Terpinolene

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J R Wells - One of the best experts on this subject based on the ideXlab platform.

  • gas phase reaction products and yields of Terpinolene with ozone and nitric oxide using a new derivatization agent
    Atmospheric Environment, 2015
    Co-Authors: Stephen R Jackson, Joel C Harrison, J R Wells
    Abstract:

    Abstract The new derivatization agent, O - tert -butylhydroxylamine hydrochloride (TBOX) was used to investigate the carbonyl reaction products from Terpinolene ozonolysis. With ozone (O 3 ) as the limiting reagent, four carbonyl compounds were detected: methylglyoxal (MG), 4-methylcyclohex-3-en-1-one, (4MCH), 6-oxo-3-(propan-2-ylidene) heptanal (6OPH), and 3,6-dioxoheptanal (36DOH). The tricarbonyl 36DOH has not been previously observed. Using cyclohexane as a hydroxyl radical (OH ) scavenger, the yields of 6OPH and 36DOH were reduced indicating the influence secondary OH radicals have on Terpinolene ozonolysis products. However, the MG yield increased and the 4MCH yield was unchanged when OH radicals were scavenged suggesting they are only made by the Terpinolene + O 3 reaction. The detection of 36DOH using TBOX highlights the advantages of a smaller molecular weight derivatization agent for the detection of multi-carbonyl compounds. The product yields from Terpinolene ozonolysis experiments conducted in the presence of 20 ppb nitric oxide (NO) remained unchanged except for MG which decreased. However, in experiments where O 3 was kept constant at 50 ppb and NO was varied (20, 50, 100 ppb) MG, 6OPH, 36DOH decreased with increasing NO while 4MCH increased with increasing NO. The use of TBOX derivatization if combined with other derivatization agents may address a recurring need to simply and accurately detect multi-functional oxygenated species in air.

  • investigation of Terpinolene ozone or Terpinolene nitrate radical reaction products using denuder filter apparatus
    Atmospheric Environment, 2013
    Co-Authors: Joel C Harrison, J R Wells
    Abstract:

    Terpinolene's (1-methyl-4-(propan-2-ylidene)cyclohexene) reaction with ozone or the nitrate radical was investigated using a denuder/filter apparatus in order to characterize gas-phase and particulate reaction products. Identification of the reaction products (i.e., aldehydes, ketones, dicarbonyls and carboxylic acids) was made using two derivatization methods; O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine (PFBHA) to derivatize the carbonyl products or 3-Ethyl-1-[3-(dimethylamino)propyl]carbodiimide hydrochloride (EDC) and 2,2,2-trifluoroethylamine hydrochloride (TFEA) to derivatize the carboxylic acid products. Proposed carbonyl products for ozonolysis of Terpinolene are: 4-methylcyclohex-3-en-1-one, 2-hydroxy-4-methylcyclohex-3-en-1-one, glyoxal, methyl glyoxal, 3-oxobutanal, and 6-oxo-3-(propan-2-ylidene)heptanal. Proposed carbonyl products for nitrate radical reaction of Terpinolene are: 2-hydroxy-4-methylcyclohex-3-en-1-one, glyoxal, methyl glyoxal, and 4-oxopentanal. No carboxylic acid products were detected with either oxidizing reactant.

  • Investigation of Terpinolene + ozone or Terpinolene + nitrate radical reaction products using denuder/filter apparatus
    Atmospheric Environment, 2013
    Co-Authors: Joel C Harrison, J R Wells
    Abstract:

