National Library of Energy BETA

Sample records for methyl tertiary-butyl ether

  1. State Restrictions on Methyl Tertiary Butyl Ether (released in AEO2006)

    Reports and Publications (EIA)

    2006-01-01

    By the end of 2005, 25 states had barred, or passed laws banning, any more than trace levels of methyl tertiary butyl ether (MTBE) in their gasoline supplies, and legislation to ban MTBE was pending in 4 others. Some state laws address only MTBE; others also address ethers such as ethyl tertiary butyl ether (ETBE) and tertiary amyl methyl ether (TAME). Annual Energy Outlook 2006 assumes that all state MTBE bans prohibit the use of all ethers for gasoline blending.

  2. Enhanced diisobutene production in the presence of methyl tertiary butyl ether

    DOE Patents [OSTI]

    Smith, L.A. Jr.

    1983-03-01

    In the liquid phase reaction of isobutene in the presence of resin cation exchange resins with itself in a C[sub 4] hydrocarbon stream to form dimers, the formation of higher polymers, oligomers, and co-dimer by-products is suppressed by the presence of 0.0001 to 1 mole per mole of isobutene of methyl tertiary butyl ether. 1 fig.

  3. Enhanced diisobutene production in the presence of methyl tertiary butyl ether

    DOE Patents [OSTI]

    Smith, Jr., Lawrence A. (Bellaire, TX)

    1983-01-01

    In the liquid phase reaction of isobutene in the presence of resin cation exchange resins with itself in a C.sub.4 hydrocarbon stream to form dimers, the formation of higher polymers, oligomers, and co-dimer by-products is suppressed by the presence of 0.0001 to 1 mole per mole of isobutene of methyl tertiary butyl ether.

  4. TABLE33.CHP:Corel VENTURA

    Gasoline and Diesel Fuel Update (EIA)

    ethyl tertiary butyl ether (ETBE), tertiary amyl methyl ether (TAME), tertiary butyl alcohol (TBA), and other aliphatic alcohols and ethers intended for motor gasoline blending...

  5. TABLE34.CHP:Corel VENTURA

    Gasoline and Diesel Fuel Update (EIA)

    ethyl tertiary butyl ether (ETBE), tertiary amyl methyl ether (TAME), tertiary butyl alcohol (TBA), and other aliphatic alcohols and ethers intended for motor gasoline blending...

  6. Petroleum Supply Annual

    U.S. Energy Information Administration (EIA) Indexed Site

    ... amyl methyl ether (TAME), tertiary butyl alcohol (TBA), and other aliphatic alcohols and ... amyl methyl ether (TAME), tertiary butyl alcohol (TBA), and other aliphatic alcohols and ...

  7. Vapor pressures of methyl tert-butyl ether, ethyl tert-butyl ether, isopropyl tert-butyl ether, tert-amyl methyl ether, and tert-amyl ethyl ether

    SciTech Connect (OSTI)

    Kraehenbuehl, M.A.; Gmehling, J. . Technische Chemie)

    1994-10-01

    The vapor pressures of methyl tert-butyl ether, ethyl tert-butyl ether, isopropyl tert-butyl ether, tert-amyl methyl ether, and tert-amyl ethyl ether were measured by ebulliometry or the static method in the pressure ranges 14--102 and 3--835 kPa (methyl tert-butyl ether), respectively. The data were correlated using the Antoine and Wagner equations. The experimental data of methyl tert-butyl ether and ethyl tert-butyl ether were compared with data available in the literature.

  8. Supply Impacts of an MTBE Ban

    Reports and Publications (EIA)

    2002-01-01

    This paper analyzes the supply impacts of removing methyl tertiary butyl ether (MTBE) from gasoline.

  9. Tropospheric oxidation mechanism of dimethyl ether and methyl formate

    SciTech Connect (OSTI)

    Good, D.A.; Francisco, J.S.

    2000-02-17

    The oxidation mechanism of dimethyl ether is investigated using ab initio methods. The structure and energetics of reactants, products, and transition structures are determined for all pathways involved in the oxidation mechanism. The detailed pathways leading to the experimentally observed products of dimethyl ether oxidation are presented. The energetics of over 50 species and transition structures involved in the oxidation process are calculated with G2 and G2(MP2) energies. The principal pathway following the initial attack of dimethyl ether (CH{sub 3}OCH{sub 3}) by the OH radical is the formation of the methoxymethyl radical (CH{sub 2}OCH{sub 3}). Oxidation steps lead to the formation of methyl formate, which is consistent with the experimentally observed products. Oxidation pathways of methyl formate are also considered.

  10. MTBE Production Economics (Released in the STEO April 2001)

    Reports and Publications (EIA)

    2001-01-01

    The purpose of this analysis is to evaluate the causes of methyl tertiary butyl ether (MTBE) price increases in 2000.

  11. Methyl aryl ethers from coal liquids as gasoline extenders and octane improvers

    SciTech Connect (OSTI)

    Singerman, G.M.

    1980-11-01

    A mixture of methyl aryl ethers derived from the phenols present in direct liquefaction coal liquids shows considerable promise as a gasoline blending agent and octane improver. The mixture of methyl aryl ethers was blended at five volume percent with a commercial, unleaded gasoline. The properties and performance of the blend in a variety of laboratory and automotive tests is reported. The tests show that the mixture of methyl aryl ethers improves gasoline octane without degrading other gasoline properties.

  12. untitled

    Gasoline and Diesel Fuel Update (EIA)

    of "other" hydrocarbons and oxygenates include hydrogen and oxygenates especially fuel ethanol and methyl tertiary butyl ether (MTBE). The adjustment is equal to the...

  13. This Week In Petroleum Printer-Friendly Version

    Annual Energy Outlook [U.S. Energy Information Administration (EIA)]

    this transition from Methyl Tertiary Butyl Ether (MTBE) reformulated gasoline (RFG) to ethanol RFG, since ethanol is not blended into the gasoline mixture until just before the...

  14. Fuel Ethanol Oxygenate Production

    Annual Energy Outlook [U.S. Energy Information Administration (EIA)]

    Product: Fuel Ethanol Methyl Tertiary Butyl Ether Merchant Plants Captive Plants Period-Unit: Monthly-Thousand Barrels Monthly-Thousand Barrels per Day Annual-Thousand Barrels ...

  15. Impact of Renewable Fuels Standard/MTBE Provisions of S. 517 Requested by Sens. Daschle & Murkowski

    Reports and Publications (EIA)

    2002-01-01

    Additional analysis of the impact of the Renewable Fuels Standard (RFS) and methyl tertiary butyl ether (MTBE) ban provisions of S. 517.

  16. Motor Gasoline Market Spring 2007 and Implications for Spring...

    Annual Energy Outlook [U.S. Energy Information Administration (EIA)]

    began to decline, and with the transition from methyl tertiary butyl ether (MTBE) to ethanol completed and the end of the summer driving season drawing near, gasoline prices...

  17. Methyl tert-butyl ether and ethyl tert-butyl ether: A comparison of properties, synthesis techniques, and operating conditions

    SciTech Connect (OSTI)

    Sneesby, M.G.; Tade, M.O.; Datta, R.

    1996-12-31

    MTBE is currently the most industrially significant oxygenate but some of the properties of ETBE and the EPA ethanol mandate suggest that ETBE could become a viable competitor. Similar synthesis techniques are used for both ethers but the phase behaviour of the ETBE system requires slightly different operating conditions and creates some alternatives for product recovery. The process control strategy for both systems must address some unusual challenges. 9 refs., 1 tab.

  18. Separation of Dimethyl Ether from Syn-Gas Components by Poly(dimethylsiloxane) and Poly(4-methyl-1-pentene) Membranes

    SciTech Connect (OSTI)

    Christopher J. Orme; Frederick F. Stewart

    2011-05-01

    Permeability and selectivity in gas transport through poly(4-methyl-1-pentene) (TPX) and poly(dimethylsiloxane) (PDMS) using variable temperature mixed gas experiments is reported. Selected gases include H2, CO, CH4, CO2, and dimethyl ether (DME). The DME data is the first to be reported through these membranes. In this paper, the chosen polymers reflect both rubbery and crystalline materials. Rubbery polymers tend to be weakly size sieving, which, in this work, has resulted in larger permeabilities, lower separation factors, and lower activation energies of permeation (Ep). Conversely, the crystalline TPX membranes showed much greater sensitivity to penetrant size; although the gas condensability also played a role in transport.

  19. APPENDXD.CHP:Corel VENTURA

    Annual Energy Outlook [U.S. Energy Information Administration (EIA)]

    Report The Form EIA-819, "Monthly Oxygenate Report" provides production data for fuel ethanol and methyl tertiary butyl ether (MTBE). End-of-month stock data held at ethanol...

  20. Preparations for Meeting New York and Connecticut MTBE Bans

    Reports and Publications (EIA)

    2003-01-01

    In response to a Congressional request, the Energy Information Administration examined the progress being made to meet the bans on the use of methyl tertiary butyl ether (MTBE) being implemented in New York and Connecticut at the end of 2003.

  1. Using physiologically based pharmacokinetic modeling to address nonlinear kinetics and changes in rodent physiology and metabolism due to aging and adaptation in deriving reference values for propylene glycol methyl ether and propylene glycol methyl ether acetate.

    SciTech Connect (OSTI)

    Kirman, C R.; Sweeney, Lisa M.; Corley, Rick A.; Gargas, M L.

    2005-04-01

    Reference values, including an oral reference dose (RfD) and an inhalation reference concentration (RfC), were derived for propylene glycol methyl ether (PGME), and an oral RfD was derived for its acetate (PGMEA). These values were based upon transient sedation observed in F344 rats and B6C3F1 mice during a two-year inhalation study. The dose-response relationship for sedation was characterized using internal dose measures as predicted by a physiologically based pharmacokinetic (PBPK) model for PGME and its acetate. PBPK modeling was used to account for changes in rodent physiology and metabolism due to aging and adaptation, based on data collected during weeks 1, 2, 26, 52, and 78 of a chronic inhalation study. The peak concentration of PGME in richly perfused tissues was selected as the most appropriate internal dose measure based upon a consideration of the mode of action for sedation and similarities in tissue partitioning between brain and other richly perfused tissues. Internal doses (peak tissue concentrations of PGME) were designated as either no-observed-adverse-effect levels (NOAELs) or lowest-observed-adverse-effect levels (LOAELs) based upon the presence or absence of sedation at each time-point, species, and sex in the two year study. Distributions of the NOAEL and LOAEL values expressed in terms of internal dose were characterized using an arithmetic mean and standard deviation, with the mean internal NOAEL serving as the basis for the reference values, which was then divided by appropriate uncertainty factors. Where data were permitting, chemical-specific adjustment factors were derived to replace default uncertainty factor values of ten. Nonlinear kinetics are were predicted by the model in all species at PGME concentrations exceeding 100 ppm, which complicates interspecies and low-dose extrapolations. To address this complication, reference values were derived using two approaches which differ with respect to the order in which these extrapolations were performed: (1) uncertainty factor application followed by interspecies extrapolation (PBPK modeling); and (2) interspecies extrapolation followed by uncertainty factor application. The resulting reference values for these two approaches are substantially different, with values from the former approach being 7-fold higher than those from the latter approach. Such a striking difference between the two approaches reveals an underlying issue that has received little attention in the literature regarding the application of uncertainty factors and interspecies extrapolations to compounds where saturable kinetics occur in the range of the NOAEL. Until such discussions have taken place, reference values based on the latter approach are recommended for risk assessments involving human exposures to PGME and PGMEA.

  2. Manipulation of the HIF–Vegf pathway rescues methyl tert-butyl ether (MTBE)-induced vascular lesions

    SciTech Connect (OSTI)

    Bonventre, Josephine A.; Kung, Tiffany S.; White, Lori A.; Cooper, Keith R.

    2013-12-15

    Methyl tert-butyl ether (MTBE) has been shown to be specifically anti-angiogenic in piscine and mammalian model systems at concentrations that appear non-toxic in other organ systems. The mechanism by which MTBE targets developing vascular structures is unknown. A global transcriptome analysis of zebrafish embryos developmentally exposed to 0.00625–5 mM MTBE suggested that hypoxia inducible factor (HIF)-regulated pathways were affected. HIF-driven angiogenesis via vascular endothelial growth factor (vegf) is essential to the developing vasculature of an embryo. Three rescue studies were designed to rescue MTBE-induced vascular lesions: pooled blood in the common cardinal vein (CCV), cranial hemorrhages (CH), and abnormal intersegmental vessels (ISV), and test the hypothesis that MTBE toxicity was HIF–Vegf dependent. First, zebrafish vegf-a over-expression via plasmid injection, resulted in significantly fewer CH and ISV lesions, 46 and 35% respectively, in embryos exposed to 10 mM MTBE. Then HIF degradation was inhibited in two ways. Chemical rescue by N-oxaloylglycine significantly reduced CCV and CH lesions by 30 and 32% in 10 mM exposed embryos, and ISV lesions were reduced 24% in 5 mM exposed zebrafish. Finally, a morpholino designed to knock-down ubiquitin associated von Hippel–Lindau protein, significantly reduced CCV lesions by 35% in 10 mM exposed embryos. In addition, expression of some angiogenesis related genes altered by MTBE exposure were rescued. These studies demonstrated that MTBE vascular toxicity is mediated by a down regulation of HIF–Vegf driven angiogenesis. The selective toxicity of MTBE toward developing vasculature makes it a potentially useful chemical in the designing of new drugs or in elucidating roles for specific angiogenic proteins in future studies of vascular development. - Highlights: • Global gene expression of MTBE exposed zebrafish suggested altered HIF1 signaling. • Over expression of zebrafish vegf-a rescues MTBE-induced vascular lesions. • Inhibiting PHD or knocking down VHL rescues MTBE-induced vascular lesions. • HIF1-Vegf driven angiogenesis is a target for MTBE vascular toxicity.

  3. Process for producing high purity isoolefins and dimers thereof by dissociation of ethers

    DOE Patents [OSTI]

    Smith, L.A. Jr.; Jones, E.M. Jr.; Hearn, D.

    1984-05-08

    Alkyl tertiary butyl ether or alkyl tertiary amyl ether is dissociated by vapor phase contact with a cation acidic exchange resin at temperatures in the range of 150 to 250 F at LHSV of 0.1 to 20 to produce a stream consisting of unreacted ether, isobutene or isoamylene and an alcohol corresponding to the alkyl radical. After the alcohol is removed, the ether/isoolefin stream may be fractionated to obtain a high purity isoolefin (99+%) or the ether/isoolefin stream can be contacted in liquid phase with a cation acidic exchange resin to selectively dimerize the isoolefin in a highly exothermic reaction, followed by fractionation of the dimerization product to produce high purity diisoolefin (97+%). In the case where the alkyl is C[sub 3] to C[sub 6] and the corresponding alcohol is produced on dissociation of the ether, combined dissociation-distillation may be carried out such that isoolefin is the overhead product and alcohol the bottom. 2 figs.

  4. Process for producing high purity isoolefins and dimers thereof by dissociation of ethers

    DOE Patents [OSTI]

    Smith, Jr., Lawrence A.; Jones, Jr., Edward M.; Hearn, Dennis

    1984-01-01

    Alkyl tertiary butyl ether or alkyl tertiary amyl ether is dissociated by vapor phase contact with a cation acidic exchange resin at temperatures in the range of 150.degree. to 250.degree. F. at LHSV of 0.1 to 20 to produce a stream consisting of unreacted ether, isobutene or isoamylene and an alcohol corresponding to the alkyl radical. After the alcohol is removed, the ether/isoolefin stream may be fractionated to obtain a high purity isoolefin (99+%) or the ether/isoolefin stream can be contacted in liquid phase with a cation acidic exchange resin to selectively dimerize the isoolefin in a highly exothermic reaction, followed by fractionation of the dimerization product to produce high purity diisoolefin (97+%). In the case where the alkyl is C.sub.3 to C.sub.6 and the corresponding alcohol is produced on dissociation of the ether, combined dissociation-distillation may be carried out such that isoolefin is the overhead product and alcohol the bottom.

  5. FCC LPG olefinicity and branching enhanced by octane catalysts

    SciTech Connect (OSTI)

    Keyworth, D.A.; Reid, T.A.; Kreider, K.R.; Yatsu, C.A.

    1989-05-29

    Refiners are increasingly recognizing the downstream opportunities for fluid catalytic cracking LPG olefins for the production of methyl tertiary butyl ether (MTBE), ethyl tertiary butyl ether (ETBE, if the ethanol subsidy is extended to the production of ETBE), and as petrochemical feedstocks. Some of new gasoline FCC octane-enhancing catalysts can support those opportunities because their low non-framework alumina (low NFA) preserve both LPG olefinicity and promote branching of the LPG streams from the FCCU. The combined effect results in more isobutane for alkylate feed, more propylene in the propane/propylene stream, and more isobutene - which makes the addition of an MTBE unit very enticing.

  6. Impact of Renewable Fuels Standard/MTBE Provisions of S. 1766

    Reports and Publications (EIA)

    2002-01-01

    This service report addresses the Renewable Fuels Standard (RFS)/methyl tertiary butyl ether (MTBE) provisions of S. 1766. The 'S. 1766' Case reflects provisions of S. 1766 including a renewable fuels standard (RFS) reaching five billion gallons by 2012, a complete phase-out of MTBE within four years, and the option for states to waive the oxygen requirement for reformulated gasoline (RFG).

  7. Eliminating MTBE in Gasoline in 2006

    Reports and Publications (EIA)

    2006-01-01

    A review of the market implications resulting from the rapid change from methyl tertiary butyl ether (MTBE) to ethanol-blended reformulated gasoline (RFG) on the East Coast and in Texas. Strains in ethanol supply and distribution will increase the potential for price volatility in these regions this summer.

  8. Status and Impacts of State MTBE Bans

    Reports and Publications (EIA)

    2003-01-01

    This paper describes legislation passed in 16 states banning or restricting the use of methyl tertiary butyl ether (MTBE) in gasoline. Analysis of the status and impact of these state MTBE bans is provided concerning the supply and potential price changes of gasoline.

  9. U.S. Oxygenate Production

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    By: Product Area May-15 Jun-15 Jul-15 Aug-15 Sep-15 Oct-15 View History Fuel Ethanol 29,666 29,684 30,256 29,621 28,543 30,139 1981-2015 Methyl Tertiary Butyl Ether (MTBE) 1,634...

  10. Motor Gasoline Outlook and State MTBE Bans

    Reports and Publications (EIA)

    2003-01-01

    The U.S. is beginning the summer 2003 driving season with lower gasoline inventories and higher prices than last year. Recovery from this tight gasoline market could be made more difficult by impending state bans on the blending of methyl tertiary butyl ether (MTBE) into gasoline that are scheduled to begin later this year.

  11. Thermodynamic properties and ideal-gas enthalpies of formation for butyl vinyl ether, 1,2-dimethoxyethane, methyl glycolate, bicyclo[2.2.1]hept-2-ene, 5-vinylbicyclo[2.2.1]hept-2-ene, trans-azobenzene, butyl acrylate, di-tert-butyl ether, and hexane-1,6-diol

    SciTech Connect (OSTI)

    Steele, W.V.; Chirico, R.D.; Knipmeyer, S.E.; Nguyen, A.; Smith, N.K.

    1996-11-01

    Ideal-gas enthalpies of formation of butyl vinyl ether, 1,2-dimethoxyethane, methyl glycolate, bicyclo-[2.2.1]hept-2-ene, 5-vinylbicyclo[2.2.1]hept-2-ene, trans-azobenzene, butyl acrylate, di-tert-butyl ether, and hexane-1,6-diol are reported. Enthalpies of fusion were determined for bicyclo[2.2.1]hept-2-ene and trans-azobenzene. Two-phase (solid + vapor) or (liquid + vapor) heat capacities were determined from 300 K to the critical region or earlier decomposition temperature for each compound studied. Liquid-phase densities along the saturation line were measured for bicyclo[2.2.1]hept-2-ene. For butyl vinyl ether and 1,2-dimethoxyethane, critical temperatures and critical densities were determined from the dsc results and corresponding critical pressures derived from the fitting procedures. Fitting procedures were used to derive critical temperatures, critical pressures, and critical densities for bicyclo[2.2.1]hept-2-ene, 5-vinylbicyclo[2.2.1]hept-2-ene, trans-azobenzene, butyl acrylate, and di-tert-butyl ether. Group-additivity parameters or ring-correction terms useful in the application of the Benson group-contribution correlations were derived.

  12. Quercetin 3-O-methyl ether protects FL83B cells from copper induced oxidative stress through the PI3K/Akt and MAPK/Erk pathway

    SciTech Connect (OSTI)

    Tseng, Hsiao-Ling; Li, Chia-Jung; Huang, Lin-Huang; Chen, Chun-Yao; Tsai, Chun-Hao; Lin, Chun-Nan; Department of Biological Science and Technology, School of Medicine, China Medical University, Taichung, Taiwan ; Hsu, Hsue-Yin

    2012-10-01

    Quercetin is a bioflavonoid that exhibits several biological functions in vitro and in vivo. Quercetin 3-O-methyl ether (Q3) is a natural product reported to have pharmaceutical activities, including antioxidative and anticancer activities. However, little is known about the mechanism by which it protects cells from oxidative stress. This study was designed to investigate the mechanisms by which Q3 protects against Cu{sup 2+}-induced cytotoxicity. Exposure to Cu{sup 2+} resulted in the death of mouse liver FL83B cells, characterized by apparent apoptotic features, including DNA fragmentation and increased nuclear condensation. Q3 markedly suppressed Cu{sup 2+}-induced apoptosis and mitochondrial dysfunction, characterized by reduced mitochondrial membrane potential, caspase-3 activation, and PARP cleavage, in Cu{sup 2+}-exposed cells. The involvement of PI3K, Akt, Erk, FOXO3A, and Mn-superoxide dismutase (MnSOD) was shown to be critical to the survival of Q3-treated FL83B cells. The liver of both larval and adult zebrafish showed severe damage after exposure to Cu{sup 2+} at a concentration of 5 μM. Hepatic damage induced by Cu{sup 2+} was reduced by cotreatment with Q3. Survival of Cu{sup 2+}-exposed larval zebrafish was significantly increased by cotreatment with 15 μM Q3. Our results indicated that Cu{sup 2+}-induced apoptosis in FL83B cells occurred via the generation of ROS, upregulation and phosphorylation of Erk, overexpression of 14-3-3, inactivation of Akt, and the downregulation of FOXO3A and MnSOD. Hence, these results also demonstrated that Q3 plays a protective role against oxidative damage in zebrafish liver and remarked the potential of Q3 to be used as an antioxidant for hepatocytes. Highlights: ► Protective effects of Q3 on Cu{sup 2+}-induced oxidative stress in vitro and in vivo. ► Cu{sup 2+} induced apoptosis in FL83B cells via ROS and the activation of Erk. ► Q3 abolishes Cu{sup 2+}-induced apoptosis through the PI3K/Akt and MAPK/Erk pathway.

  13. Oxygenates du`jour...MTBE? Ethanol? ETBE?

    SciTech Connect (OSTI)

    Wolfe, R.

    1995-12-31

    There are many different liquids that contain oxygen which could be blended into gasoline. The ones that have been tried and make the most sense are in the alcohol (R-OH) and ether (R-O-R) chemical family. The alcohols considered are: methanol (MeOH), ethanol (EtOH), tertiary butyl alcohol (TBA). The ethers are: methyl tertiary butyl ether (MTBE), ethyl tertiary butyl ether (ETBE), tertiary amyl methyl ether (TAME), tertiary amyl ethyl ether (TAEE), di-isopropyl ether (DIPE). Of the eight oxygenates listed above, the author describes the five that are still waiting for widespread marketing acceptance (methanol, TBA, TAME, TAEE, and DIPE). He then discusses the two most widely used oxygenates in the US, MTBE and ethanol, along with the up-and-coming ethanol ether, ETBE. Selected physical properties for all of these oxygenates can be found in Table 2 at the end of this paper. A figure shows a simplified alcohol/ether production flow chart for the oxygenates listed above and how they are interrelated.

  14. {gamma}-aminobutyric acid{sub A} (GABA{sub A}) receptor regulates ERK1/2 phosphorylation in rat hippocampus in high doses of Methyl Tert-Butyl Ether (MTBE)-induced impairment of spatial memory

    SciTech Connect (OSTI)

    Zheng Gang; Zhang Wenbin; Zhang Yun; Chen Yaoming; Liu Mingchao; Yao Ting; Yang Yanxia; Zhao Fang; Li Jingxia; Huang Chuanshu; Luo Wenjing Chen Jingyuan

    2009-04-15

    Experimental and occupational exposure to Methyl Tert-Butyl Ether (MTBE) has been reported to induce neurotoxicological and neurobehavioral effects, such as headache, nausea, dizziness, and disorientation, etc. However, the molecular mechanisms involved in MTBE-induced neurotoxicity are still not well understood. In the present study, we investigated the effects of MTBE on spatial memory and the expression and function of GABA{sub A} receptor in the hippocampus. Our results demonstrated that intraventricular injection of MTBE impaired the performance of the rats in a Morris water maze task, and significantly increased the expression of GABA{sub A} receptor {alpha}1 subunit in the hippocampus. The phosphorylation of ERK1/2 decreased after the MTBE injection. Furthermore, the decreased ability of learning and the reduction of phosphorylated ERK1/2 level of the MTBE-treated rats was partly reversed by bicuculline injected 30 min before the training. These results suggested that MTBE exposure could result in impaired spatial memory. GABA{sub A} receptor may play an important role in the MTBE-induced impairment of learning and memory by regulating the phosphorylation of ERK in the hippocampus.

  15. THE SEARCH FOR A COMPLEX MOLECULE IN A SELECTED HOT CORE REGION: A RIGOROUS ATTEMPT TO CONFIRM TRANS-ETHYL METHYL ETHER TOWARD W51 e1/e2

    SciTech Connect (OSTI)

    Carroll, P. Brandon; McGuire, Brett A.; Blake, Geoffrey A.; Apponi, A. J.; Ziurys, L. M.; Remijan, Anthony

    2015-01-20

    An extensive search has been conducted to confirm transitions of trans-ethyl methyl ether (tEME, C{sub 2}H{sub 5}OCH{sub 3}), toward the high-mass star forming region W51 e1/e2 using the 12 m Telescope of the Arizona Radio Observatory at wavelengths from 2 mm and 3 mm. In short, we cannot confirm the detection of tEME toward W51 e1/e2 and our results call into question the initial identification of this species by Fuchs et al. Additionally, re-evaluation of the data from the original detection indicates that tEME is not present toward W51 e1/e2 in the abundance reported by Fuchs and colleagues. Typical peak-to-peak noise levels for the present observations of W51 e1/e2 were between 10 and 30 mK, yielding an upper limit of the tEME column density of ≤1.5 × 10{sup 15} cm{sup –2}. This would make tEME at least a factor of two times less abundant than dimethyl ether (CH{sub 3}OCH{sub 3}) toward W51 e1/e2. We also performed an extensive search for this species toward the high-mass star forming region Sgr B2(N-LMH) with the National Radio Astronomy Observatory 100 m Green Bank Telescope. No transitions of tEME were detected and we were able to set an upper limit to the tEME column density of ≤4 × 10{sup 14} cm{sup –2} toward this source. Thus, we are able to show that tEME is not a new molecular component of the interstellar medium and that an exacting assessment must be carried out when assigning transitions of new molecular species to astronomical spectra to support the identification of large organic interstellar molecules.

  16. Total Crude Oil and Petroleum Products Exports

    U.S. Energy Information Administration (EIA) Indexed Site

    Exports Product: Total Crude Oil and Petroleum Products Crude Oil Natural Gas Plant Liquids and Liquefied Refinery Gases Pentanes Plus Liquefied Petroleum Gases Ethane/Ethylene Propane/Propylene Normal Butane/Butylene Isobutane/Isobutylene Other Liquids Hydrogen/Oxygenates/Renewables/Other Hydrocarbons Oxygenates (excl. Fuel Ethanol) Methyl Tertiary Butyl Ether (MTBE) Other Oxygenates Renewable Fuels (incl. Fuel Ethanol) Fuel Ethanol Biomass-Based Diesel Unfinished Oils Naphthas and Lighter

  17. Total Crude Oil and Petroleum Products Imports by Area of Entry

    U.S. Energy Information Administration (EIA) Indexed Site

    by Area of Entry Product: Total Crude Oil and Petroleum Products Crude Oil Natural Gas Plant Liquids and Liquefied Refinery Gases Pentanes Plus Liquefied Petroleum Gases Ethane Ethylene Propane Propylene Normal Butane Butylene Isobutane Isobutylene Other Liquids Hydrogen/Oxygenates/Renewables/Other Hydrocarbons Oxygenates (excl. Fuel Ethanol) Methyl Tertiary Butyl Ether (MTBE) Other Oxygenates Renewable Fuels (incl. Fuel Ethanol) Fuel Ethanol Biomass-Based Diesel Fuel Other Renewable Diesel Fuel

  18. Total number of slots consumed in long_excl.q (exclusive nodes) will be

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Product: Total Crude Oil and Petroleum Products Crude Oil Natural Gas Plant Liquids and Liquefied Refinery Gases Pentanes Plus Liquefied Petroleum Gases Ethane/Ethylene Propane/Propylene Normal Butane/Butylene Isobutane/Isobutylene Other Liquids Hydrogen/Oxygenates/Renewables/Other Hydrocarbons Oxygenates (excl. Fuel Ethanol) Methyl Tertiary Butyl Ether (MTBE) Other Oxygenates Renewable Fuels (incl. Fuel Ethanol) Fuel Ethanol Biomass-Based Diesel Unfinished Oils Naphthas and Lighter Kerosene and

  19. MTEM Map

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    MTBE Production Economics Tancred C. M. Lidderdale Contents 1. Summary 2. MTBE Production Costs 3. Relationship between price of MTBE and Reformulated Gasoline 4. Influence of Natural Gas Prices on the Gasoline Market 5. Regression Results 6. Data Sources 7. End Notes 1. Summary Last year the price of MTBE (methyl tertiary butyl ether) increased dramatically on two occasions (Figure 1) (see Data Sources at end of article.): 1. Between April and June 2000, the price (U.S. Gulf Coast waterborne

  20. Update of Summer Reformulated Gasoline Supply Assessment for New York and Connecticut

    Reports and Publications (EIA)

    2004-01-01

    In October 2003, the Energy Information Administration (EIA) published a review of the status of the methyl tertiary butyl ether (MTBE) ban transition in New York (NY) and Connecticut (CT) that noted significant uncertainties in gasoline supply for those states for the summer of 2004. To obtain updated information, EIA spoke to major suppliers to the two states over the past several months as the petroleum industry began the switch from winter- to summer-grade gasoline.

  1. Crown ethers in graphene

    SciTech Connect (OSTI)

    Guo, Junjie; Lee, Jaekwang; Contescu, Cristian I; Gallego, Nidia C; Pantelides, Sokrates T.; Pennycook, Stephen J; Moyer, Bruce A; Chisholm, Matthew F

    2014-01-01

    Crown ethers, introduced by Pedersen1, are at their most basic level neutral rings constructed of oxygen atoms linked by two- or three-carbon chains. They have attracted special attention for their ability to selectively incorporate various atoms2 or molecules within the cavity formed by the ring3-6. This property has led to the use of crown ethers and their compounds in a wide range of chemical and biological applications7,8. However, crown ethers are typically highly flexible, frustrating efforts to rigidify them for many uses that demand higher binding affinity and selectivity9,10. In this Letter, we report atomic-resolution images of the same basic structures of the original crown ethers embedded in graphene. This arrangement constrains the crown ethers to be rigid and planar and thus uniquely suited for the many applications that crown ethers are known for. First-principles calculations show that the close similarity of the structures seen in graphene with those of crown ether molecules also extends to their selectivity towards specific metal cations depending on the ring size. Atoms (or molecules) incorporated within the crown ethers in graphene offer a simple environment that can be easily and systematically probed and modeled. Thus, we expect that this discovery will introduce a new wave of investigations and applications of chemically functionalized graphene.

  2. Crown ethers in graphene

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Guo, Junjie; Lee, Jaekwang; Contescu, Cristian I; Gallego, Nidia C; Pantelides, Sokrates T.; Pennycook, Stephen J; Moyer, Bruce A; Chisholm, Matthew F

    2014-01-01

    Crown ethers, introduced by Pedersen1, are at their most basic level neutral rings constructed of oxygen atoms linked by two- or three-carbon chains. They have attracted special attention for their ability to selectively incorporate various atoms2 or molecules within the cavity formed by the ring3-6. This property has led to the use of crown ethers and their compounds in a wide range of chemical and biological applications7,8. However, crown ethers are typically highly flexible, frustrating efforts to rigidify them for many uses that demand higher binding affinity and selectivity9,10. In this Letter, we report atomic-resolution images of the same basicmore » structures of the original crown ethers embedded in graphene. This arrangement constrains the crown ethers to be rigid and planar and thus uniquely suited for the many applications that crown ethers are known for. First-principles calculations show that the close similarity of the structures seen in graphene with those of crown ether molecules also extends to their selectivity towards specific metal cations depending on the ring size. Atoms (or molecules) incorporated within the crown ethers in graphene offer a simple environment that can be easily and systematically probed and modeled. Thus, we expect that this discovery will introduce a new wave of investigations and applications of chemically functionalized graphene.« less

  3. Alternative Fuels Data Center: Dimethyl Ether

    Alternative Fuels and Advanced Vehicles Data Center [Office of Energy Efficiency and Renewable Energy (EERE)]

    Dimethyl Ether to someone by E-mail Share Alternative Fuels Data Center: Dimethyl Ether on Facebook Tweet about Alternative Fuels Data Center: Dimethyl Ether on Twitter Bookmark Alternative Fuels Data Center: Dimethyl Ether on Google Bookmark Alternative Fuels Data Center: Dimethyl Ether on Delicious Rank Alternative Fuels Data Center: Dimethyl Ether on Digg Find More places to share Alternative Fuels Data Center: Dimethyl Ether on AddThis.com... More in this section... Biobutanol Dimethyl Ether

  4. Thermodynamics of Hydrogen Production from Dimethyl Ether Steam Reforming and Hydrolysis

    SciTech Connect (OSTI)

    T.A. Semelsberger

    2004-10-01

    The thermodynamic analyses of producing a hydrogen-rich fuel-cell feed from the process of dimethyl ether (DME) steam reforming were investigated as a function of steam-to-carbon ratio (0-4), temperature (100 C-600 C), pressure (1-5 atm), and product species: acetylene, ethanol, methanol, ethylene, methyl-ethyl ether, formaldehyde, formic acid, acetone, n-propanol, ethane and isopropyl alcohol. Results of the thermodynamic processing of dimethyl ether with steam indicate the complete conversion of dimethyl ether to hydrogen, carbon monoxide and carbon dioxide for temperatures greater than 200 C and steam-to-carbon ratios greater than 1.25 at atmospheric pressure (P = 1 atm). Increasing the operating pressure was observed to shift the equilibrium toward the reactants; increasing the pressure from 1 atm to 5 atm decreased the conversion of dimethyl ether from 99.5% to 76.2%. The order of thermodynamically stable products in decreasing mole fraction was methane, ethane, isopropyl alcohol, acetone, n-propanol, ethylene, ethanol, methyl-ethyl ether and methanol--formaldehyde, formic acid, and acetylene were not observed. The optimal processing conditions for dimethyl ether steam reforming occurred at a steam-to-carbon ratio of 1.5, a pressure of 1 atm, and a temperature of 200 C. Modeling the thermodynamics of dimethyl ether hydrolysis (with methanol as the only product considered), the equilibrium conversion of dimethyl ether is limited. The equilibrium conversion was observed to increase with temperature and steam-to-carbon ratio, resulting in a maximum dimethyl ether conversion of approximately 68% at a steam-to-carbon ratio of 4.5 and a processing temperature of 600 C. Thermodynamically, dimethyl ether processed with steam can produce hydrogen-rich fuel-cell feeds--with hydrogen concentrations exceeding 70%. This substantiates dimethyl ether as a viable source of hydrogen for PEM fuel cells.

  5. Propenyl ether monomers for photopolymerization

    DOE Patents [OSTI]

    Crivello, James V.

    1996-01-01

    Propenyl ether monomers of formula V A(OCH.dbd.CHCH.sub.3).sub.n wherein n is an integer from one to six and A is selected from cyclic ethers, polyether and alkanes are disclosed. The monomers are readily polymerized in the presence of cationic photoinitiators, when exposed to actinic radiation, to form poly(propenyl ethers) that are useful for coatings, sealants, varnishes and adhesives. Compositions for preparing polymeric coatings comprising the compounds of formula V together with particular cationic photoinitiators are also disclosed, as are processes for making the monomers from allyl halides and readily available alcohols. The process involves rearranging the resulting allyl ethers to propenyl ethers.

  6. Propenyl ether monomers for photopolymerization

    DOE Patents [OSTI]

    Crivello, J.V.

    1996-10-22

    Propenyl ether monomers of formula A(OCH{double_bond}CHCH{sub 3}){sub n} wherein n is an integer from one to six and A is selected from cyclic ethers, polyether and alkanes are disclosed. The monomers are readily polymerized in the presence of cationic photoinitiators, when exposed to actinic radiation, to form poly(propenyl ethers) that are useful for coatings, sealants, varnishes and adhesives. Compositions for preparing polymeric coatings comprising the compounds of the above formula together with particular cationic photoinitiators are also disclosed, as are processes for making the monomers from allyl halides and readily available alcohols. The process involves rearranging the resulting allyl ethers to propenyl ethers.

  7. Reaction Pathways and Energetics of Etheric C−O Bond Cleavage Catalyzed by Lanthanide Triflates

    SciTech Connect (OSTI)

    Assary, Rajeev S.; Atesin, Abdurrahman C.; Li, Zhi; Curtiss, Larry A.; Marks, Tobin J.

    2013-07-15

    Efficient and selective cleavage of etheric C−O bonds is crucial for converting biomass into platform chemicals and liquid transportation fuels. In this contribution, computational methods at the DFT B3LYP level of theory are employed to understand the efficacy of lanthanide triflate catalysts (Ln(OTf)3, Ln = La, Ce, Sm, Gd, Yb, and Lu) in cleaving etheric C−O bonds. In agreement with experiment, the calculations indicate that the reaction pathway for C−O cleavage occurs via a C−H → O−H proton transfer in concert with weakening of the C−O bond of the coordinated ether substrate to ultimately yield a coordinated alkenol. The activation energy for this process falls as the lanthanide ionic radius decreases, reflecting enhanced metal ion electrophilicity. Details of the reaction mechanism for Yb(OTf)3-catalyzed ring opening are explored in depth, and for 1-methyl-d3-butyl phenyl ether, the computed primary kinetic isotope effect of 2.4 is in excellent agreement with experiment (2.7), confirming that etheric ring-opening pathway involves proton transfer from the methyl group alpha to the etheric oxygen atom, which is activated by the electrophilic lanthanide ion. Calculations of the catalytic pathway using eight different ether substrates indicate that the more rapid cleavage of acyclic versus cyclic ethers is largely due to entropic effects, with the former C−O bond scission processes increasing the degrees of freedom/particles as the transition state is approached.

  8. Oxygenate Supply/Demand Balances in the Short-Term Integrated Forecasting Model (Released in the STEO March 1998)

    Reports and Publications (EIA)

    1998-01-01

    The blending of oxygenates, such as fuel ethanol and methyl tertiary butyl ether (MTBE), into motor gasoline has increased dramatically in the last few years because of the oxygenated and reformulated gasoline programs. Because of the significant role oxygenates now have in petroleum product markets, the Short-Term Integrated Forecasting System (STIFS) was revised to include supply and demand balances for fuel ethanol and MTBE. The STIFS model is used for producing forecasts in the Short-Term Energy Outlook. A review of the historical data sources and forecasting methodology for oxygenate production, imports, inventories, and demand is presented in this report.

  9. MTBE, Oxygenates, and Motor Gasoline (Released in the STEO October 1999)

    Reports and Publications (EIA)

    1999-01-01

    The blending of methyl tertiary butyl ether (MTBE) into motor gasoline has increased dramatically since it was first produced 20 years ago. MTBE usage grew in the early 1980's in response to octane demand resulting initially from the phaseout of lead from gasoline and later from rising demand for premium gasoline. The oxygenated gasoline program stimulated an increase in MTBE production between 1990 and 1994. MTBE demand increased from 83,000 in 1990 to 161,000 barrels per day in 1994. The reformulated gasoline (RFG) program provided a further boost to oxygenate blending. The MTBE contained in motor gasoline increased to 269,000 barrels per day by 1997.

  10. Table 10.5 Estimated Number of Alternative-Fueled Vehicles in Use and Fuel Consumption, 1992-2010

    U.S. Energy Information Administration (EIA) Indexed Site

    Estimated Number of Alternative-Fueled Vehicles in Use and Fuel Consumption, 1992-2010 Year Alternative and Replacement Fuels 1 Liquefied Petroleum Gases Compressed Natural Gas Liquefied Natural Gas Methanol, 85 Percent (M85) 3 Methanol, Neat (M100) 4 Ethanol, 85 Percent (E85) 3,5 Ethanol, 95 Percent (E95) 3 Elec- tricity 6 Hydro- gen Other Fuels 7 Subtotal Oxygenates 2 Bio- diesel 10 Total Methyl Tertiary Butyl Ether 8 Ethanol in Gasohol 9 Total Alternative-Fueled Vehicles in Use 11

  11. Word Pro - Untitled1

    U.S. Energy Information Administration (EIA) Indexed Site

    1 Table 10.5 Estimated Number of Alternative-Fueled Vehicles in Use and Fuel Consumption, 1992-2010 Year Alternative and Replacement Fuels 1 Liquefied Petroleum Gases Compressed Natural Gas Liquefied Natural Gas Methanol, 85 Percent (M85) 3 Methanol, Neat (M100) 4 Ethanol, 85 Percent (E85) 3,5 Ethanol, 95 Percent (E95) 3 Elec- tricity 6 Hydro- gen Other Fuels 7 Subtotal Oxygenates 2 Bio- diesel 10 Total Methyl Tertiary Butyl Ether 8 Ethanol in Gasohol 9 Total Alternative-Fueled Vehicles in Use

  12. California's Move Toward E10 (released in AEO2009)

    Reports and Publications (EIA)

    2009-01-01

    In Annual Energy Outlook 2009, (AEO) E10a gasoline blend containing 10% ethanolis assumed to be the maximum ethanol blend allowed in California erformulated gasoline (RFG), as opposed to the 5.7% blend assumed in earlier AEOs. The 5.7% blend had reflected decisions made when California decided to phase out use of the additive methyl tertiary butyl ether in its RFG program in 2003, opting instead to use ethanol in the minimum amount that would meet the requirement for 2.0% oxygen content under the Clean Air Act provisions in effect at that time.

  13. Radiation chemistry of alternative fuel oxygenates -- Substituted ethers

    SciTech Connect (OSTI)

    Mezyk, S. P.; Cooper, W. J.; Bartels, D. M.; Tobien, T.; O'Shea, K. E.

    1999-11-15

    The electron beam process, an advanced oxidation and reduction technology, is based in the field of radiation chemistry. Fundamental to the development of treatment processes is an understanding of the underlying chemistry. The authors have previously evaluated the bimolecular rate constants for the reactions of methyl tert-butyl ether (MTBE) and with this study have extended their studies to include ethyl tert-butyl ether (ETBE), di-isopropyl ether (DIPE) and tert-amyl methyl ether (TAME) with the hydroxyl radical, hydrogen atom and solvated electron using pulse radiolysis. For all of the oxygenates the reaction with the hydroxyl radical appears to be of primary interest in the destruction of the compounds in water. The rates with the solvated electron are limiting values as the rates appear to be relatively low. The hydrogen atom rate constants are relatively low, coupled with the low yield in radiolysis, they concluded that these are of little significance in the destruction of the alternative fuel oxygenates (and MTBE).

  14. CATALYSTS FOR HIGH CETANE ETHERS AS DIESEL FUELS

    SciTech Connect (OSTI)

    Kamil Klier; Richard G. Herman; James G.C. Shen; Qisheng Ma

    2000-08-31

    A novel 1,2-ethanediol, bis(hydrogen sulfate), disodium salt precursor-based solid acid catalyst with a zirconia substrate was synthesized and demonstrated to have significantly enhanced activity and high selectivity in producing methyl isobutyl ether (MIBE) or isobutene from methanol-isobutanol mixtures. The precursor salt was synthesized and provided by Dr. T. H. Kalantar of the M.E. Pruitt Research Center, Dow Chemical Co., Midland, MI 48674. Molecular modeling of the catalyst synthesis steps and of the alcohol coupling reaction is being carried out. A representation of the methyl transfer from the surface activated methanol molecule (left) to the activated oxygen of the isobutanol molecule (right) to form an ether linkage to yield MIBE is shown.

  15. Development of specialty chemicals from dimethyl ether

    SciTech Connect (OSTI)

    Tartamella, T.L.; Lee, S.

    1996-12-31

    Dimethyl ether (DME) may be efficiently produced from coal-bases syngas in a high pressure, mechanically agitated slurry reactor. DME synthesis occurs in the liquid phase using a dual catalyst. By operating in a dual catalyst mode, DME may be converted from in-situ produced methanol resulting in higher methyl productivities and syngas conversions over methanol conversion alone. The feasibility of utilizing DME as a building block for more valuable specialty chemicals has been examined. A wide variety of petrochemicals may be produced from DME including light olefins, gasoline range hydrocarbons, oxygenates, and glycol precursors. These chemicals represent an important part of petroleum industries inventory of fine chemicals. Carbonylation, hydrocarbonylation, and oxidative dimerization are but a few of the reactions in which DME may undergo conversion. DME provides an additional route for the production of industrially important petrochemicals.

  16. Sulfonimide-containing poly(arylene ether)s and poly(arylene ether sulfone)s, methods for producing the same, and uses thereof

    DOE Patents [OSTI]

    Hofmann, Michael A.

    2006-11-14

    The present invention is directed to sulfonimide-containing polymers, specifically sulfonimide-containing poly(arylene ether)s and sulfonimide-containing poly(arylene ether sulfone)s, and processes for making the sulfonimide-containing poly(arylene ether)s and sulfonimide-containing poly(arylene ether sulfone)s, for use conductive membranes and fuel cells.

  17. Energy and crude oil input requirements for the production of reformulated gasolines

    SciTech Connect (OSTI)

    Singh, M.; McNutt, B.

    1993-10-01

    The energy and crude oil requirements for the production of reformulated gasoline (RFG) are estimated. The scope of the study includes both the energy and crude oil embodied in the final product and the process energy required to manufacture the RFG and its components. The effects on energy and crude oil use of employing various oxygenates to meet the minimum oxygen-content level required by the Clean Air Act Amendments are evaluated. The analysis shows that production of RFG requires more total energy, but uses less crude oil, than that of conventional gasoline. The energy and crude oil use requirements of the different RFGs vary considerably. For the same emissions performance level, RFG with ethanol requires substantially more total energy and crude oil than does RFG with methyl tertiary butyl ether (MTBE) or ethyl tertiary butyl ether. A specific proposal by the US Environmental Protection Agency, designed to allow the use of ethanol in RFG, would increase the total energy required to produce RFG by 2% and the total crude oil required by 2.0 to 2.5% over the corresponding values for the base RFG with MTBE.

  18. Catalytic distillation process

    DOE Patents [OSTI]

    Smith, L.A. Jr.

    1982-06-22

    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.

  19. Catalytic distillation process

    DOE Patents [OSTI]

    Smith, Jr., Lawrence A. (Bellaire, TX)

    1982-01-01

    A method 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.

  20. Aza crown ether compounds as anion receptors

    DOE Patents [OSTI]

    Lee, H.S.; Yang, X.O.; McBreen, J.

    1998-08-04

    A family of aza-ether based compounds including linear, multi-branched and aza-crown ethers is provided. When added to non-aqueous battery electrolytes, the new family of aza-ether based compounds acts as neutral receptors to complex the anion moiety of the electrolyte salt thereby increasing the conductivity and the transference number of LI{sup +} ion in alkali metal batteries. 3 figs.

  1. Aza crown ether compounds as anion receptors

    DOE Patents [OSTI]

    Lee, Hung Sui; Yang, Xiao-Oing; McBreen, James

    1998-08-04

    A family of aza-ether based compounds including linear, multi-branched and aza-crown ethers is provided. When added to non-aqueous battery electrolytes, the new family of aza-ether based compounds acts as neutral receptors to complex the anion moiety of the electrolyte salt thereby increasing the conductivity and the transference number of LI.sup.+ ion in alkali metal batteries.

  2. A laser and molecular beam mass spectrometer study of low-pressure dimethyl ether flames

    SciTech Connect (OSTI)

    Andrew McIlroy; Toby D. Hain; Hope A. Michelsen; Terrill A. Cool

    2000-12-15

    The oxidation of dimethyl ether (DME) is studied in low-pressure flames using new molecular beam mass spectrometer and laser diagnostics. Two 30.0-Torr, premixed DME/oxygen/argon flames are investigated with stoichiometries of 0.98 and 1.20. The height above burner profiles of nine stable species and two radicals are measured. These results are compared to the detailed chemical reaction mechanism of Curran and coworkers. Generally good agreement is found between the model and data. The largest discrepancies are found for the methyl radical profiles where the model predicts qualitatively different trends in the methyl concentration with stoichiometry than observed in the experiment.

  3. Alternative Fuels lDimethyl Ether Rheology and Materials Studies...

    Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site

    Fuels lDimethyl Ether Rheology and Materials Studies Alternative Fuels lDimethyl Ether Rheology and Materials Studies 2004 Diesel Engine Emissions Reduction (DEER) Conference ...

  4. Role of acid catalysis in dimethyl ether conversion processes

    SciTech Connect (OSTI)

    Tartamella, T.L.; Lee, S.

    1996-12-31

    Acidity plays an important role in the conversion of methanol and dimethyl ether (DME) to hydrocarbons and oxygenates. In the conversion to hydrocarbons over zeolite catalyst, Broensted acidity is the main contributor to the first hydrocarbon formed. Here, acidity is also an important factor in determining olefin, paraffin, and aromatic content in the final product distribution. Catalyst life has also been found to be related to acidity content in zeolites. DME conversion to oxygenates is especially dependent on high acidity catalysts. Superacids like BF{sub 3}, HF-BF{sub 3}, and CF{sub 3}COOH have been used in the past for conversion of DME in carbonylation reactions to form methyl acetate and acetic acid at high pressures. Recently, heteropoly acids and their corresponding metal substituted salts have been used to convert DME to industrially important petrochemicals resulting in shorter reaction times and without the use of harsh operating conditions.

  5. The efficient use of natural gas in transportation

    SciTech Connect (OSTI)

    Stodolsky, F.; Santini, D.J.

    1992-04-01

    Concerns over air quality and greenhouse gas emissions have prompted discussion as well as action on alternative fuels and energy efficiency. Natural gas and natural gas derived fuels and fuel additives are prime alternative fuel candidates for the transportation sector. In this study, we reexamine and add to past work on energy efficiency and greenhouse gas emissions of natural gas fuels for transportation (DeLuchi 1991, Santini et a. 1989, Ho and Renner 1990, Unnasch et al. 1989). We add to past work by looking at Methyl tertiary butyl ether (from natural gas and butane component of natural gas), alkylate (from natural gas butanes), and gasoline from natural gas. We also reexamine compressed natural gas, liquified natural gas, liquified petroleum gas, and methanol based on our analysis of vehicle efficiency potential. We compare the results against nonoxygenated gasoline.

  6. The efficient use of natural gas in transportation

    SciTech Connect (OSTI)

    Stodolsky, F.; Santini, D.J.

    1992-01-01

    Concerns over air quality and greenhouse gas emissions have prompted discussion as well as action on alternative fuels and energy efficiency. Natural gas and natural gas derived fuels and fuel additives are prime alternative fuel candidates for the transportation sector. In this study, we reexamine and add to past work on energy efficiency and greenhouse gas emissions of natural gas fuels for transportation (DeLuchi 1991, Santini et a. 1989, Ho and Renner 1990, Unnasch et al. 1989). We add to past work by looking at Methyl tertiary butyl ether (from natural gas and butane component of natural gas), alkylate (from natural gas butanes), and gasoline from natural gas. We also reexamine compressed natural gas, liquified natural gas, liquified petroleum gas, and methanol based on our analysis of vehicle efficiency potential. We compare the results against nonoxygenated gasoline.

  7. Process for making propenyl ethers and photopolymerizable compositions containing them

    DOE Patents [OSTI]

    Crivello, James V.

    1996-01-01

    Propenyl ether monomers of formula V A(OCH.dbd.CHCH.sub.3).sub.n wherein n is an integer from one to six and A is selected from cyclic ethers, polyether and alkanes are disclosed. The monomers are readily polymerized in the presence of cationic photoinitiators, when exposed to actinic radiation, to form poly(propenyl ethers) that are useful for coatings, sealants, varnishes and adhesives. Compositions for preparing polymeric coatings comprising the compounds of formula V together with particular cationic photoinitiators are also disclosed, as are processes for making the monomers from allyl halides and readily available alcohols. The process involves rearranging the resulting allyl ethers to propenyl ethers.

  8. Process for making propenyl ethers and photopolymerizable compositions containing them

    DOE Patents [OSTI]

    Crivello, J.V.

    1996-01-23

    Propenyl ether monomers of formula A(OCH{double_bond}CHCH{sub 3}){sub n} (V) wherein n is an integer from one to six and A is selected from cyclic ethers, polyether, and alkanes are disclosed. The monomers are readily polymerized in the presence of cationic photoinitiators, when exposed to actinic radiation, to form poly(propenyl ethers) that are useful for coatings, sealants, varnishes and adhesives. Compositions for preparing polymeric coatings comprising the compounds of formula V together with particular cationic photoinitiators are also disclosed, as are processes for making the monomers from allyl halides and readily available alcohols. The process involves rearranging the resulting allyl ethers to propenyl ethers.

  9. Degradation of Imidazolium- and Quaternary Ammonium-Functionalized Poly(fluorenyl ether ketone sulfone) Anion Exchange Membranes

    SciTech Connect (OSTI)

    Chen, DY; Hickner, MA

    2012-11-01

    Imidazolium and quaternary ammonium-functionalized poly(fluorenyl ether ketone sulfone)s were synthesized successfully with the same degree of cationic functionalization and identical polymer backbones for a comparative study of anion exchange membranes (AEMs) for solid-state alkaline membrane fuel cells (AMFCs). Both anion exchange membranes were synthesized using a new methyl-containing monomer that avoided the use of toxic chloromethylation reagents. The polymer chemical structures were confirmed by H-1 NMR and FTIR. The derived AEMs were fully characterized by water uptake, anion conductivity, stability under aqueous basic conditions, and thermal stability. Interestingly, both the cationic groups and the polymer backbone were found to be degraded in 1 M NaOH solution at 60 degrees C over 48 h as measured by changes of ion exchange capacity and intrinsic viscosity. Imidazolium-functionalized poly(fluorenyl ether ketone sulfone)s had similar aqueous alkaline stability to quaternary ammonium-functionalized materials at 60 degrees C but much lower stability at 80 degrees C. This work demonstrates that quaternary ammonium and imidazolium cationic groups are not stable on poly(arylene ether sulfone) backbones under relatively mild conditions. Additionally, the poly(arylene ether sulfone) backbone, which is one of the most common polymers used in ion exchange membrane applications, is not stable in the types of molecular configurations analyzed.

  10. Divinyl ether synthase gene, and protein and uses thereof

    DOE Patents [OSTI]

    Howe, Gregg A.; Itoh, Aya

    2006-12-26

    The present invention relates to divinyl ether synthase genes, proteins, and methods of their use. The present invention encompasses both native and recombinant wild-type forms of the synthase, as well as mutants and variant forms, some of which possess altered characteristics relative to the wild-type synthase. The present invention also relates to methods of using divinyl ether synthase genes and proteins, including in their expression in transgenic organisms and in the production of divinyl ether fatty acids, and to methods of suing divinyl ether fatty acids, including in the protection of plants from pathogens.

  11. Divinyl ether synthase gene and protein, and uses thereof

    DOE Patents [OSTI]

    Howe, Gregg A. (East Lansing, MI); Itoh, Aya (Tsuruoka, JP)

    2011-09-13

    The present invention relates to divinyl ether synthase genes, proteins, and methods of their use. The present invention encompasses both native and recombinant wild-type forms of the synthase, as well as mutants and variant forms, some of which possess altered characteristics relative to the wild-type synthase. The present invention also relates to methods of using divinyl ether synthase genes and proteins, including in their expression in transgenic organisms and in the production of divinyl ether fatty acids, and to methods of suing divinyl ether fatty acids, including in the protection of plants from pathogens.

  12. Arylations of coal model systems. [Benzyl phenyl ether and l-naphthylmethyl phenyl ether

    SciTech Connect (OSTI)

    Smith, B.F.; Venier, C.G.; Squires, T.G.

    1984-01-01

    Currently, coal is converted to clean liquids or low melting solids by processes which utilize high temperature, high pressure, or both. These processes occur by thermal bond cleavages and involve the intermediacy of free radicals. In a search for chemistry which could liquefy coal under milder conditions, the authors have focussed on thermally less demanding ionic reactions. Of the functional groups which commonly occur in coals, ethers are the easiest to cleave under acid conditions. Depending on the density of these linkages and their importance as crosslinks in the macromolecular structure of coals, solubilization might be greatly enhanced solely by cleaving and capping either bonds. Benzylic ethers are particularly reactive and have been implicated in the initiation of coal pyrolysis and hydropyrolysis. Arylation, the use of acids to cleave bonds in coals in the presence of aromatic rings to trap the consequent incipient carbonium ions, has a long history. This paper discusses the use of benzyl phenyl ether and l-naphthylmethyl phenyl ether and polymers related to them as models to develop and evaluate the chemistry involved in the arylations. 9 references, 1 figure, 4 tables.

  13. Process for producing dimethyl ether from synthesis gas

    DOE Patents [OSTI]

    Pierantozzi, R.

    1985-06-04

    This invention pertains to a Fischer Tropsch process for converting synthesis gas to an oxygenated hydrocarbon with particular emphasis on dimethyl ether. Synthesis gas comprising carbon monoxide and hydrogen are converted to dimethyl ether by carrying out the reaction in the presence of an alkali metal-manganese-iron carbonyl cluster incorporated onto a zirconia-alumina support.

  14. Process for producing dimethyl ether form synthesis gas

    DOE Patents [OSTI]

    Pierantozzi, Ronald

    1985-01-01

    This invention pertains to a Fischer Tropsch process for converting synthesis gas to an oxygenated hydrocarbon with particular emphasis on dimethyl ether. Synthesis gas comprising carbon monoxide and hydrogen are converted to dimethyl ether by carrying out the reaction in the presence of an alkali metal-manganese-iron carbonyl cluster incorporated onto a zirconia-alumina support.

  15. Mixed ether electrolytes for secondary lithium batteries with improved low temperature performance

    SciTech Connect (OSTI)

    Abraham, K.M.; Pasquariello, D.M.; Martin, F.J.

    1986-04-01

    Tetrahydrofuran (THF): 2-methyl-tetrahydrofuran (2Me-THF)/LiAsF/sub 6/ mixed solutions, despite their lower conductivity, have allowed significantly better low temperature performance in Li/TiS/sub 2/ cells than have THF/LiAsF/sub 6/, /sup 13/C NMR data suggest that this may be related to the structurally disordered Li/sup +/-solvates that exist in the mixed ether solutions. High cycling efficiencies for the Li electrode in THF:2Me-THF/LiAsF/sub 6/ solutions have been achieved by the use of 2Me-F as an additive. A 5 Ah capacity Li/TiS/sub 2/ cell has been cycled more than 100 times at 100, depth-of-discharge, with the cell capacity remaining at over 3 Ah at the 100th cycle.

  16. Origin of mechanical modifications in poly (ether ether ketone)/carbon nanotube composite

    SciTech Connect (OSTI)

    Pavlenko, Ekaterina; Puech, Pascal; Bacsa, Wolfgang; Boyer, François; Olivier, Philippe; Sapelkin, Andrei; King, Stephen; Heenan, Richard; Pons, François; Gauthier, Bénédicte; Cadaux, Pierre-Henri

    2014-06-21

    Variations in the hardness of a poly (ether ether ketone) beam electrically modified with multi-walled carbon nanotubes (MWCNT, 0.5%-3%) are investigated. It is shown that both rupture and hardness variations correlate with the changes in carbon nanotube concentration when using micro indentation and extended Raman imaging. Statistical analysis of the relative spectral intensities in the Raman image is used to estimate local tube concentration and polymer crystallinity. We show that the histogram of the Raman D band across the image provides information about the amount of MWCNTs and the dispersion of MWCNTs in the composite. We speculate that we have observed a local modification of the ordering between pure and modified polymer. This is partially supported by small angle neutron scattering measurements, which indicate that the agglomeration state of the MWCNTs is the same at the concentrations studied.

  17. High pressure injection of dimethyl ether

    SciTech Connect (OSTI)

    Glensvig, M.; Sorenson, S.C.; Abata, D.

    1996-12-31

    Partially oxygenated hydrocarbons produced from natural gas have been shown to be viable alternate fuels for the diesel engine, showing favorable combustion characteristics similar to that of diesel fuel but without exhaust particulates and with significantly reduced NO{sub x} emissions and lower engine noise. Further, engine studies have demonstrated that such compounds, like dimethyl ether (DME), can be injected at much lower pressures than conventional diesel fuel with better overall performance. This experimental study compares the injection of DME to that of conventional diesel fuel. Both fuels were injected into a quiescent high pressure chamber containing Nitrogen at pressures up to 25 atmospheres at room temperature with a pintle nozzle and jerk pump. Comparisons were obtained with high speed photography using a Hycam camera. Results indicate that there are significant differences in spray geometry and penetration which are not predictable with analytical models currently used for diesel fuels.

  18. Coupling of alcohols to ethers: The dominance of the surface S{sub N}2 reaction pathway

    SciTech Connect (OSTI)

    Klier, K.; Feeley, O.C.; Johansson, M.; Herman, R.G.

    1996-12-31

    Coupling of alcohols to ethers, important high value oxygenates, proceeds on acid catalysts via general pathways that uniquely control product composition, oxygen retention, chirality inversion, and kinetics. The dominant pathway is the S{sub N}2 reaction with competition of the alcohols for the surface acid sites. This is exemplified by formation of methyl(ethyl) isobutylether (M(E)IBE) from methanol(ethanol)/isobutanol mixtures, retention of oxygen ({sup 18}O) of the heavier alcohol, and optimum rate as a function of concentration of either reactant alcohol. The S{sub N}2 pathway in the confinement of zeolite pores exhibits additional features of a near-100% selectivity to dimethylether (DME) in H-mordenite and a near-100% selectivity to chiral inversion in 2-pentanol/ethanol coupling to 2-ethoxypentane in HZSM-5. A minor reaction pathway entails olefin or carbenium intermediates, as exemplified by the formation of methyl tertiarybutyl ether (MTBE) from methanol/isobutanol mixtures with oxygen retention of the lighter alcohol. Calculations of transition state and molecular modeling of the oxonium-involving pathways dramatically demonstrate how the reaction path selects the products.

  19. Preparation and characterization of polymer blend based on sulfonated poly (ether ether ketone) and polyetherimide (SPEEK/PEI) as proton exchange membranes for fuel cells

    SciTech Connect (OSTI)

    Hashim, Nordiana; Ali, Ab Malik Marwan; Lepit, Ajis; Rasmidi, Rosfayanti; Subban, Ri Hanum Yahaya; Yahya, Muhd Zu Azhan

    2015-08-28

    Blends of sulfonated poly (ether ether ketone) (SPEEK) and polyetherimide (PEI) were prepared in five different weight ratios using N-methyl-2-pyrrolidone (NMP) as solvent by the solution cast technique. The degree of sulfonation (DS) of the sulfonated PEEK was determined from deuterated dimethyl sulfoxide (DMSO-d{sub 6}) solution of the purified polymer using {sup 1}H NMR method. The properties studied in the present investigation includes conductivity, water uptake, thermal stability and structure analysis of pure SPEEK as well as SPEEK-PEI polymer blend membranes. The experimental results show that the conductivity of the membranes increased with increase in temperature from 30 to 80°C, except for that of pure SPEEK membrane which increased with temperature from 30 to 60°C while its conductivity decreased with increasing temperature from 60 to 80°C. The conductivity of 70wt.%SPEEK-30wt.%PEI blend membrane at 80% relative humidity (RH) is found to be 1.361 × 10{sup −3} Scm{sup −1} at 30°C and 3.383 × 10{sup −3} Scm{sup −1} at 80°C respectively. It was also found that water uptake and thermal stability of the membranes slightly improved upon blending with PEI. Structure analysis was carried out using Fourier Transform Infrared (FTIR) spectroscopy which revealed considerable interactions between sulfonic acid group of SPEEK and imide groups of PEI. Modification of SPEEK by blending with PEI shows good potential for improving the electrical and physical properties of proton exchange membranes.

