Characterization of E- and Z-ajoene obtained from different varieties of garlics

Synthesised E- and Z-ajoene were used to determine their amounts in food oils containing various fresh garlics. The best yield of E-ajoene (172.0 μg/g of garlic) and Z-ajoene (476.0 μg/g of garlic) was obtained from freshly prepared Japanese garlic with rice oil which was heated at 80 °C. Determination of E- and Z-ajoene from soybean oil containing 15% Japanese garlic samples prepared at 80 °C for 0.5 h gave the amount of E-ajoene (170.0 μg/g of garlic) and Z-ajoene (127.0 μg/g of garlic). After 9-month storage, 54.0% E- and 11.0% Z-ajoene remained in Japanese garlic with rice oil. Ajoene (0.1 mM) in ethyl acetate was incubated under UV-light (253.7 nm) for 3 days, 81.7% E- and 56.9% Z-ajoene remained. 4.3% and 0.5% E- and Z-ajoene remained when ajoene (0.1 mM in ethyl acetate) was incubated at 100 °C.     

Degradation of cucumber flavor aldehydes in juice

The effect of 1,10-phenanthroline (PTL) on stability of aldehydes, especially, (E,Z)-2,6-nonadienal (NDEA) and (E)-2-nonenal (NEA), produced during tissue disruption of cucumber fruit (Cucumis sativus) was studied. Volatiles in headspace of cucumber juice samples treated with 0 or 20 μg ml^{− 1} PTL were collected by SPME and analyzed by GC–MS. Within 4 h at 30 °C more than 90% of the initial NDEA, NEA, (Z)-6-nonenal, (E)-2-hexenal, hexanal, (E)-2-pentenal, propanal and ethanal disappeared in juice without PTL. During the loss of these aldehydes, several alcohols were detected. In contrast, levels of NDEA, NEA and (Z)-6-nonenal in PTL treated juice gradually declined during holding for 24 h at 30 °C; the amounts of other aldehydes remained relatively constant; and no alcohols were detected except for ethanol which was initially present. Therefore, inhibiting reduction of aldehydes to alcohols greatly hindered degradation of cucumber flavor aldehydes.     

Phenolic glucosides in the course of ligulate flower development in diploid and tetraploid Matricaria chamomilla

The main secondary metabolites of Matricaria chamomilla ligulate flowers are apigenin-7-O-glucoside derivatives and (Z)- and (E)-2-β-d-glucopyranosyloxy-4-methoxy cinnamic acids (GMCAs), which are the precursors of herniarin. The quantities of these compounds were determinated in six phases of development of ligulate flowers in diploid and tetraploid cultivar. The content of the apigenin glucoside and its main acylated derivatives in ligulate flowers of diploid plants was found to be significantly higher before the start of flowering in comparison with tetraploid plants. During the flowering and post-flowering phase their content decreased and no difference between diploid and tetraploid plants was observed. The (E)-izomer was the dominant form of 2-β-d-glucopyranosyloxy-4-methoxy cinnamic acid. These secondary stress metabolite precursors were accumulated in higher concentrations in young growing ligulate flowers, but during flowering and post-flowering phases their content decreased. Significantly higher content was found in tetraploid plants in comparison with diploid plants. Aglycones of glycosides were found in low concentrations.     

Changes in volatile compounds of Habanero chile pepper (Capsicum chinense Jack. cv. Habanero) at two ripening stages

The steam volatile components of Yucatan Habanero chile pepper (Capsicum chinense Jack. cv. Habanero) at two ripening stages (green and orange) were analyzed using GC and GC/MS. Both samples had several compounds in common. One hundred and two compounds were identified, from which (E)-2-hexenal, hexyl 3-methylbutanoate, (Z)-3-hexenyl 3-methylbutanoate, hexyl pentanoate, 3,3-dimethylcyclohexanol, and hexadecanoic acid were found to be the major constituents. During Habanero chile pepper maturation, the majority of volatile compounds decreased or even disappeared, some of them with green odour notes while esters, which have fruity odour notes, increased at the same time.     

