Sample records for butenes

  1. 21 CFR 177.1570 - Poly-1-butene resins and butene/ethylene copolymers. (United States)


    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Poly-1-butene resins and butene/ethylene copolymers... resins and butene/ethylene copolymers. The poly-1-butene resins and butene/ethylene copolymers identified... the catalytic polymerization of 1-butene liquid monomer. Butene/ethylene copolymers are produced by...

  2. An Integrated Membrane Process for Butenes Production

    Directory of Open Access Journals (Sweden)

    Leonardo Melone


    Full Text Available Iso-butene is an important material for the production of chemicals and polymers. It can take part in various chemical reactions, such as hydrogenation, oxidation and other additions owing to the presence of a reactive double bond. It is usually obtained as a by-product of a petroleum refinery, by Fluidized Catalytic Cracking (FCC of naphtha or gas-oil. However, an interesting alternative to iso-butene production is n-butane dehydroisomerization, which allows the direct conversion of n-butane via dehydrogenation and successive isomerization. In this work, a simulation analysis of an integrated membrane system is proposed for the production and recovery of butenes. The dehydroisomerization of n-butane to iso-butene takes place in a membrane reactor where the hydrogen is removed from the reaction side with a Pd/Ag alloys membrane. Afterwards, the retentate and permeate post-processing is performed in membrane separation units for butenes concentration and recovery. Four different process schemes are developed. The performance of each membrane unit is analyzed by appropriately developed performance maps, to identify the operating conditions windows and the membrane permeation properties required to maximize the recovery of the iso-butene produced. An analysis of integrated systems showed a yield of butenes higher than the other reaction products with high butenes recovery in the gas separation section, with values of molar concentration between 75% and 80%.

  3. Isolation of 3-methyl-1-butene from a hydrocarbon stream

    Energy Technology Data Exchange (ETDEWEB)

    Drake, C.A.


    A process is described for recovering 3-methyl-1-butene from a hydrocarbon stream containing 3-methyl-1-butene and compounds which form azeotropes with 3-methyl-1-butene comprising extractive distillation of the hydrocarbon stream with a solvent mixture comprising dimethylformamide and sulfolane solvent mixture present in an amount ranging from about 0.1 to about 20 times the weight of the hydrocarbon stream. The dimethylformamide in the dimethylformamide/Sulfolane solvent mixture is present in an amount ranging from about 30 weight percent to about 70 weight percent based on the weight of the mixture. This separates insolubles containing the 3-methyl-l-butene as the overhead product stream from the bottoms product containing soluble compounds, the compounds that form azeotropes with 3-methyl-l-butene and the solvent mixture and thereafter recovering the 3-methyl-1-butene from the insolubles.


    A detailed study of the alkylation of isobutane with 2-butene in ionic liquid media has been conducted using 1-alkyl-3-methylimidazolium halides?aluminum chloride encompassing various alkyl groups (butyl-, hexyl-, and octyl-) and halides (Cl, Br, and I) on its cations and anions,...

  5. Reaction rate and isomer-specific product branching ratios of C2H + C4H8: 1-butene, cis-2-butene, trans-2-butene, and isobutene at 79 K. (United States)

    Bouwman, Jordy; Fournier, Martin; Sims, Ian R; Leone, Stephen R; Wilson, Kevin R


    The reactions of C2H radicals with C4H8 isomers 1-butene, cis-2-butene, trans-2-butene, and isobutene are studied by laser photolysis-vacuum ultraviolet mass spectrometry in a Laval nozzle expansion at 79 K. Bimolecular-reaction rate constants are obtained by measuring the formation rate of the reaction product species as a function of the reactant density under pseudo-first-order conditions. The rate constants are (1.9 ± 0.5) × 10(-10), (1.7 ± 0.5) × 10(-10), (2.1 ± 0.7) × 10(-10), and (1.8 ± 0.9) × 10(-10) cm(3) s(-1) for the reaction of C2H with 1-butene, cis-2-butene, trans-2-butene, and isobutene, respectively. Bimolecular rate constants for 1-butene and isobutene compare well to values measured previously at 103 K using C2H chemiluminescence. Photoionization spectra of the reaction products are measured and fitted to ionization spectra of the contributing isomers. In conjunction with absolute-ionization cross sections, these fits provide isomer-resolved product branching fractions. The reaction between C2H and 1-butene yields (65 ± 10)% C4H4 in the form of vinylacetylene and (35 ± 10)% C5H6 in the form of 4-penten-1-yne. The cis-2-butene and trans-2-butene reactions yield solely 3-penten-1-yne, and no discrimination is made between cis- and trans-3-penten-1-yne. Last, the isobutene reaction yields (26 ± 15)% 3-penten-1-yne, (35 ± 15)% 2-methyl-1-buten-3-yne, and (39 ± 15)% 4-methyl-3-penten-1-yne. The branching fractions reported for the C2H and butene reactions indicate that these reactions preferentially proceed via CH3 or C2H3 elimination rather than H-atom elimination. Within the experimental uncertainties, no evidence is found for the formation of cyclic species.

  6. Reactions of OH with butene isomers: measurements of the overall rates and a theoretical study. (United States)

    Vasu, Subith S; Huynh, Lam K; Davidson, David F; Hanson, Ronald K; Golden, David M


    Reactions of hydroxyl (OH) radicals with 1-butene (k(1)), trans-2-butene (k(2)), and cis-2-butene (k(3)) were studied behind reflected shock waves over the temperature range 880-1341 K and at pressures near 2.2 atm. OH radicals were produced by shock-heating tert-butyl hydroperoxide, (CH(3))(3)-CO-OH, and monitored by narrow-line width ring dye laser absorption of the well-characterized R(1)(5) line of the OH A-X (0, 0) band near 306.7 nm. OH time histories were modeled using a comprehensive C(5) oxidation mechanism, and rate constants for the reaction of OH with butene isomers were extracted by matching modeled and measured OH concentration time histories. We present the first high-temperature measurement of OH + cis-2-butene and extend the temperature range of the only previous high-temperature study for both 1-butene and trans-2-butene. With the potential energy surface calculated using CCSD(T)/6-311++G(d,p)//QCISD/6-31G(d), the rate constants and branching fractions for the H-abstraction channels of the reaction of OH with 1-butene were calculated in the temperature range 300-1500 K. Corrections for variational and tunneling effects as well as hindered-rotation treatments were included. The calculations are in good agreement with current and previous experimental data and with a recent theoretical study.

  7. Association of detoxification enzymes with butene-fipronil in larvae and adults of Drosophila melanogaster. (United States)

    Arain, Muhammad Shahid; Shakeel, Muhammad; Elzaki, Mohammed Esmail Abdalla; Farooq, Muhammad; Hafeez, Muhammad; Shahid, Muhammad Rafiq; Shah, Syed Ali Haider; Khan, Fawad Zafar Ahmad; Shakeel, Qaiser; Salim, Abdalla Markaz Abdalla; Li, Guo-Qing


    Insecticide resistance is a major challenge in successful insect pest control as the insects have the ability to develop resistance to various widely used insecticides. Butene-fipronil is a novel compound with high toxicity to insects and less toxicity to the non-target organisms. In the present study, the effect of butene-fipronil alone and in combination with three enzyme inhibitors, piperonyl butoxide (PBO), diethyl maleate (DEM), and triphenyl phosphate (TPP), was carried out on larvae and adults of Drosophilia melanogaster. Our results indicated that the co-toxicity indices of butene-fipronil + PBO, butene-fipronil + TPP, and butene-fipronil + DEM mixtures were 437.3, 335.0, and 210.3, respectively, in the second-instar larvae, while 186.6, 256.2, and 238.5, respectively, in the adults, indicating synergistic effects. Interestingly, butene-fipronil increased the expression of CYP28A5 in the larvae; CYP9F2, CYP304A1, CYP28A5, and CYP318A1 in the female adults; and CYP303A1 and CYP28A5 in the male adults. Furthermore, high-level expression of Est-7 was observed in the female adults compared to larvae and male adults. Our results suggest that there is no difference in butene-fipronil metabolism in larvae and male and female adults of D. melanogaster.

  8. Butene concentration prediction in ethylene/propylene/1-butene terpolymers by FT-IR spectroscopy through multivariate statistical analysis and artificial neural networks. (United States)

    Marengo, Emilio; Longo, Valentina; Bobba, Marco; Robotti, Elisa; Zerbinati, Orfeo; Di Martino, Silvana


    This paper reports the development of calibration models for quality control in the production of ethylene/propylene/1-butene terpolymers by the use of multivariate tools and FT-IR spectroscopy. 1-Butene concentration prediction is achieved in terpolymers by coupling FT-IR spectroscopy to multivariate regression tools. A dataset of 26 terpolymers (14 coming from a constrained experimental design for mixtures, plus 12 terpolymers used for external validation) was analysed by FT-IR spectroscopy. An internal method of "Polimeri Europa" plant, based on (13)C NMR spectroscopy is used to determine the percentage of 1-butene in the samples. Then, different multivariate tools are used for 1-butene concentration prediction based on the FT-IR spectra recorded. Different multivariate calibration methods were explored: principal component regression (PCR), partial least squares (PLS), stepwise OLS regression (SWR) and artificial neural networks (ANNs). The model obtained by back-propagation neural networks turned out to be the best one. The performances of the BP-ANN model were further improved by variable selection procedures based on the calculation of the first derivative of the network. The proposed approach allows the monitoring in real time of the polymer synthesis and the estimation of the characteristics of the product attainable from the concentration of 1-butene.

  9. Continuous gas-phase hydroformylation of 1-butene using supported ionic liquid phase (SILP) catalysts

    DEFF Research Database (Denmark)

    Haumann, Marco; Dentler, Katharina; Joni, Joni


    The concept of supported ionic liquid phase (SILP) catalysis has been extended to 1-butene hydroformylation. A rhodium-sulfoxantphos complex was dissolved in [BMIM][n-C8H17OSO3] and this solution was highly dispersed on silica. Continuous gas-phase experiments in a fixed-bed reactor revealed...... another excellent hint for truly homogeneous catalysis in the SILP system. Compared to former studies using propene, the SILP system showed significantly higher activity and selectivity with 1-butene as feedstock. These findings could be elucidated by solubility measurements using a magnetic microbalance....

  10. Electron collisions with methyl-substituted ethylenes: Cross section measurements and calculations for 2-methyl-2-butene and 2,3-dimethyl-2-butene (United States)

    Szmytkowski, Czesław; Stefanowska, Sylwia; Zawadzki, Mateusz; Ptasińska-Denga, ElŻbieta; MoŻejko, Paweł


    We report electron-scattering cross sections determined for 2-methyl-2-butene [(H3C)HC = C(CH3)2] and 2,3-dimethyl-2-butene [(H3C)2C = C(CH3)2] molecules. Absolute grand-total cross sections (TCSs) were measured for incident electron energies in the 0.5-300 eV range, using a linear electron-transmission technique. The experimental TCS energy dependences for the both targets appear to be very similar with respect to the shape. In each TCS curve, three features are discernible: the resonant-like structure located around 2.6-2.7 eV, the broad distinct enhancement peaking near 8.5 eV, and a weak hump in the vicinity of 24 eV. Theoretical integral elastic (ECS) and ionization (ICS) cross sections were computed up to 3 keV by means of the additivity rule (AR) approximation and the binary-encounter-Bethe method, respectively. Their sums, (ECS+ICS), are in a reasonable agreement with the respective measured TCSs. To examine the effect of methylation of hydrogen sides in the ethylene [H2C = CH2] molecule on the TCS, we compared the TCS energy curves for the sequence of methylated ethylenes: propene [H2C = CH(CH3)], 2-methylpropene [H2C = C(CH3)2], 2-methyl-2-butene [(H3C)HC = C(CH3)2], and 2,3-dimethyl-2-butene [(H3C)2C = C(CH3)2], measured in the same laboratory. Moreover, the isomeric effect is also discussed for the C5H10 and C6H12 compounds.


    Ionic liquids as a clean catalyst for the alkylation of isobutane with 2-buteneKyesang Yoo, a Vasudevan V. Namboodiri,b Panagiotis G. Smirniotis,*a and Rajender S. Varma*b a Department of Chemical Engineering, University of Cincinnati, Cincinnati, OH 45221-0171, USA. ...

  12. Diffusion coefficient and solubility of isobutene and trans-2-butene in aqueous sulfuric acid solutions

    NARCIS (Netherlands)

    Brilman, Derk Willem Frederik; van Swaaij, Willibrordus Petrus Maria; Versteeg, Geert


    The diffusion coefficient and the physical solubility of isobutene and trans-2-butene in aqueous sulfuric acid solutions cannot be determined experimentally due to the occurrence of fast chemical reactions. In the present contribution these physicochemical parameters are estimated. For the

  13. On the Absorption of Isobutene and trans-2-Butene in Sulfuric Acid Solutions

    NARCIS (Netherlands)

    Brilman, D.W.F.; Swaaij, W.P.M. van; Versteeg, G.F.


    In reactions in which alkenes react in the presence of homogeneous Brønstedt acid catalysts, the protonation step is rate determining. Existing reaction rate correlations for protonation of butenes in sulfuric acid solutions are not consistent and limited to sulfuric acid concentrations below 80 wt

  14. Diffusion Coefficient and Solubility of Isobutene and trans-2-Butene in Aqueous Sulfuric Acid Solutions

    NARCIS (Netherlands)

    Brilman, Derk W.F.; Swaaij, Wim P.M. van; Versteeg, Geert F.


    The diffusion coefficient and the physical solubility of isobutene and trans-2-butene in aqueous sulfuric acid solutions cannot be determined experimentally due to the occurrence of fast chemical reactions. In the present contribution these physicochemical parameters are estimated. For the

  15. Cobalt Oxide on N-Doped Carbon for 1-Butene Oligomerization to Produce Linear Octenes

    Energy Technology Data Exchange (ETDEWEB)

    Zhao, Dongting [Department; Xu, Zhuoran [Department; Chada, Joseph P. [Department; Carrero, Carlos A. [Department; Rosenfeld, Devon C. [The Dow Chemical Company, 2301 N. Brazosport Boulevard, Freeport, Texas 77541-3257, United States; Rogers, Jessica L. [The Dow Chemical Company, 2301 N. Brazosport Boulevard, Freeport, Texas 77541-3257, United States; Hermans, Ive [Department; Huber, George W. [Department


    Cobalt oxide supported on N-doped carbon catalysts were investigated for 1-butene oligomerization. The materials were synthesized by treating activated carbon with nitric acid and subsequently with NH3 at 200, 400, 600, and 800 °C, followed by impregnation with cobalt. The 1-butene oligomerization selectivity increased with ammonia treatment temperature of the carbon support. The oligomerization selectivity of cobalt oxide on N-doped carbon synthesized at 800 °C (800A-CoOx/N-C) is 2.6 times higher than previously reported cobalt oxide on N-doped carbon synthesized with NH4OH (2A-CoOx/N-C). Over 70% of the butene dimers were linear C8 olefins for all catalysts. The oligomerization selectivity increased with 1-butene conversion. The catalysts were characterized by elemental analysis, N2 adsorption, X-ray diffraction (XRD), X-ray absorption spectroscopy (XAS), and X-ray photoelectron spectroscopy (XPS). The nitrogen content of the catalysts increases with ammonia treatment temperature as confirmed by elemental analysis. The surface content of pyridinic nitrogen with a binding energy of 398.4 ± 0.1 eV increased with ammonia treatment temperature as evidenced by deconvolution of N 1s XPS spectra.

  16. Production of propylene from 1-butene on highly active "bi-functional single active site" catalyst: Tungsten carbene-hydride supported on alumina

    KAUST Repository

    Mazoyer, Etienne


    1-Butene is transformed in a continuous flow reactor over tungsten hydrides precursor W-H/Al2O3, 1, giving a promising yield into propylene at 150 °C and different pressures. Tungsten carbene-hydride single active site operates as a "bi-functional catalyst" through 1-butene isomerization on W-hydride and 1-butene/2-butenes cross-metathesis on W-carbene. This active moiety is generated in situ at the initiation steps by insertion of 1-butene on tungsten hydrides precursor W-H/Al2O3, 1 followed by α-H and β-H abstraction. © 2011 American Chemical Society.

  17. Phase equilibria of binary and ternary n-alkane solutions in supercritical ethylene, 1-butene, and ethylene + 1-butene: Transition from type A through LCST to U-LCST behavior predicted and confirmed experimentally

    Energy Technology Data Exchange (ETDEWEB)

    Gregg, C.J.; Stein, F.P. (Lehigh Univ., Bethlehem, PA (United States). Dept. of Chemical Engineering); Chen, Shenjer; Radosz, M. (Exxon Research and Engineering Co., Annandale, NJ (United States))


    Binary phase equilibria of C[sub 20] +, C[sub 30] +, and C[sub 40] + ethylene are correlated with three equations of state, the Redlich-Kwong-Soave (Soave), the generalized van der Waals-Prigogine (vdW-P), and the statistical associating fluid theory (SAFT), with special emphasis on the mixture critical region. The SAFT correlation is found to be the most reliable. SAFT predictive powers are tested on C[sub 26] + ethylene and a new set of experimental data taken in this work for C[sub 36] + 1-butene and C[sub 36] + ethylene + 1-butene. The SAFT predictions are found to be in good agreement with the experimental data. Equally important, the SAFT predictions allow for understanding the continuous transition of phase behavior, from type A (C[sub 36] + 1-butene) through LCST (C[sub 36] + ethylene + 1-butene) to U-LCST (C[sub 36] + ethylene).

  18. Cytotoxicity, genotoxicity, and mutagenicity of 1-chloro-2-hydroxy-3-butene and 1-chloro-3-buten-2-one, two alternative metabolites of 1,3-butadiene

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Xin-Jie; Zeng, Fang-Mao; An, Jing; Yu, Ying-Xin [Institute of Environmental Pollution and Health, School of Environmental and Chemical Engineering, Shanghai University, Shanghai 200444 (China); Zhang, Xin-Yu, E-mail: [Institute of Environmental Pollution and Health, School of Environmental and Chemical Engineering, Shanghai University, Shanghai 200444 (China); Elfarra, Adnan A., E-mail: [Department of Comparative Biosciences, University of Wisconsin-Madison, Madison, WI 53706 (United States); Molecular and Environmental Toxicology Center, University of Wisconsin-Madison, Madison, WI 53706 (United States)


    The cytotoxicity, genotoxicity, and mutagenicity of 1-chloro-2-hydroxy-3-butene (CHB), a known in vitro metabolite of the human carcinogen 1,3-butadiene, have not previously been investigated. Because CHB can be bioactivated by alcohol dehydrogenases to yield 1-chloro-3-buten-2-one (CBO), a bifunctional alkylating agent that caused globin-chain cross-links in erythrocytes, in the present study we investigated the cytotoxic and genotoxic potential of CHB and CBO in human normal hepatocyte L02 cells using the MTT assay, the relative cloning efficiency assay and the comet assay. We also investigated the mutagenic potential of these compounds with the Ames test using Salmonella strains TA1535 and TA1537. The results provide clear evidence for CHB and CBO being both cytotoxic and genotoxic with CBO being approximately 100-fold more potent than CHB. Interestingly, CHB generated both single-strand breaks and alkali-labile sites on DNA, whereas CBO produced only alkali-labile sites. CHB did not directly result in DNA breaks, whereas CBO was capable of directly generating breaks on DNA. Interestingly, both compounds did not induce DNA cross-links as examined by the comet assay. The Ames test results showed that CHB induced point mutation but not frameshift mutation, whereas the toxic effects of CBO made it difficult to reliably assess the mutagenic potential of CBO in the two strains. Collectively, the results suggest that CHB and CBO may play a role in the mutagenicity and carcinogenicity of 1,3-butadiene. - Highlights: • 1-Chloro-2-hydroxy-3-butene (CHB) is cytotoxic and genotoxic in human liver cells. • The CHB metabolite, 1-chloro-3-buten-2-one (CBO) is ∼ 100-fold more toxic than CHB. • CHB and CBO cause DNA alkali-labile sites, but only CBO directly causes DNA breaks. • CHB is mutagenic in the Ames test, but CBO is too toxic in the assay. • The results suggest a role for CHB in 1,3-butadiene genotoxicity and mutagenicity.

  19. Conversion of n-Butane to iso-Butene on Gallium/HZSM-5 Catalysts

    Directory of Open Access Journals (Sweden)

    S.M. Gheno


    Full Text Available The conversion of n-butane to iso-butene on gallium/HZSM-5 catalysts at 350ºC and WHSV=2.5h8-1 was studied. The catalysts were prepared by ion exchange from a Ga(NO32 solution and further submitted to calcination in air at 530ºC. TEM analysis with an EDAX detector and TPR-H2 data showed that after calcination the Ga species were present mainly as Ga2O3, which are reduced to Ga2O at temperatures near 610ºC. The specific acid activity (SAA of the catalysts increased with the increase in aluminum content in the zeolite, and for a fixed Si/Al ratio, the SAA increased with Ga content. Values for specific hydro/dehydrogenation activity (SH/DHA were significantly higher than those for SAA, indicating that the catalytic process is controlled by the kinetics on acid sites. Moreover, the production of iso-butene with a selectivity higher than 25% was a evidence that in gallium/HZSM-5-based catalysts the rate of the hydrogenation reaction is lower than that of the dehydrogenation reaction; this behavior confirmed the dehydrogenation nature of gallium species, thereby showing great promise for iso-butene production.

  20. Ethene, propene, butene and isoprene emissions from a ponderosa pine forest measured by relaxed eddy accumulation (United States)

    Rhew, Robert C.; Deventer, Malte Julian; Turnipseed, Andrew A.; Warneke, Carsten; Ortega, John; Shen, Steve; Martinez, Luis; Koss, Abigail; Lerner, Brian M.; Gilman, Jessica B.; Smith, James N.; Guenther, Alex B.; de Gouw, Joost A.


    Alkenes are reactive hydrocarbons that influence local and regional atmospheric chemistry by playing important roles in the photochemical production of tropospheric ozone and in the formation of secondary organic aerosols. The simplest alkene, ethene (ethylene), is a major plant hormone and ripening agent for agricultural commodities. The group of light alkenes (C2-C4) originates from both biogenic and anthropogenic sources, but their biogenic sources are poorly characterized, with limited field-based flux observations. Here we report net ecosystem fluxes of light alkenes and isoprene from a semiarid ponderosa pine forest in the Rocky Mountains of Colorado, USA using the relaxed eddy accumulation (REA) technique during the summer of 2014. Ethene, propene, butene and isoprene emissions have strong diurnal cycles, with median daytime fluxes of 123, 95, 39 and 17 µg m-2 h-1, respectively. The fluxes were correlated with each other, followed general ecosystem trends of CO2 and water vapor, and showed similar sunlight and temperature response curves as other biogenic VOCs. The May through October flux, based on measurements and modeling, averaged 62, 52, 24 and 18 µg m-2 h-1 for ethene, propene, butene and isoprene, respectively. The light alkenes contribute significantly to the overall biogenic source of reactive hydrocarbons: roughly 18 % of the dominant biogenic VOC, 2-methyl-3-buten-2-ol. The measured ecosystem scale fluxes are 40-80 % larger than estimates used for global emissions models for this type of ecosystem.

  1. Alkyl-halogenide promoted ionic liquid catalysis of isobutane/butene-alkylation

    Energy Technology Data Exchange (ETDEWEB)

    Schilder, L.; Korth, W.; Jess, A. [Bayreuth Univ. (Germany). Dept. of Chemical Engineering


    The effect of two different types of promoters on the performance of Lewis-acidic chloroaluminate ionic liquid catalysts was studied for liquid liquid biphasic isobutane/2-butene alkylation. In particular, the activity and selectivity of such catalytic systems was investigated. Experimental results obtained from a batch reactor show, that tert-butyl halides increase the reaction rate significantly and shift the C8-selectivity towards the desired high-octane trimethylpentanes (TMPs). But, secondary reactions like oligomerization and cracking are not affected by the use of these promoters. (orig.)

  2. Acidic and basic properties of zeolite-containing cracking catalyst in the process of butene-1 isomerization (United States)

    Mursalova, L. A.; Guseinova, E. A.; Adzhamov, K. Yu.


    The process of butene-1 isomerization in the presence of two groups of samples of zeolite-containing catalyst (ZCC) that earlier participated in the traditional and oxidative catalytic cracking of vacuum gasoil is investigated. It is established that the nature of the reaction mixture and conditions of the cracking process are key factors in forming the acidic and basic properties of the catalyst. It is shown that the highest activity in the butene-1 isomerization into cis-/ trans-butene-2 is demonstrated by ZCC samples that participated in the oxidative catalytic cracking (oxycracking). It is suggested that the enhanced catalytic activity of this group of ZCC samples was related to the availability of acid-base centers in the form of radical-like oxygen along with protic- and aprotic-type acidic centers in the structure of the oxidative compaction products.

  3. Interaction of 2'-deoxyguanosine with cis-2-butene-1,4-dial: Computational approach to analysis of multistep chemical reactions

    Directory of Open Access Journals (Sweden)

    Sviatenko L. K.


    Full Text Available cis-2-Butene-1,4-dial represents a microsomal metabolite of furan, an industrially important chemical found in cigarette smoke, air pollution, and also in canned or jarred food. It is expected to be a human carcinogen. Aim. Investigation an effect of cis-2-butene-1,4-dial on the 2'-deoxyguanine which is a model of DNA site. Methods. Optimization of reaction species molecular structures, spectral parameters and Gibbs free energy calculations were performed using Gaussian09 program. Systems of differential equations for kinetics generation were solved using Mathcad15 program. Results. The predicted mechanism of the reaction of cis-2-butene-1,4-dial with 2'-deoxyguanine consists of four-step process formation of four diastereomeric primary adducts and further base-mediated five-step transformation of the primary adducts to the secondary one. The reaction kinetics, which allows defining theconcentration change of any reaction species was calculated. Conclusions. Under physiological conditions the interaction between cis-2-butene-1,4-dial and 2'-deoxyguanine leads to the formation of a stable adduct which could be responsible for the furan genotoxicity.

  4. Steam reforming of n-butanol over Rh/ZrO2 catalyst : Role of 1-butene and butyraldehyde

    NARCIS (Netherlands)

    Harju, Heikki; Lehtonen, Juha; Lefferts, Leon


    Steam reforming (SR) of n-butanol and its main reaction intermediates, i.e., 1-butene, and butyraldehyde, was studied over 0,5wt.% Rh/ZrO2 catalyst at 500 and 700°C, atmospheric pressure and steam to carbon (S/C) molar ratio of 4. Coke deposits on the spent catalyst samples were characterized using

  5. Oxidative Dehydrogenation of n-Butenes to 1,3-Butadiene over Bismuth Molybdate and Ferrite Catalysts: A Review

    KAUST Repository

    Hong, Eunpyo


    1,3-Butadiene, an important raw material for a variety of chemical products, can be produced via the oxidative dehydrogenation (ODH) of n-butenes over multicomponent oxide catalysts based on bismuth molybdates and ferrites. In this review, the basic concept, reaction mechanism, and catalysts typically used in an ODH reaction are discussed. © 2015, Springer Science+Business Media New York.

  6. Shear effects on crystallization behaviors and structure transitions of isotactic poly-1-butene

    DEFF Research Database (Denmark)

    Li, Jingqing; Guan, Peipei; Zhang, Yao


    Different melt pre-shear conditions were applied to isotactic poly-1-butene (iP-1-B) and the effect on the crystallization behaviors and the crystalline structure transitions of iP-1-B were investigated. The polarized optical microscope observations during isothermal crystallization process....... Though the orientated crystalline structures existed in the iP-1-B samples, no accelerating effect on crystal transition from II to I was found. Importantly, the final crystalline structures of iP-1-B in form I was found tunable under different melt pre-shear conditions, even though...... revealed that the applied melt pre-shear within the experimental range could enhance the nucleation of crystal II and accelerate the diameter growth of the formed spherulites. If the applied melt pre-shear rate was large enough, Shish-Kebabs structure could be formed. After the isothermal crystallization...

  7. Metallacyclobutane substitution and its effect on alkene metathesis for propylene production over W-H/Al2O3: Case of isobutene/2-butene cross-metathesis

    KAUST Repository

    Szeto, Kaï Chung


    Cross metathesis between 2-butenes and isobutene yielding the valuable products propylene and 2-methyl-2-butene has been investigated at low pressure and temperature using WH3/Al2O3, a highly active and selective catalyst. Two parallel catalytic cycles for this reaction have been proposed where the cycle involving the less sterically hindered tungstacyclobutane intermediates is most likely favored. Moreover, it has been found that the arrangement of substituents on the least thermodynamically favored tungstacyclobutane governs the conversion rate of the cross metathesis reaction for propylene production from butenes and/or ethylene. © 2013 American Chemical Society.

  8. Electron spin resonance study of oriented allyl-type free radicals of butene and butadienecarboxylic acids and derivatives

    Energy Technology Data Exchange (ETDEWEB)

    Muszkat, L.


    Single-crystal electron spin resonance studies of free radicals formed by ..gamma.. irradiation were performed on a series of unsaturated carboxylic acids and their derivatives. As a rule, allyl-type extended ..pi..-electron free radicals are the most persistent species observed in the butene series molecules (2- and 3-hexenedioic acids) and in the butadiene series molecules (sorbic acid, sorbamide, and dimethyl muconate).

  9. Etherification of Glycerol with Propylene or 1-Butene for Fuel Additives

    Directory of Open Access Journals (Sweden)

    Chakrapong Saengarun


    Full Text Available The etherification of glycerol with propylene over acidic heterogeneous catalysts, Amberlyst-15, S100, and S200 resins, produced mono-propyl glycerol ethers (MPGEs, 1,3-di- and 1,2-di-propyl glycerol ethers (DPGEs, and tri-propyl glycerol ether (TPGE. The propylation of glycerol over Amberlyst-15 yielded only TPGE. The glycerol etherification with 1-butene over Amberlyst-15 and S200 resins produced 1-mono-, 2-mono-, 1,2-di-, and 1,3-di-butyl glycerol ethers (1-MBGE, 2-MBGE, 1,2-DBGE, and 1,3-DBGE. The use of Amberlyst-15 resulted in the propylation and butylation of glycerol with higher yields than those obtained from the S100 and S200 resins. The PGEs, TPGE, and BGEs were evaluated as cold flow improvers and octane boosters. These alkyl glycerol ethers can reduce the cloud point of blended palm biodiesels with diesel. They can increase the research octane number and the motor octane number of gasoline.

  10. Temperature-dependent absorption cross-section measurements of 1-butene (1-C4H8) in VUV and IR

    KAUST Repository

    Es-sebbar, Et-touhami


    Vacuum ultraviolet (VUV) and infrared (IR) absorption cross-section measurements of 1-butene (1-C4H8; CH2=CHCH2CH3; Butylene) are reported over the temperature range of 296-529K. The VUV measurements are performed between 115 and 205nm using synchrotron radiation as a tunable VUV light source. Fourier Transform Infrared (FTIR) spectroscopy is employed to measure absorption cross-section and band strengths in the IR region between 1.54 and 25μm (~6500-400cm-1). The measured room-temperature VUV and IR absorption cross-sections are compared with available literature data and are found to be in good agreement. The oscillator strength for the electronic transition (A1A\\'→X1A\\') around 150-205nm is determined to be 0.32±0.01.The gas temperature has a strong effect on both VUV and IR spectra. Measurements made in the VUV region show that the peak value of the band cross-section decreases and the background continuum increases with increasing gas temperature. This behavior is due to a change in the rotational and vibrational population distribution of 1-butene molecule. Similar changes in rotational population are observed in the IR spectra. Moreover, variation of the IR spectra with temperature is used to measure the enthalpy difference between syn and skew conformations of 1-butene and is found to be 0.24±0.03. kcal/mol, which is in excellent agreement with values reported in the literature. The measurements reported in this work will provide the much-needed spectroscopic information for the development of high-temperature quantitative diagnostics in combustion applications and validation of atmospheric chemistry models of extra-solar planets. © 2012 Elsevier Ltd.

  11. High-pressure vapor-liquid equilibria for ethylene + 4-methyl-1-pentane and 1-butene + 1-hexene

    Energy Technology Data Exchange (ETDEWEB)

    Laugier, S. [Ecole Nationale Superieure de Chimie et Physique de Bordeaux, Talence (France); Richon, D. [Ecole Nationale Superieure des Mines de Paris, Fontainebleau (France)


    Isothermal vapor-liquid equilibria (VLE) for the ethylene + 4-methyl-1-pentene and 1-butene + 1-hexene binary systems were measured by the static method at several temperatures for pressures in the range (0.3 to 8.5) MPa. Representations of VLE data by the Soave and Peng-Robinson cubic equations of state are compared in both modes: predictive and binary parameter adjustment. As the two binary systems behave almost ideally, there is no significant difference between their representation qualities through both equations of state.

  12. Gas-Phase Pyrolytic Reaction of 4-Aryl-3-buten-2-ols and Allyl Benzyl Ethers: Kinetic and Mechanistic Study

    Directory of Open Access Journals (Sweden)

    Maher R. Ibrahim


    Full Text Available Flash vacuum pyrolysis (FVP of 4-aryl-3-buten-2-ols [ArCH=CH-CH(CH3OH, where Ar is phenyl, p-MeO, p-Me, p-Cl, p-NO2] gave the corresponding buta-1,3-dien-1-ylbenzene (ArCH=CH-CH=CH2, where Ar is Ph, p-MeO, p-Me, p-Cl, p-NO2 and 7-X-1,2-dihydronaphthalene derivatives (where X is H, MeO; FVP of 1-aryl-3-benzyloxy1-1-butenes and benzyl cinnamyl ethers [ArCH=CHCH(XOCH2Ph, where Ar is phenyl, p-MeO, p-Me, p-Cl, X is H, Me, Ph] gave the corresponding but-2-en-1-ylbenzene derivatives (ArCH2CH=CH-X, where X is H, Me, Ph together with benzaldehyde. The proposed mechanism of these pyrolytic transformations was supported by kinetic and product analysis.

  13. Kinetics, products, and stereochemistry of the reaction of chlorine atoms with cis- and trans-2-butene in 10-700 Torr of N2 or N2/O2 diluent at 297 K. (United States)

    Kaiser, E W; Donahue, C J; Pala, I R; Wallington, T J; Hurley, M D


    The reactions of Cl atoms with cis- and trans-2-butene have been studied using FTIR and GC analyses. The rate constant of the reaction was measured using the relative rate technique. Rate constants for the cis and trans isomers are indistinguishable over the pressure range 10-900 Torr of N2 or air and agree well with previous measurements at 760 Torr. Product yields for the reaction of cis-2-butene with Cl in N2 at 700 Torr are meso-2,3-dichlorobutane (47%), DL-2,3-dichlorobutane (18%), 3-chloro-1-butene (13%), cis-1-chloro-2-butene (13%), trans-1-chloro-2-butene (2%), and trans-2-butene (8%). The yields of these products depend on the total pressure. For trans-2-butene, the product yields are as follows: meso-2,3-dichlorobutane (48%), dl-2,3-dichlorobutane (17%), 3-chloro-1-butene (12%), cis-1-chloro-2-butene (2%), trans-1-chloro-2-butene (16%), and cis-2-butene (2%). The products are formed via addition, addition-elimination from a chemically activated adduct, and abstraction reactions. These reactions form (1) the stabilized 3-chloro-2-butyl radical, (2) the chemically activated 3-chloro-2-butyl radical, and (3) the methylallyl radical. These radicals subsequently react with Cl2 to form the products via a proposed chemical mechanism, which is discussed herein. This is the first detailed study of stereochemical effects on the products of a gas-phase Cl+olefin reaction. FTIR spectra (0.25 cm(-1) resolution) of meso- and DL-2,3-dichlorobutane are presented. The relative rate technique was used (at 900 Torr and 297 K) to measure: k(Cl + 3-chloro-1-butene) = (2.1 +/- 0.4) x 10(-10), k(Cl + 1-chloro-2-butene) = (2.2 +/- 0.4) x 10(-10), and k(Cl + 2,3-dichlorobutane) = (1.1 +/- 0.2) x 10(-11) cm3 molecule(-1) s(-1).


    Directory of Open Access Journals (Sweden)

    Deni Pranowo


    Full Text Available 4-(4-methoxyphenyl-3-buten-2-on has been synthesized from p-anisaldehyde and acetone via aldol condensation. The reaction was performed at room temperature under basic condition for 12 hours to give brown solid of product (m.p 64-65 oC in 66.19 % yield. p-anisaldehyde itself was produced from oxidation of anetol major component of anise oil by the use of potassium permanganate as a oxidator. The structure of the products was analyzed by FTIR, 1H NMR and GC-MS. Activity test of 4-(4-methoxyphenyl-3-buten-2-on as an attractant was carried out in Sleman with methyl eugenol as a reference. The result showed that 4-(4-methoxyphenyl-3-buten-2-on was inactive compound as a fruit flies attractant and some of fruit flies, i.e. Bactrocera papayae, B. carambolae, B. umbrosa and B. abdolonginqua was found on the test area.   Keywords: 4-(4-metoxy-phenyl-3-butene-2-on, Bactrocera spp., attractant

  15. Spectroscopic Identification of Y(C4H6) Isomers Formed by Yttrium-Mediated C-H Bond Activation of Butenes (United States)

    Kim, Jong Hyun; Yang, Dong-Sheng


    Y(C4H6) was observed from the reactions of laser-vaporized Y atom with 1-butene (CH2=CHCH2CH3) and iso-butene (CH2=C(CH3)2) in a pulsed molecular beam source, and its structural isomers were investigated with mass-analyzed threshold ionization spectroscopy combined with electronic structure calculations and spectral simulations. Y(C4H6) was identified as a five-membered metallacycle [Y(CH2-CH=CH-CH2)] from the Y + 1-butene reaction and a tetrahedral structure [YC(CH2)3] from the Y + iso-butene reaction. The metallacycle has a Cs structure with Y binding to the two terminal carbon atoms, whereas the tetrahedron has C3v symmetry with Y binding to the tertiary carbon atom of trimethylenemethane. Both isomers have a doublet ground state with the highest molecular orbital being largely a Y 5s character. Ionization removes the metal based electron, and the resultant singlet ion has a similar structure to the neutral complex. However, the adiabatic ionization energy [46309(5) cm-1] of the tetrahedron is considerably higher than that [43473(5) cm-1] of the cyclic structure.

  16. Influence of phosphorous addition on Bi3Mo2Fe1 oxide catalysts for the oxidative dehydrogenation of 1-butene

    KAUST Repository

    Park, Jung-Hyun


    Bi3Mo2Fe1Px oxide catalysts were prepared by a co-precipitation method and the influence of phosphorous content on the catalytic performance in the oxidative dehydrogenation of 1-butene was investigated. The addition of phosphorous up to 0.4mole ratio to Bi3Mo2Fe1 oxide catalyst led to an increase in the catalytic performance; however, a higher phosphorous content (above P=0.4) led to a decrease of conversion. Of the tested catalysts, Bi3Mo2Fe1P0.4 oxide catalyst exhibited the highest catalytic performance. Characterization results showed that the catalytic performance was related to the quantity of a π-allylic intermediate, facile desorption behavior of adsorbed intermediates and ability for re-oxidation of catalysts. © 2015 Korean Institute of Chemical Engineers, Seoul, Korea

  17. Fluid phase equilibria of the reaction mixture during the selective hydrogenation of 2-butenal in dense carbon dioxide

    DEFF Research Database (Denmark)

    Musko, Nikolai; Jensen, Anker Degn; Baiker, Alfons


    Knowledge of the phase behaviour and composition is of paramount importance for understanding multiphase reactions. We have investigated the effect of the phase behaviour in the palladium-catalysed selective hydrogenation of 2-butenal to saturated butanal in dense carbon dioxide. The reactions were...... cell. The results of the catalytic experiments showed that small amounts of carbon dioxide added to the system significantly decrease the conversion, whereas at higher loadings of CO2 the reaction rate gradually increases reaching a maximum. The CPA calculations revealed that this maximum is achieved...... in the so-called “expanded liquid” region, which is located near the critical point of the reacting mixture. It was also found that in this point the hydrogen concentration achieved its maximum in the CO2-expanded phase. Furthermore, the pressure – temperature regions where the multicomponent reaction...

  18. Theoretical investigation of the hydrogen shift reactions in peroxy radicals derived from the atmospheric decomposition of 3-methyl-3-buten-1-ol (MBO331)

    DEFF Research Database (Denmark)

    Knap, Hasse Christian; Jørgensen, Solvejg; Kjærgaard, Henrik Grum


    The hydroxy peroxy radical derived from the oxidation of 3-methyl-3-buten-1-ol (MBO331), can undergo four different hydrogen shift (H-shift) reactions. We have compared optimized geometries, barrier heights and reaction rate constants obtained with five different DFT functionals (BLYP, B3LYP, BHa...... of the MBO331 peroxy radical was found to undergo a 1,5-CH H-shift reaction with a reaction rate constant of about 1 s-1.......The hydroxy peroxy radical derived from the oxidation of 3-methyl-3-buten-1-ol (MBO331), can undergo four different hydrogen shift (H-shift) reactions. We have compared optimized geometries, barrier heights and reaction rate constants obtained with five different DFT functionals (BLYP, B3LYP, BHand...

  19. Olefin skeletal isomerization of n-butene, n-hexene and n-octene using alumina-based catalysts / Geertruida (Trudie) Brittz


    Brittz, Geertruida


    Stringent standards to improve air quality and to protect human health are continuously implemented due to the environmental impact of auto emissions. As a result, researching options for alternative components or alternative processes are very important to continuously improve the octane number in the fuel pool. Therefore, by exploiting the high olefin (butene, hexene and octene) content part of the feedstocks, the overall aim of this study was to obtain olefin skeletal isomerization for ...

  20. [Research on the modification of Kevlar fiber by polypropylene glycol and cis-2-butene-1,4-diol]. (United States)

    Zheng, Yu-ying; Wang, Can-yao; Fu, Ming-lian; Cai, Wei-long; Wang, Liang-en


    The mechanism of the modification of Kevlar fiber by polypropylene glycol(PPG) and cis-2-butene-1, 4-diol was studied in the paper, the authors learned the esterification of toluene-2, 4-diisocyanate (TDI) onto Kevlar fiber by infrared spectrum. In the mean time, the infrared spectrograms of the productions which steadily disposed by PPG and butendiol were analysed respectively, the result showed that the intensity of the bands was reinforced at about 1700-1720 cm(-1) after the samples were steadily disposed, that is to say, the group of --NCO has been stabilized into --NHCO group, the effect of steady disposal was obvious; but the disposal effect of butendiol was apparently better than PPG's at the same condition. Finally, the authors compared the influence of different mol rates between TDI and butendiol on the productions. Based onthe consequence, excessive butendiol would prevent the Kevlar fiber from farther reaction, therefore, the mol rate between TDI and butendiol should approach 1:1.

  1. Electrical conductivity and equation of state of liquid nitrogen, oxygen, benzene, and 1-butene shocked to 60 GPa

    Energy Technology Data Exchange (ETDEWEB)

    Hamilton, D.C.


    Measurements are reported for the electrical conductivity of liquid nitrogen (N/sub 2/), oxygen (O/sub 2/) and benzene (C/sub 6/H/sub 6/), and Hugoniot equation of state of liquid 1-butene (C/sub 4/H/sub 8/) under shock compressed conditions. The conductivity data span 7 x 10/sup -4/ to 7 x 10/sup 1/ ..cap omega../sup -1/cm/sup -1/ over a dynamic pressure range 18.1 to 61.5 GPa and are discussed in terms of amorphous semiconduction models which include such transport phenomena as hopping, percolation, pseudogaps, and metallization. Excellent agreement is found between the equation-of-state measurements, which span a dynamic pressure range 12.3 to 53.8 GPa, and Ree's calculated values which assume a 2-phase mixture consisting of molecular hydrogen and carbon in a dense diamond-like phase. There is a 2-1/2 fold increase in the thermal pressure contribution over a less dense, stoichiometrically equivalent liquid. 90 refs., 48 figs., 8 tabs.

  2. 2-Methyl-3-buten-2-ol (MBO) synthase expression in Nostoc punctiforme leads to over production of phytols. (United States)

    Gupta, Dinesh; Ip, Tina; Summers, Michael L; Basu, Chhandak


    Phytol is a diterpene alcohol of medicinal importance and it also has potential to be used as biofuel. We found over production of phytol in Nostoc punctiforme by expressing a 2-Methyl-3-buten-2-ol (MBO) synthase gene. MBO synthase catalyzes the conversion of dimethylallyl pyrophosphate (DMAPP) into MBO, a volatile hemiterpene alcohol, in Pinus sabiniana. The result of enhanced phytol production in N. punctiforme, instead of MBO, could be explained by one of the 2 models: either the presence of a native prenyltransferase enzyme with a broad substrate specificity, or appropriation of a MBO synthase metabolic intermediate by a native geranyl diphosphate (GDP) synthase. In this work, an expression vector with an indigenous petE promoter for gene expression in the cyanobacterium N. punctiforme was constructed and MBO synthase gene expression was successfully shown using reverse transcriptase (RT)-PCR and SDS-PAGE. Gas chromatography--mass spectrophotometry (GC-MS) was performed to confirm phytol production from the transgenic N. punctiforme strains. We conclude that the expression of MBO synthase in N. punctiforme leads to overproduction of an economically important compound, phytol. This study provides insights about metabolic channeling of isoprenoids in cyanobacteria and also illustrates the challenges of bioengineering non-native hosts to produce economically important compounds.

  3. Fungal Symbionts of the Spruce Bark Beetle Synthesize the Beetle Aggregation Pheromone 2-Methyl-3-buten-2-ol. (United States)

    Zhao, Tao; Axelsson, Karolin; Krokene, Paal; Borg-Karlson, Anna-Karin


    Tree-killing bark beetles depend on aggregation pheromones to mass-attack their host trees and overwhelm their resistance. The beetles are always associated with phytopathogenic ophiostomatoid fungi that probably assist in breaking down tree resistance, but little is known about if or how much these fungal symbionts contribute to the beetles' aggregation behavior. In this study, we determined the ability of four major fungal symbionts of the spruce bark beetle Ips typographus to produce beetle aggregation pheromones. The fungi were incubated on Norway spruce Picea abies bark, malt agar, or malt agar amended with 0.5% (13)C glucose. Volatiles present in the headspace of each fungus were analyzed for 7 days after incubation using a SPME autosampler coupled to a GC/MS. Two Grosmannia species (G. penicillata and G. europhioides) produced large amounts of 2-methyl-3-buten-2-ol (MB), the major component in the beetles' aggregation pheromone blend, when growing on spruce bark or malt agar. Grosmannia europhioides also incorporated (13)C glucose into MB, demonstrating that the fungi can synthesize MB de novo using glucose as a carbon source. This is the first clear evidence that fungal symbionts of bark beetles can produce components in the aggregation pheromone blend of their beetle vectors. This provides new insight into the possible ecological roles of fungal symbionts in bark beetle systems and may deepen our understanding of species interactions and coevolution in these important biological systems.

  4. 3-Methyl-2-butene-1-thiol: identification, analysis, occurrence and sensory role of an uncommon thiol in wine. (United States)

    San-Juan, Felipe; Cacho, Juan; Ferreira, Vicente; Escudero, Ana


    A highly uncommon odorant, 3-methyl-2-butene-1-thiol was detected by using Gas Chromatography-Olfactometry (GC-O) and unequivocally identified for the first time in wine. A purge and trap sampling technique which provides highly representative extracts for olfactometric analysis was used for the extraction of the volatile fraction of a Spanish red wine made from Prieto Picudo grapes. The identification of the odorant was achieved by multidimensional gas chromatography analysis of the same purge and trap extract. Mass spectrum and retention indices in both polar and non-polar columns allowed knowing unequivocally the identity. To obtain quantitative data a method was validated for the analysis of the compound at ng L(-1) level with acceptable precision. This powerful odorant presented an odor threshold in wine of 0.5-1 ng L(-1) and it has been detected in several Prieto Picudo wines at concentrations slightly above the odor threshold. Copyright © 2012 Elsevier B.V. All rights reserved.

  5. A shock tube and laser absorption study of ignition delay times and OH reaction rates of ketones: 2-Butanone and 3-buten-2-one

    KAUST Repository

    Badra, Jihad


    Ketones are potential biofuel candidates and are also formed as intermediate products during the oxidation of large hydrocarbons or oxygenated fuels, such as alcohols and esters. This paper presents shock tube ignition delay times and OH reaction rates of 2-butanone (C2H5COCH3) and 3-buten-2-one (C2H3COCH3). Ignition delay measurements were carried out over temperatures of 1100-1400K, pressures of 3-6.5atm, and at equivalence ratios (F{cyrillic}) of 0.5 and 1. Ignition delay times were monitored using two different techniques: pressure time history and OH absorption near 306nm. The reaction rates of hydroxyl radicals (OH) with these two ketones were measured over the temperature range of 950-1400K near 1.5atm. The OH profiles were monitored by the narrow-line-width ring-dye laser absorption of the well-characterized R1(5) line in the OH A-X (0, 0) band near 306.69nm. We found that the ignition delay times of 2-butanone and 3-buten-2-one mixtures scale with pressure as P-0.42 and P-0.52, respectively. The ignition delay times of 3-buten-2-one were longer than that of 2-butanone for stoichiometric mixtures, however, for lean mixtures (F{cyrillic}=0.5), 2-butanone had longer ignition delay times. The chemical kinetic mechanism of Serinyel et al. [1] over-predicted the ignition delay times of 2-butanone at all tested conditions, however, the discrepancies were smaller at higher pressures. The mechanism was updated with recent rate measurements to decrease discrepancy with the experimental data. A detailed chemistry for the oxidation of 3-buten-2-one was developed using rate estimation method and reasonable agreements were obtained with the measured ignition delay data. The measured reaction rate of 2-butanone with OH agreed well with the literature data, while we present the first high-temperature measurements for the reaction of OH with 3-buten-2-one. The following Arrhenius expressions are suggested over the temperature range of 950-1450K: kC2H5COCH3+OH=6.78×1013exp

  6. Comparison of two-body and three-body decomposition of ethanedial, propanal, propenal, n-butane, 1-butene, and 1,3-butadiene. (United States)

    Chin, Chih-Hao; Lee, Shih-Huang


    We investigated two-body (binary) and three-body (triple) dissociations of ethanedial, propanal, propenal, n-butane, 1-butene, and 1,3-butadiene on the ground potential-energy surfaces using quantum-chemical and Rice-Ramsperger-Kassel-Marcus calculations; most attention is paid on the triple dissociation mechanisms. The triple dissociation includes elimination of a hydrogen molecule from a combination of two separate terminal hydrogen atoms; meanwhile, the rest part simultaneously decomposes to two stable fragments, e.g., C(2)H(4), C(2)H(2), or CO. Transition structures corresponding to the concerted triple dissociation were identified using the B3LYP/6-311G(d,p) level of theory and total energies were computed using the method CCSD(T)/6-311+G(3df, 2p). The forward barrier height of triple dissociation has a trend of ethanedial butane butane, 1-butene, and 1,3-butadiene were investigated for the first time. To outline a whole picture of dissociation mechanisms, some significant two-body dissociation channels were investigated for the calculations of product branching ratios. The triple dissociation plays an important role in the three carbonyl compounds, but plays a minor or negligible role in the three hydrocarbons.

  7. 2-methyl-3-buten-2-ol: A Pheromone Component of Conifer Bark Beetles Found in the Bark of Nonhost Deciduous Trees

    Directory of Open Access Journals (Sweden)

    Qing-He Zhang


    Full Text Available Volatiles from bark of aspen, Populus tremula L. and two species of birch: silver birch (Betula pendula Roth. and common birch (B. pubescens Ehrh., were collected by direct solvent extraction and aeration of both newly cut bark chips and undamaged stems in June 1998 and subjected to GC-MS analysis. The results showed the presence of 2-methyl-3-buten-2-ol (MB, one of the two principal aggregation pheromone components of the spruce bark beetle, Ips typographus, in bark extraction samples of all the three deciduous tree species tested. In addition, one more oxygenated hemiterpene, 3-methyl-3-buten-2-one, and (E-3-penten-2-ol were also found in the bark extracts. Only trace amounts of MB were detected in some aeration samples of the fresh bark chips, and no MB was found from the aeration samples of undamaged stems at detectable levels. The occurrence of this compound was also confirmed in the bark of four exotic birch species: B. albosinensis Schneid., B. ermanii Cham., B. jacquemontii Spach, and B. maximowicziana Regel, but not yet in the European pines/spruces and the common yeasts. Our results raise major questions regarding the evolution, the tropospheric chemistry, and the ecological role of this hemiterpene alcohol. They also suggest that comparative studies on the biosynthetic pathways for MB in different sources would be of considerably evolutionary interest.

  8. Observation of H displacement and H2 elimination channels in the reaction of O(3P) with 1-butene from crossed beams and theoretical studies (United States)

    Caracciolo, Adriana; Vanuzzo, Gianmarco; Balucani, Nadia; Stranges, Domenico; Cavallotti, Carlo; Casavecchia, Piergiorgio


    We report preliminary combined experimental/theoretical results on O(3P) + 1-butene reaction dynamics with focus on atomic hydrogen displacement and molecular hydrogen elimination channels. Dynamics and relative yield of the ethylvinoxy + H and ethylketene + H2 product channels are characterized in crossed beam experiments. Stationary points and energetics of triplet/singlet C4H8O potential energy surfaces (PESs) are calculated at CCSD(T)/CBS and CASPT2 level. O(3P) attack occurs on both unsaturated C-atoms with preference for the less substituted one leading, among other products, to C2H5CHCHO + H via an exit barrier on the triplet PES, and to C2H5CHCO + H2 via a very high exit barrier on the singlet PES following intersystem crossing.

  9. Development of analytical methods for the gas chromatographic determination of 1,2-epoxy-3-butene, 1,2:3,4-diepoxybutane, 3-butene-1,2-diol, 3,4-epoxybutane-1,2-diol and crotonaldehyde from perfusate samples of 1,3-butadiene exposed isolated mouse and rat livers

    Energy Technology Data Exchange (ETDEWEB)

    Bhowmik, S.; Schuster, A.; Filser, J.G.


    Mutagenicity and carcinogenicity of 1,3-butadiene (BD) highly probably results from epoxide metabolites as 1,2-epoxy-3-butene (EB), 1,2:3,4-diepoxybutane (DEB) and 3,4-epoxybutane-1,2-diol (EBD). A further metabolite crotonaldehyde (CA) has also been discussed to be relevant. So far, in BD exposed rodents only EB and DEB concentrations had been quantified. However, the methods used were either not very sensitive or instrumentally expensive. Therefore, the goal of the present work was to establish simple analytical methods selective and sensitive enough to determine all of these compounds and a further secondary BD intermediate, 3-butene-1,2-diol (B-diol), in BD exposed rodent livers. The once-through perfused liver system was chosen for testing the applicability of the methods to be developed, since it enables BD exposures of this quantitatively most relevant metabolising organ near to the in-vivo situation. All the metabolites were extracted from the aqueous perfusion medium and analysed using a gas chromatograph equipped with a mass selective detector (GC/MS) in the PCI mode. (orig.)

  10. Influence of organic load rate (OLR) on the hydrolytic acidification of 2-butenal manufacture wastewater and analysis of bacterial community structure. (United States)

    Song, Guangqing; Xi, Hongbo; Zhou, Yuexi; Fu, Liya; Xing, Xin; Wu, Changyong


    The influence of organic loading rate (OLR) on the performance of hydrolytic acidification process for treating 2-butenal manufacture wastewater was comprehensively studied, while its impact on microbial community was thoroughly investigated. The results demonstrated that over 21.0% of the average COD removal rate was observed in the range of OLR from 0.52 to 3.98g COD/L·d, whereas it reduced to 15.3% with increasing OLR to 6.09g COD/L·d. The acidification degree dramatically decreased from 17.1% to 4.7% when OLR increased from 3.98 to 6.09g COD/L·d. In addition, the removal rates of three kinds of typical matters were less than 65% at the OLR 6.09g COD/L·d. Illumina MiSeq sequencing revealed that Proteobacteria, Chloroflexi, Firmicutes, and Bacteroidetes were dominant phyla at different OLRs. Finally, multivariate analysis suggested that the genera Longilinea and T78 had a positive correlation with the degradation of three kinds of typical matters and COD removal rates. Copyright © 2017 Elsevier Ltd. All rights reserved.

  11. Kinetic and Mechanistic Studies for the Gas-phase Reaction of Ozone with 2, 3-Dimethyl-2-Butene and 1, 3-Butadiene

    Directory of Open Access Journals (Sweden)

    Ismael Abdulsatar AL Mulla


    Full Text Available The reactions of ozone with 2,3-Dimethyl-2-Butene (CH32C=C(CH32 and 1,3-Butadiene CH2=CHCH=CH2 have been investigated under atmospheric conditions at 298±3K in air using both relative and absolute rate techniques, and the measured rate coefficients are found to be in good agreement in both techniques used. The obtained results show the addition of ozone to the double bond in these compounds and how it acts as function of the methyl group substituent situated on the double bond. The yields of all the main products have been determined using FTIR and GC-FID and the product studies of these reactions establish a very good idea for the decomposition pathways for the primary formed compounds (ozonides and give a good information for the effect of the methyl group on the degradation pathways. The results have been discussed from the view point of their importance in the atmospheric oxidation of these pollutants.

  12. The cross-metathesis of methyl oleate with cis-2-butene-1,4-diyl diacetate and the influence of protecting groups

    Directory of Open Access Journals (Sweden)

    Jessica Pérez Gomes


    Full Text Available Background: α,ω-Difunctional substrates are useful intermediates for polymer synthesis. An attractive, sustainable and selective (but as yet unused method in the chemical industry is the oleochemical cross-metathesis with preferably symmetric functionalised substrates. The current study explores the cross-metathesis of methyl oleate (1 with cis-2-butene-1,4-diyl diacetate (2 starting from renewable resources and quite inexpensive base chemicals.Results: This cross-metathesis reaction was carried out with several phosphine and N-heterocyclic carbene ruthenium catalysts. The reaction conditions were optimised for high conversions in combination with high cross-metathesis selectivity. The influence of protecting groups present in the substrates on the necessary catalyst loading was also investigated.Conclusions: The value-added methyl 11-acetoxyundec-9-enoate (3 and undec-2-enyl acetate (4 are accessed with nearly quantitative oleochemical conversions and high cross-metathesis selectivity under mild reaction conditions. These two cross-metathesis products can be potentially used as functional monomers for diverse sustainable polymers.

  13. Development of three stable isotope dilution assays for the quantitation of (E)-2-butenal (crotonaldehyde) in heat-processed edible fats and oils as well as in food. (United States)

    Granvogl, Michael


    Three stable isotope dilution assays (SIDAs) were developed for the quantitation of (E)-2-butenal (crotonaldehyde) in heat-processed edible fats and oils as well as in food using synthesized [¹³C₄]-crotonaldehyde as internal standard. First, a direct headspace GC-MS method, followed by two indirect methods on the basis of derivatization with either pentafluorophenylhydrazine (GC-MS) or 2,4-dinitrophenylhydrazine (LC-MS/MS), was developed. All methods are also suitable for the quantitation of acrolein using the standard [¹³C₃]-acrolein. Applying these three methods on five different types of fats and oils varying in their fatty acid compositions revealed significantly varying crotonaldehyde concentrations for the different samples, but nearly identical quantitative data for all methods. Formed amounts of crotonaldehyde were dependent not only on the type of oil, e.g., 0.29-0.32 mg/kg of coconut oil or 33.9-34.4 mg/kg of linseed oil after heat-processing for 24 h at 180 °C, but also on the applied temperature and time. The results indicated that the concentration of formed crotonaldehyde seemed to be correlated with the amount of linolenic acid in the oils. Furthermore, the formation of crotonaldehyde was compared to that of its homologue acrolein, demonstrating that acrolein was always present in higher amounts in heat-processed oils, e.g., 12.3 mg of crotonaldehyde/kg of rapeseed oil in comparison to 23.4 mg of acrolein/kg after 24 h at 180 °C. Finally, crotonaldehyde was also quantitated in fried food, revealing concentrations from 12 to 25 μg/kg for potato chips and from 8 to 19 μg/kg for donuts, depending on the oil used.

  14. Synthesis and matrix-assisted laser desorption/ionization time-of-flight characterization of bisphenol-A copolyformals containing nickel(II)/Schiff base, eicosane and 2-butene units in the main chain. (United States)

    Vitalini, Daniele; Spina, Emanuela; Rapisardi, Roberto; Scamporrino, Emilio; Mineo, Placido


    Some bisphenol-A copolyformals, containing in the main chain different amounts of a Ni-diimine nonlinear optical (NLO)-chromophore, eicosane and/or 2-butene units, were synthesized by condensation reaction between dibromomethane and suitable mixtures of Ni(II)/Schiff base complex, 1,20-di(bisphenol-A)ether-eicosane and/or 1,4-di(bisphenol-A)ether-2-butene. Structural composition and thermal properties of polymeric materials were inferred by analyses by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOFMS), nuclear magnetic resonance (NMR), gel permeation chromatography (GPC), differential scanning calorimetry (DSC) and thermogravimetry (TG). MALDI-TOF data show that both Ni-diimine and unsaturated units are present in the copolyformals with a homogeneous arrangement in all the polymer mass range (GPC data). It has also been ascertained that the glass transition temperature (Tg) of the copolymers changes as a consequence of the abundance of aliphatic units in the macromolecules (DSC data). Cross-linking experiments of the copolymer at temperatures near the Tg value and under UV irradiation were also performed. Copyright 2006 John Wiley & Sons, Ltd.