  20. Synergistic effect of mixing dimethyl ether with methane, ethane, propane, and ethylene fuels on polycyclic aromatic hydrocarbon and soot formation

    SciTech Connect (OSTI)

    Yoon, S.S.; Anh, D.H.; Chung, S.H.

    2008-08-15

    Characteristics of polycyclic aromatic hydrocarbon (PAH) and soot formation in counterflow diffusion flames of methane, ethane, propane, and ethylene fuels mixed with dimethyl ether (DME) have been investigated. Planar laser-induced incandescence and fluorescence techniques were employed to measure relative soot volume fractions and PAH concentrations, respectively. Results showed that even though DME is known to be a clean fuel in terms of soot formation, DME mixture with ethylene fuel increases PAH and soot formation significantly as compared to the pure ethylene case, while the mixture of DME with methane, ethane, and propane decreases PAH and soot formation. Numerical calculations adopting a detailed kinetics showed that DME can be decomposed to produce a relatively large number of methyl radicals in the low-temperature region where PAH forms and grows; thus the mixture of DME with ethylene increases CH{sub 3} radicals significantly in the PAH formation region. Considering that the increase in the concentration of O radicals is minimal in the PAH formation region with DME mixture, the enhancement of PAH and soot formation in the mixture flames of DME and ethylene can be explained based on the role of methyl radicals in PAH and soot formation. Methyl radicals can increase the concentration of propargyls, which could enhance incipient benzene ring formation through the propargyl recombination reaction and subsequent PAH growth. Thus, the result substantiates the importance of methyl radicals in PAH and soot formation, especially in the PAH formation region of diffusion flames. (author)

  1. Raman spectra of methane, ethylene, ethane, dimethyl ether, formaldehyde

    Office of Scientific and Technical Information (OSTI)

    and propane for combustion applications (Journal Article) | SciTech Connect Raman spectra of methane, ethylene, ethane, dimethyl ether, formaldehyde and propane for combustion applications Citation Details In-Document Search This content will become publicly available on May 27, 2017 Title: Raman spectra of methane, ethylene, ethane, dimethyl ether, formaldehyde and propane for combustion applications Authors: Magnotti, G. ; KC, U. ; Varghese, P. L. ; Barlow, R. S. Publication Date:

  2. Atmospheric and combustion chemistry of dimethyl ether

    SciTech Connect (OSTI)

    Nielsen, O.J.; Egsgaard, H.; Larsen, E.; Sehested, J.; Wallington, T.J.

    1997-12-31

    It has been demonstrated that dimethyl ether (DME) is an ideal diesel fuel alternative. DME, CH{sub 3}OCH{sub 3}, combines good fuel properties with low exhaust emissions and low combustion noise. Large scale production of this fuel can take place using a single step catalytic process converting CH{sub 4} to DME. The fate of DME in the atmosphere has previously been studied. The atmospheric degradation is initiated by the reaction with hydroxyl radicals, which is also a common feature of combustion processes. Spectrokinetic investigations and product analysis were used to demonstrate that the intermediate oxy radical, CH{sub 3}OCH{sub 2}O, exhibits a novel reaction pathway of hydrogen atom ejection. The application of tandem mass spectrometry to chemi-ions based on supersonic molecular beam sampling has recently been demonstrated. The highly reactive ionic intermediates are sampled directly from the flame and identified by collision activation mass spectrometry and ion-molecule reactions. The mass spectrum reflects the distribution of the intermediates in the flame. The atmospheric degradation of DME as well as the unique fuel properties of a oxygen containing compound will be discussed.

  3. Li-air batteries having ether-based electrolytes

    DOE Patents [OSTI]

    Amine, Khalil; Curtiss, Larry A; Lu, Jun; Lau, Kah Chun; Zhang, Zhengcheng; Sun, Yang-Kook

    2015-03-03

    A lithium-air battery includes a cathode including a porous active carbon material, a separator, an anode including lithium, and an electrolyte including a lithium salt and polyalkylene glycol ether, where the porous active carbon material is free of a metal-based catalyst.

  4. HIGH-RESOLUTION EXPANDED VERY LARGE ARRAY IMAGE OF DIMETHYL ETHER (CH{sub 3}){sub 2}O IN ORION-KL

    SciTech Connect (OSTI)

    Favre, C.; Wootten, H. A.; Remijan, A. J.; Brouillet, N.; Despois, D.; Baudry, A.; Wilson, T. L. E-mail: brouillet@obs.u-bordeaux1.fr E-mail: baudry@obs.u-bordeaux1.fr E-mail: aremijan@nrao.edu

    2011-09-20

    We report the first subarcsecond (0.''65 x 0.''51) image of the dimethyl ether molecule, (CH{sub 3}){sub 2}O, toward the Orion Kleinmann-Low nebula. The observations were carried at 43.4 GHz with the Expanded Very Large Array (EVLA). The distribution of the lower energy transition 6{sub 1,5}-6{sub 0,6}, EE (E {sub u} = 21 K) mapped in this study is in excellent agreement with the published dimethyl ether emission maps imaged with a lower resolution. The main emission peaks are observed toward the Compact Ridge and Hot Core southwest components, at the northern parts of the Compact Ridge and in an intermediate position between the Compact Ridge and the Hot Core. A notable result is that the distribution of dimethyl ether is very similar to that of another important larger O-bearing species, the methyl formate (HCOOCH{sub 3}), imaged at a lower resolution. Our study shows that higher spectral resolution (WIDAR correlator) and increased spectral coverage provided by the EVLA offer new possibilities for imaging complex molecular species. The sensitivity improvement and the other EVLA improvements make this instrument well suited for high sensitivity, high angular resolution, and molecular line imaging.

  5. Ether and ester derivatives of the perborate icosahedron

    DOE Patents [OSTI]

    Hawthorne, M. Frederick; Peymann, Toralf; Maderna, Andreas

    2003-12-16

    New boron icosahedral ethers and esters formed from Cs.sub.2 [closo-B.sub.12 (OH).sub.12 ],; Cs[closo-1-H-1-CB.sub.11 (OH).sub.11 ]; and closo-1,12-H.sub.2 -1,12-C.sub.2 B.sub.10 (OH).sub.10 are disclosed. Also set forth are their preparation by reacting the icosahedral boranes [closo-B.sub.12 H.sub.12 ].sup.2-, [closo-1-CB.sub.11 H.sub.12 ].sup.- and closo-1,12-(CH.sub.2 OH).sub.2 -1,12-C.sub.2 B.sub.10 H.sub.10 with an acid anhdride or acid chloride to form the ester or an alkylating agent to form the ether.

  6. 2' and 3' Carboranyl uridines and their diethyl ether adducts

    DOE Patents [OSTI]

    Soloway, Albert H.; Barth, Rolf F.; Anisuzzaman, Abul K.; Alam, Fazlul; Tjarks, Werner

    1992-01-01

    There is disclosed a process for preparing carboranyl uridine nucleoside compounds and their diethyl ether adducts, which exhibit a tenfold increase in boron content over prior art boron containing nucleoside compounds. Said carboranyl uridine nucleoside compounds exhibit enhanced lipophilicity and hydrophilic properties adequate to enable solvation in aqueous media for subsequent incorporation of said compounds in methods for boron neutron capture therapy in mammalian tumor cells.

  7. High octane ethers from synthesis gas-derived alcohol

    SciTech Connect (OSTI)

    Klier, K.; Herman, R.G.; Bastian, R.D.; DeTavernier, S. . Dept. of Chemistry Lehigh Univ., Bethlehem, PA . Zettlemoyer Center for Surface Studies)

    1991-01-01

    The objective of the proposed research is to synthesize high octane ethers directly from coal-derived synthesis gas via alcohol mixtures that are rich in methanol and isobutanol. The overall scheme involves gasification of coal, purification and shifting of the synthesis gas, higher alcohol synthesis, and direct synthesis of ethers. Commercial acid and superacid resin catalysts were obtained and tested under one set of conditions to compare the activities and selectivities for forming the unsymmetric methylisobutylether (MIBE) by coupling methanol with isobutanol. It was found that both Nafion-H microsaddles and Amberlyst-15 resins are active for this synthesis reaction. While and the Nafion-H catalyst does form the MIBE product fairly selectively under the reaction conditions utilized, the Amberlyst-15 catalyst formed dimethylether (DME) as the major product. In addition, significantly larger quantities of the C{sub 4} hydrocarbon products were observed over the Amberlyst-15 catalyst at 123{degree}C and 13.6 atm. It has been demonstrated that methyltertiarybutylether (MTBE) MIBE, DME and diisobutylether (DIBE) are separated and quantitatively determined by using the proper analytical conditions. In order to gain insight into the role of superacidity in promoting the selective coupling of the alcohols to form the unsymmetric ether, the strengths of the acid sites on the catalysts are being probed by thermometric titrations in non-aqueous solutions. 18 refs., 20 figs., 4 tabs.

  8. Heterogeneous catalytic process for alcohol fuels from syngas. Final technical report

    SciTech Connect (OSTI)

    Dombek, B.D.

    1996-03-01

    The primary objective of this project has been the pursuit of a catalyst system which would allow the selective production from syngas of methanol and isobutanol. It is desirable to develop a process in which the methanol to isobutanol weight ratio could be varied from 70/30 to 30/70. The 70/30 mixture could be used directly as a fuel additive, while, with the appropriate downstream processing, the 30/70 mixture could be utilized for methyl tertiary-butyl ether (MTBE) synthesis. The indirect manufacture of MTBE from a coal derived syngas to methanol and isobutanol process would appear to be a viable solution to MTBE feedstock limitations. To become economically attractive, a process fro producing oxygenates from coal-derived syngas must form these products with high selectivity and good rates, and must be capable of operating with a low-hydrogen-content syngas. This was to be accomplished through extensions of known catalyst systems and by the rational design of novel catalyst systems.

  9. Experimental study of the oxidation of methyl oleate in a jet-stirred reactor

    SciTech Connect (OSTI)

    Bax, Sarah; Hakka, Mohammed Hichem; Glaude, Pierre-Alexandre; Herbinet, Olivier; Battin-Leclerc, Frederique

    2010-06-15

    The experimental study of the oxidation of a blend containing n-decane and a large unsaturated ester, methyl oleate, was performed in a jet-stirred reactor over a wide range of temperature covering both low and high temperature regions (550-1100 K), at a residence time of 1.5 s, at quasi atmospheric pressure with high dilution in helium (n-decane and methyl oleate inlet mole fractions of 1.48 x 10{sup -3} and 5.2 x 10{sup -4}) and under stoichiometric conditions. The formation of numerous reaction products was observed. At low and intermediate temperatures, the oxidation of the blend led to the formation of species containing oxygen atoms like cyclic ethers, aldehydes and ketones deriving from n-decane and methyl oleate. At higher temperature, these species were not formed anymore and the presence of unsaturated species was observed. Because of the presence of the double bond in the middle of the alkyl chain of methyl oleate, the formation of some specific products was observed. These species are dienes and esters with two double bonds produced from the decomposition paths of methyl oleate and some species obtained from the addition of H-atoms, OH and HO{sub 2} radicals to the double bond. Experimental results were compared with former results of the oxidation of a blend of n-decane and methyl palmitate performed under similar conditions. This comparison allowed highlighting the similarities and the differences in the reactivity and in the distribution of the reaction products for the oxidation of large saturated and unsaturated esters. (author)

  10. Computational and experimental study of the effects of adding dimethyl ether and ethanol to nonpremixed ethylene/air flames

    SciTech Connect (OSTI)

    Bennett, Beth Anne V.; McEnally, Charles S.; Pfefferle, Lisa D.; Smooke, Mitchell D.; Colket, Meredith B.

    2009-06-15

    Two sets of axisymmetric laminar coflow flames, each consisting of ethylene/air nonpremixed flames with various amounts (up to 10%) of either dimethyl ether (CH{sub 3}-O-CH{sub 3}) or ethanol (CH{sub 3}-CH{sub 2}-OH) added to the fuel stream, have been examined both computationally and experimentally. Computationally, the local rectangular refinement method, which incorporates Newton's method, is used to solve the fully coupled nonlinear conservation equations on solution-adaptive grids for each flame in two spatial dimensions. The numerical model includes C6 chemical kinetic mechanisms with up to 59 species, detailed transport, and an optically thin radiation submodel. Experimentally, thermocouples are used to measure gas temperatures, and mass spectrometry is used to determine concentrations of over 35 species along the flame centerline. Computational results are examined throughout each flame, and validation of the model occurs through comparison with centerline measurements. Very good agreement is observed for temperature, major species, and several minor species. As the level of additive is increased, temperatures, some major species (CO{sub 2}, C{sub 2}H{sub 2}), flame lengths, and residence times are essentially unchanged. However, peak centerline concentrations of benzene (C{sub 6}H{sub 6}) increase, and this increase is largest when dimethyl ether is the additive. Computational and experimental results support the hypothesis that the dominant pathway to C{sub 6}H{sub 6} formation begins with the oxygenates decomposing into methyl radical (CH{sub 3}), which combines with C2 species to form propargyl (C{sub 3}H{sub 3}), which reacts with itself to form C{sub 6}H{sub 6}. (author)

  11. On the radiation stability of crown ethers in ionic liquids.

    SciTech Connect (OSTI)

    Shkrob, I.; Marin, T.; Dietz, M.

    2011-04-14

    Crown ethers (CEs) are macrocyclic ionophores used for the separation of strontium-90 from acidic nuclear waste streams. Room temperature ionic liquids (ILs) are presently being considered as replacements for traditional molecular solvents employed in such separations. It is desirable that the extraction efficacy obtained with such solvents should not deteriorate in the strong radiation fields generated by decaying radionuclides. This deterioration will depend on the extent of radiation damage to both the IL solvent and the CE solute. While radiation damage to ILs has been extensively studied, the issue of the radiation stability of crown ethers, particularly in an IL matrix, has not been adequately addressed. With this in mind, we have employed electron paramagnetic resonance (EPR) spectroscopy to study the formation of CE-related radicals in the radiolysis of selected CEs in ILs incorporating aromatic (imidazolium and pyridinium) cations. The crown ethers have been found to yield primarily hydrogen loss radicals, H atoms, and the formyl radical. In the low-dose regime, the relative yield of these radicals increases linearly with the mole fraction of the solute, suggesting negligible transfer of the excitation energy from the solvent to the solute; that is, the solvent has a 'radioprotective' effect. The damage to the CE in the loading region of practical interest is relatively low. Under such conditions, the main chemical pathway leading to decreased extraction performance is protonation of the macrocycle. At high radiation doses, sufficient to increase the acidity of the IL solvent significantly, such proton complexes compete with the solvent cations as electron traps. In this regime, the CEs will rapidly degrade as the result of H abstraction from the CE ring by the released H atoms. Thus, the radiation dose to which a CE/IL system is exposed must be maintained at a level sufficiently low to avoid this regime.

  12. An aging study of wire chambers with dimethyl ether

    SciTech Connect (OSTI)

    Jibaly, M.; Chrusch, P. Jr.; Hilgenberg, G.; Majewski, S.; Wojcik, R.; Sauli, F.; Gaudaen, J.

    1989-02-01

    The authors report results on the aging of different types of resistive and non-resistive wires in wire chambers filled with dimethyl ether (DME) of varying degrees of purity. Among the Freon impurities detected in our DME batches, only Freon-11 was found to contribute to the aging process. Of the resistive wires, Nicotin and Stablohm produced fast aging, whereas stainless steel withstood extended irradiation in purified DME (up to 1 C/cm) without any apparent damage. Gold-plated tungsten and molybdenum wires produced results comparable to those of the stainless steel.

  13. Dimethyl ether production from methanol and/or syngas

    DOE Patents [OSTI]

    Dagle, Robert A; Wang, Yong; Baker, Eddie G; Hu, Jianli

    2015-02-17

    Disclosed are methods for producing dimethyl ether (DME) from methanol and for producing DME directly from syngas, such as syngas from biomass. Also disclosed are apparatus for DME production. The disclosed processes generally function at higher temperatures with lower contact times and at lower pressures than conventional processes so as to produce higher DME yields than do conventional processes. Certain embodiments of the processes are carried out in reactors providing greater surface to volume ratios than the presently used DME reactors. Certain embodiments of the processes are carried out in systems comprising multiple microchannel reactors.

  14. DIMETHYL ETHER (DME)-FUELED SHUTTLE BUS DEMONSTRATION PROJECT

    SciTech Connect (OSTI)

    Elana M. Chapman; Shirish Bhide; Andre L. Boehman; David Klinikowski

    2003-04-01

    The objectives of this research and demonstration program are to convert a campus shuttle bus to operation on dimethyl ether, a potential ultra-clean alternative diesel fuel. To accomplish this objective, this project includes laboratory evaluation of a fuel conversion strategy, as well as field demonstration of the DME-fueled shuttle bus. Since DME is a fuel with no lubricity (i.e., it does not possess the lubricating quality of diesel fuel), conventional fuel delivery and fuel injection systems are not compatible with dimethyl ether. Therefore, to operate a diesel engine on DME one must develop a fuel-tolerant injection system, or find a way to provide the necessary lubricity to the DME. In this project, they have chosen the latter strategy in order to achieve the objective with minimal need to modify the engine. The strategy is to blend DME with diesel fuel, to obtain the necessary lubricity to protect the fuel injection system and to achieve low emissions. Within the Combustion Laboratory of the Penn State Energy Institute, they have installed and equipped a Navistar V-8 direct-injection turbodiesel engine for measurement of gaseous and particulate emissions and examination of the impact of fuel composition on diesel combustion. They have also reconfigured a high-pressure viscometer for studies of the viscosity, bulk modulus (compressibility) and miscibility of blends of diesel fuel, dimethyl ether and lubricity additives. The results include baseline emissions, performance and combustion measurements on the Navistar engine for operation on a federal low sulfur diesel fuel (300 ppm S). Most recently, they have examined blends of an oxygenated fuel additive (a liquid fuel called CETANER{trademark}) produced by Air Products, for comparison with dimethyl ether blended at the same weight of oxygen addition, 2 wt.%. While they have not operated the engine on DME yet, they are now preparing to do so. A fuel system for delivery of DME/Diesel blends has been configured and initial investigations at low DME blend ratios (around 5-10 vol%) will begin shortly. They have also performed viscosity measurements on diesel fuel, DME and 50-50 blends of DME in diesel. These tests have verified that DME has a much lower viscosity than the diesel fuel and that the viscosity of the blended fuel is also much lower than the diesel base fuel. This has implications for the injection and atomization of the DME/diesel blends.

  15. Structure and Reactivity of Alkyl Ethers Adsorbed on CeO2(111) Model Catalysts

    SciTech Connect (OSTI)

    F Calaza; T Chen; D Mullins; S Overbury

    2011-12-31

    The effect of surface hydroxyls on the adsorption of ether on ceria was explored. Adsorption of dimethyl ether (DME) and diethyl ether (DEE) on oxidized and reduced CeO{sub 2}(111) films was studied and compared with Ru(0001) using RAIRS and sXPS within a UHV environment. On Ru(0001) the ethers adsorb weakly with the molecular plane close to parallel to the surface plane. On the ceria films, the adsorption of the ethers was stronger than on the metal surface, presumably due to stronger interaction of the ether oxygen lone pair electrons with a cerium cation. This interaction causes the ethers to tilt away from the surface plane compared to the Ru(0001) surface. No pronounced differences were found between oxidized (CeO{sub 2}) and reduced (CeOx) films. The adsorption of the ethers was found to be perturbed by the presence of OH groups on hydroxylated CeOx. In the case of DEE, the geometry of adsorption resembles that found on Ru, and in the case of dimethyl ether DME is in between that one found on clean CeOx and the metal surface. Decomposition of the DEE was observed on the OH/CeOx surface following high DEE exposure at 300 K and higher temperatures. Ethoxides and acetates were identified as adsorbed species on the surface by means of RAIRS and ethoxides and formates by s-XPS. No decomposition of dimethyl ether was observed on the OH/CeOx at these higher temperatures, implying that the dissociation of the C-O bond from ethers requires the presence of {beta}-hydrogen.

  16. Structure and Reactivity of Alkyl Ethers Adsorbed on CeO(2)(111) Model Catalysts

    SciTech Connect (OSTI)

    Calaza, Florencia C; Chen, Tsung-Liang; Mullins, David R; Overbury, Steven {Steve} H

    2011-01-01

    The effect of surface hydroxyls on the adsorption of ether on ceria was explored. Adsorption of dimethyl ether (DME) and diethyl ether (DEE) on oxidized and reduced CeO{sub 2}(111) films was studied and compared with Ru(0001) using RAIRS and sXPS within a UHV environment. On Ru(0001) the ethers adsorb weakly with the molecular plane close to parallel to the surface plane. On the ceria films, the adsorption of the ethers was stronger than on the metal surface, presumably due to stronger interaction of the ether oxygen lone pair electrons with a cerium cation. This interaction causes the ethers to tilt away from the surface plane compared to the Ru(0001) surface. No pronounced differences were found between oxidized (CeO{sub 2}) and reduced (CeOx) films. The adsorption of the ethers was found to be perturbed by the presence of OH groups on hydroxylated CeOx. In the case of DEE, the geometry of adsorption resembles that found on Ru, and in the case of dimethyl ether DME is in between that one found on clean CeOx and the metal surface. Decomposition of the DEE was observed on the OH/CeOx surface following high DEE exposure at 300 K and higher temperatures. Ethoxides and acetates were identified as adsorbed species on the surface by means of RAIRS and ethoxides and formates by s-XPS. No decomposition of dimethyl ether was observed on the OH/CeOx at these higher temperatures, implying that the dissociation of the C-O bond from ethers requires the presence of {beta}-hydrogen.

  17. Dimethyl ether synthesis from syngas in slurry phase

    SciTech Connect (OSTI)

    Han, Y.Z.; Fujimoto, K.; Shikata, T.

    1997-12-31

    Dimethyl ether (DME) is one of the important chemicals derived from synthesis gas. It can be widely used in syngas conversion, production of olefins, or MTG gasoline. Recently, is has been noticed as a substitute of LPG used as home fuel. In the present study, dimethyl ether was effectively synthesized from CO rich syngas (H{sub 2}/CO=1/1) over hybrid catalyst containing a Cu-Zn-Al(O) based methanol synthesis catalyst and {gamma}-alumina in an agitated slurry reactor under relatively mild reaction conditions: temperature 230--300 C, pressure 2.0--5.0 MPa, contact time 2.0--10 gram-cat.-h/mol. The catalysts used as the methanol active components were commercially available Cu-Zn-Al(O) based catalysts, BASF S385 and ICI 51-2. Two kinds of {gamma}-alumina ALO4 (standard catalyst of the Catalysis Society of Japan) and N612N (NIKKI Co., Japan) were used as the methanol dehydration components. The slurry was prepared by mixing the fine powder (<100 mesh) of catalyst components with purified n-hexadecane. The catalysts were reduced by a mixing gas containing 20% syngas and 80% nitrogen with a three-hour programmed temperature raising from room temperature to the final temperature. All products were analyzed by gas chromatographs. Results are given and discussed.

  18. Rational Design of Cesium-Selective Ionophores and Chemosensors: Dihydrocalix[4]arene Crown-6 Ethers

    SciTech Connect (OSTI)

    Sachleben, Richard A.; Bryan, Jeffrey C.; Brown, Gilbert M.; Engle, Nancy L.; Haverlock, Tamara J.; Hay, Benjamin P.; Urvoas, Agathe; Moyer, Bruce A.

    2003-12-15

    Molecular mechanics calculations performed on calix[4]arene crown-6 ethers predict that the 1,3-dihydro derivatives will exhibit greater complementarity for potassium and cesium ions than the parent 1,3-dialkoxy calix crowns. The X-ray crystal structures of 1,3-alt bis-octyloxycalix[4]arene benzocrown-6 ether, dihydrocalix[4]arene benzocrown-6 ether, and the cesium nitrate complex of dihydrocalix[4]arene benzocrown-6 ether were determined. The cesium complex structure corresponds closely to the structure predicted by molecular mechanics. The dihydrocalix[4]arene crown-6 ethers exhibit enhanced cesium selectivity in the extraction of alkali metal salts and provide a platform for a highly sensitive and selective cesium chemosensor.

  19. Deetherification process

    DOE Patents [OSTI]

    Smith, L.A. Jr.

    1985-11-05

    Ethers such as isobutyl tertiary butyl ether are dissociated into their component alcohols and isoolefins by heat stabilized catalyst compositions prepared from nuclear sulfonic acid, for example, macroporous crosslinked polyvinyl aromatic compounds containing sulfonic acid groups are neutralized with a metal of Al, Fe, Zn, Cu, Ni, ions or mixtures and alkali, alkaline earth metals or ammonium ions by contacting the resin containing the sulfonic acid with aqueous solutions of the metals salts and alkali, alkaline earth metal or ammonium salts. The catalysts have at least 50% of the sulfonic acid groups neutralized with metal ions and the balance of the sulfonic acid groups neutralized with alkali, alkaline earth ions or ammonium ions.

  20. Deetherification process

    DOE Patents [OSTI]

    Smith, Jr., Lawrence A.

    1985-01-01

    Ethers such as isobutyl tertiary butyl ether are dissociated into their component alcohols and isolefins by heat stabilized catalyst compositions prepared from nuclear sulfonic acid, for example, macroporous crosslinked polyvinyl aromatic compounds containing sulfonic acid groups are neutralized with a metal of Al, Fe, Zn, Cu, Ni, ions or mixtures and alkali, alkaline earth metals or ammonium ions by contacting the resin containing the sulfonic acid with aqueous solutions of the metals salts and alkali, alkaline earth metal or ammonium salts. The catalysts have at least 50% of the sulfonic acid groups neutralized with metal ions and the balance of the sulfonic acid groups neutralized with alkali, alkaline earth ions or ammonium ions.

  1. Dimethyl ether fuel proposed as an alternative to LNG

    SciTech Connect (OSTI)

    Kikkawa, Yoshitsugi; Aoki, Ichizo

    1998-04-06

    To cope with the emerging energy demand in Asia, alternative fuels to LNG must be considered. Alternative measures, which convert the natural gas to liquid fuel, include the Fischer-Tropsch conversion, methanol synthesis, and dimethyl ether (DME) synthesis. Comparisons are evaluated based on both transportation cost and feed-gas cost. The analysis will show that DME, one alternative to LNG as transportation fuel, will be more economical for longer distances between the natural-gas source and the consumer. LNG requires a costly tanker and receiving terminal. The break-even distance will be around 5,000--7,000 km and vary depending on the transported volume. There will be risk, however, since there has never been a DME plant the size of an LNG-equivalent plant [6 million metric tons/year (mty)].

  2. Shape-selective catalysis in dimethyl ether conversion

    SciTech Connect (OSTI)

    Sardesai, A.; Lee, S.

    1999-07-01

    Coal-derived syngas can be effectively converted to dimethyl ether (DME) in a single-stage, liquid-phase process. This Liquid Phase Dimethyl Ether (LPDME) process utilizes a dual catalytic system, which comprises of a physical blend between the methanol synthesis and the methanol dehydration catalyst slurried in an inert mineral oil. Such produced DME has vast potential as a building block chemical in the petrochemical industry to produce value-added specialty chemicals. The current research efforts are made to exploit the utilization of shape-selective catalysis using zeolites to produce targeted petrochemicals, including lower olefinic hydrocarbons. The catalysts probed in this investigation include zeolites of different physical, morphological, and chemical configurations. The effect of acidity of ZSM-5 type zeolites as well as the effect of the different channel size and orientation of the zeolites on product selectivity and catalyst deactivation are examined. Results obtained from experimentation of this study show that ZSM-5 type zeolite with low acidity (high SiO{sub 2}/Al{sub 2}O{sub 3} ratio, in this case 150) exhibits the highest selectivity towards lower (C{sub 2}-C{sub 4}) olefins in general. Controlled selectivity toward targeted olefinic species can be accomplished via devising catalytic reaction systems in such a way that the structural property of the catalyst and reactive interaction between molecules in the pores are geared toward formation of targeted molecular species which also at the same time prevent the formation of less desirable products. The internal morphology of the catalyst also has a pronounced effect on the deactivation phenomenon, where it is observed that zeolites possessing high acidity and a unidimensional channel structure are prone towards catalyst deactivation by coking and pore blockage.

  3. DIMETHYL ETHER (DME)-FUELED SHUTTLE BUS DEMONSTRATION PROJECT

    SciTech Connect (OSTI)

    Elana M. Chapman; Shirish Bhide; Jennifer Stefanik; Andre L. Boehman; David Klinikowski

    2003-04-01

    The objectives of this research and demonstration program are to convert a campus shuttle bus to operation on dimethyl ether, a potential ultra-clean alternative diesel fuel. To accomplish this objective, this project includes laboratory evaluation of a fuel conversion strategy, as well as, field demonstration of the DME-fueled shuttle bus. Since DME is a fuel with no lubricity (i.e., it does not possess the lubricating quality of diesel fuel), conventional fuel delivery and fuel injection systems are not compatible with dimethyl ether. Therefore, to operate a diesel engine on DME one must develop a fuel-tolerant injection system, or find a way to provide the necessary lubricity to the DME. In this project, they have chosen the latter strategy in order to achieve the objective with minimal need to modify the engine. The strategy is to blend DME with diesel fuel, to obtain the necessary lubricity to protect the fuel injection system and to achieve low emissions. The laboratory studies have included work with a Navistar V-8 turbodiesel engine, demonstration of engine operation on DME-diesel blends and instrumentation for evaluating fuel properties. The field studies have involved performance, efficiency and emissions measurements with the Champion Motorcoach ''Defender'' shuttle bus which will be converted to DME-fueling. The results include baseline emissions, performance and combustion measurements on the Navistar engine for operation on a federal low sulfur diesel fuel (300 ppm S). Most recently, they have completed engine combustion studies on DME-diesel blends up to 30 wt% DME addition.

  4. Single-Step Syngas-to-Distillates (S2D) Synthesis via Methanol and Dimethyl Ether Intermediates: Final Report

    SciTech Connect (OSTI)

    Dagle, Robert A.; Lebarbier, Vanessa MC; Lizarazo Adarme, Jair A.; King, David L.; Zhu, Yunhua; Gray, Michel J.; Jones, Susanne B.; Biddy, Mary J.; Hallen, Richard T.; Wang, Yong; White, James F.; Holladay, Johnathan E.; Palo, Daniel R.

    2013-11-26

    The objective of the work was to enhance price-competitive, synthesis gas (syngas)-based production of transportation fuels that are directly compatible with the existing vehicle fleet (i.e., vehicles fueled by gasoline, diesel, jet fuel, etc.). To accomplish this, modifications to the traditional methanol-to-gasoline (MTG) process were investigated. In this study, we investigated direct conversion of syngas to distillates using methanol and dimethyl ether intermediates. For this application, a Pd/ZnO/Al2O3 (PdZnAl) catalyst previously developed for methanol steam reforming was evaluated. The PdZnAl catalyst was shown to be far superior to a conventional copper-based methanol catalyst when operated at relatively high temperatures (i.e., >300°C), which is necessary for MTG-type applications. Catalytic performance was evaluated through parametric studies. Process conditions such as temperature, pressure, gas-hour-space velocity, and syngas feed ratio (i.e., hydrogen:carbon monoxide) were investigated. PdZnAl catalyst formulation also was optimized to maximize conversion and selectivity to methanol and dimethyl ether while suppressing methane formation. Thus, a PdZn/Al2O3 catalyst optimized for methanol and dimethyl ether formation was developed through combined catalytic material and process parameter exploration. However, even after compositional optimization, a significant amount of undesirable carbon dioxide was produced (formed via the water-gas-shift reaction), and some degree of methane formation could not be completely avoided. Pd/ZnO/Al2O3 used in combination with ZSM-5 was investigated for direct syngas-to-distillates conversion. High conversion was achieved as thermodynamic constraints are alleviated when methanol and dimethyl are intermediates for hydrocarbon formation. When methanol and/or dimethyl ether are products formed separately, equilibrium restrictions occur. Thermodynamic relaxation also enables the use of lower operating pressures than what would be allowed for methanol synthesis alone. Aromatic-rich hydrocarbon liquid (C5+), containing a significant amount of methylated benzenes, was produced under these conditions. However, selectivity control to liquid hydrocarbons was difficult to achieve. Carbon dioxide and methane formation was problematic. Furthermore, saturation of the olefinic intermediates formed in the zeolite, and necessary for gasoline production, occurred over PdZnAl. Thus, yield to desirable hydrocarbon liquid product was limited. Evaluation of other oxygenate-producing catalysts could possibly lead to future advances. Potential exists with discovery of other types of catalysts that suppress carbon dioxide and light hydrocarbon formation. Comparative techno-economics for a single-step syngas-to-distillates process and a more conventional MTG-type process were investigated. Results suggest operating and capital cost savings could only modestly be achieved, given future improvements to catalyst performance. Sensitivity analysis indicated that increased single-pass yield to hydrocarbon liquid is a primary need for this process to achieve cost competiveness.

  5. CONVERSION OF DIMETHYL ETHER-BORON TRIFLUORIDE COMPLEX TO POTASSIUM FLUOBORATE

    DOE Patents [OSTI]

    Eberle, A.R.

    1957-06-18

    A method of preparing KBF/sub 4/ from the dimethyl ether complex of BF/sub 3/ is given. This may be accomplished by introducing the dimethyl ether complex of BF/sub 3/ into an aqueous solution of KF and alcohol, expelling the ether liberated from the complex by heating or stirring and recovering the KBF/sub 4/ so formed. The KBF/sub 4/ is then filtered from the alcohol-water solution, which may be recycled, to reduce the loss of KBF/sub 4/ which is not recovered by filtration.

  6. Conversion of dimethyl ether--boron trifluoride complex to potassium fluoborate

    DOE Patents [OSTI]

    Eberle, A.R.

    1957-06-18

    A method of preparing KBF/sub 4/ from the dimethyl ether complex of BF/sub 3/ is given. This may be accomplished by introducing the dimethyl ether complex of BF/sub 3/ into an aqueous solution of KF and alcohol, expelling the ether liberated from the complex by heating or stirring and recovering the KBF/sub 4/ so formed. The KBF/sub 4/ is then filtered from the alcohol-water solution, which may be recycled, to reduce the loss of KBF/sub 4/ which is not recovered by filtration.

  7. Heterogeneous catalyst for the production of acetic anhydride from methyl acetate

    DOE Patents [OSTI]

    Ramprasad, D.; Waller, F.J.

    1999-04-06

    This invention relates to a process for producing acetic anhydride by the reaction of methyl acetate, carbon monoxide, and hydrogen at elevated temperatures and pressures in the presence of an alkyl halide and a heterogeneous, bifunctional catalyst that contains an insoluble polymer having pendant quaternized phosphine groups, some of which phosphine groups are ionically bonded to anionic Group VIII metal complexes, the remainder of the phosphine groups being bonded to iodide. In contrast to prior art processes, no accelerator (promoter) is necessary to achieve the catalytic reaction and the products are easily separated from the catalyst by filtration. The catalyst can be recycled for consecutive runs without loss in activity. Bifunctional catalysts for use in carbonylating dimethyl ether are also provided.

  8. Heterogeneous catalyst for the production of acetic anhydride from methyl acetate

    DOE Patents [OSTI]

    Ramprasad, Dorai (Allentown, PA); Waller, Francis Joseph (Allentown, PA)

    1999-01-01

    This invention relates to a process for producing acetic anhydride by the reaction of methyl acetate, carbon monoxide, and hydrogen at elevated temperatures and pressures in the presence of an alkyl halide and a heterogeneous, bifunctional catalyst that contains an insoluble polymer having pendant quaternized phosphine groups, some of which phosphine groups are ionically bonded to anionic Group VIII metal complexes, the remainder of the phosphine groups being bonded to iodide. In contrast to prior art processes, no accelerator (promoter) is necessary to achieve the catalytic reaction and the products are easily separated from the catalyst by filtration. The catalyst can be recycled for consecutive runs without loss in activity. Bifunctional catalysts for use in carbonylating dimethyl ether are also provided.

  9. Sorbents for High Temperature Removal of Arsenic from Coal-Derived Synthesis Gas

    SciTech Connect (OSTI)

    Alptekin, G.O.; Copeland, R.; Dubovik, M.; Gershanovich, Y.

    2002-09-20

    Gasification technologies convert coal and other heavy feedstocks into synthesis gas feed streams that can be used in the production of a wide variety of chemicals, ranging from hydrogen through methanol, ammonia, acetic anhydride, dimethyl ether (DME), methyl tertiary butyl ether (MTBE), high molecular weight liquid hydrocarbons and waxes. Syngas can also be burned directly as a fuel in advanced power cycles to generate electricity with very high efficiency. However, the coal-derived synthesis gas contains a myriad of trace contaminants that may poison the catalysts that are used in the downstream manufacturing processes and may also be regulated in power plant emissions. Particularly, the catalysts used in the conversion of synthesis gas to methanol and other liquid fuels (Fischer-Tropsch liquids) have been found to be very sensitive to the low levels of poisons, especially arsenic, that are present in the synthesis gas from coal. TDA Research, Inc. (TDA) is developing an expendable high capacity, low-cost chemical absorbent to remove arsenic from coal-derived syngas. Unlike most of the commercially available sorbents that physically adsorb arsenic, TDA's sorbent operates at elevated temperatures and removes the arsenic through chemical reaction. The arsenic content in the coal gas stream is reduced to ppb levels with the sorbent by capturing and stabilizing the arsenic gas (As4) and arsenic hydrides (referred to as arsine, AsH3) in the solid state. To demonstrate the concept of high temperature arsenic removal from coal-derived syngas, we carried out bench-scale experiments to test the absorption capacity of a variety of sorbent formulations under representative conditions. Using on-line analysis techniques, we monitored the pre- and post-breakthrough arsine concentrations over different sorbent samples. Some of these samples exhibited pre-breakthrough arsine absorption capacity over 40% wt. (capacity is defined as lb of arsenic absorbed/lb of sorbent), while maintaining an arsine outlet concentration at less than 10 ppb.

  10. Photochemical dimerization and functionalization of alkanes, ethers, primary alcohols and silanes

    DOE Patents [OSTI]

    Crabtree, Robert H. (Bethany, CT); Brown, Stephen H. (East Haven, CT)

    1988-01-01

    The space-time yield and/or the selectivity of the photochemical dimerization of alkanes, ethers, primary alcohols and tertiary silanes with Hg and U.V. light is enhanced by refluxing the substrate in the irradiated reaction zone at a temperature at which the dimer product condenses and remains condensed promptly upon its formation. Cross-dimerization of the alkanes, ethers and silanes with primary alcohols is disclosed, as is the functionalization to aldehydes of the alkanes with carbon monoxide.

  11. Photochemical dimerization and functionalization of alkanes, ethers, primary alcohols and silanes

    DOE Patents [OSTI]

    Crabtree, R.H.; Brown, S.H.

    1988-02-16

    The space-time yield and/or the selectivity of the photochemical dimerization of alkanes, ethers, primary alcohols and tertiary silanes with Hg and U.V. light is enhanced by refluxing the substrate in the irradiated reaction zone at a temperature at which the dimer product condenses and remains condensed promptly upon its formation. Cross-dimerization of the alkanes, ethers and silanes with primary alcohols is disclosed, as is the functionalization to aldehydes of the alkanes with carbon monoxide.

  12. Metal ion complexation by ionizable crown ethers. Final report, January 1, 1988--June 30, 1994

    SciTech Connect (OSTI)

    Bartsch, R.A.

    1994-12-31

    During the report period a variety of new lipophilic ionizable crown ethers with pendent proton-ionizable groups has been synthesized. The ligands possess one or more ionizable group (carboxylic acid, phosphonic acid monoethyl ester, para-nitrophenol, phosphonic acid) attached to crown ether, monoazacrown ether or diazacrown ether frameworks. These novel chelating agents have either pendent or inward-facing proton-ionizable groups. Such lipophilic proton-ionizable crown ethers are designed for use in multiphase metal ion separations (solvent extraction, liquid membrane transport). In addition a series of proton-ionizable crown ethers without lipophilic groups was prepared to study how structural variations within the ligand influence metal ion complexation in homogeneous media as assessed by NMR spectroscopy or titration calorimetry. A third class of new metal ion-complexing agents is a series of lipophilic acyclic polyether dicarboxylic acids. Competitive solvent extractions of alkali metal and alkaline earth cations and of the mixed species have been conducted to reveal the influence of ring size, nature and attachment site of the lipophilic group, sidearm length, and proton-ionizable group identity and location upon the selectivity and efficiency of metal ion complexation. In addition to such studies of structural variation within the lipophilic proton-ionizable crown ether, the effect of changing the organic solvent and variation of the stripping conditions have been assessed. The influence of structural variations within lipophilic acyclic polyether dicarboxylic acids upon competitive solvent extraction of alkaline earth cations has been probed. Also a new chromogenic, di-ionizable crown ether with extremely high selectivity for Hg{sup 2+} has been discovered.

  13. SCALAR STRUCTURE OF TURBULENT PARTIALLY-PREMIXED DIMETHYL ETHER/AIR JET

    Office of Scientific and Technical Information (OSTI)

    FLAMES (Journal Article) | SciTech Connect SCALAR STRUCTURE OF TURBULENT PARTIALLY-PREMIXED DIMETHYL ETHER/AIR JET FLAMES Citation Details In-Document Search Title: SCALAR STRUCTURE OF TURBULENT PARTIALLY-PREMIXED DIMETHYL ETHER/AIR JET FLAMES Authors: Fuest, F. ; Magnotti, G. ; Barlow, R. S. ; Sutton, J. A. Publication Date: 2014-01-01 OSTI Identifier: 1167931 DOE Contract Number: SC0001198 Resource Type: Journal Article Resource Relation: Journal Name: Proceedings of the Combustion

  14. Scalar structure of turbulent partially-premixed dimethyl ether/air jet

    Office of Scientific and Technical Information (OSTI)

    flames (Journal Article) | SciTech Connect Scalar structure of turbulent partially-premixed dimethyl ether/air jet flames Citation Details In-Document Search This content will become publicly available on November 10, 2016 Title: Scalar structure of turbulent partially-premixed dimethyl ether/air jet flames Authors: Fuest, F. ; Magnotti, G. ; Barlow, R. S. ; Sutton, J. A. Publication Date: 2015-01-01 OSTI Identifier: 1251746 Grant/Contract Number: SC0001198 Type: Publisher's Accepted

  15. Combustion characterization of methylal in reciprocating engines

    SciTech Connect (OSTI)

    Dodge, L.; Naegeli, D.

    1994-06-01

    Methylal, CH{sub 3}OCH{sub 2}OCH{sub 3}, also known as dimethoxy-methane, is unique among oxygenates in that it has a low autoignition temperature, no carbon-carbon bonds, and is soluble in middle distillate fuels. Because of these properties, methylal has been shown to be a favorable fuel additive for reducing smoke in diesel engines. Recent measurements of ignition delay times indicate that methylal has a cetane number in the range of 45-50, which is compatible with diesel fuels. Engine tests have shown that adding methylal to diesel fuel significantly reduces smoke emissions. Gaseous emissions and combustion efficiencies obtained with methylal/diesel fuel blends remain essentially the same as those measured using neat diesel fuel. Lubricity measurements of methylal/diesel fuel blends with a ball on cylinder lubrication evaluator (BOCLE) show that methylal improves the lubricity of diesel fuel. Even though additions of methylal lower the fuel viscosity, the results of the BOCLE tests indicate that the methylal/diesel fuel blends cause less pump wear than neat diesel fuel. The one drawback is that methylal has a low boiling point (42{degrees}C) and a relatively high vapor pressure. As a result, it lowers the flash point of diesel fuel and causes a potential fuel tank flammability hazard. One solution to this increased volatility is to make polyoxymethylenes with the general formula of CH{sub 3}O(CH{sub 2}O){sub x}CH{sub 3} where x > 2. The molecules are similar to methylal, but have higher molecular weights and thus higher viscosities and substantially lower vapor pressures. Therefore, their flash points will be compatible with regular diesel fuel. The polyoxymethylenes are expected to have combustion properties similar to methylal. It is theorized that by analogy with hydrocarbons, the ignition quality (i.e., cetane number) of the polyoxymethylenes will be better than that of methylal.

  16. Wide range modeling study of dimethyl ether oxidation

    SciTech Connect (OSTI)

    Pitz, W.J.; Marinov, N.M.; Westbrook, C.K.; Dagaut, P.; Boettner, J-C; Cathonnet, M.

    1997-04-01

    A detailed chemical kinetic model has been used to study dimethyl ether (DME) oxidation over a wide range of conditions. Experimental results obtained in a jet-stirred reactor (JSR) at I and 10 atm, 0.2 < 0 < 2.5, and 800 < T < 1300 K were modeled, in addition to those generated in a shock tube at 13 and 40 bar, 0 = 1.0 and 650 :5 T :5 1300 K. The JSR results are particularly valuable as they include concentration profiles of reactants, intermediates and products pertinent to the oxidation of DME. These data test the Idnetic model severely, as it must be able to predict the correct distribution and concentrations of intermediate and final products formed in the oxidation process. Additionally, the shock tube results are very useful, as they were taken at low temperatures and at high pressures, and thus undergo negative temperature dependence (NTC) behavior. This behavior is characteristic of the oxidation of saturated hydrocarbon fuels, (e.g. the primary reference fuels, n-heptane and iso- octane) under similar conditions. The numerical model consists of 78 chemical species and 336 chemical reactions. The thermodynamic properties of unknown species pertaining to DME oxidation were calculated using THERM.

  17. EXTRACTION OF TETRAVALENT PLUTONIUM VALUES WITH METHYL ETHYL KETONE, METHYL ISOBUTYL KETONE ACETOPHENONE OR MENTHONE

    DOE Patents [OSTI]

    Seaborg, G.T.

    1961-08-01

    A process is described for extracting tetravalent plutonium from an aqueous acid solution with methyl ethyl ketone, methyl isobutyl ketone, or acetophenone and with the extraction of either tetravalent or hexavalent plutonium into menthone. (AEC)

  18. SYNTHESIS OF METHYL METHACRYLATE FROM COAL-DERIVED SYNGAS

    SciTech Connect (OSTI)

    BEN W.-L. JANG; GERALD N. CHOI; JAMES J. SPIVEY; JOSPEH R. ZOELLER; RICHARD D. COLBERG

    1999-01-20

    Research Triangle Institute (RTI), Eastman Chemical Company, and Bechtel collectively are developing a novel three-step process for the synthesis of methyl methacrylate (MMA) from coal-derived syngas that consists of the steps of synthesis of a propionate, its condensation with formaldehyde to form methacrylic acid (MAA), and esterification of MAA with methanol to produce MMA. The research team has completed the research on the three-step methanol-based route to MMA. Under an extension to the original contract, we are currently evaluating a new DME-based process for MMA. The key research need for DME route is to develop catalysts for DME partial oxidation reactions and DME condensation reactions. Over the last quarter(Oct.-Dec./98), we have investigated the condensation between methyl propionate and formaldehyde (MP/HCHO=4.5/1) at various reaction temperatures(280-360EC) over 5%, 10%, and 20% Nb O /SiO catalysts. The conversion of HCHO increases with reaction 2 5 2 temperature and niobium loading. MMA+MAA selectivity goes through a maximum with the temperature over both 10% and 20% Nb O /SiO . The selectivities to MMA+MAA are 67.2%, 2 5 2 72.3%and 58.1% at 320EC over 5%, 10%, 20% Nb O /SiO , respectively. However, the 2 5 2 conversion of formaldehyde decreases rapidly with time on stream. The results suggest that silica supported niobium catalysts are active and selective for condensation of MP with HCHO, but deactivation needs to be minimized for the consideration of commercial application. We have preliminarily investigated the partial oxidation of dimethyl ether(DME) over 5% Nb O /SiO catalyst. Reactant gas mixture of 0.1% DME, 0.1% O and balance nitrogen is 2 5 2 2 studied with temperature ranging from 200°C to 500°C. The conversion of DME first increases with temperature reaching an maximum at 400°C then decreases. The selectivity to HCHO also increases with reaction temperature first. But the selectivity to HCHO decreases at temperature above 350°C accompanied by the increasing selectivity to CO . The results suggest that silica 2 supported niobium catalysts are active for partial oxidation of DME to HCHO. Best temperatures for partial oxidation are between 300 and 400°C. A short paper submitted to the ACS National Meeting at Anaheim(March 1999) was accepted for oral presentation. The title is �Catalytic Synthesis of Methacrylates over Silica Supported Niobium Catalysts� and will appear in the ACS preprints.

  19. DIMETHYL ETHER (DME)-FUELED SHUTTLE BUS DEMONSTRATION PROJECT

    SciTech Connect (OSTI)

    Elana M. Chapman; Shirish Bhide; Jennifer Stefanik; Howard Glunt; Andre L. Boehman; Allen Homan; David Klinikowski

    2003-04-01

    The objectives of this research and demonstration program are to convert a campus shuttle bus to operation on dimethyl ether, a potential ultra-clean alternative diesel fuel. To accomplish this objective, this project includes laboratory evaluation of a fuel conversion strategy, as well as, field demonstration of the DME-fueled shuttle bus. Since DME is a fuel with no lubricity (i.e., it does not possess the lubricating quality of diesel fuel), conventional fuel delivery and fuel injection systems are not compatible with dimethyl ether. Therefore, to operate a diesel engine on DME one must develop a fuel-tolerant injection system, or find a way to provide the necessary lubricity to the DME. In this project, they have chosen the latter strategy in order to achieve the objective with minimal need to modify the engine. Their strategy is to blend DME with diesel fuel, to obtain the necessary lubricity to protect the fuel injection system and to achieve low emissions. The bulk of the efforts over the past year were focused on the conversion of the campus shuttle bus. This process, started in August 2001, took until April 2002 to complete. The process culminated in an event to celebrate the launching of the shuttle bus on DME-diesel operation on April 19, 2002. The design of the system on the shuttle bus was patterned after the system developed in the engine laboratory, but also was subjected to a rigorous failure modes effects analysis (FMEA, referred to by Air Products as a ''HAZOP'' analysis) with help from Dr. James Hansel of Air Products. The result of this FMEA was the addition of layers of redundancy and over-pressure protection to the system on the shuttle bus. The system became operational in February 2002. Preliminary emissions tests and basic operation of the shuttle bus took place at the Pennsylvania Transportation Institute's test track facility near the University Park airport. After modification and optimization of the system on the bus, operation on the campus shuttle route began in early June 2002. However, the work and challenges continued as it has been difficult to maintain operability of the shuttle bus due to fuel and component difficulties. In late June 2002, the pump head itself developed operational problems (loss of smooth function) leading to excessive stress on the magnetic coupling and excessive current draw to operate. A new pump head was installed on the system to alleviate this problem and the shuttle bus operated successfully on DME blends from 10-25 vol% on the shuttle bus loop until September 30, 2002. During the period of operation on the campus loop, the bus was pulled from service, operated at the PTI test track and real-time emissions measurements were obtained using an on-board emissions analyzer from Clean Air Technologies International, Inc. Particulate emissions reductions of 60% and 80% were observed at DME blend ratios of 12 vol.% and 25 vol.%, respectively, as the bus was operated over the Orange County driving cycle. Increases in NOx, CO and HC emissions were observed, however. In summary, the conversion of the shuttle bus was successfully accomplished, particulate emissions reductions were observed, but there were operational challenges in the field. Nonetheless, they were able to demonstrate reliable operation of the shuttle bus on DME-diesel blends.

  20. MOF-based catalysts for selective hydrogenolysis of carbon–oxygen ether bonds

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Stavila, Vitalie; Parthasarathi, Ramakrishnan; Davis, Ryan W.; El Gabaly, Farid; Sale, Kenneth L.; Simmons, Blake A.; Singh, Seema; Allendorf, Mark D.

    2015-11-23

    We demonstrate that metal–organic frameworks (MOFs) can catalyze hydrogenolysis of aryl ether bonds under mild conditions. Mg-IRMOF-74(I) and Mg-IRMOF-74(II) are stable under reducing conditions and can cleave phenyl ethers containing β-O-4, α-O-4, and 4-O-5 linkages to the corresponding hydrocarbons and phenols. Reaction occurs at 10 bar H2 and 120 °C without added base. DFT-optimized structures and charge transfer analysis suggest that the MOF orients the substrate near Mg2+ ions on the pore walls. Ti and Ni doping further increase conversions to as high as 82% with 96% selectivity for hydrogenolysis versus ring hydrogenation. Thus repeated cycling induces no loss ofmore » activity, making this a promising route for mild aryl-ether bond scission.« less

  1. MOF-based catalysts for selective hydrogenolysis of carbon–oxygen ether bonds

    SciTech Connect (OSTI)

    Stavila, Vitalie; Parthasarathi, Ramakrishnan; Davis, Ryan W.; El Gabaly, Farid; Sale, Kenneth L.; Simmons, Blake A.; Singh, Seema; Allendorf, Mark D.

    2015-11-23

    We demonstrate that metal–organic frameworks (MOFs) can catalyze hydrogenolysis of aryl ether bonds under mild conditions. Mg-IRMOF-74(I) and Mg-IRMOF-74(II) are stable under reducing conditions and can cleave phenyl ethers containing β-O-4, α-O-4, and 4-O-5 linkages to the corresponding hydrocarbons and phenols. Reaction occurs at 10 bar H2 and 120 °C without added base. DFT-optimized structures and charge transfer analysis suggest that the MOF orients the substrate near Mg2+ ions on the pore walls. Ti and Ni doping further increase conversions to as high as 82% with 96% selectivity for hydrogenolysis versus ring hydrogenation. Thus repeated cycling induces no loss of activity, making this a promising route for mild aryl-ether bond scission.

  2. DIMETHYL ETHER (DME)-FUELED SHUTTLE BUS DEMONSTRATION PROJECT

    SciTech Connect (OSTI)

    Elana M. Chapman; Shirish Bhide; Jennifer Stefanik; Howard Glunt; Andre L. Boehman; Allen Homan; David Klinikowski

    2003-04-01

    The objectives of this research and demonstration program are to convert a campus shuttle bus to operation on dimethyl ether, a potential ultra-clean alternative diesel fuel. To accomplish this objective, this project includes laboratory evaluation of a fuel conversion strategy, as well as, field demonstration of the DME-fueled shuttle bus. Since DME is a fuel with no lubricity (i.e., it does not possess the lubricating quality of diesel fuel), conventional fuel delivery and fuel injection systems are not compatible with dimethylether. Therefore, to operate a diesel engine on DME one must develop a fuel-tolerant injection system, or find a way to provide the necessary lubricity to the DME. In this project, they have chosen the latter strategy in order to achieve the objective with minimal need to modify the engine. The strategy is to blend DME with diesel fuel, to obtain the necessary lubricity to protect the fuel injection system and to achieve low emissions. The bulk of the efforts over the past year were focused on the conversion of the campus shuttle bus. This process, started in August 2001, took until April 2002 to complete. The process culminated in an event to celebrate the launching of the shuttle bus on DME-diesel operation on April 19, 2002. The design of the system on the shuttle bus was patterned after the system developed in the engine laboratory, but also was subjected to a rigorous failure modes effects analysis with help from Dr. James Hansel of Air Products. The result of this FMEA was the addition of layers of redundancy and over-pressure protection to the system on the shuttle bus. The system became operation in February 2002. Preliminary emissions tests and basic operation of the shuttle bus took place at the Pennsylvania Transportation institute's test track facility near the University Park airport. After modification and optimization of the system on the bus, operation on the campus shuttle route began in early June 2002. However, the work and challenges have continued as it has been difficult to maintain operability of the shuttle bus due to fuel and component difficulties. As of late June 2002, it appears that the pump head itself developed operational problems (loss of smooth function) leading to excessive stress on the magnetic coupling and excessive current draw to operate. A new pump head is being installed on the system to alleviate this problem and get the shuttle bus back in operation. In summary, the conversion is completed but there have been operational challenges in the field. They continue to work to make the shuttle bus as reliable to operate on DME-diesel blends as possible.

  3. Photochemical dimerization and functionalization of alkanes, ethers, primary and secondary alcohols, phosphine oxides and silanes

    DOE Patents [OSTI]

    Crabtree, Robert H. (Bethany, CT); Brown, Stephen H. (East Haven, CT)

    1989-01-01

    The space-time yield and/or the selectivity of the photochemical dimerization of alkanes, ethers, primary and secondary alcohols, phosphine oxides and primary, secondary and tertiary silanes with Hg and U.V. light is enhanced by refluxing the substrate in the irradiated reaction zone at a temperature at which the dimer product condenses and remains condensed promptly upon its formation. Cross-dimerization of the alkanes, ethers and silanes with primary alcohols is disclosed, as is the functionalization to aldehydes of the alkanes with carbon monoxide.

  4. Catalyst system and process for benzyl ether fragmentation and coal liquefaction

    DOE Patents [OSTI]

    Zoeller, Joseph Robert (Kingsport, TN)

    1998-04-28

    Dibenzyl ether can be readily cleaved to form primarily benzaldehyde and toluene as products, along with minor amounts of bibenzyl and benzyl benzoate, in the presence of a catalyst system comprising a Group 6 metal, preferably molybdenum, a salt, and an organic halide. Although useful synthetically for the cleavage of benzyl ethers, this cleavage also represents a key model reaction for the liquefaction of coal; thus this catalyst system and process should be useful in coal liquefaction with the advantage of operating at significantly lower temperatures and pressures.

  5. Photochemical dimerization and functionalization of alkanes, ethers, primary and secondary alcohols, phosphine oxides and silanes

    DOE Patents [OSTI]

    Crabtree, R.H.; Brown, S.H.

    1989-10-17

    The space-time yield and/or the selectivity of the photochemical dimerization of alkanes, ethers, primary and secondary alcohols, phosphine oxides and primary, secondary and tertiary silanes with Hg and U.V. light is enhanced by refluxing the substrate in the irradiated reaction zone at a temperature at which the dimer product condenses and remains condensed promptly upon its formation. Cross-dimerization of the alkanes, ethers and silanes with primary alcohols is disclosed, as is the functionalization to aldehydes of the alkanes with carbon monoxide.

  6. Mechanisms of Selective Cleavage of C-O Bonds in Di-aryl Ethers in Aqueous Phase

    SciTech Connect (OSTI)

    He, Jiayue; Zhao, Chen; Mei, Donghai; Lercher, Johannes A.

    2014-01-02

    A novel route for cleaving the C-O aryl ether bonds of p-substituted H-, CH3-, and OH- diphenyl ethers has been explored over Ni/SiO2 catalysts at very mild conditions. The C-O bond of diphenyl ether is cleaved by parallel hydrogenolysis and hydrolysis (hydrogenolysis combined with HO* addition) on Ni. The rates as a function of H2 pressure from 0 to 10 MPa indicate that the rate-determining step is the C-O bond cleavage on Ni. H* atoms compete with the organic reactant for adsorption leading to a maximum in the rate with increasing H2 pressure. In contrast to diphenyl ether, hydrogenolysis is the exclusive route for cleaving an ether C-O bond of di-p-tolyl ether to form p-cresol and toluene. 4,4'-dihydroxydiphenyl ether undergoes sequential surface hydrogenolysis, first to phenol and HOC6H4O* (adsorbed), which is then cleaved to phenol (C6H5O* with added H*) and H2O (O* with two added H*) in a second step. Density function theory supports the operation of this pathway. Notably, addition of H* to HOC6H4O* is less favorable than a further hydrogenolytic C-O bond cleavage. The TOFs of three aryl ethers with Ni/SiO2 in water followed the order 4,4'-dihydroxydiphenyl ether (69 h-1) > diphenyl ether (26 h-1) > di-p-tolyl ether (1.3 h-1), in line with the increasing apparent activation energies, ranging from 93 kJ∙mol-1 (4,4'-dihydroxydiphenyl ether) < diphenyl ether (98 kJ∙mol-1) to di-p-tolyl ether (105 kJ∙mol-1). D.M. thanks the support from the US Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences. Pacific Northwest National Laboratory (PNNL) is a multiprogram national laboratory operated for DOE by Battelle. Computing time was granted by the grand challenge of computational catalysis of the William R. Wiley Environmental Molecular Sciences Laboratory (EMSL) and by the National Energy Research Scientific Computing Center (NERSC). EMSL is a national scientific user facility located at Pacific Northwest National Laboratory (PNNL) and sponsored by DOE’s Office of Biological and Environmental Research.

  7. Task 4.9 -- Value-added products from syngas. Semi-annual report, July 1--December 31, 1996

    SciTech Connect (OSTI)

    Olson, E.S.; Sharma, R.K.

    1997-08-01

    The work on advanced fuel forms in 1996 focused on the synthesis of higher alcohols from mixtures of hydrogen and carbon dioxide (syngas) from coal gasification. Initial work in this project utilized a novel molybdenum sulfide catalyst previously shown to be active for hydrodesulfurization reactions of coal liquids. A pressurized fixed-bed flow-through reactor was constructed, and the MoS{sub 2} catalysts were tested with syngas under a variety of conditions. Unfortunately, the catalysts, even with higher molybdenum loading and addition of promoters, failed to give alcohol products. A batch reactor test of the catalyst was also conducted, but did not produce alcohol products. Group VIII metals have been used previously in catalysts for syngas reactions. Ruthenium and rhodium catalysts were prepared by impregnation of a hydrotalcite support. Tests with these catalysts in flow-through reactors also did not produce the desired alcohol products. The formation of higher alcohols from smaller ones, such as methanol and ethanol, could be commercially important if high selectivity could be achieved. The methanol and ethanol would be derived from syngas and fermentation, respectively. Based on previous work in other laboratories, it was hypothesized that the hydrotalcite-supported MoS{sub 2} or Ru or Rh catalysts could catalyze the formation of butyl alcohols. Although the desired 1-butanol was obtained in batch reactions with the promoted ruthenium catalyst, the reaction was not as selective as desired. Product suitable for a lower-vapor-pressure gasoline oxygenate additive was obtained, but it may not be economical to market such products in competition with methyl tertiary-butyl ether (MTBE). Flow-through catalytic bed reactions were not successful.

  8. Fuel cycle evaluations of biomass-ethanol and reformulated gasoline. Volume 1

    SciTech Connect (OSTI)

    Tyson, K.S.

    1993-11-01

    The US Department of Energy (DOE) is using the total fuel cycle analysis (TFCA) methodology to evaluate energy choices. The National Energy Strategy (NES) identifies TFCA as a tool to describe and quantify the environmental, social, and economic costs and benefits associated with energy alternatives. A TFCA should quantify inputs and outputs, their impacts on society, and the value of those impacts that occur from each activity involved in producing and using fuels, cradle-to-grave. New fuels and energy technologies can be consistently evaluated and compared using TFCA, providing a sound basis for ranking policy options that expand the fuel choices available to consumers. This study is limited to creating an inventory of inputs and outputs for three transportation fuels: (1) reformulated gasoline (RFG) that meets the standards of the Clean Air Act Amendments of 1990 (CAAA) using methyl tertiary butyl ether (MTBE); (2) gasohol (E10), a mixture of 10% ethanol made from municipal solid waste (MSW) and 90% gasoline; and (3) E95, a mixture of 5% gasoline and 95% ethanol made from energy crops such as grasses and trees. The ethanol referred to in this study is produced from lignocellulosic material-trees, grass, and organic wastes -- called biomass. The biomass is converted to ethanol using an experimental technology described in more detail later. Corn-ethanol is not discussed in this report. This study is limited to estimating an inventory of inputs and outputs for each fuel cycle, similar to a mass balance study, for several reasons: (1) to manage the size of the project; (2) to provide the data required for others to conduct site-specific impact analysis on a case-by-case basis; (3) to reduce data requirements associated with projecting future environmental baselines and other variables that require an internally consistent scenario.

  9. Location of MTBE and toluene in the channel system of the zeolite mordenite: Adsorption and host-guest interactions

    SciTech Connect (OSTI)

    Arletti, Rossella; Martucci, Annalisa; Alberti, Alberto; Pasti, Luisa; Nassi, Marianna; Bagatin, Roberto

    2012-10-15

    This paper reports a study of the location of Methyl Tertiary Butyl Ether (MTBE) and toluene molecules adsorbed in the pores of the organophylic zeolite mordenite from an aqueous solution. The presence of these organic molecules in the zeolite channels was revealed by structure refinement performed by the Rietveld method. About 3 molecules of MTBE and 3.6 molecules of toluene per unit cell were incorporated into the cavities of mordenite, representing 75% and 80% of the total absorption capacity of this zeolite. In both cases a water molecule was localized inside the side pocket of mordenite. The saturation capacity determined by the adsorption isotherms, obtained by batch experiments, and the weight loss given by thermogravimetric (TG) analyses were in very good agreement with these values. The interatomic distances obtained after the structural refinements suggest MTBE could be connected to the framework through a water molecule, while toluene could be bonded to framework oxygen atoms. The rapid and high adsorption of these hydrocarbons into the organophylic mordenite zeolite makes this cheap and environmental friendly material a suitable candidate for the removal of these pollutants from water. - graphical abstract: Location of MTBE (a) and toluene (b) in mordenite channels (projection along the [001] direction). Highlights: Black-Right-Pointing-Pointer We investigated the MTBE and toluene adsorption process into an organophilic zeolite mordenite. Black-Right-Pointing-Pointer The presence of MTBE and toluene in mordenite was determined by X-ray diffraction studies. Black-Right-Pointing-Pointer About 3 molecules of MTBE and 3.6 molecules of toluene per unit cell were incorporated into the zeolite cavities. Black-Right-Pointing-Pointer MTBE is connected to the framework through a water molecule. Black-Right-Pointing-Pointer Toluene is directly bonded to framework oxygen atoms.

