Spectrophotometric determination of manganese in steels by on-line electrochemical oxidation

The aim of this work is to propose a flow spectrophotometric procedure for manganese determination in steel based on electrochemical oxidation of Mn(II) to Mn(VII) at a Pt electrode surface by means of the catalytic effect of Ag(I). The on-line oxidation step was obtained by injecting sample and electrolyte solution directly into an electrolytic cell. After electrolysis, the injectate was homogenized by bubbling air. The permanganate ions produced were passed through the spectrophotometer where absorbance was monitored at 545 nm. Effects of direct current, silver concentration, timing, flow rates, concentration and composition of support electrolyte were investigated. Direct current and silver content manifested themselves as the most relevant parameters. For determination of manganese in the 5.00 - 150 mg L -1 range (r=0,9998) and 60 s electrolysis time, the sample throughput was 20 h -1. Accuracy was assessed by analyzing ten steel standard reference materials. Results are precise (R.S.D. <3%) and in agreement with certified values of reference materials and with standard methods at 95% confidence level.

Ceramic coating for refractories protection against carbon oxidation, Part 1: Protection mechanisms

For retarding carbon oxidation in refractories during the preheating of metallurgical furnaces, a ceramic coating, made mainly of sodium phosphosilicate and clay was developed. The coating presents high adherence to the substrate with no swelling. The coating was characterized by thermal analysis, X-ray diffraction at room temperature (XRD) and at high temperature (HTXRD), X-ray fluorescence and scanning electronic microscopy (SEM). The glass transition temperature is reached at 800 °C and only glassy phase is observed above this temperature. Thus the mechanism of protection seems to be the formation of a glassy phase on the surface of the refractory, and the coating tends to be more efficient at temperatures higher than 800 °C.

Energetic cost of predation: Aerobic metabolism during prey ingestion by juvenile rattlesnakes, Crotalus durissus

We investigated the cost of prey ingestion in the South American rattlesnake, Crotalus durissus, to see if the capacity to generate energy aerobically could be a constraint on the size of the prey that can be ingested. To accomplish this goal, we measured time and aerobic metabolism (inferred from oxygen consumption) of juvenile C. durissus ingesting prey ranging from 10 to 50% of their own body mass. Time needed for prey ingestion increased with prey size, with prey representing 10 and 20% of snake size being ingested with the same effort. Whole animal rates of oxygen consumption increased linearly with prey size, but at a slower pace for snakes ingesting prey larger than 30% of their body mass. Aerobic factorial power input necessary for prey ingestion increased with prey size, and for snakes ingesting prey representing 50% of their body mass it equaled the aerobic factorial scope for exercise. For the maximum prey size tested, the aerobic derived energy necessary for prey ingestion represented 0.02% of the total energy content of the prey. Within the prey size range we studied, the cost of ingestion did not constitute any constraint on the size of the prey that can be ingested. These constraints are set by morphological (gape size), ecological (predation risk), and, probably, by physiological parameters, as suggested by the tendency of V̇O2 during ingestion to increase at a slower pace at relative larger prey sizes.

Insulin secretion in monosodium glutamate (MSG) obese rats submitted to aerobic exercise training

The present study was designed to evaluate the effects of aerobic exercise training on glucose tolerance and insulin secretion of obese male Wistar rats (monosodium glutamate [MSG] administration, 4mg/g-body weight, each other day, from birth to the 14th day). Fourteen weeks after the drug administration, the rats were separated into two groups: MSG-S (sedentary) and MSG-T (T = swimming, 1 h/day, 5 days/week, with an overload of 5% body weight for 10 weeks). Rats of the same age and strain injected with saline were used as control (C) and subdivided into two groups: C-S and C-T. Insulin and glucose responses during an oral glucose tolerance test (GTT) were evaluated by the estimation of the total areas under serum insulin (AI) and glucose (AG) curves. Glucose-induced insulin secretion by isolated pancreatic islets was also evaluated. MSG-S rats showed higher AI than C-rats while MSG-T rats presented lower AI than MSG-S rats. No differences in AG were observed among the 4 groups. Pancreatic islets from MSG-rats showed higher insulin secretion in response to low (2.8) and moderate (8.3 mM) concentrations of glucose than those from their control counterparts and no differences were observed between MSG-S and MSG-T rats. These results provide evidences that the hyperinsulinemia at low or moderate glucose concentrations observed in MSG-obese rats is, at least in part, a consequence of direct hypersecretion of the B cells and that chronic aerobic exercise is able to partially counteract the hyperinsulinemic state of these animals without disrupting glucose homeostasis.

