RESUMEN
Quinones are electrophilic compounds that can undergo Michael addition or Schiff base reaction with nucleophilic amines, but the effect of temperature has not been systematically studied. The aim of this study was to characterize how temperature affects the reaction mechanism and kinetics of 4-methylbenzoquinone (4MBQ) with lysine (Lys), Nα-acetyl Lys or Nε-acetyl Lys. The products were identified and characterized by LC-MS/MS, which revealed formation of Michael addition products, Schiff base, and a di-adduct in Lys and Nα-acetyl Lys-containing reaction mixtures. The product profiles were not affected by temperature in the range of 15-100 °C. NMR analysis proved that Michael addition of Nα-acetyl Lys occurred on the C5 position of 4MBQ. Rate constants for the reactions studied by stopped-flow UV-vis spectrophotometry under pseudo-first-order conditions where the amines were present in excess in the range 15 °C to 45 °C showed the α-amino groups of Lys are more reactive than the ε-groups. The kinetics results revealed that the temperature dependence of reaction rates followed the Arrhenius law, with activation energies in the order: Lys < Nε-acetyl Lys < Nα-acetyl Lys. Our results provide detailed knowledge about the temperature dependence of the reaction between Lys residues and quinones under conditions relevant for storage of foods.
Asunto(s)
Lisina , Bases de Schiff , Lisina/química , Cromatografía Liquida , Temperatura , Espectrometría de Masas en Tándem , Aminas , QuinonasRESUMEN
An image-based method for determining H2O2 vapor pressures in powder systems was developed based on cellulose pellets loaded with potassium titanium oxide oxalate (PTO Pellets) as probe particles. Solid titanyl salts change color after exposure to hydrogen peroxide vapor and the quantitative response of PTO pellets to H2O2 has been established by comparing reactions with H2O2 in liquid and solid states. Analysis of pictures of the color changes of PTO Pellets mixed into powders can be used to monitor the presence of ppm levels of H2O2 vapor inside powder systems such as bleach containing dry detergent powders.â¢H2O2 vapor quantification in dry systems with titanyl loaded cellulose particles.â¢Simple fabrication of H2O2 probe particles.â¢High sensitivity with LOD 0.190 ppm H2O2 .
RESUMEN
Trace levels of copper can impact the flavor stability of beer. The main source of copper is malt, and the wort copper levels are established during mashing and lautering. This study focuses on sweet worts made from experimental roasted and caramel malts. Potentiometric titrations using ion-selective electrodes combined with electron paramagnetic resonance spectroscopy have been used to investigate Cu(II) binding in worts as well as the impact of Cu(II) ions on the wort oxidative stability. High-temperature treatment during malting decreased Cu(II) binding affinities in the worts, with roasted malt worts having lower affinities than caramel malt worts of similar color and pH. Electron paramagnetic resonance spectra indicated dipeptides as the main Cu(II) chelators. A positive correlation between Cu and free amino nitrogen levels in worts is demonstrated. In dark worts with high rates of radical formation, Cu(II) had pronounced antioxidative effects. In contrast, moderate prooxidative effects were observed when adding Cu(II) to pale worts with inherently low rates of oxidation.
Asunto(s)
Cerveza , Cobre , Cerveza/análisis , Quelantes , Espectroscopía de Resonancia por Spin del Electrón , Oxidación-Reducción , PlantonesRESUMEN
Different studies have shown that detection of free radicals by ESR spin trapping provides useful information on the susceptibility to oxidation of bulk oils and accordingly on the oxidative stability of different samples for comparative purposes. With the same goal, ESR spin trapping was evaluated in this work for in situ detection of radicals in dried microencapsulated oils (DMOs). By testing different oils, encapsulation matrices and oxidation conditions, results showed that ESR spin trapping can be useful to evaluate the oxidative susceptibility of DMOs, but ESR data should be interpreted cautiously, as the great complexity of the reactions involved may lead to data misinterpretations. Conditions for oxygen availability can have important impacts on the rates of both spin trapping and spin-adduct quenching affecting the levels of radicals observed. The kinetics of oxidation, spin trapping and spin-adduct decay should be known first in bulk oils for correct data interpretation in DMOs.
