores), also including pharmaceutical products for anemia, and results were compared with atomic absorption determinations. Very good agreement was obtained with these two different techniques, showing the potential of the present experimental conditions for the total iron spectrophotometric determinations (errors < 5%). The possibility of iron speciation was made evident by using another specific and auxiliary method for iron(II) or (III).

Ascorbic acid determination using a carbon paste electrode modified with iron(III) ions adsorbed on humic acid

An amperometric sensor was constructed, by using humic acids to immobilize Fe3+ ions on a carbon paste electrode (CPE-HA-Fe), and used for ascorbic acid (H2A) determination. The cyclic voltammogram of the electrode showed electrochemical response due to the Fe3+/Fe2+ couple at E1/2=+0.78 V vs SCE, using 0.5 mol L-1 KCl and 0.2 mol L-1 acetate/0.020 mol L-1 phosphate buffer, at pH = 5.4, as supporting electrolyte. When H2A is added to the electrolyte solution it is observed an oxidation process. The oxidation current, obtained by chronoamperommetry at +0.87 V vs SCE, is proportional to the concentration, represented by the equation I(µA) = 7.6286 [H2A] (mmol L-1) + 1.9583, r = 0.9996, for concentrations between 0.0 and 1.4 mmol L-1. The electrode showed high stability and was used for H2A determination in a natural orange juice.

Thermal behaviour of TEGMMA copolymers obtained by photopolymerization using iron complexes

Copolymers of methyl methacrylate (MMA) and triethyleneglycol dimethacrylate (TEGDMA) obtained by photoinitiated polymerization using Fe(III) complexes were submitted to thermogravimetry (TGA) under dynamic air atmosphere and N2, and differential scanning calorimetric analysis (DSC). Thermal events were observed only between 90 - 110 ºC. Glass transitions were observed at ca. 100 ºC, followed by an exothermic peak at 170 ºC. The exothermic peak was assigned to a thermal curing process due to the presence of unreacted vinyl groups of the monomers. DSC revealed to be a useful tool to evaluate the curing completeness in this kind of material, using small amounts of sample in relatively short time.

Intensidade da ferrugem asiática (Phakopsora pachyrhizi H. Sydow & P. Sydow) da soja [Glycine max (L.) Merr.] nas cultivares Conquista, Savana e Suprema sob diferentes temperaturas e períodos de molhamento foliar

A Ferrugem Asiática (Phakopsora pachyrhizi H. Sydow & P. Sydow), relatada em diversas regiões do globo terrestre de climas tropicais e subtropicais, causa redução significativa na produtividade da soja [Glycine max (L.) Merr.]. Fatores bióticos como interação patógeno-hospedeiro e abióticos influenciam o progresso da doença. Objetivou-se neste trabalho estudar os efeitos da temperatura e de períodos de molhamento foliar no progresso da Ferrugem Asiática nas cultivares Conquista, Savana e Suprema. O experimento foi conduzido no Departamento de Fitopatologia da Universidade Federal de Lavras, em junho de 2004, em câmaras de crescimento vegetal nas temperaturas de 15, 20, 25 e 30 °C e períodos de molhamento foliar de 0, 6, 12, 18 e 24 horas. A inoculação foi realizada pulverizando-se as plantas com suspensão de 10(4) uredósporos de P. pachyrhizi.mL-1 de água. Dados da incidência e da severidade foram utilizados para avaliar o progresso da doença e integrados por meio da área abaixo da curva de progresso da incidência (AACPI) e da severidade (AACPS). Modelos de regressão não-linear foram ajustados para a AACPI e AACPS. Foi calculado o volume abaixo da superfície de resposta para incidência (VASRI) e severidade (VASRS) em relação à temperatura e molhamentos foliares com o objetivo de detectar diferenças entre cultivares. Molhamentos foliares acima de 15 horas e temperaturas próximas a 20 ºC, nas 3 cultivares avaliadas, determinaram maior intensidade da Ferrugem Asiática. Temperaturas próximas a 30 e 15 ºC ocasionaram menor intensidade da doença. Períodos de molhamento foliar abaixo de 6 horas reduziram a intensidade da doença. Todas as cultivares testadas foram suscetíveis à doença, entretanto, a cultivar Conquista apresentou maior VASRI e VASRS da Ferrugem Asiática comparada às cultivares Savana e Suprema, as quais não diferiram estatisticamente. Houve diferença entre as cultivares para AACPI em cada temperatura e molhamento foliar.