Compounds from Angelica keiskei with NQO1 induction, DPPH scavenging and α-glucosidase inhibitory activities

A LC-MS method, which GSH was used as substrate, was employed to reveal the compounds with NQO1 induction activity from Angelica keiskei. Some compounds, proposed as isobavachalcone, xanthoangelol and 4-hydroxyderricin, have NQO1 induction activity. To make the actual structures and bioactivities of these compounds clear, 23 compounds, including above mentioned compounds and two new compounds 4-hydroxy-3,5,5-trimethyl-4-(1,2,3-trihydroxybutyl)cyclohex-2-enone (18) and (Z)-2-(3-hydroxypent-1-ynyl)-3-(non-1-enyl)oxiran-2-ol (23), were isolated from the 95% ethanol extract of A. keiskei. The bioassay results suggested the compounds had notable NQO1 induction activity. The radical scavenging and α-glucosidase inhibition activities of the isolated compounds were also tested. Compounds (E)-1-(2,4-dihydroxy-3-(3-methylbut-2-enyl)phenyl)-3-(4-hydroxyphenyl)prop-2-en-1-one (1), (E)-1-(3-((E)-3,7-dimethylocta-2,6-dienyl)-2,4-dihydroxyphenyl)-3-(4-hydroxyphenyl)prop-2-en-1-one (2), 1-(3-hydroxy-10,13-dimethyl-2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydro-1H-cyclopenta[α]phenanthren-17-yl)ethanone (17), 4-hydroxy-3,5,5-trimethyl-4-(1,2,3-trihydroxybutyl)cyclohex-2-enone (18) could scavenge DPPH radical by more than 20%. Compounds (E)-1-(2,4-dihydroxy-3-(3-methylbut-2-enyl)phenyl)-3-(4-hydroxyphenyl)prop-2-en-1-one (1), (E)-1-(3-((E)-3,7-dimethylocta-2,6-dienyl)-2,4-dihydroxyphenyl)-3-(4-hydroxyphenyl)prop-2-en-1-one (2), (E)-1-(2-hydroxy-4-methoxy-3-(3-methylbut-2-enyl)phenyl)-3-(4-hydroxyphenyl)prop-2-en-1-one (3), 7-hydroxy-6-(3-methylbut-2-enyl)-2H-chromen-2-one (5), 10-hydroxy-8,8-dimethyl-2-oxo-9,10-dihydropyrano[6,5-H]chromen-9-yl)-3-methylbut-2-enoate (9), 2-(4-hydroxyphenyl)-7-methoxy-8-(3-methylbut-2-enyl)-2,3-dihydrochromen-4-one (16), (10S,15R,Z)-10,15-dihydroxyheptadeca-8,16-dien-11,13-diynyl acetate (20), (3R,8S,Z)-heptadeca-1,9-dien-4,6-diyne-3,8-diol (21) exhibited excellent α-glucosidase inhibition activity.     

Thermally-induced geometrical isomerisation of lycopene and its potential influence on functional activity

About 90–98% of native lycopene exists in the all-E form, but 79–88% of the lycopene found in the human body are Z-isomeric forms. Thermally-induced geometrical isomerisation of lycopene occurred within 24 h of refluxing in ethyl acetate and the proportion of Z-isomers increased from 5.8% to 49.9%. Accordingly, the concentration of lycopene required to double quinone reductase (QR) activity in Hepa 1c1c7 cells decreased from >100 to ∼22 μg/mL following thermo-isomerisation, while cell viability was retained at >87% at levels up to 50 μg/mL. The inhibition of nitric oxide (NO) production in activated RAW 264.7 macrophages was 50% at ∼100 μg/mL thermo-isomerised lycopene and increased to >80% when the concentration in the medium was increased to 500 μg/mL. No significant inhibition of NO evolution by macrophages occurred with native (∼94% all-E) lycopene. Both QR induction and NO inhibition bioassays revealed that the structural changes evoked by thermo-isomerisation were accompanied by enhanced biological functionality.     

