Effects of olive, canola, and sunflower oils on the formation of volatiles from the Maillard reaction of lysine with xylose and glucose

Some important edible oils (extra virgin olive oil, canola oil, and sunflower oil) were added to aqueous glucose-lysine or xylose-lysine model systems to investigate their effect on the formation of volatiles from the Maillard reaction (MR). The volatile compounds were extracted by a Likens-Nickerson apparatus and quantified. Pyrazines, Maillard reaction products with an important impact on food flavor, appeared to be particularly sensitive to the presence of the oils in both the xylose-lysine and glucose-lysine model systems. The unsubstituted pyrazine was formed more with olive oil, less with canola oil, and even less with sunflower oil, whereas 2-methylpyrazine, 2,5-methylpyrazine, and 2,3-dimethylpyrazine were formed less with olive oil, more with canola oil, and even more with sunflower. The oxidative states of the oils and their fatty acid fingerprints were determined: the results indicated that the relative amounts of the pyrazines are sensitive to the degree of unsaturation of the oil. The autoxidation of the volatile compounds generated from the MR, investigated by the addition of free radical modulators (antioxidants alpha-tocopherol, 2,6-di-tert-butyl-4-methylphenol, and rosemary extract; or pro-oxidant alpha,alpha'-azobis-isobutyronitrile, a free radical initiator), was limited in respect to aqueous model systems.     

Effect of copper on the volatility of aroma compounds in a model mouth system

Copper is thought to influence aroma perception by affecting volatility of aroma compounds in the mouth through interaction with salivary components, especially proteins. Our objective was to identify the effect of copper on the volatility of aroma compounds and the role of copper-protein interaction in volatile chemistry in the mouth. Copper (2.5 mg/L) and four aroma compounds (hexanal, butyl acetate, 2-heptanone, and ethyl hexanoate, 0.5 microL/L each) were added to model systems containing water, electrolytes, and artificial saliva at different pH levels. Headspace concentration of each volatile was measured using SPME-GC analysis. Copper in the model systems increased headspace concentration of volatiles at pH 6.5, but no change in volatility was observed at pH 7.0. At pH 7.5, the presence of copper in the artificial saliva system containing mucin and alpha-amylase decreased headspace volatile concentration, whereas histatin did not cause any changes in volatility. Effect of copper on volatiles at pH 6.5 may be due to increased solubility of copper at lower pH. Salivary proteins seem to interact with copper at pH 7.5. The interaction may change configuration of binding sites for aroma compounds in mucin.     

Biotransformation and pharmacokinetics of 4-(3,4-dihydroxybenzoyloxymethyl)phenyl-O-beta-D-glucopyranoside, an antioxidant isolated from Origanum vulgare

4-(3,4-Dihydroxybenzoyloxymethyl)phenyl- O-beta-D-glucopyranoside (OV-16) is a polyphenolic glycoside isolated from oregano (Origanum vulgare L.), which is a popular Chinese herb and a common spice in Western diet. To understand the biotransformation and pharmacokinetics of OV-16, rats were orally administered OV-16 and oregano decoction. Blood samples were withdrawn at specific time points. The presence of OV-16 and its metabolites protocatechuic acid (PCA) and p-hydroxybenzyl alcohol (HBA) in serum were determined by HPLC method, whereas their conjugated metabolites were assayed indirectly through hydrolysis with beta-glucuronidase and sulfatase. Our results showed that when OV-16 was orally administered, free forms of OV-16, PCA, and HBA were not present in blood and the major metabolites were the glucuronides/sulfates of PCA and HBA sulfate. The serum metabolites of OV-16 exhibited free radical scavenging activity. When oregano decoction was given, the glucuronides and sulfates of PCA were the major metabolites in blood.     