Asunto(s)
Espectroscopía de Resonancia por Spin del Electrón/métodos , Radicales Libres/análisis , Peroxidación de Lípido/fisiología , Aceites de Plantas/química , Óxidos N-Cíclicos , Desecación , Oxígeno/química , Marcadores de SpinRESUMEN
The kinetics of the reaction between epicatechin and various carbonyl compounds typically formed in cooked and stored foods were evaluated in model systems at pH 7.4 and 37 °C, and the corresponding reaction products in stored ultrahigh temperature (UHT) milk-added epicatechin were identified by high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS). The rate constants for the reactions of carbonyl compounds with epicatechin decreased in the following the order: methylglyoxal; 1.6 ± 0.2 M-1 s-1 > glyoxal; (5.9 ± 0.3) × 10-2 M-1 s-1 ≥ 5-(hydroxymethyl)furfural; (4.0 ± 0.2) × 10-2 M-1 s-1 ≥ acetaldehyde; (2.6 ± 0.3) × 10-2 M-1 s-1 ≥ phenylacetaldehyde; (2.1 ± 0.2) × 10-2 M-1 s-1 ≥ furfural; (4.3 ± 0.1) × 10-3 M-1 s-1 > 2-methylbutanal and 3-methylbutanal; â¼0 M-1 s-1. Reaction products generated by epicatechin and methylglyoxal, glyoxal, 5-(hydroxymethyl)furfural, and acetaldehyde were detected in UHT milk samples by incubating milk samples with epicatechin at 37 °C for 24 h. The lack of reaction between epicatechin and phenylacetaldehyde, furfural, 2-methylbutanal, and 3-methylbutanal in stored UHT milk may be due to their slow reaction rates or low concentration in stored UHT milk. It is demonstrated that epicatechin traps 5-(hydroxymethyl)furfural, acetaldehyde, glyoxal, and methylglyoxal and may thereby reduce off-flavor formation in UHT milk during storage both by trapping of precursors (methylglyoxal and glyoxal) for off-flavor formation and by direct trapping of off-flavors.
Asunto(s)
Catequina/química , Leche/química , Animales , Bovinos , Cromatografía Líquida de Alta Presión , Manipulación de Alimentos , Almacenamiento de Alimentos , Calor , Cinética , Reacción de Maillard , Estructura Molecular , Espectrometría de Masas en TándemRESUMEN
Reaction kinetics for the reactions between four polyphenols (trans-resveratrol, apigenin, kaempferol and fisetin) and methylglyoxal (MGO) were determined at pH 7.4 and 37 °C, and the effect of functional groups of polyphenols on MGO trapping ability was examined. Reaction products of polyphenols with MGO were characterized by HPLC-MS/MS. The apparent second order rate constants for the reaction of MGO with trans-resveratrol, apigenin, kaempferol and fisetin were (2.7 ± 0.2) × 10-2 M-1 s-1, (4.4 ± 0.4) × 10-3 M-1 s-1, (6.3 ± 0.2) × 10-2 M-1 s-1, and (3.6 ± 0.1) × 10-3 M-1 s-1, respectively. The rate constants were used to evaluate the possible competition between MGO with nucleophilic sites on proteins and polyphenols at concentrations relevant to UHT milk. Combining this information with solubility and flavour of the polyphenols, it was concluded that kaempferol could effectively trap MGO and hereby inhibit Maillard reactions in UHT milk.