Comparison of Volatile Release in Tomatillo and Different Varieties of Tomato during Chewing

ABSTRACT: The release of volatiles from tomatillos (Physalis ixocarpa Brot.) and tomatoes in the mouthspace and nosespace was measured in real-time using selected ion flow tube mass spectrometry (SIFT-MS). (Z)-3-Hexenal, (E)-2-hexenal, hexanal, and 1-penten-3-one increased, while isobutyl alcohol, nonanal, and methylbutanal showed no significant change in the first 30 s of chewing. Cherry tomato released more (E)-2-hexenal, (Z)-3-hexenal, and 1-penten-3-one than tomatillo, Roma tomato, and vine-ripened tomato during chewing. The proportion of the average concentration of volatiles in the mouthspace after swallowing to before swallowing (MSas/MSbs) varied from 2.8% to 73.9% between different volatiles and varieties. Methylbutanal, hexanal, and nonanal were retained at a higher percentage in the mouth after swallowing than (Z)-3-hexenal, (E)-2-hexenal, 1-penten-3-one, and isobutyl alcohol. The proportion of the average volatile concentration in the mouthspace, to the headspace in a glass container (MS/HS) of 1-penten-3-one, hexanal, methylbutanal, and nonanal, and the proportion of nosespace to headspace (NS/HS) for 1-penten-3-one, hexanal, (Z)-3-hexenal, and nonanal was significantly higher in tomatillo than in tomatoes. There was no difference between tomatoes of different varieties in NS/HS ratio. Practical Application: The real-time volatile release from tomatillos and tomatoes was measured and compared. The information obtained on the dynamic generation of volatile compounds provides a better understanding of volatile release in the headspace of tomatillo and tomatoes. The compounds and their volatile release patterns were similar for the tomatillo and tomatoes. The green aldehydes released during chewing were not significantly higher than most tomato varieties, except for Roma tomatoes. Cherry tomato released relatively more volatiles during chewing, whereas Roma tomatoes were generally poor in mouthspace volatiles. The lingering of volatiles in the mouth after swallowing was different for different volatiles and varieties, which may appear as a sensory difference detected by consumers.     

Formation and characterisation of melanoidin-like polycondensation products from amino acids and lipid oxidation products

Various coloured water-soluble high molecular weight and water-nonsoluble reaction products were isolated from model reactions of an amino acid (glycine or lysine) and a lipid oxidation product (hexanal, (2E)-hexenal, (2E, 4E)-decadienal) with or without glucose. They were characterised by UV–visible absorbance measurements, elementary analysis, and thermal degradation followed by SPME–GC–MS analysis. The UV–visible absorbance spectra before and after dialysis indicated that the most important contributors to the formation of water-soluble coloured material were constituents of the low molecular fraction. Elementary analysis data indicated that a higher amount of nitrogen was incorporated in the high molecular weight fractions as compared to the water-nonsoluble fractions, except for the water-nonsoluble reaction products from amino acid/(2E, 4E)-decadienal interactions, which showed the lowest C/N ratio found. Volatile carbonyl compounds, furans, aliphatic compounds, pyridines, pyrroles and benzene derivatives were the main groups identified in the thermal degradation profile of each fraction tested. Especially pyridines seem typical indicators of amino acid–lipid oxidation product interactions.     

Effect of hot-air drying on flavour compounds of bell peppers (Capsicum annuum)

The influence of hot-air drying on the composition of both volatile and non-volatile flavour compounds of different Dutch bell pepper cultivars was investigated. Contents of glucose, fructose, ascorbic, citric, and oxalic acid decreased significantly after drying, while the levels of sucrose, malic, fumaric, and cis-aconitic acid increased. Glucose, fructose and ascorbic acid probably participate in Maillard reactions during heating. Different effects of drying could be distinguished on the composition of volatile compounds. The majority of these compounds evaporated during drying. Some compounds were partly retained in the dried bell peppers, whereas others disappeared completely. Gas chromatography-sniffing port analysis revealed that compounds with mainly “fresh” odour notes like lettuce/grassy/green bell pepper ((Z-2-3-hexenal), fruity/almond ((E)-2-hexenal), fruity (octanal), lettuce/green bell pepper ((Z)-3-hexenol), and grassy/green bell pepper ((Z)-2-hexenal) decreased or disappeared after drying. Another group of compounds increased or were formed during drying, like 4-octen-3-one, (E)-2-heptenal, (E)-2-octenal, (E,Z)- and (E,E)-2,4-heptadienal, decanal, and (E)-2-nonenal; most are known as autoxidation products of unsatu-rated fatty acids. The increased levels of 2-methylpropionic and 2- and 3-methylbutyric acid, 2-metlhylpropanal, and 2- and 3-methylbutanal seemed to be due to Strecker degradation. Gas chromatography-sniffing port analysis showed that the latter three compounds had distinct cacao, sweaty, and spicy odour characteristics.     

