Aroma properties of a homologous series of 2,3-epoxyalkanals and trans-4,5-epoxyalk-2-enals

A few odor-active epoxyaldehydes, formed during lipid peroxidation, have recently been reported as intense aroma compounds in foods. However, very little is known about their flavor properties in general. Syntheses of homologous trans-2,3-epoxyalkanals (C(6)-C(12)) and trans-4,5-epoxy-(E)-2-alkenals (C(7)-C(12)) followed by structural characterization using mass spectrometry (MS/EI; MS/CI) and (1)H NMR measurements were performed. An evaluation of their odor qualities and odor thresholds by gas chromatography-olfactometry revealed the following: within the trans-2,3-epoxyalkanals, the odor quality changed from grassy for the compounds with six and seven carbon atoms to citrus-like or soapy for aldehydes with eight and more carbon atoms. The odor thresholds lay in the range of 3-15 ng/L (in air) and were nearly identical within the series; however, a slight minimum was measured for trans-2,3-epoxyoctanal to trans-2,3-epoxydecanal. In the series of the trans-4,5-epoxyalk-(E)-2-enals the C(10) compound was characterized by the lowest odor threshold of 0.6-2.5 pg/L of air. However, all trans-4,5-epoxy-alk-(E)-2-enals smelled intensely metallic.     

Development of oxidized odor and volatile aldehydes in fermented cucumber tissue exposed to oxygen

Changes in volatile compounds in fermented cucumber tissue during exposure to oxygen were investigated by purge and trap sampling, followed by GC-MS. Hexanal and a series of trans unsaturated aldehydes, (E)-2-pentenal, (E)-2-hexenal, (E)-2-heptenal, and (E)-2-octenal, increased in fermented cucumber slurries exposed to oxygen. Sensory evaluation of oxidized odor was correlated with the increase in aldehyde concentrations. Other identified volatile components present after fermentation did not show major changes during exposure to oxygen. There was no decrease in the formation of aldehydes in fermented cucumber samples that were heated to inactivate enzymes before exposure to oxygen. These results indicated that the formation of aldehydes in oxygen was due to nonenzymatic reactions.     

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.     

Effect of oleic and linoleic acids on the production of deep-fried odor in heated triolein and trilinolein

To determine sources of desirable deep-fried flavor in frying oils, degradation products from heated triolein and trilinolein with 5-31% polar compounds representing low to high deterioration were evaluated by purge-trap gas chromatography-mass spectrometry-olfactometry. (E,E)-2,4-Decadienal, 2-heptenal, 2-octenal, 2,4-nonadienal, and 2,4-octadienal produced deep-fried odor at moderate-strong intensities in heated trilinolein. However, unexpected aldehydes-2,4-decadienal, 2,4-undecadienal, 2,4-nonadienal, and 2-octenal (all <15 ppm)-were produced in triolein heated for 6 h. These dienals possibly were produced by hydroperoxidation and/or hydroxylation followed by dehydration of 2-alkenals. The 2-alkenals were produced from thermal decomposition of hydroperoxides, epoxides, and keto and dimeric compounds produced during the heating of triolein. These aldehydes produced low intensities of deep-fried odor in triolein. This information helps to explain sources of the deep-fried flavor that is characteristic of high linoleic frying oils but which is only at low intensity levels in high oleic frying oils.     

Changes in the aroma compounds of sake during aging

Changes in the aroma of sake during aging were investigated by aroma extract dilution analysis (AEDA) and quantitative analysis using the stir bar sorptive extraction method. In AEDA, more odor zones were detected in aged sake than in fresh sake. The dilution factors of aldehydes, polysulfides, and some esters were greater in the aged sake, and their increase during aging was confirmed through a quantitative analysis of sake stored for 0-35 years. Among these compounds, 3-methylbutanal, methional, and dimethyltrisulfide (DMTS) were present in aged sake at concentrations exceeding their odor thresholds, and the highest odor active value was observed for DMTS. Sensory tests showed that supplementation with DMTS contributed to both the total odor intensity and the sulfury odor of aged sake aroma.     

