Impact odorants contributing to the fungus type aroma from grape berries contaminated by powdery mildew (Uncinula necator); incidence of enzymatic activities of the yeast Saccharomyces cerevisiae

Powdery mildew due to the fungus Uncinula necator is an important disease for the vineyard. The development of the fungus at the surface of the berries leads to the occurrence of a very characteristic and sometimes intense mushroom-type odor cited as an important default for grapes quality. Gas chromatography/olfactometry, gas chromatography, and multidimensional gas chromatogaphy/mass spectrometry techniques were used to investigate the most important odorants of grapes diseased by powdery mildew. Among 22 odorants detected, strongly odorant compounds were identified or tentatively identified in purified extracts obtained from grapes diseased by powdery mildew. Aroma extraction dilution analysis (AEDA) analysis revealed that 1-octen-3-one (mushroom odor), (Z)-1,5-octadien-3-one (geranium-leaf odor), and an unidentified odorous zone (fishy-mushroom like odor) were the most potent volatiles of the diseased grapes. In the presence of nonproliferating Saccharomyces cerevisiae yeast cells, and consequently during alcoholic fermentation, the enzymatic reduction of 1-octen-3-one and (Z)-1,5-octadien-3-one to much less odorant compounds, namely 3-octanone and (Z)-5-octen-3-one, was shown. Those results explain to some extent the disappearance of the fungal aroma specific to powdery mildew grapes during alcoholic fermentation.     

Identification of character impact odorants of different soybean lecithins.

The potent odorants of standardized, enzymatically hydrolyzed, and deoiled soybean lecithins were characterized systematically by combined gas chromatography/mass spectrometry and olfactometry. Sixty-one odorants were identified; 53 of these odor-active compounds have not previously been reported as odorants of soybean lecithin flavor. By aroma extract dilution analysis and modified combined hedonic and response measurement the following odorants showed the highest flavor dilution factors and CHARM values: (E,E)-2, 4-decadienal (deep-fried), (E)-beta-damascenone (apple-like), 2, 3-diethyl-5-methylpyrazine (roasty, earthy), (E)-2-nonenal (cardboard-like), trans-4,5-epoxy-(E)-2-decenal (metallic), 1-nonen-3-one (mushroom-like), 2-ethyl-3,5-dimethylpyrazine (roasty, earthy), and 1-octen-3-one (mushroom-like). Enzymatic hydrolysis intensified especially the roasty sensation of 2, 3-diethyl-5-methylpyrazine, whereas deoiling effected a general significant decrease in olfactory perception on the nitrogen-containing compounds. In addition, sensory profiles of nasal and retronasal lecithin odor were performed.     

Identification of ethyl 2-sulfanylacetate as an important off-odor compound in white wines

A number of Sauvignon blanc wines made from hard pressed juices in an inert atmosphere (nitrogen) or in contact with oxygen were identified as having heavy off-flavors to varying degrees. Samples were extracted and subjected to time-based HPLC fractionation. The fractions were assessed by a sensory panel and those with unpleasant, irritating, off-odors were re-extracted. The extracts evaluated by gas chromatography coupled with olfactometry revealed a number of odoriferous zones, including one with an off-odor similar to the one perceived in two HPLC fractions. The odor was less intense in fractions previously supplemented with copper sulfate, suggesting that the compound(s) responsible were possibly thiol-related. A selective thiols extraction protocol and the analysis of the extract by gas chromatography coupled with mass spectrometry identified a new potent thiol in these wines. The compound responsible for the odoriferous zone, ethyl 2-sulfanylacetate (1), had an odor reminiscent of baked beans and Fritillaria meleagris bulbs. Its perception threshold was determined and sensory studies using graduated supplementation in dry white wines demonstrated its contribution to the off-odor observed in dry white wines.     

Quantification and sensory studies of character impact odorants of different soybean lecithins.

Fifty-four potent odorants in standardized, hydrolyzed, and deoiled and hydrolyzed soybean lecithins were quantified by high-resolution gas chromatography/mass spectrometry (HRGC/MS). The characterization of their aroma impact was performed by calculation of nasal (n) and retronasal (r) odor activity values (OAVs). For this, the nasal and retronasal recognition thresholds of 18 odor-active compounds were determined in vegetable oil. The following compounds showed the highest nOAVs: 2,3-diethyl-5-methylpyrazine, methylpropanal, acetic acid, pentanoic acid, 2-ethyl-3,5-dimethylpyrazine, pentylpyridine, (Z)-1,5-octadien-3-one, 2-methylbutanal, and beta-damascenone. In addition to the compounds above, 1-octen-3-one, 1-nonen-3-one, and 3-methyl-2,4-nonandione showed potent rOAVs. The results of quantification and OAV calculation were confirmed by a model mixture of 25 impact odorants, which yielded a highly similar sensory profile to that of the original soybean lecithin. The sensory importance of pyrazines and free acids increased through enzymatic hydrolysis and decreased by the process of deoiling. The impact of unsaturated ketones on the lecithin aroma was not changed by either process.     

