Synthesis, characterization and thermal behaviour of solid state compounds of 4-methoxybenzoate with Manganese, Nickel and Copper

Solid state M-L compounds, where M stands for bivalent Mn, Ni, Cu and L is 4-methoxybenzoate, have been synthesized. Simultaneous thermogravimetry - differential thermal analysis (TG-DTA), X-ray powder diffractometry, infrared spectroscopy, elemental analysis and complexometry were used to characterize and to study the thermal behaviour of these compounds. The results led to information about the composition, dehydration, thermal stability and thermal decomposition of the isolated compounds.

THE COPPER INTERFERENCE WITH THE MELANOGENESIS OF Cryptococcus neoformans

Melanin is a pigment produced by laccase, a phenoloxydase enzyme, and is related to the virulence of Cryptococcus neoformans as it is also considered an adaption mechanism to environmental conditions and protection against UV radiation, phagocytic system attack and antifungal drugs. Laccase synthesis is stimulated by several factors, including copper metabolism. The current study shows C. neoformans strains with higher melanization intensity when grown in L-dopa medium supplemented with different concentrations of copper sulfate. This increase shows that melanization rates may be enhanced in the presence of copper ions and may also enhance the virulence of C. neoformans in infected patients that present increasing copper concentrations in serum, such as those with HIV. The virulence of these strains may also be increased in the environment, where this metal is available as CuSO4 in algicidal and fungicidal compounds.

SERUM LEVELS OF COPPER AND IRON IN DENGUE FEVER

SUMMARY The role of trace elements in dengue virulence is not yet known. The present study assessed the serum levels of two micronutrients, copper and iron, in cases of dengue fever. The study involved 96 patients of whom 48 had either severe or non-severe forms of dengue (with and without warning signs), and the remaining 48 were patients with other febrile illnesses (OFI), used as controls. Serum levels of copper and iron were evaluated at admission and by the time of defervescence using commercially available kits. At admission, no difference in the level of serum copper was observed between cases and controls. In the group of dengue cases, the copper level was found to be significantly decreased in severe and non-severe cases with warning signs, compared to non-severe cases without warning signs. In contrast, by the time of defervescence the copper level was found to be increased in all dengue cases compared to OFI controls, but no difference was observed among dengue cases. Unlike OFI controls, dengue cases showed an increasing pattern of copper levels from admission until defervescence. On the other hand, no such significant differences were observed in the serum level of iron in the clinical groups, except for a decreased iron level found in severe cases, compared to non-severe dengue without warning signs. The results show that copper is associated with dengue severity and this finding emphasizes the need to investigate the involvement of trace elements in disease severity so as to improve the prognosis of dengue.

Comparative evaluation of adverse effects in the use of powder trivalent antivenom and liquid antivenoms in Bothrops snake bites

INTRODUCTION: Snake bite, a problem in public health, generally occurs where there is no electric power. METHODS: A comparative clinical study was conducted with 102 victims of Bothrops snake bite, from the state of Amazonas, Brazil; 58 victims were treated with liofilizated trivalent antivenom serum (SATL) and 44 victims treated with liquid bivalent and monovalent antivenom serum (SAMBL). RESULTS: 17% (10/58) of patients presented adverse effects with the SATL and 25% (11/44) with the SAMBL. CONCLUSIONS: There was no statistic difference in number of adverse effects between the two types of snake bite antivenom.

Copper toxicity for Scinax ruber and Rhinella granulosa (Amphibia: Anura) of the Amazon: Potential of Biotic Ligand Model to predict toxicity in urban streams

In the last years many populations of anurans have declined and extinctions have been recorded. They were related to environmental pollution, changes of land use and emerging diseases. The main objective of this study was to determine copper sensitivity of the anuran of the Amazon Rhinella granulosa and Scinax ruber tadpoles at stage 25 and Scinax ruber eggs exposed for 96 h to copper concentrations ranging from 15 µg Cu L-1 to 94 µg Cu L-1. LC50 at 96 h of Rhinella granulosa Gosner 25, Scinax ruber Gosner 25 and Scinax ruber eggs in black water of the Amazon were 23.48, 36.37 and 50.02 µg Cu L-1, respectively. The Biotic Ligand Model was used to predict the LC50 values for these species and it can be considered a promising tool for these tropical species and water conditions. Copper toxicity depends on water physical-chemical composition and on the larval stage of the tadpoles. The Gosner stage 19-21 (related to the appearance of external gills) is the most vulnerable and the egg stage is the most resistant. In case of contamination by copper, the natural streams must have special attention, since copper is more bioavailable.

