Quantitation of furan and methylfuran formed in different precursor systems by proton transfer reaction mass spectrometry

Furan has recently received attention as a possibly hazardous compound occurring in certain thermally processed foods. Previous model studies have revealed three main precursor systems producing furan upon thermal treatment, i.e., ascorbic acid, Maillard precursors, and polyunsaturated lipids. We employed proton transfer reaction mass spectrometry (PTR-MS) as an on-line monitoring technique to study furan formation. Unambiguous identification and quantitation in the headspace was achieved by PTR-MS/gas chromatography-mass spectrometry coupling. Ascorbic acid showed the highest potential to generate furan, followed by glyceryl trilinolenate. Some of the reaction samples generated methylfuran as well, such as Maillard systems containing alanine and threonine as well as lipids based on linolenic acid. The furan yields from ascorbic acid were lowered in an oxygen-free atmosphere (30%) or in the presence of reducing agents (e.g., sulfite, 60%), indicating the important role of oxidation steps in the furan formation pathway. Furthermore, already simple binary mixtures of ascorbic acid and amino acids, sugars, or lipids reduced furan by 50-95%. These data suggest that more complex reaction systems result in much lower furan amounts as compared to the individual precursors, most likely due to competing reaction pathways.     

Factors affecting thermally induced furan formation

Furan, a potential carcinogen, can be induced by heat from sugars, ascorbic acid, and fatty acids. The objective of this research was to investigate the effect of pH, phosphate, temperature, and heating time on furan formation. Heat-induced furan formation from free sugars, ascorbic acid, and linoleic acid was profoundly affected by pH and the presence of phosphate. In general, the presence of phosphate increased furan formation in solutions of sugars and ascorbic acid. In a linoleic acid emulsion, phosphate increased the formation of furan at pH 6 but not at pH 3. When an ascorbic acid solution was heated, higher amounts of furan were produced at pH 3 than at pH 6 regardless of phosphate's presence. However, in linoleic acid emulsion, more furan was produced at pH 6 than at pH 3. The highest amount of furan was formed from the linoleic acid emulsion at pH 6. In fresh apple cider, a product with free sugars as the major components (besides water) and little fatty acids, ascorbic acid, or phosphate, small or very low amounts of furan was formed by heating at 90-120 degrees C for up to 10 min. The results indicated that free sugars may not lead to significant amounts of furan formation under conditions for pasteurization and sterilization. Importantly, this is the first report demonstrating that phosphate (in addition to pH) plays a significant role in thermally induced furan formation.     

Formation of furan from carbohydrates and ascorbic acid following exposure to ionizing radiation and thermal processing

This study was conducted to investigate the formation of furan from sugars, ascorbic acid, and organic acids as affected by ionizing radiation and thermal treatments. Results showed that both thermal treatments and irradiation induced formation of furan from ascorbic acid, fructose, sucrose, or glucose. Little furan was produced from malic acid or citric acid. The pH and concentration of sugars and ascorbic acid solutions had profound influences on furan formation due to either irradiation or thermal treatment. The rate of irradiation-induced furan formation increased with decreasing pH from 8 to 3. Approximately 1600 times less furan was formed at pH 8 as apposed to pH 3. At the same pHs, the amounts of furan formed from irradiation of ascorbic acid, fructose, and sucrose were always higher than from glucose. As pH decreased from 7 to 3, an increase in thermally induced furan was observed for sucrose and ascorbic acid solutions, but for glucose solution, less furan was formed at pH 3 than at pH 7. The levels of sugars commonly found in fruits and fruit juices, upon irradiation, would be high enough to potentially produce low parts per billion (ppb) levels of furan. The concentration of ascorbic acid at which a maximum of furan was produced upon irradiation was about 0.5 mg/mL, a level commonly found in some foods. Five furan derivatives were tentatively identified in thermally treated ascorbic acid solution, while one furan derivative was tentatively found in both irradiated and thermally treated samples.     