  10. Ethanol Demand in United States Production of Oxygenate-limited Gasoline

    SciTech Connect (OSTI)

    Hadder, G.R.

    2000-08-16

    Ethanol competes with methyl tertiary butyl ether (MTBE) to satisfy oxygen, octane, and volume requirements of certain gasolines. However, MTBE has water quality problems that may create significant market opportunities for ethanol. Oak Ridge National Laboratory (ORNL) has used its Refinery Yield Model to estimate ethanol demand in gasolines with restricted use of MTBE. Reduction of the use of MTBE would increase the costs of gasoline production and possibly reduce the gasoline output of U.S. refineries. The potential gasoline supply problems of an MTBE ban could be mitigated by allowing a modest 3 vol percent MTBE in all gasoline. In the U.S. East and Gulf Coast gasoline producing regions, the 3 vol percent MTBE option results in costs that are 40 percent less than an MTBE ban. In the U.S. Midwest gasoline producing region, with already high use of ethanol, an MTBE ban has minimal effect on ethanol demand unless gasoline producers in other regions bid away the local supply of ethanol. The ethanol/MTBE issue gained momentum in March 2000 when the Clinton Administration announced that it would ask Congress to amend the Clean Air Act to provide the authority to significantly reduce or eliminate the use of MTBE; to ensure that air quality gains are not diminished as MTBE use is reduced; and to replace the existing oxygenate requirement in the Clean Air Act with a renewable fuel standard for all gasoline. Premises for the ORNL study are consistent with the Administration announcement, and the ethanol demand curve estimates of this study can be used to evaluate the impact of the Administration principles and related policy initiatives.

  11. Methylal and Methylal-Diesel Blended Fuels from Use In Compression-Ignition Engines

    SciTech Connect (OSTI)

    Keith D. Vertin; James M. Ohi; David W. Naegeli; Kenneth H. Childress; Gary P. Hagen; Chris I. McCarthy; Adelbert S. Cheng; Robert W. Dibble

    1999-05-05

    Gas-to-liquids catalytic conversion technologies show promise for liberating stranded natural gas reserves and for achieving energy diversity worldwide. Some gas-to-liquids products are used as transportation fuels and as blendstocks for upgrading crude derived fuels. Methylal (CH{sub 3}-O-CH{sub 2}-O-CH{sub 3}) also known as dimethoxymethane or DMM, is a gas-to-liquid chemical that has been evaluated for use as a diesel fuel component. Methylal contains 42% oxygen by weight and is soluble in diesel fuel. The physical and chemical properties of neat methylal and for blends of methylal in conventional diesel fuel are presented. Methylal was found to be more volatile than diesel fuel, and special precautions for distribution and fuel tank storage are discussed. Steady state engine tests were also performed using an unmodified Cummins 85.9 turbocharged diesel engine to examine the effect of methylal blend concentration on performance and emissions. Substantial reductions of particulate matter emissions h ave been demonstrated 3r IO to 30% blends of methylal in diesel fuel. This research indicates that methylal may be an effective blendstock for diesel fuel provided design changes are made to vehicle fuel handling systems.

  12. The effect of catalyst ratio on catalytic performance in liquid phase dimethyl ether process

    SciTech Connect (OSTI)

    Guo Junwang; Niu Yuqin; Zhang Bijiang

    1997-12-31

    In the liquid phase dimethyl ether (LPDME) process, two functionally different catalysts are slurried together in an inert liquid medium. Syngas reacts on the surface of the methanol catalyst and methanol is dehydrated on the surface of the dehydration catalyst dispersed in the liquid. The process is adaptable to carbon monoxide-rich syngas derived from second generation coal gasifiers. The effect of catalyst ratio on catalytic performances of the dual catalyst was studied in liquid phase dimethyl ether synthesis from syngas at 280 C, 4.0 MPa. CO conversion, H{sub 2} conversion and DME productivity increased with an increase of catalyst ratio initially, reached their maximum at a catalyst ratio of 4.0--5.0, and then decreased. Methanol productivity and methanol equivalent productivity had a similar trend to that of DME productivity. DME selectivity and hydrocarbon selectivity increased with an increase in catalyst ratio whereas methanol selectivity decreased with catalyst ratio.

  13. Process to convert biomass and refuse derived fuel to ethers and/or alcohols

    DOE Patents [OSTI]

    Diebold, James P.; Scahill, John W.; Chum, Helena L.; Evans, Robert J.; Rejai, Bahman; Bain, Richard L.; Overend, Ralph P.

    1996-01-01

    A process for conversion of a feedstock selected from the group consisting of biomass and refuse derived fuel (RDF) to provide reformulated gasoline components comprising a substantial amount of materials selected from the group consisting of ethers, alcohols, or mixtures thereof, comprising: drying said feedstock; subjecting said dried feedstock to fast pyrolysis using a vortex reactor or other means; catalytically cracking vapors resulting from said pyrolysis using a zeolite catalyst; condensing any aromatic byproduct fraction; catalytically alkylating any benzene present in said vapors after condensation; catalytically oligomerizing any remaining ethylene and propylene to higher olefins; isomerizing said olefins to reactive iso-olefins; and catalytically reacting said iso-olefins with an alcohol to form ethers or with water to form alcohols.

  14. Process to convert biomass and refuse derived fuel to ethers and/or alcohols

    DOE Patents [OSTI]

    Diebold, J.P.; Scahill, J.W.; Chum, H.L.; Evans, R.J.; Rejai, B.; Bain, R.L.; Overend, R.P.

    1996-04-02

    A process is described for conversion of a feedstock selected from the group consisting of biomass and refuse derived fuel (RDF) to provide reformulated gasoline components comprising a substantial amount of materials selected from the group consisting of ethers, alcohols, or mixtures thereof, comprising: drying said feedstock; subjecting said dried feedstock to fast pyrolysis using a vortex reactor or other means; catalytically cracking vapors resulting from said pyrolysis using a zeolite catalyst; condensing any aromatic byproduct fraction; catalytically alkylating any benzene present in said vapors after condensation; catalytically oligomerizing any remaining ethylene and propylene to higher olefins; isomerizing said olefins to reactive iso-olefins; and catalytically reacting said iso-olefins with an alcohol to form ethers or with water to form alcohols. 35 figs.

  15. Molecular modeling of the morphology and transport properties of two direct methanol fuel cell membranes: phenylated sulfonated poly(ether ether ketone ketone) versus Nafion

    SciTech Connect (OSTI)

    Devanathan, Ramaswami; Idupulapati, Nagesh B.; Dupuis, Michel

    2012-08-14

    We have used molecular dynamics simulations to examine membrane morphology and the transport of water, methanol and hydronium in phenylated sulfonated poly ether ether ketone ketone (Ph-SPEEKK) and Nafion membranes at 360 K for a range of hydration levels. At comparable hydration levels, the pore diameter is smaller, the sulfonate groups are more closely packed, the hydronium ions are more strongly bound to sulfonate groups, and the diffusion of water and hydronium is slower in Ph-SPEEKK relative to the corresponding properties in Nafion. The aromatic carbon backbone of Ph-SPEEKK is less hydrophobic than the fluorocarbon backbone of Nafion. Water network percolation occurs at a hydration level ({lambda}) of {approx}8 H{sub 2}O/SO{sub 3}{sup -}. At {lambda} = 20, water, methanol and hydronium diffusion coefficients were 1.4 x 10{sup -5}, 0.6 x 10{sup -5} and 0.2 x 10{sup -5} cm{sup 2}/s, respectively. The pore network in Ph-SPEEKK evolves dynamically and develops wide pores for {lambda} > 20, which leads to a jump in methanol crossover and ion transport. This study demonstrates the potential of aromatic membranes as low-cost challengers to Nafion for direct methanol fuel cell applications and the need to develop innovative strategies to combat methanol crossover at high hydration levels.

  16. 2[prime] and 3[prime] Carboranyl uridines and their diethyl ether adducts

    DOE Patents [OSTI]

    Soloway, A.H.; Barth, R.F.; Anisuzzaman, A.K.; Alam, F.; Tjarks, W.

    1992-12-15

    A process is described for preparing carboranyl uridine nucleoside compounds and their diethyl ether adducts, which exhibit a tenfold increase in boron content over prior art boron containing nucleoside compounds. The carboranyl uridine nucleoside compounds exhibit enhanced lipophilicity and hydrophilic properties adequate to enable solvation in aqueous media for subsequent incorporation of the compounds in methods for boron neutron capture therapy in mammalian tumor cells. No Drawings

  17. Barrierless proton transfer across weak CH⋯O hydrogen bonds in dimethyl ether dimer

    SciTech Connect (OSTI)

    Yoder, Bruce L. West, Adam H. C.; Signorell, Ruth; Bravaya, Ksenia B.; Bodi, Andras; Sztáray, Bálint

    2015-03-21

    We present a combined computational and threshold photoelectron photoion coincidence study of two isotopologues of dimethyl ether, (DME − h{sub 6}){sub n} and (DME − d{sub 6}){sub n}n = 1 and 2, in the 9–14 eV photon energy range. Multiple isomers of neutral dimethyl ether dimer were considered, all of which may be present, and exhibited varying C–H⋯O interactions. Results from electronic structure calculations predict that all of them undergo barrierless proton transfer upon photoionization to the ground electronic state of the cation. In fact, all neutral isomers were found to relax to the same radical cation structure. The lowest energy dissociative photoionization channel of the dimer leads to CH{sub 3}OHCH{sub 3}{sup +} by the loss of CH{sub 2}OCH{sub 3} with a 0 K appearance energy of 9.71 ± 0.03 eV and 9.73 ± 0.03 eV for (DME − h{sub 6}){sub 2} and deuterated (DME − d{sub 6}){sub 2}, respectively. The ground state threshold photoelectron spectrum band of the dimethyl ether dimer is broad and exhibits no vibrational structure. Dimerization results in a 350 meV decrease of the valence band appearance energy, a 140 meV decrease of the band maximum, thus an almost twofold increase in the ground state band width, compared with DME − d{sub 6} monomer.

  18. Low temperature synthesis of methyl formate

    DOE Patents [OSTI]

    Mahajan, Devinder; Slegeir, William A.; Sapienza, Richard S.; O'Hare, Thomas E.

    1986-01-01

    A gas reaction process for the preferential production of methyl formate over the co-production of methanol wherein the reactant ratio of CO/H.sub.2 is upgraded and this reaction takes place at low temperatures of 50.degree.-150.degree. C. and moderate pressures of .gtoreq.100 psi.

  19. Synthesis of methyl methacrylate from coal-derived syngas: Quarterly report,, October 1-December 31, 1997

    SciTech Connect (OSTI)

    1998-09-01

    Research Triangle Institute (RTI), Eastman Chemical Company, and Bechtel collectively are developing a novel process for the synthesis of methyl methacrylate (MMA) from coal-derived syngas that consists of three steps of synthesis of a propionate, its condensation with formaldehyde, and esterification of resulting methacrylic acid (MAA) with methanol to produce MMA. Over the last quarter, Eastman developed two new processes which have resulted in two new invention reports. One process deals with carbonylation of benzyl ether which represents a model for coal liquefaction and the second focuses on the acceleration of carbonylation rates for propionic acid synthesis, via use of polar aprotic solvents. These two inventions are major improvements in the novel Mo-catalyzed homogeneous process for propionic acid synthesis technology, developed by Eastman. Over the last quarter, RTI completed three reaction cycles and two regeneration cycles as a part of long-term reaction regeneration cycle study on a 10% Nb{sub 2}O{sub 5}/Si0{sub 2} catalyst, for vapor phase condensation reaction of formaldehyde with propionic acid.

  20. Modulation of histone methylation and MLH1 gene silencing by...

    Office of Scientific and Technical Information (OSTI)

    ... Subject: 60 APPLIED LIFE SCIENCES; ARGININE; CARCINOGENS; CHROMIUM; DNA DAMAGES; GENES; HUMAN POPULATIONS; LUNGS; LYSINE; METHYLATION; NEOPLASMS; OCCUPATIONAL EXPOSURE; PROMOTERS ...

  1. Improvement of performance and emissions of a compression ignition methanol engine with dimethyl ether

    SciTech Connect (OSTI)

    Guo, J.; Chikahisa, Takemi; Murayama, Tadashi; Miyano, Masaharu

    1994-10-01

    Dimethyl ether (DME) has very good compression ignition characteristics and can be converted from methanol using a {gamma}-alumina catalyst. In this study a torch ignition chamber (TIC) head with TIC close to the center of the main combustion chamber was designed for the TIC method. The possibility of improvements in reducing the quantities of DME and emission were investigated by optimizing the TIC position, methanol injection timing, DME injection timing, and intake and exhaust throttling. It was found that the necessary amount of DME was greatly reduced when optimizing methanol and DME injection timings. 2 refs., 16 figs., 1 tab.

  2. High octane ethers from synthesis gas-derived alcohols. Quarterly technical progress report, April--June 1993

    SciTech Connect (OSTI)

    Klier, K.; Herman, R.G.; Menszak, J.; Johansson, M.A.; Feeley, O.C.; Kim, D.

    1993-07-01

    The results shown in Figures 10 and 11 demonstrate that the formation of butenes was very sensitive to the alcohol partial pressure. A small elevation of the alcohol pressure suppressed the formation of butenes rather drastically at both 90 and 117{degree}C. The synthesis rates of DME, MIBE, and MTBE ethers were not significantly affected at 90{degree}C, although there was a trend to increase the space time yield of DME as the alcohol pressure was increased. At the reaction temperature of 117{degree}C, all of the ethers showed increasing productivities as the pressure of the reactants was increased (Figure 11). An isotope labelling experiment was carried out to provide mechanistic insight into the manner in which methanol and isobutanol react together to form DME, MIBE, and MTBE ethers and to determine if MTBE were derived from MIBE.

  3. Commercial-scale demonstration of the Liquid Phase Methanol (LPMEOH{trademark}) Process. Peroxide formation of dimethyl ether in methanol mixtures

    SciTech Connect (OSTI)

    Waller, F.J.

    1997-11-01

    Organic peroxides could form when dimethyl ether in methanol is stored for three to six months at a time. The objective of this work was to determine the level of peroxide formation from dimethyl ether in reagent grade methanol and raw methanol at room temperature under 3 atmospheres (45 psig) of air. Raw methanol is methanol made from syngas by the LPMEOH Process without distillation. Aliphatic ethers tend to react slowly with oxygen from the air to form unstable peroxides. However, there are no reports on peroxide formation from dimethyl ether. After 172 days of testing, dimethyl ether in either reagent methanol or raw methanol at room temperature and under 60--70 psig pressure of air does not form detectable peroxides. Lack of detectable peroxides suggests that dimethyl ether or dimethyl ether and methanol may be stored at ambient conditions. Since the compositions of {approximately} 1.3 mol% or {approximately} 4.5 mol% dimethyl ether in methanol do not form peroxides, these compositions can be considered for diesel fuel or an atmospheric turbine fuel, respectively.

  4. Assessing the toxic effects of ethylene glycol ethers using Quantitative Structure Toxicity Relationship models

    SciTech Connect (OSTI)

    Ruiz, Patricia; Mumtaz, Moiz; Gombar, Vijay

    2011-07-15

    Experimental determination of toxicity profiles consumes a great deal of time, money, and other resources. Consequently, businesses, societies, and regulators strive for reliable alternatives such as Quantitative Structure Toxicity Relationship (QSTR) models to fill gaps in toxicity profiles of compounds of concern to human health. The use of glycol ethers and their health effects have recently attracted the attention of international organizations such as the World Health Organization (WHO). The board members of Concise International Chemical Assessment Documents (CICAD) recently identified inadequate testing as well as gaps in toxicity profiles of ethylene glycol mono-n-alkyl ethers (EGEs). The CICAD board requested the ATSDR Computational Toxicology and Methods Development Laboratory to conduct QSTR assessments of certain specific toxicity endpoints for these chemicals. In order to evaluate the potential health effects of EGEs, CICAD proposed a critical QSTR analysis of the mutagenicity, carcinogenicity, and developmental effects of EGEs and other selected chemicals. We report here results of the application of QSTRs to assess rodent carcinogenicity, mutagenicity, and developmental toxicity of four EGEs: 2-methoxyethanol, 2-ethoxyethanol, 2-propoxyethanol, and 2-butoxyethanol and their metabolites. Neither mutagenicity nor carcinogenicity is indicated for the parent compounds, but these compounds are predicted to be developmental toxicants. The predicted toxicity effects were subjected to reverse QSTR (rQSTR) analysis to identify structural attributes that may be the main drivers of the developmental toxicity potential of these compounds.

  5. Calixarene crown ether solvent composition and use thereof for extraction of cesium from alkaline waste solutions

    DOE Patents [OSTI]

    Moyer, Bruce A. (Oak Ridge, TN); Sachleben, Richard A. (Knoxville, TN); Bonnesen, Peter V. (Knoxville, TN); Presley, Derek J. (Ooltewah, TN)

    2001-01-01

    A solvent composition and corresponding method for extracting cesium (Cs) from aqueous neutral and alkaline solutions containing Cs and perhaps other competing metal ions is described. The method entails contacting an aqueous Cs-containing solution with a solvent consisting of a specific class of lipophilic calix[4]arene-crown ether extractants dissolved in a hydrocarbon-based diluent containing a specific class of alkyl-aromatic ether alcohols as modifiers. The cesium values are subsequently recovered from the extractant, and the solvent subsequently recycled, by contacting the Cs-containing organic solution with an aqueous stripping solution. This combined extraction and stripping method is especially useful as a process for removal of the radionuclide cesium-137 from highly alkaline waste solutions which are also very concentrated in sodium and potassium. No pre-treatment of the waste solution is necessary, and the cesium can be recovered using a safe and inexpensive stripping process using water, dilute (millimolar) acid solutions, or dilute (millimolar) salt solutions. An important application for this invention would be treatment of alkaline nuclear tank wastes. Alternatively, the invention could be applied to decontamination of acidic reprocessing wastes containing cesium-137.

  6. Catalyst activity maintenance study for the liquid phase dimethyl ether process

    SciTech Connect (OSTI)

    Peng, X.D.; Toseland, B.A.; Underwood, R.P.

    1995-12-31

    The co-production of dimethyl ether (DME) and methanol from syngas is a process of considerable commercial attractiveness. DME coproduction can double the productivity of a LPMEOH process when using coal-derived syngas. This in itself may offer chemical producers and power companies increased flexibility and more profitable operation. DME is also known as a clean burning liquid fuel; Amoco and Haldor-Topsoe have recently announced the use of DME as an alternative diesel fuel. Moreover, DME can be an interesting intermediate in the production of chemicals such as olefins and vinyl acetate. The current APCl liquid phase dimethyl ether (LPDME) process utilizes a physical mixture of a commercial methanol synthesis catalyst and a dehydration catalyst (e.g., {gamma}-alumina). While this arrangement provides a synergy that results in much higher syngas conversion per pass compared to the methanol-only process, the stability of the catalyst system suffers. The present project is aimed at reducing catalyst deactivation both by understanding the cause(s) of catalyst deactivation and by developing modified catalyst systems. This paper describes the current understanding of the deactivation mechanism.

  7. An Experimental and Kinetic Modeling Study of Methyl Decanoate Combustion

    SciTech Connect (OSTI)

    Sarathy, S M; Thomson, M J; Pitz, W J; Lu, T

    2010-02-19

    Biodiesel is typically a mixture of long chain fatty acid methyl esters for use in compression ignition engines. Improving biofuel engine performance requires understanding its fundamental combustion properties and the pathways of combustion. This research study presents new combustion data for methyl decanoate in an opposed-flow diffusion flame. An improved detailed chemical kinetic model for methyl decanoate combustion is developed, which serves as the basis for deriving a skeletal mechanism via the direct relation graph method. The novel skeletal mechanism consists of 648 species and 2998 reactions. This mechanism well predicts the methyl decanoate opposed-flow diffusion flame data. The results from the flame simulations indicate that methyl decanoate is consumed via abstraction of hydrogen atoms to produce fuel radicals, which lead to the production of alkenes. The ester moiety in methyl decanoate leads to the formation of low molecular weight oxygenated compounds such as carbon monoxide, formaldehyde, and ketene.

  8. dimethyl ether

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Predictive Simulation of Engines Transportation Energy Consortiums Engine Combustion ... Schematic representation of the experimental set-up. Shown in the figure is the jet-stirre...

  9. Conversion of Levulinic Acid to Methyl Tetrahydrofuran - Energy...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    acid is a highly desirable renewable chemical platform, which, using this process, can be converted into Methyl Tetrahydrofuran (Me-THF) with reasonable yield. The...

  10. Lithium Methyl Carbonate as a Reaction Product of Metallic Lithiumand...

    Office of Scientific and Technical Information (OSTI)

    Lithium methyl carbonate is only one of the components, the others being lithium oxalate and lithium methoxide. Authors: Zhuang, Guorong V. ; Yang, Hui ; Ross Jr., Philip N. ; Xu, ...

  11. Theoretical spectroscopic characterization at low temperatures of S-methyl thioformate and O-methyl thioformate

    SciTech Connect (OSTI)

    Senent, M. L.; Puzzarini, C.; Hochlaf, M.; Domínguez-Gómez, R.; Carvajal, M.

    2014-09-14

    Highly correlated ab initio methods are employed to determine spectroscopic properties at low temperatures of two S-analogs of methyl formate: S-methyl thioformate CH{sub 3}-S-CHO (MSCHO) and O-methyl thioformate CH{sub 3}-O-CHS (MOCHS). Both species are detectable and they are expected to play an important role in Astrochemistry. Molecular properties are compared with those of the O-analog, methyl formate. Both isomers present two conformers cis and trans. cis-CH{sub 3}-S-CHO represents the most stable structure lying 4372.2 cm{sup −1} below cis-CH{sub 3}-O-CHS. The energy difference between the cis and trans forms is drastically lower for MSCHO (1134 cm{sup −1}) than for MOCHS (1963.6 cm{sup −1}). Harmonic and anharmonic fundamentals and the corresponding intensities, as well as the rotational constants for the ground vibrational and first excited torsional states and the centrifugal distortions constants, are provided. Low torsional energy levels have been obtained by solving variationally a two dimensional Hamiltonian expressed in terms of the two torsional degrees of freedom. The corresponding 2D potential energy surfaces have been computed at the CCSD(T)/aug-cc-pVTZ level of theory. The methyl torsional barriers V{sub 3}(cis) are determined to be 139.7 cm{sup −1} (CH{sub 3}-S-CHO) and 670.4 cm{sup −1} (CH{sub 3}-O-CHS). The A/E splitting of ground torsional state has been estimated to be 0.438 cm{sup −1} for CH{sub 3}-S-CHO and negligible for CH{sub 3}-O-CHS.

  12. EPA`s proposed renewable oxygenate requirement (ROR): Pros and cons

    SciTech Connect (OSTI)

    Czeskleba, H.M.

    1995-12-31

    In December 1993, the US Environmental Protection Agency (EPA) released its final rule that sets for the details for requirements to sell reformulated gasoline (RFG) in certain ozone non-attainment areas. At the same time, EPA also issued a proposed rule to require that 30% of the oxygen required in RFG be based on a renewable oxygenate. Renewables include ethanol and its ether derivatives such as ethyl tertiary butyl ether (ETBE). The RFG rule is a final rule, while the Renewable Oxygenate Requirement (ROR) rule is a proposed rule yet to be finalized and subject to revision. Included in this paper are brief reviews of Ashland petroleum Company`s ethanol usage, oxygenated fuel and reformulated gasoline blending economics, and some comments on the EPA proposed renewable oxygenate requirement.

  13. Production of methyl-vinyl ketone from levulinic acid

    DOE Patents [OSTI]

    Dumesic, James A.; West; Ryan M.

    2011-06-14

    A method for converting levulinic acid to methyl vinyl ketone is described. The method includes the steps of reacting an aqueous solution of levulinic acid, over an acid catalyst, at a temperature of from room temperature to about 1100 K. Methyl vinyl ketone is thereby formed.

  14. Use of aluminum phosphate as the dehydration catalyst in single step dimethyl ether process

    DOE Patents [OSTI]

    Peng, Xiang-Dong; Parris, Gene E.; Toseland, Bernard A.; Battavio, Paula J.

    1998-01-01

    The present invention pertains to a process for the coproduction of methanol and dimethyl ether (DME) directly from a synthesis gas in a single step (hereafter, the "single step DME process"). In this process, the synthesis gas comprising hydrogen and carbon oxides is contacted with a dual catalyst system comprising a physical mixture of a methanol synthesis catalyst and a methanol dehydration catalyst. The present invention is an improvement to this process for providing an active and stable catalyst system. The improvement comprises the use of an aluminum phosphate based catalyst as the methanol dehydration catalyst. Due to its moderate acidity, such a catalyst avoids the coke formation and catalyst interaction problems associated with the conventional dual catalyst systems taught for the single step DME process.

  15. Using Heteropolyacids in the Anode Catalyst Layer of Dimethyl Ether PEM Fuel Cells

    SciTech Connect (OSTI)

    Ferrell III, J. R.; Turner, J. A.; Herring, A. M.

    2008-01-01

    In this study, polarization experiments were performed on a direct dimethyl ether fuel cell (DMEFC). The experimental setup allowed for independent control of water and DME flow rates. Thus the DME flow rate, backpressure, and water flow rate were optimized. Three heteropoly acids, phosphomolybdic acid (PMA), phosphotungstic acid (PTA), and silicotungstic acid (STA) were incorporated into the anode catalyst layer in combination with Pt/C. Both PTA-Pt and STA-Pt showed higher performance than the Pt control at 30 psig of backpressure. Anodic polarizations were also performed, and Tafel slopes were extracted from the data. The trends in the Tafel slope values are in agreement with the polarization data. The addition of phosphotungstic acid more than doubled the power density of the fuel cell, compared to the Pt control.

  16. Methanol with dimethyl ether ignition promotor as fuel for compression ignition engines

    SciTech Connect (OSTI)

    Brook, D.L.; Cipolat, D.; Rallis, C.J.

    1984-08-01

    Reduction of the world dependence upon crude oil necessitates the use of long term alternative fuels for internal combustion engines. Alcohols appear to offer a solution as in the short term they can be manufactured from natural gas and coal, while ultimately they may be produced from agricultural products. A fair measure of success has been achieved in using alcohols in spark ignition engines. However the more widely used compression ignition engines cannot utilize unmodified pure alcohols. The current techniques for using alcohol fuels in compression ignition engines all have a number of shortcomings. This paper describes a novel technique where an ignition promotor, dimethyl ether (DME), is used to increase the cetane rating of methanol. The systems particular advantage is that the DME can be catalyzed from the methanol base fuel, in situ. This fuel system matches the performance characteristics of diesel oil fuel.

  17. Process for the production of ethylidene diacetate from dimethyl ether using a heterogeneous catalyst

    DOE Patents [OSTI]

    Ramprasad, D.; Waller, F.J.

    1998-04-28

    This invention relates to a process for producing ethylidene diacetate by the reaction of dimethyl ether, acetic acid, hydrogen and carbon monoxide at elevated temperatures and pressures in the presence of an alkyl halide and a heterogeneous, bifunctional catalyst that is stable to hydrogenation and comprises an insoluble polymer having pendant quaternized heteroatoms, some of which heteroatoms are ionically bonded to anionic Group VIII metal complexes, the remainder of the heteroatoms being bonded to iodide. In contrast to prior art processes, no accelerator (promoter) is necessary to achieve the catalytic reaction and the products are easily separated from the catalyst by filtration. The catalyst can be recycled for 3 consecutive runs without loss in activity.

  18. Process for the production of ethylidene diacetate from dimethyl ether using a heterogeneous catalyst

    DOE Patents [OSTI]

    Ramprasad, Dorai (Allentown, PA); Waller, Francis Joseph (Allentown, PA)

    1998-01-01

    This invention relates to a process for producing ethylidene diacetate by the reaction of dimethyl ether, acetic acid, hydrogen and carbon monoxide at elevated temperatures and pressures in the presence of an alkyl halide and a heterogeneous, bifunctional catalyst that is stable to hydrogenation and comprises an insoluble polymer having pendant quaternized heteroatoms, some of which heteroatoms are ionically bonded to anionic Group VIII metal complexes, the remainder of the heteroatoms being bonded to iodide. In contrast to prior art processes, no accelerator (promoter) is necessary to achieve the catalytic reaction and the products are easily separated from the catalyst by filtration. The catalyst can be recycled for 3 consecutive runs without loss in activity.

  19. Hydrogen production from the steam reforming of Dinethyl Ether and Methanol

    SciTech Connect (OSTI)

    Semelsberger, T. A.; Borup, R. L.

    2004-01-01

    This study investigates dimethyl ether (DME) steam reforming for the generation of hydrogen rich fuel cell feeds for fuel cell applications. Methanol has long been considered as a fuel for the generation of hydrogen rich fuel cell feeds due to its high energy density, low reforming temperature, and zero impurity content. However, it has not been accepted as the fuel of choice due its current limited availability, toxicity and corrosiveness. While methanol steam reforming for the generation of hydrogen rich fuel cell feeds has been extensively studied, the steam reforming of DME, CH{sub 3}OCH{sub 3} + 3H{sub 2}O = 2CO{sub 2} + 6H{sub 2}, has had limited research effort. DME is the simplest ether (CH{sub 3}OCH{sub 3}) and is a gas at ambient conditions. DME has physical properties similar to those of LPG fuels (i.e. propane and butane), resulting in similar storage and handling considerations. DME is currently used as an aerosol propellant and has been considercd as a diesel substitute due to the reduced NOx, SOx and particulate emissions. DME is also being considered as a substitute for LPG fuels, which is used extensively in Asia as a fuel for heating and cooking, and naptha, which is used for power generation. The potential advantages of both methanol and DME include low reforming temperature, decreased fuel proccssor startup energy, environmentally benign, visible flame, high heating value, and ease of storage and transportation. In addition, DME has the added advantages of low toxicity and being non-corrosive. Consequently, DME may be an ideal candidate for the generation of hydrogen rich fuel cell feeds for both automotive and portable power applications. The steam reforming of DME has been demonstrated to occur through a pair of reactions in series, where the first reaction is DME hydration followed by MeOH steam reforming to produce a hydrogen rich stream.

  20. Host cells and methods for producing 3-methyl-2-buten-1-ol, 3-methyl-3-buten-1-ol, and 3-methyl-butan-1-ol

    DOE Patents [OSTI]

    Chou, Howard H.; Keasling, Jay D.

    2011-07-26

    The invention provides for a method for producing a 5-carbon alcohol in a genetically modified host cell. In one embodiment, the method comprises culturing a genetically modified host cell which expresses a first enzyme capable of catalyzing the dephosphorylation of an isopentenyl pyrophosphate (IPP) or dimethylallyl diphosphate (DMAPP), such as a Bacillus subtilis phosphatase (YhfR), under a suitable condition so that 5-carbon alcohol is 3-methyl-2-buten-1-ol and/or 3-methyl-3-buten-1-ol is produced. Optionally, the host cell may further comprise a second enzyme capable of reducing a 3-methyl-2-buten-1-ol to 3-methyl-butan-1-ol, such as a reductase.

  1. Role of methyl groups in dynamics and evolution of biomolecules

    SciTech Connect (OSTI)

    Nickels, Jonathan D [ORNL; Curtis, J. E. [National Institute of Standards and Technology (NIST), Gaithersburg, MD; Oneill, Hugh [Oak Ridge National Laboratory (ORNL); Sokolov, Alexei P [ORNL

    2012-01-01

    Recent studies have discovered strong differences between the dynamics of nucleic acids (RNA and DNA) and proteins, especially at low hydration and low temperatures. This difference is caused primarily by dynamics of methyl groups that are abundant in proteins, but are absent or very rare in RNA and DNA. In this paper, we present a hypothesis regarding the role of methyl groups as intrinsic plasticizers in proteins and their evolutionary selection to facilitate protein dynamics and activity. We demonstrate the profound effect methyl groups have on protein dynamics relative to nucleic acid dynamics, and note the apparent correlation of methyl group content in protein classes and their need for molecular flexibility. Moreover, we note the fastest methyl groups of some enzymes appear around dynamical centers such as hinges or active sites. Methyl groups are also of tremendous importance from a ydrophobicity/folding/entropy perspective. These significant roles, however, complement our hypothesis rather than preclude the recognition of methyl groups in the dynamics and evolution of biomolecules.

  2. Dcm methylation is detrimental to plasmid transformation in Clostridium thermocellum

    SciTech Connect (OSTI)

    Guss, Adam M; Olson, Daniel G.; Caiazza, Nicky; Lynd, Lee R

    2012-01-01

    BACKGROUND: Industrial production of biofuels and other products by cellulolytic microorganisms is of interest but hindered by the nascent state of genetic tools. Although a genetic system for Clostridium thermocellum DSM1313 has recently been developed, available methods achieve relatively low efficiency and similar plasmids can transform C. thermocellum at dramatically different efficiencies. RESULTS: We report an increase in transformation efficiency of C. thermocellum for a variety of plasmids by using DNA that has been methylated by Escherichia coli Dam but not Dcm methylases. When isolated from a dam+ dcm+ E. coli strain, pAMG206 transforms C. thermocellum 100-fold better than the similar plasmid pAMG205, which contains an additional Dcm methylation site in the pyrF gene. Upon removal of Dcm methylation, transformation with pAMG206 showed a four- to seven-fold increase in efficiency; however, transformation efficiency of pAMG205 increased 500-fold. Removal of the Dcm methylation site from the pAM205 pyrF gene via silent mutation resulted in increased transformation efficiencies equivalent to that of pAMG206. Upon proper methylation, transformation efficiency of plasmids bearing the pMK3 and pB6A origins of replication increased ca. three orders of magnitude. CONCLUSION: E. coli Dcm methylation decreases transformation efficiency in C. thermocellum DSM1313. The use of properly methylated plasmid DNA should facilitate genetic manipulation of this industrially relevant bacterium.

  3. Phase 2 Methyl Iodide Deep-Bed Adsorption Tests

    SciTech Connect (OSTI)

    Soelberg, Nick; Watson, Tony

    2014-09-01

    Nuclear fission produces fission products (FPs) and activation products, including iodine-129, which could evolve into used fuel reprocessing facility off-gas systems, and could require off-gas control to limit air emissions to levels within acceptable emission limits. Research, demonstrations, and some reprocessing plant experience have indicated that diatomic iodine can be captured with efficiencies high enough to meet regulatory requirements. Research on the capture of organic iodides has also been performed, but to a lesser extent. Several questions remain open regarding the capture of iodine bound in organic compounds. Deep-bed methyl iodide adsorption testing has progressed according to a multi-laboratory methyl iodide adsorption test plan. This report summarizes the second phase of methyl iodide adsorption work performed according to this test plan using the deep-bed iodine adsorption test system at the Idaho National Laboratory (INL), performed during the second half of Fiscal Year (FY) 2014. Test results continue to show that methyl iodide adsorption using AgZ can achieve total iodine decontamination factors (DFs, ratios of uncontrolled and controlled total iodine levels) above 1,000, until breakthrough occurred. However, mass transfer zone depths are deeper for methyl iodide adsorption compared to diatomic iodine (I2) adsorption. Methyl iodide DFs for the Ag Aerogel test adsorption efficiencies were less than 1,000, and the methyl iodide mass transfer zone depth exceeded 8 inches. Additional deep-bed testing and analyses are recommended to (a) expand the data base for methyl iodide adsorption under various conditions specified in the methyl iodide test plan, and (b) provide more data for evaluating organic iodide reactions and reaction byproducts for different potential adsorption conditions.

  4. Carbon-carbon bond cleavage of 1,2-hydroxy ethers b7 vanadium(V) dipicolinate complexes

    SciTech Connect (OSTI)

    Hanson, Susan K; Gordon, John C; Thorn, David L; Scott, Brian L; Baker, R Tom

    2009-01-01

    The development of alternatives to current petroleum-based fuels and chemicals is becoming increasingly important due to concerns over climate change, growing world energy demand, and energy security issues. Using non-food derived biomass to produce renewable feedstocks for chemicals and fuels is a particularly attractive possibility. However, the majority of biomass is in the form of lignocellulose, which is often not fully utilized due to difficulties associated with breaking down both lignin and cellulose. Recently, a number of methods have been reported to transform cellulose directly into more valuable materials such as glucose, sorbitol, 5-(chloromethyl)furfural, and ethylene glycol. Less progress has been made with selective transformations of lignin, which is typically treated in paper and forest industries by kraft pulping (sodium hydroxide/sodium sulfide) or incineration. Our group has begun investigating aerobic oxidative C-C bond cleavage catalyzed by dipicolinate vanadium complexes, with the idea that a selective C-C cleavage reaction of this type could be used to produce valuable chemicals or intermediates from cellulose or lignin. Lignin is a randomized polymer containing methoxylated phenoxy propanol units. A number of different linkages occur naturally; one of the most prevalent is the {beta}-O-4 linkage shown in Figure 1, containing a C-C bond with 1,2-hydroxy ether substituents. While the oxidative C-C bond cleavage of 1,2-diols has been reported for a number of metals, including vanadium, iron, manganese, ruthenium, and polyoxometalate complexes, C-C bond cleavage of 1,2-hydroxy ethers is much less common. We report herein vanadium-mediated cleavage of C-C bonds between alcohol and ether functionalities in several lignin model complexes. In order to explore the scope and potential of vanadium complexes to effect oxidative C-C bond cleavage in 1,2-hydroxy ethers, we examined the reactivity of the lignin model complexes pinacol monomethyl ether (A), 2-phenoxyethanol (B), and 1,2-diphenyl-2-methoxyethanol (C) (Figure 1). Reaction of (dipic)V{sup V}(O)O{sup i}Pr (1a) or (dipic)V{sup v}(O)OEt (lb) with A, B, or C in acetonitrile yielded new vanadium(V) complexes where the alcohol-ether ligand was bound in a chelating fashion. From the reaction of 1b with pinacol monomethyl ether (A) in acetonitrile solution, (dipic)V{sup v}(O)(pinOMe) (2) (PinOMe = 2,3-dimethyl-3-methoxy-2-butanoxide) was isolated in 61 % yield. Reaction of 1b with 2-phenoxyethanol (B) in acetonitrile gave the new complex (dipic)V{sup v}(O)(OPE) (3) (OPE = 2-phenoxyethoxide), which was isolated in 76% yield. In a similar fashion, 1a reacted with 1,2-diphenyl-2-methoxyethanol (C) to give (dipic)V(O)(DPME) (4) (DPME = 1,2-diphenyl-2-methoxyethoxide), which was isolated in 39% yield. Complexes 2, 3, and 4 were characterized by {sup 1}H NMR and IR spectroscopy, elemental analysis, and X-ray crystallography. Compared to the previously reported vanadium(V) pinacolate complex (dipic)V(O)(pinOH) the X-ray structure of complex 2 reveals a slightly shorter V = O bond, 1.573(2) {angstrom} vs 1.588(2) {angstrom} for the pinOH structure. Complexes 3 and 4 display similar vanadium oxo bond distances of 1.568(2) {angstrom} and 1.576(2) {angstrom}, respectively. All three complexes show longer bonds to the ether-oxygen trans to the oxo (2.388(2) {angstrom} for 2, 2.547(2) {angstrom} for 3, and 2.438(2) {angstrom} for 4) than to the hydroxy-oxygen in the pinOH structure (2.252(2) {angstrom}).

  5. The use of dimethyl ether as a starting aid for methanol-fueled SI engines at low temperatures

    SciTech Connect (OSTI)

    Kozole, K.H.; Wallace, J.S

    1988-01-01

    Methanol-fueled SI engines have proven to be difficult to start at ambient temperatures below approximately 10/sup 0/C. The use of dimethyl ether (DME) is proposed to improve the cold starting performance of methanol-fueled SI engines. Tests to evaluate this idea were carried out with a modified single-cylinder CFR research engine having a compression ratio of 12:1. The engine was fueled with combinations of gaseous dimethyl ether and liquid methanol having DME mass fractions of 30%, 40%, 60% and 70%. For comparison, tests were also carried out with 100% methanol and with winter grade premium unleaded gasoline. Overall stoichiometric mixtures were used in all tests.

  6. Synthesis of dimethyl ether and alternative fuels in the liquid phase from coal-derived synthesis gas. Final technical report

    SciTech Connect (OSTI)

    Not Available

    1993-02-01

    Through the mid-1980s, Air Products has brought the liquid phase approach to a number of other synthesis gas reactions where effective heat management is a key issue. In 1989, in response to DOE`s PRDA No. DE-RA22-88PC88805, Air Products proposed a research and development program entitled ``Synthesis of Dimethyl Ether and Alternative Fuels in the Liquid Phase from Coal Derived Syngas.`` The proposal aimed at extending the LPMEOH experience to convert coal-derived synthesis gas to other useful fuels and chemicals. The work proposed included development of a novel one-step synthesis of dimethyl ether (DME) from syngas, and exploration of other liquid phase synthesis of alternative fuel directly from syngas. The one-step DME process, conceived in 1986 at Air Products as a means of increasing syngas conversion to liquid products, envisioned the concept of converting product methanol in situ to DME in a single reactor. The slurry reactor based liquid phase technology is ideally suited for such an application, since the second reaction (methanol to DME) can be accomplished by adding a second catalyst with dehydration activity to the methanol producing reactor. An area of exploration for other alternative fuels directly from syngas was single-step slurry phase synthesis of hydrocarbons via methanol and DME as intermediates. Other possibilities included the direct synthesis of mixed alcohols and mixed ethers in a slurry reactor.

  7. Substantial improvements in methyl ketone production in E. coli and

    Office of Scientific and Technical Information (OSTI)

    insights on the pathway from in vitro studies (Journal Article) | SciTech Connect Journal Article: Substantial improvements in methyl ketone production in E. coli and insights on the pathway from in vitro studies Citation Details In-Document Search Title: Substantial improvements in methyl ketone production in E. coli and insights on the pathway from in vitro studies Authors: Goh, Ee-Been ; Baidoo, Edward E.K. ; Burd, Helcio ; Lee, Taek Soon ; Keasling, Jay D. ; Beller, Harry R. Publication

  8. Distributions of methyl group rotational barriers in polycrystalline organic solids

    SciTech Connect (OSTI)

    Beckmann, Peter A. E-mail: wangxianlong@uestc.edu.cn; Conn, Kathleen G.; Division of Education and Human Services, Neumann University, One Neumann Drive, Aston, Pennsylvania 19014-1298 ; Mallory, Clelia W.; Department of Chemistry, Bryn Mawr College, 101 North Merion Ave., Bryn Mawr, Pennsylvania 19010-2899 ; Mallory, Frank B.; Rheingold, Arnold L.; Rotkina, Lolita; Wang, Xianlong E-mail: wangxianlong@uestc.edu.cn

    2013-11-28

    We bring together solid state {sup 1}H spin-lattice relaxation rate measurements, scanning electron microscopy, single crystal X-ray diffraction, and electronic structure calculations for two methyl substituted organic compounds to investigate methyl group (CH{sub 3}) rotational dynamics in the solid state. Methyl group rotational barrier heights are computed using electronic structure calculations, both in isolated molecules and in molecular clusters mimicking a perfect single crystal environment. The calculations are performed on suitable clusters built from the X-ray diffraction studies. These calculations allow for an estimate of the intramolecular and the intermolecular contributions to the barrier heights. The {sup 1}H relaxation measurements, on the other hand, are performed with polycrystalline samples which have been investigated with scanning electron microscopy. The {sup 1}H relaxation measurements are best fitted with a distribution of activation energies for methyl group rotation and we propose, based on the scanning electron microscopy images, that this distribution arises from molecules near crystallite surfaces or near other crystal imperfections (vacancies, dislocations, etc.). An activation energy characterizing this distribution is compared with a barrier height determined from the electronic structure calculations and a consistent model for methyl group rotation is developed. The compounds are 1,6-dimethylphenanthrene and 1,8-dimethylphenanthrene and the methyl group barriers being discussed and compared are in the 212 kJ?mol{sup ?1} range.

  9. A fluorescence-based method for rapid and direct determination of polybrominated diphenyl ethers in water

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Shan, Huimei; Liu, Chongxuan; Wang, Zheming; Ma, Teng; Shang, Jianying; Pan, Duoqiang

    2015-01-01

    A new method was developed for rapid and direct measurement of polybrominated diphenyl ethers (PBDEs) in aqueous samples using fluorescence spectroscopy. The fluorescence spectra of tri- to deca-BDE (BDE 28, 47, 99, 153, 190, and 209) commonly found in environment were measured at variable emission and excitation wavelengths. The results revealed that the PBDEs have distinct fluorescence spectral profiles and peak positions that can be exploited to identify these species and determine their concentrations in aqueous solutions. The detection limits as determined in deionized water spiked with PBDEs are 1.71-5.82 ng/L for BDE 28, BDE 47, BDE 190, and BDEmore » 209 and 45.55–69.95 ng/L for BDE 99 and BDE 153. The effects of environmental variables including pH, humic substance, and groundwater chemical composition on PBDEs measurements were also investigated. These environmental variables affected fluorescence intensity, but their effect can be corrected through linear additivity and separation of spectral signal contribution. Compared with conventional GC-based analytical methods, the fluorescence spectroscopy method is more efficient as it only uses a small amount of samples (2-4 mL), avoids lengthy complicated concentration and extraction steps, and has a low detection limit of a few ng/L.« less

  10. Hydrogen-bonding interactions and protic equilibria in room-temperature ionic liquids containing crown ethers.

    SciTech Connect (OSTI)

    Marin, T.; Shkrob, I.; Dietz, M.

    2011-04-14

    Nuclear magnetic resonance (NMR) spectroscopy has been used to study hydrogen-bonding interactions between water, associated and dissociated acids (i.e., nitric and methanesulfonic acids), and the constituent ions of several water-immiscible room-temperature ionic liquids (ILs). In chloroform solutions also containing a crown ether (CE), water molecules strongly associate with the IL ions, and there is rapid proton exchange between these bound water molecules and hydronium associated with the CE. In neat ILs, the acids form clusters differing in their degree of association and ionization, and their interactions with the CEs are weak. The CE can either promote proton exchange between different clusters in IL solution when their association is weak or inhibit such exchange when the association is strong. Even strongly hydrophobic ILs are shown to readily extract nitric acid from aqueous solution, typically via the formation of a 1:1:1 {l_brace}H{sub 3}O{sup +} {center_dot} CE{r_brace}NO{sub 3}{sup -} complex. In contrast, the extraction of methanesulfonic acid is less extensive and proceeds mainly by IL cation-hydronium ion exchange. The relationship of these protic equilibria to the practical application of hydrophobic ILs (e.g., in spent nuclear fuel reprocessing) is discussed.

  11. Direct Numerical Simulations of Autoignition in Stratified Dimethyl-ether (DME)/Air Turbulent Mixtures

    SciTech Connect (OSTI)

    Bansal, Gaurav; Mascarenhas, Ajith; Chen, Jacqueline H.

    2014-10-01

    In our paper, two- and three-dimensional direct numerical simulations (DNS) of autoignition phenomena in stratified dimethyl-ether (DME)/air turbulent mixtures are performed. A reduced DME oxidation mechanism, which was obtained using rigorous mathematical reduction and stiffness removal procedure from a detailed DME mechanism with 55 species, is used in the present DNS. The reduced DME mechanism consists of 30 chemical species. This study investigates the fundamental aspects of turbulence-mixing-autoignition interaction occurring in homogeneous charge compression ignition (HCCI) engine environments. A homogeneous isotropic turbulence spectrum is used to initialize the velocity field in the domain. Moreover, the computational configuration corresponds to a constant volume combustion vessel with inert mass source terms added to the governing equations to mimic the pressure rise due to piston motion, as present in practical engines. DME autoignition is found to be a complex three-staged process; each stage corresponds to a distinct chemical kinetic pathway. The distinct role of turbulence and reaction in generating scalar gradients and hence promoting molecular transport processes are investigated. Then, by applying numerical diagnostic techniques, the different heat release modes present in the igniting mixture are identified. In particular, the contribution of homogeneous autoignition, spontaneous ignition front propagation, and premixed deflagration towards the total heat release are quantified.

  12. A fluorescence-based method for rapid and direct determination of polybrominated diphenyl ethers in water

    SciTech Connect (OSTI)

    Shan, Huimei; Liu, Chongxuan; Wang, Zheming; Ma, Teng; Shang, Jianying; Pan, Duoqiang

    2015-01-01

    A new method was developed for rapid and direct measurement of polybrominated diphenyl ethers (PBDEs) in aqueous samples using fluorescence spectroscopy. The fluorescence spectra of tri- to deca-BDE (BDE 28, 47, 99, 153, 190, and 209) commonly found in environment were measured at variable emission and excitation wavelengths. The results revealed that the PBDEs have distinct fluorescence spectral profiles and peak positions that can be exploited to identify these species and determine their concentrations in aqueous solutions. The detection limits as determined in deionized water spiked with PBDEs are 1.71-5.82 ng/L for BDE 28, BDE 47, BDE 190, and BDE 209 and 45.5569.95 ng/L for BDE 99 and BDE 153. The effects of environmental variables including pH, humic substance, and groundwater chemical composition on PBDEs measurements were also investigated. These environmental variables affected fluorescence intensity, but their effect can be corrected through linear additivity and separation of spectral signal contribution. Compared with conventional GC-based analytical methods, the fluorescence spectroscopy method is more efficient as it only uses a small amount of samples (2-4 mL), avoids lengthy complicated concentration and extraction steps, and has a low detection limit of a few ng/L.

  13. Study on systems based on coal and natural gas for producing dimethyl ether

    SciTech Connect (OSTI)

    Zhou, L.; Hu, S.Y.; Chen, D.J.; Li, Y.R.; Zhu, B.; Jin, Y.

    2009-04-15

    China is a coal-dependent country and will remain so for a long time. Dimethyl ether (DME), a potential substitute for liquid fuel, is a kind of clean diesel motor fuel. The production of DME from coal is meaningful and is studied in this article. Considering the C/H ratios of coal and natural gas (NG), the cofeed (coal and NG) system (CFS), which does not contain the water gas shift process, is studied. It can reduce CO{sub 2} emission and increase the conversion rate of carbon, producing more DME. The CFS is simulated and compared with the coal-based and NG-based systems with different recycling ratios. The part of the exhaust gas that is not recycled is burned, producing electricity. On the basis of the simulation results, the thermal efficiency, economic index, and CO{sub 2} emission ratio are calculated separately. The CFS with a 100% recycling ratio has the best comprehensive evaluation index, while the energy, economy, and environment were considered at the same time.

  14. Electron momentum spectroscopy of dimethyl ether taking account of nuclear dynamics in the electronic ground state

    SciTech Connect (OSTI)

    Morini, Filippo; Deleuze, Michael Simon; Watanabe, Noboru; Kojima, Masataka; Takahashi, Masahiko

    2015-10-07

    The influence of nuclear dynamics in the electronic ground state on the (e,2e) momentum profiles of dimethyl ether has been analyzed using the harmonic analytical quantum mechanical and Born-Oppenheimer molecular dynamics approaches. In spite of fundamental methodological differences, results obtained with both approaches consistently demonstrate that molecular vibrations in the electronic ground state have a most appreciable influence on the momentum profiles associated to the 2b{sub 1}, 6a{sub 1}, 4b{sub 2}, and 1a{sub 2} orbitals. Taking this influence into account considerably improves the agreement between theoretical and newly obtained experimental momentum profiles, with improved statistical accuracy. Both approaches point out in particular the most appreciable role which is played by a few specific molecular vibrations of A{sub 1}, B{sub 1}, and B{sub 2} symmetries, which correspond to C–H stretching and H–C–H bending modes. In line with the Herzberg-Teller principle, the influence of these molecular vibrations on the computed momentum profiles can be unraveled from considerations on the symmetry characteristics of orbitals and their energy spacing.

  15. Direct Numerical Simulations of Autoignition in Stratified Dimethyl-ether (DME)/Air Turbulent Mixtures

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Bansal, Gaurav; Mascarenhas, Ajith; Chen, Jacqueline H.

    2014-10-01

    In our paper, two- and three-dimensional direct numerical simulations (DNS) of autoignition phenomena in stratified dimethyl-ether (DME)/air turbulent mixtures are performed. A reduced DME oxidation mechanism, which was obtained using rigorous mathematical reduction and stiffness removal procedure from a detailed DME mechanism with 55 species, is used in the present DNS. The reduced DME mechanism consists of 30 chemical species. This study investigates the fundamental aspects of turbulence-mixing-autoignition interaction occurring in homogeneous charge compression ignition (HCCI) engine environments. A homogeneous isotropic turbulence spectrum is used to initialize the velocity field in the domain. Moreover, the computational configuration corresponds to amore » constant volume combustion vessel with inert mass source terms added to the governing equations to mimic the pressure rise due to piston motion, as present in practical engines. DME autoignition is found to be a complex three-staged process; each stage corresponds to a distinct chemical kinetic pathway. The distinct role of turbulence and reaction in generating scalar gradients and hence promoting molecular transport processes are investigated. Then, by applying numerical diagnostic techniques, the different heat release modes present in the igniting mixture are identified. In particular, the contribution of homogeneous autoignition, spontaneous ignition front propagation, and premixed deflagration towards the total heat release are quantified.« less

  16. New clean fuel from coal -- Direct dimethyl ether synthesis from hydrogen and carbon monoxide

    SciTech Connect (OSTI)

    Ogawa, T.; Ono, M.; Mizuguchi, M.; Tomura, K.; Shikada, T.; Ohono, Y.; Fujimoto, K.

    1997-12-31

    Dimethyl ether (DME), which has similar physical properties to propane and is easily liquefied at low pressure, has a significant possibility as a clean and non-toxic fuel from coal or coal bed methane. Equilibrium calculation also shows a big advantage of high carbon monoxide conversion of DME synthesis compared to methanol synthesis. By using a 50 kg/day DME bench scale test plant, direct synthesis of DME from hydrogen and carbon monoxide has been studied with newly developed catalysts which are very fine particles. This test plant features a high pressure three-phase slurry reactor and low temperature DME separator. DME is synthesized at temperatures around 533--553 K and at pressures around 3--5 MPa. According to the reaction stoichiometry, the same amount of hydrogen and carbon monoxide react to DME and carbon dioxide. Carbon conversion to DME is one third and the rest of carbon is converted to carbon dioxide. As a result of the experiments, make-up CO conversion is 35--50% on an once-through basis, which is extremely high compared to that of methanol synthesis from hydrogen and carbon monoxide. DME selectivity is around 60 c-mol %. Most of the by-product is CO{sub 2} with a small amount of methanol and water. No heavy by-products have been recognized. Effluent from the reactor is finally cooled to 233--253 K in a DME separator and liquid DME is recovered as a product.

  17. Experimental and Computational Study of Nonpremixed Ignition of Dimethyl Ether in Counterflow

    SciTech Connect (OSTI)

    Zheng, X L; Lu, T F; Law, C K; Westbrook, C K

    2003-12-19

    The ignition temperature of nitrogen-diluted dimethyl ether (DME) by heated air in counterflow was experimentally determined for DME concentration from 5.9 to 30%, system pressure from 1.5 to 3.0 atmospheres, and pressure-weighted strain rate from 110 to 170/s. These experimental data were compared with two mechanisms that were respectively available in 1998 and 2003, with the latter being a substantially updated version of the former. The comparison showed that while the 1998-mechanism uniformly over-predicted the ignition temperature, the 2003-mechanism yielded surprisingly close agreement for all experimental data. Sensitivity analysis for the near-ignition state based on both mechanisms identified the deficiencies of the 1998-mechanism, particularly the specifics of the low-temperature cool flame chemistry in effecting ignition at higher temperatures, as the fuel stream is being progressively heated from its cold boundary to the high-temperature ignition region around the hot-stream boundary. The 2003-mechanism, consisting of 79 species and 398 elementary reactions, was then systematically simplified by using the directed relation graph method to a skeletal mechanism of 49 species and 251 elementary reactions, which in turn was further simplified by using computational singular perturbation method and quasi-steady-state species assumption to a reduced mechanism consisting of 33 species and 28 lumped reactions. It was demonstrated that both the skeletal and reduced mechanisms mimicked the performance of the detailed mechanism with high accuracy.

  18. Slurry phase synthesis of dimethyl ether from syngas -- A reactor model simulation

    SciTech Connect (OSTI)

    Mizuguchi, Masatsugu; Ogawa, Takashi; Ono, Masami,; Tomura, Keiji; Shikada, Tsutomu; Ohno, Yotaro; Fujimoto, Kaoru

    1998-12-31

    Dimethyl ether (DME) would be an attractive alternative fuel for diesel, domestic use, and power generation, if it is economically synthesized directly from syngas (derived from coal gasification or natural gas reforming). DME, which is a colorless gas with a boiling point of {minus}25 C, is chemically stable and easily liquefied under pressure. Since the properties of DME are similar to LPG, it can be handled and stored with the same manner as LPG. The authors have performed the slurry phase DME synthesis by using the 50 kg/day bench-scale unit. DME was synthesized at high yield from syngas (H{sub 2}+CO) with the newly developed catalyst system. To establish the scale-up methodology, the reactor simulation technique is essential. The authors developed a mathematical model of the slurry phase bubble column reactor for DME synthesis, which is based on their experimental results. The performance of a commercial-scale DME reactor was simulated by this model, and the results were discussed.

  19. Rape oil methyl ester (RME) and used cooking oil methyl ester (UOME) as alternative fuels

    SciTech Connect (OSTI)

    Hohl, G.H.

    1995-12-31

    The author presents a review about the fleet tests carried out by the Austrian Armed Forces concerning the practical application of a vegetable oil, i.e Rape Oil Methyl Ester (RME) and Used Cooking Oil Methyl Ester (UOME) as alternative fuels for vehicles under military conditions, and reviews other research results carried out in Austria. As a result of over-production in Western European agriculture, the increase in crop yields has led to tremendous surpluses. Alternative agricultural products have been sought. One alternative can be seen in biological fuel production for tractors, whereby the farmer is able to produce his own fuel supply as was the case when he previously provided self-made feed for his horses. For the market introduction different activities were necessary. A considerable number of institutes and organizations including the Austrian Armed Forces have investigated, tested and developed these alternative fuels. The increasing disposal problems of used cooking oil have initiated considerations for its use. The recycling of this otherwise waste product, and its preparation for use as an alternative fuel to diesel oil, seems to be most promising.

  20. Phytoremediation of ionic and methyl mercury pollution

    SciTech Connect (OSTI)

    Meagher, R.B.

    1998-06-01

    'The long-term objective of the research is to manipulate single-gene traits into plants, enabling them to process heavy metals and remediate heavy-metal pollution by resistance, sequestration, removal, and management of these contaminants. The authors are focused on mercury pollution as a case study of this plant genetic engineering approach. The working hypothesis behind this proposal was that transgenic plants expressing both the bacterial organo mercury lyase (merB) and the mercuric ion reductase gene (merA) will: (A) remove the mercury from polluted sites and (B) prevent methyl mercury from entering the food chain. The results from the research are so positive that the technology will undoubtedly be applied in the very near future to cleaning large mercury contaminates sites. Many such sites were not remediable previously due to the excessive costs and the negative environmental impact of conventional mechanical-chemical technologies. At the time this grant was awarded 20 months ago, the authors had successfully engineered a small model plant, Arabidopsis thaliana, to use a highly modified bacterial mercuric ion reductase gene, merA9, to detoxify ionic mercury (Hg(II)), reducing it to much less toxic and volatile metallic Hg(0) (Rugh et al., 1996). Seeds from these plants germinate, grow, and set seed at normal growth rates on levels of Hg(II) that are lethal to normal plants. In assays on transgenic seedlings suspended in a solution of Hg(II), 10 ng of Hg(0) was evolved per min per mg wet weight of plant tissue. At that time, the authors had no information on expression of merA in any other plant species, nor had the authors tested merB in any plant. However, the results were so startlingly positive and well received that they clearly presaged a paradigm shift in the field of environmental remediation.'

  1. Properties of some ionic liquids based on1-methyl-3-octylimidazolium and 4-methyl-N-butylpyridinium cations.

    SciTech Connect (OSTI)

    Papaiconomou, Nicolas; Yakelis, Neal; Salminen, Justin; Bergman,Robert; Prausnitz, John M.

    2005-09-29

    Syntheses are reported for ionic liquids containing 1-methyl-3octylimidazolium and 4-methyl-N-butylpyridinium cations, and trifluoromethansulfonate, dicyanamide, bis(trifluoromethylsulfonyl)imide, and nonafluorobutanesulfonate anions. Densities, melting points and glass transition points, solubility in water as well as polarities have been measured. Ionic liquids based on pyridinium cations exhibit higher melting points, lower solubility in water, and higher polarity than those based on imidazolium cations.

  2. Mechanistic Investigation of Acid-Catalyzed Cleavage of Aryl-Ether Linkages: Implications for Lignin Depolymerization

    SciTech Connect (OSTI)

    Sturgeon, M. R.; Kim, S.; Chmely, S. C.; Foust, T. D.; Beckham, G. T.

    2013-01-01

    Carbon-oxygen bonds are the primary inter-monomer linkages lignin polymers in plant cell walls, and as such, catalyst development to cleave these linkages is of paramount importance to deconstruct biomass to its constituent monomers for the production of renewable fuels and chemicals. For many decades, acid catalysis has been used to depolymerize lignin. Lignin is a primary component of plant cell walls, which is connected primarily by aryl-ether linkages, and the mechanism of its deconstruction by acid is not well understood, likely due to its heterogeneous and complex nature compared to cellulose. For effective biomass conversion strategies, utilization of lignin is of significant relevance and as such understanding the mechanisms of catalytic lignin deconstruction to constituent monomers and oligomers is of keen interest. Here, we present a comprehensive experimental and theoretical study of the acid catalysis of a range of dimeric species exhibiting the b-O-4 linkage, the most common inter-monomer linkage in lignin. We demonstrate that the presence of a phenolic species dramatically increases the rate of cleavage in acid at 150 degrees C. Quantum mechanical calculations on dimers with the para-hydroxyl group demonstrate that this acid-catalyzed pathway differs from the nonphenolic dimmers. Importantly, this result implies that depolymerization of native lignin in the plant cell wall will proceed via an unzipping mechanism wherein b-O-4 linkages will be cleaved from the ends of the branched, polymer chains inwards toward the center of the polymer. To test this hypothesis further, we synthesized a homopolymer of b-O-4 with a phenolic hydroxyl group, and demonstrate that it is cleaved in acid from the end containing the phenolic hydroxyl group. This result suggests that genetic modifications to lignin biosynthesis pathways in plants that will enable lower severity processes to fractionate lignin for upgrading and for easier access to the carbohydrate fraction of the plant cell wall.

  3. ULEV potential of a DI/TCI diesel passenger car engine operated on dimethyl ether

    SciTech Connect (OSTI)

    Kapus, P.E.; Cartellieri, W.P.

    1995-12-31

    This paper describes a feasibility test program on a 2 liter, 4 cylinder DI/TCI passenger car engine operated on the new alternative fuel Dimethyl Ether (DME) with the aim of demonstrating its potential of meeting ULEV (ultra low emission vehicle) emissions (0.2 g/mi NOx in the FTP 75 test cycle) when installed in a full size passenger car. Special attention is drawn to the fuel injection equipment (FIE) as well as combustion system requirements towards the reduction of NOx and combustion noise while keeping energetic fuel consumption at the level of he baseline DI/TCI diesel engine. FIE and combustion system parameters were optimized on the steady state dynamometer by variation of a number of parameters, such as rate of injection, number of nozzle holes, compression ratio, piston bowl shape and exhaust gas recirculation. The paper presents engine test results achieved with DME under various operating conditions and compares these results to those achieved with the diesel version of the same engine.The FTP 75 cycle results were projected from steady state engine maps using a vehicle simulation program taking into account vehicle data and road resistance data of a given vehicle.The cycle results are also compared to actual chassis dynamometer results achieved with the diesel version of the same engine installed in the same vehicle.the passenger car DI/TCI engine adapted for and operated on DME shows very promising results with respect to meeting ULEV NOx emissions without any soot emissions and without the need for a DENOX catalyst. DME fuel consumption on energy basis can be kept very close to the DI diesel value. An oxidation catalyst will be necessary to meet the stringent CO and HC ULEV emission limits.

