Concentrations of persistant organic pollutants in Great skua eggs (Stercorarius skua) from Shetland 1980 and 2008

Concentrations of POPs in Great skua eggs from Shetland are among the highest in North Atlantic seabirds, with up to 11,600 µg/kg (ww) DDE and up to 17,900 µg/kg ww SumPCB. Concentrations of legacy POPs were significantly lower in 2008 than 1980. Decreases were greatest for least persistent compounds. Median SumPBDEs increased from 99 µg/kg ww in 1980 to 173 µg/kg ww in 2008. There were changes in Great skua breeding season diet, with more adult Herring and Mackerel and less Sandeel. These changes increase exposure to POPs, since Herring and Mackerel accumulate more POPs than Sandeels. In both years, eggs with higher d15N had higher POP concentrations. In 1980, birds feeding more on demersal discard fish from trawl fisheries and less on Sandeels, had higher POP levels in eggs. In 2008, individuals feeding more on Herring and Mackerel, and less on discards, had higher POP levels in eggs.

Functional genomics of O-glucosyltransferases from Concord grape (Vitis labrusca)

Grape (Vitis spp.) is a culturally and economically important crop plant that has been cultivated for thousands of years, primarily for the production of wine. Grape berries accumulate a myriad of phenylpropanoid secondary metabolites, many of which are glucosylated in plantae More than 90 O-glucosyltransferases have been cloned and biochemically characterized from plants, only two of which have been isolated from Vitis spp. The world-wide economic importance of grapes as a crop plant, the human health benefits associated with increased consumption of grape-derived metabolites, the biological relevance of glucosylation, and the lack of information about Vitis glucosyltransferases has inspired the identification, cloning and biochemical characterization of five novel "family 1" O-glucosyltransferases from Concord grape (Vitis labrusca cv. Concord). Protein purification and associated protein sequencIng led to the molecular cloning of UDP-glucose: resveratrollhydroxycinnamic acid O-glucosyltransferase (VLRSGT) from Vitis labrusca berry mesocarp tissue. In addition to being the first glucosyltransferase which accepts trans-resveratrol as a substrate to be characterized in vitro, the recombinant VLRSGT preferentially produces the glucose esters of hydroxycinnamic acids at pH 6.0, and the glucosides of trans-resveratrol and flavonols at 'pH 9.0; the first demonstration of pH-dependent bifunctional glucosylation for this class of enzymes. Gene expression and metabolite profiling support a role for this enzyme in the bifuncitonal glucosylation ofstilbenes and hydroxycinnamic acids in plantae A homology-based approach to cloning was used to identify three enzymes from the Vitis vinifera TIGR grape gene index which had high levels of protein sequence iii identity to previously characterized UDP-glucose: anthocyanin 5-0-glucosyltransferases. Molecular cloning and biochemical characterization demonstrated that these enzymes (rVLOGTl, rVLOGT2, rVLOGT3) glucosylate the 7-0-position of flavonols and the xenobiotic 2,4,5-trichlorophenol (TCP), but not anthocyanins. Variable gene expression throughout grape berry development and enzyme assays with native grape berry protein are consistent with a role for these enzymes in the glucosylation of flavonols; while the broad substrate specificity, the ability of these enzymes to glucosylate TCP and expression of these genes in tissues which are subject to pathogen attack (berry, flower, bud) is consistent with a role for these genes in the plant defense response. Additionally, the Vitis labrusca UDP-glucose: flavonoid 3-0-glucosyltransferase (VL3GT) was identified, cloned and characterized. VL3GT has 96 % protein sequence identity to the previously characterized Vitis vinifera flavonoid 3-0-glucosyltransferase (VV3GT); and glucosylates the 3-0-position of anthocyanidins and flavonols in vitro. Despite high levels of protein sequence identity, VL3GT has distinct biochemical characteristics (as compared to VV3GT), including a preference for B-ring methylated flavonoids and the inability to use UDP-galactose as a donor substrate. RT-PCR analysis of VL3GT gene expression and enzyme assays with native grape protein is consistent with an in planta role for this enzyme in the glucosylation of anthocyanidins,but not flavonols. These studies reveal the power of combining several biochemistry- and molecular biology-based tools to identify, clone, biochemically characterize and elucidate the in planta function of several biologically relevant O-glucosyltransferases from Vitis spp.

