Lipid peroxidation by "free" iron ions and myoglobin as affected by dietary antioxidants in simulated gastric fluids.

Grilled red turkey muscle (Doner Kabab) is a real "fast food" containing approximately 200 microM hydroperoxides, homogenized in simulated gastric fluid and oxidized more rapidly at pH 3.0 than at pH 5.0, after 180 min, producing 1200 and 600 microM hydroperoxides, respectively. The effects of "free" iron ions and metmyoglobin, two potential catalyzers of lipid peroxidation in muscle foods, were evaluated for linoleic acid peroxidation at pH 3.0 of simulated gastric fluid. The prooxidant effects of free iron ions on linoleic acid peroxidation in simulated gastric fluid was evaluated in the presence of ascorbic acid. At low concentrations of ascorbic acid, the effects were prooxidative, which was reversed at high concentrations. In the presence of metmyoglobin, ascorbic acid with or without free iron enhanced the antioxidative effect. Lipid peroxidation by an iron-ascorbic acid system was inhibited totally by 250-500 microM catechin at pH 3.0. The catechin antioxidant effect was determined also in the iron-ascorbic acid system containing metmyoglobin. In this system, catechin totally inhibited lipid peroxidation at a concentration 20-fold lower than without metmyoglobin. The ability of catechin to inhibit lipid peroxidation was also determined at a low pH with beta-carotene as a sensitive target molecule for oxidation. The results show that a significant protection was achieved only with almost 100-fold higher antioxidant concentration. Polyphenols from different groups were determined for the antioxidant activity at pH 3.0. The results show a high antioxidant activity of polyphenols with orthodihydroxylated groups at the B ring, unsaturation, and the presence of a 4-oxo group in the heterocyclic ring, as demonstrated by quercetin.

Lipid hydroperoxidase activity of myoglobin and phenolic antioxidants in simulated gastric fluid.

Our recent study demonstrated the potential of gastric fluid at pH 3.0 to accelerate lipid peroxidation and cooxidation of dietary constituents in the stomach medium. Metmyoglobin is known to catalyze the breakdown of lipid hydroperoxides to free radicals, a reaction that could enhance the propagation step and general lipid peroxidation. During this reaction, a part of the free radicals is autoreduced by metmyoglobin. At pH 3.0, metmyoglobin at low concentration was almost 7 x 10(4) times as effective as at pH 7.0 in enhancing the rate of lipid peroxidation. Our study demonstrated that metmyoglobin, at a low concentration (approximately 1:30), as compared with that of the hydroperoxides in the lipid system, worked prooxidatively increasing the amounts of linoleate hydroperoxides. However, at a high concentration (approximately 1:3), metmyoglobin acted antioxidatively and decomposed hydroperoxides, whose concentrations then remained at zero for a long time. Catechin, a known polyphenol, supports the inversion of metmyoglobin catalysis, from prooxidation to antioxidation. The antioxidative activity of the couple metmyoglobin-catechin was better at pH 3.0 than at pH 7.0, indicating that this reaction is more dependent on metmyoglobin than on catechin. During this reaction, catechin or quercetin not only donates reducing equivalents to prevent lipid peroxidation but also prevents the destruction and polymerization of metmyoglobin. The results of this research highlighted the important and possible reactions of heme proteins and polyphenols as couple antioxidants, working as hydroperoxidases or as pseudo-peroxidases. We hypothesize that the occurrence of these reactions in the stomach could have an important impact on our health and might help to better explain the health benefits of including foods rich in polyphenol antioxidants in the meal, especially when consuming red meat.

Lipid peroxidation and coupled vitamin oxidation in simulated and human gastric fluid inhibited by dietary polyphenols: health implications.

The Western diet contains large quantities of oxidized lipids, because a large proportion of the food in the diet is consumed in a fried, heated, processed, or stored form. We investigated the reaction that could occur in the acidic pH of the stomach and accelerate the generation of lipid hydroperoxides and cooxidation of dietary vitamins. To estimate the oxygen content in the stomach after food consumption, oxygen released from masticated bread (20 g) into deoxygenated water (100 mL) was measured. Under these conditions, the oxygen concentration rose by 250 microM and reached a full oxygen saturation. The present study demonstrated that heated red meat homogenized in human gastric fluid, at pH 3.0, generated hydroperoxides and malondialdehyde. The cross-reaction between free radicals produced during this reaction cooxidized vitamin E, beta-carotene, and vitamin C. Both lipid peroxidation and cooxidation of vitamin E and beta-carotene were inhibited at pH 3.0 by red wine polyphenols. Ascorbic acid (44 mg) at a concentration that represented the amount that could be ingested during a meal inhibited lipid peroxidation only slightly. Red wine polyphenols failed to prevent ascorbic acid oxidation significantly but, in conjunction with ascorbic acid, did inhibit lipid peroxidation. In the presence of catechin, a well-known polyphenol found in red wine, ascorbic acid at pH 3.0 works in a synergistic manner preventing lipid peroxidation and beta-carotene cooxidation. The present data may explain the major benefits to our health and the crucial role of consuming food products rich in dietary antioxidants such as fruits, vegetables, red wines, or green tea during the meal.

Development of polysaccharides-based edible coatings for citrus fruits: a layer-by-layer approach.

Biodegradable coatings for citrus fruits that would replace the currently used polyethylene-based waxes, are of great interest. Methylcellulose (MC), hydroxypropyl methylcellulose (HPMC), carboxymethyl cellulose (CMC) and chitosan (CH) coatings were examined on the most sensitive citrus fruit model: mandarins. Among the examined polysaccharides, CMC provided mandarins with the best firmness, lowest weight loss and satisfying gloss, while not affecting natural flavour and the respiration process. To enhance coating performance, glycerol, oleic acid and stearic acid were added; however, mandarin quality generally deteriorated with these additives. Then, a layer-by-layer (LBL) approach was applied. LbL coatings, based on a combination of two polysaccharides, CMC as an internal layer and chitosan as an external layer, gave the best performance. Different concentrations of chitosan were examined. The LbL coatings notably improved all quantified parameters of fruit quality, proving that polysaccharide-based edible coating may offer an alternative to synthetic waxes.

Durable contact active antimicrobial materials formed by a one-step covalent modification of polyvinyl alcohol, cellulose and glass surfaces.

In this work we have applied a direct covalent linkage of quaternary ammonium salts (QAS) to prepare a series of contact active antimicrobial surfaces based on widely utilized materials. Formation of antimicrobial polyvinyl alcohol (PVA-QAS), cellulose (cellulose-QAS) and glass (glass-QAS) surfaces was achieved by one step synthesis with no auxiliary linkers. The X-ray photoelectron spectroscopy (XPS) revealed tridentate binding mode of the antimicrobial agent. The antimicrobial activity of the prepared materials was tested on Bacillus cereus, Alicyclobacillus acidoterrestris, Escherichia coli and Pseudomonas aeruginosa. Active site density of the modified materials was examined and found to correlate with their antimicrobial activity. Stability studies at different pH values and temperatures confirmed that the linkage of the bioactive moiety to the surface is robust and resistant to a range of pH and temperatures. Prolonged long-term effectiveness of the contact active materials was demonstrated by their repeated usage, without loss of the antimicrobial efficacy.