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Sample records for heptenes

  1. First Biosynthetic pathway of 1-hepten-3-one in Iporangaia pustulosa (Opiliones)

    PubMed Central

    Rocha, Daniele F. O.; Wouters, Felipe C.; Machado, Glauco; Marsaioli, Anita J.

    2013-01-01

    Arthropods produce a great variety of natural compounds, many of which have unexplored biosynthesis. Among the armored harvestmen (Arachnida: Opiliones) of the suborder Laniatores, the defensive gland exudates contain vinyl ketones and other constituents of supposed polyketide origin. We have studied the biosynthesis of 1-hepten-3-one in the Neotropical harvestman Iporangaia pustulosa by feeding individuals with 13C-labeled precursors, demonstrating its mixed acetate/propionate origin. 13C NMR spectroscopy showed an unusual labeling pattern suggesting different propionate sources for starting and extender units. Our analysis also indicates the presence of methylmalonyl-CoA mutase, converting acetate into propionyl-CoA via succinyl-CoA, together with other C3 unit routes. This is the first biosynthetic study of alkyl vinyl ketones in arthropods. Our results shed light on the origin and diversification of chemical compounds in a major arthropod group. PMID:24193576

  2. First Biosynthetic pathway of 1-hepten-3-one in Iporangaia pustulosa (Opiliones)

    NASA Astrophysics Data System (ADS)

    Rocha, Daniele F. O.; Wouters, Felipe C.; Machado, Glauco; Marsaioli, Anita J.

    2013-11-01

    Arthropods produce a great variety of natural compounds, many of which have unexplored biosynthesis. Among the armored harvestmen (Arachnida: Opiliones) of the suborder Laniatores, the defensive gland exudates contain vinyl ketones and other constituents of supposed polyketide origin. We have studied the biosynthesis of 1-hepten-3-one in the Neotropical harvestman Iporangaia pustulosa by feeding individuals with 13C-labeled precursors, demonstrating its mixed acetate/propionate origin. 13C NMR spectroscopy showed an unusual labeling pattern suggesting different propionate sources for starting and extender units. Our analysis also indicates the presence of methylmalonyl-CoA mutase, converting acetate into propionyl-CoA via succinyl-CoA, together with other C3 unit routes. This is the first biosynthetic study of alkyl vinyl ketones in arthropods. Our results shed light on the origin and diversification of chemical compounds in a major arthropod group.

  3. Development of a stable isotope dilution assay for the quantification of 5-methyl-(E)-2-hepten-4-one: application to hazelnut oils and hazelnuts.

    PubMed

    Pfnuer, P; Matsui, T; Grosch, W; Guth, H; Hofmann, T; Schieberle, P

    1999-05-01

    A stable isotope dilution assay was developed for the quantitation of the hazelnut odorant 5-methyl-(E)-2-hepten-4-one by mass chromatography using synthesized [(2)H](2)-5-methyl-(E)-2-hepten-4-one as the internal standard. Application of the method on two batches of commercial hazelnut oils, processed from either roasted or unroasted nuts, revealed 6.4 microg 5-methyl-(E)-2-hepten-4-one per kg of unroasted oil whereas 315.8 microg per kg was determined in the roasted nut oil. The about 50-fold higher amount of 5-methyl-(E)-2-hepten-4-one in roasted hazelnut oil suggested the necessity of a thermal treatment to generate the flavor compound. Pan frying of raw hazelnuts (9 to 15 min) or boiling of the crushed nut material for 1 h in water led to an increase of 5-methyl-(E)-2-hepten-4-one by factors of 600 and 800, respectively, thereby corroborating that the major part of the nut flavorant is formed during heat treatment from a yet unknown precursor in hazelnuts.

  4. An exploratory study on the peroxyl-radical-scavenging activity of 2,6-dimethyl-5-hepten-2-ol and its heterocyclic analogues

    NASA Astrophysics Data System (ADS)

    Stobiecka, Agnieszka; Sikora, Magdalena; Bonikowski, Radosław; Kula, Józef

    2016-03-01

    The structural properties and radical scavenging activity of 2,6-dimethyl-5-hepten-2-ol (1) and its new heterocyclic analogues, i.e. 2-methyl-4-(5-methylfuran-2-yl)-butan-2-ol (2) and 2-methyl-4-(5-methylthiophen-2-yl)-butan-2-ol (3) and have been studied by using the experimental and theoretical methods for the first time. Activity of title compounds against the peroxyl radical was determined by using standard fluorimetric test, i.e. the Oxygen Radical Absorbance Capacity assay (ORACFL). Furthermore, the electron-donating ability of odorants has been evaluated by using colorimetric ABTS assay. According to the experimental results obtained from the ORACFL test 2,6-dimethyl-5-hepten-2-ol was characterized by the highest activity in comparison with the novel counterparts. Nevertheless, all investigated compounds exhibited pronounced anti-peroxyl radical activity comparable to that exerted by the one of the most prominent antioxidant among the monoterpene alcohols, i.e. by linalool. On the other hand, the title compounds exerted relatively low capacity to quench the radical cation of ABTS. Theoretical calculations based on the Density Functional Theory (DFT) method with the hybrid functional B3LYP were carried out in order to investigate selected structural and electronic properties including the geometrical parameters as well as the energy of frontier molecular orbitals of parent molecules and the resulting radicals. Furthermore, the possible mechanism of peroxyl-radical-scavenging has been determined by using the thermodynamic descriptors such as the bond dissociation enthalpies (BDEs) and ionization potentials (IPs). These theoretical data pointed out the relevance of HAT mechanism in the peroxyl-radical-scavenging exhibited by 2,6-dimethyl-5-hepten-2-ol and its new heterocyclic analogues in polar and non-polar medium.

  5. Mechanism and Product Distribution of the O3-Initiated Degradation of (E)-2-Heptenal, (E)-2-Octenal, and (E)-2-Nonenal.

    PubMed

    Gaona Colmán, Elizabeth; Blanco, María B; Barnes, Ian; Wiesen, Peter; Teruel, Mariano A

    2017-07-13

    The O3-molecule initiated degradation of three 2-alkenals (E)-2-heptenal, (E)-2-octenal, and (E)-2-nonenal has been investigated in a 1080 L quartz-glass environmental chamber at 298 ± 2 K and atmospheric pressure of synthetic air using in situ FTIR spectroscopy to monitor the reactants and products. The experiments were performed in the absence of an OH scavenger. The molar yields of the primary products formed were glyoxal (49 ± 4) % and pentanal (34 ± 3) % from the reaction of (E)-2-heptenal with O3, glyoxal (41 ± 3) % and hexanal (39 ± 3) % from the reaction of (E)-2-octenal with O3, and glyoxal (45 ± 3) % and heptanal (46 ± 3) % from the reaction of (E)-2-nonenal with O3. The residual bands in the infrared product spectra for each of the studied reactions are attributed to 2-oxoaldehyde compounds. Based on the observed products, a general mechanism for the ozonolysis reaction of long chain unsaturated aldehydes is proposed, and the results are compared with the available literature data.

  6. Mechanical and Transport Properties of Poly(propylene-co-1-heptene) Copolymers and Their Dependence on Monoclinic and/or Mesomorphic Polymorphs.

    PubMed

    García-Peñas, Alberto; Gómez-Elvira, José M; Lorenzo, Vicente; Pérez, Ernesto; Cerrada, María L

    2016-02-25

    Poly(propylene-co-1-heptene) copolymers have been evaluated in a wide 1-heptene content range. Two different polymorphs can be observed in this interval under the processing conditions imposed: monoclinic crystallites and mesomorphic entities. The unique presence of one or the other lattice at specific content or the coexistence of both of them at the intermediate composition interval is a key factor affecting some of the exhibited properties. The influence is observed in characteristics mainly dependent on either crystalline structure, like rigidity, or the amorphous regions, as location and intensity of glass transition. To get a deeper understanding, the transition from mesophase to monoclinic crystallites has also been studied by DSC and by WAXS and SAXS experiments using synchrotron radiation. It is observed that this transformation is only partial and just involves one-third of the initial ordered mesomorphic entities. Permeability to different gases is mainly dependent on amorphous content and hindrance that monoclinic or mesomorphic entities impose on those disordered regions.

  7. Studies of the gas phase reactions of linalool, 6-methyl-5-hepten-2-ol and 3-methyl-1-penten-3-ol with O3 and OH radicals.

    PubMed

    Bernard, François; Daële, Véronique; Mellouki, Abdelwahid; Sidebottom, Howard

    2012-06-21

    The reactions of three unsaturated alcohols (linalool, 6-methyl-5-hepten-2-ol, and 3-methyl-1-penten-3-ol) with ozone and OH radicals have been studied using simulation chambers at T ∼ 296 K and P ∼ 760 Torr. The rate coefficient values (in cm(3) molecule(-1) s(-1)) determined for the three compounds are linalool, k(O3) = (4.1 ± 1.0) × 10(-16) and k(OH) = (1.7 ± 0.3) × 10(-10); 6-methyl-5-hepten-2-ol, k(O3) = (3.8 ± 1.2) × 10(-16) and k(OH) = (1.0 ± 0.3) × 10(-10); and 3-methyl-1-penten-3-ol, k(O3) = (5.2 ± 0.6) × 10(-18) and k(OH) = (6.2 ± 1.8) × 10(-11). From the kinetic data it is estimated that, for the reaction of O(3) with linalool, attack at the R-CH═C(CH(3))(2) group represents around (93 ± 52)% (k(6-methyl-5-hepten-2-ol)/k(linalool)) of the overall reaction, with reaction at the R-CH═CH(2) group accounting for about (1.3 ± 0.5)% (k(3-methyl-1-penten-3-ol)/k(linalool)). In a similar manner it has been calculated that for the reaction of OH radicals with linalool, attack of the OH radical at the R-CH═C(CH(3))(2) group represents around (59 ± 18)% (k(6-methyl-5-hepten-2-ol)/k(linalool)) of the total reaction, while addition of OH to the R-CH═CH(2) group is estimated to be around (36 ± 6)% (k(3-methyl-1-penten-3-ol)/k(linalool)). Analysis of the products from the reaction of O(3) with linalool confirmed that addition to the R-CH═C(CH(3))(2) group is the predominant reaction pathway. The presence of formaldehyde and hydroxyacetone in the reaction products together with compelling evidence for the generation of OH radicals in the system indicates that the hydroperoxide channel is important in the loss of the biradical [(CH(3))(2)COO]* formed in the reaction of O(3) with linalool. Studies on the reactions of O(3) with the unsaturated alcohols showed that the yields of secondary organic aerosols (SOAs) are higher in the absence of OH scavengers compared to the yields in their presence. However, even under low-NO(X) concentrations, the

  8. Ozonolysis at vegetation surfaces. a source of acetone, 4-oxopentanal, 6-methyl-5-hepten-2-one, and geranyl acetone in the troposphere

    NASA Astrophysics Data System (ADS)

    Fruekilde, P.; Hjorth, J.; Jensen, N. R.; Kotzias, D.; Larsen, B.

    The present study gives a possible explanation for the ubiquitous occurrence of 6-methyl-5-hepten-2-one and acetone in ambient air and reports for the first time on a widespread occurrence of geranyl acetone and 4-oxopentanal. We have conducted a series of laboratory experiments in which it is demonstrated that significant amounts of geranyl acetone, 6-methyl-5-hepten-2-one (6-MHO), 4-oxopentanal (4-OPA), and acetone are formed by the reaction of ozone with foliage of common vegetation in the Mediterranean area ( Quercus ilex>Citrus sinensis>Quercus suber>Quercus freinetto>Pinus pinea). In order to rule out biological formation, epicuticular waxes were extracted from the leaves, dispersed on glass wool and allowed to react with a flow of artificial air. Significant amounts of 6-MHO and 4-OPA were formed at ozone concentrations of 50-100 ppbv, but not at zero ozone. A number of terpenoids common in vegetation contain the structural element necessary for ozonolytic formation of 6-MHO. Two sesquiterpenes (nerolidol; farnesol), and a triterpene (squalene) selected as representative test compounds were demonstrated to be strong precursors for acetone, 4-OPA, and 6-MHO. Squalene was also a strong precursor for geranyl acetone. The atmospheric lifetime of geranyl acetone and 6-MHO is less than 1 h under typical conditions. For the present study, we have synthesized 4-OPA and investigated the kinetics of its gas-phase reaction with OH, NO 3, and O 3. A tropospheric lifetime longer than 17 h under typical conditions was calculated from the measured reaction rate constants, which explains the tropospheric occurrence of 4-OPA. It is concluded that future atmospheric chemistry investigations should included geranyl acetone, 6-MHO, and 4-OPA. In a separate experiment it was demonstrated that human skin lipid which contains squalene as a major component is a strong precursor for the four above-mentioned compounds plus nonanal and decanal. The accidental touching of material

  9. Antinociceptive effect of Aristolochia trilobata stem essential oil and 6-methyl-5-hepten-2yl acetate, its main compound, in rodents.

    PubMed

    Quintans, Jullyana de Souza Siqueira; Alves, Rafael Dos Santos; Santos, Darlisson de Alexandria; Serafini, Mairim Russo; Alves, Péricles Barreto; Costa, Emmanoel Vilaça; Zengin, Gokhan; Quintans-Júnior, Lucindo José; Guimarães, Adriana Gibara

    2017-01-20

    Aristolochia trilobata L. is an aromatic plant, popularly known as "mil-homens", and its essential oil (EO) is generally used to treat colic, diarrhea and dysentery disorders. We evaluated the antinociceptive effect of A. trilobata stem EO and of its major compound, the (R)-(-)-6-methyl-5-hepten-2-yl acetate (sulcatyl acetate: SA), using acetic acid (0.85%)-induced writhing response and formalin-induced (20 μL of 1%) nociceptive behavior in mice. We also evaluated the EO and SA effect on motor coordination, using the rota-rod apparatus. EO (25, 50 and 100 mg/kg) or SA (25 and 50 mg/kg) reduced nociceptive behavior in the writhing test (p<0.001). EO (100 mg/kg) and SA (25 and 50 mg/kg) decreased the nociception on the first phase of the formalin test (p<0.05). On the second phase, EO (25: p<0.01; 50: p<0.05 and 100 mg/kg: p<0.001) and SA (25 and 50 mg/kg; p<0.001) reduced the nociceptive response induced by formalin. EO and SA were not able to cause changes in the motor coordination of animals. Together, our results suggest that EO has an analgesic profile and SA seems to be one of the active compounds in this effect.

  10. Behavioural response of sexually naïve and experienced male rats to the smell of 6-methyl-5-hepten-2-one and female rat faeces.

    PubMed

    Nielsen, Birte L; Jerôme, Nathalie; Saint-Albin, Audrey; Rampin, Olivier; Maurin, Yves

    2013-08-15

    Sexually experienced male rats display penile erections when exposed to faeces from mammalian females in oestrus (Rampin et al., Behav Brain Res, 172:169, 2006), suggesting that specific odours indicate female receptiveness across species. However, it is unknown to what extent the sexual response observed results from an odorous conditioning acquired during sexual experience. We tested the behavioural response of male Brown Norway rats both when sexually naïve and experienced to four odours, including oestrous rat faeces and 6-methyl-5-hepten-2-one (methylheptenone; a molecule found in higher concentrations during oestrus in female rats, foxes and horses). Odour had a significant effect on the sexual response of the naïve rats, with oestrus faeces provoking significantly more erections than herb odour, and with methylheptenone and di-oestrus faeces being intermediate. This indicates that sexually naïve male rats have an unconditioned ability to detect oestrous mediated via odour. After gaining sexual experience, the response to methylheptenone, di- and oestrus faeces was significantly higher than that observed with herb odour. These results strongly suggest that methylheptenone is part of the odorous bouquet of oestrus and contributes to the olfactory determination of female receptiveness.

  11. Atmospheric Sink of (E)-3-Hexen-1-ol, (Z)-3-Hepten-1-ol, and (Z)-3-Octen-1-ol: Rate Coefficients and Mechanisms of the OH-Radical Initiated Degradation.

    PubMed

    Gibilisco, Rodrigo G; Blanco, María B; Bejan, Iustinian; Barnes, Ian; Wiesen, Peter; Teruel, Mariano A

    2015-07-07

    A kinetic study of the gas-phase reactions of OH radicals with three unsaturated biogenic alcohols, (E)-3-hexen-1-ol, (Z)-3-hepten-1-ol, and (Z)-3-octen-1-ol, has been performed. The rate coefficients obtained are (in units of 10(-10) cm(3) molecule(-1) s(-1)) k1 (OH + (E)-CH2(OH)CH2CH═CHCH2CH3) = (1.14 ± 0.14), k2 (OH + (Z)-CH2(OH)CH2CH═CHCH2CH2CH3) = (1.28 ± 0.23), and k3 (OH + (Z)-CH2(OH)CH2CH═CHCH2CH2CH2CH3) = (1.49 ± 0.35). In addition, a product study on the reactions of OH with (E)-3-hexen-1-ol and (Z)-3-hepten-1-ol is reported. All the experiments were performed at (298 ± 2) K and 1 atm of NOx-free air in a 1080 L photoreactor with in situ FTIR detection of organics. This work constitutes the first kinetic study of the reactions of OH radicals with (Z)-3-hepten-1-ol and (Z)-3-octen-1-ol as well as the first determination of the fate of the hydroxy alkoxy radicals formed in the title reactions. An analysis of the available rates of addition of OH and Cl to the double bond of different unsaturated alcohols at 298 K has shown that they can be related by the expression log kOH = (0.29 ± 0.04) log kCl - 10.8. The atmospheric lifetimes of the alcohols studies were estimated to be around 1 h for reaction with OH radicals. The products formed in the title reactions are mainly carbonylic compounds that can contribute to the formation of ozone and PANs-type compounds in the troposphere.

  12. Kinetics of the gas-phase reaction between ozone and three unsaturated oxygenated compounds: Ethyl 3,3-dimethyl acrylate, 2-methyl-2-pentenal and 6-methyl-5-hepten-2-one at atmospheric pressure

    NASA Astrophysics Data System (ADS)

    Gaona Colmán, Elizabeth; Blanco, María B.; Barnes, Ian; Teruel, Mariano A.

    2015-05-01

    Rate coefficients for the gas-phase reactions of O3 molecules with three unsaturated oxygenated compounds have been determined using the relative kinetic technique in an environmental chamber with FTIR detection of the reactants at (298 ± 2) K in 760 Torr total pressure of synthetic air. The following rate coefficients (in units of 10-17 cm3 molecule-1 s-1) were determined: ethyl 3,3-dimethyl acrylate (0.82 ± 0.19), 2-methyl-2-pentenal (0.71 ± 0.16) and 6-methyl-5-hepten-2-one (26 ± 7). The different reactivity of the unsaturated oxygenated compounds toward O3 is discussed in terms of their chemical structure. In addition, a correlation between the reactivity of structurally different unsaturated compounds (alkenes and unsaturated oxygenated VOCs, such as ethers, esters, aldehydes, ketones and alcohols) toward O3 molecules and the HOMO (Highest Occupied Molecular Orbital) of the compounds is presented. Using the kinetic parameters determined in this work, residence times of these unsaturated compounds in the atmosphere with respect to reaction with O3 have been calculated. In urban and rural areas the main sink of 6-methyl-5-hepten-2-one is reaction with O3 molecules with a residence time in the order of few minutes.

  13. Lipase-catalyzed domino kinetic resolution/intramolecular Diels-Alder reaction: one-pot synthesis of optically active 7-oxabicyclo[2.2.1]heptenes from furfuryl alcohols and beta-substituted acrylic acids.

    PubMed

    Akai, Shuji; Naka, Tadaatsu; Omura, Sohei; Tanimoto, Kouichi; Imanishi, Masashi; Takebe, Yasushi; Matsugi, Masato; Kita, Yasuyuki

    2002-09-16

    The first lipase-catalyzed domino reaction is described in which the acyl moiety formed during the enzymatic kinetic resolution of furfuryl alcohols (+/-)-3 with a 1-ethoxyvinyl ester 2 was utilized as a part of the constituent structure for the subsequent Diels-Alder reaction. The preparation of ester 2 from carboxylic acid 1 and the subsequent domino reaction were carried out in a one-pot reaction. Therefore, this procedure provides a convenient preparation of the optically active 7-oxabicyclo[2.2.1]heptene derivatives 5, which has five chiral, non-racemic carbon centers, from achiral 1 and racemic 3. The overall efficiency of this process was dependent on the substituent at the C-3 position of 3, and the use of the 3-methylfurfuryl derivatives, (+/-)-3 b and (+/-)-3 f, exclusively produced diastereoselectivity with excellent enantioselectivity to give (2R)-syn-5 (91->/=99 % ee) and (S)-3 (96->/=99 % ee). Similar procedures starting from the 3-bromofurfuryl alcohols (+/-)-3 h-j provided the cycloadducts (2R)-syn-5 j-q (93->/=99 % ee), in which the bromo group was utilized for the installation of bulky substituents to the 7-oxabicycloheptene core.

  14. Benzocyclobutane, benzocycloheptane and heptene derivatives as melatonin agonists and antagonists.

    PubMed

    Tsotinis, Andrew; Afroudakis, Pandelis A; Garratt, Peter J; Bocianowska-Zbrog, Alina; Sugden, David

    2014-10-01

    Two series of analogues were designed, synthesised and evaluated as potential human melatonin type 1 and 2 receptor (hMT1 and hMT2 ) ligands. Their biological effects were assessed by a well-established, specific model of melatonin action, the pigment response of Xenopus laevis melanophores. Compounds containing a benzocyclobutane scaffold and a methoxy group in the "melatonin" orientation were found to be potent agonists, with one of the analogues exhibiting activity comparable to melatonin. In contrast, analogues with a methoxy group in non-melatonin positions or with multiple methoxy groups showed either weaker agonist activity or were antagonists. Benzocycloheptene derivatives with one methoxy group are found to be weak agonists, whereas those with two methoxy groups were found to be antagonists, as were all of the benzocycloheptane derivatives evaluated. The most active compounds were assessed in a human receptor radio ligand binding assay but showed little discrimination between MT1 and MT2 . These results again show that the indole nitrogen of melatonin is not a necessary component for analogue activity and also illustrate that replacement of the indole ring with a 4-membered carbocycle can provide highly active compounds when the methoxy group is in the melatonin position. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. GAS-PHASE REACTION OF OZONE WITH TRANS-2-HEXENAL, TRANS-2-HEXENYL ACETATE, ETHYLVINYL KETONE, AND 6-METHYL-5-HEPTEN-2-ONE. (R824970)

    EPA Science Inventory

    The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...

  16. 7-Chloro-5-cyclo-propyl-9-methyl-5H-4,5,6,10-tetra-aza-dibenzo[a,d]cyclo-hepten-11(10H)-one.

    PubMed

    Naveen, S; Thimmegowda, N R; Manjunath, H R; Sridhar, M A; Prasad, J Shashidhara; Rangappa, K S

    2011-06-01

    In the title compound, C(15)H(13)ClN(4)O, which is a chloro derivative of the drug Nevirapine, the diazepine ring is in a twisted boat conformation. The pyridine rings fused to the diazepine fragment form a dihedral angle of 58.44 (10)° and the mol-ecule adopts a butterfly shape. The mol-ecules are joined via N-H⋯N hydrogen bonding into polymeric chains down the b axis. All weaker C-H⋯O inter-actions involve the carbonyl O atom as acceptor.

  17. The Low Temperature Oxidation Chemistry of JP-8 and its Surrogates at High Pressure

    DTIC Science & Technology

    2006-10-01

    methyl -furan, 2-butenal, 1- Penten-3-one, pentanal, 1-heptene, trans-3-heptene, n-heptane, 2-heptene (cis & trans), 2-pentenal, 2- methyl -5- ethyl ...tetrahydrofuran (cis & trans), 2- methyl -4-propyl-oxetan, 2- ethyl -3-propyl-oxiran, 2- methyl -3-butyl- oxiran, 2-propyl-tetrahydrofuran, 3-heptanone, and 2...heptanone. The major species identified were formaldehyde, acetaldehyde, 2- methyl -5- ethyl -tetrahydrofuran, propanal, ethene, and butanal. Since the

  18. Identification and Quantitation of Volatile Organic Compounds in Poly(methyl methacrylate) Kitchen Utensils by Headspace Gas Chromatography/Mass Spectrometry.

    PubMed

    Ohno, Hiroyuki; Mutsuga, Motoh; Kawamura, Yoko

    2014-01-01

    A headspace GC/MS method was developed for identification and quantitation of residual volatile organic compounds in poly(methyl methacrylate) (PMMA) kitchen utensils. A sample was cut into small pieces, then N,N-dimethylacetamide was added in a headspace vial and sealed. After storing for more than 1 day at room temperature, the vial was incubated for 1 h at 90°C, and the headspace gas was analyzed by GC/MS. In 24 PMMA kitchen utensils, 16 volatile organic compounds including methyl methacrylate, methyl acrylate, toluene, 2-methyl-1-butene, 2-methyl-2-butene, 2-methylpropanal, methyl propionate, methyl isobutyrate, trans-3-heptene, heptane, cis-3-heptene, trans-2-heptene, cis-2-heptene, 2,4,4-trimethyl-1-pentene, 2,4,4-trimethyl-2-pentene, and 1-octene were identified and quantitated. These 15 volatile compounds except methyl methacrylate were found for the first time in PMMA kitchen utensils. Recovery rates from spiked samples were 97.4-104.0% with CV values of 2.8-9.6%. Samples contained 190-7900 μg/g of methyl methacrylate, 26-810 μg/g of methyl acrylate, and 2-1300 μg/g of toluene; other compounds were at levels less than 100 μg/g. Methyl methacrylate was the main monomer of PMMA and methyl acrylate was a comonomer; toluene should be used as a solvent.

  19. Surface chemistry of dihydromyrcenol (2,6-dimethyl-7-octen-2-ol) with ozone on silanized glass, glass, and vinyl flooring tiles

    NASA Astrophysics Data System (ADS)

    Ham, Jason E.; Raymond Wells, J.

    The surface-phase reaction products of dihydromyrcenol (2,6-dimethyl-7-octen-2-ol) with ozone (O 3), air, or nitrogen (N 2) on silanized glass, glass and vinyl flooring tile were investigated using the recently published FACS (FLEC (Field and Laboratory Emission Cell) Automation and Control System). The FACS was used to deliver ozone (100 ppb), air, or N 2 to the surface at a specified flow rate (300 mL min -1) and relative humidity (50%) after application of a 2.0% dihydromyrcenol solution in methanol. Oxidation products were detected using the derivatization agents: O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine hydrochloride (PFBHA) and N, O-bis(trimethysilyl)trifluoroacetamide (BSTFA). The positively identified reaction products were glycolaldehyde, 2,6-dimethyl-5-heptenal, and glyoxal. The proposed oxidation products based on previously published VOC/O 3 reaction mechanisms were: 2,6-dimethyl-4-heptenal, 6-methyl-7-octen-2-one and the surface-specific reaction products: 6-methyl-6-hepten-2-one, 6-methyl-5-hepten-2-one, and 6-hydroxy-6-methylheptan-2-one. Though similar products were observed in gas-phase dihydromyrcenol/O 3 reactions, the ratio, based on peak area, of the reaction products was different suggesting stabilization of larger molecular weight species by the surface. Emission profiles of these oxidation products over 72 h are also reported.

  20. ESTIMATES OF REGIONAL NATURAL VOLATILE ORGANIC COMPOUND FLUXES FROM ENCLOSURE AND AMBIENT MEASUREMENTS

    EPA Science Inventory

    The paper discusses results of an investigation at two forested sites in the Southeastern United States. A variety of VOC compounds including methanol, 2-methyl-3-buten-2-ol, 6-methyl-5-hepten-
    2-one, isoprene, and 15 monoterpenes were emitted from vegetation at these sites. D...

  1. Focused Feasibility Study Final Quality Assurance Program Plan

    DTIC Science & Technology

    1993-10-01

    other hydrocarbons attached, including specificaly: Ethylene Heptenes Cyclopentene Cyclodecene Propylene Octenes Cyclohexene Methylpentn Butylenes...8217 0.007’ Diquat 0.028 0.022 Endothall 0.18 0.16 Endrn 0.0022 0.00021 0.0022 Epichlorohydrin 02 Ethylene dibromide 02 0.00005’ Glyphosate 0.7d 0.7

  2. ESTIMATES OF REGIONAL NATURAL VOLATILE ORGANIC COMPOUND FLUXES FROM ENCLOSURE AND AMBIENT MEASUREMENTS

    EPA Science Inventory

    The paper discusses results of an investigation at two forested sites in the Southeastern United States. A variety of VOC compounds including methanol, 2-methyl-3-buten-2-ol, 6-methyl-5-hepten-
    2-one, isoprene, and 15 monoterpenes were emitted from vegetation at these sites. D...

  3. An efficient synthesis strategy to the core structure of 6-5-6-5-6-membered epipolythiodiketopiperazines.

    PubMed

    Zipfel, Hannes F; Carreira, Erick M

    2014-06-06

    A concise route to the core structure 1 of 6-5-6-5-6-membered epipolythiodiketopiperazines is described. The strategy relies on construction of the pyrrolines by double nucleophilic opening of a bis(oxabicyclo[2.2.1]heptene) 2, obtained after bidirectional condensation of N,N'-diacetyldiketopiperazine (4) with aldehyde 3.

  4. Metabolomic change precedes apple superficial scald symptoms.

    PubMed

    Rudell, David R; Mattheis, James P; Hertog, Maarten L A T M

    2009-09-23

    Untargeted metabolic profiling was employed to characterize metabolomic changes associated with 'Granny Smith' apple superficial scald development following 1-MCP or DPA treatment. Partial least-squares discriminant analyses were used to link metabolites with scald, postharvest treatments, and storage duration. Models revealed metabolomic differentiation between untreated controls and fruit treated with DPA or 1-MCP within 1 week following storage initiation. Metabolic divergence between controls and DPA-treated fruit after 4 weeks of storage preceded scald symptom development by 2 months. alpha-Farnesene oxidation products with known associations to scald, including conjugated trienols, 6-methyl-5-hepten-2-one, and 6-methyl-5-hepten-2-ol, were associated with presymptomatic as well as scalded control fruit. Likewise, a large group of putative triterpenoids with mass spectral features similar to those of ursolic acid and beta-sitosterol were associated with control fruit and scald. Results demonstrate that extensive metabolomic changes associated with scald precede actual symptom development.

  5. Polymer/Solvent and Polymer/Polymer Interaction Studies

    DTIC Science & Technology

    1980-09-01

    pentane Hl Methanol B3 2-Methyl hexane H2 Ethanol B4 i-Octane H3 l-Propanol H4 2-Propanol Cl Ethylene H5 1-Butanol C2 Allene H6 2-Butanol 03 2-Hexene H7...i-Butanol C4 2-Heptene H8 1-Pentanol C5 1- Octene H9 1-Hexanol C6 2- Octene HIO Cyclohexanol C7 2,6-Dimethyl-3-heptene HII Allyl alcohol H12 Benzyl...E2 Toluene 16 m-Methoxyl phenol E3 m-Xylene 17 Propylene glycol E4 Ethyl benzene 18 Resorcinol monoacetate 19 Ethylene glycol Fl Furan I10 1,5

  6. Identification of volatile emissions from Platypus mutatus (=sulcatus) (Coleoptera: Platypodidae) and their behavioral activity.

    PubMed

    Gonzalez Audino, Paola; Villaverde, Raul; Alfaro, Rene; Zerba, E

    2005-10-01

    We report here the identification and behavioral activity of volatile compounds emitted by male Platypus mutatus (=sulcatus) Chapuis while boring galleries in living poplar, Populus deltoides Marshall, trees. Headspace analysis using solid phase microextraction techniques showed the presence of 6-methyl-5-hepten-2-ol (sulcatol) and 6-methyl-5-hepten-2-one (sulcatone). Only one enantiomer of sulcatol, retusol, was found to be part of the volatile emission. Behavioral assays showed that females are more attracted than males to galleries with boring males inside. Both sulcatol and sulcatone elicited electroantennographic responses by female P. mutatus. Furthermore, behavioral bioassays showed that both sulcatol and sulcatone elicit behaviorally attractive responses by females. These results suggest that male P. mutatus releases a sex pheromone composed mainly of retusol and sulcatone.

  7. Validation of a headspace trap gas chromatography and mass spectrometry method for the quantitative analysis of volatile compounds from degraded rapeseed oil.

    PubMed

    Sghaier, Lilia; Cordella, Christophe B Y; Rutledge, Douglas N; Watiez, Mickaël; Breton, Sylvie; Sassiat, Patrick; Thiebaut, Didier; Vial, Jérôme

    2016-05-01

    Due to lipid oxidation, off-flavors, characterized by a fishy odor, are emitted during the heating of rapeseed oil in a fryer and affect the flavor of rapeseed oil even at low concentrations. Thus, there is a need for analytical methods to identify and quantify these products. To study the headspace composition of degraded rapeseed oil, and more specifically the compounds responsible for the fishy odor, a headspace trap gas chromatography with mass spectrometry method was developed and validated. Six volatile compounds formed during the degradation of rapeseed oil were quantified: 1-penten-3-one, (Z)-4-heptenal, hexanal, nonanal, (E,E)-heptadienal, and (E)-2-heptenal. Validation using accuracy profiles allowed us to determine the valid ranges of concentrations for each compound, with acceptance limits of 40% and tolerance limits of 80%. This method was then successfully applied to real samples of degraded oils.

  8. Reactions of adducts of phosphorus pentachloride and 1-alkenes with arsenic trifluoride

    SciTech Connect

    Fridland, S.V.; Miftakhov, M.N.; Dmitrieva, N.V.

    1986-10-20

    As a result of NMR investigations of models of sigma and ..pi.. nu complexes of 1-heptene (or 1-hexene) and phosphorus pentachloride in reactions with arsenic trifluoride it was shown that the formation of the phosphorus-containing arylated product by the Friedel-Crafts scheme is possible only with the participation of the sigma complex, but in the case of the ..pi.. nu complex the arylation of the olefin occurs.

  9. Cyclobutene formation in PtCl2-catalyzed cycloisomerizations of heteroatom-tethered 1,6-enynes.

    PubMed

    Ni, Zhenjie; Giordano, Laurent; Tenaglia, Alphonse

    2014-09-08

    Aza(oxa)bicyclo[3.2.0]heptenes are accessed through the PtCl2 -catalyzed cycloisomerizations of heteroatom-tethered 1,6-enynes featuring a terminal alkyne and amide as the solvent. It is shown that the weak coordinating properties of the solvent and alkyl substituent(s) at the propargylic carbon atom favor the formation of cyclobutenes instead of other possible cycloisomerization products such as 1,3-diene derivatives or cyclopropane-fused heterocycles.

  10. Food volatile compounds facilitating HII mesophase formation: solubilization and stability.

    PubMed

    Amar-Zrihen, Natali; Aserin, Abraham; Garti, Nissim

    2011-05-25

    Four lipophilic food volatile molecules of different chemical characteristics, phenylacetaldehyde, 2,6-dimethyl-5-heptenal, linalool, and trans-4-decenal, were solubilized into binary mixtures of monoolein/water, facilitating the formation of reverse hexagonal (H(II)) mesophases at room temperature without the need of solvents or triglycerides. Some of the flavor compounds are important building blocks of the hexagonal mesostructure, preventing phase transition with aging. The solubilization loads were relatively high: 12.6, 10.0, 12.6, and 10.0 wt % for phenylacetaldehyde, 2,6-dimethyl-5-heptenal, linalool, and trans-4-decenal, respectively. Phenylacetaldehyde formed mixtures of lamellar and cubic phases. Linalool, 2,6-dimethyl-5-heptenal, and trans-4-decenal induced structural shift from lamellar directly to H(II) mesophase, remaining stable at room temperature. Lattice parameters were found to increase with water content and to decrease with temperature and/or food volatile content. trans-4-Decenal produces more stable H(II) mesophase compared to linalool-loaded mesophase. At 40-60 °C, depending on the chemical structure and on the solubilization location of the food volatile compounds, the H(II) mesophase transforms to isotropic micellar phase, facilitating the release of the food volatile compounds. Molecular interactions suggest the existence of two consecutive stages in the solubilization process.

  11. Arm-in-cage testing of natural human-derived mosquito repellents

    PubMed Central

    2010-01-01

    Background Individual human subjects are differentially attractive to mosquitoes and other biting insects. Previous investigations have demonstrated that this can be attributed partly to enhanced production of natural repellent chemicals by those individuals that attract few mosquitoes in the laboratory. The most important compounds in this respect include three aldehydes, octanal, nonanal and decanal, and two ketones, 6-methyl-5-hepten-2-one and geranylacetone [(E)-6,10-dimethylundeca-5,9-dien-2-one]. In olfactometer trials, these compounds interfered with attraction of mosquitoes to a host and consequently show promise as novel mosquito repellents. Methods To test whether these chemicals could provide protection against mosquitoes, laboratory repellency trials were carried out to test the chemicals individually at different concentrations and in different mixtures and ratios with three major disease vectors: Anopheles gambiae, Culex quinquefasciatus and Aedes aegypti. Results Up to 100% repellency was achieved depending on the type of repellent compound tested, the concentration and the relative composition of the mixture. The greatest effect was observed by mixing together two compounds, 6-methyl-5-hepten-2-one and geranylacetone in a 1:1 ratio. This mixture exceeded the repellency of DEET when presented at low concentrations. The repellent effect of this mixture was maintained over several hours. Altering the ratio of these compounds significantly affected the behavioural response of the mosquitoes, providing evidence for the ability of mosquitoes to detect and respond to specific mixtures and ratios of natural repellent compounds that are associated with host location. Conclusion The optimum mixture of 6-methyl-5-hepten-2-one and geranylacetone was a 1:1 ratio and this provided the most effective protection against all species of mosquito tested. With further improvements in formulation, selected blends of these compounds have the potential to be exploited and

  12. Metal ion hydrocarbon bidentate bonding in alkyl acetates, methyl alkanoates, alcohols and 1-alkenes: a comparative study.

    PubMed

    Burgers, Peter C; Holmes, John L; Terlouwc, Johan K

    2016-01-01

    The relative affinity of the monovalent metal ions Li(+), Na(+), Cu(+) and Ag(+) towards a series of aliphatic alkyl acetates and some selected 1-alkenes (P) was examined using the kinetic method. A detailed analysis of the dissociation characteristics of a series of mixed metal-bound dimer ions of the type P1-M(+)-P2 and the evaluated proton affinities (PAs) of the monomers shows that the affinity of the cation towards long-chain alkyl acetates and alkenes (having a chain length ≤ C4) is markedly enhanced. In line with recent studies of nitriles, alcohols and methyl alkanoates, this is attributed to a bidentate interaction of the metal ion with the functional group or double bond and the aliphatic chain. In particular, the longer chain alkyl acetates, methyl alkanoates and alcohols show a remarkably similar behaviour with respect to silver ion hydrocarbon bonding. The Ag(+) adducts of the alkyl acetates dissociate by loss of CH3COOH. This reaction becomes more pronounced at longer chain lengths, which points to metal ion bidentate formation in [Ag(+)···1-alkene] product ions having a long hydrocarbon chain. In the same vein, the heterodimers [1- hexene···Ag(+)···1-heptene] and [1- heptene···Ag(+)···1-octene] dissociate primarily into [Ag(+)···1-heptene] and [Ag(+)···1-octene] ions, respectively. Hydrocarbon bidentate formation in [Ag(+)···1-octene] also reveals itself by the reluctance of this ion to react with water in an ion trap, as opposed to [Ag(+)···1-hexene] which readily undergoes hydration.

