Identification of potent odorants formed by autoxidation of arachidonic acid: structure elucidation and synthesis of (E,Z,Z)-2,4,7-tridecatrienal.

The aroma composition of autoxidized arachidonic acid was characterized by aroma extract dilution analysis. The most potent odorant was trans-4,5-epoxy-(E)-2-decenal followed by 1-octen-3-one, (E,Z)-2,4-decadienal, (E,Z,Z)-2,4,7-tridecatrienal, (E,E)-2,4-decadienal, and hexanal. (E,Z,Z)-2,4,7-Tridecatrienal was unequivocally identified by mass spectrometry and nuclear magnetic resonance (NMR) data. The stereochemistry of its extended double-bond system was elucidated on the basis of NMR measurements. The target compound was synthesized in four steps starting with bromination of 2-octyn-1-ol, followed by copper-catalyzed coupling of the bromide with ethylmagnesium bromide and (E)-2-penten-4-yn-1-ol. Partial hydrogenation of the resulting C(13)-compound with triple bonds in the positions C-4 and C-7 gave rise to (E,Z,Z)-2,4,7-tridecatrien-1-ol, which was finally oxidized to the target compound. It exhibits a typical egg-white-like, marine-like odor at low concentrations, and an intense orange-citrus, animal-like odor at higher concentrations. Its odor threshold was estimated by gas chromatography-olfactometry to be 0.07 ng/L air, which is of the same order of magnitude as that reported for 1-octen-3-one and (E,E)-2,4-decadienal.     

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.     

Critical comparison of three olfactometric methods for the identification of the most potent odorants in cooked mussels (Mytilus edulis)

Three olfactometric methods (olfactometry global analysis, OSME, and AEDA) were compared to evaluate the main impact odorants of cooked mussels. The results obtained from these methods were very similar and well correlated. On the basis of the three techniques, 42 odor-active compounds were detected and 28 were identified. Among these compounds, 6 odorants seem to contribute actively to the aroma of mussels: 2,3-butanedione (4) (buttery, caramel-like odor), (Z)-4-heptenal (14) (boiled potato-like odor), (E)-2-penten-1-ol (17) (mushroom-like odor), 2-ethylpyrazine (19) (nutty odor), methional (25) (boiled potato-like odor), and (E,E)-2,4-octadienal (32) (cucumber-like odor).     

Identification of the main odor-active compounds in musts from French and Romanian hybrids by three olfactometric methods

Three olfactometric methods (frequency of detection, time--intensity method, and aroma extract dilution analysis) were used to evaluate the main odorants of three musts obtained from French--Romanian hybrids (Valerien, Admira, and Brumariu). The three methods allow detection of the same odor-active compounds. The results obtained from these methods were closely related. Nineteen odor-active compounds were detected, and 13 were identified. The three methods showed the importance of an unidentified compound with a grape and grape juice aroma note in the three musts. Among the other compounds, 3-hexen-1-al, (E,Z)-2,6-nonadien-1-ol, and 1-ccten-3-one seemed to contribute actively to the odor of Valerien must. 3-(Methylthio)propanal and hexanal were contributors to the Admira and Brumariu odor. Phenylacetaldehyde was one of the main odor-active compounds in must from Admira.     

Off-vine grape drying effect on volatile compounds and aromatic series in must from Pedro Ximénez grape variety

Changes in 36 volatile compounds of must from ripe grapes dried by direct exposure to sun and must from ripe grapes were studied. Compounds not dependent on sampling site in both musts were selected, and their concentration/Brix degree ratio values, were subjected to variance analysis. Only butan-1-ol and isoamyl alcohols showed no differences, while (E)-hex-3-en-1-ol, (Z)-hex-3-en-1-ol, (E)-hex-2-en-1-ol, (E)-hex-2-enal, hexanoic acid, isobutanol, benzyl alcohol, 2-phenylethanol, gamma-butyrolactone, gamma-hexalactone, and 5-methylfurfural, showed significant differences between the two must types, which may be ascribed to the drying process. An approach to describe must odor has been carried out by grouping volatile compounds in aromatic series, increasing their values in the fruity, solvent, sweet, and roasted series and diminishing the herbaceous as a consequence of the drying process.     

