linoleic-acid and n-hexanal

Biobased polymers derived from plant oils are sustainable alternatives to petro based polymers. In recent years, multienzyme cascades have been developed for the synthesis of biobased ω-aminocarboxylic acids, which serve as building blocks for polyamides. In this work, we have developed a novel enzyme cascade for the synthesis of 12-aminododeceneoic acid, a precursor for nylon-12, starting from linoleic acid. Seven bacterial ω-transaminases (ω-TAs) were cloned, expressed in Escherichia coli and successfully purified by affinity chromatography. Activity towards the oxylipin pathway intermediates hexanal and 12-oxododecenoic acid in their 9(Z) and 10(E) isoforms was demonstrated for all seven transaminases in a coupled photometric enzyme assay. The highest specific activities were obtained with ω-TA from Aquitalea denitrificans (TR

Topics: Linoleic Acid; Lipoxygenase; Oxylipins; Polymers; Transaminases

The composition of volatile compounds in Korla fragrant pears was determined using headspace solid-phase microextraction followed by a gas chromatography-mass spectrometry analysis using fruits at 30, 90, and 150 days after bloom. Hexanal, (E)-2-hexenal, 1-hexanol, (E)-2-hexen-1-ol, (Z)-3-hexen-1-ol, and hexyl acetate were identified as the major compounds. The composition of volatile compounds was associated with fatty acid concentrations and key enzyme activity in the lipoxygenase pathway. In vitro linoleic and linolenic acid feeding experiments conducted using cubes of fruit flesh demonstrated that the concentrations of volatile esters, such as hexyl acetate, in the treated fruits increased significantly after incubation for 12 h compared with those in the control fruits, which was accompanied by a reduction in aldehyde and alcohol concentrations (p < 0.05 or p < 0.01). However, the treatments did not significantly influence the enzyme activity and expression of genes encoding the enzymes.

Topics: Aldehydes; alpha-Linolenic Acid; Esters; Fatty Acids; Food Analysis; Fruit; Gas Chromatography-Mass Spectrometry; Gene Expression Regulation, Plant; Hexanols; Linoleic Acid; Odorants; Pyrus; Solid Phase Microextraction; Volatile Organic Compounds

The health benefits of conjugated linoleic acid (CLA), a functional lipid with anti-cancer, anti-obesity, and hypotensive activity, have garnered increasing attention. The current study was conducted to determine the oxidative stability of CLA in the form of triacylglycerol (CLA-TAG) and phosphatidylcholine (CLA-PC) at the sn-2 position. Oxidation was performed at 30°C or 40°C in the dark. Hydroperoxides, as the primary oxidation products, were analyzed using diphenyl-1-pyrenylphosphine. Thiobarbituric acid reactive substances (TBARS) and volatile compounds were monitored as secondary oxidation products. The results suggest that CLA-PC was more stable against oxidation than CLA-TAG from the perspective of suppression of the generation of hydroperoxides and TBARS. However, CLA-PC produced more volatile compounds than CLA-TAG. We suggest that choline was released during the oxidation of CLA-PC, and acted as an antioxidant. The ensuing reaction between choline and hydroperoxide induced the generation of volatile compounds such as pentanal, hexanal, and heptanal.

Topics: Aldehydes; Antioxidants; Choline; Drug Stability; Hydrogen Peroxide; Linoleic Acid; Oxidation-Reduction; Phosphatidylcholines; Temperature; Thiobarbituric Acid Reactive Substances; Triglycerides

This study was investigated the chemical composition of volatile oils and aroma evaluation from the tubers of Apios americana Medikus. Theses volatile oils were obtained by the hydrodistillation (HD) and the solvent-assisted flavor evaporation (SAFE) methods. These oils were analyzed by Gas chromatography (GC), GC-mass spectrometry (GC-MS), GC-olfactometry (GC-O), aroma extract dilution analysis (AEDA) and odor activity values (OAV) for the first time. The major compounds in the HD oil were palmitic acid (36.5%), linoleic acid (10.5%) and nonadecanol (5.7%). Meanwhile, in the SAFE oil, the major compounds were 4-hydroxy-4-methyl-2-pentanone (34.2%), hexanal (11.0%) and hexanol (7.9%). Through aroma evaluation, 20 (HD) and 14 (SAFE) aroma-active compounds were identified by GC-O. As a result, the most intense aroma-active compounds in both extraction methods were 1-octen-3-ol and hexanal, both of which showed high odor activity values (OAV).

