Identification of volatile compounds in soybean at various developmental stages using solid phase microextraction

Soybean (Glycine max) seed volatiles were analyzed using a solid phase microextraction (SPME) method combined with gas chromatography-mass spectrometry (GC-MS). Thirty volatile compounds already reported for soybean were recovered, and an additional 19 compounds not previously reported were identified or tentatively identified. The SPME method was utilized to compare the volatile profile of soybean seed at three distinct stages of development. Most of the newly reported compounds in soybean seed were aldehydes and ketones. During early periods of development at maturity stage R6, several volatiles were present at relatively high concentrations, including 3-hexanone, (E)-2-hexenal, 1-hexanol, and 3-octanone. At maturity stage R7 and R8, decreased amounts of 3-hexanone, (E)-2-hexenal, 1-hexanol, and 3-octanone were observed. At maturity stage R8 hexanal, (E)-2-heptenal, (E)-2-octenal, ethanol, 1-hexanol, and 1-octen-3-ol were detected at relatively high concentrations. SPME offers the ability to differentiate between the three soybean developmental stages that yield both fundamental and practical information.     

Flavor Volatiles of Rice During Cooking Analyzed by Modified Headspace SPME/GC‐MS

The flavor volatiles in three Japanese rice cultivars, Nihonbare, Koshihikari, and Akitakomachi, during cooking were directly extracted by using a modified headspace solid‐phase microextraction (SPME) method and analyzed by gas chromatography‐mass spectrometry (GC‐MS). A total of 46 components were identified, including aldehydes, ketones, alcohols, and heterocyclic compounds, as well as fatty acids and esters, phenolic compounds, hydrocarbons, etc. The amount of key odorant compounds increased with cooking, while the amount of low‐boiling volatiles decreased. The similarities and differences of the three rice cultivars were determined through a comparison of their volatile components. Nihonbare was characterized by a higher amount of indole but an absence of the chemical class of fatty acid esters. In contrast, both Koshihikari and Akitakomachi had a higher amount of 4‐vinylphenol and an abundance of those esters. Koshihikari and Akitakomachi were quite similar in regard to those flavor volatiles. Furthermore, the observations in the research may suggest that the volatile components at cooking stage (I) were the representatives of the flavor volatiles of uncooked rice, while the volatile constituents at cooking stage (IV) were the representatives of the flavor volatiles of cooked rice.     

Identification of new strawberry sulfur volatiles and changes during maturation

Two Florida strawberry cultivars, 'Strawberry Festival' and 'Florida Radiance', were harvested at five fruit developmental stages (white, half red, three-quarter red, full ripe, and overripe) at four harvest dates. A static headspace solid-phase microextraction (SPME) sampling technique coupled with gas chromatography (GC) using pulsed flame photometric detection (PFPD) was employed to measure 16 sulfur volatiles in these strawberries. A total of 7 sulfur volatiles have been previously reported, and 9 are reported for the first time in strawberries. Newly identified sulfur volatiles include methyl thiopropionate, ethyl thiobutanoate, methyl thiohexanoate, methyl (methylthio)acetate, ethyl (methylthio)acetate, methyl 2-(methylthio)butyrate, methyl 3-(methylthio)propionate, ethyl 3-(methylthio)propionate, and methyl thiooctanoate. Identifications were based on matching sulfur peak linear retention indexes (LRIs) of unknowns with authentic standards and gas chromatography-mass spectrometry (GC-MS) data. Concentrations were determined using both internal and external standards. Most sulfur volatiles increased with increasing maturity, with only concentrations of hydrogen sulfide and methanethiol remaining relatively consistent at all five stages. At the white and half red stages, most sulfur volatiles consisted of various alkyl sulfides. At three-quarter red (commercial ripe), full ripe, and overripe stages, the majority of sulfur volatiles consisted of sulfur esters. Most sulfur volatiles increased dramatically between the commercial ripe, full ripe, and overripe stages, increasing as much as 100% between full ripe and overripe. Principal component analysis indicated that sulfur volatiles could be used to distinguish overripe from full ripe and commercial ripe berries.     