Identification of the medicinal off-flavor compound formed from ascorbic acid and (E)-hex-2-enal

A test apple beverage made up of apple juice (20%), high-fructose corn syrup (11.5%), citric acid (0.43%), trisodium citrate (0.02%), apple-odor flavor (0.1%), and ascorbic acid (0.02%) was stored at 40 °C and then analyzed for the change of odor in the beverage. Although no thermoacidophilic bacteria (TAB) were detected, a medicinal off-flavor was perceived after the 8 weeks of storage. Model experiments on the ingredients of the test apple beverage revealed that the off-flavor compound had been formed by ascorbic acid and (E)-hex-2-enal. Synthesis and NMR (1H, 13C, HMQC, and HMBC) analyses identified the compound as 6-propylbenzofuran-7-ol. The odor quality, retention index (RI), and mass spectrum of synthetic 6-propylbenzofuran-7-ol were identical with those of the medicinal odor compound from the test apple beverage. Sensory evaluation revealed the recognition thresholds for medicinal odor were 31.4 ppb in water and 24.0 ppb in apple beverage, and the detection thresholds were 19.6 ppb in water and 8.6 ppb in apple beverage, respectively. The quantified concentration of 6-propylbenzofuran-7-ol formed in test apple beverage was 90 ppb, approximately. This concentration was well above the odor threshold, so it was concluded that the compound was the source of the medicinal off-flavor.     

Evaluation of the key aroma compounds in beef and pork vegetable gravies a la chef by stable isotope dilution assays and aroma recombination experiments

Although the aroma compounds of meat processed as such have been studied previously, data on complete homemade dishes containing beef and pork meat were scarcely studied. Recently, 38 odor-active compounds were characterized in beef and pork vegetable gravies using GC-olfactometry. In the present investigation, the most odor-active compounds were quantitated in a freshly prepared stewed beef vegetable gravy (BVG) as well as a stewed pork vegetable gravy (PVG) by means of stable isotope dilution assays. Calculation of odor activity values (OAVs; ratio of concentration to odor threshold) revealed 3-mercapto-2-methylpentan-1-ol, (E,E)-2,4-decadienal, (E,Z)-2,6-nonadienal, (E)-2-decenal, (E)-2-undecanal, and 3-hydroxy-4,5-dimethyl-2(5H)-furanone as the most potent odorants in both gravies. However, significantly different OAVs were found for 12-methyltridecanal, which was much higher in the BVG, whereas (E,Z)-2,4-decadienal showed a clearly higher OAV in the PVG. Aroma recombination experiments performed on the basis of the actual concentrations of the odorants in both gravies revealed a good similarity of the aromas of both model mixtures containing all odorants with OAVs > 1 with those of the original gravies.     

Odor-active compounds of Iberian hams with different aroma characteristics

The odor-active compounds of different commercial types of Iberian hams (Montanera and Pienso) were researched by gas chromatography-olfactometry based on a detection frequency method. The hams (long- and short-Montanera and Pienso Iberian hams) showed different sensory profiles, differences being significant for Montanera ham typical odor, aroma intensity and persistence, and cured and moldy aroma. Significant differences were also found for some odorants. The largest differences appeared in 2-acetyl-1-pyrroline, hexanal, (Z)-3-hexenal, ethyl 2-methylbutyrate, (E)-2-hexenal, 1-octen-3-one, 1-octen-3-ol, 2-propionyl-1-pyrroline, octanal, and an unknown odorant. Sensory characteristics and olfactometric profiles were significantly different between Montanera and Pienso hams. Significant differences also appeared between long- and short-Montanera hams, which shows great variability in this commercial type. Otherwise, the largest scores for moldy aroma in long-Montanera hams matched with the largest detection frequency of 1-octen-3-one and 1-octen-3-ol in this group.     

