Comparison of the dehydration kinetics of solid state compounds of 2-methoxybenzylidenepyruvate with some divalent metal ions

Divalent metal complexes of ligand 2-methoxybenzylidenepyruvate with Fe, Co, Ni, Cu and Zn as well as sodium salt were synthesized and investigated in the solid state. TG curves of these compounds were obtained with masses sample of 1 and 5mg under nitrogen atmosphere. Different heating rates were used to characterize and study these compounds from the kinetic point of view. The activation energy and pre-exponential factor were obtained applying the Wall-Flynn-Ozawa method to the TG curves. The obtained data were evaluated and the values of activation energy (Ea / kJ mol-1) was plotted in function of the conversion degree (α). The results show that due to mass sample, different activation energies were obtained. The results are discussed mainly taking into account the linear dependence between the activation energy and the pre exponential factor, where was verified the effect of kinetic compensation (KCE) and possible linear relations between the dehydrations steps of these compounds.

Modulation of staphylokinase-dependent plasminogen activation by mono- and divalent ions

The effect of several ions (Cl-, Na+, K+, Ca2+) on the rate of plasminogen (Pg) activation by recombinant staphylokinase (rSTA) is reported. Both monovalent and divalent ions affect the rate at which Pg is activated by rSTA, in a concentration-dependent manner (range 0-100 mM). In almost all cases, a decrease of the initial velocity of activation was observed. Cl- showed the most striking inhibitory effect at low concentrations (64% at 10 mM). However, in the presence of a fibrin surface, this inhibition was attenuated to 38%. Surprisingly, 10 mM Ca2+ enhanced the Pg activation rate 21% when a polymerized fibrin matrix was present. These data support the idea that ions can modulate the rate of Pg activation through a mechanism that may be associated with changes in the molecular conformation of the zymogen. This effect is strongly dependent on the presence of a fibrin clot.

Correlação entre a capacidade de troca de cátions e outras propriedades de três solos da Amazônia Central

Foi determinada a capacidade de troca de cations a pH natural do solo e a pH 7,0 ao longo do perfil de três solos da Amazônia Central e correlaeionou-se os valores de CTC encontrados com outras características intrínsecas de cada solo, tais como: matéria orgânica, superfície especifica teor e mlneralogia da fração argila, as quais causam varia cão na CTC do solo. As diferenças entre os valores de CTC obtidos foram decorrentes principalmente do teor de matéria orgânica e da mlneralogla da fração argila. A matéria orgânica do solo apresentou-se altamente correlacionada com a CTC determinada a pH 7,0 dos solos Latossolos Amarelo (r - 0,998) e Podzolico l/ermelho Amarelo (r = 0,974), principalmente pana os horizontes de superfície, enquanto que para o solo Glei Pouco Húmico foram encontradas correlações significativas apenas ao nível de 5%. Para a CTC à pH natural do solo, altas correlações também foram obtidas somente para Latossolo (r= 0,980) e Podzoílco (r = 0,984). A correlação entre a superfície específica e a CTC do solo apresentou-se altamente significativa para o Latossolo (r = 0,957) e Glei Pouco Húmico (r = 0,952), enquanto que para o Podzoílco (r + 0,873), a correlação foi significativa apenas ao nível de 5%. Foi observado ainda que a classe textural, o teor de matéria orgânica e principalmente a composição mlneralóglca conferiram maiores valores ae super fície especifica para o solo Glel Pouco Húmico.

A determinação da capacidade de troca de cátions do solo e de argilas por meio da troca isotópica com cálcio radioativo

O presente trabalho descreve a determinação da capacidade de troca de cátions (CTC) do solo e de argilas, através da troca isotópica com cálcio radioativo, 20Ca45. Foi determinada a CTC de oito amostras de solo e de quatro de argilas, tendo sido feitas 5 pesagens de cada amostra de cada um dos materiais, a fim de se avaliar a precisão do método. O cálculo da CTC foi feito mediante a expressão: X = a1/a2 c - c a1 = atividade específica do cálcio da solução de equilíbrio antes de entrar em contato com o solo. a2 = atividade específica do cálcio da solução de equilíbrio após o contato com o solo. c = número de e.mg de cálcio da solução de equilíbrio e calculado para 100g de solo. X = capacidade de troca de cations em e.mg por 100g de solo.