Early detection of injuries in leaves of Clusia hilariana Schltdl. (Clusiaceae) caused by particulate deposition of iron

This study aims to evaluate the prognostic value of microscopic parameters of asymptomatic leaves of Clusia hilariana Schltdl. subjected to particulate deposition of iron (2.14 mg cm-2 day-1) for 45 consecutive days. Samples of young and expanded leaves without symptoms were collected and subjected to light and scanning electron microscopy techniques. The height of the epidermal cells on both surfaces of the leaf and the thickness of the hypodermis, the chlorophyll parenchyma, and the leaf blade were measured. Micromorphological injury occurred in the abaxial surface of young leaves and on both surfaces of expanded leaves. Erosion of the epicuticular wax and cuticle rupture were frequent on the adaxial surface, while on the abaxial surface of both leaves there was a loss of sinuosity on the anticlinal wall of the epidermal cells, stomatal deformity and obstruction. Micromorphometric alterations were seen in all leaf tissues except in the height of epidermic cells, probably due to the thick cuticle and prominent cuticular flanges. The highest difference in thickness of the leaf blade was seen in young leaves of plants subjected to SPMFe, indicating greater sensibility to particulate iron in comparison to the expanded leaves. The micromorphological and micromorphometric alterations in the leaf blade of Clusia hilariana Schltdl. showed the prognostic potential of these tools on the evaluation of impacts caused by the deposition of particulate matter, especially in the 'Restinga' natural vegetation, where the exposure is increasing due to the presence of iron ore industry in their surroundings.

Efeitos de sistemas de preparo do solo na cultura da soja (Glycine max (L.) Merrill)

Com o objetivo de avaliar o efeito de cinco equipamentos de preparo do solo sobre o desenvolvimento e a produtividade da cultura da soja (Glycine max L. (Merril)), foi conduzida uma pesquisa em Latossolo Vermelho distrófico, no município de Uberaba-MG, em delineamento experimental em blocos casualizados, com cinco tratamentos (escarificador, enxada-rotativa, arado de aivecas, arado de discos e grade aradora) e quatro repetições. Os sistemas de preparo do solo não mostraram diferenças para o número médio de dias para a emergência das plântulas, estande final, altura da primeira vagem e produtividade da cultura da soja. Os tratamentos com arado de disco, arado de aivecas e grade aradora proporcionaram as maiores populações iniciais da cultura. A altura das plantas foi afetada pelos sistemas de preparo utilizados, destacando-se o preparo com o arado de aivecas e com a enxada-rotativa, com os maiores e menores valores absolutos, respectivamente.

Mapeamento de semeaduras de soja (Glycine max (L.)Merr.) mediante dados MODIS/Terra E TM/Landsat 5: um comparativo

O objetivo deste trabalho foi comparar mapeamentos de semeadura da cultura da soja na região oeste do Paraná, realizados com imagens MODIS/Terra e TM/Landsat 5. Primeiramente, construiu-se máscara de referência, considerando seis imagens TM ao longo do ciclo da cultura, utilizando-se dos algoritmos Paralelepípedo e MaxVer com posterior análise visual. As imagens MODIS foram classificadas com o algorítimo Paralelepípedo, em quatro passagens referentes ao pico vegetativo. O desempenho das classificações foi avaliado por meio de Matrizes de Erros, calculadas pela análise de 100 pontos amostrais (soja ou não-soja), aleatoriamente distribuídos em cada um dos oito municípios da área de estudo. Os principais resultados mostraram que a Exatidão Global (EG) e o Índice Kappa (IK), que variaram entre 0,55 e 0,80, em ambos os sensores, são considerados bons a muito bons. Quando EG e IK dos sensores TM e MODIS foram comparados, não se encontrou diferença significativa. O mapeamento da soja utilizando o sensor MODIS produziu 70% de confiabilidade sob o ponto de vista do usuário. A principal conclusão é a viabilidade de mapear a soja pelo sensor MODIS com as vantagens de que as imagens MODIS têm melhor resolução temporal e são disponibilizadas gratuitamente na Internet.

Qualidade da aplicação aérea líquida com uma aeronave agrícola experimental na cultura da soja (Glycine Max L.)