  13. An experimental kinetic study and products research of the reactions of O3 with a series of unsaturated alcohols

    NASA Astrophysics Data System (ADS)

    Chen, Yi; Wang, Jing; Zhao, Sanping; Tong, Shengrui; Ge, Maofa

    2016-11-01

    The gas-phase reactions of unsaturated alcohols with O3 were investigated in FEP Teflon film chamber at 298 K and 760 torr of atmosphere pressure. The rate constants of the reactions of C6-C8 alkenols with O3 were determined using both the absolute and the relative rate method, and the measured values were (5.96 ± 0.35) × 10-17 cm3 molecule-1 s-1 for (Z)-3-hexen-1-ol, (5.12 ± 0.30) × 10-17 cm3 molecule-1 s-1 for (Z)-3-hepten-1-ol, and (5.66 ± 0.52) × 10-17 cm3 molecule-1 s-1 for (Z)-3-octen-1-ol, respectively. The gas-phase products of these reactions mentioned above were detected using proton-transfer-reaction mass spectrum (PTR-MS). HOCH2CH2CHO, CH2CH2CHO, HCHO and CH3CHO were identified as the main gas products for (Z)-3-hexen-1-ol. HOCH2CH2CHO and CH3(CH2)2CHO dominated the gaseous products for (Z)-3-hepten-1-ol. And for (Z)-3-octen-1-ol, CH3(CH2)3CHO, CH3(CH2)2CHO and HOCH2CH2CHO were the main gaseous products. The SOA yields were monitored at the same time, which were 0.184 ± 0.013, 0.213 ± 0.017, 0.232 ± 0.021 for (Z)-3-hexen-1-ol, (Z)-3-hepten-1-ol and (Z)-3-octen-1-ol, respectively. The possible reaction mechanisms were proposed and discussed. The kinetic data presented here has been used to estimate their atmosphere lifetimes and the reaction reactivity. The atmosphere implication of these reactions has also been discussed.

  14. Catalytical Photocyclization of Arylamines with a-Olefins in the Synthesis of 2-Alkylquinoline

    ERIC Educational Resources Information Center

    Makhmutov, Aynur; Usmanov, Salavat; Mustafin, Ahat

    2016-01-01

    The article deals with the results of investigation of the process of catalytical photocyclization of aniline and aniline hydrochloride with a-olefins (hexene-1, heptene-1 and octene-1). The following compounds of d- and f-metals are tested as probable catalysts: CuSO4•5H2O, EuCl3•6H2O, PrCl3•6H2O, TbCl3•6H2O, La2O3, MnO2, NiSO4•6H2O, NiCl2•6H2O,…

  15. (1S,3R,8R,9S,11R)-2,2,10,10-Tetra-chloro-3,7,7,11-tetra-methyl-tetra-cyclo-[6.5.0.0(1,3).0(9,11)]trideca-ne.

    PubMed

    Ourhriss, Najia; Benharref, Ahmed; Saadi, Mohamed; El Ammari, Lahcen; Berraho, Moha

    2013-02-01

    The title compound, C(17)H(24)Cl(4), was synthesized from β-himachalene (3,5,5,9-tetra-methyl-2,4a,5,6,7,8-hexa-hydro-1H-benzocyclo-heptene), which was isolated from the essential oil of the Atlas cedar (Cedrus Atlantica). The mol-ecule is built up from fused six- and seven-membered rings and two three-membered rings from the reaction of β-himachalene with dichloro-carbene. The six-membered ring shows a chair conformation, whereas the seven-membered ring displays a boat conformation.

  16. (1S,2R,3S,6S,7R)-3,7,11,11-Tetra-methyl-6,7-epoxybi-cyclo-[5.4.0]undecane-2-ol.

    PubMed

    Loubidi, Mohamed; Benharref, Ahmed; El Ammari, Lahcen; Saadi, Mohamed; Berraho, Moha

    2014-05-01

    The title compound, C15H26O2, was synthesized from β-himachalene (3,5,5,9-tetra-methyl-2,4a,5,6,7,8-hexa-hydro-1H-benzo-cyclo-heptene), which was isolated from the Atlas cedar (cedrus atlantica). The mol-ecule is built up from a seven-membered ring to which a six- and a three-membered ring are fused. The seven- and six-membered rings each have a twist-boat conformation. In the crystal, O-H⋯O hydrogen bonds link the mol-ecules into zigzag chains running along the b-axis direction.

  17. (1S,3R,8S,9R,10S)-2,2-Dichloro-3,7,7,10-tetra­methyl-9,10-ep­oxy­tricyclo­[6.4.0.01,3]dodeca­ne

    PubMed Central

    Benharref, Ahmed; El Ammari, Lahcen; Avignant, Daniel; Oudahmane, Abdelghani; Berraho, Moha

    2010-01-01

    The title compound, C16H24Cl2O, was synthesized from β-himachalene (3,5,5,9-tetra­methyl-2,4a,5,6,7,8-hexa­hydro-1H-benzocyclo­heptene), which was isolated from the essential oil of the Atlas cedar (cedrus atlantica). The mol­ecule forms an extended sheet of two fused rings which exhibit different conformations. The six-membered ring has a half-chair conformation, while the seven-membered ring displays a chair conformation; the dihedral angle between the two rings is 38.2 (1)°. PMID:21589429

  18. (1R,4R,6S,7R)-5,5-Di-bromo-1,4,8,8-tetra-methyl-tri-cyclo-[5.4.1.0(4,6)]dodecan-12-one.

    PubMed

    Zaki, Mohamed; Benharref, Ahmed; Daran, Jean-Claude; Berraho, Moha

    2014-05-01

    The title compound, C16H24Br2O, was synthesized from the reaction of β-himachalene (3,5,5,9-tetra-methyl-2,4a,5,6,7,8-hexa-hydro-1H-benzo-cyclo-heptene), which was isolated from Atlas cedar (Cedrus atlantica). The asymmetric unit contains two independent mol-ecules with similar conformations. Each mol-ecule is built up from two fused seven-membered rings and an additional three-membered ring. In both mol-ecules, one of the seven-membered rings has a chair conformation, whereas the other displays a screw-boat conformation.

  19. (1S,3R,8R,9S,11R)-2,2,10,10-Tetra­chloro-3,7,7,11-tetra­methyl­tetra­cyclo­[6.5.0.01,3.09,11]trideca­ne

    PubMed Central

    Ourhriss, Najia; Benharref, Ahmed; Saadi, Mohamed; El Ammari, Lahcen; Berraho, Moha

    2013-01-01

    The title compound, C17H24Cl4, was synthesized from β-himachalene (3,5,5,9-tetra­methyl-2,4a,5,6,7,8-hexa­hydro-1H-benzocyclo­heptene), which was isolated from the essential oil of the Atlas cedar (Cedrus Atlantica). The mol­ecule is built up from fused six- and seven-membered rings and two three-membered rings from the reaction of β-himachalene with dichloro­carbene. The six-membered ring shows a chair conformation, whereas the seven-membered ring displays a boat conformation. PMID:23424548

  20. (1S,3R,8R,9S,11R)-2,2-Di-bromo-10,10-di-chloro-3,7,7,11-tetra-methyl-tetra-cyclo-[6.5.0.0(1,3).0(9,11)]trideca-ne.

    PubMed

    Ourhriss, Najia; Benharref, Ahmed; Saadi, Mohamed; Berraho, Moha; El Ammari, Lahcen

    2013-05-01

    The title compound, C17H24Br2Cl2, was synthesized from β-himachalene (3,5,5,9-tetra-methyl-2,4a,5,6,7,8-hexa-hydro-1H-benzo-cyclo-heptene), which was isolated from the essential oil of the Atlas cedar (Cedrus Atlantica). The mol-ecule contains fused six-, seven- and two three-membered rings. The six-membered ring has a half-chair conformation, while the seven-membered ring displays a boat conformation. The absolute structure was unambiguously established from anomalous dispersion effects. The crystal packing exhibits no short inter-molecular contacts.

  1. Synthesis of the aggregation pheromone of the Colorado potato beetle from its degradation product.

    PubMed

    Wacławczyk-Biedroń, Weronika; Frąckowiak-Wojtasek, Bożena; Strub, Daniel; Rzechak, Magdalena; Wojtasek, Hubert

    2015-09-01

    Incubation of the Colorado potato beetle aggregation pheromone, (S)-1,3-dihydroxy-3,7-dimethyl-6-octen-2-one, with antennal or leg extracts from this beetle gave 6-methyl-5-hepten-2-one as the major product. This ketone was used as a substrate in a stereoselective synthesis of the pheromone. It was attached to the butanediacetal of glycolic acid with good stereoselectivity and the desired isomer was further enriched by purification of the product of this reaction on silica gel.

  2. Infrared study on the mechanism of olefins and alcohols conversions over H-ZSM-5 zeolite

    NASA Astrophysics Data System (ADS)

    Bezuhanova, C. P.; Lechert, H. T.; Dimitrov, C.; Nenova, V. V.

    1984-03-01

    The IR spectra of 1-hexene, 1-heptene, cyclohexene, n-propanol and tert.-butanol, adsorbed on H-ZSM-5 zeolite, evacuated at 675 K, revealed a band at 1520 cm -1 after contacting with the zeolite at 373 J. The band was absent in the case of adsorbed benzene and cyclohexane and of very low intensity by methanol and ethanol adsorption. Considerations are given in favour of very strong interaction either of the type of X-complex or of carbenium ion. The second assumption was confirmed by the subsequent disappearance of the zeolitic OH bands.

  3. High-Resolution Tunable Diode Laser Spectroscopy of Methane

    DTIC Science & Technology

    1986-03-01

    quantitative data from test 14. This table shows that ethylene is by far the most abundant species, with propane and acetylene also being major species. The...Test 14 1. Ethane 2.21 2. Ethylene 77.80 3. Propane 0.75 4. Acetylene 18.61 5. Propene 26.52 6. Acetaldehyde 1.83 7. 1-Butene 5.83 8. 1,3...21. Benzene 9.07 22. l-Heptene 3.16 23. N-Heptane 0.44 24. Toluene 3.33 25. Hexanal 1.09 26. 1- Octene 2.13 27. N-Octane 0.63 28. Ethylbenzene

  4. [Chemical composition of the essential oil from melissa].

    PubMed

    Tittel, G; Wagner, H; Bos, R

    1982-10-01

    Different oil-samples of Melissa officinalis L. were analysed by capillary GC/MS, using fused silica columns and E.I.-Mass-spectrometry. Comparing the observed mass-spectra with those of a spectral collection, 70 compounds of the oil were identified. Geranial, neral, 6-methyl-5-hepten-2-one, citronellal, geranyl-acetate, beta-caryophyllene, and beta-caryophyllene-oxide comprise about 96%. The fingerprint of the capillary gas-chromatogramm permitted differentiation of the essential oil of Melissa officinalis, Cymbopogon winterianus and Nepeta cataria var. citriodora., as well as a standardisation of pharmaceutical preparations containing Melissa oil.

  5. Rapid differentiation of new apple cultivars by headspace solid-phase microextraction in combination with chemometrical data processing.

    PubMed

    Schulz, Ines; Ulrich, Detlef; Fischer, Christa

    2003-04-01

    The aim of this study was to test a combination of automated headspace solid phase-microextraction gas chromatography (GC) with chemometrical data treatment for the rapid differentiation of enzyme-inactivated homogenates of new apple cultivars. The four cultivars Pinova, Piflora, Renora and Florina are characterized by different volatile patterns. Differences in the contents of volatiles were especially found for butyl acetate, ethyl butanoate, 2-methyl butanol, ethyl acetate and 6-methyl-5-hepten-2-ol. The used sample preparation method for GC coupled with pattern recognition of chromatograms is a useful tool for rapid and reliable determination of large numbers of samples.

  6. Effects of metal chelator, sodium azide, and superoxide dismutase on the oxidative stability in riboflavin-photosensitized oil-in-water emulsion systems.

    PubMed

    Lee, JaeHwan; Decker, Eric A

    2011-06-08

    The effects of riboflavin photosensitization on the oxidative stability of oil-in-water (O/W) emulsions were determined using lipid hydroperoxides and headspace volatile analyses. The influences of a metal chelator, sodium azide, and superoxide dismutase (SOD) on oxidation pathways were tested to gain a better understanding of the role of transition metals, singlet oxygen, and superoxide anion, respectively. Emulsions with riboflavin and visible light irradiation had significantly higher lipid hydroperoxides and volatiles (p < 0.05) as compared to samples without light irradiation or riboflavin. The addition of ethylenediammetetraacetic acid (EDTA) decreased the formation of lipid hydroperoxides, hexanal, 2-heptenal, and 1-octen-3-ol in a concentration-dependent manner. Sodium azide, a singlet oxygen physical quencher, only inhibited the formation of 2-heptenal and 1-octen-3-ol. Overall, photosensitized riboflavin participated in both type I and type II pathways in O/W emulsions, and these pathways enhance the prooxidant activity of metals through their ability to produce lipid hydroperoxides and superoxide anion.

  7. Role of calcium in phosphoinositide metabolism and inhibition of norepinephrine transport into synaptic vesicles by amphetamine analogs

    SciTech Connect

    Knepper, S.M.

    1985-01-01

    Norepinephrine-(NE) and calcium ionophore A23187-stimulated phosphoinositide (PIn) metabolism in rat brain slices was studied under varying calcium conditions. Tissue was labelled with /sup 3/H-myo-inositol and /sup 3/H-inositol phosphates (IPn), products of PIn metabolism were measured. In the absence of media calcium the response to NE was decreased while that to A23187 was little affected A23187 can release calcium from intracellular stores. Basal and stimulated accumulation of /sup 3/H-IPn was reversibly antagonized with EGTA by addition of calcium. Using calcium buffers, approximately 10/sup -7/ M free calcium was required to support hydrolysis. Free intracellular calcium is maintained at approximately this level. Thus calcium is required for PIn hydrolysis but appears to play a permissive role, basal levels being sufficient to support metabolism. Conformationally-defined (rigid) and -restricted (semi-rigid) analogs of the most stable conformations of amphetamine, antiperiplanar (exo) and gauche (endo), were utilized to probe the conformational requirements of vesicular NE transport. Analogs tested were 2-aminotetralin (2AT), 3-methyltetrahydroisoquinoline, anti- and syn-9-aminobenzobicyclo(2.2.1)heptene, and endo and exo conformers of 2-aminobenzobicyclo(2.2.1)heptene and 2-aminobenzobicyclo(2.2.2)octene.

  8. Diarylheptanoids, new phytoestrogens from the rhizomes of Curcuma comosa: Isolation, chemical modification and estrogenic activity evaluation.

    PubMed

    Suksamrarn, Apichart; Ponglikitmongkol, Mathurose; Wongkrajang, Kanjana; Chindaduang, Anon; Kittidanairak, Suthadta; Jankam, Aroon; Yingyongnarongkul, Boon-ek; Kittipanumat, Narin; Chokchaisiri, Ratchanaporn; Khetkam, Pichit; Piyachaturawat, Pawinee

    2008-07-15

    Three new diarylheptanoids, a 1:2 mixture of (3S)- and (3R)-1-(4-methoxyphenyl)-7-phenyl-(6E)-6-hepten-3-ol (13a and 13b) and 1-(4-hydroxyphenyl)-7-phenyl-(6E)-6-hepten-3-one (15), together with two synthetically known diarylheptanoids 1,7-diphenyl-(1E,3E,5E)-1,3,5-triene (9) and 1-(4-hydroxyphenyl)-7-phenyl-(4E,6E)-4,6-heptadien-3-one (16), and nine known diarylheptanoids, 2, 8, 10-12, 14, a 3:1 mixture of 17a and 17b, and 18, were isolated from the rhizomes of Curcuma comosa Roxb. The absolute stereochemistry of the isolated compounds has also been determined using the modified Mosher's method. The isolated compounds and the chemically modified analogues were evaluated for their estrogenic-like transcriptional activity using RT-PCR in HeLa cell line. Some of the isolated diarylheptanoids and their modified analogues exhibited estrogenic activity comparable to or higher than that of the phytoestrogen genistein. Based on the transcriptional activation of both estrogenic targets, Bcl-xL and ERbeta gene expression, the structural features for a diarylheptanoid to exhibit high estrogenic activity are the presence of an olefinic function conjugated with the aromatic ring at the 7-position, a keto group at the 3-position, and a phenolic hydroxyl group at the p-position of the aromatic ring attached to the 1-position of the heptyl chain.

  9. Do Flower Color and Floral Scent of Silene Species affect Host Preference of Hadena bicruris, a Seed-Eating Pollinator, under Field Conditions?

    PubMed Central

    Page, Paul; Favre, Adrien; Schiestl, Florian P.; Karrenberg, Sophie

    2014-01-01

    Specialization in plant–insect interactions is an important driver of evolutionary divergence; yet, plant traits mediating such interactions are poorly understood. In this study, we investigated how flower color and floral scent are related to seed predation by a seed-eating pollinator. We used field-transplanted recombinant F2 hybrids between Silene latifolia and S. dioica that are the preferred and alternative hosts of the moth Hadena bicruris and crosses within these species for comparison. We scored seed predation and flower color and analyzed floral scent. Pinker S. dioica-like flowers and emission of α-pinene decreased the odds of seed predation while emission of benzyl acetate and 6-methyl-5-hepten-2-one increased the odds of seed predation. Emission of these compounds did not differ significantly between the two Silene species. Our results suggest that flower color plays an important role in the specific interaction of H. bicruris with its preferred host S. latifolia. The compounds α-pinene, benzyl acetate and 6-methyl-5-hepten-2-one could represent non-specific deterrents and attractants to ovipositing moths. Alternatively, emission of these compounds could be related to herbivory or pathogen attack and act as a signal for host quality. This would weaken the predictability of the plant's costs and benefits of the interaction and act to maintain an imperfect degree of specialization. PMID:24905986

  10. Do flower color and floral scent of silene species affect host preference of Hadena bicruris, a seed-eating pollinator, under field conditions?

    PubMed

    Page, Paul; Favre, Adrien; Schiestl, Florian P; Karrenberg, Sophie

    2014-01-01

    Specialization in plant-insect interactions is an important driver of evolutionary divergence; yet, plant traits mediating such interactions are poorly understood. In this study, we investigated how flower color and floral scent are related to seed predation by a seed-eating pollinator. We used field-transplanted recombinant F2 hybrids between Silene latifolia and S. dioica that are the preferred and alternative hosts of the moth Hadena bicruris and crosses within these species for comparison. We scored seed predation and flower color and analyzed floral scent. Pinker S. dioica-like flowers and emission of α-pinene decreased the odds of seed predation while emission of benzyl acetate and 6-methyl-5-hepten-2-one increased the odds of seed predation. Emission of these compounds did not differ significantly between the two Silene species. Our results suggest that flower color plays an important role in the specific interaction of H. bicruris with its preferred host S. latifolia. The compounds α-pinene, benzyl acetate and 6-methyl-5-hepten-2-one could represent non-specific deterrents and attractants to ovipositing moths. Alternatively, emission of these compounds could be related to herbivory or pathogen attack and act as a signal for host quality. This would weaken the predictability of the plant's costs and benefits of the interaction and act to maintain an imperfect degree of specialization.

  11. Three structurally similar odorants trigger distinct signaling pathways in a mouse olfactory neuron.

    PubMed

    Yu, Y; Boyer, N P; Zhang, C

    2014-09-05

    In the mammalian olfactory system, one olfactory sensory neuron (OSN) expresses a single olfactory receptor gene. By calcium imaging of individual OSNs in intact mouse olfactory turbinates, we observed that a subset of OSNs (Ho-OSNs) located in the most ventral olfactory receptor zone can mediate distinct signaling pathways when activated by structurally similar ligands. Calcium imaging showed that Ho-OSNs were highly sensitive to 2-heptanone, heptaldehyde and cis-4-heptenal. 2-heptanone-evoked intracellular calcium elevation was mediated by cAMP signaling while heptaldehyde triggered the diacylglycerol pathway. An increase of intracellular calcium evoked by cis-4-heptenal was due to a combination of activation mediated by the adenylate cyclase pathway and suppression generated by phospholipase C signaling. Pharmacological studies demonstrated that novel mechanisms were involved in the phospholipase C-mediated intracellular calcium changes. Binary-mixture studies and cross-adaptation data indicate that three odorants acted on the same olfactory receptor. The feature that an olfactory receptor mediates multiple signaling pathways was specific for Ho-OSNs and not established in another population of OSNs characterized. Our study suggests that distinct signaling pathways triggered by ligand-induced conformational changes of an olfactory receptor constitute a complex information process mechanism in olfactory transduction. This study has important implications beyond olfaction in that it provides insights of plasticity and complexity of G-protein-coupled receptor activation and signal transduction. Copyright © 2014 IBRO. Published by Elsevier Ltd. All rights reserved.

  12. Characterization and synthesis of volatile compounds from the defensive secretions of some "daddy longlets" (Arachnida: Opiliones: Leiobunum spp.).

    PubMed

    Jones, T H; Meinwald, J; Hicks, K; Eisner, T

    1977-02-01

    Analyses of the chief volatile constituents of the defensive secretions of three oplionids were carried out. Leiobunum nigripalpi produces three closely related C7 compounds: E-4-methyl-4-hexen-3-one(I), 4-methylhexan-3-one(II), and 4-methylhexan-3-ol(III), along with E-4-methyl-4-hepten-3-one(IV), E,E-2,4-dimethylhexa-2,4-dienal(IX), and a minor, unidentified component. L. leiopenis secretion contains E-4-methyl-4-hepten-3-one(IV), 4-methylheptan-3-one(V), E,E-2,4-dimethylhexa-2,4-dien-1-ol(VII), and E,E-2,4-dimethylhepta-2,4-dien-1-ol(VIII). L. calcar yields chiefly E-4,6-dimethyl-6-octen-3-one(VI) and E,E-2,4-dimethylhexa-2,4-dien-1-ol(VII). Six of these compounds are new natural products. The structures of these compounds, which can be regarded either as polyketide-derived or as modified isoprenoids, raise interesting biosynthetic questions.

  13. An assessment of the role played by some oxidation-related aldehydes in wine aroma.

    PubMed

    Culleré, Laura; Cacho, Juan; Ferreira, Vicente

    2007-02-07

    The levels of important oxidation-related aldehydes, such as methional, phenylacetaldehyde, (E)-2-hexenal, (E)-2-heptenal, (E)-2-octenal, (E)-2-nonenal, methylpropanal, 2-methylbutanal, and 3-methylbutanal, were determined in 41 different wines belonging to different types (young whites and reds, natural sparkling wines, oxidized young whites and reds, Sherry, aged red wines, Port wines). Except (E)-2-hexenal and (E)-2-heptenal, all of them could be found at levels above threshold. Different compositional patterns were identified: Sherry wines have large amounts of branched aldehydes but not of (E)-2-alkenals, wines exposed to oxygen can have large amounts of (E)-2-alkenals but not of branched aldehydes, while aged wine and Port have relatively large amounts of both classes of compounds. Different sensory tests confirmed the active sensory role of these compounds and revealed the existence of interactions (additive or synergic) between them and with other wine volatiles. (E)-2-Alkenals are related to flavor deterioration, while branched aldehydes enhance dried fruit notes and mask the negative role of (E)-2-alkenals.

  14. Effect of release rate and enantiomeric composition on response to pheromones of Megaplatypus mutatus (Chapuis) in poplar plantations of Argentina and Italy.

    PubMed

    Funes, Hernán; Zerba, Eduardo; Gonzalez-Audino, Paola

    2013-10-01

    Megaplatypus mutatus (=Platypus sulcatus Chapuis) is an Ambrosia beetle native to South America, which was recently introduced in Italy and its presence there is causing severe damage to the local poplar plantations. The male M. mutatus pheromone is composed of (S)-(+)-6-methyl-5-hepten-2-ol [(+)-sulcatol], 6-methyl-5-hepten-2-one (sulcatone) and 3-pentanol. A series of field trials testing dose, blend and enantiomer composition performed in Argentina and Italy evaluated attraction and found that the optimal release rate of pheromone components as baits in cross vane baited traps (CIPEIN-CV) was 6, 6 and 30 mg day−1 of sulcatone, (+)-sulcatol and 3-pentanol, respectively. It was also determined that racemic sulcatol is as effective as the pure (+)-isomer for the purpose of beetle catch, due to the inert nature of the (−)-isomer allowing the usage of low cost racemic sulcatol instead of highly expensive (+)-sulcatol. The results of our work contribute to the development of pheromone-based local technologies with low environmental impact and low cost for control or monitoring of an important pest.

  15. 11,12-Dihy-droxy-10,6,8,11,13-icetexapentan-1-one.

    PubMed

    Razak, Ibrahim Abdul; Chantrapromma, Suchada; Salae, Abdul Wahab; Fun, Hoong-Kun

    2011-01-08

    THE TITLE COMPOUND [SYSTEMATIC NAME: 14,15-dihy-droxy-7,7-dimethyl-13-(propan-2-yl)tricyclo-[9.4.0.0(3,8)]penta-deca-1(11),3(8),9,12,14-pentaen-4-one], C(20)H(24)O(3), is a new icetexane diterpenoid which was isolated from the roots of Premna obtusifolia (Verbenaceae). The mol-ecule has three fused rings: a cyclo-hexenone, a central cyclo-heptene and a benzene ring. The cyclo-hexenone ring is in an envelope conformation, whereas the cyclo-heptene ring is in a twisted boat conformation. Intra-molecular O-H⋯O hydrogen bonds generate S(5) and S(8) ring motifs. In the crystal, mol-ecules are linked into dimers through O-H⋯O hydrogen bonds. These dimers are arranged in to sheets parallel to the ac plane. C-H⋯O and weak C-H⋯π inter-actions are also present.

  16. 11,12-Dihy­droxy-10,6,8,11,13-icetexapentan-1-one

    PubMed Central

    Razak, Ibrahim Abdul; Chantrapromma, Suchada; Salae, Abdul Wahab; Fun, Hoong-Kun

    2011-01-01

    The title compound [systematic name: 14,15-dihy­droxy-7,7-dimethyl-13-(propan-2-yl)tricyclo­[9.4.0.03,8]penta­deca-1(11),3(8),9,12,14-pentaen-4-one], C20H24O3, is a new icetexane diterpenoid which was isolated from the roots of Premna obtusifolia (Verbenaceae). The mol­ecule has three fused rings: a cyclo­hexenone, a central cyclo­heptene and a benzene ring. The cyclo­hexenone ring is in an envelope conformation, whereas the cyclo­heptene ring is in a twisted boat conformation. Intra­molecular O—H⋯O hydrogen bonds generate S(5) and S(8) ring motifs. In the crystal, mol­ecules are linked into dimers through O—H⋯O hydrogen bonds. These dimers are arranged in to sheets parallel to the ac plane. C—H⋯O and weak C—H⋯π inter­actions are also present. PMID:21522950

  17. Comparison of Aroma-Active Volatiles in Oolong Tea Infusions Using GC-Olfactometry, GC-FPD, and GC-MS.

    PubMed

    Zhu, JianCai; Chen, Feng; Wang, LingYing; Niu, YunWei; Yu, Dan; Shu, Chang; Chen, HeXing; Wang, HongLin; Xiao, ZuoBing

    2015-09-02

    The aroma profile of oolong tea infusions (Dongdingwulong, DDWL; Tieguanyin, TGY; Dahongpao, DHP) were investigated in this study. Gas chromatography-olfactometry (GC-O) with the method of aroma intensity (AI) was employed to investigate the aroma-active compounds in tea infusions. The results presented forty-three, forty-five, and forty-eight aroma-active compounds in the TGY, DHP, and DDWL infusions, including six, seven, and five sulfur compounds, respectively. In addition, the concentration of volatile compounds in the tea infusions was further quantitated by solid phase microextraction-gas chromatography (SPME)-GC-MS and SPME-GC-flame photometric detection (FPD). Totally, seventy-six and thirteen volatile and sulfur compounds were detected in three types of tea infusions, respectively. Quantitative results showed that forty-seven aroma compounds were at concentrations higher than their corresponding odor thresholds. On the basis of the odor activity values (OAVs), 2-methylpropanal (OAV: 230-455), 3-methylbutanal (1-353), 2-methylbutanal (34-68), nerolidol (108-184), (E)-2-heptenal (148-294), hexanal (134-230), octanal (28-131), β-damascenone (29-59), indole (96-138), 6-methyl-5-hepten-2-one (34-67), (R)-(-)-linalool (63-87), and dimethyl sulfide (7-1320) presented relatively higher OAVs than those of other compounds, indicating the importance of these compounds in the overall aroma of tea infusions.

  18. Volatile Oxidation Compounds and Stability of Safflower, Sesame and Canola Cold-Pressed Oils as Affected by Thermal and Microwave Treatments.

    PubMed

    Kiralan, Mustafa; Ramadan, Mohamed Fawzy

    2016-01-01

    The goal of this study was to investigate the effect of heating and microwave treatment on the levels of volatile oxidation products and the stability of safflower (Carthamus tinctorius L.), sesame (Sesamum indicum) and canola (Brassica napus L.) cold-pressed oils. Cold-pressed oils were subjected to conventional heating (oven test) using air-forced oven at 60°C and microwave heating for 2 and 4 min. The changes in conjugated diene (CD) and conjugated triene (CT) values were monitored during treatments. As expected, heating generates an increase in CD and CT values. The volatile compounds in treated oils were determined using solid phase micro-extraction-gas chromatography/mass spectrometry (SPME-GC/MS). The obtained GC/MS data were used to characterize volatile compounds of cold-pressed oils during heating and microeave treatments. Under oven conditions, 2-heptenal and 2,4-heptadienal isomers were identified as major components in canola oil, while hexanal and 2-heptenal were found in high levels in safflower and sesame oils. Among volatiles, p-cymene was the dominant compound found in microwave-treated canola oil. In addition, hexanal and 2-hexenal were found at high amounts upon microwave treatment especially after 4 min of application.

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

    PubMed

    Hartvigsen, K; Lund, P; Hansen, L F; Holmer, G

    2000-10-01

    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.

  20. New Approach to Evaluate the Antennal Response of an Adult Predator Insect to Different Volatile Chemical Compounds by using Electroantennogram Technique

    NASA Astrophysics Data System (ADS)

    Shonouda, Mourad L.

    The antennal response of adult syrphid flies to selected plant volatile chemical compounds was investigated in the present study. The main chemical classes and their chemical compounds were aldehydes (nonanal and benzaldehyde), monoterpene-alcohols (linalool and alpha-terpineol), ketones (6-methyl-5-heptene-2-one and 2-undecanone), hydrocarbons (tetradecane) and benzoids (methyl salicylate). Electroantennogram (EAG) records showed that the syrphid antennae were strongly responded to linalool, 6-methyl-5-heptene-2-one and methyl salicylate even at low concentrations, in addition to the high dose concentration of nonanal comparably to the other chemical compounds. The antennae of old syrphid adults were more responsive and elicited higher levels of responses to all compounds rather than young syrphid adults. The antennal sensitivity may differ from one compound to another according to the sex. The difference in responses could be attributed to the sensitivity of olfactory receptors and/or the characterization of binding protein(s). The quality of biocontrol agent could be improved if the chemical interaction between beneficial natural enemies and the surrounding environment is intensively studied and we clearly understand the chemical ecology of each natural enemy.

  1. Relationship between flavour deterioration and the volatile compound profile of semi-ripened sausage.

    PubMed

    Lorenzo, José Manuel; Bedia, Mario; Bañón, Sancho

    2013-03-01

    This study provides data on the relationship between flavour deterioration and the volatile compound profile of semi-ripened pork salami kept under retail conditions for up to 150 days. The flavour of salami deteriorated for 120 days, resulting in rancidity and a loss of acceptability. TBARS increased from 0.16 to 0.57 MDA/kg. The flavour changes during the shelf life of salami were monitored from changes in the volatile profile. The retailing time influenced (p<0.05) the level of 27 of the 30 headspace volatiles determined by SPME-GC/MS. Flavour deterioration was associated with the loss and/or degradation of volatiles resulting from spices and microbial activities, and the formation of volatiles from lipid oxidation. The levels of 2-heptenal and methyl esters of heptanoic, pentanoic and hexanoic acids were the best discriminators of storage time, and therefore seem to be promising as marker compounds of flavour deterioration and acceptability.

  2. (1S,3R,8R,11S)-2,2-Dichloro-3,7,7,10-tetra­methyl­tricyclo­[6.4.0.01,3]dodec-9-en-11-ol

    PubMed Central

    Benharref, Ahmed; Lassaba, Essêdiya; Avignant, Daniel; Oudahmane, Abdelghani; Berraho, Moha

    2011-01-01

    The title compound, C16H24Cl2O, was synthesized from β-himachalene (3,5,5,9-tetra­methyl-2,4a,5,6,7,8-hexa­hydro-1H-benzocyclo­heptene), which was isolated from essential oil of the Atlas cedar (Cedrus atlantica). The two fused rings exhibit different conformations: the six-membered ring has a screw-boat conformation, while the seven-membered ring displays a boat conformation. The dihedral angle between the two rings is 56.56 (18)°. In the crystal, mol­ecules aggregate into supra­molecular chains along the c axis mediated by O—H⋯O hydrogen bonds. PMID:21522372

  3. (1S,3R,8R)-2,2-Dibromo-3,7,7,10-tetra­methyl­tricyclo­[6.4.0.01,3]dodec-9-ene

    PubMed Central

    Benharref, Ahmed; El Ammari, Lahcen; Lassaba, Essêdiya; Ourhriss, Najia; Berraho, Moha

    2012-01-01

    The title compound, C16H24Br2, was synthesized from β-himachalene (3,5,5,9-tetra­methyl-2,4a,5,6,7,8-hexa­hydro-1H-benzocyclo­heptene), which was isolated from the essential oil of the Atlas cedar (Cedrus Atlantica). The mol­ecule is built up from two fused six- and seven-membered rings and an additional three-membered ring from the reaction of β-himachalene with dibromo­carbene. The six-membered ring shows a screw-boat conformation, whereas the seven-membered ring displays a boat conformation; the dihedral angle between the mean planes through the rings is 57.9 (4)°. The absolute structure was established unambiguously from anomalous dispersion effects. PMID:22904942

  4. (1S,3R,8R,11S)-11-Bromo-10-bromo-methyl-2,2-di-chloro-3,7,7-tri-methyl-tricyclo-[6.4.0.0(1,3)]dodec-9-ene.

    PubMed

    Benharref, Ahmed; El Karroumi, Jamal; El Ammari, Lahcen; Saadi, Mohamed; Berraho, Moha

    2013-01-01

    The title compound, C16H22Br2Cl2, was synthesized from β-him-achalene (3,5,5,9-tetra-methyl-2,4a,5,6,7,8-hexa-hydro-1H-benzo-cyclo-heptene), which was isolated from the essential oil of the Atlas cedar (Cedrus Atlantica). The mol-ecule is built up from fused six- and seven-membered rings and an appended three-membered ring. The six-membered ring has a half-chair conformation, whereas the seven-membered ring displays a chair conformation. The dihedral angle between the two best plane through each ring is 59.5 (2)°. No specific inter-molecular inter-actions were discerned in the crystal packing.

  5. (1S,3S,8R,10R,11R)-3,7,7,10-Tetra­methyl­tri­cyclo­[6.4.0.01,3]dodecan-11-ol

    PubMed Central

    Benharref, Ahmed; El karroumi, Jamal; El Ammari, Lahcen; Saadi, Mohamed; Berraho, Moha

    2013-01-01

    The title compound, C16H28O, was synthesized by three steps from β-himachalene (3,5,5,9-tetra­methyl-2,4a,5,6,7,8-hexa­hydro-1H-benzo­cyclo­heptene), which was isolated from the essential oil of the Atlas cedar (Cedrus atlantica). The mol­ecule is built up from fused six- and seven-membered rings and an appended three-membered ring. The six-membered ring has twist-boat conformation, whereas the seven-membered ring displays a chair conformation. In the crystal, mol­ecules are linked into chains propagating along the a-axis direction by O—H⋯O hydrogen bonds. PMID:24109416

  6. (1S,3R,8R)-2,2-Dibromo-3,7,7,10-tetra­methyltricyclo­[6.4.0.01,3]dodec-9-en-11-one

    PubMed Central

    Oukhrib, Abdelouahd; Benharref, Ahmed; Saadi, Mohamed; El Ammari, Lahcen; Berraho, Moha

    2012-01-01

    The title compound, C16H22Br2O, was synthesized from β-himachalene (3,5,5,9-tetra­methyl-2,4a,5,6,7,8-hexa­hydro-1H-benzocyclo­heptene), which was isolated from the essential oil of the Atlas cedar (Cedrus Atlantica). The mol­ecule is built up from fused six- and seven-membered rings and an additional three-membered ring from the reaction of himachalene with dibromo­carbene. The six-membered ring has an envelope conformation, with the C atom belonging to the three-membered ring forming the flap, whereas the seven-membered ring displays a screw-boat conformation; the dihedral angle between the rings (all atoms) is 60.92 (16)°. PMID:23476179

  7. (1S,2R,7R,8S,10R)-9,9-Di-bromo-2,6,6,10-tetra-methyl-1α,2α-ep-oxy-tri-cyclo-[5.5.0.0(8,10)]dodeca-ne.

    PubMed

    Benharref, Ahmed; El Karroumi, Jamal; El Ammari, Lahcen; Saadi, Mohamed; Berraho, Moha

    2013-01-01

    The title compound, C16H24Br2O, was synthesized from the reaction of β-himachalene (3,5,5,9-tetra-methyl-2,4a,5,6,7,8-hexa-hydro-1H-benzo-cyclo-heptene), which was isolated from Atlas cedar (Cedrus atlantica) essential oil, after reaction with di-bromo-carbene. The asymmetric unit contains two independent mol-ecules with similar conformations. Each mol-ecule is built up from fused six-and seven-membered rings and two three-membered rings. In both mol-ecules, the six-membered ring has an envelope conformation with the flap provided by the C atom of the ep-oxy ring, whereas the seven-membered ring displays a chair conformation. The crystal packing is governed only by van der Waals inter-actions. The absolute configuration was established from anomalous dispersion effects.