Estudo colorimétrico da montmorillonita: II. influência da eliminação dos óxidos de ferro livres na reação da montmorillonita com a benzidina

Este trabalho teve por objetivo estudar a influência da eliminação ou não dos óxidos de ferro livres na reação da montmorillonita com a benzidina, assim como dos métodos usados com tal finalidade. Para tal, suspensões de cinco (5) tipos de montmorillonita, sendo uma de procedência desconhecida (Mx) e quatro descritas pelo Projeto 49 (M22, M20, M22a e M31), foram submetidas a três tipos de tratamento: a) Eliminação dos sais solúveis, cations divalentes trocáveis, matéria orgânica e oxido de manganês livre; b) Mesmo tratamento citado em a e mais a eliminação dos óxidos de ferro livres pelo método do H-nascente' c) Mesmo tratamento citado em a e mais a remoção dos óxidos de ferro livres pelo método do bicarbonato - citrato - ditionito de sódio. Os resultados indicaram que houve influência do tipo de tratamento em todas as montmorillonitas testadas, sendo o teste F significativo ao nível de 1%. A conclusão geral a que se pôde chegar foi que a eliminação dos óxidos de ferro livres parece concorrer para maior uniformização da cor azul obtida, sendo que o método do H-nascente apresentou os melhores resultados, não apenas no que se refere à uniformização, mas também quanto à intensidade da cor obtida.

Contribution to the study of immune hemolysis by toad complement

EA (sheep erythrocytes carrying rabbit antibody) are lysed by toad complement under optimal conditions which include a low concentration of cells (1.54 x 10*8/ml), a low temperature of incubation (30°C) and the same amounts of Ca++ and Mg++ as required for the titration of guinea-pig complement. Kinetic studies of the role of cations mentioned above in immune lysis by toad C have disclosed a fundamental difference as compared to guinea-pig C. In a limited complement system, the lysis by amphibian C is completely blocked by EDTA, even when the chelating agent is added as late as 15 minutes after zero-time. Inhibition by EGTA is only partial and the findings suggest that Mg++ is required not only at the beginning, but also at late stages of the lytic process. It has been speculated that the activation of amphibian complement proceeds mainly by the alternative pathway.

Transport pathways in the malaria-infected erythrocyte: characterization and their use as potential targets for chemotherapy

The intraerythrocytic malarial parasite is involved in an extremely intensive anabolic activity while it resides in its metabolically quiescent host cell. The necessary fast uptake of nutrients and the discharge of waste product, are guaranteed by parasite-induced alterations of the constitutive transporters of the host cell and the production of new parallel pathways. The membrane of the host cell thus becomes permeable to phospholipids, purine bases and nucleosides, small non-electrolytes, anions and cations. When the new pathways are quantitatively unimportant, classical inhibitors of native transporters can be used to inhibit parasite growth. Several compounds were found to effectively inhibit the new pathways and consequently, parasite growth. The pathways have also been used to introduce cytotoxic agents. The parasitophorous membrane consists of channels which are highly permeable to small solutes and display no ion selectivity. Transport of some cations and anions across the parasite membrane is rapid and insensitive to classical inhibitors, and in some cases it is mediated by specific antiporters which respond to their respective inhibitors. Macromolecules have been shown to reach the parasitophorous space through a duct contiguous with the host cell membrane, and subsequently to be endocytosed at the parasite membrane. The simultaneous presence of the parasitophorous membrane channels and the duct, however, is incompatible with experimental evidences. No specific inhibitors were found as yet that would efficiently inhibit transport through the channels or the duct.