  4. Task 4.9 -- Value-added products from syngas

    SciTech Connect (OSTI)

    Olson, E.S.; Sharma, R.K.

    1997-02-01

    The work on advanced fuel forms in 1996 focused on the synthesis of higher alcohols from mixtures of hydrogen and carbon dioxide (syngas) from coal gasification. The conversion of coal gasification products to commercially valuable alcohols will provide an important new market for current and future gasification plants. Initial work in this project utilized a novel molybdenum sulfide catalyst previously shown to be active for hydrodesulfurization reactions of coal liquids. The support for the active metal sulfide is a layered mixed oxide (hydrotalcite) capable of interaction with the metal sites for catalysis of carbon monoxide reductions. These catalysts have a high surface area, are highly porous, and have basic and acidic functionality. A pressurized fixed-bed flow-through reactor was constructed, and the MoS{sub 2} catalysts were tested with syngas under a variety of conditions. Unfortunately, the catalysts, even with higher molybdenum loading and addition of promoters, failed to give alcohol products. A batch reactor test of the catalyst was also conducted, but did not produce alcohol products. Group 8 metals have been used previously in catalysts for syngas reactions. Ruthenium and rhodium catalysts were prepared by impregnation of a hydrotalcite support. Tests with these catalysts in flow-through reactors also did not produce the desired alcohol products. The formation of higher alcohols from smaller ones, such as methanol and ethanol, could be commercially important if high selectivity could be achieved. The methanol and ethanol would be derived from syngas and fermentation, respectively. Based on previous work in other laboratories, it was hypothesized that the hydrotalcite supported MoS{sub 2} or Ru or Rh catalysts could catalyze the formation of butyl alcohols. Although the desired 1-butanol was obtained in batch reactions with the promoted Ru catalyst, the reaction was not as selective as desired. Product suitable for a lower-vapor-pressure gasoline oxygenate additive was obtained, but it may not be economical to market such products in competition with methyl tertiary-butyl-ether. Flow-through catalytic bed reactions were not successful.

  5. Nested methylation-specific polymerase chain reaction cancer detection method

    DOE Patents [OSTI]

    Belinsky, Steven A.; Palmisano, William A.

    2007-05-08

    A molecular marker-based method for monitoring and detecting cancer in humans. Aberrant methylation of gene promoters is a marker for cancer risk in humans. A two-stage, or "nested" polymerase chain reaction method is disclosed for detecting methylated DNA sequences at sufficiently high levels of sensitivity to permit cancer screening in biological fluid samples, such as sputum, obtained non-invasively. The method is for detecting the aberrant methylation of the p16 gene, O 6-methylguanine-DNA methyltransferase gene, Death-associated protein kinase gene, RAS-associated family 1 gene, or other gene promoters. The method offers a potentially powerful approach to population-based screening for the detection of lung and other cancers.

  6. Geometric and Electronic Structures of the Ni(I) and Methyl-Ni(III)

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Intermediates of Methyl-Coenzyme M Reductase 9 Geometric and Electronic Structures of the Ni(I) and Methyl-Ni(III) Intermediates of Methyl-Coenzyme M Reductase Methyl-coenzyme M reductase (MCR) from methanogenic archaea catalyzes the terminal step in biological methane synthesis. Using coenzyme B (CoBSH) as the two-electron donor, MCR reduces methyl-coenzyme M (methyl-SCoM) to form methane and the heterodisulfide product, CoBS-SCoM. MCR contains an essential redox active nickel tetrapyrrolic

  7. Ligand-Thickness Effect Leads to Enhanced Preference for Large Anions in Alkali Metal Extraction by Crown Ethers

    SciTech Connect (OSTI)

    Haverlock, T.J.; Moyer, B.A.; Sachleben, R.A.

    1999-07-11

    Jean-Marie Lehn (Nobel laureate, 1987) suggested ligand thickness to be an important consideration in the design of host molecules for cation recognition. We have recently expanded the role of this simple ligand property by demonstrating a case in which ligand thickness contributes significantly to anion discrimination. It was found that in the extraction of sodium nitrate and perchlorate by a simple crown ether, bis(t-octylbenzo)-14-crown-4 (BOB 14C4), the normal preference for perchlorate is almost completely lost when the complex cation has the open-face sandwich vs. the sandwich structure.

  8. Methods for detection of methyl-CpG dinucleotides

    DOE Patents [OSTI]

    Dunn, John J.

    2013-01-29

    The invention provides methods for enriching methyl-CpG sequences from a DNA sample. The method makes use of conversion of cytosine residues to uracil under conditions in which methyl-cytosine residues are preserved. Additional methods of the invention enable to preservation of the context of me-CpG dinucleotides. The invention also provides a recombinant, full length and substantially pure McrA protein (rMcrA) for binding and isolation of DNA fragments containing the sequence 5'-C.sup.MeCpGG-3'. Methods for making and using the rMcrA protein, and derivatives thereof are provided.

  9. Methods for detection of methyl-CpG dinucleotides

    DOE Patents [OSTI]

    Dunn, John J.

    2012-09-11

    The invention provides methods for enriching methyl-CpG sequences from a DNA sample. The method makes use of conversion of cytosine residues to uracil under conditions in which methyl-cytosine residues are preserved. Additional methods of the invention enable to preservation of the context of me-CpG dinucleotides. The invention also provides a recombinant, full length and substantially pure McrA protein (rMcrA) for binding and isolation of DNA fragments containing the sequence 5'-C.sup.MeCpGG-3'. Methods for making and using the rMcrA protein, and derivatives thereof are provided.

  10. Methods for detection of methyl-CpG dinucleotides

    DOE Patents [OSTI]

    Dunn, John J

    2013-11-26

    The invention provides methods for enriching methyl-CpG sequences from a DNA sample. The method makes use of conversion of cytosine residues to uracil under conditions in which methyl-cytosine residues are preserved. Additional methods of the invention enable to preservation of the context of me-CpG dinucleotides. The invention also provides a recombinant, full length and substantially pure McrA protein (rMcrA) for binding and isolation of DNA fragments containing the sequence 5'-C.sup.MeCpGG-3'. Methods for making and using the rMcrA protein, and derivatives thereof are provided.

  11. SYNTHESIS OF NOVEL CROWN ETHERS BEARING THE exo-cis-2,3-NORBORNYL GROUP AS POTENTIAL Na+ AND K+ EXTRACTANTS

    SciTech Connect (OSTI)

    Robeson, R.M.; Bonnesen, P.

    2007-01-01

    The synthesis of a series of novel dinorbornyl-16-crown-5 and dinorbornyl-18-crown-6 ethers that incorporate the exo-cis-2,3-norbornyl moiety within the macrocycle framework is described. The key starting material for the crown ethers, exo-cis-2,3-norbornanediol, was successfully prepared on a large (>30g) scale in 88% yield from norbornylene by osmium tetroxide-catalyzed hydroxylation. The syn and anti isomers of the dinorbornyl-16-crown-5 ether family were prepared using diethylene glycol with ring closure achieved using a methallyl linkage. The isomers cis-syn-cis and cis-anti-cis di-norbornano-15-methyleno-16-crown-5 (6A and 6B) could be separated using column chromatography, and a single crystal of the syn isomer 6A suitable for X-ray crystal structure analysis was obtained, thereby confi rming the syn orientation. The syn and anti isomers of the dinorbornyl-18-crown-6 ether family were successfully prepared employing a different synthetic strategy, involving the potassium–templated cyclization of two bis-hydroxyethoxy-substituted exo-cis-2,3-norbornyl groups under high dilution conditions. Attempts to fully separate cis-syn-cis di-norbornano-18-crown-6 (10A) and cis-anti-cis di-norbornano-18-crown-6 (10B) from one another using column chromatography were unsuccessful. All intermediates and products were checked for purity using either thin layer chromatography or gas chromatography, and characterized by proton and carbon NMR. Crown ethers 6AB and 10AB are to our knowledge the fi rst crown ethers to incorporate the exo-cis-2,3-norbornyl moiety into the crown ring to be successfully synthesized and characterized.

  12. Low Temperature Autoignition of C8H16O2 Ethyl and Methyl Esters...

    Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site

    Temperature Autoignition of C8H16O2 Ethyl and Methyl Esters in a Motored Engine Low Temperature Autoignition of C8H16O2 Ethyl and Methyl Esters in a Motored Engine qThe alkyl chain ...

  13. Infant sex-specific placental cadmium and DNA methylation associations

    SciTech Connect (OSTI)

    Mohanty, April F.; Farin, Fred M.; Bammler, Theo K.; MacDonald, James W.; Afsharinejad, Zahra; Burbacher, Thomas M.; Siscovick, David S.; and others

    2015-04-15

    Background: Recent evidence suggests that maternal cadmium (Cd) burden and fetal growth associations may vary by fetal sex. However, mechanisms contributing to these differences are unknown. Objectives: Among 24 maternal-infant pairs, we investigated infant sex-specific associations between placental Cd and placental genome-wide DNA methylation. Methods: We used ANOVA models to examine sex-stratified associations of placental Cd (dichotomized into high/low Cd using sex-specific Cd median cutoffs) with DNA methylation at each cytosine-phosphate-guanine site or region. Statistical significance was defined using a false discovery rate cutoff (<0.10). Results: Medians of placental Cd among females and males were 5 and 2 ng/g, respectively. Among females, three sites (near ADP-ribosylation factor-like 9 (ARL9), siah E3 ubiquitin protein ligase family member 3 (SIAH3), and heparin sulfate (glucosamine) 3-O-sulfotransferase 4 (HS3ST4) and one region on chromosome 7 (including carnitine O-octanoyltransferase (CROT) and TP5S target 1 (TP53TG1)) were hypomethylated in high Cd placentas. Among males, high placental Cd was associated with methylation of three sites, two (hypomethylated) near MDS1 and EVI1 complex locus (MECOM) and one (hypermethylated) near spalt-like transcription factor 1 (SALL1), and two regions (both hypomethylated, one on chromosome 3 including MECOM and another on chromosome 8 including rho guanine nucleotide exchange factor (GEF) 10 (ARHGEF10). Differentially methylated sites were at or close to transcription start sites of genes involved in cell damage response (SIAH3, HS3ST4, TP53TG1) in females and cell differentiation, angiogenesis and organ development (MECOM, SALL1) in males. Conclusions: Our preliminary study supports infant sex-specific placental Cd-DNA methylation associations, possibly accounting for previously reported differences in Cd-fetal growth associations across fetal sex. Larger studies are needed to replicate and extend these findings. Such investigations may further our understanding of epigenetic mechanisms underlying maternal Cd burden with suboptimal fetal growth associations. - Highlights: • We examine sex-specific placental-Cd and -genome-wide DNA methylation associations. • In females, associated sites were at/near genes involved in cell damage response. • In males, associated sites were at/near angiogenesis and organ development genes. • Our study supports infant sex-specific placental Cd-DNA methylation associations.

  14. Phase 1 Methyl Iodide Deep-Bed Adsorption Tests

    SciTech Connect (OSTI)

    Nick Soelberg; Tony Watson

    2014-08-01

    Nuclear fission results in the production of fission products (FPs) and activation products including iodine-129, which could evolve into used fuel reprocessing facility off-gas systems, and could require off-gas control to limit air emissions to levels within acceptable emission limits. Research, demonstrations, and some reprocessing plant experience have indicated that diatomic iodine can be captured with efficiencies high enough to meet regulatory requirements. Research on the capture of organic iodides has also been performed, but to a lesser extent [Jubin 2012b]. Several questions remain open regarding the capture of iodine bound in organic compounds. Deep-bed methyl iodide adsorption testing has progressed according to a multi-laboratory methyl iodide adsorption test plan. This report summarizes the first phase of methyl iodide adsorption work performed according to this test plan using the deep-bed iodine adsorption test system at the Idaho National Laboratory (INL), performed during Fiscal Year (FY) 2013 and early FY-2014. Testing has been performed to address questions posed in the test plan, and followed the testing outline in the test plan. Tests established detection limits, developed procedures for sample analysis with minimal analytical interferences, and confirmed earlier results that show that the methyl iodide reacts when in contact with the AgZ sorbent, and not significantly in the gas flow upstream of the sorbent. The reaction(s) enable separation of the iodine from the organic moiety, so that the iodine can chemisorb onto the sorbent. The organic moiety can form other compounds, some of which are organic compounds that are detected and can be tentatively identified using GC-FID and GCMS. Test results also show that other gas constituents (NOx and/or H2O) can affect the methyl iodide reactions. With NOx and H2O present in the gas stream, the majority of uncaptured iodine exiting iodine-laden sorbent beds is in the form of I2 or HI, species that are soluble in NaOH scrubbing solution for iodine analysis. But when NOx and H2O are not present, then the majority of the uncaptured iodine exiting iodine-laden sorbent is in the form of methyl iodide. Methyl iodide adsorption efficiencies have been high enough so that initial DFs exceed 1,000 to 10,000. The methyl iodide mass transfer zone depths are estimated at 4-8 inches, possibly deeper than mass transfer zone depths estimated for I2 adsorption on AgZ. Additional deep-bed testing and analyses are recommended to (a) expand the data base for methyl iodide adsorption under various conditions specified in the methyl iodide test plan, and (b) provide more data for evaluating organic iodide reactions and reaction byproducts for different potential adsorption conditions.

  15. Chemically induced Parkinson's disease: intermediates in the oxidation of 1-methyl-4-phenyl-1,2,3,6-tetrahydropyridine to the 1-methyl-4-phenyl-pyridinium ion

    SciTech Connect (OSTI)

    Chacon, J.N.; Chedekel, M.R.; Land, E.J.; Truscott, T.G.

    1987-04-29

    Various unstable intermediate oxidation states have been postulated in the metabolic activation of 1-methyl-4-phenyl-1,2,3,6-tetrahydropyridine to the 1-methyl-4-phenyl pyridinium ion. We now report the first direct observation of these free radical intermediates by pulse radiolysis and flash photolysis. Studies are described of various reactions of such species, in particular with dopamine whose autoxidation to dopamine quinone is reported to be potentiated by 1-methyl-4-phenyl-1,2,3, 6-tetrahydropyridine.

  16. SYNTHESIS OF METHYL METHACRYLATE FROM COAL-DERIVED SYNGAS

    SciTech Connect (OSTI)

    Makarand R. Gogate; James J. Spivey; Joseph R. Zoeller; Richard D. Colberg; Gerald N. Choi; Samuel S. Tam

    1999-04-21

    Research Triangle Institute (RTI), Eastman Chemical Company, and Bechtel collectively are developing a novel three-step process for the synthesis of methyl methacrylate (MMA) from coal-derived syngas that consists of the steps of synthesis of a propionate, its condensation with formaldehyde to form methacrylic acid (MAA), and esterification of MAA with methanol to produce MMA. The research team has completed the research on the three-step methanol-based route to MMA. Under an extension to the original contract, we are currently evaluating a new DME-based process for MMA. The key research need for DME route is to develop catalysts for DME partial oxidation reactions and DME condensation reactions. Over the last quarter (January-March/99), in-situ formaldehyde generation and condensation with methyl propionate were tested over various catalysts and reaction conditions. The patent application is in preparation and the results are retained for future reports.

  17. Synthesis of 6-Methyl-9-n-propyldibenzothiophene-4-ol

    SciTech Connect (OSTI)

    Not Available

    1991-10-28

    The material presented here has been described to some extent in Status Reports 12, 13, and 14 and covers the progress toward the synthesis of the modified target molecules 9-isopropyl-4-methoxy-6-methyldibenzothiophene (13) and 9-isopropyl-6-methyldibenzothiophene-4-ol (14). It is divided into three parts: (a) Dehydrogenation experiments On tetrahydrodibenzothiophene 12. (b) methoxyl methyl cleavage of 13 to 14 using boron tribromide. (c) isolation and purification of methoxydibenzothiophene 13.

  18. FY-2015 Methyl Iodide Deep-Bed Adsorption Test Report

    SciTech Connect (OSTI)

    Soelberg, Nicholas Ray; Watson, Tony Leroy

    2015-09-30

    Nuclear fission produces fission and activation products, including iodine-129, which could evolve into used fuel reprocessing facility off-gas systems, and could require off-gas control to limit air emissions to levels within acceptable emission limits. Deep-bed methyl iodide adsorption testing has continued in Fiscal Year 2015 according to a multi-laboratory methyl iodide adsorption test plan. Updates to the deep-bed test system have also been performed to enable the inclusion of evaporated HNO3 and increased NO2 concentrations in future tests. This report summarizes the result of those activities. Test results showed that iodine adsorption from gaseous methyl iodide using reduced silver zeolite (AgZ) resulted in initial iodine decontamination factors (DFs, ratios of uncontrolled and controlled total iodine levels) under 1,000 for the conditions of the long-duration test performed this year (45 ppm CH3I, 1,000 ppm each NO and NO2, very low H2O levels [3 ppm] in balance air). The mass transfer zone depth exceeded the cumulative 5-inch depth of 4 bed segments, which is deeper than the 2-4 inch depth estimated for the mass transfer zone for adsorbing I2 using AgZ in prior deep-bed tests. The maximum iodine adsorption capacity for the AgZ under the conditions of this test was 6.2% (6.2 g adsorbed I per 100 g sorbent). The maximum Ag utilization was 51%. Additional deep-bed testing and analyses are recommended to (a) expand the data base for methyl iodide adsorption and (b) provide more data for evaluating organic iodide reactions and reaction byproducts for different potential adsorption conditions.

  19. Exploratory study of coal-conversion chemistry. Quarterly report, June 20, 1980-September 19, 1980. [Diphenylmethane, diphenyl ether

    SciTech Connect (OSTI)

    Not Available

    1981-03-04

    This report describes work accomplished under two task: Task A, Mechanism of Cleavage of Key Bond types Present in Coals, and Task B, Catalysis of Conversion in CO-H/sub 2/O Systems. Under Task A, we have made additional measurements of catalytic carbon-carbon and carbon-oxygen bond cleavage in coal-related diphenylmethane and diphenyl ether structures. The results provide further support for, but do not definitely confirm, the tentative conclusion that the highly effective iron oxide catalysts involves oxidation to radical cation species. The homogeneous scission of carbon-oxygen bonds in diphenyl ether structure has also been studied. In the Task B studies of CO-H/sub 2/O systems, we typically obtain 50% benzene-soluble product material from 20 min. reaction of beneficiated Illinois No. 6 coal. This conversion level is obtained with aqueous solutions either at a starting pH above 12.6 or in neutral solutions with water-soluble catalysts present. We have studied a number of catalysts, including the potassium or sodium salts of molybdate, chromate, manganate, and tungstate; all are effective in the 3000 to 6000 ppM range. A striking result is that sodium nitrate at 6000 ppM is as effective as the metal salts. We found that the nitrate was converted to ammonium ion; also, formate was detected in the product aqueous phase. Finally, we find that catalytic quantities of sodium formate in CO/H/sub 2/O at pH 7 are effective in the conversion. However, in a control run in N/sub 2//H/sub 2/O, with a quantity of sodium formate equivalent to twice the molar quantity of hydrogen transferred to the coal in a successful run, the coal was converted to a product totally insoluble in benzene and with a lower hydrogen content than the starting coal.

  20. Solvent Modification in Ion-Pair Extraction: Effect on Sodium Nitrate Transport in Nitrobenzene Using a Crown Ether

    SciTech Connect (OSTI)

    Levitskaia, Tatiana G.; Lumetta, Gregg J.

    2005-10-31

    A comparative quantitative analysis of the effect of solvent modifiers on an ion-pair extraction of an inorganic salt by a crown ether was conducted. Two classes of the solvent modifiers that possess electron-pair donor (EPD) or hydrogen-bond donor (HBD) groups were investigated. The equilibrium constants corresponding to the extraction of sodium nitrate into nitrobenzene (NB) employing model neutral host cis-syn-cis-dicyclohexano-18-crown-6 (1) with and without solvent modifier were determined using the SXLSQI computer model. For a series of EPD modifiers—including tri-n-butyl- and tri-phenylphosphate, tri-n-butyl- and tri-phenylphosphine oxide, N,N-di-n-butyl- and N,N-di-phenyl acetamide—the enhancement of the NaNO3 extraction by 1 was found to be dependent on the hydrogen-bond acceptance ability of the modifier quantified by the b solvatochromic parameter. Application of the solvent EPD modifier improved solvation of the sodium ion, lowering the large energy barrier of Na+ partitioning into the extraction phase. A HBD modifier 3,5-di-t-butylphenol 8 that forms strong hydrogen bonds with nitrate anion in NB, exhibited even greater enhancement of the NaNO3 extraction by 1. The determined extraction constants were correlated with the b or a solvatochromic parameters of the solvent modifiers and linear trends were observed. Hydrogen bond interaction between 3,5-di-t-butylphenol 8 and nitrate anion in the presence of the sodium-loaded crown ether in the extraction phases was studied by vibrational spectroscopy. Formation of the simple 1:1 adduct was demonstrated.

  1. Catalytic Consequences of Acid Strength in the Conversion of Methanol to Dimethyl Ether

    SciTech Connect (OSTI)

    Carr, Robert T.; Neurock, Matthew; Iglesia, Enrique

    2011-02-14

    The effects of acid identity on CH{sub 3}OH dehydration are examined here using density functional theory (DFT) estimates of acid strength (as deprotonation energies, DPE) and reaction energies, combined with rate data on Keggin polyoxometalate (POM) clusters and zeolite H-BEA. Measured first-order (k{sub mono}) and zero-order (k{sub dimer}) CH3OH dehydration rate constants depend exponentially on DPE for POM clusters; the value of k{sub mono} depends more strongly on DPE than k{sub dimer} does. The chemical significance of these rate parameters and the basis for their dependences on acid strength were established by using DFT to estimate the energies of intermediates and transition states involved in elementary steps that are consistent with measured rate equations. We conclude from this treatment that CH{sub 3}OH dehydration proceeds via direct reactions of co-adsorbed CH{sub 3}OH molecules for relevant solid acids and reaction conditions. Methyl cations formed at ion-pair transition states in these direct routes are solvated by H{sub 2}O and CH{sub 3}OH more effectively than those in alternate sequential routes involving methoxide formation and subsequent reaction with CH{sub 3}OH. The stability of ion-pairs, prevalent as intermediates and transition states on solid acids, depends sensitively on DPE because of concomitant correlations between the stability of the conjugate anionic cluster and DPE. The chemical interpretation of k{sub mono} and k{sub dimer} from mechanism-based rate equations, together with thermochemical cycles of their respective transition state formations, show that similar charge distributions in the intermediate and transition state involved in k{sub dimer} cause its weaker dependence on DPE. Values of k{sub mono} involve uncharged reactants and the same ion-pair transition state as k{sub dimer}; these species sense acid strength differently and cause the larger effects of DPE on k{sub mono}. Confinement effects in H-BEA affect the value of k{sub mono} because the different sizes and number of molecules in reactants and transition states selectively stabilize the latter; however, they do not influence k{sub dimer}, for which reactants and transition states of similar size sense spatial constraints to the same extent. This combination of theory and experiment for solid acids of known structure sheds considerable light on the relative contributions from solvation, electrostatic and van der Waals interactions in stabilizing cationic transition states and provides predictive insights into the relative contributions of parallel routes based on the size and charge distributions of their relevant intermediates and transition states. These findings also demonstrate how the consequences of acid strength on measured turnover rates depend on reaction conditions and their concomitant changes in the chemical significance of the rate parameters measured. Moreover, the complementary use of experiment and theory in resolving mechanistic controversies has given predictive guidance about how rate and equilibrium constants, often inextricably combined as measured rate parameters, individually depend on acid strength based on the magnitude and spatial distributions of charges in reactants, products and transition states involved in relevant elementary steps. The unique relations between k{sub mono}, k{sub dimer} and DPE developed here for CH{sub 3}OH dehydration can be applied in practice to assess the acid strength of any solid acid, many of which have unknown structures, preventing reliable calculations of their DPE by theory.

  2. The Structural Basis for Tight Control of PP2A Methylation and Function by

    Office of Scientific and Technical Information (OSTI)

    LCMT-1 (Journal Article) | SciTech Connect The Structural Basis for Tight Control of PP2A Methylation and Function by LCMT-1 Citation Details In-Document Search Title: The Structural Basis for Tight Control of PP2A Methylation and Function by LCMT-1 Proper formation of protein phosphatase 2A (PP2A) holoenzymes is essential for the fitness of all eukaryotic cells. Carboxyl methylation of the PP2A catalytic subunit plays a critical role in regulating holoenzyme assembly; methylation is

  3. Vacuum ultraviolet and infrared spectra of condensed methyl acetate on cold astrochemical dust analogs

    SciTech Connect (OSTI)

    Sivaraman, B.; Nair, B. G.; Mason, N. J.; Lo, J.-I.; Cheng, B.-M.; Kundu, S.; Davis, D.; Prabhudesai, V.; Krishnakumar, E.; Raja Sekhar, B. N.

    2013-12-01

    Following the recent report of the first identification of methyl acetate (CH{sub 3}COOCH{sub 3}) in the interstellar medium (ISM), we have carried out vacuum ultraviolet (VUV) and infrared (IR) spectroscopy studies on methyl acetate from 10 K until sublimation in an ultrahigh vacuum chamber simulating astrochemical conditions. We present the first VUV and IR spectra of methyl acetate relevant to ISM conditions. Spectral signatures clearly showed molecular reorientation to have started in the ice by annealing the amorphous ice formed at 10 K. An irreversible phase change from amorphous to crystalline methyl acetate ice was found to occur between 110 K and 120 K.

  4. Exploring the roles of DNA methylation in the metal-reducing bacterium Shewanella oneidensis MR-1

    SciTech Connect (OSTI)

    Bendall, Matthew L.; Luong, Khai; Wetmore, Kelly M.; Blow, Matthew; Korlach, Jonas; Deutschbauer, Adam; Malmstrom, Rex

    2013-08-30

    We performed whole genome analyses of DNA methylation in Shewanella 17 oneidensis MR-1 to examine its possible role in regulating gene expression and 18 other cellular processes. Single-Molecule Real Time (SMRT) sequencing 19 revealed extensive methylation of adenine (N6mA) throughout the 20 genome. These methylated bases were located in five sequence motifs, 21 including three novel targets for Type I restriction/modification enzymes. The 22 sequence motifs targeted by putative methyltranferases were determined via 23 SMRT sequencing of gene knockout mutants. In addition, we found S. 24 oneidensis MR-1 cultures grown under various culture conditions displayed 25 different DNA methylation patterns. However, the small number of differentially 26 methylated sites could not be directly linked to the much larger number of 27 differentially expressed genes in these conditions, suggesting DNA methylation is 28 not a major regulator of gene expression in S. oneidensis MR-1. The enrichment 29 of methylated GATC motifs in the origin of replication indicate DNA methylation 30 may regulate genome replication in a manner similar to that seen in Escherichia 31 coli. Furthermore, comparative analyses suggest that many 32 Gammaproteobacteria, including all members of the Shewanellaceae family, may 33 also utilize DNA methylation to regulate genome replication.

  5. Changes in mitogen-activated protein kinase in cerebellar granule neurons by polybrominated diphenyl ethers and polychlorinated biphenyls

    SciTech Connect (OSTI)

    Fan Chunyang; Besas, Jonathan

    2010-05-15

    Polybrominated diphenyl ethers (PBDEs) are used as additive flame retardants and have been detected in human blood, adipose tissue, and breast milk. Both in vitro and in vivo studies have shown that the effects of PBDEs are similar to the known human developmental neurotoxicants such as polychlorinated biphenyls (PCBs) on a molar basis. Previously, we reported that PBDE mixtures and congeners, perturbed calcium homeostasis which is critical for the development and function of the nervous system. In the present study, we tested whether environmentally relevant PBDE/PCB mixtures and congeners affected mitogen-activated protein kinase (MAPK) pathways, which are down-stream events of calcium signaling in cerebellar granule neuronal cultures. In this study, phosphorylated extracellular signal-regulated kinase (pERK)1/2, a widely studied MAPK cascade and known to be involved in learning and memory, levels were quantitated using western blot technique with phospho-specific antibodies. Glutamate (a positive control) increased pERK1/2 in a time- and concentration-dependent manner reaching maximum activation at 5-30 min of exposure and at doses >= 10 muM. Both Aroclor 1254 (a commercial penta PCB mixture) and DE-71 (a commercial penta PBDE mixture) elevated phospho-ERK1/2, producing maximum stimulation at 30 min and at concentrations >= 3 mug/ml; Aroclor 1254 was more efficacious than DE-71. DE-79 (an octabrominated diphenyl ether mixture) also elevated phospho-ERK1/2, but to a lesser extent than that of DE-71. PBDE congeners 47, 77, 99, and 153 also increased phospo-ERK1/2 in a concentration-dependent manner. The data indicated that PBDE congeners are more potent than the commercial mixtures. PCB 47 also increased phospho-ERK1/2 like its structural analog PBDE 47, but to a lesser extent, suggesting that these chemicals affect similar pathways. Cytotoxicity, measured as %LDH release, data showed that higher concentrations (> 30 muM) and longer exposures (> 30 min) are required to see cell death. These results show that PBDE mixtures and congeners activate MAPK pathway at concentrations where no significant cytotoxicity was observed, suggesting that perturbed intracellular signaling including MAPK pathway might be involved in the initiation of adverse effects, including learning and memory, related to these persistent chemicals.

  6. Involvement of reactive oxygen species in brominated diphenyl ether-47-induced inflammatory cytokine release from human extravillous trophoblasts in vitro

    SciTech Connect (OSTI)

    Park, Hae-Ryung Kamau, Patricia W.; Loch-Caruso, Rita

    2014-01-15

    Polybrominated diphenyl ethers (PBDEs) are widely used flame retardant compounds. Brominated diphenyl ether (BDE)-47 is one of the most prevalent PBDE congeners found in human breast milk, serum and placenta. Despite the presence of PBDEs in human placenta, effects of PBDEs on placental cell function are poorly understood. The present study investigated BDE-47-induced reactive oxygen species (ROS) formation and its role in BDE-47-stimulated proinflammatory cytokine release in a first trimester human extravillous trophoblast cell line, HTR-8/SVneo. Exposure of HTR-8/SVneo cells for 4 h to 20 ?M BDE-47 increased ROS generation 1.7 fold as measured by the dichlorofluorescein (DCF) assay. Likewise, superoxide anion production increased approximately 5 fold at 10 and 15 ?M and 9 fold at 20 ?M BDE-47 with a 1-h exposure, as measured by cytochrome c reduction. BDE-47 (10, 15 and 20 ?M) decreased the mitochondrial membrane potential by 4764.5% at 4, 8 and 24 h as assessed with the fluorescent probe Rh123. Treatment with 15 and 20 ?M BDE-47 stimulated cellular release and mRNA expression of IL-6 and IL-8 after 12 and 24-h exposures: the greatest increases were a 35-fold increased mRNA expression at 12 h and a 12-fold increased protein concentration at 24 h for IL-6. Antioxidant treatments (deferoxamine mesylate, ()?-tocopherol, or tempol) suppressed BDE-47-stimulated IL-6 release by 54.1%, 56.3% and 37.7%, respectively, implicating a role for ROS in the regulation of inflammatory pathways in HTR-8/SVneo cells. Solvent (DMSO) controls exhibited statistically significantly decreased responses compared with non-treated controls for IL-6 release and IL-8 mRNA expression, but these responses were not consistent across experiments and times. Nonetheless, it is possible that DMSO (used to dissolve BDE-47) may have attenuated the stimulatory actions of BDE-47 on cytokine responses. Because abnormal activation of proinflammatory responses can disrupt trophoblast functions necessary for placental development and successful pregnancy, further investigation is warranted of the impact of ROS and BDE-47 on trophoblast cytokine responses. - Highlights: BDE-47 induced ROS overproduction and mitochondrial dysfunction. BDE-47 stimulated production of proinflammatory cytokines. Antioxidant treatment reduced BDE-47-stimulated ROS generation and cytokine release.

  7. Heat Capacity Uncertainty Calculation for the Eutectic Mixture of Biphenyl/Diphenyl Ether Used as Heat Transfer Fluid: Preprint

    SciTech Connect (OSTI)

    Gomez, J. C.; Glatzmaier, G. C.; Mehos, M.

    2012-09-01

    The main objective of this study was to calculate the uncertainty at 95% confidence for the experimental values of heat capacity of the eutectic mixture of biphenyl/diphenyl ether (Therminol VP-1) determined from 300 to 370 degrees C. Twenty-five samples were evaluated using differential scanning calorimetry (DSC) to obtain the sample heat flow as a function of temperature. The ASTM E-1269-05 standard was used to determine the heat capacity using DSC evaluations. High-pressure crucibles were employed to contain the sample in the liquid state without vaporizing. Sample handling has a significant impact on the random uncertainty. It was determined that the fluid is difficult to handle, and a high variability of the data was produced. The heat capacity of Therminol VP-1 between 300 and 370 degrees C was measured to be equal to 0.0025T+0.8672 with an uncertainty of +/- 0.074 J/g.K (3.09%) at 95% confidence with T (temperature) in Kelvin.

  8. Calcitriol inhibits Ether-a go-go potassium channel expression and cell proliferation in human breast cancer cells

    SciTech Connect (OSTI)

    Garcia-Becerra, Rocio; Diaz, Lorenza; Camacho, Javier; Barrera, David; Ordaz-Rosado, David; Morales, Angelica; Ortiz, Cindy Sharon; Avila, Euclides; Bargallo, Enrique; Arrecillas, Myrna; Halhali, Ali; Larrea, Fernando

    2010-02-01

    Antiproliferative actions of calcitriol have been shown to occur in many cell types; however, little is known regarding the molecular basis of this process in breast carcinoma. Ether-a-go-go (Eag1) potassium channels promote oncogenesis and are implicated in breast cancer cell proliferation. Since calcitriol displays antineoplastic effects while Eag1 promotes tumorigenesis, and both factors antagonically regulate cell cycle progression, we investigated a possible regulatory effect of calcitriol upon Eag1 as a mean to uncover new molecular events involved in the antiproliferative activity of this hormone in human breast tumor-derived cells. RT real-time PCR and immunocytochemistry showed that calcitriol suppressed Eag1 expression by a vitamin D receptor (VDR)-dependent mechanism. This effect was accompanied by inhibition of cell proliferation, which was potentiated by astemizole, a nonspecific Eag1 inhibitor. Immunohistochemistry and Western blot demonstrated that Eag1 and VDR abundance was higher in invasive-ductal carcinoma than in fibroadenoma, and immunoreactivity of both proteins was located in ductal epithelial cells. Our results provide evidence of a novel mechanism involved in the antiproliferative effects of calcitriol and highlight VDR as a cancer therapeutic target for breast cancer treatment and prevention.

  9. Electrochemical Investigation of Li–Al Anodes in Oligo(ethylene glycol) Dimethyl Ether/LiPF6

    SciTech Connect (OSTI)

    Zhou, Y.N.; Yang, X.; Wang, X.J.; Lee, H.S.; Nam, K.W.; Haas, O.

    2010-11-01

    1 M LiPF{sub 6} dissolved in oligo(ethylene glycol) dimethyl ether with a molecular weight 500 g mol{sup -1} was investigated as a new electrolyte (OEGDME500, 1 M LiPF{sub 6}) for metal deposition and battery applications. At 25 C a conductivity of 0.48 x 10{sup -3} S cm{sup -1} was obtained and at 85 C, 3.78 x 10{sup -3} S cm{sup -1}. The apparent activation barrier for ionic transport was evaluated to be 30.7 kJ mol{sup -1}. OEGDME500, 1 M LiPF{sub 6} allows operating temperature above 100 C with very attractive conductivity. The electrolyte shows excellent performance at negative and positive potentials. With this investigation, we report experimental results obtained with aluminum electrodes using this electrolyte. At low current densities lithium ion reduction and re-oxidation can be achieved on aluminum electrodes at potentials about 280 mV more positive than on lithium electrodes. In situ X-ray diffraction measurements collected during electrochemical lithium deposition on aluminum electrodes show that the shift to positive potentials is due to the negative Gibbs free energy change of the Li-Al alloy formation reaction.

  10. Electrochemical Investigation of Li-Al Anodes in Oligo (ethylene glycol) Dimethyl ether/LiPF6

    SciTech Connect (OSTI)

    Y Zhou; X Wang; H Lee; K Nam; X Yang; O Haas

    2011-12-31

    LiPF{sub 6} dissolved in oligo(ethylene glycol) dimethyl ether with a molecular weight 5 g mol{sup -1} was investigated as a new electrolyte (OEGDME5, 1 M LiPF{sub 6}) for metal deposition and battery applications. At 25 C a conductivity of .48 x 1{sup -3} S cm{sup -1} was obtained and at 85 C, 3.78 x 1{sup -3} S cm{sup -1}. The apparent activation barrier for ionic transport was evaluated to be 3.7 kJ mol{sup -1}. OEGDME5, 1 M LiPF{sub 6} allows operating temperature above 1 C with very attractive conductivity. The electrolyte shows excellent performance at negative and positive potentials. With this investigation, we report experimental results obtained with aluminum electrodes using this electrolyte. At low current densities lithium ion reduction and re-oxidation can be achieved on aluminum electrodes at potentials about 28 mV more positive than on lithium electrodes. In situ X-ray diffraction measurements collected during electrochemical lithium deposition on aluminum electrodes show that the shift to positive potentials is due to the negative Gibbs free energy change of the Li-Al alloy formation reaction.

  11. Toxicity of polychlorinated diphenyl ethers in hydra attenuata and in rat whole-embryo culture. Master's thesis

    SciTech Connect (OSTI)

    Becker, M.C.

    1991-05-01

    Polychlorinated diphenyl ethers (PCDEs) are a class of biaryl compounds that have little commercial application, but appear to be widespread in the environment. They have been found in wood preservative waste dumpsites and in fly ash from municipal waste incinerators. They have been detected in bird eggs and tissues, fish, and other edible marine organisms in the United States, Canada, and Europe. There are limited reports in the extant literature on the toxicity of PCDEs. This study was designed to evaluate the toxicity of selected PCDEs in cultures of Hydra attenuata and post-implantation rat whole embryos. The toxicity of several closely related polychlorinated biphenyls (PCBs) was evaluated in both cultures and 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) was evaluated in whole embryo culture. Embryonic growth and development parameters (yolk sac diameter, crown-rump length, somite count, and DNA and protein content) and gross morphology were determined. Findings indicated that these chemicals were neither embryotoxic nor teratogenic. Thus, the PCDEs, which elicit other diverse toxic and biochemical responses in rodents, are relatively inactive in these bioassays for developmental toxicity.

  12. On the competition between hydrogen abstraction versus C-O bond fission in initiating dimethyl ether combustion

    SciTech Connect (OSTI)

    Francisco, J.

    1999-07-01

    There has been a growing interest in the potential use of dimethyl ether (DME) as a diesel fuel in compression ignition engines. There are two initiation steps involved in the combustion of DME, one involving C-O bond fission and the other involving hydrogen abstraction by molecular oxygen. The kinetics and thermodynamics of C-O bond fission were explored computationally in a previous paper. The present paper addresses the competing process--hydrogen abstraction by molecular oxygen. Ab initio molecular orbital calculations are used to study the structures and energetics of the reactants, products, and the transition state for the CH{sub 3}OCH{sub 3} + O{sub 2} reaction. The calculations predict a barrier for hydrogen abstraction from CH{sub 3}OCH{sub 3} by O{sub 2} of 47.4 kcal/mol. This is lower than the barrier height for C-O bond fission previously calculated to be 81.1 kcal/mol. The results support values used in current models for the combustion of DME. Moreover, an examination of rates for C-O bond fission versus hydrogen abstraction by O{sub 2} suggests that the bimolecular process is the dominant pathway.

  13. Unexpected methyl migrations of ethanol dimer under synchrotron VUV radiation

    SciTech Connect (OSTI)

    Xiao, Weizhan; Hu, Yongjun E-mail: lssheng@ustc.edu.cn; Li, Weixing; Guan, Jiwen; Liu, Fuyi; Shan, Xiaobin; Sheng, Liusi E-mail: lssheng@ustc.edu.cn

    2015-01-14

    While methyl transfer is well known to occur in the enzyme- and metal-catalyzed reactions, the methyl transfer in the metal-free organic molecules induced by the photon ionization has been less concerned. Herein, vacuum ultraviolet single photon ionization and dissociation of ethanol dimer are investigated with synchrotron radiation photoionization mass spectroscopy and theoretical methods. Besides the protonated clusters cation (C{sub 2}H{sub 5}OH) ⋅ H{sup +} (m/z = 47) and the β-carbon-carbon bond cleavage fragment CH{sub 2}O ⋅ (C{sub 2}H{sub 5}OH)H{sup +} (m/z = 77), the measured mass spectra revealed that a new fragment (C{sub 2}H{sub 5}OH) ⋅ (CH{sub 3}){sup +} (m/z = 61) appeared at the photon energy of 12.1 and 15.0 eV, where the neutral dimer could be vertically ionized to higher ionic state. Thereafter, the generated carbonium ions are followed by a Wagner-Meerwein rearrangement and then dissociate to produce this new fragment, which is considered to generate after surmounting a few barriers including intra- and inter-molecular methyl migrations by the aid of theoretical calculations. The appearance energy of this new fragment is measured as 11.55 ± 0.05 eV by scanning photoionization efficiency curve. While the signal intensity of fragment m/z = 61 starts to increase, the fragments m/z = 47 and 77 tend to slowly incline around 11.55 eV photon energy. This suggests that the additional fragment channels other than (C{sub 2}H{sub 5}OH) ⋅ H{sup +} and CH{sub 2}O ⋅ (C{sub 2}H{sub 5}OH)H{sup +} have also been opened, which consume some dimer cations. The present report provides a clear description of the photoionization and dissociation processes of the ethanol dimer in the range of the photon energy 12-15 eV.

  14. High Temperature Chemical Kinetic Combustion Modeling of Lightly Methylated Alkanes

    SciTech Connect (OSTI)

    Sarathy, S M; Westbrook, C K; Pitz, W J; Mehl, M

    2011-03-01

    Conventional petroleum jet and diesel fuels, as well as alternative Fischer-Tropsch (FT) fuels and hydrotreated renewable jet (HRJ) fuels, contain high molecular weight lightly branched alkanes (i.e., methylalkanes) and straight chain alkanes (n-alkanes). Improving the combustion of these fuels in practical applications requires a fundamental understanding of large hydrocarbon combustion chemistry. This research project presents a detailed high temperature chemical kinetic mechanism for n-octane and three lightly branched isomers octane (i.e., 2-methylheptane, 3-methylheptane, and 2,5-dimethylhexane). The model is validated against experimental data from a variety of fundamental combustion devices. This new model is used to show how the location and number of methyl branches affects fuel reactivity including laminar flame speed and species formation.

  15. Methyl-CpG island-associated genome signature tags

    DOE Patents [OSTI]

    Dunn, John J

    2014-05-20

    Disclosed is a method for analyzing the organismic complexity of a sample through analysis of the nucleic acid in the sample. In the disclosed method, through a series of steps, including digestion with a type II restriction enzyme, ligation of capture adapters and linkers and digestion with a type IIS restriction enzyme, genome signature tags are produced. The sequences of a statistically significant number of the signature tags are determined and the sequences are used to identify and quantify the organisms in the sample. Various embodiments of the invention described herein include methods for using single point genome signature tags to analyze the related families present in a sample, methods for analyzing sequences associated with hyper- and hypo-methylated CpG islands, methods for visualizing organismic complexity change in a sampling location over time and methods for generating the genome signature tag profile of a sample of fragmented DNA.

  16. Synthesis of dimethyl ether and alternative fuels in the liquid phase from coal-derived synthesis gas

    SciTech Connect (OSTI)

    Bhatt, B.L.

    1992-09-01

    As part of the DOE-sponsored contract for the Synthesis of Dimethyl Ether (DME) and Alternative Fuels in the Liquid Phase from Coal- Derived Syngas, the single-step, slurry phase DME synthesis process was developed. The development involved screening of catalyst systems, process variable studies, and catalyst life studies in two 300 ml stirred autoclaves. As a spin-off of the Liquid Phase Methanol (LPMEOH*) process, the new process significantly improves the syngas conversion efficiency of the LPMEOH process. This improvement can be achieved by replacing a portion of methanol catalyst with a dehydration catalyst in the reactor, resulting in the product methanol being converted to DME, thus avoiding the thermodynamic equilibrium constraint of the methanol reaction. Overall, this increases syngas conversion per-pass. The selectivity and productivity of DME and methanol are affected by the catalyst system employed as well as operating conditions. A preferred catalyst system, consisting of a physical mixture of a methanol catalyst and a gamma alumina, was identified. An improvement of about 50% in methanol equivalent productivity was achieved compared to the LPMEOH process. Results from the process variable study indicate that higher pressure and CO[sub 2] removal benefit the process significantly. Limited life studies performed on the preferred catalyst system suggest somewhat higher than expected deactivation rate for the methanol catalyst. Several DME/methanol mixtures were measured for their key properties as transportation fuels. With small amounts of DME added, significant improvements in both flash points and Reid Vapor Pressure (RVP) were observed over the corresponding values of methanol alone.

  17. Auto-ignition during instationary jet evolution of dimethyl ether (DME) in a high-pressure atmosphere

    SciTech Connect (OSTI)

    Fast, G.; Kuhn, D.; Class, A.G.; Maas, U.

    2009-01-15

    The auto-ignition process during transient injection of gaseous dimethyl ether (DME) in a constant high-pressure atmosphere is studied experimentally by laser-optical methods and compared with numerical calculations. With different non-intrusive measurement techniques jet properties and auto-ignition are investigated at high temporal and spatial resolution. The open jet penetrates a constant pressure oxidative atmosphere of up to 4 MPa. During the transient evolution, the fuel jet entrains air at up to 720 K. The subsequent auto-ignition of the ignitable part of the jet occurs simultaneously over a wide spatial extension. The ignition delay times are not affected by variation of the nozzle exit velocity. Thus, the low-temperature oxidation is slow compared with the shorter time scales of mixing, so that chemical kinetics is dominating the process. The typical two-stage ignition is resolved optically with high-speed shadowgraphy at a sampling rate of 10 kHz. The 2D fields of jet velocity and transient mixture fraction are measured phase-coupled with Particle Image Velocimetry (PIV) and Tracer Laser Induced Fluorescence (LIF) during the time-frame of ignition. The instationary Probability Density Functions (PDF) of mixture fraction are described very well by Beta functions within the complete area of the open jet. Additional 1D flamelet simulations of the auto-ignition process are computed with a detailed reaction mechanism for DME [S. Fischer, F. Dryer, H. Curran, Int. J. Chem. Kinet. 32 (12) (2000) 713-740; H. Curran, S. Fischer, F. Dryer, Int. J. Chem. Kinet. 32 (12) (2000) 741-759]. Calculated ignition delay times are in very good agreement with the measured mean ignition delay times of 3 ms. Supplemental flamelet simulations address the influence of DME and air temperature, pressure and strain. Underneath a critical strain rate the air temperature is identified to be the most sensitive factor on ignition delay time. (author)

  18. Global prevalence and distribution of genes and microorganisms involved in mercury methylation

    SciTech Connect (OSTI)

    Podar, Mircea; Gilmour, C C; Brandt, Craig C; Bullock, Allyson L; Brown, Steven D; Crable, Bryan R; Palumbo, Anthony Vito; Somenahally, Anil C; Elias, Dwayne A

    2015-01-01

    Mercury methylation produces the neurotoxic, highly bioaccumulative methylmercury (MeHg). Recent identification of the methylation genes (hgcAB) provides the foundation for broadly evaluating microbial Hg-methylation potential in nature without making explicit rate measurements. We queried hgcAB diversity and distribution in all available microbial metagenomes, encompassing most environments. The genes were found in nearly all anaerobic, but not in aerobic, environments including oxygenated layers of the open ocean. Critically, hgcAB was effectively absent in ~1500 human microbiomes, suggesting a low risk of endogenous MeHg production. New potential methylation habitats were identified, including invertebrate guts, thawing permafrost, coastal dead zones , soils, sediments, and extreme environments, suggesting multiple routes for MeHg entry into food webs. Several new taxonomic groups potentially capable of Hg-methylation emerged, including lineages having no cultured representatives. We begin to address long-standing evolutionary questions about Hg-methylation and ancient carbon fixation mechanisms while generating a new global view of Hg-methylation potential.

  19. Global prevalence and distribution of genes and microorganisms involved in mercury methylation

    SciTech Connect (OSTI)

    Podar, Mircea; Gilmour, C. C.; Brandt, Craig C.; Soren, Allyson; Brown, Steven D.; Crable, Bryan R.; Palumbo, Anthony Vito; Somenahally, Anil C.; Elias, Dwayne A.

    2015-01-01

    Mercury methylation produces the neurotoxic, highly bioaccumulative methylmercury (MeHg). Recent identification of the methylation genes (hgcAB) provides the foundation for broadly evaluating microbial Hg-methylation potential in nature without making explicit rate measurements. We first queried hgcAB diversity and distribution in all available microbial metagenomes, encompassing most environments. The genes were found in nearly all anaerobic, but not in aerobic, environments including oxygenated layers of the open ocean. Critically, hgcAB was effectively absent in ~1500 human microbiomes, suggesting a low risk of endogenous MeHg production. New potential methylation habitats were identified, including invertebrate guts, thawing permafrost, coastal dead zones, soils, sediments, and extreme environments, suggesting multiple routes for MeHg entry into food webs. Several new taxonomic groups potentially capable of Hg-methylation emerged, including lineages having no cultured representatives. We then begin to address long-standing evolutionary questions about Hg-methylation and ancient carbon fixation mechanisms while generating a new global view of Hg-methylation potential.

  20. SYNTHESIS OF METHYL METHACRYLATE FROM COAL-DERIVED SYNGAS

    SciTech Connect (OSTI)

    Makarand R. Gogate; James J. Spivey; Joseph R. Zoeller; Richard D. Colberg; Gerald N. Choi

    1999-07-19

    Research Triangle Institute (RTI), Eastman Chemical Company, and Bechtel collectively are developing a novel three-step process for the synthesis of methyl methacrylate (MMA) from coal-derived syngas that consists of the steps of synthesis of a propionate, its condensation with formaldehyde to form methacrylic acid (MAA), and esterification of MAA with methanol to produce MMA. The research team has completed the research on the three-step methanol-based route to MMA. Under an extension to the original contract, we are currently evaluating a new DME-based process for MMA. The key research need for DME route is to develop catalysts for DME partial oxidation reactions and DME condensation reactions. During the April-June quarter(04-06/99) the first in-situ formaldehyde generation from DME and condensation with methyl propionate is demonstrated and the results are summarized. The supported niobium catalyst shows better condensation activity, but supported tungsten catalyst has higher formaldehyde selectivity. The project team has also completed a 200-hour long term test of PA-HCHO condensation over 30% Nb{sub 2}O{sub 5}/SiO{sub 2}. Three activity cycles and two regeneration cycles were carried out. 30% Nb{sub 2}O{sub 5}/SiO{sub 2} showed similar MAA yields as 10% Nb{sub 2}O{sub 5}/SiO{sub 2} at 300 C. However, the deactivation appears to be slower with 30% Nb{sub 2}O{sub 5}/SiO{sub 2} than 10% Nb{sub 2}O{sub 5}/SiO{sub 2}. An detailed economic analysis of PA-HCHO condensation process for a 250 million lb/yr MMA plant is currently studied by Bechtel. Using the Amoco data-based azeotropic distillation model as the basis, an ASPEN flow sheet model was constructed to simulate the formaldehyde and propionic acid condensation processing section based on RTI's design data. The RTI MAA effluent azeotropic distillation column was found to be much more difficult to converge. The presence of non-condensible gases along with the byproduct DEK (both of which were not presented in Amoco's data) appear to the culprits.

  1. Thermochemistry of C-O, (CO)-O, and (CO)-C bond breaking in fatty acid methyl esters

    SciTech Connect (OSTI)

    Osmont, Antoine; Yahyaoui, Mohammed; Catoire, Laurent; Goekalp, Iskender; Swihart, Mark T.

    2008-10-15

    Density functional theory quantum chemical calculations corrected with empirical atomic increments have been used to examine C-O, (CO)-O, and (CO)-C bond scission enthalpies in gas-phase fatty acid methyl esters (FAMEs) present in biodiesel derived from rapeseed oil methyl ester and soybean oil methyl ester. Mechanistic information, currently not available elsewhere for these large species, is obtained based on thermochemical considerations and compared to thermochemical considerations reported for methyl butanoate, a small methyl ester sometimes used as a model for FAMEs. These results are compared to previously reported C-C and C-H bond scissions in these FAMEs, derived using this same protocol. (author)

  2. Synthesis of Methyl Methacrylate from Coal-Derived Syngas

    SciTech Connect (OSTI)

    Gerald N. Choi; James J. Spivey; Jospeh R. Zoeller; Makarand R. Gogate; Richard D. Colberg; Samuel S. Tam

    1998-04-17

    Research Triangle Institute (RTI), Eastman Chemical Company, and Bechtel collectively are developing a novel three-step process for the synthesis of methyl methacrylate (MMA) from coal-derived syngas that consists of the steps of synthesis of a propionate, its condensation with formaldehyde to form methacrylic acid (MAA), and esterification of MAA with methanol to produce MMA. RTI has completed the research on the three-step methanol-based route to MMA. Under an extension to the original contract, RTI is currently evaluating a new DME-based process for MMA. The key research need for DME route is to develop catalysts for DME partial oxidation reactions and DME condensation reactions. Over the last month, RTI has finalized the design of a fixed-bed microreactor system for DME partial oxidation reactions. RTI incorporated some design changes to the feed blending system, so as to be able to blend varying proportions of DME and oxygen. RTI has also examined the flammability limits of DME-air mixtures. Since the lower flammability limit of DME in air is 3.6 volume percent, RTI will use a nominal feed composition of 1.6 percent in air, which is less than half the lower explosion limit for DME-air mixtures. This nominal feed composition is thus considered operationally safe, for DME partial oxidation reactions. RTI is also currently developing an analytical system for DME partial oxidation reaction system.

  3. Altered cardiovascular reactivity and osmoregulation during hyperosmotic stress in adult rats developmentally exposed to polybrominated diphenyl ethers (PBDEs)

    SciTech Connect (OSTI)

    Shah, Ashini; Coburn, Cary G.; Watson-Siriboe, Abena; Whitley, Rebecca; Shahidzadeh, Anoush; Gillard, Elizabeth R.; Nichol, Robert; Leon-Olea, Martha; Gaertner, Mark; Kodavanti, Prasada Rao S.

    2011-10-15

    Polybrominated diphenyl ethers (PBDEs) and the structurally similar chemicals polychlorinated biphenyls (PCBs) disrupt the function of multiple endocrine systems. PCBs and PBDEs disrupt the secretion of vasopressin (VP) from the hypothalamus during osmotic activation. Since the peripheral and central vasopressinergic axes are critical for osmotic and cardiovascular regulation, we examined whether perinatal PBDE exposure could impact these functions during physiological activation. Rats were perinatally dosed with a commercial PBDE mixture, DE-71. Dams were given 0 (corn oil control), 1.7 (low dose) or 30.6 mg/kg/day (high dose) in corn oil from gestational day (GD) 6 through postnatal day (PND) 21 by oral gavage. In the male offspring exposed to high dose PBDE plasma thyroxine and triiodothyronine levels were reduced at PND 21 and recovered to control levels by PND 60 when thyroid stimulating hormone levels were elevated. At 14-18 months of age, cardiovascular responses were measured in four groups of rats: Normal (Oil, normosmotic condition), Hyper (Oil, hyperosmotic stress), Hyper PBDE low (1.7 mg/kg/day DE-71 perinatally, hyperosmotic stress), and Hyper PBDE high (30.6 mg/kg/day DE-71 perinatally, hyperosmotic stress). Systolic blood pressure (BP), diastolic BP, and heart rate (HR) were determined using tail cuff sphygmomanometry and normalized to pretreatment values (baseline) measured under basal conditions. Hyperosmotic treatment yielded significant changes in systolic BP in PBDE exposed rats only. Hyper PBDE low and high dose rats showed 36.1 and 64.7% greater systolic BP responses at 3 h post hyperosmotic injection relative to pretreatment baseline, respectively. No treatment effects were measured for diastolic BP and HR. Hyper and Hyper PBDE rats showed increased mean plasma osmolality values by 45 min after injection relative to normosmotic controls. In contrast to Hyper rats, Hyper PBDE (high) rats showed a further increase in mean plasma osmolality at 3 h (358.3 {+-} 12.4 mOsm/L) relative to 45 min post hyperosmotic injection (325.1 {+-} 11.4 mOsm/L). Impaired osmoregulation in PBDE-treated animals could not be attributed to decreased levels of plasma vasopressin. Our findings suggest that developmental exposure to PBDEs may disrupt cardiovascular reactivity and osmoregulatory responses to physiological activation in late adulthood. - Highlights: > We examined whether PBDE exposure could impact osmotic and cardiovascular regulation. > Hyperosmotic treatment yielded significant changes in systolic BP in PBDE exposed rats only. > PBDEs may disrupt cardiovascular and osmoregulatory responses to physiological activation.

  4. Synthesis of methanol and dimethyl ether from syngas over Pd/ZnO/Al2O3 catalysts

    SciTech Connect (OSTI)

    Lebarbier, Vanessa M.; Dagle, Robert A.; Kovarik, Libor; Lizarazo-Adarme, Jair A.; King, David L.; Palo, Daniel R.

    2012-01-01

    A Pd/ZnO/Al2O3 catalyst was developed for the synthesis of methanol and dimethyl ether (DME) from syngas. Studied were temperatures of operation ranging from 250C to 380C. High temperatures (e.g. 380C) are necessary when combining methanol and DME synthesis with a methanol to gasoline (MTG) process in a single reactor bed. A commercial Cu/ZnO/Al2O3 catalyst, utilized industrially for the synthesis of methanol at 220-280C, suffers from a rapid deactivation when the reaction is conducted at high temperature (>320C). On the contrary, a Pd/ZnO/Al2O3 catalyst was found to be highly stable for methanol and DME synthesis at 380C. The Pd/ZnO/Al2O3 catalyst was thus further investigated for methanol and DME synthesis at P=34-69 bars, T= 250-380C, GHSV= 5 000-18 000 h-1, and molar feeds H2/CO= 1, 2, and 3. Selectivity to DME increased with decreasing operating temperature, and increasing operating pressure. Increased GHSVs and H2/CO syngas feed ratios also enhanced DME selectivity. Undesirable CH4 formation was observed, however, can be minimized through choice of process conditions and by catalyst design. By studying the effect of the Pd loading and the Pd:Zn molar ratio the formulation of the Pd/ZnO/Al2O3 catalyst was optimized. A catalyst with 5% Pd and a Pd:Zn molar ratio of 0.25:1 has been identified as the preferred catalyst. Results indicate that PdZn particles are more active than Pd particles for the synthesis of methanol and less active for CH4 formation. A correlation between DME selectivity and the concentration of acid sites of the catalysts has been established. Hence, two types of sites are required for the direct conversion of syngas to DME: 1) PdZn particles are active for the synthesis of methanol from syngas, and 2) acid sites which are active for the conversion of methanol to DME. Additionally, CO2 formation was problematic as PdZn was found to be active for the water-gas-shift (WGS) reaction, under all the conditions evaluated.

  5. Optimized End-Stacking Provides Specificity of N-Methyl Mesoporphyrin...

    Office of Scientific and Technical Information (OSTI)

    Optimized End-Stacking Provides Specificity of N-Methyl Mesoporphyrin IX for Human Telomeric G-Quadruplex DNA Citation Details In-Document Search Title: Optimized End-Stacking ...

  6. The Structural Basis for Tight Control of PP2A Methylation and...

    Office of Scientific and Technical Information (OSTI)

    The Structural Basis for Tight Control of PP2A Methylation and Function by LCMT-1 Citation Details In-Document Search Title: The Structural Basis for Tight Control of PP2A ...

  7. Effects of nickel, chromate, and arsenite on histone 3 lysine methylation

    Office of Scientific and Technical Information (OSTI)

    (Journal Article) | SciTech Connect Effects of nickel, chromate, and arsenite on histone 3 lysine methylation Citation Details In-Document Search Title: Effects of nickel, chromate, and arsenite on histone 3 lysine methylation Occupational exposure to nickel (Ni), chromium (Cr), and arsenic (As) containing compounds has been associated with lung cancer and other adverse health effects. Their carcinogenic properties may be attributable in part, to activation and/or repression of gene

  8. Modulation of histone methylation and MLH1 gene silencing by hexavalent

    Office of Scientific and Technical Information (OSTI)

    chromium (Journal Article) | SciTech Connect Modulation of histone methylation and MLH1 gene silencing by hexavalent chromium Citation Details In-Document Search Title: Modulation of histone methylation and MLH1 gene silencing by hexavalent chromium Hexavalent chromium [Cr(VI)] is a mutagen and carcinogen, and occupational exposure can lead to lung cancers and other adverse health effects. Genetic changes resulting from DNA damage have been proposed as an important mechanism that mediates

  9. Optimized End-Stacking Provides Specificity of N-Methyl Mesoporphyrin IX

    Office of Scientific and Technical Information (OSTI)

    for Human Telomeric G-Quadruplex DNA (Journal Article) | SciTech Connect Optimized End-Stacking Provides Specificity of N-Methyl Mesoporphyrin IX for Human Telomeric G-Quadruplex DNA Citation Details In-Document Search Title: Optimized End-Stacking Provides Specificity of N-Methyl Mesoporphyrin IX for Human Telomeric G-Quadruplex DNA Authors: Nicoludis, John M. ; Miller, Stephen T. ; Jeffrey, Philip D. ; Barrett, Steven P. ; Rablen, Paul R. ; Lawton, Thomas J. ; Yatsunyk, Liliya A. [1] ;

  10. Radio-methyl vorozole and methods for making and using the same

    DOE Patents [OSTI]

    Kim, Sung Won; Biegon, Anat; Fowler, Joanna S.

    2014-08-05

    Radiotracer vorozole compounds for in vivo and in vitro assaying, studying and imaging cytochrome P450 aromatase enzymes in humans, animals, and tissues and methods for making and using the same are provided. [N-radio-methyl] vorozole substantially separated from an N-3 radio-methyl isomer of vorozole is provided. Separation is accomplished through use of chromatography resins providing multiple mechanisms of selectivity.

  11. Radio-methyl vorozole and methods for making and using the same

    DOE Patents [OSTI]

    Kim, Sung Won; Biegon, Anat; Fowler, Joanna S.

    2014-08-12

    Radiotracer vorozole compounds for in vivo and in vitro assaying, studying and imaging cytochrome P450 aromatase enzymes in humans, animals, and tissues and methods for making and using the same are provided. [N-radio-methyl] vorozole substantially separated from an N-3 radio-methyl isomer of vorozole is provided. Separation is accomplished through use of chromatography resins providing multiple mechanisms of selectivity.

  12. Determination of Total Lipids as Fatty Acid Methyl Esters (FAME) by in situ

    Office of Scientific and Technical Information (OSTI)

    Transesterification: Laboratory Analytical Procedure (LAP) (Technical Report) | SciTech Connect Determination of Total Lipids as Fatty Acid Methyl Esters (FAME) by in situ Transesterification: Laboratory Analytical Procedure (LAP) Citation Details In-Document Search Title: Determination of Total Lipids as Fatty Acid Methyl Esters (FAME) by in situ Transesterification: Laboratory Analytical Procedure (LAP) This procedure is based on a whole biomass transesterification of lipids to fatty acid

  13. Low cost hydrogen/novel membrane technology for hydrogen separation from synthesis gas, Phase 1. [Poly(etherimide) and poly(ether-ester-amide) membranes

    SciTech Connect (OSTI)

    Not Available

    1986-01-01

    During the last quarter several high performance membranes for the separation of hydrogen from nitrogen, carbon monoxide, hydrogen sulfide and carbon dioxide. The heat-resistant resin poly(etherimide) has been selected as the polymer with the most outstanding properties for the separation of hydrogen from nitrogen and carbon monoxide. Flat sheet and hollow fiber poly(etherimide) membranes have been prepared and evaluated with pure gases and gas mixtures at elevated pressures and temperatures. Multilayer composite poly(ether-ester-amide) membranes were also developed. These membranes are useful for the separation of carbon dioxide and hydrogen sulfide hydrogen. They have very high selectivities and extremely high normalized carbon dioxide and hydrogen sulfide fluxes. Separation of carbon dioxide/hydrogen streams is a key problem in hydrogen production from coal. The development of the two membranes now gives us two approaches to separate these gas streams, depending on the stream's composition. If the stream contains small quantities of hydrogen, the hydrogen- permeable poly(etherimide) membrane would be used to produce a hydrogen-enriched permeate. If the stream contains small quantities of carbon dioxide or hydrogen sulfide, the poly(ether-ester-amide) membrane would be used to produce a carbon dioxide/hydrogen sulfide-free, hydrogen-enriched residue stream. 6 fig., 4 tabs.