Effect of pH, temperature, and moisture on the formation of volatile compounds in glycine/glucose model systems

Mixtures of glycine, glucose, and starch were extrusion cooked using sodium hydroxide at 0, 3, and 6 g/L of extruder water feed, 18% moisture, and 120, 150, and 180 degrees C target die temperatures, giving extrudates with pH values of 5.6, 6.8, and 7.4. Freeze-dried equimolar solutions of glucose and glycine were heated either dry or after equilibration to approximately 13% moisture at 180 degrees C in a reaction-tube system designed to mimic the heating profile in an extruder. Volatile compounds were isolated onto Tenax and analyzed by gas chromatography-mass spectrometry. For the extrudates, total yields of volatiles increased with decreasing pH at 180 degrees C, reached a maximum at pH 6.8 at 150 degrees C, and increased with increasing pH at 120 degrees C. Amounts increased with temperature at all pH values. Pyrazines were the most abundant class for all sets of conditions (54-79% of total volatiles). Pyrroles, ketones, furans, oxazoles, and pyridines were also identified. Yields of volatiles from the reaction-tube samples increased by >60% in the moist system. Levels of individual classes also increased in the presence of moisture, except pyrazines, which decreased approximately 3.5-fold. Twenty-one of the compounds were common to the reaction-tube samples and the extrudates.     

Temperature and pH effect on the microbial reductive transformation of pentachloronitrobenzene

The effect of pH and temperature on the microbial reductive transformation of pentachloronitrobenzene (PCNB), an organochlorine fungicide, was investigated with a mixed fermentative/methanogenic culture developed from a contaminated estuarine sediment. Culture series were incubated at a temperature range from 4 to 45 degrees C at pH 6.9+/-0.1 and at a pH range from 2.7+/-0.1 to 7.6+/-0.1 at 22 degrees C. Significant differences were observed in terms of biotransformation rate, extent, and products as a function of temperature. Incubation at different pH values resulted in differences in biotransformation rate and extent, but not in terms of products formed. PCNB (3 microM) was transformed to pentachloroaniline (PCA) in all culture series. However, sequential dechlorination of PCA was observed only at a temperature range from 4 to 35 degrees C and at a pH range from 6.2+/-0.1 to 7.6+/-0.1. The highest PCA dechlorination rate was observed at 22 degrees C and at pH 7.6+/-0.1. The effect of temperature on the PCA dechlorination rate was modeled using an Arrhenius relationship, which accounts for both enzyme activation and deactivation. The dechlorination of PCA and chlorinated aniline intermediates was simulated using a branched-chain Michaelis-Menten model, and kinetic constants were determined.     

Effect of bread baking on the bioavailability of hydrogen-reduced iron powder added to unenriched refined wheat flour

Elemental iron powders are widely used to fortify flour and other cereal products. Our objective was to test the hypothesis that baking enhances the bioavailability of elemental iron powders by oxidizing Fe(0) to Fe(2+) or Fe(3+). An in vitro digestion/Caco-2 cell culture model and a piglet model were used to measure bioavailability. Bread flour, either unfortified or fortified with hydrogen-reduced (HR) iron powder or FeSO(4) (300 mg Fe/kg flour), was baked into bread. For the in vitro studies, bread samples were treated with pepsin at pH 2, 3, 4, 5, 6, or 7 and subsequently incubated with pancreatic enzymes at pH 7 in a chamber positioned above monolayers of cultured Caco-2 cells. Ferritin formation in the cells was used as an index of iron bioavailability. Ferritin formation in cells fed HR Fe bread was similar to cells fed FeSO(4) bread when the peptic digestion was conducted at a pH 2 but lower when the peptic phase was conducted at pH 3, 4, 5, 6, or 7 (P < 0.05). Pig diets containing 35% dried bread were prepared and fed to cross-bred (Hampshire x Landrace x Yorkshire) anemic pigs in two studies. The rate of increase in hemoglobin Fe over the feeding period was used to calculate relative biological value (RBV), an index of iron bioavailability. In the first pig study, RBV of HR Fe added to flour prior to baking was 47.9% when compared to FeSO(4) fortified flour (P < 0.05). In the second pig study, a third treatment consisting of unfortified bread with HR iron added during diet mixing (after bread baking) was included. RBVs of the HR Fe diet (Fe added after baking) and HR Fe diet (Fe added before baking) were 40.1% and 53.5%, respectively, compared to the FeSO(4) diet. Differences in RBV between the HR Fe (before and after baking) and FeSO(4) (before baking) treatment groups were significant, but the difference between the before and after HR treatment groups was not significant. We conclude that bread baking does not enhance the bioavailability of elemental iron powders.     

Use of an autosampler for dynamic headspace extraction of volatile compounds from grains and effect of added water on the extraction.