Topics: Aldehydes; Distillation; Fabaceae; Fatty Acids; Gas Chromatography-Mass Spectrometry; Indicator Dilution Techniques; Linoleic Acid; Octanols; Odorants; Oils, Volatile; Olfactometry; Palmitic Acid; Plant Oils; Plant Tubers; Volatilization

The volatile oil from Boletopsis leucomelas (Pers.) Fayod was extracted by hydrodistillation with diethylether, and the volatile components of the oil were analyzed by gas chromatography-mass spectrometry. The oil contained 86 components, representing 87.5% of the total oil. The main components of the oil were linoleic acid (15.0%), phenylacetaldehyde (11.2%), and palmitic acid (9.4%). Furthermore, sulfur-containing compounds including 3-thiophenecarboxaldehyde, 2-acetylthiazole, S-methyl methanethiosulfonate, and benzothiazole were detected using gas chromatography-pulsed flame photometric detection. The odor components were evaluated by the odor activity value, and aroma extract dilution analysis was performed through gas chromatography-olfactometry analysis. The oil had a mushroom-like, fatty, and burnt odor. The main components contributing to the mushroom-like and fatty odor were hexanal, nonanal, 1-octen-3-ol, and (2E)-nonenal, while the burnt odor was due to furfuryl alcohol, benzaldehyde, 5-methyl furfural, 2,3,5-trimethylpyrazine, 2-acethylthiazole, and indole.

Topics: Acetaldehyde; Agaricales; Aldehydes; Benzaldehydes; Chromatography, Gas; Furans; Gas Chromatography-Mass Spectrometry; Indoles; Linoleic Acid; Octanols; Odorants; Oils, Volatile; Olfactometry; Palmitic Acid; Photometry; Plant Oils; Plants, Edible; Sulfur Compounds; Volatile Organic Compounds

To examine the biochemical metabolism of aroma volatiles derived from fatty acids, pear fruits were incubated in vitro with metabolic precursors of these compounds. Aroma volatiles, especially esters, were significantly increased, both qualitatively and quantitatively, in pear fruits fed on fatty acid metabolic precursors. Cultivars having different flavor characteristics had distinctly different aroma volatile metabolisms. More esters were formed in fruity-flavored "Nanguoli" fruits than in green-flavored "Dangshansuli" fruits fed on the same quantities of linoleic acid and linolenic acid. Hexanal and hexanol were more efficient metabolic intermediates for volatile synthesis than linoleic acid and linolenic acid. Hexyl esters were the predominant esters produced by pear fruits fed on hexanol, and their contents in "Dangshansuli" fruits were higher than in "Nanguoli" fruits. Hexyl esters and hexanoate esters were the primary esters produced in pear fruits fed on hexanal, however the content of hexyl ester in "Dangshansuli" was approximately three times that in "Nanguoli". The higher contents of hexyl esters in "Dangshansuli" may have resulted from a higher level of hexanol derived from hexanal. In conclusion, the synthesis of aroma volatiles was largely dependent on the metabolic precursors presented.

Topics: Aldehydes; alpha-Linolenic Acid; Esters; Fatty Acids; Fruit; Hexanols; Linoleic Acid; Metabolic Networks and Pathways; Pyrus; Smell; Volatile Organic Compounds