Quantitative determination of sulfur-containing wine odorants at sub parts per billion levels. 2. Development and application of a stable isotope dilution assay

[(2)H(10)]-4-Mercapto-4-methylpentan-2-one (d(10)-1), [(2)H(2)]-3-mercaptohexan-1-ol (d(2)-2), and [(2)H(5)]-3-mercaptohex-1-yl acetate (d(5)-3), deuterated analogues of impact odorants of wines, were used to determine quantitatively the natural compounds in white wines (Muscadet, Sauvignon, and Bacchus) with a stable isotope dilution assay using gas chromatography coupled either with ion trap tandem mass spectrometry (GC-ITMS-MS) or with atomic emission detection monitored on sulfur-selective acquisition (GC-AED). The thiol compounds were recovered from wines by liquid-liquid extraction, then purified from the wine extracts by covalent chromatography, and analyzed. The quantitative determination of 4-mercapto-4-methylpentan-2-one 1 in the wines that were analyzed was performed better with GC-AED than with GC-ITMS-MS under the conditions that were used. However, the detection limit of the method was higher than the odor threshold of 4-mercapto-4-methylpentan-2-one 1 in wine (5 vs 0.8 ng/L). The levels of this compound in the Sauvignon and Bacchus wines were much higher than its odor threshold, but it was not detectable in the Muscadet wines. On the contrary, GC-ITMS-MS was much more sensitive than GC-AED for detection of 3-mercaptohexan-1-ol 2 and 3-mercaptohex-1-yl acetate 3, and the detection limits were much lower than their odor thresholds in wine. The former compound was detected in all of the Muscadet wines that were analyzed at levels always higher than its odor detection threshold, while the latter occurred at levels higher than its odor threshold in only one Muscadet wine.     

Odorous impact of volatile thiols on the aroma of young botrytized sweet wines: identification and quantification of new sulfanyl alcohols

Specific extraction of volatile thiols using sodium p-hydroxymercuribenzoate revealed the presence of three new sulfanylalcohols in wines made from Botrytis-infected grapes: 3-sulfanylpentan-1-ol (II), 3-sulfanylheptan-1-ol (III), and 2-methyl-3-sulfanylbutan-1-ol (IV). The first two have citrus aromas, whereas the third is reminiscent of raw onion. In addition, 2-methyl-3-sulfanylpentan-1-ol, which has a raw onion odor, was tentatively identified. Like 3-sulfanylhexan-1-ol (I), already reported in Sauternes wines, compounds II, III, and IV were absent from must. They were found in wine after alcoholic fermentation, and their concentrations were drastically higher when Botrytis cinerea had developed on the grapes. In the commercial botrytized wines analyzed, the mean levels of II, III, and IV were 209, 51, and 103 ng/L, respectively. Despite their low odor activity values, sensory tests showed additive effects among I, II, and III, thus confirming their olfactory impact on the overall aroma of botrytized wines.     

Comparison of two microalgal diets. 2. Influence on odorant composition and organoleptic qualities of raw oysters (Crassostrea gigas)

Oyster farming is of real economic interest in France. Oyster farmers attach more and more importance to improving the growth and the quality of their oysters. Some fatty acids known to be aroma precursors originate from microalgae such as Skeletonema costatum and Tahitian isochrysis clone. These microalgae were used to fatten oysters in order to observe their role in the development of oysters' aroma. This study shows that the profile of fatty acids of oysters is influenced by the contribution of fatty acids from the two microalgae (as reported in the first paper in this series: Pennarun, A.-L.; Prost, C.; Haure, J.; Demaimay, M. Comparison of Two Microalgal Diets. 1. Influence on the Biochemical and Fatty Acid Compositions of Raw Oysters (Crassostrea gigas). J. Agric. Food Chem. 2003, 51, 2006-2010 (in this issue)]. As a consequence, a microalgal diet causes changes in oysters' aroma composition. Aroma concentration depends on the content of fatty acids that are aroma precursors in oysters. Some aromas are characteristic of the diet of S. costatum, such as 6-methyl-5-hepten-2-one (ether odor), and others are characteristic of T. isochrysis, such as 3-nonyne (cucumber, marine odor), 6-(E)-nonen-1-ol (green and fresh odor), and 4-ethylbenzaldehyde (aniseed odor). Moreover, the organoleptic qualities (odor, taste, and texture) of oysters are modified by the diet of microalgae.     

