Formation of 2-alkyl-(2H)-thiapyrans and 2-alkylthiophenes in cooked beef and lamb

2-Alkyl-(2H)-thiapyrans and 2-alkylthiophenes have been identified in the volatiles of cooked beef and lamb. The quantities of both groups of compounds were higher in the meat of animals fed lipid supplements high in n-3 polyunsaturated fatty acids. 2-Alkyl-(2H)-thiapyrans were formed when (E,E)-2,4-dienals (C(6)-C(11)) and hydrogen sulfide were heated at 140 degrees C for 30 min. This confirmed their proposed route of formation in cooked meat from lipid-derived aldehydes and hydrogen sulfide; the latter was produced from the degradation of cysteine, via the Maillard reaction. The mass spectra and NMR spectra of these thiapyrans are reported for the first time. Although 2-alkyl-(2H)-thiapyrans were found to have only low odor potency, the reactions by which they are formed may have important implications for meat flavor. These reactions may remove potent aroma compounds and their intermediates from meat, thus modifying the overall aroma profile.     

Effects of carnosine on volatile generation from Maillard reaction of ribose and cysteine

Carnosine occurs naturally in meat and meat products in significant quantity, and it possesses strong antioxidant activity that inhibits lipid oxidation and enhances shelf life. In this study, the effects of carnosine on thermal flavor generation were investigated using the model system of cysteine and ribose, which was heated to the roasting temperature of 180 degrees C for 2 h at pH 5 and pH 8.5. The results indicated that carnosine affected volatile formation in a complex manner. Volatiles identified from the liquid phase of the reaction systems of ribose and cysteine showed that the sulfur-containing compounds such as thiophenes, thiazoles, and polysulfides were the most abundant compounds. The addition of carnosine into the reaction mixtures in general caused a reduction in contents of thiophenes and some important meaty flavor compounds such as 2-methyl-3-furanthiol, 2-furfurylthiol, and their associated dimers. On the other hand, it facilitated the generation of several important nitrogen-containing volatiles such as pyrazine, methylpyrazine, 2,6-dimethylpyrazine, and other alkyl pyrazines and thiazoles, which are known to elicit roasty and nutty flavor notes. The results suggested that carnosine acts as a nitrogenous source to facilitate the formation of nitrogen-containing compounds, possibly by degradation to form ammonia.     

Interactions between iron, phenolic compounds, emulsifiers, and pH in omega-3-enriched oil-in-water emulsions

The behavior of antioxidants in emulsions is influenced by several factors such as pH and emulsifier type. This study aimed to evaluate the interaction between selected food emulsifiers, phenolic compounds, iron, and pH and their effect on the oxidative stability of n-3 polyunsaturated lipids in a 10% oil-in-water emulsion. The emulsifiers tested were Tween 80 and Citrem, and the phenolic compounds were naringenin, rutin, caffeic acid, and coumaric acid. Lipid oxidation was evaluated at all levels, that is, formation of radicals (ESR), hydroperoxides (PV), and secondary volatile oxidation products. When iron was present, the pH was crucial for the formation of lipid oxidation products. At pH 3 some phenolic compounds, especially caffeic acid, reduced Fe(3+) to Fe(2+), and Fe(2+) increased lipid oxidation at this pH compared to pH 6. Among the evaluated phenols, caffeic acid had the most significant effects, as caffeic acid was found to be prooxidative irrespective of pH, emulsifier type, and presence of iron, although the degrees of lipid oxidation were different at the different experimental conditions. The other evaluated phenols were prooxidative at pH 3 in Citrem-stabilized emulsions and had no significant effect at pH 6 in Citrem- or Tween-stabilized emulsions on the basis of the formation of volatiles. The results indicated that phenol-iron complexes/nanoparticles were formed at pH 6.     

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.     