Assessment of vitamin and carotenoid concentrations of emerging food products: edible microgreens

Microgreens (seedlings of edible vegetables and herbs) have gained popularity as a new culinary trend over the past few years. Although small in size, microgreens can provide surprisingly intense flavors, vivid colors, and crisp textures and can be served as an edible garnish or a new salad ingredient. However, no scientific data are currently available on the nutritional content of microgreens. The present study was conducted to determine the concentrations of ascorbic acid, carotenoids, phylloquinone, and tocopherols in 25 commercially available microgreens. Results showed that different microgreens provided extremely varying amounts of vitamins and carotenoids. Total ascorbic acid contents ranged from 20.4 to147.0 mg per 100 g fresh weight (FW), while β-carotene, lutein/zeaxanthin, and violaxanthin concentrations ranged from 0.6 to 12.1, 1.3 to 10.1, and 0.9 to 7.7 mg/100 g FW, respectively. Phylloquinone level varied from 0.6 to 4.1 μg/g FW; meanwhile, α-tocopherol and γ-tocopherol ranged from 4.9 to 87.4 and 3.0 to 39.4 mg/100 g FW, respectively. Among the 25 microgreens assayed, red cabbage, cilantro, garnet amaranth, and green daikon radish had the highest concentrations of ascorbic acids, carotenoids, phylloquinone, and tocopherols, respectively. In comparison with nutritional concentrations in mature leaves (USDA National Nutrient Database), the microgreen cotyledon leaves possessed higher nutritional densities. The phytonutrient data may provide a scientific basis for evaluating nutritional values of microgreens and contribute to food composition database. These data also may be used as a reference for health agencies' recommendations and consumers' choices of fresh vegetables.     

Inhibition of citral degradation by oil-in-water nanoemulsions combined with antioxidants

The aim of the present study was to investigate the effects of oil-in-water (O/W) nanoemulsions combined with six different natural antioxidants on the stability of citral. Acidic emulsions (lecithin-stabilized palm kernel lipid in pH 3 buffer) containing 1000 ppm citral and 1000 ppm antioxidants (black tea extract, ascorbic acid, naringenin, tangeretin, β-carotene, and tanshinone) were stored at 25 and 50 °C, respectively. The emulsions with and without antioxidants were analyzed by solid phase microextraction gas chromatography (SPME-GC) to monitor the degradation process of citral and the formation of different off-flavor compounds, such as α,p-dimethylstyrene and p-methylacetophenone. The results suggested that encapsulation of citral in emulsions and the addition of the appropriate antioxidants (β-carotene, tanshinone, and black tea extract) could greatly enhance citral's chemical stability during storage.     

U-HPLC-MS/MS to quantify liposoluble antioxidants in red-ripe tomatoes, grown under different salt stress levels

The growing interest of consumers in healthy food challenges growers to continuously improve the nutritional quality of their crops. In this research, the potential of a more saline growth environment for improved antioxidant concentration in tomato fruit was studied, and an U-HPLC-MS/MS method for the determination of lycopene, β-carotene, and α-tocopherol was optimized. Analytes were thereby separated on a 1.9 μm Hypersil GOLD C(18) column and quantified on a TSQ Vantage triple-quadropole mass spectrometer. The method displayed a short analysis time (6 min), a high specificity, and an excellent repeatability (≤6.39%). Furthermore, it was demonstrated that the electrical conductivity level of the applied nutrient solution did not unambiguously influence antioxidant concentration in tomato fruits. Future research should focus on moderate salt stress only and should aim at reducing natural variation by more closely controlling the growth environment and a more objective determination of the ripening degree.     

Antioxidant and repellent activities of the essential oil from Colombian Triphasia trifolia (Burm. f.) P. Wilson

The chemical composition of essential oils isolated from aerial parts of Triphasia trifolia (Burm. f.) P. Wilson was analyzed using hydrodistillation by GC-MS. The main constituents found were β-pinene (64.36%), (+)-sabinene (8.75%), hexadecanoic acid (6.03%), α-limonene (4.24%) and p-cymene (2.73%). The essential oil from T. trifolia shows high antioxidant potential (94.53%), an effect that is comparable with ascorbic acid (96.40%), used as standard. In addition, these oils had high repellent effects on the insect Tribolium castaneum Herbst (99% ± 1) at 0.2 μL/cm(2) after 2 h of exposure.     

Role of the raw composition of pelagic fish muscle on the development of lipid oxidation and rancidity during storage