Characterization of volatile compounds contributing to naturally occurring fruity fermented flavor in peanuts

Published research has indicated that ethyl 2-methylpropanoate, ethyl 2-methybutanaote, ethyl 3-methylbutanoate, hexanoic acid, butanoic acid, and 3-methylbutanoic acid are responsible for fruity fermented (FF) off-flavor; however, these compounds were identified in samples that were artificially created by curing immature peanuts at a constant high temperature. The objective of this study was to characterize the volatile compounds contributing to naturally occurring FF off-flavor. Volatile compounds of naturally occurring FF and no-FF samples were characterized using solvent-assisted flavor evaporation (SAFE), solid phase microextraction (SPME), gas chromatography-olfactometry (GC-O), and gas chromatography-mass spectrometry (GC-MS). Aroma extract dilution analysis (AEDA) identified 12 potent aroma active compounds, none of which were the previously identified esters, with no consistent differences among the aroma active compounds in no-FF and FF samples. Hexanoic acid alone was identified in the naturally occurring FF sample using the SAFE GC-MS methodology, whereas two of the three previously identified esters were identified in natural and artificially created samples. The same two esters were confirmed by SPME GC-MS in natural and artificially created samples. This study demonstrated the need for caution in the direct application of data from artificially created samples until those compounds are verified in natural samples. However, these results suggest that a laboratory method using SPME-GC techniques could be developed and correlated on an ester concentration versus FF intensity basis to provide an alternative to sensory analysis for detection of FF off-flavor in peanut lots.     

Flavor Volatiles in Three Rice Cultivars with Low Levels of Digestible Protein During Cooking

A modified headspace solid‐phase microextraction (SPME) method in conjunction with gas chromatography‐mass spectrometry (GC‐MS) has been used for the analysis of the flavor volatiles in three rice cultivars with low levels of digestible protein during cooking. Altogether, 77 volatile compounds were identified, of which 13 components were not previously reported in rice. A total of 61, 71, and 74 peaks, respectively, were assigned to Shunyou, LGC‐katsu, and LGC‐soft. Compounds that have been highlighted previously as flavor molecular markers in rice, including indole, vanillin, (E,E)‐2,4‐decadienal, (E)‐2‐nonenal, 2‐pentylfuran, and 2‐methoxy‐4‐vinylphenol, etc., were on the list of those identified components. Furthermore, similarities and differences of the flavor volatiles among the three rice cultivars were observed. Shunyou was characterized by a relatively higher amount of indole and LGC‐katsu had a very high amount of 4‐vinylphenol while both rice cultivars displayed an absence of vanillin, pentyl hexanoate, and hexyl hexanoate. In contrast, LGC‐soft contained vanillin and had an abundance of fatty acid esters such as pentyl hexanoate and hexyl hexanoate, together with a higher amount of γ‐nonalactone.     

Changes in the volatile compounds and chemical and physical properties of Kuerle fragrant pear (Pyrus serotina Reld) during storage

Volatiles from stored Kuerle fragrant pears (Pyrus serotina Reld) were studied using high-resolution gas chromatography and the solid-phase microextraction (SPME) method of gas chromatography/mass spectrometry (GC/MS). The dominant components were hexanal, ethyl hexanoate, ethyl butanoate, ethyl acetate, hexyl acetate, ethanol, alpha-farnesene, butyl acetate, and ethyl (E,Z)-2,4-decadienoate. By using GC-olfactometry, it demonstrated that the volatile compounds from SPME were responsible for the aroma of the Kuerle fragrant pear. The levels of sugars, organic acids, and phenolic acids in Kuerle fragrant pears were investigated using high-performance liquid chromatography (HPLC). Fructose was the dominant sugar, followed by glucose and sucrose. With increasing storage time, sucrose levels decreased; however, changes in fructose and glucose levels were not remarkable. There was a slight decrease in flesh firmness during storage. The general soluble solids concentration (SSC) declined slightly after 5 months storage. Some aroma-related volatile components increased during storage, while others decreased, especially the esters. The organic acids and phenolic acids also changed. The flavor of the Kuerle fragrant pears was affected by the change of volatile compounds and changes in chemical and physical properties.     

