Determination of labile inorganic and organic species of Al and Cu in river waters using the diffusive gradients in thin films technique

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

Characterization of the colloidal products of pentacarbonyliron oxidation

Pentacarbonyliron was oxidized with H2O2, in organic solvents, to give colloidal sols. The aqueous-ethanolic sol is highly stable and undergoes thermally-reversible coagulation. Its solid phase was found to be a non-crystalline Fe (III) hydroxoacetate which is transformed to α-Fe2O3 when heated to 300°C. Iron-bound acetate groups are assumed to have a major role in the sol stability, by preserving the amorphous solid phase. Dry hydroxoacetate particles were heated under vacuum; scanning electron microscopy revealed that these particles coalesce and grow, as in a sintering process but at low temperatures (100-250°). © 1987.

Small angle X-ray scattering study of structural changes in silica gel modified with organofunctional groups

Silica gel surfaces, organofunctionalized with 2-mercaptobenzimidazole, iminosalicylaldehyde and imidazole groups were examined using the small angle X-ray scattering technique (SAXS). From the scattering intensity data it was concluded that particles have a uniform size after the coupling reaction. The chemical treatment of the silica gel leads to an attachment of the organofunctional groups on the solid-pore interface of the silica with an increase of the mean size of the solid phase and some coalescence of the pores. © 1989.

Laminin-binding epitope on gp43 from Paracoccidioides brasiliensis is recognized by a monoclonal antibody raised against Staphylococcus aureus laminin receptor

Adhesion is regarded as an important step in the pathogenesis of several microorganisms. Thus, the ability to recognize extracellular matrix proteins, such as laminin or fibronectin, has been correlated with invasiveness. Studying the already characterized laminin-binding protein of Paracoccidioides brasiliensis, the 43 kDa glycoprotein (gp43), we evaluated whether MAb 1.H12, raised against the laminin-binding protein from Staphylococcus aureus, cross-reacts with that fungal protein. By immunoblot analysis we show that MAb 1.H12 recognizes gp43. This interaction is able to inhibit the laminin-mediated adhesion to epithelial cells as well as the P. brasiliensis infection in vivo. Moreover, through immunoenzymatic assays, we show that MAb 1.H12 recognizes gp43 in solid phase and that this interaction is partially inhibited by the addition of anti-gp43 MAbs. These results show that MAb 1.H12 recognizes the gp43, suggesting the presence of an epitope similar to those found in the other laminin-binding proteins from phylogenetically very distant cells. These findings reinforce the possibility of evolutionary conservation of such epitopes.

Is the Thoroughbred race-horse under chronic stress?

Thoroughbred fillies were divided into three groups according to age: group 1, 7 fillies aged 1 to 2 years (G1) starting the training program; group 2, 9 fillies aged 2 to 3 years (G2) in a full training program; group 3, 8 older fillies 3 to 4 years of age (G3) training and racing. Blood samples were collected weekly from July to December. Cortisol was quantified using a solid phase DPC kit. The intra- and interassay coefficients of variation were 12.5% and 15.65% and sensitivity was 1.9 ± 0.2 nmol/ l. The semester average of cortisol levels varied between groups: G1 = 148.8 ± 6.7, G2 = 125.7 ± 5.8, G3 = 101.1 ± 5.4 nmol/l, with G3 differing statistically from the other groups. The lower cortisol levels observed in the older fillies leads us to propose that the stress stimulus, when maintained over a long period of time, may become chronic and result in a reduction of hypophyseal corticotropin-releasing hormone receptors. The secretion of endogenous opioids may also lead to low serum cortisol levels.

Comparative time-course study of aminoacyl- and dipeptidyl-resin hydrolysis

The classic hydrolysis procedure for quantification of resin-bound aminoacyl and peptidyl groups with 12 N HCl: propionic acid was recvaluated by studying the influence of the nature of the resin and the resin-bound group. Their stability during acid hydrolysis was dependent on the C-terminal amino acid, and the order of acid stability was Phe > Val > Gly. Otherwise, the dipeptides Ala-Gly, Ala-Val, and Ala-Phe displayed enhanced rates of hydrolysis of the resin if compared with their parent aminoacyl groups. Amongthe resins assayed, the order of acid stability was: benzhydrylamine-resin > p-methylbenzhydrylamine-resin ≅4-(oxymethyl)-phenylacetamidomethyl-resin > chloromethyl-copolymer of styrene-1%-divinylbenzene. Important for peptide synthesis method, the findings demonstrate that longer hydrolysis times than previously recommended in the literature (1 h at 130°C and 15 min at 160°C for peptides attached to the chloromethyl-copolymer of styrene-1%-divinylbenzene) are necessary for the quantitative acid-catalyzed cleavage of some resin-bound groups. The observed broad range of hydrolysis time varied from less than 1 h to about 100 h.