The muscle composition of a pelagic fish species, Atlantic mackerel (Scomber scombrus), has been studied to determine the relationship with its susceptibility to develop lipid oxidation during chilled storage. For such an aim, the initial concentrations of the major components (water, total lipids, protein, and PUFAs) and minor pro-oxidant and antioxidant components (ascorbic acid, α-tocopherol, hemoglobin, total iron, LMW-iron, copper, and zinc) of different batches of mackerel were characterized. For the study, several batches of mackerel were caught during the spring and summer periods. The different batches were subjected to chilled storage, and the onset of lipid oxidation was statistically related with the initial muscle composition. Results showed significant compositional differences among the mackerel lots, especially for the muscle lipid content (2.83-9.50%). In a first step, a Pearson correlation test was used to check the influence of each component on the progress of lipid oxidation. Results showed a significant relationship between shelf life and water and total lipid contents. Multiple regression was performed to reveal the contribution of each component to the susceptibility to lipid oxidation. The model obtained combines the content of PUFAs, total iron, hemoglobin, and ascorbic acid. An accurate prediction of shelf life in terms of rancidity was achieved by the model created (R(2) = 0.9975). These results establish that the levels of endogenous pro-oxidants and antioxidants present in fish muscle together with the polyunsaturated lipids are relevant factors affecting the shelf life of mackerel muscle.     

Furan formation in sugar solution and apple cider upon ultraviolet treatment

Furan is a possible human carcinogen induced by thermal processing of food. While ultraviolet C (UVC) is used to decontaminate apple cider and to sterilize sugar solutions, it is unknown whether UVC induces furan formation in cider or solutions of its major components. This study was conducted to investigate the possible formation of furan by UVC in apple cider and in solutions of common constituents of apple cider. Our results showed that UVC treatment induced furan formation in apple cider, and the major source of furan was apparently fructose. UVC treatment (at incident doses up to 9 J/cm (2)) of fructose solutions produced a higher amount of furan, while very low concentrations of furan were induced by UVC in glucose or sucrose solutions, and virtually no furan was induced by UVC from solutions of ascorbic acid or malic acid. When an isotope (d(4)-furan) of furan was treated with UVC, d(4)-furan was destroyed rapidly even at low doses in fructose solution, suggesting that the accumulation of furan is the balance between destruction and formation. The UV sensitivity of E. coli K12 (a surrogate of E. coli O157:H7) in two sources of apple cider was also determined. At UVC doses that could inactivate 5-log of E. coli, very low concentrations (<1 ppb) of furan were induced. Our results suggest that UVC could induce furan formation, but when used for the purpose of juice pasteurization, little furan was induced in apple cider.     

New insights into the role of iron in the promotion of lipid oxidation in bulk oils containing reverse micelles

Formation of physical structures, known as association colloids, in bulk oils can promote lipid oxidation. However, the cause of this accelerated lipid oxidation is unknown. Therefore, the aim of this study was to investigate whether transition metals were important prooxidants in bulk oils containing reverse micelles produced from 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC) and water. The Fe(III) chelator deferoxamine (DFO) increased the oxidative stability of stripped soybean oil (SSO) containing reverse micelles from 2 to 7 days. Because phosphatidylcholine (1,2-dibutyl-sn-glycero-3-phosphocholine) that does not form reverse micelles is not prooxidative, these results suggest that the prooxidant activity of DOPC reverse micelles could be due to their ability to concentrate both endogenous iron and lipid hydroperoxides at the water-lipid interface, thereby increasing the ability of iron to decompose lipid hydroperoxides. DFO was also able to improve the activity of α-tocopherol and Trolox in SSO containing DOPC reverse micelles increasing the lag phase from 2 to 11 and 13 days, respectively. DOPC reverse micelles decreased iron-promoted α-tocopherol and Trolox decomposition and decreased the ability of α-tocopherol and Trolox to decrease Fe(III) concentrations. Overall, these results suggest that iron is an important prooxidant in bulk oils containing reverse micelles; therefore, finding ways to control iron reactivity in association colloids could provide new technologies to increase the oxidative stability of oils.     

Effect of the simultaneous interaction among ascorbic acid, iron and pH on the oxidative stability of oil-in-water emulsions