Identification and sensory evaluation of volatile compounds in oxidized porcine liver

Headspace solid phase microextraction (HS-SPME) was used to isolate the off-flavor volatile compounds, which are formed during the oxidation of porcine liver induced by iron. Poly(dimethylsiloxane)/divinylbenzene fiber was used in the HS-SPME. Changes in the volatile compounds of oxidized porcine liver and unsaturated fatty acids induced by iron were examined. Results showed that 1-octen-3-one (metallic), hexanol (weak metallic), 1-octen-3-ol (mushroomlike), (E)-2-nonenal (cardboardlike), and (E,E)-2,4-decadienal (fatty, oily) were the main contributors to the overall off-flavor of porcine liver. The results of the sensory evaluation revealed that oxidized arachidonic acid has a major impact on metallic and liverlike off-flavor and that when liverlike off-flavor is perceived, metallic is also included. Oxidized linolenic acid was the most important contributor to the objectionable fishy off-flavor. Oxidized porcine liver exhibited distinct metallic, liverlike, and weak fishy background notes. Liverlike flavor had a high correlation coefficient with odor characteristics such as metallic (0.839) and fishy (0.777). In this study, it was clearly observed that the stronger the metallic and fishy off-flavor the higher the perception of liverlike off-flavor.     

茶叶挥发物对鞍形花蟹蛛觅食行为的影响

为了探明茶叶挥发物在鞍形花蟹蛛(Xysticus ephippiatus Simon)搜寻猎物——茶尺蠖(Ectropis obliqua Prout)过程中的作用,采用固相微萃取气相色谱质谱联用技术研究了茶尺蠖取食对茶树叶片挥发物释放的影响,并通过蜘蛛行为观测平台研究了蟹蛛在不同味源侧(觅食斑块)的活动行为。结果表明:对照叶片没有释放出挥发物,经茶尺蠖幼虫取食后的叶片能释放31种挥发物,其中有12种绿叶挥发物、9种萜类及其衍生物、4种芳香族挥发物和6种未知化合物。行为观测表明,雌、雄蟹蛛进入处理味源侧(茶尺蠖取食后的茶树叶片)和对照味源侧(未损伤茶树叶片)的初次选择均不存在差别(P>0.05),雌蛛进入处理味源侧和对照味源侧的频次分别为3.37±0.18和3.43±0.15,二者无明显区别(P>0.05);雄蛛进入两侧的频次分别为3.86±0.21和3.66±0.20,也无明显区别(P>0.05);雌蛛在处理味源侧和对照味源侧的停留时间分别为(922.57±19.59)s和(818.89±29.63)s,有极显著差异(P<0.01),雄蛛在两侧的停留时间分别为(937.97±18.05)s和(814.83±18.97)s,也有极显著差异(P<0.01),表明雌蛛、雄蛛在处理侧的停留时间明显延长。这说明,猎物取食诱导改变了茶树叶片挥发物的释放,而鞍形花蟹蛛能感知挥发物的变化并由此调整在不同觅食斑块中的停留时间。另外,本文还讨论了挥发物在蟹蛛搜寻猎物过程中的生态学意义。     

Odor potency of aroma compounds in Riesling and Vidal blanc table wines and icewines by gas chromatography-olfactometry-mass spectrometry

This study aimed to elucidate the odor potency of aroma compounds in Riesling and Vidal blanc (syn. Vidal) table wines and icewines from the Niagara Peninsula using stir bar sorptive extraction-gas chromatography-olfactometry-mass spectrometry. Dilution analysis determined the most odor-potent compounds in Vidal and Riesling icewines (n = 2) and table wines (n = 2) from a commercial producer. The top 15 odor-potent compounds in each wine were identified and quantified, resulting in 23 and 24 compounds for Riesling and Vidal, respectively. The most odor-potent compounds were β-damascenone, decanal, 1-hexanol, 1-octen-3-ol, 4-vinylguaiacol, ethyl hexanoate, and ethyl 3-methylbutyrate. In general, icewines had higher concentrations of most aroma compounds compared to table wines. Through computation of odor activity values, the compounds with the highest odor activity for the icewines were β-damascenone, 1-octen-3-ol, ethyl octanoate, cis-rose oxide, and ethyl hexanoate. In table wines the highest odor activity values were found for ethyl octanoate, β-damascenone, ethyl hexanoate, cis-rose oxide, ethyl 3-methylbutyrate, and 4-vinylguaiacol. These findings provide a foundation to determine impact odorants in icewines and the effects of viticultural and enological practices on wine aroma volatile composition.     