Fungi, mycotoxins and phytoalexin in peanut varieties, during plant growth in the field

The aim of the present study was to analyze the mycobiota, occurrence of mycotoxins (aflatoxins and cyclopiazonic acid), and production of phytoalexin (trans-resveratrol) in two peanut varieties (Runner IAC 886 and Caiapo) during plant growth in the field. Climatic factors (rainfall, relative humidity and temperature) and water activity were also evaluated. The results showed a predominance of Fusarium spp. in kernels and pods, followed by Penicillium spp. and Aspergillus flavus. Aflatoxins were detected in 20% and 10% of samples of the IAC 886 and Caiapo varieties, respectively. Analysis showed that 65% of kernel samples of the IAC 886 variety and 25% of the Caiapo variety were contaminated with cyclopiazonic acid. trans-Resveratrol was detected in 6.7% of kernel samples of the IAC 886 variety and in 20% of the Caiapo variety. However, trans-resveratrol was found in 73.3% of leaf samples in the two varieties studied. (C) 2011 Published by Elsevier Ltd.

Multivariant optimization, validation, and application of capillary electrophoresis for simultaneous determination of polyphenols and phenolic acids in Brazilian wines

A method for the simultaneous determination of the stilbene resveratrol, four phenolic acids (syringic, coumaric, caffeic, and gallic acids), and five flavonoids (catechin, rutin, kaempferol, myricetin, and quercetin) in wine by CE was developed and validated. The CE electrolyte composition and instrumental conditions were optimized using 2(7-3) factorial design and response surface analysis, showing sodium tetraborate, MeOH, and their interaction as the most influential variables. The optimal electrophoretic conditions, minimizing the chromatographic resolution statistic values, consisted of 17 mmol/L sodium tetraborate with 20% methanol as electrolyte, constant voltage of 25 kV, hydrodynamic injection at 50 mbar for 3 s, and temperature of 25 degrees C. The R(2) values for linearity varied from 0.994 to 0.999; LOD and LOQ were 0.1 to 0.3 mg/L and 0.4 to 0.8 mg/L, respectively. The RSDs for migration time and peak area obtained from ten consecutive injections were less than 2% and recoveries varied from 97 to 102%. The method was applied to 23 samples of inexpensive Brazilian wines, showing wide compositional variation.

Coumarins and phenolic fingerprints of oak and Brazilian woods extracted by sugarcane spirit

A total of 25 sugarcane spirit extracts of six different Brazilian woods and oak, commonly used by cooperage industries for aging cachaca, were analyzed for the presence of 14 phenolic compounds (ellagic acid, gallic acid, vanillin, syringaldehyde, synapaldehyde, coniferaldehyde, vanillic acid, syringic acid, quercetin, trans-resveratrol, catechin, epicatechin, eugenol, and myricetin) and two coumarins (scopoletin and coumarin) by HPLC-DAD-fluorescence and HPLC-ESI-MS(n). Furthermore, an HPLC-DAD chromatographic fingerprint was build-up using chemometric analysis based on the chromatographic elution profiles of the extracts monitored at 280 nm. Major components identified and quantified in Brazilian wood extracts were coumarin, ellagic acid, and catechin, whereas oak extracts shown a major contribution of catechin, vanillic acid, and syringaldehyde. The main difference observed among oak and Brazilian woods remains in the concentration of coumarin, catechin, syringaldehyde, and coniferaldehyde. The chemometric analysis of the quantitative profile of the 14 phenolic compounds and two coumarins in the wood extracts provides a differentiation between the Brazilian wood and oak extracts. The chromatographic fingerprint treated by multivariate analysis revealed significant differences among Brazilian woods themselves and oak, clearly defining six groups of wood extracts: (i) oak extracts, (ii) jatoba extracts, (iii) cabreuva-parda extracts, (iv) amendoim extracts, (v) canela-sassafras extracts and (vi) pequi extracts.