An autosampler attached to a purge and trap instrument was used to aid routine analyses of grain samples for volatile compounds associated with off-odors. Trapped volatiles were transferred to a gas chromatograph/mass spectrometer instrument for separation and detection. Dynamic extraction of volatiles from approximately 18 g of whole grain at 80 degrees C was accomplished by purging helium through a sample vial with a Teflon-lined septum on each end. The autosampler automatically added internal standard to the sample before purging began, which required the addition of 1 mL of water for complete transfer of the standard to the sample. The added water enhanced extraction of 1-octen-3-ol, 1-octen-3-one, and some other compounds from soybeans but not from starchy grains such as corn and wheat. Addition of a free radical scavenger, such as citric acid, greatly diminished the recovery of 1-octen-3-ol and 1-octen-3-one from soybeans.     

Aroma composition of Vitis vinifera Cv. tannat: the typical red wine from Uruguay

The free volatiles, as well as those released from the glycosidically bound forms by enzyme hydrolysis, have been analyzed to chracterize young Tannat wines from two successive vintages. The Tannat wine showed some aroma profile peculiarities detected in the free forms but, above all, in the bound fraction for the level and profile of the norisoprenoidic fraction. Among the free volatile compunds, a rather low content of C(6) alcohols with a prevalence of cis-3-hexen-1-ol on the trans form and sometimes a remarkable level of trans-2-hexen-1-ol seem to be typical for the variety. C(13)-norisoprenoidic and monoterpenic volatiles made up approximately 42% of the total level of the volatiles observed in the glycosidase enzyme-released fraction. The other volatiles were C(6) alcohols (6%) and benzenoid compounds (51%). The dominating monoterpene alcohols were the cis and trans isomers of 3,7-dimethyl-1,6-octadiene-3,8-diol (8-hydroxylinalool). The C(13)-norisoprenoid pattern was composed by 3-hydroxy-beta-damascone, 3-oxo-alpha-ionol, vomifoliol, 4-oxo-beta-ionol, 3-oxo-7,8-dihydro-alpha-ionol, 4-oxo-7,8-dihydro-beta-ionol, grasshopper ketone, and 7,8-dihydrovomifoliol.     

Effect of milk protein concentrate on lipid oxidation and formation of fishy volatiles in herring mince (Clupea harengus) during frozen storage

The effect of milk protein concentrate (MPC) at 0, 2, 4, and 6% on lipid oxidation and volatile formation in frozen stored herring mince (-18 degrees C) was evaluated by analyzing samples at 0, 2, and 4 months for fatty acid composition, volatiles, and thiobarbituric acid reactive substances (TBARS). Sensory evaluation was also conducted to assess the intensity of fishy odor, and the volatiles were analyzed using static headspace gas chromatography-mass spectrometry (SHGC-MS). The addition of 4 and 6% MPC to herring mince resulted in a 33% and 50% reduction of TBARS, respectively, at month 4 and lessened the intensity of fishy odor throughout storage. However, MPC did not protect fatty acids from enzymatic degradation unless it was added immediately after mincing. Volatile analysis using SHGC-MS showed that 4% MPC was able to reduce headspace volatiles associated with fishy odor. MPC is most effective for reducing 4-heptenal, 3-methyl-1-butanol, 2-hexenal, and 1-penten-3-ol, which are known to be potent odorants associated with lipid oxidation.     

Fabrication and optimization of a conducting polymer sensor array using stored grain model volatiles

During storage, grain can experience significant degradation in quality due to a variety of physical, chemical, and biological interactions. Most commonly, these losses are associated with insects or fungi. Continuous monitoring and an ability to differentiate between sources of spoilage are critical for rapid and effective intervention to minimize deterioration or losses. Therefore, there is a keen interest in developing a straightforward, cost-effective, and efficient method for monitoring of stored grain. Sensor arrays are currently used for classifying liquors, perfumes, and the quality of food products by mimicking the mammalian olfactory system. The use of this technology for monitoring of stored grain and identification of the source of spoilage is a new application, which has the potential for broad impact. The main focus of the work described herein is on the fabrication and optimization of a carbon black (CB) polymer sensor array to monitor stored grain model volatiles associated with insect secretions (benzene derivatives) and fungi (aliphatic hydrocarbon derivatives). Various methods of statistical analysis (RSD, PCA, LDA, t test) were used to select polymers for the array that were optimum for distinguishing between important compound classes (quinones, alcohols) and to minimize the sensitivity for other parameters such as humidity. The performance of the developed sensor array was satisfactory to demonstrate identification and separation of stored grain model volatiles at ambient conditions.     