Ten different varieties of tomatoes were separated into peel and flesh and each portion was measured separately. Headspace volatiles were measured in real time using selected ion flow tube mass spectrometry. Lipoxygenase activity was measured using the adsorption of conjugated dienes formed by lipoxygenase. Lipid was extracted and fatty acids were quantified using a gas chromatograph. Volatiles were significantly greater in the peel than flesh when there was a significant difference. The lipoxygenase activity of flesh and peel correlated with the volatiles produced by the lipoxygenase pathway. There was no correlation with other volatiles, which are not dependent on lipid oxidation by lipoxygenase. The lipoxygenase activity, total fatty acid content, and linolenic acid of the peel were greater than the flesh, which is directly related to an increase in fresh, green volatiles. Addition of exogenous lipoxygenase had no effect on lipoxygenase-derived volatiles formed. The addition of linoleic acid caused an increase in hexanal, 1-hexanol, and (E)-2-heptenal in the flesh and (E)-2-heptenal in the peel. Stored unrefrigerated peel had higher volatile concentrations, whereas refrigerated peel had significantly lower concentration than day 0. Storage decreased lipoxygenase activity in the unrefrigerated and refrigerated peel, but had no effect on the fatty acid content. Overall, linolenic acid was the most important to the formation of headspace volatiles, but lipoxygenase activity and unknown factors are also important.. The peel of a tomato is most beneficial to the production of volatiles associated with the fresh aroma of tomatoes; therefore, it should be used in the processing of tomato products to produce a fresh, green aroma rather than being removed. Knowledge of the effects of lipoxygenase activity, total fatty acid content, and fatty acid profile on flavor volatiles will allow for better selection of a variety for raw consumption.

Topics: Aldehydes; Fatty Acids; Food Storage; Fruit; Hexanols; Linoleic Acid; Lipoxygenase; Odorants; Solanum lycopersicum; Taste; Temperature; Volatile Organic Compounds

Compared to corresponding controls, 6.5 mM dithiothreitol (DTT) elevated headspace hexanal level over aqueous slurries of both commercial isolated soy proteins (ISP) and laboratory ISP prepared with 80 degrees C treatment. Further analysis revealed that lipoxygenase (LOX) activity was not detected from these ISP, indicating that LOX is not involved in the observed hexanal increase. Levels of the induced headspace hexanal over the ISP aqueous slurries were proportional to the amount of DTT added in the range of 0 to 65 mM. Subsequent systematic investigations with model systems revealed that iron was required for the reducing agent-induced hexanal formation from linoleic acid. Erythorbate, another reducing agent, can also induce hexanal formation in both ISP and model systems. As a comparison, the LOX activity and hexanal synthesis in defatted soy flour were examined. The corresponding results showed that defatted soy flour maintained high LOX activities and that hexanal synthesis in such sample was significantly inhibited by high concentration DTT (above 130 mM). Data from the current investigation demonstrate the existence of LOX independent hexanal formation induced by reducing agents in ISP and the potential requirement of iron as a catalyst.

Topics: Aldehydes; Catalysis; Dithiothreitol; Dose-Response Relationship, Drug; Food Technology; Iron; Linoleic Acid; Lipoxygenase; Odorants; Reducing Agents; Soybean Proteins; Taste; Volatilization

The formation of hydroxy radicals, hexanal, and 2,4-decadienal was demonstrated from the autocatalytic dimer peroxide which had been reported by us in autoxidizing linoleate (Morita and Tokita in Lipids 41:91-95, 2006). Then, autoxidizing linoleate containing eleostearate was investigated for new autocatalytic substances. The substances obtained were identified as peroxide-linked polymers consisting of both linoleate- and eleostearate-origin units with one hydroperoxy group, and also revealed activity of hydroxy-radical generation. The background of this study is as follows: the above paper reported this autocatalytic dimer peroxide as one of the real radical generators in linoleate autoxidation; this is a peroxide-linked dimer consisting of two linoleate moieties with two hydroperoxy groups, and was much more important than the main-product hydroperoxide in autocatalytic radical supply; its proposed decomposition mechanism has suggested the generation of hydroxy radicals, hexanal, and 2,4-decadienal; on the other hand, analogy to the formation mechanism of this dimer peroxide has predicted the formation of similar polymeric products from conjugated polyene components in lipids. In this study, these two predictions were successfully verified and a discussion is presented in connection with them.