Os avanços da tecnologia de aplicação aérea de agroquímicos têm-se dado na direção de redução do volume de calda, o que pode ocasionar má distribuição e consequente deposição irregular. O presente trabalho teve como objetivo avaliar a qualidade da aplicação de calda de pulverização em aplicação aérea, na cultura da soja (Glycine Max L.). Para a aplicação, foi utilizada uma aeronave agrícola experimental, aplicando um volume de calda de 20 L ha-1 . Para a determinação dos volumes depositados nas folhas do terço superior, médio e inferior das plantas de soja, foi utilizado corante alimentício azul brilhante adicionado à calda de pulverização. Estas folhas foram lavadas, e o volume determinado por espectrofotometria. Para a obtenção do espectro de gotas, foram utilizados alvos artificiais constituídos por papel hidrossensível, distribuídos no terço superior e médio das plantas. Os dados foram submetidos à análise de variância de fator único, considerando as diferentes posições na planta, e cartas de controle foram feitas a partir dos limites inferior e superior de controle. A aplicação aérea de calda de pulverização na cultura da soja apresentou menores valores de diâmetro da mediana volumétrica, amplitude relativa e cobertura no terço médio em relação ao terço superior da cultura da soja. Houve menor deposição da calda de pulverização no terço inferior. Os indicadores de cobertura da calda de pulverização demonstraram que a aplicação aérea com a aeronave agrícola experimental avaliada não se encontra sob controle estatístico de processo, ou seja, fora do padrão de qualidade.

Perfomance evaluation of a direct injection engine using different blends of soybean (Glycine max) methyl biodiesel

Diesel fuel is used widely in Brazil and worldwide. On the other hand, the growing environmental awareness leads to a greater demand for renewable energy resources. Thus, this study aimed to evaluate the use of different blends of soybean (Glycine max) methyl biodiesel and diesel in an ignition compression engine with direct injection fuel. The tests were performed on an electric eddy current dynamometer, using the blends B10, B50 and B100, with 10; 50 e 100% of biodiesel, respectively, in comparison to the commercial diesel B5, with 5% of biodiesel added to the fossil diesel. The engine performance was analyzed trough the tractor power take off (PTO) for each fuel, and the best results obtained for the power and the specific fuel consumption, respectively, were: B5 (44.62 kW; 234.87 g kW-1 h-1); B10 (44.73 kW; 233.78 g kW-1 h-1); B50 (44.11 kW; 250.40 g kW-1 h-1) e B100 (43.40 kW; 263.63 g kW-1 h-1). The best performance occurred with the use of B5 and B10 fuel, without significant differences between these blends. The B100 fuel showed significant differences compared to the other fuels.

Material embodiment and energy flows as efficiency indicators of soybean (Glycine max) production in Brazil

As the requirement for agriculture to be environmentally suitable there is a necessity to adopt indicators and methodologies approaching sustainability. In Brazil, biodiesel addition into diesel is mandatory and soybean oil is its main source. The material embodiment determines the convergence of inputs into the crop. Moreover, the material flows are necessary for any environmental analysis. This study evaluated distinct production scenarios, and also conventional versus GMO crops, through the material embodiment and energy analysis. GMO crops demanded less indirectly applied inputs. The energy balance showed linearity with yield, whereas for EROI, the increases in input and yield were not affected.

Controle das plantas daninhas em cultura de soja (Glycine Max L. Merril) com misturas de herbicidas

Em ensaio de campo, onde as principais plantas daninhas eram representadas por duas gramíneas e seis ervas de folhas largas, foi comparada a ação de misturas de trifluralin, pendimethalin, dinitramine e alachlor com metribuzin e de alachlor com linuron, no seu controle. Os resultados mostraram que as misturas de alachlor a 2,00 kg/ha e metribuzin a 0,35 kg/ha, e desses mesmos herbicidas a 3,00 kg/ha e 0,50 kg/ha, feitas no tanque, aplicadas em pré-emergência, seguidas da mistura de trifluralin a 1,00 kg/ha, aplicado em pré-plantio incorporado, com metribuzin a 0,50 kg/ha, aplicado em pré-emergência, foram as mais eficientes. Acanthospermum australe foi a planta daninha de mais difícil controle. Somente a mistura de tanque de alachlor a 2,00 kg/ha e linuron a 0,75 kg/ha foi eficiente no seu controle. As misturas de pendimenthalin a 1,30 kg/ha e de dinitramine a 0,50 kg/ha, ambos com metribuzin a 0,50 kg/ha, retardaram o crescimento inicial da soja, porém sem prejudicar o stand e a produção. Os demais tratamentos também não foram prejudiciais à produção dessa leguminosa.