Biomimetic oxidative treatment of spruce wood studied by pyrolysis-molecular beam mass spectrometry coupled with multivariate analysis and (13)C-labeled tetramethylammonium hydroxide thermochemolysis: implications for fungal degradation of wood

In this work, pyrolysis-molecular beam mass spectrometry analysis coupled with principal components analysis and (13)C-labeled tetramethylammonium hydroxide thermochemolysis were used to study lignin oxidation, depolymerization, and demethylation of spruce wood treated by biomimetic oxidative systems. Neat Fenton and chelator-mediated Fenton reaction (CMFR) systems as well as cellulosic enzyme treatments were used to mimic the nonenzymatic process involved in wood brown-rot biodegradation. The results suggest that compared with enzymatic processes, Fenton-based treatment more readily opens the structure of the lignocellulosic matrix, freeing cellulose fibrils from the matrix. The results demonstrate that, under the current treatment conditions, Fenton and CMFR treatment cause limited demethoxylation of lignin in the insoluble wood residue. However, analysis of a water-extractable fraction revealed considerable soluble lignin residue structures that had undergone side chain oxidation as well as demethoxylation upon CMFR treatment. This research has implications for our understanding of nonenzymatic degradation of wood and the diffusion of CMFR agents in the wood cell wall during fungal degradation processes.

Oxidative stress biomarkers of exposure in the blood of cichlid species from a metal-contaminated river

The oxidative stress biomarkers of exposure, such as reduced glutathione (GSH), activity of superoxide dismutase (SOD), catalase (CAT) and glutathione peroxidase (GPx) and the levels of lipid peroxidation (LPO), were measured in the blood of three cichlid fish (Oreochromis niloticus, Tilapia rendalli, and Geophagus brasiliensis) taken during two seasons from two sites, unpolluted and polluted by industrial effluents, to evaluate the effectiveness of these biomarkers in assessing the impact of water contamination. The LPO levels in the blood were higher in fish from the metal-contaminated site and the chronic exposure led to significant changes in GPx, CAT, and SOD activities in all three cichlid species. The considerable variation of responses in these cichlids to water contamination evidenced differences in sensitivity to the metal contamination and/or in the potential to respond to it highlighting the importance of using a set of related biomarkers to assess the impact of water contamination. (C) 2007 Elsevier Inc. All rights reserved.

Mate (Ilex paraguariensis) as dietary additive for broilers: performance and oxidative stability of meat

Aqueous extract of mate (dried leaves of Ilex paraguariensis) added to drinking water for broilers for the last 14 days prior to slaughter did not affect performance at 25 days of age, but improved oxidative stability of the chicken meat. Oxidative stability of precooked breast meat made from control meat (CON) and from meat of broilers raised on water with mate added was investigated during chill storage for up to 7 days. The use of mate showed no influence on the content of lipids in chicken breast meat; however, lipid oxidation measured as thiobarbituric acid-reactive substances (TBARS) was significantly lower for meat from broilers raised on water with mate extracts in different concentrations (MA0.1, MA0.5, and MA1.0 corresponding to 0.1, 0.5, and 1.0% of mate dried leaves). The relative effect was largest at 1 day of storage with more than 50% reduction on TBARS; the result was still significant after 3 days, but almost vanished after 7 days, when oxidative rancidity was very high in all samples. In meat from broilers raised on water with mate extract, vitamin E was protected during cooking, although in the very rancid meat balls at 7 days of storage, the protection almost disappeared. Nevertheless, mate can be an interesting natural alternative to be used in chicken diets to improve lipid stability of the meat.

Photochemical damage and comparative performance of superoxide dismutase and ascorbate peroxidase in sugarcane leaves exposed to paraquat-induced oxidative stress