Chemical changes in argisols under irrigated grape production in the central São Francisco river valley, Brazil

This study compares the chemical composition of the solution and exchange complex of soil in a 3-year-old irrigated vineyard (Vitis vinifera L., Red Globe cultivar) with that of adjacent clearing in the native hyperxerophyllic 'caatinga' vegetation. The soils are classified as Plinthic Eutrophic Red-Yellow Argisol; according to Soil Taxonomy they are isohyperthermic Plinthustalfs. Detailed physiographic characterization revealed an impermeable gravel and cobble covering the crystalline rocks; the relief of this layer was more undulating than the level surface. Significant higher concentrations of extractable Na, K, Mg and Ca were observed within the vineyard. Lower soil acidity, higher Ca/Mg ratios, as well as lower sodium adsorption and Na/K ratios reflected additions of dolomitic lime, superphosphate and K-bearing fertilizers. As the water of the São Francisco River is of good quality for irrigation (C1S1), the increases in Na were primarily attributed to capillary rise from the saline groundwater table. None of the soil in the study area was found to be sodic. About 62% of the vineyard had an Ap horizon with salinity levels above 1.5dSm-1 (considered detrimental for grape production); according to average values for this horizon, a potential 13% reduction in grape production was predicted. Differences in chemical composition in function of distance to the collector canals were observed in the clearing, but not in the vineyard. The influence of differences in the elevations of the surface and impermeable layers, as well as pediment thickness, was generally weaker under irrigation. Under irrigation, soil moisture was greater in points of convergent surface waterflow; the effect of surface curvature on chemical properties, though less consistent, was also stronger in the vineyard.

Timing, location and crop species influence the magnitude of amelioration of aluminum toxicity by magnesium

The protective effect of cations, especially Ca and Mg, against aluminum (Al) rhizotoxicity has been extensively investigated in the last decades. The mechanisms by which the process occurs are however only beginning to be elucidated. Six experiments were carried out here to characterize the protective effect of Mg application in relation to timing, location and crop specificity: Experiment 1 - Protective effect of Mg compared to Ca; Experiment 2 - Protective effect of Mg on distinct root classes of 15 soybean genotypes; Experiment 3 - Effect of timing of Mg supply on the response of soybean cvs. to Al; Experiment 4 - Investigating whether the Mg protective effect is apoplastic or simplastic using a split-root system; Experiment 5 - Protective effect of Mg supplied in solution or foliar spraying, and Experiment 6 - Protective effect of Mg on Al rhizotoxicity in other crops. It was found that the addition of 50 mmol L-1 Mg to solutions containing toxic Al increased Al tolerance in 15 soybean cultivars. This caused soybean cultivars known as Al-sensitive to behave as if they were tolerant. The protective action of Mg seems to require constant Mg supply in the external medium. Supplying Mg up to 6 h after root exposition to Al was sufficient to maintain normal soybean root growth, but root growth was not recovered by Mg addition 12 h after Al treatments. Mg application to half of the root system not exposed to Al was not sufficient to prevent Al toxicity on the other half exposed to Al without Mg in rooting medium, indicating the existence of an external protection mechanism of Mg. Foliar spraying with Mg also failed to decrease Al toxicity, indicating a possible apoplastic role of Mg. The protective effect of Mg appeared to be soybean-specific since Mg supply did not substantially improve root elongation in sorghum, wheat, corn, cotton, rice, or snap bean when grown in the presence of toxic Al concentrations.

Aluminum hydroxy-interlayered minerals and chemical properties of a subtropical Brazilian Oxisol under no-tillage and conventional tillage

No tillage systems significantly influence the soil system, but knowledge about the effects on the mineralogy of tropical and subtropical soils is limited. This study evaluated the long-term effects (26 years) of no-tillage (NT) on aluminum hydroxy-interlayered minerals of a subtropical Oxisol in Southern Brazil (Guarapuava, PR), compared to the same soil under conventional tillage (CT). The clay fraction (< 2 µm) in soil samples of the surface horizons of a field experiment under both management systems was analyzed by X-ray diffraction (XRD) to identify and characterize Al hydroxy-interlayered minerals before and after treatment with sodium citrate to remove intra-layer material. Soil liquid (solution) and solid phases were also characterized. The contents of total organic C, exchangeable cations, P, and the values of extractable acidity and cation exchange capacity as well as electrical conductivity and levels of dissolved organic C, basic cations, aluminum, Si, and sulfur in the soil solution were higher in the NT soil. Under both soil management systems, more than 90 % of the total soluble Al was complexed with organic compounds, with similar Al activity. No significant changes were detected by 2:1 clay mineral XRD analyses in terms of extension or intercalation of Al-hydroxy-polymers in the no-tilled in comparison to the conventionally tilled soil. In both soil management systems, Al and Si activities in the soil solution indicated thermodynamic stability of 2:1 clay minerals with partially occupied by hydroxy-Al, suggesting deceleration in the intercalation process and a tendency of transforming clay minerals from extensive into partial intercalation.