The objective of this study was to demonstrate how different factors can simultaneously influence the oxidative stability of an oil-in-water emulsion, and how these factors can be used to enlarge the variation range of oxidation markers, expressed as peroxide value (PV) and TBARS. Initially, a Plackett-Burman design was used to screen seven factors (temperature, pH, and iron, copper, ascorbyl palmitate, ascorbic acid, and sodium chloride concentrations). A temperature elevation of 30 to 60 °C reduced PV and TBARS, a pH change from 3.0 to 7.0 increased PV and reduced TBARS, and the presence of ascorbic acid (1 mmol/L) had no significant effect on PV but increased TBARS (p < 0.05). Thus, the temperature was fixed at 30 °C, and an emulsion was formulated with different combinations of ascorbic acid, iron, and pH according to a central composite rotatable design. Regression models were fitted to PV and TBARs responses and optimized to get the higher values of both markers of oxidation. The optimized emulsion contained 1.70 mmol/L AH (ascorbic acid) and 0.885 mmol/L FeSO(4) · 7H(2)O (1.0 mmol/L Fe(2+)) at pH 5.51 and 30 °C. The range of variation observed for oxidation markers in the optimized emulsion model (PV, 0-4.27 mequiv/L; TBARS, 0-13.55 mmol/L) was larger than the variation observed in the nonoptimized model (PV, 0-1.05 mequiv/L; TBARS, 0-1.00 mmol/L). The antioxidant activity of six compounds (Trolox, α-tocopherol, caffeic acid, gallic acid, catechin, and TBHQ) was evaluated using the optimized emulsion conditions. After application of the Tukey HSD post hoc statistical test, the samples that were not different (p < 0.05) in the nonoptimized emulsions showed a significant difference in the optimized emulsions. Considering the importance of the interactions on oxidation studies, our model represents a significant improvement in a direct methodology that can be applied to evaluate natural compounds under different combination of factors.     

Identification and thermal degradation kinetics of chlorophyll pigments and ascorbic acid from ditax nectar (Detarium senegalense J.F. Gmel)

Detarium senegalense J.F. Gmel (ditax) is a forest tree found in Senegal the fruits of which are characterized by an attractive green flesh with a high amount in ascorbic acid. It is generally consumed as a nectar in Senegal. In this study, the main pigments of ditax pulp were identified and quantified by HPLC-DAD. Pheophytin a (128 mg/kg), which represents 58% of the total pigments, followed by hydroxypheophytin a' (33 mg/kg), chlorophyll b (24 mg/kg), and chlorophyll a (20 mg/kg) was the major pigment of ditax pulp. Lutein and β-carotene were present in lower amounts (4.6 and 3.6 mg/kg, respectively). The thermal degradation kinetics of pheophytin a, hydroxypheophytin a', and ascorbic acid were determined at temperatures ranging from 60 to 95 °C in ditax nectar. Pheophytin a was the most heat sensitive. Thermal processing induced the formation of degradation products such as pyropheophytin a and pyropheophytin b. The kinetics parameters have been calculated according to the models of Arrhenius, Eyring, and Ball. Following the Arrhenius relation, activation energies of pheophytin a, hydroxypheophytin a', and ascorbic acid were, respectively, 79, 74, and 46 kJ mol(-1). Losses calculated during isothermal treatments were close to experimental losses in pheophytin a, hydroxypheophytin a', and ascorbic acid. The Eyring model can then be used to predict chlorophyll pigments and vitamin C losses during pasteurization of the nectar (<10%).     

Carotene and novel apocarotenoid concentrations in orange-fleshed Cucumis melo melons: determinations of β-carotene bioaccessibility and bioavailability

Muskmelons, both cantaloupe (Cucumis melo Reticulatus Group) and orange-fleshed honeydew (C. melo Inodorus Group), a cross between orange-fleshed cantaloupe and green-fleshed honeydew, are excellent sources of β-carotene. Although β-carotene from melon is an important dietary antioxidant and precursor of vitamin A, its bioaccessibility/bioavailability is unknown. We compared β-carotene concentrations from previously frozen orange-fleshed honeydew and cantaloupe melons grown under the same glasshouse conditions, and from freshly harvested field-grown, orange-fleshed honeydew melon to determine β-carotene bioaccessibility/bioavailability, concentrations of novel β-apocarotenals, and chromoplast structure of orange-fleshed honeydew melon. β-Carotene and β-apocarotenal concentrations were determined by HPLC and/or HPLC-MS, β-carotene bioaccessibility/bioavailability was determined by in vitro digestion and Caco-2 cell uptake, and chromoplast structure was determined by electron microscopy. The average β-carotene concentrations (μg/g dry weight) for the orange-fleshed honeydew and cantaloupe were 242.8 and 176.3 respectively. The average dry weights per gram of wet weight of orange-fleshed honeydew and cantaloupe were 0.094 g and 0.071 g, respectively. The bioaccessibility of field-grown orange-fleshed honeydew melons was determined to be 3.2 ± 0.3%, bioavailability in Caco-2 cells was about 11%, and chromoplast structure from orange-fleshed honeydew melons was globular (as opposed to crystalline) in nature. We detected β-apo-8'-, β-apo-10', β-apo-12'-, and β-apo-14'-carotenals and β-apo-13-carotenone in orange-fleshed melons (at a level of 1-2% of total β-carotene). Orange-fleshed honeydew melon fruit had higher amounts of β-carotene than cantaloupe. The bioaccessibility/bioavailability of β-carotene from orange-fleshed melons was comparable to that from carrot (Daucus carota).     