The physiological responses of sugarcane (Succharion officinarum L.) to oxidative stress induced by methyl viologen (paraquat) were examined with respect to photochemical activity, chlorophyll content, lipid peroxidation and superoxide dismutase (SOD) and ascorbate peroxidase (APX) activities. Thirty-day-old sugarcane plants were sprayed with 0, 2, 4, 6 and 8 mM methyl viologen (MV). Chlorophyll fluorescence was measured after 18 It and biochemical analyses were performed after 24 and 48 h. Concentrations of MV above 2 mM caused significant damage to photosystem II (PSII) activity. Potential and effective quantum efficiency of PSII and apparent electron transport rate were greatly reduced or practically abolished. Both chlorophyll and soluble protein contents steadily decreased with MV concentrations above 2 mM after 24 It of exposure, which became more pronounced after 48 It, achieving a 3-fold decrease. Insoluble protein contents were little affected by MV. Oxidative stress induced by MV was evidenced by increases in lipid peroxidation. Specific activity of SOD increased, even after 48 h of exposure to the highest concentrations of MV, but total activity on a fresh weight basis did not change significantly. Nondenaturing YAGE assayed with H2O2 and KCN showed that treatment with MV did not change Cu/Zn-SOD and MnSOD isoform activities. In contrast, APX specific activity increased at 2 mM MV but then dropped at higher doses. Oxidative damage induced by MV was inversely related to APX activity. It is suggested that the major MV-induced oxidative damages in sugarcane leaves were related to excess H2O2, probably in chloroplasts, caused by an imbalance between SOD and APX activities, in which APX was a limiting step. Reduced photochemical activity allowed the early detection of the ensuing oxidative stress. (c) 2007 Elsevier Inc. All rights reserved.

Correlation between sensory and chemical markers in the evaluation of Brazil nut oxidative shelf-life

Sensory analysis is one of the most suitable processes for measuring oxidative damage and determining the shelf-life of nuts, but it is an expensive and time-consuming methodology. Thus, our objective was to correlate sensory data and chemical markers obtained during the accelerated oxidation of Brazil nuts and to determine the chemical parameters values associated with the sensory shelf-life of the nuts as established by the consumers. Brazil nuts were kept at 80 A degrees C for 21 days. At intervals of 2 days, the oxidized odor of the samples was analyzed by nine trained panelists using a discriminative scale, and the oil was extracted to quantify the chemical parameters. A high (r > 0.95) and significant correlation (p < 0.05) was observed between the sensory data and the hydroperoxide concentration (PV), para-anisidine value (pAV), hexanal content, and alpha- and gamma-tocopherol concentrations. When compared with fresh samples, sensory identification of oxidized odor occurred on the 4th day, noticeably earlier than changes in chemical markers (12th day). Consumers rejected the nuts after 12 days of storage, which corresponded to PV = 18.8 meq kg(-1) oil, pAV = 7.68, hexanal = 48.95 mu mol 100 g(-1) oil, alpha-tocopherol = 15.01 mg kg(-1) oil, and gamma + beta-tocopherol = 73.88 mg kg(-1) oil. Our study suggests that simple spectrometric methods, such as PV and pAV, can be used to estimate the oxidative shelf-life of nuts based on sensory analysis.

Interaction Between Polar Components and the Degree of Unsaturation of Fatty Acids on the Oxidative Stability of Emulsions

Minor components (polar components) and the degree of unsaturation of the fatty acids are the main factors responsible for the oxidative stability of bulk oils and emulsions. The isolated effects of these two factors and their interaction were evaluated in oil-in-water emulsions stored at 32 A degrees C. Samples of coconut, olive, soybean, linseed and fish oils, both full and stripped of their polar components, were used to prepare the emulsions (1% w/w). The maximum concentration of hydroperoxide (LOOH(max)) and the rate of formation of hydroperoxides (mu mol L(-1) h(-1)) were used to measure the primary products. Hexanal, propanal and malondialdehyde were used to determine the secondary products of the oxidized emulsions containing polyunsaturated fatty acids. LOOH(max) varied from 0.16 to 12.75 mmol/kg among the samples. The interaction between the polar components and the degree of unsaturation of the fatty acids was significant (p < 0.001) when the hydroperoxides were evaluated. In general, the degree of unsaturation (beta(1)) and the absence of polar components (beta(2)), respectively, represented 30 and 20% of the contribution to increase the mean oxidation, with the interaction (beta(12)) contribution being more sensitive to the rate of formation of hydroperoxides (16%) than to the LOOH(max) (5%). The significance of this interaction suggests that both strategies present synergism and should be applied to improve the oxidative stability of food emulsions.

