Yoshiko Kurobayashi

Novel Character Impact Compounds in Yuzu (Citrus junos Sieb. ex Tanaka) Peel Oil

Yuzu ( Citrus junos Sieb. ex Tanaka), a tree-grown fruit similar to a kind of sour orange, is widely used in Japanese food/cooking for its pleasant flavor. To clarify the odor-active volatiles that differentiate yuzu from other citrus fruits, sensory evaluations were conducted on yuzu peel oil. The results revealed that the polar part of yuzu peel oil was the source of the characteristic aroma of fresh yuzu fruit. By aroma extract dilution analysis (AEDA) of the polar volatile part of yuzu peel oil, seven odorants were newly identified as odor-active volatiles in yuzu peel oil in the highest flavor dilution (FD) factors of 128 and 32: oct-1-en-3-one, (E)-non-4-enal, (E)-dec-4-enal, 4-methyl-4-mercaptopentan-2-one, (E)-non-6-enal, (6Z,8E)-undeca-6,8,10-trien-3-one (Yuzunone), and (6Z,8E)-undeca-6,8,10-trien-4-ol (Yuzuol). Among the most odor-active volatiles in yuzu, (E)-non-6-enal and Yuzunone were identified for the first time solely in yuzu peel oil and not in the peel of other citrus species, and Yuzuol was identified for the first time in nature. Sensory evaluation of yuzu aroma reconstitutions revealed that the newly identified compound, Yuzunone, contributes greatly to the distinct yuzu aroma.

Potent Odorants Characterize the Aroma Quality of Leaves and Stalks in Raw and Boiled Celery

The raw and boiled odors of celery leaves and stalks were investigated. Among 12 compounds identified as potent odorants, 3-n-butylphthalide 1, sedanenolide 2, and trans- and cis-sedanolides 3, 4 were assessed to be most contributive to the overall odor of celery. These three phthalides, (3E,5Z)-1,3,5-undecatriene, myrcene, and (E)-2-nonenal were common to both raw and boiled materials. Two compounds, ((Z)-3-hexenal and (Z)-3-hexenol), were dominant in raw materials and four compounds, (2-methylbutanoic acid, sotolon, β-damascenone, and β-ionone), were dominant in boiled materials. Sensory evaluations were performed on natural celery odor and a series of reconstructed model aromas by assigning each intensity ratings for a set of seven odor qualities which aptly describe the odors of raw and boiled celery. According to the evaluation results, six common components contributed to the moderate odor of raw celery, two components dominant in raw materials enhanced the raw celery character, and four components dominant in boiled materials reduced the raw celery character and enhanced the boiled celery character. It was clarified that boiling-induced changes in celery odor were not affected by the amounts of phthalides, but by thermally generated compounds such as sotolon, β-damascenone, and β-ionone, which reduce the “green spicy” note.

Key odorants in cured Madagascar vanilla beans (Vanilla planiforia) of differing bean quality.

The odor-active volatiles in Madagascar vanilla beans (Vanilla planiforia) of two grades, red whole beans as standard quality and cuts beans as substandard quality, were characterized by instrumental and sensory analyses. The higher contents of vanillin and β-damascenone in red whole beans than in cuts beans respectively contributed to significant differences in the sweet and dried fruit-like notes, while the higher contents of guaiacol and 3-phenylpropanoic acid in cuts beans than in red whole beans respectively contributed to significant differences in the phenolic and metallic notes. A sensory evaluation to compare red whole beans and their reconstituted aroma characterized both samples as being similar, while in respect of the phenolic note, the reconstituted aroma significantly differed from the reconstituted aroma with guaiacol added at the concentration ratio of vanillin and guaiacol in cuts beans. It is suggested from these results that the concentration ratio of vanillin and guaiacol could be used as an index for the quality of Madagascar vanilla beans.

Identification of the Key Odorants in Tahitian Cured Vanilla Beans (Vanilla tahitensis) by GC-MS and an Aroma Extract Dilution Analysis

The key odorants of Tahitian vanilla beans (Vanilla tahitensis) were characterized by a sensory evaluation, aroma extract dilution analysis (AEDA), quantification, and aroma reconstitution. Vanillin and anisaldehyde were identified in the same highest flavor dilution (FD) factor as the most characteristic odor-active compounds in Tahitian vanilla beans, followed by anisyl alcohol and anisyl acetate. Vanillin and anisyl alcohol were by far the most abundant odorants present with the highest concentration in the beans, followed by acetic acid, anisaldehyde, and anisyl acetate. A sensory evaluation of Tahitian vanilla beans and its reconstitute aroma concentrate characterized both samples as similar. These results indicated vanillin, anisaldehyde, anisyl alcohol, and anisyl acetate to be the key odorants in Tahitian vanilla beans. 3-Methylnonane-2,4-dione were identified for the first time in vanilla beans. β-Damascenone and phenylacetic acid were identified for the first time in Tahitian vanilla beans.