    Terpinolene's (1-methyl-4-(propan-2-ylidene)cyclohexene) reaction with ozone or the nitrate radical was investigated using a denuder/filter apparatus in order to characterize gas-phase and particulate reaction products. Identification of the reaction products (i.e., aldehydes, ketones, dicarbonyls and carboxylic acids) was made using two derivatization methods; O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine (PFBHA) to derivatize the carbonyl products or 3-Ethyl-1-[3-(dimethylamino)propyl]carbodiimide hydrochloride (EDC) and 2,2,2-trifluoroethylamine hydrochloride (TFEA) to derivatize the carboxylic acid products. Proposed carbonyl products for ozonolysis of Terpinolene are: 4-methylcyclohex-3-en-1-one, 2-hydroxy-4-methylcyclohex-3-en-1-one, glyoxal, methyl glyoxal, 3-oxobutanal, and 6-oxo-3-(propan-2-ylidene)heptanal. Proposed carbonyl products for nitrate radical reaction of Terpinolene are: 2-hydroxy-4-methylcyclohex-3-en-1-one, glyoxal, methyl glyoxal, and 4-oxopentanal. No carboxylic acid products were detected with either oxidizing reactant.

Joel C Harrison - One of the best experts on this subject based on the ideXlab platform.

  • gas phase reaction products and yields of Terpinolene with ozone and nitric oxide using a new derivatization agent
    Atmospheric Environment, 2015
    Co-Authors: Stephen R Jackson, Joel C Harrison, J R Wells
    Abstract:

    Abstract The new derivatization agent, O - tert -butylhydroxylamine hydrochloride (TBOX) was used to investigate the carbonyl reaction products from Terpinolene ozonolysis. With ozone (O 3 ) as the limiting reagent, four carbonyl compounds were detected: methylglyoxal (MG), 4-methylcyclohex-3-en-1-one, (4MCH), 6-oxo-3-(propan-2-ylidene) heptanal (6OPH), and 3,6-dioxoheptanal (36DOH). The tricarbonyl 36DOH has not been previously observed. Using cyclohexane as a hydroxyl radical (OH ) scavenger, the yields of 6OPH and 36DOH were reduced indicating the influence secondary OH radicals have on Terpinolene ozonolysis products. However, the MG yield increased and the 4MCH yield was unchanged when OH radicals were scavenged suggesting they are only made by the Terpinolene + O 3 reaction. The detection of 36DOH using TBOX highlights the advantages of a smaller molecular weight derivatization agent for the detection of multi-carbonyl compounds. The product yields from Terpinolene ozonolysis experiments conducted in the presence of 20 ppb nitric oxide (NO) remained unchanged except for MG which decreased. However, in experiments where O 3 was kept constant at 50 ppb and NO was varied (20, 50, 100 ppb) MG, 6OPH, 36DOH decreased with increasing NO while 4MCH increased with increasing NO. The use of TBOX derivatization if combined with other derivatization agents may address a recurring need to simply and accurately detect multi-functional oxygenated species in air.

  • investigation of Terpinolene ozone or Terpinolene nitrate radical reaction products using denuder filter apparatus
    Atmospheric Environment, 2013
    Co-Authors: Joel C Harrison, J R Wells
    Abstract:

    Terpinolene's (1-methyl-4-(propan-2-ylidene)cyclohexene) reaction with ozone or the nitrate radical was investigated using a denuder/filter apparatus in order to characterize gas-phase and particulate reaction products. Identification of the reaction products (i.e., aldehydes, ketones, dicarbonyls and carboxylic acids) was made using two derivatization methods; O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine (PFBHA) to derivatize the carbonyl products or 3-Ethyl-1-[3-(dimethylamino)propyl]carbodiimide hydrochloride (EDC) and 2,2,2-trifluoroethylamine hydrochloride (TFEA) to derivatize the carboxylic acid products. Proposed carbonyl products for ozonolysis of Terpinolene are: 4-methylcyclohex-3-en-1-one, 2-hydroxy-4-methylcyclohex-3-en-1-one, glyoxal, methyl glyoxal, 3-oxobutanal, and 6-oxo-3-(propan-2-ylidene)heptanal. Proposed carbonyl products for nitrate radical reaction of Terpinolene are: 2-hydroxy-4-methylcyclohex-3-en-1-one, glyoxal, methyl glyoxal, and 4-oxopentanal. No carboxylic acid products were detected with either oxidizing reactant.