  14. Experimental and Kinetic Modeling Study of Extinction and Ignition of Methyl Decanoate in Laminar Nonpremixed Flows

    SciTech Connect (OSTI)

    Seshadri, K; Lu, T; Herbinet, O; Humer, S; Niemann, U; Pitz, W J; Law, C K

    2008-01-09

    Methyl decanoate is a large methyl ester that can be used as a surrogate for biodiesel. In this experimental and computational study, the combustion of methyl decanoate is investigated in nonpremixed, nonuniform flows. Experiments are performed employing the counterflow configuration with a fuel stream made up of vaporized methyl decanoate and nitrogen, and an oxidizer stream of air. The mass fraction of fuel in the fuel stream is measured as a function of the strain rate at extinction, and critical conditions of ignition are measured in terms of the temperature of the oxidizer stream as a function of the strain rate. It is not possible to use a fully detailed mechanism for methyl decanoate to simulate the counterflow flames because the number of species and reactions is too large to employ with current flame codes and computer resources. Therefore a skeletal mechanism was deduced from a detailed mechanism of 8555 elementary reactions and 3036 species using 'directed relation graph' method. This skeletal mechanism has only 713 elementary reactions and 125 species. Critical conditions of ignition were calculated using this skeletal mechanism and are found to agree well with experimental data. The predicted strain rate at extinction is found to be lower than the measurements. In general, the methyl decanoate mechanism provides a realistic kinetic tool for simulation of biodiesel fuels.

  15. Synthesis of Methyl Methacrylate From Coal-Derived Syngas

    SciTech Connect (OSTI)

    Ben W.-L. Jang; Gerald N. Choi; James J. Spivey; Jospeh R. Zoeller; Richard D. Colberg; Samuel S. Tam

    1998-07-27

    Research Triangle Institute (RTI), Eastman Chemical Company, and Bechtel collectively are developing a novel three-step process for the synthesis of methyl methacrylate (MMA) from coal-derived syngas that consists of the steps of synthesis of a propionate, its condensation with formaldehyde to form methacrylic acid (MAA), and esterification of MAA with methanol to produce MMA. RTI has completed the research on the three-step methanol-based route to MMA. Under an extension to the original contract, RTI is currently evaluating a new DME-based process for MMA. The key research need for DME route is to develop catalysts for DME partial oxidation reactions and DME condensation reactions. Over the last quarter(April-June, 1998), RTI has modified the reactor system including a new preheater and new temperature settings for the preheater. Continuous condensation of formaldehyde with propionic acid were carried out over 10% Nb O /SiO at 300°C without 2 5 2 interruption. Five activity and four regeneration cycles have been completed without plugging or material balance problems. The results show that 10% Nb O /SiO deactivates slowly with time 2 5 2 but can be regenerated, at least four times, to 100% of its original activity with 2% O in nitrogen 2 at 400°C. The cycles continue with consistent 90-95% of carbon balance. The reaction is scheduled to complete with 6 activity cycles and 5 regenerations. Used catalysts will be analyzed with TGA and XPS to determine bulk and surface coke content and coke properties. RTI will start the investigation of effects of propionic acid/formaldehyde ratio on reaction activity and product selectivity over 20% Nb O /SiO catalysts.

  16. SYNTHESIS OF METHYL METHACRYLATE FROM COAL-DERIVED SYNGAS

    SciTech Connect (OSTI)

    BEN W.-L. JANG; GERALD N. CHOI; JAMES J. SPIVEY; JOSPEH R. ZOELLER; RICHARD D. COLBERG

    1998-10-20

    Research Triangle Institute (RTI), Eastman Chemical Company, and Bechtel collectively are developing a novel three-step process for the synthesis of methyl methacrylate (MMA) from coal-derived syngas that consists of the steps of synthesis of a propionate, its condensation with formaldehyde to form methacrylic acid (MAA), and esterification of MAA with methanol to produce MMA. RTI has completed the research on the three-step methanol-based route to MMA. Under an extension to the original contract, RTI is currently evaluating a new DME-based process for MMA. The key research need for DME route is to develop catalysts for DME partial oxidation reactions and DME condensation reactions. Over the last quarter (July-September, 1998), the project team has completed the continuous condensation of formaldehyde with propionic acid over 10% Nb{sub 2}O{sub 5}/SiO{sub 2} at 300 C. Six activity and five regeneration cycles have been completed. The results show that 10% Nb{sub 2}O{sub 5}/SiO{sub 2} deactivates slowly with time but can be regenerated to its original activity with 2% O{sub 2} in nitrogen over night at 400 C. We have investigated the effects of regeneration, propionic acid/formaldehyde ratio (PA/HCHO = 4.5/1 to 1.5/1) and reaction temperature(280-300 C) on reaction activity and product selectivity over 20% Nb{sub 2}O{sub 5}/SiO{sub 2} catalysts. The regeneration effect on 20% Nb{sub 2}O{sub 5}/SiO{sub 2} is similar to the effect on 10% Nb{sub 2}O{sub 5}/SiO{sub 2}. The regeneration can bring the deactivated catalyst to its original activity. However, the selectivity to MAA decreases with regeneration while the selectivity to DEK and CO{sub 2} increases. When PA/HCHO ratio is decreased from 4.5/1 to 2.25/1 then to 1.5/1 at 300 C the MAA yield decreases but the MAA selectivity first increases then decreases. Decreasing the reaction temperature from 300 C to 280 C decreases the MAA yield from 39.5% to 30.7% but increases the MAA selectivity from 73.7% to 82.2%. The results indicate that both temperature and PA/HCHO ratio are important parameters to optimize the economic of the condensation between propionic acid and formaldehyde.

  17. Synthesis of dimethyl ether and alternative fuels in the liquid phase from coal-derived syngas; Quarterly technical progress report No. 3, 1 July--30 September 1990

    SciTech Connect (OSTI)

    1991-01-25

    Contract objectives are: development of a one-step liquid phase dimethyl ether/methanol process; and investigation of the potential of liquid phase synthesis of alternative fuels from coal-derived synthesis gas. Definition of Preferred Catalyst System was completed after several commercial methanol catalysts and dehydration catalysts were tested. BASF S3-86 and Catapal gamma alumina is the preferred catalyst system of choice. Process Variable Scans on the Preferred Catalyst System was started with Shell gas. Data were obtained at various pressures (750 to 1400 psig), temperatures (250 to 280{degrees}C), and space velocities (5000 to 9000 sl/kg-hr). Increase in system pressure seems to have a very significant benefit to both DME and methanol formation. Both Texaco and Shell gases were evaluated. A ``stoichiometric`` feed composition (50% CO, 50% H{sub 2}) that yields maximum DME productivity at equilibrium was evaluated with a fresh batch of the optimum catalyst system. Productivities with the ``stoichiometric`` gas were much higher compared to Shell or Texaco gas. Following that test, Dow gas was evaluated (41% CO, 41% H{sub 2}, 16% CO{sub 2} and 2% N{sub 2}) using the same catalyst to study the effect of CO{sub 2}. Three DME/MEOH (1--4% DME) mixtures were evaluated by SWRI for their fuel properties. Results indicate that, with small amounts of DME added, significant improvements in both flash point and RVP are possible over the properties of LaPorte MEOH. the slurry-phase dehydration of alcohols to ethers was investigated by feeding 10 mol% mixed alcohols in N{sub 2} over an alumina catalyst suspended in mineral oil. Two alcohol mixture compositions were chosen for this study. One mixture contained methanol, ethanol, and 1-propanol in proportions representative of those in IFP Substifuel, while the other mixture contained methanol, ethanol, and isobutanol in proportions representative of those in Lurgi Octamix. 21 figs., 13 tabs.

  18. Synthesis Of [2h, 13c] And [2h3, 13c]Methyl Aryl Sulfides

    DOE Patents [OSTI]

    Martinez, Rodolfo A.; Alvarez, Marc A.; Silks, III, Louis A.; Unkefer, Clifford J.

    2004-03-30

    The present invention is directed to labeled compounds, [.sup.2 H.sub.1, .sup.13 C], [.sup.2 H.sub.2, .sup.13 C] and [.sup.2 H.sub.3, .sup.13 C]methyl aryl sulfides wherein the .sup.13 C methyl group attached to the sulfur of the sulfide includes exactly one, two or three deuterium atoms and the aryl group is selected from the group consisting of 1-naphthyl, substituted 1-naphthyl, 2-naphthyl, substituted 2-naphthyl, and phenyl groups with the structure ##STR1## wherein R.sub.1, R.sub.2, R.sub.3, R.sub.4, and R.sub.5 are each independently, hydrogen, a C.sub.1 -C.sub.4 lower alkyl, a halogen, an amino group from the group consisting of NH.sub.2, NHR and NRR' where R and R' are each a C.sub.1 -C.sub.4 lower alkyl, a phenyl, or an alkoxy group. The present invention is also directed to processes of preparing [.sup.2 H.sub.1, .sup.13 C], [.sup.2 H.sub.2,.sup.13 C] and [.sup.2 H.sub.3, .sup.13 C]methyl aryl sulfides wherein the .sup.13 C methyl group attached to the sulfur of the sulfide includes exactly one, two or three deuterium atoms. The present invention is also directed to the labeled compounds of [.sup.2 H.sub.1, .sup.13 C]methyl iodide and [.sup.2 H.sub.2, .sup.13 C]methyl iodide.

  19. Polylactide?Poly(6-methyl-[espilson]-caprolactone)?Polylactide Thermoplastic Elastomers

    SciTech Connect (OSTI)

    Martello, Mark T.; Hillmyer, Marc A.

    2012-11-14

    Amorphous ABA type block aliphatic polyesters can be useful as degradable and biorenewable thermoplastic elastomers. These materials can be prepared by sequential ring-opening transesterification polymerization (ROTEP) reactions and can exhibit a range of physical properties and morphologies. In this work a set of amorphous polylactide-poly(6-methyl-{epsilon}-caprolactone)-polylactide aliphatic polyester ABA triblock copolymers were prepared by consecutive controlled ring-opening polymerizations. Ring-opening polymerization of neat 6-methyl-{epsilon}-caprolactone in the presence of 1,4-benzenedimethanol and tin(II) octoate afforded {alpha},{omega}-hydroxyl-terminated poly(6-methyl-{epsilon}-caprolactone). High conversions of 6-methyl-{epsilon}-caprolactone (>96%) afforded polymers with molar masses ranging from 12 to 98 kg mol{sup -1}, depending on monomer-to-initiator ratios, polymers with narrow, monomodal molecular weight distributions. An array of polylactide-poly(6-methyl-{epsilon}-caprolactone)-polylactide triblock copolymers with controlled molecular weights and narrow molecular weight distributions were synthesized using the telechelic poly(6-methyl-{epsilon}-caprolactone) samples as macroinitiators for the ring-opening polymerization of D,L-lactide. The morphological, thermal, and mechanical behaviors of these materials were explored. Several triblocks adopted well-ordered microphase-separated morphologies, and both hexagonally packed cylindrical and lamellar structures were observed. The Flory-Huggins interaction parameter was determined, x(T) = 61.2 T{sup -1} - 0.1, based on the order-to-disorder transition temperatures of two symmetric triblocks using the calculated mean field theory result. The elastomeric mechanical behavior of two high molecular weight triblocks was characterized by tensile and elastic recovery experiments.

  20. The role of DNA methylation in catechol-enhanced erythroid differentiation of K562 cells

    SciTech Connect (OSTI)

    Li, Xiao-Fei; Wu, Xiao-Rong; Xue, Ming; Wang, Yan; Wang, Jie; Li, Yang; Suriguga,; Zhang, Guang-Yao; Yi, Zong-Chun

    2012-11-15

    Catechol is one of phenolic metabolites of benzene in vivo. Catechol is also widely used in pharmaceutical and chemical industries. In addition, fruits, vegetables and cigarette smoke also contain catechol. Our precious study showed that several benzene metabolites (phenol, hydroquinone, and 1,2,4-benzenetriol) inhibited erythroid differentiation of K562 cells. In present study, the effect of catechol on erythroid differentiation of K562 cells was investigated. Moreover, to address the role of DNA methylation in catechol-induced effect on erythroid differentiation in K562 cells, methylation levels of erythroid-specific genes were analyzed by Quantitative MassARRAY methylation analysis platform. Benzidine staining showed that exposure to catechol enhanced hemin-induced hemoglobin accumulation in K562 cells in concentration- and time-dependent manners. The mRNA expression of erythroid specific genes, including ?-globin, ?-globin, ?-globin, erythroid 5-aminolevulinate synthase, erythroid porphobilinogen deaminase, and transcription factor GATA-1 genes, showed a significant concentration-dependent increase in catechol-treated K562 cells. The exposure to catechol caused a decrease in DNA methylation levels at a few CpG sites in some erythroid specific genes including ?-globin, ?-globin and erythroid porphobilinogen deaminase genes. These results indicated that catechol improved erythroid differentiation potency of K562 cells at least partly via up-regulating transcription of some erythroid related genes, and suggested that inhibition of DNA methylation might be involved in up-regulated expression of some erythroid related genes. -- Highlights: ? Catechol enhanced hemin-induced hemoglobin accumulation. ? Exposure to catechol resulted in up-regulated expression of erythroid genes. ? Catechol reduced methylation levels at some CpG sites in erythroid genes.

  1. Crystal structure of 1-methyl-3-([2,2-dimethyl-4,6-dioxo-1,3-dioxane-5-ylidene]methyl)urea

    SciTech Connect (OSTI)

    Habibi, A. Ghorbani, H. S.; Bruno, G.; Rudbari, H. A.; Valizadeh, Y.

    2013-12-15

    The crystal structure of 1-Methyl-3-([2,2-dimethyl-4,6-dioxo-1,3-dioxane-5-ylidene]methyl)urea (C{sub 9}H{sub 12}N{sub 2}O{sub 5}) has been determined by single crystal X-ray diffraction analysis. The crystals are monoclinic, a = 5.3179(2), b = 18.6394(6), c =10.8124(3) , ? = 100.015(2), Z = 4, sp. gr. P2{sub 1}/c, R = 0.0381 for 2537 reflections with I > 2?(I). Except for C(CH{sub 3}){sub 2} group, the molecule is planar. The structure is stabilized by inter- and intramolecular N-H...O hydrogen bonds and weak C-H...O interactions.

  2. Acute environmental toxicity and persistence of methyl salicylate: A chemical agent simulant. Final report

    SciTech Connect (OSTI)

    Cataldo, D.A.; Ligotke, M.W.; Harvey, S.D.; Fellows, R.J.; Li, S.W.

    1994-06-01

    The interactions of methyl salicylate with plant foliage and soils were assessed using aerosol/vapor exposure methods. Measurements of deposition velocity and residence times for soils and foliar surfaces are reported. Severe plant contact toxicity was observed at foliar mass-loading levels above 4 {mu}g/cm{sup 2} leaf; however, recovery was noted after four to fourteen days. Methyl salicylate has a short-term effect on soil dehydrogenase activity, but not phosphatase activity. Results of the earthworm bioassay indicated only minimal effects on survival.

  3. Hydrogen-terminated silicon nanowire photocatalysis: Benzene oxidation and methyl red decomposition

    SciTech Connect (OSTI)

    Lian, Suoyuan; School of Chemical Engineering and Materials, Dalian Polytechnic University, Dalian 116034 ; Tsang, Chi Him A.; Centre of Super Diamond and Advanced Films, City University of Hong Kong, Hong Kong ; Kang, Zhenhui; Liu, Yang; Wong, Ningbew; Lee, Shuit-Tong; Centre of Super Diamond and Advanced Films, City University of Hong Kong, Hong Kong

    2011-12-15

    Graphical abstract: H-SiNWs can catalyze hydroxylation of benzene and degradation of methyl red under visible light irradiation. Highlights: Black-Right-Pointing-Pointer Hydrogen-terminated silicon nanowires were active photocatalyst in the hydroxylation of benzene under light. Black-Right-Pointing-Pointer Hydrogen-terminated silicon nanowires were also effective in the decomposition of methyl red dye. Black-Right-Pointing-Pointer The Si/SiO{sub x} core-shell structure is the main reason of the obtained high selectivity during the hydroxylation. -- Abstract: Hydrogen-terminated silicon nanowires (H-SiNWs) were used as heterogeneous photocatalysts for the hydroxylation of benzene and for the decomposition of methyl red under visible light irradiation. The above reactions were monitored by GC-MS and UV-Vis spectrophotometry, respectively, which shows 100% selectivity for the transformation of benzene to phenol. A complete decomposition of a 2 Multiplication-Sign 10{sup -4} M methyl red solution was achieved within 30 min. The high selectivity for the hydroxylation of benzene and the photodecomposition demonstrate the catalytic activity of ultrafine H-SiNWs during nanocatalysis.

  4. Impaired methylation as a novel mechanism for proteasome suppression in liver cells

    SciTech Connect (OSTI)

    Osna, Natalia A.; White, Ronda L.; Donohue, Terrence M.; Department of Internal Medicine, University of Nebraska Medical Center, Omaha, NE 68105 ; Beard, Michael R.; Tuma, Dean J.; Kharbanda, Kusum K.; Department of Internal Medicine, University of Nebraska Medical Center, Omaha, NE 68105

    2010-01-08

    The proteasome is a multi-catalytic protein degradation enzyme that is regulated by ethanol-induced oxidative stress; such suppression is attributed to CYP2E1-generated metabolites. However, under certain conditions, it appears that in addition to oxidative stress, other mechanisms are also involved in proteasome regulation. This study investigated whether impaired protein methylation that occurs during exposure of liver cells to ethanol, may contribute to suppression of proteasome activity. We measured the chymotrypsin-like proteasome activity in Huh7CYP cells, hepatocytes, liver cytosols and nuclear extracts or purified 20S proteasome under conditions that maintain or prevent protein methylation. Reduction of proteasome activity of hepatoma cell and hepatocytes by ethanol or tubercidin was prevented by simultaneous treatment with S-adenosylmethionine (SAM). Moreover, the tubercidin-induced decline in proteasome activity occurred in both nuclear and cytosolic fractions. In vitro exposure of cell cytosolic fractions or highly purified 20S proteasome to low SAM:S-adenosylhomocysteine (SAH) ratios in the buffer also suppressed proteasome function, indicating that one or more methyltransferase(s) may be associated with proteasomal subunits. Immunoblotting a purified 20S rabbit red cell proteasome preparation using methyl lysine-specific antibodies revealed a 25 kDa proteasome subunit that showed positive reactivity with anti-methyl lysine. This reactivity was modified when 20S proteasome was exposed to differential SAM:SAH ratios. We conclude that impaired methylation of proteasome subunits suppressed proteasome activity in liver cells indicating an additional, yet novel mechanism of proteasome activity regulation by ethanol.

  5. Electrochemical Investigation of Al–Li/LixFePO4 Cells in Oligo(ethylene glycol) Dimethyl Ether/LiPF6

    SciTech Connect (OSTI)

    Wang, X.J.; Zhou, Y.N.; Lee, H.S.; Nam, K.W.; Yang, X.Q.; Haas, O.

    2011-02-01

    1 M LiPF{sub 6} dissolved in oligo(ethylene glycol) dimethyl ether with a molecular weight, 500 g mol{sup -1} (OEGDME500, 1 M LiPF{sub 6}), was investigated as an electrolyte in experimental Al-Li/LiFePO{sub 4} cells. More than 60 cycles were achieved using this electrolyte in a Li-ion cell with an Al-Li alloy as an anode sandwiched between two Li x FePO{sub 4} electrodes (cathodes). Charging efficiencies of 96-100% and energy efficiencies of 86-89% were maintained during 60 cycles at low current densities. A theoretical investigation revealed that the specific energy can be increased up to 15% if conventional LiC{sub 6} anodes are replaced by Al-Li alloy electrodes. The specific energy and the energy density were calculated as a function of the active mass per electrode surface (charge density). The results reveal that for a charge density of 4 mAh cm{sup -2} about 160 mWh g{sup -1} can be reached with Al-Li/LiFePO{sub 4} batteries. Power limiting diffusion processes are discussed, and the power capability of Al-Li/LiFePO{sub 4} cells was experimentally evaluated using conventional electrolytes.

  6. Chemistry of enol ethers. LXXXIV. Condensation of acetals of saturated aldehydes with 2-trimethylsilyloxy-1,3-dienes. Synthesis of /beta/-alkoxy-alkyl vinyl and divinyl ketones

    SciTech Connect (OSTI)

    Makin, S.M.; Nazarova, O.N.; Dymshakova, G.M.; Kundryutskova, L.A.

    1988-11-10

    The addition of the acetals of saturated aldehydes (formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, and isobutyraldehyde) to 2-trimethylsilyloxy-4-methyl-1,3-pentadiene in the presence of aprotic acids (ZnCl/sub 2/, ZnBr/sub 2/, FeCl/sub 3/, SnCl/sub 4/, BF/sub 3/ /times/ OEt/sub 2/) takes place at positions 1, 2 of the diene system with the formation of /beta/-alkoxyalkyl vinyl ketones. The most effective catalysts of this reaction were stannic chloride and zinc bromide. The alkyl derivatives of divinyl ketones are formed when the obtained /beta/-alkoxyalkyl vinyl ketones are heated with p-toluenesulfonic acid.

  7. Spectroscopic investigation of the vibrational quasi-continuum arising from internal rotation of a methyl group

    SciTech Connect (OSTI)

    Hougen, J.T.

    1993-12-01

    The goal of this project is to use spectroscopic techniques to investigate in detail phenomena involving the vibrational quasi-continuum in a simple physical system. Acetaldehyde was chosen for the study because: (i) methyl groups have been suggested to be important promotors of intramolecular vibrational relaxation, (ii) the internal rotation of a methyl group is an easily describle large-amplitude motion, which should retain its simple character even at high levels of excitation, and (iii) the aldehyde carbonyl group offers the possibility of both vibrational and electronic probing. The present investigation of the ground electronic state has three parts: (1) understanding the {open_quotes}isolated{close_quotes} internal-rotation motion below, at, and above the top of the torsional barrier, (2) understanding in detail traditional (bond stretching and bending) vibrational fundamental and overtone states, and (3) understanding interactions involving states with multiquantum excitations of at least one of these two kinds of motion.

  8. Activation of water soluble amines by halogens for trapping methyl radioactive iodine from air streams

    DOE Patents [OSTI]

    Deitz, Victor R.; Blachly, Charles H.

    1977-01-01

    Gas adsorbent charcoals impregnated with an aqueous solution of the reaction product of a tertiary amine and elemental iodine or bromine are better than 99 per cent efficient in trapping methyl iodine.sup.131. The chemical addition of iodine or bromine to the tertiary amine molecule increases the efficiency of the impregnated charcoal as a trapping agent, and in conjunction with the high flash point of the tertiary amine raises the ignition temperature of the impregnated charcoal.

  9. Method of recycling lithium borate to lithium borohydride through methyl borate

    DOE Patents [OSTI]

    Filby, Evan E.

    1977-01-01

    This invention provides a method for the recycling of lithium borate to lithium borohydride which can be reacted with water to generate hydrogen for utilization as a fuel. The lithium borate by-product of the hydrogen generation reaction is reacted with hydrogen chloride and water to produce boric acid and lithium chloride. The boric acid and lithium chloride are converted to lithium borohydride through a methyl borate intermediate to complete the recycle scheme.

  10. Durability of Poly(Methyl Methacrylate) Lenses Used in Concentrating Photovoltaic Technology (Revised) (Presentation)

    SciTech Connect (OSTI)

    Miller, D. C.; Carloni, J. D.; Pankow, J. W.; Gjersing, E. L.; To, B.; Packard, C. E.; Kennedy, C. E.; Kurtz, S. R.

    2012-01-01

    Concentrating photovoltaic (CPV) technology recently gained interest based on its expected low levelized cost of electricity, high efficiency, and scalability. Many CPV systems employ Fresnel lenses composed of poly(methyl methacrylate) (PMMA) to obtain a high optical flux density on the cell. The optical and mechanical durability of these lenses, however, is not well established relative to the desired surface life of 30 years. Our research aims to quantify the expected lifetime of PMMA in key market locations (FL, AZ, and CO).

  11. Crystallization of lysozyme with (R)-, (S)- and (RS)-2-methyl-2, 4-pentanediol

    SciTech Connect (OSTI)

    Stauber, Mark; Jakoncic, Jean; Berger, Jacob; Karp, Jerome M.; Axelbaum, Ariel; Sastow, Dahniel; Buldyrev, Sergey V.; Hrnjez, Bruce J.; Asherie, Neer

    2015-03-01

    Crystallization of lysozyme with (R)-2-methyl-2, 4-pentanediol produces more ordered crystals and a higher resolution protein structure than crystallization with (S)-2-methyl-2, 4-pentanediol. The results suggest that chiral interactions with chiral additives are important in protein crystal formation. Chiral control of crystallization has ample precedent in the small-molecule world, but relatively little is known about the role of chirality in protein crystallization. In this study, lysozyme was crystallized in the presence of the chiral additive 2-methyl-2, 4-pentanediol (MPD) separately using the R and S enantiomers as well as with a racemic RS mixture. Crystals grown with (R)-MPD had the most order and produced the highest resolution protein structures. This result is consistent with the observation that in the crystals grown with (R)-MPD and (RS)-MPD the crystal contacts are made by (R)-MPD, demonstrating that there is preferential interaction between lysozyme and this enantiomer. These findings suggest that chiral interactions are important in protein crystallization.

  12. Structural basis for recognition of hemi-methylated DNA by the SRA domain of human UHRF1.

    SciTech Connect (OSTI)

    Avvakumov, George V.; Walker, John R.; Xue, Sheng; Li, Yanjun; Duan, Shili; Bronner, Christian; Arrowsmith, Cheryl H.; Dhe-Paganon, Sirano

    2008-11-17

    Epigenetic inheritance in mammals is characterized by high-fidelity replication of CpG methylation patterns during development. UHRF1 (also known as ICBP90 in humans and Np95 in mouse) is an E3 ligase important for the maintenance of global and local DNA methylation in vivo. The preferential affinity of UHRF1 for hemi-methylated DNA over symmetrically methylated DNA by means of its SET and RING-associated (SRA) domain and its association with the maintenance DNA methyltransferase 1 (DNMT1) suggests a role in replication of the epigenetic code. Here we report the 1.7 {angstrom} crystal structure of the apo SRA domain of human UHRF1 and a 2.2 {angstrom} structure of its complex with hemi-methylated DNA, revealing a previously unknown reading mechanism for methylated CpG sites (mCpG). The SRA-DNA complex has several notable structural features including a binding pocket that accommodates the 5-methylcytosine that is flipped out of the duplex DNA. Two specialized loops reach through the resulting gap in the DNA from both the major and the minor grooves to read the other three bases of the CpG duplex. The major groove loop confers both specificity for the CpG dinucleotide and discrimination against methylation of deoxycytidine of the complementary strand. The structure, along with mutagenesis data, suggests how UHRF1 acts as a key factor for DNMT1 maintenance methylation through recognition of a fundamental unit of epigenetic inheritance, mCpG.

  13. Conceptual process design and economics for the production of high-octane gasoline blendstock via indirect liquefaction of biomass through methanol/dimethyl ether intermediates

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Tan, Eric C. D.; Talmadge, Michael; Dutta, Abhijit; Hensley, Jesse; Snowden-Swan, Lesley J.; Humbird, David; Schaidle, Joshua; Biddy, Mary

    2015-10-28

    This paper describes in detail one potential conversion process for the production of high-octane gasoline blendstock via indirect liquefaction of biomass. The processing steps of this pathway include the conversion of biomass to synthesis gas via indirect gasification, gas clean-up via reforming of tars and other hydrocarbons, catalytic conversion of syngas to methanol, methanol dehydration to dimethyl ether (DME), and the homologation of DME over a zeolite catalyst to high-octane gasoline-range hydrocarbon products. The current process configuration has similarities to conventional methanol-to-gasoline (MTG) technologies, but there are key distinctions, specifically regarding the product slate, catalysts, and reactor conditions. A techno-economicmore » analysis is performed to investigate the production of high-octane gasoline blendstock. The design features a processing daily capacity of 2000 tonnes (2205 short tons) of dry biomass. The process yields 271 liters of liquid fuel per dry tonne of biomass (65 gal/dry ton), for an annual fuel production rate of 178 million liters (47 MM gal) at 90% on-stream time. The estimated total capital investment for an nth-plant is $438 million. The resulting minimum fuel selling price (MFSP) is $0.86 per liter or $3.25 per gallon in 2011 US dollars. A rigorous sensitivity analysis captures uncertainties in costs and plant performance. Sustainability metrics for the conversion process are quantified and assessed. The potential premium value of the high-octane gasoline blendstock is examined and found to be at least as competitive as fossil-derived blendstocks. A simple blending strategy is proposed to demonstrate the potential for blending the biomass-derived blendstock with petroleum-derived intermediates. Published 2015. This article is a U.S. Government work and is in the public domain in the USA. Biofuels, Bioproducts and Biorefining published by Society of Industrial Chemistry and John Wiley & Sons Ltd.« less

  14. Conceptual process design and economics for the production of high-octane gasoline blendstock via indirect liquefaction of biomass through methanol/dimethyl ether intermediates

    SciTech Connect (OSTI)

    Tan, Eric C. D.; Talmadge, Michael; Dutta, Abhijit; Hensley, Jesse; Snowden-Swan, Lesley J.; Humbird, David; Schaidle, Joshua; Biddy, Mary

    2015-10-28

    This paper describes in detail one potential conversion process for the production of high-octane gasoline blendstock via indirect liquefaction of biomass. The processing steps of this pathway include the conversion of biomass to synthesis gas via indirect gasification, gas clean-up via reforming of tars and other hydrocarbons, catalytic conversion of syngas to methanol, methanol dehydration to dimethyl ether (DME), and the homologation of DME over a zeolite catalyst to high-octane gasoline-range hydrocarbon products. The current process configuration has similarities to conventional methanol-to-gasoline (MTG) technologies, but there are key distinctions, specifically regarding the product slate, catalysts, and reactor conditions. A techno-economic analysis is performed to investigate the production of high-octane gasoline blendstock. The design features a processing daily capacity of 2000 tonnes (2205 short tons) of dry biomass. The process yields 271 liters of liquid fuel per dry tonne of biomass (65 gal/dry ton), for an annual fuel production rate of 178 million liters (47 MM gal) at 90% on-stream time. The estimated total capital investment for an nth-plant is $438 million. The resulting minimum fuel selling price (MFSP) is $0.86 per liter or $3.25 per gallon in 2011 US dollars. A rigorous sensitivity analysis captures uncertainties in costs and plant performance. Sustainability metrics for the conversion process are quantified and assessed. The potential premium value of the high-octane gasoline blendstock is examined and found to be at least as competitive as fossil-derived blendstocks. A simple blending strategy is proposed to demonstrate the potential for blending the biomass-derived blendstock with petroleum-derived intermediates. Published 2015. This article is a U.S. Government work and is in the public domain in the USA. Biofuels, Bioproducts and Biorefining published by Society of Industrial Chemistry and John Wiley & Sons Ltd.

  15. Spatial and Functional Relationships Among Pol V-Associated loci, Pol IV-Dependent siRNAs, and Cytosine Methylation in the Arabidopsis Epigenome

    SciTech Connect (OSTI)

    Wierzbicki, A. T.; Cocklin, Ross; Mayampurath, Anoop; Lister, Ryan; Rowley, M. J.; Gregory, Brian D.; Ecker, Joseph R.; Tang, Haixu; Pikaard, Craig S.

    2012-08-15

    Multisubunit RNA polymerases IV and V (Pols IV and V) mediate RNA-directed DNA methylation and transcriptional silencing of retrotransposons and heterochromatic repeats in plants. We identified genomic sites of Pol V occupancy in parallel with siRNA deep sequencing and methylcytosine mapping, comparing wild-type plants with mutants defective for Pol IV, Pol V, or both Pols IV and V. Approximately 60% of Pol V-associated regions encompass regions of 24-nucleotide (nt) siRNA complementarity and cytosine methylation, consistent with cytosine methylation being guided by base-pairing of Pol IV-dependent siRNAs with Pol V transcripts. However, 27% of Pol V peaks do not overlap sites of 24-nt siRNA biogenesis or cytosine methylation, indicating that Pol V alone does not specify sites of cytosine methylation. Surprisingly, the number of methylated CHH motifs, a hallmark of RNA-directed de novo methylation, is similar in wild-type plants and Pol IV or Pol V mutants. In the mutants, methylation is lost at 50%-60% of the CHH sites that are methylated in the wild type but is gained at new CHH positions, primarily in pericentromeric regions. These results indicate that Pol IV and Pol V are not required for cytosine methyltransferase activity but shape the epigenome by guiding CHH methylation to specific genomic sites.

  16. The interaction of organic adsorbate vibrations with substrate lattice waves in methyl-Si(111)-(1??1)

    SciTech Connect (OSTI)

    Brown, Ryan D.; Hund, Zachary M.; Sibener, S. J.; Campi, Davide; Bernasconi, M.; OLeary, Leslie E.; Lewis, Nathan S.; Benedek, G.

    2014-07-14

    A combined helium atom scattering and density functional perturbation theory study has been performed to elucidate the surface phonon dispersion relations for both the CH{sub 3}-Si(111)-(1??1) and CD{sub 3}-Si(111)-(1??1) surfaces. The combination of experimental and theoretical methods has allowed characterization of the interactions between the low energy vibrations of the adsorbate and the lattice waves of the underlying substrate, as well as characterization of the interactions between neighboring methyl groups, across the entire wavevector resolved vibrational energy spectrum of each system. The Rayleigh wave was found to hybridize with the surface rocking libration near the surface Brillouin zone edge at both the M{sup }-point and K{sup }-point. The calculations indicated that the range of possible energies for the potential barrier to the methyl rotation about the Si-C axis is sufficient to prevent the free rotation of the methyl groups at a room temperature interface. The density functional perturbation theory calculations revealed several other surface phonons that experienced mode-splitting arising from the mutual interaction of adjacent methyl groups. The theory identified a Lucas pair that exists just below the silicon optical bands. For both the CH{sub 3}- and CD{sub 3}-terminated Si(111) surfaces, the deformations of the methyl groups were examined and compared to previous experimental and theoretical work on the nature of the surface vibrations. The calculations indicated a splitting of the asymmetric deformation of the methyl group near the zone edges due to steric interactions of adjacent methyl groups. The observed shifts in vibrational energies of the -CD{sub 3} groups were consistent with the expected effect of isotopic substitution in this system.

  17. Low-lying excited states and nonradiative processes of 9-methyl-2-aminopurine

    SciTech Connect (OSTI)

    Trachsel, Maria A.; Lobsiger, Simon; Schr, Tobias; Leutwyler, Samuel

    2014-01-28

    The UV spectrum of the adenine analogue 9-methyl-2-aminopurine (9M-2AP) is investigated with one- and two-color resonant two-photon ionization spectroscopy at 0.3 and 0.05 cm{sup ?1} resolution in a supersonic jet. The electronic origin at 32252 cm{sup ?1} exhibits methyl torsional subbands that originate from the 0A{sub 1}{sup ??} (l = 0) and 1E{sup ?} (l = 1) torsional levels. These and further torsional bands that appear up to 0{sub 0}{sup 0}+230 cm{sup ?1} allow to fit the threefold (V{sub 3}) barriers of the torsional potentials as |V{sub 3}{sup ??}|=50 cm{sup ?1} in the S{sub 0} and |V{sub 3}{sup ?}|=126 cm{sup ?1} in the S{sub 1} state. Using the B3LYP density functional and correlated approximate second-order coupled cluster CC2 methods, the methyl orientation is calculated to be symmetric relative to the 2AP plane in both states, with barriers of V{sub 3}{sup ??}=20 cm{sup ?1} and V{sub 3}{sup ?}=115 cm{sup ?1}. The 0{sub 0}{sup 0} rotational band contour is 75% in-plane (a/b) polarized, characteristic for a dominantly long-axis {sup 1}??{sup *} excitation. The residual 25% c-axis polarization may indicate coupling of the {sup 1}??{sup *} to the close-lying {sup 1}n?{sup *} state, calculated at 4.00 and 4.01 eV with the CC2 method. However, the CC2 calculated {sup 1}n? oscillator strength is only 6% of that of the {sup 1}??{sup *} transition. The {sup 1}??{sup *} vibronic spectrum is very complex, showing about 40 bands within the lowest 500 cm{sup ?1}. The methyl torsion and the low-frequency out-of-plane ?{sub 1}{sup ?} and ?{sub 2}{sup ?} vibrations are strongly coupled in the {sup 1}??{sup *} state. This gives rise to many torsion-vibration combination bands built on out-of-plane fundamentals, which are without precedence in the {sup 1}??{sup *} spectrum of 9H-2-aminopurine [S. Lobsiger, R. K. Sinha, M. Trachsel, and S. Leutwyler, J. Chem. Phys. 134, 114307 (2011)]. From the Lorentzian broadening needed to fit the 0{sub 0}{sup 0} contour of 9M-2AP, the {sup 1}??{sup *} lifetime is ? ? 120 ps, reflecting a rapid nonradiative transition.

  18. Lithium cycling performance in improved lithium hexafluoroarsenate/2-Methyl tetrahydrofuran electrolytes

    SciTech Connect (OSTI)

    Desjardins, C.D.; Cadge, T.G.; Casey, E.J.; Donaldson, G.; Salter, R.S.

    1985-03-01

    Lithium hexafluoroarsenate/2-methyl tetrahydrofuran electrolytes have been prepared, purified, and evaluated using half-cell galvanostatic lithium cycling, cyclic voltammetry, plus colorimetric, gas chromatographic, and UV absorption techniques. Superior electrolytes have been prepared yielding reproducible cycling efficiencies in excess of 97%. Static aging trials at ambient temperature clearly demonstrate deterioration in cycling performance with time. This decline in performance is related to electrolyte degradation, possibly arising from the formation of peroxides. However, studies of various battery testing regimes on 1M LiAsF/sub 6//2Me-THF electrolyte support the system' battery potential with respect to both rate capability and shelf-life characteristics.

  19. Continuous realtime radioiodine monitor employing on-line methyl iodide conversion

    SciTech Connect (OSTI)

    Fernandez, S.J.; Motes, B.G.

    1980-01-01

    An integrated /sup 14/C, /sup 129/I, and /sup 85/Kr monitor was proposed by Fernandez, et al. that separates /sup 129/I from /sup 85/Kr by selective permeation across thin silicone rubber membranes. Subsequent studies of the permeation of CH/sub 3/I and I/sub 2/ through silicone rubber membranes demonstrated that I/sub 2/ transport across the membranes is too slow to be useful in a realtime monitor. Transport of methyl iodide, however, is rapid and gives a separation factor of greater than 100 from /sup 85/Kr.

  20. Theory of long-lived nuclear spin states in methyl groups and quantum-rotor induced polarisation

    SciTech Connect (OSTI)

    Dumez, Jean-Nicolas; Håkansson, Pär; Mamone, Salvatore; Meier, Benno; Stevanato, Gabriele; Hill-Cousins, Joseph T.; Roy, Soumya Singha; Brown, Richard C. D.; Pileio, Giuseppe; Levitt, Malcolm H.

    2015-01-28

    Long-lived nuclear spin states have a relaxation time much longer than the longitudinal relaxation time T{sub 1}. Long-lived states extend significantly the time scales that may be probed with magnetic resonance, with possible applications to transport and binding studies, and to hyperpolarised imaging. Rapidly rotating methyl groups in solution may support a long-lived state, consisting of a population imbalance between states of different spin exchange symmetries. Here, we expand the formalism for describing the behaviour of long-lived nuclear spin states in methyl groups, with special attention to the hyperpolarisation effects observed in {sup 13}CH{sub 3} groups upon rapidly converting a material with low-barrier methyl rotation from the cryogenic solid state to a room-temperature solution [M. Icker and S. Berger, J. Magn. Reson. 219, 1 (2012)]. We analyse the relaxation properties of methyl long-lived states using semi-classical relaxation theory. Numerical simulations are supplemented with a spherical-tensor analysis, which captures the essential properties of methyl long-lived states.

  1. systems-studies | netl.doe.gov

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    focusing on one primary product, methanol, which also serves as a readily-transportable intermediate to many other products including olefins, gasoline, and di-methyl ether (DME). ...

  2. Comparison of SPME headspace analysis to U.S. EPA method5030/8260B for MTBE monitoring

    SciTech Connect (OSTI)

    Stringfellow, William T.; Oh, Kuen-Chan

    2005-02-01

    A novel method for analysis of methyl tert-butyl ether andtert-butyl alcohol using solid phase microextraction is described andcompared to a standard method.

  3. Tracking the sources of polybrominated diphenyl ethers in birds: Foraging in waste management facilities results in higher DecaBDE exposure in males

    SciTech Connect (OSTI)

    Gentes, Marie-Line; Mazerolle, Marc J.; Giroux, Jean-François; Patenaude-Monette, Martin; and others

    2015-04-15

    Differences in feeding ecology are now recognized as major determinants of inter-individual variations in contaminant profiles of free-ranging animals, but exceedingly little attention has been devoted to the role of habitat use. Marked inter-individual variations and high levels of polybrominated diphenyl ethers (PBDEs) (e.g., DecaBDE) have previously been documented in ring-billed gulls (Larus delawarensis) breeding in a colony near Montreal (QC, Canada). However, the environmental sources of these compounds, and thus the reasons causing these large inter-individual variations remain unidentified. In the present study, we used GPS-based telemetry (±5 to 10 m precision) to track ring-billed gulls from this colony to reconstruct their movements at the landscape level. We related habitat use of individual gulls (n=76) to plasma concentrations (ng/g ww) and relative contributions (percentages) to Σ{sub 38}PBDEs of major congeners in the internationally restricted PentaBDE and current-use DecaBDE mixtures. Male gulls that visited waste management facilities (WMFs; i.e., landfills, wastewater treatment plants and related facilities; 25% of all GPS-tracked males) exhibited greater DecaBDE (concentrations and percentages) and lower PentaBDE (percentages) relative to those that did not. In contrast, no such relationships were found in females. Moreover, in males, DecaBDE (concentrations and percentages) increased with percentages of time spent in WMFs (i.e., ~5% of total foraging time), while PentaBDE (percentages) decreased. No relationships between percentages of time spent in other habitats (i.e., urban areas, agriculture fields, and St. Lawrence River) were found in either sex. These findings suggest that animals breeding in the vicinity of WMFs as well as mobile species that only use these sites for short stopovers to forage, could be at risk of enhanced DecaBDE exposure. - Highlights: • The study was conducted on breeding gulls with high levels of flame retardants. • Ring-billed gulls were GPS-tracked to associate habitat use with plasma PBDEs. • Males that visited waste management facilities had greater DecaBDE. • DecaBDE also increased with time spent in waste management facilities in males. • No relationships between habitat use and PBDEs were found in females.

  4. Polybrominated diphenyl ethers in e-waste: Level and transfer in a typical e-waste recycling site in Shanghai, Eastern China

    SciTech Connect (OSTI)

    Li, Yue; Duan, Yan-Ping, E-mail: duanyanping@tongji.edu.cn; Huang, Fan; Yang, Jing; Xiang, Nan; Meng, Xiang-Zhou; Chen, Ling

    2014-06-01

    Highlights: PBDEs were detected in the majority of e-waste. PBDEs were found in TVs made in China after 1990. The levels of ?PBDEs in e-waste made in Japan far exceed the threshold limit of RoHS. The inappropriate recycling and disposal of e-waste is an important source of PBDEs. - Abstract: Very few data for polybrominated diphenyl ethers (PBDEs) were available in the electronic waste (e-waste) as one of the most PBDEs emission source. This study reported concentrations of PBDEs in e-waste including printer, rice cooker, computer monitor, TV, electric iron and water dispenser, as well as dust from e-waste, e-waste dismantling workshop and surface soil from inside and outside of an e-waste recycling plant in Shanghai, Eastern China. The results showed that PBDEs were detected in the majority of e-waste, and the concentrations of ?PBDEs ranged from not detected to 175 g/kg, with a mean value of 10.8 g/kg. PBDEs were found in TVs made in China after 1990. The mean concentrations of ?PBDEs in e-waste made in Korea, Japan, Singapore and China were 1.84 g/kg, 20.5 g/kg, 0.91 g/kg, 4.48 g/kg, respectively. The levels of ?PBDEs in e-waste made in Japan far exceed the threshold limit of RoHS (1.00 g/kg). BDE-209 dominated in e-waste, accounting for over 93%. The compositional patterns of PBDEs congeners resembled the profile of Saytex 102E, indicating the source of deca-BDE. Among the samples of dust and surface soil from a typical e-waste recycling site, the highest concentrations of ?{sub 18}PBDEs and BDE-209 were found in dust in e-waste, ranging from 1960 to 340,710 ng/g and from 910 to 320,400 ng/g, which were 12 orders of magnitude higher than other samples. It suggested that PBDEs released from e-waste via dust, and then transferred to surrounding environment.

  5. Autoignition measurements and a validated kinetic model for the biodiesel surrogate, methyl butanoate

    SciTech Connect (OSTI)

    Dooley, S.; Curran, H.J.; Simmie, J.M.

    2008-04-15

    The autoignition of methyl butanoate has been studied at 1 and 4 atm in a shock tube over the temperature range 1250-1760 K at equivalence ratios of 1.5, 1.0, 0.5, and 0.25 at fuel concentrations of 1.0 and 1.5%. These measurements are complemented by autoignition data from a rapid compression machine over the temperature range 640-949 K at compressed gas pressures of 10, 20, and 40 atm and at varying equivalence ratios of 1.0, 0.5, and 0.33 using fuel concentrations of 1.59 and 3.13%. The autoignition of methyl butanoate is observed to follow Arrhenius-like temperature dependence over all conditions studied. These data, together with speciation data reported in the literature in a flow reactor, a jet-stirred reactor, and an opposed-flow diffusion flame, were used to produce a detailed chemical kinetic model. It was found that the model correctly simulated the effect of change in equivalence ratio, fuel fraction, and pressure for shock tube ignition delays. The agreement with rapid compression machine ignition delays is less accurate, although the qualitative agreement is reasonable. The model reproduces most speciation data with good accuracy. In addition, the important reaction pathways over each regime have been elucidated by both sensitivity and flux analyses. (author)

  6. Arbuzov rearrangement in alkoxy derivatives and chloro derivatives of methyl phosphonites

    SciTech Connect (OSTI)

    Livantsov, M.V.; Prishchenko, A.A.; Lutsenko, I.F.

    1987-10-20

    In a series of alkoxy- and chloro-substituted methyl phosphonites, the Arbuzov reaction is a preparative method for the synthesis of new types of functionally substituted methyl phosphinates. The Arbuzov reaction takes a new pathway in the case of dialkoxymethyl phosphonites, in which the phosphorus-carbon bond is ruptured at the stage where a quasiphosphonium compound forms, producing alkoxycarbonyl phosphonites that have not been available before. The IR spectra were obtained on UR-20 and IKS-22 instruments in a thin layer (NaCL). The PMR spectra were taken on a Tesla BS-497 spectrometer (100 MHz) in C/sub 6/D/sub 6/ and CDCl/sub 3/ solutions (20 to 30% concn.), with TMS as standard. The /sup 13/C NMR spectrum of phosphonite (XI) was obtained on a Varian FT-80A spectrometer (20 MHz) in an 80% solution in C/sub 6/D/sub 6/ and with TMS as standard. The /sup 31/P NMR spectra were obtained on JEOL 6-50OHL (24.3 MHz), Varian FT-80A (32.2 MHz), and JOEL FX-100 (42 MHz) spectrometers with an 85% solution of H/sub 3/PO/sub 4/ in D/sub 2/O as standard.

  7. Dipole Alignment at the Carbon Nanotube and Methyl Ammonium Lead Iodide Perovskite Interface

    SciTech Connect (OSTI)

    Przepioski, Joshua

    2015-08-28

    This work correlates resonant peaks from first principles calculation on ammonia (NH3) Nitrogen 1s x-ray absorption spectroscopy (XAS) within the methyl ammonium lead iodide perovskite (CH3NH3PbI3), and proposes a curve to determine the alignment of the methyl ammonium dipole if there exists angular dependence. The Nitrogen 1s XAS was performed at varying incident angles on the perovskite with and without a carbon nanotube (CNT) interface produced from an ultrasonic spray deposition. We investigated the peak contribution from PbI2 and the poly(9,9-dioctylfluorene- 2,7-diyl) with bipyridine (PFO-BPy) wrapped around the CNT, and used normalization techniques to better identify the dipole alignment. There was angular dependence on samples containing the CNT interface suggesting an existing dipole alignment, but there was no angular dependence on the perovskite samples alone; however, more normalization techniques and experimental work must be performed in order to ensure its validity and to better describe its alignment, and possible controlling factors.

  8. Production of FAME biodiesel in E. coli by direct methylation with an insect enzyme

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Sherkhanov, Saken; Korman, Tyler P.; Clarke, Steven G.; Bowie, James U.

    2016-04-07

    Here, most biodiesel currently in use consists of fatty acid methyl esters (FAMEs) produced by transesterification of plant oils with methanol. To reduce competition with food supplies, it would be desirable to directly produce biodiesel in microorganisms. To date, the most effective pathway for the production of biodiesel in bacteria yields fatty acid ethyl esters (FAEEs) at up to ~1.5 g/L. A much simpler route to biodiesel produces FAMEs by direct S-adenosyl-L-methionine (SAM) dependent methylation of free fatty acids, but FAME production by this route has been limited to only ~16 mg/L. Here we employ an alternative, broad spectrum methyltransferase,more » Drosophila melanogaster Juvenile Hormone Acid O-Methyltransferase (DmJHAMT). By introducing DmJHAMT in E. coli engineered to produce medium chain fatty acids and overproduce SAM, we obtain medium chain FAMEs at titers of 0.56 g/L, a 35-fold increase over titers previously achieved. Although considerable improvements will be needed for viable bacterial production of FAMEs and FAEEs for biofuels, it may be easier to optimize and transport the FAME production pathway to other microorganisms because it involves fewer enzymes.« less

  9. Covalent Coupling of Organophosphorus Hydrolase Loaded Quantum Dots to Carbon Nanotube/Au Nanocomposite for Enhanced Detection of Methyl Parathion

    SciTech Connect (OSTI)

    Du, Dan; Chen, Wenjuan; Zhang, Weiying; Liu, Deli; Li, Haibing; Lin, Yuehe

    2010-02-15

    An amperometric biosensor for highly selective and sensitive determination of methyl parathion (MP) was developed based on dual signal amplification: (1) a large amount of introduced enzyme on the electrode surface and (2) synergistic effects of nanoparticles towards enzymatic catalysis. The fabrication process includes (1) electrochemical deposition of gold nanoparticles by a multi-potential step technique at multiwalled carbon nanotube (MWCNT) film pre-cast on a glassy carbon electrode and (2) immobilization of methyl parathion degrading enzyme (MPDE) onto a modified electrode through CdTe quantum dots (CdTe QDs) covalent attachment. The introduced MWCNT and gold nanoparticles significantly increased the surface area and exhibited synergistic effects towards enzymatic catalysis. CdTe QDs are further used as carriers to load a large amount of enzyme. As a result of these two important enhancement factors, the proposed biosensor exhibited extremely sensitive, perfectly selective, and rapid response to methyl parathion in the absence of a mediator.

  10. Reactions of methyl groups on a non-reducible metal oxide: The reaction of iodomethane on stoichiometric α-Cr2O3(0001)

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Dong, Yujung; Brooks, John D.; Chen, Tsung-Liang; Mullins, David R.; Cox, David F.

    2015-06-10

    The reaction of iodomethane on the nearly stoichiometric α-Cr2O3(0001) surface produces gas phase ethylene, methane, and surface iodine adatoms. The reaction is first initiated by the dissociation of iodomethane into surface methyl fragments, -CH3, and iodine adatoms. Methyl fragments bound at surface Cr cation sites undergo a rate-limiting dehydrogenation reaction to methylene, =CH2. The methylene intermediates formed from methyl dehydrogenation can then undergo coupling reactions to produce ethylene via two principle reaction pathways: (1) direct coupling of methylene and (2) methylene insertion into the methyl surface bond to form surface ethyl groups which undergo β-H elimination to produce ethylene. Themore » liberated hydrogen also combines with methyl groups to form methane. Iodine adatoms from the dissociation of iodomethane deactivate the surface by simple site blocking of the surface Cr3+ cations.« less

  11. Reactions of methyl groups on a non-reducible metal oxide: The reaction of iodomethane on stoichiometric ?-Cr2O3(0001)

    SciTech Connect (OSTI)

    Dong, Yujung; Brooks, John D.; Chen, Tsung-Liang; Mullins, David R.; Cox, David F.

    2015-06-10

    The reaction of iodomethane on the nearly stoichiometric ?-Cr2O3(0001) surface produces gas phase ethylene, methane, and surface iodine adatoms. The reaction is first initiated by the dissociation of iodomethane into surface methyl fragments, -CH3, and iodine adatoms. Methyl fragments bound at surface Cr cation sites undergo a rate-limiting dehydrogenation reaction to methylene, =CH2. The methylene intermediates formed from methyl dehydrogenation can then undergo coupling reactions to produce ethylene via two principle reaction pathways: (1) direct coupling of methylene and (2) methylene insertion into the methyl surface bond to form surface ethyl groups which undergo ?-H elimination to produce ethylene. The liberated hydrogen also combines with methyl groups to form methane. Iodine adatoms from the dissociation of iodomethane deactivate the surface by simple site blocking of the surface Cr3+ cations.

  12. Generation kinetics of color centers in irradiated poly(4-methyl-1-pentene)

    SciTech Connect (OSTI)

    Peng, J. S.; Li, C. L.; Lee, Sanboh; Chou, K. F.

    2011-09-15

    The transient absorbance of poly(4-methyl-1-pentene) (PMP) irradiated with gamma rays at elevated temperatures has been investigated. The absorbance in the ultraviolet and visible range increases with gamma ray dose. A bathochromic shift in transmission spectra emerges significantly upon irradiation. A first-order generation model is proposed to analyze the kinetics of color centers during annealing. The activation energy of the color center increases with increasing gamma ray dose. The equilibrium behavior of color centers in PMP is similar to that of vacancies in metals, and the formation energy of color centers in PMP decreases with increasing gamma ray dose. However, annealable color centers are not observed in this study.

  13. Interactions in 1-ethyl-3-methyl imidazolium tetracyanoborate ion pair: Spectroscopic and density functional study

    SciTech Connect (OSTI)

    Mao, James X.; Lee, Anita S.; Kitchin, John R.; Nulwala, Hunaid B; Luebke, David R.; Damodaran, Krishnan

    2013-04-24

    Density Functional Theory is used to investigate a weakly coordinating room-temperature ionic liquid, 1-ethyl-3-methyl imidazolium tetracyanoborate ([Emim]{sup +}[TCB]{sup -}). Four locally stable conformers of the ion pair were located. Atoms-in-molecules (AIM) and electron density analysis indicated the existence of several hydrogen bonds. Further investigation through the Natural Bond Orbital (NBO) and Natural Energy Decomposition Analysis (NEDA) calculations provided insight into the origin of interactions in the [Emim]{sup +}[TCB]{sup -} ion pair. Strength of molecular interactions in the ionic liquid was correlated with frequency shifts of the characteristic vibrations of the ion pair. Harmonic vibrations of the ion pair were also compared with the experimental Raman and Infrared spectra. Vibrational frequencies were assigned by visualizing displacements of atoms around their equilibrium positions and through Potential Energy Distribution (PED) analysis.

  14. Interfacial hydrothermal synthesis of SnO{sub 2} nanorods towards photocatalytic degradation of methyl orange

    SciTech Connect (OSTI)

    Hou, L.R. Lian, L.; Zhou, L.; Zhang, L.H.; Yuan, C.Z.

    2014-12-15

    Highlights: Efficient interfacial hydrothermal strategy was developed. 1D SnO{sub 2} nanorods as an advanced photocatalyst. SnO{sub 2} nanorods exhibit photocatalytic degradation of the MO. - Abstract: One-dimensional (1D) SnO{sub 2} nanorods (NRs) have been successfully synthesized by means of an efficient interfacial hydrothermal strategy. The resulting product was physically characterized by X-ray powder diffraction, scanning electron microscopy, transmission electron microscope, etc. The as-fabricated SnO{sub 2} NRs exhibited excellent photocatalytic degradation of the methyl orange with high degradation efficiency of 99.3% with only 60 min ultra violet light irradiation. Meanwhile, the 1D SnO{sub 2} NRs exhibited intriguing photostability after four recycles.

  15. Investigation of methyl decanoate combustion in an optical direct-injection diesel engine

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Cheng, A. S.; Dumitrescu, Cosmin E.; Mueller, Charles J.

    2014-11-24

    In this study, an optically accessible heavy-duty diesel engine was used to investigate the impact of methyl decanoate (MD) on combustion and emissions. A specific goal of the study was to determine if MD could enable soot-free leaner-lifted flame combustion (LLFC) – a mode of mixing-controlled combustion associated with fuel-air equivalence ratios below approximately two. An ultra-low sulfur diesel certification fuel (CF) was used as the baseline fuel, and experiments were conducted at two fuel-injection pressures with three levels of charge-gas dilution. In addition to conventional pressure-based and engine-out emissions measurements, exhaust laser-induced incandescence, in-cylinder natural luminosity (NL), and in-cylindermore » chemiluminescence (CL) diagnostics were used to provide detailed insight into combustion processes.« less

  16. Investigation of methyl decanoate combustion in an optical direct-injection diesel engine

    SciTech Connect (OSTI)

    Cheng, A. S.; Dumitrescu, Cosmin E.; Mueller, Charles J.

    2014-11-24

    In this study, an optically accessible heavy-duty diesel engine was used to investigate the impact of methyl decanoate (MD) on combustion and emissions. A specific goal of the study was to determine if MD could enable soot-free leaner-lifted flame combustion (LLFC) – a mode of mixing-controlled combustion associated with fuel-air equivalence ratios below approximately two. An ultra-low sulfur diesel certification fuel (CF) was used as the baseline fuel, and experiments were conducted at two fuel-injection pressures with three levels of charge-gas dilution. In addition to conventional pressure-based and engine-out emissions measurements, exhaust laser-induced incandescence, in-cylinder natural luminosity (NL), and in-cylinder chemiluminescence (CL) diagnostics were used to provide detailed insight into combustion processes.

  17. Crystallization of lysozyme with (R)-, (S)- and (RS)-2-methyl-2,4-pentanediol

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Stauber, Mark; Jakoncic, Jean; Berger, Jacob; Karp, Jerome M.; Axelbaum, Ariel; Sastow, Dahniel; Buldyrev, Sergey V.; Hrnjez, Bruce J.; Asherie, Neer

    2015-03-01

    Chiral control of crystallization has ample precedent in the small-molecule world, but relatively little is known about the role of chirality in protein crystallization. In this study, lysozyme was crystallized in the presence of the chiral additive 2-methyl-2,4-pentanediol (MPD) separately using the R and S enantiomers as well as with a racemic RS mixture. Crystals grown with (R)-MPD had the most order and produced the highest resolution protein structures. This result is consistent with the observation that in the crystals grown with (R)-MPD and (RS)-MPD the crystal contacts are made by (R)-MPD, demonstrating that there is preferential interaction between lysozymemore » and this enantiomer. These findings suggest that chiral interactions are important in protein crystallization.« less

  18. Mesoscale simulation of shocked poly-(4-methyl-1-pentene) (PMP) foams.

    SciTech Connect (OSTI)

    Schroen, Diana Grace; Flicker, Dawn G.; Haill, Thomas A.; Root, Seth; Mattsson, Thomas Kjell Rene

    2011-06-01

    Hydrocarbon foams are commonly used in HEDP experiments, and are subject to shock compression from tens to hundreds of GPa. Modeling foams is challenging due to the heterogeneous character of the foam. A quantitative understanding of foams under strong dynamic compression is sought. We use Sandia's ALEGRA-MHD code to simulate 3D mesoscale models of pure poly(4-methyl-1-petene) (PMP) foams. We employ two models of the initial polymer-void structure of the foam and analyze the statistical properties of the initial and shocked states. We compare the simulations to multi-Mbar shock experiments at various initial foam densities and flyer impact velocities. Scatter in the experimental data may be a consequence of the initial foam inhomogeneity. We compare the statistical properties the simulations with the scatter in the experimental data.

  19. Methyl Chloride from Direct Methane Partial Oxidation: A High-Temperature Shilov-Like Catalytic System

    SciTech Connect (OSTI)

    Yongchun Tang; John Ma

    2012-03-23

    The intention of this study is to demonstrate and evaluate the scientific and economic feasibility of using special solvents to improve the thermal stability of Pt-catalyst in the Shilov system, such that a high reaction temperature could be achieved. The higher conversion rate (near 100%) of methyl chloride from partial oxidation of methane under the high temperature ({approx} 200 C) without significant Pt0 precipitation has been achieved. High concentration of the Cl- ion has been identified as the key for the stabilization of the Pt-catalysts. H/D exchange measurements indicated that the over oxidation will occur at the elevated temperature, developments of the effective product separation processes will be necessary in order to rationalize the industry-visible CH4 to CH3Cl conversion.

  20. Homogeneous Hydrogenation of CO? to Methyl Formate Utilizing Switchable Ionic Liquids

    SciTech Connect (OSTI)

    Yadav, Mahendra; Linehan, John C.; Karkamkar, Abhijeet J.; Van Der Eide, Edwin F.; Heldebrant, David J.

    2014-09-15

    Capture of CO? and subsequent hydrogenation allows for base/alcohol-catalyzed conversion of CO? to methylformate in one pot. The conversion of CO? proceeds via alkylcarbonates, to formate salts and then formate esters, which can be catalyzed by base and alcohol with the only byproduct being water. The system operates at mild conditions (300 psi H?, 140 C). Reactivity is strongly influenced by temperature and choice of solvent. In the presence of excess of base (DBU) formate is predominant product while in excess of methanol methyl formate is major product. 110 C yields formate salts, 140 C promotes methylformate. The authors acknowledge internal Laboratory Directed Re-search and Development (LDRD) funding from Pacific Northwest National Laboratory (PNNL). PNNL is operated by Battelle for the U.S. Department of Energy.

  1. Enantioselective hydrogenation. III. Methyl pyruvate hydrogenation catalyzed by alkaloid-modified iridium

    SciTech Connect (OSTI)

    Simons, K.E.; Johnston, P.; Plum, H.; Wells, P.B.; Ibbotson, A.

    1994-12-01

    Enantioselective hydrogenation of methyl pyruvate, MeCOCOOMe to methyl lactate, MeCH(OH)COOMe, is catalyzed in solution at room temperature by supported iridium catalysts modified with cinchona alkaloids. Modification with cinchonidine or quinine yields R-lactate in excess, whereas modification with cinchonine or quinidine favors S-lactate formation. Ir/SiO{sub 2} catalysts (20%) calcined at 393 to 573 K and reduced at 523 to 593 K were highly active for racemic hydrogenation in the absence of a modifier (rates typically 1.8 mol h{sup -1} g{sub cat}{sup -1}) and were comparably active when modified with cinchonidine but gave an enantiomeric excess of about 30%. Use of higher calcination or reduction temperatures led to substantially inferior activity and selectivity. The high rates recorded for both racemic and enantioselective reactions are dependent on the catalysts being activated before use by a procedure involving exposure of the catalyst to air after the initial reduction. Use of a Cl-free precursor gave an Ir/SiO{sub 2} catalyst (20%) of superior activity but inferior enantioselectivity. Ir/CaCO{sub 3} (5%) was more active for racemic hydrogenation than for enantioselective hydrogenation, but provided the highest value of the enantiomeric excess 39%. Kinematics of reaction are reported. Exchange of H for D in 10,11-dihydrocinchonidine at room temperature over Ir/CaCO{sub 3} occurred in the quinoline moiety but not in the quinuclidine ring system, indicating that the alkaloid was adsorbed to the Ir surface via the interaction of its {pi}-electron system. For both silica-supported and calcium carbonate-supported Ir, the presence of chloride ion in the catalyst was advantageous for the achievement of enantioselectivity. 25 refs., 2 figs., 3 tabs.