Study of electrochemical oxidation and determination of albendazole using a glassy carbon-rotating disk electrode

In this work, electrochemical oxidation of albendazole (ABZ) was carried out using a glassy carbon-rotating disk electrode. Development of electroanalytical methodology for ABZ quantification in pharmaceutical formulations was also proposed by using linear sweep voltammetric technique. Electrochemical oxidation is observed for ABZ at E 1/2 = 0.99:V vs. Ag/AgCl sat, when an anodic wave is observed. Kinetic parameters obtained for ABZ oxidation exhibited a standard heterogeneous rate constant for the electrodic process equal to (1.51 ± 0.07) ± 10 -5:cm:s -1, with a αn a value equal to 0.76. Limiting current dependence against ABZ concentration exhibited linearity on 5.0 ± 10 -5 to 1.0 ± 10 -2:mol:l -1 range, being obtained a detection limit of 2.4 ± 10 -5:mol:l -1. Proposed methodology was applied to ABZ quantification in pharmaceutical formulations. © 2005 Elsevier SAS. All rights reserved.

Horseradish peroxidase-catalyzed oxidation of rifampicin: Reaction rate enhancement by co-oxidation with anti-inflammatory drugs

The tuberculostatic drug rifampicin has been described as a scavenger of reactive species. Additionally, the recent demonstration that oral therapy with a complex of rifampicin and horseradish peroxidase (HRP) was more effective than rifampicin alone, in an animal model of experimental leprosy, suggested the importance of redox reactions involving rifampicin and their relevance to the mechanism of action. Hence, we studied the oxidation of rifampicin catalyzed by HRP, since this enzyme may represent the prototype of peroxidation-mediated reactions. We found that the antibiotic is efficiently oxidized and that rifampicin-quinone is the product, in a reaction dependent on both HRP and hydrogen peroxide. The steady-state kinetic constants Km app (101±23 mmol/l), Vmax app (0.78±0.09 μmol/l·s-1) and kcat (5.1±0.6 s-1) were measured (n=4). The reaction rate was increased by the addition of co-substrates such as tetramethylbenzidine, salicylic acid, 5-aminosalicylic acid and paracetamol. This effect was explained by invoking an electron-transfer mechanism by which these drugs acted as mediators of rifampicin oxidation. We suggested that this drug interaction might be important at the inflammatory site. © 2005 Pharmaceutical Society of Japan.

Photo-oxidation of polyphenylenevinylene chains in Langmuir-Blodgett and cast films

Poly(p-phenylene vinylene) (PPV) derivatives are well known for their applications in polymer light emitting diodes (PLEDs). These derivatives are highly susceptible to photooxidation though, which is mainly caused by the scission of the vinyl double bond on the polymer backbone. In this work, we show that Langmuir-Blodgett (LB) films are less degraded than cast films of a PPV derivative (OC1OC6-PPV). Both films had similar thickness (∼50 nm) to allow for a more realistic comparison. Photodegradation experiments were carried out by illuminating the films with white light from a halogen lamp (50W, 12 V), placed at a fixed dstance from the sample. The decay was monitored by UV-Vis and FTIR spectroscopies. The results showed that cast films are completely degraded in ca. 300 min, while LB took longer times, ca. 1000 min, i.e. 3 times the values for the cast films. The degradation process occurs in at least two stages, the rates of which were calculated assuming that the reaction follows a first order kinetics. The characteristic times for the first stage were 3.6×10-2 and 1.3×10-3 min-1 for cast and LB films, respectively. For the second stage the characteristic times were 5.6×10-2 and 5.0×10 -3 min-1. The differences can be attributed to the more compact morphology in the LB than in the cast films. With a compact morphology the diffusion of oxygen in the LB film is hampered and this causes a delay in the degradation process.