  • Investigation of Terpinolene + ozone or Terpinolene + nitrate radical reaction products using denuder/filter apparatus
    Atmospheric Environment, 2013
    Co-Authors: Joel C Harrison, J R Wells
    Abstract:

    Terpinolene's (1-methyl-4-(propan-2-ylidene)cyclohexene) reaction with ozone or the nitrate radical was investigated using a denuder/filter apparatus in order to characterize gas-phase and particulate reaction products. Identification of the reaction products (i.e., aldehydes, ketones, dicarbonyls and carboxylic acids) was made using two derivatization methods; O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine (PFBHA) to derivatize the carbonyl products or 3-Ethyl-1-[3-(dimethylamino)propyl]carbodiimide hydrochloride (EDC) and 2,2,2-trifluoroethylamine hydrochloride (TFEA) to derivatize the carboxylic acid products. Proposed carbonyl products for ozonolysis of Terpinolene are: 4-methylcyclohex-3-en-1-one, 2-hydroxy-4-methylcyclohex-3-en-1-one, glyoxal, methyl glyoxal, 3-oxobutanal, and 6-oxo-3-(propan-2-ylidene)heptanal. Proposed carbonyl products for nitrate radical reaction of Terpinolene are: 2-hydroxy-4-methylcyclohex-3-en-1-one, glyoxal, methyl glyoxal, and 4-oxopentanal. No carboxylic acid products were detected with either oxidizing reactant.

Yuji Tsutsumi - One of the best experts on this subject based on the ideXlab platform.

  • Airborne Monoterpenes Emitted from a Cupressus lusitanica Cell Culture Induce a Signaling Cascade that Produces β-Thujaplicin.
    Journal of Chemical Ecology, 2016
    Co-Authors: Koki Fujita, Ransika De Alwis, Ryo Kambe, Tatsuya Yagi, Yuji Tsutsumi
    Abstract:

    A cell culture of Cupressus lusitanica was used to investigate the reaction of a plant to certain airborne chemicals. Compared with laboratory and field methods using intact plants or tissues, a cell culture is advantageous because it is not affected by environmental factors, and the experiments are easier to reproduce. When exposed to an elicitor, our cell line produces 10 monoterpenes and β-thujaplicin, which is a strong phytoalexin. These monoterpenes are emitted into the vapor phase and are expected to play a role in airborne signaling. In the present study, the cells were exposed to monoterpene vapors, and the volatiles present in the culture flasks were monitored. When the culture cells were exposed to low doses of sabinene, we detected γ-terpinene and p-cymene. After exposure to γ-terpinene, we found p-cymene and Terpinolene, whereas p-cymene exposure resulted in Terpinolene emission. By contrast, the other seven monoterpenes we investigated did not induce any emissions of other monoterpenes. These results strongly suggest that in C. lusitanica a signaling cascade exists that starts with the emission of sabinene and moves to γ-terpinene, p-cymene, and finally to Terpinolene, which accelerates the production of the phytoalexin β-thujaplicin.

  • stereo selective oxidations of Terpinolene by cytochrome p450 monooxygenases in the microsomal fraction of cupressus lusitanica cultured cells
    Journal of Wood Science, 2014
    Co-Authors: Takako Harada, Koki Fujita, Jun Shigeto, Yuji Tsutsumi
    Abstract:

    We showed previously that in Cupressus lusitanica (Mexican cypress), the first two steps of Terpinolene oxidation, beginning at hydroxylation at the aryl position and then forming epoxide at the double bond, were driven by cytochrome P450s. The significance of enantio differences, in general, has received attention because those enantiomers often have their own biological activities. We, therefore, investigated the stereo-specificity of the substrate and the enantio-selectivity of these reactions. The hydroxylation of Terpinolene by cytochrome P450 in the microsomal fraction from C. lusitanica cells gave a single product with an S configuration of 5-isopropylidene-2-methylcyclohex-2-enol. Next, epoxidizing enzyme accepted only the S-configuration substrate and produced a single enantiomer product, (1R, 2S, 6S)-(+)-1,6-epoxy-4(8)-p-menthen-2-ol. No isomer was detected at our gas chromatography/mass spectrometry sensitivity; therefore, the calculated enantiomeric excess values were 100 %. These results indicate that the cytochrome P450s involved in Terpinolene metabolism in C. lusitanica cells have very strict stereo-selective ability. Our findings may be helpful in the stereo-selective synthesis of fine chemicals, although the physiological meanings of these chiral products are still not unclear.