  15. Study of ethylene/2-butene cross-metathesis over W-H/Al2O 3 for propylene production: Effect of the temperature and reactant ratios on the productivity and deactivation

    KAUST Repository

    Mazoyer, Etienne


    A highly active and selective catalyst based on supported tungsten hydride for the cross-metathesis between ethylene and 2-butenes yielding propylene has been investigated at low pressure with various temperatures and feed ratios. At low temperature (120 °C), the catalyst deactivates notably with time on stream. This phenomenon was extensively examined by DRIFTS, TGA, DSC, and solid-state NMR techniques. It was found that a large amount of carbonaceous species were formed due to a side-reaction such as olefin polymerization which took place simultaneously with the metathesis reaction. However, at 150 °C, the catalyst was stable with time and thereby gave a high productivity in propylene. Importantly, the slight increase in temperature clearly disfavored the side reaction. The ratio of ethylene to trans-2-butene was also studied, and surprisingly, the W-H/Al2O3 catalyst is stable and highly selective to propylene even at substoichiometric ethylene ratios. © 2013 Elsevier Inc. All rights reserved.

  16. Selective Skeletal Butene Isomerization Through a Bimolecular Mechanism Isomérisation bimoléculaire sélective du n-butène en isobutène

    Directory of Open Access Journals (Sweden)

    Benazzi E.


    Full Text Available n-Butene transformation was carried out at 350°C over medium pore size zeolites (H-FER, H-TON, H-EU-1 and H-MFI and at 500°C over alumina. With fresh catalysts, not only isobutene but also propene and pentenes are primary products, which indicates that at least some of the butene isomerization occurs through oligomerization-isomerization-cracking steps (bimolecular mechanism. The large differences in selectivity are due to many factors, including whether or not trimer intermediates participate in the mechanism and limited product desorption. All the catalysts exhibit increasing isobutene selectivity with increasing time on-stream. This increase in selectivity can be explained by the selective isomerization of n-butene through a reaction process whose first step is the formation of trimethylpentene intermediates from isobutene product and n-butene reactant. This autocatalytic reaction can render the bimolecular transformation of n-butenes very selective to isobutene. La transformation du n-butène a été étudiée en réacteur dynamique à 350°C sur des zéolithes à taille de pore intermédiaire (H-FER, H-TON, H-EU-1 et H-MFI et à 500°C sur alumine. Sur les catalyseurs frais, l'isobutène mais aussi le propène et les pentènes sont directement formés (produits primaires, ce qui démontre que l'isomérisation de squelette du n-butène se produit au moins en partie par des étapes successives d'oligomérisation, isomérisation et craquage (mécanisme bimoléculaire. Les différences importantes de sélectivité entre les catalyseurs sont dues à de nombreux facteurs : participation ou non d'intermédiaires trimères, limitations dans la désorption des produits branchés, etc. Sur tous les catalyseurs, la sélectivité en isobutène augmente avec le temps de travail. Cette augmentation s'explique par un nouveau mode d'isomérisation très sélectif impliquant comme intermédiaires des triméthylpentènes formés par réaction du n

  17. Calculation of electric dipole intensity parameter to explore some interaction between hard metal ions Pr(III) and Nd(III) with π-electron density of butene-1,4 and butyne-1,4-diols in non-aqueous solutions: An absorption spectral study (United States)

    Singh, Th. David; Sumitra, Ch.; Bag, G. C.; Devi, M. Indira; Singh, N. Rajmuhon


    Pr(III) and Nd(III) are hard acceptors in HSAB (hard and soft acid base) sense and hence are known to exhibit practically a little affinity towards electrons. At the same time these metal ions show strong preference for oxygen donor chelating ligands. The ligands chosen for this study are structurally related diols, viz. butane-1,4, butene-1,4 and butyne-1,4-diols which form identical seven membered chelate ring by coordinating to metals in a bidentate manner through oxygen on 1 and 4 positions of the diol molecules. Complexation of these diols with Pr(III) and Nd(III) was carried out in DMF, CH3OH, CH3CN and their equimolar binary mixtures using comparative absorption spectrophotometry of 4f-4f transitions. The variation of oscillator strengths (P) of different 4f-4f bands as well as the magnitude and variation of Judd-Ofelt electric dipole intensity parameters (Tλ, λ = 2, 4, 6) was discussed. They correlate the interaction between the metal 4f-orbitals of Pr(III) and Nd(III) with the π-electron densities of the double and triple bonds present in butene-1,4 and butyne-1,4-diols, respectively. The value of empirical intensity parameter [Tλ(complex)/Tλ (aquo)] was calculated and its plot against oscillator strength (P) is drawn.

  18. Henry's law constants and infinite dilution activity coefficients of cis-2-butene, dimethylether, chloroethane, and 1,1-difluoroethane in methanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutanol, tert-butanol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, 3-methyl-1-butanol, and 2-methyl-2-butanol

    Energy Technology Data Exchange (ETDEWEB)

    Miyano, Yoshimori [Department of Chemistry and Bioscience, Kurashiki University of Science and the Arts, 2640 Nishinoura, Tsurajimacho, Kurashiki 712-8505 (Japan)]. E-mail:; Kobashi, Takahiro [Department of Chemistry and Bioscience, Kurashiki University of Science and the Arts, 2640 Nishinoura, Tsurajimacho, Kurashiki 712-8505 (Japan); Shinjo, Hiroshi [Department of Chemistry and Bioscience, Kurashiki University of Science and the Arts, 2640 Nishinoura, Tsurajimacho, Kurashiki 712-8505 (Japan); Kumada, Shinya [Department of Chemistry and Bioscience, Kurashiki University of Science and the Arts, 2640 Nishinoura, Tsurajimacho, Kurashiki 712-8505 (Japan); Watanabe, Yusuke [Department of Chemistry and Bioscience, Kurashiki University of Science and the Arts, 2640 Nishinoura, Tsurajimacho, Kurashiki 712-8505 (Japan); Niya, Wataru [Department of Chemistry and Bioscience, Kurashiki University of Science and the Arts, 2640 Nishinoura, Tsurajimacho, Kurashiki 712-8505 (Japan); Tateishi, Yoko [Department of Chemistry and Bioscience, Kurashiki University of Science and the Arts, 2640 Nishinoura, Tsurajimacho, Kurashiki 712-8505 (Japan)


    Henry's law constants and infinite dilution activity coefficients of cis-2-butene, dimethylether, chloroethane, and 1,1-difluoroethane in methanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutanol, tert-butanol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, 3-methyl-1-butanol, and 2-methyl-2-butanol in the temperature range of 250 K to 330 K were measured by a gas stripping method and partial molar excess enthalpies were calculated from the activity coefficients. A rigorous formula for evaluating the Henry's law constants from the gas stripping measurements was used for the data reduction of these highly volatile mixtures. The uncertainty is about 2% for the Henry's law constants and 3% for the estimated infinite dilution activity coefficients. In the evaluation of the infinite dilution activity coefficients, the nonideality of the solute such as the fugacity coefficient and Poynting correction factor cannot be neglected, especially at higher temperatures. The estimated uncertainty of the infinite dilution activity coefficients includes 1% for nonideality.

  19. Valorisation de la coupe C4 de vapocraquage via l'hydrogénation du butadiène, l'isomérisation des butènes et la métathèse, en MTBE ou en propylène Upgrading the C4 Cut from Steam Cracking via the Hydrogenation of Butadiene, the Isomerization of Butenes and Metathesis Into Mtbe Or Propylene

    Directory of Open Access Journals (Sweden)

    Chaumette S.


    of the cut can be transformed into MTBE by implementing the new n-butene isomerization process. Another upgrading scheme consits in transforming isobutene into MTBE and n-butenes into propylene by metathesis with ethylene. These new route may find competition in the transformation of butenes into alkylates, for automotive gasoline, with or without MTBE production. After a brief review of the different markets for the products involved, a technico-economic study serves to classify the different upgrading routes of the C4 cut from steam cracking, by comparing both the minimum profitable selling prices for a discounting rate of 12% and the discounted cash-flow rate of return for fixed selling prices. Calculations are performed within a context in which the C4 cut is devalorized in relation to naphtha with a price of $152/t. When butadiene no longer finds any outlets, and when its price is at a very low level such as $270/t, its extraction is hardly profitable, and propylene production by methatesis proves to be more advantageous. However, if the steam cracker is integrated in a refinery, butenes may also be advantageously transformed into alkylates or MTBE, more especially to meet a demand for octane or oxygenated products for fuels. These different routes for upgrading MTBE are more advantageous than MTBE production from butanes, requiring heavy investments for the separation of butanes, the isomerization of n-butane and the dehydrogenation of isobutane. Likewise, the transformation of butenes into propylene is more profitable than obtaining propylene by the dehydrogenation of proprane. A sensitivity study, for the price of butadiene and also for the price of other products, enables isoprofitability curves to be plotted, which delimite price zones favorable to one or the other of the products considered, taken two by two.

  20. 21 CFR 177.1430 - Isobutylene-butene copolymers. (United States)


    ... 4. Used as production aids in the manufacture of expanded (foamed) polystyrene articles complying... polypropylene complying with § 177.1520, and in polystyrene complying with § 177.1640 300 to 5,000 40 to 20,000...

  1. Catalytic skeletal isomerization of linear butenes to isobutene

    CSIR Research Space (South Africa)

    Butler, AC


    Full Text Available since the late 1970s in implementing the catalytic skeletal isomerization reaction of these linear alkenes. Halogenated catalysts, especially those based on alumina, and prepared using a variety of compounds of fluorine, chlorine or bromine, have been...

  2. Role of aromatic substituents on the antiproliferative effects of diphenyl ferrocenyl butene compounds. (United States)

    Zekri, Ouardia; Hillard, Elizabeth A; Top, Siden; Vessières, Anne; Pigeon, Pascal; Plamont, Marie-Aude; Huché, Michel; Boutamine, Sultana; McGlinchey, Michael J; Müller-Bunz, Helge; Jaouen, Gérard


    We have been exploring the cytotoxic effects of conjugated phenylferrocene systems on breast cancer cells. Complexes with p-OH, p-NH(2), and p-NHC(O)CH(3) substitution show particularly high activity, with IC(50) values in the low or sub micromolar range for both the hormone-dependent MCF-7 and hormone-independent MDA-MB-231 breast cancer cell lines. We now present the synthesis, X-ray crystal structures and biochemical studies of analogous halogen or pseudo-halogen para-substituted compounds with R = Cl, (Z)-7a; Br, (Z)-7b; CF(3), (E)-7c; and CN, (E)-7d and (Z)-7d. Lacking hydrogen bonding groups, the compounds have low, but non-zero, relative binding affinity values for the oestrogen receptor alpha (RBA


    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...

  4. Spectrophotometric method for exploring 3-methyl-2-butene-1-thiol (MBT) formation in lager. (United States)

    Pozdrik, Richard; Roddick, Felicity A; Rogers, Peter J; Nguyen, Thang


    The disappearance of riboflavin absorbance at 445 nm from beers or model beers on light exposure is directly linked to light-struck character formation. The addition of (+)-catechin, (-)-epicatechin, tryptophol, or ascorbic acid was able to reduce, but not stop, absorbance loss or light-struck character formation in either model beer or mainstream lager that was exposed to light. When isohumulone was present in model beer, the inhibitory effect of (+)-catechin, (-)-epicatechin, or tryptophol decreased with increasing isohumulone. The spectrophotometric method used in this study is a simple and effective method for determining light-struck susceptibility.

  5. Grubbs's Cross Metathesis of Eugenol with cis-2-butene-1, 4-diol to Make a Natural Product: An Organometallic Experiment for the Undergraduate Lab (United States)

    Taber, Douglass F.; Frankowski, Kevin J.


    A modified experimental procedure for the one-step synthesis that is suitable for the undergraduate organic lab is presented. In the course of work towards the more routine use of air-sensitive organometallic complexes such as the Grubb's catalyst, the natural product (E)-4-(4-hydroxy-3-methoxyphenyl) but-2-en-ol, 4, was synthesized.


    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...

  7. Isomerization of C[sub 4] alkenes (United States)

    Smith, L.A. Jr.


    A method is described for isomerizing isobutene or n-butene to produce a mixture of isobutene and normal butene, and polymerizing at least a portion thereof to produce isobutene/n-butene co-dimer, which comprises feeding at least 80 weight % of either the isobutene or n-butene to a catalytic distillation reactor containing a fixed bed acidic cation exchange resin catalyst packing which provides both the catalyst sites and distillation sites for the reaction products, isomerizing a portion of the isobutene or n-butene to produce a mixture of isobutene and n-butene and reacting at least a portion of the isobutene and n-butene to form co-dimer of isobutene and n-butene, whereby an overhead fraction containing any unreacted isobutene and n-butene and a bottoms fraction containing co-dimer is produced. The result of the reaction is substantially the same regardless whether the feed is isobutene or n-butene. Other aspects of the invention, include combinations of procedures to produce high purity isobutene and n-butene. Either isobutene or n-butene product (depending on the desired product) can be recycled as feed, thus substantially carrying out the isomerization to extinction and total conversion to the desired product. 1 fig.

  8. A Large Scale Formal Synthesis of CoQ{sub 10}: Highly Stereoselective Friedel-Crafts Allylation Reaction of Tetramethoxytoluene with (E)-4-Chloro-2-methyl-1-phenylsulfonyl-2-butene in the Presence of Montmorillonite K-10

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Sang Who; Lee, Hee Bong; Kim, Bong Chan; Sadaiah, Kadivendi; Lee, Kyuwoong; Shin, Hyunik [LG Life Sciences, Ltd., Daejeon (Korea, Republic of)


    We disclosed that MK-10 is a highly effective catalyst for the Friedel-Crafts reaction of 6 and 7 in terms of yield and of stereoselectivity. Although there are numerous applications of clays in Friedel-Crafts reaction, there is very limited example which demonstrated its effect on the stereoselectivity. In that context, our result is significant and further expansion in this direction is highly envisioned. Ubiquinone, as its name represents, exists ubiquitously in human body, particularly in the heart. It mediates the electron transfer process in mitochondria and also exerts strong antioxidant effect in its reduced form. In clinical trial, it showed beneficial effect on heart-related diseases such as myocardial infarction, angina, and other related symptoms to cause decreased mortality compared to the placebo group.

  9. Conjugation of isoprene monoepoxides with glutathione, catalyzed by α, μ, π and θ-class glutathione S-transferases of rat and man

    NARCIS (Netherlands)

    Bogaards, J.J.P.; Venekamp, J.C.; Salmon, F.G.C.; Bladeren, P.J. van


    In the present study, the enzymatic conjugation of the isoprene monoepoxides 3,4 epoxy-3-methyl-1-butene (EPOX-I) and 3,4-epoxy-2-methyl-1-butene (EPOX-II) with glutathione was investigated, using purified glutathione S-transferases (GSTs) of the α, μ, π and θ-class of rat and man. HPLC analysis of

  10. Insights into the deactivation mechanism of supported tungsten hydride on alumina (W-H/Al2O3) catalyst for the direct conversion of ethylene to propylene

    KAUST Repository

    Mazoyer, Etienne


    Tungsten hydride supported on alumina prepared by the surface organometallic chemistry method is an active precursor for the direct conversion of ethylene to propylene at low temperature and pressure. An extensive contact time study revealed that the dimerization of ethylene to 1-butene is the primary and also the rate limiting step. The catalytic cycle further involves isomerization of 1-butene to 2-butene, followed by cross-metathesis of ethylene and 2-butene to yield propylene with high selectivity. The deactivation mechanism of this reaction has been investigated. The used catalyst was extensively examined by DRIFTS, solid-state NMR, EPR, UV-Vis, TGA and DSC techniques. It was found that a large amount of carbonaceous species, which were due to side reaction like olefin polymerization took place with time on stream, significantly hindering the dimerization of ethylene to 1-butene and therefore the production of propylene. Crown Copyright © 2014 Published by Elsevier B.V. All rights reserved.

  11. Synthesis and E/Z Configuration Determination of Novel Derivatives of 3-Aryl-2-(benzothiazol-2'-ylthio Acrylonitrile, 3-(Benzothiazol-2'-ylthio-4-(furan-2''-yl-3-buten-2-one and 2-(1-(Furan-2''-yl-3'-oxobut-1''-en-2-ylthio-3-phenylquinazolin-4(3H-one

    Directory of Open Access Journals (Sweden)

    Adel Abou El-Khair


    Full Text Available Knoevenagel condensation of 2-(benzothiazol-2-ylthio acetonitrile (2 with either furan-2-carbaldehyde or thiophene-2-carbaldehydes leads to E-isomers 4a–b exclusively, while the condensation of the compound 2 with benzaldehyde or para-substituted benzaldehydes with an electron-donating group afforded E/Z mixtures 4c–e with preferentially formation of the E-isomer. Condensation of furan-2-carbaldehyde (3a with either 1-(benzothiazol-2'-ylthio propan-2-one (5 or 2-(2'-oxo propylthio-3-phenyl-quinazolin-4(3H-one (9 leads exclusively to the Z-isomers of 6 and 10, respectively. The structures of the newly synthesized compounds were elucidated by elemental analyses, 1H-NMR and 13C-NMR spectra, COSY, HSQC, HMBC, NOE, MS and X-ray crystallographic investigations.

  12. Netradiční polyolefiny: Struktura, vlastnosti a perspektivy

    Czech Academy of Sciences Publication Activity Database

    Chvátalová, L.; Výchopňová, J.; Čermák, R.; Raab, Miroslav


    Roč. 44, 7-8 (2007), s. 202-208 ISSN 0322-7340 Institutional research plan: CEZ:AV0Z40500505 Keywords : polyolefins * hierarchical structure * poly-1-butene Subject RIV: CD - Macromolecular Chemistry

  13. 40 CFR Appendix Ix to Part 264 - Ground-Water Monitoring List (United States)


    ...′-Dichlorobenzidine 91-94-1 -4,4′-diamine, 3,3′-dichloro- trans-1,4-Dichloro-2-butene 110-57-6 2-Butene, 1,4-dichloro... ester Dimethoate 60-51-5 Phosphorodithioic acid, O,O-dimethyl S- ester p-(Dimethylamino)azobenzene 60-11...,12-dimethyl- 3,3′-Dimethylbenzidine 119-93-7 -4,4′-diamine, 3,3′-dimethyl- alpha, alpha...

  14. Selective hydrogenation of 1,3-butadiene from crude C{sub 4} cracker stream with a solid catalyst with ionic liquid layer (SCILL). DSC and solubility study

    Energy Technology Data Exchange (ETDEWEB)

    Mangartz, T.; Korth, W.; Kern, C.; Jess, A. [Bayreuth Univ. (Germany). Dept. of Chemical Engineering


    In petroleum as well as in fine chemical industry, selective catalytic hydrogenation is an important reaction. The selective hydrogenation of 1,3-butadiene (BD) to butene (trans-,1- and cis-butene) from the crude C4 steam cracker fraction represents one example, but under today's technical conditions undesired butane forms inevitably in relevant amounts. To increase the butene yield, the concept of Solid Catalyst with Ionic Liquid Layer (SCILL) was employed. The SCILL catalyst, in contrast to the uncoated catalyst, yielded a remarkably high selectivity to butenes (S{sub butenes} > 99 %) even at high residence times or at high hydrogen partial pressure. Nearly no butane (S{sub butane} {approx} 0 %) was analytically detected. We expected that due to different solubility, the poorer soluble compounds discharged from the ionic liquid and, thus, caused the shift in selectivity to a great extent. Temperature dependent solubility measurements in the used ionic liquid ([DMIM][DMP]) revealed that the order of increasing solubility is 1,3-butadiene > butenes > butane which matches the assumption. However, since differences in solubility cannot explain this SCILL effect satisfyingly, ionic liquids are expected to affect the surface of the catalyst (side-specific ligand-type effect). Investigations using spectroscopic methods (e.g. FTIR) confirmed this suggestion. (orig.)

  15. Evaluation of concentrations of volatile organic compounds (VOCs) and particulate matter (PM) in an urban area downwind of major petrochemical complexes, in Harris County, Texas (United States)

    Wilkerson, Daryl F.

    Highly Reactive Volatile Organic Compounds (HRVOCs), in particular, the toxic ozone precursors, ethylene, propylene, butenes (1-butene, cis-2-butene, trans-2-butene) and 1, 3 butadiene found in the Houston area are the most critical in the formation of ozone. Exposure to such chemical can cause adverse health effect on the local population of the area, ranging from respiratory distress, asthma, COPD to Cancer. Urban ambient air samples were collected and analyzed from eight monitoring stations (Sites), encompassing the Houston Ship Channel (HSC), in Harris County, Texas. The data was interpreted and analyzed for changes in the concentration of air pollutants, data was collected daily (24 hours) over a time period from September 2013 to August 2014. One 40-minute sample was collected each hour and analyzed by automated gas chromatograph (Auto-GCs) on-site. A total of 70 compounds are measured hourly at each site, in this research the following chemicals were analysis for their average, seasonal and monthly concentrations: ethane, ethylene, propane, propylene, isobutane, n-butane, 1-butene, c-2-butene, t-2-butene and 1,3-butadiene. In this study, seasonal conditions in the area produced ranges from low to high concentrations of these compounds at certain locations. Two Stations had extremely high yearly average concentrations of butane and its isomers (c-2-butene, t-2-butene) and three stations, 1-butene and isobutene concentrations exceeded normal safety limits along with 1,3-butadiene. One station, in particular, close to the HSC had the highest yearly average propylene concentration. Local meteorology also promotes risk issues to the local health of persons within the area/community of interest. This research concluded that the analyzed results of ambient air samples in the urban areas surrounding the Houston Ship Channel (HSC) in Harris County, Texas posed a dual threat. The production of ozone in the daylight hours and depletion of ozone at night, as well as the

  16. Metabolic engineering for the high-yield production of isoprenoid-based C5 alcohols in E. coli (United States)

    George, Kevin W.; Thompson, Mitchell G.; Kang, Aram; Baidoo, Edward; Wang, George; Chan, Leanne Jade G.; Adams, Paul D.; Petzold, Christopher J.; Keasling, Jay D.; Soon Lee, Taek


    Branched five carbon (C5) alcohols are attractive targets for microbial production due to their desirable fuel properties and importance as platform chemicals. In this study, we engineered a heterologous isoprenoid pathway in E. coli for the high-yield production of 3-methyl-3-buten-1-ol, 3-methyl-2-buten-1-ol, and 3-methyl-1-butanol, three C5 alcohols that serve as potential biofuels. We first constructed a pathway for 3-methyl-3-buten-1-ol, where metabolite profiling identified NudB, a promiscuous phosphatase, as a likely pathway bottleneck. We achieved a 60% increase in the yield of 3-methyl-3-buten-1-ol by engineering the Shine-Dalgarno sequence of nudB, which increased protein levels by 9-fold and reduced isopentenyl diphosphate (IPP) accumulation by 4-fold. To further optimize the pathway, we adjusted mevalonate kinase (MK) expression and investigated MK enzymes from alternative microbes such as Methanosarcina mazei. Next, we expressed a fusion protein of IPP isomerase and the phosphatase (Idi1~NudB) along with a reductase (NemA) to diversify production to 3-methyl-2-buten-1-ol and 3-methyl-1-butanol. Finally, we used an oleyl alcohol overlay to improve alcohol recovery, achieving final titers of 2.23 g/L of 3-methyl-3-buten-1-ol (~70% of pathway-dependent theoretical yield), 150 mg/L of 3-methyl-2-buten-1-ol, and 300 mg/L of 3-methyl-1-butanol. PMID:26052683

  17. Transfer hydrogenation of olefin from alcohol using a hydrogen-absorbing alloy (CaNi{sub 5}) catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Imamura, H.; Tanaka, T.; Sakata, Y.; Tsuchiya, S. [Yamaguchi Univ., Ube (Japan). Faculty of Engineering


    Gas-phase reactions between 2-butene and 2-propanol on a hydrogen-absorbing alloy CaNi{sub 5} have been studied in the temperature range of 393 to 473 K. CaNi{sub 5} showed interesting characteristics as an active catalyst for the transfer hydrogenation of butene from propanol as a hydrogen donor. 2-Propanol was effectively dehydrogenated to yield acetone, in which the dissociated hydrogen was completely absorbed by CaNi{sub 5} to form the metal hydride. When the alloy was hydrided to some extent, butene was effectively hydrogenated by the absorbed hydrogen in the metal hydride to produce butane. The overall reaction was expressed as catalytic transfer hydrogenation through the formation of metal hydride intermediates (CaNi{sub 5}H{sub n}). Catalytic transfer hydrogenation on CaNi{sub 5} occurred at 423 K via hydriding of CaNi{sub 5} by 2-propanol dehydrogenation with subsequent dehydriding for the hydrogenation of 2-butene, rather than the direct reaction between 2-butene and 2-propanol on the alloy. (orig.)

  18. [The analysis of C4 and C5 olefins in cracking gasoline]. (United States)

    Zhang, Z; Yang, H; Wang, H


    The paper described the analytical method of butenes and pentenes in cracking gasoline with a boiling point range from initial to 210 degrees C. Beside the C3 (propane + protene) and n, i-C4 = (n-butene + i-butene) combine peaks, all C2-C5 components in the sample were separated on the OV-1 column. The proportion of the combined peaks was determined on the Al2O3 column. The quantitative results were calculated on the data determined from the above one-column analytical systems with a relative standard deviation ASTM D2427-87, the simple operation, easy application, good repetition and all component results were characteristic of the method.

  19. Structure Sensitivity in Pt Nanoparticle Catalysts for Hydrogenation of 1,3-Butadiene: In Situ Study of Reaction Intermediates Using SFG Vibrational Spectroscopy

    KAUST Repository

    Michalak, William D.


    The product selectivity during 1,3-butadiene hydrogenation on monodisperse, colloidally synthesized, Pt nanoparticles was studied under reaction conditions with kinetic measurements and in situ sum frequency generation (SFG) vibrational spectroscopy. SFG was performed with the capping ligands intact in order to maintain nanoparticle size by reduced sintering. Four products are formed at 75 C: 1-butene, cis-2-butene, trans-2-butene, and n-butane. Ensembles of Pt nanoparticles with average diameters of 0.9 and 1.8 nm exhibit a ∼30% and ∼20% increase in the full hydrogenation products, respectively, as compared to Pt nanoparticles with average diameters of 4.6 and 6.7 nm. Methyl and methylene vibrational stretches of reaction intermediates observed under working conditions using SFG were used to correlate the stable reaction intermediates with the product distribution. Kinetic and SFG results correlate with previous DFT predictions for two parallel reaction pathways of 1,3-butadiene hydrogenation. Hydrogenation of 1,3-butadiene can initiate with H-addition at internal or terminal carbons leading to the formation of 1-buten-4-yl radical (metallocycle) and 2-buten-1-yl radical intermediates, respectively. Small (0.9 and 1.8 nm) nanoparticles exhibited vibrational resonances originating from both intermediates, while the large (4.6 and 6.7 nm) particles exhibited vibrational resonances originating predominately from the 2-buten-1-yl radical. This suggests each reaction pathway competes for partial and full hydrogenation and the nanoparticle size affects the kinetic preference for the two pathways. The reaction pathway through the metallocycle intermediate on the small nanoparticles is likely due to the presence of low-coordinated sites. © 2012 American Chemical Society.

  20. Direct measurement of OH radicals from ozonolysis of selected alkenes: a EUPHORE simulation chamber study. (United States)

    Siese, M; Becker, K H; Brockmann, K J; Geiger, H; Hofzumahaus, A; Holland, F; Mihelcic, D; Wirtz, K


    Reactions of ozone with alkenes can be a significant source of hydroxyl radicals in the atmosphere. In the present paper, the formation of OH radicals in the ozonolysis of selected alkenes under atmospheric conditions was directly observed. The experiments were carried out in the European photoreactor EUPHORE (Valencia, Spain). OH radicals were quantitatively detected by means of laser-induced fluorescence (LIF) using a new analytical instrument, which has been constructed on the basis of an existing setup already established in field studies. The OH radicals observed resulted directly from the reaction of ozone with the corresponding alkene. There was no indication that OH radicals were produced in the system by secondary processes. The experimentally observed concentration-time profiles of OH and ozone were excellently described by chemical modeling using explicit reaction mechanisms. The following OH yields were derived: 2,3-dimethyl-2-butene: (1.00 +/- 0.25); 2-methyl-2-butene: (0.89 +/- 0.22); trans-2-butene: (0.75 +/- 0.19); alpha-pinene: (0.91 +/- 0.23). In addition, the experiments carried out were modeled using the Regional Atmospheric Chemistry Mechanism (RACM), an established condensed chemical model applied in tropospheric chemistry. For 2,3-dimethyl-2-butene, 2-methyl-2-butene, and trans-2-butene the calculated concentration-time profiles of OH and ozone are in quite good agreement with the experimental data. However, in the case of alpha-pinene, the model fails for the simulation of OH due to the high grade of mechanism condensation, which results in a poor characterization of the primary reaction products.

  1. Sources of C₂-C₄ alkenes, the most important ozone nonmethane hydrocarbon precursors in the Pearl River Delta region. (United States)

    Zhang, Yanli; Wang, Xinming; Zhang, Zhou; Lü, Sujun; Huang, Zhonghui; Li, Longfeng


    Surface ozone is becoming an increasing concern in China's megacities such as the urban centers located in the highly industrialized and densely populated Pearl River Delta (PRD) region, where previous studies suggested that ozone production is sensitive to VOC emissions with alkenes being important precursors. However, little was known about sources of alkenes. Here we present our monitoring of ambient volatile organic compounds at four representative urban, suburban and rural sites in the PRD region during November-December 2009, which experienced frequent ozone episodes. C2-C4 alkenes, whose total mixing ratios were 11-20% of non-methane hydrocarbons (NMHCs) quantified, accounted for 38-64% of ozone formation potentials (OFPs) and 30-50% of the total hydroxyl radical (OH) reactivity by NMHCs. Ethylene was the most abundant alkene, accounting for 8-15% in total mixing ratios of NMHCs and contributed 25-46% of OFPs. Correlations between C2-C4 alkenes and typical source tracers suggested that ethylene might be largely related to vehicle exhausts and industry activities, while propene and butenes were much more LPG-related. Positive Matrix Factorization (PMF) confirmed that vehicle exhaust and liquefied petroleum gas (LPG) were two major sources that altogether accounted for 52-62%, 58-77%, 73-83%, 68-79% and 73-84% for ethylene, propene, 1-butene, trans-2-butene and cis-2-butene, respectively. Vehicle exhausts alone contributed 32-49% ethylene and 35-41% propene. Industry activities contributed 13-23% ethylene and 7-20% propene. LPG instead contributed the most to butenes (38-65%) and substantially to propene (23-36%). Extensive tests confirmed high fractions of propene and butenes in LPG then used in Guangzhou and in LPG combustion plumes; therefore, limiting alkene contents in LPG would benefit regional ozone control. Copyright © 2014 Elsevier B.V. All rights reserved.

  2. Identification of Halohydrins as Potential Disinfection By-Products in Treated Drinking Water

    Directory of Open Access Journals (Sweden)

    Karl J. Jobst


    It appears that DBP-A is 3-chloro-2-methylbutan-2-ol and that DBP-B is its bromo analogue. DBP-B has been detected in ozonated waters containing bromide. Our study also shows that these DBPs can be laboratory artefacts, generated by the reaction of residual chlorine in the sample with 2-methyl-2-butene, the stabilizer in the CH2Cl2 used for extraction. This was shown by experiments using CH2Cl2 stabilized with deuterium labelled 2-methyl-2-butene. Quenching any residual chlorine in the drinking water sample with sodium thiosulfate minimizes the formation of these artefacts.

  3. Combine selective hydrogenation and distillation to upgrade C[sub 4] and C[sub 5] streams

    Energy Technology Data Exchange (ETDEWEB)

    Barchas, R.; Samarth, R. (ABB Lummus Crest Inc., Houston, TX (United States)); Gildert, G. (Chemical Research and Licensing, Houston, TX (United States))

    Selective hydrogenation of C[sub 4] and C[sub 5] diolefins is attracting wide interest from refiners and petrochemical producers for a variety of reasons. When treating refinery and petrochemical C[sub 4] streams, selective hydrogenation increases normal butenes available for alkylation or isomerization to isobutylene, reduces acid consumption in alkylation units, and greatly improves the quality of HF alkylate. It is also a preferred processing step in the production of comonomer grade butene-1. When treating refinery C[sub 5] streams, selective hydrogenation is a required pretreatment step for TAME production and alkylation, improving product quality in both, and reducing acid consumption in the latter.


    In the presence of a catalytic amount of RuCl2(PPh3)3, a cross-coupling of 3-buten-2-ol with aldehydes and imines was developed via a tandem olefin migration--aldol--Mannich reaction in bmim[PF6]. With In(OAc)3 as a co-catalyst, a-vinylbenzyl alcohol and aldehydes underwent sim...

  5. Paraffin Alkylation Using Zeolite Catalysts in a slurry reactor: Chemical Engineering Principles to Extend Catalyst Lifetime

    NARCIS (Netherlands)

    Jong, K.P. de; Mesters, C.M.A.M.; Peferoen, D.G.R.; Brugge, P.T.M. van; Groot, C. de


    The alkylation of isobutane with 2-butene is carried out using a zeolitic catalyst in a well stirred slurry reactor. Whereas application of fixed bed technology using a solid acid alkylation catalyst has in the led to catalysts lifetimes in the range of minutes, in this work we report catalyst

  6. Cladobotryal: a Fungal Metabolite with a Novel Ring System

    DEFF Research Database (Denmark)

    Breinholt, Jens; Jensen, Helle C.; Kjær, Anders


    In screening for antifungal metabolites a novel compound, cladobotryal, was isolated from the mycoparasitic fungus Cladobotryum varium. Its structure was established as (+)-(2R*,3R*)-2-[(Z)- 2-buten-2-yl]-3,7-dihydro-3-formyl-3-methyl-5-phenylfuro[2,3-b]pyr idin-4(2H)-one on the basis...

  7. Two new compounds from Trollius chinensis Bunge. (United States)

    Jie-Shi, Ya; Wei-Sang, Lin; Yan, Rui; Zhao, Qiang; Zhang, Yang; Yun-Zhao, Gui; Cong-Li, Yun; Chen, Xue; Yu-Zhang, Chong; Qiao, Hua; Gang-Zhang, Guo


    Two new compounds, 2″-O-feruloylisoswertiajaponin (1) and (2E)-2-methyl-1-O-vaniloyl-4-β-D-glucopyranoside-2-butene (2), along with one indole alkaloid and five known flavonoids, were isolated from the flowers of Trollius chinensis Bunge. Their structures were elucidated on the basis of spectroscopic evidence (UV, IR, HR-ESI-MS, NMR).

  8. The effect of the pore structure of medium-pore zeolites on the dehydroisomerization of n-butane: A comparison of Pt-FER, Pt-TON and Pt-ZSM5

    NARCIS (Netherlands)

    Pirngruber, G.D.; Zinck, O.P.E.; Seshan, Kulathuiyer; Lercher, J.A.


    The catalytic dehydroisomerization of n-butane over Pt–ZSM5, Pt–TON, and Pt–FER was investigated. Pt–ZSM5 showed the highest yield and selectivity to isobutene. Most of the by-products of Pt–ZSM5 were formed by oligomerization/cracking of butene, while acid-catalyzed cracking and metal-catalyzed

  9. Sum Frequency Generation Vibrational Spectroscopy of 1,3-Butadiene Hydrogenation on 4 nm Pt@SiO 2 , Pd@SiO 2 , and Rh@SiO 2 Core–Shell Catalysts

    KAUST Repository

    Krier, James M.


    © 2014 American Chemical Society. 1,3-Butadiene (1,3-BD) hydrogenation was performed on 4 nm Pt, Pd, and Rh nanoparticles (NPs) encapsulated in SiO2 shells at 20, 60, and 100 °C. The core-shells were grown around polyvinylpyrrolidone (PVP) coated NPs (Stöber encapsulation) prepared by colloidal synthesis. Sum frequency generation (SFG) vibrational spectroscopy was performed to correlate surface intermediates observed in situ with reaction selectivity. It is shown that calcination is effective in removing PVP, and the SFG signal can be generated from the metal surface. Using SFG, it is possible to compare the surface vibrational spectrum of Pt@SiO2 (1,3-BD is hydrogenated through multiple paths and produces butane, 1-butene, and cis/trans-2-butene) to Pd@SiO2 (1,3-BD favors one path and produces 1-butene and cis/trans-2-butene). In contrast to Pt@SiO2 and Pd@SiO2, SFG and kinetic experiments of Rh@SiO2 show a permanent accumulation of organic material.

  10. Synthesis and reduction of 2-nitroalkyl polysaccharide ethers

    NARCIS (Netherlands)

    Heeres, A.; Spoelma, F.F.; Doren, H.A. van; Gotlieb, K.F.; Bleeker, I.P.; Kellogg, R.M.


    Several 2-nitroalkyl polysaccharide ethers (from pullulan (1), guar (2), agarose (3), inulin (4), cellulose (5), Na-α-polyglucuronate (6) and hydroxyethyl cellulose (7)) were synthesized by reaction with 2-nitro-1-alkenes (2-nitro-1-propene and 2-nitro-1-butene) formed in situ from 2-nitroalkyl

  11. Synthesis and reduction of 2-nitroalkyl polysaccharide ethers

    NARCIS (Netherlands)

    Heeres, A; Spoelma, FF; van Doren, HA; Gotlieb, KF; Bleeker, IP; Kellogg, RM

    Several 2-nitroalkyl polysaccharide ethers (from pullulan (1), guar (2), agarose (3), inulin (4), cellulose (5), Na-alpha-polyglucuronate (6) and hydroxyethyl cellulose (7)) were synthesized by reaction with 2-nitro-1-alkenes (2-nitro-1-propene and 2-nitro-1-butene) formed in situ from 2-nitroalkyl

  12. Industrial processes of olefin metathesis. Pt. 1

    Energy Technology Data Exchange (ETDEWEB)

    Warwel, S.


    Olefin metathesis opens new synthetic routes to typical petrochemicals (ethylene, propylene, n-butenes), special olefins (neohexene, higher molecular linear olefins, , -dienes) and unsaturated polymers (polynorbornene, -cyclooctene, -dicyclopentadiene) in an industrial scale. The 8 metathesis processes used in industry and further possible applications of olefin metathesis are reviewed.

  13. Studies of vanadium-phosphorus-oxygen selective oxidation catalysts by sup 31 P and sup 51 V NMR spin-echo and volume susceptibility measurements

    Energy Technology Data Exchange (ETDEWEB)

    Li, Juan.


    The purpose of this work is to characterize the vanadium-phosphorous oxide (V-P-O) catalysts for the selective oxidation of n-butane and 1-butene to maleic anhydride. The utility of solid state nuclear magnetic resonance as an analytical tool in this investigation lies in its sensitivity to the electronic environment surrounding the phosphorous and vanadium nuclei, and proximity of paramagnetic species. Spin-echo mapping NMR of {sup 31}p and {sup 51}v and volume magnetic susceptibility measurements were used as local microscopic probes of the presence of V{sup 5+}, V{sup 4+}, V{sup 3+} species in the model compounds: {beta}-VOPO{sub 4}, {beta}-VOPO{sub 4} treated with n-butane/1-butene, (VO){sub 2}P{sub 2}O{sub 7} treated with n-butane/1-butene; and industrial catalysts with P/V (phosphorus to vanadium) ratio of 0.9, 1.0 and 1.1, before and after treatment with n-butane and 1-butene. The NMR spectra provide a picture of how the oxidation states of vanadium are distributed in these catalysts. 73 refs., 32 figs., 8 tabs.

  14. Controlled Functionalization of Olefin/styrene Copolymers through Free Radical Processes

    NARCIS (Netherlands)

    Passaglia, Elisa; Aglietto, Mauro; Ciardelli, Francesco; Picchioni, Francesco


    The functionalization of styrene-b-(ethylene-co-1-butene)-b-styrene triblock copolymer (SEBS) and styrene-co-butadiene (SBR) random copolymer by free radical processes is presented. SEBS was functionalized in the melt with diethyl maleate (DEM) and dicumyl peroxide (DCP) as initiator. The

  15. elementary mechanistic steps and the influence of process variables in isobutane alkylation over H-BEA

    NARCIS (Netherlands)

    Nivarthy, G.S.; He, Y.; Seshan, Kulathuiyer; Lercher, J.A.


    Liquid phase conversion of n-butene in excess iso-butane was investigated over zeolite BEA as catalyst in a continuously operated slurry reactor. Single and multiple alkylation and cracking were the main reaction pathways. Only saturated products were observed indicating that hydride transfer

  16. Survival of aerosolized bacteriophage phiX174 in air containing ozone olefin mixtures

    NARCIS (Netherlands)

    Mik, G. de; Groot, I. de; Gerbrandy, J.L.F.


    The effects of ozone and ozonized olefins on aerosol survival of bacteriophage phiX174 were studied. The ozone concentrations used were between 0 and 110 parts/109, giving decay rates up to 0.03 min-1. The olefins used were trans 2 butene and cyclohexene in concentrations of 500 parts/109 and 2.4

  17. Particle position in the Middle English Northern and Southern dialects Evidence for Scandinavian influence?

    NARCIS (Netherlands)

    Elenbaas, M.B.


    In the transition from Old to Middle English, particle-verb combinations were rapidly transformed into verb-particle combinations, in which particles are invariably postverbal (Hiltunen 1983). (1) a. & lahte ut his tunge se long þæt he swong hire a-buten his swire. (St.Margaret, 69) 'and took

  18. Identification of novel aroma-active thiols in pan-roasted white sesame seeds. (United States)

    Tamura, Hitoshi; Fujita, Akira; Steinhaus, Martin; Takahisa, Eisuke; Watanabe, Hiroyuki; Schieberle, Peter


    Screening for aroma-active compounds in an aroma distillate obtained from freshly pan-roasted sesame seeds by aroma extract dilution analysis revealed 32 odorants in the FD factor range of 2-2048, 29 of which could be identified. The highest FD factors were found for the coffee-like smelling 2-furfurylthiol, the caramel-like smelling 4-hydroxy-2,5-dimethyl-3(2H)-furanone, the coffee-like smelling 2-thenylthiol (thiophen-2-yl-methylthiol), and the clove-like smelling 2-methoxy-4-vinylphenol. In addition, 9 odor-active thiols with sulfurous, meaty, and/or catty, black-currant-like odors were identified for the first time in roasted sesame seeds. Among them, 2-methyl-1-propene-1-thiol, (Z)-3-methyl-1-butene-1-thiol, (E)-3-methyl-1-butene-1-thiol, (Z)-2-methyl-1-butene-1-thiol, (E)-2-methyl-1-butene-1-thiol, and 4-mercapto-3-hexanone were previously unknown as food constituents. Their structures were confirmed by comparing their mass spectra and retention indices as well as their sensory properties with those of synthesized reference compounds. The relatively unstable 1-alkene-1-thiols represent a new class of food odorants and are suggested as the key contributors to the characteristic, but quickly vanishing, aroma of freshly ground roasted sesame seeds.

  19. One Step Formation of Propene from Ethene or Ethanol through Metathesis on Nickel Ion-loaded Silica

    Directory of Open Access Journals (Sweden)

    Masakazu Iwamoto


    Full Text Available Increased propene production is presently one of the most significant objectives in petroleum chemistry. Especially the one-step conversion of ethene to propene (ETP reaction, 3C2H4 ® 2C3H6 is the most desired process. In our efforts, nickel ion-loaded mesoporous silica could turn a new type of ETP reaction into reality. The one-step conversion of ethene was 68% and the propene selectivity was 48% in a continuous gas-flow system at 673 K and atmospheric pressure. The reactivity of lower olefins and the dependences of the ETP reaction on the contact time and the partial pressure of ethene were consistent with a reaction mechanism involving dimerization of ethene to 1-butene, isomerization of 1-butene to 2-butene, and metathesis of 2-butene and ethene to yield propene. The reaction was then expanded to an ethanol-to-propene reaction on the same catalyst, in which two possible reaction routes are suggested to form ethene from ethanol. The catalysts were characterized mainly by EXAFS and TPR techniques. The local structures of the nickel species active for the ETP reaction were very similar to that of layered nickel silicate, while those on the inert catalysts were the same as that of NiO particles. 

  20. A Research-Based Undergraduate Organic Laboratory Project: Investigation of a One-Pot, Multicomponent, Environmentally Friendly Prins-Friedel-Crafts-Type Reaction (United States)

    Dintzner, Matthew R.; Maresh, Justin J.; Kinzie, Charles R.; Arena, Anthony F.; Speltz, Thomas


    Students in the undergraduate organic laboratory synthesize tetrahydro-2-(4-nitrophenyl)-4-phenyl-2"H"-pyran via the Montmorillonite K10 clay-catalyzed reaction of p-nitrobenzaldehye with methanol, 3-buten-1-ol, and benzene. The synthesis comprises an environmentally friendly tandem Prins-Friedel-Crafts-type multicomponent reaction (MCR) and sets…

  1. 77 FR 3750 - Notice of Intent To Grant a Partially Exclusive License; Cobalt Technologies, Inc. (United States)


    ...: Dehydration of Bio- Derived Alcohols to Alkenes Using Highly Selective Catalysts, filed on August 26, 2011.//patent application 12/511796: Diesel and Jet Fuels Based on the Oligomerization of 1-Butene, filed on July 29, 2009.// patent application 12/769757: Turbine and Diesel Fuels and Methods of Making the Same...

  2. Fluid catalytic cracking : Feedstocks and reaction mechanism

    NARCIS (Netherlands)

    Dupain, X.


    The Fluid Catalytic Cracking (FCC) process is one of the key units in a modern refinery. Traditionally, its design is primarily aimed for the production of gasoline from heavy oil fractions, but as co-products also diesel blends and valuable gasses (e.g. propene and butenes) are formed in

  3. Direct conversion of n-butane to isobutene over Pt-MCM22

    NARCIS (Netherlands)

    Pirngruber, G.D.; Seshan, Kulathuiyer; Lercher, J.A.


    MCM22 is a very active and selective catalyst for the skeletal isomerization of butene. At temperatures up to 775 K, Pt–MCM22 gives good results in the dehydroisomerization of n-butane, achieving higher yields of isobutene than does Pt–ZSM5. Most notably, the formation of cracking products is low.

  4. jjL.,_~ ___ L

    African Journals Online (AJOL)


    Mar 13, 1987 ... (Mustela vison) by Sokolov et al. (1980 compound V) but was then incorrectly identified as a dimethylthiacy- clobutane isomer (compare Brinck, Erlinge & Sandell. 1983 compound 5). The offensive, odorous compounds of the anal gland of the striped skunk are trans-2-butene-. I-thiol, 3-methyl-l-butanethiol ...

  5. Atmospheric fate of methyl vinyl ketone

    DEFF Research Database (Denmark)

    Praske, Eric; Crounse, John D; Bates, Kelvin H


    First generation product yields from the OH-initiated oxidation of methyl vinyl ketone (3-buten-2-one, MVK) under both low and high NO conditions are reported. In the low NO chemistry, three distinct reaction channels are identified leading to the formation of (1) OH, glycolaldehyde, and acetyl p...

  6. The chemistry of tributyl phosphate at elevated temperatures in the Plutonium Finishing Plant Process Vessels

    Energy Technology Data Exchange (ETDEWEB)

    Barney, G.S.; Cooper, T.D.


    Potentially violent chemical reactions of the tributyl phosphate solvent used by the Plutonium Finishing Plant at the Hanford Site were investigated. There is a small probability that a significant quantity of this solvent could be accidental transferred to heated process vessels and react there with nitric acid or plutonium nitrate also present in the solvent extraction process. The results of laboratory studies of the reactions show that exothermic oxidation of tributyl phosphate by either nitric acid or actinide nitrates is slow at temperatures expected in the heated vessels. Less than four percent of the tributyl phosphate will be oxidized in these vented vessels at temperatures between 125{degrees}C and 250{degrees}C because the oxidant will be lost from the vessels by vaporization or decomposition before the tributyl phosphate can be extensively oxidized. The net amounts of heat generated by oxidation with concentrated nitric acid and with thorium nitrate (a stand-in for plutonium nitrate) were determined to be about -150 and -220 joules per gram of tributyl phosphate initially present, respectively. This is not enough heat to cause violent reactions in the vessels. Pyrolysis of the tributyl phosphate occurred in these mixtures at temperatures of 110{degrees}C to 270{degrees}C and produced mainly 1-butene gas, water, and pyrophosphoric acid. Butene gas generation is slow at expected process vessel temperatures, but the rate is faster at higher temperatures. At 252{degrees}C the rate of butene gas generated was 0.33 g butene/min/g of tributyl phosphate present. The measured heat absorbed by the pyrolysis reaction was 228 J/g of tributyl phosphate initially present (or 14.5 kcal/mole of tributyl phosphate). Release of flammable butene gas into process areas where it could ignite appears to be the most serious safety consideration for the Plutonium Finishing Plant.

  7. A sedge plant as the source of Kangaroo Island propolis rich in prenylated p-coumarate ester and stilbenes. (United States)

    Duke, Colin C; Tran, Van H; Duke, Rujee K; Abu-Mellal, Abdallah; Plunkett, George T; King, Douglas I; Hamid, Kaiser; Wilson, Karen L; Barrett, Russell L; Bruhl, Jeremy J


    Propolis samples from Kangaroo Island, South Australia, were investigated for chemical constituents using high-field nuclear magnetic resonance spectral profiling. A type of propolis was found containing a high proportion of prenylated hydroxystilbenes. Subsequently, the botanical origin of this type of propolis was identified using a beehive propolis depletion method and analysis of flora. Ligurian honey bees, Apis mellifera ligustica Spinola, were found to produce propolis from resin exuded by the Australian native sedge plant Lepidosperma sp. Montebello (Cyperaceae). The plants, commonly known as sword sedge, were found to have resin that matched with the propolis samples identified as the most abundant propolis type on the island containing C- and O-prenylated tetrahydroxystilbenes (pTHOS) in addition to a small amount of prenylated p-coumarate. The isolation of five pTHOS not previously characterized are reported: (E)-4-(3-methyl-2-buten-1-yl)-3,4',5-trihydroxy-3'-methoxystilbene, (E)-2,4-bis(3-methyl-2-buten-1-yl)-3,3',4',5-tetrahydroxystilbene, (E)-2-(3-methyl-2-buten-1-yl)-3-(3-methyl-2-butenyloxy)-3',4',5-trihydroxystilbene, (E)-2,6-bis(3-methyl-2-buten-1-yl)-3,3',5,5'-tetrahydroxystilbene and (E)-2,6-bis(3-methyl-2-buten-1-yl)-3,4',5-trihydroxy-3'-methoxystilbene. A National Cancer Institute 60 human cell line anticancer screen of three of these compounds showed growth inhibitory activity. The large Australasian genus Lepidosperma is identified as a valuable resource for the isolation of substances with medicinal potential. Copyright © 2016 The Authors. Published by Elsevier Ltd.. All rights reserved.

  8. Reactions of butadiyne. 1: The reaction with hydrogen atoms (United States)

    Schwanebeck, W.; Warnatz, J.


    The reaction of hydrogen (H) atoms with butadiene (C4H2) was studied at room temperature in a pressure range between w mbar and 10 mbar. The primary step was an addition of H to C4H2 which is in its high pressure range at p 1 mbar. Under these conditions the following addition of a second H atom lies in the transition region between low and high pressure range. Vibrationally excited C4H4 can be deactivated to form buten-(1)-yne-(3)(C4H4) or decomposes into two C2H2 molecules. The rate constant at room temperature for primary step is given. The second order rate constant for the consumption of buten-(1)-yne-(3) is an H atom excess at room temperature is given.

  9. The driving force role of ruthenacyclobutanes

    KAUST Repository

    Vummaleti, Sai V. C.


    DFT calculations have been used to determine the thermodynamic and kinetic preference for ruthenacyclobutanes resulting from the experimentally proposed interconversion pathways (olefin and alkylidene rotations) through the investigation of cross-metathesis reaction mechanism for neutral Grubbs catalyst, RuCl2(=CHEt)NHC (A), with ethylene and 1-butene as the substrates. Our results show that although the proposed interconversions are feasible due to the predicted low energy barriers (2-6 kcal/mol), the formation of ruthenacyclobutane is kinetically favored over the competitive reactions involving alkylidene rotations. In comparison with catalyst A, the reaction energy profile for cationic Piers catalyst [RuCl2(=CHPCy3)NHC+] (B) is more endothermic in nature with both ethylene and 1-butene substrates.

  10. Catalytic distillation process (United States)

    Smith, L.A. Jr.


    A method is described for conducting chemical reactions and fractionation of the reaction mixture comprising feeding reactants to a distillation column reactor into a feed zone and concurrently contacting the reactants with a fixed bed catalytic packing to concurrently carry out the reaction and fractionate the reaction mixture. For example, a method for preparing methyl tertiary butyl ether in high purity from a mixed feed stream of isobutene and normal butene comprising feeding the mixed feed stream to a distillation column reactor into a feed zone at the lower end of a distillation reaction zone, and methanol into the upper end of said distillation reaction zone, which is packed with a properly supported cationic ion exchange resin, contacting the C[sub 4] feed and methanol with the catalytic distillation packing to react methanol and isobutene, and concurrently fractionating the ether from the column below the catalytic zone and removing normal butene overhead above the catalytic zone.

  11. Olefin metathesis reaction on a MoS/sub 2/ catalyst

    Energy Technology Data Exchange (ETDEWEB)


    Olefin metathesis reaction was found to take place on rather pure MoS/sub 2/ evacuated at 450/sup 0/C for several hours. Systematic studies of the isotopic scrambling in ethylene, propylene, 1-butene, and 2-butene on MoS/sub 2/ using microwave spectroscopy are reported. These studies were made using /sup 12/C- and /sup 13/C-labelled compounds and D-labelled compounds. Results indicated that the MoS/sub 2/ catalyst evacuated at 450/sup 0/C has two kinds of active sites, one is effective for the isomerization and the hydrogen isotopic mixing of olefins, and the other is effective for the hydrogenation reaction. This may be explained by assuming different degrees of coordinative unsaturation for the active sites. (BLM)

  12. Synthesis of amphiphilic diblock copolymer for surface modification of Ethylene-Norbornene copolymers

    DEFF Research Database (Denmark)

    Levinsen, Simon; Svendsen, Winnie Edith; Horsewell, Andy


    consisting of a bulk material compatible block and a hydrophilic block. To utilize the possibility of incorporating diblock copolymers into ethylenenorbornene copolymers, we have in this work developed a model poly(ethylene-1-butene) polymer compatible with the commercial available ethylene......-norbornene copolymer TOPAS. Through matching of the radius of gyration for the model polymer and TOPAS the miscibility was achieved. The poly(ethylene-1-butene) polymer was synthesized from a hydrogenated anionic polymerized polybutadiene polymer. As hydrophilic block poly(ethylene oxide) was subsequently added also......The aim of this work is to produce polymer modifiers in order to develop hydrophilic polymeric surfaces for use in microfluidics. The use of hydrophilic polymers in microfluidics will have many advantages e.g. preventing protein absorbance. Here we present an amphiphilic diblock copolymer...

  13. Inhibition and Promotion of Pyrolysis by Hydrogen Sulfide (H2S) and Sulfanyl Radical (SH)

    DEFF Research Database (Denmark)

    Zeng, Zhe; Altarawneh, Mohammednoor; Oluwoye, Ibukun


    the weakest C–H sites in alkenes and alkynes, except for ethylene, appears noticeably exothermic. Furthermore, abstraction of H from propene, 1-butene, and iso-butene displays pronounced spontaneity (i.e., ΔrG° hydrogen bond. However...... findings demonstrate that the documented inhibition effect of hydrogen sulfide (H2S) on pyrolysis of alkanes does not apply to alkenes and alkynes. During interaction with hydrocarbons, the inhibitive effect of H2S and promoting interaction of SH radical depend on the reversibility of the H abstraction...... processes. For the three groups of hydrocarbon, Evans–Polanyi plots display linear correlations between the bond dissociation enthalpies of the abstracted hydrogens and the relevant activation energies. In the case of methane, we demonstrated that the reactivity of SH radicals toward abstracting H atoms...

  14. Catalytic conversion of cellulose to liquid hydrocarbon fuels by progressive removal of oxygen to facilitate separation processes and achieve high selectivities

    Energy Technology Data Exchange (ETDEWEB)

    Dumesic, James A [Verona, WI; Ruiz, Juan Carlos Serrano [Madison, WI; West, Ryan M [Madison, WI


    Described is a method to make liquid chemicals. The method includes deconstructing cellulose to yield a product mixture comprising levulinic acid and formic acid, converting the levulinic acid to .gamma.-valerolactone, and converting the .gamma.-valerolactone to pentanoic acid. Alternatively, the .gamma.-valerolactone can be conveted to a mixture of n-butenes. The pentanoic acid can be decarboxylated yield 1-butene or ketonized to yield 5-nonanone. The 5-nonanone can be hydrodeoxygenated to yield nonane, or 5-nonanone can be reduced to yield 5-nonanol. The 5-nonanol can be dehydrated to yield nonene, which can be dimerized to yield a mixture of C.sub.9 and C.sub.18 olefins, which can be hydrogenated to yield a mixture of alkanes.

  15. Catalytic conversion of cellulose to liquid hydrocarbon fuels by progressive removal of oxygen to facilitate separation processes and achieve high selectivities

    Energy Technology Data Exchange (ETDEWEB)

    Dumesic, James A.; Ruiz, Juan Carlos Serrano; West, Ryan M.


    Described is a method to make liquid chemicals. The method includes deconstructing cellulose to yield a product mixture comprising levulinic acid and formic acid, converting the levulinic acid to .gamma.-valerolactone, and converting the .gamma.-valerolactone to pentanoic acid. Alternatively, the .gamma.-valerolactone can be converted to a mixture of n-butenes. The pentanoic acid can be decarboxylated yield 1-butene or ketonized to yield 5-nonanone. The 5-nonanone can be hydrodeoxygenated to yield nonane, or 5-nonanone can be reduced to yield 5-nonanol. The 5-nonanol can be dehydrated to yield nonene, which can be dimerized to yield a mixture of C.sub.9 and C.sub.18 olefins, which can be hydrogenated to yield a mixture of alkanes.

  16. A new process for the valorisation of a bio-alcohol. The oxidehydration of 1-butanol into maleic anhydride

    Energy Technology Data Exchange (ETDEWEB)

    Caldarelli, A.; Cavani, F.; Garone, O.; Pavarelli, G. [Bologna Univ. (Italy). Dipt. di Chimica Industriale e dei Materiali; Bologna Univ. (Italy). CIRCC, Research Unit; Dubois, J.L. [ARKEMA, Colombes (France); Mitsova, I.; Simeonova, L. [JSC, Russe (Bulgaria). Orgachim


    This paper deals with a study on the gas-phase transformation of 1-butanol into maleic anhydride, using different types of catalysts. Indeed, catalytic acid properties are needed to dehydrate 1-butanol into 1-butene, whereas redox-type properties are required for the oxidation of the olefin into maleic anhydride. The two types of active sites can be combined in bifunctional systems, showing both acid and redox-type properties. We found that vanadyl pyrophosphate catalyzes the one-pot reaction, giving a maximum selectivity to maleic anhydride of 28%. In fact, various side reactions contributed to the formation of by-products, eg, 1-butanol (oxidative) dehydrogenation into butyraldehyde, formation of light carboxylic acids and carbon oxides, and condensation of unsaturated C{sub 4} intermediates (butenes and butadiene) with the formed maleic anhydride to yield heavier compounds. (orig.)

  17. Reduce the cost of producing TAME. [Tertiary Amyl Methyl Ethers

    Energy Technology Data Exchange (ETDEWEB)

    Rock, K.L.; Gildert, G.R. (CDTECH, Houston, TX (United States))


    The high atmospheric reactivity and resulting high ozone formation have been previously documented for C5 olefins. Other features such as low octane number and high vapor pressure limit their usefulness as gasoline blendstocks. Conversion of C[sub 5] olefins to TAME is a good way to upgrade these components into high value gasoline blendstocks. The TAME product has high octane and low vapor pressure as well as contained oxygen. The other option is to alkylate the C[sub 5] olefins. This route produces greater volume but with higher vapor pressure and lower octane value. The TAME route also achieves lower capital and operating cost than alkylation. The paper describes a process in which reactive Isoamylenes can be converted to TAME by etherification with methanol. The reactive isoamylenes include 2-methyl butene-1 and 2-methyl butene-2.

  18. Data Gap Analysis and Database Expansion of Parameters for Munitions Constitutents (United States)


    toluidinoanthraquinone (PTA) solvent green 3 128-80-3 biocides/dyes 14 1- butanol 71-36-3 alchohols/ketones 15 1-butene 106-98-9 hydrocarbons 16 1-chloro-2-methylbenzene...1 alcohols/ketones 57 acetonitrile 75-05-8 hydrocarbons 58 acetophenone 98-86-2 alcohols/ketones 59 acetylene 74-86-2 hydrocarbons 60 acrolein...80-3 418.4856 6.72 -5.93 -18.28 -11.44 1- butanol 71-36-3 74.1212 0.9 -0.31 -1.84 -4.71 1-butene 106-98-9 56.106 2.08 -2.25 0.4 -0.65 1-chloro-2

  19. Data Gap Analysis and Database Expansion of Parameters for Munitions Constituents (United States)


    toluidinoanthraquinone (PTA) solvent green 3 128-80-3 biocides/dyes 14 1- butanol 71-36-3 alchohols/ketones 15 1-butene 106-98-9 hydrocarbons 16 1-chloro-2...acetone 67-64-1 alcohols/ketones 57 acetonitrile 75-05-8 hydrocarbons 58 acetophenone 98-86-2 alcohols/ketones 59 acetylene 74-86-2 hydrocarbons 60...3 128-80-3 418.4856 6.72 -5.93 -18.28 -11.44 1- butanol 71-36-3 74.1212 0.9 -0.31 -1.84 -4.71 1-butene 106-98-9 56.106 2.08 -2.25 0.4 -0.65 1-chloro


    Directory of Open Access Journals (Sweden)

    Z. Bensetiti


    Full Text Available A model is proposed for the average effective diffusivity for an arbitrary pore size distribution. It is shown that the average diffusivity must also depend on the distribution of the catalyst sites. The reaction diffusivity is compared with the average diffusivities defined by Wakao and Smith (1962 and Johnson and Stewart (1965. For the methanol dehydration and n-butene isomerization, the reaction diffusivity gives a better estimation of the effectiveness factor than the other models

  1. Olefin hydroformylation catalysis with RuCl2(DMSO4.

    Directory of Open Access Journals (Sweden)

    Marisela Reyes*


    Full Text Available The RuCl2(DMSO4 complex was used as catalytic precursor in olefin hydroformylation reactions, giving good percent yield and better selectivity for linear aldehydes. The reactions were tested in homogeneous medium and biphasic organic solvent/ water systems. The substrates tried were 1-hexene, cyclohexene, 2-methyl-2-pentene, 2,3-dimethyl-2-butene; binary mixtures and synthetic naphtha and real naphtha. The activity is better for linear olefins compared with substituted olefins.