EFFECT OF n-3 POLYUNSATURATED FATTY ACIDS ON OXIDATIVE STRESS IN RATS SUPPLEMENTED WITH DIFFERENT DOSES OF FISH OIL

The diet and plasma lipid patterns associated with lipid oxidation susceptibility in rats fed different doses of polyunsaturated fatty acids (n-3 PUFA) from fish oil were evaluated. Wistar rats were assigned into three groups and received diets containing 8% soybean oil (SOY), 4% soybean oil + 4% fish oil (SOY-FISH) and 8% fish oil (FISH) for 21 days. Linoleic, oleic and alpha-linolenic acids in SOY diets were substituted by myristic, palmitic, palmitoleic, eicosapentaenoic (EPA) and docosahexaenoic (DHA) acids in SOY-FISH and FISH diets reducing the n-6/n-3 ratio and increasing the peroxidability index (PI). Increased dietary EPA and DHA were observed in SOY-FISH and FISH plasma at the expense of linoleic and arachidonic acid levels. Saturated fatty acids, which were significantly different between the three diets (P < 0.01), were found at the same concentration in the plasma (P = 0.23). No changes were observed in oxidative stress as measured by the concentration of thiobarbituric acid reactive substances (TBARS) expressed in brain homogenates. However, TBARS concentration in the plasma of the SOY-FISH group was higher than the other two groups (P = 0.02). The major differences between these three groups were the n-3 PUFA content (0.4, 1.8 and 3.2 g/100 g diet) and the saturates/polyunsaturates ratio (0.3, 0.5 and 0.8) for SOY, SOY-FISH, and FISH groups, respectively. Thus, n-3 PUFA intake from fish oil only when followed by a decrease in saturated/polyunsaturated fatty acids ratio increased oxidative susceptibility in rats measured by plasma TBARS concentration. PRACTICAL APPLICATIONS Because fish oil intake is associated with risk reduction for cardiovascular disease, individuals are taking supplements containing a high dose of fish oil. However, there is no scientific consensus if the intake of a high dose of fish oil could increase the oxidative stress. Thus, more studies are necessary to assure the safety of this kind of supplementation.

Effect of n-3 fatty acids and statins on oxidative stress in statin-treated hypercholestorelemic and normocholesterolemic women

Introduction: Although the combination of statins with n-3 fatty acids seems to be beneficial under the lipid profile aspect, there is little information about the interaction of these two compounds on oxidative stress. Objective: Evaluate the interaction between statins and n-3 fatty acids on oxidative stress in women, using a 2(2) factorial design. Methods: Forty-three women participated in this crossover design. They were separated into two groups in which 20 were under statin treatment for more than 6 months, and 23 were normolipidemic. Within each group, half of the patients received capsules containing 2.4 g/day of a mixture of EPA and DHA for 6 weeks, while the other half received a mixture of soya and corn oil. After a period of 90 days of washout, the groups were switched, and received the supplementation for 6 weeks more. Results: Statins reduced serum LDL and increased SOD expression. n-3 fatty acids increased the plasma malondialdehyde and SOD activity but reduced catalase expression (p < 0.05). The interaction involving statins and n-3 fatty acids was nearly significant to the serum triacylglycerol reduction (p = 0.054). Conclusion: Combining statins and n-3 fatty acids is an excellent strategy to reduce plasma cholesterol and triacylglycerol concentration in women. However, n-3 fatty acids increased the oxidative stress and the pleiotropic effect of statins seemed to be not enough to counterbalance this result. Our data also suggested that the mechanism by which n-3 fatty acids interfere in oxidative stress can be associated with antioxidant enzymes expression and activity. (C) 2010 Elsevier Ireland Ltd. All rights reserved.

Classification of individuals with dyslipidaemia controlled by statins according to plasma biomarkers of oxidative stress using cluster analysis

Oxidative stress is a physiological condition that is associated with atherosclerosis. and it can be influenced by diet. Our objective was to group fifty-seven individuals with dyslipidaemia controlled by statins according to four oxidative biomarkers, and to evaluate the diet pattern and blood biochemistry differences between these groups. Blood samples were collected and the following parameters were evaluated: diet intake; plasma fatty acids; lipoprotein concentration; glucose; oxidised LDL (oxLDL); malondialdehyde (MDA): total antioxidant activity by 2,2-diphenyl-1-picrylhydrazyl (DPPH) and ferric reducing ability power assays. Individuals were separated into five groups by cluster analysis. All groups showed a difference with respect to at least one of the four oxidative stress biomarkers. The separation of individuals in the first axis was based upon their total antioxidant activity. Clusters located on the right side showed higher total antioxidant activity, higher myristic fatty acid and lower arachidonic fatty acid proportions than clusters located on the left side. A negative correlation was observed between DPPH and the peroxidability index. The second axis showed differences in oxidation status as measured by MDA and oxLDL concentrations. Clusters located on the Upper side showed higher oxidative status and lower HDL cholesterol concentration than clusters located on the lower side. There were no differences in diet among the five clusters. Therefore, fatty acid synthesis and HDL cholesterol concentration seem to exert a more significant effect on the oxidative conditions of the individuals with dyslipidaemia controlled by statins than does their food intake.