Evening primrose meal: a source of natural antioxidants and scavenger of hydrogen peroxide and oxygen-derived free radicals.

Evening primrose meal (EPM: 1% and 2%, w/w) reduced (p 相似文献   

Effect of pH on the Maillard reaction of [13C5]xylose, cysteine, and thiamin

The influence of different pH values, ranging from 4.0 to 7.0, on the formation of sulfur volatiles in the Maillard reaction was studied using a model system with [13C5]xylose, cysteine, and thiamin. The use of 13C-labeled xylose allowed, by analysis of the mass spectra, volatiles that incorporated xylose carbons in the molecule from other carbon sources to be discerned. For 2-furaldehyde and 2-furfurylthiol, which were favored at low pH, the labeling experiments clearly indicated that xylose was the exclusive carbon source. On the other hand, xylose was virtually not involved in the formation of 3-mercapto-2-butanone, 4,5-dihydro-2-methyl-3-furanthiol, and 5-(2-hydroxyethyl)-4-methylthiazole, which apparently stemmed from thiamin degradation. Both xylose and thiamin seemed to significantly contribute to the formation of 2-methyl-3-furanthiol, 3-mercapto-2-pentanone, and 2-mercapto-3-pentanone, and therefore different formation pathways must exist for each of these molecules. In general, the pH determined strongly which volatiles were formed, and to what extent. However, the relative contribution of xylose to the C-skeleton of a particular compound changed only slightly within the investigated pH range, when both xylose and thiamin were involved in the formation.     

Comparison of fast gas chomatography-surface acoustic wave (FGC-SAW) detection and GC-MS for characterizing blueberry cultivars and maturity

A novel analytical method using fast gas chromatography-surface acoustic wave detection (FGC-SAW) was employed to rapidly characterize blueberry volatile profiles according to genotypes and fruit maturity. Fourteen FGC-SAW peaks were observed and 11 peaks were tentatively identified in the 15 s chromatogram. Peak identifications were confirmed by matching retention index values with similar values from GC-MS analyses of the same samples. Eighty peaks were observed in the 40 min GC-MS analysis of identical samples. Principal component analysis (PCA) score plots of FGC-SAW and GC-MS data both differentiated blueberries according to genotype, maturity stage, and harvest date even though FGC-SAW PCA's used far fewer peak area values. PCA plots clearly separated 'FL02-40', 'Snowchaser', 'Jewel', and 'Primadonna' blueberry cultivars into four quarters using two-dimensional PCA projections. FGC-SAW was also successful in differentiating three berry maturity stages in PCA score plots for both 'Jewel' and 'Primadonna' cultivars. FGC-SAW is an effective technique for rapid analysis of major blueberry volatiles, but could not determine many mid- and low-level volatiles as they were often coeluted with higher concentration volatiles.     

Black Sesame Pigment: DPPH Assay-Guided Purification, Antioxidant/Antinitrosating Properties, and Identification of a Degradative Structural Marker

An improved purification procedure leading to black sesame ( Sesamum Indicum L.) pigment was developed involving fat removal by treatment of ground black sesame seeds with dichloromethane followed by an optimized hydrolytic protocol with 6 M HCl, at 100 °C, overnight. The black pigment thus obtained displayed good antioxidant efficiency by the 2,2-diphenyl-1-picrylhydrazyl (DPPH) radical assay (82% reduction at 0.5 mg/mL), good ferric ion-reducing capacity (61 μM Trolox equivalent concentration at 0.5 mg/mL), and potent antinitrosating properties (74% inhibition of 2,3-diaminonaphthalene (DAN) nitrosation at gastric pH at 2.5 mg/mL). A synthetic pigment obtained by oxidative polymerization of coniferyl alcohol (polyconiferyl alcohol, PCA), the putative biosynthetic precursor to the sesame pigment, was characterized as a reference standard. FT IR spectra of the purified sesame pigment and PCA supported the structural similarity. HPLC analysis of degradation products by alkaline hydrogen peroxide of purified black sesame pigment showed the formation of vanillic acid (VA) as the main isolable fragment. Similar yields of VA were obtained by degradation of PCA. A positive correlation between VA yields and DPPH activity was determined in samples of different purities. It is suggested that VA is a structural marker of black sesame pigment, confirming the biosynthetic origin from coniferyl alcohol and pointing to the o-methoxyphenol motif as the key factor accounting for the potent antioxidant properties of the pigment.     