  2. Volatile carbonylic compounds in downtown Santiago, Chile. (United States)

    Rubio, María A; Zamorano, Natalia; Lissi, Eduardo; Rojas, Alicia; Gutiérrez, Luis; von Baer, Dietrich


    Formaldehyde, acetaldehyde, acetone, propanal, butanal, 2-butenal, 3-methylbutanal, hexanal, benzaldehyde, 2-methylbenzaldehyde, and 2,5-dimethylbenzaldehyde were measured during six spring days at downtown Santiago de Chile. Measurements were performed 24h/day and averaged over three hour periods. The averages of the maxima (ppbv) were, formaldehyde: 3.9+/-1.4; butanal: 3.3+/-3.4; acetaldehyde: 3.0+/-0.9; acetone: 2.4+/-1.0; 2-butenal: 0.56+/-0.52; propanal: 0.46+/-0.21; benzaldehyde: 0.34+/-0.3; 3-butanal: 0.11+/-0.05; hexanal: 0.11+/-0.08; 2-methylbenzaldehyde: 0.08+/-0.05; 2,5-dimethylbenzaldehyde: 0.05+/-0.03. Aliphatic aldehydes (C1-C3) are strongly correlated among them and weakly with primary (toluene) and secondary (ozone plus nitrogen dioxide or PAN) pollutants. In particular, the correlation between acetaldehyde and propanal values remains even if diurnal and nocturnal data are considered separately, indicating similar sources. All these aldehydes present maxima values in the morning (9-12h) and minima at night (0-3h). The best correlation is observed when butanal and 2-butenal data are considered (r=0.99, butanal/2-butenal=6.2). These compounds present maxima values during the 3-6h period, with minima values in the 0-3h period. These data imply a strong pre-dawn emission. Other aldehydes show different daily profiles, suggesting unrelated origins. Formaldehyde is the aldehyde whose concentration values best correlate with the levels of oxidants. The contribution of primary emissions and photochemical processes to formaldehyde concentrations were estimated by using a multiple regression. This treatment indicates that (32+/-16)% of measured values arise from direct emissions, while (79+/-23)% is attributable to secondary formation.

  3. Scramjet Combustor Simulations Using Reduced Chemical Kinetics for Practical Fuels (United States)


    mol% n-dodecane, 5.5 mol% iso-octane, 10 mol% methylcyclohexane, 11 mol% toluene , and 1 mol% benzene. The mechanism reproduces the profiles of fuel...C12H25, butadiene, butene, isobutane, C5H10, methyl-cylcohexane, H2O, CO, CO2, O2, OH, H2O2, C7H14, CH2O, CH2CO, benzaldehyde , iso-octane, dodecane

  4. 40 CFR Appendix II to Part 258 - List of Hazardous Inorganic and Organic Constituents (United States)


    ...-dichloro- 3,3′-Dichlorobenzidine 91-94-1 -4,4′-diamine, 3,3′-dichloro- trans-1,4-Dichloro-2-butene 110-57-6... Phosphorodithioic acid, O,O-dimethyl S- ester p-(Dimethylamino)azobenzene 60-11-7 Benzenamine, N,N-dimethyl-4...-93-7 -4,4′-diamine, 3,3′-dimethyl- alpha, alpha-Dimethylphenethylamine 122-09-8 Benzeneethanamine, α...

  5. Encapsulation of N,N′,N″-tricyclohexylguanidine in hydrophobic zeolite Y: Synthesis and catalytic activity


    Sercheli, Ricardo; Ferreira, Alfredo L. B.; Guerreiro, Mário C.; Vargas, Rogério Matheus; Sheldon, Roger A.; Schuchardt, Ulf


    Texto completo: acesso restrito. p.1325–1328 N,N′,N″-Tricyclohexylguanidine was encapsulated in hydrophobic zeolite Y by reacting N,N′-dicyclohexylcarbodiimide with cyclohexylamine within the supercage. The encapsulated guanidine catalyzes the addition reaction of acetone to benzaldehyde forming 4-phenyl-4-hydroxybutan-2-one as the principal product, as opposed to the homogeneous system which produces 4-phenyl-3-buten-2-one via condensation reaction.

  6. Synthèse catalytique de lévulinates de butyle à partir de biomasse en présence d’alcools ou d’oléfines


    Demolis, Alexandre


    The objective of this work was to study in details the catalytic synthesis of butyl levulinates from biomass, first by using butanol isomers, then butene isomers as esterifying agents. Usually obtained by esterification of levulinic acid, levulinic esters including butyl levulinates possess physical and chemical properties making them potential fuel additives, platform molecules, solvents or additives for the food or pharmaceutical industry. By selectively converting cellulose into butyl levu...

  7. Phase behavior for the poly(alkyl methacrylate)+supercritical CO{sub 2}+DME mixture at high pressures

    Energy Technology Data Exchange (ETDEWEB)

    Choi, Yong-Seok; Chio, Sang-Won; Byun, Hun-Soo [Chonnam National University, Yeosu (Korea, Republic of)


    The phase behavior curves of binary and ternary system were measured for poly(alkyl methacrylate) in supercritical CO{sub 2}, as well as for the poly(alkyl methacrylate)+dimethyl ether (DME) (or 1-butene) in CO{sub 2}. The solubility curves are reported for the poly(alkyl methacrylate)+DME in supercritical CO{sub 2} at temperature from (300 to 465) K and a pressure from (3.66 to 248) MPa. Also, The high-pressure static-type apparatus of cloud-point curve was tested by comparing the measured phase behavior data of the poly(methyl methacrylate) [PMMA]+CO{sub 2}+20.0 and 30.4 wt% methyl methacrylate (MMA) system with literature data of 10.4, 28.8 and 48.4 wt% MMA concentration. The phase behavior data for the poly(alkyl methacrylate)+CO{sub 2}+DME mixture were measured in changes of the pressure-temperature (p, T) slope and with DME concentrations. Also, the cloud-point pressure for the poly(alkyl methacrylate)+1- butene solution containing supercritical CO{sub 2} shows from upper critical solution temperature (UCST) region to lower critical solution temperature (LCST) region at concentration range from (0.0 to 95) wt% 1-butene at below 455 K and at below 245MPa.

  8. Catalytic conversion of cellulose to liquid hydrocarbon fuels by progressive removal of oxygen to facilitate separation processes and achieve high selectivities

    Energy Technology Data Exchange (ETDEWEB)

    Dumesic, James A [Verona, WI; Ruiz, Juan Carlos Serrano [Madison, WI; West, Ryan M [Madison, WI


    Described is a method to make liquid chemicals, such as functional intermediates, solvents, and liquid fuels from biomass-derived cellulose. The method is cascading; the product stream from an upstream reaction can be used as the feedstock in the next downstream reaction. The method includes the steps of deconstructing cellulose to yield a product mixture comprising levulinic acid and formic acid, converting the levulinic acid to .gamma.-valerolactone, and converting the .gamma.-valerolactone to pentanoic acid. Alternatively, the .gamma.-valerolactone can be converted to a mixture of n-butenes. The pentanoic acid so formed can be further reacted to yield a host of valuable products. For example, the pentanoic acid can be decarboxylated yield 1-butene or ketonized to yield 5-nonanone. The 5-nonanone can be hydrodeoxygenated to yield nonane, or 5-nonanone can be reduced to yield 5-nonanol. The 5-nonanol can be dehydrated to yield nonene, which can be dimerized to yield a mixture of C.sub.9 and C.sub.18 olefins, which can be hydrogenated to yield a mixture of alkanes. Alternatively, the nonene may be isomerized to yield a mixture of branched olefins, which can be hydrogenated to yield a mixture of branched alkanes. The mixture of n-butenes formed from .gamma.-valerolactone can also be subjected to isomerization and oligomerization to yield olefins in the gasoline, jet and Diesel fuel ranges.

  9. A New Process for Maleic Anhydride Synthesis from a Renewable Building Block: The Gas-Phase Oxidehydration of Bio-1-butanol. (United States)

    Pavarelli, Giulia; Velasquez Ochoa, Juliana; Caldarelli, Aurora; Puzzo, Francesco; Cavani, Fabrizio; Dubois, Jean-Luc


    We investigated the synthesis of maleic anhydride by oxidehydration of a bio-alcohol, 1-butanol, as a possible alternative to the classical process of n-butane oxidation. A vanadyl pyrophosphate catalyst was used to explore the one-pot reaction, which involved two sequential steps: 1) 1-butanol dehydration to 1-butene, catalysed by acid sites, and 2) the oxidation of butenes to maleic anhydride, catalysed by redox sites. A non-negligible amount of phthalic anhydride was also formed. The effect of different experimental parameters was investigated with chemically sourced 1-butanol, and the results were then confirmed by using genuinely bio-sourced 1-butanol. In the case of bio-1-butanol, however, the purity of the product remarkably affected the yield of maleic anhydride. It was found that the reaction mechanism includes the oxidation of butenes to crotonaldehyde and the oxidation of the latter to either furan or maleic acid, both of which are transformed to produce maleic anhydride. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Rate coefficients for the reaction of OH with a series of unsaturated alcohols between 263 and 371 K. (United States)

    Cometto, Pablo M; Dalmasso, Pablo R; Taccone, Raúl A; Lane, Silvia I; Oussar, Fátima; Daële, Véronique; Mellouki, Abdelwahid; Le Bras, Georges


    Rate coefficients for the gas-phase reactions of OH radicals with four unsaturated alcohols, 3-methyl-3-buten-1-ol (k1), 2-buten-1-ol (k2), 2-methyl-2-propen-1-ol (k3) and 3-buten-1-ol (k4), were measured using two different techniques, a conventional relative rate method and the pulsed laser photolysis-laser induced fluorescence technique. The Arrhenius rate coefficients (in units of cm(3) molecule(-1) s(-1)) over the temperature range 263-371 K were determined from the kinetic data obtained as k1 = (5.5 +/- 1.0) x 10(-12) exp [(836 +/- 54)/T]; k2 = (6.9 +/- 0.9) x 10(-12) exp [(744 +/- 40)/T]; k3 = (10 +/- 1) x 10(-12) exp [(652 +/- 27)/T]; and k4 = (4.0 +/- 0.4) x 10(-12) exp [(783 +/- 32)/T]. At 298 K, the rate coefficients obtained by the two methods for each of the alcohols studied were in good agreement. The results are presented and compared with those obtained previously for the same and related reactions of OH radicals. Reactivity factors for substituent groups containing the hydroxyl group are determined. The atmospheric implications for the studied alcohols are considered briefly.

  11. Chemical Kinetics of Hydrogen Atom Abstraction from Allylic Sites by3O2; Implications for Combustion Modeling and Simulation. (United States)

    Zhou, Chong-Wen; Simmie, John M; Somers, Kieran P; Goldsmith, C Franklin; Curran, Henry J


    Hydrogen atom abstraction from allylic C-H bonds by molecular oxygen plays a very important role in determining the reactivity of fuel molecules having allylic hydrogen atoms. Rate constants for hydrogen atom abstraction by molecular oxygen from molecules with allylic sites have been calculated. A series of molecules with primary, secondary, tertiary, and super secondary allylic hydrogen atoms of alkene, furan, and alkylbenzene families are taken into consideration. Those molecules include propene, 2-butene, isobutene, 2-methylfuran, and toluene containing the primary allylic hydrogen atom; 1-butene, 1-pentene, 2-ethylfuran, ethylbenzene, and n-propylbenzene containing the secondary allylic hydrogen atom; 3-methyl-1-butene, 2-isopropylfuran, and isopropylbenzene containing tertiary allylic hydrogen atom; and 1-4-pentadiene containing super allylic secondary hydrogen atoms. The M06-2X/6-311++G(d,p) level of theory was used to optimize the geometries of all of the reactants, transition states, products and also the hinder rotation treatments for lower frequency modes. The G4 level of theory was used to calculate the electronic single point energies for those species to determine the 0 K barriers to reaction. Conventional transition state theory with Eckart tunnelling corrections was used to calculate the rate constants. The comparison between our calculated rate constants with the available experimental results from the literature shows good agreement for the reactions of propene and isobutene with molecular oxygen. The rate constant for toluene with O 2 is about an order magnitude slower than that experimentally derived from a comprehensive model proposed by Oehlschlaeger and coauthors. The results clearly indicate the need for a more detailed investigation of the combustion kinetics of toluene oxidation and its key pyrolysis and oxidation intermediates. Despite this, our computed barriers and rate constants retain an important internal consistency. Rate constants

  12. Transport of hop aroma compounds across Caco-2 monolayers. (United States)

    Heinlein, A; Metzger, M; Walles, H; Buettner, A


    Although being reported and used as a sedative remedy for several years, the bioactive principle of hop preparations is still not decisively clarified. Understanding absorption and transformation processes of potential physiologically active constituents is essential to evaluate the likeliness of biological effects on humans. Therefore, single hop aroma compounds as well as digestive transformation products thereof have been investigated in view of their human intestinal absorption, applying Caco-2 transport experiments as well as investigations on potential biotransformation processes. Selective and sensitive identification and quantification were thereby achieved by application of two-dimensional high resolution gas chromatography-mass spectrometry in conjunction with stable isotope dilution analysis, leading to the determination of apparent permeability values by different mathematical approaches considering sink and non-sink conditions. Overall, calculated permeability values ranged from 2.6 × 10(-6) to 1.8 × 10(-4) cm s(-1) with all mathematical approaches, indicating high absorption potential and almost complete bioavailability for all tested compounds with hydroxyl-functionalities. Considering this high permeability together with the high lipophilicity of these substances, a passive transcellular uptake route can be speculated. Investigated sesquiterpenes and β-myrcene showed flat absorption profiles while the investigated esters showed decreasing profiles. In view of the lipophilic and volatile nature of the investigated substances, special attention was paid to recovery and mass balance determination. Furthermore, in the course of the transport experiments of 1-octen-3-ol and 3-methyl-2-buten-1-ol, additional biotransformation products were observed, namely 3-octanone and 3-methyl-2-butenal, respectively. The absence of these additional substances in control experiments strongly indicates an intestinal first-pass metabolism of the

  13. Ice core records of monoterpene- and isoprene-SOA tracers from Aurora Peak in Alaska since 1660s: Implication for climate change variability in the North Pacific Rim (United States)

    Pokhrel, Ambarish; Kawamura, Kimitaka; Ono, Kaori; Seki, Osamu; Fu, Pingqing; Matoba, Sumio; Shiraiwa, Takayuki


    Monoterpene and isoprene secondary organic aerosol (SOA) tracers are reported for the first time in an Alaskan ice core to better understand the biological source strength before and after the industrial revolution in the Northern Hemisphere. We found significantly high concentrations of monoterpene- and isoprene-SOA tracers (e.g., pinic, pinonic, and 2-methylglyceric acids, 2-methylthreitol and 2-methylerythritol) in the ice core, which show historical trends with good correlation to each other since 1660s. They show positive correlations with sugar compounds (e.g., mannitol, fructose, glucose, inositol and sucrose), and anti-correlations with α-dicarbonyls (glyoxal and methylglyoxal) and fatty acids (e.g., C18:1) in the same ice core. These results suggest similar sources and transport pathways for monoterpene- and isoprene-SOA tracers. In addition, we found that concentrations of C5-alkene triols (e.g., 3-methyl-2,3,4-trihydroxy-1-butene, cis-2-methyl 1,3,4-trihydroxy-1-butene and trans-2-methyl-1,3,4-trihydroxy-1-butene) in the ice core have increased after the Great Pacific Climate Shift (late 1970s). They show positive correlations with α-dicarbonyls and fatty acids (e.g., C18:1) in the ice core, suggesting that enhanced oceanic emissions of biogenic organic compounds through the marine boundary layer are recorded in the ice core from Alaska. Photochemical oxidation process for these monoterpene- and isoprene-/sesquiterpene-SOA tracers are suggested to be linked with the periodicity of multi-decadal climate oscillations and retreat of sea ice in the Northern Hemisphere.

  14. Intermediate species measurement during iso-butanol auto-ignition

    KAUST Repository

    Ji, Weiqi


    © 2015 The Combustion Institute.Published by Elsevier Inc. All rights reserved. This work presents the time histories of intermediate species during the auto-ignition of iso-butanol at high pressure and intermediate temperature conditions obtained using a rapid compression machine and recently developed fast sampling system. Iso-butanol ignition delays were acquired for iso-butanol/O2 mixture with an inert/O2 ratio of 7.26, equivalence ratio of 0.4, in the temperature range of 840-950 K and at pressure of 25 bar. Fast sampling and gas chromatography were used to acquire and quantify the intermediate species during the ignition delay of the same mixture at P = 25.3 bar and T = 905 K. The ignition delay times and quantitative measurements of the mole fraction time histories of methane, ethene, propene, iso-butene, iso-butyraldehyde, iso-butanol, and carbon monoxide were compared with predictions from the detailed mechanisms developed by Sarathy et al., Merchant et al., and Cai et al. It is shown that while the Sarathy mechanism well predicts the overall ignition delay time, it overpredicts ethene by a factor of 6-10, underpredicts iso-butene by a factor of 2, and overpredicts iso-butyraldehyde by a factor of 2. Reaction path and sensitivity analyses were carried out to identify the reactions responsible for the observed inadequacy. The rates of iso-butanol hydrogen atom abstraction by OH radical and the beta-scission reactions of hydroxybutyl radicals were updated based on recently published quantum calculation results. Significant improvements were achieved in predicting ignition delay at high pressures (25 and 30 bar) and the species concentrations of ethene and iso-butene. However, the updated mechanism still overpredicts iso-butyraldehyde concentrations. Also, the updated mechanism degrades the prediction in ignition delay at lower pressure (15 bar) compared to the original mechanism developed by Sarathy et al.

  15. End-labeled amino terminated monotelechelic glycopolymers generated by ROMP and Cu(I-catalyzed azide–alkyne cycloaddition

    Directory of Open Access Journals (Sweden)

    Ronald Okoth


    Full Text Available Functionalizable monotelechelic polymers are useful materials for chemical biology and materials science. We report here the synthesis of a capping agent that can be used to terminate polymers prepared by ring-opening metathesis polymerization of norbornenes bearing an activated ester. The terminating agent is a cis-butene derivative bearing a Teoc (2-trimethylsilylethyl carbamate protected primary amine. Post-polymerization modification of the polymer was accomplished by amidation with an azido-amine linker followed by Cu(I-catalyzed azide–alkyne cycloaddition with propargyl sugars. Subsequent Teoc deprotection and conjugation with pyrenyl isothiocyanates afforded well-defined end-labeled glycopolymers.

  16. Relationships between Chemical Structure and Rat Repellency. 2. Compounds Screened Between 1950 and 1960 (United States)


    chlorophenoxy)- 61 3107 Naphthalene , 2-(2-chloroethoxy)- 69 2844, 4218 Phenetole, O-chloro- 22, 68 7206 - ,~chloro- 65 2851 f-chloro-o-phenyl- 70...d6357 Pyromellitic acid, diimide , HIW-bis(rn-ethoxy- penyl)- -7 6358, 6359 ---- diimide , N N-bis(p-toyhey) ~ -16 6355 , diimid ,IIN-bis(m-methoxyphenyl...3 Ij6355 diimide , Nbiomehxpey) -11 63564 diimide , jNN-bis(3-methoxyphenyl)- -59 H Ketones 6003 3-Buten-2-ote,, 4-(g-methoxyphenyl)- 50 5274 Chalcone

  17. Volatile compounds in noni (Morinda citrifolia L. at two ripening stages Compostos voláteis em noni (Morinda citrifolia L. em dois estágios de maturação

    Directory of Open Access Journals (Sweden)

    Jorge Antonio Pino


    Full Text Available The volatile components of noni at two ripening stages were isolated by headspace solid-phase microextraction using 65 µm Polydimethylsiloxane-Divinylbenzene (PDMS/DVB fibers and analyzed using GC/MS. Both maturation stages had several compounds in common. Ninety-six compounds were identified, from which octanoic acid ( 70% of total extract and hexanoic acid ( 8% of total extract were found to be the major constituents. Due to noni maturation, octanoic acid, decanoic acid and 2E-nonenal decreased their concentrations, while some esters (methyl hexanoate, methyl octanoate, ethyl octanoate and methyl 4E-decenoate, which their fruity odor notes, increased their contents. Two unsaturated esters, reported for the first time in this fruit, 3-methyl-3-buten-1-yl hexanoate and 3-methyl-3-buten-1-yl octanoate, significantly decreased their concentration in the ripe to over-ripe fruits.Los compuestos volátiles del noni en los dos estados de madurez se aislaron mediante microextracción en fase sólida por headspace con fibras de 65 mm Polidimetilsiloxano-Divinilbenceno (PDMS/DVB y se analizaron por cromatografía de gases/espectrometría de masas. Ambos estados de madurez poseen numerosos constituyentes en común. Se identificaron 96 compuestos, de los cuales el ácido octanoico ( 70% del extracto total y ácido hexanoico ( 8% del extracto total fueron los componentes mayoritarios. Debido a la maduración del noni, el ácido octanoico, ácido decanoico y 2E-nonenal disminuyeron su contenido, mientras que algunos ésteres (hexanoato de metilo, octanoato de metilo, octanoato de etilo y 4E-decenoato de metilo, con sus olororosas notas frutales, incrementaron la concentración. Dos ésteres insaturados, reportados por primera vez en esta fruta, hexanoato de 3-metil-3-buten-1-ilo y octanoato de 3-metil-3-buten-1-ilo, disminuyeron significativamente su concentración al pasar la fruta del estado maduro al sobremaduro.

  18. A Ruthenium Catalyst for Olefin Metathesis Featuring an Anti-Bredt N-Heterocyclic Carbene Ligand. (United States)

    Martin, David; Marx, Vanessa M; Grubbs, Robert H; Bertrand, Guy


    A ruthenium complex bearing an "anti-Bredt" N-heterocyclic carbene was synthesized, characterized and evaluated as a catalyst for olefin metathesis. Good conversions were observed at room temperature for the formation of di- and tri-substituted olefins by ring-closing metathesis. It also allowed for the ring-opening metathesis polymerization of cyclooctadiene, as well as for the cross-metathesis of cis-1,4-diacetoxy-2-butene with allyl-benzene, with enhanced Z/E kinetic selectivity over classical NHC-based catalysts.

  19. Application of olefin metathesis in petrochemistry

    Energy Technology Data Exchange (ETDEWEB)

    Warwel, S.


    A survey covers the catalysts used in olefin metathesis; olefin types which undergo metathesis, e.g., ring-opening metathetic polymerization of cycloolefins; equilibria and side reactions; the Phillips Triolefin process for 2-butene production; the Shell Higher Olefin Process (SHOP) for the production of C/sub 11/-C/sub 14/ ..cap alpha..-olefins; the Phillips Petroleum 225 ton/yr process for the conversion of trimethylpentane to neohexene, which is used in gasoline and pharmaceutical manufacture; the production of isoprene precursors; and various other metathesis reactions used in synthesizing specific olefins.

  20. Bioenvironmental Engineer’s Guide to TVA-1000B Toxic Vapor Analyzer (United States)


    Acetaldehyde 10.21 3-Butene nitrile 10.39 2-Chloro-2-methylpropane 10.61 Acetamide 9.77 Benzaldehyde 9.53 2-Chlorobutane 10.65 Acetic acid 10.69 Benzene...9.96 Propylene dichloride 10.87 V O Propylene imine 9.00 o-Vinyl toluene 8.20 Octane 9.82 Propylene oxide 10.22 Valeraldehyde 9.82 Oxygen 12.08...Propane 11.07 Thiophene 8.86 Propargyl alcohol 10.51 Toluene 8.82 Propiolactone 9.70 Tribromoethene 9.27 Propionaldehyde 9.98 Tribromofluoromethane

  1. Volatile components in defensive spray of the spotted skunk,Spilogale putorius. (United States)

    Wood, W F; Morgan, C G; Miller, A


    GC-MS analysis of the anal sac secretion from the spotted skunk,Spilogale putorius, showed three major volatile components: (E)-2-butene-1-thiol, 3-methyl-1-butanethiol, and 2-phenylethanethiol. Minor volatile components identified from this secretion were: phenylmethanethiol, 2-methylquinoline, 2-quinolinemethanethiol, bis[(E)-2-butenyl] disulfide, (E)-2-butenyl 3-methylbufyl disulfide, bis(3-methylbutyl) disulfide. All of these compounds except 2-phenylethanethioi have been identified previously from the striped skunk,Mephitis mephitis. The thioacetate derivativesS- (E)-2-butenyl thioacetate,S-3-methylbutanyl thioacetate, andS-2-quinolinemethyl thioacetate found in the striped skunk were not seen in this species.

  2. New components in defensive secretion of the striped skunk,Mephitis mephitis. (United States)

    Wood, W F


    GC-MS analysis of the anal sac secretion of the striped skunk (Mephitis mephitis), shows seven major components: (E)-2-butene-1-thiol, 3-methyl-1-butanethiol, S-(E)-2-butenyl thioacetate,S-3-methylbutanyl thioacetate, 2-methylquinoline, 2-quinolinemethanethiol, andS-2-quinolinemethyl thioacetate. The following compounds previously reported from this secretion could not be confirmed: bis(2-butenyl) sulfide, (E)-2-Butenyl methyl disuffide, (E)-2-butenyl propyl sulfide, butyl 3-methylbutyl disulfide, and 2-butenyl butyl disulfide.

  3. Volatile components in defensive spray of the hog-nosed skunk,Conepatus mesoleucus. (United States)

    Wood, W F; Fisher, C O; Graham, G A


    GC-MS analysis of the anal sac secretion from the hog-nosed skunk,Conepatus mesoleucus, showed two major volatile components, (E)-2-butene-1-thiol and (E)-S-2-butenyl thioacetate. Minor volatile components identified from this secretion were phenylmethanethiol, 2-methylquinoline, 2-quinolinemethanethiol, and bis[(E)-2-butenyl] disulfide. 3-Methyl-1-butanethiol, a major component in the defensive spray of the striped skunk,Mephitis mephitis, and the spotted skunk,Spilogale putorius, was absent from this secretion.

  4. Synthesis of Branch Fluorinated Cationic Surfactant and Surface Properties

    Directory of Open Access Journals (Sweden)

    Hongke Wu


    Full Text Available A novel fluorinated quaternary ammonium salt cationic surfactant N,N,N-trimethyl-2-[[4-[[3,4,4,4-tetrafluoro-2-[1,2,2,2-tetrafluoro-1-(trifluoromethylethyl]-1,3-bis(tri-fluoromethyl-1-buten-1-yl]oxy]-benzoyl]amino]-iodide (FQAS was synthesized successfully, and its structure was characterized by FTIR, 1H-NMR, 19F-NMR, and MS. The surface activities of FQAS and the effect of temperature, electrolyte, and combination with hydrocarbon surfactant were investigated. The results showed that FQAS exhibited excellent surface activity and combination with hydrocarbon surfactant.

  5. Scope and limitations of chiral bis(oxazoline) ligands in the copper-catalysed asymmetric cyclopropanation of trisubstituted alkenes

    DEFF Research Database (Denmark)

    Østergaard, N.; Jensen, Jakob Feldthusen; Tanner, David Ackland


    A series of derivatives of 3-methyl-2-buten-1-ol has been used to test the scope and limitations of the copper-catalysed asymmetric cyclopropanation of trisubstituted alkenes by ethyl diazoacetate in the presence of C-2-symmetric bis(oxazoline) ligands. In the best case, a trans/cis ratio of 91......:9, with 92% ee for the major isomer, was obtained from the reaction of the p-methoxybenzoate derivative. The highest ee was 95%, for the trans isomer of a 80:20 diastereomer mixture (acetate derivative)....

  6. Potential roles of myeloperoxidase and hypochlorous acid in metabolism and toxicity of alkene hydrocarbons and drug molecules containing olefinic moieties. (United States)

    Zhang, Xin-Yu; Elfarra, Adnan A


    Adverse drug reactions (ADRs) pose a significant health problem and are generally attributed to reactive metabolites. Olefinic moieties in drugs can undergo cytochrome P450-mediated bioactivation to produce reactive metabolites but myeloperoxidase (MPO)-mediated bioactivation of these moieties has not been reported. Thus, small molecules of alkene hydrocarbons are used as model compounds to characterize the MPO-mediated metabolism. Areas covered: The authors focus on MPO-mediated metabolism of alkene hydrocarbons to form chlorohydrins and the potential role of chlorohydrins in alkene toxicity and carcinogenicity. A case study is presented, in which a carcinogenic alkene, 1,3-butadiene, is demonstrated to form 1-chloro-2-hydroxy-3-butene (CHB) through the MPO-mediated pathway. Further bioactivation of CHB yields a cross-linking metabolite, 1-chloro-3-buten-2-one (CBO), which is highly reactive toward glutathione, proteins, nucleosides, and DNA. Toxicity and mutagenicity of CHB and CBO are also presented. Expert opinion: Alkene hydrocarbons readily undergo MPO-mediated bioactivation to form chlorohydrins, which can further be biotransformed into proteins/DNA-modifying reactive metabolites. Therefore, chlorohydrin formation may play an important role in alkene toxicity and carcinogenicity. Olefinic moieties in drugs are expected to undergo similar bioactivation, which may contribute to ADRs. Studies to investigate the roles of MPO and chlorohydrin formation in ADRs are thus warranted.

  7. New insights into the structure of polypropylene polymorphs and propylene copolymers probed by low-frequency Raman spectroscopy (United States)

    Sagitova, E. A.; Donfack, P.; Nikolaeva, G. Yu; Prokhorov, K. A.; Pashinin, P. P.; Nedorezova, P. M.; Klyamkina, A. N.; Materny, A.


    We present a low-frequency (or low-wavenumber) Raman spectroscopy study of isotactic polypropylene, namely the different modifications - α, γ, and smectic, with a degree of crystallinity ranging from 0 to 70 %, as well as of random propylene/1-butene and propylene/1-octene copolymers with the incorporated monomer contents of 5.3 and 19.5 mol % for 1-butene and 4.5 and 24.0 mol % for 1-octene. In the Raman spectra of the propylene/1-octene copolymers and the neat isotactic polypropylene, we have found that the band at 105 cm-1, which is connected to the torsion vibrations of CH2-CHCH3 groups in the polymer backbone, can be assigned to the vibrations of helical macromolecules in the α and γ crystallites and the smectic phase. If the smectic phase is absent in the corresponding polymer system, then the intensity of the 105 cm-1 band is related to the molecular vibrations in the crystallites. We have also observed a broadening of the band at 398 cm-1 accompanied by the appearance of a high-wavenumber shoulder in the Raman spectra of the copolymers with the increase in the incorporated monomer content. This experimental finding can be explained by the reduction of the degree of crystallinity, conformational disordering or by the increase in the dimensions of the crystal unit cell.

  8. Volatile fingerprinting of the plum brandies produced from different fruit varieties. (United States)

    Vyviurska, Olga; Matura, František; Furdíková, Katarína; Špánik, Ivan


    Nowadays, fingerprinting of food became one of the most perspective analytical tools to resolve a problem of food quality and authentication, especially in difficult cases like differentiation of fruit varieties. In this work, plum brandies distillated by the same technology from 25 plum cultivars were distinguished by comprehensive two-dimensional gas chromatographic analysis and sensory evaluation. The number of identified compounds in studied samples varied between 91 and 195 depending on the plum variety. Enriched volatile organic compounds (VOC) profile was identified for the samples received from "Chrudimer", "Cacak Fruitful" and "Hanita" plum varieties, whereas in the case of "Gabrovská", "Presenta", Elena" and "President" plum varieties, the VOC profile was significantly reduced. From qualitative point of view, the particular plum brandies showed differences in the presence of unsaturated fusel alcohols (e.g. 3-methyl-3-buten-1-ol, trans-3-hexenol), unsaturated aldehydes (2-butenal, 2-nonenal), monoterpene derivatives (e.g. linalool acetate, geraniol acetate) and lactones, which were mainly detected at the trace level.

  9. [Extraction and determination of essential oils in Indocalamus latifolius leaves and Indocalamus tessellatus leaves]. (United States)

    Li, Shuifang; Wen, Ruizhi; Zeng, Dong; Li, Zhonghai


    Indocalamus leaves are the generic name of the leaves of Indocalamus (Graminales) plants. The essential oils in Indocalamus latifolius leaves and Indocalamus tessellatus leaves were extracted by steam distillation method. Ether was used as the solvent to extract volatile compounds many times. Both the volatile compounds in Indocalamus latifolius leaves and Indocalamus tessellatus leaves were analyzed by gas chromatography-mass spectrometry (GC-MS). The results showed that thirty-seven compounds were identified for the essential oils extracted from Indocalamus latifolius leaves, and its main components were found to be 3-hexen-1-ol, (Z)-; 1-hexanol; benzyl alcohol; hexanal; furan, 2-ethyl-; 3-buten-2-one, 4-(2,6, 6-trimethyl-1-cyclohexen-1-yl), (E)-; etc. Forty-nine components were identified for the essential oils extracted from Indocalamus tessellatus leaves, and its main components were found to be 3-hexen-1-ol, (Z)-; benzyl alcohol; 3-buten-2-one, 4-(2,6,6-trimethyl-1-cyclohexen-1-yl)-, (E)-; 2-hexenal; phenylethyl alcohol, 2-methoxy-4-vinylphenol; furan, 2-ethyl-; etc. 3-Hexen-1-ol, (Z)- was the most abundant compound in the essential oils from both Indocalamus leaves. There were ketone, aldehyde, alcohol, phenol and ester in them. The contents of ketones, aldehydes, and alcohols were found higher than those of other compounds in the two essential oils.

  10. Catalytic behavior and reaction routes of MEK oxidation over Pd/ZSM-5 and Pd-Ce/ZSM-5 catalysts. (United States)

    Yue, Lin; He, Chi; Zhang, Xinyan; Li, Peng; Wang, Zhuo; Wang, Hailin; Hao, Zhengping


    Catalytic oxidation is a widely used pollution control technology for removing volatile organic compounds. Pd-Ce/ZSM-5 catalysts with different Ce contents were prepared by a co-impregnation method, and their catalytic performance was investigated for the oxidation of methyl ethyl ketone (MEK). The by-products of the reaction were monitored using gas chromatography and collected in thermal desorption tubes, which were further analyzed by gas chromatography/mass spectrometry. The PdCe(9.6)/ZSM-5 catalyst displayed the highest catalytic efficiency, as a consequence of a higher amount of strong acid sites and a superior PdO-Pd redox cycle in the presence of a CeO(2) additive. The introduction of CeO(2) enriched the by-product species. The formation mechanisms and oxidation routes of typical by-products, such as methyl acetate, 1-penten-3-one and 3-buten-2-one, 3-methyl, during MEK oxidation over Pd-Ce/ZSM-5 catalysts was also analyzed. CH(3)* species that formed on the catalyst were identified as reaction intermediaries. Trace amounts of acetic acid and methyl vinyl ketone were also detected and were further oxidized to methyl acetate, 1-penten-3-one and 3-buten-2-one, 3-methyl. Copyright © 2012 Elsevier B.V. All rights reserved.

  11. Speciated VOC emission inventory and spatial patterns of ozone formation potential in the Pearl River Delta, China. (United States)

    Zheng, Junyu; Shao, Min; Che, Wenwei; Zhang, Lijun; Zhong, Liuju; Zhang, Yuanhang; Streets, David


    The Pearl River Delta region (PRD) of China has long suffered from severe ground-level ozone pollution. Knowledge of the sources of volatile organic compounds (VOCs) is essential for ozone chemistry. In this work, a speciated VOC emission inventory was established on the basis of updated emissions and local VOC source profiles. The top 10 species, in terms of ozone formation potentials (OFPs), consisted of isoprene, mp-xylene, toluene, ethylene, propene, o-xylene, 1,2,4-trimethylbenzene, 2-methyl-2-butene, 1-butene, and alpha-pinene. These species contributed only 35.9% to VOCs emissions but accounted for 64.1% of the OFP in the region. The spatial patterns of the VOC source inventory agreed well with city-based source apportionment results, especially for vehicle emissions and industry plus VOC product-related emissions. Mapping of the OFPs and measured ozone concentrations indicated that the formation of higher ozone in the south and southeast of the PRD region differed from that in the Conghua area, a remote area in the north of the PRD. We recommend that the priorities for the control of VOC sources include motorcycles, gasoline vehicles, and solvent use because of their larger OFP contributions.

  12. Oxime-mediated in vitro reactivation kinetic analysis of organophosphates-inhibited human and electric eel acetylcholinesterase. (United States)

    Sahu, Arvind Kumar; Sharma, Rahul; Gupta, Bhanushree; Musilek, Kamil; Kuca, Kamil; Acharya, Jyotiranjan; Ghosh, Kallol K


    Organophosphate (OP)-based pesticides and nerve agents are highly toxic compounds which interrupt the catalytic mechanism of acetylcholinesterase (AChE) by phosphorylating the hydroxyl moiety of serine residue. The inhibited enzyme can be reactivated by the nucleophilic action of oxime reactivators. To analyze the effect of different AChE sources on reactivation efficacy of reactivators, several in vivo studies have carried out using variety of AChE sources like pig, rat and monkey. Investigations on species differences provide a better insight for the development of new reactivators. Hence, present study was mainly targeted on comparative analysis of the reactivation of electric eel and human AChE inhibited by different OP. A series of butene-linked bis-pyridinium mono oximes which vary in functional groups present at the second pyridinium ring have been examined against sarin, VX, tabun and ethyl-paraoxon-poisoned AChE. In case of tabun-inhibited AChEs, tested oximes were better than reference oximes. For VX-poisoned human AChE, reactivator K251 (kr2;1.51 mM (-) (1 )min (-) (1)) showed good reactivation efficacy with standard oximes. Studies stipulated that butene-linked oximes consisting of different functional moieties are good reactivators and found to have better efficacy to reactivate nerve agent-inhibited human AChE in comparison to eel AChE.

  13. Experimental validation of concentration profiles in an HCCI engine, modelled by a multi-component kinetic mechanism: Outline for auto-ignition and emission control

    Energy Technology Data Exchange (ETDEWEB)

    Machrafi, Hatim, E-mail: hatim-machrafi@enscp.f [UPMC Universite Paris 06, Ecole Nationale Superieure de Chimie de Paris, 11, rue de Pierre et Marie Curie, 75005 Paris (France); Universite de Liege, Thermodynamique des Phenomenes Irreversibles, 17, Allee du Six-Aout, 4000 Liege (Belgium)


    In order to contribute to the auto-ignition and emission control for Homogeneous Charge Compression Ignition (HCCI), a kinetic multi-component mechanism, containing 62 reactions and 49 species for mixtures of n-heptane, iso-octane and toluene is validated in this work, comparing for the concentration profiles of the fuel, the total hydrocarbons, O{sub 2}, CO{sub 2}, CO, acetaldehyde and iso-butene. These species are sampled during the combustion and quantified. For these measurements an automotive exhaust analyser, a gas chromatograph, coupled to a mass spectrometer and a flame ionisation detector are used, depending on the species to be measured. The fuel, total hydrocarbons, O{sub 2}, CO{sub 2}, iso-butene and acetaldehyde showed a satisfactory quantitative agreement between the mechanism and the experiments. Both the experiments and the modelling results showed the same formation behaviour of the different species. An example is shown of how such a validated mechanism can provide for a set of information of the behaviour of the auto-ignition process and the emission control as a function of engine parameters.

  14. Solid-state molecular organometallic chemistry. Single-crystal to single-crystal reactivity and catalysis with light hydrocarbon substrates. (United States)

    Chadwick, F Mark; McKay, Alasdair I; Martinez-Martinez, Antonio J; Rees, Nicholas H; Krämer, Tobias; Macgregor, Stuart A; Weller, Andrew S


    Single-crystal to single-crystal solid/gas reactivity and catalysis starting from the precursor sigma-alkane complex [Rh(Cy2PCH2CH2PCy2)(η2η2-NBA)][BArF4] (NBA = norbornane; ArF = 3,5-(CF3)2C6H3) is reported. By adding ethene, propene and 1-butene to this precursor in solid/gas reactions the resulting alkene complexes [Rh(Cy2PCH2CH2PCy2)(alkene) x ][BArF4] are formed. The ethene (x = 2) complex, [Rh(Cy2PCH2CH2PCy2)(ethene)2][BArF4]-Oct, has been characterized in the solid-state (single-crystal X-ray diffraction) and by solution and solid-state NMR spectroscopy. Rapid, low temperature recrystallization using solution methods results in a different crystalline modification, [Rh(Cy2PCH2CH2PCy2)(ethene)2][BArF4]-Hex, that has a hexagonal microporous structure (P6322). The propene complex (x = 1) [Rh(Cy2PCH2CH2PCy2)(propene)][BArF4] is characterized as having a π-bound alkene with a supporting γ-agostic Rh···H3C interaction at low temperature by single-crystal X-ray diffraction, variable temperature solution and solid-state NMR spectroscopy, as well as periodic density functional theory (DFT) calculations. A fluxional process occurs in both the solid-state and solution that is proposed to proceed via a tautomeric allyl-hydride. Gas/solid catalytic isomerization of d3-propene, H2C 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000

  15. Solid-state molecular organometallic chemistry. Single-crystal to single-crystal reactivity and catalysis with light hydrocarbon substrates† †Electronic supplementary information (ESI) available: Full details of experimental details, spectroscopic and other analytical data, X-ray crystallography, catalytic conditions, and computational studies. CCDC 1539832–1539836. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c7sc01491k Click here for additional data file. Click here for additional data file. Click here for additional data file. (United States)

    Chadwick, F. Mark; McKay, Alasdair I.; Martinez-Martinez, Antonio J.; Rees, Nicholas H.; Krämer, Tobias


    Single-crystal to single-crystal solid/gas reactivity and catalysis starting from the precursor sigma-alkane complex [Rh(Cy2PCH2CH2PCy2)(η2η2-NBA)][BArF4] (NBA = norbornane; ArF = 3,5-(CF3)2C6H3) is reported. By adding ethene, propene and 1-butene to this precursor in solid/gas reactions the resulting alkene complexes [Rh(Cy2PCH2CH2PCy2)(alkene)x][BArF4] are formed. The ethene (x = 2) complex, [Rh(Cy2PCH2CH2PCy2)(ethene)2][BArF4]-Oct, has been characterized in the solid-state (single-crystal X-ray diffraction) and by solution and solid-state NMR spectroscopy. Rapid, low temperature recrystallization using solution methods results in a different crystalline modification, [Rh(Cy2PCH2CH2PCy2)(ethene)2][BArF4]-Hex, that has a hexagonal microporous structure (P6322). The propene complex (x = 1) [Rh(Cy2PCH2CH2PCy2)(propene)][BArF4] is characterized as having a π-bound alkene with a supporting γ-agostic Rh···H3C interaction at low temperature by single-crystal X-ray diffraction, variable temperature solution and solid-state NMR spectroscopy, as well as periodic density functional theory (DFT) calculations. A fluxional process occurs in both the solid-state and solution that is proposed to proceed via a tautomeric allyl-hydride. Gas/solid catalytic isomerization of d3-propene, H2C 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000

  16. Synthesis of the Key Intermediate of Coenzyme Q10

    Directory of Open Access Journals (Sweden)

    Yuan-Gang Zu


    Full Text Available (2’E-1-(3-methyl-4-p-toluenesulfonyl-2-butene-6-methyl-2,3,4,5-tetramethoxybenzene (4 is the key intermediate in the synthesis of coenzyme Q10 via a coupling reaction with solanesyl bromide. In this paper, we report a simple and effective synthesis of compound 4, starting with the readily available and inexpensive precursors p-toluenesulfonyl chloride (TsCl and isoprene to obtain (2E-1-p-toluenesulfonyl-2-methyl-4-hydroxy-2-butene (3 by addition, esterification and hydrolysis. Application of the Friedel-Crafts alkylation to compound 3, followed by the addition of 2,3,4,5-tetramethoxytoluene (TeMT, assembled the two parts into compound 4. The key parameters of each reaction were optimized at the same time, and the four total operations needed to produced compound 4 had a 27.9% overall yield under the optimized conditions. The structures of the compounds were characterized by 1H-NMR, IR and MS. This alternative process has the potential to be used for large-scale process.

  17. The thermodynamic and structural properties of metallocenes-type random ethylene copolymers

    Energy Technology Data Exchange (ETDEWEB)

    Simanke, Adriane G.; Mauler, Raquel S.; Galland, Griselda B. [Rio Grande do Sul Univ., Porto Alegre, RS (Brazil). Inst. de Quimica]. E-mail:; Alamo, Rufina G. [Florida State Univ., Tallahassee, FL (UNited States). College of Engineering. Dept. of Chemical Engineering]. E-mail:


    The properties of a series of random ethylene copolymers prepared with the metallocenes catalytic system rac-Et[Ind]{sub 2} ZrCl{sub 2}/MAO were studied for a large variety of comonomer types. These include the classical 1-alkene type with length up to 10 carbons and those of the cyclic type such as cyclopentadiene and dicyclopentadiene. Under rapid crystallization, the melting temperatures of the newly synthesized copolymers followed the relation of model random copolymers indicating a behavior that conforms to that predicted by Flory's phase equilibrium theory. The molar entropy of fusion is not significantly altered by the comonomer type including the dicyclopentadiene type. All types of comonomers studied showed, for a fixed comonomer content, the same change in properties during annealing, except the ethylene 1-butenes. These latter copolymers and the hydrogenated poly butadiene showed a faster rate of change in thermal properties. This is consistent with a higher molecular diffusion for the butene comonomer than for the rest of comonomers analyzed. The properties of the inter lamellar region were also studied as a function of comonomer type and content following the variation of the amorphous halo extracted from the WAXS diffractograms. The observed systematic decrease in the peak scattering angle with increasing comonomer content indicates a variation of the intermolecular liquid structure. (author)

  18. Enantioselective decomposition of chiral alkyl bromides on Cu(6 4 3) R&S: Effects of moving the chiral center (United States)

    Rampulla, D. M.; Gellman, A. J.


    The enantioselective surface chemistry of two chiral alkyl halides, S-1-bromo-2-methylbutane and R-2-bromobutane, have been compared on the naturally chiral Cu(6 4 3) R&S surfaces. Temperature programmed reaction spectroscopy was used to quantify the yields of the various decomposition products during heating. A fraction of the adsorbed alkyl bromides desorb intact while the remainder decomposes by debromination to form either S-2-methyl-1-butyl or R-2-butyl groups on the surfaces. The S-2-methyl-1-butyl group then reacts by β-hydride elimination to form 2-methyl-1-butene or by hydrogenation to form 2-methylbutane. The R-2-butyl group reacts by β-hydride elimination to form butene or by hydrogenation to form butane. This surface chemistry on Cu(6 4 3) R&S is not enantioselective at low coverages but is enantioselective at high coverages. In R-2-bromobutane the chiral carbon atom coincides with the debromination reaction center while the β-hydride elimination centers are achiral. In S-1-bromo-2-methylbutane the chiral carbon atom coincides with the β-hydride elimination reaction center while the center for debromination is achiral. Results show that the enantioselectivities are influenced by the surface structure to a greater extent than they are by the adsorbate structure.

  19. Volatile organic compound constituents from an integrated iron and steel facility. (United States)

    Tsai, Jiun-Horng; Lin, Kuo-Hsiung; Chen, Chih-Yu; Lai, Nina; Ma, Sen-Yi; Chiang, Hung-Lung


    This study measured the volatile organic compound (VOC) constituents of four processes in an integrated iron and steel industry; cokemaking, sintering, hot forming, and cold forming. Toluene, 1,2,4-trimethylbenzene, isopentane, m,p-xylene, 1-butene, ethylbenzene, and benzene were the predominant VOC species in these processes. However, some of the chlorinated compounds were high (hundreds ppbv), i.e., trichloroethylene in all four processes, carbon tetrachloride in the hot forming process, chlorobenzene in the cold forming process, and bromomethane in the sintering process. In the sintering process, the emission factors of toluene, benzene, xylene, isopentane, 1,2,4-trimethylbenzene, and ethylbenzene were over 9 g/tonne-product. In the vicinity of the manufacturing plant, toluene, isopentane, 1,2,4-trimethylbenzene, xylene and ethylbenzene were high. Toluene, 1,2,4-trimethylbenzene, xylene, 1-butene and isopentane were the major ozone formation species. Aromatic compounds were the predominant VOC groups, constituting 45-70% of the VOC concentration and contributing >70% to the high ozone formation potential in the stack exhaust and workplace air. The sequence of VOC concentration and ozone formation potential was as follows: cold forming>sintering>hot forming>cokemaking. For the workplace air, cokemaking was the highest producer, which was attributed to the fugitive emissions of the coke oven and working process release.

  20. Hydrogen transfer on USY zeolites during gas oil cracking: Influence of the adsorption characteristics of the zeolite catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Corma, A.; Faraldos, M.; Martinez, A.; Mifsud, A. (CSIC, Madrid (Spain))


    In this work, the hydrogen transfer activity of two series of HY zeolites dealuminated by steam and by SiCl{sub 4} (24.47-24.24 {angstrom} unit cell) has been measured from the butene/butane ratio in the products obtained during the cracking of a vacuum gas oil at 756 K. With the steam-dealuminated zeolites, a sharp decrease in the ratio of hydrogen transfer to cracking is observed when the number of Al atoms per unit cell falls below 10. On the other hand, in samples dealuminated by SiCl{sub 4}, this ratio changes very little with dealumination. These results cannot be explained assuming the need for adjacent acid sites for the hydrogen transfer. The authors have found, by adsorption measurements of n-butane and 1-butene, that the changes in the relative rates of bimolecular (hydrogen transfer) to monomolecular (cracking) reactions, observed with dealuminated HY zeolites, can be explained by the changes in the adsorption capacity and adsorption selectivity which occur on zeolites dealuminated at different levels by different dealumination procedures, and which are due to changes in the electric fields inside the pores.

  1. Identification of the volatile component(s) causing the characteristic foxy odor in various cultivars of Fritillaria imperialis L. (Liliaceae). (United States)

    Helsper, Johannes Petrus Franciscus Gerardus; Bücking, Mark; Muresan, Sorel; Blaas, Jan; Wietsma, Willem Anne


    To identify the component(s) causing the foxy odor, characteristic for some Fritillaria imperialis cultivars, the headspace of flower bulbs was analyzed using gas chromatography-olfactometry (GC-O) and GC-mass spectrometry (GC-MS). Six Fritillaria species and cultivars were selected as follows: F. imperialis cv. Premier (very strong foxy odor), F. imperialis cv. Lutea (strong foxy odor), F. imperialis ssp. Inodora (no odor), Fritillaria eduardii (weak mousy odor), Fritillaria raddeana (no odor), and an F1 of F. imperialis Lutea x Inodora (weak foxy odor). Volatiles from these flower bulbs were accumulated on Tenax and injected into the GC by thermodesorption. The majority of the volatiles consisted of low molecular weight aliphatic compounds. GC-O revealed that the foxy odor was caused by a single component, identified as 3-methyl-2-butene-1-thiol on the basis of smell in GC-O analyses (two GC columns), mass spectra, and retention times. Chemical identification was substantiated by GC-O and GC-MS of an authentic standard of 3-methyl-2-butene-1-thiol, prepared by organic synthesis.

  2. Catalytic cracking of lignites

    Energy Technology Data Exchange (ETDEWEB)

    Seitz, M.; Nowak, S.; Naegler, T.; Zimmermann, J. [Hochschule Merseburg (Germany); Welscher, J.; Schwieger, W. [Erlangen-Nuernberg Univ. (Germany); Hahn, T. [Halle-Wittenberg Univ., Halle (Germany)


    A most important factor for the chemical industry is the availability of cheap raw materials. As the oil price of crude oil is rising alternative feedstocks like coal are coming into focus. This work, the catalytic cracking of lignite is part of the alliance ibi (innovative Braunkohlenintegration) to use lignite as a raw material to produce chemicals. With this new one step process without an input of external hydrogen, mostly propylene, butenes and aromatics and char are formed. The product yield depends on manifold process parameters. The use of acid catalysts (zeolites like MFI) shows the highest amount of the desired products. Hydrogen rich lignites with a molar H/C ratio of > 1 are to be favoured. Due to primary cracking and secondary reactions the ratio between catalyst and lignite, temperature and residence time are the most important parameter to control the product distribution. Experiments at 500 C in a discontinuous rotary kiln reactor show yields up to 32 wt-% of hydrocarbons per lignite (maf - moisture and ash free) and 43 wt-% char, which can be gasified. Particularly, the yields of propylene and butenes as main products can be enhanced four times to about 8 wt-% by the use of catalysts while the tar yield decreases. In order to develop this innovative process catalyst systems fixed on beads were developed for an easy separation and regeneration of the used catalyst from the formed char. (orig.)

  3. Inhibition and Promotion of Pyrolysis by Hydrogen Sulfide (H2S) and Sulfanyl Radical (SH). (United States)

    Zeng, Zhe; Altarawneh, Mohammednoor; Oluwoye, Ibukun; Glarborg, Peter; Dlugogorski, Bogdan Z


    This study resolves the interaction of sulfanyl radical (SH) with aliphatic (C1-C4) hydrocarbons, using CBS-QB3 based calculations. We obtained the C-H dissociation enthalpies and located the weakest link in each hydrocarbon. Subsequent computations revealed that, H abstraction by SH from the weakest C-H sites in alkenes and alkynes, except for ethylene, appears noticeably exothermic. Furthermore, abstraction of H from propene, 1-butene, and iso-butene displays pronounced spontaneity (i.e., ΔrG° hydrogen bond. However, an alkyl radical readily abstracts H atom from H2S, with H2S acting as a potent scavenger for alkyl radicals in combustion processes. That is, these reactions proceed in the opposite direction than those involving SH and alkene or alkyne species, exhibiting shallow barriers and strong spontaneity. Our findings demonstrate that the documented inhibition effect of hydrogen sulfide (H2S) on pyrolysis of alkanes does not apply to alkenes and alkynes. During interaction with hydrocarbons, the inhibitive effect of H2S and promoting interaction of SH radical depend on the reversibility of the H abstraction processes. For the three groups of hydrocarbon, Evans-Polanyi plots display linear correlations between the bond dissociation enthalpies of the abstracted hydrogens and the relevant activation energies. In the case of methane, we demonstrated that the reactivity of SH radicals toward abstracting H atoms exceeds that of HO2 but falls below those of OH and NH2 radicals.

  4. A widely-tunable and sensitive optical sensor for multi-species detection in the mid-IR (United States)

    Alquaity, Awad B. S.; Al-Saif, Bidoor; Farooq, Aamir


    Pulsed cavity ringdown spectroscopy (CRDS) technique was used to develop a novel widely-tunable laser-based sensor for sensitive measurements of ethylene, propene, 1-butene and allene in the mid-IR. The use of an external-cavity quantum cascade laser (EC-QCL) enabled the sensor to cover a wide wavelength range from 10 to 11.1 µm (900–1000 cm‑1) to detect multiple gases relevant to combustion and environment. The sensor operation was validated in a room-temperature static cell using well-characterized absorption lines of carbon dioxide near 938.69 cm‑1 and 974.62 cm‑1. Detection limits for ethylene, propene, 1-butene, and allene were measured to be 17, 134, 754 and 378 ppb, respectively, at 296 K and 760 Torr for a single-pass path-length of 70 cm with averaging time of 4 ms. The excellent sensitivity of the optical sensor enabled it to measure the aforementioned gases at levels smaller than 1% of their recommended exposure limits. To the best of our knowledge, this is one of the first successful applications of the pulsed CRDS technique to measure trace levels of multiple gases in the 10–11 µm wavelength region.

  5. Widely-tunable and sensitive optical sensor for multi-species detection in the mid-IR

    KAUST Repository

    Alquaity, Awad


    Pulsed cavity ringdown spectroscopy (CRDS) technique was used to develop a novel widely-tunable laser-based sensor for sensitive measurements of ethylene, propene, 1-butene and allene in the mid-IR. The use of an external-cavity quantum cascade laser (EC-QCL) enabled the sensor to cover a wide wavelength range from 10 to 11.1 µm (900 – 1000 cm-1) to detect multiple gases relevant to combustion and environment. The sensor operation was validated in a room-temperature static cell using well-characterized absorption lines of carbon dioxide near 938.69 cm-1 and 974.62 cm-1. Detection limits for ethylene, propene, 1-butene, and allene were measured to be 17, 134, 754 and 378 ppb, respectively, at 296 K and 760 Torr for a single-pass path-length of 70 cm. The excellent sensitivity of the optical sensor enabled it to measure the aforementioned gases at levels smaller than 1% of their recommended exposure limits. To the best of our knowledge, this is one of the first successful applications of the pulsed CRDS technique to measure trace levels of multiple gases in the 10 – 11 µm wavelength region.

  6. Evidence for singlet-oxygen generation and biocidal activity in photoresponsive metallic nitride fullerene-polymer adhesive films. (United States)

    McCluskey, D Michelle; Smith, Tiffany N; Madasu, Praveen K; Coumbe, Curtis E; Mackey, Mary A; Fulmer, Preston A; Wynne, James H; Stevenson, Steven; Phillips, J Paige


    The adhesive properties, as measured by bulk tack analysis, are found to decrease in blends of isomerically pure Sc3N@I(h)-C80 metallic nitride fullerene (MNF) and polystyrene-block-polyisoprene-block-polystyrene (SIS) copolymer pressure-sensitive adhesive under white light irradiation in air. The reduction of tack is attributed to the in situ generation of 1O2 and subsequent photooxidative cross-linking of the adhesive film. Comparisons are drawn to classical fullerenes C60 and C70 for this process. This work represents the first demonstration of 1O2 generating ability in the general class of MNFs (M3N@C80). Additional support is provided for the sensitizing ability of Sc3N@I(h)-C80 through the successful photooxygenation of 2-methyl-2-butene to its allylic hydroperoxides in benzene-d(6) under irradiation at 420 nm, a process that occurs at a rate comparable to that of C(60). Photooxygenation of 2-methyl-2-butene is found to be influenced by the fullerene sensitizer concentration and O2 flow rate. Molar extinction coefficients are reported for Sc3N@I(h)-C80 at 420 and 536 nm. Evaluation of the potential antimicrobial activity of films prepared in this study stemming from the in situ generation of 1O2 led to an observed 1 log kill for select Gram-positive and Gram-negative bacteria.

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

    Ohno, Hiroyuki; Mutsuga, Motoh; Kawamura, Yoko


    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.