HPLC-DAD methodology for the quantification of organic acids, furans and polyphenols by direct injection of wine samples

This article proposes a simple and sensitive HPLC method with photo-diode array detection for the analysis of organic acids, monomeric polyphenols and furanic compounds in wine samples by direct injection. The chromatographic separation of 8 organic acids, 2 furans and 22 phenolic compounds was carried out with a buffered solution (pH 2.70) and acetonitrile as mobile phases and a difunctionally bonded C18 stationary phase, Atlantis dC18 (250 4.6 mm, 5mm) column. The elution was performed in 12 min for the organic acids and in 60 min for the phenolic compounds, including phenolic acids, stilbenes and flavonoids. Target compounds were detected at 210 nm (organic acids, flavan-3-ols and benzoic acids), 254 nm (ellagic acid), 280 nm (furans and cinnamic acid), 315 nm (hydroxycinnamic acids and trans-resveratrol) and 360 nm (flavonoids). The RSD for the repeatability test (n55) of peak area and retention times were below 3.1 and 0.3%, respectively, for phenolics and below 1.0 and 0.2% for organic acids. The RSDs expressing the reproducibility of the method were higher than for the repeatability results but all below 9.0%. Method accuracy was evaluated by the recovery results, with averaged values between 80 and 104% for polyphenols and 97–105% for organic acids. The calibration curves, obtained by triplicate injection of standard solutions, showed good linearity with regression coefficients higher than 0.9982 for polyphenols and 0.9997 for organic acids. The LOD was in the range of 0.07–0.49 mg/L for polyphenols (cinnamic and gallic acids, respectively) and 0.001–0.046 g/L for organic acids (oxalic and lactic acids, respectively). The method was successfully used to measure and assess the polyphenolic fingerprint and organic acids profile of red, white, rose ´ and fortified wines.

A new and improved strategy combining a dispersive-solid phase extraction-based multiclass method with ultra high pressure liquid chromatography for analysis of low molecular weight polyphenols in vegetables

This paper reports on the development and optimization of a modified Quick, Easy, Cheap Effective, Rugged and Safe (QuEChERS) based extraction technique coupled with a clean-up dispersive-solid phase extraction (dSPE) as a new, reliable and powerful strategy to enhance the extraction efficiency of free low molecular-weight polyphenols in selected species of dietary vegetables. The process involves two simple steps. First, the homogenized samples are extracted and partitioned using an organic solvent and salt solution. Then, the supernatant is further extracted and cleaned using a dSPE technique. Final clear extracts of vegetables were concentrated under vacuum to near dryness and taken up into initial mobile phase (0.1% formic acid and 20% methanol). The separation and quantification of free low molecular weight polyphenols from the vegetable extracts was achieved by ultrahigh pressure liquid chromatography (UHPLC) equipped with a phodiode array (PDA) detection system and a Trifunctional High Strength Silica capillary analytical column (HSS T3), specially designed for polar compounds. The performance of the method was assessed by studying the selectivity, linear dynamic range, the limit of detection (LOD) and limit of quantification (LOQ), precision, trueness, and matrix effects. The validation parameters of the method showed satisfactory figures of merit. Good linearity (View the MathML sourceRvalues2>0.954; (+)-catechin in carrot samples) was achieved at the studied concentration range. Reproducibility was better than 3%. Consistent recoveries of polyphenols ranging from 78.4 to 99.9% were observed when all target vegetable samples were spiked at two concentration levels, with relative standard deviations (RSDs, n = 5) lower than 2.9%. The LODs and the LOQs ranged from 0.005 μg mL−1 (trans-resveratrol, carrot) to 0.62 μg mL−1 (syringic acid, garlic) and from 0.016 μg mL−1 (trans-resveratrol, carrot) to 0.87 μg mL−1 ((+)-catechin, carrot) depending on the compound. The method was applied for studying the occurrence of free low molecular weight polyphenols in eight selected dietary vegetables (broccoli, tomato, carrot, garlic, onion, red pepper, green pepper and beetroot), providing a valuable and promising tool for food quality evaluation.