Detection of free radical transfer in lipoxygenase I-B-catalyzed linoleic acid-soybean protein interaction by electron spin resonance spectroscopy (ESR)

Effects of lipoxygenase I-B (LOX)-catalyzed oxidation of linoleic acid on soybean proteins was evaluated by electron spin resonance (ESR) and fluorescence spectroscopy in different model systems in the presence or absence of antioxidants. A strong central singlet signal was detected by ESR spectroscopy and identified as the carbon radical (g value range 2.0041-2.0054). A downfield shoulder attributed to the sulfur radical (g value 2.019-2.028) was also observed. The changes in soybean proteins were accompanied by an increase in fluorescence, indicating the formation of cross-links. Natural antioxidants such as ascorbic acid and alpha-tocopherol as well as synthetic antioxidants butyl hydroxytoluene (BHT) inhibited the development of both the free radical signal and the fluorescence when added to soybean proteins prior to incubation with linoleic acid and lipoxygenase I-B; the central singlet signal attributed to the carbon radical was reduced by 35-65%. This paper clearly indicates direct free radical transfer from oxidizing linoleic acid catalyzed by LOX to soybean proteins.     

Formation of sulfur aroma compounds in reaction mixtures containing cysteine and three different forms of ribose

The headspace volatiles produced from buffered and unbuffered cysteine model systems, containing inosine 5'-monophosphate, ribose 5-phosphate, or ribose, were examined by GC-MS. Sulfur compounds dominated the volatiles of all systems and included mercaptoketones, furanthiols, and disulfides. The inosine monophosphate systems produced much lower quantities of volatiles than ribose phosphate or ribose systems. In the systems buffered with phosphate or phthalate buffers, both ribose and ribose phosphate systems gave similar quantities of sulfur volatiles. However, in the absence of buffer, the ribose system was relatively unreactive, especially for volatiles formed via the 2,3-enolization route in the Maillard reaction, where 4-hydroxy-5-methyl-3(2H)-furanone is a key intermediate. A number of keto-enol tautomerisms, which are known to be acid-base-catalyzed, occur in the 2,3-enolization route. This may explain the catalysis of the ribose systems by the buffers. In the ribose phosphate systems, however, Maillard mechanisms probably played a less important role, because ribose 5-phosphate readily dephosphorylated to give 4-hydroxy-5-methyl-3(2H)-furanone on heating and thus provided an easier route to aroma compounds than the Maillard reaction.     

Effects of alpha-, gamma-, and delta-tocopherols on the autoxidation of purified rapeseed oil triacylglycerols in a system containing low oxygen

Controversial data on the antioxidant effects of tocopherols have already been shown in different test systems, yet delta-tocopherol was hardly considered. This study was designed to assess the effects and degradation of alpha-, gamma-, and delta-tocopherol in four concentrations from between 0.01 and 0.25% on the oxidation of purified rapeseed oil trigacylglycerols (RO-TAG) at 40 degrees C in the dark in a low oxygen containing system for 11 weeks. Oxidation experiments were performed weekly by assessing primary (peroxide value, PV; conjugated dienes, CD) and secondary (p-anisidine reactive products, p-AV; hexanal) oxidation products, the degree of unsaturation with the iodine value (IV), and the stability of tocopherols. Test approaches were performed with and without the addition of 0.01% alpha,alpha'-azoisobutyronitrile (AIBN), which is a known radical initiator. alpha- and gamma-Tocopherols increased the rate of lipid oxidation, which was more pronounced in the presence of AIBN. Only the lowest amount of 0.01% gamma-tocopherol was comparable to the control sample in the test without AIBN. The most effective was shown to be delta-tocopherol, which did not elevate lipid oxidation except the PV in the AIBN test, but they did not delay it either. delta-Tocopherol was the most stable followed by gamma- and alpha-tocopherol. For alpha- and gamma-tocopherol, but not for delta-tocopherol, strong correlations were found between the tocopherol degradation and the extent of oxidation. Results suggest that (i). at concentrations higher than 0.05%, tocopherols are less efficient and turn their mode of action or participate in side reactions in RO-TAG and (ii). delta-tocopherol was shown to be the most stable and effective under these low oxygen conditions.     