  8. In Situ Methylene Capping: A General Strategy for Efficient Stereoretentive Catalytic Olefin Metathesis. The Concept, Methodological Implications, and Applications to Synthesis of Biologically Active Compounds. (United States)

    Xu, Chaofan; Shen, Xiao; Hoveyda, Amir H


    In situ methylene capping is introduced as a practical and broadly applicable strategy that can expand the scope of catalyst-controlled stereoselective olefin metathesis considerably. By incorporation of commercially available Z-butene together with robust and readily accessible Ru-based dithiolate catalysts developed in these laboratories, a large variety of transformations can be made to proceed with terminal alkenes, without the need for a priori synthesis of a stereochemically defined disubstituted olefin. Reactions thus proceed with significantly higher efficiency and Z selectivity as compared to when other Ru-, Mo-, or W-based complexes are utilized. Cross-metathesis with olefins that contain a carboxylic acid, an aldehyde, an allylic alcohol, an aryl olefin, an α substituent, or amino acid residues was carried out to generate the desired products in 47-88% yield and 90:10 to >98:2 Z:E selectivity. Transformations were equally efficient and stereoselective with a ∼70:30 Z-:E-butene mixture, which is a byproduct of crude oil cracking. The in situ methylene capping strategy was used with the same Ru catechothiolate complex (no catalyst modification necessary) to perform ring-closing metathesis reactions, generating 14- to 21-membered ring macrocyclic alkenes in 40-70% yield and 96:4-98:2 Z:E selectivity; here too, reactions were more efficient and Z-selective than when the other catalyst classes are employed. The utility of the approach is highlighted by applications to efficient and stereoselective syntheses of several biologically active molecules. This includes a platelet aggregate inhibitor and two members of the prostaglandin family of compounds by catalytic cross-metathesis reactions, and a strained 14-membered ring stapled peptide by means of macrocyclic ring-closing metathesis. The approach presented herein is likely to have a notable effect on broadening the scope of olefin metathesis, as the stability of methylidene complexes is a generally

  9. An experimental and theoretical study of reaction steps relevant to the methanol-to-hydrocarbons reaction

    Energy Technology Data Exchange (ETDEWEB)

    Svelle, Stian


    The primary objective of the present work is to obtain new insight into the reaction mechanism of the zeolite catalyzed methanol-to-hydrocarbons (MTH) reaction. It was decided to use both experimental and computational techniques to reach this goal. An investigation of the n-butene + methanol system was therefore initiated. Over time, it became apparent that it was possible to determine the rate for the methylation of n-butene by methanol. The ethene and propene systems were therefore reexamined in order to collect kinetic information also for those cases. With the development of user-friendly quantum chemistry programs such as the Gaussian suite of programs, the possibility of applying quantum chemical methods to many types of problems has become readily available even for non-experts. When performing mechanistic studies, there is quite often a considerable synergy effect when combining experimental and computational approaches. The methylation reactions mentioned above turned out to be an issue well suited for quantum chemical investigations. The incentive for examining the halomethane reactivity was the clear analogy to the MTH reaction system. Alkene dimerization was also a reaction readily examined with quantum chemistry. As discussed in the introduction of this thesis, polymethylbenzenes, or their cationic counterparts, are suspected to be key intermediates in the MTH reaction. It was therefore decided to investigate the intrinsic reactivity of these species in the gas-phase by employing sophisticated mass spectrometric (MS) techniques in collaboration with the MS group at the Department of Chemistry, University of Oslo The data thus obtained will also be compared with results from an ongoing computational study on gas phase polymethylbenzenium reactivity. 6 papers presenting various studies are included. The titles are: 1) A Theoretical Investigation of the Methylation of Alkenes with Methanol over Acidic Zeolites. 2) A Theoretical Investigation of the

  10. Hydrogen Abstraction from Hydrocarbons by NH2. (United States)

    Siddique, Kamal; Altarawneh, Mohammednoor; Gore, Jeff; Westmoreland, Phillip R; Dlugogorski, Bogdan Z


    This contribution investigates thermokinetic parameters of bimolecular gas-phase reactions involving the amine (NH2) radical and a large number of saturated and unsaturated hydrocarbons. These reactions play an important role in combustion and pyrolysis of nitrogen-rich fuels, most notably biomass. Computations performed at the CBS-QB3 level and based on the conventional transition-state theory yield potential-energy surfaces and reaction rate constants, accounting for tunnelling effects and the presence of hindered rotors. In an analogy to other H abstraction systems, we demonstrate only a small influence of variational effects on the rate constants for selected reaction. The studied reactions cover the abstraction of hydrogen atoms by the NH2 radical from the C-H bonds in C1-C4 species, and four C5 hydrocarbons of 2-methylbutane, 2-methyl-1-butene, 3-methyl-1-butene, 3-methyl-2-butene, and 3-methyl-1-butyne. For the abstraction of H from methane, in the temperature windows 300-500 and 1600-2000 K, the calculated reaction rate constants concur with the available experimental measurements, i.e., kcalculated/kexperimetal = 0.3-2.5 and 1.1-1.4, and the previous theoretical estimates. Abstraction of H atom from ethane attains the ratio of kcalculated/kexperimetal equal to 0.10-1.2 and 1.3-1.5 over the temperature windows of available experimental measurements, i.e., 300-900 K and 1500-2000 K, respectively. For the remaining alkanes (propane and n-butane), the average kexperimental/kcalculated ratio remains 2.6 and 1.3 over the temperature range of experimental data. Also, comparing the calculated standard enthalpy of reaction (ΔrH°298) with the available experimental measurements for alkanes, we found the mean unsigned error of computations as 3.7 kJ mol-1. This agreement provides an accuracy benchmark of our methodology, affording the estimation of the unreported kinetic parameters for H abstractions from alkenes and alkynes. On the basis of the Evans-Polanyi plots

  11. Development of segmented polyurethane elastomers with low iodine content exhibiting radiopacity and blood compatibility. (United States)

    Dawlee, S; Jayabalan, Muthu


    Biofunctionally active and inherently radiopaque polymers are the emerging need for biomedical applications. Novel segmented polyurethane elastomer with inherent radiopacity was prepared using aliphatic chain extender 2,3-diiodo-2-butene-1,4-diol, polyol polytetramethylene glycol and 4,4'-methylenebis(phenyl isocyanate) (MDI) for blood compatible applications. Aliphatic polyurethane was also prepared using hexamethylene diisocyanate for comparison. X-ray analysis of the polyurethanes revealed good radiopacity even at a relatively low concentration of 3% iodine in aromatic polyurethane and 10% in aliphatic polyurethane. The polyurethanes also possessed excellent thermal stability. MDI-based polyurethane showed considerably higher tensile strength than the analogous HDI-based polyurethane. MDI-based aromatic polyurethane exhibited a dynamic surface morphology in aqueous medium, resulting in the segregation of hydrophilic domains which was more conducive to anti-thrombogenic properties. The polyurethane was cytocompatible with L929 fibroblast cells, non-hemolytic, and possessed good blood compatibility.

  12. Correlation of Volatile Compounds and Sensory Attributes of Chinese Traditional Sweet Fermented Flour Pastes Using Hierarchical Cluster Analysis and Partial Least Squares-Discriminant Analysis

    Directory of Open Access Journals (Sweden)

    Meigui Huang


    Full Text Available The aroma compositions, sensory attributes, and their correlations of various traditional Chinese sweet fermented flour pastes (SFFPs were investigated. SFFPs, including LEEJ, LEEH, and XH6, showed high overall acceptance scores of 8.00, 8.21, and 7.50, respectively. Ninety-six volatile compounds were detected using solid-phase microextraction gas chromatography mass spectrometry. Hierarchical cluster analysis grouped SFFPs into three clusters according to their concentrations and compositions of volatile components. Partial least squares-discriminant analysis showed that volatile compounds, including ethyl phenylacetate, 5-methyl furfural, amyl cinnamal, ethyl myristate, decyl aldehyde, 1-phenylethyl acetate, 1-octen-3-ol, 3-buten-2-ol, butanoic acid, and caproaldehyde, were highly negatively correlated with saltiness, sourness, and bitterness, while they were positively correlated with sweetness, umami, richness, and acceptance. The obvious correlation between flavor profiles and sensory attributes could help online monitoring of SFFPs’ flavor quality during production.

  13. Thermal Synthesis of Polypeptides from N-Butyloxycarbonyl Oligopeptides Containing Aspartyl Residue at C-Terminus

    Directory of Open Access Journals (Sweden)

    Toratane Munegumi


    Full Text Available The thermal reactions of amino acids have been investigated for pure organic synthesis, materials preparation in industry, and prebiotic chemistry. N-t-Butyloxycarbonyl aspartic acid (Boc-Asp releases 2-butene and carbon dioxide upon heating without solvents. The resulting mixture of the free molten aspartic acid was dehydrated to give peptide bonds. This study describes the thermal reactions of N-t-butyloxycarbonyl peptides (Boc-Gly-L-Asp, Boc-L-Ala-L-Asp, Boc-L-Val-L-Asp, and Boc-Gly-Gly-L-Asp having an aspartic residue at the carboxyl terminus. The peptides were deprotected upon heating at a constant temperature between 110 and 170°C for 1 to 24 h to afford polypeptides in which the average molecular weight reached 7800.

  14. Influence of Engage® copolymer type on the properties of Engage®/silicone rubber-based thermoplastic dynamic vulcanizates

    Directory of Open Access Journals (Sweden)


    Full Text Available Thermoplastic vulcanizates (TPVs are a special class of thermoplastic elastomers, which are produced by simultaneously mixing and crosslinking a rubber with a thermoplastic polymer at an elevated temperature. Peroxide-cured TPVs based on blends of silicone rubber and thermoplastic Engage of two different types, mainly ethylene-octene and ethylenebutene copolymers at different blend ratios have been developed. A detailed comparative study of ethylene-octene vs. ethylene-butene based TPVs are mainly focused in this paper. These TPVs exhibit very good overall mechanical and electrical properties. With increasing amount of Engage in the blends at a fixed concentration of peroxide and coagent, tensile strength, modulus and hardness of the TPVs were found to increase considerably. Ageing characteristics and recyclability of silicone rubber based TPVs are also found excellent. Rheological studies confirm the pseudoplastic nature of these TPVs.

  15. Determination of VOCs in traffic exhaust by FTIR absorption spectrometry (United States)

    Sedlmaier, Achim; Schaefer, Klaus; Becker, K. H.; Brockmann, Klaus; Heland, Joerg; Kurtenbach, Ralf; Loerzer, J.; Wiesen, Peter


    Infrared spectral features of organic hydrocarbons were investigated with respect to single compounds. A separation and consequently a quantitative concentration determination is possible for ethane, ethene, ethyne, propene, iso-butene, benzene, toluene, o-xylene, m-xylene and p-xylene using a MCT detector with a cut-off frequency below 660 cm-1. The spectral features of propane, butane, pentane and hexane cannot be separated. In order to be able to derive parameters, such as detection limits, accuracy, precision and the influence of interfering species or different reference data, validation measurements were carried out in a road tunnel and in the laboratory using an open White mirror compartment and closed White cells. FTIR spectra were collected with two spectrometers at different spectral resolutions. Parallel GC measurements were made for comparison.

  16. Production of Low-Freezing-Point Highly Branched Alkanes through Michael Addition. (United States)

    Jing, Yaxuan; Xia, Qineng; Liu, Xiaohui; Wang, Yanqin


    A new approach for the production of low-freezing-point, high-quality fuels from lignocellulose-derived molecules was developed with Michael addition as the key step. Among the investigated catalysts, CoCl 2 ⋅6 H 2 O was found most active for the Michael addition of 2,4-pentanedione with FA (single aldol adduct of furfural and acetone, 4-(2-furanyl)-3-butene-2-one). Over CoCl 2 ⋅6 H 2 O, a high carbon yield of C 13 oxygenates (about 75 %) can be achieved under mild conditions (353 K, 20 h). After hydrodeoxygenation, low-freezing-point (freezing-point (freezing point from renewable biomass. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Cytotoxic Constituents from the Stems of Clausena lansium (Lour. Skeels

    Directory of Open Access Journals (Sweden)

    Shu Shan Du


    Full Text Available Six compounds were isolated from the stems of Clausena lansium (Lour. Skeels by repeated sillica gel column chromatography. Their chemical structures were elucidated on the basic of physicochemical and spectroscopic data. Among them, 8-geranyloxypsolaren (3 and 2-methoxy-1-(3-methyl-buten-1-yl-9H-carbazole-3-carbaldehyde (6 were isolated for the first time from this plant. These compounds were screened for cytotoxicity in human cervical cancer (Hela, leukemia (K562, lung cancer (A549, non-small lung carcinoma (H1299 and liver cancer (SMMC-7721. Within the series of cytotoxic tests, compounds 4–6 displayed potent cytotoxic activity against H1299 and SMMC-7721, with the IC50 values of 6.19 to 26.84 μg/mL.

  18. Kinetic Selectivity of Olefin Metathesis Catalysts Bearing Cyclic (Alkyl)(Amino)Carbenes (United States)

    Anderson, Donde R.; Ung, Thay; Mkrtumyan, Garik; Bertrand, Guy; Grubbs, Robert H.; Schrodi, Yann


    The evaluation of ruthenium olefin metathesis catalysts 4–6 bearing cyclic (alkyl)(amino)carbenes (CAACs) in the cross-metathesis of cis-1,4-diacetoxy-2-butene (7) with allylbenzene (8) and the ethenolysis of methyl oleate (11) is reported. Relative to most NHC-substituted complexes, CAAC-substituted catalysts exhibit lower E/Z ratios (3:1 at 70% conversion) in the cross-metathesis of 7 and 8. Additionally, complexes 4–6 demonstrate good selectivity for the formation of terminal olefins versus internal olefins in the ethenolysis of 11. Indeed, complex 6 achieved 35 000 TONs, the highest recorded to date. CAAC-substituted complexes exhibit markedly different kinetic selectivity than most NHC-substituted complexes. PMID:18584055

  19. Studies of the mechanism of the olefin metathesis reaction and the process of active site formation on photoreduced molybdenum-silicate catalysts. I. Mechanism of formation of molybdenum-carbene intermediates

    Energy Technology Data Exchange (ETDEWEB)

    Elev, I.V.; Shelimov, B.N.; Kazanskii, V.B.


    The products of the initial stages of the reaction of ethylene and propylene with Mo/sup 4 +/ ions in photoreduced molybdenum-silicate olefin metathesis catalysts have been studied by mass spectroscopy. The reaction of C/sub 2/H/sub 4/ with Mo/sup 4 +/ has been found to yield propylene, whereas interaction of C/sub 3/H/sub 6/ with Mo/sup 4 +/ gives a superequilibrium concentration of butenes and a small amount of pentenes. A significant kinetic isotope effect for the metathesis reaction was observed upon substitution of C/sub 3/H/sub 6/ by C/sub 3/D/sub 6/. The results can be interpreted in terms of a stepwise mechanism involving carbene intermediates, which are formed via isomerization of surface-bound ..pi..-complexes of olefins with Mo/sup 4 +/ ions as a result of intramolecular 1,2-H atom transfer.

  20. Molybdenum chloride catalysts for Z-selective olefin metathesis reactions (United States)

    Koh, Ming Joo; Nguyen, Thach T.; Lam, Jonathan K.; Torker, Sebastian; Hyvl, Jakub; Schrock, Richard R.; Hoveyda, Amir H.


    The development of catalyst-controlled stereoselective olefin metathesis processes has been a pivotal recent advance in chemistry. The incorporation of appropriate ligands within complexes based on molybdenum, tungsten and ruthenium has led to reactivity and selectivity levels that were previously inaccessible. Here we show that molybdenum monoaryloxide chloride complexes furnish higher-energy (Z) isomers of trifluoromethyl-substituted alkenes through cross-metathesis reactions with the commercially available, inexpensive and typically inert Z-1,1,1,4,4,4-hexafluoro-2-butene. Furthermore, otherwise inefficient and non-stereoselective transformations with Z-1,2-dichloroethene and 1,2-dibromoethene can be effected with substantially improved efficiency and Z selectivity. The use of such molybdenum monoaryloxide chloride complexes enables the synthesis of representative biologically active molecules and trifluoromethyl analogues of medicinally relevant compounds. The origins of the activity and selectivity levels observed, which contradict previously proposed principles, are elucidated with the aid of density functional theory calculations.

  1. Phase equilibrium measurements on nine binary mixtures

    Energy Technology Data Exchange (ETDEWEB)

    Wilding, W.V. [Brigham Young Univ., Provo, UT (United States). Chemical Engineering Dept.; Giles, N.F.; Wilson, L.C. [Wiltec Research Co. Inc., Provo, UT (United States)


    Phase equilibrium measurements have been performed on nine binary mixtures. The PTx method was used to obtain vapor-liquid equilibrium data for the following systems at two temperatures each: (aminoethyl)piperazine + diethylenetriamine; 2-butoxyethyl acetate + 2-butoxyethanol; 2-methyl-2-propanol + 2-methylbutane; 2-methyl-2-propanol + 2-methyl-2-butene; methacrylonitrile + methanol; 1-chloro-1,1-difluoroethane + hydrogen chloride; 2-(hexyloxy)ethanol + ethylene glycol; butane + ammonia; propionaldehyde + butane. Equilibrium vapor and liquid phase compositions were derived form the PTx data using the Soave equation of state to represent the vapor phase and the Wilson or the NRTL activity coefficient model to represent the liquid phase. A large immiscibility region exists in the butane + ammonia system at 0 C. Therefore, separate vapor-liquid-liquid equilibrium measurements were performed on this system to more precisely determine the miscibility limits and the composition of the vapor phase in equilibrium with the two liquid phases.

  2. Synthesis of Ni-SiO2/silicalite-1 core-shell micromembrane reactors and their reaction/diffusion performance

    KAUST Repository

    Khan, Easir A.


    Core-shell micromembrane reactors are a novel class of materials where a catalyst and a shape-selective membrane are synergistically housed in a single particle. In this work, we report the synthesis of micrometer -sized core-shell particles containing a catalyst core and a thin permselective zeolite shell and their application as a micromembrane reactor for the selective hydrogenation of the 1-hexene and 3,3-dimethyl-1-butene isomers. The bare catalyst, which is made from porous silica loaded with catalytically active nickel, showed no reactant selectivity between hexene isomers, but the core-shell particles showed high selectivities up to 300 for a 1-hexene conversion of 90%. © 2010 American Chemical Society.

  3. 6-(Hex-5-enyloxynaphthalene-2-carboxylic acid

    Directory of Open Access Journals (Sweden)

    Md. Lutfor Rahman


    Full Text Available The asymmetric unit of the title compound, C17H18O3, comprises three independent molecules with similar geometries. In each molecule, the carbonyl group is twisted away from the napthalene ring system, making dihedral angles of 1.0 (2, 1.05 (19° and 1.5 (2°. The butene group in all three molecules are disordered over two sets of sites, with a refined occupancy ratio of 0.664 (6:0.336 (6. In the crystal, molecules are oriented with respect to their carbonyl groups, forming head-to-head dimers via O—H...O hydrogen bonds. Adjacent dimers are further interconnected by C—H...O hydrogen bonds into chains along the a-axis direction. The crystal structure is further stabilized by weak C—H...π interactions.

  4. Substantially isotactic, linear, alternating copolymers of carbon monoxide and an olefin (United States)

    Sen, A.; Jiang, Z.


    The compound, [Pd(Me-DUPHOS)(MeCN){sub 2}](BF{sub 4}){sub 2}, [Me-DUPHOS: 1,2-bis(2,5-dimethylphospholano)benzene] is an effective catalyst for the highly enantioselective, alternating copolymerization of olefins, such as aliphatic {alpha}-olefins, with carbon monoxide to form optically active, isotactic polymers which can serve as excellent starting materials for the synthesis of other classes of chiral polymers. For example, the complete reduction of a propylene-carbon monoxide copolymer resulted in the formation of a novel, optically active poly(1,4-alcohol). Also, the previously described catalyst is a catalyst for the novel alternating isomerization cooligomerization of 2-butene with carbon monoxide to form optically active, isotactic poly(1,5-ketone).

  5. Study of volatile alcohols and esters from the subcutaneous fat during ripening of Iberian dry-cured ham. A tool for predicting the dry-curing time; Estudio de los alcoholes y ésteres volátiles de la grasa subcutánea durante la maduración del jamón ibérico. Una herramienta para predecir el tiempo de curación

    Energy Technology Data Exchange (ETDEWEB)

    Narvaez-Rivas, M.; Gallardo, E.; Leon-Camacho, M.


    Variations in the amounts of volatile alcohols and esters from subcutaneous fat have been assessed during the dry-curing process (1022 days) of Iberian ham according to a purge and trap-gas chromatography-mass spectroscopy method, using the same hams throughout the process. During processing time, the subcutaneous adipose tissues of ten hams obtained from five Iberian pigs fed on acorns and pasture were sampled and analyzed once per month. Fifteen alcohols and five esters have been identified. All volatile alcohols detected in this work have been previously identified by other authors on Iberian ham, except 3-buten-2-ol, 5-methyl-3-hexanol and 2-isononanol. A linear discriminant analysis (LDA) was applied and the two discriminant functions were obtained using backward stepwise analysis retaining the following variables: butyl ester formic acid, 1-penten-3-ol, methyl ester 2-propenoic acid, 5-methyl-3-hexanol, 1-nonanol, ethyl ester pentanoic acid, ethyl ester hexanoic acid, 2-isononanol, ethanol and 3-buten-2-ol. A complete separation among the three periods was obtained, suggesting that the retained variables are powerful descriptors to distinguish samples from these three dry-curing stages. [Spanish] Se han evaluado durante el proceso de curación (1022 días), las variaciones en los contenidos de alcoholes y ésteres volátiles de la grasa subcutánea del jamón ibérico mediante la técnica de acoplamiento purga y trampa- cromatografía de gases-espectrometría de masas, utilizando los mismos jamones a lo largo de todo el proceso. Durante el tiempo de curación se muestreó y analizó una vez al mes el tejido adiposo subcutáneo de diez jamones procedente de cinco cerdos ibéricos alimentados con bellotas y pastos. Se han identificado quince alcoholes y cinco ésteres volátiles. Todos los alcoholes descritos en este trabajo han sido identificados previamente por otros autores en el jamón ibérico, excepto el 3-buten-2-ol, el 5-metil-3-hexanol y el 2

  6. Zeolites as Catalysts for Fuels Refining after Indirect Liquefaction Processes

    Directory of Open Access Journals (Sweden)

    Arno de Klerk


    Full Text Available The use of zeolite catalysts for the refining of products from methanol synthesis and Fisher–Tropsch synthesis was reviewed. The focus was on fuels refining processes and differences in the application to indirect liquefaction products was compared to petroleum, which is often a case of managing different molecules. Processes covered were skeletal isomerisation of n-butenes, hydroisomerisation of n-butane, aliphatic alkylation, alkene oligomerisation, methanol to hydrocarbons, ethanol and heavier alcohols to hydrocarbons, carbonyls to hydrocarbons, etherification of alkenes with alcohols, light naphtha hydroisomerisation, catalytic naphtha reforming, hydroisomerisation of distillate, hydrocracking and fluid catalytic cracking. The zeolite types that are already industrially used were pointed out, as well as zeolite types that have future promise for specific conversion processes.

  7. Zeolites as Catalysts for Fuels Refining after Indirect Liquefaction Processes. (United States)

    Klerk, Arno de


    The use of zeolite catalysts for the refining of products from methanol synthesis and Fisher-Tropsch synthesis was reviewed. The focus was on fuels refining processes and differences in the application to indirect liquefaction products was compared to petroleum, which is often a case of managing different molecules. Processes covered were skeletal isomerisation of n -butenes, hydroisomerisation of n -butane, aliphatic alkylation, alkene oligomerisation, methanol to hydrocarbons, ethanol and heavier alcohols to hydrocarbons, carbonyls to hydrocarbons, etherification of alkenes with alcohols, light naphtha hydroisomerisation, catalytic naphtha reforming, hydroisomerisation of distillate, hydrocracking and fluid catalytic cracking. The zeolite types that are already industrially used were pointed out, as well as zeolite types that have future promise for specific conversion processes.

  8. Homo-polymerization of α-Olefins and Co-polymerization of Higher α-Olefins with Ethylene in the Presence of CpTiCl2(OC6H4X-p/MAO Catalysts (X = CH3, Cl

    Directory of Open Access Journals (Sweden)

    Z. Wieczorek


    Full Text Available Cyclopentadienyl-titanium complexes containing –OC6H4X ligands (X = Cl,CH3 activated with methylaluminoxane (MAO were used in the homo-polymerizationof ethylene, propylene, 1-butene, 1-pentene, 1-butene, and 1-hexene, and also in co-polymerization of ethylene with the α-olefins mentioned. The -X substituents exhibitdifferent electron donor-acceptor properties, which is described by Hammett’s factor (σ.The chlorine atom is electron acceptor, while the methyl group is electron donor. Thesecatalysts allow the preparation of polyethylene in a good yield. Propylene in the presenceof the catalysts mentioned dimerizes and oligomerizes to trimers and tetramers at 25oCunder normal pressure. If the propylene pressure was increased to 7 atmospheres,CpTiCl2(OC6H4CH3/MAO catalyst at 25oC gave mixtures with different contents ofpropylene dimers, trimers and tetramers. At 70oC we obtained only propylene trimer.Using the catalysts with a -OC6H4Cl ligand we obtained atactic polymers with Mw182,000 g/mol (at 25oC and 100,000 g/mol (at 70oC. The superior activity of theCpTiCl2(OC6H4Cl/MAO catalyst used in polymerization of propylene prompted us tocheck its activity in polymerization of higher α-olefins (1-butene, 1-pentene, 1-hexeneand in co-polymerization of these olefins with ethylene. However, when homo-polymerization was carried out in the presence of this catalyst no polymers wereobtained. Gas chromatography analysis revealed the presence of dimers. The activity ofthe CpTiCl2(OC6H4Cl/MAO catalyst in the co-polymerization of ethylene with higher α-olefins is limited by the length of the co-monomer carbon chain. Hence, the highest catalyst activities were observed in co-polymerization of ethylene with propylene (here a lower pressure of the reagents and shorter reaction time were applied to obtain catalytic activity similar to that for other co-monomers. For other co-monomers the activity of the catalyst

  9. Model studies on the influence of coffee melanoidins on flavor volatiles of coffee beverages. (United States)

    Hofmann, T; Czerny, M; Calligaris, S; Schieberle, P


    Addition of the total melanoidin fraction isolated by water extraction from medium-roasted coffee powder to a model solution containing a set of 25 aroma compounds mimicking the aroma of a coffee brew reduced, in particular, the intensity of the roasty, sulfury aroma quality. Model studies performed by static headspace analysis revealed that especially three well-known coffee odorants, that is, 2-furfurylthiol (FFT), 3-methyl-2-butene-1-thiol, and 3-mercapto-3-methylbutyl formate, were significantly reduced in the headspace above an aqueous model solution when melanoidins were added. In particular, the low molecular weight melanoidins (1500-3000 Da) led to the most significant decrease in FFT. In contrast, for example, aldehydes remained unaffected by melanoidin addition.

  10. Volatile components in defensive spray of the hooded skunk, Mephitis macroura. (United States)

    Wood, William F; Sollers, Brian G; Dragoo, Gwen A; Dragoo, Jerry W


    GC-MS analysis of the anal sac secretion from the hooded skunk, Mephitis macroura, showed the following seven major components comprised 99% of the volatiles in this secretion: (E)-2-butene-1-thiol, 3-methyl-1-butanethiol, S-(E)-2-butenyl thioacetate, S-3-methylbutenyl thioacetate, 2-phenylethanethiol, 2-methylquinoline, and 2-quinolinemethanethiol. Minor volatile components identified in this secretion are phenylmethanethiol, S-phenylmethyl thioacetate. S-2-phenylethyl thioacetate, bis[(E)-2-butenyl] disulfide, (E)-2-butenyl 3-methylbutyl disulfide, bis(3-methylbutyl) disulfide, and S-2-quinolinemethyl thioacetate. This secretion is similar to that of the striped skunk, Mephitis mephitis, differing only in that it contains four compounds not reported from the striped skunk: phenylmethanethiol, S-phenylmethyl thioacetate, 2-phenylethanethiol, and S-2-phenylethyl thioacetate.

  11. Single Site Silica Supported Tetramethyl Niobium by the SOMC Strategy: Synthesis, Characterization and Structure-Activity Relationship in Ethylene Oligomerization Reaction

    KAUST Repository

    Hamieh, Ali Imad Ali


    Silica supported Tetramethyl niobium complex [(≡SiO)NbMe4] 2 has been isolated by surface alkylation of [(≡SiO-)NbCl3Me] 1 with dimethyl zinc in pentane. 1 can be easily synthesized by grafting of NbCl3Me2 on to the surface of partially dehydroxylated silica by the SOMC strategy. Precise structural analysis was carried out by the FTIR, advance solid state NMR, elemental analysis and mass balance techniques (gas quantification after treating 2 with degassed water) . Complex 1 was found to be active in the ethylene oligomerization to produce up to C30, whereas to our surprise complex 2 selectively dimerizes ethylene into 1-butene in the absence of a co-catalyst at the same conversion levels.

  12. Ethylene Polymerization Using (Iminovanadium(V Dichloride Complexes Containing (Anilidomethyl-pyridine, -quinoline Ligands–Halogenated Al Alkyls Catalyst Systems

    Directory of Open Access Journals (Sweden)

    Atsushi Igarashi


    Full Text Available The effect of ligand and Al cocatalysts in ethylene polymerization, using V(N-1-adamantylCl2(L [L = 2-(2,6-Me2C6H3NCH2(C9H6N, 8-(2,6-Me2C6H3NCH2(C9H6N] and V(N-2-MeC6H3Cl2[2-(2,6-R'2C6H3NCH2(C5H4N] (R' = Me, iPr, has been explored. The reaction products in the presence of Et2AlCl or Me2AlCl cocatalyst were polyethylene whereas the reaction product of the 2-methylphenylimido analogues in the presence of MAO cocatalyst was 1-butene with high selectivity, suggesting that the catalyst/cocatalyst nuclearity effect plays a role in this catalysis.

  13. Efficient Pd@MIL-101(Cr) hetero-catalysts for 2-butyne-1,4-diol hydrogenation exhibiting high selectivity

    KAUST Repository

    Yin, Dongdong


    Pd@MIL-101(Cr) hetero-catalysts have been successfully prepared using the metal-organic chemical vapour deposition (MOCVD) approach, by choosing [Pd(η-CH)(η-CH)] as a volatile precursor, and the hydrothermally stable metal-organic framework, MIL-101(Cr) as a support. The prepared Pd@MIL-101(Cr) hetero-catalysts characterized with various analytical techniques, exhibited highly monodispersed immobilized Pd nanoparticles in the MIL-101(Cr) cavities, while retaining the pristine crystallinity and porosity. The intact hybrid Pd@MIL-101(Cr) has been demonstrated to be an efficient catalyst for 2-butyne-1,4-diol hydrogenation with excellent activity, stability and selectivity (2-butene-1,4-diol (>94%)).

  14. Comparison of aroma-active volatiles and their sensory characteristics of mangosteen wines prepared by Saccharomyces cerevisiae with GC-olfactometry and principal component analysis. (United States)

    Xiao, Zuo Bing; Liu, Jun Hua; Chen, Feng; Wang, Ling Ying; Niu, Yun Wei; Feng, Tao; Zhu, Jian Cai


    Mangosteen fruit is fermented with five different strains (i.e. GRE (Y1), Lalvin RC212 (Y2), Lalvin D254 (Y3), CGMCC2.23 (Y4) and CGMCC2.4 (Y5)) of the yeast Saccharomyces cerevisiae to make mangosteen wines. A total of 36 volatile compounds of the mangosteen wines were identified by gas chromatography-mass spectrometry and gas chromatography-pulsed flame photometric detection. A total of 35 odour-active compounds were identified by gas chromatography-olfactometry analysis and by the detection frequency (DF) method. The compounds with high DF values included ethyl octanoate, ethyl hexanoate and 3-methyl-2-butene-1-thiol. Principal component analysis was used to characterise the differences of the flavour profiles of those mangosteen wines. The result demonstrated that the samples could be divided into three groups that were associated closely with aroma-active compounds.

  15. Application of gas chromatography analysis to quality control of residual organic solvents in clopidogrel bisulphate

    Directory of Open Access Journals (Sweden)

    Pavlović Aleksandar D.


    Full Text Available A direct-injection, split-mode capillary gas chromatographic procedure with a flame ionization detection is developed for the analysis of eight solvents used in the synthesis and purification of an anti-thrombotic drug clopidogrel bisulphate. The solvents analyzed were methanol, acetone, dichloromethane (DCM, 2-butanol, cyclohexane, toluene, acetic acid and N, N-dimethyl formamide (DMF. In addition, as a result of dehydration of 2-butanol during drying process, in clopidogrel bisulphate samples, significant amounts of 2-butanol dehydration products (1-butene, cis and trans isomers of 2-butene, 2,2'-oxydibutane and 1-(1-methylpropoxybutane may be detected. The content of each of these volatile products can be evaluated using the same gas-chromatographic method, with quantification based on the response factor established for the chromatographic peak of 2-butanol. For each solvent used in the process of clopidogrel bisulphate preparation, the procedure is validated for selectivity, linearity, recovery, precision, robustness, quantitation limit, and detection limit. All eight solvents plus five 2-butanol degradation products are fully separated. System suitability test is validated, and requirements are set. Based on a large number of result sets, retrospectively, from many different batches analyzed, conclusions were made about process variations and reliability and a lack of consistency was identified in the quality of the active substance from a particular producer source. Multivariate analysis was used as statistical technique to classify samples. From the analyzed set of 11 solvents, 6 of them were preselected based upon their occurrence in the samples and both Principal Component Analysis (PCA and Hierarchical Cluster Analysis (HCA were performed.

  16. Mg3(VO4)2-MgO-ZrO2 nano-catalysts for oxidative dehydrogenation of n-butane. (United States)

    Lee, Jong Kwon; Seo, Hyun; Hong, Ung Gi; Yoo, Yeonshick; Cho, Young-Jin; Lee, Jinsuk; Park, Gle; Chang, Hosik; Song, In Kyu


    A series of X-Mg3(VO4)2-MgO-ZrO2 nano-catalysts with different vanadium content (X = 3.3, 5.3, 7.0, 10.2, and 13.4) were prepared by a single-step citric acid-derived sol-gel method for use in the oxidative dehydrogenation of n-butane to n-butene and 1,3-butadiene. The effect of vanadium content of X-Mg3(VO4)2-MgO-ZrO2 nano-catalysts on their physicochemical properties and catalytic activities in the oxidative dehydrogenation of n-butane was investigated. Successful formation of X-Mg3(VO4)2-MgO-ZrO2 nano-catalysts was confirmed by XRD, Raman spectroscopy, and ICP-AES analyses. The catalytic performance of X-Mg3(VO4)2-MgO-ZrO2 nano-catalysts strongly depended on vanadium content. All the X-Mg3(VO4)2-MgO-ZrO2 nano-catalysts showed a stable catalytic performance without catalyst deactivation during the reaction. Among the catalysts tested, 7.0-Mg3(VO4)2-MgO-ZrO2 nano-catalyst showed the best catalytic performance in terms of yield for total dehydrogenation products (TDP, n-butene and 1,3-butadiene). TPRO (temperature-programmed reoxidation) experiments were carried out to measure the oxygen capacity of the catalyst. Experimental results revealed that oxygen capacity of the catalyst was closely related to the catalytic performance. Yield for TDP increased with increasing oxygen capacity of the catalyst.

  17. Role of rare earth cations in Y zeolite for hydrocarbon cracking. (United States)

    Sanchez-Castillo, Marco A; Madon, Rostam J; Dumesic, James A


    Reaction kinetics data were collected for isobutane conversion over a series of ultra stable Y (USY) zeolite catalysts with and without rare earth cations and subjected to various extents of dealumination by steaming. We conducted these reaction studies at low temperatures (523-573 K) using isobutane feed streams containing known levels of isobutylene (100-400 ppm) so that the kinetics were controlled by bimolecular hydride transfer and oligomerization/beta-scission processes with little or no participation of monomolecular initiation reactions. These experimental conditions led to stable catalyst performance with the main products of isobutane conversion being propane, n-butane, and isopentane, with smaller amounts of propylene, trans-2-butene, and cis-2-butene. The rates of formation of these products per Brønsted acid site (as counted by pyridine adsorption) depended exponentially on Brønsted acid site density, regardless of whether the catalyst contained rare earth cations. Kinetic modeling showed an exponential dependence of hydride transfer and oligomerization/ beta-scission reaction rates on Brønsted acid site density which translated into composite activation energies for these reactions having a linear relationship with site density. Based on results in the literature from theoretical calculations, we suggest that increasing Brønsted acid site density in zeolite Y leads to larger zeolite elasticity, increased stabilization of cationic transition states, and lower composite activation barriers for hydride transfer and beta-scission steps. The role of rare earth cations, therefore, is to ensure the retention of high Brønsted acid site density under hydrothermal conditions, such as in fluid catalytic cracking (FCC) regenerators, where steam would dealuminate the Y zeolite framework and reduce this site density. It is for this reason that hydride transfer reaction rates are high in the presence of rare earth cations and lead to higher yields of less

  18. Synthesis and activity of ruthenium olefin metathesis catalysts coordinated with thiazol-2-ylidene ligands. (United States)

    Vougioukalakis, Georgios C; Grubbs, Robert H


    A new family of ruthenium-based olefin metathesis catalysts bearing a series of thiazole-2-ylidene ligands has been prepared. These complexes are readily accessible in one step from commercially available (PCy3)2Cl2Ru=CHPh or (PCy3)Cl2Ru=CH(o-iPrO-Ph) and have been fully characterized. The X-ray crystal structures of four of these complexes are disclosed. In the solid state, the aryl substituents of the thiazole-2-ylidene ligands are located above the empty coordination site of the ruthenium center. Despite the decreased steric bulk of their ligands, all of the complexes reported herein efficiently promote benchmark olefin metathesis reactions such as the ring-closing of diethyldiallyl and diethylallylmethallyl malonate and the ring-opening metathesis polymerization of 1,5-cyclooctadiene and norbornene, as well as the cross metathesis of allyl benzene with cis-1,4-diacetoxy-2-butene and the macrocyclic ring-closing of a 14-membered lactone. The phosphine-free catalysts of this family are more stable than their phosphine-containing counterparts, exhibiting pseudo-first-order kinetics in the ring-closing of diethyldiallyl malonate. Upon removing the steric bulk from the ortho positions of the N-aryl group of the thiazole-2-ylidene ligands, the phosphine-free catalysts lose stability, but when the substituents become too bulky the resulting catalysts show prolonged induction periods. Among five thiazole-2-ylidene ligands examined, 3-(2,4,6-trimethylphenyl)- and 3-(2,6-diethylphenyl)-4,5-dimethylthiazol-2-ylidene afforded the most efficient and stable catalysts. In the cross metathesis reaction of allyl benzene with cis-1,4-diacetoxy-2-butene increasing the steric bulk at the ortho positions of the N-aryl substituents results in catalysts that are more Z-selective.

  19. Transferable Potentials for Phase Equilibria. 4. United-Atom Description of Linear and Branched Alkenes and Alkylbenzenes

    Energy Technology Data Exchange (ETDEWEB)



    The Transferable Potentials for Phase Equilibria-United Atom (TraPPE-UA) force field for hydrocarbons is extended to alkenes and alkylbenzenes by introducing the following pseudo-atoms: CH{sub 2}(sp{sup 2}), CH(sp{sup 2}), CH(aro), R-C(aro) for the link to aliphatic side chains, and C(aro) for the link of two benzene rings. In this united-atom force field, the nonbonded interactions of the hydrocarbon pseudo-atoms are solely governed by Lennard-Jones 12-6 potentials, and the Lennard-Jones well depth and size parameters for the new pseudo-atoms were determined by fitting to the single-component vapor-liquid phase equilibria of a few selected model compounds. Configurational-bias Monte Carlo simulations in the NVT version of the Gibbs ensemble were carried out to calculate the single-component vapor-liquid coexistence curves for ethene, propene, 1-butene, trans- and cis-2-butene. 2-methylpropene, 1,5-hexadiene, 1-octene, benzene, toluene, ethylbenzene, propylbenzene, isopropylbenzene, o-, m-, and p-xylene, and naphthalene. The phase diagrams for the binary mixtures of (supercritical) ethene/n-heptane and benzene/n-pentane were determined from simulations in the NpT Gibbs ensemble. Although the TraPPE-UA force field is rather simple and makes use of relatively few different pseudo-atoms, its performance, as judged by comparisons to other popular force fields and available experimental data, is very satisfactory.

  20. Peroxidase-catalyzed oxidative damage of DNA and 2'-deoxyguanosine by model compounds of lipid hydroperoxides: involvement of peroxyl radicals. (United States)

    Adam, W; Kurz, A; Saha-Möller, C R


    The peroxidase-catalyzed decomposition of 3-hydroperoxy-1-butene (1), 2,3-dimethyl-3-hydroperoxy-1-butene (2), tert-butyl hydroperoxide (3), ethyl oleate hydroperoxide 4, and linoleic acid hydroperoxide 5 was applied as a chemical model system to assess whether lipid hydroperoxides may cause DNA damage under peroxidase catalysis. For this purpose, the Coprinus peroxidase (CIP), horseradish peroxidase (HRP), and the physiologically important lactoperoxidase (LP) were tested. Indeed, hydroperoxides 1-5 induce strand breaks in pBR 322 DNA upon peroxidase catalysis. For the nucleoside dG, the enzymatic decomposition of hydroperoxides 1-4 led to significant amounts of 4, 8-dihydro-4-hydroxy-8-oxo-2'-deoxyguanosine (4-HO-8-oxo-dG) and guanidine-releasing products (GRP), whereas 7, 8-dihydro-8-oxo-2'-deoxyguanosine (8-oxo-dG) was not obtained. In isolated calf thymus DNA, the efficient conversion of the guanine base (Gua) was observed. Peroxyl radicals, which are generated in situ from the hydroperoxides by one-electron oxidation with the peroxidases, are proposed as the active oxidants on the basis of the following experimental facts. (i) Radical scavengers strongly inhibit the guanine oxidation in dG and DNA and strand-break formation in the latter. (ii) EPR spectral studies with 5, 5-dimethyl-1-pyrroline N-oxide (DMPO) as a spin trap confirmed the formation of peroxyl radicals. (iii) The release of molecular oxygen was demonstrated, produced through the disproportionation of peroxyl radicals. The biological relevance of these findings should be seen in the potential role of the combined action of lipid hydroperoxides and peroxidases in damaging cellular DNA through peroxyl radicals.

  1. Observation of 2-methyltetrols and related photo-oxidation products of isoprene in boreal forest aerosols from Hyytiälä, Finland

    Directory of Open Access Journals (Sweden)

    I. Kourtchev


    Full Text Available Oxidation products of isoprene including 2-methyltetrols (2-methylthreitol and 2-methylerythritol, 2-methylglyceric acid and triol derivatives of isoprene (2-methyl-1,3,4-trihydroxy-1-butene (cis and trans and 3-methyl-2,3,4-trihydroxy-1-butene have been detected in boreal forest PM1 aerosols collected at Hyytiälä, southern Finland, during a 2004 summer period, at significant atmospheric concentrations (in total 51 ng m−3 in summer versus 0.46 ng m−3 in fall. On the basis of these results, it can be concluded that photo-oxidation of isoprene is an important atmospheric chemistry process that contributes to secondary organic aerosol formation during summer in this conifer forest ecosystem. In addition to isoprene oxidation products, malic acid, which can be regarded as an intermediate in the oxidation of unsaturated fatty acids, was also detected at high concentrations during the summer period (46 ng m−3 in summer versus 5.2 ng m−3 in fall, while levoglucosan, originating from biomass burning, became relatively more important during the fall period (29 ng m−3 in fall versus 10 ng m−3 in summer. Pinic acid, a major photo-oxidation product of α-pinene in laboratory experiments, could only be detected at trace levels in the summer samples, suggesting that further oxidation of pinic acid occurs and/or that different oxidation pathways are followed. We hypothesize that photo-oxidation of isoprene may participate in the early stages of new particle formation, a phenomenon which has been well documented in the boreal forest environment.

  2. Heterogeneous Catalytic Oligomerization of Ethylene (United States)

    Jan, Oliver Dennis

    Throughout this work, we report results for the oligomerization of ethylene over Ni-Hbeta in a packed bed reactor. We performed a parameterized study over temperature (30ºC-190ºC), pressure (8.5-25.6 bar), and weighted hourly space velocity (2.0-5.5 hr-1). We observed that the ethylene conversion increased with reaction pressure due primarily to the slower velocities at higher pressures. Increasing the temperature of the reactor led to the formation of larger oligomers and coke, but its effect on the conversion was small. The space velocity played an important role on ethylene conversion and product selectivity, with higher conversions observed at lower space velocities and higher selectivities to butene at higher space velocities. We also conducted a long experiment to determine the activity of the Ni-Hbeta catalyst over 72 hours-on-stream at 19.0 bar partial pressure of ethylene, 120ºC, and 3.1 hr-1 WHSV. We observed that catalyst deactivation occurred only during the startup period largely due to coke formation. Despite this initial deactivation, negligible coke formation occurred after 8 hours time-on-stream, as the conversion remained steady at 47% for the duration of the experiment. We also carried out oligomerization of ethylene using Ni-Hbeta in a laboratory-scale packed bed reactor for the synthesis of liquid hydrocarbons. We evaluated the effect of several process variables (temperature, pressure, weighted hourly space velocity, and nickel loading) on the liquid hydrocarbon/coke yield, ethylene conversion, and oligomeric product selectivity. Increases in pressure resulted in higher ethylene conversion, corresponding to a liquid yield of 12.4 wt.% with 5.7 wt.% coke. As the pressure increased, the selectivity towards octenes doubled alongside a decrease in butenes, which suggested that higher pressures promoted butene dimerization. Under the conditions studied, a minimum temperature of 120ºC was required to produce liquid hydrocarbons. The liquid yield

  3. Cogeneration of electricity and organic chemicals using a polymer electrolyte fuel cell

    Energy Technology Data Exchange (ETDEWEB)

    Yuan, X.; Ma, Z. [Department of Chemical Engineering, Shanghai Jiao Tong University, Shanghai 200240 (China); Bueb, H.; Drillet, J.-F.; Hagen, J.; Schmidt, V.M. [Institutes of Chemical and Electrochemical Process Engineering, Mannheim University of Applied Sciences, Windeckstrasse 110, D-68163 Mannheim (Germany)


    Several unsaturated organic alcohols (allyl alcohol, propargyl alcohol, 2-butin-1,4-diol, 2- buten-1,4-diol) and acids (maleic acid, acrylic acid, crotonic acid, acetylendicarboxylic acid) were used as oxidants together with hydrogen as fuel in a polymer electrolyte fuel cell (PEFC). The standard free enthalpies ({delta}{sub R}G{sup {theta}}) of the overall fuel cell reactions H{sub 2}/oxidant were calculated to be negative and the equilibrium voltages of such systems are in the range of U{sub 00} = 0.4-0.6 V. In this way, the cogeneration of electric energy and desired hydrogenated products in a fuel cell reactor is apparent. Nafion {sup registered} 117, as polymer electrolyte, and commercial gas diffusion electrodes (ETEK) with carbon supported Pt were used in a PEFC reactor. The aqueous solutions of unsaturated alcohols and organic acids (c 1-2 mol dm{sup -3}) were pumped under ambient pressure through the cathode compartment of the cell whereas hydrogen was fed into the cell at p = 0.15 MPa. The open circuit voltages were measured to be in the range of 0.1-0.25 V. Current densities up to 50 mA cm{sup -2} and maximum power densities of around 1 mW cm{sup -2} has been achieved in the case of allyl alcohol, 2-butene-1,4-diol and acrylic acid. HPLC analysis indicates that the double or triple bond in unsaturated alcohols and organic acids is selectively hydrogenated. In addition, the electrochemical behaviour of the alcohols and acids was studied by means of cyclic voltammetry at a smooth polycrystalline Pt electrode in H{sub 2}SO{sub 4}. Reduction reactions were observed at potentials of E < 200 mV versus RHE. It was found that the onset potential for electrochemical hydrogenation of the double and triple bond in the cyclic voltamogram correlates well with the fuel cell performances using these compounds as oxidants. (author)

  4. Estudos dos compostos orgânicos voláteis precursores de ozônio na cidade de São Paulo Studies of the volatile organic compounds precursors of ozone in São Paulo city

    Directory of Open Access Journals (Sweden)

    Débora Souza Alvim


    Full Text Available O ozônio é o principal problema de poluição do ar na cidade de São Paulo. Este estudo, que foi realizado em uma estação de monitoramento da qualidade do ar da Companhia de Tecnologia de Saneamento Ambiental (CETESB, enfoca a elucidação dos principais compostos orgânicos voláteis precursores de ozônio na atmosfera paulistana. Foram coletadas 36 amostras nos meses de agosto e setembro de 2006, nos quais o consumo de etanol era de aproximadamente 50% nesta época. Foram quantificadas 69 espécies de compostos orgânicos voláteis, nos quais os dez compostos mais importantes na formação de O3 foram: 1-buteno (6,8%, eteno (6,5%, formaldeído (6,1%, acetaldeído (5,5%, tolueno (4,8%, 1-etil-4-metilbenzeno (3,7%, trans-2-penteno (3,7%, propeno (3,7%, trans-2-buteno (3,5% e 1-metilciclopenteno (3,5%. As classes mais abundantes em concentração no ar foram: alcanos (45%, alcenos (26%, aromáticos (14%, aldeídos (13% e alcadienos (2%.Ozone is the main problem of air pollution in the city of São Paulo. This study, which was carried out in the Brazilian Basic Sanitation Engineering Company (CETESB, acronym in Portuguese monitoring station of air quality, focused on the elucidation of the main volatile organic compounds ozone precursors in São Paulo atmosphere. Thirty-six samples were collected in August and September 2006, when the consumption of ethanol was about 50%, 69 species of volatile organic compounds were quantified, the ten major urban pollutants compounds in the formation of O3 were: 1-butene (6.8%, ethylene (6.5%, formaldehyde (6.1%, acetaldehyde (5.5%, toluene (4.8%, 1-ethyl-4-methylbenzene (3.7%, trans-2-pentene (3.7%, propylene (3.7%, trans-2-butene (3.5%, and 1-methylcyclopentene (3.5%. The most abundant classes of air concentration were: alkanes (45%, alkenes (26%, aromatics (14%, aldehydes (13%, and alkadyenes (2%.

  5. The metabolism and molecular toxicology of chloroprene. (United States)

    Munter, Tony; Cottrell, Lisa; Ghai, Rikas; Golding, Bernard T; Watson, William P


    Chloroprene (2-chloro-1,3-butadiene, 1) is oxidised by cytochrome P450 enzymes in mammalian liver microsomes to several metabolites, some of which are reactive towards DNA and are mutagenic. Much less of the metabolite (1-chloroethenyl)oxirane (2a/2b) was formed by human liver microsomes compared with microsomes from Sprague-Dawley rats and B6C3F1 mice. Epoxide (2a/2b) was a substrate for mammalian microsomal epoxide hydrolases, which showed preferential hydrolysis of the (S)-enantiomer (2b). The metabolite 2-chloro-2-ethenyloxirane (3a/3b) was rapidly hydrolysed to 1-hydroxybut-3-en-2-one (4) and in competing processes rearranged to 1-chlorobut-3-en-2-one (5) and 2-chlorobut-3-en-1-al (6). The latter compound isomerised to (Z)-2-chlorobut-2-en-1-al (7). In microsomal preparations from human, rat and mouse liver, compounds 4, 5 and 7 were conjugated by glutathione both in the absence and presence of glutathione transferases. There was no evidence for the formation of a chloroprene diepoxide metabolite in any of the microsomal systems. The major adducts from the reaction of (1-chloroethenyl)oxirane (2a/2b) with calf thymus DNA were identified as N7-(3-chloro-2-hydroxy-3-buten-1-yl)-guanine (20) and N3-(3-chloro-2-hydroxy-3-buten-1-yl)-2'-deoxyuridine (23), with the latter being derived by alkylation at N-3 of 2'-deoxycytidine, followed by deamination. Adducts in DNA were identified by comparison with those derived from individual deoxyribonucleosides. The metabolite (Z)-2-chlorobut-2-en-1-al (7) formed principally two adducts with 2'-deoxyadenosine which were identified as a pair of diastereoisomers of 3-(2'-deoxy-beta-d-ribofuranosyl)-7-(1-hydroxyethyl)-3H-imidazo[2,1-i]purine (25). The chlorine atom of chloroprene thus leads to different intoxication and detoxication profiles compared with those for butadiene and isoprene. The results infer that in vivo oxidations of chloroprene catalysed by cytochrome P450 are more important in rodents, whereas hydrolytic

  6. Non-methane hydrocarbons (NMHCs) and their contribution to ozone formation potential in a petrochemical industrialized city, Northwest China (United States)

    Jia, Chenhui; Mao, Xiaoxuan; Huang, Tao; Liang, Xiaoxue; Wang, Yanan; Shen, Yanjie; Jiang, Wanyanhan; Wang, Huiqin; Bai, Zhilin; Ma, Minquan; Yu, Zhousuo; Ma, Jianmin; Gao, Hong


    Hourly air concentrations of fifty-three non-methane hydrocarbons (NMHCs) were measured at downtown and suburb of Lanzhou, a petrochemical industrialized city, Northwest China in 2013. The measured data were used to investigate the seasonal characteristics of NMHCs air pollution and their contributions to the ozone formation in Lanzhou. Annually averaged NMHCs concentration was 38.29 ppbv in downtown Lanzhou. Among 53 NMHCs, alkanes, alkenes, and aromatics accounted for 57%, 23% and 20% of the total NMHCs air concentration, respectively. The atmospheric levels of toluene and propane with mean values of 4.62 and 4.56 ppbv were higher than other NMHCs, respectively. The ambient levels of NMHCs in downtown Lanzhou were compared with measured NMHCs data collected at a suburban site of Lanzhou, located near a large-scale petrochemical industry. Results show that the levels of alkanes, alkenes, and aromatics in downtown Lanzhou were lower by factors of 3-11 than that in west suburb of the city. O3-isopleth plots show that ozone was formed in VOCs control area in downtown Lanzhou and NOx control area at the west suburban site during the summertime. Propylene-equivalent (Prop-Equiv) concentration and the maximum incremental reactivity (MIR) in downtown Lanzhou indicate that cis-2-butene, propylene, and m/p-xylene were the first three compounds contributing to ozone formation potentials whereas in the petrochemical industrialized west suburb, ethane, propene, and trans-2-Butene played more important role in the summertime ozone formation. Principal component analysis (PCA) and multiple linear regression (MLR) were further applied to identify the dominant emission sources and examine their fractions in total NMHCs. Results suggest that vehicle emission, solvent usage, and industrial activities were major sources of NMHCs in the city, accounting for 58.34%, 22.19%, and 19.47% of the total monitored NMHCs in downtown Lanzhou, respectively. In the west suburb of the city

  7. Theoretical Kinetics Analysis for Ḣ Atom Addition to 1,3-Butadiene and Related Reactions on the Ċ4H7Potential Energy Surface. (United States)

    Li, Yang; Klippenstein, Stephen J; Zhou, Chong-Wen; Curran, Henry J


    The oxidation chemistry of the simplest conjugated hydrocarbon, 1,3-butadiene, can provide a first step in understanding the role of polyunsaturated hydrocarbons in combustion and, in particular, an understanding of their contribution toward soot formation. On the basis of our previous work on propene and the butene isomers (1-, 2-, and isobutene), it was found that the reaction kinetics of Ḣ-atom addition to the C═C double bond plays a significant role in fuel consumption kinetics and influences the predictions of high-temperature ignition delay times, product species concentrations, and flame speed measurements. In this study, the rate constants and thermodynamic properties for Ḣ-atom addition to 1,3-butadiene and related reactions on the Ċ 4 H 7 potential energy surface have been calculated using two different series of quantum chemical methods and two different kinetic codes. Excellent agreement is obtained between the two different kinetics codes. The calculated results including zero-point energies, single-point energies, rate constants, barrier heights, and thermochemistry are systematically compared among the two quantum chemical methods. 1-Methylallyl (Ċ 4 H 7 1-3) and 3-buten-1-yl (Ċ 4 H 7 1-4) radicals and C 2 H 4 + Ċ 2 H 3 are found to be the most important channels and reactivity-promoting products, respectively. We calculated that terminal addition is dominant (>80%) compared to internal Ḣ-atom addition at all temperatures in the range 298-2000 K. However, this dominance decreases with increasing temperature. The calculated rate constants for the bimolecular reaction C 4 H 6 + Ḣ → products and C 2 H 4 + Ċ 2 H 3 → products are in excellent agreement with both experimental and theoretical results from the literature. For selected C 4 species, the calculated thermochemical values are also in good agreement with literature data. In addition, the rate constants for H atom abstraction by Ḣ atoms have also been calculated, and it is

  8. γ-Fe2O3 nanoparticle surface controls PtFe nanoparticle growth and catalytic properties (United States)

    Gumina, Gregory; Easterday, Rosemary; Malyutin, Andrey G.; Budgin, Angela M.; Stein, Barry D.; Nikoshvili, Linda Zh.; Matveeva, Valentina G.; Sulman, Esther M.; Morgan, David Gene; Bronstein, Lyudmila M.


    We report a novel method for synthesis of alloy PtFe nanoparticles (NPs) of different compositions using γ-Fe2O3 NPs as an iron source. We show here other growth mechanisms than conventional nucleation on a NP surface leading to core-shell NP or seeded NP growth. Depending on reaction conditions, different compositions of PtFe NPs can be obtained. PtFe NPs may coexist with γ-Fe2O3 NPs in the reaction product. This mixture obtained in situ allows much higher catalytic activity in hydrogenation of methyl-3-buten-2-ol than that of only PtFe nanoparticles or merely mixed PtFe and γ-Fe2O3 NPs. The presence of both PtFe and γ-Fe2O3 NPs allows formation of dense and stable NP arrays which hold promise for catalytic applications in microreactors or other reactor designs where a catalytic film is favoured.We report a novel method for synthesis of alloy PtFe nanoparticles (NPs) of different compositions using γ-Fe2O3 NPs as an iron source. We show here other growth mechanisms than conventional nucleation on a NP surface leading to core-shell NP or seeded NP growth. Depending on reaction conditions, different compositions of PtFe NPs can be obtained. PtFe NPs may coexist with γ-Fe2O3 NPs in the reaction product. This mixture obtained in situ allows much higher catalytic activity in hydrogenation of methyl-3-buten-2-ol than that of only PtFe nanoparticles or merely mixed PtFe and γ-Fe2O3 NPs. The presence of both PtFe and γ-Fe2O3 NPs allows formation of dense and stable NP arrays which hold promise for catalytic applications in microreactors or other reactor designs where a catalytic film is favoured. Electronic supplementary information (ESI) available: XRD, TGA, TEM, STEM and EDS of Pt, PtFe and iron oxide NPs; photograph of magnetic separation. See DOI: 10.1039/c3nr33879g

  9. Pathway and Surface Mechanism Studies of 1,3-butadiene Selective Oxidation Over Vanadium-Molybdenum-Oxygen Catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Schroeder, William David [Iowa State Univ., Ames, IA (United States)


    The partial oxidation of 1,3-butadiene has been investigated over VMoO catalysts synthesized by sol-gel techniques. Surface areas were 9-14 m2/g, and compositions were within the solid solution regime, i.e. below 15.0 mol % MoO3/(MoO3 + V2O5). Laser Raman Spectroscopy and XRD data indicated that solid solutions were formed, and pre- and post-reaction XPS data indicated that catalyst surfaces contained some V+4 and were further reduced in 1,3-butadiene oxidation. A reaction pathway for 1,3-butadiene partial oxidation to maleic anhydride was shown to involve intermediates such as 3,4-epoxy-1-butene, crotonaldehyde, furan, and 2-butene-1,4-dial. The addition of water to the reaction stream substantially increased catalyst activity and improved selectivity to crotonaldehyde and furan at specific reaction temperatures. At higher water addition concentrations, furan selectivity increased from 12% to over 25%. The catalytic effects of water addition were related to competitive adsorption with various V2O5-based surface sites, including the vanadyl V=O, corner sharing V-O-V and edge sharing V-O oxygen. Higher levels of water addition were proposed to impose acidic character by dissociative adsorption. In addition, a novel combinatorial synthesis technique for VMoO was used to investigate the phase transitions of V2O5, solid solutions of Mo in V2O5, V9Mo6O40, and other reduced VMoO compounds, characterized by laser Raman spectroscopy. The natural composition gradient imposed by the sputter deposition apparatus was used to create VMoO arrays containing 225 samples ranging from 7.0-42 mol% MoO3/(V2O5 + MoO3), determined by EDS analysis.