  8. (1S,3S,8R,9S,11R)-10,10-Di­bromo-3,7,7,11-tetra­methyl­tetra­cyclo­[6.5.0.01,3.09,11]trideca­ne

    PubMed Central

    Benharref, Ahmed; El karroumi, Jamal; El Ammari, Lahcen; Saadi, Mohamed; Berraho, Moha

    2013-01-01

    The title compound, C17H26Br2, was synthesized from β-himachalene (3,5,5,9-tetra­methyl-2,4a,5,6,7,8-hexa­hydro-1H-benzo­cyclo­heptene), which was isolated from the essential oil of the Atlas cedar (Cedrus Atlantica). The asymmetric unit contains two independent mol­ecules with similar conformations. Each mol­ecule is built up from fused six- and seven-membered rings and two appended three-membered rings. In both mol­ecules, the six-membered ring has a screw boat conformation, whereas the seven-membered ring displays a boat conformation. No specific inter­molecular inter­actions were discerned in the crystal packing. PMID:24109345

  9. (1S,3R,8R,11S)-11-Bromo-10-bromo­methyl-2,2-di­chloro-3,7,7-tri­methyl­tricyclo­[6.4.0.01,3]dodec-9-ene

    PubMed Central

    Benharref, Ahmed; El karroumi, Jamal; El Ammari, Lahcen; Saadi, Mohamed; Berraho, Moha

    2013-01-01

    The title compound, C16H22Br2Cl2, was synthesized from β-him­achalene (3,5,5,9-tetra­methyl-2,4a,5,6,7,8-hexa­hydro-1H-benzo­cyclo­heptene), which was isolated from the essential oil of the Atlas cedar (Cedrus Atlantica). The mol­ecule is built up from fused six- and seven-membered rings and an appended three-membered ring. The six-membered ring has a half-chair conformation, whereas the seven-membered ring displays a chair conformation. The dihedral angle between the two best plane through each ring is 59.5 (2)°. No specific inter­molecular inter­actions were discerned in the crystal packing. PMID:24109365

  10. 1-[(1S,6R,7S,9R)-8,8-Di-bromo-5,5,9-tri-methyl-tri-cyclo-[4.4.0.1(7,9)]decan-1-yl]ethanone.

    PubMed

    Zaki, Mohamed; Benharref, Ahmed; El Ammari, Lahcen; Saadi, Mohamed; Berraho, Moha

    2014-04-01

    The title compound, C16H24Br2O, was synthesized by three steps from β-himachalene (3,5,5,9-tetra-methyl-2,4a,5,6,7,8-hexa-hydro-1H-benzo-cyclo-heptene), which was isolated from essential oil of the Atlas cedar cedrus atlantica. The asymmetric unit contains two independent mol-ecules with almost identical conformations. Each mol-ecule is built up from two fused six-membered rings, one having a chair conformation and the other a boat conformation, and an additional three-membered ring arising from the reaction of himachalene with di-bromo-carbene. In the crystal, there are no significant intermolecular interactions present. The absolute structure of the title compound was confirmed by resonance scattering.

  11. (1S,3R,8R)-2,2-Dibromo-3,7,7,10-tetra-methyltricyclo-[6.4.0.0(1,3)]dodec-9-en-11-one.

    PubMed

    Oukhrib, Abdelouahd; Benharref, Ahmed; Saadi, Mohamed; El Ammari, Lahcen; Berraho, Moha

    2012-12-01

    The title compound, C16H22Br2O, was synthesized from β-himachalene (3,5,5,9-tetra-methyl-2,4a,5,6,7,8-hexa-hydro-1H-benzocyclo-heptene), which was isolated from the essential oil of the Atlas cedar (Cedrus Atlantica). The mol-ecule is built up from fused six- and seven-membered rings and an additional three-membered ring from the reaction of himachalene with dibromo-carbene. The six-membered ring has an envelope conformation, with the C atom belonging to the three-membered ring forming the flap, whereas the seven-membered ring displays a screw-boat conformation; the dihedral angle between the rings (all atoms) is 60.92 (16)°.

  12. (1S,3R,8R,9S,11R)-2,2-Di­bromo-10,10-di­chloro-3,7,7,11-tetra­methyl­tetra­cyclo­[6.5.0.01,3.09,11]trideca­ne

    PubMed Central

    Ourhriss, Najia; Benharref, Ahmed; Saadi, Mohamed; Berraho, Moha; El Ammari, Lahcen

    2013-01-01

    The title compound, C17H24Br2Cl2, was synthesized from β-himachalene (3,5,5,9-tetra­methyl-2,4a,5,6,7,8-hexa­hydro-1H-benzo­cyclo­heptene), which was isolated from the essential oil of the Atlas cedar (Cedrus Atlantica). The mol­ecule contains fused six-, seven- and two three-membered rings. The six-membered ring has a half-chair conformation, while the seven-membered ring displays a boat conformation. The absolute structure was unambiguously established from anomalous dispersion effects. The crystal packing exhibits no short inter­molecular contacts. PMID:23723876

  13. 1-[(1S,6R,7S,9R)-8,8-Di­bromo-5,5,9-tri­methyl­tri­cyclo­[4.4.0.17,9]decan-1-yl]ethanone

    PubMed Central

    Zaki, Mohamed; Benharref, Ahmed; El Ammari, Lahcen; Saadi, Mohamed; Berraho, Moha

    2014-01-01

    The title compound, C16H24Br2O, was synthesized by three steps from β-himachalene (3,5,5,9-tetra­methyl-2,4a,5,6,7,8-hexa­hydro-1H-benzo­cyclo­heptene), which was isolated from essential oil of the Atlas cedar cedrus atlantica. The asymmetric unit contains two independent mol­ecules with almost identical conformations. Each mol­ecule is built up from two fused six-membered rings, one having a chair conformation and the other a boat conformation, and an additional three-membered ring arising from the reaction of himachalene with di­bromo­carbene. In the crystal, there are no significant intermolecular interactions present. The absolute structure of the title compound was confirmed by resonance scattering. PMID:24826147

  14. (1S,3R,8R,9S,11R)-10,10-Di-bromo-2,2-di-chloro-3,7,7,11-tetra-methyl-tetra-cyclo-[6.5.0.0(1,3).0(9,11)]trideca-ne.

    PubMed

    Oukhrib, Abdelouahd; Benharref, Ahmed; Saadi, Mohamed; Berraho, Moha; El Ammari, Lahcen

    2013-05-01

    The title compound, C17H24Br2Cl2, was synthesized from β-himachalene (3,5,5,9-tetra-methyl-2,4a,5,6,7,8-hexa-hydro-1H-benzo-cyclo-heptene), which was isolated from the essential oil of the Atlas cedar (Cedrus Atlantica). The asymmetric unit contains two independent mol-ecules. Each mol-ecule is built up from fused six-, seven- and two three-membered rings. In both mol-ecules, the six-membered ring has a half-chair conformation, whereas the seven-membered ring displays a boat conformation. No specific inter-molecular inter-actions are noted in the crystal packing.

  15. (1R,4R,6S,7S)-5,5-Di-chloro-1,4,8,8-tetra-methyl-tri-cyclo-[5.4.1(1,7).0(4,6)]dodecan-12-one.

    PubMed

    Benharref, Ahmed; El Karroumi, Jamal; Daran, Jean-Claude; Berraho, Moha

    2013-10-26

    The title compound, C16H24Cl2O, was synthesized in three steps from β-himachalene (3,5,5,9-tetra-methyl-2,4a,5,6,7,8-hexa-hydro-1H-benzo-cyclo-heptene), which was isolated from essential oil of the Atlas cedar (cedrus atlantica). The asymmetric unit contains two independent mol-ecules with similar conformations. Each mol-ecule is built up from two fused seven-membered rings and an additional three-membered ring arising from the reaction of himachalene with di-chloro-carbene. The dihedral angles between the mean planes of the two seven-membered rings are 75.03 (9) and 75.02 (9)° in the two independent mol-ecules.

  16. Crystal structure of (1S,3R,8R,9S,10R)-10-bromo-methyl-2,2-di-chloro-9,10-ep-oxy-3,7,7-tri-methyl-tri-cyclo-[6.4.0.0(1,3)]dodeca-ne.

    PubMed

    Benharref, Ahmed; El Ammari, Lahcen; Saadi, Mohamed; Berraho, Moha

    2015-05-01

    The title compound, C16H23BrCl2O, was synthesized in three steps from β-himachalene (3,5,5,9-tetra-methyl-2,4a,5,6,7,8-hexa-hydro-1H-benzo-cyclo-heptene), which was isolated from the essential oil of the Atlas cedar (cedrus atlantica). The mol-ecule is built up from two fused six- and seven-membered rings, each linked to a three-membered ring. The six-membered ring has a screw-boat conformation, whereas the seven-membered ring displays a twist-boat conformation. The absolute structure was established unambiguously from anomalous dispersion effects.

  17. (1S,3S,8R,10R,11R)-3,7,7,10-Tetra-methyl-tri-cyclo-[6.4.0.0(1,3)]dodecan-11-ol.

    PubMed

    Benharref, Ahmed; El Karroumi, Jamal; El Ammari, Lahcen; Saadi, Mohamed; Berraho, Moha

    2013-01-01

    The title compound, C16H28O, was synthesized by three steps from β-himachalene (3,5,5,9-tetra-methyl-2,4a,5,6,7,8-hexa-hydro-1H-benzo-cyclo-heptene), which was isolated from the essential oil of the Atlas cedar (Cedrus atlantica). The mol-ecule is built up from fused six- and seven-membered rings and an appended three-membered ring. The six-membered ring has twist-boat conformation, whereas the seven-membered ring displays a chair conformation. In the crystal, mol-ecules are linked into chains propagating along the a-axis direction by O-H⋯O hydrogen bonds.

  18. (1S,3R,8R)-2,2-Di-chloro-3,7,7,10-tetra-methyl-tri-cyclo-[6.4.0.0(1,3)]dodec-9-en-11-one.

    PubMed

    Ourhriss, Naja; Benharref, Ahmed; Oukhrib, Abdelouahd; Daran, Jean-Claude; Berraho, Moha

    2013-06-01

    The title compound, C16H22Cl2O, was synthesized from β-himachalene (3,5,5,9-tetra-methyl-2,4a,5,6,7,8-hexa-hydro-1H-benzo-cyclo-heptene), which was isolated from the essential oil of the Atlas cedar (Cedrus Atlantica). The mol-ecule is built up from fused six- and seven-membered rings and an additional three-membered ring arising from the reaction of himachalene with di-chloro-carbene. The six-membered ring has an envelope conformation, with the C atom belonging to the three-membered ring forming the flap, whereas the seven-membered ring displays a screw-boat conformation; the dihedral angle between the rings (all atoms) is 59.65 (14)°.

  19. (1S,3S,8R,9S,11R)-10,10-Di-chloro-3,7,7,11-tetra-methyl-tetra-cyclo[6.5.0.0(1,3).0(9,11)]trideca-ne.

    PubMed

    Benharref, Ahmed; Ourhriss, Najia; El Ammari, Lahcen; Saadi, Mohamed; Berraho, Moha

    2013-06-01

    The title compound, C17H26Cl2, was synthesized from β-himachalene (3,5,5,9-tetra-methyl-2,4a,5,6,7,8-hexa-hydro-1H-benzo-cyclo-heptene), which was isolated from the essential oil of the Atlas cedar (Cedrus Atlantica). The asymmetric unit contains two independent mol-ecules with similar conformations. Each mol-ecule is built up from fused six- and seven-membered rings and two three-membered rings from the reaction of β-himachalene with di-chloro-carbene. In both mol-ecules, the six-membered ring has a half-chair conformation, whereas the seven-membered ring displays a boat conformation. The absolute configuration was established from anomalous dispersion effects.

  20. (1S,3R,8R,10R)-2,2-Di­bromo-3,7,7,10-tetra­methyl­tri­cyclo­[6.4.0.01,3]dodecan-9-one

    PubMed Central

    Benharref, Ahmed; Mazoir, Noureddine; Daran, Jean-Claude; Berraho, Moha

    2013-01-01

    The title compound, C16H24Br2O was synthesized by three steps from β-himachalene (3,5,5,9-tetra­methyl-2,4a,5,6,7,8-hexa­hydro-1H-benzo­cyclo­heptene), which was isolated from essential oil of the Atlas cedar (Cedrus atlantica). The mol­ecule is built up from a seven-membered ring to which a six- and a three-membered ring are fused. The six-membered ring shows a chair conformation. One C atom in the seven-membered ring and two methyl groups attached to the ring are disordered over two sets of sites, with an occupancy ratio of 0.658 (7):0.342 (7). PMID:24454223

  1. (1S,3R,8R,10R)-2,2-Di-bromo-3,7,7,10-tetra-methyl-tri-cyclo-[6.4.0.0(1,3)]dodecan-9-one.

    PubMed

    Benharref, Ahmed; Mazoir, Noureddine; Daran, Jean-Claude; Berraho, Moha

    2013-11-16

    The title compound, C16H24Br2O was synthesized by three steps from β-himachalene (3,5,5,9-tetra-methyl-2,4a,5,6,7,8-hexa-hydro-1H-benzo-cyclo-heptene), which was isolated from essential oil of the Atlas cedar (Cedrus atlantica). The mol-ecule is built up from a seven-membered ring to which a six- and a three-membered ring are fused. The six-membered ring shows a chair conformation. One C atom in the seven-membered ring and two methyl groups attached to the ring are disordered over two sets of sites, with an occupancy ratio of 0.658 (7):0.342 (7).

  2. (1S,3R,8R)-2,2-Dibromo-10-bromo-methyl-3,7,7-trimethyl-tricyclo-[6.4.0.0(1,3)]dodec-9-ene.

    PubMed

    Oukhrib, Abdelouahd; Benharref, Ahmed; Saadi, Mohamed; Daran, Jean-Claude; Berraho, Moha

    2012-12-01

    The title compound, C16H23Br3, was synthesized from β-himachalene (3,5,5,9-tetra-methyl-2,4a,5,6,7,8-hexa-hydro-1H-benzocyclo-heptene), which was isolated from the essential oil of the Atlas cedar (Cedrus Atlantica). The mol-ecule is built up from fused six- and seven-membered rings and an additional three-membered ring from the reaction of himachalene with dibromo-carbene. The six-membered ring has an envelope conformation (the flap atom being the C atom shared with the three-membered ring, whereas the seven-membered ring displays a screw boat conformation; the dihedral angle between the rings (defined by the near coplanar atoms) is 56.5 (2)°.

  3. (1S,3S,8R,9S,11R)-10,10-Di-bromo-3,7,7,11-tetra-methyl-tetra-cyclo-[6.5.0.0(1,3).0(9,11)]trideca-ne.

    PubMed

    Benharref, Ahmed; El Karroumi, Jamal; El Ammari, Lahcen; Saadi, Mohamed; Berraho, Moha

    2013-01-01

    The title compound, C17H26Br2, was synthesized from β-himachalene (3,5,5,9-tetra-methyl-2,4a,5,6,7,8-hexa-hydro-1H-benzo-cyclo-heptene), which was isolated from the essential oil of the Atlas cedar (Cedrus Atlantica). The asymmetric unit contains two independent mol-ecules with similar conformations. Each mol-ecule is built up from fused six- and seven-membered rings and two appended three-membered rings. In both mol-ecules, the six-membered ring has a screw boat conformation, whereas the seven-membered ring displays a boat conformation. No specific inter-molecular inter-actions were discerned in the crystal packing.

  4. Aroma of fresh oysters Crassostrea gigas: composition and aroma notes.

    PubMed

    Piveteau, F; Le Guen, S; Gandemer, G; Baud, J P; Prost, C; Demaimay, M

    2000-10-01

    In contrast to many foods, very little is known about the aroma of fresh oysters. This study deals with the relationship between extracted volatiles of oysters and their olfactory properties. Nearly 50 volatiles were identified: most of them were principally related to fatty acid oxidation (86%) and particularly to n-3 polyunstaturated fatty acid oxidation (66%). Only one volatile arose from amino acid degradation. Panelists detected 42 odors by sniffing. Among them, only 12 odors were definitely attributed to identified volatile. These odors were green/sulfur/crustacean, mushroom/citrus, and marine/cucumber notes and were attributed to dimethyl sulfide, 1-penten-3-one, hexanal, (2,4)-E,E-heptadienal, 1-octen-3-one, 1-octen-3-ol, 6-methyl-5-hepten-3-one, octanal, (E,Z)-2,6-nonadienal, (E)-2-octenal, and decanal, respectively.

  5. Evaluation of the representativeness of the odor of cooked mussel extracts and the relationship between sensory descriptors and potent odorants.

    PubMed

    Le Guen, S; Prost, C; Demaimay, M

    2001-03-01

    The representativeness of the odor of mussel extract was assessed after each step of the distillation-extraction-concentration process. Results showed that the whole process was convenient for cooked mussels, but the extract was representative only when it was reincorporated into a suitable matrix such as water. Sensory and gas chromatography-olfactometry (GC-O) analyses were then performed on representative extracts of wild and bouchot mussels. Most of the sensory attributes were related to odors detected during olfactometry. Methional and (Z)-4-heptenal were two of the most potent odorants of mussels and, thus, were identified as the major contributors to the characteristic boiled potato-like odor of cooked mussels distinguished during sensory analysis. The sulfury note, highlighted for wild mussels during sensory analysis, could be linked to dimethyl disulfide, which was significantly more perceived in wild mussels by GC-O. Dimethyl disulfide could then be considered to be a characteristic compound of wild mussels.

  6. Identification of vertebrate volatiles stimulating olfactory receptors on tarsus I of the tick Amblyomma variegatum Fabricius (Ixodidae). I. Receptors within the Haller's organ capsule.

    PubMed

    Steullet, P; Guerin, P M

    1994-01-01

    Gas chromatography-coupled electrophysiological recordings (GC-EL) from olfactory sensilla within the capsule of Haller's organ of the tick Amblyomma variegatum indicate the presence of a number of stimulants in rabbit and bovine odours, and in steer skin wash. Some of these stimulants were fully identified by gas chromatography-mass spectrometry analysis and by matching electrophysiological activity of synthetic analogues as: 1) hexanal, 2-heptenal, nonanal, furfural, benzaldehyde, and 2-hydroxybenzaldehyde (in all extracts); 2) heptanal, 2-, 3-, and 4-methylbenzaldehyde, and gamma-valerolactone (only in bovine and rabbit odour). Careful examination of the electrophysiological responses permit characterization of 6 receptor types: 1) a benzaldehyde receptor, 2) a 2-hydroxybenzaldehyde receptor, 3) three types of receptors responding differently to aliphatic aldehydes, and 4) a lactone receptor.

  7. Adsorptive recovery of olefins from mixtures with paraffins

    SciTech Connect

    Zhuravlev, A.M.; Alekseeva, R.V.; Gerasimenko, E.G.; Alekseev, Yu.A.

    1987-11-01

    The recovery of olefins from mixtures with paraffins by adsorption on synthetic zeolites, aimed at obtaining experimental data for developing a mathematical model, was examined for the purpose of finding a linear olefin source for biodegradable detergents and achieving commensurate reductions in water pollution. Studies were performed under static and dynamic conditions. Test mixtures were prepared from individual hydrocarbons with purities of 98-99.5% by weight. Isotherms of excess sorption and selectivity coefficients for solutions of dodecene mixed with dodecane, octane, cyclohexane, and heptene were determined. Calculations were performed by methods of excess quantities and total content. Data shows the dynamic capacity of the olefins to breakthrough in proportion to their concentration in the original mixture.

  8. Aldehyde-induced xanthine oxidase activity in raw milk.

    PubMed

    Steffensen, Charlotte L; Andersen, Henrik J; Nielsen, Jacob H

    2002-12-04

    In the present study, the aldehyde-induced pro-oxidative activity of xanthine oxidase was followed in an accelerated raw milk system using spin-trap electron spin resonance (ESR) spectroscopy. The aldehydes acetaldehyde, propanal, hexanal, trans-2-hexenal, trans-2-heptenal, trans-2-nonenal, and 3-methyl-2-butenal were all found to initiate radical reactions when added to milk. Formation of superoxide through aldehyde-induced xanthine oxidase activity is suggested as the initial reaction, as all tested aldehydes were shown to trigger superoxide formation in an ultrahigh temperature (UHT) milk model system with added xanthine oxidase. It was found that addition of aldehydes to milk initially increased the ascorbyl radical concentration with a subsequent decay due to ascorbate depletion, which renders the formation of superoxide in milk with added aldehyde. The present study shows for the first time potential acceleration of oxidative events in milk through aldehyde-induced xanthine oxidase activity.

  9. Cooking impact in color, pigments and volatile composition of grapevine leaves (Vitis vinifera L. var. Malvasia Fina and Touriga Franca).

    PubMed

    Lima, Adriano; Pereira, José Alberto; Baraldi, Ilton; Malheiro, Ricardo

    2017-04-15

    Grapevine leaves (Vitis vinifera L. var. Malvasia Fina and Touriga Franca) under culinary treatment (blanching and boiling at 60, 75 and 90min) were studied for their color, pigments and volatile fraction changes. Blanching and boiling caused a decrease in luminosity and a loss of green coloration in both varieties, while a yellow-brownish color arose. Significant correlations were established between the loss of green color (monochromatic variable a(∗)) and the total chlorophylls content. The main volatiles in fresh leaves [(Z)-3-hexenal, (Z)-3-hexen-1-ol, and (Z)-3-hexenyl acetate] were drastically reduced by blanching and suppressed by boiling. Other compounds like pentanal and 6-methyl-5-hepten-2 one arose from blanching and boiling. A boiling time of 60min is adequate for the culinary process of grapevine leaves, since the product is considered edible and the pigments and volatile changes are not as drastic as observed at 75 and 90min of boiling.

  10. Highly stereocontrolled synthesis of trans-enediynes via carbocupration of fluoroalkylated diynes

    PubMed Central

    Kishi, Misato; Ishihara, Takashi

    2012-01-01

    Summary Treatment of readily prepared (Z)-6-benzyloxy-1,1,1,2-tetrafluoro-6-methyl-2-hepten-4-yne with 1.5 equiv of LHMDS in −78 °C for 1 h gave the corresponding trifluoromethylated diyne in an excellent yield. This diyne was found to be a good substrate for the carbocupration with various higher-ordered cyanocuprates to give the corresponding vinylcuprates in a highly regio- and stereoselective manner. The in situ generated vinylcuprates could react very smoothly with an excess amount of iodine, the vinyl iodides being obtained in high yields. Thus-obtained iodides underwent a very smooth Sonogashira cross-coupling reaction to afford various trans-enediynes in high yields. PMID:23365631

  11. Reaction of deuterium with olefins on nickel catalysts: evidence for adsorbed vinylic species

    SciTech Connect

    Mintsa-Eya, V.; Hilaire, L.; Choplin, A.; Touroude, R.; Gault, F.G.

    1983-08-01

    The interaction of deuterium with 1,2-dimethylcyclopentene, 2,3-dimethylcyclopentene, 1-methyl-2-methylenecyclopentane, 1,2-dimethylcyclobutene, 1-methyl-2-methylenecyclobutane, bicyclo(2,2,1)heptene, but-1-ene, and cis-but-2-ene was studied from -85 to 50/sup 0/C on nickel films in a static apparatus and on Ni/pumice in a flow system. Unexpected d/sub 3/ and d/sub 4/ molecules were obtained in the deuteration of bicyclo(2,2,1)heptene. The position of the double bond in the ring of the other cycloolefins was the main factor governing their behavior: in the deuteration of 1,2-dimethylcycloalkenes, the saturated products, especially the trans somers, were much more exchanged and the percentage of trans was lower than when the starting material consisted of the olefins with the double bond in 2,3 or exocyclic positions. The hyperfine distribution, obtained by microwave analysis, of the exchanged d/sub 1/ but-1-ene, revealed that the major part of the deuterium was introduced on C/sub 2/; the cis-trans isomerization was much faster than the double bond migration with the introduction of zero or one deuterium atom while the isomerized but-1-ene showed a multiple exchange up to d/sub 4/; in the isomerized d/sub 1/ but-1-ene, the deuterium atom was distributed on the three carbon atoms C/sub 1/, C/sub 2/, C/sub 3/. Most of these results clearly show that the classical Horiuti-Polanyi mechanism is not the only one taking part in the reactions. The introduction of other intermediaries, sigma-vinylic, sigma-vinylic ..pi..-olefinic, and sigma-vinylic ..pi..-allylic species, provides a coherent explanation for all our findings. It is shown that nickel and iron behave in a very similar way. 5 tables.

  12. Formation of volatile compounds during heating of spice paprika (Capsicum annuum) powder.

    PubMed

    Cremer, D R; Eichner, K

    2000-06-01

    Spice paprika (red pepper; Capsicum annuum) is the most cultivated spice worldwide and is used mainly for its color and pungency. However, current research is also focusing on the flavor as an important parameter. This paper deals with the kinetics of the formation of those volatiles that indicate a decrease in spice paprika quality due to Maillard reaction, hydrolytic reactions, and oxidative degradation reactions of lipids such as fatty acids and carotenoids. Spice paprika volatiles were quantitatively analyzed by means of headspace gas chromatography (HS-GC) and solid-phase microextraction (SPME) followed by gas chromatography-mass spectrometry (GC-MS). The kinetics of their formation were investigated, and the respective activation energies determined. Strecker aldehyde, acetone, and methanol formation followed a pseudo-zero-order reaction kinetic, and formation of dimethyl sulfide (DMS) was characterized by a first-order kinetic. The activation energies determined were between 86.3 and 101.8 for the Strecker aldehydes acetaldehyde (AA), 2-methylpropanal (2-MP), 3-methylbutanal (3-MB), and 2-methylbutanal (2-MB), 130.7 for acetone, 114.2 for methanol, and 109.7 kJ/mol for DMS. The amounts of Strecker aldehydes formed were correlated to the concentrations of the corresponding free amino acids present in the samples. The formation of hexanal and 6-methyl-5-hepten-2-one in Capsicum annuum during processing was confirmed, and the formation of beta-ionone was probably described for the first time. During heating, the concentration of hexanal increased rapidly. The formation of 6-methyl-5-hepten-2-one confirms that Capsicum annuum fruits contain lycopene.

  13. Silicon nanocrystals as handy biomarkers

    NASA Astrophysics Data System (ADS)

    Fujioka, Kouki; Hoshino, Akiyoshi; Manabe, Noriyoshi; Futamura, Yasuhiro; Tilley, Richard; Yamamoto, Kenji

    2007-02-01

    Quantum dots (QDs) have brighter and longer fluorescence than organic dyes. Therefore, QDs can be applied to biotechnology, and have capability to be applied to medical technology. Currently, among the several types of QDs, CdSe with a ZnS shell is one of the most popular QDs to be used in biological experiments. However, when the CdSe QDs were applied to clinical technology, potential toxicological problems due to CdSe core should be considered. To eliminate the problem, silicon nanocrystals, which have the potential of biocompatibility, could be a candidate of alternate probes. Silicon nanocrystals have been synthesized using several techniques such as aerosol, electrochemical etching, laser pyrolysis, plasma deposition, and colloids. Recently, the silicon nanocrystals were reported to be synthesized in inverse micelles and also stabilized with 1-heptene or allylamine capping. Blue fluorescence of the nanocrystals was observed when excited with a UV light. The nanocrystals covered with 1-heptene are hydrophobic, whereas the ones covered with allylamine are hydrophilic. To test the stability in cytosol, the water-soluble nanocrystals covered with allylamine were examined with a Hela cell incorporation experiment. Bright blue fluorescence of the nanocrystals was detected in the cytosol when excited with a UV light, implying that the nanocrystals were able to be applied to biological imaging. In order to expand the application range, we synthesized and compared a series of silicon nanocrystals, which have variable surface modification, such as alkyl group, alcohol group, and odorant molecules. This study will provide a wider range of optoelectronic applications and bioimaging technology.

  14. Products of ozone-initiated chemistry in a simulated aircraft environment.

    PubMed

    Wisthaler, Armin; Tamás, Gyöngyi; Wyon, David P; Strøm-Tejsen, Peter; Space, David; Beauchamp, Jonathan; Hansel, Armin; Märk, Tilmann D; Weschler, Charles J

    2005-07-01

    We used proton-transfer-reaction mass spectrometry (PTR-MS) to examine the products formed when ozone reacted with the materials in a simulated aircraft cabin, including a loaded high-efficiency particulate air (HEPA) filter in the return air system. Four conditions were examined: cabin (baseline), cabin plus ozone, cabin plus soiled T-shirts (surrogates for human occupants), and cabin plus soiled T-shirts plus ozone. The addition of ozone to the cabin without T-shirts, at concentrations typically encountered during commercial air travel, increased the mixing ratio (v:v concentration) of detected pollutants from 35 ppb to 80 ppb. Most of this increase was due to the production of saturated and unsaturated aldehydes and tentatively identified low-molecular-weight carboxylic acids. The addition of soiled T-shirts, with no ozone present, increased the mixing ratio of pollutants in the cabin air only slightly, whereas the combination of soiled T-shirts and ozone increased the mixing ratio of detected pollutants to 110 ppb, with more than 20 ppb originating from squalene oxidation products (acetone, 4-oxopentanal, and 6-methyl-5-hepten-2-one). For the two conditions with ozone present, the more-abundant oxidation products included acetone/propanal (8-20 ppb), formaldehyde (8-10 ppb), nonanal (approximately 6 ppb), 4-oxopentanal (3-7 ppb), acetic acid (approximately 7 ppb), formic acid (approximately 3 ppb), and 6-methyl-5-hepten-2-one (0.5-2.5 ppb), as well as compounds tentatively identified as acrolein (0.6-1 ppb) and crotonaldehyde (0.6-0.8 ppb). The odor thresholds of certain products were exceeded. With an outdoor air exchange of 3 h(-1) and a recirculation rate of 20 h(-1), the measured ozone surface removal rate constant was 6.3 h(-1) when T-shirts were not present, compared to 11.4 h(-1) when T-shirts were present.

  15. Simultaneous determination of cyclodol and diprazin by thin layer chromatography and high performance liquid chromatography.

    PubMed

    Makharadze, R; Adeishvili, L; Chelidze, T; Imnadze, N; Nizharadze, N

    2009-11-01

    Ciklodol (trihexyphenidil)--the central and peripheral m-cholinoblocker is currently used with other antipsychotic drugs such as phenotiazines and tricycle antidepressants. For the purpose of simultaneous determination of ciklodol and diprazine, were selected two methods of analysis: Thin Layer Chromatography (TLC) and High Performance Liquid Chromatography (HPLC). During development of TLC method was studied the 10 visualizing system and 24 mobile systems. For individual or simultaneous determination of ciklodol and diprazine were recommended the following solvents' systems: 1. Toluene-acetone-ethanole-25%NH(4)OH (45:45: 7.5:2.5), 2. Hexane-ethyl acetate (15:5), 3. Chloroform-heptene-25%NH(4)OH (16:3:3), 4. Ethylacetate-hexane (10:10), 5. Acetonitrile-metanol (10:10) and 6.Heptene-chloroform-ethanol-25% NH(4)OH (5:10:3:1). As visualizing systems were chosen: Iodine vapors, blacklight (UV254) and reagent of FNP. Reagent of FNP gives colored spot just with diprazine and it is also could be used for separation of both objects in simultaneous analysis. Developed HPLC method of simultaneous determination of ciklodol and diprazine: like mobile phase is recommended: Acetonitril- 0.05M KH(2)PO4 (55:45) (v/v) +H(3)PO(4) (pH3.5), column EC250 x 4.6mm, with solid phase Nucleosil, flow rate 1ml/min, sample volume 40 microl. In given conditions, the retention time of ciklodol is 6.005min and diprazine 7.227min. Developed method of simultaneous determination and separation of ciklodol and diprazine in respective mixtures could be successfully applied as in the pharmaceutical, as well in the chemical-toxicological laboratories.

  16. Evaluation of process parameters governing the aroma generation in three hazelnut cultivars (Corylus avellana L.) by correlating quantitative key odorant profiling with sensory evaluation.

    PubMed

    Kiefl, Johannes; Schieberle, Peter

    2013-06-05

    The majority of the world hazelnut crop is roasted, thus developing a unique aroma that depends on the cultivar used and on the roasting conditions applied. Although several studies have investigated the volatile fraction of different cultivars and have correlated the data with overall sensory profiles, studies establishing a correlation between key odorants among the bulk of odorless volatiles and the respective aroma profiles are not yet available. On the basis of recently published stable isotope dilution assays (SIDAs) using comprehensive two-dimensional gas chromatography-time-of-flight mass spectrometry (GC×GC-TOF-MS), differences in concentrations of key odorants in different hazelnut cultivars roasted under defined conditions were monitored and compared with sensory data obtained by projective mapping, aroma profile analysis, and triangle tests. The results showed that the aroma-active compounds 2-acetyl-1-pyrroline, 2-propionyl-1-pyrroline, 5-methyl-(E)-2-hepten-4-one, 2,3-diethyl-5-methylpyrazine, 3,5-dimethyl-2-ethylpyrazine, and 2-furfurylthiol are appropriate marker odorants to differentiate the various nut aromas. In particular, the appreciated roasty, nutty aroma of optimally roasted hazelnuts was developed if both 5-methyl-(E)-2-hepten-4-one and 3-methyl-4-heptanone were >450 μg/kg, whereas the sum of the two 2-acyl-1-pyrrolines and two pyrazines should not exceed 400 μg/kg to avoid an over-roasted smell. Such a desired aroma can be obtained for each cultivar, but obviously specific roasting times, temperatures, and roasting techniques had to be applied.

  17. Functional characterization of SlscADH1, a fruit-ripening-associated short-chain alcohol dehydrogenase of tomato.

    PubMed

    Moummou, Hanane; Tonfack, Libert Brice; Chervin, Christian; Benichou, Mohamed; Youmbi, Emmanuel; Ginies, Christian; Latché, Alain; Pech, Jean-Claude; van der Rest, Benoît

    2012-10-15

    A tomato short-chain dehydrogenase-reductase (SlscADH1) is preferentially expressed in fruit with a maximum expression at the breaker stage while expression in roots, stems, leaves and flowers is very weak. It represents a potential candidate for the formation of aroma volatiles by interconverting alcohols and aldehydes. The SlscADH1 recombinant protein produced in Escherichia coli exhibited dehydrogenase-reductase activity towards several volatile compounds present in tomato flavour with a strong preference for the NAD/NADH co-factors. The strongest activity was observed for the reduction of hexanal (K(m)=0.175mM) and phenylacetaldehyde (K(m)=0.375mM) in the presence of NADH. The oxidation process of hexanol and 1-phenylethanol was much less efficient (K(m)s of 2.9 and 23.0mM, respectively), indicating that the enzyme preferentially acts as a reductase. However activity was observed only for hexanal, phenylacetaldehyde, (E)-2-hexenal and acetaldehyde and the corresponding alcohols. No activity could be detected for other aroma volatiles important for tomato flavour, such as methyl-butanol/methyl-butanal, 5-methyl-6-hepten-2-one/5-methyl-6-hepten-2-ol, citronellal/citronellol, neral/nerol, geraniol. In order to assess the function of the SlscADH1 gene, transgenic plants have been generated using the technique of RNA interference (RNAi). Constitutive down-regulation using the 35S promoter resulted in the generation of dwarf plants, indicating that the SlscADH1 gene, although weakly expressed in vegetative tissues, had a function in regulating plant development. Fruit-specific down-regulation using the 2A11 promoter had no morphogenetic effect and did not alter the aldehyde/alcohol balance of the volatiles compounds produced by the fruit. Nevertheless, SlscADH1-inhibited fruit unexpectedly accumulated higher concentrations of C5 and C6 volatile compounds of the lipoxygenase pathway, possibly as an indirect effect of the suppression of SlscADH1 on the catabolism of

  18. Theoretical Analysis of the Effect of C═C Double Bonds on the Low-Temperature Reactivity of Alkenylperoxy Radicals.

    PubMed

    You, Xiaoqing; Chi, Yawei; He, Tanjin

    2016-08-04

    Biodiesel contains a large proportion of unsaturated fatty acid methyl esters. Its combustion characteristics, especially its ignition behavior at low temperatures, have been greatly affected by these C═C double bonds. In this work, we performed a theoretical analysis of the effect of C═C double bonds on the low-temperature reactivity of alkenylperoxy radicals, the key intermediates from the low-temperature combustion of biodiesel. To understand how double bonds affect the fate of peroxy radicals, we selected three representative peroxy radicals from heptane, heptene, and heptadiene having zero, one, and two double C═C bonds, respectively, for study. The potential energy surfaces were explored at the CBS-QB3 level, and the reaction rate constants were computed using canonical/variational transition state theories. We have found that the double bond is responsible for the very different bond dissociation energies of the various types of C-H bonds, which in turn affect significantly the reaction kinetics of alkenylperoxy radicals.

  19. Carotenoid pigmentation affects the volatile composition of tomato and watermelon fruits, as revealed by comparative genetic analyses.

    PubMed

    Lewinsohn, Efraim; Sitrit, Yaron; Bar, Einat; Azulay, Yaniv; Meir, Ayala; Zamir, Dani; Tadmor, Yaakov

    2005-04-20

    Tomato near-isogenic lines differing in fruit carotenogenesis genes accumulated different aroma volatiles, in a strikingly similar fashion as compared to watermelon cultivars differing in fruit color. The major volatile norisoprenoids present in lycopene-containing tomatoes and watermelons were noncyclic, such as geranial, neral, 6-methyl-5-hepten-2-one, 2,6-dimethylhept-5-1-al, 2,3-epoxygeranial, (E,E)-pseudoionone, geranyl acetone, and farnesyl acetone, seemingly derived from lycopene and other noncyclic tetraterpenoids. Beta-ionone, dihydroactinodiolide, and beta-cyclocitral were prominent in both tomato and watermelon fruits containing beta-carotene. Alpha-ionone was detected only in an orange-fleshed tomato mutant that accumulates delta-carotene. A yellow flesh (r) mutant tomato bearing a nonfunctional psy1 gene and the yellow-fleshed watermelon Early Moonbeam, almost devoid of carotenoid fruit pigments, also lacked norisoprenoid derivatives and geranial. This study provides evidence, based on comparative genetics, that carotenoid pigmentation patterns have profound effects on the norisoprene and monoterpene aroma volatile compositions of tomato and watermelon and that in these fruits geranial (trans-citral) is apparently derived from lycopene in vivo.

  20. Inhibition of the mitogenic response to platelet-derived growth factor by terbinafine

    SciTech Connect

    St. Denny, I.H.; Glinka, K.G.; Nemecek, G.M. ); Stuetz, A. )

    1987-05-01

    Terbinafine (T;(E)-N-(6,6-dimethyl-2-hepten-4-ynyl)-N-methyl-1-naphthalenemethanamine), an antimycotic which inhibits fungal squalene epoxidase activity, was examined for its effects on platelet-derived growth factor (PDGF)-stimulated mitogenesis. The inclusion of 1.5-5{mu}M T in fibroblast incubation media was associated with increased ({sup 3}H)thymidine incorporation into DNA in the presence and absence of PDGF. However, T at concentrations above 6{mu}M reduced DNA synthesis in control and PDGF-exposed cultures to nearly undetectable levels. Under a phase-contrast microscope, fibroblasts appeared morphologically normal at T concentrations as high as 25 {mu}M. Neither the uptake of ({sup 3}H)thymidine nor the specific binding of {sup 125}I-PDGF to fibroblast receptors was significantly affected by 10 {mu}M T. Furthermore, concentrations of T which antagonized the mitogenic response to PDGF also interfered with fibroblast growth factor-induced mitogenesis. Together, these data suggest that T has the ability to inhibit the in vitro action of PDGF via a post-receptor mechanism.

  1. Comparative study between synthetic and phospholipids of natural origin: effect of phospholipid selection on the behavior of a topical liposomal dosage form incorporating terbinafine.