Heterocyclic volatiles formed by heating cysteine or hydrogen sulfide with 4-hydroxy-5-methyl-3(2H)-furanone at pH 6.5

The reaction of 4-hydroxy-5-methyl-3(2H)-furanone (HMF) with cysteine or hydrogen sulfide at pH 6.5 for 60 min at 140 degrees C produced complex mixtures of volatile compounds, the majority of these containing either sulfur or nitrogen. Of the 68 compounds detected, 63 were identified, some tentatively, by GC-MS. Among the identified compounds were thiophenes (10), thiophenones (6), thienothiophenes (5), thiazoles (5), trithiolanes (4), pyrazines (6), and oxazoles (4). More compounds were produced in the reaction of HMF with cysteine (63) than were formed in the reaction with hydrogen sulfide (33). In both systems, thiophenones were major reaction products, accounting for 25-36% of the total volatiles formed. Possible reasons for the differences in the composition of the two systems are discussed. The contributions of these reactions, and their products, to the flavor of heated foods are considered.     

Free radical scavenging and antioxidative activity of caffeic acid amide and ester analogues: structure-activity relationship.

The structure-activity relationships of synthetic caffeic acid amide and ester analogues as potential antioxidants and free radical scavengers have been investigated. The 2,2-diphenyl-1-picrylhydrazyl radical (DPPH.) scavenging activity of the test compounds was N-trans-caffeoyl-L-cysteine methyl ester (5) > N-trans-caffeoyldopamine (4) > N-trans-caffeoyltyramine (3) > N-trans-caffeoyl-beta-phenethylamine (2) > Trolox C (8) > caffeic acid phenethyl ester (1) > caffeic acid (6) > ferulic acid (7). This established that the radical scavenging activity of the compounds increased with increasing numbers of hydroxyl groups or catechol moieties and also with the presence of other hydrogen-donating groups (-NH, -SH). The antioxidative activity of the compounds was also investigated in an emulsified linoleic acid oxidation system accelerated by 2,2'-azobis(2-amidinopropane) dihydrochloride. The order was 1 > 2 > 4 > 3 > or = 5 > 6 > 8 > 7. Therefore, in the emulsion system, the antioxidative activity of the test compounds depends not only on the hydroxyl groups or catechol rings but also on the partition coefficient (log P) or hydrophobicity of the compounds. This supports the concept that hydrophobic antioxidants tend to exhibit better antioxidative activity in an emulsion system.     

The influence of pH,soil type and time on adsorbtion and uptake by plants of Cd added to the soil

Adsorption of Cd by two soils and its uptake by perennial ryegrass (Lolium perenne) and winter rape (Brassica napus) as a function of pH (pH 4 to 7) and the amount of Cd added to the soil (0 to 5 mg kg^?1 soil) were studied in a 2-yr pot experiment. In the soils, the more soluble fractions of Cd increased as the pH was lowered. Increasing the pH from 5 to 7 by adding CaO invariably reduced the Cd-content of ryegrass plants, but this decrease was less consistent where the pH had only been increased to 6. In some cases, acidifying the soil with S to reach a pH of 4 also led to a decrease in plant Cd-content. The Cd-content of rapeseed plants was markedly higher at pH 4 than at pH 5. Plant damage at low pH was observed in this crop. Water-leachable and CaCl₂-extractable soil Cd levels as well as plant uptake were higher in the sand soil than in the clay soil, whereas 1M NH₄AcO (buffered at pH 4.8 and 7) extracted roughly equal amounts from both soils. Adding more Cd to the soil did not change the relation between Cd levels in soil and those in plants; instead the amounts of Cd in both increased in direct proportion to the amounts added. Fixation of added Cd apparently did not occur continuously at any pH or Cd-level during the 2-yr period, but seasonal variations in solubility and uptake were observed.