电子鼻结合HS-SPME-GC-MS分析辐照对甲鱼预制菜挥发性风味成分的影响

为了探究辐照对甲鱼预制菜挥发性风味成分的影响,采用0、4.7、7.1、9.9 kGy剂量⁶⁰Co-γ射线辐照处理甲鱼预制菜,通过感官评定并利用电子鼻结合顶空固相微萃取-气相色谱-质谱联用技术(HS-SPME-GC-MS)分析辐照前后挥发性风味成分的变化。结果表明,5 kGy以内剂量辐照对甲鱼预制菜的感官品质无明显影响,高于5 kGy会影响其气味和滋味,进而可能产生异味。辐照对甲鱼预制菜特征气味引起的差异主要表现在传感器响应值较高的芳香成分和有机硫化物、氮氧化合物、甲烷、醇类和醛酮类物质,利用主成分分析(PCA)和线性判别分析(LDA)能够有效区分经不同剂量辐照处理的甲鱼预制菜。4.7 kGy组与对照组气味差异较小,7.1、9.9 kGy组与对照组差异相对较大。不同剂量辐照后甲鱼预制菜挥发性成分的种类增加,醛类、酸类相对含量降低,烃类、芳香族类、酮类、酯类相对含量升高,醇类、含氮含硫及杂环类相对含量先降低后升高。相对气味活度值(ROAV)分析结果表明,壬醛、癸醛、辛醛、己醛、庚醛、1-辛烯-3-醇和2-戊基呋喃是甲鱼预制菜的关键风味成分,苯甲醛、苯乙醛、(E,E)-2, 4-癸二烯醛对其风味具有重要修饰作用。辐照后辛醛、己醛、1-辛烯-3-醇对甲鱼预制菜总体风味的贡献率降低,庚醛、2-戊基呋喃的贡献率先降低后增加,苯乙醛的贡献率增加并成为关键风味成分。因此,建议采用不超过5 kGy剂量的⁶⁰Co-γ射线辐照处理甲鱼预制菜,在杀菌的同时最大限度保持其原有风味。本研究结果为辐照技术在甲鱼预制菜杀菌保鲜中的应用提供了科学依据。     

生物质颗粒燃料成型的黏弹性本构模型

为研究生物质颗粒成型燃料压缩成型机理,该文用玉米秸秆、花生壳、小麦秸秆、大豆秸秆、棉花秸秆、木屑等6种生物质原料,采用生物质颗粒燃料成型机进行压缩成型,研究生物质颗粒燃料压缩成型过程,采用黏弹性理论,建立生物质颗粒成型燃料的本构模型,从力学角度提出生物质颗粒成型燃料的压缩成型机理,并研究对比不同种类生物质原料压缩的最大应力与能耗.结果表明,6种生物质原料中棉杆和木屑的最大应力较高,其余4种原料略低;木屑的压缩能耗最高,其次为棉秆、花生壳和豆秸,小麦秸秆和玉米秸秆较小.该研究结论为解决生物质颗粒成型燃料成型加工能耗高,关键部件受力磨损导致寿命低等问题提供一定参考.     

Oxidation products of alpha-farnesene associated with superficial scald development in d'Anjou pear fruits are conjugated trienols

Conjugated triene (CT) oxidation products of the acyclic sesquiterpene (E,E)-alpha-farnesene are thought to induce development of the physiological storage disorder superficial scald in apple and pear fruits of susceptible cultivars. CTs that accumulate in peel tissues of Granny Smith and Delicious apples after several weeks of cold storage are known to be conjugated trienols (CTols) rather than the corresponding hydroperoxides produced by in vitro autoxidation of alpha-farnesene. Here, it is shown that CTols are also the predominant in vivo oxidation products of alpha-farnesene in cold-stored pear fruit of the highly scald-susceptible d'Anjou cultivar. Analysis by octadecylsilane reversed phase high-performance liquid chromatography with diode array detection, gas chromatography with flame ionization detection, gas chromatography-mass spectrometry, and proton nuclear magnetic resonance spectroscopy identified 3,7,11-trimethyldodeca-1,3(E),5(E),10-tetraen-7-ol as the major CT in hexane extracts of peel tissue from d'Anjou pears stored for 3-5 months in air at -1 degrees C. The possible origins of CTols in apples and pears and the hypothesized role of these oxidation products of alpha-farnesene in the induction of scald are discussed. .     

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。     

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.