Volatile profiles of dry-cured meat products from three different Iberian x Duroc genotypes

Volatile profiles of two Iberian dry-cured products, dry-cured loin and ham, from three different Iberian x Duroc genotypes, was assessed. Three groups of 10 pigs, each (5 males and 5 females) from different genotypes, were studied: GEN1 = male Iberian x female Duroc1; GEN2 = male Duroc1 x female Iberian; and GEN3 = male Duroc2 x female Iberian. The genotype Duroc1 (DU1) corresponded to pigs selected for the production of dry-cured meat products (hams, loins, and shoulders), with a high level of fattening, while the genotype Duroc2 (DU2) corresponded to animals selected for meat production. Genotype slightly affected the volatile profiles of both dry-cured meat products, although dry-cured loin from GEN3 showed higher hexanal content. Dry-cured loin showed a volatile profile very different to that found in dry-cured ham. Volatile compounds of dry-cured meat products were mainly originated by lipid and protein degradation. Most of the volatile detected in both meat products came from lipid oxidation such as acids, aldehydes, ketones, alcohols, and hydrocarbons. In addition, a high proportion of volatile compounds from the Maillard reaction was found. Branched aldehydes and some sulfur and nitrogen compounds have their origin in the amino acids degradation by the Strecker reaction, while branched alcohols and acids come from the lipid oxidation of branched aldehydes. Dry-cured ham showed a higher number and a higher level of compounds with origin in protein and lipid degradation than dry-cured loin, which agrees with the longer ripening of the hams (24 months) with respect to the loins (4 months). In dry-cured loins, apart from these compounds, seasoning mixture provides high amount of volatiles, such as terpenes (from paprika and oregano) and sulfur compounds (from garlic), which have great importance in the overall aroma of this product.     

Comparison of lipid content and Fatty Acid composition in the edible meat of wild and cultured freshwater and marine fish and shrimps from china

The lipid content and fatty acid composition in the edible meat of twenty-nine species of wild and cultured freshwater and marine fish and shrimps were investigated. Both the lipid content and fatty acid composition of the species were specified due to their unique food habits and trophic levels. Most of the marine fish demonstrated higher lipid content than the freshwater fish, whereas shrimps had the lowest lipid content. All the marine fish and shrimps had much higher total n-3 PUFA than n-6 PUFA, while most of the freshwater fish and shrimps demonstrated much lower total n-3 PUFA than n-6 PUFA. This may be the biggest difference in fatty acid composition between marine and freshwater species. The cultured freshwater fish demonstrated higher percentages of total PUFA, total n-3 PUFA, and EPA + DHA than the wild freshwater fish. Two freshwater fish, including bighead carp and silver carp, are comparable to the marine fish as sources of n-3 PUFA.     

Formation of aroma compounds from ribose and cysteine during the Maillard reaction

The headspace volatiles produced from a phosphate-buffered solution (pH 5) of cysteine and a 1 + 1 mixture of ribose and [(13)C(5)]ribose, heated at 95 degrees C for 4 h, were examined by headspace SPME in combination with GC-MS. MS data indicated that fragmentation of ribose did not play a significant role in the formation of the sulfur aroma compounds 2-methyl-3-furanthiol, 2-furfurylthiol, and 3-mercapto-2-pentanone in which the carbon skeleton of ribose remained intact. The methylfuran moiety of 2-methyl-3-(methylthio)furan originated from ribose, whereas the methylthio carbon atoms came partly from ribose and partly from cysteine. In 3-mercapto-2-butanone one carbon unit was split from the ribose chain. On the other hand, all carbon atoms in 3-thiophenethiol stemmed from cysteine. In another trial cysteine, 4-hydroxy-5-methyl-3(2H)-furanone and [(13)C(5)]ribose were reacted under the same conditions. The resulting 2-methyl-3-furanthiol was mainly (13)C(5)-labeled, suggesting that it stems from ribose and that 4-hydroxy-5-methyl-3(2H)-furanone is unimportant as an intermediate. Whereas 2-mercapto-3-pentanone was found unlabeled and hence originated from 4-hydroxy-5-methyl-3(2H)-furanone, its isomer 3-mercapto-2-pentanone was formed from both 4-hydroxy-5-methyl-3(2H)-furanone and ribose. A new reaction pathway from ribose via its 1,4-dideoxyosone is proposed, which explains both the formation of 2-methyl-3-furanthiol without 4-hydroxy-5-methyl-3(2H)-furanone as an intermediate and a new way to form 3-mercapto-2-pentanone.     