  • a novel synthetic pathway for tropolone ring formation via the olefin monoterpene intermediate Terpinolene in cultured cupressus lusitanica cells
    Journal of Plant Physiology, 2014
    Co-Authors: Koki Fujita, Yasufumi Bunyu, Kenich Kuroda, Tatsuya Ashitani, Jun Shigeto, Yuji Tsutsumi
    Abstract:

    Summary β-Thujaplicin is a wood monoterpene and tropolone compound with a unique conjugated 7-membered ring. Because of its strong antifungal and antitumor activities, β-thujaplicin is used in several fields. The biosynthesis pathway of β-thujaplicin has not yet been elucidated. Using Cupressus lusitanica cell cultures in a radioisotope feeding experiment, our group previously demonstrated that geranyl pyrophosphate (GPP) is the starting material of β-thujaplicin biosynthesis. The results of our previous terpene synthase assay suggested that Terpinolene is the first olefin terpenoid intermediate from GPP to β-thujaplicin, although there was no experimental evidence of this at that time. In the present study, we fed deuterium-labeled Terpinolene to cultured C. lusitanica cells to determine whether Terpinolene is an intermediate metabolite of β-thujaplicin biosynthesis. A gas chromatography–mass spectroscopy analysis of the cell extracts from labeled Terpinolene cultures revealed a peak of labeled β-thujaplicin that was not observed after treatment with non-labeled Terpinolene. The identification of labeled β-thujaplicin was also performed by mass spectrum assignment. The outcome indicated that Terpinolene is indeed an intermediate metabolite of β-thujaplicin biosynthesis. To the best of our knowledge, there has been no prior report that tropolone compounds are biosynthesized via a terpene biosynthesis system, and our results thus suggest the existence of a novel biosynthetic pathway that produces the conjugated 7-membered ring.

Koki Fujita - One of the best experts on this subject based on the ideXlab platform.

  • Airborne Monoterpenes Emitted from a Cupressus lusitanica Cell Culture Induce a Signaling Cascade that Produces β-Thujaplicin.
    Journal of Chemical Ecology, 2016
    Co-Authors: Koki Fujita, Ransika De Alwis, Ryo Kambe, Tatsuya Yagi, Yuji Tsutsumi
    Abstract:

    A cell culture of Cupressus lusitanica was used to investigate the reaction of a plant to certain airborne chemicals. Compared with laboratory and field methods using intact plants or tissues, a cell culture is advantageous because it is not affected by environmental factors, and the experiments are easier to reproduce. When exposed to an elicitor, our cell line produces 10 monoterpenes and β-thujaplicin, which is a strong phytoalexin. These monoterpenes are emitted into the vapor phase and are expected to play a role in airborne signaling. In the present study, the cells were exposed to monoterpene vapors, and the volatiles present in the culture flasks were monitored. When the culture cells were exposed to low doses of sabinene, we detected γ-terpinene and p-cymene. After exposure to γ-terpinene, we found p-cymene and Terpinolene, whereas p-cymene exposure resulted in Terpinolene emission. By contrast, the other seven monoterpenes we investigated did not induce any emissions of other monoterpenes. These results strongly suggest that in C. lusitanica a signaling cascade exists that starts with the emission of sabinene and moves to γ-terpinene, p-cymene, and finally to Terpinolene, which accelerates the production of the phytoalexin β-thujaplicin.