“Aqua-space®”, a New Headspace Method for Isolation of Natural Floral Aromas Using Humidified Air as a Carrier Gas

A new method called “Aqua-space®” was developed for the isolation of the natural fragrances of plants. Living flowers were enclosed in a space under simulated natural conditions, and humidified air was pumped into the space as a fragrance carrier. In a comparison among three isolation methods, i.e., Aqua-space®, headspace, and solvent extraction, the Aqua-space® method proved to be the most effective in retaining natural fragrances with abundant oxygenated components key to floral fragrances.

Identification of Rotundone as a Potent Odor-Active Compound of Several Kinds of Fruits

An investigation of the aromas of grapefruit, orange, apple, and mango revealed the presence of an odor-active compound that gave off a strong woody odor when assessed by gas chromatography-olfactometry. We isolated the compound from a high-boiling fraction of an orange essential oil, and subsequent nuclear magnetic resonance analyses of the isolated compound identified it as rotundone. Mass spectra and retention indices obtained from aroma concentrates of grapefruit, apple, and mango were identical to those of rotundone, which was therefore determined to be the common woody compound in these fruits. Sensory analyses were performed to assess the effects of rotundone on model beverages of the various fruits. It was revealed that rotundone added at even subthreshold levels to model beverages did not confer directly the woody odor, but had significant effects on the overall flavors of the beverages, helping them to better approximate the natural flavors of the fruits.

Quantitation of Rotundone in Grapefruit (Citrus paradisi) Peel and Juice by Stable Isotope Dilution Assay

Aroma extract dilution analyses of the aromas of peels and juices of white and pink grapefruits revealed that rotundone, responsible for peppery, spicy, and woody odors, was detected for the first time at high flavor dilution factors of 256-1024. In both juices, rotundone was detected at the highest flavor dilution factor of 1024. Rotundone in grapefruits was quantitated by a stable isotope dilution assay with a newly synthesized deuterium-labeled internal standard, rotundone-d2,3: its levels were 2180 and 1920 ng/kg in white and pink grapefruit peels and 29.6 and 49.8 ng/kg in white and pink grapefruit juices, respectively. On the basis of these results, sensory analysis was performed to assess the effects of rotundone on a white grapefruit juice aroma reconstitute. This sensory analysis revealed that rotundone does not impart a woody odor or affect any of the existing attributes, but increases various attributes, thus confirming that rotundone is indispensable for the aroma of grapefruit juice.

Flavor Characteristics and Stereochemistry of the Volatile Constituents of Greater Galangal ( Alpinia Galanga Willd.)

The rhizomes of greater galangal (Alpinia galanga Willd. L.) are widely used as a spice throughout south-east Asian countries. A flavor concentrate was prepared by steam distillation under reduced pressure, and the odor character and some potent odorants of the oxygenated compound fraction that presented the characteristic odor of galanga were investigated by GCMS and aroma extract dilution analysis. Monoterpenoids of linalool and geranyl acetate, 1,8- cineole and acetoxy-I,8-cineoles, and some C6-C3 compounds of the derivatives of eugenol and chavicol were determined as important odor components. In addition, the optical purity and odor difference between the enantiomers were determined by GC and GC eluate sniffing, using a cyclodextrin column. I’ -Acetoxychavicol acetate was present in the optically active 5- configuration in the essential oil of the rhizomes. Only the (S)-enantiomer possessed the characteristic cool, woody and ginger-like odor, in contrast of no odor of the (R)-enantiomer which played an important role in the odor of the fresh rhizomes, because this compound was degraded during cooking. Among the eight isomers of acetoxy-l ,8-cineoles, (1R, 4S, 6R)- 1,3,3-trimethyl-2-oxabicyclo[2,2,2]oct-6-yl acetate (trans-2-acetoxy-l,8-cineole) which presented a woody and galanga-like odor was the most important odor constituent in the rhizomes of greater galangal.

Identification and Characterization of 3-epi-Rotundone, a Novel Stereoisomer of Rotundone, in Several Kinds of Fruits

A novel stereoisomer of rotundone, 3-epi-rotundone, was identified in the aroma of grapefruit, orange, apple, and mango. 3-epi-Rotundone was prepared by the isomerization of rotundone, and its structural elucidation was confirmed by comparing the 1D and 2D nuclear magnetic resonance and nuclear Overhauser effect spectroscopy spectra with those of rotundone. The odor thresholds of rotundone and 3-epi-rotundone in water were determined by a triangle test as 5 and 19100 ng/kg, respectively. The odor of 3-epi-rotundone was evaluated as woody, spicy, peppery, citrus, grapefruit-like, powdery, and celery-like, which was a greater range of odor characteristics than that for rotundone. Results of odor evaluation of 3-epi-rotundone revealed that its unique organoleptic properties, which were odor description (woody, spicy, and peppery), anosmic properties in neat form, and strong adaptation, were similar to those of rotundone. 3-epi-Rotundone might be a valuable substance to apply new types of woody, peppery, and spicy notes.