Structured fluids as microreactors for flavor formation by the Maillard reaction

Thermal reactions of cysteine/furfural and cysteine/ribose mixtures were studied in model systems to gain more insight into the influence of structured fluids such as L(2) microemulsions and cubic phases on the generation of aroma compounds. Formation of 2-furfurylthiol from cysteine/furfural was particularly efficient in L(2) microemulsions and cubic phases compared to aqueous systems. The reaction led to the formation of two new sulfur compounds, which were identified as 2-(2-furyl)thiazolidine and, tentatively, N-(2-mercaptovinyl)-2-(2-furyl)thiazolidine. Similarly, generation of 2-furfurylthiol and 2-methyl-3-furanthiol from cysteine/ribose mixtures was strongly enhanced in structured fluids. The cubic phase was shown to be even more efficient in flavor generation than the L(2) microemulsion. It was denoted "cubic catalyst" or "cubic selective microreactor". The obtained results are interpreted in terms of a surface and curvature control of the reactions defined by the structural properties of the formed surfactant associates.     

Formation of volatile sulfur compounds by microbial decomposition of sulfur-containing amino acids in soils

Evolution of volatile sulfur compounds from soils treated with S-containing amino acids was studied by sensitive gas chromatographic techniques involving use of a flame photometric detector fitted with a sulfur filter. The following volatile sulfur compounds were identified as products of microbial decomposition of S-containing amino acids in soils under aerobic or waterlogged conditions: methyl mercaptan, dimethyl sulfide and dimethyl disulfide (evolved from soils treated with methionine, methionine sulfoxide, methionine sulfone or S-methyl cysteine); ethyl mercaptan, ethyl methyl sulfide and diethyl disulfide (evolved from soils treated with ethionine or S-ethyl cysteine); and carbon disulfide (evolved from soils treated with cystine, cysteine, lanthionine or djenkolic acid). Small amounts of dimethyl sulfide and carbon disulfide were evolved from soils treated with homocystine, and trace amounts of carbonyl sulfide were evolved from soils treated with lanthionine or djenkolic acid. No volatile sulfur compounds were evolved from soils treated with cysteic acid, taurine, or S-methyl methionine. The amounts of sulfur volatilized from soils treated with the 14 S-containing amino acids studied represented from less than 0·1 per cent to more than 50 per cent of the sulfur added as amino acid. Hydrogen sulfide could not be detected as a gaseous product of microbial decomposition of S-containing amino acids in soils under aerobic or waterlogged conditions.     

Extensive analysis of long-chain polyunsaturated fatty acids, CLA, trans-18:1 isomers, and plasmalogenic lipids in different retail beef types

The objective of this investigation was to provide a comprehensive analysis of the total lipid composition of present-day retail beef meat available at the consumer level and to evaluate the total lipid composition with special emphasis on the nutritional value. For this purpose, 40 beef cuts were obtained from four cattle farms based on either a natural grazing system (NGS) or an intensive production system (IPS). The total lipid composition was analyzed using complementary chemical and chromatographic procedures. The content of n-3 LC-PUFA, CLA, total trans-18:1, and branched-chain fatty acids was significantly higher in NGS beef than in IPS beef. The trans-18:1 and CLA profiles were affected by the different production systems, whereby they can be utilized empirically to differentiate between feeding regimen and production management. Fatty acid ratios that have health implications ( n-6/ n-3, LA/alphaLNA, and AA/EPA) were remarkably beneficial for NGS beef compared with IPS beef. In conclusion, from the human health perspective, beef raised on NGS is clearly superior with regard to a more favorable fatty acid profile in comparison to IPS beef.     

Influence of different dietary doses of n-3- or n-6-rich vegetable fats and alpha-tocopheryl acetate supplementation on raw and cooked rabbit meat composition and oxidative stability

This study evaluates the effects of replacing beef tallow added to rabbit feeds (3% w/w) by different doses (0%, 1.5% and 3% w/w) of n-6- or n-3-rich vegetable fat sources (sunflower and linseed oil, respectively) and alpha-tocopheryl acetate supplementation (0 and 100 mg/kg) on the fatty acid composition, alpha-tocopherol content, and oxidation levels [assessed by analyzing thiobarbituric acid (TBA) and lipid hydroperoxide values] in rabbit meat. We also measured these parameters after cooking and refrigerated storage of cooked rabbit meat. Both dietary alpha-tocopheryl acetate supplementation and the dose and source of fat added to feeds influenced meat fatty acid composition, modifying the n-6/n-3 ratio, which was more nutritionally favorable when linseed oil was used. Furthermore, the addition of linseed oil and the supplementation with alpha-tocopheryl acetate enhanced long-chain PUFA biosynthesis. However, the addition of 3% linseed oil increased meat oxidation, and although it was reduced by dietary supplementation with alpha-tocopheryl acetate in raw meat, this reduction was not as effective after cooking. Therefore, dietary supplementation with 1.5% linseed oil plus 1.5% beef tallow and with alpha-tocopheryl acetate would be recommended to improve the nutritional quality of rabbit meat.     