Long-term creatine supplementation improves the aerobic capacity of horses

The aim of the present study was to investigate the effect of long-term oral supplementation of creatine on the physiological responses to aerobic training. Twelve purebred Arabian horses were submitted to aerobic training for 90 days, with and without creatine supplementation which consisted of the daily administration of 75g of creatine monohydrate mixed into the ration for 90 days of training. Physical conditioning was conducted on a high performance treadmill and training intensity was stipulated by calculating the V 4 (velocity at which blood lactate reaches 4mmol L -1) determined monthly for each animal. The individual intensity of physical force at 80% of aerobic threshold was established. An incremental exercise test was used to set the individual V4. After a warm up period of 4 min at 4m s -1), the speed was increased at 2min intervals to 6, 8 and 10m s -1). The blood samples were collected 15s before the end of each step to determine the concentration of lactate, packed cell volume, hemoglobin and red cell values. The results demonstrated a significant increase (P<0.05) in V4 in the groups that received creatine supplementation for 60 days or more when compared to the animals without creatine supplememntation. The other hematological variables were similar to all groups. The results showed that the prolonged creatine supplementation may have a beneficial al effect on the equine athletic performance.

Aerobic Training, But Not Creatine, Modifies Longissimus Dorsi Muscle Composition

The goal of this study was to investigate by means of an ultrasound examination the composition of the longissimus dorsi muscle in 12 purebred Arabian horses submitted to aerobic training for 90 days, with and without creatine supplementation. Creatine supplementation was carried out by daily administration of 75 g creatine monohydrate mixed into the ration during 90 days of training. Physical conditioning was conducted on a high-performance treadmill, and training intensity was stipulated by calculating the velocity at which blood lactate reaches 4 mmol/l, determined monthly for each animal. The individual intensity of physical force was established at 80% of velocity that resulted in a blood lactate level of 4 mmol/l. The cross-sectional area and the thickness of the layer of fat of the longissimus dorsi muscle were measured for each group at the end of 8 months of inactivity and after 30, 60, and 90 days of training without (control groups) or with creatine supplementation (experimental groups). The results showed that aerobic training combined with or without creatine supplementation caused significant longissimus dorsi hypertrophy and reduction in the thickness of the fat layer. No beneficial effect from prolonged creatine supplementation on the body composition of horses was detected. © 2007 Elsevier Inc. All rights reserved.

The effect of pH on horseradish peroxidase-catalyzed oxidation of melatonin: Production of N1-acetyl-N2-formyl-5- methoxykynuramine versus radical-mediated degradation

There is a growing body of evidence that melatonin and its oxidation product, N1-acetyl-N2-formyl-5-methoxykynuramine (AFMK), have anti-inflammatory properties. From a nutritional point of view, the discovery of melatonin in plant tissues emphasizes the importance of its relationship with plant peroxidases. Here we found that the pH of the reaction mixture has a profound influence in the reaction rate and products distribution when melatonin is oxidized by the plant enzyme horseradish peroxidase. At pH 5.5, 1 mm of melatonin was almost completely oxidized within 2 min, whereas only about 3% was consumed at pH 7.4. However, the relative yield of AFMK was higher in physiological pH. Radical-mediated oxidation products, including 2-hydroxymelatonin, a dimer of 2-hydroxymelatonin and O-demethylated dimer of melatonin account for the fast consumption of melatonin at pH 5.5. The higher production of AFMK at pH 7.4 was explained by the involvement of compound III of peroxidases as evidenced by spectral studies. On the other hand, the fast oxidative degradation at pH 5.5 was explained by the classic peroxidase cycle. © 2007 The Authors.

Methanol oxidation on PtRu/C electrocatalysts prepared by a microemulsion method

PtRu/C nanocatalysts were prepared by a microemulsion method using different values of water/surfactant molar ratio in order to get different particle sizes. Crystallite sizes and structural properties were determined by X-ray diffraction. Particle size and distribution were characterized by transmission electron microscopy and average composition was determined by energy dispersive X-ray analysis. Differential scanning calorimetry measurements indicated the presence of oxides in the as-prepared catalysts. The general electrochemical behavior was evaluated by cyclic voltammetry in 0.5 M sulfuric acid and the electrocatalytic activity towards the oxidation of methanol was studied in 0.5 M methanol acid solutions by potential sweeps and chronoamperometry. copyright The Electrochemical Society.

Inibição da mineralização de compostos nitrogenados de lixiviado de macrófita aquática: Adequação metodológica

This study aimed to establish the adequate concentrations of nitrapyrin for the effective inhibition of oxygen demand required for the oxidation of nitrogen compounds during aerobic mineralization of leachate. The aquatic macrophyte Myriophyllum aquaticum was used as a source of dissolved organic matter (DOM). The leachate was incubated in several chambers, containing different composition and treatments: (i) treatment with leachate (DOM), (ii) treatment with DOM plus nitrapyrin in different concentrations (10; 25 and 50 mg L-1), aiming at finding the right concentration that inhibits the nitrification process, (iii) treatment with DOM plus NH4SO 2, (iv) treatment containing DOM and nitrapyrin plus NH 4SO2, and (v) treatment with DOM plus azide. The dissolved oxygen amount in each incubation treatment was periodically measured. The results indicated that the ratio of 10 mg L-1 of nitrapyrin for each 10 mg C of leachate is efficient in inhibiting the oxidation of nitrogen compounds from aquatic macrophytes.