Identification of the odour-active aldehyde trans-4,5-epoxy-(E,Z)-2,7-decadienal in yuzu (Citrus junos Sieb. ex Tanaka)

Yuzu (Citrus junos Sieb. ex Tanaka) is a variety of sour citrus fruit that is popular in Japan. In this study, we investigated its aroma, which many people, especially in Japan, find appealing. Aroma extract dilution analysis was used to screen the odour-active compounds in the yuzu volatile oil. An unknown odorant with an albedo-like odour and a high flavour-dilution factor was detected. To identify this odorant, it was separated via flash column chromatography on silica gel and then fractionated by preparative high-performance liquid chromatography on a reverse-phase column. The volatile fraction, which contained a significant amount of the target unknown compound, was analysed by gas chromatography–mass spectrometry and gas chromatography–olfactometry to determine its mass spectrum, retention index, and odour quality. By comparing the resultant data with that of a synthesised authentic reference compound, it was evident that the unknown odorant was trans-4,5-epoxy-(E,Z)-2,7-decadienal (3); this is the first time that it has been identified as an odour-active unsaturated aldehyde in yuzu volatile oil. From the results of a model formation experiment, we propose that trans-4,5-epoxy-(E,Z)-2,7-decadienal originates from α-linolenic acid via 13(S)-hydroperoxy-(Z,E,Z)-9,11,15-octadecatrienoic acid (13(S)-HPOT), which is a lipoxygenase-induced oxidation product of α-linolenic acid.     

Character impact odorants of boiled chicken: changes during refrigerated storage and reheating

 The most potent odorants of freshly boiled chicken and boiled, refrigerated and reheated chicken showing warmed-over flavour (WOF) were screened by dilution experiments. In total, 20 odorants were selected for quantification by stable isotope dilution assays. Calculation of odour activity values (ratio of concentration to odour threshold) indicated methanethiol, (E,E)- and (E,Z)-2,4-decadienal, (E,E)-2,4-nondienal, 2-furfurylthiol, hexanal, octanal and acetaldehyde as the character impact odorants of freshly boiled chicken. Refrigerated storage and reheating of boiled chicken led to a loss of meaty, chicken-like and sweet odour notes and to the formation of green, cardboard-like, metallic off-odours. These changes were mainly caused by a sevenfold increase of hexanal and a sixfold decrease of both (E,E)-2,4-decadienal and 2-furfurylthiol. Sensory experiments confirmed this conclusion. Received: 11 February 1997     

Character impact odorants of boiled chicken: changes during refrigerated storage and reheating

 The most potent odorants of freshly boiled chicken and boiled, refrigerated and reheated chicken showing warmed-over flavour (WOF) were screened by dilution experiments. In total, 20 odorants were selected for quantification by stable isotope dilution assays. Calculation of odour activity values (ratio of concentration to odour threshold) indicated methanethiol, (E,E)- and (E,Z)-2,4-decadienal, (E,E)-2,4-nondienal, 2-furfurylthiol, hexanal, octanal and acetaldehyde as the character impact odorants of freshly boiled chicken. Refrigerated storage and reheating of boiled chicken led to a loss of meaty, chicken-like and sweet odour notes and to the formation of green, cardboard-like, metallic off-odours. These changes were mainly caused by a sevenfold increase of hexanal and a sixfold decrease of both (E,E)-2,4-decadienal and 2-furfurylthiol. Sensory experiments confirmed this conclusion. Received: 11 February 1997     

Insecticidal activity of asarones identified in Acorus gramineus rhizome against three coleopteran stored-product insects