  2. Insights antifibrotic mechanism of methyl palmitate: Impact on nuclear factor kappa B and proinflammatory cytokines

    SciTech Connect (OSTI)

    Mantawy, Eman M.; Tadros, Mariane G.; Awad, Azza S.; Hassan, Dina A.A.; El-Demerdash, Ebtehal

    2012-01-01

    Fibrosis accompanies most chronic liver disorders and is a major factor contributing to hepatic failure. Therefore, the need for an effective treatment is evident. The present study was designed to assess the potential antifibrotic effect of MP and whether MP can attenuate the severity of oxidative stress and inflammatory response in chronic liver injury. Male albino rats were treated with either CCl{sub 4} (1 ml/kg, twice a week) and/or MP (300 mg/kg, three times a week) for six weeks. CCl{sub 4}-intoxication significantly increased liver weight, serum aminotransferases, total cholesterol and triglycerides while decreased albumin level and these effects were prevented by co-treatment with MP. As indicators of oxidative stress, CCl{sub 4}-intoxication caused significant glutathione depletion and lipid peroxidation while MP co-treatment preserved them within normal values. As markers of fibrosis, hydroxyproline content and ?-SMA expression increased markedly in the CCl{sub 4} group and MP prevented these alterations. Histopathological examination by both light and electron microscope further confirmed the protective efficacy of MP. To elucidate the antifibrotic mechanisms of MP, the expression of NF-?B, iNOS and COX-2 and the tissue levels of TNF-? and nitric oxide were assessed; CCl{sub 4} increased the expression of NF-?B and all downstream inflammatory cascade while MP co-treatment inhibited them. Collectively these findings indicate that MP possesses a potent antifibrotic effect which may be partly a consequence of its antioxidant and anti-inflammatory properties. -- Highlights: ? Methyl palmitate is free fatty acid methyl ester. ? It possesses a strong antifibrotic effect. ? It inhibits NF-?B and the consequent proinflammatory and oxidative stress response.

  3. NMR Analysis of Methyl Groups at 100-500 kDa: Model Systems and Arp2/3 Complex

    SciTech Connect (OSTI)

    Kreishman-Deitrick, Mara; Egile, Coumaran; Hoyt, David W.; Ford, Joseph J.; Rong, Li; Rosen, Michael K.

    2003-07-01

    Large macromolecular machines are among the most important and challenging targets for structural and mechanistic analyses. Consequently, there is great interest in development of NMR methods for the study of multicomponent systems in the 50-500 kDa range. Biochemical methods also must be developed in concert to produce such systems in selectively labeled form. Here, we present 1H/13C-HSQC spectra of protonated methyl groups in a model system that mimics molecular weights up to ~560 kDa. Signals from side chain methyl groups of Ile, Leu, and Val residues are clearly detectable at correlation times up to ~330 ns. We have also developed a biochemical procedure to produce the 240 kDa, heteroheptameric Arp2/3 actin nucleation complex selectively labeled at one subunit and obtained 1H/13C-HSQC spectra of this assembly. Sensitivity in spectra of both the Arp2/3 complex and the model system indicate that methyl groups will be useful sources of information in nonsymmetric systems with molecular weights greater than 600 kDa at concentrations less than 100 μM. Methyl analyses will complement TROSY and CRINEPT analyses of amides in NMR studies of structure and molecular interactions of extremely large macromolecules and assemblies.

  4. Determination of Total Lipids as Fatty Acid Methyl Esters (FAME) by in situ Transesterification: Laboratory Analytical Procedure (LAP)

    SciTech Connect (OSTI)

    Van Wychen, S.; Laurens, L. M. L.

    2013-12-01

    This procedure is based on a whole biomass transesterification of lipids to fatty acid methyl esters to represent an accurate reflection of the potential of microalgal biofuels. Lipids are present in many forms and play various roles within an algal cell, from cell membrane phospholipids to energy stored as triacylglycerols.

  5. Photoimaging of the multiple filamentation of femtosecond laser pulses in poly(methyl methacrylate) doped with 2,2-difluoro-4-(9-anthracyl)-6-methyl-1,3,2-dioxaborine

    SciTech Connect (OSTI)

    Kulchin, Yu N; Vitrik, O B; Chekhlenok, A A; Zhizhchenko, A Yu; Proschenko, D Yu; Mirochnik, A G; Lyu Guohui

    2013-12-31

    We have studied the filamentation of femtosecond laser pulses (? = 800 nm, ?42 fs pulse duration) in poly(methyl methacrylate) doped with 2,2-difluoro-4-(9-anthracyl)-6-methyl-1,3,2- dioxaborine and the associated photomodification of the material. The results demonstrate that multiple filamentation occurs at pulse energies above 5 ?J. At a pulse energy of 1.5 mJ, it is accompanied by supercontinuum generation. The average filament length in PMMA is 9 mm and the filament diameter is ?10 ?m. An incident power density of ?10{sup 12} W cm{sup -2} ensures inscription of the filament pattern owing to two-photon photochemical processes. Preliminary exposure to continuous light at ? = 400 nm enables an ordered filament pattern to be written. (interaction of laser radiation with matter)

  6. Synthesis and properties of poly(methyl methacrylate-2-acrylamido-2-methylpropane sulfonic acid)/PbS hybrid composite

    SciTech Connect (OSTI)

    Preda, N.; Rusen, E.; Musuc, A.; Enculescu, M.; Matei, E.; Marculescu, B.; Fruth, V.; Enculescu, I.

    2010-08-15

    The synthesis of a new hybrid composite based on PbS nanoparticles and poly(methyl methacrylate-2-acrylamido-2-methylpropane sulfonic acid) [P(MMA-AMPSA)] copolymer is reported. The chemical synthesis consists in two steps: (i) a surfactant-free emulsion copolymerization between methyl methacrylate and 2-acrylamido-2-methylpropane sulfonic acid and (ii) the generation of PbS particles in the presence of the P(MMA-AMPSA) latex, from the reaction between lead nitrate and thiourea. The composite was studied by scanning electron microscopy (SEM), X-ray diffraction, FTIR spectroscopy, thermogravimetric analysis and differential scanning calorimetry. The microstructure observed using SEM proves that the PbS nanoparticles are well dispersed in the copolymer matrix. The X-ray diffraction measurements demonstrate that the PbS nanoparticles have a cubic rock salt structure. It was also found that the inorganic semiconductor nanoparticles improve the thermal stability of the copolymer matrix.

  7. On the role of chemical reactions in initiating ultraviolet laser ablation in poly(methyl methacrylate)

    SciTech Connect (OSTI)

    Prasad, Manish; Conforti, Patrick F.; Garrison, Barbara J.

    2007-05-15

    The role of chemical reactions is investigated versus the thermal and mechanical processes occurring in a polymer substrate during irradiation by a laser pulse and subsequent ablation. Molecular dynamics simulations with an embedded Monte Carlo based reaction scheme were used to study ultraviolet ablation of poly(methyl methacrylate) at 157 nm. We discuss the onset of ablation, the mechanisms leading to ablation, and the role of stress relaxation of the polymer matrix during ablation. Laser induced heating and chemical decomposition of the polymer substrate are considered as ablation pathways. It is shown that heating the substrate can set off ablation via mechanical failure of the material only for very short laser pulses. For longer pulses, the mechanism of ejection is thermally driven limited by the critical number of bonds broken in the substrate. Alternatively, if the photon energy goes towards direct bond breaking, it initiates chemical reactions, polymer unzipping, and formation of gaseous products, leading to a nearly complete decomposition of the top layers of substrates. The ejection of small molecules has a hollowing out effect on the weakly connected substrates which can lead to lift-off of larger chunks. Excessive pressure buildup upon the creation of gaseous molecules does not lead to enhanced yield. The larger clusters are thermally ejected, and an entrainment of larger polymer fragments in gaseous molecules is not observed.

  8. Phosphorylation and Methylation of Proteasomal Proteins of the HaloarcheonHaloferax volcanii

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Humbard, Matthew A.; Reuter, Christopher J.; Zuobi-Hasona, Kheir; Zhou, Guangyin; Maupin-Furlow, Julie A.

    2010-01-01

    Proteasomes are composed of 20S core particles (CPs) of?- and?-type subunits that associate with regulatory particle AAA ATPases such as the proteasome-activating nucleotidase (PAN) complexes of archaea. In this study, the roles and additional sites of post-translational modification of proteasomes were investigated using the archaeonHaloferax volcaniias a model. Indicative of phosphorylation, phosphatase-sensitive isoforms of?1and?2were detected by 2-DE immunoblot. To map these and other potential sites of post-translational modification, proteasomes were purified and analyzed by tandem mass spectrometry (MS/MS). Using this approach, several phosphosites were mapped including?1Thr147,?2 Thr13/Ser14 and PAN-A Ser340. Multiple methylation sites were also mapped to?1, thus, revealing amorenew type of proteasomal modification. Probing the biological role of?1and PAN-A phosphorylation by site-directed mutagenesis revealed dominant negative phenotypes for cell viability and/or pigmentation for?1variants including Thr147Ala, Thr158Ala and Ser58Ala. AnH. volcaniiRio1p Ser/Thr kinase homolog was purified and shown to catalyze autophosphorylation and phosphotransfer to?1. The?1variants in Thr and Ser residues that displayed dominant negative phenotypes were significantly reduced in their ability to accept phosphoryl groups from Rio1p, thus, providing an important link between cell physiology and proteasomal phosphorylation.less

  9. Electron Affinity of Phenyl-C61-Butyric Acid Methyl Ester (PCBM)

    SciTech Connect (OSTI)

    Larson, Bryon W.; Whitaker, James B.; Wang, Xue B.; Popov, Alexey A.; Rumbles, Garry; Kopidakis, Nikos; Strauss, Steven H.; Boltalina, Olga V.

    2013-07-25

    The gas-phase electron affinity (EA) of phenyl-C61-butyric acid methyl ester (PCBM), one of the best-performing electron acceptors in organic photovoltaic devices, is measured by lowtemperature photoelectron spectroscopy for the first time. The obtained value of 2.63(1) eV is only ca. 0.05 eV lower than that of C60 (2.68(1) eV), compared to a 0.09 V difference in their E1/2 values measured in this work by cyclic voltammetry. Literature E(LUMO) values for PCBM that are typically estimated from cyclic voltammetry, and commonly used as a quantitative measure of acceptor properties, are dispersed over a wide range between -4.3 and -3.62 eV; the reasons for such a huge discrepancy are analyzed here, and the protocol for reliable and consistent estimations of relative fullerene-based acceptor strength in solution is proposed.

  10. Durability of Poly(Methyl Methacrylate) Lenses Used in Concentrating Photovoltaic Modules: Preprint

    SciTech Connect (OSTI)

    Miller, D. C.; Gedvilas, L. M.; To, B.; Kennedy, C. E.; Kurtz, S. R.

    2010-08-01

    Concentrating photovoltaic (CPV) technology has recently gained interest based on their expected low levelized cost of electricity, high efficiency, and scalability. Many CPV systems use Fresnel lenses made of poly(methyl methacrylate)(PMMA) to obtain a high optical flux density. The optical and mechanical durability of such components, however, are not well established relative to the desired service life of 30 years. Specific reliability issues may include: reduced optical transmittance, discoloration, hazing, surface erosion, embrittlement, crack growth, physical aging, shape setting (warpage), and soiling. The initial results for contemporary lens- and material-specimens aged cumulatively to 6 months are presented. The study here uses an environmental chamber equipped with a xenon-arc lamp to age specimens at least 8x the nominal field rate. A broad range in the affected characteristics (including optical transmittance, yellowness index, mass loss, and contact angle) has been observed to date, depending on the formulation of PMMA used. The most affected specimens are further examined in terms of their visual appearance, surface roughness (examined via atomic force microscopy), and molecular structure (via Fourier transform infrared spectroscopy).

  11. Phosphorylation and Methylation of Proteasomal Proteins of the Haloarcheon Haloferax volcanii

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Humbard, Matthew A.; Reuter, Christopher J.; Zuobi-Hasona, Kheir; Zhou, Guangyin; Maupin-Furlow, Julie A.

    2010-01-01

    Promore » teasomes are composed of 20S core particles (CPs) of α - and β -type subunits that associate with regulatory particle AAA ATPases such as the proteasome-activating nucleotidase (PAN) complexes of archaea. In this study, the roles and additional sites of post-translational modification of proteasomes were investigated using the archaeon Haloferax volcanii as a model. Indicative of phosphorylation, phosphatase-sensitive isoforms of α 1 and α 2 were detected by 2-DE immunoblot. To map these and other potential sites of post-translational modification, proteasomes were purified and analyzed by tandem mass spectrometry (MS/MS). Using this approach, several phosphosites were mapped including α 1 Thr147, α 2 Thr13/Ser14 and PAN-A Ser340. Multiple methylation sites were also mapped to α 1 , thus, revealing a new type of proteasomal modification.bing the biological role of α 1 and PAN-A phosphorylation by site-directed mutagenesis revealed dominant negative phenotypes for cell viability and/or pigmentation for α 1 variants including Thr147Ala, Thr158Ala and Ser58Ala. An H. volcanii Rio1p Ser/Thr kinase homolog was purified and shown to catalyze autophosphorylation and phosphotransfer to α 1 . The α 1 variants in Thr and Ser residues that displayed dominant negative phenotypes were significantly reduced in their ability to accept phosphoryl groups from Rio1p, thus, providing an important link between cell physiology and proteasomal phosphorylation.« less

  12. Anti-inflammatory activity of methyl palmitate and ethyl palmitate in different experimental rat models

    SciTech Connect (OSTI)

    Saeed, Noha M.; El-Demerdash, Ebtehal; Abdel-Rahman, Hanaa M.; Algandaby, Mardi M.; Al-Abbasi, Fahad A.; Abdel-Naim, Ashraf B.

    2012-10-01

    Methyl palmitate (MP) and ethyl palmitate (EP) are naturally occurring fatty acid esters reported as inflammatory cell inhibitors. In the current study, the potential anti-inflammatory activity of MP and EP was evaluated in different experimental rat models. Results showed that MP and EP caused reduction of carrageenan-induced rat paw edema in addition to diminishing prostaglandin E2 (PGE2) level in the inflammatory exudates. In lipopolysaccharide (LPS)-induced endotoxemia in rats, MP and EP reduced plasma levels of tumor necrosis factor-? (TNF-?) and interleukin-6 (IL-6). MP and EP decreased NF-?B expression in liver and lung tissues and ameliorated histopathological changes caused by LPS. Topical application of MP and EP reduced ear edema induced by croton oil in rats. In the same animal model, MP and EP reduced neutrophil infiltration, as indicated by decreased myeloperoxidase (MPO) activity. In conclusion, this study demonstrates the effectiveness of MP and EP in combating inflammation in several experimental models. -- Highlights: ? Efficacy of MP and EP in combating inflammation was displayed in several models. ? MP and EP reduced carrageenan-induced rat paw edema and prostaglandin E2 level. ? MP and EP decreased TNF-? and IL-6 levels in experimental endotoxemia. ? MP and EP reduced NF-?B expression and histological changes in rat liver and lung. ? MP and EP reduced croton oil-induced ear edema and neutrophil infiltration.

  13. Nonpremixed ignition, laminar flame propagation, and mechanism reduction of n-butanol, iso-butanol, and methyl butanoate

    SciTech Connect (OSTI)

    Lu, Wei; Kelley, A. P.; Law, C. K.

    2011-01-01

    The non-premixed ignition temperature of n-butanol (CH{sub 3}CH{sub 2}CH{sub 2}CH{sub 2}OH), iso-butanol ((CH{sub 3}){sub 2}CHCH{sub 2}OH) and methyl butanoate (CH{sub 3}CH{sub 2}CH{sub 2}COOCH{sub 3}) was measured in a liquid pool assembly by heated oxidizer in a stagnation flow for system pressures of 1 and 3 atm. In addition, the stretch-corrected laminar flame speeds of mixtures of airn-butanol/iso-butanol/methyl butanoate were determined from the outwardly propagating spherical flame at initial pressures of up to 2 atm, for an extensive range of equivalence ratio. The ignition temperature and laminar flame speeds of n-butanol and methyl butanoate were computationally simulated with three recently developed kinetic mechanisms in the literature. Dominant reaction pathways to ignition and flame propagation were identified and discussed through a chemical explosive mode analysis (CEMA) and sensitivity analysis. The detailed models were further reduced through a series of systematic strategies. The reduced mechanisms provided excellent agreement in both homogeneous and diffusive combustion environments and greatly improved the computation efficiency.

  14. Phytoremediation of ionic and methyl mercury pollution. 1997 annual progress report

    SciTech Connect (OSTI)

    Meagher, R.B.

    1997-01-01

    'The long-term goal of this research is to manipulate single-gene traits into plants, enabling them to process heavy metals and remediate heavy-metal pollution by resistance, sequestration, removal, and management of these contaminants (Meagher and Rugh, 1996; Meagher et al., 1997). The working hypothesis behind this proposal was that transgenic plants expressing both the bacterial organo mercury lyase (merB) and the mercuric ion reductase gene (merA) will (A) remove the mercury from polluted sites and (B) prevent methyl mercury from entering the food chain. The authors have had a very successful first year either testing aspects of this hypothesis directly or preparing material needed for future experiments. The results are outlined below under goals A and B, which are explicit in this hypothesis. There were less than 10% of the funds remaining in any category as projected in the first 12 month budget at the end of the first year, with the exception of the equipment category which had 25% of the funds remaining ({approximately} $8,000). Much of this remaining equipment money is being spent this week on a mercury vapor analyzer. It might be useful to remember that at the time this grant was awarded, the authors had successfully engineered a small model plant, Arabidopsis thalianat to use a highly modified bacterial mercuric ion reductase gene, merA9, to detoxify ionic mercury (Hg(II)), reducing it to Hg(0) (Rugh et al., 1996). Seeds from these plants germinate, grow, and set seed at normal growth rates on levels of Hg(II) that are lethal to normal plants. In assays on transgenic seedlings suspended in a solution of Hg(II), 10 ng of Hg(0) was evolved per min per mg wet weight of plant tissue. However, at that time, they had no information on expression of merA in any other plant species, nor had they expressed merB in any plant.'

  15. Methyl-parathion decreases sperm function and fertilization capacity after targeting spermatocytes and maturing spermatozoa

    SciTech Connect (OSTI)

    Pina-Guzman, Belem; Sanchez-Gutierrez, M.; Marchetti, Francesco; Hernandez-Ochoa, I.; Solis-Heredia, M.J .; Quintanilla-Vega, B.

    2009-05-03

    Paternal germline exposure to organophosphorous pesticides (OP) has been associated with reproductive failures and adverse effects in the offspring. Methyl parathion (Me-Pa), a worldwide-used OP, has reproductive adverse effects and is genotoxic to sperm. Oxidative damage has been involved in the genotoxic and reproductive effects of OP. The purpose of this study was to determine the effects of Me-Pa on spermatozoa function and ability to fertilize. Male mice were exposed to Me-Pa (20 mg/kg bw, i.p.) and spermatozoa from epididymis-vas deferens were collected at 7 or 28 days post-treatment (dpt) to assess the effects on maturing spermatozoa and spermatocytes, respectively. DNA damage was evaluated by nick translation (NT-positive cells) and SCSA (percentDFI); lipoperoxidation (LPO) by malondialdehyde production; sperm function by spontaneous- and induced-acrosome reactions (AR); mitochondrial membrane potential (MMP) by using the JC-1 flurochrome; and, fertilization ability by an in vitro assay and in vivo mating. Results showed alterations in DNA integrity (percentDFI and NT-positive cells) at 7 and 28 dpt, in addition to decreased sperm quality and a decrease in induced-AR; reduced MMP and LPO was observed only at 7 dpt. We found negative correlations between LPO and all sperm alterations. Altered sperm functional parameters were associated with reduced fertilization rates at both times, evaluated either in vitro or in vivo. These results show that Me-Pa exposure of maturing spermatozoa and spermatocytes affects many sperm functional parameters that result in a decreased fertilizing capacity. Oxidative stress seems to be a likely mechanism ofthe detrimental effects of Me-Pa in male germ cells.

  16. Methyl chloride via oxyhydrochlorination of methane. Quarterly technical progress report No. 13, October--December 1994

    SciTech Connect (OSTI)

    1995-02-01

    The purpose of this contract is to develop a process for converting light alkane gases to methyl chloride via oxyhydrochlorination using highly selective, stable catalysts in fixed-bed reactors designed to remove the large amount of heat generated, so as to control the reaction temperature. Further, the objective is to obtain the engineering data base necessary for developing a commercially feasible process and to evaluate t economics of the process. Significant progress was made in six different technical areas during this quarter. These key highlights are: (1) Evaluation of catalyst samples from UCI led to the ordering of the OHC PDU catalyst batch. This catalyst batch arrived, was screened and found to be defective, and was reordered. (2) Natural gas containing higher hydrocarbons was used as a methane source. The reactant mixture formed oxygenates at temperatures lower than observed in the past. Burning at such low temperatures seems to create a product stream containing very little CH{sub 2}Cl{sub 2}. (3) Although it has not been decided if the PDU will use natural gas from the plant or methane or natural gas from cylinders as a methane feed source, it was concluded that an adsorption unit to remove sulfur and higher hydrocarbons is not necessary at this time. (4) PDU construction was completed in December. The bulk of insulation work was completed at the end of November. Much effort has been put into pressure testing the PDU`s systems. The startup team has become adept at finding and correcting such leaks. (5) SOP writing for the PDU was completed this quarter with communication with the software programmer to insure agreement between the software and SOP.

  17. Methyl Formate Oxidation: Speciation Data, Laminar Burning Velocities, Ignition Delay Times and a Validated Chemical Kinetic Model

    SciTech Connect (OSTI)

    Dooley, S.; Burke, M. P.; Chaos, M.; Stein, Y.; Dryer, F. L.; Zhukov, V. P.; Finch, O.; Simmie, J. M.; Curran, H. J.

    2010-07-16

    The oxidation of methyl formate (CH{sub 3}OCHO) has been studied in three experimental environments over a range of applied combustion relevant conditions: 1. A variable-pressure flow reactor has been used to quantify reactant, major intermediate and product species as a function of residence time at 3 atm and 0.5% fuel concentration for oxygen/fuel stoichiometries of 0.5, 1.0, and 1.5 at 900 K, and for pyrolysis at 975 K. 2. Shock tube ignition delays have been determined for CH{sub 3}OCHO/O{sub 2}/Ar mixtures at pressures of ? 2.7, 5.4, and 9.2 atm and temperatures of 12751935 K for mixture compositions of 0.5% fuel (at equivalence ratios of 1.0, 2.0, and 0.5) and 2.5% fuel (at an equivalence ratio of 1.0). 3. Laminar burning velocities of outwardly propagating spherical CH{sub 3}OCHO/air flames have been determined for stoichiometries ranging from 0.81.6, at atmospheric pressure using a pressure-release-type high-pressure chamber. A detailed chemical kinetic model has been constructed, validated against, and used to interpret these experimental data. The kinetic model shows that methyl formate oxidation proceeds through concerted elimination reactions, principally forming methanol and carbon monoxide as well as through bimolecular hydrogen abstraction reactions. The relative importance of elimination versus abstraction was found to depend on the particular environment. In general, methyl formate is consumed exclusively through molecular decomposition in shock tube environments, while at flow reactor and freely propagating premixed flame conditions, there is significant competition between hydrogen abstraction and concerted elimination channels. It is suspected that in diffusion flame configurations the elimination channels contribute more significantly than in premixed environments.

  18. Using the apparent diffusion coefficient to identifying MGMT promoter methylation status early in glioblastoma: importance of analytical method

    SciTech Connect (OSTI)

    Rundle-Thiele, Dayle; Day, Bryan; Stringer, Brett; Fay, Michael; Martin, Jennifer; Jeffree, Rosalind L; Thomas, Paul; Bell, Christopher; Salvado, Olivier; Gal, Yaniv; Coulthard, Alan; Crozier, Stuart; Rose, Stephen

    2015-06-15

    Accurate knowledge of O{sup 6}-methylguanine methyltransferase (MGMT) gene promoter subtype in patients with glioblastoma (GBM) is important for treatment. However, this test is not always available. Pre-operative diffusion MRI (dMRI) can be used to probe tumour biology using the apparent diffusion coefficient (ADC); however, its ability to act as a surrogate to predict MGMT status has shown mixed results. We investigated whether this was due to variations in the method used to analyse ADC. We undertook a retrospective study of 32 patients with GBM who had MGMT status measured. Matching pre-operative MRI data were used to calculate the ADC within contrast enhancing regions of tumour. The relationship between ADC and MGMT was examined using two published ADC methods. A strong trend between a measure of ‘minimum ADC’ and methylation status was seen. An elevated minimum ADC was more likely in the methylated compared to the unmethylated MGMT group (U = 56, P = 0.0561). In contrast, utilising a two-mixture model histogram approach, a significant reduction in mean measure of the ‘low ADC’ component within the histogram was associated with an MGMT promoter methylation subtype (P < 0.0246). This study shows that within the same patient cohort, the method selected to analyse ADC measures has a significant bearing on the use of that metric as a surrogate marker of MGMT status. Thus for dMRI data to be clinically useful, consistent methods of data analysis need to be established prior to establishing any relationship with genetic or epigenetic profiling.

  19. Synthesis Of [2h, 13c]M [2h2m 13c], And [2h3,, 13c] Methyl Aryl Sulfones And Sulfoxides

    DOE Patents [OSTI]

    Martinez, Rodolfo A.; Alvarez, Marc A.; Silks, III, Louis A.; Unkefer, Clifford J.; Schmidt, Jurgen G.

    2004-07-20

    The present invention is directed to labeled compounds, [.sup.2 H.sub.1, .sup.13 C], [.sup.2 H.sub.2, .sup.13 C] and [.sup.2 H.sub.3, .sup.13 C]methyl aryl sulfones and [.sup.2 H.sub.1, .sup.13 C], [.sup.2 H.sub.2, .sup.13 C] and [.sup.2 H.sub.3, .sup.13 C]methyl aryl sulfoxides, wherein the .sup.13 C methyl group attached to the sulfur of the sulfone or sulfoxide includes exactly one, two or three deuterium atoms and the aryl group is selected from the group consisting of 1-naphthyl, substituted 1-naphthyl, 2-naphthyl, substituted 2-naphthyl, and phenyl groups with the structure: ##STR1## wherein R.sub.1, R.sub.2, R.sub.3, R.sub.4 and R.sub.5 are each independently, hydrogen, a C.sub.1 -C.sub.4 lower alkyl, a halogen, an amino group from the group consisting of NH.sub.2, NHR and NRR' where R and R' are each a C.sub.1 -C.sub.4 lower alkyl, a phenyl, or an alkoxy group. The present invention is also directed to processes of preparing methyl aryl sulfones and methyl aryl sulfoxides.

  20. High Temperature, Low Relative Humidity, Polymer-type Membranes Based on Disulfonated Poly(arylene ether) Block and Random Copolymers Optionally Incorporating Protonic Conducting Layered Water insoluble Zirconium Fillers

    SciTech Connect (OSTI)

    McGrath, James E.; Baird, Donald G.

    2010-06-03

    Our research group has been engaged in the past few years in the synthesis of biphenol based partially disulfonated poly(arylene ether sulfone) random copolymers as potential PEMs. This series of polymers are named as BPSH-xx, where BP stands for biphenol, S stands for sulfonated, H stands for acidified and xx represents the degree of disulfonation. All of these sulfonated copolymers phase separate to form nano scale hydrophilic and hydrophobic morphological domains. The hydrophilic phase containing the sulfonic acid moieties causes the copolymer to absorb water. Water confined in hydrophilic pores in concert with the sulfonic acid groups serve the critical function of proton (ion) conduction and water transport in these systems. Both Nafion and BPSH show high proton conductivity at fully hydrated conditions. However proton transport is especially limited at low hydration level for the BPSH random copolymer. It has been observed that the diffusion coefficients of both water and protons change with the water content of the pore. This change in proton and water transport mechanisms with hydration level has been attributed to the solvation of the acid groups and the amount of bound and bulk-like water within a pore. At low hydration levels most of the water is tightly associated with sulfonic groups and has a low diffusion coefficient. This tends to encourage isolated domain morphology. Thus, although there may be significant concentrations of protons, the transport is limited by the discontinuous morphological structure. Hence the challenge lies in how to modify the chemistry of the polymers to obtain significant protonic conductivity at low hydration levels. This may be possible if one can alter the chemical structure to synthesize nanophase separated ion containing block copolymers. Unlike the BPSH copolymers, where the sulfonic acid groups are randomly distributed along the chain, the multiblock copolymers will feature an ordered sequence of hydrophilic and hydrophobic segments. If, like in Nafion, connectivity is established between the hydrophilic domains in these multiblock copolymers, they will not need as much water, and hence will show much better protonic conductivity than the random copolymers (with similar degree of sulfonation, or IEC) at partially hydrated conditions. The goal of this research is to develop a material suitable for use as a polymer electrolyte membrane which by the year 2010 will meet all the performance requirements associated with fuel cell operation at high temperatures and low relative humidity, and will out-perform the present standard Nafion{reg_sign}. In particular, it is our objective to extend our previous research based on the use of thermally, oxidatively, and hydrolytically, ductile, high Tg ion containing polymers based on poly(arylene ethers) to the production of polymer electrolyte membranes which will meet all the performance requirements in addition to having an areal resistance of < 0.05 ohm-cm{sup 2} at a temperature of up to 120 C, relative humidity of 25 to 50%, and up to 2.5 atm total pressure. In many instances, our materials already out performs Nafion{reg_sign}, and it is expected that with some modification by either combining with conductive inorganic fillers and/or synthesizing as a block copolymer it will meet the performance criteria at high temperatures and low relative humidity. A key component in improving the performance of the membranes (and in particular proton conductivity) and meeting the cost requirements of $40/m{sup 2} is our development of a film casting process, which shows promise for generation of void free thin films of uniform thickness with controlled polymer alignment and configuration.

  1. M-transfer activity of MCM-41 materials in 1-hexene isomerization reactions

    SciTech Connect (OSTI)

    Dominguez, J.M.; Hernandez, F.; Terres, E.; Toledo, A.; Navarrete, J.

    1996-10-01

    The gasoline reformulation scheme includes the use of oxygenated additives MTBE (methyl-ter-butyl-ether), TAME (ter-amyl-methyl-ether), ETBE (ethyl-ter-butyl-ether) and DIPE (di-isopropyl-ether), which have the iso-olefins (i-C{sub 3}{sup =}, i-C{sub 4}{sup =}, i-C{sub 5}{sup =}) as precursors. In this respect, olefin production from FCC units must be enhanced to cover the demand. A series of new catalytic materials with lower hydrogen transfer activity could enhance the olefin yield from the FCC reactors.

  2. Process Design and Economics for the Conversion of Lignocellulosic Biomass to Hydrocarbons via Indirect Liquefaction. Thermochemical Research Pathway to High-Octane Gasoline Blendstock Through Methanol/Dimethyl Ether Intermediates

    SciTech Connect (OSTI)

    Tan, Eric C. D.; Talmadge, Michael; Dutta, Abhijit; Hensley, Jesse; Schaidle, Josh; Biddy, Mary; Humbird, David; Snowden-Swan, Lesley J.; Ross, Jeff; Sexton, Danielle; Yap, Raymond; Lukas, John

    2015-03-01

    This report was developed as part of the U.S. Department of Energy’s Bioenergy Technologies Office’s (BETO’s) efforts to enable the development of technologies for the production of infrastructure-compatible, cost-competitive liquid hydrocarbon fuels from lignocellulosic biomass feedstocks. The research funded by BETO is designed to advance the state of technology of biomass feedstock supply and logistics, conversion, and overall system sustainability. It is expected that these research improvements will be made within the 2022 timeframe. As part of their involvement in this research and development effort, the National Renewable Energy Laboratory and the Pacific Northwest National Laboratory investigate the economics of conversion pathways through the development of conceptual biorefinery process models and techno-economic analysis models. This report describes in detail one potential conversion process for the production of high-octane gasoline blendstock via indirect liquefaction of biomass. The processing steps of this pathway include the conversion of biomass to synthesis gas or syngas via indirect gasification, gas cleanup, catalytic conversion of syngas to methanol intermediate, methanol dehydration to dimethyl ether (DME), and catalytic conversion of DME to high-octane, gasoline-range hydrocarbon blendstock product. The conversion process configuration leverages technologies previously advanced by research funded by BETO and demonstrated in 2012 with the production of mixed alcohols from biomass. Biomass-derived syngas cleanup via reforming of tars and other hydrocarbons is one of the key technology advancements realized as part of this prior research and 2012 demonstrations. The process described in this report evaluates a new technology area for the downstream utilization of clean biomass-derived syngas for the production of high-octane hydrocarbon products through methanol and DME intermediates. In this process, methanol undergoes dehydration to DME, which is subsequently converted via homologation reactions to high-octane, gasoline-range hydrocarbon products.

  3. High optical and switching performance electrochromic devices based on a zinc oxide nanowire with poly(methyl methacrylate) gel electrolytes

    SciTech Connect (OSTI)

    Chun, Young Tea; Chu, Daping; Neeves, Matthew; Placido, Frank; Smithwick, Quinn

    2014-11-10

    High performance electrochromic devices have been fabricated and demonstrated utilizing a solid polymer electrolyte and zinc oxide (ZnO) nanowire (NW) array counter electrode. The poly(methyl methacrylate) based polymer electrolyte was spin coated upon hydrothermally grown ZnO NW array counter electrodes, while electron beam evaporated NiO{sub x} thin films formed the working electrodes. Excellent optical contrast and switching speeds were observed in the fabricated devices with active areas of 2?cm{sup 2}, exhibiting an optical contrast of 73.11% at the wavelength of 470?nm, combined with a fast switching time of 0.2 s and 0.4 s for bleaching and coloration, respectively.

  4. (E)-2-[(2-Bromophenylimino)methyl]-5-methoxyphenol: X-ray and DFT-calculated structures

    SciTech Connect (OSTI)

    Kosar, B. Albayrak, C.; Odabasoglu, M.; Bueyuekguengoer, O.

    2010-12-15

    The crystal structure of (E)-2-[(2-Bromophenylimino)methyl]-5-methoxyphenol is determined by using X-ray diffraction and then the molecular structure is investigated with density functional theory (DFT). X-Ray study shows that the title compound has a strong intramolecular O-H-N hydrogen bond and three dimensional crystal structure is primarily determined by C-H-{pi} and weak van der Waals interactions. The strong O-H-N bond is an evidence of the preference for the phenol-imine tautomeric form in the solid state. Optimized molecular geometry is calculated with DFT at the B3LYP/6-31G(d,p) level. The IR spectra of compound were recorded experimentally and calculated to compare with each other. The results from both experiment and theoretical calculations are compared in this study.

  5. Sub-5 nm Domains in Ordered Poly(cyclohexylethylene)-block-poly(methyl methacrylate) Block Polymers for Lithography.

    SciTech Connect (OSTI)

    Kennemur, Justin; Yao, Li; Bates, Frank Stephen; Hillmyer, Marc

    2014-01-01

    A series of poly(cyclohexylethylene)-block-poly- (methyl methacrylate) (PCHE PMMA) diblock copolymers with varying molar mass (4.9 kg/mol Mn 30.6 kg/mol) and narrow molar mass distribution were synthesized through a combination of anionic and atom transfer radical polymerization (ATRP) techniques. Heterogeneous catalytic hydrogenation of -(hydroxy)polystyrene (PS-OH) yielded -(hydroxy)poly(cyclohexylethylene) (PCHEOH) with little loss of hydroxyl functionality. PCHE-OH was reacted with -bromoisobutyryl bromide (BiBB) to produce an ATRP macroinitiator used for the polymerization of methyl methacrylate. PCHE PMMA is a glassy, thermally stable material with a large effective segment segment interaction parameter, eff = (144.4 6.2)/T (0.162 0.013), determined by meanfield analysis of order-to-disorder transition temperatures (TODT) measured by dynamic mechanical analysis and differential scanning calorimetry. Ordered lamellar domain pitches (9 D 33 nm) were identified by small-angle X-ray scattering from neat BCPs containing 43 52 vol % PCHE ( f PCHE). Atomic force microscopy was used to show 7.5 nm lamellar features (D = 14.8 nm) which are some of the smallest observed to date. The lowest molar mass sample (Mn = 4.9 kg/mol, f PCHE = 0.46) is characterized by TODT = 173 3 C and sub-5 nm nanodomains, which together with the sacrificial properties of PMMA and the high overall thermal stability place this material at the forefront of high- systems for advanced nanopatterning applications.

  6. Differences in volatile methyl siloxane (VMS) profiles in biogas from landfills and anaerobic digesters and energetics of VMS transformations

    SciTech Connect (OSTI)

    Tansel, Berrin Surita, Sharon C.

    2014-11-15

    Highlights: • In the digester gas, D4 and D5 comprised the 62% and 27% if siloxanes, respectively. • In landfill gas, the bulk of siloxanes were TMSOH (58%) followed by D4 (17%). • Methane utilization may be a possible mechanism for TMSOH formation in the landfills. • The geometric configurations of D4 and D5 molecules make them very stable. - Abstract: The objectives of this study were to compare the types and levels of volatile methyl siloxanes (VMS) present in biogas generated in the anaerobic digesters and landfills, evaluate the energetics of siloxane transformations under anaerobic conditions, compare the conditions in anaerobic digesters and municipal solid waste (MSW) landfills which result in differences in siloxane compositions. Biogas samples were collected at the South District Wastewater Treatment Plant and South Dade Landfill in Miami, Florida. In the digester gas, D4 and D5 comprised the bulk of total siloxanes (62% and 27%, respectively) whereas in the landfill gas, the bulk of siloxanes were trimethylsilanol (TMSOH) (58%) followed by D4 (17%). Presence of high levels of TMSOH in the landfill gas indicates that methane utilization may be a possible reaction mechanism for TMSOH formation. The free energy change for transformation of D5 and D4 to TMSOH either by hydrogen or methane utilization are thermodynamically favorable. Either hydrogen or methane should be present at relatively high concentrations for TMSOH formation which explains the high levels present in the landfill gas. The high bond energy and bond distance of the Si–O bond, in view of the atomic sizes of Si and O atoms, indicate that Si atoms can provide a barrier, making it difficult to break the Si–O bonds especially for molecules with specific geometric configurations such as D4 and D5 where oxygen atoms are positioned inside the frame formed by the large Si atoms which are surrounded by the methyl groups.

  7. Supramolecular organization of calix[4]pyrrole with a methyl-trialkylammonium anion exchanger leads to remarkable reversal of selectivity for sulfate extraction vs. nitrate

    SciTech Connect (OSTI)

    Borman, Christopher J; Custelcean, Radu; Hay, Benjamin; Bill, Nathan; Sessler, Jonathan L.; Moyer, Bruce A

    2011-01-01

    meso-Octamethylcalix[4]pyrrole (C4P) enhances sulfate selectivity in solvent extraction by Aliquat 336N, an effect ascribed to the supramolecular preorganization and thermodynamic stability imparted by insertion of the methyl group of the Aliquat cation into the cup of C4P in its cone conformation.

  8. Acute alteration of cardiac ECG, action potential, I{sub Kr} and the human ether-a-go-go-related gene (hERG) K{sup +} channel by PCB 126 and PCB 77

    SciTech Connect (OSTI)

    Park, Mi-Hyeong; Park, Won Sun; Jo, Su-Hyun

    2012-07-01

    Polychlorinated biphenyls (PCBs) have been known as serious persistent organic pollutants (POPs), causing developmental delays and motor dysfunction. We have investigated the effects of two PCB congeners, 3,3′,4,4′-tetrachlorobiphenyl (PCB 77) and 3,3′,4,4′,5-pentachlorobiphenyl (PCB 126) on ECG, action potential, and the rapidly activating delayed rectifier K{sup +} current (I{sub Kr}) of guinea pigs' hearts, and hERG K{sup +} current expressed in Xenopus oocytes. PCB 126 shortened the corrected QT interval (QTc) of ECG and decreased the action potential duration at 90% (APD{sub 90}), and 50% of repolarization (APD{sub 50}) (P < 0.05) without changing the action potential duration at 20% (APD{sub 20}). PCB 77 decreased APD{sub 20} (P < 0.05) without affecting QTc, APD{sub 90}, and APD{sub 50}. The PCB 126 increased the I{sub Kr} in guinea-pig ventricular myocytes held at 36 °C and hERG K{sup +} current amplitude at the end of the voltage steps in voltage-dependent mode (P < 0.05); however, PCB 77 did not change the hERG K{sup +} current amplitude. The PCB 77 increased the diastolic Ca{sup 2+} and decreased Ca{sup 2+} transient amplitude (P < 0.05), however PCB 126 did not change. The results suggest that PCB 126 shortened the QTc and decreased the APD{sub 90} possibly by increasing I{sub Kr}, while PCB 77 decreased the APD{sub 20} possibly by other modulation related with intracellular Ca{sup 2+}. The present data indicate that the environmental toxicants, PCBs, can acutely affect cardiac electrophysiology including ECG, action potential, intracellular Ca{sup 2+}, and channel activity, resulting in toxic effects on the cardiac function in view of the possible accumulation of the PCBs in human body. -- Highlights: ► PCBs are known as serious environmental pollutants and developmental disruptors. ► PCB 126 shortened QT interval of ECG and action potential duration. ► PCB 126 increased human ether-a-go-go-related K{sup +} current and I{sub Kr}. ► PCB 77 decreased action potential duration and increased intracellular Ca{sup 2+} content. ► PCBs acutely change cardiac electrophysiology and rhythmicity.

  9. Development of alternative fuels from coal derived syngas. Topical report: Task 2.2, Demonstration of a one-step slurry-phase process for the production of dimethyl ether/methanol mixtures at the LaPorte Alternative Fuels Development Unit

    SciTech Connect (OSTI)

    Not Available

    1993-06-01

    This report documents engineering, modification, and operations efforts of demonstration of dimethyl-ether/methanol coproduction in a slurry-phase reactor, carried out in a 2-ft diameter bubble column reactor. Equipment modifications made it possible to remove the product DME and by-product CO{sub 2} from the reactor effluent. Coproduction of dimethyl-ether (DME) and methanol (MeOH) was accomplished in the slurry reactor by physically mixing two different catalysts. The catalyst used to produce MeOH from syngas was manufactured by BASF (type S3-86); the catalyst used to convert MeOH to DME was Catapal {gamma}-alumina. Ratio of MeOH to DME catalysts determined the selectivity towards DME. The demonstration sought to study effect of cocatalyst ratio on product selectivity. Three different proportions of DME catalyst were examined: 0, 6.6, and 19.3 wt % alumina. At each catalyst proportion, the plant was operated at two different gas space velocities. Some process variables were maintained at fixed conditions; most important variables included: reactor temperature (482F), reactor pressure (750 psig), and reactor feed gas composition (35% H{sub 2}, 51% CO,13% CO{sub 2} 1% other, nominal-molar basis).

  10. Role for DNA methylation in the regulation of miR-200c and miR-141 expression in normal and cancer cells

    SciTech Connect (OSTI)

    Vrba, Lukas; Jensen, Taylor J.; Garbe, James C.; Heimark, Ronald L.; Cress, Anne E.; Dickinson, Sally; Stampfer, Martha R.; Futscher, Bernard W.

    2009-12-23

    BACKGROUND: The microRNA-200 family participates in the maintenance of an epithelial phenotype and loss of its expression can result in epithelial to mesenchymal transition (EMT). Furthermore, the loss of expression of miR-200 family members is linked to an aggressive cancer phenotype. Regulation of the miR-200 family expression in normal and cancer cells is not fully understood. METHODOLOGY/ PRINCIPAL FINDINGS: Epigenetic mechanisms participate in the control of miR-200c and miR-141 expression in both normal and cancer cells. A CpG island near the predicted mir-200c/mir-141 transcription start site shows a striking correlation between miR-200c and miR-141 expression and DNA methylation in both normal and cancer cells, as determined by MassARRAY technology. The CpG island is unmethylated in human miR-200/miR-141 expressing epithelial cells and in miR-200c/miR-141 positive tumor cells. The CpG island is heavily methylated in human miR-200c/miR-141 negative fibroblasts and miR-200c/miR-141 negative tumor cells. Mouse cells show a similar inverse correlation between DNA methylation and miR-200c expression. Enrichment of permissive histone modifications, H3 acetylation and H3K4 trimethylation, is seen in normal miR-200c/miR-141-positive epithelial cells, as determined by chromatin immunoprecipitation coupled to real-time PCR. In contrast, repressive H3K9 dimethylation marks are present in normal miR-200c/miR-141-negative fibroblasts and miR-200c/miR-141 negative cancer cells and the permissive histone modifications are absent. The epigenetic modifier drug, 5-aza-2'-deoxycytidine, reactivates miR-200c/miR-141 expression showing that epigenetic mechanisms play a functional role in their transcriptional control. CONCLUSIONS/ SIGNIFICANCE: We report that DNA methylation plays a role in the normal cell type-specific expression of miR-200c and miR-141 and this role appears evolutionarily conserved, since similar results were obtained in mouse. Aberrant DNA methylation of the miR-200c/141 CpG island is closely linked to their inappropriate silencing in cancer cells. Since the miR-200c cluster plays a significant role in EMT, our results suggest an important role for DNA methylation in the control of phenotypic conversions in normal cells.

  11. Gestational exposure to diethylstilbestrol alters cardiac structure/function, protein expression and DNA methylation in adult male mice progeny

    SciTech Connect (OSTI)

    Haddad, Rami, E-mail: rami.haddad@mail.mcgill.ca [Lady Davis Institute for Medical Research, Jewish General Hospital, 3755 chemin Cote Ste Catherine, Montral, Qubec, Canada H3T 1E2 (Canada) [Lady Davis Institute for Medical Research, Jewish General Hospital, 3755 chemin Cote Ste Catherine, Montral, Qubec, Canada H3T 1E2 (Canada); Division of Experimental Medicine, Department of Medicine, McGill University, 850 Sherbrooke Street, Montral, Qubec, Canada H3A 1A2 (Canada); Kasneci, Amanda, E-mail: amanda.kasneci@mail.mcgill.ca [Lady Davis Institute for Medical Research, Jewish General Hospital, 3755 chemin Cote Ste Catherine, Montral, Qubec, Canada H3T 1E2 (Canada)] [Lady Davis Institute for Medical Research, Jewish General Hospital, 3755 chemin Cote Ste Catherine, Montral, Qubec, Canada H3T 1E2 (Canada); Mepham, Kathryn, E-mail: katherine.mepham@mail.mcgill.ca [Lady Davis Institute for Medical Research, Jewish General Hospital, 3755 chemin Cote Ste Catherine, Montral, Qubec, Canada H3T 1E2 (Canada) [Lady Davis Institute for Medical Research, Jewish General Hospital, 3755 chemin Cote Ste Catherine, Montral, Qubec, Canada H3T 1E2 (Canada); Division of Experimental Medicine, Department of Medicine, McGill University, 850 Sherbrooke Street, Montral, Qubec, Canada H3A 1A2 (Canada); Sebag, Igal A., E-mail: igal.sebag@mcgill.ca [Division of Cardiology, Jewish General Hospital, 3755 chemin Cote Ste Catherine, Montral, Qubec, Canada H3T 1E2 (Canada); and others

    2013-01-01

    Pregnant women, and thus their fetuses, are exposed to many endocrine disruptor compounds (EDCs). Fetal cardiomyocytes express sex hormone receptors making them potentially susceptible to re-programming by estrogenizing EDCs. Diethylstilbestrol (DES) is a proto-typical, non-steroidal estrogen. We hypothesized that changes in adult cardiac structure/function after gestational exposure to the test compound DES would be a proof in principle for the possibility of estrogenizing environmental EDCs to also alter the fetal heart. Vehicle (peanut oil) or DES (0.1, 1.0 and 10.0 ?g/kg/da.) was orally delivered to pregnant C57bl/6n dams on gestation days 11.514.5. At 3 months, male progeny were left sedentary or were swim trained for 4 weeks. Echocardiography of isoflurane anesthetized mice revealed similar cardiac structure/function in all sedentary mice, but evidence of systolic dysfunction and increased diastolic relaxation after swim training at higher DES doses. The calcium homeostasis proteins, SERCA2a, phospholamban, phospho-serine 16 phospholamban and calsequestrin 2, are important for cardiac contraction and relaxation. Immunoblot analyses of ventricle homogenates showed increased expression of SERCA2a and calsequestrin 2 in DES mice and greater molecular remodeling of these proteins and phospho-serine 16 phospholamban in swim trained DES mice. DES increased cardiac DNA methyltransferase 3a expression and DNA methylation in the CpG island within the calsequestrin 2 promoter in heart. Thus, gestational DES epigenetically altered ventricular DNA, altered cardiac function and expression, and reduced the ability of adult progeny to cardiac remodel when physically challenged. We conclude that gestational exposure to estrogenizing EDCs may impact cardiac structure/function in adult males. -- Highlights: ? Gestational DES changes cardiac SERCA2a and CASQ2 expression. ? Echocardiography identified systolic dysfunction and increased diastolic relaxation. ? DES increased DNMT3a expression and increased CpG DNA methylation. ? DES impacts fetal heart reducing cardiac reserve on challenge in adulthood. ? Fetal heart can be re-programmed by a non-steroidal estrogen.

  12. Photocatalytic degradation of methyl orange dye in water solutions in the presence of MWCNT/TiO{sub 2} composites

    SciTech Connect (OSTI)

    Da Dalt, S.; Alves, A.K.; Bergmann, C.P.

    2013-05-15

    Highlights: ? MWCNTs/TiO{sub 2} composites were obtained to degrade organic dyes in water. ? MWCNT/TiO{sub 2} composites were analyzed by photocatalysis and structural characterization. ? The photocatalytic shows efficient method for the degradation of dyes from aqueous effluents. - Abstract: The textile and dyestuff industries are the primary sources of the release of synthetic dyes into the environment and usually there are major pollutants in dye wastewaters. Because of their toxicity and slow degradation, these dyes are categorized as environmentally hazardous materials. In this context, carbon nanotubes/TiO{sub 2} (CNTs/TiO{sub 2}) composites were prepared using multi-walled CNTs (MWCNTs), titanium (IV) propoxide and commercial TiO{sub 2} (P25{sup }) as titanium oxide sources, to degrade the methyl orange dye in solution through photocatalyst activity using UV irradiation. The composites were prepared by solution processing followed by thermal treatment at 400, 500 and 600 C. The heterojunction between nanotubes and TiO{sub 2} was confirmed by XRD, specific surface area. The coating morphology was observed with SEM and TEM.

  13. Effects of Turbulence on the Combustion Properties of Partially Premixed Flames of Canola Methyl Ester and Diesel Blends

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Dhamale, N.; Parthasarathy, R. N.; Gollahalli, S. R.

    2011-01-01

    Canola methyl ester (CME) is a biofuel that is a renewable alternative energy resource and is produced by the transesterification of canola oil. The objective of this study was to document the effects of turbulence on the combustion characteristics of blends of CME and No 2 diesel fuel in a partially-premixed flame environment. The experiments were conducted with mixtures of pre-vaporized fuel and air at an initial equivalence ratio of 7 and three burner exit Reynolds numbers, 2700, 3600, and 4500. Three blends with 25, 50, and 75% volume concentration of CME were studied. The soot volume fraction was highestmore » for the pure diesel flames and did not change significantly with Reynolds number due to the mutually compensating effects of increased carbon input rate and increased air entrainment as the Reynolds number was increased. The global NOx emission index was highest and the CO emission index was the lowest for the pure CME flame, and varied non-monotonically with biofuel content in the blend The mean temperature and the NOx concentration at three-quarter flame height were generally correlated, indicating that the thermal mechanism of NOx formation was dominant in the turbulent biofuel flames also.« less

  14. Hydrothermal synthesis of Mn vanadate nanosheets and visible-light photocatalytic performance for the degradation of methyl blue

    SciTech Connect (OSTI)

    Pei, L.Z. Xie, Y.K.; Pei, Y.Q.; Jiang, Y.X.; Yu, H.Y.; Cai, Z.Y.

    2013-07-15

    Graphical abstract: - Highlights: Mn vanadate nanosheets have been synthesized by simple hydrothermal process. The formation of Mn vanadate nanosheets can be controlled by growth conditions. Mn vanadate nanosheets exhibit good photocatalytic activities for methyl blue. - Abstract: Mn vanadate nanosheets have been synthesized via a facile hydrothermal route using ammonium metavanadate and Mn acetate as the raw materials, polyvinyl pyrrolidone (PVP) as the surfactant. X-ray diffraction (XRD) shows that the Mn vanadate nanosheets are composed of monoclinic MnV{sub 2}O{sub 6} phase. Scanning electron microscopy (SEM) observation indicates that the nanosheets have the average thickness of about 50 nm, length of 210 ?m and width of 800 nm to 2 ?m. The growth process of the Mn vanadate nanosheets has also been discussed based on the analysis of the roles of the growth conditions on the formation of the Mn vanadate nanosheets. The nanosheets show good photocatalytic activities for the degradation of methylene blue (MB) under visible light irradiation. About 72.96% MB can be degraded after visible light irradiation for 1 h over 10 mg Mn vanadate nanosheets in 10 mL MB solution with the concentration of 10 mg L{sup ?1}.

  15. Synthesis of 6-Methyl-9-n-propyldibenzothiophene-4-ol. Quarterly technical progress report No. 5, July 28--October 28, 1991

    SciTech Connect (OSTI)

    Not Available

    1991-10-28

    The material presented here has been described to some extent in Status Reports 12, 13, and 14 and covers the progress toward the synthesis of the modified target molecules 9-isopropyl-4-methoxy-6-methyldibenzothiophene (13) and 9-isopropyl-6-methyldibenzothiophene-4-ol (14). It is divided into three parts: (a) Dehydrogenation experiments On tetrahydrodibenzothiophene 12. (b) methoxyl methyl cleavage of 13 to 14 using boron tribromide. (c) isolation and purification of methoxydibenzothiophene 13.

  16. Structures of Escherichia coli DNA adenine methyltransferase (Dam) in complex with a non-GATC sequence: Potential implications for methylation-independent transcriptional repression

    SciTech Connect (OSTI)

    Horton, John R.; Zhang, Xing; Blumenthal, Robert M.; Cheng, Xiaodong

    2015-04-06

    DNA adenine methyltransferase (Dam) is widespread and conserved among the γ-proteobacteria. Methylation of the Ade in GATC sequences regulates diverse bacterial cell functions, including gene expression, mismatch repair and chromosome replication. Dam also controls virulence in many pathogenic Gram-negative bacteria. An unexplained and perplexing observation about Escherichia coli Dam (EcoDam) is that there is no obvious relationship between the genes that are transcriptionally responsive to Dam and the promoter-proximal presence of GATC sequences. Here, we demonstrate that EcoDam interacts with a 5-base pair non-cognate sequence distinct from GATC. The crystal structure of a non-cognate complex allowed us to identify a DNA binding element, GTYTA/TARAC (where Y = C/T and R = A/G). This element immediately flanks GATC sites in some Dam-regulated promoters, including the Pap operon which specifies pyelonephritis-associated pili. In addition, Dam interacts with near-cognate GATC sequences (i.e. 3/4-site ATC and GAT). All together, these results imply that Dam, in addition to being responsible for GATC methylation, could also function as a methylation-independent transcriptional repressor.

  17. Solgel auto combustion synthesis of CoFe{sub 2}O{sub 4}/1-methyl-2-pyrrolidone nanocomposite with ethylene glycol: Its magnetic characterization

    SciTech Connect (OSTI)

    Topkaya, R.; Kurtan, U.; Junejo, Y.; Baykal, A.

    2013-09-01

    Graphical abstract: - Highlights: CoFe{sub 2}O{sub 4} was generated by solgel autocombustion using 1-methyl-2-pyrrolidone and ethylene glycol. The presence of spin-disordered surface layer on magnetic core was established. A linear dependence of the coercivity on temperature was fitted to Kneller's law. - Abstract: Magnetic nanoparticles were generated by solgel auto combustion synthesis of metal salts in the presence of 1-methyl-2-pyrrolidone, a functional solvent and ethylene glycol as usual solvent. The average crystallite size was obtained by using line profile fitting as 11 5 nm. The saturation magnetization value decreases with usage of the ethylene glycol in synthesis. The observed exchange bias effect further confirms the existence of the magnetically ordered core surrounded by spin-disordered surface layer and the ethylene glycol. Square-root temperature dependence of coercivity can be fitted to Kneller's law in the temperature range of 10400 K. The reduced remanent magnetization values lower than the theoretical value of 0.5 for non-interacting single domain particles indicate the CoFe{sub 2}O{sub 4}-1-methyl-2-pyrrolidone nanocomposite to have uniaxial anisotropy instead of the expected cubic anisotropy according to the StonerWohlfarth model.

  18. Structures of Escherichia coli DNA adenine methyltransferase (Dam) in complex with a non-GATC sequence: Potential implications for methylation-independent transcriptional repression

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Horton, John R.; Zhang, Xing; Blumenthal, Robert M.; Cheng, Xiaodong

    2015-04-06

    DNA adenine methyltransferase (Dam) is widespread and conserved among the γ-proteobacteria. Methylation of the Ade in GATC sequences regulates diverse bacterial cell functions, including gene expression, mismatch repair and chromosome replication. Dam also controls virulence in many pathogenic Gram-negative bacteria. An unexplained and perplexing observation about Escherichia coli Dam (EcoDam) is that there is no obvious relationship between the genes that are transcriptionally responsive to Dam and the promoter-proximal presence of GATC sequences. Here, we demonstrate that EcoDam interacts with a 5-base pair non-cognate sequence distinct from GATC. The crystal structure of a non-cognate complex allowed us to identify amore » DNA binding element, GTYTA/TARAC (where Y = C/T and R = A/G). This element immediately flanks GATC sites in some Dam-regulated promoters, including the Pap operon which specifies pyelonephritis-associated pili. In addition, Dam interacts with near-cognate GATC sequences (i.e. 3/4-site ATC and GAT). All together, these results imply that Dam, in addition to being responsible for GATC methylation, could also function as a methylation-independent transcriptional repressor.« less

  19. The Vital Function of Fe3O4@Au nanocomposites for Hydrolase Biosensor Design and Its Application in Detection of Methyl Parathion

    SciTech Connect (OSTI)

    Zhao, Yuting; Zhang, Weiying; Lin, Yuehe; Du, Dan

    2013-02-04

    A nanocomposite of gold nanoparticles (AuNPs) decorating a magnetic Fe3O4 core was synthesized using cysteamine (SHNH2) as linker, and characterized by TEM, XPS, UV and electrochemistry. Then a hydrolase biosensor, based on self-assembly of methyl parathion hydrolase (MPH) on the Fe3O4@Au nanocomposite, was developed for sensitive and selective detection of the organophosphorus pesticide (OP) methyl parathion. The magnetic nanocomposite provides an easy way to construct the enzyme biosensor by simply exerting an external magnetic field, and also provides a simple way to renew the electrode surface by removing the magnet. Unlike inhibition-based enzyme biosensors, the hydrolase is not poisoned by OPs and thus is reusable for continuous measurement. AuNPs not only provide a large surface area, high loading efficiency and fast electron transfer, but also stabilize the enzyme through electrostatic interactions. The MPH biosensor shows rapid response and high selectivity for detection of methyl parathion, with a linear range from 0.5 to 1000 ng/mL and a detection limit of 0.1 ng/mL. It also shows acceptable reproducibility and stability. The simplicity and ease of operation of the proposed method has great potential for on-site detection of PS containing pesticides and provides a promising strategy to construct a robust biosensor.

  20. A CHRONIC INHALATION STUDY OF METHYL BROMIDE TOXICITY IN B6C3F1 MICE. (FINAL REPORT TO THE NATIONAL TOXICOLOGY PROGRAM)

    SciTech Connect (OSTI)

    HABER, S.B.

    1987-06-26

    This report provides a detailed account of a two year chronic inhalation study of methyl bromide toxicity in B6C3Fl mice conducted for the National Toxicology Program. Mice were randomized into three dose groups (10, 33 and 100 ppm methyl bromide) and one control group (0 ppm) per sex and exposed 5 days/week, 6 hours/day, for a total of 103 weeks. Endpoints included body weight; clinical signs and mortality, and at 6, 15 and 24 months of exposure, animals were sacrificed for organ weights, hematology and histopathology. In addition, a subgroup of animals in each dosage group was monitored for neurobehavioral and neuropathological changes. After only 20 weeks of exposure, 48% of the males and 12% of the females in the 100 ppm group had died. Exposures were terminated in that group and the surviving mice were observed for the duration of the study. Exposure of B6C3Fl mice to methyl bromide, even for only 20 weeks, produced significant changes in growth rate, mortality, organ weights and neurobehavioral functioning. These changes occurred in both males and females, but were more pronounced in males.

  1. Structural and biochemical insights into 2′-O-methylation at the 3′-terminal nucleotide of RNA by Hen1

    SciTech Connect (OSTI)

    Chan, Chio Mui; Zhou, Chun; Brunzelle, Joseph S.; Huang, Raven H.

    2010-01-28

    Small RNAs of {approx}20-30 nt have diverse and important biological roles in eukaryotic organisms. After being generated by Dicer or Piwi proteins, all small RNAs in plants and a subset of small RNAs in animals are further modified at their 3'-terminal nucleotides via 2'-O-methylation, carried out by the S-adenosylmethionine-dependent methyltransferase (MTase) Hen1. Methylation at the 3' terminus is vital for biological functions of these small RNAs. Here, we report four crystal structures of the MTase domain of a bacterial homolog of Hen1 from Clostridium thermocellum and Anabaena variabilis, which are enzymatically indistinguishable from the eukaryotic Hen1 in their ability to methylate small single-stranded RNAs. The structures reveal that, in addition to the core fold of the MTase domain shared by other RNA and DNA MTases, the MTase domain of Hen1 possesses a motif and a domain that are highly conserved and are unique to Hen1. The unique motif and domain are likely to be involved in RNA substrate recognition and catalysis. The structures allowed us to construct a docking model of an RNA substrate bound to the MTase domain of bacterial Hen1, which is likely similar to that of the eukaryotic counterpart. The model, supported by mutational studies, provides insight into RNA substrate specificity and catalytic mechanism of Hen1.

  2. Top Value-Added Chemicals from Biomass - Volume II„Results of...

    Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site

    ... Laboratory RVP Reid Vapor Pressure TAME methyl tertiary-amyl ether Tg glass transition temperature WGS water gas shift yr ... An approach that only considers process heat would be ...

  3. {sup 13}C-METHYL FORMATE: OBSERVATIONS OF A SAMPLE OF HIGH-MASS STAR-FORMING REGIONS INCLUDING ORION-KL AND SPECTROSCOPIC CHARACTERIZATION

    SciTech Connect (OSTI)

    Favre, Ccile; Bergin, Edwin A.; Crockett, Nathan R.; Neill, Justin L.; Carvajal, Miguel; Field, David; Jrgensen, Jes K.; Bisschop, Suzanne E.; Brouillet, Nathalie; Despois, Didier; Baudry, Alain; Kleiner, Isabelle; Marguls, Laurent; Huet, Thrse R.; Demaison, Jean E-mail: miguel.carvajal@dfa.uhu.es

    2015-01-01

    We have surveyed a sample of massive star-forming regions located over a range of distances from the Galactic center for methyl formate, HCOOCH{sub 3}, and its isotopologues H{sup 13}COOCH{sub 3} and HCOO{sup 13}CH{sub 3}. The observations were carried out with the APEX telescope in the frequency range 283.4-287.4GHz. Based on the APEX observations, we report tentative detections of the {sup 13}C-methyl formate isotopologue HCOO{sup 13}CH{sub 3} toward the following four massive star-forming regions: Sgr B2(N-LMH), NGC6334 IRS 1, W51 e2, and G19.61-0.23. In addition, we have used the 1mm ALMA science verification observations of Orion-KL and confirm the detection of the {sup 13}C-methyl formate species in Orion-KL and image its spatial distribution. Our analysis shows that the {sup 12}C/{sup 13}C isotope ratio in methyl formate toward the Orion-KL Compact Ridge and Hot Core-SW components (68.4 10.1 and 71.4 7.8, respectively) are, for both the {sup 13}C-methyl formate isotopologues, commensurate with the average {sup 12}C/{sup 13}C ratio of CO derived toward Orion-KL. Likewise, regarding the other sources, our results are consistent with the {sup 12}C/{sup 13}C in CO. We also report the spectroscopic characterization, which includes a complete partition function, of the complex H{sup 13}COOCH{sub 3} and HCOO{sup 13}CH{sub 3} species. New spectroscopic data for both isotopomers H{sup 13}COOCH{sub 3} and HCOO{sup 13}CH{sub 3}, presented in this study, have made it possible to measure this fundamentally important isotope ratio in a large organic molecule for the first time.

  4. Photophysics and morphology of poly (3-dodecylthienylenevinylene)-[6,6]-phenyl-C{sub 61}-butyric acid methyl ester composite

    SciTech Connect (OSTI)

    Lafalce, E.; Toglia, P.; Jiang, X.; Zhang, C.

