Incorporation of Ca, P, and Si on bioactive coatings produced by plasma electrolytic oxidation: The role of electrolyte concentration and treatment duration

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

Oxidation of Bovine Albumin by Hypochlorous and Hypobromous Acids: Structural and Functional Alterations

Aims: Hypochlorous (HOCl) and hypobromous (HOBr) acids are among the most powerful oxidants produced by the innate immune cells. Albumin is the predominant protein in most body fluids and is considered the most important antioxidant of blood plasma. Study Design: Oxidation of bovine albumin (BSA) and study of its structural and functional alterations. Place and Duration of Study: Faculty of Science and Faculty of Pharmaceutical Science, University of the State of Sao Paulo UNESP, between June and December 2012. Methodology: BSA was oxidized with excess of HOCl or HOBr and its structural and functional alterations were analyzed by spectroscopic techniques as UV-Vis absorption, intrinsic and synchronous fluorescence, fluorescence quenching, Rayleigh scattering and circular dichroism. Results: Both oxidants were able to deplete the intrinsic fluorescence of BSA, but HOBr was more effective than HOCl. The alterations in the synchronous fluorescence, UV-Vis absorption, and the appearance of a fluorescence band centered at 450 nm confirmed the difference between the oxidants. The oxidation did not induce aggregation of BSA as measured by Rayleigh scattering. The far-UV circular dichroism spectra showed a loss in the helical content and the near-UV-circular dichroism showed an alteration in the tertiary structure; HOBr was the more effective of the oxidants in this case. However, the oxidations did not induce significant alterations in the binding capacity of BSA, which was evaluated using hydrophobic (norfloxacin) and hydrophilic (ascorbic acid) drugs. Conclusion: These results suggest that, although highly susceptible to oxidation, the alterations did not inhibit BSA’s physiological function as a transport protein.

Oxidation of amino acids by chlorpromazine cation radical and co-catalysis by chlorpromazine

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

Selenium and vitamin A and E in the nutrition of very low-birth weight preterm infants

Deficient antioxidant defenses in preterm infants have been implicated in diseases such as bronchopulmonary dysplasia, retinopathy of prematurity, necrotizing enterocolitis, periventricular leukomalacia, and intraventricular hemorrhage. The antioxidant properties of selenium, vitamin A, and vitamin E make these elements important in the nutrition of Very Low-Birth Weight (VLBW) infants. Selenium is a component of glutathione peroxidase, an enzyme that prevents the production of free radicals. The decrease in plasma selenium in VLBW infants in the first month after birth makes evident that preterm infants have low selenium store and require supplementation by parenteral and enteral nutrition. A meta-analysis, with only three trials, showed that selenium supplementation did not affect mortality, and the incidence of neonatal chronic lung disease or retinopathy of prematurity, but was associated with a reduction in lateonset sepsis. Most VLBW infants and extremely Low-Birth Weight Infants (ELBW) are born with low vitamin A stores and need vitamin A supplementation by intramuscular or enteral route. Low plasma retinol concentrations increase the risk of chronic lung disease/bronchopulmonary dysplasia and long-term respiratory disabilities in preterm infants. There is evidence that vitamin A supplementation decreases the mortality or oxygen requirement at one month of age, and oxygen requirement at 36 weeks’ postmenstrual age. Vitamin E blocks natural peroxidation of polyunsaturated fatty acids from lipid layers of cell membranes. VLBW infants have a decrease in plasma concentrations in the first month after birth suggesting the need of vitamin E supplementation. A meta-analysis on vitamin E supplementation concluded that vitamin E did not affect mortality, risk of bronchopulmonary dysplasia, and necrotizing enterocolitis but reduced the risk of intraventricular hemorrhage and increased the risk of sepsis. Serum vitamin E concentrations higher than 3.5 mg/dL are associated with a decrease in the risk of severe retinopathy of prematurity, and blindness, but also with an increase in neonatal sepsis. Caution is recommended with the supplementation of high doses of parenteral vitamin E and supplementation that increases serum levels above 3.5 mg/dL. In conclusion: although it is known that preterm infants are deficient in selenium, vitamin A and E, more studies are required to determine the best way to supplement and the impact of supplementation on neonatal outcome.

Effects of selenium supplementation on serum cortisol in repeatedly handled cattle

This study evaluated the relationship between Se supplementation and serum cortisol in repeatedly handled cattle. Sixty Nellore calves were randomly distributed into four experimental groups, which were fed a mineral-protein mixture added with Se to achieve individual daily supplementation of 0 (Gc), 3.6 (G3.6), 5.4 (G5.4) and 6.4 (G6.4) mg Se. Stressful handling procedures and blood sampling were performed on days 0, 15, 30, 60, 90 and 120. Serum cortisol increased until day 90 and decreased on day 120, irrespective of Se supplementation. This finding shows that cattle reached a stress state but adapted. Cortisol and Se levels were not markedly correlated. Serum Se increased over the course of the experiment in the supplemented groups. However, because serum Se decreased in Gc, it may have mobilized to form the selenoproteins needed to remove metabolic wastes from handling-related oxidative stress.