    PubMed

    Koutsoulas, Charalampos; Suleiman, Ehsan; Wagner, Andreas; Žabka, Marian

    2014-12-01

    Selection of excipients used is a critical step in the design of a pharmaceutical dosage form as it affects its behavior upon application, as during storage. The purpose of the present study is to evaluate and compare the behavior of six liposomal formulations intended for topical application composed of two widely used phospholipids 1,2-diacyl-sn-glycero-3-phosphocholine and 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine with and without incorporation of cholesterol. Liposomal hydrogels made of hydroxyethylcellulose 3% and incorporating the anti-fungal agent terbinafine hydrochloride (E)-N-(6,6-dimethyl-2-hepten-4-inyl)-N-methyl-1-naphthalene-methanamine (-hydrochloride) were prepared, their viscosity was measured and in vitro drug release was studied. Moreover, physical stability and drug retention during storage at two different temperatures (2-8 °C and RT) were examined over time. The results showed differences in the behavior between the two phospholipids while incorporation of cholesterol at the studied concentrations was found to be of minor importance. Drug release was found to be favorable from 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC) liposomal hydrogels and drug retention was found to be higher at lower storage temperature for all batches. Original physicochemical properties of all batches were found to be retained at least for a week.

  2. Terbinafine: effects on platelet-derived growth factor-stimulated smooth muscle cells in vitro and myointimal proliferation in vivo

    SciTech Connect

    McCarthy, L.; Van Halen, R.G.; St. Denny, I.H.; Glinka, K.G.; Handley, D.A.; Stuetz, A.; Nemecek, G.M.

    1987-05-01

    Terbinafine (T; (E)-N-(6,6-dimethyl-2-hepten-4-ynyl)-N-methyl-1-naphthalenemethanamine), an antimycotic agent with antimitogenic activity in fibroblasts, was examined for its effects on platelet-derived growth factor (PDGF)-stimulated aortic smooth muscle cell DNA synthesis in vitro and myointimal proliferation in vivo. Exposure of smooth muscle cells to 1-25 ..mu..M T resulted in a concentration-dependent inhibition of PDGF-induced mitogenesis as determined by (/sup 3/H)thymidine incorporation or cell number. The IC/sub 50/ for T was approximately 5 ..mu..M. The inhibitory effect of terbinafine persisted in the presence of 0.4-8.0 ..mu..g/ml cholesterol or 130 ..mu..g/ml mevalonate. Administration of T to rats for 2 d before and 14 d after balloon catheter carotid injury resulted in a 40% decrease in lesion area. These observations indicate that T is both a potent in vitro antagonist of the smooth muscle cell mitogenic response to PDGF and an effective, well-tolerated, orally active inhibitor of myointimal proliferation in vivo.

  3. Re-evaluation of peroxide value as an indicator of the quality of edible oils.

    PubMed

    Shiozawa, Satoshi; Tanaka, Masaharu; Ohno, Katsutoshi; Nagao, Yasuhiro; Yamada, Toshihiro

    2007-06-01

    The oxidation of oils has important effects on the quality of oily foods, such as instant noodles. In particular, the generation of aldehydes, which accompanies the oxidation of oils, is one of the first factors to reduce food quality. We examined various indicators of oil quality during temperature-accelerated storage and found that peroxide value (POV) was highly correlated with the total concentration of major odorants. Moreover, the correlation of POV with the total concentration of five unsaturated aldehydes (t-2-heptenal, t-2-octenal, t-2-decenal, t-2-undecenal and t,t-2,4-decadienal) that show strong cytotoxicity was greater than the correlation of POV with the total concentration of major odorants. The maximum allowable concentration of the five aldehydes was calculated based on the 'no observed adverse-effect level' of the aldehyde that showed the highest cytotoxicity, t,t-2,4-decadienal, along with the human daily oil intake. We showed that it is useful to utilize POV as an indicator to control food quality and safety.

  4. Chemical features of Pericarpium Citri Reticulatae and Pericarpium Citri Reticulatae Viride revealed by GC-MS metabolomics analysis.

    PubMed

    Yi, Lunzhao; Dong, Naiping; Liu, Shao; Yi, Zhibiao; Zhang, Yi

    2015-11-01

    This paper introduces a detailed method to apply metabolic profiles conducting on tangerine peels (Citrus reticulata 'Dahongpao') at three maturity stages from July to December. Principal component analysis not only demonstrated the metabolic footprints of tangerine peels during ripening but also revealed the compounds (D-limonene and linalool) that mostly contributed to it. Furthermore, some other characteristic compounds were screened to further reveal the chemical features of Pericarpium Citri Reticulatae (PCR) and Pericarpium Citri Reticulatae Viride (PCRV). In particular, compounds such as 4-carene (r = -0.94), 3-carene (r = -0.91), β-pinene (r = -0.85) and γ-terpinene (r = -0.87) were screened as major components for the pungent smell of PCRV. Geranyl acetate (r = 0.81), farnesyl acetate (r = 0.87) and three alcohols (6-hepten-1-ol, 3-methyl-1-hexanol, 1-octanol) may lead to the pleasant odour of PCR. We therefore propose that the metabolomics analysis focusing on ripening process will be an effective strategy for quality control of closely related herbal medicines. Copyright © 2014 Elsevier Ltd. All rights reserved.

  5. Determination of Carbonyl Compounds in Cork Agglomerates by GDME-HPLC-UV: Identification of the Extracted Compounds by HPLC-MS/MS.

    PubMed

    Brandão, Pedro Francisco; Ramos, Rui Miguel; Almeida, Paulo Joaquim; Rodrigues, José António

    2017-02-08

    A new approach is proposed for the extraction and determination of carbonyl compounds in solid samples, such as wood or cork materials. Cork products are used as building materials due to their singular characteristics; however, little is known about its aldehyde emission potential and content. Sample preparation was done by using a gas-diffusion microextraction (GDME) device for the direct extraction of volatile aldehydes and derivatization with 2,4-dinitrophenylhydrazine. Analytical determination of the extracts was done by HPLC-UV, with detection at 360 nm. The developed methodology proved to be a reliable tool for aldehyde determination in cork agglomerate samples with suitable method features. Mass spectrometry studies were performed for each sample, which enabled the identification, in the extracts, of the derivatization products of a total of 13 aldehydes (formaldehyde, acetaldehyde, furfural, propanal, 5-methylfurfural, butanal, benzaldehyde, pentanal, hexanal, trans-2-heptenal, heptanal, octanal, and trans-2-nonenal) and 4 ketones (3-hydroxy-2-butanone, acetone, cyclohexanone, and acetophenone). This new analytical methodology simultaneously proved to be consistent for the identification and determination of aldehydes in cork agglomerates and a very simple and straightforward procedure.

  6. Multi-trait mimicry of ants by a parasitoid wasp

    PubMed Central

    Malcicka, Miriama; Bezemer, T. Martijn; Visser, Bertanne; Bloemberg, Mark; Snart, Charles J. P.; Hardy, Ian C. W.; Harvey, Jeffrey A.

    2015-01-01

    Many animals avoid attack from predators through toxicity or the emission of repellent chemicals. Defensive mimicry has evolved in many species to deceive shared predators, for instance through colouration and other morphological adaptations, but mimicry hardly ever seems to involve multi-trait similarities. Here we report on a wingless parasitoid wasp that exhibits a full spectrum of traits mimicing ants and affording protection against ground-dwelling predators (wolf spiders). In body size, morphology and movement Gelis agilis (Ichneumonidae) is highly similar to the black garden ant (Lasius niger) that shares the same habitat. When threatened, G. agilis also emits a volatile chemical that is similar to an ant-produced chemical that repels spiders. In bioassays with L. niger, G. agilis, G. areator, Cotesia glomerata and Drosophila melanogaster, ants and G. agilis were virtually immune to spider attack, in contrast the other species were not. Volatile characterisation with gas chromatography-mass spectrometry identified G. agilis emissions as 6-methyl-5-hepten-2-one, a known insect defence semiochemical that acts as an alarm pheromone in ants. We argue that multi-trait mimicry, as observed in G. agilis, might be much more common among animals than currently realized. PMID:25622726

  7. Chemical Constituents of Supercritical Extracts from Alpinia officinarum and the Feeding Deterrent Activity against Tribolium castaneum.

    PubMed

    Xin, Mintong; Guo, Shanshan; Zhang, Wenjuan; Geng, Zhufeng; Liang, Junyu; Du, Shushan; Deng, Zhiwei; Wang, Yongyan

    2017-04-18

    Alpinia officinarum has been confirmed to possess bioactivities against some pests. In this work, a sample was obtained from A. officinarum rhizomes by supercritical fluid CO₂ extraction (SFE). According to GC-MS analysis, the main chemical components for SFE-sample included benzylacetone (26.77%), 1,7-diphenyl-5-hydroxy-3-heptanone (17.78%), guaiacylacetone (10.03%) and benzenepropanal (7.42%). The essential oil of A. officinarum rhizomes (LD50 = 20.71 μg/adult) exhibited more contact toxicity than SFE extract (LD50 = 82.72 μg/adult) against Tribolium castaneum. From SFE extracts, one new compound, 1-phenyl-4-(16,17-dimethyl-9,13-octadiene)-5-isopentenyl-7-(4"-methoxyl-3"-hydroxyl-phenyl)-3-heptanone (3), together with five known compounds identified as 5-hydroxy-1,7-diphenyl-3-heptanone (1), 1,7-diphenyl-4-hepten-3-one (2), galangin (4), galangin-3-methyl ether (5) and pinocembrin (6), were isolated and their feeding deterrent activities against T. castaneum adults were assessed. It was found that compounds 1-6 had feeding deterrent activities against T. castaneum with feeding deterrent indices of 18.21%, 18.94%, 19.79%, 26.99%, 20.34%, and 35.81%, respectively, at the concentration of 1500 ppm. Hence, the essential oil and SFE extracts/compounds of A. officinarum rhizomes represent promising alternatives in the control of T. castaneum adults.

  8. Combined untargeted and targeted fingerprinting with comprehensive two-dimensional chromatography for volatiles and ripening indicators in olive oil.

    PubMed

    Magagna, Federico; Valverde-Som, Lucia; Ruíz-Samblás, Cristina; Cuadros-Rodríguez, Luis; Reichenbach, Stephen E; Bicchi, Carlo; Cordero, Chiara

    2016-09-14

    Comprehensive two-dimensional gas chromatography (GC × GC) is the most effective multidimensional separation technique for in-depth investigations of complex samples of volatiles (VOC) in food. However, each analytical run produces dense, multi-dimensional data, so elaboration and interpretation of chemical information is challenging. This study exploits recent advances of GC × GC-MS chromatographic fingerprinting to study VOCs distributions from Extra Virgin Olive Oil (EVOO) samples of a single botanical origin (Picual), cultivated in well-defined plots in Granada (Spain), and harvested at different maturation stages. A new integrated work-flow, fully supported by dedicated and automated software tools, combines untargeted and targeted (UT) approaches based on peak-region features to achieve the most inclusive fingerprinting. Combined results from untargeted and targeted methods are consistent, reliable, and informative on discriminant features (analytes) correlated with optimal ripening of olive fruits and sensory quality of EVOOs. The great flexibility of the UT fingerprinting here adopted enables retrospective analysis with great confidence and provides data to validate the transferability of ripening indicators ((Z)-3-hexenal, (Z)-2-hexenal, (E)-2-pentenal, nonanal, 6-methyl-5-hepten-2-one, octane) to external samples sets. Direct image comparison, based on visual features, also is investigated for quick and effective pair-wise investigations. Its implementation with reliable metadata generated by UT fingerprinting confirms the maturity of 2D data elaboration tools and makes advanced image processing a real perspective.

  9. Key Odorants of Lazur, a Polish Mold-Ripened Cheese.

    PubMed

    Majcher, Małgorzata A; Myszka, Kamila; Gracka, Anna; Grygier, Anna; Jeleń, Henryk H

    2017-02-15

    Application of gas chromatography-olfactometry (GC-O) carried out on the volatile fraction isolated by solvent-assisted flavor evaporation (SAFE) and solid phase microextraction (SPME) from Lazur mold-ripened cheese revealed 17 odor-active compounds. The highest flavor dilution factor (FD) has been obtained for methanethiol (2048) with a burnt odor note and for 2(3)-methylbutanoic acid (2048) with a cheesy, pungent odor. Further quantitation of the 15 most aroma-active compounds allowed for calculation of their odor activity values (OAV). The highest OAVs were obtained for methanethiol (500), 3(2)-methylbutanoic acid (321), 3-(methylthio)propanal (210), 2,3-butanedione (65), dimethyl trisulfide (22), butanoic acid (20), 1-octen-3-ol (18), (Z)-4-heptenal (14), dimethyl disulfide (14), dimethyl sulfide (13), phenylacetaldehyde (6), 2-ethyl-3,5-dimethylpyrazine (5), and acetic acid (4). An aroma recombination experiment showed slight differences in the perception of cheesy/sweaty and moldy/musty notes. To verify the influence of methyl ketones on the aroma profile of mold-ripened cheese, recombinant has been additionally supplemented with 2-pentanone, 2-heptanone, and 2-nonanone in concentrations determined in Lazur cheese. The aroma profile remained unchanged, which would suggest that methyl ketones, in this particular cheese, do not play a significant role in the formation of aroma.

  10. Attraction Behaviors of Entomopathogenic Nematodes (Steinernematidae and Heterorhabditidae) to Synthetic Volatiles Emitted by Insect Damaged Potato Tubers.

    PubMed

    Laznik, Žiga; Trdan, Stanislav

    2016-04-01

    Entomopathogenic nematodes (EPNs) play a role in indirect defense of plants under attack by root herbivores. Several investigations have shown that EPNs are attracted or repelled by various volatile compounds (VOCs) released from insect damaged plant roots. We hypothesized that the directional responses of EPNs to the VOCs would be affected by foraging strategy and would vary among species, VOC type, and VOC concentrations. We tested the chemotactic responses of four commercial EPN species (Steinernema feltiae, S. carpocapsae, S. kraussei, and Heterorhabditis bacteriophora) to seven compounds released from insect (Melolontha hippocastani)-damaged (decanal, nonanal, octanal, undecane, 6-methyl-5-hepten-2-one, and 1,2,4-trimethylbenzene) and undamaged (2-ethyl-1-hexanol) potato tubers. Our results suggest that EPNs are able to distinguish herbivore-induced VOCs from those that are typical for healthy potato tubers. In our investigation, nonanal, octanal, and decanal had a greater influence on the movement of EPNs than other tested synthetic volatiles. Decanal was an attractant for H. bacteriophora and S. kraussei at both tested concentrations (as a pure compound and at a concentration of 0.03 ppm). The results suggest that the susceptibility to perception of chemical stimuli from the environment is a species-specific characteristic that prevails over the influence of the foraging strategy.

  11. Electrophysiological and Behavioral Responses of Male Fall Webworm Moths (Hyphantria cunea) to Herbivory-Induced Mulberry (Morus alba) Leaf Volatiles

    PubMed Central

    Tang, Rui; Zhang, Jin Ping; Zhang, Zhong Ning

    2012-01-01

    Volatile organic compounds (VOCs) were collected from damaged and intact mulberry leaves (Morus alba L., Moraceae) and from Hyphantria cunea larvae by headspace absorption with Super Q columns. We identified their constituents using gas chromatography-mass spectrometry, and evaluated the responses of male H. cunea antennae to the compounds using gas chromatography-flame ionization detection coupled with electroantennographic detection. Eleven VOC constituents were found to stimulate antennae of male H. cunea moths: β-ocimene, hexanal, cis-3-hexenal, limonene, trans-2-hexenal, cyclohexanone, cis-2-penten-1-ol, 6-methyl-5-hepten-2-one, 4-hydroxy-4-methyl-2-pentanone, trans-3-hexen-1-ol, and 2,4-dimethyl-3-pentanol. Nine of these chemicals were released by intact, mechanically-damaged, and herbivore-damaged leaves, while cis-2-penten-1-ol was released only by intact and mechanically-damaged leaves and β-ocimene was released only by herbivore-damaged leaves. Results from wind tunnel experiments conducted with volatile components indicated that male moths were significantly more attracted to herbivory-induced volatiles than the solvent control. Furthermore, male moths' attraction to a sex pheromone lure was increased by herbivory-induced compounds and β-ocimene, but reduced by cis-2-penten-1-ol. A proof long-range field trapping experiment showed that the efficiency of sex pheromone lures in trapping male moths was increased by β-ocimene and reduced by cis-2-penten-1-ol. PMID:23166622

  12. Is H Atom Abstraction Important in the Reaction of Cl with 1-Alkenes?

    PubMed

    Walavalkar, M P; Vijayakumar, S; Sharma, A; Rajakumar, B; Dhanya, S

    2016-06-23

    The relative yields of products of the reaction of Cl atoms with 1-alkenes (C4-C9) were determined to see whether H atom abstraction is an important channel and if it is to identify the preferred position of abstraction. The presence of all the possible positional isomers of long chain alkenones and alkenols among the products, along with chloroketones and chloroalcohols, confirms the occurrence of H atom abstraction. A consistent pattern of distribution of abstraction products is observed with oxidation at C4 (next to allyl) being the lowest and that at CH2 groups away from the double bond being the highest. This contradicts with the higher stability of allyl (C3) radical. For a better understanding of the relative reactivity, ab initio calculations at MP2/6-311+G (d,p) level of theory are carried out in the case of 1-heptene. The total rate coefficient, calculated using conventional transition state theory, was found to be in good agreement with the experimental value at room temperature. The preferred position of Cl atom addition is predicted to be the terminal carbon atom, which matches with the experimental observation, whereas the rate coefficients calculated for individual channels of H atom abstraction do not explain the observed pattern of products. The distribution of abstraction products except at C4 is found to be better explained by reported structure activity relationship, developed from experimental rate coefficient data. This implies the reactions to be kinetically dictated and emphasizes the importance of secondary reactions.

  13. Interactions of Anopheles gambiae Odorant-binding Proteins with a Human-derived Repellent

    PubMed Central

    Murphy, Emma J.; Booth, Jamie C.; Davrazou, Foteini; Port, Alex M.; Jones, David N. M.

    2013-01-01

    The Anopheles gambiae mosquito, which is the vector for Plasmodium falciparum malaria, uses a series of olfactory cues emanating from human sweat to select humans as their source for a blood meal. Perception of these odors within the mosquito olfactory system involves the interplay of odorant-binding proteins (OBPs) and odorant receptors and disrupting the normal responses to those odorants that guide mosquito-human interactions represents an attractive approach to prevent the transmission of malaria. Previously, it has been shown that DEET targets multiple components of the olfactory system, including OBPs and odorant receptors. Here, we present the crystal structure of A. gambiae OBP1 (OBP1) in the complex it forms with a natural repellent 6-methyl-5-heptene-2-one (6-MH). We find that 6-MH binds to OBP1 at exactly the same site as DEET. However, key interactions with a highly conserved water molecule that are proposed to be important for DEET binding are not involved in binding of 6-MH. We show that 6-MH and DEET can compete for the binding of attractive odorants and in doing so disrupt the interaction that OBP1 makes with OBP4. We further show that 6-MH and DEET can bind simultaneously to OBPs with other ligands. These results suggest that the successful discovery of novel reagents targeting OBP function requires knowledge about the specific mechanism of binding to the OBP rather than their binding affinity. PMID:23261834

  14. Combined effects of reduced malaxation oxygen levels and storage time on extra-virgin olive oil volatiles investigated by a novel chemometric approach.

    PubMed

    Raffo, Antonio; Bucci, Remo; D'Aloise, Antonio; Pastore, Gianni

    2015-09-01

    Combined effects of oxygen level reduction in the malaxation headspace and storage time up to 6 months on the volatile composition of a monovarietal extra-virgin olive oil (EVOO), obtained from cv. Carboncella olives, were investigated by applying a full factorial design approach (4 oxygen levels × 4 storage times) on EVOOs extracted on an industrial scale in two mills, equipped with "two-phase" and "three-phase" centrifugation systems, respectively. The outcoming data were analysed by the chemometric technique called ANOVA-simultaneous component analysis (ASCA). Both reduction of oxygen malaxation levels and storage time significantly affected the volatile profile of the extracted EVOOs. Reduction of oxygen malaxation levels hindered the formation of lipoxygenase derived volatiles (hexanal, 1-hexanol, (Z)-2-hexenal, (E)-2-hexen-1-ol, (Z)-2-penten-1-ol, 2,4-hexadienals), whereas prolonged storage times were associated with increased levels of autoxidation products (octane, hexanal, C10 hydrocarbons) and other compounds that could originate from exogenous microbial activity (1-octen-3-ol, 6-methyl-5-hepten-2-one, benzaldehyde, methyl salicylate).

  15. Volatile organic compounds from feces and their potential for diagnosis of gastrointestinal disease.

    PubMed

    Garner, Catherine E; Smith, Stephen; de Lacy Costello, Ben; White, Paul; Spencer, Robert; Probert, Chris S J; Ratcliffe, Norman M

    2007-06-01

    Little is known about the volatile organic compounds (VOCs) in feces and their potential health consequences. Patients and healthcare professionals have observed that feces often smell abnormal during gastrointestinal disease. The aim of this work was to define the volatiles emitted from the feces of healthy donors and patients with gastrointestinal disease. Our hypotheses were that i) VOCs would be shared in health; ii) VOCs would be constant in individuals; and iii) specific changes in VOCs would occur in disease. Volatile emissions in health were defined in a cohort and a longitudinal study. Subsequently, the pattern of volatiles found in the cohort study were compared to that found from patients with ulcerative colitis, Campylobacter jejuni, and Clostridium difficile. Volatiles from feces were collected by solid-phase microextraction and analyzed by gas chromatography/mass spectrometry. In the cohort study, 297 volatiles were identified. In all samples, ethanoic, butanoic, pentanoic acids, benzaldehyde, ethanal, carbon disulfide, dimethyldisulfide, acetone, 2-butanone, 2,3-butanedione, 6-methyl-5-hepten-2-one, indole, and 4-methylphenol were found. Forty-four compounds were shared by 80% of subjects. In the longitudinal study, 292 volatiles were identified, with some inter and intra subject variations in VOC concentrations with time. When compared to healthy donors, volatile patterns from feces of patients with ulcerative colitis, C. difficile, and C. jejuni were each significantly different. These findings could lead the way to the development of a rapid diagnostic device based on VOC detection.

  16. Characterization of aroma-active compounds, sensory properties, and proteolysis in Ezine cheese.

    PubMed

    Yuceer, Y Karagul; Tuncel, B; Guneser, O; Engin, B; Isleten, M; Yasar, K; Mendes, M

    2009-09-01

    Ezine cheese is a white pickled cheese ripened in tinplate containers for at least 8 mo. A mixture of milk from goat, sheep, and cow is used to make Ezine cheese. Ezine cheese has geographical indication status. The purposes of this study were to determine and compare the changes in basic composition, aroma, and sensory characteristics, and proteolytic activity of Ezine cheese stored in tinplate containers and plastic vacuum packages during storage. Aroma-active compounds were determined by thermal desorption gas chromatography olfactometry. To evaluate the proteolytic activity, casein and nitrogen fractions were determined. The results indicated that compounds identified at high intensities were dimethyl sulfide, ethyl butyrate, hexanal, ethyl pentanoate, (Z)-4-heptenal, 1-octen-3-one, acetic acid, butyric acid, and p-cresol. Characteristic descriptive terms were cooked, whey, creamy, animal-like, sour, and salty. The level of proteolysis increased in Ezine cheese during storage. Ezine cheese can be ripened in small-size packaging after 3 mo of storage. Approximately 6 mo is sufficient to produce the characteristic properties of Ezine cheese.

  17. (1S,2R,7R,8S,10R)-9,9-Di­bromo-2,6,6,10-tetra­methyl-1α,2α-ep­oxy­tri­cyclo­[5.5.0.08,10]dodeca­ne

    PubMed Central

    Benharref, Ahmed; El Karroumi, Jamal; El Ammari, Lahcen; Saadi, Mohamed; Berraho, Moha

    2013-01-01

    The title compound, C16H24Br2O, was synthesized from the reaction of β-himachalene (3,5,5,9-tetra­methyl-2,4a,5,6,7,8-hexa­hydro-1H-benzo­cyclo­heptene), which was isolated from Atlas cedar (Cedrus atlantica) essential oil, after reaction with di­bromo­carbene. The asymmetric unit contains two independent mol­ecules with similar conformations. Each mol­ecule is built up from fused six-and seven-membered rings and two three-membered rings. In both mol­ecules, the six-membered ring has an envelope conformation with the flap provided by the C atom of the ep­oxy ring, whereas the seven-membered ring displays a chair conformation. The crystal packing is governed only by van der Waals inter­actions. The absolute configuration was established from anomalous dispersion effects. PMID:24046614

  18. 2,2-Dichloro-3,7,7,11-tetra-methyl-10-aza-tetra-cyclo-[6.5.0.0(1,3).0(9,11)]trideca-ne.

    PubMed

    Oukhrib, Abdelouahd; Benharref, Ahmed; Saadi, Mohamed; Berraho, Moha; El Ammari, Lahcen

    2013-04-01

    The title compound, C16H25Cl2N, was synthesized from β-himachalene (3,5,5,9-tetra-methyl-2,4a,5,6,7,8-hexa-hydro-1H-benzocyclo-heptene), which was isolated from the essential oil of the Atlas cedar (Cedrus Atlantica). The mol-ecule is built up from fused six- and seven-membered rings linked to two three-membered rings. The six-membered ring shows a half-chair conformation, whereas the seven-membered ring displays a boat conformation. The dihedral angle between the mean planes through the six- and seven-membered rings is 59.8 (2)°. The two three-membered rings lie to one side and each is nearly perpendicular to the six-membered ring, forming dihedral angles of 83.2 (2) and 86.0 (2)°. The absolute structure was established unambiguously from anomalous dispersion effects. No specific inter-molecular inter-actions are noted in the crystal structure.

  19. (1S,3R,8R,9R,10S)-2,2-Dibromo-3,7,7,10-tetra-methyl-9β,10β-ep-oxy-3,7,7,10-tetra-methyl-tricyclo-[6.4.0.0(1,3)]dodeca-ne.

    PubMed

    Oukhrib, Abdelouahd; Benharref, Ahmed; Saadi, Mohamed; Berraho, Moha; El Ammari, Lahcen

    2013-04-01

    The title compound, C16H24Br2O, was synthesized from β-himachalene (3,5,5,9-tetra-methyl-2,4a,5,6,7,8-hexa-hydro-1H-benzocyclo-heptene), which was isolated from the essential oil of the Atlas cedar (Cedrus atlantica). The mol-ecule contains fused six- and seven-membered rings, each linked to a three-membered ring. The six-membered ring has a half-chair conformation, while the seven-membered ring displays a chair conformation. The dihedral angle between the mean planes through the six- and seven-membered rings is 39.55 (12)°. The two three-membered rings, linked to the six- and seven-membered rings, are nearly perpendicular to the six-membered ring, making dihedral angles of 78.6 (2) and 80.5 (2)°, respectively. The absolute structure was established unambiguously from anomalous dispersion effects. In the crystal, each mol-ecule is linked to its symmetry-equivalent partner by C-H⋯O hydrogen bonds, forming zigzag chains parallel to [100].

  20. Multi-trait mimicry of ants by a parasitoid wasp.

    PubMed

    Malcicka, Miriama; Bezemer, T Martijn; Visser, Bertanne; Bloemberg, Mark; Snart, Charles J P; Hardy, Ian C W; Harvey, Jeffrey A

    2015-01-27

    Many animals avoid attack from predators through toxicity or the emission of repellent chemicals. Defensive mimicry has evolved in many species to deceive shared predators, for instance through colouration and other morphological adaptations, but mimicry hardly ever seems to involve multi-trait similarities. Here we report on a wingless parasitoid wasp that exhibits a full spectrum of traits mimicing ants and affording protection against ground-dwelling predators (wolf spiders). In body size, morphology and movement Gelis agilis (Ichneumonidae) is highly similar to the black garden ant (Lasius niger) that shares the same habitat. When threatened, G. agilis also emits a volatile chemical that is similar to an ant-produced chemical that repels spiders. In bioassays with L. niger, G. agilis, G. areator, Cotesia glomerata and Drosophila melanogaster, ants and G. agilis were virtually immune to spider attack, in contrast the other species were not. Volatile characterisation with gas chromatography-mass spectrometry identified G. agilis emissions as 6-methyl-5-hepten-2-one, a known insect defence semiochemical that acts as an alarm pheromone in ants. We argue that multi-trait mimicry, as observed in G. agilis, might be much more common among animals than currently realized.

  1. Effect of management (organic vs conventional) on volatile profiles of six plum cultivars (Prunus salicina Lindl.). A chemometric approach for varietal classification and determination of potential markers.

    PubMed

    Cuevas, F J; Moreno-Rojas, J M; Arroyo, F; Daza, A; Ruiz-Moreno, M J

    2016-05-15

    The volatile profiles of six plum cultivars ('Laetitia', 'Primetime', 'Sapphire', 'Showtime', 'Songold' and 'Souvenir') produced under two management systems (conventional and organic) and harvested in two consecutive years were obtained by HS-SPME-GC-MS. Twenty-five metabolites were determined, five of which (pentanal, (E)-2-heptenal, 1-octanol, eucalyptol and 2-pentylfuran) are reported for the first time in Prunus salicina Lindl. Hexanal stood out as a major volatile compound affected by the management system. In addition, partial least square discriminant analysis (PLS-DA) achieved an effective classification of genotypes based on their volatile profiles. A high classification accuracy model was obtained with a sensitivity of 97.9% and a specificity of 99.6%. Furthermore, the application of a dual criterion, based on a method of variable selection, VIP (variable importance in projection) and the results of a univariate analysis (ANOVA), allowed the identification of potential volatile markers in 'Primetime', 'Showtime' and 'Souvenir' genotypes (cultivars not characterised to date).

  2. Comparison of two microalgal diets. 2. Influence on odorant composition and organoleptic qualities of raw oysters (Crassostrea gigas).

    PubMed

    Pennarun, Anne-Laure; Prost, Carole; Haure, Joël; Demaimay, Michel

    2003-03-26

    Oyster farming is of real economic interest in France. Oyster farmers attach more and more importance to improving the growth and the quality of their oysters. Some fatty acids known to be aroma precursors originate from microalgae such as Skeletonema costatum and Tahitian isochrysis clone. These microalgae were used to fatten oysters in order to observe their role in the development of oysters' aroma. This study shows that the profile of fatty acids of oysters is influenced by the contribution of fatty acids from the two microalgae (as reported in the first paper in this series: Pennarun, A.-L.; Prost, C.; Haure, J.; Demaimay, M. Comparison of Two Microalgal Diets. 1. Influence on the Biochemical and Fatty Acid Compositions of Raw Oysters (Crassostrea gigas). J. Agric. Food Chem. 2003, 51, 2006-2010 (in this issue)]. As a consequence, a microalgal diet causes changes in oysters' aroma composition. Aroma concentration depends on the content of fatty acids that are aroma precursors in oysters. Some aromas are characteristic of the diet of S. costatum, such as 6-methyl-5-hepten-2-one (ether odor), and others are characteristic of T. isochrysis, such as 3-nonyne (cucumber, marine odor), 6-(E)-nonen-1-ol (green and fresh odor), and 4-ethylbenzaldehyde (aniseed odor). Moreover, the organoleptic qualities (odor, taste, and texture) of oysters are modified by the diet of microalgae.

  3. Skimming behaviour and spreading potential of Stenus species and Dianous coerulescens (Coleoptera: Staphylinidae)

    NASA Astrophysics Data System (ADS)

    Lang, Carolin; Seifert, Karlheinz; Dettner, Konrad

    2012-11-01

    Rove beetles of the genus Stenus Latreille and the genus Dianous Leach possess pygidial glands containing a multifunctional secretion of piperidine and pyridine-derived alkaloids as well as several terpenes. One important character of this secretion is the spreading potential of its different compounds, stenusine, norstenusine, 3-(2-methyl-1-butenyl)pyridine, cicindeloine, α-pinene, 1,8-cineole and 6-methyl-5-heptene-2-one. The individual secretion composition enables the beetles to skim rapidly and far over the water surface, even when just a small amount of secretion is emitted. Ethological investigations of several Stenus species revealed that the skimming ability, skimming velocity and the skimming behaviour differ between the Stenus species. These differences can be linked to varied habitat claims and secretion saving mechanisms. By means of tensiometer measurements using the pendant drop method, the spreading pressure of all secretion constituents as well as some naturally identical beetle secretions on the water surface could be established. The compound 3-(2-methyl-1-butenyl)pyridine excelled stenusine believed to date to be mainly responsible for skimming relating to its surface activity. The naturally identical secretions are not subject to synergistic effects of the single compounds concerning the spreading potential. Furthermore, evolutionary aspects of the Steninae's pygidial gland secretion are discussed.

  4. Chemical and olfactometric characterization of volatile flavor compounds in a fish oil enriched milk emulsion.

    PubMed

    Venkateshwarlu, Gudipati; Let, Mette B; Meyer, Anne S; Jacobsen, Charlotte

    2004-01-28

    Development of objectionable fishy off-flavors is an obstacle in the development of fish oil enriched foods. Only little is known about the sensory impact of specific volatile fish oil oxidation products in food emulsions. This study examined the volatiles profiles of fish oil enriched milk during cold storage (2 degrees C) for 14 days by dynamic headspace sampling followed by gas chromatography-mass spectrometry analyses. Different volatiles (n = 60) comprising alkenals, alkadienals, alkatrienals, and vinyl ketones were identified in the fish oil enriched milk. The potent odorants identified by gas chromatography-olfactometry were 1-penten-3-one, (Z)-4-heptenal, 1-octen-3-one, (Z)-1,5-octadien-3-one, (E,E)-2,4-heptadienal, and (E,Z)-2,6-nonadienal, but despite their potency, none of the separated volatiles imparted a fishy or metallic odor. Two isomers, (E,Z,Z) and (E,E,Z) of 2,4,7-decatrienal were identified in fish oil enriched milk emulsions with peroxide values 0.8 and 3.4 meq/kg, respectively. To our knowledge, this is the first report on appearance of these decatrienals in food emulsions having a relatively low peroxide value.

  5. Atmospheric carbon dioxide changes photochemical activity, soluble sugars and volatile levels in broccoli (Brassica oleracea var. italica).

    PubMed

    Krumbein, Angelika; Kläring, Hans-Peter; Schonhof, Ilona; Schreiner, Monika

    2010-03-24

    Atmospheric carbon dioxide (CO(2)) concentration is an environmental factor currently undergoing dramatic changes. The objective of the present study was to determine the effect of doubling the ambient CO(2) concentration on plant photochemistry as measured by photochemical quenching coefficient (qP), soluble sugars and volatiles in broccoli. Elevated CO(2) concentration increased qP values in leaves by up to 100% and 89% in heads, while glucose and sucrose in leaves increased by about 60%. Furthermore, in broccoli heads elevated CO(2) concentration induced approximately a 2-fold increase in concentrations of three fatty acid-derived C(7) aldehydes ((E)-2-heptenal, (E,Z)-2,4-heptadienal, (E,E)-2,4-heptadienal), two fatty acid-derived C(5) alcohols (1-penten-3-ol, (Z)-2-pentenol), and two amino acid-derived nitriles (phenyl propanenitrile, 3-methyl butanenitrile). In contrast, concentrations of the sulfur-containing compound 2-ethylthiophene and C(6) alcohol (E)-2-hexenol decreased. Finally, elevated CO(2) concentration increased soluble sugar concentrations due to enhanced photochemical activity in leaves and heads, which may account for the increased synthesis of volatiles.

  6. Epoxyalkenal-trapping ability of phenolic compounds.

    PubMed

    Zamora, Rosario; Aguilar, Isabel; Hidalgo, Francisco J

    2017-12-15

    Lipid oxidation products have been shown to produce changes in food quality and safety as a consequence of carbonyl-amine reactions. Some of these reactions can be prevented by the use of phenolics, although the lipid-derived carbonyl trapping ability of phenolics is still poorly understood. In an attempt to fill this gap, the reactions of 4,5-epoxy-2-hexenal, 4,5-epoxy-2-heptenal, and 4,5-epoxy-2-decenal, with 2-methylresorcinol and 2,5-dimethylresorcinol were studied. These reactions produced diverse 1,3a,4,9b-tetrahydro-2H-furo[2,3-c]chromene-2,7-diols and 3,4,4a,9a-tetrahydro-1H-pyrano[3,4-b]benzofuran-3,7-diols, which were isolated and characterized by 1D and 2D nuclear magnetic resonance (NMR) and mass spectrometry (MS). The produced epoxyalkenal-phenol reaction was characterized and carbonyl-phenol adducts were produced firstly by epoxide-ring opening initiated by the attack of one phenolic hydroxyl group and, then, by addition of one aromatic phenol carbon to the carbon-carbon double bond of the epoxyalkenal. This reaction rapidly deactivated the most important reactive groups of epoxyalkenals, decreasing in this way their ability to modify amino compounds. Copyright © 2017 Elsevier Ltd. All rights reserved.

  7. Microbial Production of Aliphatic (S)-Epoxyalkanes by Using Rhodococcus sp. Strain ST-10 Styrene Monooxygenase Expressed in Organic-Solvent-Tolerant Kocuria rhizophila DC2201

    PubMed Central

    Toda, Hiroshi; Ohuchi, Takuya; Imae, Ryouta

    2015-01-01

    We describe the development of biocatalysis for producing optically pure straight-chain (S)-epoxyalkanes using styrene monooxygenase of Rhodococcus sp. strain ST-10 (RhSMO). RhSMO was expressed in the organic solvent-tolerant microorganism Kocuria rhizophila DC2201, and the bioconversion reaction was performed in an organic solvent-water biphasic reaction system. The biocatalytic process enantioselectively converted linear terminal alkenes to their corresponding (S)-epoxyalkanes using glucose and molecular oxygen. When 1-heptene and 6-chloro-1-hexene were used as substrates (400 mM) under optimized conditions, 88.3 mM (S)-1,2-epoxyheptane and 246.5 mM (S)-1,2-epoxy-6-chlorohexane, respectively, accumulated in the organic phase with good enantiomeric excess (ee; 84.2 and 95.5%). The biocatalysis showed broad substrate specificity toward various aliphatic alkenes, including functionalized and unfunctionalized alkenes, with good to excellent ee. Here, we demonstrate that this biocatalytic system is environmentally friendly and useful for producing various enantiopure (S)-epoxyalkanes. PMID:25556188

  8. Phytosterol structured algae oil nanoemulsions and powders: improving antioxidant and flavor properties.

    PubMed

    Chen, Xiao-Wei; Chen, Ya-Jun; Wang, Jin-Mei; Guo, Jian; Yin, Shou-Wei; Yang, Xiao-Quan

    2016-09-14

    Algae oil, enriched with omega-3 long-chain polyunsaturated fatty acids (ω-3 LC-PUFA), is known for its health benefits. However, protection against lipid oxidation as well as masking of unpleasant fishy malodors in algae oil enriched foods is a big challenge to achieve. In this study, we firstly achieved a one-pot ultrasound emulsification strategy (alternative heating-homogenization) to prepare phytosterol structured thermosensitive algae oil-in-water nanoemulsion stabilized by quillaja saponin. After spray drying, the resulting algae oil powders from the structured nanoemulsion templates exhibit an excellent reconstructed behavior, even after 30 d of storage. Furthermore, an enhanced oxidative stability was obtained by reducing both the primary and secondary oxidation products through formulation with β-sitosterol and γ-oryzanol, which are natural antioxidants. Following the results of headspace volatiles using dynamic headspace-gas chromatography-mass spectrometry (DHS-GC-MS), it was clear that the structured algae oil-loaded nanoemulsion and powder had lower levels of fishy off-flavour (e.g., (Z)-heptenal, decanal, ethanone, and hexadecenoic acid), whereas the control emulsion and oil powder without structure performed worse. This study demonstrated that the structure from phytosterols is an effective strategy to minimize the fishy off-flavour and maximize oxidative stability of both algae oil nanoemulsions and spray-dried powders, and opens up the possibility of formulation design in polyunsaturated oil encapsulates as novel delivery systems to apply in functional foods and beverages.