Effect of the polyunsaturated fatty acid composition of beef muscle on the profile of aroma volatiles

The effect of n-3 polyunsaturated fatty acids (PUFAs) in beef muscle on the composition of the aroma volatiles produced during cooking was measured. The meat was obtained from groups of steers fed different supplementary fats: (i) a palm-oil-based control; (ii) bruised whole linseed, which increased muscle levels of alpha-linolenic (C18:3 n-3) and eicosapentaenoic acid (EPA, C20:5 n-3); (iii) fish oil, which increased EPA and docosahexaenoic acid (C22:6 n-3); (iv) equal quantities of linseed and fish oil. Higher levels of lipid oxidation products were found in the aroma extracts of all of the steaks with increased PUFA content, after cooking. In particular, n-alkanals, 2-alkenals, 1-alkanols, and alkylfurans were increased up to 4-fold. Most of these compounds were derived from the autoxidation of the more abundant mono- and di-unsaturated fatty acids during cooking, and such autoxidation appeared to be promoted by increased levels of PUFAs.     

Model studies on the pattern of volatiles generated in mixtures of amino acids, lipid-oxidation-derived aldehydes, and glucose

The development of flavor and browning in thermally treated foods results mainly from the Maillard reaction and lipid degradation but also from the interactions between both reaction pathways. To study these interactions, we analyzed the volatile compounds resulting from model reactions of lysine or glycine with aldehydes originating from lipid oxidation [hexanal, (E)-2-hexenal, or (2E,4E)-decadienal] in the presence and absence of glucose. The main reaction products identified in these model mixtures were carbonyl compounds, resulting essentially from amino-acid-catalyzed aldol condensation reactions. Several 2-alkylfurans were detected as well. Only a few azaheterocyclic compounds were identified, in particular 5-butyl-2-propylpyridine from (E)-2-hexenal model systems and 2-pentylpyridine from (2E,4E)-decadienal model reactions. Although few reaction products were found resulting from the condensation of an amino acid with a lipid-derived aldehyde, the amino acid plays an important role in catalyzing the degradation and further reaction of these carbonyl compounds. These results suggest that amino-acid-induced degradations and further reactions of lipid oxidation products may be of considerable importance in thermally processed foods.     

Effect of urea on volatile generation from Maillard reaction of cysteine and ribose

Urea occurs naturally in many food products, and its presence affects food quality. However, little is known about its impact on flavor generation in food production. In this study, the urea contents in beef, pork, and chicken were determined. The effects of urea and pH on thermal flavor generation were investigated using the model system of cysteine with ribose, which was heated to the roasting temperature of 180 degrees C for 2 h at pH 5 and pH 8.5. The results revealed relatively large amounts of urea in these meats and demonstrated that pH affects aroma generation. Volatiles identified from the reaction system of ribose and cysteine showed that sulfur-containing compounds such as thiophenes, thiazoles, and thiophenethiols were the most abundant compounds. The addition of urea into the reaction mixture caused the disappearance or reduction in content of some sulfur-containing compounds but resulted in the generation of several important nitrogen-containing volatiles, like pyrazine, methylpyrazine, 2,5- (and 2,6-)dimethylpyrazine and other alkylpyrazines, which are known to elicit roasty, nutty flavor notes. A plausible explanation for this phenomenon is that ammonia can be released from urea upon heating and the formed ammonia competes with hydrogen sulfide to react with Maillard reaction precursors to produce nitrogen-containing compounds such as alkylpyrazines.     

Precursors of chicken flavor. II. Identification of key flavor precursors using sensory methods

Sensory evaluation was used to identify flavor precursors that are critical for flavor development in cooked chicken. Among the potential flavor precursors studied (thiamin, inosine 5'-monophosphate, ribose, ribose-5-phosphate, glucose, and glucose-6-phosphate), ribose appears most important for chicken aroma. An elevated concentration (added or natural) of only 2-4-fold the natural concentration gives an increase in the selected aroma and flavor attributes of cooked chicken meat. Assessment of the volatile odor compounds by gas chromatography-odor assessment and gas chromatography-mass spectrometry showed that ribose increased odors described as "roasted" and "chicken" and that the changes in odor due to additional ribose are probably caused by elevated concentrations of compounds such as 2-furanmethanethiol, 2-methyl-3-furanthiol, and 3-methylthiopropanal.     