  10. Theoretical Kinetics Analysis for $\\dot{H}$ Atom Addition to 1,3-Butadiene and Related Reactions on the $\\dot{C}$4H7 Potential Energy Surface

    Energy Technology Data Exchange (ETDEWEB)

    Li, Yang [National Univ. of Ireland, Galway (Ireland). Combustion Chemistry Centre; Klippenstein, Stephen J. [Argonne National Lab. (ANL), Argonne, IL (United States). Chemical Sciences and Engineering Division; Zhou, Chong-Wen [Beihang Univ., Beihang (China). School of Energy and Power Engineering; Curran, Henry J. [National Univ. of Ireland, Galway (Ireland). Combustion Chemistry Centre


    The oxidation chemistry of the simplest conjugated hydrocarbon, 1,3-butadiene, can provide a first step in understanding the role of poly-unsaturated hydrocarbons in combustion and, in particular, an understanding of their contribution towards soot formation. Based on our previous work on propene and the butene isomers (1-, 2- and isobutene), it was found that the reaction kinetics of H-atom addition to the C=C double bond plays a significant role in fuel consumption kinetics and influences the predictions of high-temperature ignition delay times, product species concentrations and flame speed measurements. In this study, the rate constants and thermodynamic properties for $\\dot{H}$-atom addition to 1,3-butadiene and related reactions on the $\\dot{C}$4H7 potential energy surface have been calculated using two different series of quantum chemical methods and two different kinetic codes. Excellent agreement is obtained between the two different kinetics codes. The calculated results including zero point energies, single point energies, rate constants, barrier heights and thermochemistry are systematically compared among the two quantum chemical methods. 1-methylallyl ($\\dot{C}$4H71-3) and 3-buten-1- yl ($\\dot{C}$4H71-4) radicals and C2H4 + $\\dot{C}$2H3 are found to be the most important channels and reactivity promoting products, respectively. We calculated that terminal addition is dominant (> 80%) compared to internal $\\dot{H}$-atom addition at all temperatures in the range 298 – 2000 K. However, this dominance decreases with increasing temperature. The calculated rate constants for the bimolecular reaction C4H6 + $\\dot{H}$ → products and C2H4 + $\\dot{C}$2H3 → products are in excellent agreement with both experimental and theoretical results from the literature. For selected C4 species the

  11. Substituted tridentate pyrazolyl ligands for chromium and nickel-catalyzed ethylene oligomerization reactions: effect of auxiliary ligand on activity and selectivity

    Energy Technology Data Exchange (ETDEWEB)

    Oliveira, Lucilene L. de; Campedelli, Roberta R.; Bergamo, Adao L.; Santos, Ana H.D.P dos; Casagrande, Osvaldo L., E-mail: osvaldo.casagrande@ufrgs.b [Universidade Federal do Rio Grande do Sul (UFRGS), Porto Alegre, RS (Brazil). Inst. de Quimica. Lab. de Catalise Molecular


    Two new chromium(III) complexes [CrCl{sub 3}(L)] based on tridentate ligands (1a, L = bis[2-(3-phenyl-1-pyrazolyl)ethyl)]amine; 2a, L bis[2-(3-methyl-5-phenyl-l-pyrazolyl)ethyl]sulfide) have been prepared and characterized by elemental analysis. Upon activation with methylaluminoxane (MAO), these pre-catalysts showed high turnover frequencies for ethylene oligomerization under optimized conditions (TOFs = 22.9-36.4 x 103 mol C{sub 2}H{sub 4} (mol Cr{sup III}){sup -1} h{sup -1}, [Cr] = 10.0 mumol, 80 deg C, 20 bar ethylene, MAO: Cr = 300, oligomerization time = 20 min), producing alpha-olefins in the range C{sub 4}-C{sub 14+} with high selectively (67.71-73.47%). The catalytic performances are substantially affected by the ligand environment, especially the substituents at the 3- and 5-positions of the pyrazolyl rings. In parallel, the use of nickel complexes such as NiCl{sub 2}{l_brace}bis[2-(3,5-dimethyl-1-pyrazolyl)methyl]benzylamine{r_brace} (3) and NiCl{sub 2}{l_brace}bis[2-(3,5-dimethyl-1-pyrazolyl)ethyl)]ether{r_brace} (5) in oligomerization reactions carried out in the presence of triphenylphosphine (PPh{sub 3}) afforded highly active catalytic systems with turnover frequencies (TOFs) varying from 36.4 to 154.2 x 10{sup 3} mol C{sub 2}H{sub 4} (mol Ni{sup II}){sup -1} h{sup -1}. The presence of this auxiliary ligand has a strong impact on the selectivity towards the production of a-olefins, decreasing substantially the amount of 1-butene with a concomitant increase of the 2-butene fractions. Attempts to crystallize the nickel complex 3 afforded the tetrametallic [{l_brace} (L)(mu{sub 3}-Cl)NiCl{r_brace}{sub 4}] (4, L 1-anilinomethyl-3,5-dimethylpyrazole) which was characterized by X-ray diffraction analysis. (author)

  12. Zeolite catalysis in the synthesis of isobutylene from hydrous ethanol (United States)

    Phillips, Cory Bernard


    This work deals with the synthesis of isobutylene from a hydrous ethanol feedstock over zeolites. The synthesis is accomplished in three steps: (1) low-temperature direct ethanol conversion to ethylene on H-ZSM-5 zeolite, (2) ethylene conversion to butene products over metal-exchanged zeolites, and (3) butene skeletal rearrangement to isobutylene over FER zeolites. The key to understanding and optimizing each synthesis step lies in the ability to control and regulate the zeolite acidity (Bronsted and Lewis)---both strength and number. Therefore, the continuous temperature programmed amine desorption (CTPAD) technique was further developed to simultaneously count the Bronsted acid sites and quantitatively characterize their strength. The adsorption of ethanol, reaction products, amines, coke and ethanol-derived residue (EDR) were monitored gravimetrically using the highly sensitive, novel Tapered Element Oscillating Microreactor (TEOM) apparatus. The TEOM was also used also in conjunction with CTPAD to characterize Bronsted acidity which is a new application for the instrument. For the first synthesis step, a parallel reaction exists which simultaneously produces diethyl ether and ethylene directly over H-ZSM-5. The reaction rates for each pathway were measured directly using a differential reactor operating at low temperatures (<473 K). Water in the ethanol feed enhances the rate of ethylene formation. A mechanism and kinetic expression are proposed for this reaction over H-ZSM-5, with diethyl-ether desorption and ethylene formation as the rate limiting steps. Heat of adsorption values measured from the independent microcalorimetry work reported in the literature are incorporated into the kinetic analysis which reduces the number of regressed parameters. For the remaining synthesis steps, several zeolite structures (ZSM-5, Y, FER) partially exchanged with Pd, Ti, Ni and Au were prepared and tested. It was determined from this screening study that the zeolites

  13. Dissociative Ionization and Thermal Decomposition of Cyclopentanone. (United States)

    Pastoors, Johan I M; Bodi, Andras; Hemberger, Patrick; Bouwman, Jordy


    Despite the growing use of renewable and sustainable biofuels in transportation, their combustion chemistry is poorly understood, limiting our efforts to reduce harmful emissions. Here we report on the (dissociative) ionization and the thermal decomposition mechanism of cyclopentanone, studied using imaging photoelectron photoion coincidence spectroscopy. The fragmentation of the ions is dominated by loss of CO, C 2 H 4 , and C 2 H 5 , leading to daughter ions at m/z 56 and 55. Exploring the C 5 H 8 O . + potential energy surface reveals hydrogen tunneling to play an important role in low-energy decarbonylation and probably also in the ethene-loss processes, yielding 1-butene and methylketene cations, respectively. At higher energies, pathways without a reverse barrier open up to oxopropenyl and cyclopropanone cations by ethyl-radical loss and a second ethene-loss channel, respectively. A statistical Rice-Ramsperger-Kassel-Marcus model is employed to test the viability of this mechanism. The pyrolysis of cyclopentanone is studied at temperatures ranging from about 800 to 1100 K. Closed-shell pyrolysis products, namely 1,3-butadiene, ketene, propyne, allene, and ethene, are identified based on their photoion mass-selected threshold photoelectron spectrum. Furthermore, reactive radical species such as allyl, propargyl, and methyl are found. A reaction mechanism is derived incorporating both stable and reactive species, which were not predicted in prior computational studies. © 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

  14. Emissions of putative isoprene oxidation products from mango branches under abiotic stress (United States)

    Jardine, Kolby J.; Meyers, Kimberly; Abrell, Leif; Alves, Eliane G.; Yanez Serrano, Ana Maria; Kesselmeier, Jürgen; Karl, Thomas; Guenther, Alex; Vickers, Claudia; Chambers, Jeffrey Q.


    Although several per cent of net carbon assimilation can be re-released as isoprene emissions to the atmosphere by many tropical plants, much uncertainty remains regarding its biological significance. In a previous study, we detected emissions of isoprene and its oxidation products methyl vinyl ketone (MVK) and methacrolein (MACR) from tropical plants under high temperature/light stress, suggesting that isoprene is oxidized not only in the atmosphere but also within plants. However, a comprehensive analysis of the suite of isoprene oxidation products in plants has not been performed and production relationships with environmental stress have not been described. In this study, putative isoprene oxidation products from mango (Mangifera indica) branches under abiotic stress were first identified. High temperature/light and freeze–thaw treatments verified direct emissions of the isoprene oxidation products MVK and MACR together with the first observations of 3-methyl furan (3-MF) and 2-methyl-3-buten-2-ol (MBO) as putative novel isoprene oxidation products. Mechanical wounding also stimulated emissions of MVK and MACR. Photosynthesis under 13CO2 resulted in rapid (<30min) labelling of up to five carbon atoms of isoprene, with a similar labelling pattern observed in the putative oxidation products. These observations highlight the need to investigate further the mechanisms of isoprene oxidation within plants under stress and its biological and atmospheric significance. PMID:23881400

  15. Investigation of working pressure on the surface roughness controlling technology of glow discharge polymer films based on the diagnosed plasma (United States)

    Zhang, Ling; Chen, Guo; He, Zhibing; Ai, Xing; Huang, Jinglin; Liu, Lei; Tang, Yongjian; He, Xiaoshan


    The effects of working pressure on the component, surface morphology, surface roughness, and deposition rate of glow discharge polymer (GDP) films by a trans-2-butene/hydrogen gas mixture were investigated based on plasma characteristics diagnosis. The composition and ion energy distributions of a multi-carbon (C4H8/H2) plasma mixture at different working pressures were diagnosed by an energy-resolved mass spectrometer (MS) during the GDP film deposition process. The Fourier transform infrared spectroscopy (FT-IR), field emission scanning electron microscope (SEM) and white-light interferometer (WLI) results were obtained to investigate the structure, morphology and roughness characterization of the deposited films, respectively. It was found that the degree of ionization of the C4H8/H2 plasma reduces with an increase in the working pressure. At a low working pressure, the C-H fragments exhibited small-mass and high ion energy in plasma. In this case, the film had a low CH3/CH2 ratio, and displayed a smooth surface without any holes, cracks or asperities. While the working pressure increased to 15 Pa, the largest number of large-mass fragments led to the deposition rate reaching a maximum of 2.11 μm h-1, and to hole defects on the film surface. However, continuing to increase the working pressure, the film surface became smooth again, and the interface between clusters became inconspicuous without etching pits.

  16. Stability, Deactivation, and Regeneration of Chloroaluminate Ionic Liquid as Catalyst for Industrial C4 Alkylation

    Directory of Open Access Journals (Sweden)

    Xiang Li


    Full Text Available Alkylation of isobutane and 2-butene was carried out in a continuous unit using triethylamine hydrochloride (Et3NHCl-aluminum chloride (AlCl3 ionic liquid (IL as catalyst. The effects of impurities such as water, methanol, and diethyl ether on the stability of the catalytic properties and deactivation of the ionic liquid were studied in the continuous alkylation. In the Et3NHCl-2AlCl3 ionic liquid, only one half of the aluminum chloride could act as the active site. With a molar ratio of 1:1, the active aluminum chloride in the ionic liquid was deactivated by water by reaction or by diethyl ether through complexation while the complexation of aluminum chloride with two molecular proportions of methanol inactivated the active aluminum chloride in the ionic liquid. The deactivation of chloroaluminate ionic liquid was observed when the active aluminum chloride, i.e., one half of the total aluminum chloride in the ionic liquid, was consumed completely. The regeneration of the deactivated ionic liquid was also investigated and the catalytic activity could be recovered by means of replenishment with fresh aluminum chloride.

  17. [Emission Characteristics of VOCs from Typical Restaurants in Beijing]. (United States)

    Cui, Tong; Cheng, Jing-chen; He, Wan-qing; Ren, Pei-fang; Nie, Lei; Xu, Dong-yao; Pan, Tao


    Using the EPA method, emission of volatile organic compounds (VOCs) , sampled from barbecue, Chinese and Western fast-food, Sichuan cuisine and Zhejiang cuisine restaurants in Beijing was investigated. VOCs concentrations and components from different cuisines were studied. The results indicated that based on the calibrated baseline ventilation volume, the VOCs emission level from barbecue was the highest, reaching 12.22 mg · m(-3), while those from fast-food of either Chinese or Western, Sichuan cuisine and Zhejiang cuisine were about 4 mg · m(-3). The components of VOCs from barbecue were different from those in the other cuisines, which were mainly propylene, 1-butene, n-butane, etc. The non-barbecue cuisines consisted of high concentration of alcohols, and Western fast-food contained relatively high proportion of aldehydes and ketones organic compounds. According to emission concentration of baseline ventilation volume, barbecue released more pollutants than the non-barbecue cuisines at the same scale. So, barbecue should be supervised and controlled with the top priority.

  18. Thermal and rheological behavior of reactive blends from metallocene olefin elastomers and polypropylene

    Directory of Open Access Journals (Sweden)

    Nei S. Domingues Junior


    Full Text Available Reactive blends of metallocene polyolefin elastomers (POE/polypropylene (PP with 60/40 composition were prepared with an organic peroxide, 2,5-dimethyl-2,5-di-(t-butylperoxyhexane, and a bis-azide derivative, diphenyloxid-4,4'-bis(sulfonylazide (BSA. Ethylene-1-butene (EB and ethylene-1-octene (EO copolymers and elastomeric polypropylene (ePP were used as the elastomeric phase. The effect of elastomeric phase on the thermal, rheological, morphological and mechanical properties of the thermoplastic vulcanizates (TPVs or dynamic vulcanizates were studied. All TPVs depicted pseudoplastic behavior and blends cured with azide curative showed higher viscosities. The TPVs showed both dispersed and continuous phase morphology that depends on the elastomeric phase type revealing a limited degree of compatibility between PP and the elastomers EO or EB. On the other hand, the TPV PP/ePP showed a uniform morphology suggesting an improved compatibility. Substantial changes observed in physical properties were explained on the basis of blends' morphology and dynamic vulcanization. The results confirm that the mechanical properties are more influenced by the elastomeric phase than by the curative agent. This study revealed a broad new range of opportunities for POE-based TPVs.

  19. QCM studies of gel spreading: Kraton gels on polystyrene surfaces. (United States)

    Nunalee, F Nelson; Shull, Kenneth R


    Contact of a polymer gel made from a styrene/ethylene-butene/styrene triblock copolymer in mineral oil was investigated by bringing the gel into contact with the coated surface of a quartz crystal microbalance (QCM). The experimental apparatus enabled simultaneous measurement of the load, displacement, and contact area, in addition to the resonant frequency and dissipation of the oscillating quartz crystal. The QCM response was determined by the linear viscoelastic properties of the gel at the frequency of oscillation. A geometric correction factor involving the contact area provided a means for quantitatively determining these viscoelastic parameters as the gel spread over the QCM surface. When the gel was removed from the surface, a thin solvent layer was left behind. The thickness of this solvent layer was determined from the QCM response and was compared to predictions from a simple model involving the disjoining pressure of the film and the osmotic pressure of the gel. Qualitative agreement with the model required that tensile, adhesive forces at the perimeter of the gel/QCM contact area were taken into account when calculating the film thickness.

  20. Pyrolysis of methyl tert-butyl ether (MTBE). 1. Experimental study with molecular-beam mass spectrometry and tunable synchrotron VUV photoionization. (United States)

    Zhang, Taichang; Wang, Jing; Yuan, Tao; Hong, Xin; Zhang, Lidong; Qi, Fei


    An experimental study of methyl tert-butyl ether (MTBE) pyrolysis (3.72% MTBE in argon) has been performed at low pressure (267 Pa) within the temperature range from 700 to 1420 K. The pyrolysis process was detected with the tunable synchrotron vacuum ultraviolet (VUV) photoionization and molecular-beam mass spectrometry (MBMS). About thirty intermediates are identified from near-threshold measurements of photoionization mass spectrum and photoionization efficiency spectrum. Among them, H2, CO, CH4, CH3OH and C4H8 are the major pyrolysis products. The radicals such as methyl, methoxy, propargyl, allyl, C4H5 and C4H7 are detected. The isomers of pyrolysis products are identified as well, i.e., propyne and allene, 1,2,3-butatriene and vinylacetylene, isobutene and 1-butene, propanal and acetone. Furthermore, the mole fractions of the pyrolysis products have been evaluated under various temperatures. Meanwhile, the initial formation temperatures of different pyrolysis products can be obtained. This work is anticipated to present a new experimental method for pyrolysis study and help understand the pyrolysis and combustion chemistry of MTBE and other oxygenated fuels.

  1. Characterization of Sulfur Compounds in MTBE

    Directory of Open Access Journals (Sweden)

    Mingqing Wu


    Full Text Available A study is carried out on chemical constitution of sulfur compounds in MTBE and their formation mechanisms. These sulfur compounds are classified into three types: common sulfur compounds, newly formed sulfur compounds, and high boiling sulfur compounds. Common sulfur compounds which include mercaptans, low molecule sulfides and disulfides, are directly from C4, one of the stocks for production of MTBE. The newly formed sulfur compounds, with one sulfur atom and five or more total carbon atoms in one molecule, are mainly tert-butyl methyl sulfide and tert-butyl ethyl sulfide, thioetherification products of thiols with butenes. Many high boiling sulfur compounds, including polysulfides such as dimethyl trisulfide, multisulfur heterocyclic compounds such as 3,5-dimethyl-1,2,4-trithiolane, and oxygen-containing sulfur compounds such as 2-methoxy-3-methylthio-butane, are also found newly formed in the processes of LPG refining and succedent etherification reaction for producing MTBE. Polysulfides are additional products of elemental sulfur to disulfides, and other high boiling sulfur compounds may be formed by thiols reacting with dienes.

  2. Pyrolysis of methyl tert-butyl ether (MTBE). 2. Theoretical study of decomposition pathways. (United States)

    Zhang, Taichang; Zhang, Lidong; Wang, Jing; Yuan, Tao; Hong, Xin; Qi, Fei


    The thermal decomposition pathways of MTBE have been investigated using the G3B3 method. On the basis of the experimental observation and theoretical calculation, the pyrolysis channels are provided, especially for primary pyrolysis reactions. The primary decomposition pathways include formation of methanol and isobutene, CH4 elimination, H2 elimination and C-H, C-C, C-O bond cleavage reactions. Among them, the formation channel of methanol and isobutene is the lowest energy pathway, which is in accordance with experimental observation. Furthermore, the secondary pyrolysis pathways have been calculated as well, including decomposition of tert-butyl radical, isobutene, methanol and acetone. The radicals play an important role in the formation of pyrolysis products, for example, tert-butyl radical and allyl radical are major precursors for the formation of allene and propyne. Although some isomers (isobutene and 1-butene, allene and propyne, acetone and propanal) are identified in our experiment, these isomerization reaction pathways occur merely at the high temperature due to their high activation energies. The theoretical calculation can explain the experimental results reported in part 1 and shed further light on the thermal decomposition pathways.

  3. On the Radiolysis of Ethylene Ices by Energetic Electrons and Implications to the Extraterrestrial Hydrocarbon Chemistry (United States)

    Zhou, Li; Maity, Surajit; Abplanalp, Matt; Turner, Andrew; Kaiser, Ralf I.


    The chemical processing of ethylene ices (C2H4) by energetic electrons was investigated at 11 K to simulate the energy transfer processes and synthesis of new molecules induced by secondary electrons generated in the track of galactic cosmic ray particles. A combination of Fourier transform infrared spectrometry (solid state) and quadrupole mass spectrometry (gas phase) resulted in the identification of six hydrocarbon molecules: methane (CH4), the C2 species acetylene (C2H2), ethane (C2H6), the ethyl radical (C2H5), and—for the very first time in ethylene irradiation experiments—the C4 hydrocarbons 1-butene (C4H8) and n-butane (C4H10). By tracing the temporal evolution of the newly formed molecules spectroscopically online and in situ, we were also able to fit the kinetic profiles with a system of coupled differential equations, eventually providing mechanistic information, reaction pathways, and rate constants on the radiolysis of ethylene ices and the inherent formation of smaller (C1) and more complex (C2, C4) hydrocarbons involving carbon-hydrogen bond ruptures, atomic hydrogen addition processes, and radical-radical recombination pathways. We also discuss the implications of these results on the hydrocarbon chemistry on Titan's surface and on ice-coated, methane-bearing interstellar grains as present in cold molecular clouds such as TMC-1.

  4. Air-borne xylene degradation by Bougainvillea buttiana and the role of epiphytic bacteria in the degradation. (United States)

    Sangthong, S; Suksabye, P; Thiravetyan, P


    The efficiency of xylene removal from contaminated air by thirteen perennial plants was studied. The results showed that Bougainvillea buttiana had the highest xylene removal efficiency. Different parts of B. buttiana such as stems, epicuticular waxes, and plant stomata (including microorganism-associated plant leaves) can uptake xylene 53.1±1.9%, 32.3±0.9, and 14.6±0.0%, respectively. Metabolite products found in treated plants may result from stress or defense compounds triggered by exposure to xylene. Moreover, possible degradation products in B. buttiana stems were analyzed after treatment with xylene at 100 ppm. Various metabolites in B. buttiana stems such as 2,6-dimethoxyphenol, 4-hydroxy-3,5-dimethoxy benzoic acid, 1-isopropyl-4-methylbenzene, p-tolualdehyde, 2,5-dimethoxy-4-methylbenzaldehyde, 2,4-dihydroxy-2,5-dimethyl-3(2H)-furanone, 3-methyl-2-butenal, dihydroxy acetone, propanedial, and many organic acids are related to the xylene degradation pathway. In addition, microorganism-associated B. buttiana leaves especially Enterobacter cloacae LSRC11, Staphylococcus sp. A1 and Pseudomonas aeruginosa enhanced the plant resulting in quicker xylene removal. Copyright © 2015 Elsevier Inc. All rights reserved.

  5. Optimal Catalyst and Cocatalyst Precontacting in Industrial Ethylene Copolymerization Processes

    Directory of Open Access Journals (Sweden)

    Paul Aigner


    Full Text Available In industrial-scale catalytic olefin copolymerization processes, catalyst and cocatalyst precontacting before being introduced in the polymerization reactor is of profound significance in terms of catalyst kinetics and morphology control. The precontacting process takes place under either well-mixing (e.g., static mixers or plug-flow (e.g., pipes conditions. The scope of this work is to study the influence of mixing on catalyst/cocatalyst precontacting for a heterogeneous Ziegler-Natta catalyst system under different polymerization conditions. Slurry ethylene homopolymerization and ethylene copolymerization experiments with 1-butene are performed in a 0.5 L reactor. In addition, the effect of several key parameters (e.g., precontacting time, and ethylene/hydrogen concentration on catalyst activity is analyzed. Moreover, a comprehensive mass transfer model is employed to provide insight on the mass transfer process and support the experimental findings. The model is capable of assessing the external and internal mass transfer limitations during catalyst/cocatalyst precontacting process. It is shown that catalyst/cocatalyst precontacting is very important for the catalyst activation as well as for the overall catalyst kinetic behavior. The study reveals that there is an optimum precontacting time before and after which the catalyst activity decreases, while this optimum time depends on the precontacting mixing conditions.

  6. Gas-Phase Reactions of Doubly Charged Lanthanide Cations with Alkanes and Alkenes. Trends in Metal(2+) Reactivity

    Energy Technology Data Exchange (ETDEWEB)

    Gibson, John K.; Marcalo, Joaquim; Santos, Marta; Pires de Matos, Antonio; Haire, Richard G.


    The gas-phase reactivity of doubly-charged lanthanide cations, Ln2+ (Ln = La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu), with alkanes (methane, ethane, propane, n-butane) and alkenes (ethene, propene, 1-butene) was studied by Fourier transform ion cyclotron resonance mass spectrometry. The reaction products consisted of different combinations of doubly-charged organometallic ions?adducts or species formed via metal-ion-induced hydrogen, dihydrogen, alkyl, or alkane eliminations from the hydrocarbons?and singly-charged ions that resulted from electron, hydride, or methide transfers from the hydrocarbons to the metal ions. The only lanthanide cations capable of activating the hydrocarbons to form doubly-charged organometallic ions were La2+, Ce2+, Gd2+, and Tb2+, which have ground-state or low-lying d1 electronic configurations. Lu2+, with an accessible d1 electronic configuration but a rather high electron affinity, reacted only through transfer channels. The remaining Ln2+ reacted via transfer channels or adduct formation. The different accessibilities of d1 electronic configurations and the range of electron affinities of the Ln2+ cations allowed for a detailed analysis of the trends for metal(2+) reactivity and the conditions for occurrence of bond activation, adduct formation, and electron, hydride, and methide transfers.

  7. Highly Active Copolymerization of Ethylene and N-Acetyl-O-(ω-Alkenyl-l-Tyrosine Ethyl Esters Catalyzed by Titanium Complex

    Directory of Open Access Journals (Sweden)

    Jing Wang


    Full Text Available A series of N-acetyl-O-(ω-alkenyl-l-tyrosine ethyl esters were synthesized by the reaction of vinyl bromides (4-bromo-1-butene, 6-bromo-1-hexene, 8-bromo-1-octene and 10-bromo-1-decene with N-acetyl-l-tyrosine ethyl ester. 1H NMR, elemental analysis, FT-IR, and mass spectra were performed for these N-acetyl-O-(ω-alkenyl-l-tyrosine ethyl esters. The novel titanium complex can catalyze the copolymerization of ethylene and N-acetyl-O-(ω-alkenyl-l-tyrosine ethyl esters efficiently and the highest catalytic activity was up to 6.86 × 104 gP·(molTi−1·h−1. The structures and properties of the obtained copolymers were characterized by FT-IR, (1H13C NMR, GPC, DSC, and water contact angle. The results indicated that the obtained copolymers had a uniformly high average molecular weight of 2.85 × 105 g·mol−1 and a high incorporation ratio of N-acetyl-O-(but-3-enyl-l-tyrosine ethyl ester of 2.65 mol % within the copolymer chain. The units of the comonomer were isolated within the copolymer chains. The insertion of the polar comonomer into a copolymer chain can effectively improve the hydrophilicity of a copolymer.

  8. Volatile metabolites associated with one aflatoxigenic and one nontoxigenic Aspergillus flavus strain grown on two different substrates

    Directory of Open Access Journals (Sweden)

    Z. Jurjevic


    Full Text Available Aflatoxigenic and non-toxigenic Aspergillus flavus strains were grown on corn and on peanut substrates. Microbial volatile organic compounds (MVOCS were collected by trapping headspace volatiles using thermal desorption tubes (TDT packed with Tenax® TA and Carbotrap™ B. Samples were collected at various fungal growth stages. Trapped compounds were thermally desorbed from the adsorbent tubes, separated by gas chromatography, and identified by mass spectrometry. The fungal stage did not have many differences in the MVOCs but the concentrations of some volatiles changed over time depending on the substrate. Volatiles that were associated with both the aflatoxigenic A. flavus strain and the nontoxigenic strain on both substrates included: ethanol, 1-propanol, butanal, 2-methyl-1-propanol, 3-methylfuran, ethyl acetate, 1-butanol, 3-methylbutanal, 3-methyl-1-butanol, propanoic acid-2-methyl-ethyl-ester, 2-methyl-1-butanol, 1-pentanol, 2-pentanol, 3-methyl-3-buten-1-ol, benzaldehyde, 3-octanone, 2-ethyl-1-hexanol and octane. Volatiles that were associated only with the aflatoxigenic A. flavus strain included: dimethyl disulfide and nonanal. Volatiles that were associated only with the nontoxigenic A. fl avus strain included: hexanal, 1-hexanol, 1-octene-3-ol, 1-octen-3-one and 2-pentyl furan.

  9. Oxidative Dehydrogenation of n-Butane over LaV Catalysts Supported on TiO2

    Directory of Open Access Journals (Sweden)

    Le Minh Cam


    Full Text Available The catalytic performance of vanadia catalysts with 15 wt% V supported on TiO2 and (15 wt% V + 4.6 wt% La supported on TiO2 in oxidative dehydrogenation (ODH of n-butane was investigated. The catalysts were characterized by means of TPD-NH3, TPR-H2, UV-Vis, and BET. Testing of samples showed that vanadia catalysts were active for the reaction. It was found that La doping of V/TiO2 catalyst had a negative effect on the dispersion of V species and led to formation of V2O5 clusters. This resulted in a loss of activity. Although slight improvement of selectivity was observed in comparison to undoped V/TiO2 samples due to lower acidity of La-doped –V/TiO2, this could not compensate the loss of activity and finally did not lead to higher butene yields.

  10. {alpha}-Sb{sub 2}O{sub 4}-induced improvements of the catalytic behavior of MoO{sub 3}-(010) in the oxygen-assisted dehydration of 2-butanol: implications in selective oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Gaigneaux, E.M. [Fonds National de la Recherche Scientifique of Belgium (Belgium); Naeye, M.L.; Dupont, O.; Ruiz, P.; Delmon, B. [Unite de Catalyse et Chimie des Materiaux Divises, Universite Catholique de Louvain, Louvain-La-Neuve (Belgium); Callant, M.; Kartheuser, B. [CERTECH, Senefffe (Belgium)


    This article concerns the synergetic effects between an MoO{sub 3} sample composed of crystallites exposing preferentially the (010) basal faces and {alpha}-Sb{sub 2}O{sub 4} in the oxygen-assisted dehydration of 2-butanol at 220 C. The conversion of 2-butanol and the yield to butene improved when MoO{sub 3} was reacted in the presence of {alpha}-Sb{sub 2}O{sub 4}. The origin of the synergism is discussed. When reacted in the absence of {alpha}-Sb{sub 2}O{sub 4}, MoO{sub 3} got over-reduced and fragmented to MoO{sub 2}. MoO{sub 2} is intrinsically less active than MoO{sub 3} thus explaining that the deep reduction of MoO{sub 3} corresponds to its tendency to deactivate. In the presence of {alpha}-Sb{sub 2}O{sub 4}, the formation of MoO{sub 2} is inhibited with, as a consequence, the absence of deactivation. This leads to the synergetic effects obtained with the mechanical mixture of MoO{sub 3} with {alpha}-Sb{sub 2}O{sub 4}. (orig.)

  11. Oxygen atom transfer from {mu}-Oxo-bis[1,4,8,11,15,18,22,25-octakis(trifluoromethyl)ph-thalocya ninato]diiron(III) : evidence for an Fe(IV)=O intermediate.

    Energy Technology Data Exchange (ETDEWEB)

    Chen, M. J.; Rathke, J. W.; Chemical Engineering


    The dimeric [(FPc)Fe]2({mu}-O) (1) (FPc is the dianion of 1,4,8,11,15,18,22,25-octakis(trifluoromethyl)phthalocyanine) has been shown to transfer its -oxo atom quantitatively to trimethylphosphine and triphenylphosphine. In the case of triphenylphosphine a base such as 1-methylimidazole (MeIm) or pyridine (py) is needed to induce the oxygen atom transfer. The reaction of 1 with MeIm at -40 C and below gives [(MeIm)(FPc)Fe]2({mu}-O) (4), which disproportionates to give (MeIm)2(FPc)Fe (5) and (FPc)Fe=O (6) at higher temperatures. The oxo atom of 6 has been shown to transfer to triphenylphosphine. Similarly, 6 is generated by the disproportionation of 1 with py. It has also been generated by the oxidation of 1 with t-butyl hydroperoxide. [(FPc)Fe]2({mu}-O) catalyzes the oxidation of hydrocarbons by iodosylbenzene. With stilbenes, styrenes, cyclohexenes and butenes as substrates, both epoxidations and alkyl C-H bond oxidations have been observed. The epoxidation of cis-stilbene leads to a mixture of cis- and trans-stilbene oxides, indicating that epoxidation of cis-stilbene, and possibly other olefins as well, proceeds through a non-concerted mechanism.

  12. Cytotoxic Evaluation of (2S-5,7-Dihydroxy-6-prenylflavanone Derivatives Loaded PLGA Nanoparticles against MiaPaCa-2 Cells

    Directory of Open Access Journals (Sweden)

    Berenice Andrade-Carrera


    Full Text Available The search for new alternatives for the prevention and treatment of cancer is extremely important to minimize human mortality. Natural products are an alternative to chemical drugs, since they are a source of many potential compounds with anticancer properties. In the present study, the (2S-5,7-dihydroxy-6-prenylflavanone (semi-systematic name, also called (2S-5,7-dihydroxy-6-(3-methyl-2-buten-1-yl-2-phenyl-2,3-dihydro-4H-1-Benzopyran-4-one (CAS Name registered (1 was isolated from Eysenhardtia platycarpa leaves. This flavanone 1 was considered as the lead compound to generate new cytotoxic derivatives 1a, 1b, 1c and 1d. These compounds 1, 1a, 1b, 1c, and 1d were then loaded in nanosized drug delivery systems such as polymeric nanoparticles (NPs. Small homogeneous spherical shaped NPs were obtained. Cytotoxic activity of free compounds 1, 1a, 1b, 1c, and 1d and encapsulated in polymeric NPs (NPs1, NPs1a, NPs1b, NPs1c and NPs1d were evaluated against the pancreatic cancer cell line MiaPaCa-2. The obtained results demonstrated that NPs1a and NPs1b exhibited optimal cytotoxicity, and an even higher improvement of the cytotoxic efficacy was exhibited with the encapsulation of 1a. Based on these results, NPs1a were proposed as promising anticancer agent candidates.

  13. Retrofit of an MTBE-unit to ETBE

    Energy Technology Data Exchange (ETDEWEB)

    Rix, A.; Peters, U. [Degussa GmbH, Marl (Germany)


    New European policies on renewable fuels have created substantial market pressure to increase the share of bio-fuels. For blending in gasoline, ETBE formed by etherification of isobutene with bio-ethanol is an interesting alternative to direct blending of bio-ethanol. Since the physical properties of methanol and ethanol - and consequently MTBE and ETBE - are quite similar, MTBE-plants can be retrofitted for ETBE-production. Experience from a retrofit-project at Marl is presented. In an integrated C4-plant, isobutene removal is one the most important tasks of the etherification unit to purify the raffinate 2 stream for butene-1 production. Compared to MTBE, reaction rate and equilibrium constant are lower and suitable means of maintaining isobutene conversion on former levels must be found. Furthermore, the extraction of excess alcohol and its recovery by distillation is more difficult. The ethanol-water azeotrope formed on top of the alcohol recovery column has to undergo a further drying process. Alternatives for ethanol drying have been evaluated and performance data for a membrane process is presented. (orig.)

  14. Diosmacycloalkanes as models for the formation of hydrocarbons from surface methylenes. Final report

    Energy Technology Data Exchange (ETDEWEB)

    Norton, J.R.


    Assignment of the vibrational modes Of Os{sub 2}(CO){sub 8}(CHCH{sub 3}) and Os(CO){sub 4}(C{sub 2}H{sub 4)} has given fingerprint vibrational spectra for the following species when chemisorbed on metal catalyst surfaces: ethylidene and ethylene bound in a metallacyclopropane mode. The formation and fragmentation of diosmacyclobutanes have been shown to involve slippage of the outgoing olefin onto a single osmium, and associative exchange of the olefin from that site. The incorporation of vinylcyclopropane without rearrangement has confirmed the absence of a diradical intermediate. The anomalous stability of the diosmacyclobutane derived from trans-2-butene has proven due to greater destabilization (by the substituent methyls) of the slipped intermediate than of the ground state. Reaction of an osmacyclobutane with 1,3- or 1,2-dienes (allenes) gives 1,2 rather than 1,4 addition to the diosmium unit. Treatment of Os(CO){sub 4}(C{sub 2}H{sub 4}) with triflic acid results in the formation of Os(CO){sub 4}(C{sub 2}H{sub 5})OTf. The authors have found that the reaction of an aryl iodine(III) reagent with propargyl stannanes or silanes results in o-iodo propargyl arenes.

  15. Characteristics of volatile organic compounds from motorcycle exhaust emission during real-world driving (United States)

    Tsai, Jiun-Horng; Huang, Pei-Hsiu; Chiang, Hung-Lung


    The number of motorcycles has increased significantly in Asia, Africa, Latin American and Europe in recent years due to their reasonable price, high mobility and low fuel consumption. However, motorcycles can emit significant amounts of air pollutants; therefore, the emission characteristics of motorcycles are an important consideration for the implementation of control measures for motorcycles in urban areas. Results of this study indicate that most volatile organic compound (VOC) emission factors were in the range of several decades mg/km during on-road driving. Toluene, isopentane, 1,2,4-trimethylbenzene, m,p-xylene, and o-xylene were the most abundant VOCs in motorcycle exhaust, with emission factors of hundreds mg/km. Motorcycle exhaust was 15.4 mg/km for 15 carbonyl species. Acetaldehyde, acetone, formaldehyde and benzaldehyde were the major carbonyl species, and their emission factors ranged from 1.4 to 3.5 mg/km 1,2,4-trimethylbenzene, m,p-xylene, 1-butene, toluene, o-xylene, 1,2,3-trimethylbenzene, propene, 1,3,5-trimethylbenzene, isoprene, m-diethylbenzene, and m-ethyltoluene were the main ozone formation potential (OFP) species, and their OFP was 200 mg-O3/km or higher.

  16. Host seeking parasitic nematodes use specific odors to assess host resources. (United States)

    Baiocchi, Tiffany; Lee, Grant; Choe, Dong-Hwan; Dillman, Adler R


    Entomopathogenic nematodes (EPNs) are insect parasites used as biological control agents. Free-living infective juveniles (IJs) of EPNs employ host-seeking behaviors to locate suitable hosts for infection. We found that EPNs can differentiate between naïve and infected hosts, and that host attractiveness changes over time in a species-specific manner. We used solid-phase microextraction and gas chromatography/mass spectrometry to identify volatile chemical cues that may relay information about a potential host's infection status and resource availability. Among the chemicals identified from the headspace of infected hosts, 3-Methyl-2-buten-1-ol (prenol) and 3-Hydroxy-2-butanone (AMC) were selected for further behavioral assays due to their temporal correlation with the behavioral changes of IJs towards the infected hosts. Both compounds were repulsive to IJs of Steinernema glaseri and S. riobrave in a dose-dependent manner when applied on an agar substrate. Furthermore, the repulsive effects of prenol were maintained when co-presented with the uninfected host odors, overriding attraction to uninfected hosts. Prenol was attractive to dauers of some free-living nematodes and insect larvae. These data suggest that host-associated chemical cues may have several implications in EPN biology, not only as signals for avoidance and dispersal of conspecifics, but also as attractants for new potential hosts.

  17. Obesity impairs γδ T cell homeostasis and antiviral function in humans.

    Directory of Open Access Journals (Sweden)

    Anne E Costanzo

    Full Text Available Obese patients are susceptible to increased morbidity and mortality associated with infectious diseases such as influenza A virus. γδ T cells and memory αβ T cells play key roles in reducing viral load by rapidly producing IFN-γ and lysing infected cells. In this article we analyze the impact of obesity on T lymphocyte antiviral immunity. Obese donors exhibit a reduction in γδ T cells in the peripheral blood. The severity of obesity negatively correlates with the number of γδ T cells. The remaining γδ T cells have a skewed maturation similar to that observed in aged populations. This skewed γδ T cell population exhibits a blunted antiviral IFN-γ response. Full γδ T cell function can be restored by potent stimulation with 1-Hydroxy-2-methyl-buten-4yl 4-diphosphate (HDMAPP, suggesting that γδ T cells retain the ability to produce IFN-γ. Additionally, γδ T cells from obese donors have reduced levels of IL-2Rα. IL-2 is able to restore γδ T cell antiviral cytokine production, which suggests that γδ T cells lack key T cell specific growth factor signals. These studies make the novel finding that the γδ T cell antiviral immune response to influenza is compromised by obesity. This has important implications for the development of therapeutic strategies to improve vaccination and antiviral responses in obese patients.

  18. A New Route for Evaluating Short Chain Branching Distribution of High Density Polyethylene by Measuring Crystallizability of Molar Mass Fractions

    Directory of Open Access Journals (Sweden)

    Andres KRUMME


    Full Text Available A bimodal high density polyethylene (HDPE has been successfully fractionated by analytical size exclusion chromatography into molar mass fractions with Mw's ranging from 3.6 kg/mol to 8 000 kg/mol, and subsequently deposited on germanium disks using the Lab Connections Transform method. After removal of the fractions from the disks, having masses in between 10 µg - 150 µg, differential scanning calorimetry has been successful in measuring the (recrystallization and melting behavior of these fractions. Comparing the crystallization and melting peak temperatures of the fractions with those of narrow molar mass linear polyethylenes points to the HDPE being linear below and short chain branched above 100 kg/mol respectively. This value coincides roughly with the 'split' between the molar mass distributions resulting from the first and the second polymerization reactor - confirming the addition of 1-butene in the second reactor.

  19. Nature of active centers and mechanism of olefin metathesis on applied oxide catalysts of molybdenum, tungsten and rhenium

    Energy Technology Data Exchange (ETDEWEB)

    Kadushin, A.A. (USSR Academy of Sciences); Aliyev, R.K.; Krylov, O.V.; Andreyev, A.A.; Yedreva-Kardzhiyeva, R.M.; Shopov, D.M.


    The authors undertook a systematic study of the effects of the carrier, activation conditions and the reaction itself on the formation and structure of active centers. Spectral characteristics of the systems studied were compared by infrared, ultraviolet, X-ray-electron and electron absorption spectroscopy, and X-ray-phase and chromatographic analyses. Catalytic activity in a metathesis reaction of propylene and butene-1 was tested in a quartz flow reactor at atmospheric pressure in a temperature range of 25-600/sup 0/C, with contact time of 3-50 seconds. The deposited oxide catalysts of the title minerals are discussed in terms of preparing the catalysts, studying their activity, and observing optical spectra. Tungsten ions were found to reduce at higher temperatures than molbydenum ions. Olefin treatment brought reduction of rhenium to lower oxidation levels. The low activities of Re/sub 2/O/sub 7//MgO at low temperatures is related to difficult electron transfer. The studies indicated the presence of a mobile center in the metathesis of olefins for oxide catalysis of all 3 title minerals, which is dependent on the chemical nature of the carrier and its crystalline structure.

  20. Olefin metathesis : tapping into breakthrough chemical technology

    Energy Technology Data Exchange (ETDEWEB)

    Granson, E.


    Olefin metathesis is a catalyst technology where 2 double bond-containing molecules or olefins are split in order to exchange atoms and result in the formation of 2 new molecules or substances. Earlier researchers used a variety of materials to convert propylene into a mixture of butenes and ethylenes. A method developed by Shell researchers produces linear olefins used as detergent feedstocks. In 1971, scientists used a metal-carbene catalyst to react with the olefins to produce both a new olefin and a new metal carbene in order to perpetuate the process. In 2002, a new metathesis technology was developed using renewable natural oils as a feedstock. The catalyst is introduced as a solid into the oil, and then agitated by stirring. The modified oil is then reacted with hydrogen to remove the double bonds and filter off the catalyst. The method is offered on a contract basis by Elevance Renewable Sciences in a variety of application. The process was designed to take place at lower temperatures with the release of fewer greenhouse gases (GHGs). New metathesis technologies are also being developed to reduce the molecular weight of polymers in order to reduce viscosity and increase flow. 3 figs.

  1. Catalytic studies of nitric oxide: A. Reduction of nitric oxide with methane over alumina supported rhidium. B. Characterization of alumina supported cobalt molybdate for olefin metathesis

    Energy Technology Data Exchange (ETDEWEB)

    Hardee, J.R.


    Kinetic studies at 300/sup 0/-400/sup 0/C in a gradientless recirculating reactor showed that nitric oxide reduction was first order in methane and -0.63 order in nitric oxide, with an activation energy of 18.4 kcal/mole, and a deuterium kinetic isotope effect of 1.9, suggesting that dissociative methane adsorption is the rate-determining step. Nitrogen-15 tracer studies showed that the reaction involves N/sub 2/O as a surface intermediate, and a mechanism is proposed involving two-step dissociation of adsorbed NO to adsorbed N/sub 2/O and N/sub 2/ and surface oxygen atoms, which rapidly poison the catalyst unless removed by methane. Propylene metathesis to ethylene and 2-butene over cobalt molybdate was studied by nitric oxide poisoning and shown to follow Langmuir-Hinshelwood kinetics. Two different dual-site mechanisms, one involving propylene adsorption on adjacent molybdenum atoms and the other involving adsorption of two propylene molecules on one molybdenum atom, fit the data equally well. An upper limit to the active site density was determined as 2.5 x 10/sup 13//sq cm at 27/sup 0/C, i.e., only 9Vertical Bar3< of the surface molybdenum atom density.

  2. Preparation of highly dispersed tungsten oxide on MCM-41 via atomic layer deposition and its application to butanol dehydration. (United States)

    Kim, Hyeonjoo; Jeong, Soyeon; Kim, Do Heui; Park, Young-Kwon; Jeon, Jong-Ki


    Highly dispersed tungsten oxide on MCM-41 was synthesized using a novel atomic layer deposition (ALD) method. BET, XRD, XPS, NH3-TPD, and pyridine-IR were used to study the physicochemical properties of the supported tungsten oxides. In this study, the maximum loading of tungsten oxide on MCM-41 that could be prepared using the modified ALD method was 27.0 wt%. It was confirmed that the textural properties of the mesoporous silica were maintained after tungsten oxide loading. The NH3-TPD and Py-IR results indicated that weak acid sites, mainly Lewis acid sites, were produced over the WO3/MCM-41 samples. Moreover, 2-butanol dehydration was performed to demonstrate the potential advantages of the WO3/MCM-41 catalysts. The WO3/MCM-41 catalyst with 27.0 wt% tungsten oxide loading showed the highest activity in the dehydration of 2-butanol, which was attributed to the highest overall number of acid sites among the WO3/MCM-41 catalysts. The highly dispersed tungsten oxide on MCM-41 prepared via ALD can be an effective catalyst for producing butenes through 2-butanol dehydration.

  3. Contribution from biogenic organic compounds to particle growth during the 2010 BEACHON-ROCS campaign in a Colorado temperate needleleaf forest

    Energy Technology Data Exchange (ETDEWEB)

    Zhou, L.; Gierens, R.; Sogachev, A.; Mogensen, D.; Ortega, J.; Smith, J. N.; Harley, P. C.; Prenni, A. J.; Levin, E. J. T.; Turnipseed, A.; Rusanen, A.; Smolander, S.; Guenther, A. B.; Kulmala, M.; Karl, T.; Boy, M.


    New particle formation (NPF) is an important atmospheric phenomenon. During an NPF event, particles first form by nucleation and then grow further in size. The growth step is crucial because it controls the number of particles that can become cloud condensation nuclei. Among various physical and chemical processes contributing to particle growth, condensation by organic vapors has been suggested as important. In order to better understand the influence of biogenic emissions on particle growth, we carried out modeling studies of NPF events during the BEACHON-ROCS (Bio–hydro–atmosphere interactions of Energy, Aerosol, Carbon, H2O, Organics & Nitrogen – Rocky Mountain Organic Carbon Study) campaign at Manitou Experimental Forest Observatory in Colorado, USA. The site is representative of the semi-arid western USA. With the latest Criegee intermediate reaction rates implemented in the chemistry scheme, the model underestimates sulfuric acid concentration by 50 %, suggesting either missing sources of atmospheric sulfuric acid or an overestimated sink term. The results emphasize the contribution from biogenic volatile organic compound emissions to particle growth by demonstrating the effects of the oxidation products of monoterpenes and 2-Methyl-3-buten-2-ol (MBO). Monoterpene oxidation products are shown to influence the nighttime particle loadings significantly, while their concentrations are insufficient to grow the particles during the day. The growth of ultrafine particles in the daytime appears to be closely related to the OH oxidation products of MBO.


    Directory of Open Access Journals (Sweden)

    Narenda Narain


    Full Text Available Most of the volatile flavoring substances are formed during maturation of fruit when it ripens. In this study, the mangaba (Hancornia speciosa Gomes fruit was harvested at half-ripe and ripe stages of maturity and analyzed for its volatile components. The extracts were obtained from the fruit pulp by using simultaneous distillation and extraction technique. Several extraction parameters such as weight of the pulp, dilution with water, solvent volume and extraction period were standardized to obtain highly characteristic fruit aroma extracts. The extracts were analyzed for the identification of volatile compounds by using a system of high resolution gas chromatograph coupled with mass spectrometer. Eighty-six components were separated out of which 46 compounds were positively identified. The volatile flavoring substances pertaining to classes of esters and terpenes increased from 6.19 to 35.487% and from 7.51 to 10.40%, respectively. The principal volatile compounds present in the pulp of ripe mangaba fruit were isopropyl acetate (19.23%, 3-hexanol (10.74%, linalool (7.38%, ä-limonene (2.43%, 3-pentanol (3.80%, 3-ethyl 2-buten-1-ol (2.53% and furfural (1.52%. Biogeneration of mangaba flavor is mainly characterized due to the presence of compounds pertaining to esters, aldehydes and terpenes.

  5. Kinetics of the Epoxidation of Geraniol and Model Systems by Dimethyldioxirane

    Directory of Open Access Journals (Sweden)

    B. S. Crow


    Full Text Available The mono-epoxidation of geraniol by dimethyldioxirane was carried out invarious solvents. In all cases, the product ratios for the 2,3 and 6,7 mono-epoxides werein agreement with literature values. Kinetic studies were carried out at 23 oC in thefollowing dried solvent systems: acetone (k2 = 1.49 M-1s-1, carbon tetrachloride/acetone(9/1, k2=2.19 M-1s-1, and methanol/acetone (9/1, k2 = 17 M-1s-1. Individual k2 valueswere calculated for epoxidation of the 2,3 and 6,7 positions in geraniol. The non-conjugated diene system was modeled employing two simple independent alkenes:2-methyl-2-pentene and 3-methyl-2-buten-1-ol by determining the respective k2 valuesfor epoxidation in various solvents. The kinetic results for each independent alkeneshowed that the relative reactivity of the two epoxidation sites in geraniol as a function ofsolvent was not simply a summation of the independent alkene systems.

  6. Induction of adventitious buds on buds of Norway spruce (picea abies) grown in vitro

    Energy Technology Data Exchange (ETDEWEB)

    Von Arnold, S.; Eriksson, T.


    Isolated resting vegetative buds of P. abies were cultured on a defined medium to which auxins or cytokinins were added. At concentrations of 10 to the power of -6 to 10 to the power of -4 M, 6-benzylaminopurine (BAP) or 6-(3-methyl-2-buten-1-ylamino)-purine (2iP) induced formation of adentitious bud primordia; these arose from meristems formed de novo in the needle primordia. Adventitious buds developed when these buds were transferred to medium lacking cytokinin. At lower concentrations of BAP or 2iP, only elongation of needle primordia was induced; at higher concentrations, buds were killed. Other growth regulators induced only needle primordia elongation and were also lethal at higher concentrations. No major differences were found in the ability to form adventitious buds among buds from: a 75-year-old hedge, 5-year-old greenhouse-grown plants, and trees in a stand near Uppsala, Sweden ranging in age from 5 to 50 year old.

  7. Conjugated di-anionic dinitro compounds as inhibitors of oxidative deamination of monoamines

    Energy Technology Data Exchange (ETDEWEB)

    Gureyeva, Z.P.; Mostyayeva, L.V.


    Comparative studies were conducted on the inhibition kinetics of monoamine oxidase (MO) of mitochondrial fractions derived from bovine liver, to elucidate the chemical features leading to inhibition. The study showed that in the case of a mitochondrial preparation in 0.2 M phosphate buffer, pH 7.4, the disodium salts of 1,4-dinitrobutene-2,1,4-dinitro-2-methyl-butene, and 1,4-dinitro-2, 3-diphenylbutene-2, (I), as well as sodium dinitromethane, and beta-nitrostyrene, inhibited MO, catalyzing the oxidative deamination of tyramine, serotonin and tryptamine. Oxidative deamination of benzylamine was inhibited to a significantly lesser degree. The di-anionic dinitro compounds were established to function as reversible, competitive inhibitors of MO, with the exception of I which behaved as a noncompetitive inhibitor in the Lineweaver-Burke plots. The kinetics and inhibition constants obtained with these inhibitors indicate that inhibition was due to the =C-C=OO-bond in the dinitro compounds, with the inhibitory parameters modified by the introduction of electron donor radicals (methyl, phenyl groups). In addition, diminished inhibition of benzylamine deamination indicated that the inhibitors exhibit considerable specificity for the A form of MO. 10 references, 4 figures.

  8. Transition-metal catalyzed synthesis of Ketoprofen

    Directory of Open Access Journals (Sweden)

    Ramminger Carolina


    Full Text Available Transition metal-catalyzed reactions including carbonylations, hydrovinylations and hydrogenations have been applied in the synthesis of alpha-(3-benzoylphenylpropanoic acid (Ketoprofen. 3-Vinylbenzophenone was obtained from 3-bromobenzophenone by a Pd-catalyzed Heck coupling reaction. Pd-catalyzed carbonylation of this olefin gave the isopropyl alpha-(3-benzoylphenyl propionate in high yield (95% and with high regioselectivity (>99.5%. Ketoprofen was obtained in 90% yield by hydrolysis of the isopropyl ester. It was also obtained in two steps from 3-vinylbenzophenone by a Ni-catalyzed hydrovinylation selectively affording 3-(3'-benzoylphenyl-1-butene, followed by an oxidation. 3-Ethynylbenzophenone was obtained from 3-bromobenzophenone by Pd-catalyzed coupling reaction. By means of a Pd-catalyzed carbonylation, this alkyne was converted regioselectively (97% into methyl alpha-(3-benzoylphenyl acrylate (93% yield. Hydrolysis of the ester afforded the alpha-(3-benzoylphenylacrylic acid. Asymmetric hydrogenation of this acid to give (S-ketoprofen in 95% optical yield was achieved using a chiral Ru-(S-BINAP catalyst.

  9. Reactivity of palladium nano-particles supported in hydrogenation: role of particles surface density; Reactivite des nanoparticules de palladium supportees en hydrogenation: role de la densite surfacique de particules

    Energy Technology Data Exchange (ETDEWEB)

    Benkhaled, M.


    The objective of this work is to investigate the influence of the particle surface density on the hydrogenation of polyunsaturated compounds (buta-1,3-diene, ortho-xylene). Highly dispersed Pd/Al{sub 2}O{sub 3} ({gamma} and {delta}-Al{sub 2}O{sub 3}) catalysts were prepared from Pd(nitrite) complexes (size < 7 angstrom, controlled by TEM, HAADF, EXAFS and CO chemisorption). Increasing the particle surface density from 2240 to 12880 particles/{mu}m{sup 2} leads to a modification of the electronic properties as evidenced by CO-FTIR, XPS and XANES. By contrast, the comparison of the supports at iso-density showed no significant difference of the physico-chemical properties of the supported metal particles. In parallel, the catalytic performances in hydrogenation of butadiene and butenes are very sensitive both to the nature of the support for the same density and to the surface density for the same support. It was shown that the reactions of hydrogenation could be controlled at the same time by the electronic properties of the metal nano-particles but also by the phenomenon of hydrogen diffusion around the particles on a zone of support. In this case, the support can play the part of hydrogen tank. (author)

  10. Thiophene occurrence in different Tagetes species: agricultural biomasses as sources of biocidal substances. (United States)

    Marotti, Ilaria; Marotti, Mauro; Piccaglia, Roberta; Nastri, Anna; Grandi, Silvia; Dinelli, Giovanni


    Tagetes species produce thiophenes, polyacetylenic compounds that possess strong biocidal activity, thus making Tagetes plants very useful for suppressing nematode populations in the soil and as sources of natural pesticides. In the present study, Tagetes species (T. erecta, T. filifolia, T. lucida, T. minuta, T. patula and T. tenuifolia) grown in northern Italy were evaluated for their morphophenological parameters and thiophene pattern in different plant parts (roots, shoots and flowers). Roots had the highest diversity and contents of thiophenes (from 64 to 100% of the total thiophene amount), with 5-(3-buten-1-ynyl)-2,2'-bithienyl (BBT) as the main component followed by 5-(4-acetoxy-1-butynyl)-2,2'-bithienyl (BBTOAc), 2,2':5',2''-terthienyl (alpha-T) and 5-(4-hydroxy-1-butynyl)-2,2'-bithienyl (BBTOH). Tagetes lucida and T. tenuifolia possessed the highest amounts of total thiophenes (6717.3 and 6452.5 mg kg(-1) dry weight respectively), while T. minuta had the highest total thiophene yield (518.8 mg m(-2)), with BBT accounting for 98% of the total. Considering both thiophene concentrations and biomass yields, T. minuta and T. lucida appeared to be the most promising Tagetes species, with high potential for use as biocidal crops for the implementation of pest control practices that are less harmful to human health and natural resources.

  11. Synthesis and Characterization of Plant based Polythiophene Copolymers for Light Harvesting Applications (United States)

    Kodithuwakku, Udari; Malavi Arachchi, Prashantha; Ratnaweera, Dilru

    Polythiophenes became more attractive in diverse applications due to some of their inherent properties including thermal and environmental stability as well as optical and electronic conductive properties. Commonly thiophene monomers are obtained from byproducts of crude oils. The current study discuss for the first time the synthesis and characterization of light harvesting polythiophenes copolymers from thiophene derivatives extracted from Tagetes species. There were mainly two thiophenes derivatives, 5-(3-buten-1-ynyl)-2, 2-bithienyl and 2, 2', 5, 2''-terthienyl (terthiophene), in the roots of the plant. Chemical oxidative radical polymerization was followed during the synthesis of copolymers with various block compositions of plant based terthiophenes and 3-hexyl terthiophenes. Structural characterization of the synthetic products was done using FTIR, NMR, Uv-vis, XRD and DSC techniques. Polythiophene homopolymers obtained from plant based terthiophenes have limited processability of solar cells due to poor solubility in common organic solvents. A significant solubility improvement was observed with copolymers having minor contributions of 3-hexylthiophenes. Research Grants, University of Sri Jayewardenepura, Sri Lanka.

  12. Characterizations of volatile organic compounds (VOCs) from vehicular emissions at roadside environment: The first comprehensive study in Northwestern China (United States)

    Li, Bowei; Ho, Steven Sai Hang; Xue, Yonggang; Huang, Yu; Wang, Liqin; Cheng, Yan; Dai, Wenting; Zhong, Haobin; Cao, Junji; Lee, Shuncheng


    Vehicular emission (VE) is one of the important anthropogenic sources for ground-level volatile organic compounds (VOCs) in both urban and suburban areas. A first comprehensive campaign was conducted at an urban roadside in Xi'an, China in summer, 2016. A total of 57 VOCs, as known as critical surface ozone (O3) precursors, and other trace gases were measured simultaneously during the sampling period. Iso-pentane, a tracer of gasoline evaporation, was the most abundant VOC in the roadside samples, followed by isobutane and benzene, attributed to the largest composition (∼70%) of gasoline-fueled vehicles on the road. The molar ratio of toluene/benzene (T/B) in our study (0.36) is far lower than the range reported in other cities, indicating the stronger contributions from diesel emissions. The results of source apportionment achieved with positive matrix factorization (PMF) receptor model were highly consistent with the vehicles compositions, strongly evidenced that the precise characterization of the VE sources from those marker species. The degrees of individual compound contributed to O3 production were weighed by ozone formation potential (OFP). Propylene (20%), 1-butene (11%) and iso-pentane(10%) were the top three contributors at the roadside. The information of this study complements the VOCs database regarding to the VE sources in Northwestern China.

  13. Virtual disjunct eddy covariance measurements of organic compound fluxes from a subalpine forest using proton transfer reaction mass spectrometry

    Directory of Open Access Journals (Sweden)

    T. G. Karl


    Full Text Available A `virtual' disjunct eddy covariance (vDEC device was tested with field measurements of biogenic VOC fluxes at a subalpine forest site in the Rocky Mountains of the USA. A PTR-MS instrument was used as the VOC sensor. Daily peak emission fluxes of 2-methyl-3-buten-2-ol (MBO, methanol, acetone and acetaldehyde were around 1.5, 1, 0.8 and 0.4 mg m-2 h-1, respectively. High pass filtering due to long sampling lines was investigated in laboratory experiments, and suggested that VOC losses in PTFA lines are generally governed by diffusion laws. Memory effects and surface reactions did not seem to play a dominant role. Model estimates of MBO fluxes compared well with measured fluxes. The results also suggest that latent heat and sensible heat fluxes are reasonably well correlated with VOC fluxes and could be used to predict variations in VOC emissions. The release of MBO, methanol, acetone and acetaldehyde resulted in significant change of tropospheric oxidant levels and a 10--40% increase in ozone levels, as inferred from a photochemical box model. We conclude that vDEC with a PTR-MS instrument is a versatile tool for simultaneous field analysis of multiple VOC fluxes.

  14. A dynamic dilution system-based evaluation of the procedure adopted for determining ozone precursor volatile compounds. (United States)

    Palluau, Fabienne; Mirabel, Philippe; Millet, Maurice


    A dynamic dilution system was created to evaluate the performance and the reliability of ozone precursor volatile organic compound (VOC) sampling ("TO-Can" canisters) and analysis (thermal desorption/gas chromatography/flame ionisation detection) techniques used by the "Laboratoire Interregional de Chimie du Grand Est (LIC)". Different atmospheres of VOCs were generated at concentrations between 0.8 and 25 ppb, with temperatures of 0, 10, 20 and 30 degrees C, and with relative humidities of 0, 30, 50, 70 and 90%. These conditions are generally representative of those commonly observed in ambient air in the eastern France. This dynamic dilution allows the simulation of a wide range of scenarios (concentrations, temperatures and relative humidities). After assessing the capacity and performance of the system, it was applied in order to evaluate the recoveries and stabilities of VOCs from canisters used for the collection and analysis of two mixtures of VOCs. The first mixture contained six alkanes (ethane, propane, butane, pentane, hexane and heptane), and the second contained five alkenes (ethene, propene, butene, 1-pentene and 1-hexene), five aromatics (benzene, toluene, ethylbenzene, m-xylene and o-xylene), acetylene, and 1,3-butadiene. No significant losses of alkanes from the canisters were observed after 21 days of storage, and good recoveries of alkanes from the canisters (>80%) were obtained regardless of the concentration, the temperature and the relative humidity. However, losses of certain aromatics were noted at low relative humidity.

  15. Emission of VOC Compounds from Ta-Shan Chemical Industrial Park in Middle China (United States)

    Li, Jian; Xie, Chunjuan; Cao, Qun; Yan, Liushui; Zhong, Jiaochan


    VOCs emission from a Ta-Shan Chemical Industrial Park in January 1-8, 2014 and summer (July 16-20, 2014) have been studied in this paper. VOCs were collected by the stainlessteel canisters and following pre-concentrate and analyzing by GC/MSD. The results showed that a total of 33 VOC species in winter samplers and 41 VOC species in summer samplers were detected. Among the 41 VOC species detected in the winter and summer samplers, 1-Butene and Ethane were the two most abundant compounds. Their highest average mean concentrations were 6013±1758 and 3188±1025 pptv in summer (contributed more than 12.5% and 4.8 % of the total VOC concentrations), and about 5895±1246 and 2763±789 pptv in winter (contributed more than12.9% and 7.8% of the total VOC concentrations), respectively. In winter, stack emission was found to be the main souce of VOCs emission, while in summer, fugitive emission become the primary source.

  16. Contribution of carbonyl photochemistry to aging of atmospheric secondary organic aerosol. (United States)

    Mang, Stephen A; Henricksen, Dana K; Bateman, Adam P; Andersen, Mads P Sulbaek; Blake, Donald R; Nizkorodov, Sergey A


    The photodegradation of secondary organic aerosol (SOA) material by actinic UV radiation was investigated. SOA was generated via the dark reaction of ozone and d-limonene, collected onto quartz-fiber filters, and exposed to wavelength-tunable radiation. Photochemical production of CO was monitored in situ by infrared cavity ring-down spectroscopy. A number of additional gas-phase products of SOA photodegradation were observed by gas chromatography, including methane, ethene, acetaldehyde, acetone, methanol, and 1-butene. The absorption spectrum of SOA material collected onto CaF2 windows was measured and compared with the photolysis action spectrum for the release of CO, a marker for Norrish type-I photocleavage of carbonyls. Both spectra had a band at approximately 300 nm corresponding to the overlapping n --> pi* transitions in nonconjugated carbonyls. The effective extinction coefficient of freshly prepared SOA was estimated to be on the order of 15 L mol(-1) cm(-1) at 300 nm, implying one carbonyl group in every SOA constituent. The absorption by the SOA material slowly increased in the visible and near-UV during storage of SOA in open air in the dark, presumably as a result of condensation reactions that increased the degree of conjugation in the SOA constituents. These observations suggest that photolysis of carbonyl functional groups represents a significant sink for monoterpene SOA compounds in the troposphere, with an estimated lifetime of several hours over the continental United States.