Fortifying Bread with Each of Three Antioxidants

White bread was fortified individually with fat-coated l -ascorbic acid (AsA), cold-water-dispersible (CWD) β-carotene, and CWD all-rac-α-tocopheryl acetate (ToAc) at levels of 64, 5, and 100 mg, respectively, of active ingredient per 100 g of flour (14% mb). The freshly baked puploaves retained 76, 67, and 96% of added antioxidant, respectively. To extract ToAc quantitatively from bread or dough, dimethyl sulfoxide (DMSO) gave better results than hexane, which indicated that ToAc was in a partially bound state. “Protein-encased” (PE) β-carotene did not impart a yellow color to bread crumb and had one-fourth higher retention in fresh bread when compared to CWD β-carotene. In loaves stored at 25°C for one to seven days, AsA disappeared rapidly and PE β-carotene disappeared slowly; CWD β-carotene and ToAc were stable. In spite of storage loss, bread fortified with PE β-carotene retained significantly higher levels of β-carotene when compared to CWD β-carotene. One serving size (one slice, 28 g) of three-day-old bread fortified with one of the three antioxidants was calculated to provide 7, 120–150, and 13–16%, respectively, of the adult recommended daily allowances (RDA) for vitamins C, E, and A. When bread was fortified with both fat-coated AsA and CWD β-carotene and stored for five days, no protecting effect on the retention of the antioxidants was found.     

Flavonoids with potent antioxidant activity found in young green barley leaves

Saponarin, a flavonoid found in young green barley leaves, possesses potent antioxidant activities, which are determined by its inhibition of malonaldehyde (MA) formation from various lipids oxidized by UV light or Fenton's reagent. Lipids used were squalene, ethyl linoleate, ethyl linolenate, ethyl arachidonate, octadecatetraenoic acid (ODTA), eicosapentaenoic acid (EPA), docosahexaenoic acid (DHA), cod liver oil, lecithin I, lecithin II, and blood plasma. The addition of saponarin inhibited the formation of MA from squalene upon UV irradiation at the level of 2 μmol/mL by almost 100%, whereas BHT inhibited its formation by 75% at the same level. Saponarin showed potent antioxidant activity toward fatty acid ethyl esters at levels >100 μg/mL. Saponarin inhibited MA formation in ODTA by 60%, in EPA by 50%, and in DHA by 43% at the level of 15 μmol/mL. Saponarin exhibited strong antioxidant activities with dose-response levels toward cod liver oil and lipoproteins (lecithins I and II), higher than those of α-tocopherol. A mixture of saponarin/lutonarin (4.5:1, w/w) inhibited MA formation appreciably from all lipids tested with dose response. This mixture exhibited highest effect toward cod liver oil (86%), followed by DHA, lecithin II, blood plasma, EPA, and lecithin I. Supplementation of young green barley leaves containing saponarin should be beneficial to health and may prevent diseases caused by oxidative damage such as various cancers, inflammations, and cardiovascular diseases.     

Isoprenoid, lipid, and protein contents in intact plastids isolated from mesocarp cells of traditional and high-pigment tomato cultivars at different ripening stages

This study reports quali-quantitative analyses on isoprenoids, phospholipids, neutral lipids, phytosterols, and proteins in purified plastids isolated from fresh fruits of traditional (Donald and Incas) and high-pigment (Kalvert and HLY-18) tomato cultivars at four ripening stages. In all of the investigated cultivars, lycopene, β-catotene, lutein, and total carotenoids varied significantly during ripening. Chromoplasts of red-ripe tomato fruits of high-pigment cultivars accumulated twice as much as lycopene (307.6 and 319.2 μg/mg of plastid proteins in Kalvert and HLY-18, respectively) than ordinary cultivars (178.6 and 151.7 μg/mg of plastid proteins in Donald and Incas, respectively); differences in chlorophyll and α-tocopherol contents were also evidenced. Phospholipids and phytosterols increased during ripening, whereas triglycerides showed a general decrease. Regardless of the stage of ripening, palmitic acid was the major fatty acid in all cultivars (ranging from 35 to 52% of the total fatty acids), followed by stearic, oleic, linoleic, linolenic, and myristic acids, but their relative percentage was affected by ripening. Most of the bands detected on the SDS-PAGEs of plastid proteins were constantly present during chloroplast-to-chromoplast conversion, some others disappeared, and only one, with a molecular weight of ~41.6 kDa, was found to increase in intensity.     