Headspace solid phase microextraction (SPME) analysis of flavor compounds in wines. Effect of the matrix volatile composition in the relative response factors in a wine model.

The application of headspace solid phase microextraction (SPME) for flavor analysis has been studied. Headspace SPME sampling was tested for nine common wine flavor compounds in 10% (v/v) aqueous ethanol: linalool, nerol, geraniol, 3-methyl-1-butanol, hexanol, 2-phenylethanol, ethyl hexanoate, ethyl octanoate, and ethyl decanoate. The chemical groups (monoterpenoids, aliphatic and aromatic alcohols, and esters) showed specific behavior in SPME analysis. SPME sampling parameters were optimized for these components. Relative response factors (RRFs), which establish the relationship between the concentration of the compound in the matrix liquid solution and the GC peak area, were estimated for all compounds. Log(10)(RRF) varied from 0 (3-methyl-1-butanol) to 3 (ethyl decanoate), according to their molecular weight. Quantification by SPME was shown to be highly dependent on the matrix composition; the compounds with higher RRF were the less affected. As a consequence, the data obtained with this methodology should be used taking into consideration these limitations, as shown in the analysis of four monovarietal Bairrada white wines (Arinto, Bical, Cerceal, and Maria Gomes).     

Headspace solid phase microextraction and gas chromatography-olfactometry dilution analysis of young and aged Chinese "Yanghe Daqu" liquors

The aroma compounds of young and aged Chinese "Yanghe Daqu" liquor samples were extracted by solid phase microextraction (SPME) and analyzed by gas chromatography (GC)-olfactometry dilution analysis. The original liquor samples were diluted with deionized water to give a final alcohol content of 14% (v/v). The samples were stepwise diluted (1:1) with 14% (by volume) ethanol-water solution and then extracted by headspace SPME. The samples were preequilibrated at 50 degrees C for 15 min and extracted with stirring at the same temperature for 30 min prior to injection into GC. The aroma compounds were identified by both GC-MS and GC-olfactometry using DB-Wax and DB-5 columns. The results suggested that esters were the major contributors to Yanghe Daqu liquor aroma. Ethyl hexanoate, ethyl butanoate, and ethyl pentanoate had very high flavor dilution values in both young and aged liquors (FD > 8192). Methyl hexanoate, ethyl heptanoate, ethyl benzoate, and butyl hexanoate could also be very important because of their high flavor dilution values (FD > or = 256). Moreover, two acetals, 1,1-diethoxyethane and 1,1-diethoxy-3-methylbutane, also were shown high flavor dilution values in Yanghe Daqu liquors (FD > or = 256). Other aroma compounds having moderate flavor dilution values included acetaldehyde, 3-methylbutanol, and 2-pentanol (FD > or = 32). Comparing young and aged liquors, the aroma profiles were similar, but the aroma compounds in the aged sample had higher flavor dilution values than in the young ones.     

Direct Extraction of Volatiles of Rice During Cooking Using Solid-Phase Microextraction

An apparatus that allows extraction and enrichment of flavor volatiles of rice during cooking using solid-phase microextraction (SPME) was designed and tested in the Japanese rice cultivar Akitakomachi. Because it is a solvent-free technique, no solvent contaminants were extracted during sampling. This technique enables one to place the fiber of SPME in the effluent of the flavor volatiles of the rice during cooking and it can also be used for simultaneous extraction of those volatiles in the course of the cooking process. Therefore, variations in the composition and amount of volatile compounds of rice during cooking can be determined. The overall flavor volatiles of rice during cooking have been analyzed by using this SPME method. Compounds that have been previously highlighted as flavor volatile markers, such as volatiles from oxidative degradation of lipids, products from thermal decomposition, and fatty acids existing in rice, were extracted directly by SPME in conjunction with this apparatus.     