Thiamin, selenium, and copper levels in patients with idiopathic dilated cardiomyopathy taking diuretics

OBJECTIVE: To analyze the association of thiamin, selenium, and copper serum levels with cardiac function in patients with idiopathic dilated cardiomyopathy using diuretics, and also to compare them with levels in control patients with no evidence of disease. METHODS: The study comprised 30 patients with heart disease and 30 healthy control individuals. Thiamin was analyzed by measuring the activity of erythrocytic transketolase and the effect of thiamin pyrophosphate. Selenium and copper serum levels were measured by hydride generation and flame atomic absorption spectrophotometry, respectively. RESULTS: Thiamin deficiency was observed in 10% of the control individuals and in 33% of the patients with heart disease (p=0.02). The mean selenium and copper serum levels in control individuals and patients with heart disease were, respectively, 73.2±9.9 µg/L (56.5 to 94.5 µg/L) and 72.3±14.3 µg/L (35.5 to 94 µg/L) (p=0.77); 1.1±0.4mg/L (0.6 to 1.8mg/L) and 1.2± 0.4mg/L (0.6 to 2.2mg/L) (p=0.27). No association between the levels of these nutrients and cardiac function was observed. CONCLUSION: Thiamin deficiency was significantly more frequent in patients with heart disease. No significant difference was observed between the mean selenium and copper serum levels in control individuals and in patients with heart disease. The results suggest possible benefits with thiamin replacement in patients taking diuretics.

Combination of diatomaceous earth and powder deltamethrin for insect control in stored corn

The use of diatomaceous earth (DE) is a very efficient insect control measure in stored grain IPM due to its low cost, easy application, reduction of active ingredient residues, lower environmental contamination and operator safety. The objective of this research was to evaluate the efficacy of different dosages of DE mixed with powder deltamethrin for controlling Sitophilus zeamais in stored corn. Samples of 100 g of clean and dry corn, in three replicates, were submitted to the following treatments: DE (Keepdry®), at the dosages of 500, 750 and 1000 g/t; powder deltamethrin (K-Obiol®) at 0,5 g a.i. /t and 1,0 g a.i. /t; and combinations of the lowest and highest DE dosages with the two dosages of deltamethrin. Thirty adults of S. zeamais were placed in each vial with the treated grains and kept in environment chambers at 25ºC. Mortality was evaluated from the 1st to the 28th day. In the treatments mixing DE with deltamethrin or deltamethrin alone, the mortalyti was registered since the first day. In the treatments using only DE, the first dead insects were recorded after the 3rd day, especially in the highest dosages. After the 7th day, however, there was no statistical difference among all treatments, except for the lowest dosage of DE which reached a satisfactory control level only by the 14th day. It was concluded that treatments using DE combined with low dosages of powder deltamethrin represent an efficient control measure against S. zeamais in stored corn because insect mortality is faster than in treatments using DE alone and residues of active ingredients are much lower than using the insecticide in high dosages.

Copper, zinc and manganese in soils of two watersheds in Santa Catarina with intensive use of pig slurry

Systematic pig slurry application to crop soils may lead to the accumulation of heavy metals in regions with intensive pig raising. The aim of this study was to evaluate the accumulation of Cu, Zn and Mn in soils under systematic pig slurry application. For this purpose, soil samples were collected from two of the most representative watersheds of Santa Catarina where the predominant activity is pig raising. In each watershed, 12 properties were chosen to evaluate the different systems of pig husbandry (complete cycle (CC), farrowing (FaU) and finishing units (FiU)). Based on information of the producers, soil samples were collected in areas with and without systematic manure application. To determine the total Cu, Zn and Mn content in soils and manure, a methodology proposed by the Environmental Protection Agency of the United States (USEPA), method nº 3050B, was used. For the available heavy metal content, Cu and Zn was extracted with HCl 0.1 mol L-1 and Mn with KCl 1 mol L-1. Data were subjected to multivariate analysis, using the canonical discriminant analysis to identify the metals that best differentiate the soils studied within each swine housing system. Successive pig slurry applications cause an increase in Cu, Zn and Mn availability in the soil and this indicates the need for monitoring of the metal concentrations over time. The critical values of Cu in the soil can be reached and exceeded more rapidly than Zn. The results showed that the soil type may be one of the attribute underlying the determination of public policies in pig raising and waste management because soils such as Inceptisols were shown to be more prone to possible contamination since they may more rapidly reach total critical Cu levels.