Topics: Aldehydes; Catalysis; Chromatography, High Pressure Liquid; Esters; Gas Chromatography-Mass Spectrometry; Hydroxyl Radical; Linoleic Acid; Linolenic Acids; Molecular Structure; Oxidation-Reduction; Plant Oils

To utilize soy protein isolate (SPI) more widely, a convenient and effective method for deodorizing it is required. This paper reports a new deodorizing method using various types of solid adsorbents made of polystyrene, polymethacrylate, and zeolite, as well as charcoal. Treatment of the SPI solution with them decreased the hexanal content in the solution, whereas the content of linoleic acid was not much decreased. A brominated polystyrene adsorbent (SEPABEADS SP207) and a zeolite adsorbent (HSZ-360HUD) removed hexanal most effectively, although 30-40% of the total hexanal remained. A model experiment showed that their hexanal adsorption capacity was much higher than the hexanal content in the SPI solution and that an excess amount of hexanal added to the SPI solution was mostly removed by them. These results suggest that hexanal in the SPI solution can be classified into two types. Hexanal of type I may be free or bound weakly on the surface of proteins and is removable by the adsorbents, whereas hexanal of type II may be bound tightly inside proteins and is unremovable by the adsorbents. Despite the considerable amount of hexanal remaining in the SPI solution even in the most successful cases, the SPI solution was well deodorized as shown by the sensory test. Accordingly, type I hexanal may be closely related to the soybean odor. Removal of hexanal by the adsorbents was not much improved by alpha-chymotryptic digestion of SPI. Type II hexanal might be in similar states even in the chymotryptic digests.

Topics: Adsorption; Aldehydes; Charcoal; Chemical Phenomena; Chemistry, Physical; Chymotrypsin; Linoleic Acid; Odorants; Polymethacrylic Acids; Polystyrenes; Soybean Proteins; Zeolites

Soybean seeds contain three lipoxygenase isozymes. The functions of these lipoxygenase isozymes in n-hexanal generation were investigated by using mutant lines which lack two or three isozymes. In the presence of linoleic acid, the level of n-hexanal produced was highest in the lipoxygenase-1, -3 double deficient line, followed by the lipoxygenase-2, -3 double deficient, wild type, and lipoxygenase-1, -2, -3 triple deficient lines in that order, and lowest in the lipoxygenase-1, -2 double deficient line. This suggests that lipoxygenase-3 itself cannot produce the n-hexanal precursor and inhibits the n-hexanal generation through other pathways.

Topics: Aldehydes; Electrophoresis, Polyacrylamide Gel; Glycine max; Isoenzymes; Linoleic Acid; Linoleic Acids; Lipoxygenase; Mutation

Peroxidation of lipids produces carbonyl compounds; some of these, e.g., malonaldehyde and 4-hydroxynonenal, are genotoxic because of their reactivity with biological nucleophiles. Analysis of the reactive carbonyl compounds is often difficult. The methylhydrazine method developed for malonaldehyde analysis was applied to simultaneously measure the products formed from linoleic acid, linolenic acid, arachidonic acid, and squalene upon ultraviolet-irradiation (UV-irradiation). The photoreaction products, saturated monocarbonyl, alpha,beta-unsaturated carbonyls, and beta-dicarbonyls, were derivatized with methylhydrazine to give hydrazones, pyrazolines, and pyrazoles, respectively. The derivatives were analyzed by gas chromatography and gas chromatography-mass spectrometry. Lipid peroxidation products identified included formaldehyde, acetaldehyde, acrolein, malonaldehyde, n-hexanal, and 4-hydroxy-2-nonenal. Malonaldehyde levels formed upon 4 hr of irradiation were 0.06 micrograms/mg from squalene, 2.4 micrograms/mg from linolenic acid, and 5.7 micrograms/mg from arachidonic acid. Significant levels of acrolein (2.5 micrograms/mg) and 4-hydroxy-2-nonenal (0.17 micrograms/mg) were also produced from arachidonic acid upon 4 hr irradiation.

Topics: Acetaldehyde; Acrolein; Aldehydes; Arachidonic Acid; Arachidonic Acids; Chromatography, Gas; Formaldehyde; Gas Chromatography-Mass Spectrometry; Linoleic Acid; Linoleic Acids; Linolenic Acids; Lipid Peroxidation; Lipids; Malondialdehyde; Monomethylhydrazine; Squalene; Ultraviolet Rays