Asunto(s)
Polifenoles/química , Piruvaldehído/química , Animales , Cromatografía Líquida de Alta Presión , Flavonoides , Flavonoles , Cinética , Reacción de Maillard , Leche/química , Estructura Molecular , Espectrometría de Masas en TándemRESUMEN
Thiol groups of cysteine (Cys) residues in proteins react with quinones, oxidation products of polyphenols, to form protein-polyphenol adducts. The aim of the present work was to quantify the amount of adduct formed between Cys residues and 4-methylcatechol (4MC) in minced beef. A Cys-4MC adduct standard was electrochemically synthesized and characterized by liquid chromatography-mass spectrometry (LC-MS) as well as NMR spectroscopy. Cys-4MC adducts were quantified after acidic hydrolysis of myofibrillar protein isolates (MPIs) and LC-MS/MS analysis of meat containing either 500 or 1500 ppm 4MC and stored at 4 °C for 7 days under a nitrogen or oxygen atmosphere. The concentrations of Cys-4MC were found to be 2.2 ± 0.3 nmol/mg MPI and 8.1 ± 0.9 nmol/mg MPI in meat containing 500 and 1500 ppm 4MC, respectively, and stored for 7 days under oxygen. The formation of the Cys-4MC adduct resulted in protein thiol loss, and ca. 62% of the thiol loss was estimated to account for the formation of the Cys-4MC adduct for meat containing 1500 ppm 4MC. Furthermore, protein polymerization increased in samples containing 4MC as evaluated by sodium dodecyl sulfate-polyacrylamide gel electrophoresis (SDS-PAGE), and the polymerization was found to originate from protein-polyphenol interactions as evaluated by a blotting assay with staining by nitroblue tetrazolium.
Asunto(s)
Cisteína/química , Guayacol/química , Carne/análisis , Fenol/química , Animales , Bovinos , Proteínas Musculares/química , Oxidación-Reducción , Quinonas/química , Espectrometría de Masas en TándemRESUMEN
In this work, we developed a novel approach combining bioinformatics, testing of functionality and bottom-up proteomics to obtain peptide emulsifiers from potato side-streams. This is a significant advancement in the process to obtain emulsifier peptides and it is applicable to any type of protein. Our results indicated that structure at the interface is the major determining factor of the emulsifying activity of peptide emulsifiers. Fish oil-in-water emulsions with high physical stability were stabilized with peptides to be predicted to have facial amphiphilicity: (i) peptides with predominantly α-helix conformation at the interface and having 18-29 amino acids, and (ii) peptides with predominantly ß-strand conformation at the interface and having 13-15 amino acids. In addition, high physically stable emulsions were obtained with peptides that were predicted to have axial hydrophobic/hydrophilic regions. Peptides containing the sequence FCLKVGV showed high in vitro antioxidant activity and led to emulsions with high oxidative stability. Peptide-level proteomics data and sequence analysis revealed the feasibility to obtain the potent emulsifier peptides found in this study (e.g. γ-1) by trypsin-based hydrolysis of different side streams in the potato industry.
Asunto(s)
Emulsiones/aislamiento & purificación , Ácidos Grasos Omega-3/química , Péptidos/aislamiento & purificación , Solanum tuberosum/metabolismo , Algoritmos , Secuencia de Aminoácidos , Biología Computacional , Emulsiones/química , Aceites de Pescado/química , Interacciones Hidrofóbicas e Hidrofílicas , Péptidos/química , Proteínas de Plantas/química , Proteínas de Plantas/metabolismo , Estructura Secundaria de Proteína , Proteómica , Solanum tuberosum/química , Agua/químicaRESUMEN
The kinetics and mechanism of the stepwise cis-trans isomerization reactions of all-trans-ß-carotene dissolved in MCT (medium-chain triglyceride) oil at temperatures in the range of 80-160 °C have been analyzed using multiresponse modeling. Quantitation of the cis-isomers was performed using HPLC-DAD and quantitation at the reaction isosbestic point at 421 nm. Multiresponse kinetic modeling using the Bayesian criterion was initially performed at 120 °C to determine the best model. Subsequently, the reparametrized Arrhenius equation was used to calculate the activation energies of all reactions. The equilibrium constants for the individual isomerization reactions were determined from the rate constants and the final product distributions. The enthalpies and entropies of the isomerization reactions were determined from the temperature dependence of the equilibrium constants. The 13-cis and 13,13'-di-cis isomers were found to be the fastest formed isomers followed by the 9-cis, 9,13-di-cis, and 13,15-di-cis isomers, where the latter was found to be formed from 13-cis and not the 15-cis isomer. The relative free energies of the ß-carotene isomers were determined as all-trans < 13-cis < 9-cis < 13,13'-di-cis < 9,13-di-cis ≈ 15-cis < 13,15-di-cis. The entropic contribution of each reaction was found to play an important role in the ordering. It is concluded that the ß-carotene system is quite labile at temperatures ranging from 80 to 160 °C and resulting in equilibrium distributions of the cis-trans isomers.