    2012-05-21

    A series of low band gap poly(3-dodecylthienylenevinylene) (PTV) with controlled morphological order have been synthesized and blended with the electron acceptor [6,6]-phenyl-C{sub 61}-butyric acid methyl ester (PCBM) for organic photovoltaic devices. Two polymers with the most and least side chain regioregularity were chosen in this work, namely the PTV010 and PTV55, respectively. Using photoluminescence, photo-induced absorption spectroscopy, and atomic force microscopy, we find no direct evidence of photoinduced charge transfer between the two constituents, independent of the bulk-heterojunction morphology of the film, although the possibility of formation of P{sup +}/C{sub 60}{sup -} charge transfer complex was not completely ruled out. The large exciton binding energy (E{sub b} = 0.6 eV) in PTV inhibits the photoinduced electron transfer from PTV to PCBM. In addition, excitons formed on polymer chains suffer ultrafast (

  5. Accurate and Reliable Quantification of Total Microalgal Fuel Potential as Fatty Acid Methyl Esters by in situ Transesterfication

    SciTech Connect (OSTI)

    Laurens, L. M. L.; Quinn, M.; Van Wychen, S.; Templeton, D. W.; Wolfrum, E. J.

    2012-04-01

    In the context of algal biofuels, lipids, or better aliphatic chains of the fatty acids, are perhaps the most important constituents of algal biomass. Accurate quantification of lipids and their respective fuel yield is crucial for comparison of algal strains and growth conditions and for process monitoring. As an alternative to traditional solvent-based lipid extraction procedures, we have developed a robust whole-biomass in situ transesterification procedure for quantification of algal lipids (as fatty acid methyl esters, FAMEs) that (a) can be carried out on a small scale (using 4-7 mg of biomass), (b) is applicable to a range of different species, (c) consists of a single-step reaction, (d) is robust over a range of different temperature and time combinations, and (e) tolerant to at least 50% water in the biomass. Unlike gravimetric lipid quantification, which can over- or underestimate the lipid content, whole biomass transesterification reflects the true potential fuel yield of algal biomass. We report here on the comparison of the yield of FAMEs by using different catalysts and catalyst combinations, with the acid catalyst HCl providing a consistently high level of conversion of fatty acids with a precision of 1.9% relative standard deviation. We investigate the influence of reaction time, temperature, and biomass water content on the measured FAME content and profile for 4 different samples of algae (replete and deplete Chlorella vulgaris, replete Phaeodactylum tricornutum, and replete Nannochloropsis sp.). We conclude by demonstrating a full mass balance closure of all fatty acids around a traditional lipid extraction process.

  6. Controlling DNA Methylation

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    ... Induced DNA bending. Primary Citation Sawaya, M. R. Zhu, Z., Mersha, F., Chan, S-h., ... restriction-modification system control element C.BclI and mapping of its binding site. ...

  7. Analytical Methodologies for Detection of Gamma-Valerolactone, Delta-Valerolactone, Acephate and Azinphos Methyl and Their Associated Metabolites in Complex Biological Matrices

    SciTech Connect (OSTI)

    Zink, E.; Clark, R.; Grant, K.; Campbell, J.; Hoppe, E.

    2005-01-01

    Non-invasive biomonitoring for chemicals of interest in law enforcement and similar monitoring of pesticides, together with their metabolites, can not only save money but can lead to faster medical attention for individuals exposed to these chemicals. This study describes methods developed for the analysis of gamma-valerolactone (GVL), delta-valerolactone (DVL), acephate, and azinphos methyl in saliva and serum. Liquid chromatography/mass spectrometry (LC/MS) operated in the negative and positive ion mode and gas chromatography/mass spectrometry (GC/MS) were used to analyze GVL and DVL. Although both analytical techniques worked well, lower detection limits were obtained with GC/MS. The lactones and their corresponding sodium salts were spiked into both saliva and serum. The lactones were isolated from saliva or serum using newly developed extraction techniques and then subsequently analyzed using GC/MS. The sodium salts of the lactones are nonvolatile and require derivatization prior to analysis by this method. N-methyl-N-(t-butyldimethylsilyl)-trifluoroacetamide (MTBSTFA) was ultimately selected as the reagent for derivatization because the acidic conditions required for reactions with diazomethane caused the salts to undergo intramolecular cyclization to the corresponding lactones. In vitro studies were conducted using rat liver microsomes to determine other metabolites associated with these compounds. Azinphos methyl and acephate are classified as organophosphate pesticides, and are known to be cholinesterase inhibitors in humans and insects, causing neurotoxicity. For this reason they have both exposure and environmental impact implications. These compounds were spiked into serum and saliva and prepared for analysis by GC/MS. Continuation of this research would include analysis by GC/MS under positive ion mode to determine the parent ions of the unknown metabolites. Further research is planned through an in vivo analysis of the lactones and pesticides. These methodologies could be extended for further analysis of other similar compounds.

  8. Properties of electrospun CdS and CdSe filled poly(methyl methacrylate) (PMMA) nanofibres

    SciTech Connect (OSTI)

    Mthethwa, T.P.; Moloto, M.J.; De Vries, A.; Matabola, K.P.

    2011-04-15

    Graphical abstract: SEM images of CdS/PMMA showing coiling as loading of CdS nanoparticles is increased. Thermal stability is increased with increase in %loading of both CdS and CdSe nanoparticles. Research highlights: {yields} TOPO-capped CdS and HDA-capped CdSe nanoparticles were synthesized and fully characterized. {yields} The nanoparticles were mixed with the polymer, PMMA using electrospinning technique using 2, 5 and 10% weight loadings. {yields} The mixture was spun to produce fibres with optical and thermal properties showing significant change and also the increase in loading causing bending or spiraling. {yields} Both TEM images for nanoparticles and SEM for fibres shows the morphology and sizes of the particles. -- Abstract: Electrospinning technique was used to fabricate poly(methyl methacrylate) (PMMA) fibres incorporating CdS and CdSe quantum dots (nanoparticles). Different nanoparticle loadings (2, 5 and 10 wt% with respect to PMMA) were used and the effect of the quantum dots on the properties of the fibres was studied. The optical properties of the hybrid composite fibres were investigated by photoluminescence and UV-vis spectrophotometry. Scanning electron microscopy (SEM), X-ray diffraction and FTIR spectrophotometry were also used to investigate the morphology and structure of the fibres. The optical studies showed that the size-tunable optical properties can be achieved in the polymer fibres by addition of quantum dots. SEM images showed that the morphologies of the fibres were dependent on the added amounts of quantum dots. A spiral type of morphology was observed with an increase in the concentration of CdS and CdSe nanoparticles. Less beaded structures and bigger diameter fibres were obtained at higher quantum dot concentrations. X-ray diffractometry detected the amorphous peaks of the polymer and even after the quantum dots were added and the FTIR analysis shows that there was no considerable interaction between the quantum dots and the polymer fibres at low concentration of quantum dots however at higher concentrations some interactions were observed which shows that QDs were present on the surfaces of the fibres.

  9. Analysis of methyl neodecanamide in lake water by reversed-phase high performance liquid chromatography and gas chromatography-mass spectrometry

    SciTech Connect (OSTI)

    Rasmussen, H.T.; Friedman, S.K.; Mustilli, A.J.; McDonough, R.; McPherson, B.P. )

    1994-01-01

    Methyl Neodecanamide (MNDA) has been quantified in lake water at levels of 0.1 to 1,000 ppm. Total recoveries from spiked placebos were 99.8 [+-] 2.3% at the 1,000 ppm level and 98.3 [+-] 4.3% at the 0.1 ppm level (based on 54 determinations at each level). Plots of actual concentrations vs. determined concentrations were linear from 0.07--0.13 and 700--1,300 ppm (r > 0.999). Stability of MNDA in lake water was verified by determining the composition by GC/MS immediately after dissolution and after 3 days.

  10. Synthesis of 6-Methyl-9-propyldibenzothiophene-4-ol amended to 9-isopropyl-6-methyldibenzothiophene-4-ol. Final technical report, July 25, 1991--January 25, 1993

    SciTech Connect (OSTI)

    Eisenbraun, E.J.

    1992-02-17

    This is a draft final technical report on Task 1 of a contract to synthesize 6-Methyl-9-propyldibenzothiophene-4-ol, as amended to 9- isopropyl-6-methyldibenzothiophene-4-ol. This report is a compilation of data presented in earlier reports. The first annual report dealt with an attempted synthesis of 4-methoxy-6-methyl-9- propyldibenzothiophene (the original target compound), the successful synthesis and delivery of 200 grams of the sulfide 1,4-diethyl-2- [(2{prime}-methoxyphenyl)-thio]benzene, and initial work on a new synthesis route for the preparation of the new target compound 9- isopropyl-6-methyldibenzothiophene-4-ol. The change to the new target compound and the new synthesis route became necessary when it was learned that the sulfide mixture could not be cyclized to the substituted dibenzothiophene mixture. The second annual report described the successful preparation of 45 g of the new target compound using the new synthesis route. Subsequently funds were provided to synthesize an additional 45 g of the new target using the same reaction scheme. This task was recently completed.

  11. INSIGHTS INTO SURFACE HYDROGENATION IN THE INTERSTELLAR MEDIUM: OBSERVATIONS OF METHANIMINE AND METHYL AMINE IN Sgr B2(N)

    SciTech Connect (OSTI)

    Halfen, D. T.; Ziurys, L. M.; Ilyushin, V. V. E-mail: lziurys@as.arizona.edu

    2013-04-10

    Multiple observations of methanimine (CH{sub 2}NH) and methyl amine (CH{sub 3}NH{sub 2}) have been performed toward Sgr B2(N) at 1, 2, and 3 mm using the Submillimeter Telescope and the 12 m antenna of the Arizona Radio Observatory. In the frequency range 68-280 GHz, 23 transitions of CH{sub 2}NH and 170 lines of CH{sub 3}NH{sub 2} have been observed as individual, distinguishable features, although some are partially blended with other lines. For CH{sub 2}NH, the line profiles indicate V{sub LSR} = 64.2 {+-} 1.4 km s{sup -1} and {Delta}V{sub 1/2} = 13.8 {+-} 2.8 km s{sup -1}, while V{sub LSR} = 63.7 {+-} 1.6 km s{sup -1} and {Delta}V{sub 1/2} = 15.1 {+-} 3.0 km s{sup -1} for CH{sub 3}NH{sub 2}, parameters that are very similar to those of other organic species in Sgr B2(N). From these data, rotational diagrams were constructed for both species. In the case of CH{sub 2}NH, a rotational temperature of T{sub rot} = 44 {+-} 13 K and a column density of N{sub tot} = (9.1 {+-} 4.4) Multiplication-Sign 10{sup 14} cm{sup -2} were determined from the analysis. For CH{sub 3}NH{sub 2}, T{sub rot} = 159 {+-} 30 K and N{sub tot} = (5.0 {+-} 0.9) Multiplication-Sign 10{sup 15} cm{sup -2}, indicating that this species is present in much warmer gas than CH{sub 2}NH. The fractional abundances for CH{sub 2}NH and CH{sub 3}NH{sub 2} were established to be f (H{sub 2}) Almost-Equal-To 3.0 Multiplication-Sign 10{sup -10} and f (H{sub 2}) Almost-Equal-To 1.7 Multiplication-Sign 10{sup -9}, respectively. It has been proposed that CH{sub 2}NH is formed on grains via hydrogenation of HCN; further hydrogenation of CH{sub 2}NH on surfaces leads to CH{sub 3}NH{sub 2}. However, given the dissimilarity between the rotational temperatures and distributions of CH{sub 2}NH and CH{sub 3}NH{sub 2} in Sgr B2, it is improbable that these species are closely related synthetically, at least in this source. Both CH{sub 2}NH and CH{sub 3}NH{sub 2} are more likely created by neutral-neutral processes in the gas phase.

  12. [Research and workshop on alternative fuels for aviation. Final report

    SciTech Connect (OSTI)

    1999-09-01

    The Renewable Aviation Fuels Development Center (RAFDC) at Baylor University was granted U. S. Department of Energy (US DOE) and Federal Aviation Administration (FAA) funds for research and development to improve the efficiency in ethanol powered aircraft, measure performance and compare emissions of ethanol, Ethyl Tertiary Butyl Ether (ETBE) and 100 LL aviation gasoline. The premise of the initial proposal was to use a test stand owned by Engine Components Inc. (ECI) based in San Antonio, Texas. After the grant was awarded, ECI decided to close down its test stand facility. Since there were no other test stands available at that time, RAFDC was forced to find additional support to build its own test stand. Baylor University provided initial funds for the test stand building. Other obstacles had to be overcome in order to initiate the program. The price of the emission testing equipment had increased substantially beyond the initial quote. Rosemount Analytical Inc. gave RAFDC an estimate of $120,000.00 for a basic emission testing package. RAFDC had to find additional funding to purchase this equipment. The electronic ignition unit also presented a series of time consuming problems. Since at that time there were no off-the-shelf units of this type available, one had to be specially ordered and developed. FAA funds were used to purchase a Super Flow dynamometer. Due to the many unforeseen obstacles, much more time and effort than originally anticipated had to be dedicated to the project, with much of the work done on a volunteer basis. Many people contributed their time to the program. One person, mainly responsible for the initial design of the test stand, was a retired engineer from Allison with extensive aircraft engine test stand experience. Also, many Baylor students volunteered to assemble the. test stand and continue to be involved in the current test program. Although the program presented many challenges, which resulted in delays, the RAFDC's test stand is an asset which provides an ongoing research capability dedicated to the testing of alternative fuels for aircraft engines. The test stand is now entirely functional with the exception of the electronic ignition unit which still needs adjustments.

  13. On the correlation between the photoexcitation pathways and the critical energies required for ablation of poly(methyl methacrylate): A molecular dynamics study

    SciTech Connect (OSTI)

    Conforti, Patrick F.; Prasad, Manish; Garrison, Barbara J.

    2008-05-15

    The energetics initiating ablation in poly(methyl methacrylate) (PMMA) are studied using molecular dynamics (MD) simulation. The critical energy to initiate ablation in PMMA following the absorption of photons is investigated for two penetration depths along a range of fluences using a coarse-grained, hybrid Monte Carlo-MD scheme. Both heating and direct bond scission are simulated separately after photon absorption with additional transformation of material occurring via chemical reactions following the photochemical bond cleavage. For a given type of absorption and reaction channel, a critical energy can well describe the amount of energy required to initiate ablation. The simulations show a decrease in the critical energy when a greater amount of photochemistry is introduced in the system. The simulations complement experimental studies and elucidate how enhanced photochemistry lowers ablation thresholds in polymer substrates.

  14. Crystallization of lysozyme with (R)-, (S)- and (RS)-2-methyl-2,4-pentanediol

    SciTech Connect (OSTI)

    Stauber, Mark; Jakoncic, Jean; Berger, Jacob; Karp, Jerome M.; Axelbaum, Ariel; Sastow, Dahniel; Buldyrev, Sergey V.; Hrnjez, Bruce J.; Asherie, Neer

    2015-03-01

    Chiral control of crystallization has ample precedent in the small-molecule world, but relatively little is known about the role of chirality in protein crystallization. In this study, lysozyme was crystallized in the presence of the chiral additive 2-methyl-2,4-pentanediol (MPD) separately using the R and S enantiomers as well as with a racemic RS mixture. Crystals grown with (R)-MPD had the most order and produced the highest resolution protein structures. This result is consistent with the observation that in the crystals grown with (R)-MPD and (RS)-MPD the crystal contacts are made by (R)-MPD, demonstrating that there is preferential interaction between lysozyme and this enantiomer. These findings suggest that chiral interactions are important in protein crystallization.

  15. Synthesis ofN-(2-chloro-5-methylthiophenyl)-N'-(3-methyl-thiophenyl)-N'-[3H3]methylguanidine, l brace [3H3]CNS-5161 r brace

    SciTech Connect (OSTI)

    Gibbs, Andrew R.; Morimoto, Hiromi; VanBrocklin, Henry F.; Williams, Philip G.; Biegon, Anat

    2001-09-28

    The preparation of the title compound, [{sup 3}H{sub 3}]CNS-5161, was accomplished in three steps starting with the production of [{sup 3}H{sub 3}]iodomethane (CT{sub 3}I). The intermediate N-[{sup 3}H{sub 3}]methyl-3-(thiomethylphenyl)cyanamide was prepared in 77% yield by the addition of CT{sub 3}I to 3-(thiomethylphenyl)cyanamide, previously treated with sodium hydride. Reaction of this tritiated intermediate with 2-chloro-5-thiomethylaniline hydrochloride formed the guanidine compound [{sup 3}H{sub 3}]CNS-5161. Purification by HPLC gave the desired labeled product in an overall yield of 9% with greater than 96% radiochemical purity and a final specific activity of 66 Ci mmol{sup -1}.

  16. K20E, an oxidative-coupling compound of methyl caffeate, exhibits anti-angiogenic activities through down-regulations of VEGF and VEGF receptor-2

    SciTech Connect (OSTI)

    Pan, Chun-Hsu; Lin, Wen-Hsin; Chien, Yi-Chung; Liu, Fon-Chang; Sheu, Ming-Jyh; Kuo, Yueh-Hsiung; Wu, Chieh-Hsi

    2015-01-15

    Anti-angiogenesis is one of the most popular clinical interventions for cancer chemotherapy. A series of synthesized derivative of methyl caffeate were used to evaluate the anti-angiogenic activity and to investigate possible pharmacological mechanisms in the present study. The most potent anti-angiogenic compound was evaluated in the experiments of murine allograft tumor model and Matrigel plug assay as well as cell models in the human umbilical vascular endothelial cells (HUVECs) and the LLC1 lung cancer cells. Our results suggested that K20E suppressed the tumor growth in the allograft tumor model and exhibited anti-angiogenic activity in Matrigel plug assay. Besides, HUVEC viability was found to be significantly reduced by arresting cell cycle at G{sub 2}/M phase and apoptosis. Cell migration, invasion, and tube formation of the HUVECs were also markedly suppressed by K20E treatment. K20E largely down-regulated the intracellular and secreted vascular endothelial growth factor (VEGF) in the LLC1 cancer cells. Besides, VEGF receptor-2 (VEGFR-2) and its downstream signaling cascades (AKT-mTOR and MEK1/2-ERK1/2) as well as gelatinases were all evidently reduced in the HUVECs treated with K20E. Inversely, K20E can up-regulate the expression levels of p53 and p21 proteins in the HUVECs. Based on these results, our study suggested that K20E possessed inhibiting angiogenesis through regulation of VEGF/VEGFR-2 and its downstream signaling cascades in the vascular endothelial cells (VECs). - Highlights: • K20E is an oxidative-coupling compound of methyl caffeate. • K20E exhibits anti-tumor and anti-angiogenesis effects. • K20E suppresses the expressions of VEGF and VEGF receptor-2 (VEGFR-2) proteins. • K20E deactivates VEGFR-2-mediated downstream signaling pathways to inhibit angiogenesis. • K20E up-regulates p53-p21 pathway to induce apoptosis and cell arrest at G2/M phase.

  17. Synthesis of [.sup.13C] and [.sup.2H] substituted methacrylic acid, [.sup.13C] and [.sup.2H] substituted methyl methacrylate and/or related compounds

    DOE Patents [OSTI]

    Alvarez, Marc A.; Martinez, Rodolfo A.; Unkefer, Clifford J.

    2008-01-22

    The present invention is directed to labeled compounds of the formulae ##STR00001## wherein Q is selected from the group consisting of --S--, --S(.dbd.O)--, and --S(.dbd.O).sub.2--, Z is selected from the group consisting of 1-naphthyl, substituted 1-naphthyl, 2-naphthyl, substituted 2-naphthyl, and phenyl groups with the structure ##STR00002## wherein R.sub.1, R.sub.2, R.sub.3, R.sub.4 and R.sub.5 are each independently selected from the group consisting of hydrogen, a C.sub.1-C.sub.4 lower alkyl, a halogen, and an amino group selected from the group consisting of NH.sub.2, NHR and NRR' where R and R' are each independently selected from the group consisting of a C.sub.1-C.sub.4 lower alkyl, an aryl, and an alkoxy group, and X is selected from the group consisting of hydrogen, a C.sub.1-C.sub.4 lower alkyl group, and a fully-deuterated C.sub.1-C.sub.4 lower alkyl group. The present invention is also directed to a process of preparing labeled compounds, e.g., process of preparing [.sup.13C]methacrylic acid by reacting a (CH.sub.3CH.sub.2O--.sup.13C(O)--.sup.13CH.sub.2)-- aryl sulfone precursor with .sup.13CHI to form a (CH.sub.3CH.sub.2O--.sup.13C(O)--.sup.13C(.sup.13CH.sub.3).sub.2)-- aryl sulfone intermediate, and, reacting the (CH.sub.3CH.sub.2O--.sup.13C(O)--.sup.13C(.sup.13CH.sub.3).sub.2)-- aryl sulfone intermediate with sodium hydroxide, followed by acid to form [.sup.13C]methacrylic acid. The present invention is further directed to a process of preparing [.sup.2H.sub.8]methyl methacrylate by reacting a (HOOC--C(C.sup.2H.sub.3).sub.2-- aryl sulfinyl intermediate with CD.sub.3I to form a (.sup.2H.sub.3COOC--C(C.sup.2H.sub.3).sub.2)-- aryl sulfinyl intermediate, and heating the(.sup.2H.sub.3COOC--C(C.sup.2H.sub.3).sub.2)-- aryl sulfinyl intermediate at temperatures and for time sufficient to form [.sup.2H.sub.8]methyl methacrylate.

  18. Synthesis of dimethyl ether and alternative fuels in the liquid phase from coal-derived synthesis gas. Task 2.2: Definition of preferred catalyst system; Task 2.3: Process variable scans on the preferred catalyst system; Task 2.4: Life-test on the preferred catalyst system

    SciTech Connect (OSTI)

    Bhatt, B.L.

    1992-09-01

    As part of the DOE-sponsored contract for the Synthesis of Dimethyl Ether (DME) and Alternative Fuels in the Liquid Phase from Coal- Derived Syngas, the single-step, slurry phase DME synthesis process was developed. The development involved screening of catalyst systems, process variable studies, and catalyst life studies in two 300 ml stirred autoclaves. As a spin-off of the Liquid Phase Methanol (LPMEOH*) process, the new process significantly improves the syngas conversion efficiency of the LPMEOH process. This improvement can be achieved by replacing a portion of methanol catalyst with a dehydration catalyst in the reactor, resulting in the product methanol being converted to DME, thus avoiding the thermodynamic equilibrium constraint of the methanol reaction. Overall, this increases syngas conversion per-pass. The selectivity and productivity of DME and methanol are affected by the catalyst system employed as well as operating conditions. A preferred catalyst system, consisting of a physical mixture of a methanol catalyst and a gamma alumina, was identified. An improvement of about 50% in methanol equivalent productivity was achieved compared to the LPMEOH process. Results from the process variable study indicate that higher pressure and CO{sub 2} removal benefit the process significantly. Limited life studies performed on the preferred catalyst system suggest somewhat higher than expected deactivation rate for the methanol catalyst. Several DME/methanol mixtures were measured for their key properties as transportation fuels. With small amounts of DME added, significant improvements in both flash points and Reid Vapor Pressure (RVP) were observed over the corresponding values of methanol alone.

  19. Stereochemical effects in the gas-phase pinacol rearrangement. 2. Ring contraction versus methyl migration in cis- and trans-1,2-dimethylcyclohexane-1,2-diol

    SciTech Connect (OSTI)

    de Petris, G.; Giacomello, P.; Pizzabiocca, A.; Renzi, G.; Speranza, M.

    1988-02-17

    The gas-phase pinacol rearrangement of cis- and trans-1,2-dimethylcyclohexane-1,2-diols, promoted by D/sub 3//sup +/, CH/sub 5//sup +//C/sub 2/H/sub 5//sup +/ and t-C/sub 4/H/sub 9//sup +/ ions, was studied by mass spectrometric and radiolytic methods in the pressure range 0.5-760 Torr. When product isomerization is inhibited, by using N(CH/sub 3/)/sub 3/ as a trapping reagent at high pressure, mixtures of 2,2-dimethylcyclohexanone and 1-acetyl-1-methylcyclopentane were recovered from the reaction. In methane, the trend of the measured relative rates for ring contraction (k/sub 5/), methyl or hydroxyl group migration (k/sub 6/) versus the rearrangement rate of pincaol itself (k/sub p/), is k/sub 6/(trans) approx. k/sub 5/(trans) greater than or equal to k/sub 5/(cis) > k/sub 6/(cis) greater than or equal to k/sub p/. No evidence for the formation of an intermediate carbenium ion was found. Stereochemical aspects of the mechanism are discussed and compared with solution data.

  20. Emissions characteristics of ethyl and methyl ester of rapeseed oil compared with low sulfur diesel control fuel in a chassis dynamometer test of a pickup truck

    SciTech Connect (OSTI)

    Peterson, C.; Reece, D.

    1996-05-01

    Comprehensive tests were performed on an on-road vehicle in cooperation with the Los Angeles County Metropolitan Transit Authority emissions test facility. All tests were with a transient chassis dynamometer. Tests included both a double arterial cycle of 768 s duration and an EPA heavy duty vehicle cycle of 1,060 s duration. The test vehicle was a 1994 pickup truck with a 5.9-L turbocharged and intercooled, direct injection diesel engine. Rapeseed methyl (RME) and ethyl esters (REE) and blends were compared with low sulfur diesel control fuel. Emissions data include all regulated emissions: hydrocarbons (HC), carbon monoxide (CO), carbon dioxide (CO{sub 2}), oxides of nitrogen (NO{sub x}), and particulate matter (PM). In these tests the average of 100% RME and 100% REE reduced HC (52.4%), CO (47.6%), NO{sub x} (10.0%), and increases in CO{sub 2} (0.9%) and PM (9.9%) compared to the diesel control fuel. Also, 100% REE reduced HC (8.7%), CO (4.3%), and NO{sub x} (3.4%) compared to 100% RME. 33 refs., 1 figs., 8 tabs.

  1. Molecular and crystal structures of 4'-hydroxy derivative of (3R,6R)-3-methyl-6-isopropyl-2-(4-phenylbenzylidene)cyclohexanone

    SciTech Connect (OSTI)

    Kutulya, L. A.; Kulishov, V. I.; Shishkina, S. V.; Tolochko, A. S.; Roshal', A. D.; Shishkin, O. V.

    2008-05-15

    The molecular and crystal structures of the 4-hydroxy derivative of (3R,6R)-3-methyl-6-isopropyl-2-(4-phenylbenzylidene)cyclohexanone are determined by X-ray diffraction analysis. Single crystals are orthorhombic, a = 9.147(2) A, b = 12.959(2) A, c = 15.695(5) A, V = 1860.4(7) A{sup 3}, Z = 4, and space group P2{sub 1}2{sub 1}2{sub 1}. The cyclohexanone ring in the crystal structure has an asymmetric chair conformation. The puckering parameters are as follows: the puckering amplitude S is 0.91, and the puckering angles {theta} and {psi} are equal to 20.2{sup o} and 10.4{sup o}, respectively. It is established that the enone fragment and the cyclohexanone ring in molecules are flattened considerably. In the crystal structure, the molecules are linked by the hydrogen bonds (bond length, 1.85 A). The structural features and the strength of the hydrogen bonds for the compound under investigation and its analogue with one benzene ring are compared using the X-ray diffraction and IR spectroscopic data.

  2. EXAFS investigations of the mechanism of facilitated ion transfer into a room-temperature ionic liquid.

    SciTech Connect (OSTI)

    Jensen, M. P.; Dzielawa, J. A.; Rickert, P.; Dietz, M. L.; Chemistry

    2002-09-11

    The Sr(II)-crown ether complexes formed in a room-temperature ionic liquid (RTIL), 1-methyl-3-pentylimidazolium bis[(trifluoromethyl)sulfonyl]amide, have been studied by X-ray absorption fine structure measurements at the Sr K-edge. When a Sr(NO{sub 3}){sub 2}-crown ether complex is directly dissolved in a water-saturated RTIL, both nitrate ligands and the crown ether coordinate the Sr, as observed in a conventional two-phase water-octanol system. When the cationic Sr-crown ether complex is created in a two-phase water-RTIL system, however, only cationic Sr-crown ether complexes are observed in the RTIL phase. This difference in the coordination complexes arises from differences in the mechanism of cation extraction between the RTIL and conventional molecular organic solvents, a finding with important implications for synthesis, catalysis, and ion separations using two-phase water-RTIL systems.

  3. Word Pro - Untitled1

    U.S. Energy Information Administration (EIA) Indexed Site

    chemical compounds composed of carbon, hydrogen, and oxygen. The series of molecules vary in chain length and are composed of a hydrocarbon plus a hydroxyl group: CH 3 -(CH 2 )n-OH (e.g., metha- nol, ethanol, and tertiary butyl alcohol). See Fuel Ethanol. Alternative Fuel: Alternative fuels, for transportation applications, include the following: methanol; denatured ethanol, and other alcohols; fuel mixtures contain- ing 85 percent or more by volume of methanol, denatured ethanol, and other

  4. "Seeing" Mercury Methylation in Progress

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    ... Wiener JG, Krabbgenhoft DP, Heinz GH, Scheuhammer AM (2003). Ecotoxicology of mercury. In Handbook of Ecotoxicology; Hoffman DJ, Rattner BA, Burton GA Jr, Cairns J Jr, Eds.; CRC ...

  5. Characterization of DGEBA (diglycidyl ethers bisphenol-A) epoxy resins

    SciTech Connect (OSTI)

    Larsen, F.N.; Spieker, D.A.

    1987-04-01

    High-resolution gel permeation chromatography and high-performance liquid chromatography can be applied to commercially available DGEBA epoxy resins to elucidate small but significant differences in the oligomer and impurity compositions of these resins. The GPC profiles can be used to type or identify the various commercial grades of these DGEBA resins. Lot-to-lot consistency and aging characteristics can also be determined using GPC and HPLC. Quantitation of the various oligomers and impurities such as the ..cap alpha..-glycol, isomer, and chlorohydrin species is possible. Using 20% isoconversion predictive cure thermal analysis data, the relative resin reactivity of several liquid, low-molecular DGEBA resins has been measured. These data show that the higher viscosity, higher oligomer content resins, which have higher hydroxyl content, reacted faster with amine cure agents than the lower viscosity, higher purity - and consequently lower hydroxyl content - resins. Thus, a combination of liquid chromatography (GPC or HPLC) and DSC kinetics can be used to establish a correlation or equivalency beween the commercially available low-molecular-weight DGEBA epoxy resins.

  6. Raman spectra of methane, ethylene, ethane, dimethyl ether, formaldehy...

    Office of Scientific and Technical Information (OSTI)

    Additional Journal Information: Journal Volume: 163; Journal Issue: C; Journal ID: ISSN 0022-4073 Publisher: Elsevier Sponsoring Org: USDOE Office of Science (SC), Basic Energy ...

  7. Scalar structure of turbulent partially-premixed dimethyl ether...

    Office of Scientific and Technical Information (OSTI)

    Additional Journal Information: Journal Volume: 35; Journal Issue: 2; Related Information: CHORUS Timestamp: 2016-05-06 21:25:01; Journal ID: ISSN 1540-7489 Publisher: Elsevier ...

  8. Alternative Fuels lDimethyl Ether Rheology and Materials Studies

    Broader source: Energy.gov [DOE]

    2004 Diesel Engine Emissions Reduction (DEER) Conference Presentation: The Pennsylvania State University

  9. SCALAR STRUCTURE OF TURBULENT PARTIALLY-PREMIXED DIMETHYL ETHER...

    Office of Scientific and Technical Information (OSTI)

    Sponsoring Org: USDOE SC Office of Basic Energy Sciences (SC-22) Country of Publication: United States Language: English Subject: biofuels (including algae and biomass), hydrogen ...

  10. Extractant composition including crown ether and calixarene extractants

    DOE Patents [OSTI]

    Meikrantz, David H.; Todd, Terry A.; Riddle, Catherine L.; Law, Jack D.; Peterman, Dean R.; Mincher, Bruce J.; McGrath, Christopher A.; Baker, John D.

    2009-04-28

    An extractant composition comprising a mixed extractant solvent consisting of calix[4] arene-bis-(tert-octylbenzo)-crown-6 ("BOBCalixC6"), 4',4',(5')-di-(t-butyldicyclo-hexano)-18-crown-6 ("DtBu18C6"), and at least one modifier dissolved in a diluent. The DtBu18C6 may be present at from approximately 0.01M to approximately 0.4M, such as at from approximately 0.086 M to approximately 0.108 M. The modifier may be 1-(2,2,3,3-tetrafluoropropoxy)-3-(4-sec-butylphenoxy)-2-propanol ("Cs-7SB") and may be present at from approximately 0.01M to approximately 0.8M. In one embodiment, the mixed extractant solvent includes approximately 0.15M DtBu18C6, approximately 0.007M BOBCalixC6, and approximately 0.75M Cs-7SB modifier dissolved in an isoparaffinic hydrocarbon diluent. The extractant composition further comprises an aqueous phase. The mixed extractant solvent may be used to remove cesium and strontium from the aqueous phase.

  11. Spatiotemporal temperature and density characterization of high-power atmospheric flashover discharges over inert poly(methyl methacrylate) and energetic pentaerythritol tetranitrate dielectric surfaces

    SciTech Connect (OSTI)

    Tang, V.; Grant, C. D.; McCarrick, J. F.; Zaug, J. M.; Glascoe, E. A.; Wang, H.

    2012-03-01

    A flashover arc source that delivered up to 200 mJ on the 100s-of-ns time-scale to the arc and a user-selected dielectric surface was characterized for studying high-explosive kinetics under plasma conditions. The flashover was driven over thin pentaerythritol tetranitrate (PETN) and poly(methyl methacrylate) (PMMA) dielectric films and the resultant plasma was characterized in detail. Time- and space-resolved temperatures and electron densities of the plasma were obtained using atomic emission spectroscopy. The hydrodynamics of the plasma was captured through fast, visible imaging. Fourier transform infrared spectroscopy (FTIR) was used to characterize the films pre- and post-shot for any chemical alterations. Time-resolved infrared spectroscopy (TRIR) provided PETN depletion data during the plasma discharge. For both types of films, temperatures of 1.6-1.7 eV and electron densities of {approx}7-8 x 10{sup 17}/cm{sup 3}{approx}570 ns after the start of the discharge were observed with temperatures of 0.6-0.7 eV persisting out to 15 {mu}s. At 1.2 {mu}s, spatial characterization showed flat temperature and density profiles of 1.1-1.3 eV and 2-2.8 x 10{sup 17}/cm{sup 3} for PETN and PMMA films, respectively. Images of the plasma showed an expanding hot kernel starting from radii of {approx}0.2 mm at {approx}50 ns and reaching {approx}1.1 mm at {approx}600 ns. The thin films ablated or reacted several hundred nm of material in response to the discharge. First TRIR data showing the in situ reaction or depletion of PETN in response to the flashover arc were successfully obtained, and a 2-{mu}s, 1/e decay constant was measured. Preliminary 1 D simulations compared reasonably well with the experimentally determined plasma radii and temperatures. These results complete the first steps to resolving arc-driven PETN reaction pathways and their associated kinetic rates using in situ spectroscopy techniques.

  12. Two new coordination polymers constructed by naphthalene-1,4-dicarboxylic acid and 2,4-diamino-6-methyl-triazine

    SciTech Connect (OSTI)

    Li, Yamin; Xiao, Changyu; Zhang, Xudong; Xu, Yanhui; Li, Junrui; Lun, Huijie; Chen, Qi

    2013-08-15

    Two new transition metal coordination complexes, ([MnO(nda)](H{sub 2}dmt)(H{sub 2}O)){sub n} (1), [Ag{sub 5}(nda){sub 2.5}(dmt)]{sub n} (2), (H{sub 2}nda=naphthalene-1,4-dicarboxylic acid, dmt=2,4-diamine-6-methyl-1,3,5-triazine) have been hydrothermally synthesized by the reactions of H{sub 2}nda and dmt with the homologous MnCl{sub 2}·4H{sub 2}O and AgNO{sub 3}, respectively, and characterized by single-crystal X-ray diffraction, IR spectra, elemental analysis, thermogravimetric analysis (TGA). The compound 1 exhibits a 3D network comprising 1D metal chain (MnO(CO{sub 2}){sub 2}){sub n} connected by the ligand nda{sup 2−}, featuring a four-connected uninodal diamond -like topology. In compound 2, it is firstly observed that decanuclear silver units as secondary building units to construct 3D network by the ligands dmt and nda{sup 2−}, with a rare 2-nodal (3,8)-connected tfz-d topology ((4{sup 3}){sub 2}(4{sup 6}.6{sup 18}.8{sup 4})). The interactions within each Mn(II)—Mn(II) pair of compound 1 are antiferromagnetic (g=2.07, J=−1.42(1) cm{sup −1}, zj′=−0.73(2) cm{sup −1}). In addition, compound 2 exhibits photoluminescent property at about 472 nm (λ{sub ex}=394 nm). - Graphical abstract: Two new transition metal coordination complexes 1–2 have been hydrothermally synthesized and characterized by single-crystal X-ray diffraction, IR spectra, elemental analysis thermogravimetric analysis (TGA). Highlights: • The compound 1 exhibits a 3D network with four-connected uninodal diamond-like topology. • The first 3D network of 2 with a rare tfz-d topology consists of decanuclear silver clusters as secondary building units. • The magnetic measurement indicates the compound 1 shows antiferromagnetic interactions. • The photoluminescent property of 2 has been measured.

  13. Synthesis of oxygenates from H{sub 2}/CO synthesis gas and use as fuel additives

    SciTech Connect (OSTI)

    Herman, R.G.; Klier, K.; Feeley, O.C.

    1994-12-31

    Alternative processes for synthesizing fuel-grade oxygenates are centered on conversion of synthesis gas into C{sub 1}-C{sub 8} alcohols and ethers. Over Cs/Cu/ZnO-based catalysts, mixtures of methanol/isobutanol are predominantly formed. It has been found that these alcohols can be directly coupled over certain strong acid organic-based catalysts to form unsymmetric C{sub 5} ethers, mainly the kinetically favored methyl isobutyl ether (MIBE) with some of the thermodynamically favored methyl tertiarybutyl ether (MTBE), the symmetric ethers of dimethylether (DME) and diisobutylether (DIBE), or selectively dehydrated to form isobutene over sulfated zirconia. Based on these reactions, a 2-stage, dual catalyst configuration can be utilized to give MTBE as the dominant ether product. The octane numbers and cetane ratings of the oxygenates have been determined and are compared, e.g. adding 10 vol% MIBE and MTBE to 82.3 MON gasoline altered the MON of the gasoline by -1.5 and +1.4 units, respectively, and MIBE has a high cetane number of 53, compared to 42 for typical U.S. diesel fuel.

  14. Graphene composite for improvement in the conversion efficiency of flexible poly 3-hexyl-thiophene:[6,6]-phenyl C{sub 71} butyric acid methyl ester polymer solar cells

    SciTech Connect (OSTI)

    Chauhan, A. K., E-mail: akchau@barc.gov.in, E-mail: akc.barc@gmail.com; Gusain, Abhay; Jha, P.; Koiry, S. P.; Saxena, Vibha; Veerender, P.; Aswal, D. K.; Gupta, S. K. [Technical Physics Division, Bhabha Atomic Research Centre, Trombay, Mumbai-400085 (India)

    2014-03-31

    The solution of thin graphene-sheets obtained from a simple ultrasonic exfoliation process was found to chemically interact with [6,6]-phenyl C{sub 71} butyric acid methyl ester (PCBM) molecules. The thinner graphene-sheets have significantly altered the positions of highest occupied molecular orbital and lowest unoccupied molecular orbital of PCBM, which is beneficial for the enhancement of the open circuit voltage of the solar cells. Flexible bulk heterojunction solar cells fabricated using poly 3-hexylthiophene (P3HT):PCBM-graphene exhibited a power conversion efficiency of 2.51%, which is a ?2-fold increase as compared to those fabricated using P3HT:PCBM. Inclusion of graphene-sheets not only improved the open-circuit voltage but also enhanced the short-circuit current density owing to an improved electron transport.

  15. Solvate Structures and Computational/Spectroscopic Characterization of

    Office of Scientific and Technical Information (OSTI)

    LiBF4 Electrolytes (Journal Article) | SciTech Connect Solvate Structures and Computational/Spectroscopic Characterization of LiBF4 Electrolytes Citation Details In-Document Search Title: Solvate Structures and Computational/Spectroscopic Characterization of LiBF4 Electrolytes Crystal structures have been determined for both LiBF4 and HBF4 solvates-(acetonitrile)2:LiBF4, (ethylene glycol diethyl ether)1:LiBF4, (diethylene glycol diethyl ether)1:LiBF4, (tetrahydrofuran)1:LiBF4, (methyl

  16. Petroleum Supply Monthly

    U.S. Energy Information Administration (EIA) Indexed Site

    June 2015 Alcohol. The family name of a group of organic chemical compounds composed of carbon, hydrogen, and oxygen. The series of molecules vary in chain length and are composed of a hydrocarbon plus a hydroxyl group; CH3-(CH2)n-OH (e.g., methanol, ethanol, and tertiary butyl alcohol). Alkylate. The product of an alkylation reaction. It usually refers to the high octane product from alkylation units. This alkylate is used in blending high octane gasoline. Alkylation. A refning process for

  17. Petroleum Supply Monthly

    U.S. Energy Information Administration (EIA) Indexed Site

    0 January 2016 Alcohol. The family name of a group of organic chemical compounds composed of carbon, hydrogen, and oxygen. The series of molecules vary in chain length and are composed of a hydrocarbon plus a hydroxyl group; CH3-(CH2)n-OH (e.g., methanol, ethanol, and tertiary butyl alcohol). Alkylate. The product of an alkylation reaction. It usually refers to the high octane product from alkylation units. This alkylate is used in blending high octane gasoline. Alkylation. A refning process for

  18. chemicals | netl.doe.gov

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    chemicals Overview Key end products from coal gasification include hydrogen (and synthetic natural gas as a closely related product), electric power, fuels (mainly diesel fuel and gasoline), and fertilizer (which hinges on the large quantities of ammonia produced from gasification). In the context of liquid fuels, methanol can be added as an end product; in some locations (China in particular) methanol is a heavily-used fuel blending stock and feedstock for methyl tert-butyl ether (MTBE)

  19. Synthesis of oxygenate products for high volume fuels applications. Quarterly status report No. 3 for the period April through June 1995

    SciTech Connect (OSTI)

    Not Available

    1995-09-26

    A rudimentary process variables study of the reaction of acetylene with methanol indicates high activity for the formation of ethanol, n- propanol, and i-butanol with a pure low temperature activated MgO catalyst. Initial results indicate that higher conversions and space- time yields may be obtainable by operation at higher temperatures and reactant feed rates, respectively. Also, ethanol formation was consistently observed to rise with decreasing reaction temperature between 454{degrees}C and 370{degrees}C. A 10% Al{sub 2}O{sub 3}/MgO catalyst exhibited high activity for methanol-dimethyl ether interconversion but was not very active for the condensation of these reactants to either the product alcohols or their methyl ethers. Neither catalyst exhibited significant activity for the condensation to dimethyl ether/water with acetylene to form such products. This lack of activity in the ether systems is attributed to insufficient hydrolysis of dimethyl ether to methanol, and it is expected that feeds containing additional water or methanol (which produces water via condensation) will exhibit higher activity. The aluminum- containing catalyst exhibited diminished condensation activity possibly as a result of deactivation of Mg sites by Al sites. The overall objective of this project is to develop catalyst and process technology for evaluation as potential routes for the production of high volume fuel oxygenates.

  20. Synthesis of oxygenate products for high volume fuels applications. Quarterly status report No. 4 for the period July through September 1995

    SciTech Connect (OSTI)

    Not Available

    1995-12-29

    A rudimentary process variables study of the reaction of acetylene with methanol indicates high activity for the formation of ethanol, n- propanol, and i-butanol with a pure low temperature activated MgO catalyst. Initial results indicate that higher conversions and space- time yields may be obtainable by operation at higher temperatures and reactant feed rates, respectively. Also, ethanol formation was consistently observed to rise with decreasing reaction temperature between 454{degrees}C and 370{degrees}C. A 10% Al{sub 2}O{sub 3}/MgO catalyst exhibited high activity for methanol-dimethyl ether interconversion but was not very active for the condensation of these reactants to either the product alcohols or their methyl ethers. Neither catalyst exhibited significant activity for the condensation of dimethyl ether/water with acetylene to form such products. This lack of activity in the ether systems us attributed to insufficient hydrolysis of dimethyl ether to methanol, and it is expected that feeds containing additional water or methanol (which produces water via condensation) will exhibit higher activity. The aluminum- containing catalyst exhibited diminished condensation activity possibly as the result of deactivation of Mg sites by Al sites. The overall objective of this project is to develop catalyst and process technology for evaluation as potential routes for the production of high volume fuel oxygenates.

  1. Microsoft Word - LBNL 53866_SPME-MTBE_Final_112103.doc

    Office of Scientific and Technical Information (OSTI)

    Determination of Methyl tert-Butyl Ether and tert-Butyl Alcohol in Water by Solid-Phase Microextraction/Head Space Analysis in Comparison to EPA Method 5030/8260B Keun-Chan Oh & William T. Stringfellow* Center for Environmental Biotechnology Lawrence Berkeley National Laboratory 1 Cyclotron Rd., MS70A-3317 Berkeley, CA 94720 September 9, 2003 *Corresponding author, phone: (510) 486-7093, fax: (510) 486-7152 email: wstringfellow@lbl.gov Oh & Stringfellow Page 2 of 28 Abstract Methyl

  2. Dehydrogenation links LPG to more octanes

    SciTech Connect (OSTI)

    Gussow, S.; Spence, D.C.; White, E.A.

    1980-01-01

    Air Products and Chemicals Inc.'s Houdry Catofin process, a new application of well-known Houdry catalytic dehydrogenation technology, is an adiabatic, fixed-bed, multireactor catalytic process which produces propylene, isobutylene, and mixed n-butylenes by dehydrogenation of the corresponding saturates. The process is very flexible in that propylene, isobutylene, and mixed n-butylenes can be produced either separately or simultaneously from the corresponding saturates. The process will be used to prepare purity propylene at a Morelos, Mex., plant, which is now in the engineering stage. Five variations of the procedure for producing propylene; methyl tert.-butyl ether; propylene and alkylate; methyl tert.-butyl ether and alkylate; and methyl tert.-butyl ether, alkylate, and 1-butylene are compared with respect to typical product yields, costs and values for process economics, the dehydrogenation route to the three products, manufacturing costs, the sensitivity of return on investment to feedstock costs, and the return on investment, which varies from a low of 11.5% for the third case to a high of 14.4% for the fourth case. The Catofin process is discussed.

  3. Cesium and strontium extraction using a mixed extractant solvent including crown ether and calixarene extractants

    DOE Patents [OSTI]

    Meikrantz, David H.; Todd, Terry A.; Riddle, Catherine L.; Law, Jack D.; Peterman, Dean R.; Mincher, Bruce J.; McGrath, Christopher A.; Baker, John D.

    2007-11-06

    A mixed extractant solvent including calix[4]arene-bis-(tert-octylbenzo)-crown-6 ("BOBCalixC6"), 4',4',(5')-di-(t-butyldicyclo-hexano)-18-crown-6 ("DtBu18C6"), and at least one modifier dissolved in a diluent. The mixed extractant solvent may be used to remove cesium and strontium from an acidic solution. The DtBu18C6 may be present from approximately 0.01 M to approximately 0.4M, such as from approximately 0.086 M to approximately 0.108 M. The modifier may be 1-(2,2,3,3-tetrafluoropropoxy)-3-(4-sec-butylphenoxy)-2-propanol ("Cs-7SB") and may be present from approximately 0.01M to approximately 0.8M. In one embodiment, the mixed extractant solvent includes approximately 0.15M DtBu18C6, approximately 0.007M BOBCalixC6, and approximately 0.75M Cs-7SB modifier dissolved in an isoparaffinic hydrocarbon diluent. The mixed extractant solvent may form an organic phase in an extraction system that also includes an aqueous phase. Methods of extracting cesium and strontium as well as strontium alone are also disclosed.

  4. Chlorine resistant desalination membranes based on directly sulfonated poly(arylene ether sulfone) copolymers

    DOE Patents [OSTI]

    McGrath, James E.; Park, Ho Bum; Freeman, Benny D.

    2011-10-04

    The present invention provides a membrane, kit, and method of making a hydrophilic-hydrophobic random copolymer membrane. The hydrophilic-hydrophobic random copolymer membrane includes a hydrophilic-hydrophobic random copolymer. The hydrophilic-hydrophobic random copolymer includes one or more hydrophilic monomers having a sulfonated polyarylsulfone monomer and a second monomer and one or more hydrophobic monomers having a non-sulfonated third monomer and a fourth monomer. The sulfonated polyarylsulfone monomer introduces a sulfonate into the hydrophilic-hydrophobic random copolymer prior to polymerization.

  5. Extraction of protactinium-233 and separation from thermal neutron-irradiated thorium-232 using crown ethers

    SciTech Connect (OSTI)

    Jalhoom, Moayyed G.; Mohammed, Dawood A.; Khalaf, Jumah S.

    2008-07-01

    A new method was developed for the extraction and separation of {sup 233}Pa from thermal neutron-irradiated {sup 232}Th. Solutions of Pa{sup 233} were prepared in LiCI-HCl solutions from which appreciable extraction was obtained using dibenzo-18-crown-6 in 1,2-dichloroethane. The effects of cavity size, substitutions on the crown ring, type of the organic solvent, and temperature on extraction are discussed. Very high separation factors were obtained for the pairs {sup 233}Pa/{sup 232}Th (>105), {sup 233}Pa/{sup 233}U (> 1000), and {sup 232}U/{sup 232}Th (>60). (authors)

  6. The processing of alcohols, hydrocarbons and ethers to produce hydrogen for a PEMFC for transportation applications

    SciTech Connect (OSTI)

    Dams, R.A.J.; Hayter, P.R.; Moore, S.C.

    1997-12-31

    Wellman CJB Limited is involved in a number of projects to develop fuel processors to provide a hydrogen-rich fuel in Proton Exchange Membrane Fuel Cells (PEMFC) systems for transportation applications. This work started in 1990 which resulted in the demonstration of 10kW PEMFC system incorporating a methanol reformer and catalytic gas clean-up system. Current projects include: The development of a compact fast response methanol reformer and gas clean-up system for a motor vehicle; Reforming of infrastructure fuels including gasoline, diesel, reformulated fuel gas and LPG to produce a hydrogen rich gas for PEMFC; Investigating the potential of dimethylether (DME) as source of hydrogen rich gas for PEMFCs; The use of thin film palladium diffusers to produce a pure hydrogen stream from the hydrogen rich gas from a reformer; and Processing of naval logistic fuels to produce a hydrogen rich gas stream for PEMFC power system to replace diesel generators in surface ships. This paper outlines the background to these projects and reports their current status.

  7. The potential for alcohols and related ethers to displace conventional gasoline components

    SciTech Connect (OSTI)

    Hadder, G.R.; McNutt, B.D.

    1996-02-01

    The United States Department of Energy is required by law to determine the feasibility of producing sufficient replacement fuels to replace 30 percent of the projected United States consumption of motor fuels by light duty vehicles in the year 2010. A replacement fuel is a non-petroleum portion of gasoline, including alcohols, natural gas and certain other components. A linear program has been used to study refinery impacts for production of ``low petroleum`` gasolines, which contain replacement fuels. The analysis suggests that high oxygenation is the key to meeting the replacement fuel target, and major contributors to cost increase can include investment in processes to produce olefins for etherification with alcohols. High oxygenation can increase the costs of control of vapor pressure, distillation properties, and pollutant emissions of gasolines. Year-round low petroleum gasoline with near-30 percent non-petroleum might be produced with cost increases of 23 to 37 cents per gallon, with substantial decreases in greenhouse gas emissions in some cases. Cost estimates are sensitive to assumptions about extrapolation of a national model for pollutant emissions, availability of raw materials and other issues. Reduction in crude oil use, a major objective of the low petroleum gasoline program, is 10 to 17 percent in the analysis.

  8. Development of a Dimethyl Ether (DME)-Fueled Shuttle Bus | Department of

    Broader source: Energy.gov (indexed) [DOE]

    Phenolic Foam for Building Insulation | Department of Energy Inside the lab of Fraunhofer Center for Sustainable Energy Systems (CSE) in Boston, MA<br /> Photo Courtesy of Fraunhofer CSE, Photo Credit: Trent Bell Inside the lab of Fraunhofer Center for Sustainable Energy Systems (CSE) in Boston, MA Photo Courtesy of Fraunhofer CSE, Photo Credit: Trent Bell Inside the lab of Fraunhofer Center for Sustainable Energy Systems (CSE) in Boston, MA<br /> Photo Courtesy of Fraunhofer

  9. Synthesis of oxygenate products for high volume fuels applications. Quarterly technical progress report, November 1, 1994--January 31, 1995

    SciTech Connect (OSTI)

    1995-03-08

    The objective of this project is to develop high yield syntheses of oxygenate products that are liquid at room temperature using as starting materials dimethy ether (DME) or methanol. The identified products include: Dimethyl Carbonate (DMC), 1,1-Dimethoxyethane (DMOE), C{sub 2}{sup +} Alcohols/Ethers (C{sub 2}AE). The technical strategy is outlined below: (A) Synthesis of DMC via oxidative carbonylation of DME instead of methanol. Since this synthesis would not co-produce water as a byproduct, there is a potential for very high DME conversions in contrast to the low (ca 20%) conversions obtained in conventional plants. Technical emphasis will be placed on development of a supported copper catalyst with a capability for cleavage of DME into its chemisorbed organic moieties. (B) Synthesis of 1,1-dimethoxymethane (DMOE) from acetylene/CO/H{sub 2} process streams obtained from commercial methane oxidative pyrolysis processes. In the overall processing scheme the syngas would be converted to DME. The wet acetylene stream would be partially condensed to retain an equivalent of water and then condensed with DME to produce EMOE. (C) Direct conversion of DME or DME/methanol to ethanol/propanol or their methyl ethers. Under the influence of functionalized alcohol condensation catalysts developed exclusively at Amoco it should be possible to achieve direct conversion of dimethyl ether (or methanol) to ethanol/propanol and/or the methyl ethers of these alcohols. Although this reaction is not currently known, a combination of key catalyst components from identified systems should result in a DME conversion catalyst to C{sub 2}+ oxygenates. (D) Reaction of DME or acetylene with synthesis gas (CO/H{sub 2}) or methanol. A variety of catalysts will be tested for conversion of acetylene/CO/H{sub 2} or acetylene/methanol to propylene and conversion of DME/CO/H{sub 2} or DME/methanol to dimenthyoxymethane (DMM) and/or other oxygenates.

  10. The use of CETANER{trademark} for the reduction of particulate matter emissions in a turbocharged direct injection (TDI) diesel engine

    SciTech Connect (OSTI)

    Hess, H.S.; Chiodo, J.A.; Boehman, A.L.; Tijim, P.J.A.; Waller, F.J.

    1999-07-01

    In this experimental study, the effects of the addition of CETANER{trademark} to a premium diesel fuel at various blend levels (5%, 10% and 15% by weight) were evaluated using a 1.9 liter turbocharged direct injection diesel engine. CETANER{trademark}, a product developed by Air Products and Chemicals, Inc., can be manufactured from coal-derived syngas through a two-stage process: (i) Liquid Phase DiMethyl Ether synthesis (LPDME); and (ii) oxidative coupling of DiMethyl Ether (DME) to form long chain linear ethers. When compared to other oxygenated components currently being researched, CETANER has several key advantages: (1) it is derived from a non-petroleum feedstock; (2) it has a cetane number greater than 100; and (3) it will have a cost comparable to diesel fuel. Particulate matter emissions and exhaust gas composition (NOx and CO), were determined at six steady-state engine operating conditions. In addition, fuel properties (viscosity, cloud point, pour point, density, flash point and calorific value) of the various blends were also determined. Engine test results indicate that CETANER is effective in reducing particulate matter emissions at all blend levels tested, without any modifications to engine operating parameters. At the highest blend level (15% CETANER by weight), particulate matter emissions were reduced by greater than 20% when compared to premium diesel fuel.

  11. Petrochemicals from coal-derived syngas

    SciTech Connect (OSTI)

    Sardesai, A.; Lee, S.

    1996-12-31

    The development of the Liquid Phase Dimethyl Ether (LPDME) process has established a means to effectively convert CO-rich syngas to dimethyl ether (DME) in a mechanically agitated slurry reactor. By operating in a dual catalyst mode, in-situ produced methanol may be converted to DME, thereby alleviating the chemical equilibrium limitation imposed on the methanol synthesis reaction. As a result, higher syngas conversions and methyl productivities are seen over methanol synthesis alone. This effective route to DME production over methanol has led to the development of conversion technologies based on a DME feedstock. Oxygenates, in particular, ethers and their precursors, are very important as potential clean fuel additives and have been postulated through vinylation/hydrogenation and oxidative coupling reactions. Specialty chemicals such as methyl acetate and acetic acid have widescale industrial importance in the conversion to ethanol from a non-agricultural feedstock. Vapor phase oxidative dimerization of DME over tin based catalysts produced precursors of ethylene glycol. Finally, DME has been extensively used as a feedstock for hydrocarbon synthesis including olefins, paraffins and gasoline range hydrocarbons, over zeolite based catalysts with a 46% increase in product selectivity over methanol. The efficient production of DME in the liquid phase has given it widescale industrial significance as a potential replacement for methanol and as a keystone for more important petrochemicals.

  12. Ozone-forming potential of a series of oxygenated organic compounds

    SciTech Connect (OSTI)

    Japar, S.M.; Wallington, T.J.; Rudy, S.J.; Chang, Tai Y. )

    1991-03-01

    An incremental reactivity approach has been used to assess the relative ozone-forming potentials of various important oxygenated fuels/fuel additives, i.e., tert-butyl alcohol (TBA), dimethyl ether (DME), diethyl ether (DEE), methyl tert-butyl ether (MTBE), and ethyl tert-butyl ether (ETBE), in a variety of environments. Calculations were performed using a single-cell trajectory model, combined with the Lurmann-Carter-Coyner chemical mechanism, with (NMOC)/(NO{sub x}) ratios ranging from 4 to 20. This work provides the first quantitative assessment of the air quality impact of release of these important oxygenated compounds. ETBE and DEE are the two most reactive compounds on a per carbon equivalent basis, while TBA is the least reactive species. At a (NMOC)/(NO{sub x}) ratio of 8, which is generally typical of polluted urban areas in the United States, TBA, DME, MTBE, and ETBE all have incremental reactivities less than or equal to that of the urban NMHC mix. Thus, use of these additives in fuels may have a beneficial impact on urban ozone levels.

  13. Development of candidate chemical simulant list: the evaluation of candidate chemical simulants which may be used in chemically hazardous operations. Final report 15 Jun-15 Dec 82

    SciTech Connect (OSTI)

    Not Available

    1982-12-01

    The objectives of this task were threefold: (1) to provide additional data for the proposed candidate simulates dipentene, methyl benzoate and benzyl alcohol by means of in-depth literature searches encompassing both computerized data bases and a manual search of the older literature; (2) to fully evaluate twelve possible candidate simulants under more flexible simulant criteria; and (3) to develop a list of candidate simulants in the low and non-volatile categories. Computerized literature searches were conducted for the twelve possible candidate simulants under more flexible intake simulant criteria as well as for dimethyl methylphosphonate, a compound selected for evaluation by the USAF. The twelve possible candidates included: cyclohexanone, n-dodecanethiol, methyl salicylate, dihexyl ether, dypnone, n-aminopropyl morpholine, n-(2-hydroxyethyl) morpholine, butyl salicylate, di(2-ethyl hexyl) ether, 2-undecanol, 2-hydroxyethyl-n-octyl sulfide and n,n-diethyl-m-toluamide. Full assessments of the potential health hazards associated with exposure to n-dodecanethiol, methyl salicylate, butyl salicylate and n,n-diethyl-m-toluamide were completed. All of these compounds meet the majority of USAF criteria for candidate simulants. Cyclohexanone was disqualified for reasons of toxicity, while the available toxicological data for the seven remaining candidates were considered inadequate for full assessment of hazard.

  14. Ionic Transport Across Interfaces of Solid Glass and Polymer Electrolytes

    SciTech Connect (OSTI)

    Tenhaeff, Wyatt E; Yu, Xiang; Hong, Kunlun; Perry, Kelly A; Dudney, Nancy J

    2011-01-01

    A study of lithium cation transport across solid-solid electrolyte interfaces to identify critical resistances in nanostructured solid electrolytes is reported. Bilayers of glass and polymer thin film electrolytes were fabricated and characterized for this study. The glass electrolyte was lithium phosphorous oxynitride (Lipon), and two polymer electrolytes were studied: poly(methyl methacrylate-co-poly(ethylene glycol) methyl ether methacrylate) and poly(styrene-co-poly(ethylene glycol) methyl ether methacrylate). Both copolymers contained LiClO{sub 4} salt. In bilayers where polymer electrolyte layers are fabricated on top of Lipon, the interfacial resistance dominates transport. At 25 C, the interfacial resistance is at least three times greater than the sum of the Lipon and polymer electrolyte resistances. By reversing the structure and fabricating Lipon on top of the polymer electrolytes, the interfacial resistance is eliminated. Experiments to elucidate the origin of the interfacial resistance in the polymer-on-Lipon bilayers reveal that the solvent mixtures used to fabricate the polymer layers do not degrade the Lipon layer. The importance of the polymer electrolytes' mechanical properties is also discussed.

  15. Synthesis and crystal structure studies of ethyl 5-methyl-1,...

    Office of Scientific and Technical Information (OSTI)

    investigated by single crystal X-ray diffraction method. It crystallizes in monoclinic class under the space group P2sub 1c with cell parameters a 8.4593(4) , b15.6284(6)...

  16. Total and methyl mercury in selected Great Lakes tributaries

    SciTech Connect (OSTI)

    Hurley, J.P.; Cowell, S.E.; Shafer, M.M.

    1995-12-31

    Eleven Lake Michigan tributaries were chosen to investigate the effects of chemical and physical conditions in rivers on mercury partitioning and transport. Preliminary results from 1994 indicate that mean unfiltered Hg{sub T} ranged from about 1-2 ng L{sup -1} in the Manistique and Muskegon R. to 10-30 ng L{sup -1} in the St. Joseph and Fox R. Highest Hg{sub T} fluxes were generally associated with increased particle loads. Preliminary estimates from a subset of Lake Michigan tributaries also suggest that methylmercury loading from riverine inputs may be important. Additional work on 19 Lake Superior tributaries in Spring 1993 reveal that MeHg and DOC are correlated. Results from these tributaries are consistent with our {open_quotes}Background Trace Metals in Wisconsin Rivers{close_quotes} study, where greater yields of Hg{sub T} were observed with increased particle loading and elevated MeHg yields were observed from watersheds with significant forest and wetland regions.

  17. Lithium Methyl Carbonate as a Reaction Product of Metallic Lithiumand...

    Office of Scientific and Technical Information (OSTI)

    Visit OSTI to utilize additional information resources in energy science and technology. A ... Sponsoring Org: USDOE. Assistant Secretary for Energy Efficiency andRenewable Energy. ...

  18. Substantial improvements in methyl ketone production in E. coli...

    Office of Scientific and Technical Information (OSTI)

    Additional Journal Information: Journal Volume: 26; Journal Issue: C; Journal ID: ISSN 1096-7176 Publisher: Elsevier Sponsoring Org: USDOE Office of Science (SC), Biological and ...

  19. Synthesis of 6-Methyl-9-propyldibenzothiophene-4-ol

    SciTech Connect (OSTI)

    Eisenbraun, E.J.

    1991-02-15

    The synthesis route for preparing the title compound, has been carried out on a small scale for the preparation of a mixture of isomers. Alternative routes for the cyclization are being explored. (DLC)

  20. Determination of Total Lipids as Fatty Acid Methyl Esters (FAME...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    ... Storage of samples should ideally be in an inert (nitrogen) atmosphere and at least at -20C. 10. Procedure 10.1 Preparation of the samples for transesterification 10.1.1 Label ...

  1. Proceedings of the 1995 SAE alternative fuels conference. P-294

    SciTech Connect (OSTI)

    1995-12-31

    This volume contains 32 papers and five panel discussions related to the fuel substitution of trucks, automobiles, buses, cargo handling equipment, diesel passenger cars, and pickup trucks. Fuels discussed include liquefied natural gas, natural gas, ethanol fuels, methanol fuels, dimethyl ether, methyl esters from various sources (rape oil, used cooking oils, soya, and canola oils), hydrogen fuels, and biodiesel. Other topics include fuel cell powered vehicles, infrastructure requirements for fuel substitution, and economics. Papers have been processed separately for inclusion on the data base.