Oxidative dissolution of covellite by Thiobacillus ferrooxidans

Oxidation of research-grade covellite was investigated in respirometric and growth experiments with Thiobacillus ferrooxidans. Covellite was directly oxidized by T. ferrooxidans in respirometric experiments, but the pH of mineral salts medium increased to prohibitively high values because of high sulfide concentrations. In glycine-H 2SO 4 buffered medium the pH remained steady and the oxygen uptake activity of T. ferrooxidans was not inhibited. In cultures growing with covellite as the sole source of energy, the pH increased to about 4. Redox potential increased to 500-600 mV during bacterial oxidation of covellite in the presence and absence of additional Fe 2+, whereas it remained mostly at about 350 mV in abiotic control. Jarosite was a major solid-phase product in T. ferrooxidans cultures. The solubilization of copper from covellite in inoculated flasks was higher than that obtained in control flasks and was not enhanced in the presence of additional Fe 2+.The sample also contained bornite (Cu 5FeS 4) which released iron in solution under all experimental conditions. Accumulation of S 0 was apparent only in inoculated covellite samples. © 1997 Elsevier B.V. All rights reserved.

Oxidative dissolution of chalcopyrite by Thiobacillus ferrooxidans

The oxidative dissolution of research-grade chalcopyrite was characterized in respirometric and growth experiments with Thiobacillus ferrooxidans. In respirometric experiments with chalcopyrite, the pH of mineral salts medium increased to values that inhibited the oxygen uptake activity of T. ferrooxidans. In glycine-H 2SO 4 buffered medium the pH remained stable and oxygen uptake was not inhibited. In cultures growing with chalcopyrite as the sole source of energy, pH changes were only minor during the incubation. The redox potential values increased to about 600 mV during the bacterial oxidation of chalcopyrite in the presence and absence of additional Fe 2+, while they remained at about 350 mV in abiotic control flasks. Iron in chalcopyrite was solubilized and oxidized to Fe 3+ by T. ferrooxidans. In the abiotic controls, by comparison, less iron was solubilized and it remained as Fe 2+. Jarosite was a major solid- phase product in T. ferrooxidans cultures. The solub'flization of copper from chalcopyrite in inoculated flasks was enhanced in the presence of additional Fe 2+.Accumulation of S 0, reflecting partial oxidation of the S-entity of chalcopyrite, was apparent from the x-ray diffraction analysis of solid residues from the inoculated flasks as well the abiotic controls. © 1997 Elsevier B.V. All rights reserved.

Degradation of rice pesticides and their stability during storage of samples

Transformation of pesticides is directly related to the environmental conditions during application and transport of these compounds in the ecosystem. Rice fields include peculiar conditions, relatively high temperatures and wet conditions, leading to degradation processes, different from that observed in other agricultural systems. This article presents the degradation routes of some characteristic rice insecticides and herbicides under field conditions. A compilation of the pesticides that are usually applied during rice cultivation is included, with their main physico-chemical parameters. The stability of the pesticides by solid phase extraction systems during storage of rice samples is also discussed.

Two short peptides including segments of subunit A of Escherichia coli DNA gyrase as potential probes to evaluate the antibacterial activity of quinolones

Quinolones constitute a family of compounds with a potent antibiotic activity. The enzyme DNA gyrase, responsible for the replication and transcription processes in DNA of bacteria, is involved in the mechanism of action of these drugs. In this sense, it is believed that quinolones stabilize the so-called 'cleavable complex' formed by DNA and gyrase, but the whole process is still far from being understood at the molecular level. This information is crucial in order to design new biological active products. As an approach to the problem, we have designed and synthesized low molecular weight peptide mimics of DNA gyrase. These peptides correspond to sequences of the subunit A of the enzyme from Escherichia coli, that include the quinolone resistance-determining region (positions 75-92) and a segment containing the catalytic Tyr-122 (positions 116-130). The peptide mimic of the non-mutated enzyme binds to ciprofloxin (CFX) only when DNA and Mg2+ were present (Kd = 1.6 × 10 -6 m), a result previously found with DNA gyrase. On the other hand, binding was reduced when mutations of Ser-83 to Leu-83 and Asp-87 to Asn-87 were introduced, a double change previously found in the subunit A of DNA gyrase from several CFX-resistant clinical isolates of E. coli. These results suggest that synthetic peptides designed in a similar way to that described here can be used as mimics of gyrases (topoisomerases) in order to study the binding of the quinolone to the enzyme-DNA complex as well as the mechanism of action of these antibiotics. Copyright © 2001 European Peptide Society and John Wiley & Sons, Ltd.

Flow evolution of a metallic slurry during thixoextrusion of an automotive valve

The aim of this work is to characterize a metallic slurry (Al-4.5%Cu) flow during thixoforming of an automotive valve. The necessary globular structure was obtained by first inoculating the alloy with TIBAL (5%Ti, 1%B, Al - rest) at 750.0°C, and then reheating to a state between liquidus and solidus prior to thixoforming. Two metallic slurries, with a solid phase of approximately 86.1 and 78.2 percent, were used to generate different experimental flow patterns during the thixoforming process. The flow of the material into the die was observed for total, and partial displacement (2.7, 5.4, 7.5mm) of the punch. The first displacement shows formation of the valve rod. The patterns at each step of displacement of the punch were preserved by quenching in water, thus revealing the profile of the die fill and microstructural evolution. Degeneration of the globular phase was observed along the piece thixoextruded. Thixoextrusion forces versus time curves were generated for partial and full displacement of the punch. Porosity was visible along the billet prior to thixoforming. However, some areas show that the porosity gradually decreased to zero as the thixoextrusion pressure increased. Turbulent, transient and laminar flow are analyzed in this work.