  9. Odour characteristics of seafood flavour formulations produced with fish by-products incorporating EPA, DHA and fish oil.

    PubMed

    Peinado, I; Miles, W; Koutsidis, G

    2016-12-01

    Thermal degradation of eicosapentaenoic (EPA) and docosahexaenoic (DHA) acids was investigated. As a novelty, EPA, DHA or fish oil (FO) were incorporated as ω-fatty acid sources into model systems containing fish powder produced via Maillard reactions. Aroma composition of the resulting products was determined and complemented with sensory evaluation. Heating of the oils led to a fast decrease of both, EPA and DHA, and to the development of characteristic volatile compounds including hexanal, 2,4-heptadienal and 4-heptenal, the most abundant being (E,E)-2,4-heptadienal (132±44-329±122μmol/g). EPA and DHA addition to the model systems increased the concentration of these characteristic volatile compounds. However, it did not have a considerable impact on the development of characteristic Maillard reaction products, such as pyrazines and some aldehydes. Finally, the results of the sensory evaluation illustrated that panellists would chose samples fortified with FO as the ones with a more pleasant aroma. Copyright © 2016 Elsevier Ltd. All rights reserved.

  10. Degradation mechanisms of geosmin and 2-MIB during UV photolysis and UV/chlorine reactions.

    PubMed

    Kim, Tae-Kyoung; Moon, Bo-Ram; Kim, Taeyeon; Kim, Moon-Kyung; Zoh, Kyung-Duk

    2016-11-01

    We conducted chlorination, UV photolysis, and UV/chlorin reactions to investigate the intermediate formation and degradation mechanisms of geosmin and 2-methylisoborneol (2-MIB) in water. Chlorination hardly removed geosmin and 2-MIB, while the UV/chlorine reaction at 254 nm completely removed geosmin and 2-MIB within 40 min and 1 h, respectively, with lesser removals of both compounds during UV photolysis. The kinetics during both UV photolysis and UV/chlorine reactions followed a pseudo first-order reaction. Chloroform was found as a chlorinated intermediate during the UV/chlorine reaction of both geosmin and 2-MIB. The pH affected both the degradation and chloroform production during the UV/chlorine reaction. The open ring and dehydration intermediates identified during UV/chlorine reactions were 1,4-dimethyl-adamantane, and 1,3-dimethyl-adamantane from geosmin, 2-methylenebornane, and 2-methyl-2-bornene from 2-MIB, respectively. Additionally, 2-methyl-3-pentanol, 2,4-dimethyl-1-heptene, 4-methyl-2-heptanone, and 1,1-dichloro-2,4-dimethyl-1-heptane were newly identified intermediates from UV/chlorine reactions of both geosmin and 2-MIB. These intermediates were degraded as the reaction progressed. We proposed possible degradation pathways during the UV photolysis and UV/chlorine reactions of both compounds using the identified intermediates. Copyright © 2016 Elsevier Ltd. All rights reserved.

  11. Identification and biotransformation of aliphatic hydrocarbons during co-composting of sewage sludge-Date Palm waste using Pyrolysis-GC/MS technique.

    PubMed

    El Fels, Loubna; Lemee, Laurent; Ambles, André; Hafidi, Mohamed

    2016-08-01

    The behavior of aliphatic hydrocarbons during co-composting of sewage sludge activated with palm tree waste was studied for 6 months using Py-GC/MS. The main aliphatic compounds represented as doublet alkenes/alkanes can be classified into three groups. The first group consists of 11 alkenes (undecene, tridecene, pentadecene, hexadecene, heptadecene, octadecene, nonadecene, eicosene, uncosene, docosene, tricosene) and 15 alkanes (heptane, octane, nonane, decane, undecane, dodecane, tetradecane, pentadecane, heptadecane, octadecane, nonadecane, eicosane, uncosane, docosane, and tricosane), which remain stable during the co-composting process. The stability of these compounds is related to their recalcitrance behavior. The second group consists of five alkenes (heptene, octene, nonene, decene, dodecene) and tridecane as a single alkane that decreases during co-composting. The decrease in these compounds is the combined result of their metabolism and their conversion into other compounds. The third group is constituted with tetradecene and hexadecane that increase during composting, which could be explained by accumulation of these compounds, which are released by the partial breakdown of the substrate. As a result, these molecules are incorporated or adsorbed in the structure of humic substances.

  12. Selective Estrogen Receptor Modulator (SERM)-like Activities of Diarylheptanoid, a Phytoestrogen from Curcuma comosa, in Breast Cancer Cells, Pre-osteoblast Cells, and Rat Uterine Tissues.

    PubMed

    Thongon, Natthakan; Boonmuen, Nittaya; Suksen, Kanoknetr; Wichit, Patsorn; Chairoungdua, Arthit; Tuchinda, Patoomratana; Suksamrarn, Apichart; Winuthayanon, Wipawee; Piyachaturawat, Pawinee

    2017-05-03

    Diarylheptanoids from Curcuma comosa, of the Zingiberaceae family, exhibit diverse estrogenic activities. In this study we investigated the estrogenic activity of a major hydroxyl diarylheptanoid, 7-(3,4 -dihydroxyphenyl)-5-hydroxy-1-phenyl-(1E)-1-heptene (compound 092) isolated from C. comosa. The compound elicited different transcriptional activities of estrogen agonist at low concentrations (0.1-1 μM) and antagonist at high concentrations (10-50 μM) using luciferase reporter gene assay in HEK-293T cells. In human breast cancer (MCF-7) cells, compound 092 showed an anti-estrogenic activity by down-regulating ERα-signaling and suppressing estrogen-responsive genes, whereas it attenuated the uterotrophic effect of estrogen in immature ovariectomized rats. Of note, compound 092 promoted mouse pre-osteoblastic (MC3T3-E1) cell differentiation and the related bone markers, indicating its positive osteogenic effect. Our findings highlight a new, nonsteroidal, estrogen agonist/antagonist of catechol diarylheptanoid from C. comosa, which is scientific evidence supporting its potential as a dietary supplement to prevent bone loss with low risk of breast and uterine cancers in postmenopausal women.

  13. Rate coefficients at 298 K and 1 atm for the tropospheric degradation of a series of C6, C7 and C8 biogenic unsaturated alcohols initiated by Cl atoms

    NASA Astrophysics Data System (ADS)

    Gibilisco, Rodrigo G.; Bejan, Iustinian; Barnes, Ian; Wiesen, Peter; Teruel, Mariano A.

    2014-09-01

    Rate coefficients for the gas-phase reactions of Cl atoms with a series of unsaturated biogenic alcohols at 298 ± 3 K and 1 atm have been measured by the relative technique in an environmental chamber with in situ FTIR detection of reactants. The rate coefficients obtained using 1-butene and isobutene as reference compounds were (in units of 10-10 cm3 molecule-1 s-1): k1((E)-2-hexen-1-ol) = (3.49 ± 0.82), k2((E)-3-hexen-1-ol) = (3.42 ± 0.79), k3 ((Z)-3-hexen-1-ol) = (2.94 ± 0.72), k4((Z)-3-hepten-1-ol) = (3.80 ± 0.86) and k5((Z)-3-octen-1-ol) = (4.13 ± 0.68). This work constitutes the first kinetic study of the reactions cited above. The rate coefficients are compared with those for other unsaturated alcohols and a correlation between the reactivity of unsaturated alcohols toward Cl atoms and the energy of the HOMO of the unsaturated alcohols is presented. Based on the obtained results, the atmospheric lifetimes of the unsaturated alcohols have been estimated and possible atmospheric implications assessed.

  14. Assessment of the oxidative stability of conventional and high-oleic sunflower oil by means of solid-phase microextraction-gas chromatography.

    PubMed

    Petersen, Katharina Domitila; Kleeberg, Kim Karen; Jahreis, Gerhard; Fritsche, Jan

    2012-03-01

    Headspace-solid-phase microextraction-gas chromatography (HS-SPME-GC) was used to identify in total 74 volatile lipid oxidation compounds altogether in thermally stressed conventional and high-oleic sunflower (HOSF) oil samples (in accelerated storage conditions for 14 days at 80°C). Out of the volatile compounds identified, six volatile compounds were selected as marker compounds for the assessment of lipid oxidation of sunflower (SF) and HOSF oils due to their low odour threshold values and fatty-rancid odour impression. Additionally, other oxidation parameters such as fatty acid composition, peroxide value (PV), anisidine value and tocopherol and tocotrienol composition were determined. Multivariate statistical methods (principal component analysis and agglomerative hierarchical cluster analysis) were applied to identify sensitive oxidation marker compounds. Preliminary results revealed that hexanal, E-2-heptenal, E-2-decenal and E,E-2,4-nonadienal were the most suitable in differentiating HOSF and SF oil varieties from each other and SF samples with differing oxidative properties. Differentiation of SF samples according to their volatile compound composition was done in accordance with the results from the well-known oil quality parameters (e.g. PV or fatty acid composition). In conclusion, the combination of volatile compound analysis with HS-SPME-GC and multivariate statistical methods provides a sensitive tool in differentiating conventional SF and HOSF oils by means of volatile lipid oxidation marker compounds.

  15. The effects of inferior olive lesion on strychnine seizure

    SciTech Connect

    Anderson, M.C.; Chung, E.Y.; Van Woert, M.H. )

    1990-10-01

    Bilateral inferior olive lesions, produced by systemic administration of the neurotoxin 3-acetylpyridine (3AP) produce a proconvulsant state specific for strychnine-induced seizures and myoclonus. We have proposed that these phenomena are mediated through increased excitation of cerebellar Purkinje cells, through activation of glutamate receptors, in response to climbing fiber deafferentation. An increase in quisqualic acid (QA)-displaceable ({sup 3}H)AMPA ((RS)-alpha-amino-3-hydroxy-5-methyl-isoxazole-4-propionic acid) binding in cerebella from inferior olive-lesioned rats was observed, but no difference in ({sup 3}H)AMPA binding displaced by glutamate, kainic acid (KA) or glutamate diethylester (GDEE) was seen. The excitatory amino acid antagonists GDEE and MK-801 ((+)-5-methyl-10,11-dihydro-5H-dibenzo(a,d)cyclo-hepten-5,10 imine) were tested as anticonvulsants for strychnine-induced seizures in 3AP inferior olive-lesioned and control rats. Neither drug effected seizures in control rats, however, both GDEE and MK-801 produced a leftward shift in the strychnine-seizure dose-response curve in 3AP inferior olive-lesioned rats. GDEE also inhibited strychnine-induced myoclonus in the lesioned group, while MK-801 had no effect on myoclonus. The decreased threshold for strychnine-induced seizures and myoclonus in the 3AP-inferior olive-lesioned rats may be due to an increase in glutamate receptors as suggested by the ({sup 3}H)AMPA binding data.

  16. Characterization of the antennal olfactory system of the bed bug (Cimex lectularius).

    PubMed

    Harraca, Vincent; Ignell, Rickard; Löfstedt, Christer; Ryne, Camilla

    2010-03-01

    The common bed bug Cimex lectularius (Hemiptera; Cimicidae) is a temporary ectoparasite on humans that is currently reinvading the developed countries. Like other haematophagous arthropods, host seeking and orientation in C. lectularius is partially mediated by olfaction. In this study, we reconfirmed the distribution of the 44 olfactory sensilla and identified 3 different sensillum types located at the distal tip of C. lectularius antenna by external morphology mapping. Using a panel of relevant odorants previously reported to be bioactive in various haematophagous arthropods, we correlated the morphological mapping with an electrophysiological characterization of the olfactory receptor neurons housed in each specific sensillum. We found that all 9 grooved peg sensilla responded specifically in a dose-dependent manner to ammonia, whereas (E)-2-hexenal, (E)-2-octenal, dimethyl trisulfide, 6-methyl-5-hepten-2-one, alpha-pinene, indole, and ethyl butyrate evoked dose-dependent responses within the 6 smooth peg sensilla. Based on the pattern of response to the tested compounds, we were able to separate the 6 smooth peg sensilla of the bed bug into 3 distinct functional classes. We compare our results with previous electrophysiological recordings made with these compounds on other haematophagous arthropods.

  17. Effect of milk protein concentrate on lipid oxidation and formation of fishy volatiles in herring mince (Clupea harengus) during frozen storage.

    PubMed

    Joaquin, H J F; Tolasa, S; Oliveira, A C M; Lee, C M; Lee, K H

    2008-01-09

    The effect of milk protein concentrate (MPC) at 0, 2, 4, and 6% on lipid oxidation and volatile formation in frozen stored herring mince (-18 degrees C) was evaluated by analyzing samples at 0, 2, and 4 months for fatty acid composition, volatiles, and thiobarbituric acid reactive substances (TBARS). Sensory evaluation was also conducted to assess the intensity of fishy odor, and the volatiles were analyzed using static headspace gas chromatography-mass spectrometry (SHGC-MS). The addition of 4 and 6% MPC to herring mince resulted in a 33% and 50% reduction of TBARS, respectively, at month 4 and lessened the intensity of fishy odor throughout storage. However, MPC did not protect fatty acids from enzymatic degradation unless it was added immediately after mincing. Volatile analysis using SHGC-MS showed that 4% MPC was able to reduce headspace volatiles associated with fishy odor. MPC is most effective for reducing 4-heptenal, 3-methyl-1-butanol, 2-hexenal, and 1-penten-3-ol, which are known to be potent odorants associated with lipid oxidation.

  18. Volatile composition in raspberry cultivars grown in the Pacific Northwest determined by stir bar sorptive extraction-gas chromatography-mass spectrometry.

    PubMed

    Malowicki, Sarah M M; Martin, Robert; Qian, Michael C

    2008-06-11

    Twenty-nine volatile compounds in 'Chilliwack', 'Tulameen', 'Willamette', 'Yellow Meeker', and 'Meeker' raspberries were quantified using stir bar sorptive extraction (SBSE) paired with gas chromatography-mass spectrometry (GC-MS). Good correlation coefficients were obtained with most aroma-active compounds in raspberry, with quantification limits of 1 microg/kg. However, poor recoveries were observed for raspberry ketone and zingerone. Quantitative data showed that volatile concentrations varied for different cultivars. Large variations for alpha-ionone, beta-ionone, geraniol, linalool, and ( Z)-3-hexenol were observed in different raspberry cultivars. In addition, the volatile compositions in 'Meeker' raspberry grown at different locations also varied. The chiral isomeric ratios of raspberry ketone, alpha-ionone, alpha-pinene, linalool, terpinen-4-ol, delta-octalactone, delta-decalactone, and 6-methyl-5-hepten-2-ol were studied using a CyclosilB column. alpha-Ionone, alpha-pinene, delta-octalactone, and delta-decalactone had strong chiral isomeric preference, with more than 96% for one isomeric form. Much weaker chiral isomeric preference was observed for terpinen-4-ol, while linalool was almost a racemic mixture. Both growing locations and cultivars affect the isomeric ratio of linalool with a range of 37-51% for ( R)-linalool.

  19. Assessing the efficacy of candidate mosquito repellents against the background of an attractive source that mimics a human host.

    PubMed

    Menger, D J; Van Loon, J J A; Takken, W

    2014-12-01

    Mosquito repellents are used around the globe to protect against nuisance biting and disease-transmitting mosquitoes. Recently, there has been renewed interest in the development of repellents as tools to control the transmission of mosquito-borne diseases. We present a new bioassay for the accurate assessment of candidate repellent compounds, using a synthetic odour that mimics the odour blend released by human skin. Using DEET (N,N-diethyl-meta-toluamide) and PMD (p-menthane-3,8-diol) as reference compounds, nine candidate repellents were tested, of which five showed significant repellency to the malaria mosquito Anopheles gambiae sensu stricto (Diptera: Culicidae). These included: 2-nonanone; 6-methyl-5-hepten-2-one; linalool; δ-decalactone, and δ-undecalactone. The lactones were also tested on the yellow fever mosquito Aedes aegypti (Stegomyia aegypti) (Diptera: Culicidae), against which they showed similar degrees of repellency. We conclude that the lactones are highly promising repellents, particularly because these compounds are pleasant-smelling, natural products that are also present in human food sources. © 2014 The Royal Entomological Society.

  20. Chemical Analysis of Suspected Unrecorded Alcoholic Beverages from the States of São Paulo and Minas Gerais, Brazil

    PubMed Central

    Negri, Giuseppina; Soares Neto, Julino Assunção Rodrigues; de Araujo Carlini, Elisaldo Luiz

    2015-01-01

    Our study analyzed 152 samples of alcoholic beverages collected from the states of São Paulo and Minas Gerais, Brazil, using gas chromatography with flame ionization detection (GC-FID) and mass spectrometry (GC-MS), Fourier transform infrared spectroscopy (FT-IR), and inductively coupled plasma atomic emission spectrometry (ICP-AES). The methanol content varied from 20 to 180 ppm in 28 samples, and the limit of the accepted level of 200 ppm was exceeded in only one sample. High content of cyanide derivatives and ethyl carbamate, above the accepted level of 150 ppb, was observed in 109 samples. Carbonyl compounds were also observed in 111 samples, showing hydroxy 2-propanone, 4-methyl-4-hepten-3-one, furfural, and 2-hydroxyethylcarbamate as main constituents. Copper was found at concentrations above 5 ppm in 26 samples; the maximum value observed was 28 ppm. This work evaluated the human health risk associated with the poor quality of suspected unrecorded alcohols beverages. PMID:26495155

  1. Ozone-initiated chemistry in an occupied simulated aircraft cabin.

    PubMed

    Weschler, Charles J; Wisthaler, Armin; Cowlin, Shannon; Tamás, Gyöngyi; Strøm-Tejsen, Peter; Hodgson, Alfred T; Destaillats, Hugo; Herrington, Jason; Zhang, Junfeng; Nazaroff, William W

    2007-09-01

    We have used multiple analytical methods to characterize the gas-phase products formed when ozone was added to cabin air during simulated 4-hour flights that were conducted in a reconstructed section of a B-767 aircraft containing human occupants. Two separate groups of 16 females were each exposed to four conditions: low air exchange (4.4 (h-1)), <2 ppb ozone; low air exchange, 61-64 ppb ozone; high air exchange (8.8 h(-1)), <2 ppb ozone; and high air exchange, 73-77 ppb ozone. The addition of ozone to the cabin air increased the levels of identified byproducts from approximately 70 to 130 ppb at the lower air exchange rate and from approximately 30 to 70 ppb at the higher air exchange rate. Most of the increase was attributable to acetone, nonanal, decanal, 4-oxopentanal (4-OPA), 6-methyl-5-hepten-2-one (6-MHO), formic acid, and acetic acid, with 0.25-0.30 mol of quantified product volatilized per mol of ozone consumed. Several of these compounds reached levels above their reported odor thresholds. Most byproducts were derived from surface reactions with occupants and their clothing, consistent with the inference that occupants were responsible for the removal of >55% of the ozone in the cabin. The observations made in this study have implications for other indoor settings. Whenever human beings and ozone are simultaneously present, one anticipates production of acetone, nonanal, decanal, 6-MHO, geranyl acetone, and 4-OPA.

  2. First Characterisation of Volatile Organic Compounds Emitted by Banana Plants

    PubMed Central

    Berhal, Chadi; De Clerck, Caroline; Fauconnier, Marie-Laure; Levicek, Carolina; Boullis, Antoine; Kaddes, Amine; Jijakli, Haïssam M.; Verheggen, François; Massart, Sébastien

    2017-01-01

    Banana (Musa sp.) ranks fourth in term of worldwide fruit production, and has economical and nutritional key values. The Cavendish cultivars correspond to more than 90% of the production of dessert banana while cooking cultivars are widely consumed locally around the banana belt production area. Many plants, if not all, produce Volatile Organic Compounds (VOCs) as a means of communication with their environment. Although flower and fruit VOCs have been studied for banana, the VOCs produced by the plant have never been identified despite their importance in plant health and development. A volatile collection methodology was optimized to improve the sensitivity and reproducibility of VOCs analysis from banana plants. We have identified 11 VOCs for the Cavendish, mainly (E,E)-α-farnesene (87.90 ± 11.28 ng/μl), methyl salicylate (33.82 ± 14.29) and 6-methyl-5-hepten-2-one (29.60 ± 11.66), and 14 VOCs for the Pacific Plantain cultivar, mainly (Z,E)-α-farnesene (799.64 ± 503.15), (E,E)-α-farnesene (571.24 ± 381.70) and (E) β ocimene (241.76 ± 158.49). This exploratory study paves the way for an in-depth characterisation of VOCs emitted by Musa plants. PMID:28508885

  3. First Characterisation of Volatile Organic Compounds Emitted by Banana Plants.

    PubMed

    Berhal, Chadi; De Clerck, Caroline; Fauconnier, Marie-Laure; Levicek, Carolina; Boullis, Antoine; Kaddes, Amine; Jijakli, Haïssam M; Verheggen, François; Massart, Sébastien

    2017-05-16

    Banana (Musa sp.) ranks fourth in term of worldwide fruit production, and has economical and nutritional key values. The Cavendish cultivars correspond to more than 90% of the production of dessert banana while cooking cultivars are widely consumed locally around the banana belt production area. Many plants, if not all, produce Volatile Organic Compounds (VOCs) as a means of communication with their environment. Although flower and fruit VOCs have been studied for banana, the VOCs produced by the plant have never been identified despite their importance in plant health and development. A volatile collection methodology was optimized to improve the sensitivity and reproducibility of VOCs analysis from banana plants. We have identified 11 VOCs for the Cavendish, mainly (E,E)-α-farnesene (87.90 ± 11.28 ng/μl), methyl salicylate (33.82 ± 14.29) and 6-methyl-5-hepten-2-one (29.60 ± 11.66), and 14 VOCs for the Pacific Plantain cultivar, mainly (Z,E)-α-farnesene (799.64 ± 503.15), (E,E)-α-farnesene (571.24 ± 381.70) and (E) β ocimene (241.76 ± 158.49). This exploratory study paves the way for an in-depth characterisation of VOCs emitted by Musa plants.

  4. Identification of volatile compounds used in host location by the black bean aphid, Aphis fabae.

    PubMed

    Webster, Ben; Bruce, Toby; Dufour, Samuel; Birkemeyer, Claudia; Birkett, Michael; Hardie, Jim; Pickett, John

    2008-09-01

    Behavioral and electrophysiological responses of winged Aphis fabae to volatiles of faba bean, Vicia faba (var. Sutton dwarf), plants were studied and semiochemicals used in host location were identified. In olfactometer bioassays, aphids spent significantly more time in the region of the olfactometer where V. faba volatiles from an intact plant were present than in control regions with clean air. This response also occurred when an air entrainment sample of a V. faba plant was used as the odor source. Coupled gas chromatography-electroantennography revealed the presence of 16 electrophysiologically active compounds in the air entrainment sample. Fifteen of these were identified as (Z)-3-hexen-1-ol, 1-hexanol, (E)-2-hexenal, benzaldehyde, 6-methyl-5-hepten-2-one, octanal, (Z)-3-hexen-1-yl acetate, (R)-(-)-linalool, methyl salicylate, decanal, undecanal, (E)-caryophyllene, (E)-beta-farnesene, (S)-(-)-germacrene D, and (E,E,)-4,8,12-trimethyl-1,3,7,11-tridecatetraene. An olfactometer response was observed to a 15-component synthetic blend that comprised all identified compounds at the same concentration and ratio as in the natural sample, with the aphids spending significantly more time in the treated regions of the olfactometer where volatiles were present than in the control regions. These data are discussed in the context of insect host location and crop protection.

  5. Metal and precursor effect during 1-heptyne selective hydrogenation using an activated carbon as support.

    PubMed

    Lederhos, Cecilia R; Badano, Juan M; Carrara, Nicolas; Coloma-Pascual, Fernando; Almansa, M Cristina; Liprandi, Domingo; Quiroga, Mónica

    2013-01-01

    Palladium, platinum, and ruthenium supported on activated carbon were used as catalysts for the selective hydrogenation of 1-heptyne, a terminal alkyne. All catalysts were characterized by temperature programmed reduction, X-ray diffraction, transmission electron microscopy, and X-ray photoelectron spectroscopy. TPR and XPS suggest that the metal in all catalysts is reduced after the pretreatment with H2 at 673 K. The TPR trace of the PdNRX catalyst shows that the support surface groups are greatly modified as a consequence of the use of HNO3 during the catalyst preparation. During the hydrogenation of 1-heptyne, both palladium catalysts were more active and selective than the platinum and ruthenium catalysts. The activity order of the catalysts is as follows: PdClRX>PdNRX>PtClRX≫RuClRX. This superior performance of PdClRX was attributed in part to the total occupancy of the d electronic levels of the Pd metal that is supposed to promote the rupture of the H2 bond during the hydrogenation reaction. The activity differences between PdClRX and PdNRX catalysts could be attributed to a better accessibility of the substrate to the active sites, as a consequence of steric and electronic effects of the superficial support groups. The order for the selectivity to 1-heptene is as follows: PdClRX=PdNRX>RuClRX>PtClRX, and it can be mainly attributed to thermodynamic effects.

  6. Differentiation of the volatile profile of microbiologically contaminated canned tomatoes by dynamic headspace extraction followed by gas chromatography-mass spectrometry analysis.

    PubMed

    Bianchi, F; Careri, M; Mangia, A; Mattarozzi, M; Musci, M; Concina, I; Falasconi, M; Gobbi, E; Pardo, M; Sberveglieri, G

    2009-01-15

    The aromatic profile of microbiologically contaminated canned tomatoes was analyzed by the dynamic headspace extraction technique coupled with gas chromatography-mass spectrometry. Canned tomatoes contaminated with Escherichia coli, Saccharomyces cerevisiae and Aspergillus carbonarius were analyzed after 2 and 7 days. About 100 volatiles were detected, among which alcohols, aldehydes and ketones were the most abundant compounds. Gas chromatographic peak areas were used for statistical purposes. First, principal component analysis was carried out in order to visualize data trends and clusters. Then, linear discriminant analysis was performed in order to detect the set of volatile compounds ables to differentiate groups of analyzed samples. Five volatile compounds, i.e. ethanol, beta-myrcene, o-methyl styrene, 6-methyl-5-hepten-2-ol and 1-octanol, were found to be able to better discriminate between uncontaminated and contaminated samples. Prediction ability of the calculated model was estimated to be 100% by the "leave-one-out" cross-validation. An electronic nose device was then used to analyze the same contaminated and not contaminated canned tomato samples. Preliminary results were compared with those obtained by dynamic headspace gas chromatography-mass spectrometry, showing a good agreement.

  7. Quantitative analysis by GC-MS/MS of 18 aroma compounds related to oxidative off-flavor in wines.

    PubMed

    Mayr, Christine M; Capone, Dimitra L; Pardon, Kevin H; Black, Cory A; Pomeroy, Damian; Francis, I Leigh

    2015-04-08

    A quantitation method for 18 aroma compounds reported to contribute to "oxidative" flavor in wines was developed. The method allows quantitation of the (E)-2-alkenals ((E)-2-hexenal, (E)-2-heptenal, (E)-2-octenal, and (E)-2-nonenal), various Strecker aldehydes (methional, 2-phenylacetaldehyde, 3-methylbutanal, and 2-methylpropanal), aldehydes (furfural, 5-methylfurfural, hexanal, and benzaldehyde), furans (sotolon, furaneol, and homofuraneol), as well as alcohols (methionol, eugenol, and maltol) in the same analysis. The aldehydes were determined after derivatization directly in the wine with O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine hydrochloride; the formed oximes along with the underivatized aroma compounds were isolated by solid-phase extraction and analyzed by means of GC-MS/MS. The method was used to investigate the effect of different closures (synthetic closures, natural corks, and screw cap) on the formation of oxidation-related compounds in 14 year old white wine. Results showed a significant increase in the concentration of some of the monitored compounds in the wine, particularly methional, 2-phenylacetaldehyde, and 3-methylbutanal.

  8. Ozone removal by occupants in a classroom

    NASA Astrophysics Data System (ADS)

    Fischer, Andreas; Ljungström, Evert; Langer, Sarka

    2013-12-01

    Ozone concentrations were measured in a classroom with and without occupants, with the purpose to quantify effects on indoor O3 concentrations. The teacher and 24 11-year old pupils each removed O3 at a rate, first order in O3, corresponding to a rate constant of (2.5 ± 0.6) × 10-5 s-1 in the present locality and to a deposition velocity of 0.45 cm s-1. The O3-removal caused by the occupants was approximately 2.6 times larger than that of the available surfaces belonging to the classroom and its furniture. Observation of 6-methyl-5-hepten-2-one and 4-oxopentanal at maximum concentrations of 0.2 ppb and 0.7 ppb, respectively, suggested squalene from human skin oil as a reactive, ozone-consuming substance. There are indications of a source of 4-oxopentanal in the classroom, even some time after the pupils left for the day. The work presented is important for a proper description of indoor exposure, both to ozone itself and some of its reaction products when trying to quantify relations between exposure and health effects.

  9. Fate in digestion in vitro of several food components, including some toxic compounds coming from omega-3 and omega-6 lipids.

    PubMed

    Goicoechea, Encarnación; Brandon, Esther F A; Blokland, Marco H; Guillén, María D

    2011-01-01

    In this study it was proved the formation of oxygenated alpha,beta-unsaturated aldehydes (OαβUAs) of 6, 7, 9 and 10 carbon atoms during the thermal treatment (190°C with aeration) of a commercial vegetable oil rich in omega-3 and omega-6 acyl groups, which also contained small amounts of added proteins and carbohydrates to produce barbecue aroma when heated. The OαβUAs detected by Solid Phase Microextraction (SPME) followed by Gas Chromatography/Mass Spectrometry (GC/MS) were: 4-hydroxy-2-hexenal, 4-oxo-2-hexenal and 4,5-epoxy-2-heptenals, coming from omega-3 acyl groups; and 4-hydroxy-2-nonenal, 4-oxo-2-nonenal and 4,5-epoxy-2-decenals, coming from omega-6 acyl groups. Mixtures of this oil, either thermodegraded or not, with standard food were submitted to an in vitro digestion model. The study of the digestion products obtained revealed that OαβUAs remained unaltered, being bioaccessible in the gastrointestinal tract and so able to reach the systemic circulation. Besides, it was evidenced that during digestion Maillard, esterification and oxidation reactions take place. Copyright © 2010 Elsevier Ltd. All rights reserved.

  10. Odours of Plasmodium falciparum-infected participants influence mosquito-host interactions.

    PubMed

    de Boer, Jetske G; Robinson, Ailie; Powers, Stephen J; Burgers, Saskia L G E; Caulfield, John C; Birkett, Michael A; Smallegange, Renate C; van Genderen, Perry J J; Bousema, Teun; Sauerwein, Robert W; Pickett, John A; Takken, Willem; Logan, James G

    2017-08-24

    Malaria parasites are thought to influence mosquito attraction to human hosts, a phenomenon that may enhance parasite transmission. This is likely mediated by alterations in host odour because of its importance in mosquito host-searching behaviour. Here, we report that the human skin odour profile is affected by malaria infection. We compared the chemical composition and attractiveness to Anopheles coluzzii mosquitoes of skin odours from participants that were infected by Controlled Human Malaria Infection with Plasmodium falciparum. Skin odour composition differed between parasitologically negative and positive samples, with positive samples collected on average two days after parasites emerged from the liver into the blood, being associated with low densities of asexual parasites and the absence of gametocytes. We found a significant reduction in mosquito attraction to skin odour during infection for one experiment, but not in a second experiment, possibly due to differences in parasite strain. However, it does raise the possibility that infection can affect mosquito behaviour. Indeed, several volatile compounds were identified that can influence mosquito behaviour, including 2- and 3-methylbutanal, 3-hydroxy-2-butanone, and 6-methyl-5-hepten-2-one. To better understand the impact of our findings on Plasmodium transmission, controlled studies are needed in participants with gametocytes and higher parasite densities.

  11. Identification and Structure-Activity Relationships of a Novel Series of Estrogen Receptor Ligands Based on 7-Thiabicyclo[2.2.1]hept-2-ene-7-oxide1

    PubMed Central

    Wang, Pengcheng; Min, Jian; Nwachukwu, Jerome C.; Cavett, Valerie; Carlson, Kathryn E.; Guo, Pu; Zhu, Manghong; Zheng, Yangfan; Dong, Chune; Katzenellenbogen, John A.; Nettles, Kendall W.; Zhou, Hai-Bing

    2012-01-01

    To develop estrogen receptor (ER) ligands having novel structures and activities, we have explored compounds in which the central hydrophobic core has a more three-dimensional topology than typically found in estrogen ligands and thus exploit the unfilled space in the ligand-binding pocket. Here, we build upon our previous investigations of 7-oxabicyclo[2.2.1]heptene core ligands, by replacing the oxygen bridge with a sulfoxide. These new 7-thiabicyclo[2.2.1]hept-2-ene-7-oxides were conveniently prepared by a Diels-Alder reaction of 3,4-diarylthiophenes with dienophiles in the presence of an oxidant and give cycloadducts with endo stereochemistry. Several new compounds demonstrated high binding affinities with excellent ERα selectivity, but unlike oxabicyclic compounds, which are transcriptional antagonists, most thiabicyclic compounds are potent, ERα-selective agonists. Modeling suggests that the gain in activity of the thiabicyclic compounds arises from their endo stereochemistry that stabilizes an active ER conformation. Further, the disposition of methyl substituents in the phenyl groups attached to the bicyclic core unit contribute to their binding affinity and subtype selectivity. PMID:22283328

  12. Ozone and Ozone By-Products in the Cabins of Commercial Aircraft

    PubMed Central

    Weisel, Clifford; Weschler, Charles J.; Mohan, Kris; Vallarino, Jose; Spengler, John D.

    2013-01-01

    The aircraft cabin represents a unique indoor environment due to its high surface-to-volume ratio, high occupant density and the potential for high ozone concentrations at cruising altitudes. Ozone was continuously measured and air was sampled on sorbent traps, targeting carbonyl compounds, on 52 transcontinental U.S. or international flights between 2008 and 2010. The sampling was predominantly on planes that did not have ozone scrubbers (catalytic converters). Peak ozone levels on aircraft without catalytic convertors exceeded 100 ppb, with some flights having periods of more than an hour when the ozone levels were > 75ppb. Ozone was greatly reduced on relatively new aircraft with catalytic convertors, but ozone levels on two flights whose aircraft had older convertors were similar to those on planes without catalytic convertors. Hexanal, heptanal, octanal, nonanal, decanal and 6-methyl-5-hepten-2-one (6-MHO) were detected in the aircraft cabin at sub- to low ppb levels. Linear regression models that included the log transformed mean ozone concentration, percent occupancy and plane type were statistically significant and explained between 18 and 25% of the variance in the mixing ratio of these carbonyls. Occupancy was also a significant factor for 6-MHO, but not the linear aldehydes, consistent with 6-MHO’s formation from the reaction between ozone and squalene, which is present in human skin oils. PMID:23517299

  13. Effect of Fresh Garlic on Lipid Oxidation and Microbiological Changes of Pork Patties during Refrigerated Storage

    PubMed Central

    2014-01-01

    The effects of two levels (1.4 vs 2.8%) of fresh garlic on lipid oxidation and microbial growth in pork patties were evaluated. Hunter color (L, a, b), pH, thiobarbituric acid reactive substances (TBARS), oxidative volatile compounds, total bacteria and Enterobacteriaceae in the pork patties with or without fresh garlic were measured during storage at 4℃. Addition of fresh garlic decreased redness (a), while increased pH and yellowness (b) values of the fresh pork patties were observed, regardless of the levels added. The TBARS values of the pork patties were increased with the addition of fresh garlic (p<0.05). Similar results were observed in oxidative volatile compounds. A total of 13 volatile compounds were detected in the patties (5 sulfur-containing compounds, including allyl mercaptan, allyl methyl sulfide, diallyl sulfide, methyl-(E)-propenyl-disulfide, and diallyl disulfide, and the 8 other oxidative compounds, including 1-pentanol, hexanal, 1-hexanol, heptanal, (E)-2-heptenal, 1-octen-3-ol, (E)-2-octenal and nonanal). Fresh garlic accelerated development of oxidative products in the pork patties, especially hexanal and the total oxidative volatile compounds. However, the addition of 1.4 and 2.8% of fresh garlic inhibited the growth of total bacteria and Enterobacteriaceae, indicating low total bacterial counts and Enterobacteriaceae than the controls. PMID:26761498

  14. Volatile Organic Compound Emissions from Humans Indoors.

    PubMed

    Tang, Xiaochen; Misztal, Pawel K; Nazaroff, William W; Goldstein, Allen H

    2016-12-06

    Research on the sources of indoor airborne chemicals has traditionally focused on outdoor air, building materials, furnishings, and activities such as smoking, cooking, and cleaning. Relatively little research has examined the direct role of occupant emissions, even though this source clearly contributes to indoor volatile organic compounds (VOCs) and influences indoor chemistry. In this work, we quantify occupant-related gaseous VOC emissions in a university classroom using a proton-transfer-reaction time-of-flight mass spectrometer. Time-resolved concentrations of VOCs in room air and supply air were measured continuously during occupied and unoccupied periods. The emission factor for each human-emitted VOC was determined by dividing the occupant-associated source rate by the corresponding occupancy. Among the most abundant species detected were compounds associated with personal care products. Also prominent were human metabolic emissions, such as isoprene, methanol, acetone, and acetic acid. Additional sources included human skin oil oxidation by ozone, producing compounds such as 4-oxopentanal (4-OPA) and 6-methyl-5-hepten-2-one (6-MHO). By mass, human-emitted VOCs were the dominant source (57%) during occupied periods in a well-ventilated classroom, with ventilation supply air the second most important (35%), and indoor nonoccupant emissions the least (8%). The total occupant-associated VOC emission factor was 6.3 mg h(-1) per person.

  15. Determination of the adsorption model of alkenes and alcohols on sulfonic copolymer by inverse gas chromatography.

    PubMed

    Słomkiewicz, P M

    2004-04-23

    The determination of a number of adsorption sites on sulfonated styrene-divinylbenzene copolymer for alkenes (propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, isobutene, 2-methyl-1-butene, 2-methyl-2-butene, 2-methyl-1-pentene, 2-methyl-2-pentene and 2-methyl-2-hexene) and alcohols (methanol, ethanol and n-propanol, n-butanol, 2-butanol and tert-butanol) was performed by the saturation copolymer with vapors of adsorbate, by removing the excess of adsorbate from copolymer by blowing the inert gas through copolymer bed and by the desorption of adsorbed alcohol in the programmed increase of temperature. The adsorption measurements were performed on sulfonated ion-exchange resin (Amberlyst 15) with different concentrations of the acid group, which means with a varying number of adsorption sites. The following adsorption models for alkenes were suggested: the first in which one molecule of alkene is adsorbed by two sulfonic groups, for linear alcohols, the second in which one sulfonic group can adsorb one molecule of alcohol and for non-linear alcohols the third where one molecule of alcohol is adsorbed by two or more sulfonic groups.