Chemical characterization of commercial Sherry vinegar aroma by headspace solid-phase microextraction and gas chromatography-olfactometry

The sensorial representativeness of the headspace solid-phase microextraction (HS-SPME) aroma extract from commercial Sherry vinegars has been determined by direct gas chromatography-olfactometry (D-GCO). Extracts obtained under optimal conditions were used to characterize the aroma of these vinegars by means of GCO and aroma extract dilution analysis (AEDA). Among the 37 different odorants determined, 13 of them were identified for the first time in Sherry vinegars: 2 pyrazines (3-isopropyl-2-methoxypyrazine, 3-isobutyl-2-methoxypyrazine), 2 sulfur compounds (methanethiol, dimethyl trisulfide), 1 unsaturated ketone (1-octen-3-one), 1 norisoprenoid (β-damascenone), 1 ester (ethyl trans-cinnamate) and 6 aldehydes (2- and 3-methylbutanal, octanal, nonanal, (E)-2-nonenal and (E,E)-2,4-decadienal). The determination of the odor thresholds in a hydroacetic solution together with the quantitative analysis-which was also performed using the simple and fast SPME technique-allowed obtaining the odor activity values (OAV) of the aromatic compounds found. Thus, a first pattern of their sensory importance on commercial Sherry vinegar aroma was provided.     

Characteristic odor components of Citrus sphaerocarpa Tanaka (Kabosu) cold-pressed peel oil

The volatile components of Citrus sphaerocarpa Tanaka (Kabosu) cold-pressed peel oil were investigated by chemical and sensory analyses. Monoterpene hydrocarbons (more than 94.6%) were predominant in Kabosu peel oil, with limonene and myrcene accounting for the major proportions (70.5% and 20.2%, respectively). The Kabosu oxygenated fraction was characterized by quantitative abundance in aldehydes and a relatively wide variety of alcohols. The weight percentages of aldehydes, alcohols, and esters in Kabosu cold-pressed oil were 1.3%, 0.1%, and 0.1%, respectively. Aroma extract dilution analysis was employed for determination of the odors of Kabosu volatile components, flavor dilution factors, and relative flavor activities. Gas chromatography/olfactometry using Kabosu cold-pressed oil and its oxygenated fraction completed by a chiral analysis revealed that (R)-(+)-citronellal is a characteristic element of Kabosu peel oil odor. Careful sniff testing demonstrated that aqueous solutions of both 0.25% and 0.016% (R)-(+)-citronellal gave an odor similar to that of Kabosu.     

Changes in key aroma compounds of Criollo cocoa beans during roasting

Application of a comparative aroma extraction dilution analysis on unroasted and roasted Criollo cocoa beans revealed 42 aroma compounds in the flavor dilution (FD) factor range of 1-4096 for the unroasted and 4-8192 for the roasted cocoa beans. While the same compounds were present in the unroasted and roasted cocoa beans, respectively, these clearly differed in their intensity. For example, 2- and 3-methylbutanoic acid (rancid) and acetic acid (sour) showed the highest FD factors in the unroasted beans, while 3-methylbutanal (malty), 4-hydroxy-2,5-dimethyl-3(2H)-furanone (caramel-like), and 2- and 3-methylbutanoic acid (sweaty) were detected with the highest FD factors in the roasted seeds. Quantitation of 30 odorants by means of stable isotope dilution assays followed by a calculation of odor activity values (ratio of the concentration/odor threshold) revealed concentrations above the odor threshold for 22 compounds in the unroasted and 27 compounds in the roasted cocoa beans, respectively. In particular, a strong increase in the concentrations of the Strecker aldehydes 3-methylbutanal and phenylacetaldehyde as well as 4-hydroxy-2,5-dimethyl-3(2H)-furanone was measured, suggesting that these odorants should contribute most to the changes in the overall aroma after roasting. Various compounds contributing to the aroma of roasted cocoa beans, such as 3-methylbutanoic acid, ethyl 2-methylbutanoate, and 2-phenylethanol, were already present in unroasted, fermented cocoa beans and were not increased during roasting.     