Multiresidue determination of herbicides in environmental waters from Primavera do Leste region (Middle West of Brazil) by SPE-GC-NPD

A study on the presence of herbicides, namely simazine, metribuzin, metolachlor, trifluralin, atrazine and two metabolites, deisopropylatrazine (DIA) and deethylatrazine (DEA), was performed in ground and surface waters from Primavera do Leste region, Mato Grosso state (Middle West of Brazil). The analytical procedure was based on solid-phase extraction (SPE) with Sep-Pak C18 disposable cartridges and ethyl acetate for elution solvent. Residue levels were determined by gas chromatography with nitrogen-phosphorus detection. For most of the pesticides average recoveries at different fortification levels were >with relative standard deviation < The recoveries of DIA and trifluralin in water were 25% and 56%, respectively, which were attributed to the incomplete retention of DIA and strong retention on the sorbing material and high volatility of trifluralin. Detection limits ranged from 0.023 to 0.088 μg L-1. This method was applied for the analysis of 5 superficial water samples and 28 groundwater samples, in places used for human consumption without previous treatment, collected in Primavera do Leste, Mato Grosso, Brazil. Results indicated that the highest level of contamination in a water sample was 1.732 μg L-1 for metolachlor, while metribuzin was the most frequently detected herbicide with maximum concentration of 0.351 μg L-1. ©2006 Sociedade Brasileira de Química.

Reproductive cycle, ovarian development, and vertebrate-type steroids profile in the freshwater prawn Macrobrachium rosenbergii

This study is intended to characterize the ovarian development and hemolymph vertebrate-type steroids concentration during the reproductive cycle of the freshwater prawn, Macrobrachium rosenbergii. A five-stage classification based on the external observation of the ovary's size and color as seen through the tegument was used. The results showed the existence of a direct correspondence between the ovarian stages and the gonadosomatic index, the oöcyte diameter, and the characteristics of ovarian histology. In each stage total bleeding of the prawns was conducted and the hemolymph concentrations of 17β-estradiol (E 2), testosterone (T) and 17α-hydroxyprogesterone (17-OHP; conjugated and unconjugated) were determined by solid-phase radioimmunoassay (RIA). High levels of unconjugated 17-OHP, relatively constant concentrations of unconjugated T, and null concentration of unconjugated E 2 were found throughout the five stages considered. Nonetheless, low levels of E 2 were determined in all stages, in conjugated (glucoronide) form. The highest levels were obtained in stage II and III (18.14 ± 14.52 pg/ml hemolymph) and progressively declined in the other stages (7.53 ± 6.76 pg/ml hemolymph). These results point out the possible involvement of vertebrate-type steroids in the endocrine regulation of the Macrobrachium rosenbergii's ovarian cycle. To our knowledge this is the first study concerning the vertebrate-like steroid levels throughout the ovarian cycle and is a step needed to characterize the hemolymph profile of these steroids in order to elucidate the possible role in the regulation of the reproductive crustacean cycle.

Concentraçãeo plasmática de progesterona durante o ciclo estral de jumentas (equus asinus) com ovulaçõees simples e duplas

Ten estrous cycles of seven Machador Brasileiro jennies located at Estaçãeo Experimental de Zootecnia - Colina - Sãeo Paulo were monitored and the plasmatic progesterone concentration determined by the radioimmunoassay method in solid phase, employing commercial kits (DPC). For progesterone concentration determination and CL diameter there were excluded the animals which presented diestrus ovulations. The corpora lutea formed from single ovulations or double ovulations presented a mean diameter of 26.2 ± 4.4 and 22.1 ± 2.7 mm, respectively, which represented 66.1% and 64.1% of the preovulatory follicle diameter. The presence of two CLs from double ovulations was not reflected by a significant increase on progesterone concentrations.

Diffuse Effect of the Tungsten Doped Ba(Zr0.10Ti0.90)O3 Ferroelectric Ceramics

Barium zirconate titanate Ba(Ti0.90Zr0.10)O3 ceramics doped with WO3 (BZT:2W) have been prepared by a traditional solid phase reaction. The effect of temperature on the structural and electrical properties was investigated. X ray diffraction data evidenced formation of secondary phases for the samples sintered at 1300oC end 1350oC while the pure phase was attained at 1200oC. A modified Curie-Weiss law was used to describe the diffuseness of a phase transition. As temperature increases, the maximum dielectric permittivity decreased. The fine-grained sample showed a 'diffuse-like' ferroelectric behavior. The dielectric permittivity reaches a maximum value (εm ~6420 at 10 kHz) for the ceramics sintered at 1200oC for 4 hours.