A fast method using a new hydrophilic–lipophilic balanced sorbent in combination with ultra-high performance liquid chromatography for quantification of significant bioactive metabolites in wines

This manuscript describes the development and validation of an ultra-fast, efficient, and high throughput analytical method based on ultra-high performance liquid chromatography (UHPLC) equipped with a photodiode array (PDA) detection system, for the simultaneous analysis of fifteen bioactive metabolites: gallic acid, protocatechuic acid, (−)-catechin, gentisic acid, (−)-epicatechin, syringic acid, p-coumaric acid, ferulic acid, m-coumaric acid, rutin, trans-resveratrol, myricetin, quercetin, cinnamic acid and kaempferol, in wines. A 50-mm column packed with 1.7-μm particles operating at elevated pressure (UHPLC strategy) was selected to attain ultra-fast analysis and highly efficient separations. In order to reduce the complexity of wine extract and improve the recovery efficiency, a reverse-phase solid-phase extraction (SPE) procedure using as sorbent a new macroporous copolymer made from a balanced ratio of two monomers, the lipophilic divinylbenzene and the hydrophilic N-vinylpyrrolidone (Oasis™ HLB), was performed prior to UHPLC–PDA analysis. The calibration curves of bioactive metabolites showed good linearity within the established range. Limits of detection (LOD) and quantification (LOQ) ranged from 0.006 μg mL−1 to 0.58 μg mL−1, and from 0.019 μg mL−1 to 1.94 μg mL−1, for gallic and gentisic acids, respectively. The average recoveries ± SD for the three levels of concentration tested (n = 9) in red and white wines were, respectively, 89 ± 3% and 90 ± 2%. The repeatability expressed as relative standard deviation (RSD) was below 10% for all the metabolites assayed. The validated method was then applied to red and white wines from different geographical origins (Azores, Canary and Madeira Islands). The most abundant component in the analysed red wines was (−)-epicatechin followed by (−)-catechin and rutin, whereas in white wines syringic and p-coumaric acids were found the major phenolic metabolites. The method was completely validated, providing a sensitive analysis for bioactive phenolic metabolites detection and showing satisfactory data for all the parameters tested. Moreover, was revealed as an ultra-fast approach allowing the separation of the fifteen bioactive metabolites investigated with high resolution power within 5 min.

Quantification of polyphenols with potential antioxidant properties in wines using reverse phase HPLC

A RP-HPLC method with photodiode array detection (DAD) was developed to separate, identify and quantify simultaneously the most representative phenolic compounds present in Madeira and Canary Islands wines. The optimized chromatographic method was carefully validated in terms of linearity, precision, accuracy and sensitivity. A high repeatability and a good stability of phenolics retention times (a3%) were obtained, as well as relative peak area. Also high recoveries were achieved, over 80.3%. Polyphenols calibration curves showed a good linearity (r2 A0.994) within test ranges. Detection limits ranged between 0.03 and 11.5 lg/mL for the different polyphenols. A good repeatability was obtained, with intra-day variations less than 7.9%. The described method was successfully applied to quantify several polyphenols in 26 samples of different kinds of wine (red, ros and white wines) from Madeira and Canary Islands. Gallic acid was by far the most predominant acid. It represents more than 65% of all phenolics, followed by p-coumaric and caffeic acids. The major flavonoid found in Madeira wines was trans-resveratrol. In some wines, (–)-epicatechin was also found in highest amount. Canary wines were shown to be rich in gallic, caffeic and p-coumaric acids and quercetin.