Asunto(s)
Triglicéridos/química , beta Caroteno/química , Calor , Cinética , Modelos Químicos , EstereoisomerismoRESUMEN
Methylglyoxal (MGO) is a highly reactive É-dicarbonyl compound that may adversely impact food quality and human health by modifying proteins. The kinetics of the reaction of naringenin with MGO was studied at pH 6-8 and 37⯰C by UV-Vis spectrophotometry and reaction products were characterized by liquid chromatography-mass spectrometry (LC-MS/MS). The apparent second order rate constant (k2) increased at pH above the lowest pKa value of naringenin, indicating deprotonated naringenin as the main reactant. A Lederer-Manasse type reaction mechanism is suggested, with dehydration of the MGO-dihydrate as a rate determining step. The quantitative data obtained in the present study was used to simulate the competitive reaction between MGO and nucleophilic amino acid residues (Lys, Arg and Cys) and naringenin in milk. It is predicted that naringenin will be able to efficiently trap MGO during storage of milk, although the reversible trapping of MGO by Cys residues is initially kinetically favourable.
Asunto(s)
Flavanonas/química , Piruvaldehído/química , Aminoácidos/química , Cromatografía Liquida , Concentración de Iones de Hidrógeno , Cinética , Proteínas de la Leche/química , Espectrometría de Masa por Ionización de Electrospray , Espectrofotometría Ultravioleta , Espectrometría de Masas en TándemRESUMEN
The oxygen permeability and oxidative stability of fish oil-loaded electrosprayed capsules were studied by Electron Spin Resonance (ESR). Electrosprayed capsules with dextran as main biopolymer showed a significantly faster broadening (ΔHpp) of 16-doxyl-stearate ESR spectrum when compared to glucose syrup capsules. This finding indicates a higher oxygen permeability of dextran capsules than glucose syrup capsules, which is explained by a reduced average free volume in the glucose syrup matrix than in the dextran shell. Moreover, glucose syrup capsules showed a significantly lower increase in the peak-to-peak amplitude of N-tert-butyl-α-phenylnitrone (PBN) ESR spectrum during storage when compared to dextran capsules. This implies a higher oxidative stability of glucose syrup capsules than dextran capsules, which correlated well with the lower oxygen permeability of the former. These results indicated the importance of the oxygen barrier properties of the wall materials when encapsulating long chain omega-3 polyunsaturated fatty acids by electrospraying.
Asunto(s)
Cápsulas/química , Dextranos/química , Aceites de Pescado/química , Oxígeno/química , Óxidos N-Cíclicos/análisis , Óxidos N-Cíclicos/química , Estabilidad de Medicamentos , Espectroscopía de Resonancia por Spin del Electrón , Ácidos Grasos Omega-3/química , Glucosa/química , Oxidación-Reducción , PermeabilidadRESUMEN
Thiol-containing proteins have been suggested to have antioxidative properties in beer. A kinetic model has been setup for the reactivity of thiols during early stages of oxidative degradation of beer. Kinetic analysis based on the proposed reaction mechanism allowed evaluation of the relative reactivity of beer components, such as bitter acids from hops and polyphenols. The rate constants for the reaction of 1-hydroxyethyl radicals, which are generated during radical mediated oxidation of ethanol in beer, with hop bitter acids and thiols were very similar, and the concentration of these compounds in beer is therefore essential for the relative reactivity. For a standard pilsner beer with 35 international bitter units with typical concentrations of thiols and hop bitter acids, thiols were found to react with ca. 9% of 1-hydroxyethyl radicals, while bitter acids from hops accounted for ca. 88% of the reaction with 1-hydroxyethyl radicals. Polyphenols were not found to account for any major part of the reaction with 1-hydroxyethyl radicals due to low reaction rates and low concentrations in pilsner beer compared to the other components. The kinetic model suggests that the concentration of thiols has to be increased in order to contribute with any significant antioxidative protection and that the fate of thiols during oxidation must be considered since some thiol oxidation products may induce further damage.