The insecticidal activities of Acorus gramineus rhizome-derived materials against adults of Sitophilus oryzae (L.), Callosobruchus chinensis (L.) and Lasioderma serricorne (F.) were examined using direct contact application and fumigation methods. The biologically active constituents of the Acorus rhizome were characterized as the phenylpropenes (Z)- and (E)-asarones by spectroscopic analysis. Responses varied with insect species, compound and exposure time rather than dose. In a filter paper diffusion test, (Z)-asarone caused 70% and 90% mortality against S. oryzae adults at 0.064 and 0.255 mg/cm² at 4 days after treatment, respectively, with 100% mortality at 7 days after treatment. (E)-Asarone at 0.255 mg/cm² was almost ineffective against S. oryzae adults at 7 days after treatment. Against C. chinensis adults at 0.064 mg/cm², (Z)- and (E)-asarones gave 100% mortality at 3 and 7 days after treatment, respectively. Against L. serricorne adults, (Z)-asarone gave 90% and 83% mortality at 0.255 and 0.064 mg/cm² at 7 days after treatment, respectively, whereas (E)-asarone at 0.255 mg/cm² was almost ineffective at 7 days after treatment. These results indicate that the toxicity of asarones might be due to the cis configuration rather than to the position of the double bond. In a fumigation test, (Z)-asarone at 0.577 mg/cm² was much more effective against adults of all three insect species in sealed containers than in open ones, indicating that the insecticidal activity of the compound was largely attributable to fumigant action.     

Identification and olfactometry of French fries flavour extracted at mouth conditions

The aim of this study was to isolate and identify odour active compounds from French fries at mouth conditions. Volatile compounds were released from French fries by purge-and-trap, trapped on Tenax TA, and identified with GC–MS. GC–olfactometry was used to determine odour active compounds with a trained panel using the detection frequency method. A total of 122 compounds were identified of which 85% originated from either sugar degradation and/or Maillard reaction and 15% from lipid degradation, based on relative areas. About 50 odour active compounds were, due to coelution, responsible for 41 odours perceived by the panel. 3-Methylbutanal and 2-methylbutanal, hexanal, 2,3-dimethylpyrazine, 2-methylpropanal, 2,3-butanedione, pyridine, heptanal, 2,5-dimethylpyrazine and/or 2,6-diemethylpyrazine and/or ethylpyrazine, dimethyl trisulfide, octanal, phenylacetaldehyde, 2,5-diethylpyrazine, (E)-2-nonenal, 3-methylbutanoic acid and/or 2-methylbutanoic acid, (E,Z)-2,4-heptadienal, (E)-2-octenal, 5-ethyl-2,3-dimethylpyrazine and/or 2-ethyl- 3,5-dimethylpyrazine, nonanal, and tentatively 2-methylpyrrole had the highest detection frequencies. This resulted in a strong malty and fried potato note, combined with caramel/buttery, green, spicy, and deep-fried notes. Also chemical and sweaty odours were observed.     

Study of the aroma compounds of rose apple (<Emphasis Type="Italic">Syzygium jambos</Emphasis> Alston) fruit from Brazil

Volatiles of the headspace and total aqueous extract from the rose apple fruit were investigated by gas chromatography (GC)–flame ionization detection, GC–mass spectrometry and GC–olfactometry/aroma extract dilution analysis O/AEDA). The headspace fraction was rich in low boiling compounds, while medium and high volatility components predominated in the total aqueous extract. GC–O/AEDA revealed that hexanal, 3-penten-2-one, hexanol, (Z)-3-hexen-1-ol, linalool, isovaleric acid, benzyl alcohol, 2-phenylethylalcohol and (E)-cinnamaldehyde were potent odorants contributing to the headspace aroma. Thus, they might be related to the first odour impression of the fruit. Other potent volatiles, such as caproic and phenylacetic acids, methyl-(E)-cinnamate and (E)-cinnamyl alcohol were identified in the total aqueous extract, only. These results indicated that some volatiles, with medium and high boiling points, might also contribute to the overall rose apple flavour. Besides them, volatiles with lower odour potency, such as 7-octen-4-ol, acetic acid, 2-octen-1-ol and cinnamic acid, could have some additional effect for the overall fruit aroma.     