Characterization of some mushroom and earthy off-odors microbially induced by the development of rot on grapes

Grape rot is one of the major causes of degradation of many grape components and, thus, of deterioration in wine quality. In particular, the association of Botrytis cinerea with other, less visible, fungi frequently leads to the development of organoleptic defects in grapes and sometimes in wines. This study examines the nature of the volatile compounds responsible for mushroom, mossy, or earthy odors detected by gas chromatography-olfactometry in organic extracts of rotten grapes and musts. 2-Methylisoborneol, (-)-geosmin, 1-octen-3-one, 1-octen-3-ol, 2-octen-1-ol, and 2-heptanol were identified or tentatively identified. Their concentrations in musts were determined, and the impact of alcoholic fermentation by the yeast Saccharomyces cerevisiae was studied. The ability of fungi isolated from rotten grapes (Botrytis cinerea; Penicillium species including P. brevicompactum, P. expansum, P. miczynskii, P. pinophilum, P. purpurogenum, and P. thomii; Aspergillus section nigri; Rhizopus nigricans; and Coniothyrium sp.) to produce some of the identified compounds was evidenced.     

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.     

Aroma-active components in fermented bamboo shoots.

Bamboo shoots (Phyllostachys pubescens) were fermented and prepared in a traditional Taiwanese manner. Static and dynamic headspace extractions of volatile compounds were conducted by solid phase microextraction (SPME) and by cryogenic focusing purge and trap, respectively. Volatile analysis was conducted with gas chromatography and mass spectrometry. Gas chromatography-olfactometry (GCO) was conducted utilizing the Osme time-intensity method. Of 70 volatile compounds detected, 29 possessed aroma activity, and the most odor active included p-cresol (barn-like), 2-heptanol (mushroom), acetic acid (vinegar), and 1-octen-3-ol (mushroom). SPME extracted 66 compounds, purge and trap extracted 14 compounds, and 12 compounds were common to both methods. The Osme GCO technique coupled with SPME is an effective tool for the extraction and evaluation of aroma-active headspace volatiles.     

Dynamic headspace gas chromatography/mass spectrometry characterization of volatiles produced in fish oil enriched mayonnaise during storage

Protection against lipid oxidation and formation of unpleasant fishy and rancid off-flavors in oil-in-water food emulsions, such as fish oil enriched mayonnaise, is difficult to achieve. Volatile profiles from stored mayonnaises with different oil phase compositions were collected using a developed dynamic headspace sampling technique, in which interfering acetic acid was removed in situ with potassium hydroxide, and subsequently 148 volatiles were characterized and monitored by gas chromatography/mass spectrometry. Multivariate statistics showed correlation between the concentration of 62 volatiles and the fish oil and storage parameters, indicating the formation of lipid oxidation products, which impose fishy off-flavors. Further verification was obtained by gas chromatography/olfactometry, by which, among 78 odors, cis-4-heptenal and trans,cis-2,4-heptadienal were detected as distinct fishy notes. In total, 27 volatiles, including 1-penten-3-one, cis-2-penten-1-ol, cis-3-hexenal, cis-4-heptenal, 1-octen-3-one, 1,cis-5-octadien-3-one, 1-octen-3-ol, trans,cis-2, 4-heptadienal, and trans,cis-2,6-nonadienal, were suggested to contribute to the developed unpleasant fishy and rancid off-flavors.     

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.     

Composition of the essential oil of Mentha microphylla from the Gennargentu Mountains (Sardinia,Italy)

The essential oil obtained by hydrodistillation of the fresh aerial parts of Mentha microphylla C. Kock (Lamiaceae) collected on the Gennargentu Mountains (Sardinia, Italy) has been investigated by gas chromatography (GC) and GC/mass spectrometry (MS). The main constituents that resulted were pulegone (34.1%), piperitenone oxide (32.9%), and piperitenone (11.3%). The presence of small amounts of compounds such as ethyl hexanoate, 1-octen-3-ol, nonanal, and ethyl 2-methylbutanoate could justify the particular odorous profile of the plant, resembling the aroma of milk and other dairy products such as mozzarella.     