Characterization and nutrient release from silicate rocks and influence on chemical changes in soil

The expansion of Brazilian agriculture has led to a heavy dependence on imported fertilizers to ensure the supply of the growing food demand. This fact has contributed to a growing interest in alternative nutrient sources, such as ground silicate rocks. It is necessary, however, to know the potential of nutrient release and changes these materials can cause in soils. The purpose of this study was to characterize six silicate rocks and evaluate their effects on the chemical properties of treated soil, assessed by chemical extractants after greenhouse incubation. The experimental design consisted of completely randomized plots, in a 3 x 6 factorial scheme, with four replications. The factors were potassium levels (0-control: without silicate rock application; 200; 400; 600 kg ha-1 of K2O), supplied as six silicate rock types (breccia, biotite schist, ultramafic rock, phlogopite schist and two types of mining waste). The chemical, physical and mineralogical properties of the alternative rock fertilizers were characterized. Treatments were applied to a dystrophic Red-Yellow Oxisol (Ferralsol), which was incubated for 100 days, at 70 % (w/w) moisture in 3.7 kg/pots. The soil was evaluated for pH; calcium and magnesium were extracted with KCl 1 mol L-1; potassium, phosphorus and sodium by Mehlich 1; nickel, copper and zinc with DTPA; and the saturation of the cation exchange capacity was calculated for aluminum, calcium, magnesium, potassium, and sodium, and overall base saturation. The alternative fertilizers affected soil chemical properties. Ultramafic rock and Chapada mining byproduct (CMB) were the silicate rocks that most influenced soil pH, while the mining byproduct (MB) led to high K levels. Zinc availability was highest in the treatments with mining byproduct and Cu in soil fertilized with Chapada and mining byproduct.

Forms and accumulation of copper and zinc in a sandy typic hapludalf soil after long-term application of pig slurry and deep litter

Successive applications of pig slurry and pig deep litter may lead to an accumulation of copper (Cu) and zinc (Zn) fractions in the soil profile. The objective of this study was to evaluate the Cu and Zn forms and accumulation in a Sandy Typic Hapludalf soil after long-term application of pig slurry and deep litter. In March 2010, eight years after initiating an experiment in Braço do Norte, Santa Catarina (SC), Brazil, on a Sandy Typic Hapludalf soil, soil samples were collected from the 0-2.5, 2.5-5.0, 5-10 and 10-15 cm layers in treatments consisting of no manure application (control) and with applications of pig slurry and deep litter at two levels: the single and double rate of N requirement for maize and black oat succession. The soil was dried, ground in an agate mortar and analyzed for Cu and Zn contents by 0.01 mol L-1 EDTA and chemically fractionated to determine Cu and Zn. The applications of Pig deep litter and slurry at doses equivalent to 90 kg ha-1 N increased the contents of available Cu and Zn in the surface soil layer, if the double of this dose was applied in pig deep litter or double this dose in pig slurry, Cu and Zn migrated to a depth of 15 cm. Copper is accumulated mainly in the organic and residual fractions, and zinc preferentially in the fraction linked to clay minerals, especially in the surface soil layers.