Biomarkers of oxidative stress and endothelial dysfunction in glucose intolerance and diabetes mellitus

Objectives: To evaluate biomarkers of endothelial dysfunction and oxidative stress in glucose intolerance (GI) compared to overt diabetes (DM2). Design and methods: 140 volunteers including 96 with DM2, 32 with GI and 12 controls (C) were Studied. NO metabolites, NO synthase inhibitors. thiols and N-acetyl-beta-glucosaminidase (NAGase) activity were analyzed by chemiluminescence, capillary electrophoresis, ELISA and colorimetric assay, respectively. Results: (center dot)NO metabolites were higher in GI (NOx: P=0.03 S-nitrosothiols: p=0.001) and DM2 (p=0.006; p=0.0006) groups in relation to group C, while nitrotyrosine was higher only in the DM2 group in comparison 10 the other groups. NAGase activity was elevated in GI (p=0.003) and DM2 (p=0.0004) groups in relation to group C, as well as, ADMA (p=0.01: p=0.003) and GSSG (p=0.01 p=0.002). Conclusions: (center dot)NO metabolites. (center dot)NO synthase inhibitors. thiols and NAGase are biomarkers Suitable to indicate endothelial dysfunction and oxidative stress in the early stages of impaired response to insulin. (c) 2008 The Canadian Society of Clinical Chemists. Published by Elsevier Inc. All rights reserved.

Effect of natural pigments on the oxidative stability of sausages stored under refrigeration

The objective was to use natural pigments to replace sodium erythorbate (NaEry), a synthetic compound used as an antioxidant in sausage formulations, and to evaluate the oxidative stability of the samples. Six assays were prepared in which sodium erythorbate (ERY) at 0.05 g/100 g was substituted by norbixin (NOR), lycopene (LYC), zeaxanthin (ZEA), beta-carotene (CAR) or dextrose (used as a control (CON)). Physical, chemical, color, texture and sensory parameters were measured on the first day and after 45 days of storage at 4 degrees C. All pigments used in the sausage formulations were able to maintain the oxidative stability of the sausages (MDA equivalents <038 mg/kg). Zeaxanthin and norbixin were the most efficient antioxidants of those tested. This antioxidant effect might be associated with the intermediate polarities of these two compounds, which would allow them to concentrate in the membrane lipids or emulsion interface, where lipid oxidation is most prevalent. Other volatile secondary products of oxidation besides MDA should be evaluated in further studies involving natural pigments and sensory oxidative stability. (C) 2009 Elsevier Ltd. All rights reserved.

Modulation of human neutrophil oxidative metabolism and degranulation by extract of Tamarindus indica L. fruit pulp

The tamarind (Tamarindus indica L) is indigenous to Asian countries and widely cultivated in the American continents. The tamarind fruit pulp extract (ExT), traditionally used in spices, food components and juices, is rich in polyphenols that have demonstrated anti-atherosclerotic, antioxidant and immunomodulatory activities. This study evaluated the modulator effect of a crude hydroalcoholic ExT on some peripheral human neutrophil functions. The neutrophil reactive oxygen species generation, triggered by opsonized zymosan (OZ), n-formyl-methionyl-leucyl-phenylalanine (fMLP) or phorbol myristate acetate (PMA), and assessed by luminol- and lucigenin-enhanced chemiluminescence (LumCL and LucCL, respectively), was inhibited by ExT in a concentration-dependent manner. ExT was a more effective inhibitor of the PMA-stimulated neutrophil function [IC(50) (in mu g/10(6)cells) = 115.7 +/- 9.7 (LumCL) and 174.5 +/- 25.9 (LucCL)], than the OZ- [IC(50) = 248.5 +/- 23.1 (LumCL) and 324.1 +/- 34.6 (LucCL)] or fMLP-stimulated cells [IC(50) = 178.5 +/- 12.2 (LumCL)]. The ExT also inhibited neutrophil NADPH oxidase activity (evaluated by O(2) consumption), degranulation and elastase activity (evaluated by spectrophotometric methods) at concentrations higher than 200 mu g/10(6) cells, without being toxic to the cells, under the conditions assessed. Together, these results indicate the potential of ExT as a source of compounds that can modulate the neutrophil-mediated inflammatory diseases. (C) 2008 Elsevier Ltd. All rights reserved.