Corn Gluten Meal Odorants and Volatiles After Treatment to Improve Flavor

Production of corn gluten meal (CGM), a high‐protein coproduct from wet milling of corn, is increasing as production of fuel ethanol from corn increases. Unpleasant taste and odor have limited the use of CGM in human food. Adjustment of pH and extraction with water have been reported to reduce the off‐flavor of CGM but the improvement is not enough for substantial addition of CGM to the human diet. More study of CGM is needed. In this study, volatile compounds released under different conditions of pH, water extraction, and temperature were identified and compared using solid‐phase microextraction‐gas chromatography‐mass spectrometry (SPME‐GC‐MS). The water‐extractable portion, which improves the taste of CGM by its absence, was dried and analyzed by SPME‐GC‐MS. In addition, materials extractable from CGM with methylene chloride were identified by gas chromatography‐mass spectrometry (GC‐MS). Further, the spontaneous generation of a CGM‐like odor accompanied by a change in physical appearance of the CGM sample was described. Flavors and odors known to be associated with the identified CGM compounds were listed. Some possible origins of the volatiles, from degradation of corn constituents or as fermentation products of the corn steeping process, were noted.     

Identification of monomenthyl succinate, monomenthyl glutarate, and dimenthyl glutarate in nature by high performance liquid chromatography-tandem mass spectrometry

Menthol, menthone, and other natural compounds provide a cooling effect and a minty flavor and have found wide application in chewing gum and oral care products. Monomenthyl succinate, monomenthyl glutarate, and dimenthyl glutarate provide a cooling effect without the burning sensation associated with menthol. Additionally, because they do not have a distinct flavor, they can be used in applications other than mint flavors. Because these menthyl esters have not been reported in nature, we undertook to identify a natural source for these cooling compounds. Using high performance liquid chromatography-tandem mass spectrometry, monomenthyl succinate was identified in Lycium barbarum and Mentha piperita, and monomenthyl glutarate and dimenthyl glutarate were identified in Litchi chinesis. The identifications were based on the correlation of mass spectrometric and chromatographic retention time data for the menthyl esters in the extracts with authentic standards which resulted in a 99.980% confidence in the identifications.     

Monitoring ester formation in grape juice fermentations using solid phase microextraction coupled with gas chromatography-mass spectrometry

Volatile esters contribute important floral and fruity sensory properties to wine. Numerous factors influence the biosynthesis and hydrolysis of esters throughout yeast fermentation; however, methods to monitor the dynamic changes in ester production that occur during winemaking processes are limited. In this study, we showed that solid phase microextraction (SPME), a rapid, solventless sampling procedure, combined with GC/MS analysis is a useful method for the nearly continuous analysis of volatile compounds such as esters that are produced during fermentation. Accuracy, precision, and limits of quantification were comparable to those of other sample preparation methods such as liquid-liquid extraction. Using GC/MS-SPME to monitor fatty acid ethyl esters and acetate esters, we obtained detailed information on the production patterns of ester formation during fermentation. This method now enables the monitoring of volatiles during fermentation and can provide greater insight into yeast metabolism and flavor formation.     

Postharvest changes in physicochemical properties and volatile constituents of apricot (Prunus armeniaca L.). Characterization of 28 Cultivars

To investigate the changes in physicochemical properties and volatile constituents in apricot during postharvest ripening, the volatile compounds of 28 apricot cultivars were investigated by means of liquid-liquid microextraction (LLME), GC-FID, and GC-MS. Fruits picked at their optimal harvestable stage of maturity were analyzed at harvest and after ripening at 20 degrees C under controlled conditions. Soluble solids (SS), titratable acidity (TA), levels of sugars (saccharose, fructose, and glucose), and organic acids (citric and malic acids) were also determined. Thirty-three volatile compounds, including 6 esters, 5 C6 compounds, 4 alcohols, 3 carbonyl compounds, 6 terpenic compounds, and 9 lactones, were identified. Changes in the levels of volatiles have been found to increase greatly during post-harvest ripening in comparison to the modifications observed for the other physicochemical characteristics. The discrimination of the 28 apricot cultivars into four distinguishable aroma groups was achieved by statistical treatment of the data including ANOVA, principal component, and cluster analyses.     