Selenium and sulfur: mitigation in plant stresses

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Selenium and sulfur: mitigation in plant stresses

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

The impact of the alkali cation on the mechanism of the electro-oxidation of ethylene glycol on Pt

By means of in situ IR spectroscopy we investigate the effect of dissolved alkali cations on the electro-oxidation of ethylene glycol on platinum in alkaline media. The results revealed that the increase in the oxidation currents (Li(+) < Na(+) < K(+)) is reflected in the increase in the ratio between carbonate and oxalate produced.

Electrocatalytic Activity of Platinum-Niobium Nanoparticles for Ethanol Oxidation

Three nanostructured platinum-niobium supported on Vulcan XC-72R carbon black materials were prepared as catalysts for the ethanol electroxidation: (i) deposition of platinum and niobium on Vulcan XC-72R carbon black, (ii) platinum decorated on a mixture of commercial amorphous Nb2O5/carbon black, and (iii) the same than ii but using crystalline Nb2O5, by reduction of the precursors with sodium borohydride in ethanol. All the catalysts showed platinum crystal sizes in the range of 3-4 nm, with no or little modification of the lattice parameter. The analyses of the electronic structure from the XANES region of the XAS spectra displayed some interactions between platinum and niobium, despite the niobium was primarily in the form of pentoxide in all the catalysts. CO stripping exhibited a promising low onset potential and a large current density, especially in the case of the deposited catalyst. Ethanol electroxidation experiments revealed that the Pt-Nb(2)O(5)crystalline/C generated the largest current. However it was not effective to completely oxidize ethanol, leading to acetic acid as the main product. In this sense, the highest efficiency for the complete oxidation of ethanol was obtained for the deposited catalyst. These results were interpreted in terms of the physico-chemical characteristic displayed by the different catalysts. (C) 2012 The Electrochemical Society. [DOI: 10.1149/2.040210jes] All rights reserved.

On the stability of the extracellular hemoglobin of Glossoscolex paulistus, in two iron oxidation states, in the presence of urea

The stability of the Glossoscolex paulistus hemoglobin (HbGp), in two iron oxidation states (and three forms), as monitored by optical absorption, fluorescence emission and circular dichroism (CD) spectroscopies, in the presence of the chaotropic agent urea, is studied. HbGp oligomeric dissociation, denaturation and iron oxidation are observed. CD data show that the cyanomet-HbGp is more stable than the oxy-form. Oxy- and cyanomet-HbGp show good fits on the basis of a two state model with critical urea concentrations at 220-222 nm of 5.1 +/- 0.2 and 6.1 +/- 0.1 mol/L, respectively. The three-state model was able to reveal a subtle second transition at lower urea concentration (1.0-2.0 mol/L) associated to partial oligomeric dissociation. The intermediate state for oxy- and cyanomet-HbGp is very similar to the native state. For met-HbGp, a different equilibrium, in the presence of urea, is observed. A sharp transition at 1.95 +/- 0.05 mol/L of denaturant is observed, associated to oligomeric dissociation and hemichrome formation. In this case, analysis by a three-state model reveals the great similarity between the intermediate and the unfolded states. Analysis of spectroscopic data, by two-state and three-state models, reveals consistency of obtained thermodynamic parameters for HbGp urea denaturation. (C) 2012 Elsevier Inc. All rights reserved.

Synthesis of selenium-linked neoglycoconjugates and pseudodisaccharides

The introduction of organoselenium moieties within the structure of carbohydrates has received attention recently. Herein, we report on the synthesis of selenium-containing neoglycoconjugates and pseudodisaccharides by the reaction of nucleophilic selenium species, generated from sugar diselenides, with chiral N-Boc aziridines and sugar tosylates. The reaction proceeds with moderate to good yields for various substrates. The introduction of organoselenium moieties within the framework of various sugars, with increased levels of complexity, thus allowing the synthesis of disaccharide and glycoconjugate mimetics. (C) 2012 Elsevier Ltd. All rights reserved.