Characteristic volatiles from young and aged fruiting bodies of wild Polyporus sulfureus (Bull.:Fr.) Fr

The volatile compounds of fresh fruiting bodies of wild Polyporus sulfureus (Bull.:Fr.) Fr. growing on oak trees were isolated by continuous liquid-liquid extraction (CLLE) and investigated by high-resolution gas chromatography-mass spectrometry (HRGC-MS) on two GC columns of different polarity (DB-5 and ZB-WAX), and by gas chromatography-olfactometry (GC-O). A total of 40 major volatile compounds from the young samples were identified and semiquantified. Five odorous compounds were determined to be responsible for the characteristic flavor of young Polyporus sulfureus: 1-octen-3-one, 1-octen-3-ol, 3-methylbutanoic acid, phenylethanol, and phenylacetic acid. Four volatiles investigated by GC-O and detected by GC-MS were determined as the characteristic odorants of aged species: 2-methylpropanoic acid, butanoic acid, 3-methylbutanoic acid, and phenylacetic acid. The comparative results revealed that the volatile composition of the fruiting bodies even from the same fungal species may greatly vary with its host, location, and age.     

Identification of metallic-smelling 1-octen-3-one and 1-nonen-3-one from solutions of ferrous sulfate

Taste threshold tests of ferrous sulfate (FeSO4) solutions have been confounded by the presence of putative odorants. To detect the presence of odorants released from these solutions solid-phase microextraction (SPME) was used to collect volatiles in the headspace above FeSO4 solutions. Gas chromatography-olfactometry of samples collected over three time periods (1, 5, and 16 h) and at two temperatures (22 and 37 degrees C) revealed the presence of several metallic-smelling odorants in the headspace. Using authentic standards, two of the odorants were conclusively identified as 1-octen-3-one and 1-nonen-3-one. Trace levels of other odorants were also detected, but dilution experiments indicated that 1-nonen-3-one was at least 10 times more potent than anything else released from the solutions. 1-Octen-3-one and 1-nonen-3-one are excellent candidates for the metallic odor responses often observed in threshold testing of solutions of FeSO4.     

微波烫漂和速冻加工黑毛豆仁挥发性风味成分分析

采用固相微萃取（SPME）与气相色谱-质谱（GC-MS）联用技术,分析微波烫漂和速冻后新大粒1号黑毛豆仁挥发性风味成分的变化。结果表明：黑毛豆仁鲜样、微波烫漂和速冻处理后分别检测到31、34和32种挥发性风味成分,主要为醇类、醛类、酮类化合物。1-辛烯-3-酮、己醛、（E,Z）-2,6-壬二烯醛、1-戊烯-3-酮、（E...     

热风联合压差膨化干燥对苏99-8毛豆仁风味和品质的影响

使用固相微萃取(HS/SPME)-气质联用(GC/MS)技术对苏99-8毛豆仁鲜样和热风干燥毛豆仁挥发性成分进行分析,同时对2种干燥产品的感官品质、营养成分含量和质构特性进行比较。结果表明,在毛豆仁鲜样、热风干燥和热风联合压差膨化干燥制备的毛豆仁产品中分别检测出32、31、35种风味成分。鲜样中(Z)-3-己烯醇、正己醛、(E)-2-己烯醛、1-辛烯-3酮和1-戊烯-3酮对其风味相对贡献较大。热风联合压差膨化干燥后毛豆仁醛类化合物明显增多,出现了杂环类、酯类、酸类及含硫化合物,2-庚烯醛、正己醛、正戊醛、1-辛烯-3-醇、2-辛烯醇、1-辛烯-3酮、乙酸异丙烯酯、2,3,5-三甲基吡嗪和2,6-二甲基吡嗪、二甲基亚砜对热风联合压差膨化干燥后毛豆仁风味贡献较大,使毛豆具有较浓的豆类清香味和浓厚的焙烤香气,造就了热风联合压差膨化干燥毛豆仁脆粒的独特风味。热风联合压差膨化干燥毛豆仁的感官品质和质构特性明显优于热风干燥毛豆仁。     

Influence of prefermentative treatments to the major volatile compounds of Assyrtiko wines