Alterations of soil chemical properties by eucalyptus cultivation in five regions in the Rio Doce Valley

Little is currently known about modifications in edaphic characteristics caused by short-rotation eucalyptus and the impacts of these alterations on the sustainability of eucalyptus wood production. This study was carried out to identify theses changes at five sites of eucalyptus plantation in the region of the Rio Doce Valley, state of Minas Gerais, Brazil. Areas with more than three previous eucalyptus cycles, adjacent to pasture land or native forest, were chosen. Soil samples were collected and soil fertility analyzed by routine methods and other fractionation methods in order to measure alterations in the K, Ca and Mg contents as a consequence of eucalyptus cultivation. In the eucalyptus areas, reductions in the exchangeable Ca2+, Mg2+ and K+ contents and pH were observed and increased Al3+ and H + Al contents. Of all nutrients, only P contents (Mehlich-1 P) increased in the eucalyptus areas. The reduction in exchangeable forms and in medium-term soil nutrient pools indicates the need for higher nutrient rates than the currently applied in order to prevent nutritional limitations and soil nutrient exhaustion. After several eucalyptus rotations there was a recovery in the SOM content in comparison to degraded pasture soils, although not to the level of the native forest soil. The positive correlation between effective CEC and medium-term non-exchangeable Ca, Mg and K with SOM emphasizes the need for adequate fertilizer and plant residue management to sustain or even increase forest productivity in future cycles.

Irrigation with domestic wastewater: a multivariate analysis of main soil changes

Irrigation with treated domestic sewage wastewater (TSE) is an agricultural practice to reduce water requirements of agroecossystems and the nutrient load impact on freshwaters, but adverse effects on soil chemical (salinization, sodification, etc.) and soil physical properties (alteration in soil porosity and hydraulic conductivity, etc.) have been reported. This study aimed to define some relationships among these changes in an Oxisol using multivariate analysis. Corn (Zea mays L.) and sunflower (Helianthus annuus L.) were grown for two years, irrigated with TSE. The following soil properties were determined: Ca2+; Mg2+; Na+; K+ and H + Al contents, cationic exchangeable capacity (CEC), sum of bases (SB), base saturation (V), texture (sand, silt and clay), macro-, micro-, and cryptoporosity (V MA, V MI and V CRI), water content at soil saturation (θS) and at field capacity (θFC), residual water content (θR), soil bulk density (d s), water dispersed clay (WDC) and saturated hydraulic conductivity (K SAT). Factor analysis revealed the following six principal factors: Fine Porosity (composed of Na+; K+; WDC, θR, θRFC, and V CRI); Large Porosity (θS, d s, V MA, Vs); Soil CEC (Ca2+; Mg2+; CEC, SB, V); Soil Acidity (H + Al); and Soil Texture (factors 5 and 6). A dual pore structure appears clearly to the factors 1 and 2, with an apparent relationship between fine porosity and the monovalent cations Na+ and K+. The irrigation (with potable sodic tap water or sewage wastewater) only had a significant effect on Fine Porosity and Large Porosity factors, while factors 3 and 4 (Soil CEC and Soil Acidity) were correlated with soil depth. The main conclusion was a shift in pore distribution (large to fine pores) during irrigation with TSE, which induces an increase of water storage and reduces the capacity of drainage of salts.