Asunto(s)
Cerveza/análisis , Humulus/química , Humulus/metabolismo , Proteínas/química , Compuestos de Sulfhidrilo/química , Ácidos/química , Antioxidantes/química , Etanol/química , Análisis de los Alimentos/métodos , Humanos , Cinética , Simulación de Dinámica Molecular , Polifenoles/química , GustoRESUMEN
The interactions between free and macromolecule-bound antioxidants were investigated in order to evaluate their combined effects on the antioxidant environment. Dietary fiber (DF), protein and lipid-bound antioxidants, obtained from whole wheat, soybean and olive oil products, respectively and Trolox were used for this purpose. Experimental studies were carried out in autoxidizing liposome medium by monitoring the development of fluorescent products formed by lipid oxidation. Chemometric methods were used both at experimental design and multivariate data analysis stages. Comparison of the simple addition effects of Trolox and bound antioxidants with measured values on lipid oxidation revealed synergetic interactions for DF and refined olive oil-bound antioxidants, and antagonistic interactions for protein and extra virgin olive oil-bound antioxidants with Trolox. A generalized version of logistic function was successfully used for modelling the oxidation curve of liposomes. Principal component analysis revealed two separate phases of liposome autoxidation.
Asunto(s)
Antioxidantes/química , Cromanos , Liposomas , Aceite de Oliva , Oxidación-Reducción , Aceites de PlantasRESUMEN
Oxidation of polyphenols to quinones serves as an antioxidative mechanism, but the resulting quinones may induce damage to proteins as they react through a Michael addition with nucleophilic groups, such as thiols and amines to give protein adducts. In this study, rate constants for the reaction of 4-methylbenzoquinone (4MBQ) with proteins, thiol and amine compounds were determined under pseudo first-order conditions by UV-vis stopped-flow spectrophotometry. The chemical structures of the adducts were identified by LC-ESI-MS/MS. Proteins with free thiols were rapidly modified by 4MBQ with apparent second order rate constants, k2 of (3.1±0.2)×10(4)M(-1)s(-1) for bovine serum albumin (BSA) and (4.8±0.2)×10(3)M(-1)s(-1) for human serum albumin at pH 7.0. These values are at least 12-fold greater than that for α-lactalbumin (4.0±0.2)×10(2)M(-1)s(-1), which does not contain any free thiols. Reaction of Cys-34 of BSA with N-ethylmaleimide reduced the thiol concentration by ~59%, which resulted in a decrease in k2 by a similar percentage, consistent with rapid adduction at Cys-34. Reaction of 4MBQ with amines (Gly, Nα-acetyl-l-Lys, Nε-acetyl-l-Lys and l-Lys) and the guanidine group of Nα-acetyl-l-Arg was at least 5×10(5) slower than with low-molecular-mass thiols (l-Cys, Nα-acetyl-l-Cys, glutathione). The thiol-quinone interactions formed colorless thiol-phenol products via an intermediate adduct, while the amine-quinone interactions generated colored amine-quinone products that require oxygen involvement. These data provide strong evidence for rapid modification of protein thiols by quinone species which may be of considerable significance for biological and food systems.