Characterization and semiquantitative analysis of volatiles in seedless watermelon varieties using solid-phase microextraction

Seedless triploid watermelons have increased in popularity since the early 1990s, and the demand for seedless fruit is on the rise. Sweetness and sugars are crucial breeding focuses for fruit quality. Volatiles also play an important role; yet, we found no literature for seedless varieties and no reports using solid-phase microextraction (SPME) in watermelon. The objective of this experiment was to identify volatile and semivolatile compounds in five seedless watermelon varieties using carboxen divinylbenzene polydimethylsiloxane solid-phase microextraction (SPME) with gas chromatography-mass spectrometry (GC-MS). Fully ripe watermelon was squeezed through miracloth to produce rapid juice extracts for immediate headspace SPME GC-MS. Aldehydes, alcohols, ketones, and one furan (2-pentyl furan, a lipid oxidation product) were recovered. On the basis of total ion count peak area, the most abundant compounds in five varieties were 3-nonen-1-ol/(E,Z)-2,6-nonadienal (16.5-28.2%), (E)-2-nonenal (10.6-22.5%), and (Z)-6-nonenal (2.0-11.3%). Hexanal was most abundant (37.7%) in one variety (Petite Perfection) [corrected] The most abundant ketone was 6-methyl-5-hepten-2-one (2.7-7.7%). Some sensory attributes reported for these compounds are melon, citrus, cucumber, orange, rose, floral, guava, violet, vegetable, green, grassy, herbaceous, pungent, fatty, sweet, and waxy. Identifying and relating these compounds to sensory attributes will allow for future monitoring of the critical flavor compounds in seedless watermelon after processing and throughout fresh-cut storage.     

Solid-phase microextraction (SPME) technique for measurement of generation of fresh cucumber flavor compounds

Investigations were carried out to determine whether flavor compounds characteristic for fresh cucumbers could be rapidly determined using a solid-phase microextraction (SPME) dynamic headspace sampling method combined with gas chromatography and flame ionization detection. Cucumbers were sampled, during blending, for fresh cucumber flavor compounds (E,Z)-2,6-nonadienal and (E)-2-nonenal. The GC was such that the two target compounds were separated and baseline-resolved. Relative standard deviations for analysis of both (E,Z)-2,6-nonadienal and (E)-2-nonenal using this SPME sampling method were +/-10%. Utility of the analytical method was demonstrated by determining the effect of heat treatments on the ability of cucumbers to produce these flavor impact compounds.     

Changes in physicochemical characteristics and volatile constituents of strawberry (Cv. Cigaline) during maturation

Changes in the volatile composition of strawberries (cv. Cigaline) at six stages of maturity, from 28 to 44 days after anthesis, were investigated over two harvesting seasons. Volatiles were isolated by direct solvent extraction and analyzed by means of GC-FID and GC-MS, with special attention to the quantification of furanones. Firmness, skin color, soluble solids (SS), titratable acidity (TA), SS/TA ratio, organic acids, and sugars were also determined. With increasing maturity, soluble solids, SS/TA ratio, Minolta a value, and levels of sucrose, glucose, fructose, and malic acid increased, whereas Minolta L value, hue angle (), titratable acidity, and levels of citric acid decreased. Furanones and esters were generally not detected before half-red fruits, whereas C(6) compounds were the main compounds in immature fruits. During maturation, levels of these so-called green components decreased drastically, whereas levels of key flavor compounds increased significantly and were closely correlated with skin color development. Maximum volatile production was observed in fully red fruits.     