Electrocatalytic performance of environmentally friendly synthesized gold nanoparticles towards the borohydride electro-oxidation reaction

In this paper we report a simple and environmentally friendly synthesis of gold nanoparticles (AuNps) and their electrocatalytic activity for borohydride oxidation reaction (BOR). Ultraviolet spectroscopy (UV- vis) and transmission electron microscopy (TEM) confirmed the formation of poly(vinyl pyrrolidone)protected colloidal AuNps through direct reduction of Au3+ by glycerol in alkaline medium at room temperature. For the BOR tests the AuNps were directly produced onto carbon to yield the Au/C catalyst. Levich plots revealed that the process occured via 7.2 electrons, therefore near the theoretical value of 8 electrons. When compared to bulk Au, the gold nanoparticles presented enhanced catalytic properties since the onset potential for BOR was shifted 200 mV towards negative potentials. (C) 2012 Elsevier B.V. All rights reserved.

Lipid and selenium sources on fatty acid composition of intramuscular fat and muscle selenium concentration of Nellore steers

The objective of this study was to evaluate the effect of lipid and selenium sources in diets for finishing Nellore steers on the fatty acid composition and selenium concentration of the longissimus muscle. Fifty Nellore steers (body weight = 458 +/- 39 kg) were assigned to one of six dietary treatments: 1) diet containing sunflower seed and inorganic selenium; 2) sunflower seed and organic selenium; 3) whole cottonseed and inorganic selenium; 4) whole cottonseed and organic selenium; 5) soybeans and inorganic selenium; and 6) soybeans and organic selenium. Diets were formulated with the same amount of nitrogen and calories and supplied once daily to steers in collective pens, with three animals per pen, for 120 d. At the end of the trial, steers were slaughtered and samples of the longissimus muscle were collected for fatty acid and selenium analysis. Effect of selenium sources was detected for selenium concentration in the longissimus muscle. Organic selenium had higher concentrations in the meat compared with inorganic selenium. The total saturated, monounsaturated and polyunsaturated fatty acids did not differ between the sources of lipids and selenium. For selenium sources, no differences were observed between the concentrations of polyunsaturated fat. Also, no differences in C18:2 cis-9 trans-11 concentrations were noted; however, steers fed sunflower seed presented greater proportions of this fatty acid in the meat. The results indicated that the use of sunflower seed, cottonseed or soybeans and organic or inorganic selenium in feedlot diets to Nellore cattle does not alter the great part of the fatty acid profile of the longissimus muscle. However, the inclusion of sunflower seed in the diet increases the meat CLA cis-9, trans-11, which is desirable and beneficial for the health of consumers.

Partial oxidation of methane on NiO-MgO-ZrO2 catalysts

Catalysts containing mixtures of NiO, MgO and ZrO2 were synthesized by the polymerization method. They were characterized by X-ray diffraction (XRD), physisorption of N-2 (BET), X-ray photoelectron spectroscopy (XPS) and X-ray absorption near-edge structure (XANES), and then tested in the partial oxidation of methane (POM) in the presence of air (2CH(4):1O(2)) at 750 degrees C for 6 h. Among the ternary oxides, the catalyst with 40 mol% MgO showed the highest conversion rates in the catalytic processes, but also the highest carbon deposition values (48 mmol h (1)). The greater the amount of NiO-MgO solid solution formed, the higher was the conversion rate of reactants (CH4), peaking at 40 mol% of MgO. Catalysts with lower Ni content on the surface achieved a high rate of CH4 conversion into synthesis gas (H-2 + CO). The formation of more NiO-MgO solid solution seemed to inhibit the deactivation of Ni degrees during reaction. The values of the H-2/CO product ratio were generally found to be slightly lower than stoichiometric. (C) 2012 Elsevier Ltd. All rights reserved.

Photo-Fenton oxidation of phenol and organochlorides (2,4-DCP and 2,4-D) in aqueous alkaline medium with high chloride concentration

A highly concentrated aqueous saline-containing solution of phenol, 2,4-dichlorophenoxyacetic acid (2,4-D) and 2,4-dichlorophenol (2.4-DCP) was treated by the photo-Fenton process in a system composed of an annular reactor with a quartz immersion well and a medium-pressure mercury lamp (450 W). The study was conducted under special conditions to minimize the costs of acidification and neutralization, which are usual steps in this type of process. Photochemical reactions were carried out to investigate the influence of some process variables such as the initial concentration of Fe2+ ([Fe2+](0)) from 1.0 up to 2.5 mM, the rate in mmol of H2O2 fed into the system (F-H2O2,F-in) from 3.67 up to 7.33 mmol of H2O2/min during 120 min of reaction time, and the initial pH (pH(0)) from 3.0 up to 9.0 in the presence and absence of NaCl (60.0 g/L). Although the optimum pH for the photo-Fenton process is about 3.0, this particular system performed well in experimental conditions starting at alkaline and neutral pH. The results obtained here are promising for industrial applications, particularly in view of the high concentration of chloride, a known hydroxyl radical scavenger and the main oxidant present in photo-Fenton processes. (C) 2012 Elsevier Ltd. All rights reserved.