On the role of (-)-2-methylisoborneol for the aroma of Robusta coffee

The role of 2-methylisoborneol (MIB) in coffee aroma is controversially discussed in the literature. MIB is known as an off-flavor compound in drinking water and food, but it has also been suggested as a key flavor component of Robusta coffee, discriminating Robusta from Arabica coffee. To check this hypothesis the role of MIB in coffee brews was studied. Two reference samples containing pure Arabica and Robusta coffee brews were compared with five samples of Arabica coffee brews containing increasing amounts of MIB. The sensory panel consisting of 12 assessors perceived a distinct difference in the Arabica coffee odor and flavor in the presence of 10-25 ng/kg MIB, which is close to its threshold value in water. The sensory impression was described as musty, mold-like, and earthy. The intensity increased with increasing concentration of MIB. The panelists agreed that there was no similarity with the Robusta reference sample. The Arabica coffee brew spiked with MIB was no longer palatable due to the odor and flavor defect formed.     

Comparison of odor-active compounds from six distinctly different rice flavor types

Using a dynamic headspace system with Tenax trap, GC-MS, GC-olfactometry (GC-O), and multivariate analysis, the aroma chemistry of six distinctly different rice flavor types (basmati, jasmine, two Korean japonica cultivars, black rice, and a nonaromatic rice) was analyzed. A total of 36 odorants from cooked samples were characterized by trained assessors. Twenty-five odorants had an intermediate or greater intensity (odor intensity >or= 3) and were considered to be major odor-active compounds. Their odor thresholds in air were determined using GC-O. 2-Acetyl-1-pyrroline (2-AP) had the lowest odor threshold (0.02 ng/L) followed by 11 aldehydes (ranging from 0.09 to 3.1 ng/L), guaiacol (1.5 ng/L), and 1-octen-3-ol (2.7 ng/L). On the basis of odor thresholds and odor activity values (OAVs), the importance of each major odor-active compound was assessed. OAVs for 2-AP, hexanal, ( E)-2-nonenal, octanal, heptanal, and nonanal comprised >97% of the relative proportion of OAVs from each rice flavor type, even though the relative proportion varied among samples. Thirteen odor-active compounds [2-AP, hexanal, ( E)-2-nonenal, octanal, heptanal, nonanal, 1-octen-3-ol, ( E)-2-octenal, ( E, E)-2,4-nonadienal, 2-heptanone, ( E, E)-2,4-decadienal, decanal, and guaiacol] among the six flavor types were the primary compounds explaining the differences in aroma. Multivariate analysis demonstrated that the individual rice flavor types could be separated and characterized using these compounds, which may be of potential use in rice-breeding programs focusing on flavor.     

Studies on the aroma of five fresh tomato cultivars and the precursors of cis- and trans-4,5-epoxy-(E)-2-decenals and methional

Three tasty (BR-139, FA-624, and FA-612) and two less tasty (R-144 and R-175) fresh greenhouse tomato cultivars, which significantly differ in their flavor profiles, were screened for potent odorants using aroma extract dilution analysis (AEDA). On the basis of AEDA results, 19 volatiles were selected for quantification in those 5 cultivars using gas chromatography-mass spectrometry (GC-MS). Compounds such as 1-penten-3-one, ( E, E)- and ( E, Z)-2,4-decadienal, and 4-hydroxy-2,5-dimethyl-3(2 H)-furanone (Furaneol) had higher odor units in the more preferred cultivars, whereas methional, phenylacetaldehyde, 2-phenylethanol, or 2-isobutylthiazole had higher odor units in the less preferred cultivars. Simulation of the odor of the selected tomato cultivars by preparation of aroma models and comparison with the corresponding real samples confirmed that all important fresh tomato odorants were identified, that their concentrations were determined correctly in all five cultivars, and that differences in concentration, especially of the compounds mentioned above, make it possible to distinguish between them and are responsible for the differential preference. To help elucidate formation pathways of key odorants, labeled precursors were added to tomatoes. Biogenesis of cis- and trans-4,5-epoxy-( E)-2-decenals from linoleic acid and methional from methionine was confirmed.     