Potent odorants causing the warmed-over flavour in boiled beef

Summary The flavour compounds showing higher odour units resulting from peroxidation of unsaturated fatty acids were analysed comparatively in freshly boiled beef and in a stored (48 h, 4° C) sample exhibiting warmed-over flavour. The results obtained by aroma extract dilution analysis revealed that this flavour was mainly caused by hexanal, 1-octen-3-one, (E)- and (Z)-2-octenal, (Z)-2-nonenal, (E, E)-2,4-nonadienal andtrans-4,5-epoiiy-(E)-2-decenal.

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Intensive Geruchsstoffe des Warmed-over Flavour (WOF) von gekochtem Rindfleisch

Zusammenfassung Die Aromastoffe mit hohen Aromawerten, die aus der Peroxidation ungesättigter Fettsäuren hervorgehen, wurden in frisch gekochtem Rindfleisch und in einer gelagerten (48 h, 4 °C) Probe mit WOF analysiert. Ein Vergleich der Ergebnisse von Aromaextraktverdünnungsanalysen ergab, daß der WOF hauptsächlich durch Hexanal, 1-Octen-3-on, (E)- und (Z)2-Octenal, (Z)-2-Nonenal, (E, E)-2,4-Nonadienal sowietrans-4,5-Epoxy-(E)-2-decenal verursacht wird.

     

Predicting the organoleptic stability of beer from chemical data using multivariate analysis

Delaying flavour staling, to prolong the shelf life of beer, is one of the greatest challenges facing the brewing industry today. In this study, a series of lager beers were brewed using five European barley varieties and four chemical indicators of the degree of beer ageing were correlated with the sensory evaluation: E-2-nonenal, β-damascenone, 2-furaldehyde and 5-hydroxymethyl-2-furaldehyde (5-HMF). A statistical strategy using principal component analysis and multiple linear regression was applied to draw relationships between the sensory and chemical data sets. Additionally, the relative significance of each of the chemical data on the organoleptic stability of beer was evaluated within the method. 5-HMF was the only studied carbonyl compound whose concentration cannot be used for predicting the total taste score of beers. E-2-nonenal, in contrast, was found to be the most discriminant carbonyl compound under consideration for predicting the flavour stability of beer.     

Profiles of volatile compounds from some monovarietal Tunisian virgin olive oils. Comparison with French PDO

The volatile profiles of seven Tunisian and four French virgin olive oils were established by solid phase micro-extraction (SPME) and gas chromatography (GC), using flame ionisation and mass spectrometer detectors. Eighty-six compounds were identified and characterized, representing 97.4–99.9% of the total GC area. (E)-2-hexenal, the main compound extracted by SPME, characterized the olive oil headspace for approximately 90% of the oils examined. Significant differences in the proportions of volatile constituents from oils of different varieties were detected. The results demonstrated that the accumulation of the different metabolites in the oils obtained from the various cultivars was strictly connected with the varietal parameters on the basis of the enzyme differences genetically determined. This feature made possible the differentiation of the examined cultivars on the basis of the percent of each metabolite.     

Effect of dietary lipid sources on odour‐active compounds in muscle of turbot (Psetta maxima)

Odour‐active compounds in muscle of turbot (Psetta maxima) fed experimental diets containing fish oil (FO), soybean oil (SO) or linseed oil (LO) were investigated by a gas chromatography/olfactometry technique. Thirty‐one areas associated with odours were detected in muscle extracts. Among the compounds responsible for these odours, 23 were formed by oxidation of unsaturated fatty acids. Independently of diet, (E)‐2‐penten‐1‐ol and (E)‐3‐hexen‐1‐ol contribute strongly to the odour of turbot. (E,Z)‐2,6‐Nonadienal, (E)‐2‐pentenal and (E,E)‐1,3‐(Z)‐5‐octatriene seem to contribute strongly to the odour of turbot fed diets containing high levels of n‐3 PUFA (FO and LO groups). Hexanal and decanal show a high detection frequency in turbot fed diets containing vegetable oils. Odorous compounds which are not formed by lipid oxidation (methional, 1‐acetyl pyrazine, 4‐ethyl benzaldehyde and 2‐acetyl‐2‐thiazoline) were not affected by dietary lipid sources. © 2001 Society of Chemical Industry