A study of the volatile fraction of Assyrtiko wines, using gas chromatography coupled with olfactometry, was realized. Twenty-seven volatile compounds were identified as potent odorants, most of them originating from the fermentation process. Quantification of the major volatile compounds was realized developing a rapid analytical method based on fractionation of a 50 mL wine aliquot using C 18-reversed phase adsorbent. After elution of the volatile compounds with pentane-diethyl ether and concentration under nitrogen, the final wine extract was injected in a gas chromatography-flame ionization detection system. The method allows satisfactory determination of more than 15 volatile compounds of wine. The linearity of the method gave a typical r (2) between 0.990 and 0.999, while reproducibility ranged from 5.1 to 12.2% (as relative standard deviation) with 9.5% as the average. The method was applied to wines produced by Assyrtiko grapes (AOC Santorini), for two consecutive years, to compare the effect of skin contact prior to fermentation and the must clarification process. Direct press and skin contact wines were differentiated analytically; however, highly significant differences were not. Inversely, the differences found between direct press/clarified and nonclarified wines were significant. Wines produced by direct press and clarified must presented significantly higher levels of ethylic esters and fusel alcohol acetates but lower fusel alcohol levels, leading probably to more fruity wines. This difference, between clarified and nonclarified grape musts, was not significant in the case of the wines produced by skin contact of Assyrtiko berries. These findings were validated by preference sensory analysis tests.     

Aroma active components in aqueous kiwi fruit essence and kiwi fruit puree by GC-MS and multidimensional GC/GC-O

Gas chromatography-mass spectrometry (GC-MS) and multidimensional gas chromatography olfactometry (GC/GC-O) were utilized to study the aroma profile and the aroma active components of commercial kiwi essence and the initial fresh fruit puree. Totals of 29 and 33 components were identified and quantified in the essence and the puree, respectively. Ten components were quantified for the first time as constituents of the kiwi fruit including 3-penten-2-ol, 3-hydroxy-2-butanone, 3-methyl-2-butenal, 2-hexanol, nonanal, 3-methyl-1-butanol, 2-methyl-1-butanol, 3-methyl-2-butanone, 3-methyl 3-buten-2-one, and octane. Analysis of these samples by multidimensional gas chromatography-olfactometry (GC-O) allowed for the identification of >80% of the aroma active components present at level traces in this fruit. A total of 35 components appear to contribute to the aroma of kiwi fresh puree and its aqueous essence. Components described for the first time as constituents of the aroma profile in this fruit were 2-ethylfuran, 3-methyl-1-butanol, 2-cyclohexen-1-one, (E,E)-2,6-nonadienal, diethyl succinate, and hexyl hexanoate.     

Identification and characterization of complex bioactive oligosaccharides in white and red wine by a combination of mass spectrometry and gas chromatography

Over forty-five complex free oligosaccharides (of which several are novel) have been isolated and chemically characterized by gas chromatography and high resolution and high mass accuracy matrix-assisted laser desorption/ionization mass spectrometry (MALDI-FTICR MS) in red and white wines, Grignolino and Chardonnay, respectively. Oligosaccharides with a degree of polymerization between 3 and 14 were separated from simple monosaccharides and disaccharides by solid-phase extraction. The concentrations of free oligosaccharides were over 100 mg/L in both red and white wines. The free oligosaccharides-characterized for the first time in the present study-include hexose-oligosaccharides, xyloglucans, and arabinogalactans and may be the natural byproduct of the degradation of cell wall polysaccharides. The coupled gas chromatography and accurate mass spectrometry approach revealed an effective method to characterize and quantify complex functional oligosaccharides in both red and white wine.     

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.     

Volatile compounds in samples of cork and also produced by selected fungi

The production of volatile compounds by microbial communities of cork samples taken during the cork manufacturing process was investigated. The majority of volatiles were found in samples collected at two stages: resting after the first boiling and nontreated cork disks. Volatile profiles produced by microbiota in both stages are similar. The releasable volatile compounds and 2,4,6-trichloroanisole (TCA) produced in cork-based culture medium by five isolated fungal species in pure and mixed cultures were also analyzed by gas chromatography coupled with mass spectrometry (GC-MS).The results showed that 1-octen-3-ol and esters of fatty acids (medium chain length C8-C20) were the main volatile compounds produced by either pure fungal species or their mixture. Apparently, Penicillium glabrum is the main contributor to the overall volatile composition observed in the mixed culture. The production of releasable TCA on cork cannot be attributed to any of the assayed fungal isolates.