Bioaccessibility of tocopherols, carotenoids, and ascorbic acid from milk- and soy-based fruit beverages: influence of food matrix and processing

A study was made of the effect of high-pressure processing (HPP) and thermal treatment (TT) on plant bioactive compounds (tocopherols, carotenoids, and ascorbic acid) in 12 fruit juice-milk beverages and of how the food matrix [whole milk (JW), skimmed milk (JS), and soy milk (JSy)] modulates their bioaccessibility (%). HPP (400 MPa/40 °C/5 min) produced a significant decrease in carotenoid and ascorbic acid bioaccessibility in all three beverages and maintained the bioaccessibility of tocopherols in JW and JS while decreasing it in JSy. TT (90 °C/30 s) produced a significant decrease in tocopherol and carotenoid bioaccessibility in all three beverages and increased the bioaccessibility of ascorbic acid. With regard to the food matrix, α-tocopherol and ascorbic acid bioaccessibility was greatest in JW beverages and lowest in JSy beverages, whereas no significant differences were found among the three beverages in terms of carotenoid bioaccessibility. HPP-treated samples showed higher tocopherol and carotenoid bioaccessibility than TT-treated samples, thus indicating that HPP combined with a milk matrix positively modulates the bioaccessibility of certain types of bioactive components of food, mainly those of a lipophilic nature.     

Enhancement of plant essential oils' aqueous solubility and stability using alpha and beta cyclodextrin

Sodium benzoate has been shown to produce benzene in combination with ascorbic acid. This has led to research for safe alternatives from plant essential oils and parabens that have shown some antimicrobial activity, but many of these compounds exhibit poor solubility in aqueous solutions. Cyclodextrins can increase the solubility of many compounds. This work aimed to investigate the solubility of 23 plant essential oils and 4 parabens in water and an apple juice medium. Four of these compounds were chosen for their low aqueous solubility to determine if complexing the compound with α- and β-cyclodextrin would increase solubility. Three of the complexes were dissolved in an acidified aqueous solution and then studied in glass and polyethylene terephthalate (PET) to determine if storage material would affect the stability. Solubility of the 27 compounds in distilled water ranged from 1.6 mg/L to 2460.6 mg/L and the solubility of 18 of the compounds decreased from 2.5 to 84.7% in apple juice medium (pH = 3.4, 12-13 °Brix). Complexation with cyclodextrin dramatically increased the solubility of the compounds, up to 10-fold. Packaging material had no effect on concentration of compounds present over 7 days. Cyclodextrins were able to increase solubility of these compounds to more suitable concentrations, and may lead to viable natural alternatives to sodium benzoate.     

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.     

Origin and mechanistic pathways of formation of the parent furan--a food toxicant

Studies performed on model systems using pyrolysis-GC-MS analysis and (13)C-labeled sugars and amino acids in addition to ascorbic acid have indicated that certain amino acids such as serine and cysteine can degrade and produce acetaldehyde and glycolaldehyde that can undergo aldol condensation to produce furan after cyclization and dehydration steps. Other amino acids such as aspartic acid, threonine, and alpha-alanine can degrade and produce only acetaldehyde and thus need sugars as a source of glycolaldehyde to generate furan. On the other hand, monosaccharides are also known to undergo degradation to produce both acetaldehyde and glycolaldehyde; however, (13)C-labeling studies have revealed that hexoses in general will mainly degrade into the following aldotetrose derivatives to produce the parent furan-aldotetrose itself, incorporating the C3-C4-C5-C6 carbon chain of glucose (70%); 2-deoxy-3-ketoaldotetrose; incorporating the C1-C2-C3-C4 carbon chain of glucose (15%); and 2-deoxyaldotetrose, incorporating the C2-C3-C4-C5 carbon chain of glucose (15%). Furthermore, it was also proposed that under nonoxidative conditions of pyrolysis, ascorbic acid can generate the 2-deoxyaldotetrose moiety, a direct precursor of the parent furan. In addition, 4-hydroxy-2-butenal-a known decomposition product of lipid peroxidation-was proposed as a precursor of furan originating from polyunsaturated fatty acids. Among the model systems studied, ascorbic acid had the highest potential to produce furan, followed by glycolaldehyde/alanine > erythrose > ribose/serine > sucrose/serine > fructose/serine > glucose/cysteine.