Exercise training in the aerobic/anaerobic metabolic transition prevents glucose intolerance in alloxan-treated rats

Background: Ninety percent of cases of diabetes are of the slowly evolving non-insulin-dependent type, or Type 2 diabetes. Lack of exercise is regarded as one of the main causes of this disorder. In this study we analyzed the effects of physical exercise on glucose homeostasis in adult rats with type 2 diabetes induced by a neonatal injection of alloxan. Methods: Female Wistar rats aged 6 days were injected with either 250 mg/ kg of body weight of alloxan or citrate buffer 0.01 M (controls). After weaning, half of the animals in each group were subjected to physical training adjusted to meet the aerobic-anaerobic metabolic transition by swimming 1 h/day for 5 days a week with weight overloads. The necessary overload used was set and periodically readjusted for each rat through effort tests based on the maximal lactate steady state procedure. When aged 28, 60, 90, and 120 days, the rats underwent glucose tolerance tests (GTT) and their peripheral insulin sensitivity was evaluated using the HOMA index. Results: The area under the serum glucose curve obtained through GTT was always higher in alloxan-treated animals than in controls. A decrease in this area was observed in trained alloxan-treated rats at 90 and 120 days old compared with non-trained animals. At 90 days old the trained controls showed lower HOMA indices than the non-trained controls. Conclusion: Neonatal administration of alloxan induced a persistent glucose intolerance in all injected rats, which was successfully counteracted by physical training in the aerobic/anaerobic metabolic transition. © 2008 Mota et al; licensee BioMed Central Ltd.

Effects of heat treatments on the electrocatalytic activity of Pt-Ru/C for methanol oxidation

The Pt-Ru/C materials of this study were prepared by a microemulsion method with fixed water to surfactant molar ratio and heat treated at low temperatures, to avoid changes in the average particle size, in different atmospheres. All samples were characterized by X-ray diffraction (XRD) and the mean crystallite size was estimated by using Scherrer's equation. Catalysts morphology was characterized by transmission electron microscopy (TEM). Average composition was obtained by energydispersive X-ray analysis (EDX). The general electrochemical behavior was evaluated by cyclic voltammetry in 0.5 M sulfuric acid and the electrocatalytic activity towards the oxidation of methanol was studied in 0.5 M methanol acid solutions by potential sweeps and chronoamperometry. Oxidation of adsorbed CO was used to estimate the electrochemical active area and to infer the surface properties. ©The Electrochemical Society.

Qualidade de salsichas elaboradas com carne mecanicamente separada de tilápias do nilo e armazenadas sob refrigeração

Filleting yield of Nile tilapia Oreochromis niloticus (L.) is low (30%) and generates large amount of wastes that may turn into environmental and economic problem. However, these wastes can be used for the extraction of minced fish (MF) which can be used in the preparation of sausages. The objective of this study was to assess the quality of sausages prepared with 0, 20, 40, 60, 80 and 100% of MF from Nile tilapia filleting waste during storage at 0±0.3°C. Alterations in the instrumental color (L*, a* and b*), lipid oxidation (TBARS), total volatile nitrogenous bases (TVB-N), pH, microbiological condition (pathogenic bacteria and aerobic psychrotrophic bacteria), and sensory attributes (color, odor, flavor, texture and overall acceptability) were evaluated for up to 40 days. The addition of MF to sausages increased TBARS values and decreases TVB- N, L*, a* and b* values. Acceptability of color attribute decreased with increasing MF; best flavor, texture and overall acceptability scores were registered for sausages containing 40 and 60% MF; best odor was registered for 100% MF. Pathogenic microorganisms were not detected, but decrease in pH and proliferation of aerobic psychrotrophic bacteria which, however, did not compromise sensory evaluation of sausages were registered throughout storage. Sausages prepared with MF from tilapia filleting waste have a shelf-life of 40 days when stored at 0±0.3°C, and the maximum recommended MF inclusion to maintain good sensory quality is 60%.