Mate as Dietary Supplement for Broiler Chickens: Effect on the Metabolic Profile and Redox Chemistry of Meat

Moderate supplementation with extract of mate to a standard broiler diet in feeding experiment with 5 treatment groups was found to increase production of endogenous antioxidants in muscles, improving meat quality and storage stability. For addition of 250 or 500 mg extract per kg feed, pre-cooked meatballs made from the breast muscles had a significant lower level of secondary lipid oxidation products during one week of chill storage. Addition of 750 or 1000 mg extract per kg feed had an increasing prooxidative effect during storage of the meatballs. For the moderate levels of plant phenols in feed, a metabolic study based on nuclear magnetic resonance (NMR) spectroscopy of meat extracts showed that mate extract added to the feed increased the muscle level of antioxidative peptides like anserine, while indication of toxic effects was noted for the higher levels of feed additives. Rate of formation of radicals as detected by electron paramagnetic resonance (EPR) spectroscopy was found to correlate with the oxidative damage and a kinetic analysis demonstrated that the antioxidative effect of mate supplemented to the feed could be assigned to radical scavengers present in the meat. These findings for the monogastric animals are different from results previously obtained for ruminants, where plant phenols rather seem to affect the microflora of the digestive tract

Reactions involving NOx mediated by heme iron in foods and biological systems

Os ânions inorgânicos nitrato (NO3-) e nitrito (NO2-) por muito tempo foram considerados produtos finais inertes do metabolismo do óxido nítrico (NO) e constituintes indesejáveis da dieta. Entretanto, é crescente o interesse das potenciais reações que podem se processar em meio fisiológico e, que envolvem especialmente o íon nitrito mediadas por complexos de metais de transição. Ferro-heme presente em proteínas como a mioglobina podem formar complexos porfirínicos com NO, gerando espécies que podem atuar principalmente como catalisadores em diversas vias biológicos importantes. Complexos com NOx coordenado a ferro-heme estão envolvidos tanto no processo da cura da carne (pigmentação da carne), como em processos redox, nos quais são capazes de oxidar substratos indiretamente pela produção de espécies reativas ou diretamente por reações de transferência de átomo de oxigênio (TAO). Os lipídeos, constituintes celulares fundamentais na composição de membranas e lipoproteínas, podem servir como substratos para essas reações e, sua oxidação pode ocasionar danos ao organismo. Tióis, importantes antioxidantes e constituintes de proteínas, também podem participar desse tipo de reações e, conseqüentemente gerar danos ao organismo. Considerando que o mecanismo e os parâmetros cinéticos e termodinâmicos destas reações ainda não foram completamente estabelecidos para explicar a vasta funcionalidade destes complexos, o presente projeto de pesquisa visa proporcionar um melhor conhecimento das reações redox envolvendo NOx e mediadas por porfirinas de ferro em alimentos e sistemas biológicos.For long time, the anions nitrate (NO3-) and nitrite (NO2-) were considered inert end products of nitric oxide (NO) metabolism and undesirable constituents of the diet. Currently, there is an increasing interest for potential reactions which may occur in physiological conditions involving specially the nitrite ion and mediated by transition metal complexes. Heme NOx iron complexes are involved in meat curing process (meat pigmentation) and are able to oxidize substrates indirectly generating reactive species or directly by oxygen atom transfer reactions (OAT). Lipids, fundamental cellular constituents of membranes and lipoproteins, and thiols, important antioxidants and protein constituents, may serve as substrates to OAT and their oxidation may promote damage to the organism Considering that the mechanism and kinetic and thermodinamic parameters of these reaction have not yet been fully elucidated to explain the varied functionality of these complexes, the present research project aim to bring a better understanding of redox reactions involving NOx mediated by iron porphyrins in foods and biological systems. Thiols, important antioxidants and protein constituents, may serve as substrates to OAT and their oxidation may promote damage to the organism. The present work aims to bring a better understanding of the mechanism, kinetic and thermodynamic parameters of the reaction involving nitrite mediated by iron-porphyrins in food and biological systems

Improving meat quality through cattle feed enriched with mate extract: an integrated approach of the metabolic profile and redox chemistry of meat