  17. Kinetic study of the gas-phase reaction of atomic chlorine with a series of aldehydes

    Directory of Open Access Journals (Sweden)

    D. Rodríguez


    Full Text Available The reactions of Cl atoms with a series of unsaturated aldehydes have been investigated for the first time using a relative method. In order to obtain additional information for a qualitative structure versus reactivity discussion, we have also determined the rate coefficients for the reactions of atomic chlorine with their respective saturated aldehydes. These relative measurements were performed at room temperature and atmospheric pressure of air and N2, by using ethane, propene and 1-butene as reference compounds. The weighted average relative rate constants obtained, kCl±2σ (in units of cm3 molecule−1 s−1 were: trans-2-pentenal (1.31±0.19×10−10; trans-2-hexenal (1.92±0.22×10−10; trans-2-heptenal (2.40±0.29×10−10; n-pentanal (2.56±0.27×10−10; n-hexanal (2.88±0.37×10−10; n-heptanal (3.00±0.34×10−10. Finally, results and atmospheric implications are discussed and compared with the reactivity with OH and NO3 radicals.

  18. An oxidoreductase from 'Alphonso' mango catalyzing biosynthesis of furaneol and reduction of reactive carbonyls. (United States)

    Kulkarni, Ram; Chidley, Hemangi; Deshpande, Ashish; Schmidt, Axel; Pujari, Keshav; Giri, Ashok; Gershenzon, Jonathan; Gupta, Vidya


    Two furanones, furaneol (4-hydroxy-2,5-dimethyl-3(2H)-furanone) and mesifuran (2,5-dimethyl-4-methoxy-3(2H)-furanone), are important constituents of flavor of the Alphonso cultivar of mango (Mangifera indica). To get insights into the biosynthesis of these furanones, we isolated an enone oxidoreductase gene from the Alphonso mango. It has high sequence similarity to an alkenal/one oxidoreductase from cucumber (79% identity) and enone oxidoreductases from tomato (73% identity) and strawberry (72% identity). The complete open reading frame was expressed in E. coli and the (his)6-tagged recombinant protein was purified by affinity chromatography. The purified protein assayed with NADH as a reducing agent converted D-fructose-1,6-diphosphate into furaneol, the immediate precursor of mesifuran. The enzyme was also able to convert two highly reactive carbonyls, 3-buten-2-one and 1-penten-3-one, produced by lipid peroxidation in plants, into their saturated derivatives. Expression profiling in various ripening stages of Alphonso fruits depicted an expression maxima at 10 days after harvest stage, shortly before the appearance of the maximum amount of furanones (completely ripe stage, 15 days after harvest). Although no furanones were detected at the 0 day after harvest stage, significant expression of this gene was detected in the fruits at this stage. Overall, the results suggest that this oxidoreductase plays important roles in Alphonso mango fruits.

  19. Comparison of aroma active and sulfur volatiles in three fragrant rice cultivars using GC-olfactometry and GC-PFPD. (United States)

    Mahattanatawee, Kanjana; Rouseff, Russell L


    Aroma volatiles from three cooked fragrant rice types (Jasmine, Basmati and Jasmati) were characterised and identified using SPME GC-O, GC-PFPD and confirmed using GC-MS. A total of 26, 23, and 22 aroma active volatiles were observed in Jasmine, Basmati and Jasmati cooked rice samples. 2-Acetyl-1-pyrroline was aroma active in all three rice types, but the sulphur-based, cooked rice character impact volatile, 2-acetyl-2-thiazoline was aroma active only in Jasmine rice. Five additional sulphur volatiles were found to have aroma activity: dimethyl sulphide, 3-methyl-2-butene-1-thiol, 2-methyl-3-furanthiol, dimethyl trisulphide, and methional. Other newly-reported aroma active rice volatiles were geranyl acetate, β-damascone, β-damascenone, and ɑ-ionone, contributing nutty, sweet floral attributes to the aroma of cooked aromatic rice. The first two principal components from the principal component analysis of sulphur volatiles explained 60% of the variance. PC1 separated Basmati from the other two cultivars and PC2 completely separated Jasmine from Jasmati cultivars. Copyright © 2014 Elsevier Ltd. All rights reserved.

  20. Alternative to conventional extraction of vetiver oil: Microwave hydrodistillation of essential oil from vetiver roots (Vetiveria zizanioides) (United States)

    Kusuma, H. S.; Altway, A.; Mahfud, M.


    In this study the extraction of essential oil from vetiver roots (Vetiveria zizanioides) has been carried out by using microwave hydrodistillation. In the extraction of vetiver oil using microwave hydrodistillation method is studied the effect of microwave power, feed to solvent (F/S) ratio and extraction time on the yield of vetiver oil. Besides, in this study can be seen that microwave hydrodistillation method offers important advantages over hydrodistillation, such as shorter extraction time (3 h vs. 24 h for hydrodistillation); better yields (0.49% vs. 0.46% for hydrodistillation); and environmental impact (energy cost is appreciably higher for performing hydrodistillation than that required for extraction using microwave hydrodistillation). Based on the analysis using GC-MS can be seen 19 components on vetiver oil that has been extracted using microwave hydrodistillation. In addition, GC-MS analysis showed that the main components of vetiver oil that has been extracted using microwave hydrodistillation method were β-Gurjunene (30.12%), α-Vetivone (20.12%), 4-(1-cyclohexenyl)-2-trimethylsilymethyl-1-buten-3-yne (13.52%) and δ-Selinene (7.27%).

  1. The first results from HIRAC - the Highly Instrumented Reactor for Atmospheric Chemistry (United States)

    Malkin, T. L.; Smith, S. C.; Goddard, A.; Glowacki, D. R.; Heemavibool, K.; Wada, R.; Winiberg, F.; Pilling, M. J.; Heard, D. E.; Seakins, P.


    The Highly Instrumented Reactor for Atmospheric Chemistry, HIRAC, is a recently commissioned stainless steel environmental chamber. Uniquely, the structure allows for simultaneous temperature and pressure variation and for the monitoring of radical species by Fluorescence Assay by Gas Expansion (FAGE) and Cavity Ring Down Spectroscopy (CRDS). HIRAC is cylindrical in shape with internal dimensions of 2.0 m long and 1.2 m diameter giving a total volume of ~2.25 m3. It is fitted with a broad range of instrumentation based on different detection techniques (detailed in the table below) to allow accurate monitoring of the chemistry occurring inside the chamber. Light for photochemical studies is be provided by lamps housed in eight quartz tubes mounted radially inside the reactive volume parallel to the chamber's principle axis providing a homogenous radiation profile. In this paper we present example of work relating to the three major objectives for HIRAC: 1) Mechanism development linked to the Master Chemical Mechanism - Measurements of pressure dependent OH and HO2 yields from the reaction of O3 with trans-2-butene and isoprene. 2) Field instrument development and calibration - Development of a CRDS system for measuring NO3 radicals inside HIRAC and the first pressure dependent calibrations of a FAGE HOx instrument. 3) Kinetics and Structural Activity Relationship (SAR) development - Relative rate studies of the reaction of Cl atoms with a series of acetates. The range of detection techniques employed in HIRAC and the species detected.

  2. Construction and evaluation of self-cloning bottom-fermenting yeast with high SSU1 expression. (United States)

    Iijima, K; Ogata, T


    To construct a self-cloning brewer's yeast that can minimize the unfavourable flavours caused by oxidation and certain kinds of sulfur compounds. DNA fragments of a high-expression promoter from the TDH3 gene originating from Saccharomyces cerevisiae were integrated into the promoter regions of the S. cerevisiae-type and Saccharomyces bayanus-type SSU1 genes of bottom-fermenting brewer's yeast. PCR and sequencing confirmed the TDH3 promoter was correctly introduced into the SSU1 regions of the constructed yeasts, and no foreign DNA sequences were found. Using the constructed yeasts, the concentration of sulfite in fermenting wort was higher when compared with the parent strain. In addition, the concentrations of hydrogen sulfide, 3-methyl-2-buten-1-thiol (MBT) and 2-mercapto-3-methyl-1-butanol (2M3MB) were lower when compared with the parent strain. We successfully constructed a self-cloning brewer's yeast with high SSU1 expression that enhanced the sulfite-excreting ability and diminished the production ability of hydrogen sulfide, MBT and 2M3MB. The self-cloning brewer's yeast with high SSU1 expression would contribute to the production of superior quality beer with a high concentration of sulfite and low concentrations of hydrogen sulfide, MBT and 2M3MB. © 2010 The Authors. Journal of Applied Microbiology © 2010 The Society for Applied Microbiology.

  3. Emission characteristics of volatile organic compounds from coal-, coal gangue-, and biomass-fired power plants in China (United States)

    Yan, Yulong; Yang, Chao; Peng, Lin; Li, Rumei; Bai, Huiling


    Face the large electricity demand, thermal power generation still derives the main way of electricity supply in China, account for 78.19% of total electricity production in 2013. Three types of thermal power plants, including coal-fired power plant, coal gangue-fired power plant and biomass-fired power plant, were chosen to survey the source profile, chemical reactivity and emission factor of VOCs during the thermal power generation. The most abundant compounds generated during coal- and coal gangue-fired power generation were 1-Butene, Styrene, n-Hexane and Ethylene, while biomass-fired power generation were Propene, 1-Butenen, Ethyne and Ethylene. The ratios of B/T during thermal power generation in this study was 0.8-2.6, which could be consider as the characteristics of coal and biomass burning. The field tested VOCs emission factor from coal-, coal gangue- and biomass-fired power plant was determined to be 0.88, 0.38 and 3.49 g/GJ, or showed as 0.023, 0.005 and 0.057 g/kg, with the amount of VOCs emission was 44.07, 0.08, 0.45 Gg in 2013, respectively. The statistical results of previous emission inventory, which calculated the VOCs emission used previous emission factor, may overestimate the emission amount of VOCs from thermal power generation in China.

  4. Cumene cracking on modified mesoporous material type MCM-41

    Directory of Open Access Journals (Sweden)

    Ahmed Belhakem


    Full Text Available The effect of ionic exchange degree of aluminated mesoporous materials H(X-AlMCM-41 materials, the method of its exchange mode and its grains form were investigated for the mesoporous catalytic activity in the cumene (i.e. isopropylbenzene cracking reaction. Benzene, propylene and xylene derivatives are the main products of this reaction. Olefins like butene and pentene appeared as the products of secondary reactions. No saturated hydrocarbons, except traces of butane, nor ethylbenzene and toluene were formed and seemed to be typical products of secondary reactions obtained with HNaY zeolites. Generally the exchanged H(X-AlMCM-41 materials by the substitution of Na+ by NH4+ are more active than those exchanged directly with acid solution (substitution of Na+ by H+ even if both the two methods used exhibit a comparable content of acid sites within catalysts at a low exchange degrees. However, the first method of exchange has exhibited an important acidity for mesoporous materials when the ionic exchange degree was increased up to 90%; it was probably due not only to the percentage of exchanged degree but also to the distribution of acid sites within the materials.

  5. Co-immobilization of enoate reductase with a cofactor-recycling partner enzyme. (United States)

    Li, Han; Xiao, Wenhua; Xie, Panpan; Zheng, Liangyu


    Herein we established co-immobilized methods for enoate reductases (ERs) and glucose dehydrogenase (GDH), forming a cofactor regeneration system. In cross-linked enzyme aggregates (CLEAs), ammonium sulfate and oxidized dextran were selected as a precipitant and a cross-linker, respectively. In biomimetic immobilization (BI), ER-GDH-silica particles (ER-GDH-SPs) were rapidly formed through a one-step approach by using a silicic acid precursor. Under the optimal conditions, the ER activity recovery in ER-GDH-CLEAs and ER-GDH-SPs were 44.9±1.8% and 44.5±2.1%, and the immobilization efficiency was 93.5±1.2% and 92.4±1.2%, respectively. ER-GDH-CLEAs and ER-GDH-SPs exhibit excellent thermal and pH stability, and superior reusability. The activity of ER-GDH-SPs toward the substrate is also better than that of free ER and GDH in reduction of 4-(4-Methoxyphenyl)-3-buten-2-one. This study introduces simple and inexpensive co-immobilization strategies to construct novel and efficient ER-GDH-CLEAs and ER-GDH-SPs with high activity and stability. Copyright © 2017 Elsevier Inc. All rights reserved.

  6. Sulforaphene promotes Bax/Bcl2, MAPK-dependent human gastric cancer AGS cells apoptosis and inhibits migration via EGFR, p-ERK1/2 down-regulation. (United States)

    Mondal, Arindam; Biswas, Raktim; Rhee, Yun-Hee; Kim, Jongkee; Ahn, Jin-Chul


    Gastric cancer migration and invasion considered as main causes of this cancer-related death around the world. Sulforaphene (4-isothiocyanato-4R-(methylsulfinyl)-1-butene), a structural analog of sulforaphane, has been found to exhibit anticancer potential against different cancers. Our aim was to investigate whether dietary isothiocyanate sulforaphene (SFE) can promote human gastric cancer (AGS) cells apoptosis and inhibit migration. Cells were treated with various concentrations of SFE and cell viability, morphology, intracellular ROS, migration and different signaling protein expressions were investigated. The results indicate that SFE decreases AGS cell viability and induces apoptosis in a dose-dependent manner. Intracellular ROS generation, dose- and time-dependent Bax/Bcl2 alteration and signaling proteins like cytochrome c, Casp-3, Casp-8 and PARP-1 higher expression demonstrated the SFE-induced apoptotic pathway in AGS cells. Again, SFE induced apoptosis also accompanied by the phosphorylation of mitogen-activated protein kinases (MAPKs) like JNK and P-38. Moreover, dose-dependent EGFR, p-ERK1/2 down-regulation and cell migration inhibition at non-toxic concentration confirms SFE activity in AGS cell migration inhibition. Thus, this study demonstrated effective chemotherapeutic potential of SFE by inducing apoptisis as well as inhibiting migration and their preliminary mechanism for human gastric cancer management.

  7. New Chiral P-N Ligands for the Regio- and Stereoselective Pd-Catalyzed Dimerization of Styrene

    Directory of Open Access Journals (Sweden)

    Sergio Castillon


    Full Text Available Two new chiral, enantiomerically pure, hybrid P-N ligands, namely (2R,5S-2-phenyl-3-(2-pyridyl-1,3-diaza-2-phosphanicyclo[3,3,0]octan-4-one (1 and (2R,5S-2-phenyl-3-(2-pyridyl-1,3-diaza-2-phosphanicyclo[3,3,0]octane (2, have been synthesized starting from L-proline. The two ligands differ in the presence or not of a carbonyl group in the diazaphosphane ring. Their coordination chemistry towards Pd(II was studied by reacting them with [Pd(CH3Cl(cod]. A different behaviour was observed: ligand 2 shows the expected bidentate chelating behaviour leading to the mononuclear Pd-complex, while ligand 1 acts as a terdentate ligand giving a dinuclear species. The corresponding cationic derivatives were obtained from the palladium neutral complexes, both as mono- and dinuclear derivatives, and tested as precatalysts for styrene dimerization, yielding E-1,3-diphenyl-1-butene regio- and stereoselectively as the sole product. A detailed analysis of the catalytic behaviour is reported.

  8. Identifikasi Komponen Minyak Atsiri Daun Kawista (Feronia limonia dengan Metode Gas Cromatography-Mass Spectroscopy (GC-MS

    Directory of Open Access Journals (Sweden)

    Saadatul Husna


    Full Text Available Indonesia has a vast variety of plants species which largely unexplored. Several researches have conducted to explore the potentials of the plants. However, the chemical constituents of Kawista plant have not been widely investigated. This study aimed to identify the components of the essential oil from Kawista leaves (Feronia limonia. This study consisted of two stages, namely the extraction of essential oil by distillation method and the analysis of the essential oil components by GC-MS method. The results showed that there are sixteen volatile components in the essential oil of Kawista leaves (Feronia limonia. They are 3-pentanol, 1-methyl siklopenatnol, 3methyl siklopentanol, 1,1-dimethyl 2-propenol, 4-tujanol, 2 methyl 3buten-2-ol, 1-(2-oksiranil etanon, 2-heksanon, 1-butanone cyclohexyl, 3-methyl 2 pentanon, 1-heksanal, 2-heksenal, 1-ethyl acetaldehyde, 2,5-tetrahidrodimethyl furan and γ-terpinen.

  9. Chemoenzymatic synthesis and properties of novel lactone-type anionic surfactants. (United States)

    Mori, Keisuke; Matsumura, Shuichi


    Two series of lactone-type surfactants with and without a hexyl side chain were prepared by the cyclocondensation of dimethyl alkanedioates with unsaturated diols, such as cis-2-butene-1,4-diol and ricinoleyl alcohol, using a lipase, followed by the addition of hydrophilic 3-mercaptopropionic acid in the presence of triethylamine. The lactone-type surfactants showed clear cmc values and surface tension lowering in aqueous solution irrespective of the hexyl side chain. It was found that the cmc values of lactone-type surfactants were lower than that of typical anionics, e.g., sodium laurate, and the cmc value became lower with increasing size of the lactone ring. The adsorption area at the surface of the aqueous lactone-type surfactant solution was larger when compared to the corresponding non-lactone-type surfactants. Lactone-type surfactants without the hexyl side chain aggregated quickly, forming 3-10 nm micelles; on the other hand, lactone-type surfactants with the hexyl side chain formed significantly larger micelles. This is due to the steric hindrance of the hexyl group on the lactone ring. The solubilization ability of the lactone-type surfactants with a hexyl side chain was superior to those without a hexyl side chain. The lactone-type surfactants showed a high foaming power and low foaming stability. They were also biodegraded by activated sludge.

  10. Characterisation of the acidity and the basicity of transition alumina by NMR and FTIR spectroscopy of adsorption of probe molecules; Caracterisation par RMN et infrarouge de molecules sondes adsorbees, de l'acidite et de la basicite d'alumines de transition

    Energy Technology Data Exchange (ETDEWEB)

    Mathonneau, E.


    This work has been devoted to characterization of the acidity and the basicity of the surface of transition alumina. Three different alumina (Alumina-{gamma}, -{delta} et -{theta} ({gamma}-Al, {delta}-Al, {theta}-Al)) have been studied by adsorption of probe molecules such trimethyl phosphine and carbon monoxide (acidity study); and tri-ethyl borane (basicity study). We emphasized that the acidity increases with an increasing pretreatment temperature where as the basicity decreases. Comparing quantitative results from the different probe molecules we could show an increasing strength acidity following: {gamma}-Al > {theta}-Al > {delta}-Al, and basicity following: {delta}-Al > {gamma}-Al > {theta}-Al. We could evaluate on a qualitative (nature and repartition) and on a quantitative point of view the impact of the transformations {gamma}-Al {yields} {delta}-Al and {gamma}-Al > {theta}-Al on the acid-basicity of the surface. We could also explain catalytic reactivity differences between alumina for the position isomerization of butene-1. (author)

  11. Kinetics of the reactions of NO/sub 3/ with OH and HO/sub 2/

    Energy Technology Data Exchange (ETDEWEB)

    Mellouki, A.; Le Bras, G.; Poulet, G.


    The kinetics of the title reactions have been studied by using the discharge flow method at 298 K. NO/sub 3/ was used in excess over OH and HO/sub 2/ and was titrated with NO or 2,3-dimethyl-2-butene. Since OH was found to be produced in the reaction of HO/sub 2/ with NO/sub 3/, the OH and HO/sub 2/ decays were analyzed by computer simulations to obtain the rate constants for the reactions OH + NO/sub 3/ ..-->.. HO/sub 2/ + NO/sub 2/ (1), HO/sub 2/ + NO/sub 3/ ..-->.. OH + NO/sub 2/ + O/sub 2/ (2a), and HO/sub 2/ + NO/sub 3/ ..-->.. HNO/sub 3/ + O/sub 2/ (2b). The results are k/sub 1/ = (2.6 +- 0.6) x 10/sup -11/ cm/sup 3/ molecule/sup -1/ s/sup -1/, k/sub 2a/ = (3.6 +- 0.9) x 10/sup -12/ cm/sup 3/ molecule/sup -1/ s/sup -1/, and k/sub 2b/ = (9.2 +- 4.8) x 10/sup -13/ cm/sup 3/ molecule/sup -1/ s/sup -1/. The data for reaction 2 are discussed in relation with the HNO/sub 3/ nighttime production in the atmospheric gas phase.

  12. Discharge flow kinetic study of NO/sub 3/ reactions with free radicals: the reaction of NO/sub 3/ with Cl

    Energy Technology Data Exchange (ETDEWEB)

    Mellouki, A.; Le Bras, G.; Poulet, G.


    The discharge flow technique was used to perform a direct measurement of the rate constant for the reaction NO/sub 3/ + Cl ..-->.. ClO + NO/sub 2/ (1) under pseudo-first-order conditions with NO/sub 3/ in excess. NO/sub 3/ was produced via the reaction F + HNO/sub 3/ ..-->.. HF + NO/sub 3/ (2) for which the rate constant was also determined: k/sub 2/ = (2.7 +/- 0.5) x 10/sup -11/ cm/sup 3/ molecule/sup -1/ s/sup -1/ at 298 K. Absolute titration of NO/sub 3/ was done using NO and 2,3-dimethyl-2-butene as the titrants. The titration experiments with NO were simulated, and the analysis of potential errors resulting from the secondary chemistry indicated that NO is a precise titrant of NO/sub 3/ in discharge flow studies. In the kinetic investigation of reaction 1, the obtained value of k/sub 1/ at 298 K was k/sub 1/ = (2.6 +/- 0.5) x 10/sup -11/ cm/sup 3/ molecule/sup -1/ s/sup -1/.

  13. OH, HO2, partially speciated RO2 and OH reactivity measurements over a range of NOx during day and night (Invited) (United States)

    Heard, D. E.; Whalley, L. K.; Gallaway, S.; Stone, D. J.; Ingham, T.; Walker, H.; Evans, M. J.


    partitioning. Measurements of HO2 at night made during the RONOCO campaign onboard the BAe-146 research aircraft will be reported with HO2 significantly higher in summer than in winter and with the highest HO2 observed for altitudes < 1.0 km. A strong positive correlation between HO2 and NO3 was observed (average r=0.89, as high as r=0.97 on one flight) and attributed to the production of HO2 from reactions of NO3 with alkenes, particularly trans-2-butene and other isomers of butene. Nighttime production of HO2 was dominated by NO3 in summer and O3 in winter. If time permits, field and laboratory studies of heterogeneous processing of HO2 by clouds and aerosols will be discussed. [1] S. Vaughan et al., Atmos. Chem. Phys., 12, 2149-2172, 2012.

  14. Insights into functional-group-tolerant polymerization catalysis with phosphine-sulfonamide palladium (II) complexes

    KAUST Repository

    Jian, Zhongbao


    Two series of cationic palladium(II) methyl complexes {[(2-MeOC6H4)2PC6H4SO2NHC6H3(2,6-R1,R2)]PdMe}2[A]2 (X1+-A: R1=R2=H: H1+-A; R1=R2=CH(CH3)2: DIPP1+-A; R1=H, R2=CF3: CF31+-A; A=BF4 or SbF6) and neutral palladium(II) methyl complexes {[(2-MeOC6H4)2PC6H4SO2NC6H3(2,6-R1,R2)]PdMe(L)} (X1-acetone: L=acetone; X1-dmso: L=dimethyl sulfoxide; X1-pyr: L=pyridine) chelated by a phosphine-sulfonamide were synthesized and fully characterized. Stoichiometric insertion of methyl acrylate (MA) into all complexes revealed that a 2,1 regiochemistry dominates in the first insertion of MA. Subsequently, for the cationic complexes X1+-A, β-H elimination from the 2,1-insertion product X2+-AMA-2,1 is overwhelmingly favored over a second MA insertion to yield two major products X4+-AMA-1,2 and X5+-AMA. By contrast, for the weakly coordinated neutral complexes X1-acetone and X1-dmso, a second MA insertion of the 2,1-insertion product X2MA-2,1 is faster than β-H elimination and gives X3MA as major products. For the strongly coordinated neutral complexes X1-pyr, no second MA insertion and no β-H elimination (except for DIPP2-pyrMA-2,1) were observed for the 2,1-insertion product X2-pyrMA-2,1. The cationic complexes X1+-A exhibited high catalytic activities for ethylene dimerization, affording butenes (C4) with a high selectivity of up to 97.7% (1-butene: 99.3%). Differences in activities and selectivities suggest that the phosphine-sulfonamide ligands remain coordinated to the metal center in a bidentate fashion in the catalytically active species. By comparison, the neutral complexes X1-acetone, X1-dmso, and X1-pyr showed very low activity towards ethylene to give traces of oligomers. DFT analyses taking into account the two possible coordination modes (O or N) of the sulfonamide ligand for the cationic system CF31+ suggested that the experimentally observed high activity in ethylene dimerization is the result of a facile first ethylene insertion into the O-coordinated PdMe isomer and

  15. Investigation of potential interferences in the detection of atmospheric ROx radicals by laser-induced fluorescence under dark conditions (United States)

    Fuchs, Hendrik; Tan, Zhaofeng; Hofzumahaus, Andreas; Broch, Sebastian; Dorn, Hans-Peter; Holland, Frank; Künstler, Christopher; Gomm, Sebastian; Rohrer, Franz; Schrade, Stephanie; Tillmann, Ralf; Wahner, Andreas


    Direct detection of highly reactive, atmospheric hydroxyl radicals (OH) is widely accomplished by laser-induced fluorescence (LIF) instruments. The technique is also suitable for the indirect measurement of HO2 and RO2 peroxy radicals by chemical conversion to OH. It requires sampling of ambient air into a low-pressure cell, where OH fluorescence is detected after excitation by 308 nm laser radiation. Although the residence time of air inside the fluorescence cell is typically only on the order of milliseconds, there is potential that additional OH is internally produced, which would artificially increase the measured OH concentration. Here, we present experimental studies investigating potential interferences in the detection of OH and peroxy radicals for the LIF instruments of Forschungszentrum Jülich for nighttime conditions. For laboratory experiments, the inlet of the instrument was over flowed by excess synthetic air containing one or more reactants. In order to distinguish between OH produced by reactions upstream of the inlet and artificial signals produced inside the instrument, a chemical titration for OH was applied. Additional experiments were performed in the simulation chamber SAPHIR where simultaneous measurements by an open-path differential optical absorption spectrometer (DOAS) served as reference for OH to quantify potential artifacts in the LIF instrument. Experiments included the investigation of potential interferences related to the nitrate radical (NO3, N2O5), related to the ozonolysis of alkenes (ethene, propene, 1-butene, 2,3-dimethyl-2-butene, α-pinene, limonene, isoprene), and the laser photolysis of acetone. Experiments studying the laser photolysis of acetone yield OH signals in the fluorescence cell, which are equivalent to 0.05 × 106 cm-3 OH for a mixing ratio of 5 ppbv acetone. Under most atmospheric conditions, this interference is negligible. No significant interferences were found for atmospheric concentrations of reactants

  16. Propriedades mecânicas e morfologia de blendas de polipropileno com Tpes Morphology and mechanical properties of polypropylenes/Tpes blends

    Directory of Open Access Journals (Sweden)

    Flávia O. M. S. Abreu


    Full Text Available Blendas de polipropileno e elastômeros termoplásticos (TPEs, estireno-b-butadieno-b-estireno (SBS e estireno-b-etileno-co-butileno-b-estireno(SEBS foram preparadas com o objetivo de avaliar a influência do tipo e da concentração do elastômero nas propriedades mecânicas e na morfologia das blendas. Foram utilizados dois tipos de polipropileno, um homopolímero de propileno (PP-H e um copolímero randômico de propileno-etileno (PP-R, sendo avaliado também o efeito das características da matriz termoplástica. O elastômero termoplástico aumentou a resistência ao impacto do PP, e a variação da rigidez das blendas foi dependente somente da quantidade de TPE adicionada, sendo estas comparativamente mais rígidas que aquelas com igual teor de elastômero convencional, tipo EPDM e EPR. A blenda com melhor balanço rigidez-impacto foi aquela de PP-R com 10% de SEBS. As blendas do copolímero de propileno-etileno com os TPEs apresentaram maior deformação do que aquelas com o homopolímero, devido à natureza menos cristalina da matriz do copolímero de propileno. As blendas tanto do homo quanto do copolímero de propileno com SEBS ficaram mais homogêneas em função da maior afinidade do bloco central poliolefínico EB (etileno-co-butileno do primeiro com a região amorfa da matriz, sendo esta mais significativa no PP-R.Blends of polypropylene and thermoplastic elastomers (TPEs of styrene-butadiene-styrene (SBS and styrene-ethylene-co-butene-styrene (SEBS triblock copolymers were prepared to evaluate the effect of the elastomer and its concentration on the material properties. For this purpose, a polypropylene homopolymer (PP-H and a propylene-ethylene random copolymer (PP-R were used to evaluate the matrix effect on the tensile properties and morphology of the blends. The addition of TPEs to PP promotes increase on impact resistance and the PP-R/SEBS 10%wt blend showed the best balance in stiffness-impact resistance. The morphology of

  17. Oligomer formation during gas-phase ozonolysis of small alkenes and enol ethers: new evidence for the central role of the Criegee Intermediate as oligomer chain unit

    Directory of Open Access Journals (Sweden)

    A. Sadezky


    Full Text Available An important fraction of secondary organic aerosol (SOA formed by atmospheric oxidation of diverse volatile organic compounds (VOC has recently been shown to consist of high-molecular weight oligomeric species. In our previous study (Sadezky et al., 2006, we reported the identification and characterization of oligomers as main constituents of SOA from gas-phase ozonolysis of small enol ethers. These oligomers contained repeated chain units of the same chemical composition as the main Criegee Intermediates (CI formed during the ozonolysis reaction, which were CH2O2 (mass 46 for alkyl vinyl ethers (AVE and C2H4O2 (mass 60 for ethyl propenyl ether (EPE. In the present work, we extend our previous study to another enol ether (ethyl butenyl ether EBE and a variety of structurally related small alkenes (trans-3-hexene, trans-4-octene and 2,3-dimethyl-2-butene.

    Experiments have been carried out in a 570 l spherical glass reactor at atmospheric conditions in the absence of seed aerosol. SOA formation was measured by a scanning mobility particle sizer (SMPS. SOA filter samples were collected and chemically characterized off-line by ESI(+/TOF MS and ESI(+/TOF MS/MS, and elemental compositions were determined by ESI(+/FTICR MS and ESI(+/FTICR MS/MS. The results for all investigated unsaturated compounds are in excellent agreement with the observations of our previous study. Analysis of the collected SOA filter samples reveal the presence of oligomeric compounds in the mass range 200 to 800 u as major constituents. The repeated chain units of these oligomers are shown to systematically have the same chemical composition as the respective main Criegee Intermediate (CI formed during ozonolysis of the unsaturated compounds, which is C3H6O2 (mass 74 for ethyl butenyl ether (EBE, trans-3-hexene, and 2,3-dimethyl-2-butene, and C4H8

  18. Study of the Thermodynamics (Thermal and Cl Catalyzed) and Kinetics of the Cis and Trans Isomerizations of CF3CF═CHF, CF3CH═CHCF3, and CH3CH═CHCH3 in 100-950 Torr of N2 Diluent at 296-875 K: Effect of F and CF3 Substitution on the Isomerization Process Including the Fluorine "Cis Effect". (United States)

    Kaiser, E W; Pierce, David S


    The equilibrium constants for the Z to E isomerizations of CF3CF═CHF (K1) and CF3CH═CHCF3 (K2) have been measured using GC/FID analysis over the temperature ranges 360–850 and 297–850 K, respectively. At lower temperature, K was determined using Cl atom catalysis. At higher temperature, K was measured without a catalyst. The temperature-dependent expressions are K1 (Z to E) = 1.45(±0.15)e(–[2845(±100)/RT]) and K2 (Z to E) = 1.9(±0.22)e(+[4330(±120)/RT]) (where the gas constant R ≡ 1.986 cal mol(–1) K(–1)). For isomerization 1, the Z (fluorine cis) isomer is 2.85 kcal mol(–1) lower in energy than the E (fluorine trans) isomer, providing another example of the fluorine "cis effect" in olefins. For isomerization 2, the E(trans) isomer is 4.3 kcal mol(–1) lower in energy than the corresponding Z(cis) isomer as is normal for olefins. The isomerization rate constant in a single direction was also measured for each fluorinated compound: k–1(E to Z) = 10(13.87±0.24)e(–59530(±887)/RT) s(–1); and k2(Z to E) = 10(13.89±0.23)e(–58845(±675)/RT) s(–1). To verify the experimental method, cis to trans (k3) and trans to cis (k–3) isomerization rate constants were also measured for cis- and trans-2-butene for comparison to several previous studies. The rate constants determined herein are k3 (cis to trans) = 10(13.95±0.23)e(–63245(±815)/RT) s(–1); and k–3 (trans to cis) = 10(14.32±0.28)e(–64993(±1132)/RT) s(–1). k3 agrees well with four previous measurements and represents the best available rate constant for 2-butene. All errors quoted here are 2σ. The typical total pressure for these experiments was 760 ± 100 Torr. Limited experiments performed at 100 Torr showed no pressure dependence for any of the compounds above 100 Torr. Thus, all isomerization rate constants represent high-pressure limits. The rates of the addition reactions of Cl to the double bonds of CF3CF═CHF (k4) and CF3CH═CHCF3 (k7) (used in Cl catalysis) were

  19. Methods for measurement of reactive metabolites as a basis for cancer risk assessment: Application to 1,3-butadiene and isoprene

    Energy Technology Data Exchange (ETDEWEB)

    Fred, Charlotta [Stockholm Univ. (Sweden). Dept. of Environmental Chemistry


    1,3-Butadiene is a general air pollutant associated with combustion of organic matter and is also an extensively used monomer in polymer production. The cancer risk estimation of 1,3-butadiene is encumbered with large uncertainties. Extrapolation from tumour frequencies in long-term animal tests has led to a relatively high figure for the risk associated with 1,3-butadiene exposure. This is mainly based on observations of very high tumour incidences in butadiene-exposed mice, which in this respect are about 100 times more sensitive than rats. It has been hypothesized that a high cancer risk from 1,3-butadiene could be associated with its metabolism to the bifunctional 1,2:3,4-diepoxybutane (DEB) which, in comparison with monofunctional epoxides, 1,2-epoxy-3-butene (EB) and 1,2-epoxy-3,4-butanediol (EBdiol), is a highly effective mutagen, i.e. cancer initiator. Measurement of in vivo doses of DEB is therefore essential for the risk assessment of 1,3-butadiene. Reaction products with hemoglobin offer a possibility of measuring reactive metabolites in vivo. Hemoglobin adducts from EBdiol have in this study been measured with available methods, which are, however, not applicable to the bifunctional DEB, and method development was therefore needed. This work presents a procedure for measurement of a specific, ring-closed adduct, Pyr-Val, formed from the reaction of DEB with N-terminal valines in hemoglobin. It is based on LC-ESI-MS/MS analysis of the Pyr-modified N-terminal peptides enriched after trypsin digestion of globin. Mouse and rat could be compared regarding the metabolism of EB, DEB and EBdiol. From the data it was concluded that, in 1,3-butadiene exposure, about 60 times higher levels of DEB are formed in mice compared to rats. Estimates of in vivo doses in published cancer tests showed that carcinogenesis in mice is mainly due to DEB, whereas in rat, and possibly man, the monofunctional EBdiol is the predominant causative factor. Preliminarily, the cancer


    Energy Technology Data Exchange (ETDEWEB)



    Houston's ozone problem has been linked to the occurrence of very high light olefin concentrations. We have analyzed the DOE G-1 aircraft hydrocarbon data set to provide additional information on the geographic distribution and prevalence of air samples with high olefin concentration as well as an identification of other compounds which contribute to the high hydrocarbon reactivity in Houston. In order to identify high concentrations we need a definition of normal. For that purpose we use aircraft samples collected during a 1999 aircraft based field campaign in Philadelphia relying on the circumstance that the frequency distributions of NO{sub x} and C{sub 2}H{sub 2} in Philadelphia are nearly the same as in Houston. Comparison is made also with hydrocarbons collected in Phoenix which exhibit nearly the same NO{sub x} and C{sub 2}H{sub 2} frequency distribution as the other 2 cities, but in spite of that similarity have a much lower hydrocarbon reactivity. As in other studies we find that there is a subset of Houston hydrocarbon samples with very high OH-reactivity due to elevated concentrations of ethylene, propylene and less often butenes, including 1,3 butadiene. Although these samples stand out as being qualitatively different we present evidence that ethylene and propylene are significantly elevated in at least half of the Houston samples, covering a wide geographic area apart from the Ship Channel region. Frequency distributions for these compounds are log normal suggesting that Houston's atmosphere is a single entity rather than separate industrial and urban areas. The comparison between Houston and Philadelphia also identifies C{sub 2}-C{sub 5} alkanes, n-hexane, and benzene as having elevated concentrations. Emission reductions of these less reactive compounds sufficient to yield the concentrations observed in Philadelphia would have a minor effect on the most reactive samples, but about a 20% effect on samples with more typical (median

  1. Single-Site Cobalt Catalysts at New Zr 82 -O) 82 -OH) 4 Metal-Organic Framework Nodes for Highly Active Hydrogenation of Alkenes, Imines, Carbonyls, and Heterocycles

    Energy Technology Data Exchange (ETDEWEB)

    Ji, Pengfei; Manna, Kuntal; Lin, Zekai; Urban, Ania; Greene, Francis X.; Lan, Guangxu; Lin, Wenbin


    We report here the synthesis of robust and porous metal–organic frameworks (MOFs), M-MTBC (M = Zr or Hf), constructed from the tetrahedral linker methane-tetrakis(p-biphenylcarboxylate) (MTBC) and two types of secondary building units (SBUs): cubic M82-O)82-OH)4 and octahedral M6(μ3-O)43-OH)4. While the M6-SBU is isostructural with the 12-connected octahedral SBUs of UiO-type MOFs, the M8-SBU is composed of eight MIV ions in a cubic fashion linked by eight μ2-oxo and four μ2-OH groups. The metalation of Zr-MTBC SBUs with CoCl2, followed by treatment with NaBEt3H, afforded highly active and reusable solid Zr-MTBC-CoH catalysts for the hydrogenation of alkenes, imines, carbonyls, and heterocycles. Zr-MTBC-CoH was impressively tolerant of a range of functional groups and displayed high activity in the hydrogenation of tri- and tetra-substituted alkenes with TON > 8000 for the hydrogenation of 2,3-dimethyl-2-butene. Our structural and spectroscopic studies show that site isolation of and open environments around the cobalt-hydride catalytic species at Zr8-SBUs are responsible for high catalytic activity in the hydrogenation of a wide range of challenging substrates. MOFs thus provide a novel platform for discovering and studying new single-site base-metal solid catalysts with enormous potential for sustainable chemical synthesis.

  2. Conversion of Dimethyl Ether to Branched Hydrocarbons Over Cu/BEA: the Roles of Lewis Acidic and Metallic Sites in H2 Incorporation

    Energy Technology Data Exchange (ETDEWEB)

    Hensley, Jesse E.; Schaidle, Joshua A.; Ruddy, Daniel A.; Cheah, Singfoong; Habas, Susan E.; Pan, Ming; Zhang, Guanghui; Miller, Jeffrey T.


    Conversion of biomass to fuels remains as one of the most promising approach to support our energy needs. It has been previously shown that the gasification of non-edible cellulosic biomass can be used to derive fuels like methanol and dimethyl ether (DME). However, the use of methanol and DME is limited due to the fact that they have low energy densities, poor lubricity and lower viscosity when compared to long-chain hydrocarbons. Increasing the blending percentage can also lead to undesired amounts of oxygenated molecules in the transportation fuel infrastructure, which restrict their applicability as jet or diesel fuels. Consequently, the petroleum-derived hydrocarbons remain as the main constituent of the middle-distillate based fuels. One way to increase the share of biofuels in middle-distillates is to use methanol/DME as building blocks for producing renewable, energy-dense hydrocarbons. One way to achieve this is by catalytically converting the DME and methanol to light olefins, followed by oligomerization to higher molecular weight premium alkanes, which can directly be used as kerosene/diesel fuels. Here, we report the catalytic dimerization of biomass-derived deoxygenated olefins into transportation fuel-range hydrocarbons under liquid-phase stirred-batch conditions. Specifically, the effect of operating conditions, such as reaction temperature, solvent-type, reaction duration and olefin-structure, on the conversion, selectivity and kinetics of dimerization of triptene (2,3,3-trimethyl-1-butene) were investigated. Triptene, as previously reported, is one of the major products of DME-homologation reaction over a BEA zeolite4. We show that triptene can be converted to high quality middle-distillates using a commercially available ion-exchange acid resin, Amberlyst-35 (dry) by the process of catalytic dimerization.

  3. A continuous fluorescent assay for the determination of plasma and tissue angiotensin I-converting enzyme activity

    Directory of Open Access Journals (Sweden)

    Alves M.F.


    Full Text Available A continuous assay using internally quenched fluorescent peptides with the general sequence Abz-peptidyl-(DnpP-OH (Abz = ortho-aminobenzoic acid; Dnp = 2,4-dinitrophenyl was optimized for the measurement of angiotensin I-converting enzyme (ACE in human plasma and rat tissues. Abz-FRK(DnpP-OH, which was cleaved at the Arg-Lys bond by ACE, was used for the enzyme evaluation in human plasma. Enzymatic activity was monitored by continuous recording of the fluorescence (lambdaex = 320 nm and lambdaem = 420 nm at 37ºC, in 0.1 M Tris-HCl buffer, pH 7.0, with 50 mM NaCl and 10 µM ZnCl2. The assays can be performed directly in the cuvette of the fluorimeter and the hydrolysis followed for 5 to 10 min. ACE measurements in the plasma of 80 healthy patients with Hip-His-Leu and with Abz-FRK(DnpP-OH correlated closely (r = 0.90, P < 0.001. The specificity of the assay was demonstrated by the complete inhibition of hydrolysis by 0.5 µM lisinopril or captopril. Abz-FRK(DnpP-OH cleavage by ACE was monitored in rat lung, kidney, heart, and liver homogenates in the presence of a cocktail of inhibitors containing trans-epoxy-succinyl-L-leucylamido-(4-guanido-butene, pepstatin, phenyl-methylsulfonyl fluoride, N-tosyl-L-phenylalanyl-chloromethyl ketone, and N-tosyl-lysyl-chloromethyl ketone to prevent undesirable hydrolysis. ACE activity in lung, heart and kidney homogenates, but not in liver homogenates, was completely abolished by 0.5 µM lisinopril or captopril. The advantages of the method are the procedural simplicity and the high sensitivity providing a rapid assay for ACE determinations.

  4. Polyphenylenesulfide, noxon® an ozone scavenger for the analysis of oxygenated terpenes in air (United States)

    Calogirou, A.; Duane, M.; Kotzias, D.; Lahaniati, M.; Larsen, B. R.

    During sampling, oxygenated terpenes may undergo decomposition through reaction with atmospheric ozone. We have studied their ozonolytic decomposition during preconcentration on Tenax. The saturated. terpenoids 1,8-cineole, bornyl acetate nopinone and pinonaldehyde are practically unaffected by ozone in the range of 8 to 120 ppbv. Compounds which contain one or more C-C double bonds are decomposed in the order: linalool ≈ citronellal ≈ 6-methyl-5-hepten-2-one > citral > 4-acetyl-1-methyl-cyclohexane > 3-(1-methylethenyl)-6-oxo-heptanal > myrtenal ≈ 2-methyl-3-buten-2-ol. The degree of decomposition varies from 0 to 5% for the least reactive to 80 to 90% for the most reactive compounds. A broad range of material was investigated as potential ozone scavengers. By using the polymer noXon (polyphenylenesulfide) all the investigated compounds could be sampled with quantitative recoveries even at high ozone mixing ratios (95-110 ppbv). This ozone scrubber was tested for sampling of terpene oxidation products on Tenax and dinitrophenylhydrazine impregnated C 18-silicagel cartridges. Recoveries from 85 to 110% were obtained for all investigated compounds. The method was used for the analysis of oxidation products of terpenes in ambient air in three campaigns. Attention was focused on nopinone from β-pinene, pinonaldehyde from α-pinene, 3-(1-methylethenyl)-6-oxo-heptanal and 4-acetyl-1-methyl-cyclohexane from limonene, and 5-(1-methylethyl)-bicyclo[3.1.0] hexan-2-one from sabinene. Nopinone was the only product which could be frequently detected in ratios from 0 to 90% of the measured β-pinene concentrations. Pinonaldehyde was encountered only once (30% of α-pinene) while the other products were not found. These data have to be seen as a first attempt to measure terpene oxidation products in the troposphere.

  5. Rate coefficients for the reaction of OH radicals with cis-3-hexene: an experimental and theoretical study. (United States)

    Barbosa, Thaís da Silva; Peirone, Silvina; Barrera, Javier A; Abrate, Juan P A; Lane, Silvia I; Arbilla, Graciela; Bauerfeldt, Glauco Favilla


    The kinetics of the cis-3-hexene + OH reaction were investigated by an experimental relative rate method and at the density functional theory level. The experimental set-up consisted of a 200 L Teflon bag, operated at atmospheric pressure and 298 K. OH radicals were produced by the photolysis of H2O2 at 254 nm. Relative rate coefficients were determined by comparing the decays of the cis-3-hexene and reference compounds (cyclohexene, 2-buten-1-ol and allyl ether). The mean second-order rate coefficient value found was (6.27 ± 0.66) × 10(-11) cm(3) molecule(-1) s(-1), the uncertainty being estimated by propagation of errors. Theoretical calculations for the addition reaction of OH to cis-3-hexene have also been performed, at the BHandHLYP/aug-cc-pVDZ level, in order to investigate the reaction mechanism, to clarify the experimental observations and to model the reaction kinetics. Different conformations of the reactants, pre-barrier complexes and saddle points were considered in our calculations. The individual rate coefficients, calculated for each conformer of the reactant, at 298 K, using a microcanonical variational transition state method, are 4.19 × 10(-11) and 1.23 × 10(-10) cm(3) molecule(-1) s(-1). The global rate coefficient was estimated from the Boltzmann distribution of the conformers to be 8.10 × 10(-11) cm(3) molecule(-1) s(-1), which is in agreement with the experimental value. Rate coefficients calculated over the temperature range from 200-500 K are also given. Our results suggest that the complex mechanism, explicitly considering different conformations for the stationary points, must be taken into account for a proper description of the reaction kinetics.

  6. On the radiolysis of ethylene ices by energetic electrons and implications to the extraterrestrial hydrocarbon chemistry

    Energy Technology Data Exchange (ETDEWEB)

    Zhou, Li [Department of Chemistry, Nanchang University, Nanchang 330031 (China); Maity, Surajit; Abplanalp, Matt; Turner, Andrew; Kaiser, Ralf I., E-mail: [Department of Chemistry, University of Hawaii at Manoa, Honolulu, HI 96822 (United States)


    The chemical processing of ethylene ices (C{sub 2}H{sub 4}) by energetic electrons was investigated at 11 K to simulate the energy transfer processes and synthesis of new molecules induced by secondary electrons generated in the track of galactic cosmic ray particles. A combination of Fourier transform infrared spectrometry (solid state) and quadrupole mass spectrometry (gas phase) resulted in the identification of six hydrocarbon molecules: methane (CH{sub 4}), the C2 species acetylene (C{sub 2}H{sub 2}), ethane (C{sub 2}H{sub 6}), the ethyl radical (C{sub 2}H{sub 5}), and—for the very first time in ethylene irradiation experiments—the C4 hydrocarbons 1-butene (C{sub 4}H{sub 8}) and n-butane (C{sub 4}H{sub 10}). By tracing the temporal evolution of the newly formed molecules spectroscopically online and in situ, we were also able to fit the kinetic profiles with a system of coupled differential equations, eventually providing mechanistic information, reaction pathways, and rate constants on the radiolysis of ethylene ices and the inherent formation of smaller (C1) and more complex (C2, C4) hydrocarbons involving carbon-hydrogen bond ruptures, atomic hydrogen addition processes, and radical-radical recombination pathways. We also discuss the implications of these results on the hydrocarbon chemistry on Titan's surface and on ice-coated, methane-bearing interstellar grains as present in cold molecular clouds such as TMC-1.

  7. Organic Compounds, WSOC, and OC in summer aerosol during SOAS 2013 from RTP, NC and Centerville, AL (United States)

    Jaoui, M.; Kleindienst, T. E.; Offenberg, J. H.; Lewandowski, M.; Docherty, K.


    PM2.5 samples were taken from an intensive field study conducted during 2013 Southern Oxidant Aerosol Study (SOAS) campaign from sites at Research Triangle Park (RTP) in Durham, NC and Centerville (CTR), AL to investigate the composition of organic compounds in the particle phase. These samples were subjected to solvent extraction, followed by BSTFA derivatization, then the derivatized extracts were analyzed by GC-MS for primary and secondary organic compounds. A set of tracer compounds are used to estimate the contributions from secondary sources using a mass fraction method. In addition to organic carbon, a second set of samples was used for water soluble organic compounds (WSOC) analysis. The chemical analysis of PM2.5 originated from these two sites show the presence of a series of organic compounds associated with biogenic (e.g. isoprene, monoterpene, sesquiterpenes (SQT), 2-methyl-3-buten-2-ol (MBO)) and anthropogenic (e.g. 1, 3-butadiene, benzene, naphthalene, and toluene) sources. The link between the source of these compounds and ambient aerosol was demonstrated in our laboratory by conducting a series of smog chamber experiments under a wide range of conditions. An organic tracer-based method was then used to estimate ambient SOA and the contribution of individual SOA precursors, which allows assessment of model predictions using ambient data. Other organic compounds were also identified and quantified (e.g. phthalic acid and levoglucosan). A comparison of the concentration of tracer compounds obtained in RTP and Centerville sites shows that isoprene and monoterpene tracers were measured at high concentrations compared to other site previously analyzed in our laboratory. SQT and toluene tracers were detected at low concentrations. MBO tracer was detected at relatively high concentrations compared to others sites. 1, 3-Butadiene tracers were present and consistent throughout the sampling period. Comparison between WSOC, organic carbon, and biomass burning

  8. Production and use of light olefins. Preprints of the conference

    Energy Technology Data Exchange (ETDEWEB)

    Ernst, S.; Buzzoni, R.; Leitner, W.; Lercher, J.A.; Lichtscheidl, J.; Nees, F.; Santacesaria, E. (eds.)


    Within the conference of the German Society for Petroleum and Coal Science and Technology e.V. (Hamburg, Federal Republic of Germany) in Berlin (Federal Republic of Germany) at 28th to 30th September, 2009, the following lectures were held: (1) Steamcracking - State of the Art (H. Zimmermann); (2) Diversify Feedstock Options to Olefin Production (Q. Ling et al.); (3) Syngas to lower olefins (E. Schwab et al.); (4) STAR process registered for the on-purpose production of propylene (K. Bueker); (5) The catalytic activity of zinc oxide supported on aerosil for C-H activation of light alkanes (S. Arndt et al.); (6) Novel catalytic approaches for the oxidative dehydrogenation of ethane (D. Hartmann); (7) A comparison of the active sites structures of homogeneous and heterogeneous olefin polymerisation catalysts (A. Zecchina); (8) Catalytic strategies in metathesis (C. Coperet); (9) Multi-technology integrated production and consumption of olefins (J. Popp et al.); (10) Olefin oligomerization for the production of fuels and petrochemicals (H. Olivier-Bourbigou et al.); (11) Dieselization of the world - How to increase diesel yield in a refinery (A. Dueker); (12) Isomerization of butenes: LyondellBasell's Isomplus technology development (T. Zak et al.); (13) Valuable products from butadiene, carbon dioxide and further base chemicals (A. Behr); (14) The partial oxidation of propene to propylene oxide using N{sub 2}O as an oxidant (T. Thoemmes); (15) Alternative feedstocks for olefin production: What role will ethanol play? (B.R. Maughon); (16) Production of light olefins from renewable resources - The effect of deoxygenation degree on yields of light olefins (D. Kubicka et al.); (17) Recovery of low olefins from refinery offgases (M. Bender).

  9. Oxidative dehydrogenation of n-butane over magnesium vanadate nano-catalysts supported on magnesia-zirconia: effect of vanadium content. (United States)

    Lee, Jong Kwon; Hong, Ung Gi; Yoo, Yeonshick; Cho, Young-Jin; Lee, Jinsuk; Chang, Hosik; Song, In Kyu


    Magnesia-zirconia (MgO-ZrO2) support was prepared by a sol-gel method, and magnesium vanadate nano-catalysts supported on magnesia-zirconia (X-Mg3(VO4)2/MgO-ZrO2) were then prepared by a wet impregnation method with a variation of vanadium content (X = 6.6, 9.9, 12.8, 15.2, and 19.1 wt%). X-Mg3(VO4)2/MgO-ZrO2 nano-catalysts were applied to the oxidative dehydrogenation of n-butane to n-butene and 1,3-butadiene. The formation of X-Mg3(VO4)2/MgO-ZrO2 nano-catalysts was well confirmed by XRD, XPS, and ICP-AES analyses. 15.2-Mg3(VO4)2/MgO-ZrO2 and 19.1-Mg3(VO4)2/MgO-ZrO2 catalysts experienced a catalyst deactivation, while the other Mg3(VO4)2/MgO-ZrO2 catalysts showed a stable catalytic performance during the whole reaction time. The effect of oxygen property of X-Mg3(VO4)2/MgO-ZrO2 nano-catalysts on the catalytic performance in the oxidative dehydrogenation of n-butane was investigated. Experimental results revealed that oxygen capacity of the catalyst was closely related to the catalytic performance, while oxygen mobility of the catalyst played an important role in the catalyst stability. Among the catalysts tested, 12.8-Mg3(VO4)2/MgO-ZrO2 catalyst showed the best catalytic performance in terms of yield for TDP (total dehydrogenation products).


    Energy Technology Data Exchange (ETDEWEB)



    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.

  11. Characterization of antiproliferative activity constituents from Artocarpus heterophyllus. (United States)

    Zheng, Zong-Ping; Xu, Yang; Qin, Chuan; Zhang, Shuang; Gu, Xiaohong; Lin, Yingying; Xie, Guobin; Wang, Mingfu; Chen, Jie


    Artocarpus heterophyllus is an evergreen fruit tree cultivated in many tropical regions. Previous studies have shown that some of its compositions exhibited potential tyrosinase inhibition activities. This study indentified 8 new phenolic compounds, artoheterophyllins E-J (1-6), 4-geranyl-2',3,4',5-tetrahydroxy-cis-stilbene (7), and 5-methoxymorican M (8) and 2 new natural compounds (9 and 10), 2,3-dihydro-5,7-dihydroxy-2-(2-hydroxy-4-methoxyphenyl)-4H-benzopyran-4-one and 6-[(1S,2S)-1,2-dihydroxy-3-methylbutyl]-2-(2,4-dihydroxyphenyl)-5-hydroxy-7-methoxy-3-(3-methyl-2-buten-1-yl)-4H-1-benzopyran-4-one, together with 23 known compounds (11-33), from the ethanol extract of the wood of A. heterophyllus. The structures of the eight new compounds (1-8) and two new natural compounds were established by extensive 1D- and 2D-NMR experiments. The anticancer effects of the isolated compounds were examined in MCF-7, H460, and SMMC-7721 human cancer cell lines by MTT assay. Compounds 5, 11, 12, and 30 significantly reduced the cell viabilities of these cell lines. Especially, compounds 11 and 30 resulted in more potent cytotoxicity than the positive control, 5-fluorouracil (5-Fu), in SMMC-7721 cell line, with IC50 values of 15.85 and 12.06 μM, whereas compound 30 exhibited more potent cytotoxicity than 5-Fu in NCI-H460 cell line, with an IC50 value of 5.19 μM. In addition, this study suggests that compounds 11 and 30 from the wood of A. heterophyllus have anticancer potential via MAPK pathways.

  12. Active groups for oxidative activation of C-H bond in C{sub 2}-C{sub 5} paraffins on V-P-O catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Zazhigalov, V.A. [AN Ukrainskoj SSR, Kiev (Ukraine). Inst. Fizicheskoj Khimii


    For the first time in scientific literature, in our joint work with Dr. G. Ladwig in 1978 it was established phase portraite of the oxide vanadium-phosphorus system within wide range of P/V ratios from 0.5 to 3.2. Some later those data were confirmed. By investigation of the properties of individual vanadium-phosphorus phases it was also shown that the active component of such catalysts in n-butane oxidation was vanadyl pyrophosphate phase (VO){sub 2}Pr{sub 2}O{sub 7}. From then the conclusion has been evidenced by numerous publications and at present it has been out of doubt practically all over the world. It was hypothized that the unique properties of (VO){sub 2}P{sub 2}O{sub 7} in the reaction of n-butane oxidation could be explained by the presence of paired vanadyl groups and nearness of the distances between neighbouring vanadyl pairs and that between the first and fourth carbon atoms in n-butane molecule. The molecule activation occured at the latter atoms by proton abstraction. A comparison of the results on n-butane and butenes oxidation over vanadyl pyrophosphate allowed to conclude that the paraffin oxidation did not take place due to the molecule dehydrogenation process at the first stage of its conversion. Up to now, more than 100 papers related to paraffins oxidation over vanadyl pyrophosphate and the physico-chemical properties of the catalyst have been published. The process of n-butane oxidation is realized in practice. But still, the question about the nature of active sites of the catalyst and the reaction mechanism remains open and provokes further investigations. The present paper deals with our opinion about the problem and the experimental results supporting it. (orig.)

  13. Diphosphines with expandable bite angles: highly active ethylene dimerisation catalysts based on upper rim, distally diphosphinated calix[4]arenes. (United States)

    Lejeune, Manuel; Sémeril, David; Jeunesse, Catherine; Matt, Dominique; Peruch, Frédéric; Lutz, Pierre J; Ricard, Louis


    The binding properties of two large diphosphines, cone-5,17-dibromo-11,23-bis(diphenylphosphino)-25,26,27,28-tetrapropoxycalix[4]arene (1) and cone-5,17-bis(diphenylphosphino)-25,26,27,28-tetrapropoxycalix[4]arene (2) toward Ni(II) centres have been investigated. Whatever the starting complex, NiBr2 or [NiCp]BF4, quantitative formation of a chelate complex was observed, illustrating the preorganisation of the ligands. An X-ray structure determination was carried out for [NiCp1]BF4 which revealed that the nickel atom is positioned to one side of the calixarene axis, the PNiP plane being roughly parallel to the calixarene reference plane. The molecule has C(1) symmetry in the solid state, a feature which is also observed in solution at low temperature. As shown by variable-temperature 1H and 31P NMR studies, the complex undergoes two distinct motions: 1) a fan-like swinging of the coordination plane which displaces the metal from one side of the calixarene axis to the other, a motion during which the PNiP angle is likely to undergo a significant enlargement; 2) a rapid oscillation of each PPh2 unit about the corresponding Ni--P bond. In the latter dynamics the two endo-oriented PPh rings alternately occupy the calixarene entry. The two flexible ligands were assessed in ethylene oligomerisation. Activation with methylaluminoxane of the paramagnetic complexes [NiBr2.(1 or 2)] afforded highly active ethylene dimerisation catalysts, with turnover frequencies up to 10(6) (mol C2H4) (mol Ni)(-1) h(-1). The selective formation of 1-butene can be rationally controlled by using low catalyst concentrations.

  14. Influences of the molecular fuel structure on combustion reactions towards soot precursors in selected alkane and alkene flames. (United States)

    Ruwe, Lena; Moshammer, Kai; Hansen, Nils; Kohse-Höinghaus, Katharina


    In this study, we experimentally investigate the high-temperature oxidation kinetics of n-pentane, 1-pentene and 2-methyl-2-butene (2M2B) in a combustion environment using flame-sampling molecular beam mass spectrometry. The selected C 5 fuels are prototypes for linear and branched, saturated and unsaturated fuel components, featuring different C-C and C-H bond structures. It is shown that the formation tendency of species, such as polycyclic aromatic hydrocarbons (PAHs), yielded through mass growth reactions increases drastically in the sequence n-pentane fuel-dependent reaction sequences of the gas-phase combustion mechanism that provide explanations for the observed difference in the PAH formation tendency. First, we investigate the fuel-structure-dependent formation of small hydrocarbon species that are yielded as intermediate species during the fuel decomposition, because these species are at the origin of the subsequent mass growth reaction pathways. Second, we review typical PAH formation reactions inspecting repetitive growth sequences in dependence of the molecular fuel structure. Third, we discuss how differences in the intermediate species pool influence the formation reactions of key aromatic ring species that are important for the PAH growth process underlying soot formation. As a main result it was found that for the fuels featuring a C[double bond, length as m-dash]C double bond, the chemistry of their allylic fuel radicals and their decomposition products strongly influences the combination reactions to the initially formed aromatic ring species and as a consequence, the PAH formation tendency.