Involvement of oxidative stress in the hepatotoxicity induced by aromatic antiepileptic drugs

The use of the classic aromatic antiepileptic drugs (AAEDs) has recently been expanded to a broad spectrum of psychiatric and neurological disorders. However, the clinical use of these drugs is limited by several adverse effects, mainly idiosyncratic hepatotoxicity. AAED-induced hepatotoxicity has been attributed to a defective detoxification by the epoxide hydrolase and accumulation of arene oxides. The underlying mechanism has been proposed as immune-mediated, but direct toxicity has also been suggested. In general, idiosyncratic drug-induced hepatotoxicity may be mediated, at least in part, by oxidative stress. On the other hand, the oxidative stress induced by the AAED metabolites has not been demonstrated yet. Therefore, in the present study we have evaluated the induction of oxidative stress by three classical AAEDs: carbamazepine. phenytoin and phenobarbital as well as by their metabolites. The toxic effects of the metabolites were evaluated by incubating the drug with rat liver microsomes. The AAED-induced oxidative stress was demonstrated by the increased malondialdehyde levels, oxidation of cardiolipin; oxidation of sulfhydryl proteins and alteration of the cellular redox status. Results suggest that the hepatotoxicity associated with AAED might be mediated by the oxidative stress induced by the drugs metabolites. (C) 2008 Elsevier Ltd. All rights reserved

Inhibition of immune complex-mediated neutrophil oxidative metabolism: A pharmacophore model for 3-phenylcoumarin derivatives using GRIND-based 3D-QSAR and 2D-QSAR procedures

In this study, twenty hydroxylated and acetoxylated 3-phenylcoumarin derivatives were evaluated as inhibitors of immune complex-stimulated neutrophil oxidative metabolism and possible modulators of the inflammatory tissue damage found in type III hypersensitivity reactions. By using lucigenin- and luminol-enhanced chemiluminescence assays (CL-luc and CL-lum, respectively), we found that the 6,7-dihydroxylated and 6,7-diacetoxylated 3-phenylcoumarin derivatives were the most effective inhibitors. Different structural features of the other compounds determined CL-luc and/or CL-lum inhibition. The 2D-QSAR analysis suggested the importance of hydrophobic contributions to explain these effects. In addition, a statistically significant 3D-QSAR model built applying GRIND descriptors allowed us to propose a virtual receptor site considering pharmacophoric regions and mutual distances. Furthermore, the 3-phenylcoumarins studied were not toxic to neutrophils under the assessed conditions. (C) 2007 Elsevier Masson SAS. All rights reserved.

Protective effects of Mangifera indica L extract (Vimang), and its major component mangiferin, on iron-induced oxidative damage to rat serum and liver

In vivo preventive effects of a Mangifera indica L extract (Vimang) or its major component mangiferin on iron overload injury have been studied in rats given respectively, 50, 100, 250 mg kg(-1) body weight of Vimang, or 40 mg kg(-1) body weight of mangiferin, for 7 days prior to, and for 7 days following the administration of toxic amounts of iron-dextran. Both Vimang or mangiferin treatment prevented iron overload in serum as well as liver oxidative stress, decreased serum and liver lipid peroxidation, serum GPx activity, and increased serum and liver GSH, serum SOD and the animals overall antioxidant condition. Serum iron concentration was decreased although at higher doses, Vimang tended to increase it; percent tranferrin saturation, liver weight/body mass ratios, liver iron content was decreased. Treatment increased serum iron-binding capacity and decreased serum levels of aspartate-amine transferase (ASAT) and alanine-amine transferase (ALAT), as well as the number of abnormal Kupffer cells in iron-loaded livers. It is suggested that besides acting as antioxidants, Vimang extract or its mangiferin component decrease liver iron by increasing its excretion. Complementing earlier in vitro results from our group, it appears possible to support the hypothesis that Vimang and mangiferin present therapeutically useful effects in iron overload related diseases. (C) 2007 Elsevier Ltd. All rights reserved.