Cation dynamics in soils with different salinity levels growing irrigated rice

Salinity levels in soils of the Outer Coastal Plain of Rio Grande do Sul, Brazil, can be high, due to excess of Na in the irrigation water, evapotranspiration and soil development from marine sediments. The cultivation of irrigated rice could be an alternative, since ion uptake as well as leaching by the establishment of a water layer could mitigate the effects of soil salinity. This study aimed to evaluate the dynamics of basic cations in the solution of Albaqualf soils with different salinity levels growing irrigated rice. The plow layer contained exchangeable Na percentages (ESP) of 5.6, 9.0, 21.2 and 32.7 %. The plant stand, dry matter, Na, K and Ca + Mg uptake at full flowering and grain yield were evaluated. The levels of Na, K, Ca + Mg and electrical conductivity (EC) in the soil solution were also measured weekly during the rice cycle at four soil depths, in the water layer and irrigation water. The Na, K and Ca + Mg uptake by rice at full flowering was used to estimate ion depletion from the layer under root influence. Soil salinity induced a reduction in the rice stand, especially in the soil with ESP of 32.7 %, resulting in lower cation uptake and very low yield at that site. As observed in the water layer and irrigation water, the Na, K, Ca + Mg and EC levels in the soil solution decreased with time at depths of 5, 10 and 20 cm, regardless of the original soil salinity, showing that cation dynamics in the plow layer was determined by leaching and root uptake, rather than by the effect of evapoconcentration of basic cations in the soil surface layer.

Nitrate role in basic cation leaching under no-till

Especially under no-tillage, subsuface soil acidity has been a problem, because it depends on base leaching, which has been associated with the presence of low molecular weigth organic acids and companion anions. The objective of this study was to evaluate exchangeable base cation leaching as affected by surface liming along with annual urea side-dressing of maize and upland rice. Treatments consisted of four lime rates (0, 1500, 3000, and 6000 kg ha-1) combined with four nitrogen rates (0, 50, 100, and 150 kg ha-1) applied to maize (Zea mays) and upland rice (Oryza sativa), in two consecutive years. Maize was planted in December, three months after liming. In September of the following year, pearl millet (Pennisetum glaucum) was planted without fertilization and desiccated 86 days after plant emergence. Afterwards, upland rice was grown. Immediately after upland rice harvest, 18 months after surface liming, pH and N-NO3-, N-NH4+, K, Ca, and Mg levels were evaluated in soil samples taken from the layers 0-5, 5-10, 10-20 and 20-40 cm. Higher maize yields were obtained at higher N rates and 3000 kg ha-1 lime. Better results for upland rice and pearl millet yields were also obtained with this lime rate, irrespective of N levels. The vertical mobility of K, Ca and Mg was higher in the soil profiles with N fertilization. Surface liming increased pH in the upper soil layers causing intense nitrate production, which was leached along with the base cations.

Soil composition and nutritional status of apple as affected by long-term application of gypsum

Gypsum does not affect the soil negative charges and maintains sulfate in the soil solution, making it one of the cheapest products to increase Ca activity in soil solution, especially in the deeper soil layers. Higher Ca levels in the soil solution can increase the uptake of this nutrient by apple trees, reducing the risk of physiological disorders caused by Ca deficiency. This study assessed the effect of long-term gypsum application on some soil properties and on the chemical composition of leaves and fruits of an apple cultivar susceptible to fruit disorders associated with low Ca. The experiment was conducted in São Joaquim, in the South of Brazil, from 2001 to 2009. Gypsum rates of 0, 1.0, 2.0 and 3.0 t ha-1 were annually broadcast over the soil surface, without incorporation, in an apple orchard with cultivar ´Catarina´, planted in 1997. Gypsum application over eight consecutive years had no effect on soil exchangeable K and Al to a depth of 80 cm, but increased exchangeable Ca in the sampled layers (0-10, 10-20, 40-60 and 60-80 cm), while exchangeable Mg decreased only in the surface layer (0-20 cm). Gypsum did not affect the concentration of any nutrient in the fruits, including Ca. The same was verified in the leaves, except for Mg which decreased with increased gypsum rate. Despite increasing the availability of Ca in the soil profile to a depth of 80 cm, gypsum was not effective to increase the Ca content in leaves and fruits of an apple cultivar susceptible to Ca deficiency grown in an appropriately limed soil.