Extração, caracterização e avaliação bioativa do extrato de Rumex acetosa

Studies show the great influence of free radicals and other oxidants as responsible for aging and degenerative diseases. On the other hand, the natural phenolic compounds has shown great as antioxidants to inhibit lipid peroxidation and lipoxygenase in vitro. Among these, is highlighted trans-resveratrol ( 3,5,4 `- trihydroxystilbene ) phenolic compound , characterized as a polyphenol stilbene class. The vegetables popularly known as "Azedinha" (Rumex Acetosa) has trans-resveratrol in its composition and from this, the present work aimed to study on the supercritical extraction and conventional extraction (Soxhlet and sequential) in roots of Rumex Acetosa, evaluating the efficiency of extractive processes, antioxidant activity, total phenolic content and quantification of trans-resveratrol contained in the extracts. Extractions using supercritical CO2 as solvent, addition of co-solvent (ethanol) and were conducted by the dynamic method in a fixed bed extractor. The trial met a 23 factorial design with three replications at the central point, with the variable reply process yield and concentration of trans-resveratrol and pressure as independent variables, temperature and concentration of co-solvent (% v/v). Yields ( mass of dry extract / mass of raw material used ) obtained from the supercritical extraction ranged from 0,8 to 7,63 % , and the best result was obtained at 250 bar and 90 °C using the co-solvent 15% ethanol (% v/v). The value was calculated for YCER a flow rate of 1,0 ± 0,17 g/min resulting in 0,0469 CO2 ( g solute / g solvent ). The results of the mass yield varied between conventional extractions 0,78 % ( hexane) and 9,97 % (ethanol). The statistical model generated from the data of the concentration of trans-resveratrol performed as meaningful and predictive for a 95% confidence. GC analysis on HPLC (High Performance Liquid Chromatography), transresveratrol was quantified in all extracts and concentration values ranged between 0,0033 and 0,42 ( mg / g extract) for supercritical extracts and between 0,449 and 17,046 (mg / g extract) to conventional extractions and therefore, the Soxhlet extraction with ethanol for more selective trans-resveratrol than the supercritical fluid. Evaluation of antioxidant (radical method to sequester 2,2- diphenyl-1- picryl - hydrazyl - DPPH) the supercritical extracts resulted in EC50 values (concentration effective to neutralize 50% of free radicals) of between 7,89 and 18,43 mg/mL , while resulting in a Soxhlet extraction with EC50 values in the range of 6,05 and 7,39 mg/mL. As for quantification of the phenolic compounds (Method Spectrophotometer Folin-Ciocalteau) the supercritical extracts resulted in values between 85,3 and 194,79 mg GAE / g extract, whereas values derived from the Soxhlet extract resulted in values between 178,5 and 237,8 mg GAE / g extract. The high antioxidant activity can not be attributed solely to the presence of phenolic compounds, but the presence of other antioxidants in the existing Rumex acetosa

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

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

Dihydroflavonols from the leaves of Derris urucu (Leguminosae): structural elucidation and DPPH radical-scavenging activity

Derris urucu é uma planta da Amazônia com propriedades inseticida e ictiotóxica. Estudos com esta espécie reportam a presença de flavonóides, principalmente rotenóides, bem como de estilbenos. A partir do extrato etanólico das folhas de Derris urucu (Leguminosae), três novos diidroflavonóides, denominados urucuol A (1), B (2) e C (3) e o diidroflavonol isotirumalina (4), foram isolados e identificados. As estruturas destes compostos foram elucidadas por uma extensiva análise espectroscópica de RMN uni e bidimensional, UV, IV e dados de EM, além de comparação com dados da literatura. Os compostos isolados (1-4) foram avaliados quanto ao seu potencial sequestrador do radical DPPH• e apresentaram baixo poder antioxidante quando comparados ao antioxidante comercial trans-resveratrol.

Processo de obtenção de nanopartículas lipídicas sólidas, nanopartículas lipídicas sólidas e seu uso

A presente invenção descreve um processo de obtenção de nanopartículas lipídicas sólidas com trans-resveratrol (res) por sonicação, utilizando lipídio peguilado, bem como as nanopartículas obtidas e seu uso na terapia antitumoral do melanoma.

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.

Secondary metabolites from Spirotropis longifolia (DC) Baill and their antifungal activity against human pathogenic fungi

A phytochemical study of the ethyl acetate extract of the roots and adventitious roots of Spirotropis longifolia, a monodominant tree species of the Guianan rainforest, has allowed the isolation of three compounds: 2- hydroxy-8,9-methylenedioxy-2',2'-dimethylpyrano-[5',6':4,3]-6a-prenyl-[6aS,11aS]-pterocarpan (spirotropin A), 2-hydroxy-8,9-methylenedioxy-2',2'-dimethy1-3',4'-dihydropyrano-[5',6':4,3]-6a-prenyl-(6aS,11aS]-pterocarpan (spirotropin B), and 5,7-dihydroxy-6.8-dipreny1-2 ''''.2 ''''-dimethylpyrano[5 '''',6 '''': 3',4]-isoflavone (spirotropone). In addition, 10 known compounds, trans-oxyresveratrol, trans-resveratrol, piceatannol, daidzein, genistein, isoprunetin, lupeol, latifolol, gnetin D and gnetin E, were also isolated. These compounds were evaluated for their antifungal activity and their cytotoxicity, and their structures were established by 1D and 2D NMR, HRMS, CD and optical rotation measurements. (C) 2011 Elsevier Ltd. All rights reserved.