  15. Attraction modulated by spacing of pheromone components and anti-attractants in a bark beetle and a moth. (United States)

    Andersson, Martin N; Binyameen, Muhammad; Sadek, Medhat M; Schlyter, Fredrik


    Orientation for insects in olfactory landscapes with high semiochemical diversity may be a challenging task. The partitioning of odor plumes into filaments that are interspersed with pockets of 'clean air' may help filament discrimination and upwind flight to attractive sources in the face of inhibitory signals. We studied the effect of distance between odor sources on trap catches of the beetle, Ips typographus, and the moth, Spodoptera littoralis. Insects were tested both to spatially separated pheromone components [cis-verbenol and 2-methyl-3-buten-2-ol for Ips; (Z,E)-9,11-tetradecadienyl acetate and (Z,E)-9,12-tetradecadienyl acetate for Spodoptera], and to separated pheromone and anti-attractant sources [non-host volatile (NHV) blend for Ips; (Z)-9-tetradecenyl acetate for Spodoptera]. Trap catch data were complemented with simulations of plume structure and plume overlap from two separated sources using a photo ionization detector and soap bubble generators. Trap catches of the beetle and the moth were both affected when odor sources in the respective traps were increasingly separated. However, this effect on trap catch occurred at smaller (roughly by an order of magnitude) odor source separation distances for the moth than for the beetle. This may reflect differences between the respective olfactory systems and central processing. For both species, the changes in trap catches in response to separation of pheromone components occurred at similar spacing distances as for separation of pheromone and anti-attractant sources. Overlap between two simulated plumes depended on distance between the two sources. In addition, the number of detected filaments and their concentration decreased with downwind distance. This implies that the response to separated odor sources in the two species might take place under different olfactory conditions. Deploying multiple sources of anti-attractant around a pheromone trap indicated long-distance (meter scale) effects of NHV on

  16. Importance of biogenic precursors to the budget of organic nitrates: observations of multifunctional organic nitrates by CIMS and TD-LIF during BEARPEX 2009

    Directory of Open Access Journals (Sweden)

    M. R. Beaver


    Full Text Available Alkyl and multifunctional organic nitrates, molecules of the chemical form RONO2, are products of chain terminating reactions in the tropospheric HOx and NOx catalytic cycles and thereby impact ozone formation locally. Many of the molecules in the class have lifetimes that are long enough that they can be transported over large distances. If the RONO2 then decompose to deliver NOx to remote regions they affect ozone production rates in locations distant from the original NOx source. While measurements of total RONO2 (ΣANs and small straight chain alkyl nitrates are routine, measurements of the specific multifunctional RONO2 molecules that are believed to dominate the total have rarely been reported and never reported in coincidence with ambient ΣANs measurements. Here we describe observations obtained during the BEARPEX 2009 experiment including ΣANs and a suite of multifunctional nitrates including isoprene derived hydroxynitrates, oxidation products of those nitrates, 2-methyl-3-buten-2-ol (MBO derived hydroxynitrates, and monoterpene nitrates. At the BEARPEX field site, the sum of the individual biogenically derived nitrates account for two-thirds of the ΣANs, confirming predictions of the importance of biogenic nitrates to the NOy budget. Isoprene derived nitrates, transported to the site, are a much larger fraction of the ΣANs at the site than the nitrates derived from the locally emitted MBO. Evidence for additional nitrates, possibly from nocturnal chemistry of isoprene and α-pinene, is presented.

  17. The sedative effect of non-alcoholic beer in healthy female nurses.

    Directory of Open Access Journals (Sweden)

    Lourdes Franco

    Full Text Available INTRODUCTION: The hop (Humulus lupulus L., a component of beer, is a sedative plant whose pharmacological activity is principally due to its bitter resins, in particular to the α-acid degradation product 2-methyl-3-buten-2-ol. The mechanism of action of hop resin consists of raising the levels of the neurotransmitter γ-aminobutyric acid (GABA, an inhibitory neurotransmitter acting in the central nervous system (CNS. OBJECTIVES: To analyze the sedative effect of hops as a component of non-alcoholic beer on the sleep/wake rhythm in a work-stressed population. METHODS: The experiment was conducted with healthy female nurses (n = 17 working rotating and/or night shifts. Overnight sleep and chronobiological parameters were assessed by actigraphy (Actiwatch® after moderate ingestion of non-alcoholic beer containing hops (333 ml with 0.0% alcohol with supper for 14 days (treatment. Data were obtained in comparison with her own control group without consumption of beer during supper. RESULTS: Actigraphy results demonstrated improvement of night sleep quality as regards the most important parameters: Sleep Latency diminished (p≤0.05 in the Treatment group (12.01±1.19 min when compared to the Control group (20.50±4.21 min, as also did Total Activity (p≤0.05; Treatment group = 5284.78±836.99 activity pulses vs Control = 7258.78±898.89 activity pulses. In addition, anxiety as indexed by the State-Trait Anxiety Inventory (STAI decreased in the Treatment group (State Anxiety 18.09±3.8 vs Control 20.69±2.14. CONCLUSION: The moderate consumption of non-alcoholic beer will favour night-time rest, due in particular to its hop components, in addition to its other confirmed benefits for the organism.

  18. Aqueous oxidation of green leaf volatiles by hydroxyl radical as a source of SOA: Kinetics and SOA yields (United States)

    Richards-Henderson, Nicole K.; Hansel, Amie K.; Valsaraj, Kalliat T.; Anastasio, Cort


    Green leaf volatiles (GLVs) are a class of oxygenated hydrocarbons released from vegetation, especially during mechanical stress or damage. The potential for GLVs to form secondary organic aerosol (SOA) via aqueous-phase reactions is not known. Fog events over vegetation will lead to the uptake of GLVs into water droplets, followed by aqueous-phase reactions with photooxidants such as the hydroxyl radical (OH). In order to determine if the aqueous oxidation of GLVs by OH can be a significant source of secondary organic aerosol, we studied the partitioning and reaction of five GLVs: cis-3-hexen-1-ol, cis-3-hexenyl acetate, methyl salicylate, methyl jasmonate, and 2-methyl-3-butene-2-ol. For each GLV we measured the kinetics of aqueous oxidation by OH, and the corresponding SOA mass yield. The second-order rate constants for GLVs with OH were all near diffusion controlled, (5.4-8.6) × 109 M-1 s-1 at 298 K, and showed a small temperature dependence, with an average activation energy of 9.3 kJ mol-1 Aqueous-phase SOA mass yields ranged from 10 to 88%, although some of the smaller values were not statistically different from zero. Methyl jasmonate was the most effective aqueous-phase SOA precursor due to its larger Henry's law constant and high SOA mass yield (68 ± 8%). While we calculate that the aqueous-phase SOA formation from the five GLVs is a minor source of aqueous-phase SOA, the availability of other GLVs, other oxidants, and interfacial reactions suggest that GLVs overall might be a significant source of SOA via aqueous reactions.

  19. Thickness, Doping Accuracy, and Roughness Control in Graded Germanium Doped Ch{sub x} Micro-shells for Lmj

    Energy Technology Data Exchange (ETDEWEB)

    Legay, G.; Theobald, M.; Barnouin, J.; Peche, E.; Bednarczyk, S.; Hermerel, C. [CEA Valduc, Dept Rech Mat Nucl, Serv Microcibles, 21 - Is-sur-Tille (France)


    In the Commissariat a l'Energie Atomique Laser Megajoule (LMJ) facility, amorphous hydrogenated carbon (a-C: H or CH{sub x}) is the nominal ablator used to achieve inertial confinement fusion experiments. These targets are filled with of fusible mixture of deuterium-tritium in order to perform ignition. The a-C: H shell is deposited on a poly-alpha-methylstyrene (PAMS) mandrel by glow discharge polymerization with trans-2-butene, hydrogen, and helium. Graded germanium doped CH{sub x} micro-shells are supposed to be more stable regarding hydrodynamic instabilities. The shells are composed of four layers for a total thickness of 180 {mu}m. The germanium gradient is obtained by doping the different a-C: H layers with the addition of tetra-methylgermanium in the gas mixture. As the achievement of ignition greatly depends on the physical properties of the shell, the thicknesses, doping concentration, and roughness must be precisely controlled. Quartz microbalances were used to perform an in situ and real-time measurement of the thickness in order to reduce the variations and so our fabrication tolerances on each layer thickness. Ex situ control of the thickness of each layer was carried out, with both optical coherent tomography and interferometry, (wall-mapper). High-quality, PAMS and a rolling system have been used to lower the low-mode roughness [root-mean-square (rms) (mode 2) {<=} 70 nm]. High modes were clearly, reduced by, coating the pan containing the shells with polyvinyl alcohol + CH{sub x} instead of polystyrene + CH{sub x} resulting in an rms ({>=}mode 10) {<=} 20 nm, which can be {<=}15 nm for the best micro-shells. The germanium concentration (0. 4 and 0. 75 at. %) in the a-CH layer is obtained by regulating the tetramethyl-germanium flow. Low range mass flow controllers have been used to improve the doping accuracy. (authors)

  20. Characterization of the 1,1-HF Elimination Reaction from the Competition between the 1,1-HF and 1,2-DF Unimolecular Elimination Reactions of CD3CD2CHF2. (United States)

    Wormack, Leah N; McGreal, Meghan E; McClintock, Corey E; Heard, George L; Setser, D W; Holmes, Bert E


    The recombination of CHF2 and C2D5 radicals was used to produce CD3CD2CHF2* molecules with 96 kcal mol(-1) of vibrational energy in a room temperature bath gas. The formation of CD3CD═CHF and CD3CD═CDF was used to identify the 1,2-DF and 1,1-HF unimolecular elimination channels; CD3CD═CDF is formed by isomerization of the singlet-state CD3CD2CF carbene. The total unimolecular rate constant is 1.6 × 10(6) s(-1), and the branching ratio for 1,1-HF elimination is 0.25. Threshold energies of 64 ± 2 and 73 ± 2 kcal mol(-1) were assigned to the 1,2-DF and 1,1-HF reaction channels. The E and Z isomers of 1-fluoropropene were observed for each reaction; approximately 30% of the CD3CD═CDF molecules derived from 1,1-HF elimination retained enough energy to undergo cis-trans isomerization. Electronic structure calculations with density-functional theory were used to characterize the transition-state structures and the H atom migration barrier for CD3CD2CF. Adjustment of the rate constants to account for kinetic-isotope effects suggest that the branching ratio would be 0.20 for 1,1-HF elimination from C2H5CHF2. The results from an earlier study of CD3CHF2 and CH3CHF2 are also reinterpreted to assign a threshold energy of 74 kcal mol(-1) for the 1,1-HF elimination reaction. Because CHF2CHF2* is generated in the photolysis system, the 1,1-and 1,2-HF-elimination reactions of CHF2CHF2* are discussed. The 1,1-HF channel was identified by trapping the CF2HCF carbene with cis-butene-2.

  1. Novel modified zeolites for energy-efficient hydrocarbon separations.

    Energy Technology Data Exchange (ETDEWEB)

    Arruebo, Manuel (University of Colorado, Boulder, CO); Dong, Junhang; Anderson, Thomas (Burns and McDonnell, Kansas City, MO); Gu, Xuehong; Gray, Gary (Goodyear Chemical Company, Akron, OH); Bennett, Ron (Goodyear Chemical Company, Akron, OH); Nenoff, Tina Maria; Kartin, Mutlu; Johnson, Kaylynn (Goodyear Chemical Company, Akron, OH); Falconer, John (University of Colorado, Boulder, CO); Noble, Richard (University of Colorado, Boulder, CO)


    We present synthesis, characterization and testing results of our applied research project, which focuses on the effects of surface and skeletal modification of zeolites for significant enhancements in current hydrocarbon (HC) separations. Zeolites are commonly used by the chemical and petroleum industries as catalysts and ion-exchangers. They have high potential for separations owing to their unique pore structures and adsorption properties and their thermal, mechanical and chemical properties. Because of zeolites separation properties, low cost, and robustness in industrial process, they are natural choice for use as industrial adsorbents. This is a multidisciplinary effort to research, design, develop, engineer, and test new and improved materials for the separation of branched vs. linear organic molecules found in commercially important HC streams via adsorption based separations. The focus of this project was the surface and framework modification of the commercially available zeolites, while tuning the adsorption properties and the selectivities of the bulk and membrane separations. In particular, we are interested with our partners at Goodyear Chemical, on how to apply the modified zeolites to feedstock isoprene purification. For the characterization and the property measurements of the new and improved materials powder X-ray diffraction (PXRD), Residual Gas Analyzer-Mass Spectroscopy (RGA-MS), Electron Microscopy (SEM/EDAX), temperature programmed desorption (TPD) and surface area techniques were utilized. In-situ carbonization of MFI zeolite membranes allowed for the maximum separation of isoprene from n-pentane, with a 4.1% enrichment of the binary stream with n-pentane. In four component streams, a modified MFI membrane had high selectivities for n-pentane and 1-3-pentadiene over isoprene but virtually no separation for the 2-methyl-2-butene/isoprene pair.

  2. Design of and initial results from a Highly Instrumented Reactor for Atmospheric Chemistry (HIRAC

    Directory of Open Access Journals (Sweden)

    D. R. Glowacki


    Full Text Available The design of a Highly Instrumented Reactor for Atmospheric Chemistry (HIRAC is described and initial results obtained from HIRAC are presented. The ability of HIRAC to perform in-situ laser-induced fluorescence detection of OH and HO2 radicals with the Fluorescence Assay by Gas Expansion (FAGE technique establishes it as internationally unique for a chamber of its size and pressure/temperature variable capabilities. In addition to the FAGE technique, HIRAC features a suite of analytical instrumentation, including: a multipass FTIR system; a conventional gas chromatography (GC instrument and a GC instrument for formaldehyde detection; NO/NO2, CO, O3, and H2O vapour analysers. Ray tracing simulations and NO2 actinometry have been utilized to develop a detailed model of the radiation field within HIRAC. Comparisons between the analysers and the FTIR coupled to HIRAC have been performed, and HIRAC has also been used to investigate pressure dependent kinetics of the chlorine atom reaction with ethene and the reaction of O3 and t-2-butene. The results obtained are in good agreement with literature recommendations and Master Chemical Mechanism predictions. HIRAC thereby offers a highly instrumented platform with the potential for: (1 high precision kinetics investigations over a range of atmospheric conditions; (2 detailed mechanism development, significantly enhanced according to its capability for measuring radicals; and (3 field instrument intercomparison, calibration, development, and investigations of instrument response at a range of atmospheric conditions.

  3. Chemical dynamics in time and energy space

    Energy Technology Data Exchange (ETDEWEB)

    Myers, James Douglas [Univ. of California, Berkeley, CA (United States)


    The development of a versatile picosecond ultraviolet/vacuum ultraviolet temporal spectrometer and its potential use for measuring internal energy redistribution in isolated molecules are described in detail. A detailed description of the double-pass Nd:YAG amplifier and the dye amplifiers is given with the pulse energies achieved in the visible, ultraviolet, and vacuum ultraviolet. The amplified visible pulses are shown to be of sub-picosecond duration and near transform limited. The instrument`s temporal response (≤10 ps) is derived from an instrument limited measurement of the dissociation lifetime of methyl iodide at 266 nm. The methyl iodide experiment is used to discuss the various sources of noise and background signals that are intrinsic to this type of experiment. Non-time-resolved experiments measuring the branching ratio and kinetic energy distributions of products from the 193 nm photodissociation of cyclopentadiene and thiophene are presented. These studies were done using the molecular beam Photofragment Translational Spectroscopy (PTS) technique. The results from the cyclopentadiene experiment confirm that H atom elimination to yield the cyclopentadienyl radical is the dominant dissociation channel. A barrier of ≥5 kcal/mol can be understood in terms of the delocalization of the radical electron of the cyclopentadienyl fragment. A concerted elimination yielding cyclopropene and acetylene was also observed and is proposed to occur via a bicyclo-[2.1.0]pent-2-ene intermediate. Two other channels, yielding acetylene plus the CH2CHCH triplet carbene, and CH2 plus 1-buten-3-yne, are postulated to occur via ring opening. The implications of the experimental results for bulk thermal oxidation and pyrolysis models are discussed. The thiophene experiment shows six competing dissociation channels. The postulated intermediates for the various thiophene dissociation channels include bicyclo, ring opened, and possibly ring contracted

  4. Construction and validation of detailed kinetic models for the combustion of gasoline surrogates; Construction et validation de modeles cinetiques detailles pour la combustion de melanges modeles des essences

    Energy Technology Data Exchange (ETDEWEB)

    Touchard, S.


    The irreversible reduction of oil resources, the CO{sub 2} emission control and the application of increasingly strict standards of pollutants emission lead the worldwide researchers to work to reduce the pollutants formation and to improve the engine yields, especially by using homogenous charge combustion of lean mixtures. The numerical simulation of fuel blends oxidation is an essential tool to study the influence of fuel formulation and motor conditions on auto-ignition and on pollutants emissions. The automatic generation helps to obtain detailed kinetic models, especially at low temperature, where the number of reactions quickly exceeds thousand. The main purpose of this study is the generation and the validation of detailed kinetic models for the oxidation of gasoline blends using the EXGAS software. This work has implied an improvement of computation rules for thermodynamic and kinetic data, those were validated by numerical simulation using CHEMKIN II softwares. A large part of this work has concerned the understanding of the low temperature oxidation chemistry of the C5 and larger alkenes. Low and high temperature mechanisms were proposed and validated for 1 pentene, 1-hexene, the binary mixtures containing 1 hexene/iso octane, 1 hexene/toluene, iso octane/toluene and the ternary mixture of 1 hexene/toluene/iso octane. Simulations were also done for propene, 1-butene and iso-octane with former models including the modifications proposed in this PhD work. If the generated models allowed us to simulate with a good agreement the auto-ignition delays of the studied molecules and blends, some uncertainties still remains for some reaction paths leading to the formation of cyclic products in the case of alkenes oxidation at low temperature. It would be also interesting to carry on this work for combustion models of gasoline blends at low temperature. (author)

  5. Metabolic signature of electrosurgical liver dissection.

    Directory of Open Access Journals (Sweden)

    Witigo von Schönfels

    Full Text Available BACKGROUND AND AIMS: High frequency electrosurgery has a key role in the broadening application of liver surgery. Its molecular signature, i.e. the metabolites evolving from electrocauterization which may inhibit hepatic wound healing, have not been systematically studied. METHODS: Human liver samples were thus obtained during surgery before and after electrosurgical dissection and subjected to a two-stage metabolomic screening experiment (discovery sample: N = 18, replication sample: N = 20 using gas chromatography/mass spectrometry. RESULTS: In a set of 208 chemically defined metabolites, electrosurgical dissection lead to a distinct metabolic signature resulting in a separation in the first two dimensions of a principal components analysis. Six metabolites including glycolic acid, azelaic acid, 2-n-pentylfuran, dihydroactinidiolide, 2-butenal and n-pentanal were consistently increased after electrosurgery meeting the discovery (p<2.0 × 10(-4 and the replication thresholds (p<3.5 × 10(-3. Azelaic acid, a lipid peroxidation product from the fragmentation of abundant sn-2 linoleoyl residues, was most abundant and increased 8.1-fold after electrosurgical liver dissection (preplication = 1.6 × 10(-4. The corresponding phospholipid hexadecyl azelaoyl glycerophosphocholine inhibited wound healing and tissue remodelling in scratch- and proliferation assays of hepatic stellate cells and cholangiocytes, and caused apoptosis dose-dependently in vitro, which may explain in part the tissue damage due to electrosurgery. CONCLUSION: Hepatic electrosurgery generates a metabolic signature with characteristic lipid peroxidation products. Among these, azelaic acid shows a dose-dependent toxicity in liver cells and inhibits wound healing. These observations potentially pave the way for pharmacological intervention prior liver surgery to modify the metabolic response and prevent postoperative complications.

  6. Tempo-spatial variation of emission inventories of speciated volatile organic compounds from on-road vehicles in China

    Directory of Open Access Journals (Sweden)

    H. Cai


    Full Text Available Emission inventories of sixty-seven speciated non-methane volatile organic compounds (NMVOC from on-road vehicles in China were estimated for the period of 1980–2005, using seven NMVOC emission profiles, which were summarized based on local and international measurements from published literatures dealing with specific vehicle categories running under particular modes.

    Results show an exponential growth trend of China's historical emissions of alkanes, alkenes, alkines, aromatics and carbonyls during the period of 1980–2005, increasing from 63.9, 39.3, 6.9, 36.8 and 24.1 thousand tons, respectively, in 1980 to 2778.2, 1244.5, 178.7, 1351.7 and 406.0 thousand tons, respectively, in 2005, which coincided well with China's economic growth. Emission inventories of alkenes, aromatics and carbonyls were gridded at a high resolution of 40 km×40 km for air quality simulation and health risk evaluation, using the geographic information system (GIS methodology. Spatial distribution of speciated NMVOC emissions shows a clear difference in emission densities between developed eastern and relatively underdeveloped western and inland China. Besides, the appearance and expansion of high-emission areas was another notable characteristic of spatial distribution of speciated NMVOC emissions during the period.

    Emission contributions of vehicle categories to speciated NMVOC groups showed annual variation, due to the variance in the provincial emissions and in the relative fractions of the seven emission profiles adopted at the provincial level. Highly reactive and toxic compounds accounted for high proportions of emissions of speciated NMVOC groups. The most abundant compounds were isopentane, pentane and butane from alkanes; ethene, propene, 2-methyl-2-butene and ethyne from alkenes and alkines; benzene, toluene, ethylbenzene, o-xylene, and m,p-xylene (BTEX and 1,2,4-trimethylbenzene from aromatics and formaldehyde, acetaldehyde

  7. Methyl chavicol: characterization of its biogenic emission rate, abundance, and oxidation products in the atmosphere

    Directory of Open Access Journals (Sweden)

    N. C. Bouvier-Brown


    Full Text Available We report measurements of ambient atmospheric mixing ratios for methyl chavicol and determine its biogenic emission rate. Methyl chavicol, a biogenic oxygenated aromatic compound, is abundant within and above Blodgett Forest, a ponderosa pine forest in the Sierra Nevada Mountains of California. Methyl chavicol was detected simultaneously by three in-situ instruments – a gas chromatograph with mass spectrometer detector (GC-MS, a proton transfer reaction mass spectrometer (PTR-MS, and a thermal desorption aerosol GC-MS (TAG – and found to be abundant within and above Blodgett Forest. Methyl chavicol atmospheric mixing ratios are strongly correlated with 2-methyl-3-buten-2-ol (MBO, a light- and temperature-dependent biogenic emission from the ponderosa pine trees at Blodgett Forest. Scaling from this correlation, methyl chavicol emissions account for 4–68% of the carbon mass emitted as MBO in the daytime, depending on the season. From this relationship, we estimate a daytime basal emission rate of 0.72–10.2 μgCg−1 h−1, depending on needle age and seasonality. We also present the first observations of its oxidation products (4-methoxybenzaldehyde and 4-methyoxy benzene acetaldehyde in the ambient atmosphere. Methyl chavicol is a major essential oil component of many plant species. This work suggests that methyl chavicol plays a significant role in the atmospheric chemistry of Blodgett Forest, and potentially other sites, and should be included explicitly in both biogenic volatile organic carbon emission and atmospheric chemistry models.

  8. Effects of rf power on chemical composition and surface roughness of glow discharge polymer films

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Ling; He, Xiaoshan; Chen, Guo; Wang, Tao; Tang, Yongjian; He, Zhibing, E-mail:


    Graphical abstract: - Highlights: • The growth mechanism of defects in GDP films was studied upon plasma diagnosis. • Increasing rf power enhanced the etching effects of smaller-mass species. • The “void” defect was caused by high energy hydrocarbons bombardment on the surface. • The surface roughness was only 12.76 nm, and no “void” defect was observed at 30 W. - Abstract: The glow discharge polymer (GDP) films for laser fusion targets were successfully fabricated by plasma enhanced chemical vapor deposition (PECVD) at different radio frequency (rf) powers. The films were deposited using trans-2-butene (T{sub 2}B) mixed with hydrogen as gas sources. The composition and state of plasma were diagnosed by quadrupole mass spectrometer (QMS) and Langmuir probe during the deposition process. The composition, surface morphology and roughness were investigated by Fourier transform infrared spectroscopy (FTIR), scanning electron microscope (SEM) and white-light interferometer (WLI), respectively. Based on these observation and analyses, the growth mechanism of defects in GDP films were studied. The results show that, at low rf power, there is a larger probability for secondary polymerization and formation of multi-carbon C-H species in the plasma. In this case, the surface of GDP film turns to be cauliflower-like. With the increase of rf power, the degree of ionization is high, the relative concentration of smaller-mass hydrocarbon species increases, while the relative concentration of larger-mass hydrocarbon species decreases. At higher rf power, the energy of smaller-mass species are high and the etching effects are strong correspondingly. The GDP film's surface roughness shows a trend of decrease firstly and then increase with the increasing rf power. At rf power of 30 W, the surface root-mean-square roughness (Rq) drops to the lowest value of 12.8 nm, and no “void” defect was observed.

  9. Unité micropilote pour l'étude de charges de vapocraquage. Exemple d'un mélange de normales paraffines Micropilot Plant for the Study of Steam-Cracking Feedstocks. Example of a Mixture of Normal Paraffins

    Directory of Open Access Journals (Sweden)

    Billaud F.


    Full Text Available La décomposition thermique d'un mélange de normales paraffines (nom commercial Solpar , provenance British Petroleum a été étudiée dans une unité micropilote entre 640 et 820 °C ; les produits principaux dosés par chromatographie en phase gazeuse sont : hydrogène, méthane, éthylène, propène, butène-1, pentène-1, hexène-1, heptène-1, octène-1 et nonène-1. Un des intérêts du travail est la description mécanistique de la pyrolyse d'un hydrocarbure lourd qui permet d'interpréter la formation primaire de ces produits principaux. On a aussi montré expérimentalement l'intérêt du vapocraquage haute température et faible temps de séjour lorsque l'on veut produire sélectivement des oléfines légères en minimisant la production d'aromatiques. The thermal decomposition of a mixture of normal paraffins (trademark Solpar, by British Petroleum has been studied in a micropilot plant in a temperature range of 640 to 820°C. The main products determined by gas chromatography are hydrogen, methane, ethylene, propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene and 1-nonene. On of the important results of the present work is the mechanistic description of heavy hydrocarbon pyrolysis so that the primary formation of these principal products can be interpreted. Moreover, the advantage of using high-temperature steam cracking and short residence time for the selective production of light olefins, thus minimizing production of aromatics, is experimentally demonstrated.

  10. Observations and models of emissions of volatile terpenoid compounds from needles of ponderosa pine trees growing in situ: control by light, temperature and stomatal conductance

    Energy Technology Data Exchange (ETDEWEB)

    Harley, Peter; Eller, Allyson; Guenther, Alex; Monson, Russell K.


    Terpenoid emissions from ponderosa pine (Pinus ponderosa subsp. scopulorum) were measured in Colorado, USA over two growing seasons to evaluate the role of incident light, needle temperature and stomatal conductance in controlling emissions of 2-methyl-3-buten-2-ol (MBO) and several monoterpenes. MBO was the dominant daylight terpenoid emission, comprising on average 87% of the total flux, and diurnal variations were largely determined by light and temperature. During daytime, oxygenated monoterpenes (especially linalool) comprised up to 75% of the total monoterpenoid flux from needles. A significant fraction of monoterpenoid emissions was light dependent and 13CO2 labeling studies confirmed de novo production. Thus, modeling of monoterpenoid emissions required a hybrid model in which a significant fraction of emissions was dependent on both light and temperature, while the remainder was dependent on temperature alone. Experiments in which stomata were forced to close using abscisic acid demonstrated that MBO and a large fraction of the monoterpene flux, presumably linalool, could be limited at the scale of seconds to minutes by stomatal conductance. Using a previously published model of terpenoid emissions which explicitly accounts for the physico-chemical properties of emitted compounds, we are able to simulate these observed stomatal effects, whether induced through experimentation or arising under naturally fluctuation conditions of temperature and light. This study shows unequivocally that, under naturally occurring field conditions, de novo light dependent monoterpenes can comprise a large fraction of emissions. Differences between the monoterpene composition of ambient air and needle emissions imply a significant non-needle emission source enriched in Δ-3-carene.

  11. Effects of aliphatic aldehydes on the growth and patulin production of Penicillium expansum in apple juice. (United States)

    Taguchi, Tomoyasu; Kozutsumi, Daisuke; Nakamura, Ruka; Sato, Yoshio; Ishihara, Atsushi; Nakajima, Hiromitsu


    The effects of 16 aliphatic aldehydes with 3-10 carbons on the growth and patulin production of Penicillium expansum were examined. When P. expansum spores were inoculated into apple juice broth, some alkenals, including 2-propenal, (E)-2-butenal, (E)-2-pentenal, and (E)-2-hexenal, inhibited fungal growth and patulin production. Their minimal inhibitory concentrations were 5, 50, 80, and 80 µg/mL respectively. Vital staining indicated that these alkenals killed mycelia within 4 h. Treatment of the spores with these aldehydes also resulted in rapid loss of germination ability, within 0.5-2 d. On the other hand, aliphatic aldehydes with 8-10 carbons significantly enhanced patulin production without affecting fungal growth: 300 µg/mL of octanal and 100 µg/mL of (E)-2-octenal increased the patulin concentrations in the culture broth by as much as 8.6- and 7.8-fold as compared to that of the control culture respectively. The expression of the genes involved in patulin biosynthesis in P. expansum was investigated in mycelia cultured in apple juice broth containing 300 µg/mL of octanal for 3.5, 5, and 7 d. Transcription of the msas gene, encoding 6-methylsalicylic acid synthase, which catalyzed the first step in the patulin biosynthetic pathway was remarkably high in the 3.5-d and 5-d-old cultures as compared with the control. However, octanal did not any increase the transcription of the msas in the 7-d-old culture or that of the other two genes, IDH and the peab1, in culture. Thus the enhanced patulin accumulation with supplementation with these aldehydes is attributable to the increased amount of the msas transcript.

  12. Preparação e Avaliação Térmica e Reológica de Misturas de PEBD/PELBD Preparation of LDPE/LLDPE Blends and Thin Rheological and Calorimetric Evaluation

    Directory of Open Access Journals (Sweden)

    Márcia R. Becker


    Full Text Available Misturas de Polietileno de Baixa Densidade (PEBD com diferentes tipos e proporções de Polietilenos Lineares de Baixa Densidade (PELBD foram preparadas em extrusora de rosca simples e dupla a fim de verificar a influência destes últimos na viscosidade e cristalinidade das misturas. As misturas de PEBD com PELBD foram avaliadas através de reometria capilar e calorimetria (DSC. As misturas de PEBD com PELBD com comonômero de 1-buteno e de 1-octeno, preparadas em extrusora de rosca simples ou dupla, não apresentaram diferenças no perfil das curvas reológicas. Entretanto, as misturas de PEBD com PELBD com comonômero 1-hexeno apresentaram diferenças nas curvas de viscosidade. Verificou-se que a adição de PELBD na mistura modifica significativamente a viscosidade principalmente em altas taxas de cisalhamento. Pela avaliação das curvas de fusão, observou-se que o aumento da concentração de PELBD nas misturas provoca uma variação no comportamento térmico das mesmas com o conseqüente alargamento da faixa de fusão.LDPE and LLDPE blends were prepared in a single and twin screw mixer, using different kinds and proportions of the LLDPE in order to evaluate their influence on the viscosity and cristallinity of the blends. The blends with LLDPE made with butene or hexene or octene comonomer, prepared in a twin or single screw mixer, did not show significant differences in their curves of viscosity versus shear rate. The addition of LLDPE in the PEBD changes the viscosimetric behavior of the blends especially at higher shear rate. With Differential Scanning Calorimetry we observed that the incorporation of LLDPE in the blends changes the behavior of melting curves due to its different types of crystallites.

  13. Products of the gas-phase reactions of 1,3-butadiene with OH and NO{sub 3} radicals

    Energy Technology Data Exchange (ETDEWEB)

    Tuazon, E.C.; Alvarado, A.; Aschmann, S.M.; Atkinson, R.; Arey, J.


    1,3-Butadiene is emitted into the atmosphere from a number of sources including combustion sources and is listed in the US as a hazardous air pollutant. In the atmosphere, 1,3-butadiene reacts with OH radicals, NO{sub 3} radicals, and O{sub 3} with the dominant tropospheric removal processes being daytime reaction with the OH radical and nighttime reaction with the NO{sub 3} radical. The authors have used gas chromatography, in situ Fourier transform infrared (FT-IR) absorption spectroscopy, and in situ atmospheric pressure ionization tandem mass spectrometry (API-MS) to identify and quantify the products formed from the reactions of 1,3-butadiene with OH radicals (in the presence of NO) and NO{sub 3} radicals. Acrolein, formaldehyde, and furan were identified and quantified from the OH radical-initiated reaction, with formation yields of 0.58 {+-} 0.04, 0.62 {+-} 0.05, and 0.03--0.04, respectively. Organic nitrates were observed by FT-IR spectroscopy with an estimated yield of 0.07 {+-} 0.03, and the API-MS analyses indicated that these organic nitrates are mainly the hydroxynitrate HOCH{sub 2}CH=CHCH{sub 2}ONO{sub 2} and/or its isomers. API-MS analyses showed the formation of a hydroxycarbonyl with the formula C{sub 4}H{sub 6}O{sub 2}, attributed to HOCH{sub 2}CH=CHCHO and/or its isomers. The major products of the NO{sub 3} radical-initiated reaction were organic nitrates; the API-MS analyses indicated the formation of acrolein, 1,2-epoxy-3-butene, and unsaturated C{sub 4}-hydroxycarbonyls, hydroxynitrates, carbonyl nitrates, and nitrooxyhydroperoxides. Acrolein, HCHO, and furan were again quantified by gas chromatographic and FT-IR analyses. The data is compared with previous literature studies, and detailed reaction mechanisms are presented and discussed.

  14. The progress of SINOPEC methanol-to-olefins (S-MTO) technology

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Hongxing; Xie, Zaiku; Zhao, Guoliang [SINOPEC Shanghai Research Institute of Petrochemical Technology (China)


    It is widely recognized that naphtha steam crackers and FCC units are the main current sources of ethylene and propylene. On the condition of high oil price, olefin producers are striving to develop new economical routes to produce ethylene and propylene with low-cost feedstocks. Methanol to olefins (MTO) has aroused great attention in recent years, and SINOPEC has developed a new kind of MTO process named S-MTO which features high olefins selectivity, high methanol conversion and low catalyst consumption. Puyang Zhongyuan 200 KTA S-MTO has been in steady operation for more than 17 months. The catalyst used in the process is based on a silicoaluminophosphate, SAPO-34, which has very high carbon selectivity to low carbon olefins. Results from the commercial plant show that S-MTO process converts methanol to ethylene and propylene at about 81% carbon selectivity. The carbon selectivity approaches 92% if butenes are also accounted for as part of the product. Typically, the ratio of propylene to ethylene can range from 0.6 to 1.3. When combined with OCC (Olefin Catalytic Cracking) process to convert the heavier olefins, the overall yield of ethylene and propylene can increase to 85% {proportional_to} 87% and propylene-ethylene ratios of more than 1.5 are achievable. Other co-products include very small amounts of C1-C4 paraffins, hydrogen, CO and CO{sub 2}, as well as heavier oxygenates only with ppm level. Because of the quick deactivation of MTO catalyst, a kind of high efficiency fast fluidized bed reactor is adopted. The activity of deactivated catalyst is recovered by burning the coke in the regenerator. This paper gives an updated introduction of S-MTO technology developed by SINOPEC SRIPT. (orig.)

  15. Polystyrene Chain Growth from Di-End-Functional Polyolefins for Polystyrene-Polyolefin-Polystyrene Block Copolymers

    Directory of Open Access Journals (Sweden)

    Chung Sol Kim


    Full Text Available Triblock copolymers of polystyrene (PS and a polyolefin (PO, e.g., PS-block-poly(ethylene-co-1-butene-block-PS (SEBS, are attractive materials for use as thermoplastic elastomers and are produced commercially by a two-step process that involves the costly hydrogenation of PS-block-polybutadiene-block-PS. We herein report a one-pot strategy for attaching PS chains to both ends of PO chains to construct PS-block-PO-block-PS directly from olefin and styrene monomers. Dialkylzinc compound containing styrene moieties ((CH2=CHC6H4CH2CH22Zn was prepared, from which poly(ethylene-co-propylene chains were grown via “coordinative chain transfer polymerization” using the pyridylaminohafnium catalyst to afford di-end functional PO chains functionalized with styrene and Zn moieties. Subsequently, PS chains were attached at both ends of the PO chains by introduction of styrene monomers in addition to the anionic initiator Me3SiCH2Li·(pmdeta (pmdeta = pentamethyldiethylenetriamine. We found that the fraction of the extracted PS homopolymer was low (~20% and that molecular weights were evidently increased after the styrene polymerization (ΔMn = 27–54 kDa. Transmission electron microscopy showed spherical and wormlike PS domains measuring several tens of nm segregated within the PO matrix. Optimal tensile properties were observed for the sample containing a propylene mole fraction of 0.25 and a styrene content of 33%. Finally, in the cyclic tensile test, the prepared copolymers exhibited thermoplastic elastomeric properties with no breakage up over 10 cycles, which is comparable to the behavior of commercial-grade SEBS.

  16. Pyrolysis of waste electrical and electronic equipment: effect of antinomy trioxide on the pyrolysis of styrenic polymers. (United States)

    Hall, W J; Bhaskar, T; Merpati, N M M; Muto, A; Sakata, Y; Williams, P T


    This work has investigated the effect that antimony trioxide has on the pyrolysis of styrenic polymers and the effect that different types of brominated flame retardants used in plastics have on the composition of the pyrolysis products. Brominated high impact polystyrene (Br-HIPS) which contained either 5% or 0% antimony trioxide and either decabromodiphenyl oxide (DDO) or decabromodiphenyl ethane (DDE) was pyrolysed in a fixed bed reactor at 430 degrees C. Some experiments on the fixed bed reactor involved mixing the Br-HIPS with polystyrene. The gaseous products were analysed by GC-FID and GC-TCD and it was found that antimony trioxide caused an increase in the proportion of ethane and ethene and suppressed the proportion of butane and butene. When DDE was the flame retardant increased proportions of ethane and ethene were found in the pyrolysis gas compared to when DDO used. When polystyrene was mixed with the Br-HIPS it suppressed the trends observed in the gas composition during the pyrolysis of Br-HIPS. The pyrolysis oils were characterised using FT-IR, GC-MS, GC-FID, and GC-ECD. It was found that the plastic which did not contain antimony trioxide pyrolysed to form mainly toluene, ethylbenzene, styrene, cumene, and alpha-methylstyrene. The oils produced from the pyrolysis of the plastic that contained antimony trioxide did not contain any styrene or alpha-methylstyrene, but instead contained greater concentrations of ethylbenzene and cumene. The absence of styrene and alpha-methylstyrene from the pyrolysis oil occurred even when the Br-HIPS was mixed with polystyrene. GC-ECD analysis of the oils showed that the plastics which did not contain antimony trioxide pyrolysed to form (1-bromoethyl)benzene, which was totally absent from the pyrolysis oils when antimony trioxide was present in the plastic.

  17. Emission factors and characteristics of criteria pollutants and volatile organic compounds (VOCs) in a freeway tunnel study

    Energy Technology Data Exchange (ETDEWEB)

    Hung-Lung, Chiang [Department Health Risk Management, China Medical University, Taichung, 40402 (China); Ching-Shyung, Hwu [Department of Environmental Engineering, Hung Kuang University, Taichung, 43302 (China); Shih-Yu, Chen; Sen-Yi, Ma; Yao-Sheng, Huang [Department of Environmental Engineering, Fooyin University, 831, Kaohsiung (China); Ming-Ching, Wu [Department of Technology Management, The Open University of Kaohsiung, Kaohsiung 812 (China)


    Carbon monoxide (CO), nitrogen oxide (NO{sub x}), hydrocarbon (HC), sulfur oxide (SO{sub 2}), particulate matter < 10 {mu}m (PM{sub 10}), and 57 VOC species of emissions were confirmed in a freeway tunnel in southern Taiwan. Emission factors were 1.89 (CO), 0.73 (NO{sub x}), 0.46 (HC), 0.02 (SO{sub 2}) and 0.06 (PM{sub 10}) g/km-vehicle for all vehicle fleets. Heavy-duty truck and trailer vehicles contributed 20% of the emissions on workdays and 9.5% on weekends in this study. Paraffins and aromatics were the main VOC groups in the tunnel. Isopentane, toluene, n-pentane, isoprene, 2,3-dimethylbutane, acetone, 2-methylpentane, 1-hexene, 1,2,4-trimethybenzene, 1-butene and propene emissions were the major VOC species. Their emission factors were over 10 mg/km-vehicle. Rainfall and high humidity in the tunnel could have reduced the VOC concentrations and increased the portion of aromatics. In addition to paraffins, olefins, and aromatic compounds, oxygenated compounds (i.e., acetone) were found. The pollutant ratios between the inside center and the outside of the tunnel were about 2-3 for CO, SO{sub 2}, and PM{sub 10} and 42 for NO{sub x}. In addition, the emission factors of the vehicles could reflect real-world vehicle emissions on the highway and be used as baseline information for development of a vehicle control strategy. (author)

  18. Stability of bound species during alkene reactions on solid acids (United States)

    Sarazen, Michele L.; Iglesia, Enrique


    This study reports the thermodynamics of bound species derived from ethene, propene, n-butene, and isobutene on solid acids with diverse strength and confining voids. Density functional theory (DFT) and kinetic data indicate that covalently bound alkoxides form C-C bonds in the kinetically relevant step for dimerization turnovers on protons within TON (0.57 nm) and MOR (0.67 nm) zeolitic channels and on stronger acids HPW (polyoxometalate clusters on silica). Turnover rates for mixed alkenes give relative alkoxide stabilities; the respective adsorption constants are obtained from in situ infrared spectra. Tertiary alkoxides (from isobutene) within larger voids (MOR, HPW) are more stable than less substituted isomers but are destabilized within smaller concave environments (TON) because framework distortions are required to avoid steric repulsion. Adsorption constants are similar on MOR and HPW for each alkoxide, indicating that binding is insensitive to acid strength for covalently bound species. DFT-derived formation free energies for alkoxides with different framework attachments and backbone length/structure agree with measurements when dispersion forces, which mediate stabilization by confinement in host-guest systems, are considered. Theory reveals previously unrecognized framework distortions that balance the C-O bond lengths required for covalency with host-guest distances that maximize van der Waals contacts. These distortions, reported here as changes in O-atom locations and dihedral angles, become stronger for larger, more substituted alkoxides. The thermodynamic properties reported here for alkoxides and acid hosts differing in size and conjugate-anion stability are benchmarked against DFT-derived free energies; their details are essential to design host-guest pairs that direct alkoxide species toward specific products.

  19. Nitric oxide inhibitory substances from Curcuma mangga rhizomes

    Directory of Open Access Journals (Sweden)

    Kanidta Kaewkroek


    Full Text Available Curcuma mangga Val. & Zijp. is a member of the Zingiberaceae family commonly grown in Thailand. It is locally known as mango tumeric because of its mango-like smell when the fresh rhizomes are cut. C. mangga is a popular vegetable, the tips of the young rhizomes and shoots are consumed raw with rice. Medicinally, the rhizomes are used as a stomachic and for chest pains, fever, and general debility. It is also used in postpartum care. In the present study, we investigated the anti-inflammatory effect of the extract and compounds from C. mangga rhizomes against lipopolysaccharide (LPS-induced nitric oxide (NO production in RAW 264.7 cell line. From bioassay-guided fractionation, the chloroform fraction exhibited the most potent inhibitory activity with an IC50 value of 2.1 g/ml, followed by the hexane fraction (IC50 = 3.8 g/ml and the ethyl acetate fraction (IC50 = 23.5 g/ml, respectively. Demethoxycurcumin (1 and 3-buten-2-one, 4-[(1R, 4aR, 8aR-decahydro-5, 5, 8a-trimethyl-2-methylene-1-naphthalenyl]-, (3E-rel- (2 were isolated from the chloroform- and hexane fractions, respectively. Bisdemethoxycurcumin (3 whose structure is similar to that of 1 was also tested for NO inhibitory activity. Of the tested compounds, compound 1 exhibited the highest activity with an IC50 value of 12.1 μM, followed by 3(IC50 = 16.9 M and 2 (IC50 = 30.3 M. These results suggest that C. mangga and its compounds exert NO inhibitory activity and have a potential to be developed as a pharmaceutical preparation for treatment of inflammatory-related diseases. Moreover, this is the first report of compound 2 that was isolated from C. mangga rhizomes.

  20. Polyphenol extract from Phellinus igniarius protects against acrolein toxicity in vitro and provides protection in a mouse stroke model. (United States)

    Suabjakyong, Papawee; Saiki, Ryotaro; Van Griensven, Leo J L D; Higashi, Kyohei; Nishimura, Kazuhiro; Igarashi, Kazuei; Toida, Toshihiko


    The basidiomycetous mushroom Phellinus igniarius (L.) Quel. has been used as traditional medicine in various Asian countries for many years. Although many reports exist on its anti-oxidative and anti-inflammatory activities and therapeutic effects against various diseases, our current knowledge of its effect on stroke is very limited. Stroke is a neurodegenerative disorder in which oxidative stress is a key hallmark. Following the 2005 discovery by Igarashi's group that acrolein produced from polyamines in vivo is a major cause of cell damage by oxidative stress, we now describe the effects of anti-oxidative extracts from P. igniarius on symptoms of experimentally induced stroke in mice. The toxicity of acrolein was compared with that of hydrogen peroxide in a mouse mammary carcinoma cell line (FM3A). We found that the complete inhibition of FM3A cell growth by 5 μM acrolein could be prevented by crude ethanol extract of P. igniarius at 0.5 μg/ml. Seven polyphenol compounds named 3,4-dihydroxybenzaldehyde, 4-(3,4-dihydroxyphenyl-3-buten-2one, inonoblin C, phelligridin D, inoscavin C, phelligridin C and interfungin B were identified from this ethanolic extract by LCMS and 1H NMR. Polyphenol-containing extracts of P. igniarius were then used to prevent acrolein toxicity in a mouse neuroblastoma (Neuro-2a) cell line. The results suggested that Neuro-2a cells were protected from acrolein toxicity at 2 and 5 μM by this polyphenol extract at 0.5 and 2 μg/ml, respectively. Furthermore, in mice with experimentally induced stroke, intraperitoneal treatment with P. igniarius polyphenol extract at 20 μg/kg caused a reduction of the infarction volume by 62.2% compared to untreated mice. These observations suggest that the polyphenol extract of P. igniarius could serve to prevent ischemic stroke.

  1. Polyphenol extract from Phellinus igniarius protects against acrolein toxicity in vitro and provides protection in a mouse stroke model.

    Directory of Open Access Journals (Sweden)

    Papawee Suabjakyong

    Full Text Available The basidiomycetous mushroom Phellinus igniarius (L. Quel. has been used as traditional medicine in various Asian countries for many years. Although many reports exist on its anti-oxidative and anti-inflammatory activities and therapeutic effects against various diseases, our current knowledge of its effect on stroke is very limited. Stroke is a neurodegenerative disorder in which oxidative stress is a key hallmark. Following the 2005 discovery by Igarashi's group that acrolein produced from polyamines in vivo is a major cause of cell damage by oxidative stress, we now describe the effects of anti-oxidative extracts from P. igniarius on symptoms of experimentally induced stroke in mice. The toxicity of acrolein was compared with that of hydrogen peroxide in a mouse mammary carcinoma cell line (FM3A. We found that the complete inhibition of FM3A cell growth by 5 μM acrolein could be prevented by crude ethanol extract of P. igniarius at 0.5 μg/ml. Seven polyphenol compounds named 3,4-dihydroxybenzaldehyde, 4-(3,4-dihydroxyphenyl-3-buten-2one, inonoblin C, phelligridin D, inoscavin C, phelligridin C and interfungin B were identified from this ethanolic extract by LCMS and 1H NMR. Polyphenol-containing extracts of P. igniarius were then used to prevent acrolein toxicity in a mouse neuroblastoma (Neuro-2a cell line. The results suggested that Neuro-2a cells were protected from acrolein toxicity at 2 and 5 μM by this polyphenol extract at 0.5 and 2 μg/ml, respectively. Furthermore, in mice with experimentally induced stroke, intraperitoneal treatment with P. igniarius polyphenol extract at 20 μg/kg caused a reduction of the infarction volume by 62.2% compared to untreated mice. These observations suggest that the polyphenol extract of P. igniarius could serve to prevent ischemic stroke.

  2. Cytotoxic evaluation of volatile oil from Descurainia sophia seeds on MCF-7 and HeLa cell lines. (United States)

    Khodarahmi, E; Asghari, G H; Hassanzadeh, F; Mirian, M; Khodarahmi, G A


    Descurainia sophia is a plant widely distributed and used as folk medicine throughout the world. Different extracts of aerial parts and seeds of this plant have been shown to inhibit the growth of different cancer cell lines in vitro. In this study, cytotoxic activity of D. sophia seed volatile oil was evaluated. D. sophia seed powder was mixed with distilled water and left at 25 °C for 17 h (E1), 23 h (E2) and 28 h (E3) to autolyse. Then, the volatile fractions of E1, E2, and E3 were collected after steam distillation for 3 h. Cytotoxic effects of the volatile oils alone or in combination with doxorubicin (mixture of E1 or E2 at 50 μg/ml or E1 at 100 μg/ml with doxorubicin at 0.1, 1, 10 μM) against MCF-7 cell line were determined using MTT assay. Cytotoxic effect of E1 volatile oil was also determined on HeLa cell line. The results indicated that 1-buten-4-isothiocyanate was the major isothiocyanate found in the volatile oils. The results of cytotoxic evaluations showed that volatile constituents were more toxic on MCF-7 cells with IC50 100 μg/ml. No significant differences were observed between cytotoxic activities of E1, E2 and E3 on MCF-7 cell line. Concomitant use of E1 and E2 (50 μg/ml) with doxurubicin (1 μM) significantly reduced the viability of MCF-7 cells compared to the negative control, doxorubicin alone, or each volatile fraction. The same result was obtained on HeLa cells, when E1 (100 μg/ml) was concurrently used with doxorubicin (1 μM).

  3. Selective hydrogenation of 2-methyl-3-butyn-2-ol catalyzed by embedded polymer-protected PdZn nanoparticles (United States)

    Okhlopkova, Lyudmila B.; Matus, Ekaterina V.; Prosvirin, Igor P.; Kerzhentsev, Michail A.; Ismagilov, Zinfer R.


    PdZn/TiO2 catalysts were synthesized by sol-gel method using a template Pluronic F127. PdZn nanoparticles with the size ranging from 1.7 to 2 nm were prepared by ethylene glycol reduction of ZnCl2 and Pd(CH3COO)2 in the presence of stabilizer and introduced into the matrix by addition into TiO2 sol, followed by different activation procedures. The structure, particles size, and chemical composition of nanoparticles and catalysts were characterized by transmission electron microscopy, X-ray photoelectron spectroscopy, X-ray fluorescence spectroscopy, and energy dispersive spectroscopy. The prepared catalysts have been tested in the selective hydrogenation of 2-methyl-3-butyn-2-ol, and the results have been compared with catalysts prepared by conventional impregnation. The results indicate that bimetallic PdZn nanoparticles-based catalysts show higher selectivity than corresponding monometallic Pd/TiO2. Embedded on titania, bimetallic nanoparticles stabilized with polyvinylpyrrolidone exhibit good activity (1.1-1.8 mol MBY/mol Pd/s-1) and high selectivity to 2-methyl-3-buten-2-ol (81.5-88.9 % at 95 % conversion). The influence of the nature of the stabilizer, the stabilizer/metal molar ratio, and activation conditions on the catalytic behavior of the samples was analyzed. It is shown that the particle size does not significantly affect the catalytic properties in the range of 4.4-6.5 nm. The nature and amount of stabilizer seem to be crucial to prepare efficient catalyst.

  4. Potato wound-healing tissues: A rich source of natural antioxidant molecules with potential for food preservation. (United States)

    Dastmalchi, Keyvan; Wang, Isabel; Stark, Ruth E


    The need for safe, effective preservatives is a prominent issue in the food and drug industries, reflecting demand for natural alternatives to synthetic chemicals viewed as harmful to consumers and the environment. Thus, this study determined the identities and scavenging capacities of antioxidant metabolites produced as a response to potato tuber wounding, using activity-guided fractionation of polar extracts from a Yukon Gold cultivar that had previously exhibited exceptionally high radical-scavenging activity. Activity-guided fractionation using the ABTS(+) radical scavenging assay and LC-MS with TOF-MS for compositional analysis of the most potent antioxidant fractions yielded identification of nine constituents: coumaroylputrescine; feruloylquinic acid; isoferuloylputrescine; ferulic acid; 22,25-dimethoxy-3-[[2,3,4-tri-O-methyl-6-O-(2,3,4,6-tetra-O-methyl-β-d-glucopyranosyl)-β-d-glucopyranosyl]oxy]-(3β)-lanost-9(11)-en-24-one; 4-(2Z)-2-decen-1-yl-5-[1-(4-hydroxyphenyl)decyl]-1,2-benzenediol; 8-[(2E)-3,7-dimethyl-2,6-octadien-1-yl]-5-hydroxy-2,8-dimethyl-6-(3-methyl-2-buten-1-yl)-2H-1-benzopyran-4,7(3H,8H)-dione; 3-[(2-O-β-d-glucopyranosyl-β-d-glucopyranosyl)oxy]-20-[(6-O-β-d-xylopyranosyl-β-d-glucopyranosyl)oxy]-dammar-24-en-19-al; (3β)-28-oxo-28-(phenylmethoxy)oleanan-3-yl 2-O-β-d-galactopyranosyl-3-O-(phenylmethyl)-, butyl ester β-d-glucopyranosiduronic acid. A positive correlation was observed between the scavenging activities and the polarities of the active fractions. The antioxidant capacities of the fractions were also characterised by monitoring the activity throughout a 45-minute assay period. Copyright © 2016 Elsevier Ltd. All rights reserved.

  5. [Pollution characteristics and health risk assessment of atmospheric VOCs in the downtown area of Guangzhou, China]. (United States)

    Li, Lei; Li, Hong; Wang, Xue-Zhong; Zhang, Xin-Min; Wen, Chong


    The measurements of 31 kinds of VOCs in the ambient air of a site were carried out in the downtown of Guangzhou by online method from November 5, 2009 to November 9, 2009. The ambient level and composition characteristics, temporal variation characteristics, sources identification, and chemical reactivity of VOCs were studied, and the health risk of VOCs in the ambient air in the study area was assessed by using the international recognized health risk assessment method. Results showed that the mean and the range of the mass concentrations of 31 VOCs were 114.51 microg x m(-3) and 29.42-546.06 microg x m(-3), respectively. The mass concentrations of 31 VOCs, and those of alkanes, alkenes, and aromatics all showed a changing trend of higher in the morning and in the evening, and lower at noontime. Vehicular exhaust, gasoline and liquefied petroleum gas evaporates were the main sources of VOCs with the volatilization of paints and solvents being important emission sources. Toluene, trans-2-butene, m/p-xylene, i-butane, and 1,3,5-trimethylbenzene were the key reactive species among the 31 VOCs. Vehicular exhaust and gasoline evaporation were the main sources of VOCs leading to the formation of ozone. Health risk assessment showed that n-hexane, 1,3-butadiene, benzene, toluene, ethylbenzene, m/p-xylene and o-xylene had no appreciable risk of adverse non-cancer health effect on the exposed population, but 1, 3-butadiene and benzene had potential cancer risk. By comparing the corresponding data about health risk assessment of benzene compounds in some cities in China, it is concluded that benzene can impose relatively high cancer risk to the exposed populations in the ambient air of some cities in China. Therefore, strict countermeasures should be taken to further control the pollution of benzene in the ambient air of cities, and it is imperative to start the related studies and develop the atmospheric environmental health criteria and national ambient air quality

  6. Sensitive Mid-IR Laser Sensor Development and Mass Spectrometric Measurements in Shock Tube and Flames

    KAUST Repository

    Alquaity, Awad


    With global emission regulations becoming stringent, development of new combustion technologies that meet future emission regulations is essential. In this vein, this dissertation presents the application of sensitive diagnostic tools to validate and improve chemical kinetic mechanisms that play a fundamental role in the design of new combustion technologies. First, a novel high sensitivity laser-based sensor with a wide frequency tuning range (900 – 1000 cm-1) was developed utilizing pulsed cavity ringdown spectroscopy (CRDS) technique. The novel laser-based sensor was illustrated by measuring trace amounts of multiple combustion intermediates, namely ethylene, propene, allene, and 1-butene in a static cell at ambient conditions. Subsequently, pulsed CRDS technique was utilized to develop an ultra-fast, high sensitivity diagnostic to monitor trace concentrations of ethylene in shock tube pyrolysis experiments. This diagnostic represented the first ever successful application of CRDS technique to transient species measurements in a shock tube. The high sensitivity and fast time response (10μs) diagnostic may be utilized for measuring other key neutrals and radicals which are crucial in the oxidation chemistry of practical fuels. Secondly, a quadrupole mass spectrometer (QMS) was employed to measure relative cation mole fractions in atmospheric and low-pressure (30 Torr) flames of methane/oxygen diluted in argon. Lean, stoichiometric and rich flames were 4 examined to evaluate the dependence of ion chemistry on flame stoichiometry. Spatial distribution of cations was compared with predictions of an existing ion chemistry model. Based on the extensive measurements carried out in this work, modifications were suggested to improve the ion chemistry model to enhance the fidelity of such mechanisms. In-depth understanding of flame ion chemistry is vital to model the interaction of flames with electric fields and thereby pave the way to enable active combustion control

  7. Emissions of BVOC from lodgepole pine in response to mountain pine beetle attack in high and low mortality forest stands

    Directory of Open Access Journals (Sweden)

    T. R. Duhl


    Full Text Available In this screening study, biogenic volatile organic compound (BVOC emissions from intact branches of lodgepole pine (Pinus contorta trees were measured from trees at two forested sites that have been impacted differently by the mountain pine beetle (MPB, with one having higher mortality and the other with lower mortality. Differences in the amounts and chemical diversity of BVOC between the two sites and from apparently healthy trees versus trees in different stages of MPB attack are presented, as well as (for one site observed seasonal variability in emissions. A brief comparison is made of geological and climatic characteristics as well as prior disturbances (both natural and man-made at each site. Trees sampled at the site experiencing high MPB-related tree mortality had lower chemodiversity in terms of monoterpene (MT emission profiles, while profiles were more diverse at the lower-mortality site. Also at the higher-mortality site, MPB-infested trees in various stages of decline had lower emissions of sesquiterpenes (SQTs compared to healthy trees, while at the site with lower mortality, MPB-survivors had significantly higher SQT emissions during part of the growing season when compared to both uninfested and newly infested trees. SQT profiles differed between the two sites and, like monoterpene and oxygenated VOC profiles, varied through the season. For the low-mortality site in which repeated measurements were made over the course of the early summer–late fall, higher chemical diversity was observed in early- compared to late-season measurements for all compound classes investigated (MT, oxygenated VOC, and SQT, with the amount of change appearing to correlate to the MPB status of the trees studied. Emissions of 2-methyl-3-buten-2-ol (MBO had a distinct seasonal signal but were not much different between healthy or infested trees, except in trees with dead needles, from which emissions of this compound were negligible, and in late

  8. Aqueous geochemistry of low molecular weight hydrocarbons at elevated temperatures and pressures: constraints from mineral buffered laboratory experiments (United States)

    Seewald, Jeffrey S.


    Organic matter, water, and minerals coexist at elevated temperatures and pressures in sedimentary basins and participate in a wide range of geochemical processes that includes the generation of oil and natural gas. A series of laboratory experiments were conducted at 300 to 350°C and 350 bars to examine chemical interactions involving low molecular weight aqueous hydrocarbons with water and Fe-bearing minerals under hydrothermal conditions. Mineral buffers composed of hematite-magnetite-pyrite, hematite-magnetite, and pyrite-pyrrhotite-magnetite were added to each experiment to fix the redox state of the fluid and the activity of reduced sulfur species. During each experiment the chemical system was externally modified by addition of ethene, ethane, propene, 1-butene, or n-heptane, and variations in the abundance of aqueous organic species were monitored as a function of time and temperature. Results of the experiments indicate that decomposition of aqueous n-alkanes proceeds through a series of oxidation and hydration reactions that sequentially produce alkenes, alcohols, ketones, and organic acids as reaction intermediaries. Organic acids subsequently undergo decarboxylation and/or oxidation reactions to form carbon dioxide and shorter chain saturated hydrocarbons. This alteration assemblage is compositionally distinct from that produced by thermal cracking under anhydrous conditions, indicating that the presence of water and minerals provide alternative reaction pathways for the decomposition of hydrocarbons. The rate of hydrocarbon oxidation decreases substantially under reducing conditions and in the absence of catalytically active aqueous sulfur species. These results represent compelling evidence that the stability of aqueous hydrocarbons at elevated temperatures in natural environments is not a simple function of time and temperature alone. Under the appropriate geochemical conditions, stepwise oxidation represents a mechanism for the decomposition of low

  9. Promoted neuronal differentiation after activation of alpha4/beta2 nicotinic acetylcholine receptors in undifferentiated neural progenitors.