  16. Kinetics of thermal gas-phase isomerizations and fragmentations of cis- and trans-1-(E)-propenyl-2-methylcyclobutanes at 275 degrees C.

    PubMed

    Baldwin, John E; Burrell, Richard C

    2002-05-17

    Kinetic studies of the thermal isomerization and fragmentation reactions exhibited by cis- and trans-1-(E)-propenyl-2-methylcyclobutanes at 275 degrees C in the gas phase have provided first-order rate constants for cis,trans interconversions of the cyclobutanes, 1,3-carbon migrations leading to 3,4- and 3,6-dimethylcyclohexenes, isomerizations providing directly and indirectly four acyclic dienes, and fragmentations to ethylene, propene, and mixtures of pentadienes and hexadienes. Both cis and trans isomers of 1-(E)-propenyl-2-methylcyclobutane form trans-3,4-dimethylcyclohexene faster than they are converted to cis-3,4-dimethylcyclohexene; the trans reactant gives rise to cis-3,6-dimethylcyclohexene in preference to its trans isomer, while the cis starting material gives neither at measurable rates; both form the relatively minor product 1,6-(Z)-octadiene. The rate constants derived from 35 kinetic runs starting with four distinct 1-(E)-propenyl-2-methylcyclobutane samples are consistent to within narrow error limits. The stereomutations, isomerizations, and fragmentations of the 1-(E)-propenyl-2-methylcyclobutanes are interpreted in terms of competitive processes involving conformationally flexible short-lived 2-(E)-octene-4,7-diyl and 3-methyl-5-(E)-heptene-1,4-diyl diradicals.

  17. Mechanistic Studies of Ethylene and α-Olefin Co-oligomerization Catalyzed by Chromium-PNP Complexes

    PubMed Central

    Do, Loi H.; Labinger, Jay A.; Bercaw, John E.

    2012-01-01

    To explore the possibility of producing a narrow distribution of mid- to long-chain hydrocarbons from ethylene as a chemical feedstock, co-oligomerization of ethylene and linear α-olefins (LAOs) was investigated, using a previously reported chromium complex, [CrCl3(PNPOMe)] (1, where PNPOMe = N,N-bis(bis(o-methoxyphenyl)phosphino)methylamine). Activation of 1 by treatment with modified methylaluminoxane (MMAO) in the presence of ethylene and 1-hexene afforded mostly C6 and C10 alkene products. The identities of the C10 isomers, assigned by detailed gas chromatographic and mass spectrometric analyses, strongly support a mechanism that involves five- and seven-membered metallacyclic intermediates comprising of ethylene and LAO units. Using 1-heptene as a mechanistic probe, it was established that 1-hexene formation from ethylene is competitive with formation of ethylene/LAO co-trimers, and that co-trimers derived from one ethylene and two LAO molecules are also generated. Complex 1/MMAO is also capable of converting 1-hexene to C12 dimers and C18 trimers, albeit with poor efficiency. The mechanistic implications of these studies are discussed and compared to previous reports of olefin co-trimerization. PMID:22904593

  18. Preparation of liposomal nanoparticles incorporating terbinafine in vitro drug release studies.

    PubMed

    Koutsoulas, Charalampos; Pippa, Natassa; Demetzos, Costas; Zabka, Marian

    2014-06-01

    Terbinafine hydrochloride (TBH) (E)-N-(6,6-dimethyl-2-hepten-4-inyl)-N-methyl-1-naphthaline-methanamine(-hydrochloride) is an effective antifungal agent already existing on the market in the form of topical formulations. The present study deals with the preparation and physicochemical characterization (size, polydispersity, zeta-potential) of 1,2-Diacyl-sn-glycero-3-phosphocholine (EggPC) incorporating TBH in two different dispersion media (tris-buffered saline (TBS) of pH 7.4 or in phosphate buffer solution (PS) of pH 5.5) in order to investigate how pH of dispersion media affects the incorporation efficiency of TBH into liposomes. There were further prepared three Carbopol 934 hydrogels of different concentrations (0.5, 1 and 2%) and their viscosity was measured and evaluated. Moreover, the in vitro drug release from three liposomal gels was studied, in order to investigate the ability of liposomes to act as carriers for TBH in a gel. All formulations were found to retain their original physicochemical properties at least for three weeks. These early studies on the release kinetics from liposomal gel show that Korsmeyer-Peppas model could be the best fitted model concerning the TBH release profile and could be supported biophysically from extended Derjaguin-Landau-Verwey-Overbeek (DLVO) theory.

  19. Suboptimal Larval Habitats Modulate Oviposition of the Malaria Vector Mosquito Anopheles coluzzii.

    PubMed

    Suh, Eunho; Choe, Dong-Hwan; Saveer, Ahmed M; Zwiebel, Laurence J

    2016-01-01

    Selection of oviposition sites by gravid females is a critical behavioral step in the reproductive cycle of Anopheles coluzzii, which is one of the principal Afrotropical malaria vector mosquitoes. Several studies suggest this decision is mediated by semiochemicals associated with potential oviposition sites. To better understand the chemosensory basis of this behavior and identify compounds that can modulate oviposition, we examined the generally held hypothesis that suboptimal larval habitats give rise to semiochemicals that negatively influence the oviposition preference of gravid females. Dual-choice bioassays indicated that oviposition sites conditioned in this manner do indeed foster significant and concentration dependent aversive effects on the oviposition site selection of gravid females. Headspace analyses derived from aversive habitats consistently noted the presence of dimethyl disulfide (DMDS), dimethyl trisulfide (DMTS) and 6-methyl-5-hepten-2-one (sulcatone) each of which unitarily affected An. coluzzii oviposition preference. Electrophysiological assays across the antennae, maxillary palp, and labellum of gravid An. coluzzii revealed differential responses to these semiochemicals. Taken together, these findings validate the hypothesis in question and suggest that suboptimal environments for An. coluzzii larval development results in the release of DMDS, DMTS and sulcatone that impact the response valence of gravid females.

  20. Analysis of volatile compounds from various types of barley cultivars.

    PubMed

    Cramer, Anne-Chrystelle J; Mattinson, D Scott; Fellman, John K; Baik, Byung-Kee

    2005-09-21

    We identified volatile compounds of barley flour and determined the variation in volatile compound profiles among different types and varieties of barley. Volatile compounds of 12 barley and two wheat cultivars were analyzed using solid phase microextraction (SPME) and gas chromatography. Twenty-six volatiles comprising aldehydes, ketones, alcohols, and a furan were identified in barley. 1-Octen-3-ol, 3-methylbutanal, 2-methylbutanal, hexanal, 2-hexenal, 2-heptenal, 2-nonenal, and decanal were identified as key odorants in barley as their concentration exceeded their odor detection threshold in water. Hexanal (46-1269 microg/L) and 1-pentanol (798-1811 microg/L) were the major volatile compounds in barley cultivars. In wheat, 1-pentanol (723-748 microg/L) was a major volatile. Hulled barley had higher total volatile, aldehyde, ketone, alcohol, and furan contents than hulless barley, highlighting the importance of the husk in barley grain aroma. The proanthocyanidin-free varieties generally showed higher total volatile and aldehyde contents than wild-type varieties, potentially due to decreased antioxidant activity by the absence of proanthocyanidins.

  1. Suboptimal Larval Habitats Modulate Oviposition of the Malaria Vector Mosquito Anopheles coluzzii

    PubMed Central

    Suh, Eunho; Choe, Dong-Hwan; Saveer, Ahmed M.; Zwiebel, Laurence J.

    2016-01-01

    Selection of oviposition sites by gravid females is a critical behavioral step in the reproductive cycle of Anopheles coluzzii, which is one of the principal Afrotropical malaria vector mosquitoes. Several studies suggest this decision is mediated by semiochemicals associated with potential oviposition sites. To better understand the chemosensory basis of this behavior and identify compounds that can modulate oviposition, we examined the generally held hypothesis that suboptimal larval habitats give rise to semiochemicals that negatively influence the oviposition preference of gravid females. Dual-choice bioassays indicated that oviposition sites conditioned in this manner do indeed foster significant and concentration dependent aversive effects on the oviposition site selection of gravid females. Headspace analyses derived from aversive habitats consistently noted the presence of dimethyl disulfide (DMDS), dimethyl trisulfide (DMTS) and 6-methyl-5-hepten-2-one (sulcatone) each of which unitarily affected An. coluzzii oviposition preference. Electrophysiological assays across the antennae, maxillary palp, and labellum of gravid An. coluzzii revealed differential responses to these semiochemicals. Taken together, these findings validate the hypothesis in question and suggest that suboptimal environments for An. coluzzii larval development results in the release of DMDS, DMTS and sulcatone that impact the response valence of gravid females. PMID:26900947

  2. Identification of human-derived volatile chemicals that interfere with attraction of the Scottish biting midge and their potential use as repellents.

    PubMed

    Logan, James G; Seal, Nicola J; Cook, James I; Stanczyk, Nina M; Birkett, Michael A; Clark, Suzanne J; Gezan, Salvador A; Wadhams, Lester J; Pickett, John A; Mordue, A Jennifer

    2009-03-01

    The Scottish biting midge, Culicoides impunctatus (Diptera: Ceratopogonidae), is a major pest in Scotland, causing a significant impact to the Scottish tourist and forestry industries. C. impunctatus is a generalist feeder, preferring to feed on large mammals, and is notorious for its attacks on humans. Until now, there was anecdotal evidence for differential attraction of female host-seeking C. impunctatus to individual human hosts, and the mechanism for this phenomenon was unknown. Using extracts of human odor collected by air entrainment, electroantennogram recordings to identify the physiologically active components, followed by behavioral assays, we show, for the first time, the differential attraction of female C. impunctatus to human odors and the chemical basis for this phenomenon. Certain chemicals, found in greater amounts in extracts that cause low attractiveness to midges, elicit a repellent effect in laboratory assays and repellency trials in the field. Differences in the production of these natural human-derived compounds could help to explain differential "attractiveness" between different human hosts. A mixture of two compounds in particular, 6-methyl-5-hepten-2-one and geranylacetone [(E)-6,10-dimethylundeca-5,9-dien-2-one], showed significant repellency (87, 77.4, 74.2, and 31.6% at hours 0, 1, 2, and 3, respectively) in the field and have the potential to be developed as novel repellents.

  3. Ion mobility spectrometry versus classical physico-chemical analysis for assessing the shelf life of extra virgin olive oil according to container type and storage conditions.

    PubMed

    Garrido-Delgado, Rocío; Dobao-Prieto, M Mar; Arce, Lourdes; Aguilar, Joaquín; Cumplido, José L; Valcárcel, Miguel

    2015-03-04

    An experimental study was conducted to assess the stability of a single-variety (Arbequina) extra virgin olive oil (EVOO) as a function of container type and storage conditions over a period of 11 months. EVOO quality was assessed by using ion mobility spectrometry (IMS), which provides increased simplicity, expeditiousness, and relative economy. The results were compared with the ones obtained by using the official method based on classical physico-chemical analysis. Bag-in-box, metal, dark glass, clear glass, and polyethylene terephthalate containers holding EVOO were opened on a periodic basis for sampling to simulate domestic use; in parallel, other containers were kept closed until analysis to simulate the storage conditions on market shelves. The results of the physico-chemical and instrumental analyses led to similar conclusions. Thus, samples packaged in bag-in-box containers preserved oil quality for 11 months, better than other container types. The HS-GC-IMS results confirm that 2-heptenal and 1-penten-3-one are two accurate markers of EVOO quality.

  4. Microbial production of aliphatic (S)-epoxyalkanes by using Rhodococcus sp. strain ST-10 styrene monooxygenase expressed in organic-solvent-tolerant Kocuria rhizophila DC2201.

    PubMed

    Toda, Hiroshi; Ohuchi, Takuya; Imae, Ryouta; Itoh, Nobuya

    2015-03-01

    We describe the development of biocatalysis for producing optically pure straight-chain (S)-epoxyalkanes using styrene monooxygenase of Rhodococcus sp. strain ST-10 (RhSMO). RhSMO was expressed in the organic solvent-tolerant microorganism Kocuria rhizophila DC2201, and the bioconversion reaction was performed in an organic solvent-water biphasic reaction system. The biocatalytic process enantioselectively converted linear terminal alkenes to their corresponding (S)-epoxyalkanes using glucose and molecular oxygen. When 1-heptene and 6-chloro-1-hexene were used as substrates (400 mM) under optimized conditions, 88.3 mM (S)-1,2-epoxyheptane and 246.5 mM (S)-1,2-epoxy-6-chlorohexane, respectively, accumulated in the organic phase with good enantiomeric excess (ee; 84.2 and 95.5%). The biocatalysis showed broad substrate specificity toward various aliphatic alkenes, including functionalized and unfunctionalized alkenes, with good to excellent ee. Here, we demonstrate that this biocatalytic system is environmentally friendly and useful for producing various enantiopure (S)-epoxyalkanes.

  5. Assessment of dominance hierarchy through urine scent marking and its chemical constituents in male blackbuck Antelope cervicapra, a critically endangered species.

    PubMed

    Rajagopal, Thangavel; Archunan, Govindaraju; Geraldine, Pitchairaj; Balasundaram, Chellam

    2010-09-01

    In ungulates the process of chemical communication by urinary scent marking has been directly related to reproductive dominance, territorial defense and proximity to resources. The differences in the frequency of urine marking and chemical composition of urine of males Antelope cervicapra before, during and after the dominance hierarchy period were assessed. The variations in the urine marking and its chemical profiles of dominant males (n=9), bachelors (n=5) and sub-adult males (n=5) were compared to find out how the dominance hierarchy influences the confined blackbuck herd under semi-natural captive conditions. The frequency of urine marking is significantly higher (p<0.001) in dominant males. Twenty-eight major constituents were identified in the urine of dominant males (before, during and after the dominance hierarchy period), bachelor and sub-adult males. Among these, three specific compounds namely, 3-hexanone (I), 6-methyl-5-hepten-2-one (II) and 4-methyl-3-heptanone (III) were seen only in dominant males urine during the dominance hierarchy period. Based on the behavioural observation and the unique chemical constituents in the urine, it is concluded that the dominant male scent odor suppresses aggression, scent marking, scent production and territorial patrolling activities of subordinate males, through which the dominant male establish their hierarchy and attains success in reproduction.

  6. Identification of characteristic flavour precursors from enzymatic hydrolysis-mild thermal oxidation tallow by descriptive sensory analysis and gas chromatography-olfactometry and partial least squares regression.

    PubMed

    Shi, Xiaoxia; Zhang, Xiaoming; Song, Shiqing; Tan, Chen; Jia, Chengsheng; Xia, Shuqin

    2013-01-15

    The "enzymatic hydrolysis-mild thermal oxidation" method was employed to obtain oxidized tallow. Nine beeflike flavours (BFs) were prepared through Maillard reaction with oxidized tallow and other ingredients. Volatile compounds of oxidized tallow and beeflike flavours were analysed by SPME/GC-MS. Six sensory attributes (meaty, beefy, tallowy, simulate, burnt and off-flavour) were selected to assess BFs. Thirty four odour-active compounds were identified to represent beef odour through GC-O analysis based on detection frequency method. GC-MS profiles of oxidized tallow were correlated with GC-O responses and sensory attributes of BFs using partial least squares regression modelling (PLSR). Twenty nine compounds were considered as the potential precursors of oxidized tallow. Among them, tetradecanoic acid, d-limonene, 1,7-heptandiol, 2-butyltetrahydrofuran, (Z)-4-undecenal, (Z)-4-decenal, (E)-4-nonenal and 5-pentyl-2(3H)-furanone were unique products generated from enzymatic hydrolysis-mild thermal oxidation of tallow, while hexanal, heptanal, octanal, nonanal, decanal, pentanal, acetic acid, butanoic acid, hexanoic acid, 1-heptanol, 1-octanol, 3-methylbutanal, 2-pentylfuran, γ-nonalactone, 2-undecenal, (E,E)-2,4-decadienal, (E,E)-2,4-nonadienal, (E)-2-nonenal, (E)-2-octenal, (E)-2-decenal and (Z)-2-heptenal were common products generated from thermal oxidation of tallow.

  7. Protective effect of phenolic compounds on carbonyl-amine reactions produced by lipid-derived reactive carbonyls.

    PubMed

    Hidalgo, Francisco J; Delgado, Rosa M; Zamora, Rosario

    2017-08-15

    The degradation of phenylalanine initiated by 2-pentenal, 2,4-heptadienal, 4-oxo-2-pentenal, 4,5-epoxy-2-heptenal, or 4,5-epoxy-2-decenal in the presence of phenolic compounds was studied to determine the structure-activity relationship of phenolic compounds on the protection of amino compounds against modifications produced by lipid-derived carbonyls. The obtained results showed that flavan-3-ols were the most efficient phenolic compounds followed by single m-diphenols. The effectiveness of these compounds was found to be related to their ability to trap rapidly the carbonyl compound, avoiding in this way the reaction of the carbonyl compound with the amino acid. The ability of flavan-3-ols for this reaction is suggested to be related to the high electronic density existing in some of the aromatic carbons of their ring A. This is the first report showing that carbonyl-phenol reactions involving lipid-derived reactive carbonyls can be produced more rapidly than carbonyl-amine reactions, therefore providing a satisfactory protection of amino compounds.

  8. Electrophysiological and behavioral responses of male fall webworm moths (Hyphantria cunea) to Herbivory-induced mulberry (Morus alba) leaf volatiles.

    PubMed

    Tang, Rui; Zhang, Jin Ping; Zhang, Zhong Ning

    2012-01-01

    Volatile organic compounds (VOCs) were collected from damaged and intact mulberry leaves (Morus alba L., Moraceae) and from Hyphantria cunea larvae by headspace absorption with Super Q columns. We identified their constituents using gas chromatography-mass spectrometry, and evaluated the responses of male H. cunea antennae to the compounds using gas chromatography-flame ionization detection coupled with electroantennographic detection. Eleven VOC constituents were found to stimulate antennae of male H. cunea moths: β-ocimene, hexanal, cis-3-hexenal, limonene, trans-2-hexenal, cyclohexanone, cis-2-penten-1-ol, 6-methyl-5-hepten-2-one, 4-hydroxy-4-methyl-2-pentanone, trans-3-hexen-1-ol, and 2,4-dimethyl-3-pentanol. Nine of these chemicals were released by intact, mechanically-damaged, and herbivore-damaged leaves, while cis-2-penten-1-ol was released only by intact and mechanically-damaged leaves and β-ocimene was released only by herbivore-damaged leaves. Results from wind tunnel experiments conducted with volatile components indicated that male moths were significantly more attracted to herbivory-induced volatiles than the solvent control. Furthermore, male moths' attraction to a sex pheromone lure was increased by herbivory-induced compounds and β-ocimene, but reduced by cis-2-penten-1-ol. A proof long-range field trapping experiment showed that the efficiency of sex pheromone lures in trapping male moths was increased by β-ocimene and reduced by cis-2-penten-1-ol.

  9. Detection of fungal development in closed spaces through the determination of specific chemical targets.

    PubMed

    Moularat, Stéphane; Robine, Enric; Ramalho, Olivier; Oturan, Mehmet A

    2008-05-01

    In addition to the biodegradation problems encountered in buildings, exposure of their occupants to moulds is responsible for numerous diseases: infections (invasive nosocomial aspergillosis), immediate or delayed allergies, food-borne infections and different types of irritation. In this context, the aim of our work has been to determine specific chemical tracers for fungal development on construction materials. More generally, by detecting a specific chemical fingerprint of fungal development, our objective was to propose a microbiological alert system which could control systems and/or procedures for the microbiological treatment of indoor areas. We therefore characterized the chemical emissions from six types of construction material contaminated artificially by moulds. Chemical fingerprints were established for 19 compounds arising specifically from fungal metabolism: 2-ethylhexanoic acid methyl ester, 1-octen-3-ol, 3-heptanol, 3-methyl-1-butanol, 2-methyl-1-butanol, 1,3-octadiene, 2-(5H)-furanone, 2-heptene, alpha-pinene, 2-methylisoborneol, 4-heptanone, 2-methylfuran, 3-methylfuran, dimethyldisulfide, methoxybenzene, a terpenoid and three sesquiterpenes. Determining the origin of these compounds and their specific links with a growth substrate or fungal species made it possible to judge the pertinence of choosing these compounds as tracers. Thus the detecting specific volatile organic compounds emitted as from the second day of fungal growth demonstrated that this approach had the advantage of detecting fungal development both reliably and rapidly before any visible signs of contamination could be detected.

  10. Substrate promiscuity of RdCCD1, a carotenoid cleavage oxygenase from Rosa damascena.

    PubMed

    Huang, Fong-Chin; Horváth, Györgyi; Molnár, Péter; Turcsi, Erika; Deli, József; Schrader, Jens; Sandmann, Gerhard; Schmidt, Holger; Schwab, Wilfried

    2009-03-01

    Several of the key flavor compounds in rose essential oil are C(13)-norisoprenoids, such as beta-damascenone, beta-damascone, and beta-ionone which are derived from carotenoid degradation. To search for genes putatively responsible for the cleavage of carotenoids, cloning of carotenoid cleavage (di-)oxygenase (CCD) genes from Rosa damascena was carried out by a degenerate primer approach and yielded a full-length cDNA (RdCCD1). The RdCCD1 gene was expressed in Escherichia coli and recombinant protein was assayed for its cleavage activity with a multitude of carotenoid substrates. The RdCCD1 protein was able to cleave a variety of carotenoids at the 9-10 and 9'-10' positions to produce a C(14) dialdehyde and two C(13) products, which vary depending on the carotenoid substrates. RdCCD1 could also cleave lycopene at the 5-6 and 5'-6' positions to produce 6-methyl-5-hepten-2-one. Expression of RdCCD1 was studied by real-time PCR in different tissues of rose. The RdCCD1 transcript was present predominantly in rose flower, where high levels of volatile C(13)-norisoprenoids are produced. Thus, the accumulation of C(13)-norisoprenoids in rose flower is correlated to the expression of RdCCD1.

  11. Emission rates of selected volatile organic compounds from skin of healthy volunteers.

    PubMed

    Mochalski, Paweł; King, Julian; Unterkofler, Karl; Hinterhuber, Hartmann; Amann, Anton

    2014-05-15

    Gas chromatography with mass spectrometric detection (GC-MS) coupled with solid phase micro-extraction as pre-concentration method (SPME) was applied to identify and quantify volatile organic compounds (VOCs) emitted by human skin. A total of 64 C4-C10 compounds were quantified in skin emanation of 31 healthy volunteers. Amongst them aldehydes and hydrocarbons were the predominant chemical families with eighteen and seventeen species, respectively. Apart from these, there were eight ketones, six heterocyclic compounds, six terpenes, four esters, two alcohols, two volatile sulphur compounds, and one nitrile. The observed median emission rates ranged from 0.55 to 4,790 fmol cm(-2)min(-1). Within this set of analytes three volatiles; acetone, 6-methyl-5-hepten-2-one, and acetaldehyde exhibited especially high emission rates exceeding 100 fmol cm(-2)min(-1). Thirty-three volatiles were highly present in skin emanation with incidence rates over 80%. These species can be considered as potential markers of human presence, which could be used for early location of entrapped victims during Urban Search and Rescue Operations (USaR).

  12. Cytotoxicity and genotoxicity in human lung epithelial A549 cells caused by airborne volatile organic compounds emitted from pine wood and oriented strand boards.

    PubMed

    Gminski, Richard; Tang, Tao; Mersch-Sundermann, Volker

    2010-06-16

    Due to the massive reduction of air-change rates in modern, energy-saving houses and dwellings, the contribution of volatile organic compound (VOCs) emissions from wood-based materials to indoor air quality has become increasingly important. To evaluate toxicity of VOC mixtures typically emitted from pine wood and oriented strand boards (OSB) and their main constituents (selected terpenes and aldehydes), cytotoxicity and genotoxicity were investigated in human A549 lung cells. To facilitate exposure directly via gas phase, a 250 L emission chamber was combined with a Vitrocell exposure system. VOC exposure concentrations were measured by GC/MSD. Biological effects were determined after an exposure time of 1h by measuring cytotoxicity (erythrosine B staining) and genotoxicity (comet assay). Neither cytotoxic nor genotoxic effects were observed for VOC mixtures emitted from pine wood or OSB at loading factors of approximately 13 m(2)/m(3) (worst case conditions) of the panels (with maximum VOC levels of about 80 mg/m(3)) in comparison to clean air. While alpha-pinene and Delta(3)-carene did not induce toxic effects even at exposure concentrations of up to 1800 mg/m(3) and 600 mg/m(3), respectively, hexanal showed a cytotoxic effect at 2000 mg/m(3). The alpha,beta-unsaturated aldehydes 2-heptenal and 2-octenal caused genotoxic effects in concentrations exceeding 100mg/m(3) and 40 mg/m(3), respectively. In conclusion, high concentrations of VOCs and VOC mixtures emitted from pine wood and OSB did not lead to adverse effects in A549 human lung cells even at concentrations 10(2) to 10(5)-fold higher than those found in normal indoor air. Attention must be paid to mutagenic and possibly carcinogenic alpha,beta-unsaturated aldehydes.

  13. Chemical structures of low-pressure premixed methylcyclohexane flames as benchmarks for the development of a predictive combustion chemistry model

    DOE PAGES

    Skeen, Scott A.; Yang, Bin; Jasper, Ahren W.; ...

    2011-11-14

    The chemical compositions of three low-pressure premixed flames of methylcyclohexane (MCH) are investigated with the emphasis on the chemistry of MCH decomposition and the formation of aromatic species, including benzene and toluene. The flames are stabilized on a flat-flame (McKenna type) burner at equivalence ratios of φ = 1.0, 1.75, and 1.9 and at low pressures between 15 Torr (= 20 mbar) and 30 Torr (= 40 mbar). The complex chemistry of MCH consumption is illustrated in the experimental identification of several C7H12, C7H10, C6H12, and C6H10 isomers sampled from the flames as a function of distance from the burner.more » Three initiation steps for MCH consumption are discussed: ring-opening to heptenes and methyl-hexenes (isomerization), methyl radical loss yielding the cyclohexyl radical (dissociation), and H abstraction from MCH. Mole fraction profiles as a function of distance from the burner for the C7 species supplemented by theoretical calculations are presented, indicating that flame structures resulting in steeper temperature gradients and/or greater peak temperatures can lead to a relative increase in MCH consumption through the dissociation and isomerization channels. Trends observed among the stable C6 species as well as 1,3-pentadiene and isoprene also support this conclusion. Relatively large amounts of toluene and benzene are observed in the experiments, illustrating the importance of sequential H-abstraction steps from MCH to toluene and from cyclohexyl to benzene. Furthermore, modeled results using the detailed chemical model of Pitz et al. (Proc. Combust. Inst.2007, 31, 267–275) are also provided to illustrate the use of these data as a benchmark for the improvement or future development of a MCH mechanism.« less

  14. Origins of volatile organic compounds emerging from tank 241-C-106 during sluicing

    SciTech Connect

    STAUFFER, L.A.

    1999-06-02

    Unexpectedly high concentrations of inorganic gases and volatile organic compounds (VOC) were released from the ventilation stack of tank 241-C-106 during sluicing operations on November 18, 1998. Workers experienced serious discomfort. They reported an obnoxious acrid odor and the 450 ppm VOC in ventilation stack 296-C-006 exceeded the level approved in the air discharge permit. Consequently, the operation was terminated. Subsequent analyses of samples collected opportunistically from the stack indicated many organic compounds including heptenes, heptanones, and normal paraffin hydrocarbons (NPH) and their remnants were present. Subsequently, a process test designed to avoid unnecessary worker exposure and enable collection of analytical samples from the stack, the breathing area, and the receiver tank was conducted on December 16, 1998. The samples obtained during that operation, in which the maximum VOC content of the stack was approximately 35 ppm, have been analyzed by teams at Pacific Northwest National Laboratory and Special Analytic Services (SAS). This report examines the results of these investigations. Future revisions of the report will examine the analytical results obtained for samples collected during sluicing operations in March. This report contains the available evidence about the source term for these emissions. Chapter 2 covers characterization work, including historical information about the layers of waste in the tank, the location of organic compounds in these layers, the total organic carbon (TOC) content and the speciation of organic compounds. Chapter 3 covers the data for the samples from the ventilation stack, which has the highest concentrations of organic compounds. Chapter 4 contains an interpretation of the information connecting the composition of the organic emissions with the composition of the original source term. Chapter 5 summarizes the characterization work, the sample data, and the interpretation of the results.

  15. Structural elucidation of chemical constituents from Benincasa hispida seeds and Carissa congesta roots by gas chromatography: Mass spectroscopy

    PubMed Central

    Doshi, Gaurav M.; Nalawade, Vivek V.; Mukadam, Aaditi S.; Chaskar, Pratip K.; Zine, Sandeep P.; Somani, Rakesh R.; Une, Hemant D.

    2015-01-01

    Background: Benincasa hispida (BH) and Carissa congesta (CC) are regarded as ethnopharmacological imperative plants in Asian countries. Objective: Phytochemical screening of the extracts has shown the presence of steroids, flavonoids, saponins, glycosides, tannins, phenolic compounds, fixed oils, and fats in the BH and CC extracts. The presence of lupeol has been reported previously by us using high-performance thin-layer chromatography and high-performance liquid chromatography. Materials and Methods: Present research studies encompasses identification of chemical constituents in BH seeds and CC roots petroleum ether extracts by hyphenated technique such as gas chromatography-mass spectroscopy (MS) which when coupled gives a clear insight of constituents. Results: The components were identified by matching mass spectra with MS libraries. There were 13 and 10 different compounds analyzed from CC and BH, respectively. The components present were Pentanoic acid, 5-hydroxy, 2,4-butylphenyl; n-Hexadecanoic acid (Palmitic acid); Sulfurous acid, 2-ethylhexylhepatdecyl ester; n-Tridecane; 6-methyltridecane; (9E, 12E)-9,12-Octadecadienyl chloride, Hexadecanoic acid, 3-(trimethylsilyl)-oxy] propyl ester; 9,12-Octadecadenoic acid, 2 hydroxy-1-(hyroxymethylethyl) ester; 9,12-Octadecadienoic acid, 2,3 dihydroxypropyl ester; n-Propyl-9,12-Octadecadienoate, Lupeol; Taraxasterol; 6a, 14a-Methanopicene, perhydro-12,4a, 61a, 9,9,12a-hepatmethyl-10-hydoxy and 9-Octadecene; 2-Isoprpenyl-5-methyl-6-hepten-1-ol; n-Hexadecanoic acid, 2-hyroxy-1-(hydroxymethyl) ethyl ether; Butyl-9,12-Octadecadieonate; Friedoolean-8-en-3-one; friedours-7-en-3-one; 13,27-Cyclosuran-3-one; Stigmaste-7,25-dien-3-ol (3β, 5α); Stigmasta-7,16-dien-3-ol; chrondrillasterol in BH seeds and CC roots extracts respectively. Conclusion: Eluted components from the extracts could provide further researchers to work with various pharmacological activities related models and studies. PMID:26130941

  16. Chemical structures of low-pressure premixed methylcyclohexane flames as benchmarks for the development of a predictive combustion chemistry model

    SciTech Connect

    Skeen, Scott A.; Yang, Bin; Jasper, Ahren W.; Pitz, William J.; Hansen, Nils

    2011-11-14

    The chemical compositions of three low-pressure premixed flames of methylcyclohexane (MCH) are investigated with the emphasis on the chemistry of MCH decomposition and the formation of aromatic species, including benzene and toluene. The flames are stabilized on a flat-flame (McKenna type) burner at equivalence ratios of φ = 1.0, 1.75, and 1.9 and at low pressures between 15 Torr (= 20 mbar) and 30 Torr (= 40 mbar). The complex chemistry of MCH consumption is illustrated in the experimental identification of several C7H12, C7H10, C6H12, and C6H10 isomers sampled from the flames as a function of distance from the burner. Three initiation steps for MCH consumption are discussed: ring-opening to heptenes and methyl-hexenes (isomerization), methyl radical loss yielding the cyclohexyl radical (dissociation), and H abstraction from MCH. Mole fraction profiles as a function of distance from the burner for the C7 species supplemented by theoretical calculations are presented, indicating that flame structures resulting in steeper temperature gradients and/or greater peak temperatures can lead to a relative increase in MCH consumption through the dissociation and isomerization channels. Trends observed among the stable C6 species as well as 1,3-pentadiene and isoprene also support this conclusion. Relatively large amounts of toluene and benzene are observed in the experiments, illustrating the importance of sequential H-abstraction steps from MCH to toluene and from cyclohexyl to benzene. Furthermore, modeled results using the detailed chemical model of Pitz et al. (Proc. Combust. Inst.2007, 31, 267–275) are also provided to illustrate the use of these data as a benchmark for the improvement or future development of a MCH mechanism.

  17. Semi-field evaluation of several novel alkenol analogs of 1-octen-3-ol as attractants to adult Aedes albopictus and Culex quinquefasciatus.

    PubMed

    Cilek, J E; Ikediobi, C O; Hallmon, C F; Johnson, R; Onyeozili, E N; Farah, S M; Mazu, T; Latinwo, L M; Ayuk-Takem, L; Berniers, U R

    2011-09-01

    The compound 1-octen-3-ol is a known attractant of some mosquito species, which has led to the hypothesis that olfactory stimulation by this alkenol may be associated with the following structural elements: a terminal site of unsaturation or high electron density; a structural capability for hydrogen bonding, e.g., -OH, -NH2, NHR, NR2, etc.; a saturated hydrocarbon chain of a certain minimum length; and a certain relative distance between the region of high electron density and the alcohol (or other hydrogen-bonding) functional group. Using this logic, we synthesized 20 alkenol analogs based on the octenol double-bonded carbon skeleton. The attraction of female Aedes albopictus and Culex quinquefasciatus to these analogs was compared with 1-octen-3-ol as a standard in semi-field trials. For both species, collections from Mosquito Magnet-X (MMX) suction traps baited with the alkenol analogs in the absence of carbon dioxide were not significantly different from octenol-only baited traps, with the exception of (Z)-3-hepten-1-ol which collected significantly more Ae. albopictus. In the presence of CO2, most of the collections from traps baited with an alkenol were considerably increased for both species but not different from octenol plus CO2, with the exception of Ae. albopictus where (Z)-3-decen-1-ol, (Z)-4-hexen-1-ol, 7-octen-2-ol, and 8-nonen-3-ol significantly depressed trap catches. Although no clearly identifiable structure-activity relationship could be determined from our collected data, we did find that MMX traps baited with carbon dioxide and 4-penten-2-ol or (E)-2-decen-4-ol significantly enhanced Cx. quinquefasciatus collections up to nearly 3-fold compared with octenol plus carbon dioxide.

  18. Metabolism of 4-Hydroxy-7-oxo-5-heptenoic Acid (HOHA) Lactone by Retinal Pigmented Epithelial Cells.

    PubMed

    Wang, Hua; Linetsky, Mikhail; Guo, Junhong; Yu, Annabelle O; Salomon, Robert G

    2016-07-18

    4-Hydroxy-7-oxo-5-heptenic acid (HOHA)-lactone is a biologically active oxidative truncation product released (t1/2 = 30 min at 37 °C) by nonenzymatic transesterification/deacylation from docosahexaenoate lipids. We now report that HOHA-lactone readily diffuses into retinal pigmented epithelial (RPE) cells where it is metabolized. A reduced glutathione (GSH) Michael adduct of HOHA-lactone is the most prominent metabolite detected by LC-MS in both the extracellular medium and cell lysates. This molecule appeared inside of ARPE-19 cells within seconds after exposure to HOHA-lactone. The intracellular level reached a maximum concentration at 30 min and then decreased with concomitant increases in its level in the extracellular medium, thus revealing a unidirectional export of the reduced GSH-HOHA-lactone adduct from the cytosol to extracellular medium. This metabolism is likely to modulate the involvement of HOHA-lactone in the pathogenesis of human diseases. HOHA-lactone is biologically active, e.g., low concentrations (0.1-1 μM) induce secretion of vascular endothelial growth factor (VEGF) from ARPE-19 cells. HOHA-lactone is also a precursor of 2-(ω-carboxyethyl)pyrrole (CEP) derivatives of primary amino groups in proteins and ethanolamine phospholipids that have significant pathological and physiological relevance to age-related macular degeneration (AMD), cancer, and wound healing. Both HOHA-lactone and the derived CEP can contribute to the angiogenesis that defines the neovascular "wet" form of AMD and that promotes the growth of tumors. While GSH depletion can increase the lethality of radiotherapy, because it will impair the metabolism of HOHA-lactone, the present study suggests that GSH depletion will also increase levels of HOHA-lactone and CEP that may promote recurrence of tumor growth.

  19. Identification of host kairomones from maize, Zea mays, for the maize weevil, Sitophilus zeamais.

    PubMed

    Ukeh, Donald A; Woodcock, Christine M; Pickett, John A; Birkett, Michael A

    2012-11-01

    The maize weevil, Sitophilus zeamais, is an economically important pest of stored grains in tropical and subtropical regions of the world. The behavioral responses of adult S. zeamais to volatile organic compounds (VOCs) from maize seeds, Zea mays, were studied to identify semiochemicals used in host location and provide potential tools for managing this pest. VOCs released directly from crude seed extracts, vacuum distilled extracts, hexane and diethyl ether fractions from silica gel chromatography of the vacuum distillates, air entrainment samples, and identified volatile compounds were assayed using a Perspex four-arm olfactometer. Weevils spent significantly more time, and made a higher number of visits, to the region of the olfactometer where Z. mays volatiles were present than in control regions comprising solvent only. When white and yellow Z. mays VOCs were compared in a choice test, the mean time spent in the two olfactometer treatment arms was significantly greater than the mean time spent in the control arms. However, weevils did not show any preference for either of the two treatments, thus demonstrating that both varieties of maize have similar activity. Gas chromatography (GC), coupled gas chromatography-mass spectrometry (GC-MS), GC peak enhancement and electroantennography (EAG) identified hexanal, (E)-2-heptenal, and octanal as biologically active compounds in air entrainment samples and diethyl ether fractions of vacuum distillates. A 3-component synthetic blend of the identified compounds was significantly attractive to both sexes of the weevil. These host kairomones could be deployed in semiochemical based monitoring and management of S. zeamais in the tropics.

  20. Response of the aphid parasitoid Aphidius funebris to volatiles from undamaged and aphid-infested Centaurea nigra.

    PubMed

    Pareja, Martín; Moraes, Maria C B; Clark, Suzanne J; Birkett, Michael A; Powell, Wilf

    2007-04-01

    Two issues have hindered the understanding of the ecology and evolution of volatile-mediated tritrophic interactions: few studies have addressed noncrop systems; and few statistical techniques have been applied that are suitable for the analysis of complex volatile blends. In this paper, we addressed both of these issues by studying the noncrop system involving the plant Centaurea nigra, the specialist aphid Uroleucon jaceae, and the parasitoid Aphidius funebris. In a Y-tube olfactometer, A. funebris was attracted to the odor from undamaged C. nigra, but preferred the plant-host complex (PHC) after 3 d of feeding by 200 U. jaceae over the undamaged plant, but not after three or 5 d of feeding by 50 U. jaceae. When aphids were removed, the initial preference for the damaged plant remained, but the final preference was not greater than for the undamaged plant. No qualitative differences were detected between the headspaces of C. nigra and the C. nigra-U. jaceae PHC. For quantitative analysis, we used a compositional approach, which treats each compound produced as part of a blend, and not as a compound released in isolation, thus allowing analysis of the relative contribution of each compound to the blend as a whole. With this approach, subtle increases and decreases of some green leaf volatiles and monoterpenoids on the third day of aphid infestation were detected. Mechanically damaged C. nigra had a volatile profile that differed from undamaged C. nigra and the PHC. One and 10 ng of (Z)-3-hexenyl acetate, and 10 or 100 ng of 6-methyl-5-hepten-2-one were attractive to the parasitoid when placed in solution on filter paper. A. funebris appears to be using a combination of chemical cues to locate host-infested plants.