O uso de extrato de plantas na suplementação tem sido considerado uma potencial alternativa para melhorar a estabilidade redox da carne. Alguns compostos bioativos presentes nos extratos de plantas atuam como antioxidantes e podem melhorar a saúde e o bem estar do animal e proteger a carne da oxidação. Propriedades farmacológicas e efeitos antioxidantes têm sido demonstrados em extratos de lúpulo e erva mate. Porém, os efeitos do uso de extrato de lúpulo e de erva mate como suplemento em dieta animal no perfil metabólico e na estabilidade redox da carne ainda não foram reportados. A adição de 0,5%, 1,0% e 1,5% de extrato de erva mate a uma ração composta de milho e soja destinada à alimentação de gado resultou no aumento da concentração de inosina monofosfato, creatina, carnosina e ácido linoléico conjugado na carne. A tendência à formação de radicais livres em homogenatos de carne diminuiu conforme aumentou o teor de erva mate na ração indicando um aumento da resistência da carne à oxidação. A adição de extrato de lúpulo (0, 30 ppm, 60 ppm e 240 ppm) à ração de frangos de corte promoveu efeitos significativos na concentração média de metabólitos polares que são de relevância para a qualidade da carne. As maiores diferenças nos perfis metabólicos entre o grupo controle (sem suplemento) e as amostras de carne de frango que foi alimentado com ração suplementada com β-ácidos foram obtidas usando 30 ppm de lupulonas na dieta. Como determinado pela técnica de spin-trapping, uma maior estabilidade redox foi observada nas amostras relacionadas aos animais alimentados com 30 ppm de lupulonas e podem ser relacionadas a um maior nível de antioxidantes endógenos, especialmente anserina, carnosina e NADH. Miosina e actina demonstraram ser os alvos principais da oxidação de proteínas em carne de frango. As proteínas miofibrilares de animais alimentos com β-ácidos mostraram ser menos susceptíveis à oxidação quando comparado ao grupo controle. Extratos de mate e de β-ácidos demonstraram ser aditivos promissores para dieta animal de gado e frango, respectivamente, e podem melhorar a estabilidade oxidativa, o valor nutricional, a qualidade sensorial e a aceitação da carne.The use of plant extracts in animal feeding trials has been considered as a potential alternative to improve the redox stability of meat. Bioactive compounds from plant extracts can provide the antioxidative mechanisms required to improve animal health and welfare and, to protect meat against oxidation. Pharmacological properties and antioxidant effects have been associated to the extract of hops and to the extracts of yerba mate. However, the effects of hops and yerba mate as dietary supplement for animal feeding on the metabolic profile and the redox stability of meat have not been reported yet. Addition of extract of mate to a standard maize/soy feed at a level of 0.5, 1.0 or 1.5% to the diet of feedlot for cattle resulted in an increased level of inosine monophosphate, creatine, carnosine and of conjugated linoleic acid in the fresh meat. The tendency to radical formation in meat slurries as quantified by EPR spin-trapping decreased for increasing mate extract addition to feed especially after storage of the meat indicating an increased resistance to oxidation for meat. Addition of hops extract at different levels (0, 30 ppm, 60 ppm, 240 ppm) to the diet of broilers demonstrated to have significant effects on the averaged concentration of polar metabolites that are of relevance for meat quality. The major metabolic differences between control group (no supplements) and broilers fed different levels of β-acids were achieved using 30 ppm of supplement. As determined by EPR spin-trapping, increased redox stability was obtained in the samples referring to the animals fed 30 ppm of lupulones and may be related to the highest level of endogenous antioxidants, especially anserine, carnosine and NADH. Myosin and actin were recognized as the main targets of protein oxidation in meat. Myofibrillar proteins from animals fed with hops β-acids showed to be less susceptible to oxidation when compared to control group. Mate and hops β-acids extracts demonstrated to be promising additives to feedlot for, respectively, cattle and broilers and can improve the oxidative stability, nutritive value, sensory quality, and consumer acceptance of meat

Synthesis-Gas Production from Methane over Ni/CeO2 Catalysts Synthesized by Co-Precipitation Method in Different Solvents

Ni/CeO2 catalysts were synthesized by the coprecipitation method in a basic medium, using different solvents: water, methanol, ethanol, and isopropanol (Ni content, 10% wt.). These catalysts were tested in the production of syngas through the oxidative reforming of methane (ORM), and partial oxidation of methane (POM). The results of this research demonstrated that the use of alcohols (methanol, ethanol, and isopropanol) during the preparation of the Ni/CeO2 catalysts by the coprecipitation method, improved their characteristics such as crystallite size (nm), surface area (m2·g−1), and reducibility (measured by H2-TPR) that influenced on their catalytic performance in ORM and POM reactions. The best solvent of this study was isopropanol. The use of alcohols (methanol, ethanol, isopropanol) in the co-precipitation method led to the formation of filamentous carbon on the catalyst after the reactions. The catalyst synthesized in the water proved to be inefficient in the POM and ORM reactions and led to the formation of amorphous carbon after the reactions

Kinetics and Thermodynamics of 1‑Hydroxyethyl Radical Reaction with Unsaturated Lipids and Prenylflavonoids

Hydroxyalkyl radicals have been reported to induce lipid oxidation as the key aspect of the pathogenesis of alcoholic fatty liver disease and are responsible for the alkylation and cleavage of DNA during the metabolism of a wide range of genotoxic compounds. However, relevant kinetic data for the oxidation of unsaturated lipids by 1-hydroxyethyl radical (HER) has not been reported. In this study, the rate constants for the reaction of unsaturated fatty acid methyl esters and sterols with HER have been determined using a competitive kinetic approach employing the spin-trap α-(4-pyridyl-1-oxide)-<i>N-tert</i>-butylnitrone (4-POBN) as the competitive substrate. Polyunsaturated fatty acid methyl ester is shown to react with HER with an apparent second-order rate constant ranging from (3.7 ± 0.1) × 10⁶ L mol^–1 s^–1 for methyl linoleate to (2.7 ± 0.2) × 10⁷ L mol^–1 s^–1 for methyl docosahexanoate at 25.0 ± 0.2 °C in ethanol. The apparent second-order rate constant for polyunsaturated fatty acid methyl ester oxidation by HER is dependent on the number of bisallylic hydrogen atoms rather than on the bond dissociation energy value for the weakest CH bond as determined by ab initio density functional theory calculations. Sterols displayed higher reactivity compared to unsaturated fatty acid methyl esters with apparent second-order rate constants of (2.7 ± 0.1) × 10⁶ and (5.2 ± 0.1) × 10⁷ L mol^–1 s^–1 at 25.0 ± 0.2 °C in ethanol for cholesterol and ergosterol, respectively. Similar experiments with prenylflavonoids as potential herbal chemopreventive agents for preventing alcoholic liver diseases yield apparent second-order rate constants close to the diffusion control with <i>k</i>_app values of (1.5 ± 0.2) and (3.6 ± 0.1) × 10⁹ L mol^–1s^–1 for 6-prenylnarigerin and xanthohumol at 25.0 ± 0.2 °C in ethanol solution, respectively. Polyunsaturated lipids were revealed to be highly reactive oxidizable substrates toward HER-induced oxidation in biological systems leading to damage of membranes and sensitive structures