Formation of methanethiol and dimethyl disulfide in crushed tissues of broccoli florets and their inhibition by freeze-thawing

The formation of methanethiol and dimethyl disulfide in crushed, homogenized, and frozen-thawed tissues of broccoli florets was investigated. These volatile sulfur compounds were produced in crushed florets, but their formation was inhibited in frozen-thawed tissues. Only dimethyl disulfide was formed in homogenized tissues. High pH treatment triggered the release of dimethyl disulfide in frozen-thawed tissues and also enhanced the action of cysteine sulfoxide lyase in all disrupted tissues. Methyl methanethiosulfinate and methyl methanethiosulfonate were not detected in crushed florets; thus, the favored mechanism for the formation of methanethiol and dimethyl disulfide is the chemical disproportionation of methanesulfenic acid. In contrast, the formation of dimethyl disulfide in frozen-thawed and homogenized tissues occurs from the chemical disproportionation of methyl methanethiosulfinate that was detected in these tissues. The inhibition of dimethyl disulfide production during freeze-thawing must be caused by a sudden drop in the pH of the tissue, adherence of dimethyl disulfide on the tissue surfaces, and weakening of the cysteine sulfoxide lyase activity under acidic conditions.     

Characterization of a new Maillard type reaction product generated by heating 1-deoxymaltulosyl-glycine in the presence of cysteine

The reaction between Amadori compounds and cysteine was investigated. When 1-deoxymaltulosyl-glycine (glycyl-fructosyl-glucose) was heated at 100 degrees C with cysteine in a neutral aqueous solution, a novel intermediate composed of 1-deoxyosone and cysteine was detected. NMR and mass spectrometry studies revealed the structure of the isolated intermediate to be 7,8a-dihydroxy-4a-methyl-8-(alpha-d-glucopyranosyloxy)hexahydro-5-oxa-4-thia-1-azanaphthalene-2-carboxylic acid. This intermediate easily generated isomaltol and acetylfuran as volatile compounds in 1 mol/L HCl at 100 degrees C.     

Investigation of the reaction between 4-hydroxy-5-methyl-3(2H)-furanone and cysteine or hydrogen sulfide at pH 4.5

Reaction of 4-hydroxy-5-methyl-3(2H)-furanone (HMF) with cysteine or hydrogen sulfide at pH 4.5 for 60 min at 140 degrees C produced complex mixtures of volatile compounds, the majority of which contained sulfur. Sixty-nine compounds were identified, some tentatively, by GC/MS. These included disulfides (26), thiols (7), dithiolanones (6), thiophenones (4), dithianones (3), and thienothiophenes (6). The main non-sulfur compounds were 2, 3-pentanedione, 2,4-pentanedione, and 3,4-hexanedione. Both systems produced approximately the same total quantity of volatile compounds, but the reaction containing cysteine gave the larger number of individual compounds, with thiols quantitatively the dominant components. By comparison, the major products formed in the reaction with hydrogen sulfide were the dithiolanones. Reaction pathways are presented for the major products and, where applicable, possible reasons for the differences in composition of the two systems are discussed. The contribution of these reactions, and their products, to the flavor of roasted foods is considered.     

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.     

Volatile compounds from potato-like model systems

The volatile reaction products of aqueous mixtures comprising combinations of methionine, glucose, linoleic acid, and starch heated in a modified Likens-Nickerson apparatus were extracted and analyzed by gas chromatography-mass spectrometry (GC-MS). The majority of volatile compounds were formed from linoleic acid degradation, hexanal, 2,4-decadienal, and 2-pentylfuran being identified in the greatest amounts. Dimethyl disulfide and dimethyl trisulfide were detected in every system containing methionine. 3-(Methylthio)propanal (methional) and other sulfur compounds were detected when methionine was heated with another precursor. No binding of volatile compounds to starch was observed; rather, starch appeared to act as an additional source of reactive carbohydrate. Almost all the components identified have been identified among the aroma components of cooked potato. No pyrazines, pyridines, or thiazoles were identified, probably due to the relatively low temperature/high moisture conditions.