  1. Characterization of the key odorants in raw Italian hazelnuts ( Corylus avellana L. var. Tonda Romana) and roasted hazelnut paste by means of molecular sensory science.

    PubMed

    Burdack-Freitag, Andrea; Schieberle, Peter

    2012-05-23

    The concentrations of 19 odorants, recently characterized by GC-olfactometry and aroma extract dilution analysis as the most odor-active compounds in raw hazelnuts, were quantitated by stable isotope dilution assays (SIDA). Calculation of odor activity values (OAV) on the basis of odor thresholds in oil revealed high OAVs, in particular for linalool, 5-methyl-4-heptanone, 2-methoxy-3,5-dimethylpyrazine, and 4-methylphenol. A model mixture in sunflower oil containing the 13 odorants showing OAVs above 1 in their natural concentrations resulted in a good similarity compared to the overall nut-like, fruity aroma of the raw hazelnuts. Quantitation of the 25 most odor-active compounds in roasted hazelnut paste by SIDA showed clear changes in the concentrations of most odorants, and formation of new odor-active compounds induced by the roasting process was observed. The highest OAVs were calculated for 3-methylbutanal (malty), 2,3-pentanedione (buttery), 2-acetyl-1-pyrroline (popcorn), and (Z)-2-nonenal (fatty), followed by dimethyl trisulfide, 2-furfurylthiol, 2,3-butanedione, and 4-hydroxy-2,5-dimethyl-3(2H)-furanone. The aroma of a model mixture containing the 19 odorants with OAVs above 1 in their actual concentrations in the roasted nut material was judged to elicit a very good similarity to the popcorn-like, coffee-like, and sweet-smoky aroma of the roasted hazelnut paste. New SIDAs were developed for the quantitation of 5-methyl-4-heptanone, 5-methyl-(E)-2-hepten-4-one, 2-thenylthiol, and 3,5,5-trimethyl-2(5H)-furanone.

  2. The difference in effect of mGlu2/3 and mGlu5 receptor agonists on cognitive impairment induced by MK-801.

    PubMed

    Vales, Karel; Svoboda, Jan; Benkovicova, Kristina; Bubenikova-Valesova, Vera; Stuchlik, Ales

    2010-08-10

    The manipulation of glutamate neurotransmission could represent a potential strategy for the pharmacotherapy of schizophrenic symptoms. Preclinical studies suggest that two subtypes of metabotropic glutamate (mGlu) receptors such as mGlu2/3 and mGlu5 receptors have the potential to ameliorate deficits in schizophrenia. In our study we evaluated the role of a non-specific mGlu receptor agonist ((1S,3R)-1-aminocyclopentane-1,3-dicarboxylic acid; 1S,3R-ACPD), mGlu5 receptor agonist or positive modulators ((RS)-2-Chloro-5-hydroxyphenylglycine;CHPG; [(3-Fluoro-phenyl)methylene]hydrazone-3-fluorobenzaldehyde; DFB; 3-Cyano-N-(1,3-diphenyl-1H-pyrazol-5-yl)benzamide; CDPPB) and a mGlu2/3 receptor agonist (2,2,2-Trifluoro-N-[4-(2-methoxyphenoxy)phenyl]-N-(3-pyrdinylmethyl)ethanesulfonamide hydrochloride; LY-487379) on performance in a cognitive task (Active Allothetic Place Avoidance) after sub-chronic administration of 5R,10S)-(+)-5-methyl-10,11-dihydro-5H-dibenzo(a,d)-cyclo-hepten-5,10-imine; MK-801 . The Active Allothetic Place Avoidance task is suitable for assessing the executive function and attention of animals and was previously validated for testing the effect of anti-psychotics. Application of the mGlu2/3 receptor agonist had no effect on cognitive impairment induced by MK-801. However, the mGlu5 receptor agonists ameliorated cognitive impairment induced by MK-801 without affecting locomotion. In conclusion, the mGlu5 receptor agonists could be effective in the treatment of cognitive deficits in patients with schizophrenia. However, the pro-cognitive effect of the agonist of mGlu2/3 receptors was not demonstrated in the present study. Copyright (c) 2010 Elsevier B.V. All rights reserved.

  3. Bicyclic core estrogens as full antagonists: synthesis, biological evaluation and structure-activity relationships of estrogen receptor ligands based on bridged oxabicyclic core arylsulfonamides.

    PubMed

    Zhu, Manghong; Zhang, Chen; Nwachukwu, Jerome C; Srinivasan, Sathish; Cavett, Valerie; Zheng, Yangfan; Carlson, Kathryn E; Dong, Chune; Katzenellenbogen, John A; Nettles, Kendall W; Zhou, Hai-Bing

    2012-11-21

    Compounds that block estrogen action through the estrogen receptor (ER) or downregulate ER levels are useful for the treatment of breast cancer and endocrine disorders. In our search for structurally novel estrogens having three-dimensional core scaffolds, we found some compounds with a 7-oxabicyclo[2.2.1]heptene core that bound well to the ERs. The best of these compounds, a phenyl sulfonate ester (termed OBHS for oxabicycloheptene sulfonate), was a partial antagonist on both ERα and ERβ. Although OBHS bears no structural resemblance to other estrogen antagonists, it appears to achieve its partial antagonist character by stabilizing a novel conformation of the ER that involves a significant distortion of helix-11. To enhance the antagonist properties of these oxabicyclo[2.2.1]heptane core ligands, we expanded the functional diversity of OBHS by replacing the sulfonate with secondary or tertiary sulfonamides (-SO(2)NR-), isoelectronic and potentially isostructural molecular replacements. An array of 16 OBHS sulfonamide analogues were prepared through a Diels-Alder reaction of a 3,4-diarylfuran using various N-aryl vinyl sulfonamide dienophiles. While the more polar secondary sulphonamides were weak ligands, certain of the tertiary sulfonamides had very good ER binding affinity. In HepG2 cell reporter gene assays, the sulphonamides had moderate potency, but they showed lower intrinsic transcriptional activity on ERα than the selective estrogen receptor modulator (SERM) hydroxytamoxifen or OBHS, and they were inverse agonists on ERβ. Thus, the behaviour of these OBH-sulfonamides more closely mirrors the activity of full antagonists like the drug fulvestrant (ICI 182 780), and their greater antagonist biocharacter appears to arise from an accentuated distortion of helix-11.

  4. Geographical variation in the exhaled volatile organic compounds.

    PubMed

    Amal, Haitham; Leja, Marcis; Broza, Yoav Y; Tisch, Ulrike; Funka, Konrads; Liepniece-Karele, Inta; Skapars, Roberts; Xu, Zhen-Qin; Liu, Hu; Haick, Hossam

    2013-12-01

    Breath-gas analysis has demonstrated that concentration profiles of volatile organic compounds (VOCs) could be used for detecting a variety of diseases, among them gastric cancer (GC) and peptic ulcer disease (PUD). Here, we explore how geographical variation affects the disease-specific changes in the chemical composition of breath samples, as compared to control states (less severe gastric conditions). Alveolar exhaled breath samples from 260 patients were collected at two remotely different geographic locations (China and Latvia), following similar breath-collection protocols. Each cohort included 130 patients that were matched in terms of diagnosis (37 GC/32 PUD/61 controls), average age, gender ratio and smoking habits. Helicobacter Pylori infection, which is a major cause for GC and PUD, was found in part of the patients, as well as in part of the controls, at both locations. The breath samples were analyzed by gas chromatography/mass spectrometry, using the same equipment and protocol-of-experiment. We observed similar characteristic differences in the chemical composition of the breath samples between the study groups at the two locations, even though the exact composition of the breath samples differed. Both in China and Latvia, the GC patients and controls could be distinguished by differences in the average levels of 6-methyl-5-hepten-2-one; PUD patients were distinguished from controls by the levels of aromatic compounds and alcohols; GC and PUD patients could not be distinguished at either site. This pilot study indicates the limitations of chemical breath-gas analysis alone for identifying gastric diseases based on the concentration profiles of separate VOCs in international patient cohorts. We assume that these limitations would apply to other diseases as well. The presented data could potentially be useful for developing an alternative, universally applicable diagnostic method that relies on the detection of changes in the collective patterns of

  5. Simultaneous indoor and outdoor on-line hourly monitoring of atmospheric volatile organic compounds in an urban building. The role of inside and outside sources.

    PubMed

    de Blas, Maite; Navazo, Marino; Alonso, Lucio; Durana, Nieves; Gomez, Maria Carmen; Iza, Jon

    2012-06-01

    Indoor air quality (IAQ) has become a very important issue in recent years. As in developed countries people spend more than 90% of their time indoors, besides outdoor pollution assessment, the indoor one is also required. IAQ is not only affected by indoor sources linked to indoor activities, outdoor sources such as road or street traffic and industrial and commercial activities have their role too. Volatile organic compounds (VOCs) frequently show higher indoor mixing ratios with respect to the outdoor ones, and monitoring is required to report their indoor mixing ratios. Many studies have reported average indoor VOCs' mixing ratios in different environments, but their temporal variability has not been well documented. The main objective of this work was to simultaneously measure VOCs' indoor and outdoor mixing ratios with high time-resolution in order to assess the effect of sources inside and outside the building upon indoor mixing ratios of individual VOCs. Simultaneous hourly, continuous, and on-line measurements of C(2)-C(11) VOCs were performed inside and outside the School of Engineering of Bilbao (ETSI) building, located in the city center of Bilbao, an urban area in Northern Spain. The analysis of simultaneous data allowed the classification of VOCs based on their main sources. Some VOCs were mainly emitted by indoor sources (1-pentene, 2-methylpentane, n-hexane, methylcyclopentane, benzene, 1-heptene+2,2,4-trimethylbenzene, and tetrachloroethylene) or by outdoor sources (n-heptane, C(8) alkanes except trimethylpentanes and C(9) aromatics). Other VOCs, such as toluene, were emitted by both indoor and outdoor sources. The isoprene indoor pattern indicated that its main indoor source could be the air exhaled by people occupying the building. Some halocarbons, such as trichloroethylene, tetrachloroethylene, and carbon tetrachloride may be generated from the use inside the building of chlorine bleach containing products.

  6. Mono- and disaccharides enhance the activity and enantioselectivity of Burkholderia cepacia lipase in organic solvent but do not significantly affect its conformation.

    PubMed

    Secundo, Francesco; Carrea, Giacomo

    2005-11-20

    Sucrose, trehalose, and mannitol were colyophilized with lipase from Burkholderia cepacia and their effects on the activity and enantioselectitivity of the enzyme evaluated using as model reactions the transesterification between n-octanol or 6-methyl-5-hepten-2-ol with vinyl acetate. The lipase co-lyophilized with sugars showed an activity which was up to 4.7-fold higher (at a sugar/lipase ratio >or= 20) than that observed without sugar. Analogously, lipase enantioselectivity, expressed as the enantiomeric ratio, increased up to 2.8-fold in the presence of sugars. The conformation of the lipase was investigated by means of Fourier transform infrared spectroscopy (FT/IR) in water and as lyophilized powder. The infrared spectra of lyophilized lipase in the presence and, even more so, in the absence of sugars were different from that of the enzyme in water. In particular, the band at around 1,654/cm, typically assigned to alpha-helix, was less intense in the lyophilized samples. Nevertheless, the enzyme in the presence of sugars showed a decrease of the bands at 1,614-1,620/cm and at 1,680-1,695/cm that indicates a lower content of intermolecular beta-sheets (typical of protein aggregates). Additionally the increase of the component at 1,546/cm in the amide II region is consistent with a hydrogen bond pattern of the enzyme more similar to that shown in water. These results suggest that although sugars are not able to fully preserve the native secondary structure, they might contribute to reduce the conformational changes caused by protein/protein interactions. These factors in combinations with others (e.g., ability to reduce deleterious interactions between the enzyme and inert supports) make sugars (both mono- and disaccharides) an interesting class of additives for improving the performance of biocatalysts in organic solvents.

  7. Smelling your way to food: can bed bugs use our odour?

    PubMed

    Harraca, V; Ryne, C; Birgersson, G; Ignell, R

    2012-02-15

    The resurgence in developed countries of the common bed bug, Cimex lectularius, has led to a search for new sustainable methods to monitor and control this human ectoparasite. Because of increased resistance to insecticides, traps baited with attractive cues are considered a promising method to be developed into efficient monitoring tools for bed bugs. Despite their potential as attractants, only a few studies have investigated the odorant cues implicated in the attraction of bed bugs to human hosts. In this study, we used aeration extracts from human volunteers to assess the role of olfaction in host searching by bed bugs. By coupled gas chromatography and single sensillum recordings on all the antennal sensilla, we measured the electrophysiological response elicited by the compounds present in our human odour extracts. Only five compounds were clearly detected by the olfactory receptor neurons housed in the smooth-peg sensilla of the bed bugs. We tested the behavioural effect of these extracts in a still-air arena and showed a gradient of repellence linked to the dose, as well as a higher propensity of local search behaviour associated with human odours containing a lower ratio of 6-methyl-5-hepten-2-one to C(7)-C(10) aldehydes. We conclude that human odour alone has a weak influence on the behaviour of C. lectularius and we propose that human kairomones may have a significant impact on bed bug behaviour in combination with heat and carbon dioxide, the only two currently known attractive vertebrate cues used by bed bugs for host seeking.

  8. Protective Effects of a Diarylheptanoid from Curcuma comosa Against Hydrogen Peroxide-Induced Astroglial Cell Death.

    PubMed

    Vattanarongkup, Jaturavit; Piyachaturawat, Pawinee; Tuchinda, Patoomratana; Sanvarinda, Pimtip; Sanvarinda, Yupin; Jantaratnotai, Nattinee

    2016-11-01

    Oxidative stress is one of the major mechanisms causing neuronal and astroglial cell death in various neurological disorders such as Alzheimer's disease, Parkinson's disease, and brain ischemia. Two diarylheptanoids, (3R)-1,7-diphenyl-(4E,6E)-4,6-heptadien-3-ol (ASPP 049) and (3S)-7-(3,4-dihydroxyphenyl)-1-phenyl-(1E)-1-hepten-3-ol (ASPP 092), isolated from Curcuma comosa were investigated for cytoprotective effects on C6 astroglial cells using hydrogen peroxide (H2O2) exposure as a model of oxidative stress. ASPP 092 demonstrated free radical scavenging activity comparable to that of vitamin C, while ASPP 049 showed no antioxidant activity. Treatment with H2O2 at 400 µM for 12 h caused 79 % C6 astroglial cell death which was significantly reduced to 37 % by pretreatment with ASPP 092 (5 µM). In addition, ASPP 092 attenuated the increase in reactive oxygen species production and the decrease in total glutathione level induced by H2O2. The mechanism of ASPP 092 protection against H2O2-induced apoptotic signaling appeared to involve prevention of increase in the level of phosphorylated p53 and the Bax/Bcl-2 ratio as well as cleaved caspase-3. These findings provide new evidence that the diarylheptanoid ASPP 092 from C. comosa possesses antiapoptotic properties and could be further developed as a potential treatment for oxidative stress-related neuronal diseases. Georg Thieme Verlag KG Stuttgart · New York.

  9. Identification of aroma active compounds of cereal coffee brew and its roasted ingredients.

    PubMed

    Majcher, Małgorzata A; Klensporf-Pawlik, Dorota; Dziadas, Mariusz; Jeleń, Henryk H

    2013-03-20

    Cereal coffee is a coffee substitute made mainly from roasted cereals such as barley and rye (60-70%), chicory (15-20%), and sugar beets (6-10%). It is perceived by consumers as a healthy, caffeine free, non-irritating beverage suitable for those who cannot drink regular coffee made from coffee beans. In presented studies, typical Polish cereal coffee brew has been subjected to the key odorants analysis with the application of gas chromatography-olfactometry (GC-O) and aroma extract dilution analysis (AEDA). In the analyzed cereal coffee extract, 30 aroma-active volatiles have been identified with FD factors ranging from 16 to 4096. This approach was also used for characterization of key odorants in ingredients used for the cereal coffee production. Comparing the main odors detected in GC-O analysis of roasted cereals brew to the odor notes of cereal coffee brew, it was evident that the aroma of cereal coffee brew is mainly influenced by roasted barley. Flavor compound identification and quantitation has been performed with application of comprehensive multidimentional gas chromatography and time-of-flight mass spectrometry (GCxGC-ToFMS). The results of the quantitative measurements followed by calculation of the odor activity values (OAV) revealed 17 aroma active compounds of the cereal coffee brew with OAV ranging from 12.5 and 2000. The most potent odorant was 2-furfurylthiol followed by the 3-mercapto-3-methylbutyl formate, 3-isobutyl-2-methoxypyrazine and 2-ethyl-3,5-dimethylpyrazine, 2-thenylthiol, 2,3-butanedione, 2-methoxy phenol and 2-methoxy-4-vinyl phenol, 3(sec-butyl)-2-methoxypyrazine, 2-acetyl-1-pyrroline, 3-(methylthio)-propanal, 2,3-pentanedione, 4-hydroxy-2,5-dimethyl-3-(2H)-furanone, (E,E)-2,4-decadienal, (Z)-4-heptenal, phenylacetaldehyde, and 1-octen-3-one.

  10. A Visual Reporter System for Virus-Induced Gene Silencing in Tomato Fruit Based on Anthocyanin Accumulation1[C][W

    PubMed Central

    Orzaez, Diego; Medina, Aurora; Torre, Sara; Fernández-Moreno, Josefina Patricia; Rambla, José Luis; Fernández-del-Carmen, Asun; Butelli, Eugenio; Martin, Cathie; Granell, Antonio

    2009-01-01

    Virus-induced gene silencing (VIGS) is a powerful tool for reverse genetics in tomato (Solanum lycopersicum). However, the irregular distribution of the effects of VIGS hampers the identification and quantification of nonvisual phenotypes. To overcome this limitation, a visually traceable VIGS system was developed for fruit, comprising two elements: (1) a transgenic tomato line (Del/Ros1) expressing Antirrhinum majus Delila and Rosea1 transcription factors under the control of the fruit-specific E8 promoter, showing a purple-fruited, anthocyanin-rich phenotype; and (2) a modified tobacco rattle virus VIGS vector incorporating partial Rosea1 and Delila sequences, which was shown to restore the red-fruited phenotype upon agroinjection in Del/Ros1 plants. Dissection of silenced areas for subsequent chemometric analysis successfully identified the relevant metabolites underlying gene function for three tomato genes, phytoene desaturase, TomloxC, and SlODO1, used for proof of concept. The C-6 aldehydes derived from lipid 13-hydroperoxidation were found to be the volatile compounds most severely affected by TomloxC silencing, whereas geranial and 6-methyl-5-hepten-2-one were identified as the volatiles most severely reduced by phytoene desaturase silencing in ripening fruit. In a third example, silencing of SlODO1, a tomato homolog of the ODORANT1 gene encoding a myb transcription factor, which regulates benzenoid metabolism in petunia (Petunia hybrida) flowers, resulted in a sharp accumulation of benzaldehyde in tomato fruit. Together, these results indicate that fruit VIGS, enhanced by anthocyanin monitoring, can be a powerful tool for reverse genetics in the study of the metabolic networks operating during fruit ripening. PMID:19429602

  11. Metal and Precursor Effect during 1-Heptyne Selective Hydrogenation Using an Activated Carbon as Support

    PubMed Central

    Lederhos, Cecilia R.; Badano, Juan M.; Carrara, Nicolas; Coloma-Pascual, Fernando; Almansa, M. Cristina; Liprandi, Domingo; Quiroga, Mónica

    2013-01-01

    Palladium, platinum, and ruthenium supported on activated carbon were used as catalysts for the selective hydrogenation of 1-heptyne, a terminal alkyne. All catalysts were characterized by temperature programmed reduction, X-ray diffraction, transmission electron microscopy, and X-ray photoelectron spectroscopy. TPR and XPS suggest that the metal in all catalysts is reduced after the pretreatment with H2 at 673 K. The TPR trace of the PdNRX catalyst shows that the support surface groups are greatly modified as a consequence of the use of HNO3 during the catalyst preparation. During the hydrogenation of 1-heptyne, both palladium catalysts were more active and selective than the platinum and ruthenium catalysts. The activity order of the catalysts is as follows: PdClRX > PdNRX > PtClRX ≫ RuClRX. This superior performance of PdClRX was attributed in part to the total occupancy of the d electronic levels of the Pd metal that is supposed to promote the rupture of the H2 bond during the hydrogenation reaction. The activity differences between PdClRX and PdNRX catalysts could be attributed to a better accessibility of the substrate to the active sites, as a consequence of steric and electronic effects of the superficial support groups. The order for the selectivity to 1-heptene is as follows: PdClRX = PdNRX > RuClRX > PtClRX, and it can be mainly attributed to thermodynamic effects. PMID:24348168

  12. Ozone-initiated terpene reaction products in five European offices: replacement of a floor cleaning agent.

    PubMed

    Nørgaard, A W; Kofoed-Sørensen, V; Mandin, C; Ventura, G; Mabilia, R; Perreca, E; Cattaneo, A; Spinazzè, A; Mihucz, V G; Szigeti, T; de Kluizenaar, Y; Cornelissen, H J M; Trantallidi, M; Carrer, P; Sakellaris, I; Bartzis, J; Wolkoff, P

    2014-11-18

    Cleaning agents often emit terpenes that react rapidly with ozone. These ozone-initiated reactions, which occur in the gas-phase and on surfaces, produce a host of gaseous and particulate oxygenated compounds with possible adverse health effects in the eyes and airways. Within the European Union (EU) project OFFICAIR, common ozone-initiated reaction products were measured before and after the replacement of the regular floor cleaning agent with a preselected low emitting floor cleaning agent in four offices located in four EU countries. One reference office in a fifth country did not use any floor cleaning agent. Limonene, α-pinene, 3-carene, dihydromyrcenol, geraniol, linalool, and α-terpineol were targeted for measurement together with the common terpene oxidation products formaldehyde, 4-acetyl-1-methylcyclohexene (4-AMCH), 3-isopropenyl-6-oxo-heptanal (IPOH), 6-methyl-5-heptene-2-one, (6-MHO), 4-oxopentanal (4-OPA), and dihydrocarvone (DHC). Two-hour air samples on Tenax TA and DNPH cartridges were taken in the morning, noon, and in the afternoon and analyzed by thermal desorption combined with gas chromatography/mass spectrometry and HPLC/UV analysis, respectively. Ozone was measured in all sites. All the regular cleaning agents emitted terpenes, mainly limonene and linalool. After the replacement of the cleaning agent, substantially lower concentrations of limonene and formaldehyde were observed. Some of the oxidation product concentrations, in particular that of 4-OPA, were also reduced in line with limonene. Maximum 2 h averaged concentrations of formaldehyde, 4-AMCH, 6-MHO, and IPOH would not give rise to acute eye irritation-related symptoms in office workers; similarly, 6-AMCH, DHC and 4-OPA would not result in airflow limitation to the airways.

  13. Cl atom initiated oxidation of 1-alkenes under atmospheric conditions

    NASA Astrophysics Data System (ADS)

    Walavalkar, M.; Sharma, A.; Alwe, H. D.; Pushpa, K. K.; Dhanya, S.; Naik, P. D.; Bajaj, P. N.

    2013-03-01

    In view of the importance of the oxidation pathways of alkenes in the troposphere, and the significance of Cl atom as an oxidant in marine boundary layer (MBL) and polluted industrial atmosphere, the reactions of four 1-alkenes (C6-C9) with Cl atoms are investigated. The rate coefficients at 298 K are measured to be (4.0 ± 0.5), (4.4 ± 0.7), (5.5 ± 0.9) and (5.9 ± 1.7) × 10-10 cm3 molecule-1 s-1 for 1-hexene, 1-heptene, 1-octene and 1-nonene, respectively. The quoted errors include the experimental 2σ, along with the error in the reference rate coefficients. From the systematic increase in the rate coefficients with the number of carbon atoms, an approximate value for the average rate coefficient for hydrogen abstraction per CH2 group in alkenes is estimated to be (4.9 ± 0.3) × 10-11 cm3 molecule-1 s-1. Based on these rate coefficients, the contribution of Cl atom reactions towards the degradation of these molecules is found to be comparable to that of OH radical reactions, under MBL conditions. The products identified in gas phase indicate that Cl atom addition occurs mainly at the terminal carbon, leading to the formation of 1-chloro-2-ketones and 1-chloro-2-ols. The major gas phase products from the alkenyl radicals (formed by H atom abstraction) are different positional isomers of long chain enols and enones. A preference for dissociation leading to an allyl radical, resulting in aldehydes, lower by three carbon atoms, is indicated. The observed relative yields suggest that in general, the increased contribution of the reactions of Cl atoms towards degradation of 1-alkenes in NOx free air does not result in an increase in the generation of small aldehydes (carbon number < 4), including chloroethanal, as compared to that in the reaction of 1-butene.

  14. Ozone consumption and volatile byproduct formation from surface reactions with aircraft cabin materials and clothing fabrics

    NASA Astrophysics Data System (ADS)

    Coleman, Beverly K.; Destaillats, Hugo; Hodgson, Alfred T.; Nazaroff, William W.

    We measured ozone consumption and byproduct formation on materials commonly found in aircraft cabins at flight-relevant conditions. Two series of small-chamber experiments were conducted, with most runs at low relative humidity (10%) and high air-exchange rate (˜20 h -1). New and used cabin materials (seat fabric, carpet, and plastic) and laundered and worn clothing fabrics (cotton, polyester, and wool) were studied. We measured ozone deposition to many material samples, and we measured ozone uptake and primary and secondary emissions of volatile organic compounds (VOCs) from a subset of samples. Deposition velocities ranged from 0.06 to 0.54 cm s -1. Emissions of VOCs were higher with ozone than without ozone in every case. The most commonly detected secondary emissions were C 1 through C 10 saturated aldehydes and the squalene oxidation products 6-methyl-5-hepten-2-one and acetone. For the compounds measured, summed VOC emission rates in the presence of 55-128 ppb (residual level) ozone ranged from 1.0 to 8.9 μmol h -1 m -2. Total byproduct yield ranged from 0.07 to 0.24 moles of product volatilized per mole of ozone consumed. Results were used to estimate the relative contribution of different materials to ozone deposition and byproduct emissions in a typical aircraft cabin. The dominant contributor to both was clothing fabrics, followed by seat fabric. Results indicate that ozone reactions with surfaces substantially reduce the ozone concentration in the cabin but also generate volatile byproducts of potential concern for the health and comfort of passengers and crew.

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

    PubMed

    Beaulieu, John C; Lea, Jeanne M

    2006-10-04

    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.

  16. Inhibition of cholesterol synthesis causes both hypercholesterolemia and hypocholesterolemia in hamsters.

    PubMed

    Sawada, Masae; Matsuo, Masahiko; Seki, Jiro

    2002-12-01

    Effects of FR194738 ((E)-N-ethyl-N-(6,6-dimethyl-2-hepten-4-ynyl)-3-[2-methyl-2-(3-thienylmethoxy)propyloxy]benzylamine hydrochloride), a squalene epoxidase inhibitor, on lipid metabolism were compared with those of pravastatin, a 3-hydroxy-3-methylglutaryl coenzyme A (HMG-CoA) reductase inhibitor, in hamsters. Drugs were given for 10 d either as a diet mixture or as a bolus oral gavage, and similar results were obtained with each type of administration. FR194738 (0.01-0.32% as a diet mixture; 10-100 mg/kg as an oral gavage) dose-dependently decreased serum total cholesterol, non high density lipoprotein (HDL) cholesterol, HDL cholesterol and triglyceride levels, and the changes in serum parameters were similar. Pravastatin (0.01-0.32% as a diet mixture; 1-100 mg/kg as an oral gavage) increased serum cholesterol levels, and dose-dependently decreased serum triglyceride levels. Although oral gavage of FR194738 at 32 mg/kg and pravastatin at 3.2 and 10 mg/kg increased hepatic HMG-CoA reductase activity, the degree of the changes was far greater with the latter than the former drug. FR194738 slightly increased hepatic cholesterol content at 32 mg/kg, whereas pravastatin dose-dependently increased hepatic cholesterol content until it leveled off at 32 and 100 mg/kg. It is concluded that inhibition of squalene epoxidase and HMG-CoA reductase triggers both hypercholesterolemic (hepatic cholesterol synthesis) and hypocholesterolemic (hepatic cholesterol uptake) mechanisms. FR194738 appears to induce a greater enhancement of the latter rather than the former, whereas pravastatin has a greater effect on the former.

  17. Composition of the essential oil constituents from leaves and stems of Korean Coriandrum sativum and their immunotoxicity activity on the Aedes aegypti L.

    PubMed

    Chung, Ill-Min; Ahmad, Ateeque; Kim, Sun-Jin; Naik, Poornanand Madhava; Nagella, Praveen

    2012-02-01

    The leaves and stems of Coriandrum sativum were extracted and the essential oil composition and immunotoxicity effects were studied. The analyses were conducted by gas chromatography-mass spectroscopy (GC-MS), which revealed the essential oils of C. sativum leaves and stems. Thirty-nine components representing 99.62% of the total oil were identified from the leaves. The major components are cyclododecanol (23.11%), tetradecanal (17.86%), 2-dodecenal (9.93%), 1-decanol (7.24%), 13-tetradecenal (6.85%), 1-dodecanol (6.54%), dodecanal (5.16%), 1-undecanol (2.28%), and decanal (2.33%). Thirty-eight components representing 98.46% of the total oil were identified from the stems of the coriander. The major components are phytol (61.86%), 15-methyltricyclo[6.5.2(13,14),0(7,15)]-pentadeca-1,3,5,7,9,11,13-heptene (7.01%), dodecanal (3.18%), and 1-dodecanol (2.47%). The leaf oil had significant toxic effects against the larvae of Aedes aegypti with an LC₅₀ value of 26.93 ppm and an LC₉₀ value of 37.69 ppm and the stem oil has toxic effects against the larvae of A. aegypti with an LC₅₀ value of 29.39 ppm and an LC₉₀ value of 39.95 ppm. Also, the above data indicate that the major compounds may play an important role in the toxicity of essential oils.

  18. The effect of feed solids concentration and inlet temperature on the flavor of spray dried whey protein concentrate.

    PubMed

    Park, Curtis W; Bastian, Eric; Farkas, Brian; Drake, MaryAnne

    2014-01-01

    Previous research has demonstrated that unit operations in whey protein manufacture promote off-flavor production in whey protein. The objective of this study was to determine the effects of feed solids concentration in liquid retentate and spray drier inlet temperature on the flavor of dried whey protein concentrate (WPC). Cheddar cheese whey was manufactured, fat-separated, pasteurized, bleached (250 ppm hydrogen peroxide), and ultrafiltered (UF) to obtain WPC80 retentate (25% solids, wt/wt). The liquid retentate was then diluted with deionized water to the following solids concentrations: 25%, 18%, and 10%. Each of the treatments was then spray dried at the following temperatures: 180 °C, 200 °C, and 220 °C. The experiment was replicated 3 times. Flavor of the WPC80 was evaluated by sensory and instrumental analyses. Particle size and surface free fat were also analyzed. Both main effects (solids concentration and inlet temperature) and interactions were investigated. WPC80 spray dried at 10% feed solids concentration had increased surface free fat, increased intensities of overall aroma, cabbage and cardboard flavors and increased concentrations of pentanal, hexanal, heptanal, decanal, (E)2-decenal, DMTS, DMDS, and 2,4-decadienal (P < 0.05) compared to WPC80 spray dried at 25% feed solids. Product spray dried at lower inlet temperature also had increased surface free fat and increased intensity of cardboard flavor and increased concentrations of pentanal, (Z)4-heptenal, nonanal, decanal, 2,4-nonadienal, 2,4-decadienal, and 2- and 3-methyl butanal (P < 0.05) compared to product spray dried at higher inlet temperature. Particle size was higher for powders from increased feed solids concentration and increased inlet temperature (P < 0.05). An increase in feed solids concentration in the liquid retentate and inlet temperature within the parameters evaluated decreased off-flavor intensity in the resulting WPC80.

  19. Microbiological spoilage and investigation of volatile profile during storage of sea bream fillets under various conditions.

    PubMed

    Parlapani, Foteini F; Mallouchos, Athanasios; Haroutounian, Serkos A; Boziaris, Ioannis S

    2014-10-17

    Volatile organic compound (VOC) profile was determined during storage of sea bream (Sparus aurata) fillets under air and Modified Atmosphere Packaging (MAP - CO2/O2/N2: 60/10/30) at 0, 5 and 15°C. Microbiological, TVB-N (Total Volatile Base Nitrogen) and sensory changes were also monitored. Shelf-life of sea bream fillets stored under air was 14, 5 and 2days (d) at 0, 5 and 15°C respectively, while under MAP was 18, 8, and 2d at 0, 5 and 15°C respectively. At the end of shelf life, the total microbial population ranged from 7.5 to 8.5logcfu/g. Pseudomonas spp. were among the dominant spoilage microorganisms in all cases, however growth of Brochothrix thermosphacta and Lactic Acid Bacteria (LAB) were favoured under MAP compared to air. TVB-N production was favoured at higher temperatures and under air compared to lower temperatures and MAP. TVB-N increased substantially from the middle of storage and its value never reached concentrations higher than 30-35mgN/100g, which is the legislation limit, making it a poor chemical spoilage index (CSI). A lot of alcohols, aldehydes, ketones and ethyl esters that were detected in the present study have been reported as bacterial metabolites, others as products of chemical oxidation while others as aroma constituents. VOCs such as 3-methylbutanal, acetic acid, ethanol, ethyl esters of isovaleric and 2-methylbutyric acids, 1-penten-3-ol, 1-octen-3-ol and cis-4-heptenal appeared from the early or middle stages and increased until the end of storage. From those only 3-methylbutanal, acetic acid, ethanol and the ethyl esters have been reported as microbial origin, making them potential CSI candidates of sea bream fillets.

  20. Ozone interactions with human hair: Ozone uptake rates and product formation

    NASA Astrophysics Data System (ADS)

    Pandrangi, Lakshmi S.; Morrison, Glenn C.

    In this study, the cumulative ozone uptake, the ozone reaction probability and product yields of volatile aldehydes and ketones were quantified for human scalp hair. Hair was chosen because ozone reacts readily with skin oils and the personal-care products that coat hair. Due to their proximity to the breathing zone, these reactions can influence personal exposure to ozone and its volatile reaction products. Hair samples were collected before and after washing and/or application of personal hair-care products. Samples were exposed to ozone for 24 h in a tubular Teflon reactor; ozone consumption rates and product emission rates were quantified. The mean values of integrated ozone uptake, initial and final follicle reaction probability values for eight washed and unwashed samples were, respectively, 5.1±4.4 μmol O 3 g -1, (13±8)×10 -5, and (1.0±1.3)×10 -5. Unwashed hair taken close to the scalp exhibited the highest integrated ozone uptake and reaction probability, indicating that scalp oils are responsible for much of the ozone reactivity. Otherwise there was no significant difference between washed and unwashed hair. Compounds (geranyl acetone, 6-methyl-5-hepten-2-one, and decanal) associated with ozone reacting with sebum were observed as secondary products more frequently from unwashed hair than for washed hair and the summed yield of aldehydes ranged from 0.00 to 0.86. Based on reaction probabilities, cumulative ozone uptake and typical sebum generation rates, ozone flux to skin and hair is anticipated to be nearly transport limited, reducing personal exposure to ozone and increasing exposure to reaction products.

  1. Target metabolite and gene transcription profiling during the development of superficial scald in apple (Malus x domestica Borkh)

    PubMed Central

    2014-01-01

    Background Fruit quality features resulting from ripening processes need to be preserved throughout storage for economical reasons. However, during this period several physiological disorders can occur, of which superficial scald is one of the most important, due to the development of large brown areas on the fruit skin surface. Results This study examined the variation in polyphenolic content with the progress of superficial scald in apple, also with respect to 1-MCP, an ethylene competitor interacting with the hormone receptors and known to interfere with this etiology. The change in the accumulation of these metabolites was further correlated with the gene set involved in this pathway, together with two specific VOCs (Volatile Organic Compounds), α-farnesene and its oxidative form, 6-methyl-5-hepten-2-one. Metabolite profiling and qRT-PCR assay showed these volatiles are more heavily involved in the signalling system, while the browning coloration would seem to be due more to a specific accumulation of chlorogenic acid (as a consequence of the activation of MdPAL and MdC3H), and its further oxidation carried out by a polyphenol oxidase gene (MdPPO). In this physiological scenario, new evidence regarding the involvement of an anti-apoptotic regulatory mechanism for the compartmentation of this phenomenon in the skin alone was also hypothesized, as suggested by the expression profile of the MdDAD1, MdDND1 and MdLSD1 genes. Conclusions The results presented in this work represent a step forward in understanding the physiological mechanisms of superficial scald in apple, shedding light on the regulation of the specific physiological cascade. PMID:25038781

  2. Target metabolite and gene transcription profiling during the development of superficial scald in apple (Malus x domestica Borkh).

    PubMed

    Busatto, Nicola; Farneti, Brian; Tadiello, Alice; Vrhovsek, Urska; Cappellin, Luca; Biasioli, Franco; Velasco, Riccardo; Costa, Guglielmo; Costa, Fabrizio

    2014-07-20

    Fruit quality features resulting from ripening processes need to be preserved throughout storage for economical reasons. However, during this period several physiological disorders can occur, of which superficial scald is one of the most important, due to the development of large brown areas on the fruit skin surface. This study examined the variation in polyphenolic content with the progress of superficial scald in apple, also with respect to 1-MCP, an ethylene competitor interacting with the hormone receptors and known to interfere with this etiology. The change in the accumulation of these metabolites was further correlated with the gene set involved in this pathway, together with two specific VOCs (Volatile Organic Compounds), α-farnesene and its oxidative form, 6-methyl-5-hepten-2-one. Metabolite profiling and qRT-PCR assay showed these volatiles are more heavily involved in the signalling system, while the browning coloration would seem to be due more to a specific accumulation of chlorogenic acid (as a consequence of the activation of MdPAL and MdC3H), and its further oxidation carried out by a polyphenol oxidase gene (MdPPO). In this physiological scenario, new evidence regarding the involvement of an anti-apoptotic regulatory mechanism for the compartmentation of this phenomenon in the skin alone was also hypothesized, as suggested by the expression profile of the MdDAD1, MdDND1 and MdLSD1 genes. The results presented in this work represent a step forward in understanding the physiological mechanisms of superficial scald in apple, shedding light on the regulation of the specific physiological cascade.

  3. Identification of volatiles from oxidised phosphatidylcholine molecular species using headspace solid-phase microextraction (HS-SPME) and gas chromatography-mass spectrometry (GC-MS).