HS-SPME/GC-MS和电子感官技术分析毛霉型豆豉发酵过程中风味品质

为了对毛霉型豆豉发酵过程中风味进行综合评价,本试验采用顶空固相微萃取/气相色谱-质谱法(HS-SPME/GC-MS)结合电子鼻、电子舌对其发酵过程进行研究。结果表明,毛霉型豆豉不同发酵时期的11个样品共鉴定出68种挥发性风味成分,其中包括酯类18种、醛类7种、酸类3种、醇类26种、酮类4种、其他类10种。挥发性风味成分的种类由前发酵的15种上升至豆豉发酵成熟时(35~42 d)的31种,含量由前发酵1.69 μg·g^-1上升至发酵终点44.20 μg·g^-1,呈递增趋势,至发酵成熟期稳定,与电子鼻测定结果一致。电子舌测定结果显示,后发酵35 d时,成品的涩味、苦味及苦味回味降到适宜程度,鲜味和丰富性较高,而此时的挥发性风味成分种类丰富、含量高、香味浓郁、丰富性好,滋味和气味俱佳。因此,HS-SPME/GC-MS结合电子感官技术对毛霉型豆豉产品品质的判别具有可行性,可为生产条件的优化提供理论依据。     

Preharvest calcium sprays improve volatile emission at commercial harvest of 'Fuji Kiku-8' apples

Apple (Malus × domestica Borkh.) fruit intended for long-term storage are frequently harvested commercially before becoming fully ripe, often resulting in poor aroma development. Since postharvest calcium dips have proved effective for the enhancement of flavor-related volatile esters after cold storage of apples, this study was undertaken in order to assess whether preharvest calcium sprays (7 weekly applications at 1.6%, w/v, 81-123 days after full bloom) could also aid in improving this important attribute at harvest. This procedure significantly increased calcium content in treated fruit. The emission of aroma-related volatile esters by untreated and calcium-treated 'Fuji' apples was then monitored during maturation and ripening over two months prior to commercial harvest. Results indicate that most of the compounds contributing to overall flavor in ripe fruit were enhanced in response to preharvest calcium applications, suggesting that this procedure may be suitable for the improvement of fruit aroma at harvest. The emission of acetate esters was particularly favored, consistent with higher acetaldehyde contents in treated fruit. These effects arose apparently from increased pyruvate decarboxylase (PDC) and alcohol dehydrogenase (ADH) activities, possibly leading to a better supply of alcohols and acyl CoAs for ester biosynthesis.     

Optimization of solid-phase microextraction analysis for studying change of headspace flavor compounds of banana during ripening

The changes of headspace flavor compounds of banana during ripening were studied by a solid-phase microextraction (SPME) method. Three temperatures, 20, 25, and 30 degrees C, were used to investigate the temperature effect on the changes of headspace flavor compounds of banana during ripening over a period of 8 days. Banana juice concentration, salt concentration, time, and temperature were investigated for optimizing the SPME method. The most suitable concentrations of banana juice and salt were 33.3 and 20%, respectively. The optimal temperature and time are about 50 degrees C and 48 min, respectively. Increasing ripening temperature could accelerate ripening rate. Ethanol developed most rapidly at 30 degrees C, whereas amounts of the other investigated flavor compounds stored at 25 degrees C were greater than those of the ones stored at 20 or 30 degrees C.     

Influence of harvest time on the quality of oil-based compounds in sea buckthorn (Hippophae rhamnoides L. ssp. sinensis) seed and fruit

The effect of the harvest time on oil-based bioactive compounds in sea buckthorn berries ( Hippophae rhamnoides L. ssp. sinensis) was investigated. Sea buckthorn berries were collected at early maturity (September), maturity (November), and postmaturity (January) during the 2003-2004 harvest year. Whole berries were analyzed for physical characteristics, and fruit and seed fractions were analyzed for bioactive content. November-harvested berries yielded the highest values for berry sizes, CIELab factor a*, and total carotenoid content in the fruit fraction ( p < 0.05). September yielded significantly higher ( p < 0.05) levels of major compounds, alpha-tocopherol and beta-sitosterol, in the fruit fraction. Seed characteristics and bioactive compounds did not vary significantly with respect to the harvest time ( p > 0.05). These results have identified the most suitable level of maturity for the optimization of certain compounds and the losses that may occur with winter harvest, commonly practiced in cold climates.