Asunto(s)
Antioxidantes/metabolismo , Benzoquinonas/metabolismo , Oxidación-Reducción , Albúmina Sérica Bovina/metabolismo , Aminas/química , Aminas/metabolismo , Animales , Antioxidantes/química , Benzoquinonas/farmacología , Bovinos , Cromatografía Liquida , Cisteína/metabolismo , Humanos , Polifenoles/química , Polifenoles/metabolismo , Procesamiento Proteico-Postraduccional/efectos de los fármacos , Albúmina Sérica Bovina/química , Espectrofotometría Ultravioleta , Compuestos de Sulfhidrilo/química , Compuestos de Sulfhidrilo/metabolismo , Espectrometría de Masas en TándemRESUMEN
The initiation of lipid autoxidation within single oil droplets in Tween-20-stabilized oil-in-water emulsion was achieved by highly focused two-photon (2P) irradiation at excitation wavelength (λex) 700 nm. The radical formation was enhanced by inclusion of the photo-cleavable radical initiator di-tert-butyl peroxide (DTBP) into the droplets, and demonstrated with confocal microscopy using radical-sensitive probe BODIPY(665/676). The radical chain reactions progressed up to 60 µm; however, there were no indications of oxidation in neighboring droplets demonstrating that radicals and oxidized probe molecules were not able to migrate between oil droplets. In addition, the spatial propagation of lipid autoxidation increased with the degree of oil unsaturation.
Asunto(s)
Lípidos/química , Aceites/química , Agua/química , Emulsiones , Oxidación-ReducciónRESUMEN
The radical-mediated reactions occurring during the early stages of beer storage were studied by following the rate of oxygen consumption, radical formation as detected by electron spin resonance spectroscopy, and concentrations of the antioxidant compounds sulfite and thiols. Addition of either Fe(III) or Fe(II) had similar effects, indicating that a fast redox equilibrium is obtained between the two species in beer. Addition of iron in combination with hydrogen peroxide gave the most pronounced levels of oxidation due to a direct initiation of ethanol oxidation through generation of hydroxyl radicals by the Fenton reaction. The concentration of sulfite decreased more than the thiol concentration, suggesting that thiols play a secondary role as antioxidants by mainly quenching 1-hydroxyethyl radicals that are intermediates in the oxidation of ethanol. Increasing the temperature had a minor effect on the rate of oxygen consumption.
Asunto(s)
Antioxidantes/farmacología , Cerveza/análisis , Metales/química , Compuestos de Sulfhidrilo/farmacología , Sulfitos/farmacología , Espectroscopía de Resonancia por Spin del Electrón , Etanol/química , Compuestos Férricos/farmacología , Compuestos Ferrosos/farmacología , Manipulación de Alimentos/métodos , Radicales Libres/química , Peróxido de Hidrógeno/farmacología , Radical Hidroxilo/química , Oxidación-Reducción , Oxígeno/química , Compuestos de Sulfhidrilo/química , Sulfitos/químicaRESUMEN
Detection of free radicals in biological systems is challenging due to their short half-lives. We have applied electron spin resonance (ESR) spectroscopy combined with spin traps using the probes PBN (N-tert-butyl-α-phenylnitrone) and DMPO (5,5-dimethyl-1-pyrroline N-oxide) to assess free radical formation in the human pathogen Staphylococcus aureus treated with a bactericidal antibiotic, vancomycin or ciprofloxacin. While we were unable to detect ESR signals in bacterial cells, hydroxyl radicals were observed in the supernatant of bacterial cell cultures. Surprisingly, the strongest signal was detected in broth medium without bacterial cells present and it was mitigated by iron chelation or by addition of catalase, which catalyzes the decomposition of hydrogen peroxide to water and oxygen. This suggests that the signal originates from hydroxyl radicals formed by the Fenton reaction, in which iron is oxidized by hydrogen peroxide. Previously, hydroxyl radicals have been proposed to be generated within bacterial cells in response to bactericidal antibiotics. We found that when S. aureus was exposed to vancomycin or ciprofloxacin, hydroxyl radical formation in the broth was indeed increased compared to the level seen with untreated bacterial cells. However, S. aureus cells express catalase, and the antibiotic-mediated increase in hydroxyl radical formation was correlated with reduced katA expression and catalase activity in the presence of either antibiotic. Therefore, our results show that in S. aureus, bactericidal antibiotics modulate catalase expression, which in turn influences the formation of free radicals in the surrounding broth medium. If similar regulation is found in other bacterial species, it might explain why bactericidal antibiotics are perceived as inducing formation of free radicals.