    PubMed

    Zhou, Li; Zhao, Minjie; Khalil, Ali; Marcic, Christophe; Bindler, Françoise; Marchioni, Eric

    2013-11-01

    Headspace solid-phase microextraction (HS-SPME) followed by gas chromatography-mass spectrometry analysis (GC-MS) was used to investigate the volatile compounds from oxidised phosphatidylcholine molecular species. 1-stearoyl-2-oleoyl-sn-glycero-3-phosphocholine (SOPC) and 1-stearoyl-2-linoleoyl-sn-glycero-3-phosphocholine (SLPC) were chosen as models. The influence of several parameters on the efficiency of volatile oxidised compounds (VOCs) microextraction, such as type of fibre, extraction duration and temperature were studied. The best results were obtained with a polydimethylsiloxane/divinylbenzene (PDMS/DVB) fibre used at 50 °C during 25 min. The effect of oxidation temperature on the yield of VOCs from SOPC and SLPC was investigated. Oxidative kinetics of SOPC and SLPC were investigated by measuring both the production of VOCs and the degradation of starting materials. More than 30 VOCs were detected by means of the reference mass spectra of the National Institute of Standards and Technology mass spectral library, and most of them were further confirmed by comparing their mass spectra and retention time with those obtained from authentic reference compounds under the same analytical conditions. Moreover, the origins of VOCs from oxidised PLs were studied by comparing those obtained from their corresponding triacylglycerides under the same experimental conditions. The main VOCs identified from oxidised SOPC were (E)-2-decenal, nonanal and octanal and from oxidised SLPC were (E)-2-heptenal, (E)-2-octenal and (E, E)-2,4-decadienal. The proposed method was applied to a real food sample, soy lecithin.

  4. A visual reporter system for virus-induced gene silencing in tomato fruit based on anthocyanin accumulation.

    PubMed

    Orzaez, Diego; Medina, Aurora; Torre, Sara; Fernández-Moreno, Josefina Patricia; Rambla, José Luis; Fernández-Del-Carmen, Asun; Butelli, Eugenio; Martin, Cathie; Granell, Antonio

    2009-07-01

    Virus-induced gene silencing (VIGS) is a powerful tool for reverse genetics in tomato (Solanum lycopersicum). However, the irregular distribution of the effects of VIGS hampers the identification and quantification of nonvisual phenotypes. To overcome this limitation, a visually traceable VIGS system was developed for fruit, comprising two elements: (1) a transgenic tomato line (Del/Ros1) expressing Antirrhinum majus Delila and Rosea1 transcription factors under the control of the fruit-specific E8 promoter, showing a purple-fruited, anthocyanin-rich phenotype; and (2) a modified tobacco rattle virus VIGS vector incorporating partial Rosea1 and Delila sequences, which was shown to restore the red-fruited phenotype upon agroinjection in Del/Ros1 plants. Dissection of silenced areas for subsequent chemometric analysis successfully identified the relevant metabolites underlying gene function for three tomato genes, phytoene desaturase, TomloxC, and SlODO1, used for proof of concept. The C-6 aldehydes derived from lipid 13-hydroperoxidation were found to be the volatile compounds most severely affected by TomloxC silencing, whereas geranial and 6-methyl-5-hepten-2-one were identified as the volatiles most severely reduced by phytoene desaturase silencing in ripening fruit. In a third example, silencing of SlODO1, a tomato homolog of the ODORANT1 gene encoding a myb transcription factor, which regulates benzenoid metabolism in petunia (Petunia hybrida) flowers, resulted in a sharp accumulation of benzaldehyde in tomato fruit. Together, these results indicate that fruit VIGS, enhanced by anthocyanin monitoring, can be a powerful tool for reverse genetics in the study of the metabolic networks operating during fruit ripening.

  5. Volatile profiling of high quality hazelnuts (Corylus avellana L.): chemical indices of roasting.

    PubMed

    Nicolotti, Luca; Cordero, Chiara; Bicchi, Carlo; Rubiolo, Patrizia; Sgorbini, Barbara; Liberto, Erica

    2013-06-01

    The study proposes an investigation strategy to identify sensitive, robust and reliable chemical markers of hazelnut roasting. A fully-automated and validated analytical method, based on Headspace Solid Phase Microextraction (HS-SPME) coupled with Gas Chromatography-Mass Spectrometric detection (GC-MS), for effective off-line monitoring of changes in the volatile profile of high-quality hazelnuts was developed. Samples from two different harvests were submitted to roasting, following different time/temperature protocols and different technologies, enabling chemical changes to be correlated with technological processing and sensory quality. Chemical indices, expressed as analyte response ratio, were defined and their trend observed across roasting profiles. Reliability and robustness of chemical indices were also evaluated, in view of their application to on-line monitoring with Mass Spectrometry-based electronic nose technology (MS-nose). Experiments, simulating on-line chemical characterisation of the volatile fraction, were performed through a fully-automated system. The results confirmed: (a) the effectiveness of single process indicators of roasting selected by the separative method (5-methylfurfural, 1(H)-pyrrole, furfuryl alcohol, 1(H)-pyrrole-2-carboxaldehyde, 1-hydroxy-2-propanone, dihydro-2(3H)-furanone, 5-methyl-(E)-2-hepten-4-one, acetic acid, pyridine, furfural, pyrazine, and several alkyl-pyrazines); and, (b) the reliability of proposed chemical indices: 5-methylfurfural/2,5-dimethylpyrazine, 5-methylfurfural/2-methylpyrazine, 2,5-dimethylpyrazine/2,3-dimethylpyrazine; these maintained a consistent trend versus harvest and sampling/analysis technology.

  6. Characterization of the Key Aroma Volatile Compounds in Cranberry (Vaccinium macrocarpon Ait.) Using Gas Chromatography-Olfactometry (GC-O) and Odor Activity Value (OAV).

    PubMed

    Zhu, JianCai; Chen, Feng; Wang, LingYing; Niu, YunWei; Chen, HeXing; Wang, HongLin; Xiao, ZuoBing

    2016-06-22

    The volatile compounds of cranberries obtained from four cultivars (Early Black, Y1; Howes, Y2; Searles, Y3; and McFarlin, Y4) were analyzed by gas chromatography-olfactometry (GC-O), gas chromatography-mass spectrometry (GC-MS), and GC-flame photometric detection (FPD). The result presented that a total of thirty-three, thirty-four, thirty-four, and thirty-six odor-active compounds were identified by GC-O in the Y1, Y2, Y3, and Y4, respectively. In addition, twenty-two, twenty-two, thirty, and twenty-seven quantified compounds were demonstrated as important odorants according to odor activity values (OAVs > 1). Among these compounds, hexanal (OAV: 27-60), pentanal (OAV: 31-51), (E)-2-heptenal (OAV: 17-66), (E)-2-hexenal (OAV: 18-63), (E)-2-octenal (OAV: 10-28), (E)-2-nonenal (OAV: 8-77), ethyl 2-methylbutyrate (OAV: 10-33), β-ionone (OAV: 8-73), 2-methylbutyric acid (OAV: 18-37), and octanal (OAV: 4-24) contributed greatly to the aroma of cranberry. Partial least-squares regression (PLSR) was used to process the mean data accumulated from sensory evaluation by the panelists, odor-active aroma compounds (OAVs > 1), and samples. Sample Y3 was highly correlated with the sensory descriptors "floral" and "fruity". Sample Y4 was greatly related to the sensory descriptors "mellow" and "green and grass". Finally, an aroma reconstitution (Model A) was prepared by mixing the odor-active aroma compounds (OAVs > 1) based on their measured concentrations in the Y1 sample, indicating that the aroma profile of the reconstitution was pretty similar to that of the original sample.

  7. Utilisation of chemical signals by inquiline wasps in entering their host figs.

    PubMed

    Gu, Ding; Yang, Da-Rong

    2013-10-01

    The fig tree, Ficus curtipes, hosts an obligate pollinating wasp, an undescribed Eupristina sp., but can also be pollinated by two inquiline (living in the burrow, nest, gall, or other habitation of another animal) wasps, Diaziella yangi and an undescribed Lipothymus sp. The two inquilines are unable to independently induce galls and depend on the galls induced by the obligate pollinator for reproduction and, therefore, normally enter receptive F. curtipes figs colonised by the obligate pollinators. However, sometimes the inquilines also enter figs that are not colonised by the pollinators, despite consequent reproductive failure. It is still unknown which signal(s) the inquilines use in entering the colonised and non-colonised figs. We conducted behavioural experiments to investigate several possible signals utilised by the inquilines in entering their host receptive figs. Our investigation showed that both inquiline species enter the receptive F. curtipes figs in response to the body odours of the obligate wasps and one of the main compounds emitted by the figs, 6-methyl-5-hepten-2-one. The compound was not found in the pollinator body odours, suggesting that the two inquiline wasps can utilise two signals to enter their host figs, which is significant for the evolution of the fig-fig wasp system. These inquilines could evolve to become mutualists of the figs if they evolve the ability to independently gall fig flowers; there is, however, another possibility that a monoecious Ficus species hosting such inquilines may evolve into a dioecious one if these inquilines cannot evolve the above-mentioned ability. Additionally, this finding provides evidence for the evolution of chemical communication between plants and insects. Copyright © 2013 Elsevier Ltd. All rights reserved.

  8. ANALYSIS OF VAPORS FROM METHYLENE CHLORIDE EXTRACTS OF NUCLEAR GRADE HEPA FILTER FIBERGLASS SAMPLES

    SciTech Connect

    FRYE JM; ANASTOS HL; GUTIERREZ FC

    2012-06-07

    While several organic compounds were detected in the vapor samples used in the reenactment of the preparation of mounts from the extracts of nuclear grade high-efficiency particulate air filter fiberglass samples, the most significant species present in the samples were methylene chloride, phenol, phenol-d6, and 2-fluorophenol. These species were all known to be present in the extracts, but were expected to have evaporated during the preparation of the mounts, as the mounts appeared to be dry before any vapor was collected. These species were present at the following percentages of their respective occupational exposure limits: methylene chloride, 2%; phenol, 0.4%; and phenol-d6, 0.6%. However, there is no established limit for 2-fluorophenol. Several other compounds were detected at low levels for which, as in the case of 2-fluorophenol, there are no established permissible exposure limits. These compounds include 2-chlorophenol; N-nitroso-1-propanamine; 2-fluoro-1,1{prime}-biphenyl; 1,2-dihydroacenaphthylene; 2,5-cyclohexadiene-1,4-dione,2,6-bis(1,1-dimethylethyl); trimethyl oxirane; n-propylpropanamine; 2-(Propylamino)ethanol; 4-methoxy-1-butene; 6-methyl-5-hepten-2-one; and 3,4-dimethylpyridine. Some of these were among those added as surrogates or spike standards as part ofthe Advanced Technologies and Laboratories International, Inc. preparation ofthe extract of the HEPA filter media and are indicated as such in the data tables in Section 2, Results; other compounds found were not previously known to be present. The main inorganic species detected (sulfate, sodium, and sulfur) are also consistent with species added in the preparation of the methylene chloride extract of the high-efficiency particulate air sample.

  9. Asplenioideae Species as a Reservoir of Volatile Organic Compounds with Potential Therapeutic Properties.

    PubMed

    Froissard, Didier; Rapior, Sylvie; Bessière, Jean-Marie; Buatois, Bruno; Fruchier, Alain; Sol, Vincent; Fons, Françoise

    2015-06-01

    Twelve French Asplenioideae ferns (genera Asplenium and subgenera Ceterach and Phyllitis) were investigated for the first time for volatile organic compounds (VOC) using GC-MS. Sixty-two VOC biosynthesized from the lipidic, shikimic, terpenic and carotenoid pathways were identified. Several VOC profiles can be highlighted from Asplenium jahandiezii and A. xalternifolium with exclusively lipidic derivatives to A. onopteris with an equal ratio of lipidic/shikimic compounds. Very few terpenes as caryophyllene derivatives were identified, but only in A. obovatum subsp. bilotii. The main odorous lipidic derivatives were (E)-2-decenal (waxy and fatty odor), nonanal (aldehydic and waxy odor with a fresh green nuance), (E)-2-heptenal (green odor with a fatty note) and 1-octen-3-ol (mushroom-like odor), reported for all species. A few VOC are present in several species in high content, i.e., 9-oxononanoic acid used as a precursor for biopolymers (19% in A. jahandiezii), 4-hydroxyacetophenone with a sweet and heavy floral odor (17.1% in A. onopteris), and 4-hydroxybenzoic acid used as a precursor in the synthesis of parabens (11.3% in A. foreziense). Most of the identified compounds have pharmacological activities, i.e., octanoic acid as antimicrobial, in particular against Salmonellas, with fatty and waxy odor (41.1% in A. petrarchae), tetradecanoic acid with trypanocidal activity (13.3% in A. obovatum subsp. bilotii), 4-hydroxybenzoic acid (8.7% in A. onopteris) with antimicrobial and anti-aging effects, 3,4-dihydroxybenzaldehyde as an inhibitor of growth of human cancer cells (6.7% in Ceterach officinarum), and phenylacetic acid with antifungal and antibacterial activities (5.8% in A. onopteris). Propionylfilicinic acid was identified in the twelve species. The broad spectrum of odorous and bioactive VOC identified from the Asplenium, Ceterach and Phyllitis species are indeed of great interest to the cosmetic and food industries.

  10. A nanomaterial-based breath test for distinguishing gastric cancer from benign gastric conditions

    PubMed Central

    Xu, Z-q; Broza, Y Y; Ionsecu, R; Tisch, U; Ding, L; Liu, H; Song, Q; Pan, Y-y; Xiong, F-x; Gu, K-s; Sun, G-p; Chen, Z-d; Leja, M; Haick, H

    2013-01-01

    Background: Upper digestive endoscopy with biopsy and histopathological evaluation of the biopsy material is the standard method for diagnosing gastric cancer (GC). However, this procedure may not be widely available for screening in the developing world, whereas in developed countries endoscopy is frequently used without major clinical gain. There is a high demand for a simple and non-invasive test for selecting the individuals at increased risk that should undergo the endoscopic examination. Here, we studied the feasibility of a nanomaterial-based breath test for identifying GC among patients with gastric complaints. Methods: Alveolar exhaled breath samples from 130 patients with gastric complaints (37 GC/32 ulcers / 61 less severe conditions) that underwent endoscopy/biopsy were analyzed using nanomaterial-based sensors. Predictive models were built employing discriminant factor analysis (DFA) pattern recognition, and their stability against possible confounding factors (alcohol/tobacco consumption; Helicobacter pylori) was tested. Classification success was determined (i) using leave-one-out cross-validation and (ii) by randomly blinding 25% of the samples as a validation set. Complementary chemical analysis of the breath samples was performed using gas chromatography coupled with mass spectrometry. Results: Three DFA models were developed that achieved excellent discrimination between the subpopulations: (i) GC vs benign gastric conditions, among all the patients (89% sensitivity; 90% specificity); (ii) early stage GC (I and II) vs late stage (III and IV), among GC patients (89% sensitivity; 94% specificity); and (iii) ulcer vs less severe, among benign conditions (84% sensitivity; 87% specificity). The models were insensitive against the tested confounding factors. Chemical analysis found that five volatile organic compounds (2-propenenitrile, 2-butoxy-ethanol, furfural, 6-methyl-5-hepten-2-one and isoprene) were significantly elevated in patients with GC and

  11. Hydrosols of orange blossom (Citrus aurantium), and rose flower (Rosa damascena and Rosa centifolia) support the growth of a heterogeneous spoilage microbiota.

    PubMed

    Labadie, Cécile; Ginies, Christian; Guinebretiere, Marie-Hélène; Renard, Catherine M G C; Cerutti, Céline; Carlin, Frédéric

    2015-10-01

    Hydrosols are hydrodistillation products of aromatic plants. They contain less than 1g/L of dispersed essential oils giving organoleptic properties. Hydrosols are subjected to microbial proliferation. Reasons for spoilage have to be found in the nature of substrates supporting growth and of microbiological contaminants. The composition in essential oils and the microbiota of 22 hydrosol samples of Citrus aurantium L. ssp. amara L. (orange blossom), Rosa damascena Miller (rose D.), and Rosa centifolia L. (rose C.) flowers were analyzed to determine the factors responsible for decay. The median concentrations in essential oils were 677mg/L for orange blossom hydrosols, 205mg/L for rose D. hydrosols, and 116mg/L for rose C. hydrosols. The dry matter content of these hydrosols varied between 4.0mg/L and 702mg/L, and the carbohydrate content varied between 0.21mg/L and 0.38mg/L. These non-volatile compounds were likely carried over during distillation by a priming and foaming effect, and could be used as nutrients by microorganisms. A microbial proliferation at ambient temperature and also at 5°C has been observed in all studied hydrosols when stored in a non-sterile container. In contaminated hydrosols, maximal counts were about 7log10CFU/mL, while the French pharmacopeia recommends a maximal total bacterial count of 2log10CFU/mL. Neither yeast nor mold was detected. The isolated microbial population was composed of environmental Gram-negative bacteria, arranged in four major genera: Pseudomonas sp., Burkholderia cepacia complex, and presumably two new genera belonging to Acetobacteraceae and Rhodospirillaceae. Among those bacteria, Burkholderia vietnamiensis and Novosphingobium capsulatum were able to metabolize volatile compounds, such as geraniol to produce 6-methyl-5-hepten-2-one or geranic acid, or phenylethyl acetate to produce 2-phenylethanol. EO concentrations in hydrosols or cold storage are not sufficient to insure microbiological stability. Additional

  12. Heterogeneous oxidation of squalene film by ozone under various indoor conditions.

    PubMed

    Petrick, L; Dubowski, Y

    2009-10-01

    Abstract The effects of indoor conditions (ozone concentration, temperature, relative humidity (RH), and the presence of NO(x)) on heterogeneous squalene oxidation were studied with Attenuated Total Reflectance-Fourier Transform Infrared spectroscopy. The heterogeneous kinetics of squalene-ozone reaction revealed a pseudo-first-order reaction rate constant of 1.22 x 10(-5)/s at [O(3)] = 40 ppb. Oxidation kinetics were insensitive to temperature over the range of 24-58 +/- 2 degrees C as well as to RH and presence of NO(x). Products, however, were affected by the environmental parameters. As temperature was increased, fewer surface products and more low molecular weight gaseous products were observed. Lower air exchange rates also enhanced gas phase reactions, allowing for formation of secondary gas phase products. As RH increased, there was a shift in product distribution from ketones to aldehydes, and the presence of NO(x) during squalene ozonolysis resulted in the formation of nitrated oxidation products. Identified surface products included 6-methyl-5-hepten-2-one, geranyl acetone, and long chain ketones and aldehydes, while gas phase products included formaldehyde, acetone, 4-oxopentanal (4-OPA), glyoxal, and pyruvic acid. Practical Implications Heterogeneous oxidation of squalene resulted in surface products including long chain aldehydes and ketones, and gas phase products including formaldehyde, a known human carcinogen (IARC 2006), and bicarbonyl compounds like: 4-oxopentanal (4-OPA), glyoxal, and pyruvic acid that are characterized as asthma triggers and sensitizers (Anderson et al., 2007; Jarvis et al., 2005). In addition, ozonolysis experiments in the presence of NO(x) showed the formation of nitrated surface oxidation products. Such nitrated products may have higher mutagenicity, carcinogenicity, or allergenic potential than their nitrate free counterparts (Franze et al., 2005; Pitts, 1983). Kinetic studies determined that at moderate ozone levels of 40

  13. Volatile generation in bell peppers during frozen storage and thawing using selected ion flow tube mass spectrometry (SIFT-MS).

    PubMed

    Wampler, Brendan; Barringer, Sheryl A

    2012-06-01

    To determine volatile formation during storage and thawing, whole, pureed, blanched, and raw green and red bell peppers (Capsicum annuum) were frozen quickly or slowly then stored at -18 °C for up to 7 mo, with and without SnCl(2) addition during thawing. Headspace analysis was performed by a Selected Ion Flow Tube Mass Spectrometer (SIFT-MS). After blanching, (Z)-3-hexenal had a large significant decrease in concentration since it is a heat labile compound while most other volatiles did not change in concentration. The freezing process increased volatile levels in the puree only. Slow freeze peppers had higher levels of some LOX generated volatiles during storage than quick freeze. During frozen storage of blanched samples (E)-2-hexenal, (Z and E)-hexen-1-ol, and (E)-2-pentenal increased likely because of nonenzymatic autoxidation of fatty acids while other volatiles remained constant. In Raw Whole peppers, (Z)-3-hexenal, hexanal, and 2-pentylfuran were generated during storage likely because the LOX enzyme is still active during frozen storage. However, blanched samples had higher concentrations of (E)-2-hexenal, (Z and E)-hexen-1-ol, 1-penten-3-one, and (E)-2-heptenal because of enzymatic destruction of these volatiles in the raw samples. The levels of many of the volatiles in the raw samples, including (Z)-3-hexenal, (E)-2-hexenal, (Z and E)-hexen-1-ol, hexanal, (E)-2-pentenal, and 2-pentylfuran, appeared to peak around 34 d after freezing. Pureed samples had significantly higher levels of volatiles than the whole samples, and volatiles peaked earlier. Green bell pepper volatile levels were always higher than red bell pepper. Significantly higher volatile formation occurred during thawing than it did during frozen storage. Studying and monitoring the headspace volatiles with a SIFT-MS can give information that will help manufacturers better understand how the volatiles in bell peppers change during frozen storage. This will give valuable information to

  14. Superficial scald and bitter pit development in cold-stored transgenic apples suppressed for ethylene biosynthesis.

    PubMed

    Pesis, Edna; Ibáñez, Ana M; Phu, My Lin; Mitcham, Elizabeth J; Ebeler, Susan E; Dandekar, Abhaya M

    2009-04-08

    The plant hormone ethylene regulates climacteric fruit ripening and plays a major role in the development of superficial scald in apple fruits during cold storage. The effect of cold storage at 0 degrees C on development of superficial scald and bitter pit (BP) in transgenic Greensleeves (GS) apples suppressed for ethylene biosynthesis was investigated. Four apple lines were used: untransformed GS; line 68G, suppressed for 1-aminocyclopropane-1-carboxylic acid (ACC) oxidase (ACO); and lines 103Yand 130Y, suppressed for ACC synthase (ACS). Fruits from the transformed lines 68G, 103Y, and 130Y produced very little ethylene during 3 months of cold storage at 0 degrees C and after subsequent transfer to 20 degrees C, whereas untransformed fruits produced significant ethylene during cold storage, which increased dramatically at 20 degrees C. Respiration, expressed as CO(2) production, was similar in all four apple lines. After 2 months at 0 degrees C, all apple lines showed some BP symptoms, but lines 68G and 103Y were more affected than untransformed GS or line 130Y. Both transformed and untransformed apples produced alpha-farnesene, but concentrations were lower in yellow fruit than in green fruit in all lines but 68G. Line 68G produced the most alpha-farnesene after 2 months at 0 degrees C, including both (E,E) alpha-farnesene and (Z,E) alpha-farnesene. Concentrations of (E,E) alpha-farnesene were 100 times greater than those of (Z,E) alpha-farnesene in all lines. After 4 months at 0 degrees C plus 1 week at 20 degrees C, untransformed GS apples exhibited the most superficial scald, whereas fruits from lines 68G and 103Y were less affected and line 130Y had no scald. Superficial scald severity was higher in green fruit than in yellow fruit in all affected lines. These lines also exhibited significant production of 6-methyl-5-hepten-2-one (MHO), a major oxidation product of (E,E) alpha-farnesene. Line 130Y neither exhibited superficial scald nor produced MHO. It is

  15. Combined Experimental and Computational Study on the Unimolecular Decomposition of JP-8 Jet Fuel Surrogates. I. n-Decane (n-C10H22).

    PubMed

    Zhao, Long; Yang, Tao; Kaiser, Ralf I; Troy, Tyler P; Ahmed, Musahid; Belisario-Lara, Daniel; Ribeiro, Joao Marcelo; Mebel, Alexander M

    2017-02-16

    Exploiting a high temperature chemical reactor, we explored the pyrolysis of helium-seeded n-decane as a surrogate of the n-alkane fraction of Jet Propellant-8 (JP-8) over a temperature range of 1100-1600 K at a pressure of 600 Torr. The nascent products were identified in situ in a supersonic molecular beam via single photon vacuum ultraviolet (VUV) photoionization coupled with a mass spectroscopic analysis of the ions in a reflectron time-of-flight mass spectrometer (ReTOF). Our studies probe, for the first time, the initial reaction products formed in the decomposition of n-decane-including radicals and thermally labile closed-shell species effectively excluding mass growth processes. The present study identified 18 products: molecular hydrogen (H2), C2 to C7 1-alkenes [ethylene (C2H4) to 1-heptene (C7H14)], C1-C3 radicals [methyl (CH3), vinyl (C2H3), ethyl (C2H5), propargyl (C3H3), allyl (C3H5)], small C1-C3 hydrocarbons [methane (CH4), acetylene (C2H2), allene (C3H4), methylacetylene (C3H4)], along with higher-order reaction products [1,3-butadiene (C4H6), 2-butene (C4H8)]. On the basis of electronic structure calculations, n-decane decomposes initially by C-C bond cleavage (excluding the terminal C-C bonds) producing a mixture of alkyl radicals from ethyl to octyl. These alkyl radicals are unstable under the experimental conditions and rapidly dissociate by C-C bond β-scission to split ethylene (C2H4) plus a 1-alkyl radical with the number of carbon atoms reduced by two and 1,4-, 1,5-, 1,6-, or 1,7-H shifts followed by C-C β-scission producing alkenes from propene to 1-octene in combination with smaller 1-alkyl radicals. The higher alkenes become increasingly unstable with rising temperature. When the C-C β-scission continues all the way to the propyl radical (C3H7), it dissociates producing methyl (CH3) plus ethylene (C2H4). Also, at higher temperatures, hydrogen atoms can abstract hydrogen from C10H22 to yield n-decyl radicals, while methyl (CH3) can

  16. A Measurement of Gaseous and Particulate Biogenic Semi-Volatile Organic Compounds in the Forest Atmosphere with an Annular Denuder Sampling System

    NASA Astrophysics Data System (ADS)

    Matsunaga, S.; Mochida, M.; Guenther, A. B.; Schnell, R.; Greenberg, J.; Kawamura, K.; Kajii, Y.

    2003-12-01

    Atmospheric concentrations of biogenic semi-volatile organic compounds (SOCs) in both gas and particle phase have been measured in two experimental forests with an annular denuder sampling system. The sampling sites were an experimental forest of Hokkaido University at Moshiri in Hokkaido Island, northern Japan (from August 22 to 29, 2002) and an experimental forest of Duke University at Chapel Hill in North Carolina, east coast of the United States (from July 9 to 12, 2003). The compounds detected in the forest atmosphere are glycolaldehyde, hydroxyacetone, n-nonanal, n-decanal, glyoxal, methylglyoxal and 4-oxopental. Glycolaldehyde, hydroxyacetone and methylglyoxal are known as oxidation products of isoprene which has the largest emission rate of any hydrocarbon species. Nonanal and decanal are probably directly emitted from vegetation. 4-oxopentanal is an oxidation product of 6-methyl-5-hepten-2-one. This is an oxidation product of organic compounds which are abundant on plant surfaces. All of these compounds were detected in both gas and particle phases. Their concentrations ranged from the detection limit (approximately 1 pptv) to 154 pptv (630 ng m-3, 4-oxopentanal), and the particulate concentrations ranged from the detection limit (approximately 3 ng m-3) to 200 ng m-3 (4-oxopentanal) in Moshiri, 2002. The gaseous concentrations of these compounds showed a clear diurnal variation on fine days. Although their production processes are different each other, the variation showed the same pattern which was quite similar to the ambient temperature. On the other hand, partition ratios (particle/(gas+particle)) of these compounds suggested that the process of gas-to-particle conversion of these SOCs is different between water soluble compounds and insoluble compounds. The partition ratios of water soluble compounds such as glycolaldehyde, hydroxyacetone and 4-oxopentanal (their Henry_fs constant exceed 10000 mol kg-1 atm-1) depends on relative humidity at the

  17. Iron-lactoferrin complex reduces iron-catalyzed off-flavor formation in powdered milk with added fish oil.

    PubMed

    Ueno, Hiroshi M; Shiota, Makoto; Ueda, Noriko; Isogai, Tomoyuki; Kobayashi, Toshiya

    2012-08-01

    The iron-lactoferrin complex (FeLf) is useful for dietary iron supplementation. However, the effects of FeLf on iron-catalyzed off-flavors in lipid-containing food products have not been reported. In this study, we investigated the effects of FeLf on off-flavors development during the production and storage of powdered milk with added fish oil. Powdered milk samples were formulated with FeLf or iron (II) sulfate, then stored at 37 °C for 5 mo. A sensory evaluation revealed that FeLf delayed the development of oxidized flavor and reduced metallic taste in the powdered milk compared with iron (II) sulfate. Headspace gas chromatography-mass spectrometry analysis showed that oxidized volatile compounds, such as pentanal, hexanal, heptanal, octanal, 1-penten-3-one, (Z)-4-heptenal, (E, E)-2,4-heptadienal, and (E)-2-octenal, were less developed in the powdered milk containing FeLf than in that containing iron (II) sulfate. Iron and lactoferrin (Lf) were retained in the high-molecular-weight (>10000 Da) fraction of the reconstituted FeLf-containing powdered milk after its manufacture and storage, whereas the antigenicity of Lf was lost after ultrahigh-temperature processing at 120 °C for 5 s. These results suggest that FeLf reduces the iron-catalyzed off-flavors that develop during the production and storage of powdered milk. The stable iron-holding property of FeLf contributes to the inhibition of oxidized and metallic volatile formation, although the loss of Lf antigenicity did not affect the stability of FeLf and the iron-catalyzed formation of off-flavors in the powdered milk. Consequently, FeLf is a suitable candidate for the simultaneous supplementation of a single food with iron and fish oil. The supplementation of food products with iron and fish oil is a useful approach to redressing their inadequate intake in many populations. The iron-lactoferrin complex can protect food products against the off-flavors caused by iron-catalyzed lipid oxidation. Our results

  18. Identification of oxidation products of solanesol produced during air sampling for tobacco smoke by electrospray mass spectrometry and HPLC.

    PubMed

    Tucker, Samuel P; Pretty, Jack R

    2005-10-01

    Solanesol, a 45-carbon, trisesquiterpenoid alcohol found in tobacco leaves and tobacco smoke, has been used as a quantitative marker for tobacco smoke for years. However, solanesol appears to be unreliable as a quantitative marker for tobacco smoke during environmental air sampling because it can be degraded substantially when present as a component of tobacco smoke and by as much as 100% when present as pure solanesol on fortified filters during air sampling. Since there is strong evidence that ozone is the agent responsible for the degradation, solanesol appears to be unreliable as a quantitative marker during indoor air sampling when indoor levels of ozone are greater than about 15 ppb. The degree of loss of pure solanesol is directly proportional to the concentration of ozone and the length of the sampling period and depends on the type of 37 mm membrane filter used for air sampling (PTFE or quartz fiber). While the degree of loss of solanesol is inversely proportional to the relative humidity of the air at a sampling rate of 1.7 L min(-1), the degree of loss is virtually independent of relative humidity at a lower sampling rate; i.e., 0.25 L min(-1). A curve of loss of solanesol on a filter versus concentration of ozone from an ozone generator is virtually identical to a curve segment based on atmospheric ozone under the same conditions of air sampling. Oxidation of solanesol by ozone to approximately 25 to 60% completion produces at least three series of products for a total of at least 26 compounds: (1) isoprenoid acetones, (2)omega-hydroxyisoprenoid acetaldehydes, and (3) isoprenoid oxoaldehydes. All products in each series were tentatively identified as their derivatives with 2-(p-aminophenyl)ethanol (APE) by electrospray mass spectrometry (ES-MS). Ten ozonation products were detected as their 2,4-dinitrophenylhydrazine derivatives by HPLC at 360 nm: 4-oxopentanal and nine isoprenoid acetones (acetone, 6-methyl-5-hepten-2-one, geranylacetone

  19. Ozone-initiated VOC and particle emissions from a cleaning agent and an air freshener: risk assessment of acute airway effects.

    PubMed

    Nørgaard, A W; Kudal, J D; Kofoed-Sørensen, V; Koponen, I K; Wolkoff, P

    2014-07-01

    Emissions of volatile organic compounds and ultrafine particles from a kitchen cleaning agent (cream) and plug-in air freshener were investigated in a 20 m(3) walk-in climate chamber at low (~5 ppb) and high ozone (~50 ppb) test concentrations and 0.6 air exchange rate. The products emitted terpenes, inter alia limonene, dihydromyrcenol, geraniol, linalool, and glycol ethers. The ozone-initiated reaction products of these compounds were measured by air sampling on Tenax TA followed by thermal desorption GC-MS and air sampling on DNPH cartridges followed by liquid extraction and HPLC-UV analysis. Particle formation was monitored simultaneously. A number of oxygenated and poly-oxygenated reaction products were identified and risk assessed for acute airway effects: formaldehyde, acetaldehyde, acetone, 4-acetyl-1-methylcyclohexene, 6-methyl-5-heptene-2-one, 3-isopropenyl-6-oxo-heptanal, and 4-oxo-pentanal. These compounds generally increased initially at the high ozone concentration, while the terpenes decayed, concurrent with their consumption of ozone. At high ozone concentration, the plug-in air freshener resulted in concentrations of formaldehyde and 4-oxopentanal that may give rise to concern about sensory irritation and airflow limitation, respectively. At high ozone concentration, the kitchen cleaning agent and air freshener resulted in peak particle mass concentrations at 81 μg/m(3) (8.5×10(5) #/cm(3)) and 24 μg/m(3) (2.3×10(4) #/cm(3)), respectively. At low ozone concentration, the particle concentration peaked at 4 μg/m(3) (1.0×10(5) #/cm(3)) after the application of the kitchen cleaning agent, while no increase was observed for the air freshener. The particles, in view of their organic composition and concentration, are not considered to cause acute airway effects. Testing under realistic conditions that mimic user pattern behavior is warranted to obtain acute and longer-term exposure data at realistic indoor ozone concentrations.

  20. On the search for NNO-donor enantiopure scorpionate ligands and their coordination to group 4 metals.

    PubMed

    Otero, Antonio; Fernández-Baeza, Juan; Tejeda, Juan; Lara-Sánchez, Agustín; Sánchez-Molina, Margarita; Franco, Sonia; López-Solera, Isabel; Rodríguez, Ana M; Sánchez-Barba, Luis F; Morante-Zarcero, Sonia; Garcés, Andrés

    2009-06-15

    The preparation of new chiral bis(pyrazol-1-yl)methane-based NNO-donor scorpionate ligands in the form of the lithium derivatives [Li(bpzb)(THF)] [1; bpzb = 1,1-bis(3,5-dimethylpyrazol-1-yl)-3,3-dimethyl-2-butoxide] and [Li(bpzte)(THF)] [2; bpzte = 2,2-bis(3,5-dimethylpyrazol-1-yl)-1-p-tolylethoxide] or the alcohol ligands (bpzbH) (3) and (bpzteH) (4) has been carried out by 1,2-addition reactions with trimethylacetaldehyde or p-tolualdehyde. The separation of a racemic mixture of the alcohol ligand 3 has been achieved and gave an enantiopure NNO alcohol-scorpionate ligand in three synthetic steps: (i) 1,2-addition of the appropriate lithium derivative to trimethylacetaldehyde, (ii) esterification and separation of diastereoisomers 5, (iii) saponification. Subsequently, the enantiopure scorpionate ligand (R,R)-bpzmmH {6; R,R-bpzmmH = (1R)-1-[(1R)-6,6-dimethylbicyclo[3.1.1]2-hepten-2-yl]-2,2-bis(3,5-dimethylpyrazol-1-yl)ethanol} was obtained with an excellent diastereomeric excess (>99% de) in a one-pot process utilizing the aldehyde (1R)-(-)-myrtenal as a chiral substrate to control the stereochemistry of the newly created asymmetric center. These new chiral heteroscorpionate ligands reacted with [MX(4)] (M = Ti, Zr; X = NMe(2), O(i)Pr, OEt, O(t)Bu) in a 1:1 molar ratio in toluene to give, after the appropriate workup, the complexes [MX(3)(kappa(3)-NNO)] (7-18). The reaction of Me(3)SiCl with [Ti(NMe(2))(3)(bpzb)] (7) or [Ti(NMe(2))(3)(R,R-bpzmm)] (11) in different molar ratios gave the halide-amide-containing complexes [TiCl(NMe(2))(2)(kappa(3)-NNO)] (19 and 20) and [TiCl(2)(NMe(2))(kappa(3)-NNO)] (21 and 22) and the halide complex [TiCl(3)(kappa(3)-NNO)] (23 and 24). The latter complexes can also be obtained by reaction of the lithium compound 1 with TiCl(4)(THF)(2) and deprotonation of the alcohol group of 6 with NaH, followed by reaction with TiCl(4)(THF)(2) in a 1:1 molar ratio, respectively. Isolation of only one of the three possible diastereoisomers of the

  1. Combined Experimental and Computational Study on the Unimolecular Decomposition of JP-8 Jet Fuel Surrogates. II: n-Dodecane (n-C12H26).

    PubMed

    Zhao, Long; Yang, Tao; Kaiser, Ralf I; Troy, Tyler P; Ahmed, Musahid; Ribeiro, Joao Marcelo; Belisario-Lara, Daniel; Mebel, Alexander M

    2017-02-16

    We investigated temperature-dependent products in the pyrolysis of helium-seeded n-dodecane, which represents a surrogate of the n-alkane fraction of Jet Propellant-8 (JP-8) aviation fuel. The experiments were performed in a high temperature chemical reactor over a temperature range of 1200 K to 1600 K at a pressure of 600 Torr, with in situ identification of the nascent products in a supersonic molecular beam using single photon vacuum ultraviolet (VUV) photoionization coupled with the analysis of the ions in a reflectron time-of-flight mass spectrometer (ReTOF). For the first time, the initial decomposition products of n-dodecane-including radicals and thermally labile closed-shell species-were probed in experiments, which effectively exclude mass growth processes. A total of 15 different products were identified, such as molecular hydrogen (H2), C2 to C7 1-alkenes [ethylene (C2H4) to 1-heptene (C7H14)], C1-C3 radicals [methyl (CH3), ethyl (C2H5), allyl (C3H5)], small C1-C3 hydrocarbons [acetylene (C2H2), allene (C3H4), methylacetylene (C3H4)], as well as the reaction products [1,3-butadiene (C4H6), 2-butene (C4H8)] attributed to higher-order processes. Electronic structure calculations carried out at the G3(CCSD,MP2)//B3LYP/6-311G(d,p) level of theory combined with RRKM/master equation of rate constants for relevant reaction steps showed that n-dodecane decomposes initially by a nonterminal C-C bond cleavage and producing a mixture of alkyl radicals from ethyl to decyl with approximately equal branching ratios. The alkyl radicals appear to be unstable under the experimental conditions and to rapidly dissociate either directly by C-C bond β-scission to produce ethylene (C2H4) plus a smaller 1-alkyl radical with the number of carbon atoms diminished by two or via 1,5-, 1,6-, or 1,7- 1,4-, 1,9-, or 1,8-H shifts followed by C-C β-scission producing alkenes from propene to 1-nonene together with smaller 1-alkyl radicals. The stability and hence the branching ratios