    Directory of Open Access Journals (Sweden)

    Takeshi Takarada

    Full Text Available BACKGROUND: Neural progenitor is a generic term used for undifferentiated cell populations of neural stem, neuronal progenitor and glial progenitor cells with abilities for proliferation and differentiation. We have shown functional expression of ionotropic N-methyl-D-aspartate (NMDA and gamma-aminobutyrate type-A receptors endowed to positively and negatively regulate subsequent neuronal differentiation in undifferentiated neural progenitors, respectively. In this study, we attempted to evaluate the possible functional expression of nicotinic acetylcholine receptor (nAChR by undifferentiated neural progenitors prepared from neocortex of embryonic rodent brains. METHODOLOGY/PRINCIPAL FINDINGS: Reverse transcription polymerase chain reaction analysis revealed mRNA expression of particular nAChR subunits in undifferentiated rat and mouse progenitors prepared before and after the culture with epidermal growth factor under floating conditions. Sustained exposure to nicotine significantly inhibited the formation of neurospheres composed of clustered proliferating cells and 3-[4,5-dimethylthiazol-2-yl]-2,5-diphenyltetrazolium bromide reduction activity at a concentration range of 1 µM to 1 mM without affecting cell survival. In these rodent progenitors previously exposed to nicotine, marked promotion was invariably seen for subsequent differentiation into cells immunoreactive for a neuronal marker protein following the culture of dispersed cells under adherent conditions. Both effects of nicotine were significantly prevented by the heteromeric α4β2 nAChR subtype antagonists dihydro-β-erythroidine and 4-(5-ethoxy-3-pyridinyl-N-methyl-(3E-3-buten-1-amine, but not by the homomeric α7 nAChR subtype antagonist methyllycaconitine, in murine progenitors. Sustained exposure to nicotine preferentially increased the expression of Math1 among different basic helix-loop-helix proneural genes examined. In undifferentiated progenitors from embryonic mice

  10. A shock tube study of C4–C6 straight chain alkenes + OH reactions

    KAUST Repository

    Khaled, Fathi


    Alkenes are known to be good octane boosters and they are major components of commercial fuels. Detailed theoretical calculations and direct kinetic measurements of elementary reactions of alkenes with combustion radicals are scarce for C4 alkenes and they are practically absent for C5 and larger alkenes. The overall rate coefficients for the reaction of OH radical with 1-butene (CH CHCH CH, k ), 1-pentene (CH CHCH CH-CH, k ), cis/trans 2-pentene (CH CHCHCH CH, k and k ), 1-hexene (CH CHCH CH CH CH, k ) and cis/trans 2-hexene (CH CHCHCH CH CH, k and k ) were measured behind reflected shock waves over the temperature range of 833-1377K and pressures near 1.5atm. The reaction progress was followed by measuring mole fraction of OH radicals near 306.7nm using UV laser absorption technique. It is found that the rate coefficients of OH+trans-2-alkenes are larger than those of OH+cis-2-alkenes, followed by OH+1-alkenes. The derived Arrhenius expressions for the overall rate coefficients (in cm.mol.s) are:. kI=(4.83±0.03)104.T2.72±0.01.exp(940.8±2.9cal/molRT)(946K-1256K) + kII=(5.66±0.54)10-1.T4.14±0.80.exp(4334±227cal/molRT)(875K-1379K) + kIII=(3.25±0.12)104.T2.76±0.5.exp(1962±83cal/molRT)(877K-1336K) + kIV=(3.42±0.09)104.T2.76±0.5.exp(1995±59cal/molRT)(833K-1265K) + kV=(7.65±0.58)10-4.T5±1.exp(5840±175cal/molRT)(836K-1387K) + kVI=(2.58±0.06)106.T2.17±0.37.exp(1461±55cal/molRT)(891K-1357K) + kVII=(3.08±0.05)106.T2.18±0.37.exp(1317±38cal/molRT)(881K-1377K) +

  11. Atmospheric chemistry of (Z)-CF3CH═CHCF3: OH radical reaction rate coefficient and global warming potential. (United States)

    Baasandorj, Munkhbayar; Ravishankara, A R; Burkholder, James B


    Rate coefficients, k, for the gas-phase reaction of the OH radical with (Z)-CF(3)CH═CHCF(3) (cis-1,1,1,4,4,4-hexafluoro-2-butene) were measured under pseudo-first-order conditions in OH using pulsed laser photolysis (PLP) to produce OH and laser-induced fluorescence (LIF) to detect it. Rate coefficients were measured over a range of temperatures (212-374 K) and bath gas pressures (20-200 Torr; He, N(2)) and found to be independent of pressure over this range of conditions. The rate coefficient has a non-Arrhenius behavior that is well-described by the expression k(1)(T) = (5.73 ± 0.60) × 10(-19) × T(2) × exp[(678 ± 10)/T] cm(3) molecule(-1) s(-1) where k(1)(296 K) was measured to be (4.91 ± 0.50) × 10(-13) cm(3) molecule(-1) s(-1) and the uncertainties are at the 2σ level and include estimated systematic errors. Rate coefficients for the analogous OD radical reaction were determined over a range of temperatures (262-374 K) at 100 Torr (He) to be k(2)(T) = (4.81 ± 0.20) × 10(-19) × T(2) × exp[(776 ± 15)/T], with k(2)(296 K) = (5.73 ± 0.50) × 10(-13) cm(3) molecule(-1) s(-1). OH radical rate coefficients were also measured at 296, 345, and 375 K using a relative rate technique and found to be in good agreement with the PLP-LIF results. A room-temperature rate coefficient for the O(3) + (Z)-CF(3)CH═CHCF(3) reaction was measured using an absolute method with O(3) in excess to be reaction was estimated to be ~20 days. Infrared absorption spectra of (Z)-CF(3)CH═CHCF(3) measured in this work were used to determine a (Z)-CF(3)CH═CHCF(3) global warming potential (GWP) of ~9 for the 100 year time horizon. A comparison of the OH reactivity of (Z)-CF(3)CH═CHCF(3) with other unsaturated fluorinated compounds is presented.

  12. Mid-IR Absorption Cross-Section Measurements of Hydrocarbons

    KAUST Repository

    Alrefae, Majed Abdullah


    Laser diagnostics are fast-response, non-intrusive and species-specific tools perfectly applicable for studying combustion processes. Quantitative measurements of species concentration and temperature require spectroscopic data to be well-known at combustion-relevant conditions. Absorption cross-section is an important spectroscopic quantity and has direct relation to the species concentration. In this work, the absorption cross-sections of basic hydrocarbons are measured using Fourier Transform Infrared (FTIR) spectrometer, tunable Difference Frequency Generation laser and fixed wavelength helium-neon laser. The studied species are methane, methanol, acetylene, ethylene, ethane, ethanol, propylene, propane, 1-butene, n-butane, n-pentane, n-hexane, and n-heptane. The Fourier Transform Infrared (FTIR) spectrometer is used for the measurements of the absorption cross-sections and the integrated band intensities of the 13 hydrocarbons. The spectral region of the spectra is 2800 – 3400 cm-1 (2.9 – 3.6 μm) and the temperature range is 673 – 1100 K. These valuable data provide huge opportunities to select interference-free wavelengths for measuring time-histories of a specific species in a shock tube or other combustion systems. Such measurements can allow developing/improving chemical kinetics mechanisms by experimentally determining reaction rates. The Difference Frequency Generation (DFG) laser is a narrow line-width, tunable laser in the 3.35 – 3.53 μm wavelength region which contains strong absorption features for most hydrocarbons due to the fundamental C-H vibrating stretch. The absorption cross-sections of propylene are measured at seven different wavelengths using the DFG laser. The temperature range is 296 – 460 K which is reached using a Reflex Cell. The DFG laser is very attractive for kinetic studies in the shock tube because of its fast time response and the potential possibility of making species-specific measurements. The Fixed wavelength

  13. Qualitative and quantitative analysis of atmospheric organosulfates in Centreville, Alabama (United States)

    Hettiyadura, Anusha P. S.; Jayarathne, Thilina; Baumann, Karsten; Goldstein, Allen H.; de Gouw, Joost A.; Koss, Abigail; Keutsch, Frank N.; Skog, Kate; Stone, Elizabeth A.


    .13-0.57 % of the total bisulfate ion signal. Precursors of m/z 96 mainly consisted of nitro-oxy organosulfates. Organosulfates identified were mainly associated with biogenic VOC precursors, particularly isoprene and to a lesser extent monoterpenes and 2-methyl-3-buten-2-ol (MBO). While a small number of molecules dominated the total organosulfate signal, a large number of minor species were also present. This study provides insights into the major organosulfate species in the southeastern US, as measured by tandem mass spectrometry that should be targets for future standard development and quantitative analysis.

  14. Alexip: an Expert System Coupled with a Dynamic Simulator for the Supervision of the Alphabutol Process ALEXIP : système couplé à un simulateur dynamique pour la supervision du procédé Alphabutol

    Directory of Open Access Journals (Sweden)

    Cauvin S.


    Full Text Available ALEXIP (ALphabutol EXpert IFP is a knowledge-based system designed to improve the operation of the Alphabutol petrochemical process (IFP process which produces 1-butene by dimerizing ethylene by helping the operators in their process control tasks in running industrial units. Coupled with a dynamic simulator, this system assesses the situation of the process at any time and determines the measures to be taken to maintain it or to bring it into a state of optimal operation. The structure developed is generic. The knowledge is stored in the form of facts easily read by the experts and processed by general rules written in second-order logic using the Genesia 2 software. It accordingly helps to accommodate new knowledge easily, and can be adapted to other processes. ALEXIP (ALphabutol Expert IFP est un système à base de connaissances dont le but est d'améliorer l'exploitation du procédé pétrochimique Alphabutol (procédé IFP qui produit du butène-1 par dimérisation de l'éthylène en aidant les opérateurs dans leurs tâches de conduite des unités industrielles. Couplé à un simulateur dynamique, ce système analyse l'état dans lequel se trouve le procédé à un instant donné et détermine les actions à entreprendre pour le maintenir ou le ramener dans un état de fonctionnement optimal. La structure élaborée est générique ; la connaissance est stockée sous forme de faits lisibles facilement par les experts et traités par des règles générales écrites en logique d'ordre 2 à l'aide du logiciel Génésia 2. Elle permet donc d'accueillir facilement de nouvelles connaissances et peut être adaptée à d'autres procédés.

  15. The Unimolecular Reactions of CF3CHF2Studied by Chemical Activation: Assignment of Rate Constants and Threshold Energies to the 1,2-H Atom Transfer, 1,1-HF and 1,2-HF Elimination Reactions, and the Dependence of Threshold Energies on the Number of F-Atom Substituents in the Fluoroethane Molecules. (United States)

    Smith, Caleb A; Gillespie, Blanton R; Heard, George L; Setser, D W; Holmes, Bert E


    The recombination of CF 3 and CHF 2 radicals in a room-temperature bath gas was used to prepare vibrationally excited CF 3 CHF 2 * molecules with 101 kcal mol -1 of vibrational energy. The subsequent 1,2-H atom transfer and 1,1-HF and 1,2-HF elimination reactions were observed as a function of bath gas pressure by following the CHF 3 , CF 3 (F)C: and C 2 F 4 product concentrations by gas chromatography using a mass spectrometer as the detector. The singlet CF 3 (F)C: concentration was measured by trapping the carbene with trans-2-butene. The experimental rate constants are 3.6 × 10 4 , 4.7 × 10 4 , and 1.1 × 10 4 s -1 for the 1,2-H atom transfer and 1,1-HF and 1,2-HF elimination reactions, respectively. These experimental rate constants were matched to statistical RRKM calculated rate constants to assign threshold energies (E 0 ) of 88 ± 2, 88 ± 2, and 87 ± 2 kcal mol -1 to the three reactions. Pentafluoroethane is the only fluoroethane that has a competitive H atom transfer decomposition reaction, and it is the only example with 1,1-HF elimination being more important than 1,2-HF elimination. The trend of increasing threshold energies for both 1,1-HF and 1,2-HF processes with the number of F atoms in the fluoroethane molecule is summarized and investigated with electronic-structure calculations. Examination of the intrinsic reaction coordinate associated with the 1,1-HF elimination reaction found an adduct between CF 3 (F)C: and HF in the exit channel with a dissociation energy of ∼5 kcal mol -1 . Hydrogen-bonded complexes between HF and the H atom migration transition state of CH 3 (F)C: and the F atom migration transition state of CF 3 (F)C: also were found by the calculations. The role that these carbene-HF complexes could play in 1,1-HF elimination reactions is discussed.

  16. Transferable Anisotropic United-Atom Force Field Based on the Mie Potential for Phase Equilibrium Calculations: n-Alkanes and n-Olefins. (United States)

    Hemmen, Andrea; Gross, Joachim


    A new transferable force field parametrization for n-alkanes and n-olefins is proposed in this work. A united-atom approach is taken, where hydrogen atoms are lumped with neighboring atoms to single interaction sites. A comprehensive study is conducted for alkanes, optimizing van der Waals force field parameters in 6 dimensions. A Mie n-6 potential is considered for the van der Waals interaction, where for n-alkanes we simultaneously optimize the energy parameters ϵCH3 and ϵCH2 as well as the size parameters σCH3 and σCH2 of the CH3(sp(3)) and CH2(sp(3)) groups. Further, the repulsive exponent n of the Mie n-6 potential is varied. Moreover, we investigate the bond length toward the terminal CH3 group as a degree of freedom. According to the AUA (anisotropic united-atom) force field, the bond length between the terminal CH3 group and the neighboring interaction site should be increased by Δl compared with the carbon-carbon distance in order to better account for the hydrogen atoms. The parameter Δl is considered as a degree of freedom. The intramolecular force field parametrization is taken from existing force fields. A single objective function for the optimization is defined as squared relative deviations in vapor pressure and in liquid density of propane, n-butane, n-hexane, and n-octane. A similar study is also done for olefins, where the objective function includes 1-butene, 1-hexene, 1-octene, cis-2-pentene, and trans-2-pentene. Molecular simulations are performed in the grand canonical ensemble with transition-matrix sampling where the phase equilibrium properties are obtained with the histogram reweighting technique. The 6-dimensional optimization of strongly correlated parameters is possible, because the analytic PC-SAFT equation of state is used to locally correlate simulation results. The procedure is iterative but leads to very efficient convergence. An implementation is proposed, where the converged result is not affected (disturbed) by the

  17. Floral characteristics and pollination ecology of Manglietia ventii (Magnoliaceae, a plant species with extremely small populations (PSESP endemic to South Yunnan of China

    Directory of Open Access Journals (Sweden)

    Bin Wang


    Full Text Available Manglietia ventii is a highly endangered plant species endemic to Yunnan province in China, where there are only five known small populations. Despite abundant flowering there is very low fruit and seed set, and very few seedlings in natural populations, indicating problems with reproduction. The causes of low fecundity in M. ventii are not known, largely because of insufficient knowledge of the species pollination ecology and breeding system. We conducted observations and pollination experiments, and analyzed floral scents to understand the pollinator–plant interactions and the role of floral scent in this relationship, as well as the species breeding system. Like the majority of Magnoliaceae, M. ventii has protogynous and nocturnal flowers that emit a strong fragrance over two consecutive evenings. There is a closing period (the pre-staminate stage during the process of anthesis of a flower, and we characterize the key flowering process as an “open-close-reopen” flowering rhythm with five distinct floral stages observed throughout the floral period of this species: pre-pistillate, pistillate, pre-staminate, staminate, and post-staminate. Flowers are in the pistillate stage during the first night of anthesis and enter the staminate stage the next night. During anthesis, floral scent emission occurs in the pistillate and staminate stages. The effective pollinators were weevils (Sitophilus sp. and beetles (Anomala sp., while the role of Rove beetles (Aleochara sp. and thrips (Thrips sp. in pollination of M. ventii appears to be minor or absent. The major chemical compounds of the floral scents were Limonene, β-Pinene, α-Pinene, 1,8-Cineole, Methyl-2-methylbutyrate, p-Cymene, Methyl-3-methyl-2-butenoate and 2-Methoxy-2-methyl-3-buten, and the relative proportions of these compounds varied between the pistillate and staminate stages. Production of these chemicals coincided with flower visitation by weevils and beetles. The results of

  18. Boreal forest BVOC exchange: emissions versus in-canopy sinks (United States)

    Zhou, Putian; Ganzeveld, Laurens; Taipale, Ditte; Rannik, Üllar; Rantala, Pekka; Petteri Rissanen, Matti; Chen, Dean; Boy, Michael


    A multilayer gas dry deposition model has been developed and implemented into a one-dimensional chemical transport model SOSAA (model to Simulate the concentrations of Organic vapours, Sulphuric Acid and Aerosols) to calculate the dry deposition velocities for all the gas species included in the chemistry scheme. The new model was used to analyse in-canopy sources and sinks, including gas emissions, chemical production and loss, dry deposition, and turbulent transport of 12 featured biogenic volatile organic compounds (BVOCs) or groups of BVOCs (e.g. monoterpenes, isoprene+2-methyl-3-buten-2-ol (MBO), sesquiterpenes, and oxidation products of mono- and sesquiterpenes) in July 2010 at the boreal forest site SMEAR II (Station for Measuring Ecosystem-Atmosphere Relations). According to the significance of modelled monthly-averaged individual source and sink terms inside the canopy, the selected BVOCs were classified into five categories: 1. Most of emitted gases are transported out of the canopy (monoterpenes, isoprene + MBO). 2. Chemical reactions remove a significant portion of emitted gases (sesquiterpenes). 3. Bidirectional fluxes occur since both emission and dry deposition are crucial for the in-canopy concentration tendency (acetaldehyde, methanol, acetone, formaldehyde). 4. Gases removed by deposition inside the canopy are compensated for by the gases transported from above the canopy (acetol, pinic acid, β-caryophyllene's oxidation product BCSOZOH). 5. The chemical production is comparable to the sink by deposition (isoprene's oxidation products ISOP34OOH and ISOP34NO3). Most of the simulated sources and sinks were located above about 0.2 hc (canopy height) for oxidation products and above about 0.4 hc for emitted species except formaldehyde. In addition, soil deposition (including deposition onto understorey vegetation) contributed 11-61 % to the overall in-canopy deposition. The emission sources peaked at about 0.8-0.9 hc, which was higher than 0.6 hc

  19. Molecular analysis of volatile metabolites released specifically by staphylococcus aureus and pseudomonas aeruginosa

    Directory of Open Access Journals (Sweden)

    Filipiak Wojciech


    Full Text Available Abstract Background The routinely used microbiological diagnosis of ventilator associated pneumonia (VAP is time consuming and often requires invasive methods for collection of human specimens (e.g. bronchoscopy. Therefore, it is of utmost interest to develop a non-invasive method for the early detection of bacterial infection in ventilated patients, preferably allowing the identification of the specific pathogens. The present work is an attempt to identify pathogen-derived volatile biomarkers in breath that can be used for early and non- invasive diagnosis of ventilator associated pneumonia (VAP. For this purpose, in vitro experiments with bacteria most frequently found in VAP patients, i.e. Staphylococcus aureus and Pseudomonas aeruginosa, were performed to investigate the release or consumption of volatile organic compounds (VOCs. Results Headspace samples were collected and preconcentrated on multibed sorption tubes at different time points and subsequently analyzed with gas chromatography mass spectrometry (GC-MS. As many as 32 and 37 volatile metabolites were released by S. aureus and P. aeruginosa, respectively. Distinct differences in the bacteria-specific VOC profiles were found, especially with regard to aldehydes (e.g. acetaldehyde, 3-methylbutanal, which were taken up only by P. aeruginosa but released by S. aureus. Differences in concentration profiles were also found for acids (e.g. isovaleric acid, ketones (e.g. acetoin, 2-nonanone, hydrocarbons (e.g. 2-butene, 1,10-undecadiene, alcohols (e.g. 2-methyl-1-propanol, 2-butanol, esters (e.g. ethyl formate, methyl 2-methylbutyrate, volatile sulfur compounds (VSCs, e.g. dimethylsulfide and volatile nitrogen compounds (VNCs, e.g. 3-methylpyrrole. Importantly, a significant VOC release was found already 1.5 hours after culture start, corresponding to cell numbers of ~8*106 [CFUs/ml]. Conclusions The results obtained provide strong evidence that the detection and perhaps even

  20. Receptor modelling and risk assessment of volatile organic compounds measured at a regional background site in South Africa (United States)

    Jaars, Kerneels; Vestenius, Mika; van Zyl, Pieter G.; Beukes, Johan P.; Hellén, Heidi; Vakkari, Ville; Venter, Marcell; Josipovic, Miroslav; Hakola, Hannele


    Volatile organic compounds (VOCs) can have significant impacts on climate and human health. Certain VOCs are proven to be carcinogenic and toxic, which can affect human health directly and indirectly. In order to develop climate change reduction strategies and to assess the impacts of VOCs on human health, it is crucial to determine the sources of VOCs, which can be emitted from biogenic and anthropogenic sources. The aim of this study was to perform source apportionment using positive matrix factorisation (PMF) analysis on VOC data collected at a regional background location affected by the major sources in the interior of South Africa, which include the western- and eastern Bushveld Igneous Complex, the Johannesburg-Pretoria metropolitan conurbation, the Vaal Triangle, the Mpumalanga Highveld and also a region of anti-cyclonic recirculation of air mass over the interior of South Africa. In addition, a risk assessment study was also performed in view of the major source regions affecting Welgegund in order to quantify the impacts of anthropogenic VOCs measured at Welgegund on human health. Measurements were conducted at the Welgegund measurement station located on a commercial farm approximately 100 km west of Johannesburg for a period of more than two years. PMF analysis revealed ten meaningful factor solutions, of which five factors were associated with biogenic emissions and five with anthropogenic sources. Three of the biogenic factors were characterised by a specific biogenic species, i.e. isoprene, limonene and 2-methyl-3-buten-2-ol (MBO), while the other two biogenic factors comprised mixtures of biogenic species with different tracer species. The temporal factor contribution for the isoprene, limonene and MBO factors correlated relatively well with the seasonal wet pattern. One anthropogenic factor was associated with emissions from a densely populated anthropogenic source region to the east of Welgegund with a large number of industrial activities, while

  1. Reactions of hydroxyl radicals with alkenes in low-temperature matrices. (United States)

    Feltham, E J; Almond, M J; Marston, G; Wiltshire, K S; Goldberg, N


    The reactions of hydroxyl radicals with a number of stable alkenes have been studied in low-temperature matrices. The reactions were initiated by broad band UV-visible irradiation of matrices containing H2O2, and the alkene under investigation. The hydroxyalkyl radical products were identified principally by comparison of their spectra with the spectra of corresponding stable alcohols. Accordingly, IR spectra were recorded for the following series of alcohols isolated in argon matrices--methanol, ethanol, ethanol-d6, propan-1-ol, propan-2-ol, butan-2-ol, 2-methylpropan-1-ol (iso-butyl alcohol), 2-methylpropan-2-ol (tert-butyl alcohol), 2-methylbutan-2-ol (tert-amyl alcohol), 3-methylbutan-2-ol and 2,3-dimethylbutan-2-ol. The hydroxyalkyl radicals, which appear to be formed from the alkenes studied were as follows--from ethene, 2-hydroxyethyl radical: from cis- or trans-but-2-ene. 1-methyl-2-hydroxypropyl radical; from propene, 1-methyl-2-hydroxyethyl and 2-hydroxypropyl radicals; from but-1-ene. 1-hydroxymethylpropyl and 2-hydroxybutyl radicals; from 2-methylpropene (iso-butene), 1,1-dimethyl-2-hydroxyethyl and 2-methyl-2-hydroxypropyl radicals; the radical products from buta-1,3-diene and isoprene could not be identified. In the cases, where two radical products were possible, i.e. when propene, but-1-ene or 2-methylpropene were the substrates, it was found that the concentration of the secondary or tertiary radical always exceeded that of the primary radical. However, the relative concentration of these radicals appears to be determined by subsequent photolysis to give carbonyl compounds. There seems, therefore, to be little preference for the secondary and tertiary radicals over the primary radicals in the primary addition process. Comments on the mechanism of the transformation from radical to carbonyl compound based upon identification of intermediates within the matrix and isotopic substitution experiments are made. The characterisation of the 2-hydroxyethyl

  2. New insights into the degradation of terpenoids with OH: a study of the OH budget in the atmosphere simulation chamber SAPHIR (United States)

    Kaminski, Martin; Fuchs, Hendrik; Acir, Ismail-Hakki; Bohn, Birger; Brauers, Theo; Dorn, Hans-Peter; Häseler, Rolf; Hofzumahaus, Andreas; Li, Xin; Lutz, Anna; Nehr, Sascha; Rohrer, Franz; Tillmann, Ralf; Wegener, Robert; Kiendler-Scharr, Astrid; Wahner, Andreas


    The hydroxyl radical (OH) is the main oxidation agent in the atmosphere during daytime. Recent field campaigns studying the radical chemistry in forested areas showed large discrepancies between measured and modeled OH concentration at low NOx conditions and when OH reactivity was dominated by VOC. These observations were only partially explained by the evidence for new efficient hydroxyl radical regeneration pathways in the isoprene oxidation mechanism. The question arises if other reactive VOCs with high global emission rates are also capable of additional OH recycling. Beside isoprene, monoterpenes and 2-methyl-3-buten-2-ol (MBO) are the volatile organic compounds (VOC) with the highest global emission rates. Due to their high reactivity towards OH monoterpenes and MBO can dominate the radical chemistry of the atmosphere in forested areas under certain conditions. In the present study the photochemical degradation mechanism of α-pinene, β-pinene, limonene, myrcene and MBO was investigated in the Jülich atmosphere simulation chamber SAPHIR. The focus of this study was in particular on the investigation of the OH budget in the degradation process. The photochemical degradation of these terpenoids was studied in a dedicated series of experiments in the years 2012 and 2013. The SAPHIR chamber was equipped with instrumentation to measure radicals (OH, HO2, RO2), the total OH reactivity, all important OH precursors (O3, HONO, HCHO), the parent VOC, its main oxidation products and photolysis frequencies to investigate the radical budget in the SAPHIR chamber. All experiments were carried out under low NOx conditions (≤ 2ppb) and atmospheric terpenoid concentrations (≤ 5ppb) with and without addition of ozone into the SAPHIR chamber. For the investigation of the OH budget all measured OH production terms were compared to the measured OH destruction. Within the limits of accuracy of the instruments the OH budget was balanced in all cases. Consequently unaccounted

  3. Terpenoid emissions from fully grown east Siberian Larix cajanderi trees (United States)

    Kajos, M. K.; Hakola, H.; Holst, T.; Nieminen, T.; Tarvainen, V.; Maximov, T.; Petäjä, T.; Arneth, A.; Rinne, J.


    While emissions of many biogenic volatile organic compounds (BVOCs), such as terpenoids, have been studied quite intensively in North American and Scandinavian boreal forests, the vast Siberian boreal forests have remained largely unexplored by experimental emission studies. In this study the shoot-scale terpenoid emission rates from two mature Larix cajanderi trees growing in their natural habitat in eastern Siberia were measured at the Spasskaya Pad flux measurement site (62°15´18.4" N, 129°37´07.9" E) located on the western bank of the Lena river. The measurements were conducted during three campaigns: 3-24 June, 8-26 July, and 14-30 August, in the summer of 2009. A dynamic flow-through enclosure technique was applied for adsorbent sampling, and the samples were analysed offline with a gas chromatograph. Between 29 and 45 samples were taken from each shoot during all three campaigns. Seven different monoterpenes, six different sesquiterpenes, linalool isoprene, and 2-methyl-3-buten-2-ol (MBO) were identified. The monthly median value of the total terpenoid emissions varied between 0.006 and 10.6 μg gdw-1 h-1. The emissions were dominated by monoterpenes, which constituted between 61 and 92% of the total emissions. About half of the monoterpene emissions were comprised of Δ 3-carene; α- and β-pinene had significant emissions as well. Linalool emissions were also substantial, comprising 3-37% of the total emissions, especially in June. Sesquiterpenes accounted for less than 3% and isoprene less than 1% of the total emissions. Based on the measured emission rates, the relative atmospheric concentration of each compound was estimated. Monoterpenes were the species with the highest relative concentration, while linalool and sesquiterpenes had a notably smaller contribution to the estimated atmospheric concentration than to the emission rates. A temperature-dependent pool algorithm with a constant β (0.09 °C-1 for monoterpenes and 0.143 °C-1 for

  4. Terpenoid emissions from fully grown east Siberian Larix cajanderi trees

    Directory of Open Access Journals (Sweden)

    M. K. Kajos


    Full Text Available While emissions of many biogenic volatile organic compounds (BVOCs, such as terpenoids, have been studied quite intensively in North American and Scandinavian boreal forests, the vast Siberian boreal forests have remained largely unexplored by experimental emission studies. In this study the shoot-scale terpenoid emission rates from two mature Larix cajanderi trees growing in their natural habitat in eastern Siberia were measured at the Spasskaya Pad flux measurement site (62°15´18.4" N, 129°37´07.9" E located on the western bank of the Lena river. The measurements were conducted during three campaigns: 3–24 June, 8–26 July, and 14–30 August, in the summer of 2009. A dynamic flow-through enclosure technique was applied for adsorbent sampling, and the samples were analysed offline with a gas chromatograph. Between 29 and 45 samples were taken from each shoot during all three campaigns. Seven different monoterpenes, six different sesquiterpenes, linalool isoprene, and 2-methyl-3-buten-2-ol (MBO were identified. The monthly median value of the total terpenoid emissions varied between 0.006 and 10.6 μg gdw−1 h−1. The emissions were dominated by monoterpenes, which constituted between 61 and 92% of the total emissions. About half of the monoterpene emissions were comprised of Δ 3-carene; α- and β-pinene had significant emissions as well. Linalool emissions were also substantial, comprising 3–37% of the total emissions, especially in June. Sesquiterpenes accounted for less than 3% and isoprene less than 1% of the total emissions. Based on the measured emission rates, the relative atmospheric concentration of each compound was estimated. Monoterpenes were the species with the highest relative concentration, while linalool and sesquiterpenes had a notably smaller contribution to the estimated atmospheric concentration than to the emission rates. A temperature-dependent pool algorithm with a constant β (0.09 °C−1 for monoterpenes

  5. Effect of the nature of the substrate on the surface chemistry of atomic layer deposition precursors (United States)

    Yao, Yunxi; Coyle, Jason P.; Barry, Seán T.; Zaera, Francisco


    The thermal chemistry of Cu(I)-sec-butyl-2-iminopyrrolidinate, a promising copper amidinate complex for atomic layer deposition (ALD) applications, was explored comparatively on several surfaces by using a combination of surface-sensitive techniques, specifically temperature-programmed desorption and x-ray photoelectron spectroscopy (XPS). The substrates explored include single crystals of transition metals (Ni(110) and Cu(110)), thin oxide films (NiO/Ni(110) and SiO2/Ta), and oxygen-treated metals (O/Cu(110)). Decomposition of the pyrrolidinate ligand leads to the desorption of several gas-phase products, including CH3CN, HCN and butene from the metals and CO and CO2 from the oxygen-containing surfaces. In all cases dehydrogenation of the organic moieties is accompanied by hydrogen removal from the surface, in the form of H2 on metals and mainly as water from the metal oxides, but the threshold for this chemistry varies wildly, from 270 K on Ni(110) to 430 K on O/Cu(110), 470 K on Cu(110), 500 K on NiO/Ni(110), and 570 K on SiO2/Ta. Copper reduction is also observed in both the Cu 2p3/2 XPS and the Cu L3 VV Auger (AES) spectra, reaching completion by 300 K on Ni(110) but occurring only between 500 and 600 K on Cu(110). On NiO/Ni(110), both Cu(I) and Cu(0) coexist between 200 and 500 K, and on SiO2/Ta a change happens between 500 and 600 K but the reduction is limited, with the copper atoms retaining a significant ionic character. Additional experiments to test adsorption at higher temperatures led to the identification of temperature windows for the self-limiting precursor uptake required for ALD between approximately 300 and 450 K on both Ni(110) and NiO/Ni(110); the range on SiO2 had been previously determined to be wider, reaching an upper limit at about 500 K. Finally, deposition of copper metal films via ALD cycles with O2 as the co-reactant was successfully accomplished on the Ni(110) substrate.

  6. Knowledge Based Catalyst Design by High Throughput Screening of Model Reactions and Statistical Modelling Conception de catalyseur par criblage à haut débit de réactions modèles et modélisation statistique

    Directory of Open Access Journals (Sweden)

    Morra G.


    Full Text Available Material design and synthesis are key steps in the development of catalysts. They are usually based on an empiric and/or theoretical approach. The recently developed high-throughput experimentation can accelerate optimisation of new catalytic formulations by systematic screening in a predefined study domain. This work aims at developing a QSAR (Quantitative Structure Activity Relationship method based on kinetic and mechanistic descriptors for metal and acid catalysis. Physico-chemicalfeatures of approximately sixty bimetallic catalysts have been measured according to their performance in two model reactions: xylene hydrogenation for catalysis on metallic sites and isomerisation of 3,3-dimethyl-l-butene for catalysis on acid sites. These descriptors were finally used to model the performances of around twenty catalysts for a more complex reaction: n-decane dehydrogenation. La définition et la préparation de matériaux sont des étapes clés dans le développement de catalyseurs. Celles-ci peuvent être effectuées de façon empirique et/ou à partir de bases théoriques. Par ailleurs, l’expérimentation à haut débit, technologie récente, permet d’accélérer l’optimisation de formulations catalytiques par exemple par criblage systématique d’un espace d’étude prédéfini. Cet article a pour objet de développer une méthode QSAR (Quantitative Structure Activity Relationship basée sur la recherche de descripteurs cinétiques et mécanistiques, dans le domaine de la catalyse acide et métallique supportée. Des caractéristiques physico-chimiques (descripteurs d’une soixantaine de catalyseurs bimétalliques ont été mesurées suivant leur performance dans deux réactions modèles : l’hydrogénation de ro-xylène pour rendre compte de la catalyse par le métal et l’isomérisation du diméthyl-3,3butène-1 pour la catalyse par les sites acides. Ces descripteurs ont été ensuite mis à profit pour modéliser les performances

  7. Avaliação do desempenho de catalisadores híbridos Ziegler-Natta/metaloceno na homo- e copolimerização de etileno The performance evaluation of hybrid Ziegler-Natta/metallocene catalysts in homo- and copolymerization of ethylene

    Directory of Open Access Journals (Sweden)

    Fernanda O. V. Cunha


    Full Text Available Foram preparados catalisadores híbridos a partir de um catalisador do tipo Ziegler-Natta heterogêneo (MgCl2.TiCl4 e de um metalocênico (CpTiCl3, afim de se obter catalisadores com diferentes tipos de centros ativos. Foi proposta a formação de um novo centro ativo (CpTi(iBuCl2 na face 100 do suporte de MgCl2. Estes catalisadores foram avaliados na síntese de polietileno de alta densidade (PEAD e de polietileno linear de baixa densidade (PELBD, utilizando-se somente trietilalumínio (TEA como cocatalisador. Foi verificada a influência da razão molar Al/Ti, temperatura e tempo de polimerização na produtividade dos catalisadores e nas propriedades dos polímeros obtidos. Os catalisadores mistos apresentaram atividade catalítica da ordem de 5,0 kgPol/g cat.h na polimerização de etileno e da ordem de 7,0 kgPol/g cat.h na copolimerização etileno-1-buteno.Hybrid catalysts formed by a heterogeneous Ziegler-Natta catalyst (MgCl2.TiCl4 and a metallocene (CpTiCl3 were prepared in this work. The formation of a new catalytic species CpTi(iBuCl2 on the (100 MgCl2 face has been proposed. These catalyst systems were applied to synthesize high density polyethylene (HDPE and linear low density polyethylene (LLDPE, using only triethyl aluminium (TEA as a cocatalyst. The influence of Al/Ti molar ratio, temperature and time of polymerization on the catalyst activity and on the polymer properties were evaluated. The catalyst activities were about 5.0 kgPol/g cat.h for ethylene polymerization and 7.0 kgPol/g cat.h for ethylene-1-butene coplymerization.

  8. Studies of the Atmospheric Chemsitry of Energy-Related Volatile Organic Compounds and of their Atmospheric Reaction Products

    Energy Technology Data Exchange (ETDEWEB)

    Roger Atkinson; Janet Arey


    The focus of this contract was to investigate selected aspects of the atmospheric chemistry of volatile organic compounds (VOCs) emitted into the atmosphere from energy-related sources as well as from biogenic sources. The classes of VOCs studied were polycyclic aromatic hydrocarbons (PAHs) and nitro-PAHs, the biogenic VOCs isoprene, 2-methyl-3-buten-2-ol and cis-3-hexen-1-ol, alkenes (including alkenes emitted from vegetation) and their oxygenated atmospheric reaction products, and a series of oxygenated carbonyl and hydroxycarbonyl compounds formed as atmospheric reaction products of aromatic hydrocarbons and other VOCs. Large volume reaction chambers were used to investigate the kinetics and/or products of photolysis and of the gas-phase reactions of these organic compounds with hydroxyl (OH) radicals, nitrate (NO3) radicals, and ozone (O3), using an array of analytical instrumentation to analyze the reactants and products (including gas chromatography, in situ Fourier transform infrared spectroscopy, and direct air sampling atmospheric pressure ionization tandem mass spectrometry). The following studies were carried out. The photolysis rates of 1- and 2-nitronaphthalene and of eleven isomeric methylnitronaphthalenes were measured indoors using blacklamp irradiation and outdoors using natural sunlight. Rate constants were measured for the gas-phase reactions of OH radicals, Cl atoms and NO3 radicals with naphthalene, 1- and 2-methylnaphthalene, 1- and 2-ethylnaphthalene and the ten dimethylnaphthalene isomers. Rate constants were measured for the gas-phase reactions of OH radicals with four unsaturated carbonyls and with a series of hydroxyaldehydes formed as atmospheric reaction products of other VOCs, and for the gas-phase reactions of O3 with a series of cycloalkenes. Products of the gas-phase reactions of OH radicals and O3 with a series of biogenically emitted VOCs were identified and quantified. Ambient atmospheric measurements of the concentrations of a

  9. The Low Temperature Oxidation of 2,7-Dimethyloctane in a Pressurized Flow Reactor (United States)

    Farid, Farinaz

    n-decane resulted primarily in the formation of ethene near the NTC start, propene and isobutene were the major olefins produced from 2,7-DMO. A comparative analysis of experimental data with respect to a detailed chemical kinetic model for 2,7-DMO was performed and discrepancies were noted. Based on these results, a collaborative effort with Dr. Charles Westbrook (Lawrence Livermore National Laboratory) was initiated to refine the model predictions in the low temperature and NTC regimes. The effort resulted in an updated version of the 2,7-DMO mechanism, improving some of the key features such as calculated CO2 profile and final yields of iso-butene over the studied range of temperature. Fuel pyrolysis in the intermediate temperature regime, 850 -- 1000 K, also was investigated for the first time in the PFR facility. However, preliminary n-decane experiments measured only a small amount of fuel decomposition, indicating that higher temperature operation would be beneficial. The major species produced from n-decane decomposition, in descending order of molar fraction, were ethene, propene, and 1-butene. These results were compared with the predictions of two existing chemical kinetic models and the sources of variations between the experiments and the models as well as among the mechanisms were investigated. At 1000 K, the mechanisms predicted higher levels of fuel depletion and ethene production. Also, while the mechanisms were similar in their predicted pathways for fuel depletion and formation of ethene, inconsistencies were observed in relative contribution of these pathways to the final yields as well as the rate parameter determination for several sensitive reactions with respect to n-decane and ethene. Overall, the research aided in achieving a data set quantifying the oxidation characteristics of 2,7-DMO (and n-decane for comparison) as well as an elucidation of critical reaction pathways based on experimental results. Preliminary pyrolysis experiments were

  10. Characterization of submicron particles influenced by mixed biogenic and anthropogenic emissions using high-resolution aerosol mass spectrometry: results from CARES

    Energy Technology Data Exchange (ETDEWEB)

    Setyan, Ari; Zhang, Qi; Merkel, M.; Knighton, Walter B.; Sun, Y.; Song, Chen; Shilling, John E.; Onasch, Timothy B.; Herndon, Scott C.; Worsnop, Douglas R.; Fast, Jerome D.; Zaveri, Rahul A.; Berg, Larry K.; Wiedensohler, A.; Flowers, B. A.; Dubey, Manvendra K.; Subramanian, R.


    due to local traffic. Twenty three periods of urban plumes from T0 (Sacramento) to T1 (Cool) were identified using the Weather Research and Forecasting model coupled with Chemistry (WRF-Chem). The average PM1 mass loading was much higher in urban plumes (3.9 {micro}gm{sup -3}) than in air masses dominated by biogenic SOA (1.8 {micro}gm{sup -3}). The change in OA mass relative to CO ({Delta}OA/{Delta}CO) varied in the range of 5-196 {micro}gm{sup -3} ppm{sup -1}, reflecting large variability in SOA production. The highest {Delta}OA/{Delta}CO were reached when urban plumes arrived at Cool in the presence of a high concentration of biogenic volatile organic compounds (BVOCs=isoprene+monoterpenes+2-methyl-3-buten-2- ol [MBO]+methyl chavicol). This ratio, which was 77 {micro}gm{sup -3} ppm{sup -1} on average when BVOCs > 2 ppb, is much higher than when urban plumes arrived in a low biogenic VOCs environment (28 {micro}gm{sup -3} ppm{sup -1} when BVOCs < 0.7 ppb) or during other periods dominated by biogenic SOA (40 {micro}gm{sup -3} ppm{sup -1}). The results from this study demon10 strate that SOA formation is enhanced when anthropogenic emissions interact with biogenic precursors.

  11. Multinuclear group 4 catalysis: olefin polymerization pathways modified by strong metal-metal cooperative effects. (United States)

    McInnis, Jennifer P; Delferro, Massimiliano; Marks, Tobin J


    Polyolefins are produced today catalytically on a vast scale, and the manufactured polymers find use in everything from artificial limbs and food/medical packaging to automotive and electrical components and lubricants. Although polyolefin monomers are typically cheap (e.g., ethylene, propylene, α-olefins), the resulting polymer properties can be dramatically tuned by the particular polymerization catalyst employed, and reflect a rich interplay of macromolecular chemistry, materials science, and physics. For example, linear low-density polyethylene (LLDPE), produced by copolymerization of ethylene with linear α-olefin comonomers such as 1-butene, 1-hexene, or 1-octene, has small but significant levels of short alkyl branches (C2, C4, C6) along the polyethylene backbone, and is an important technology material due to outstanding rheological and mechanical properties. In 2013, the total world polyolefin production was approximately 211 million metric tons, of which about 11% was LLDPE. Historically, polyolefins were produced using ill-defined but highly active heterogeneous catalysts composed of supported groups 4 or 6 species (usually halides) activated by aluminum alkyls. In 1963, Karl Ziegler and Giulio Natta received the Nobel Prize for these discoveries. Beginning in the late 1980s, a new generation of group 4 molecule-based homogeneous olefin polymerization catalysts emerged from discoveries by Walter Kaminsky, a team led by James Stevens at The Dow Chemical Company, this Laboratory at Northwestern University, and a host of talented groups in Germany, Italy, Japan, the United Kingdom, and the United States. These new "single-site" catalysts and their activating cocatalysts were far better defined and more rationally tunable in terms of structure, mechanism, thermodynamics, and catalyst activity and selectivity than ever before possible. An explosion of research advances led to new catalysts, cocatalysts, deeper mechanistic understanding of both the

  12. Molecular metal catalysts on supports: organometallic chemistry meets surface science. (United States)

    Serna, Pedro; Gates, Bruce C


    -support bonding and structure, which identify the supports as ligands with electron-donor properties that influence reactivity and catalysis. Each of the catalyst design variables has been varied independently, illustrated by mononuclear and tetranuclear iridium on zeolite HY and on MgO and by isostructural rhodium and iridium (diethylene or dicarbonyl) complexes on these supports. The data provide examples resolving the roles of the catalyst design variables and place the catalysis science on a firm foundation of organometallic chemistry linked with surface science. Supported molecular catalysts offer the advantages of characterization in the absence of solvents and with surface-science methods that do not require ultrahigh vacuum. Families of supported metal complexes have been made by replacement of ligands with others from the gas phase. Spectroscopically identified catalytic reaction intermediates help to elucidate catalyst performance and guide design. The methods are illustrated for supported complexes and clusters of rhodium, iridium, osmium, and gold used to catalyze reactions of small molecules that facilitate identification of the ligands present during catalysis: alkene dimerization and hydrogenation, H-D exchange in the reaction of H2 with D2, and CO oxidation. The approach is illustrated with the discovery of a highly active and selective MgO-supported rhodium carbonyl dimer catalyst for hydrogenation of 1,3-butadiene to give butenes.

  13. VOC and VOX in fluid inclusions of quartz: New chemical insights into hydrothermal vein mineralization by GC-MS and GC-IRMS measurements (United States)

    Sattler, Tobias; Kirnbauer, Thomas; Keppler, Frank; Greule, Markus; Fischer, Jan; Spiekermann, Patrik; Schreiber, Ulrich; Mulder, Ines; Schöler, Heinz Friedrich


    Fluid inclusions (FIs) in minerals are known to contain a variety of different liquids, gases, and solids. The fluids get trapped during mineral growth and can preserve the original mineral-forming fluid or fluids of later events. A new analytical technique developed by Mulder et al. (2013) [1] allows to measure trace gases in FIs. For the measurements, grains of 3-5 mm diameter are ground in an airtight grinding device, releasing the volatiles from FIs into the gas phase, where they can be measured by GC-MS, GC-FID and GC-IRMS. The Taunus covers the southeastern part of the thrust-and-fold-belt of the Rhenish Massif (Germany). The Variscan rock sequences comprise sedimentary and volcanic units ranging from Ordovician to Lower Carboniferous. Several types of hydrothermal mineralization can be distinguished, which are - in regard to the Variscan orogeny - pre-orogenic, orogenic, late-orogenic, post-orogenic and recent in age [2]. They include SEDEX, vein, Alpine fissure, disseminated and stockwerk mineralizations. Thus, the Taunus mineralizations enable investigations of different hydrothermal systems at different age in one region. For most of them extensive studies of stable and radiogenic isotopes exist. Quartz crystals of post-orogenic quartz veins and Pb-Zn-Cu bearing veins [3] were selected for our FI investigation. Sulphur containing compounds like COS and CS2 dominate the FIs but there are also volatile hydrocarbons (VOC) like different butenes, benzene, toluene and cyclopentene that were found very often. In some samples volatile halogenated organic carbons (VOX) like chloro- and bromomethane were found. Some FIs even contain iodomethane, chlorobenzene, vinyl chloride and -bromide. The non-fossil-fuel subsurface chemistry of VOC and VOX is not fully understood. There are a lot of unknown geogenic sources [4][5]. For a better understanding δ13C- and δ2H-values of CH4 were measured by GC-IRMS to examine if the detected organic compounds are formed biotic

  14. Impacts of mechanistic changes on HOx formation and recycling in the oxidation of isoprene

    Directory of Open Access Journals (Sweden)

    R. G. Derwent


    Full Text Available Recently reported model-measurement discrepancies for the concentrations of the HOx radical species (OH and HO2 in locations characterized by high emission rates of isoprene have indicated possible deficiencies in the representation of OH recycling and formation in isoprene mechanisms currently employed in numerical models; particularly at low levels of NOx. Using version 3.1 of the Master Chemical Mechanism (MCM v3.1 as a base mechanism, the sensitivity of the system to a number of detailed mechanistic changes is examined for a wide range of NOx levels, using a simple box model. The studies consider sensitivity tests in relation to three general areas for which experimental and/or theoretical evidence has been reported in the peer-reviewed literature, as follows: (1 implementation of propagating channels for the reactions of HO2 with acyl and β-oxo peroxy radicals with HO2, with support from a number of studies; (2 implementation of the OH-catalysed conversion of isoprene-derived hydroperoxides to isomeric epoxydiols, as characterised by Paulot et al.~(2009a; and (3 implementation of a mechanism involving respective 1,5 and 1,6 H atom shift isomerisation reactions of the β-hydroxyalkenyl and cis-δ-hydroxyalkenyl peroxy radical isomers, formed from the sequential addition of OH and O2 to isoprene, based on the theoretical study of Peeters et al. (2009. All the considered mechanistic changes lead to simulated increases in the concentrations of OH, with (1 and (2 resulting in respective increases of up to about 7% and 16%, depending on the level of NOx. (3 is found to have potentially much greater impacts, with enhancements in OH concentrations of up to a factor of about 3.3, depending on the level of NOx, provided the (crucial rapid photolysis of the hydroperoxy-methyl-butenal products of the cis-δ-hydroxyalkenyl peroxy radical isomerisation reactions is represented, as also postulated by Peeters et al.~(2009. Additional tests suggest that

  15. Chromatography and mass spectrometry of prebiological and biological molecules (United States)

    Navale, Vivek

    The detection and identification of prebiological and biological molecules are of importance for understanding chemical and biological processes occurring within the solar system. Molecular mass measurements, peptide mapping, and disulfide bond analysis of enzymes and recombinant proteins are important in the development of therapeutic drugs for human diseases. Separation of hydrocarbons (C1 to C6) and nitriles was achieved by 14%-cyanopropylphenyl-86%- dimethylpolysiloxane (CPPS-DMPS) stationary phase in a narrow bore metal capillary column. The calculation of modeling numbers enabled the differentiation of the C4 hydrocarbon isomers of 1-butene (cis and trans). The modeled retention time values for benzene, toluene, xylene, acetonitrile, propane, and propene nitriles were in good agreement with the measurements. The separation of C2 hydrocarbons (ethane and ethene) from predominantly N2 matrix was demonstrated for the first time on wall coated narrow bore low temperature glassy carbon column. Identification and accurate mass measurements of pepsin, an enzymatic protein with less number of basic amino acid residues were successfully demonstrated by matrix- assisted laser desorption ionization mass spectrometry (MALDI-MS). The molecular mass of pepsin was found to be 34,787 Da. Several decomposition products of pepsin, in m/z range of 3,500 to 4,700 were identified. Trypsin, an important endopeptidase enzyme had a mass of 46829.7 Da. Lower mass components with m/z 8047.5, 7776.6, 5722, 5446.2 and 5185 Da were also observed in trypsin spectrum. Both chemokine and growth factor recombinant proteins were mass analyzed as 8848.1 ± 3.5 and 16178.52 ± 4.1 Da, respectively. The accuracy of the measurements was in the range of 0.01 to 0.02%. Reduction and alkylation experiments on the chemokine showed the presence of six cysteines and three disulfide bonds. The two cysteines of the growth factor contained the free sulfhydryl groups and the accurate average mass of the

  16. Theoretical investigations of the thermochemistry, structures, and internal rotation of conjugated polyynes (United States)

    Jarowski, Peter D.

    Chapter 1 discusses the thermochemistry of conjugated double and triple bonds. The conjugation stabilization energies of dienes and diynes are considerably larger than estimates based on heat of hydrogenation differences between 1,3-butadiyne and 1-butyne as well as between 1,3-butadiene and 1-butene. Such comparisons do not take into account the counterbalancing hyperconjugative stabilization of the partially hydrogenated products by their ethyl groups. When alkyl hyperconjugation is considered, the conjugation stabilization of diynes (≈ 9.3 kcal/mol) is found by two methods (involving isomerization of non-conjugated into conjugated isomers and heats of hydrogenation) to be larger than that of dienes (≈ 8.2 kcal/mol). In Chapter 2 the stabilization of substituted organic radicals, relative to methyl, are computed using bond separation energies and the block localized wavefunction method. These energies are typically evaluated from C-H bond dissociation energies (computed here by the CBS-RAD method). However, this method gives stabilization energies of an increasing number of mono-, di-, and tri-substituted vinyl and ethynyl substituents, which differ from the predictions of Perturbation Molecular Orbital (PMO) and Huckel Molecular Orbital (HMO) theory. The saturation (attenuation) effect for both series should be monotonic and small. Instead, the attenuation computed by the allylic series is larger than that predicted by HMO theory and the behavior of the propargylic series is erratic. These discrepancies arise from the use of bond dissociation energy data in the evaluations, which depend not only on the stabilization of the radicals, but also on the substantial substituent effects (e.g., hyperconjugation) on the energies of the reference hydrocarbons. New evaluation schemes are proposed that avoid such complications and thus estimate radical stabilization effects directly; the results agree with PMO and HMO theories. Substitution effects are analyzed using

  17. Caracterização de polietilenos lineares de baixa densidade II: fracionamento por cristalização isotérmica a partir do estado fundido Linear low-density polyethylene characterization II: fractionation by multiple-step isothermal crystallization from the melting state

    Directory of Open Access Journals (Sweden)

    Antonio C. Quental


    copolymerization with ethene. The alpha-olefins commonly used are 1-butene, 1-hexene and 1-octene. Depending on the alpha-olefin and the catalyst used for the polymerization, LLDPE presents different microstructures which determine the thermal and mechanical properties. One simple and efficient method to evaluate the microstructure of LLDPE is the fractionation by Multiple-Step Isothermal Crystallization from Melting State conducted by DSC. This method is based on several steps of isothermal crystallization of the polymer on decreasing the temperature from the melt. This process favors the separation of the crystalline material into groups having different lamellae thickness depending on the amount and distribution of the alpha-olefin units in the macromolecular chains and on the molar mass. The melting endotherm of a fractionated sample is made up of the same number of peaks as the isothermal crystallization steps, which inform the relative comonomers distributions between different LLDPE chains. In this work, this methodology was applied to determine the relative comonomers distribution of different LLDPE. The isothermal temperature, temperature range and the time influence the efficiency of the fractionation and these parameters must be chosen according to the LLDPE microstructure.

  18. Impact of hydrofluorocarbon molecular structure parameters on plasma etching of ultra-low-K dielectric

    Energy Technology Data Exchange (ETDEWEB)

    Li, Chen [Department of Physics and Institute for Research in Electronics and Applied Physics, University of Maryland, College Park, Maryland 20742 (United States); Gupta, Rahul; Pallem, Venkateswara [American Air Liquide, Newark, Delaware 19702 (United States); Oehrlein, Gottlieb S., E-mail: [Department of Materials Science and Engineering, University of Maryland, College Park, Maryland 20742 and Institute for Research in Electronics and Applied Physics, University of Maryland, College Park, Maryland 20742 (United States)


    The authors report a systematic study aimed at evaluating the impact of molecular structure parameters of hydrofluorocarbon (HFC) precursors on plasma deposition of fluorocarbon (FC) films and etching performance of a representative ultra-low-k material, along with amorphous carbon. The precursor gases studied included fluorocarbon and hydrofluorocarbon gases whose molecular weights and chemical structures were systematically varied. Gases with three different degrees of unsaturation (DU) were examined. Trifluoromethane (CHF{sub 3}) is the only fully saturated gas that was tested. The gases with a DU value of one are 3,3,3-trifluoropropene (C{sub 3}H{sub 3}F{sub 3}), hexafluoropropene (C{sub 3}F{sub 6}), 1,1,3,3,3-pentafluoro-1-propene (C{sub 3}HF{sub 5}), (E)-1,2,3,3,3-pentafluoropropene (C{sub 3}HF{sub 5} isomer), heptafluoropropyl trifluorovinyl ether (C{sub 5}F{sub 10}O), octafluorocyclobutane (C{sub 4}F{sub 8}), and octafluoro-2-butene (C{sub 4}F{sub 8} isomer). The gases with a DU value of two includes hexafluoro-1,3-butadiene (C{sub 4}F{sub 6}), hexafluoro-2-butyne (C{sub 4}F{sub 6} isomer), octafluorocyclopentene (C{sub 5}F{sub 8}), and decafluorocyclohexene (C{sub 6}F{sub 10}). The work was performed in a dual frequency capacitively coupled plasma reactor. Real-time characterization of deposition and etching was performed using in situ ellipsometry, and optical emission spectroscopy was used for characterization of CF{sub 2} radicals in the gas phase. The chemical composition of the deposited FC films was examined by x-ray photoelectron spectroscopy. The authors found that the CF{sub 2} fraction, defined as the number of CF{sub 2} groups in a precursor molecule divided by the total number of carbon atoms in the molecule, determines the CF{sub 2} optical emission intensity of the plasma. CF{sub 2} optical emission, however, is not the dominant factor that determines HFC film deposition rates. Rather, HFC film deposition rates are determined by the number of

  19. Mechanistic studies of olefin and alkyne trimerization with chromium catalysts: deuterium labeling and studies of regiochemistry using a model chromacyclopentane complex. (United States)

    Agapie, Theodor; Labinger, Jay A; Bercaw, John E


    chromacycloheptane intermediate on route to 1-hexene formation. Reactions of olefins with a model of a chromacyclopentane were investigated starting from Cr(PNP(O4))(o,o'-biphenyldiyl)Br. alpha-Olefins react with cationic biphenyldiyl chromium species to generate products from 1,2-insertion. A study of the reaction of 2-butenes indicated that beta-H elimination occurs preferentially from the ring CH rather than exo-CH bond in the metallacycloheptane intermediates. A study of cotrimerization of ethylene with propylene correlates with these findings of regioselectivity. Competition experiments with mixtures of two olefins indicate that the relative insertion rates generally decrease with increasing size of the olefins.

  20. La consommation de propylène en Europe occidentale Propylene Consumption in Western Europe

    Directory of Open Access Journals (Sweden)

    Barraqué M.


    'éthylène; - le craquage du méthanol. The needs of Western Europe for propylene used in petrochemistry are currently 7. 4 x 10 to the power of 6 metric tons per year. In the coming years, the average rate of increase should be about 1. 8 % per year. Hence in 1995 European petrochemicals should use about 8. 7 x 10 to the power of 6 tons of propylene,Most of this increase in consumption will be due to the sharp rise in polypropylene production and to a lesser extent in propylene oxide, isopropanol and 2-ethyl hexanol production. However, uses for acrylonitrile and cumene will remain fairly stable. Propylene consumption for butanol production should decrease. The share of propylene needs met by European steam crackers, which was 82% in 1986, should be less than 75% in 1995. It will be more and more necessary to turn to other sources of supply. In 1986 European refineries produced 1. 05 x 10 to the power of 6 tons of propylene used for petrochemicals, and imports amounted to 0. 3 x 10 to the power of 6 tons. In 1995 the difference between consumption and production by steam crackers could be beyond 2. 0 x 10 to the power of 6 tons. It seems improbable that catalytic cracking plants can make up for the deficit except if propylene yields were to increase a great deal. The construction of propylene/propane splitters can be expected along with an increase in imports. Likewise, due to the tension that risks could appear in propylene prices, the advantage of some synthesis routes now considered not to be profitable might increase. These new routes are :(a dehydrogenation of propane as is already being considered in other regions (Mexico, Indonesia, Malaysia;(b metathesis between ethylene and butenes-2, which themselves can be produced from ethylene;(c methanol cracking.

  1. Effects of Zeolite Structure and Si/Al Ratio on Adsorption Thermodynamics and Intrinsic Kinetics of Monomolecular Cracking and Dehydrogenation of Alkanes over Bronsted Acid Sites (United States)

    Janda, Amber Leigh

    butene products. Theoretical calculations suggest that this effect originates from the adsorption of isobutene at channel intersections, indicating that dehydrogenation occurs with stronger preference for these locations than does cracking. In order to analyze the effects of zeolite structure on monomolecular alkane activation reactions, it is necessary to separate the contributions of the adsorption and reaction steps to observed kinetics. A method is developed in Chapter 3 for obtaining the enthalpy and entropy changes for adsorption of n-alkanes from the gas phase onto Bronsted protons (DeltaH ads·H+ and DeltaSads·H+) using configurational-bias Monte Carlo (CBMC) simulations. In Chapter 4 the effects of zeolite structural confinement on n-butane cracking and dehydrogenation are characterized for zeolites that differ predominately in the size and abundance of cavities. Values of DeltaHads·H+ and DeltaSads·H+ are obtained from CBMC simulations and used to extract intrinsic rates and activation parameters. As DeltaS ads·H+ (a proxy for confinement) becomes more negative, DeltaH ‡int and DeltaS‡int decrease for terminal cracking and dehydrogenation when the channel topology (e.g., straight, sinusoidal) is fixed. This observation, as well as positive values for DeltaS‡int, indicate that the transition states for these reactions resemble the products. Finally, in Chapter 5 the influence of channel and cage topology on n-alkane adsorption are characterized for zeolites and zeotypes with one-dimensional pore systems. When cages are not present, DeltaHads·H+ and DeltaSads·H+ at fixed pore-limiting diameter (PLD; the diameter of the largest sphere that can traverse the pores) decrease in magnitude as the ratio of the smallest to largest channel diameter decreases and the pore become less circular. The higher entropy of alkanes in non-circular pores is attributed to greater freedom of movement and can cause the free energy to be lower in these environments relative

  2. X-Ray Absorption Studies of Vanadium-Containing Metal Oxide Nanocrystals

    Energy Technology Data Exchange (ETDEWEB)

    Hohn, Keith, L.


    Metal oxide nanocrystals offer significant potential for use as catalysts or catalyst supports due to their high surface areas and unique chemical properties that result from the high number of exposed corners and edges. However, little is known about the catalytic activity of these materials, especially as oxidation catalysts. This research focused on the preparation, characterization and use of vanadium-containing nanocrystals as selective oxidation catalysts. Three vanadium-containing nanocrystals were prepared using a modified sol-gel procedure: V/MgO, V/SiO2, and vanadium phosphate (VPO). These represent active oxidation catalysts for a number of industrially relevant reactions. The catalysts were characterized by x-ray diffraction and Raman, UV-VIS, infrared and x-ray absorption spectroscopies with the goal of determining the primary structural and chemical differences between nanocrystals and microcrystals. The catalytic activity of these catalysts was also studied in oxidative dehydrogenation of butane and methanol oxidation to formaldehyde. V/MgO nanocrystals were investigated for activity in oxidative dehydrogenation of butane and compared to conventional V/MgO catalysts. Characterization of V/MgO catalysts using Raman spectroscopy and x-ray absorption spectroscopy showed that both types of catalysts contained magnesium orthovanadate at vanadium loadings below 15 weight%, but above that loading, magnesium pyrovanadate may have been present. In general, MgO nanocrystals had roughly half the crystal size and double the surface area of the conventional MgO. In oxidative dehydrogenation of butane, nanocrystalline V/MgO gave higher selectivity to butene than conventional V/MgO at the same conversion. This difference was attributed to differences in vanadium domain size resulting from the higher surface areas of the nanocrystalline support, since characterization suggested that similar vanadium phases were present on both types of catalysts. Experiments in

  3. Toxicology and carcinogenesis studies of methyl trans-styryl ketone (CAS NO 1896-62-4) in F344/N rats and B6C3F1 mice (feed and dermal studies). (United States)


    male or female F344/N rats or in male or female B6C3F1 mice administered 10, 30, or 90 mg/kg. Administration of methyl trans-styryl ketone resulted in nonneoplastic lesions of the skin at the site of application in male and female rats and mice. Synonyms: Acetocinnamone; benzalacetone; benzylideneacetone; methyl 2-phenylvinyl ketone; methyl styryl ketone; methyl β-styryl ketone; MSK; 4-phenyl-3-butene-2-one; 4-phenylbutenone; 2-phenylvinyl methyl ketone; styryl methyl ketone Systematic name: (3E)-4-Phenylbut-3-en-2-one.