Effect of rock powder and vinasse on two types of soils

Can vinasse accelerate the change of minerals in rock dust to obtain fertilizers, using residues from alcohol agro-industries and mining? Answering this question was the main objective of this study. Therefore, an experiment was set up in the laboratory in a completely randomized design using Polyvinyl Chloride (PVC) columns, in which the 0-50 cm layers of a clayey soil (eutroferric Red Oxisol) and sandy soil (Typic Quartzipsamment) were reproduced. We applied three different rates of basalt powder (0.0; 2.0, and 4.0 t ha-1) and one rate of vinasse (200 m³ ha-1) to the soils. The control was made by treatments with water (200 m³ ha-1) with the same rates of rock powder. Samples were first collected on the surface of each column (1, 15, 30, 45, 60, and 90 days after the application of vinasse and rock powder), and, at the end of the experiment, at the various depths and in leached water, to determine pH and the concentration of soluble Ca2+, Mg2+, and K+. There was a significant effect of the solvent and the soil on the surface layer, with higher concentrations found in the treatments with vinasse and in clayey soil, confirming the potential of vinasse to alter minerals in basalt powder. The resulting levels from the beginning to the end of the experiment suggest that sorption phenomena with neoformed mineral phases or organic acids may have occurred. It may be concluded that the use of rock powder and vinasse mixtures is a promising alternative for soil fertilization and recycling of waste from the sugarcane and mining industries.

PHYTOAVAILABILITY OF COPPER IN INDUSTRIAL BY-PRODUCTS AND MINERAL FERTILIZERS

Alternative copper (Cu) sources could be used in fertilizer production, although the bioavailability of copper in these materials is unknown. The objective of this study was to evaluate the extractants neutral ammonium citrate (NAC), 2 % citric acid, 1 % acetic acid, 10 % HCl, 10 % H2SO4, buffer solution pH 6.0, DTPA, EDTA, water, and hot water in the quantification of available Cu content in several sources, relating them to the relative agronomic efficiency (RAE) of wheat grown in a clayey Latossolo Vermelho eutrófico (Oxisol) and Neossolo Quartzarênico (Typic Quartzipsamment). Copper was applied at the rate of 1.5 mg kg-1 as scrap slag, brass slag, Cu ore, granulated copper, and copper sulfate. The extractants 10 % HCl, 10 % H2SO4, and NAC extracted higher Cu concentrations. The RAE values of brass slag and Cu ore were similar to or higher than those of Cu sulfate and granulated Cu. Solubility in the 2nd NAC extractant, officially required for mineral fertilizers with Cu, was lower than 60 % for the scrap slag, Cu ore, and granulated copper sources. This fact indicates that adoption of the NAC extractant may be ineffective for industrial by-products, although no extractant was more efficient in predicting Cu availability for wheat fertilized with the Cu sources tested.

X-ray fluorescence determination of adsorbed copper on activated charcoal after glycerin complexation

X-This work shows an alternative method to copper determination by X-Ray Fluorescence (XRF). Since copper concentration in natural waters is not enough to reach XRF detection limit, a liquid-solid preconcentration procedure was proposed. Glycerin was used to complex the metal increasing its adsorption on activated charcoal. The solid phase was used to XRF determination. Several parameters were evaluated, such as, the complexation pH, the charcoal adsorption limit and the glycerin concentration. The interferences are lead and bismuth and the sensitivities decreased in the order Cu2+, Bi3+ and Pb2+. The advantages of the method are its simplicity, low cost and low spectral interference.

Preparation and thermal decomposition of copper(II), zinc(II) and cadmium(II) chelates with 8-hydroxyquinoline

When the compounds are heated in an inert atmosphere it can be verified the consecutive partial sublimation, fusion, partial volatilization and partial thermal decomposition of the anhydrous complexes. When in an oxidating atmosphere the above process is only verified to Cu(II) chelates. Anhydrous copper(II) complexes present a monoclinic structure in the b form and the volatilized compound in a a form. Zinc(II) and cadmium(II) hydrated complexes are isomorphous and they present different cell dimensions from those reported previously.

Synthesis and characterization of manganese-glycine and copper-glycine adducts

This work reports the synthesis and characterization of adducts of general formula MCl2.ngly, where M= Mn and Cu; n= 2 and 4, and gly= glycine. The manganese adducts were synthesized by dissolution of both, manganese chloride and glycine in water, whereas the copper adducts were obtained by using an alternative solid state synthesis approach. For all adducts, the obtained infrared data shows that the coordination involves the amine nitrogen atom, as well as an oxygen atom of the COO- group. The TG curves for the synthesized adducts exhibit only one mass loss step associated with the release of glycine molecules.