Chemoenzymatic synthesis of aroma active 5,6-dihydro- and tetrahydropyrazines from aliphatic acyloins produced by baker's yeast

Twenty-five acyloins were generated by biotransformation of aliphatic aldehydes and 2-ketocarboxylic acids using whole cells of baker's yeast as catalyst. Six of these acyloins were synthesized and tentatively characterized for the first time. Subsequent chemical reaction with 1,2-propanediamine under mild conditions resulted in the formation of thirteen 5,6-dihydropyrazines and six tetrahydropyrazines. Their odor qualities were evaluated, and their odor thresholds were estimated. Among these pyrazine derivatives, 2-ethyl-3,5-dimethyl-5,6-dihydropyrazine (roasted, nutty, 0.002 ng/L air), 2,3-diethyl-5-methyl-5,6-dihydropyrazine (roasted, 0.004 ng/L air), and 2-ethyl-3,5-dimethyltetrahydropyrazine (bread crustlike, 1.9 ng/L air) were the most intensive-smelling aroma active compounds.     

基于HS-SPME-GC-MS法比较瓢鸡和盐津乌骨鸡不同部位挥发性风味成分

为了研究优质地方鸡种瓢鸡和盐津乌骨鸡不同部位的主体风味成分,以300日龄瓢鸡和盐津乌骨鸡的胸肌和腿肌作为试验对象,利用顶空固相微萃取(HS-SPME)技术提取,采用气相色谱质谱联用(GC-MS)技术分离和鉴定鸡肉中的挥发性物质,结合相对活度值(ROAV)确定主体风味活性物质。结果表明,鸡肉样品中共检出76种挥发性化合物,主要包括醛类、醇类、酮类、酯类、酸类、烃类化合物,不同品种不同部位之间挥发性风味物质的组分和含量存在差异。瓢鸡主体风味物质由2-甲基丁醛、戊醛、己醛、庚醛、辛醛、反-2-辛烯醛、壬醛、1-辛烯-3-醇、辛烷构成;盐津乌骨鸡主体风味物质主要由2-甲基丁醛、己醛、壬醛、1-辛烯-3-醇构成。主体风味物质对不同部位不同品种鸡肉样品的贡献程度不同,其中醛类化合物对鸡肉的整体风味贡献最大。本研究结果为瓢鸡和盐津乌骨鸡的风味特性研究和开发利用提供了理论依据。     

Representativeness of extracts of offset paper packaging and analysis of the main odor-active compounds

Packagings often carry odors due to the support and printing inks. The aim of the investigation was to define a representative solvent-free extract of paper-based packaging materials printed by the offset process, for the identification of the odor-causing volatile compounds. Static headspace and solid-phase microextraction were the two applied extraction methods. Representativeness tests showed that the odor of the PDMS fiber extract gave satisfying odor similarities with the original packaging. The sample incubation was performed at 40 degrees C for 30 min, whereas the extraction time was 3 min at 40 degrees C. Extracts of both the nonprinted and printed papers of different batches were analyzed by gas chromatography-olfactometry. 4-Phenylcyclohexene was identified as the most potent compound contributing to the latex-like odor of the nonprinted paper. Among the 13 major odorants identified by mass spectrometry, 10 were aldehydes and ketones generated by oxidation of the printing ink resins. The ratio of odorants to interferences was too low for a possible detection of the key odorants by nonseparative techniques such as sensor arrays.     

Volatile Profiles of 13 Foxtail Millet Commercial Cultivars (Setaria italica Beauv.) from China

The volatile components from 13 commercially valuable foxtail millets from China were investigated by means of gas chromatography–mass spectrometry combined with simultaneous distillation extraction. A total of 52 volatile compounds were identified in all of the samples: 19 aldehydes, 5 alcohols, 10 ketones, 9 hydrocarbons, 6 benzene derivatives, and 3 others. Here, 23 common constituents were found in all samples. Aldehydes were the predominant volatile components in various cultivars. The importance of each volatile was assessed on the basis of odor thresholds and odor activity values (OAVs). Here, 35 volatile compounds were described using aroma character, and 24 volatile compounds were found to be odor‐active compounds. Another 11 common constituents were found in all samples. The components with the highest OAVs in most cultivars were (E )‐2‐nonenal and (E,E )‐2,4‐decadienal. Most of the other aldehydes also had high OAVs. Some of the ketones, alcohols, benzene derivatives, and other compounds were found to contain an odor‐active compound in several cultivars of foxtail millet. Principal component analysis was employed to evaluate the differences among cultivars. The results demonstrated that the volatile profile based on the OAVs of aroma compounds enabled good differentiation of most cultivars.