Asunto(s)
Catalasa/metabolismo , Ciprofloxacina/farmacología , Radicales Libres/metabolismo , Staphylococcus aureus/efectos de los fármacos , Staphylococcus aureus/metabolismo , Vancomicina/farmacología , Catalasa/biosíntesis , Catalasa/genética , Medios de Cultivo , Óxidos N-Cíclicos , Espectroscopía de Resonancia por Spin del Electrón , Humanos , Peróxido de Hidrógeno/metabolismo , Radical Hidroxilo/metabolismo , Hierro/metabolismo , Oxidación-Reducción , Staphylococcus aureus/genéticaRESUMEN
Male Comisana lambs were individually stalled and, for 56 days, were fed concentrates with 60% barley (n = 8 lambs), or concentrates in which barley was partially replaced by 24% or 35% carob pulp (n = 9 lambs in each group). The intramuscular fatty acids were analyzed and the color stability, lipid and protein oxidation were measured in fresh meat overwrapped with polyvinyl chloride film at 0, 3 or 6 days of storage at 4 °C in the dark. Carob pulp increased the concentration of polyunsaturated fatty acids (PUFA) in muscle, including the rumenic acid (P < 0.01), and reduced the saturated fatty acids (P < 0.01) and the n-6/n-3 PUFA ratio (P = 0.01). The meat did not undergo extensive oxidative deterioration and the diet did not affect the oxidative stability parameters. Therefore, carob in lamb diet could increase PUFA in muscle without compromising meat oxidative stability.
Asunto(s)
Alimentación Animal/efectos adversos , Ácidos Grasos/química , Galactanos/química , Mananos/química , Carne/análisis , Gomas de Plantas/química , Animales , Dieta , Masculino , Oxidación-Reducción , OvinosRESUMEN
(E,E)-3,5-Bis(4-phenyl-1,3-butadienyl)-4,4-difluoro-4-bora-3a,4a-diaza-s-indacene, BODIPY(665/676), is a lipophilic radical-sensitive fluorescent probe that can be used to study radical-driven lipid autoxidation. The sensitivity of BODIPY(665/676) was studied in the presence of radical initiators di-tert-butyl peroxide and 2,2'-azobis(2,4-dimethyl)valeronitrile (AMVN). In both cases the fluorescence of BODIPY(665/676) changed more in saturated medium-chain triglyceride oil than in linseed or sunflower oils, where the high degree of unsaturation is expected to give more pronounced radical-derived lipid oxidation. It was suggested that BODIPY(665/676), as the only available oxidizable substance in the saturated oil, was directly attacked by radicals, resulting in high rates of probe oxidation, while in the unsaturated oils, radicals attacked either unsaturated fatty acids or BODIPY(665/676), resulting in lower rates of probe oxidation. Confocal microscopy studies with BODIPY(665/676) as a radical-sensitive probe combined with oxygen consumption measurements of mixtures of oil-in-water emulsions showed that radicals could be transferred between oil droplets and thereby spread radical-driven oxidation between neighboring droplets.
Asunto(s)
Compuestos de Boro/química , Colorantes Fluorescentes/química , Radicales Libres/química , Aceites/química , Agua/química , Emulsiones/química , Estructura Molecular , Oxidación-Reducción , Espectrometría de FluorescenciaRESUMEN
The antioxidant effects of dried citrus pulp on proteins in lamb meat, when used as a replacement of concentrate in the feed, was studied using meat from 26 male Comisana lambs. The lambs of age 90 days had been grouped randomly to receive one of the three dietary treatments: (1) commercial concentrate with 60% barley (Control, n=8), (2) concentrate with 35% barley and 24% citrus pulp (Cp24, n=9), or (3) concentrate with 23% barley and 35% citrus pulp (Cp35, n=9). Slices from the longissimus thoracis et lomborum muscle were packed aerobically and stored for up to 6days at 4°C in the dark. The citrus pulp groups, Cp24 and Cp35, significantly decreased protein radicals and carbonyls, and preserved more thiols within six days of storage compared to the Control group. The citrus pulp groups significantly slowed down the rate of protein oxidation, indicating that dietary citrus pulp reduced oxidative changes in meat proteins.