  • stereo selective oxidations of Terpinolene by cytochrome p450 monooxygenases in the microsomal fraction of cupressus lusitanica cultured cells
    Journal of Wood Science, 2014
    Co-Authors: Takako Harada, Koki Fujita, Jun Shigeto, Yuji Tsutsumi
    Abstract:

    We showed previously that in Cupressus lusitanica (Mexican cypress), the first two steps of Terpinolene oxidation, beginning at hydroxylation at the aryl position and then forming epoxide at the double bond, were driven by cytochrome P450s. The significance of enantio differences, in general, has received attention because those enantiomers often have their own biological activities. We, therefore, investigated the stereo-specificity of the substrate and the enantio-selectivity of these reactions. The hydroxylation of Terpinolene by cytochrome P450 in the microsomal fraction from C. lusitanica cells gave a single product with an S configuration of 5-isopropylidene-2-methylcyclohex-2-enol. Next, epoxidizing enzyme accepted only the S-configuration substrate and produced a single enantiomer product, (1R, 2S, 6S)-(+)-1,6-epoxy-4(8)-p-menthen-2-ol. No isomer was detected at our gas chromatography/mass spectrometry sensitivity; therefore, the calculated enantiomeric excess values were 100 %. These results indicate that the cytochrome P450s involved in Terpinolene metabolism in C. lusitanica cells have very strict stereo-selective ability. Our findings may be helpful in the stereo-selective synthesis of fine chemicals, although the physiological meanings of these chiral products are still not unclear.

  • a novel synthetic pathway for tropolone ring formation via the olefin monoterpene intermediate Terpinolene in cultured cupressus lusitanica cells
    Journal of Plant Physiology, 2014
    Co-Authors: Koki Fujita, Yasufumi Bunyu, Kenich Kuroda, Tatsuya Ashitani, Jun Shigeto, Yuji Tsutsumi
    Abstract:

    Summary β-Thujaplicin is a wood monoterpene and tropolone compound with a unique conjugated 7-membered ring. Because of its strong antifungal and antitumor activities, β-thujaplicin is used in several fields. The biosynthesis pathway of β-thujaplicin has not yet been elucidated. Using Cupressus lusitanica cell cultures in a radioisotope feeding experiment, our group previously demonstrated that geranyl pyrophosphate (GPP) is the starting material of β-thujaplicin biosynthesis. The results of our previous terpene synthase assay suggested that Terpinolene is the first olefin terpenoid intermediate from GPP to β-thujaplicin, although there was no experimental evidence of this at that time. In the present study, we fed deuterium-labeled Terpinolene to cultured C. lusitanica cells to determine whether Terpinolene is an intermediate metabolite of β-thujaplicin biosynthesis. A gas chromatography–mass spectroscopy analysis of the cell extracts from labeled Terpinolene cultures revealed a peak of labeled β-thujaplicin that was not observed after treatment with non-labeled Terpinolene. The identification of labeled β-thujaplicin was also performed by mass spectrum assignment. The outcome indicated that Terpinolene is indeed an intermediate metabolite of β-thujaplicin biosynthesis. To the best of our knowledge, there has been no prior report that tropolone compounds are biosynthesized via a terpene biosynthesis system, and our results thus suggest the existence of a novel biosynthetic pathway that produces the conjugated 7-membered ring.

  • Volatile and non-volatile monoterpenes produced by elicitor-stimulated Cupressus lusitanica cultured cells
    Journal of Plant Physiology, 2008
    Co-Authors: Ransika De Alwis, Koki Fujita, Tatsuya Ashitani, Ken’ichi Kuroda
    Abstract:

    Elicitor treatment initiates defense responses in cultured Cupressus lusitanica cells. In order to investigate the defense mechanism with a yeast extract elicitor, we carried out solid-phase microextraction coupled with gas chromatography for monoterpene analysis. Ten hydrocarbon monoterpenes, including high amounts of sabinene and limonene, were detected in the gas phase of the elicitor-treated cell cultures. Six oxidized monoterpenes including β-thujaplicin were also detected in the ether extract of the cells and the medium. Time-course profiles of volatile monoterpenes showed that one group of hydrocarbon monoterpenes was maximized on the second day after elicitation, while the other group was maximized on the third day. There were no oxidized monoterpenes that are structurally related to sabinene and limonene in the gas phase or cell extracts, suggesting that these compounds are produced exclusively for emission. Other monoterpenes, which are produced during later stages of elicitation, are metabolized into more complex compounds such as oxidized monoterpenes, including β-thujaplicin. Although Terpinolene synthase was the principal monoterpene synthase in these cell cultures, Terpinolene was detected only as a minor compound in the gas phase. The time course for Terpinolene synthase activity coincided with β-thujaplicin biosynthesis. Thus, most of the Terpinolene is metabolized rapidly to oxidized terpenes such as β-thujaplicin rather than emitted.

Ian A Southwell - One of the best experts on this subject based on the ideXlab platform.

  • monoterpenoid accumulation in 1 8 cineole Terpinolene and terpinen 4 ol chemotypes of melaleuca alternifolia seedlings
    Phytochemistry, 2003
    Co-Authors: Michael F Russell, Ian A Southwell
    Abstract:

    Abstract Individual leaves of the three most common chemotypes of Melaleuca alternifolia were examined both quantitatively and qualitatively for volatile constituents from the emergence of the first true leaves, through to 6-week-old tenth leaf set material. The 1,8-cineole and Terpinolene chemotypes were investigated and compared with the recently reported commercial terpinen-4-ol chemotype. The 1,8-cineole chemotype was found to accumulate 1,8-cineole and associated p-menthanes limonene, terpinen-4-ol and α-terpineol gradually with increasing leaf set number. As with the terpinen-4-ol variety, higher than expected concentrations of the pinenes and Terpinolene were found only in the early leaf sets. The Terpinolene variety showed two stages of Terpinolene accumulation, the first at leaf sets 2–3 similar to the unexpected biosynthesis of Terpinolene in the terpinen-4-ol chemotype and the second at leaf sets 8–9 which is characteristic of the Terpinolene variety.

  • Volatile oil comparison of cotyledon leaves of chemotypes of Melaleuca alternifolia.
    Phytochemistry, 2002
    Co-Authors: Ian A Southwell, Michael F Russell
    Abstract:

    Abstract Oil quantity and quality were measured for the cotyledon leaves of the commercial terpinen-4-ol chemical variety of Melaleuca alternifolia . Oil yield obtained by ethanolic extraction was 3.8 micrograms per leaf or 2.6% (dry weight basis). The major components of the oil were α-pinene (7.4%), β-pinene (12.0%) and Terpinolene (27.3%). The non-commercial Terpinolene chemical variety was found to be rich in 1,8-cineole (12.5%) and Terpinolene (25.4%). The non-commercial 1,8-cineole chemical variety was rich in 1,8-cineole (37%) with significant quantities of α-pinene (15.5%), β-pinene (23.3%) and Terpinolene (10.9%). The cotyledon leaf composition, when compared with that of mature leaf from the same chemical variety, was found to be biased toward pinene and Terpinolene biogenetic pathway constituents and hence not a good indicator of mature tree quality especially for the commercial terpinen-4-ol chemical variety. The implications of these analyses for the determination of M. alternifolia plantation quality and the understanding of oil formation, are discussed.

  • Terpinolene varieties of melaleuca
    Journal of Essential Oil Research, 1992
    Co-Authors: Ian A Southwell, Ian A Stiff, Joseph J Brophy
    Abstract:

    ABSTRACT Terpinolene-rich chemical varieties of Melaleuca alternifolia and M. trichostachya have been found in both natural and cultivated stands. The variation in chemical composition of these varieties, which also contain substantial quantities of 1, 8-cineole, is reported. An investigation of along-the-branch leaf pairs suggested that Terpinolene may be formed along with the l, 8-cineole via a terpinen-8-yl moiety rather than the terpinen-4-yl moiety that leads to γ-terpinene in the terpinen-4-ol rich chemical variety of Melaleuca.