  2. pH-sensitive methacrylic copolymer gels and the production thereof

    DOE Patents [OSTI]

    Mallapragada, Surya K.; Anderson, Brian C.

    2007-05-15

    The present invention provides novel gel forming methacrylic blocking copolymers that exhibit cationic pH-sensitive behavior as well as good water solubility. The copolymers are constructed by polymerization of a tertiary amine methacrylate with either a (poly(ethylene oxide)-b-poly(propylene oxide)-b-poly(ethylene oxide) polymer, such as the commercially available Pluronic.RTM. polymers, or a poly(ethylene glycol)methyl ether polymer. The polymers may be used for drug and gene delivery, protein separation, as structural supplements, and more.

  3. Polystyrene-poly(vinylphenol) copolymers as compatibilzers for organic-inorganic composites

    SciTech Connect (OSTI)

    Landry, C.J.T.; Coltrain, B.K.; Teegarden, D.M.

    1996-12-31

    Random, graft, and block copolymers of polystyrene (PS) and poly(4-vinylphenol) (PVPh), and PVPh homopolymer are shown to act as compatibilizers for incompatible organic-inorganic composite materials. The VPh component reacts, or interacts strongly with the polymerizing inorganic (titanium or zirconium) alkoxide. The organic components studied were PS, poly(vinyl methyl ether), and poly(styrene-co-acrylonitrile). The use of such compatibilizers provides a means of combining in situ polymerized inorganic oxides and hydrophobic polymers. This is seen as a reduction in the size of the dispersed inorganic phase and results in improved optical and mechanical properties.

  4. Hybrid sol-gel optical materials

    DOE Patents [OSTI]

    Zeigler, John M.

    1993-01-01

    Hybrid sol-gel materials comprise silicate sols cross-linked with linear polysilane, polygermane, or poly(silane-germane). The sol-gel materials are useful as optical identifiers in tagging and verification applications and, in a different aspect, as stable, visible light transparent non-linear optical materials. Methyl or phenyl silicones, polyaryl sulfides, polyaryl ethers, and rubbery polysilanes may be used in addition to the linear polysilane. The linear polymers cross-link with the sol to form a matrix having high optical transparency, resistance to thermooxidative aging, adherence to a variety of substrates, brittleness, and a resistance to cracking during thermal cycling.

  5. Hybrid sol-gel optical materials

    DOE Patents [OSTI]

    Zeigler, John M.

    1992-01-01

    Hybrid sol-gel materials comprise silicate sols cross-linked with linear polysilane, polygermane, or poly(silane-germane). The sol-gel materials are useful as optical identifiers in tagging and verification applications and, in a different aspect, as stable, visible light transparent non-linear optical materials. Methyl or phenyl silicones, polyaryl sulfides, polyaryl ethers, and rubbery polysilanes may be used in addition to the linear polysilane. The linear polymers cross-link with the sol to form a matrix having high optical transparency, resistance to thermooxidative aging, adherence to a variety of substrates, brittleness, and a resistance to cracking during thermal cycling.

  6. Injectible bodily prosthetics employing methacrylic copolymer gels

    DOE Patents [OSTI]

    Mallapragada, Surya K.; Anderson, Brian C.

    2007-02-27

    The present invention provides novel block copolymers as structural supplements for injectible bodily prosthetics employed in medical or cosmetic procedures. The invention also includes the use of such block copolymers as nucleus pulposus replacement materials for the treatment of degenerative disc disorders and spinal injuries. The copolymers are constructed by polymerization of a tertiary amine methacrylate with either a (poly(ethylene oxide)-b-poly(propylene oxide)-b-poly(ethylene oxide) polymer, such as the commercially available Pluronic.RTM. polymers, or a poly(ethylene glycol) methyl ether polymer.

  7. Hybrid sol-gel optical materials

    DOE Patents [OSTI]

    Zeigler, J.M.

    1993-04-20

    Hybrid sol-gel materials comprise silicate sols cross-linked with linear polysilane, polygermane, or poly(silane-germane). The sol-gel materials are useful as optical identifiers in tagging and verification applications and, in a different aspect, as stable, visible light transparent non-linear optical materials. Methyl or phenyl silicones, polyaryl sulfides, polyaryl ethers, and rubbery polysilanes may be used in addition to the linear polysilane. The linear polymers cross-link with the sol to form a matrix having high optical transparency, resistance to thermooxidative aging, adherence to a variety of substrates, brittleness, and a resistance to cracking during thermal cycling.

  8. Aggregation behavior of hexaoxyethyleneglycol myristate and hexaoxyethyleneglycol mono (1-methyltridecane) ether and dynamics of their micelles in aqueous solution

    SciTech Connect (OSTI)

    Alami, E.; Zana, R. ); Van Os, N.M.; Jong, B. de; Kerkhof, F.J.M. ); Rupert, L.A.M. )

    1993-10-01

    The title surfactants have similar critical micelle concentrations and cloud temperatures. Their micellar solutions have been investigated by time resolved fluorescence quenching in the range 2--25 c. The micelle aggregation numbers of both surfactants do not differ much, and increase with temperature. Aggregation numbers are large, suggesting anisotropic micelles, and the results show that the micelles are polydisperse. Fast intermicellar exchange of material becomes detectable on the fluorescence timescale ([approximately]1 [mu]s) above T [approx] 10 C, i.e., some 35--40 C below the cloud temperature of the solution. This exchange probably occurs via micelle collisions with temporary merging. Overall the behavior of these two surfactants is very similar to that of the other ethoxylated nonionic surfactants previously examined.

  9. Chain architecture and micellization: A mean-field coarse-grained model for poly(ethylene oxide) alkyl ether surfactants

    SciTech Connect (OSTI)

    García Daza, Fabián A.; Mackie, Allan D.; Colville, Alexander J.

    2015-03-21

    Microscopic modeling of surfactant systems is expected to be an important tool to describe, understand, and take full advantage of the micellization process for different molecular architectures. Here, we implement a single chain mean field theory to study the relevant equilibrium properties such as the critical micelle concentration (CMC) and aggregation number for three sets of surfactants with different geometries maintaining constant the number of hydrophobic and hydrophilic monomers. The results demonstrate the direct effect of the block organization for the surfactants under study by means of an analysis of the excess energy and entropy which can be accurately determined from the mean-field scheme. Our analysis reveals that the CMC values are sensitive to branching in the hydrophilic head part of the surfactant and can be observed in the entropy-enthalpy balance, while aggregation numbers are also affected by splitting the hydrophobic tail of the surfactant and are manifested by slight changes in the packing entropy.

  10. DESIGN AND SYNTHESIS OF THE NEXT GENERATION OF CROWN ETHERS FOR WASTE SEPARATIONS: AN INTER-LABORATORY COMPREHENSIVE PROPOSAL

    SciTech Connect (OSTI)

    Moyer, Bruce A.

    2000-12-31

    The objectives of this project were to develop the techniques, materials, and fundamental understanding necessary to solve difficult separations problems of the USDOE in the 21st century. The specific goals included developing new, powerful molecular modeling tools for ligand design, performing computational and structural studies to reveal fundamental properties of ligand-metal ion interactions, studying solvent extraction behavior to provide basic understanding of solution speciation and equilibria, and preparing new ion-exchange resins for the separation of metal ions of environmental significance to the USDOE. Contaminants of special interest included alkali and alkaline-earth metal ions, especially, lithium, cesium, and strontium. For example, Li+ ions contaminate the groundwater at the Oak Ridge Y-12 Plant; Cs+ and Sr2+ represent fission products in groundwater (e.g., INEEL, Hanford), stored waste (e.g., Savannah River Site, Hanford tanks), and process-water streams (e. g., ORNL).

  11. Extraction of Cesium by a Calix[4]arene-Crown-6 Ether Bearing a Pendant amine Group

    SciTech Connect (OSTI)

    Harmon, Ben; Ensor, Dale; Delmau, Laetitia Helene; Moyer, Bruce A

    2007-01-01

    The goal of this work was to evaluate the role of the amino group of 5-aminomethylcalix[4]arene-[bis-4-(2-ethylhexyl)benzo-crown-6] (AMBEHB) in the extraction of cesium from acidic and basic mixtures of sodium nitrate and other concentrated salts. The extraction of cesium from nitrate media was measured as a function of extractant concentration, nitrate concentration, cesium concentration, and pH over the range 1-13. The initial studies showed a moderate decrease in the extraction of cesium in acidic media, which indicated the binding of cesium by the calixarene-crown was weakened by the protonation of the amine group. The results also indicated that a 1:1:1 Cs-ligand-nitrate complex is formed in the organic phase. To further evaluate AMBEHB, the empirical data were mathematically modeled to determine the formation constants of the complexes formed in the organic phase. The resulting formation constants showed that the attachment of the amine group to the calixarene-crown molecule reduced the binding stability for the cesium ion upon contact with an acidic solution. This supports the hypothesis of charge repulsion as the basis for more efficient stripping of cesium via pH-switching.

  12. Fluoroalkyl containing salts combined with fluorinated solvents for electrolytes

    SciTech Connect (OSTI)

    Tikhonov, Konstantin; Yip, Ka Ki; Lin, Tzu-Yuan; Erickson, Michael Jason

    2015-04-21

    Provided are electrochemical cells and electrolytes used to build such cells. An electrolyte may include a fluoroalkyl-substituted LiPF.sub.6 salt or a fluoroalkyl-substituted LiBF.sub.4 salt. In some embodiments, at least one fluorinated alkyl of the salt has a chain length of from 1 to 8 or, more specifically, between about 2 and 8. These fluorinated alkyl groups, in particular, relatively large fluorinated alkyl groups improve solubility of these salts in fluorinated solvents that are less flammable than, for example, conventional carbonate solvents. At the same time, the size of fluoroalkyl-substituted salts should be limited to ensure adequate concentration of the salt in an electrolyte and low viscosity of the electrolyte. In some embodiments, the concentration of a fluoroalkyl-substituted salt is at least about 0.5M. Examples of fluorinated solvents include various fluorinated esters, fluorinated ethers, and fluorinated carbonates, such a 1-methoxyheptafluoropropane, methyl nonafluorobutyl ether, ethyl nonafluorobutyl ether, 1,1,1,2,2,3,4,5,5,5-decafluoro-3-methoxy-4-(trifluoromethyl)-pentane, 3-ethoxy-1,1,1,2,3,4,4,5,5,6,6,6-dodecafluoro-2-trifluoromethyl-hexane, and 1,1,1,2,3,3-hexafluoro-4-(1,1,2,3,3,3-hexafluoropropoxy)-pentane.

  13. The census of complex organic molecules in the solar-type protostar IRAS16293-2422

    SciTech Connect (OSTI)

    Jaber, Ali A.; Ceccarelli, C.; Kahane, C.; Caux, E.

    2014-08-10

    Complex organic molecules (COMs) are considered to be crucial molecules, since they are connected with organic chemistry, at the basis of terrestrial life. More pragmatically, they are molecules which in principle are difficult to synthesize in harsh interstellar environments and, therefore, are a crucial test for astrochemical models. Current models assume that several COMs are synthesized on lukewarm grain surfaces (≳30-40 K) and released in the gas phase at dust temperatures of ≳100 K. However, recent detections of COMs in ≲20 K gas demonstrate that we still need important pieces to complete the puzzle of COMs formation. Here, we present a complete census of the oxygen- and nitrogen-bearing COMs, previously detected in different Interstellar Medium (ISM) regions, toward the solar-type protostar IRAS16293-2422. The census was obtained from the millimeter-submillimeter unbiased spectral survey TIMASSS. Of the 29 COMs searched for, 6 were detected: methyl cyanide, ketene, acetaldehyde, formamide, dimethyl ether, and methyl formate. Multifrequency analysis of the last five COMs provides clear evidence that they are present in the cold (≲30 K) envelope of IRAS16293-2422, with abundances of 0.03-2 × 10{sup –10}. Our data do not allow us to support the hypothesis that the COMs abundance increases with increasing dust temperature in the cold envelope, as expected if COMs were predominately formed on lukewarm grain surfaces. Finally, when also considering other ISM sources, we find a strong correlation over five orders of magnitude between methyl formate and dimethyl ether, and methyl formate and formamide abundances, which may point to a link between these two couples of species in cold and warm gas.

  14. Process for conversion of lignin to reformulated, partially oxygenated gasoline

    DOE Patents [OSTI]

    Shabtai, Joseph S. (Salt Lake City, UT); Zmierczak, Wlodzimierz W. (Salt Lake City, UT); Chornet, Esteban (Golden, CO)

    2001-01-09

    A high-yield process for converting lignin into reformulated, partially oxygenated gasoline compositions of high quality is provided. The process is a two-stage catalytic reaction process that produces a reformulated, partially oxygenated gasoline product with a controlled amount of aromatics. In the first stage of the process, a lignin feed material is subjected to a base-catalyzed depolymerization reaction, followed by a selective hydrocracking reaction which utilizes a superacid catalyst to produce a high oxygen-content depolymerized lignin product mainly composed of alkylated phenols, alkylated alkoxyphenols, and alkylbenzenes. In the second stage of the process, the depolymerized lignin product is subjected to an exhaustive etherification reaction, optionally followed by a partial ring hydrogenation reaction, to produce a reformulated, partially oxygenated/etherified gasoline product, which includes a mixture of substituted phenyl/methyl ethers, cycloalkyl methyl ethers, C.sub.7 -C.sub.10 alkylbenzenes, C.sub.6 -C.sub.10 branched and multibranched paraffins, and alkylated and polyalkylated cycloalkanes.

  15. Kinetically Trapped Co-Continuous Polymer Morphologies through Intraphase Gelation of Nanoparticles

    SciTech Connect (OSTI)

    Li, Le; Miesch, Caroline; Sudeep, P. K.; Balazs, Anna C.; Emrick, Todd; Russell, Thomas P.; Hayward, Ryan C.

    2011-05-11

    We describe an approach to prepare co-continuous microstructured blends of polymers and nanoparticles by formation of a percolating network of particles within one phase of a polymer mixture undergoing spinodal decomposition. Nanorods or nanospheres of CdSe were added to near-critical blends of polystyrene and poly(vinyl methyl ether) quenched to above their lower critical solution temperature. Beyond a critical loading of nanoparticles, phase separation is arrested due to the aggregation of particles into a network (or colloidal gel) within the poly(vinyl methyl ether) phase, yielding a co-continuous spinodal-like structure with a characteristic length scale of several micrometers. The critical concentration of nanorods to achieve kinetic arrest is found to be smaller than for nanospheres, which is in qualitative agreement with the expected dependence of the nanoparticle percolation threshold on aspect ratio. Compared to structural arrest by interfacial jamming, our approach avoids the necessity for neutral wetting of particles by the two phases, providing a general pathway to co-continuous micro- and nanoscopic structures.

  16. Economic contribution of lignins to ethanol production from biomass

    SciTech Connect (OSTI)

    Chum, H.L.; Parker, S.K.; Feinberg, D.A.; Wright, J.D.; Rice, P.A.; Sinclair, S.A.; Glasser, W.G.

    1985-05-01

    Lignin, one of the three major polymeric components of biomass (16% to 33% by weight in wood), has the highest specific heat content. Therefore, it can be burned for process fuel. Compared to coal, its fuel value is 2.2 cents/lb. This report investigates markets for lignin utilization of higher value. After lignin isolation from the process, purchase of replacement fuel (coal was analyzed), lignin sale for the manufacture of solid materials or higher value octane enhancers was evaluated. Polymeric applications evaluated were: surfactants, asphalt, carbon black, adhesives, and lignin plastics; agricultural applications were briefly reviewed. These lignins would generate coproduct credits of 25 cents to 150 cents/gallon of ethanol respectively for 7.5 cents to 60 cents/lb lignin value (isolation and eventual modification costs were taken into account). Overall markets for these polymeric applications were projected at 11 billion lb/year by the year 2000. These projections are intensities of demand and not actual shipments of lignins. In addition, this report investigates the possibility of converting lignins into mixtures of methyls aryl ethers and methyl substituted-aryl ethers which are high value octane enhancers, fully compatible with gasoline. The report intends to show that if fuel ethanol production in the billions of gallons scale occurs lignin markets would not be saturated. 10 refs., 14 figs., 36 tabs.

  17. Synthesis of new high performance lubricants and solid lubricants. Progress report, April 1992--March 1993

    SciTech Connect (OSTI)

    Lagow, R.J.

    1993-04-01

    Synthesis and testing was begun on a number of new classes of lubricants: perfluoropolyethers (branching effects), perfluoromethylene oxide ethers, chlorine-substituted fluorocarbon polyethers, fluorine-containing branched ether lubricants, glycerine- based perfluoropolyesters, perfluoro epoxy ether chains, etc.

  18. Synthesis of new high performance lubricants and solid lubricants

    SciTech Connect (OSTI)

    Lagow, R.J.

    1993-04-01

    Synthesis and testing was begun on a number of new classes of lubricants: perfluoropolyethers (branching effects), perfluoromethylene oxide ethers, chlorine-substituted fluorocarbon polyethers, fluorine-containing branched ether lubricants, glycerine- based perfluoropolyesters, perfluoro epoxy ether chains, etc.

  19. Synthesis of 6-Methyl-9-n-propyldibenzothiophene-4-ol ammended to 6-Methyl-9-(1-methylethyl)-dibenzothiophene-4-ol

    SciTech Connect (OSTI)

    Not Available

    1992-02-28

    The material presented below is taken from Status Reports 15, 16 and 17 and covers the progress made toward the synthesis of the modified target molecules 9-isopropyl-4-methoxy-6 methyldibenzothiophene (13) and 9-isopropyl-6methyldibenzothiophene-4-ol (14).

  20. Zelenay named Electrochemical Society Fellow

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    including non-precious metalprecious metal electrocatalysis of oxygen reduction and methanol and dimethyl ether oxidation; hydrogen, direct methanol, and direct dimethyl ether...

  1. Natural Abundance 17O Nuclear Magnetic Resonance and Computational Modeling Studies of Lithium Based Liquid Electrolytes

    SciTech Connect (OSTI)

    Deng, Xuchu; Hu, Mary Y.; Wei, Xiaoliang; Wang, Wei; Chen, Zhong; Liu, Jun; Hu, Jian Z.

    2015-07-01

    Natural abundance 17O NMR measurements were conducted on electrolyte solutions consisting of Li[CF3SO2NSO2CF3] (LiTFSI) dissolved in the solvents of ethylene carbonate (EC), propylene carbonate (PC), ethyl methyl carbonate (EMC), and their mixtures at various concentrations. It was observed that 17O chemical shifts of solvent molecules change with the concentration of LiTFSI. The chemical shift displacements of carbonyl oxygen are evidently greater than those of ethereal oxygen, strongly indicating that Li+ ion is coordinated with carbonyl oxygen rather than ethereal oxygen. To understand the detailed molecular interaction, computational modeling of 17O chemical shifts was carried out on proposed solvation structures. By comparing the predicted chemical shifts with the experimental values, it is found that a Li+ ion is coordinated with four double bond oxygen atoms from EC, PC, EMC and TFSI- anion. In the case of excessive amount of solvents of EC, PC and EMC the Li+ coordinated solvent molecules are undergoing quick exchange with bulk solvent molecules, resulting in average 17O chemical shifts. Several kinds of solvation structures are identified, where the proportion of each structure in the liquid electrolytes investigated depends on the concentration of LiTFSI.

  2. Solvate Structures and Computational/Spectroscopic Characterization of LiBF4 Electrolytes

    SciTech Connect (OSTI)

    Seo, D. M.; Boyle, Paul D.; Allen, Joshua L.; Han, Sang D.; Jonsson, Erlendur; Johansson, Patrik; Henderson, Wesley A.

    2014-07-21

    Crystal structures have been determined for both LiBF4 and HBF4 solvates—(acetonitrile)2:LiBF4, (ethylene glycol diethyl ether)1:LiBF4, (diethylene glycol diethyl ether)1:LiBF4, (tetrahydrofuran)1:LiBF4, (methyl methoxyacetate)1:LiBF4, (suc-cinonitrile)1:LiBF4, (N,N,N',N",N"-pentamethyldiethylenetriamine)1:HBF4, (N,N,N',N'-tetramethylethylenediamine)3/2:HBF4 and (phenanthroline)2:HBF4. These, as well as other known LiBF4 solvate structures, have been characterized by Raman vibrational spectroscopy to unambiguously assign the anion Raman band positions to specific forms of BF4-...Li+ cation coordination. In addition, complementary DFT calculations of BF4-...Li+ cation complexes have provided additional insight into the challenges associated with accurately interpreting the anion interactions from experimental Raman spectra. This information provides a crucial tool for the characterization of the ionic association interactions within electrolytes.

  3. POLYETHERSULFONE COATING FOR MITIGATING CORROSION OF STEEL IN GEOTHERMAL ENVIRONMENT.

    SciTech Connect (OSTI)

    SUGAMA, T.

    2005-06-01

    Emphasis was directed toward evaluating the usefulness of a polyethersulfone (PES)-dissolved N-methyl pyrrolidone (NMP) solvent precursor as a low-temperature film-forming anti-corrosion coating for carbon steel in simulated geothermal environments at brine temperatures up to 300 C. A {approx} 75 {micro}m thick PES coating performed well in protecting the steel against corrosion in brine at 200 C. However, at {>=} 250 C, the PES underwent severe hydrothermal oxidation that caused the cleavage of sulfone- and ether-linkages, and the opening of phenyl rings. These, in turn, led to sulfone {yields} benzosulfonic acid and ether {yields} benzophenol-type oxidation derivative transformations, and the formation of carbonyl-attached open rings, thereby resulting in the incorporation of the functional groups, hydroxyl and carbonyl, into the coating. The presence of these functional groups raised concerns about the diminutions in water-shedding and water-repellent properties that are important properties of the anti-corrosion coatings; such changes were reflected in an enhancement of the magnitude of susceptibility of the coatings surfaces to moisture. Consequently, the disintegration of the PES structure by hydrothermal oxidation was detrimental to the maximum efficacy of the coating in protecting the steel against corrosion, allowing the corrosive electrolytes to infiltrate easily through it.

  4. Eastman, AP start on coal unit

    SciTech Connect (OSTI)

    1995-10-25

    Eastman Chemical and Air Products and Chemicals (AP) have started construction of a $214-million, coal-to-methanol demonstration unit at Eastmans site in Kingsport, TN. The project is part of the Department of Energy`s clean coal technology program and is receiving $93 million in federal support. The demonstration unit-which will have a methanol capacity of 260 tons/day-will use novel catalyst technology for converting coal-derived synthesis gas (syngas) to methanol. Unlike conventional technology that processes syngas through a fixed bed of dry catalyst particles, the liquid-phase methanol process converts the syngas in a single vessel containing catalysts suspended in mineral oil. The companies say the innovation allows the process to better able handle the gases from coal gasifiers and is more stable and reliable than existing processes. Eastman says it will use the methanol produced by the plant as a chemical feedstock. It currently uses methanol as an intermediate in making acetic anhydride and dimethyl terephthalate. In addition, the companies say the methanol will be evaluated as a feedstock in making methyl tert-butyl ether for reformulated fuels. Eastman also says it will evaluate coproducing dimethyl ether (DME) with the methanol. DME can be used as a fuel additive or blended with methanol for a chemical feedstock, according to Eastman.

  5. Arco to enter European PGE production with new Rotterdam plant

    SciTech Connect (OSTI)

    Young, I.

    1993-03-03

    Arco Chemical (Newtown Square, PA) will enter production of propylene glycol ethers (PGEs) in Europe by building a 70,000-m.t./year plant at its Rotterdam site. Arco's board has approved the project, with construction to begin this year and completion expected in mid-1995. This new plant supports the company's long-standing strategy to increase its downstream integration in value-added derivatives of propylene oxide,' says Jack Oppasser, president of Arco Chemical Europe (Maidenhead, U.K.). It allows the company to sustain its strong position in the growing European glycol ether market.' Arco's move represents a challenge to Dow Europe (Horgen, Switzerland), which dominates the European PGE market. Dow is Europe's biggest producer of PGEs, with its Dowanol brands commanding a share greater than 50% of the estimated 90,000-m.t./year methyl-based PGE market. This was recently boosted by completion of the expansion of its plant at Stade, Germany, from 60,000 m.t./year to 110,000 m.t./year. While Arco does not currently make PGEs in Europe, it is the second-largest supplier, with about 15,000 m.t.-20,000 m.t./year, via third-party manufacturing arrangements' with European producers, including BP Chemicals, and imports from its 90-million lbs/year plant at Bayport, TX. However, Arco refuses to comment on this because of antitrust aspects.'

  6. Low-temperature superacid catalysis: Reactions of n-butane catalyzed by iron- and manganese-promoted sulfated zirconia

    SciTech Connect (OSTI)

    Cheung, T.K.; D`Itri, J.L.; Gates, B.C.

    1995-02-01

    Environmental concerns are leading to the replacement of aromatic hydrocarbons in gasoline with high-octane-number branched paraffins and oxygenated compounds such as methyl t-butyl ether, which is produced from methanol and isobutylene. The latter can be formed from n-butane by isomerization followed by dehydrogenation. To meet the need for improved catalysts for isomerization of n-butane and other paraffins, researchers identified solid acids that are noncorrosive and active at low temperatures. Sulfated zirconia catalyzes the isomerization of n-butane even at 25{degrees}C, and the addition of Fe and Mn promoters increases its activity by three orders of magnitude. Little is known about this new catalyst. Here the authors provide evidence of its performance for n-butane conversion, demonstrating that isomerization is accompanied by disproportionation and other, less well understood, acid-catalyzed reactions and undergoes rapid deactivation associated with deposition of carbonaceous material. 10 refs., 3 figs.

  7. Methanol synthesis using a catalyst combination of alkali or alkaline earth salts and reduced copper chromite

    DOE Patents [OSTI]

    Tierney, J.W.; Wender, I.; Palekar, V.M.

    1995-01-24

    The present invention relates to a novel route for the synthesis of methanol, and more specifically to the production of methanol by contacting synthesis gas under relatively mild conditions in a slurry phase with a catalyst combination comprising reduced copper chromite and basic alkali salts or alkaline earth salts. The present invention allows the synthesis of methanol to occur in the temperature range of approximately 100--160 C and the pressure range of 40--65 atm. The process produces methanol with up to 90% syngas conversion per pass and up to 95% methanol selectivity. The only major by-product is a small amount of easily separated methyl formate. Very small amounts of water, carbon dioxide and dimethyl ether are also produced. The present catalyst combination also is capable of tolerating fluctuations in the H[sub 2]/CO ratio without major deleterious effect on the reaction rate. Furthermore, carbon dioxide and water are also tolerated without substantial catalyst deactivation.

  8. Methanol synthesis using a catalyst combination of alkali or alkaline earth salts and reduced copper chromite for methanol synthesis

    DOE Patents [OSTI]

    Tierney, John W.; Wender, Irving; Palekar, Vishwesh M.

    1993-01-01

    The present invention relates to a novel route for the synthesis of methanol, and more specifically to the production of methanol by contacting synthesis gas under relatively mild conditions in a slurry phase with a catalyst combination comprising reduced copper chromite and basic alkali salts or alkaline earth salts. The present invention allows the synthesis of methanol to occur in the temperature range of approximately 100.degree.-160.degree. C. and the pressure range of 40-65 atm. The process produces methanol with up to 90% syngas conversion per pass and up to 95% methanol selectivity. The only major by-product is a small amount of easily separated methyl formate. Very small amounts of water, carbon dioxide and dimethyl ether are also produced. The present catalyst combination also is capable of tolerating fluctuations in the H.sub.2 /CO ratio without major deleterious effect on the reaction rate. Furthermore, carbon dioxide and water are also tolerated without substantial catalyst deactivation.

  9. Methanol synthesis using a catalyst combination of alkali or alkaline earth salts and reduced copper chromite

    DOE Patents [OSTI]

    Tierney, John W.; Wender, Irving; Palekar, Vishwesh M.

    1995-01-01

    The present invention relates to a novel route for the synthesis of methanol, and more specifically to the production of methanol by contacting synthesis gas under relatively mild conditions in a slurry phase with a catalyst combination comprising reduced copper chromite and basic alkali salts or alkaline earth salts. The present invention allows the synthesis of methanol to occur in the temperature range of approximately 100.degree.-160.degree. C. and the pressure range of 40-65 atm. The process produces methanol with up to 90% syngas conversion per pass and up to 95% methanol selectivity. The only major by-product is a small amount of easily separated methyl formate. Very small amounts of water, carbon dioxide and dimethyl ether are also produced. The present catalyst combination also is capable of tolerating fluctuations in the H.sub.2 /CO ratio without major deleterious effect on the reaction rate. Furthermore, carbon dioxide and water are also tolerated without substantial catalyst deactivation.

  10. Ecofuel plans MTBE plant in Italy

    SciTech Connect (OSTI)

    Alperowicz, N.

    1992-04-29

    Ecofuel (Milan), an ENI company, is evaluating construction of a new methyl tert-butyl ether (MTBE) plant in Italy, but has shelved plans for a world-scale MTBE unit in Mexico. The Italian unit is tied to ethylene expansion now under way. Later this year EniChem (Milan), a sister company, is due to complete construction of a 360,000-m.t./year cracker at Brindisi. The C{sub 4} stream available there and from the existing cracker at Priolo in Sicily should provide enough feed for a unit of up to 100,000 m.t./year of MTBE capacity. Some of the feedstock could also come from the Ravenna cracker.

  11. APPLICATIONS OF LAYERED DOUBLE HYDROXIDES IN REMOVING OXYANIONS FROM OIL REFINING AND COAL MINING WASTEWATER

    SciTech Connect (OSTI)

    Song Jin; Paul Fallgren

    2006-03-01

    Western Research Institute (WRI), in conjunction with the U.S. Department of Energy (DOE), conducted a study of using the layered double hydroxides (LDH) as filter material to remove microorganisms, large biological molecules, certain anions and toxic oxyanions from various waste streams, including wastewater from refineries. Results demonstrate that LDH has a high adsorbing capability to those compounds with negative surface charge. Constituents studied include model bacteria, viruses, arsenic, selenium, vanadium, diesel range hydrocarbons, methyl tert-butyl ether (MTBE), mixed petroleum constituents, humic materials and anions. This project also attempted to modify the physical structure of LDH for the application as a filtration material. Flow characterizations of the modified LDH materials were also investigated. Results to date indicate that LDH is a cost-effective new material to be used for wastewater treatment, especially for the treatment of anions and oxyanions.

  12. The HD molecule in small and medium cages of clathrate hydrates: Quantum dynamics studied by neutron scattering measurements and computation

    SciTech Connect (OSTI)

    Colognesi, Daniele; Celli, Milva; Ulivi, Lorenzo; Powers, Anna; Xu, Minzhong; Bačić, Zlatko

    2014-10-07

    We report inelastic neutron scattering (INS) measurements on molecular hydrogen deuteride (HD) trapped in binary cubic (sII) and hexagonal (sH) clathrate hydrates, performed at low temperature using two different neutron spectrometers in order to probe both energy and momentum transfer. The INS spectra of binary clathrate samples exhibit a rich structure containing sharp bands arising from both the rotational transitions and the rattling modes of the guest molecule. For the clathrates with sII structure, there is a very good agreement with the rigorous fully quantum simulations which account for the subtle effects of the anisotropy, angular and radial, of the host cage on the HD microscopic dynamics. The sH clathrate sample presents a much greater challenge, due to the uncertainties regarding the crystal structure, which is known only for similar crystals with different promoter, but nor for HD (or H{sub 2}) plus methyl tert-butyl ether (MTBE-d12)

  13. Crosslinked polymer gel electrolytes based on polyethylene glycol methacrylate and ionic liquid for lithium battery applications

    SciTech Connect (OSTI)

    Liao, Chen; Sun, Xiao-Guang; Dai, Sheng

    2013-01-01

    Gel polymer electrolytes were synthesized by copolymerization polyethylene glycol methyl ether methacrylate with polyethylene glycol dimethacrylate in the presence of a room temperature ionic liquid, methylpropylpyrrolidinium bis(trifluoromethanesulfonyl)imide (MPPY TFSI). The physical properties of gel polymer electrolytes were characterized by thermal analysis, impedance spectroscopy, and electrochemical tests. The ionic conductivities of the gel polymer electrolytes increased linearly with the amount of MPPY TFSI and were mainly attributed to the increased ion mobility as evidenced by the decreased glass transition temperatures. Li||LiFePO4 cells were assembled using the gel polymer electrolytes containing 80 wt% MPPY TFSI via an in situ polymerization method. A reversible cell capacity of 90 mAh g 1 was maintained under the current density of C/10 at room temperature, which was increased to 130 mAh g 1 by using a thinner membrane and cycling at 50 C.

  14. Argentina set for privatization

    SciTech Connect (OSTI)

    Chynoweth, E.

    1992-12-09

    Buyers are lining up for Argentina's two big state-controlled petrochemical groups, Buenos Aires-based Petroquimica General Mosconi (PGM) and Petroquimica Bahia Blance (PBB). However, feedstock supply contracts with government-owned oil group Yacientos Petroliferos Fiscales (YPG) and gas group Gas del Estado hold the key to both sales. Shell Compania Argentina Petroleo SA (CAPSA), Perez Companc, and Global Petroleum have already bought PGM tender documentation. Shell says it will bid for PGM if the feedstock contract with YPF is acceptable. In addition to price and volume, Shell says the length is critical; it wants a 15-year deal, but would settle for 11. YPF initially sought a five-year contract. PGM, which produces 300,000 m.t./year of aromatics, plus oxo alcohols, methanol, and methyl tert-butyl ether, has sales of $150 million/year.

  15. Performance and emissions characteristics of alternative fuels in spark ignition engines

    SciTech Connect (OSTI)

    Swain, M.R.; Maxwell, R.L.; Swain, M.N.; Bedsworth, K.; Adt, R.R. Jr.; Pappas, J.M.

    1984-01-01

    A formal ongoing program to characterize the performance and exhaust characteristics of automotive-type powerplants fueled by conventional and alternative fuels is reported. This report contains the information obtained during the past three years when four alternative fuels and two baseline fuels were evaluated in three engines. The four alternative fuels were a simulated gasoline made to represent coal derived gasoline, methyl aryl ethers blended at the 10% level in an unleaded gasoline, gasoline made from methanol, and a blend of Indolene plus methanol and higher alcohols. The two baseline fuels were, Indolene and Gulf unleaded regular gasoline. The engines tested were a pre-mixed carbureted SI (spark ignition) engine, a carbureted three-valve stratified-charge SI engine and a pre-mixed carbureted SI engine with a closed-loop three-way catalyst emission control system.

  16. Aromatase imaging with [N-methyl-C-11]vorozole PET in healthy men and women

    SciTech Connect (OSTI)

    Biegon, Anat; Fowler, Joanna S.; Alexoff, David L.; Kim, Sung Won; Logan, Jean; Pareto, Deborah; Schlyer, David; Wang, Gene-Jack

    2015-02-19

    Aromatase, the last and obligatory enzyme catalyzing estrogen biosynthesis from androgenic precursors, can be labeled in vivo with C-vorozole. Aromatase inhibitors are widely used in breast cancer and other endocrine conditions. The present study aims to provide baseline information defining aromatase distribution in healthy men and women, against which its perturbation in pathological situations can be studied. Methods: C-vorozole (111-296 MBq/subject) was injected I.V in 13 men and 20 women (age range 23 to 67). PET data were acquired over a 90 minute period. Each subject had 4 scans, 2/day separated by 2-6 weeks, including brain and torso or pelvis scans. Young women were scanned at 2 discrete phases of the menstrual cycle (midcycle and late luteal). Men and postmenopausal women were also scanned following pretreatment with a clinical dose of the aromatase inhibitor letrozole (blocking studies). Time activity curves were obtained and standard uptake values (SUV) calculated for major organs including brain, heart, lungs, liver, kidneys, spleen, muscle, bone and male and female reproductive organs (penis, testes, uterus, ovaries). Organ and whole body radiation exposures were calculated using Olinda software. Results: Liver uptake was higher than all other organs, but was not blocked by pretreatment with letrozole. Mean SUVs in men were higher than in women, and brain uptake was blocked by letrozole. Male brain SUVs were also higher than all other organs (ranging from 0.480.05 in lungs to 1.50.13 in kidneys). Mean ovarian SUVs (3.080.7) were comparable to brain levels and higher than all other organs. Furthermore, ovarian SUVs In young women around the time of ovulation (midcycle) were significantly higher than those measured in the late luteal phase, while aging and cigarette smoking reduced C-vorozole uptake. Conclusions: PET with C-vorozole is useful for assessing physiological changes in estrogen synthesis capacity in the human body. Baseline levels in breasts, lungs and bones are low, supporting further investigation of this tracer as a new tool for detection of aromatase-overexpressing primary tumors or metastases in these organs and optimization of treatment in cancer and other disorders in which aromatase inhibitors are useful.

  17. Effect of Unburned Methyl Esters on the NOx Conversion of Fe-Zeolite SCR Catalyst

    SciTech Connect (OSTI)

    Williams, A.; Ratcliff, M.; Pedersen, D.; McCormick, R.; Cavataio, G.; Ura, J.

    2010-03-01

    Engine and flow reactor experiments were conducted to determine the impact of biodiesel relative to ultra-low-sulfur diesel (ULSD) on inhibition of the selective catalytic reduction (SCR) reaction over an Fe-zeolite catalyst. Fe-zeolite SCR catalysts have the ability to adsorb and store unburned hydrocarbons (HC) at temperatures below 300 C. These stored HCs inhibit or block NO{sub x}-ammonia reaction sites at low temperatures. Although biodiesel is not a hydrocarbon, similar effects are anticipated for unburned biodiesel and its organic combustion products. Flow reactor experiments indicate that in the absence of exposure to HC or B100, NO{sub x} conversion begins at between 100 and 200 C. When exposure to unburned fuel occurs at higher temperatures (250-400 C), the catalyst is able to adsorb a greater mass of biodiesel than of ULSD. Experiments show that when the catalyst is masked with ULSD, NO{sub x} conversion is inhibited until it is heated to 400 C. However, when masked with biodiesel, NO{sub x} conversion is observed to begin at temperatures as low as 200 C. Engine test results also show low-temperature recovery from HC storage. Engine tests indicate that, overall, the SCR system has a faster recovery from HC masking with biodiesel. This is at least partially due to a reduction in exhaust HCs, and thus total HC exposure with biodiesel.

  18. Aromatase imaging with [N-methyl-C-11]vorozole PET in healthy men and women

    SciTech Connect (OSTI)

    Biegon, Anat; Fowler, Joanna S.; Alexoff, David L.; Kim, Sung Won; Logan, Jean; Pareto, Deborah; Schlyer, David; Wang, Gene-Jack

    2015-02-19

    Aromatase, the last and obligatory enzyme catalyzing estrogen biosynthesis from androgenic precursors, can be labeled in vivo with ¹¹C-vorozole. Aromatase inhibitors are widely used in breast cancer and other endocrine conditions. The present study aims to provide baseline information defining aromatase distribution in healthy men and women, against which its perturbation in pathological situations can be studied. Methods: ¹¹C-vorozole (111-296 MBq/subject) was injected I.V in 13 men and 20 women (age range 23 to 67). PET data were acquired over a 90 minute period. Each subject had 4 scans, 2/day separated by 2-6 weeks, including brain and torso or pelvis scans. Young women were scanned at 2 discrete phases of the menstrual cycle (midcycle and late luteal). Men and postmenopausal women were also scanned following pretreatment with a clinical dose of the aromatase inhibitor letrozole (“blocking” studies). Time activity curves were obtained and standard uptake values (SUV) calculated for major organs including brain, heart, lungs, liver, kidneys, spleen, muscle, bone and male and female reproductive organs (penis, testes, uterus, ovaries). Organ and whole body radiation exposures were calculated using Olinda software. Results: Liver uptake was higher than all other organs, but was not blocked by pretreatment with letrozole. Mean SUVs in men were higher than in women, and brain uptake was blocked by letrozole. Male brain SUVs were also higher than all other organs (ranging from 0.48±0.05 in lungs to 1.5±0.13 in kidneys). Mean ovarian SUVs (3.08±0.7) were comparable to brain levels and higher than all other organs. Furthermore, ovarian SUVs In young women around the time of ovulation (midcycle) were significantly higher than those measured in the late luteal phase, while aging and cigarette smoking reduced ¹¹C-vorozole uptake. Conclusions: PET with ¹¹C-vorozole is useful for assessing physiological changes in estrogen synthesis capacity in the human body. Baseline levels in breasts, lungs and bones are low, supporting further investigation of this tracer as a new tool for detection of aromatase-overexpressing primary tumors or metastases in these organs and optimization of treatment in cancer and other disorders in which aromatase inhibitors are useful.

  19. Arsenic methylation and lung and bladder cancer in a case-control study in northern Chile

    SciTech Connect (OSTI)

    Melak, Dawit; Ferreccio, Catterina; Kalman, David; Parra, Roxana; Acevedo, Johanna; Pérez, Liliana; Cortés, Sandra; Smith, Allan H.; Yuan, Yan; Liaw, Jane; Steinmaus, Craig

    2014-01-15

    In humans, ingested inorganic arsenic is metabolized to monomethylarsenic (MMA) then to dimethylarsenic (DMA), although this process is not complete in most people. The trivalent form of MMA is highly toxic in vitro and previous studies have identified associations between the proportion of urinary arsenic as MMA (%MMA) and several arsenic-related diseases. To date, however, relatively little is known about its role in lung cancer, the most common cause of arsenic-related death, or about its impacts on people drinking water with lower arsenic concentrations (e.g., < 200 μg/L). In this study, urinary arsenic metabolites were measured in 94 lung and 117 bladder cancer cases and 347 population-based controls from areas in northern Chile with a wide range of drinking water arsenic concentrations. Lung cancer odds ratios adjusted for age, sex, and smoking by increasing tertiles of %MMA were 1.00, 1.91 (95% confidence interval (CI), 0.99–3.67), and 3.26 (1.76–6.04) (p-trend < 0.001). Corresponding odds ratios for bladder cancer were 1.00, 1.81 (1.06–3.11), and 2.02 (1.15–3.54) (p-trend < 0.001). In analyses confined to subjects only with arsenic water concentrations < 200 μg/L (median = 60 μg/L), lung and bladder cancer odds ratios for subjects in the upper tertile of %MMA compared to subjects in the lower two tertiles were 2.48 (1.08–5.68) and 2.37 (1.01–5.57), respectively. Overall, these findings provide evidence that inter-individual differences in arsenic metabolism may be an important risk factor for arsenic-related lung cancer, and may play a role in cancer risks among people exposed to relatively low arsenic water concentrations. - Highlights: • Urine arsenic metabolites were measured in cancer cases and controls from Chile. • Higher urine %MMA values were associated with increased lung and bladder cancer. • %MMA-cancer associations were seen at drinking water arsenic levels < 200 μg/L.

  20. Photodetachment and electron reactivity in 1-methyl-1-butyl-pyrrolidinium bis(trifluoromethylsulfonyl)amide

    SciTech Connect (OSTI)

    Molins i Domenech, Francesc; FitzPatrick, Benjamin; Healy, Andrew T.; Blank, David A.

    2012-07-21

    The transient absorption spectrum in the range 500 nm-1000 nm was measured with ultrafast time resolution on a flowing neat, aliphatic, room-temperature ionic liquid following anion photodetachment. In this region the spectrum was shown to be a combination of absorption from the electron and the hole. Spectrally-resolved electron quenching determined a bimodal shape for the hole spectrum in agreement with recent computational predictions on a smaller aliphatic ionic liquid [Margulis et al., J. Am. Chem. Soc. 133, 20186 (2011)]. For time delays beyond 15 ps, spectral evolution qualitatively agrees with recent radiolysis experiments [Wishart et al., Faraday Discuss. 154, 353 (2012)]. However, the shape of the spectrum is different, reflecting the contrast in ionization energy between the two methods. Previously unobserved reactivity of the electron was found with a time constant of 300 fs. The results demonstrate solvent control of the rate coefficient for reaction between the electron and proton, with a rapid decline in the rate within the first picosecond.

  1. Type II restriction-modification system methylation subunit of Alicyclobacillus acidocaldarius

    DOE Patents [OSTI]

    Lee, Brady D; Newby, Deborah T; Lacey, Jeffrey A; Thompson, David N; Thompson, Vicki S; Apel, William A; Roberto, Francisco F; Reed, David W

    2013-10-29

    Isolated and/or purified polypeptides and nucleic acid sequences encoding polypeptides from Alicyclobacillus acidocaldarius are provided. Further provided are methods for modulating or altering recombination inside or outside of a cell using isolated and/or purified polypeptides and/or nucleic acid sequences from Alicyclobacillus acidocaldarius.

  2. Type II restriction-modification system methylation subunit of Alicyclobacillus acidocaldarius

    DOE Patents [OSTI]

    Lee, Brady D; Newby, Deborah T; Lacey, Jeffrey A; Thompson, David N; Thompson, Vicki S; Apel, William A; Roberto, Francisco F; Reed, David W

    2015-05-12

    Isolated and/or purified polypeptides and nucleic acid sequences encoding polypeptides from Alicyclobacillus acidocaldarius are provided. Further provided are methods for modulating or altering recombination inside or outside of a cell using isolated and/or purified polypeptides and/or nucleic acid sequences from Alicyclobacillus acidocaldarius.

  3. Phase 1 Methyl Iodide Deep-Bed Adsorption Tests (Technical Report...

    Office of Scientific and Technical Information (OSTI)

    Research on the capture of organic iodides has also been performed, but to a lesser extent Jubin 2012b. Several questions remain open regarding the capture of iodine bound in ...

  4. Aromatase imaging with [N-methyl-C-11]vorozole PET in healthy men and women

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Biegon, Anat; Fowler, Joanna S.; Alexoff, David L.; Kim, Sung Won; Logan, Jean; Pareto, Deborah; Schlyer, David; Wang, Gene-Jack

    2015-02-19

    Aromatase, the last and obligatory enzyme catalyzing estrogen biosynthesis from androgenic precursors, can be labeled in vivo with ¹¹C-vorozole. Aromatase inhibitors are widely used in breast cancer and other endocrine conditions. The present study aims to provide baseline information defining aromatase distribution in healthy men and women, against which its perturbation in pathological situations can be studied. Methods: ¹¹C-vorozole (111-296 MBq/subject) was injected I.V in 13 men and 20 women (age range 23 to 67). PET data were acquired over a 90 minute period. Each subject had 4 scans, 2/day separated by 2-6 weeks, including brain and torso or pelvismore » scans. Young women were scanned at 2 discrete phases of the menstrual cycle (midcycle and late luteal). Men and postmenopausal women were also scanned following pretreatment with a clinical dose of the aromatase inhibitor letrozole (“blocking” studies). Time activity curves were obtained and standard uptake values (SUV) calculated for major organs including brain, heart, lungs, liver, kidneys, spleen, muscle, bone and male and female reproductive organs (penis, testes, uterus, ovaries). Organ and whole body radiation exposures were calculated using Olinda software. Results: Liver uptake was higher than all other organs, but was not blocked by pretreatment with letrozole. Mean SUVs in men were higher than in women, and brain uptake was blocked by letrozole. Male brain SUVs were also higher than all other organs (ranging from 0.48±0.05 in lungs to 1.5±0.13 in kidneys). Mean ovarian SUVs (3.08±0.7) were comparable to brain levels and higher than all other organs. Furthermore, ovarian SUVs In young women around the time of ovulation (midcycle) were significantly higher than those measured in the late luteal phase, while aging and cigarette smoking reduced ¹¹C-vorozole uptake. Conclusions: PET with ¹¹C-vorozole is useful for assessing physiological changes in estrogen synthesis capacity in the human body. Baseline levels in breasts, lungs and bones are low, supporting further investigation of this tracer as a new tool for detection of aromatase-overexpressing primary tumors or metastases in these organs and optimization of treatment in cancer and other disorders in which aromatase inhibitors are useful.« less

  5. Thermoset epoxy polymers from renewable resources

    DOE Patents [OSTI]

    East, Anthony; Jaffe, Michael; Zhang, Yi; Catalani, Luiz H

    2009-11-17

    Novel thermoset epoxy polymers using the bisglycidyl ethers of anhydrosugars, such as isosorbide, isomannide, and isoidide, are disclosed. The bisglycidyl ethers are useful as substitutes for bisphenol A in the manufacture of thermoset epoxy ethers. The anhydrosugars are derived from renewable sources and the bisglycidyl ethers are not xenoestrogenic and the thermoset curing agents are likewise derived form renewable resources.

  6. Silver-mordenite for radiologic gas capture from complex streams. Dual catalytic CH3I decomposition and I confinement

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Nenoff, Tina M.; Rodriguez, Mark A.; Soelberg, Nick R.; Chapman, Karena W.

    2014-05-09

    The selective capture of radiological iodine (129I) is a persistent concern for safe nuclear energy. In these nuclear fuel reprocessing scenarios, the gas streams to be treated are extremely complex, containing several distinct iodine-containing molecules amongst a large variety of other species. Silver-containing mordenite (MOR) is a longstanding benchmark for radioiodine capture, reacting with molecular iodine (I2) to form AgI. However the mechanisms for organoiodine capture is not well understood. Here we investigate the capture of methyl iodide from complex mixed gas streams by combining chemical analysis of the effluent gas stream with in depth characterization of the recovered sorbent.more » Tools applied include infrared spectroscopy, thermogravimetric analysis with mass spectrometry, micro X-ray fluorescence, powder X-ray diffraction analysis, and pair distribution function analysis. Moreover, the MOR zeolite catalyzes decomposition of the methyl iodide through formation of surface methoxy species (SMS), which subsequently reacts with water in the mixed gas stream to form methanol, and with methanol to form dimethyl ether, which are both detected downstream in the effluent. The liberated iodine reacts with Ag in the MOR pore to the form subnanometer AgI clusters, smaller than the MOR pores, suggesting that the iodine is both physically and chemically confined within the zeolite.« less

  7. HOW COMPLETE ARE ASTROPHYSICAL CATALOGS FOR THE MILLIMETER AND SUBMILLIMETER SPECTRAL REGION?

    SciTech Connect (OSTI)

    Fortman, Sarah M.; Medvedev, Ivan R.; Neese, Christopher F.; De Lucia, Frank C.

    2010-12-10

    With the growth in sensitivity and angular resolution of millimeter and submillimeter telescopes, the number of unidentified molecular spectral lines in surveys of the interstellar medium has grown rapidly. While some of these unidentified lines are due to as yet unidentified astrophysical species, it is the general consensus that most are due to lines from a limited number of well-known interstellar species, the interstellar weeds. These unidentified lines do not appear in astrophysical line catalogs, which are based on quantum mechanical models and are incomplete primarily because of the difficulty of performing the usual bootstrap assignment and analysis process in their often highly perturbed low-lying vibrational states. To address this problem, we have proposed and demonstrated an alternative catalog approach that is based on the analysis of intensity-calibrated spectra taken over a range of temperatures in the laboratory. These analyses also make it possible to quantitatively address the astrophysical completeness of existing catalogs. In this Letter, we use extensive new experimental data in the 210-270 GHz window to address this question for eight molecules that are considered to be the leading candidates for astronomical weeds-methyl formate, methanol, dimethyl ether, acetaldehyde, sulfur dioxide, methyl cyanide, vinyl cyanide, and ethyl cyanide. Additionally, for each of the eight molecules, we use these results and knowledge of the molecular vibrational/torsional energy levels to predict completeness as a function of astronomical source temperature.

  8. DISCOVERY OF THE METHOXY RADICAL, CH{sub 3}O, TOWARD B1: DUST GRAIN AND GAS-PHASE CHEMISTRY IN COLD DARK CLOUDS

    SciTech Connect (OSTI)

    Cernicharo, J.; Jimenez-Escobar, A.; Munoz Caro, G. M.; Marcelino, N.; Roueff, E.; Gerin, M.

    2012-11-10

    We report on the discovery of the methoxy radical (CH{sub 3}O) toward the cold and dense core B1-b based on the observation, with the IRAM 30 m radio telescope, of several lines at 3 and 2 mm wavelengths. Besides this new molecular species we also report on the detection of many lines arising from methyl mercaptan (CH{sub 3}SH), formic acid (HCOOH), propynal (HCCCHO), acetaldehyde (CH{sub 3}CHO), dimethyl ether (CH{sub 3}OCH{sub 3}), methyl formate (CH{sub 3}OCOH), and the formyl radical (HCO). The column density of all these species is {approx_equal}10{sup 12} cm{sup -2}, corresponding to abundances of {approx_equal}10{sup -11}. The similarity in abundances for all these species strongly suggest that they are formed on the surface of dust grains and ejected to the gas phase through non-thermal desorption processes, most likely cosmic rays or secondary photons. Nevertheless, laboratory experiments indicate that the CH{sub 3}O isomer released to the gas phase is CH{sub 2}OH rather than the methoxy one. Possible gas-phase formation routes to CH{sub 3}O from OH and methanol are discussed.

  9. Silver-mordenite for radiologic gas capture from complex streams. Dual catalytic CH3I decomposition and I confinement

    SciTech Connect (OSTI)

    Nenoff, Tina M.; Rodriguez, Mark A.; Soelberg, Nick R.; Chapman, Karena W.

    2014-05-09

    The selective capture of radiological iodine (129I) is a persistent concern for safe nuclear energy. In these nuclear fuel reprocessing scenarios, the gas streams to be treated are extremely complex, containing several distinct iodine-containing molecules amongst a large variety of other species. Silver-containing mordenite (MOR) is a longstanding benchmark for radioiodine capture, reacting with molecular iodine (I2) to form AgI. However the mechanisms for organoiodine capture is not well understood. Here we investigate the capture of methyl iodide from complex mixed gas streams by combining chemical analysis of the effluent gas stream with in depth characterization of the recovered sorbent. Tools applied include infrared spectroscopy, thermogravimetric analysis with mass spectrometry, micro X-ray fluorescence, powder X-ray diffraction analysis, and pair distribution function analysis. Moreover, the MOR zeolite catalyzes decomposition of the methyl iodide through formation of surface methoxy species (SMS), which subsequently reacts with water in the mixed gas stream to form methanol, and with methanol to form dimethyl ether, which are both detected downstream in the effluent. The liberated iodine reacts with Ag in the MOR pore to the form subnanometer AgI clusters, smaller than the MOR pores, suggesting that the iodine is both physically and chemically confined within the zeolite.

  10. Low temperature (550-700 K) oxidation pathways of cyclic ketones: Dominance of HO2-elimination channels yielding conjugated cyclic coproducts

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Scheer, Adam M.; Welz, Oliver; Vasu, Subith S.; Osborn, David L.; Taatjes, Craig A.

    2015-04-13

    The low-temperature oxidation of three cyclic ketones, cyclopentanone (CPO; C5H8O), cyclohexanone (CHO; C6H10 O), and 2-methyl-cyclopentanone (2-Me-CPO; CH3–C5H7 O), is studied between 550 and 700 K and at 4 or 8 Torr total pressure. Initial fuel radicals R are formedvia fast H-abstraction from the ketones by laser-photolytically generated chlorine atoms. Intermediates and products from the subsequent reactions of these radicals in the presence of excess O2 are probed with time and isomeric resolution using multiplexed photoionization mass spectrometry with tunable synchrotron ionizing radiation. For CPO and CHO the dominant product channel in the R + O2 reactions is chain-terminating HO2-eliminationmore » yielding the conjugated cyclic coproducts 2-cyclopentenone and 2-cyclohexenone, respectively. Results on oxidation of 2-Me-CPO also show a dominant contribution from HO2-elimination. Moreover, the photoionization spectrum of the co-product suggests formation of 2-methyl-2-cyclopentenone and/or 2-cyclohexenone, resulting from a rapid Dowd–Beckwith rearrangement, preceding addition to O2, of the initial (2-oxocyclopentyl)methyl radical to 3-oxocyclohexyl. Cyclic ethers, markers for hydroperoxyalkyl radicals (QOOH), key intermediates in chain-propagating and chain-branching low-temperature combustion pathways, are only minor products. The interpretation of the experimental results is supported by stationary point calculations on the potential energy surfaces of the associated R + O2 reactions at the CBS-QB3 level. Furthermore, the calculations indicate that HO2-elimination channels are energetically favored and product formation via QOOH is disfavored. Lastly, the prominence of chain-terminating pathways linked with HO2 formation in low-temperature oxidation of cyclic ketones suggests little low-temperature reactivity of these species as fuels in internal combustion engines.« less

  11. Incorporating Amino Acid Esters into Catalysts for Hydrogen Oxidation: Steric and Electronic Effects and the Role of Water as a Base

    SciTech Connect (OSTI)

    Lense, Sheri; Ho, Ming-Hsun; Chen, Shentan; Jain, Avijita; Raugei, Simone; Linehan, John C.; Roberts, John A.; Appel, Aaron M.; Shaw, Wendy J.

    2012-10-08

    Four derivatives of a hydrogen oxidation catalyst, [Ni(PCy2NBn-R2)]2+ (Cy=cyclohexyl, Bn=benzyl, R= OMe, COOMe, CO-Alanine-methyl ester or CO-Phenylalanine-methyl ester), have been prepared to investigate steric and electronic effects on catalysis. Each complex was characterized spectroscopically and electrochemically, and thermodynamic data were determined. Crystal structures are also reported for the -OMe and -COOMe derivatives. All four catalysts were found to be active for H2 oxidation. The methyl ester (R = COOMe) and amino acid ester containing complexes (R = CO-Alanine-methyl ester or CO-Phenylalanine-methyl ester) had slower rates (4 s-1) than that of the parent complex (10 s-1), in which R = H, consistent with the lower amine pKa’s and less favorable GH2’s found for these electron-withdrawing substituents. Dynamic processes for the amino acid ester containing complexes were also investigated and found not to hinder catalysis. The electron-donating methoxy ether derivative (R = OMe) was prepared to compare electronic effects and has a similar catalytic rate as the parent complex. In the course of these studies, it was found that water could act as a weak base for H2 oxidation, although catalytic turnover requires a significantly higher potential and utilizes a different sequence of catalytic steps than when using a base with a higher pKa. Importantly, these catalysts provide a foundation upon which larger peptides can be attached to [Ni(PCy2NBn2)2]2+ hydrogen oxidation catalysts in order to more fully investigate and implement the effects of the outer-coordination sphere. This work was funded by the DOE Office of Science Early Career Research Program through the Office of Basic Energy Sciences (SL and WJS), by the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the US Department of Energy, Office of Science, Office of Basic Energy Sciences (JR), and by the US DOE Basic Energy Sciences, Chemical Sciences, Geoscience and Biosciences Division (AMA, AJ). Pacific Northwest National Laboratory is operated by Battelle for the U.S. Department of Energy.

  12. Superacid catalysis of light hydrocarbon conversion. DOE PETC third quarterly report, February 25, 1994--May 24, 1994

    SciTech Connect (OSTI)

    Gates, B.C.

    1995-12-31

    Environmental concerns are leading to the replacement of aromatic hydrocarbons in gasoline by high-octane-number branched paraffins and oxygenated compounds such as methyl t-butyl ether. The ether is produced from methanol and isobutylene, and the latter can be formed from n-butane by isomerization followed by dehydrogenation. Paraffin isomerization reactions are catalyzed by very strong acids such as aluminum chloride supported on alumina. The aluminum chloride-containing catalysts are corrosive, and their disposal is expensive. Alternatively, hydroisomerization is catalyzed by zeolite-supported metals at high temperatures, but high temperatures do not favor branched products at equilibrium. Thus there is a need for improved catalysts and processes for the isomerization of n-butane and other straight-chain paraffins. Consequently, researchers have sought for solid acids that are noncorrosive and active enough to catalyze isomerization of paraffins at low temperatures. For example, sulfated zirconia catalyzes isomerization of n-butane at temperatures as low as 25{degrees}C. The addition of iron and manganese promoters has been reported to increase the activity of sulfated zirconia for n-butane isomerization by three orders of magnitude. Although the high activity of this catalyst is now established, the reaction network is not known, and the mechanism has not been investigated. The goal of this work is to investigate low-temperature reactions of light paraffins catalyzed by solid superacids of the sulfated zirconia type. The present report is concerned with catalysis of n-butane conversion catalyzed by the Fe- and Mn- promoted sulfated zirconia described in the previous report in this series.

  13. Synthesis of 6-Methyl-9-n-propyldibenzo thiophene-4-ol ammended to 6-Methyl-9-(1-methylethyl)-dibenzo thiophene-4-ol. Quarterly technical progress report No. 6, October 28, 1991--January 26, 1992

    SciTech Connect (OSTI)

    Not Available

    1992-02-28

    The material presented below is taken from Status Reports 15, 16 and 17 and covers the progress made toward the synthesis of the modified target molecules 9-isopropyl-4-methoxy-6 methyldibenzothiophene (13) and 9-isopropyl-6methyldibenzothiophene-4-ol (14).

  14. East Coast (PADD 1) Net Receipts of Crude Oil and Petroleum Products...

    U.S. Energy Information Administration (EIA) Indexed Site

    RBOB for Blending with Alcohol* 2005-2009 RBOB for Blending with Ether* 2005-2009 GTAB* ... Notes: RBOB with Ether and RBOB with Alcohol are discontinued as of the January 2010 ...

  15. Exposure Evaluation for Benzene, Lead and Noise in Vehicle and Equipment Repair Shops

    SciTech Connect (OSTI)

    Sweeney, Lynn C.

    2013-04-10

    An exposure assessment was performed at the equipment and vehicle maintenance repair shops operating at the U. S. Department of Energy Hanford site, in Richland, Washington. The maintenance shops repair and maintain vehicles and equipment used in support of the Hanford cleanup mission. There are three general mechanic shops and one auto body repair shop. The mechanics work on heavy equipment used in construction, cranes, commercial motor vehicles, passenger-type vehicles in addition to air compressors, generators, and farm equipment. Services include part fabrication, installation of equipment, repair and maintenance work in the engine compartment, and tire and brake services. Work performed at the auto body shop includes painting and surface preparation which involves applying body filler and sanding. 8-hour time-weighted-average samples were collected for benzene and noise exposure and task-based samples were collected for lead dust work activities involving painted metal surfaces. Benzene samples were obtained using 3M™ 3520 sampling badges and were analyzed for additional volatile organic compounds. These compounds were selected based on material safety data sheet information for the aerosol products used by the mechanics for each day of sampling. The compounds included acetone, ethyl ether, toluene, xylene, VM&P naphtha, methyl ethyl ketone, and trichloroethylene. Laboratory data for benzene, VM&P naphtha, methyl ethyl ketone and trichloroethylene were all below the reporting detection limit. Airborne concentrations for acetone, ethyl ether, toluene and xylene were all less than 10% of their occupational exposure limit. The task-based samples obtained for lead dusts were submitted for a metal scan analysis to identify other metals that might be present. Laboratory results for lead dusts were all below the reporting detection limit and airborne concentration for the other metals observed in the samples were less than 10% of the occupational exposure limit. Noise dosimetry sampling was performed on a random basis and was representative of the different work activities within the four shops. Twenty three percent of the noise samples exceeded the occupational exposure limit of 85 decibels for an 8-hour time-weightedaverage. Work activities where noise levels were higher included use of impact wrenches and grinding wheels.

  16. Kinetic Model Development for the Combustion of Particulate Matter from Conventional and Soy Methyl Ester Diesel Fuels

    SciTech Connect (OSTI)

    Strzelec, Andrea

    2009-12-01

    The primary objective of this research has been to investigate how the oxidation characteristics of diesel particulate matter (PM) are affected by blending soy-based biodiesel fuel with conventional ultra low sulfur diesel (ULSD) fuel. PM produced in a light duty engine from different biodiesel-conventional fuel blends was subjected to a range of physical and chemical measurements in order to better understand the mechanisms by which fuel-related changes to oxidation reactivity are brought about. These observations were then incorporated into a kinetic model to predict PM oxidation. Nanostructure of the fixed carbon was investigated by HR-TEM and showed that particulates from biodiesel had a more open structure than particulates generated from conventional diesel fuel, which was confirmed by BET surface area measurements. Surface area evolution with extent of oxidation reaction was measured for PM from ULSD and biodiesel. Biodiesel particulate has a significantly larger surface area for the first 40% of conversion, at which point the samples become quite similar. Oxidation characteristics of nascent PM and the fixed carbon portion were measured by temperature programmed oxidation (TPO) and it was noted that increased biodiesel blending lowered the light-off temperature as well as the temperature where the peak rate of oxidation occurred. A shift in the oxidation profiles of all fuels was seen when the mobile carbon fraction was removed, leaving only the fixed carbon, however the trend in temperature advantage of the biofuel blending remained. The mobile carbon fraction was measured by temperature programmed desorption found to generally increase with increasing biodiesel blend level. The relative change in the light-off temperatures for the nascent and fixed carbon samples was found to be related to the fraction of mobile carbon. Effective Arrhenius parameters for fixed carbon oxidation were directly measured with isothermal, differential oxidation experiments. Normalizing the reaction rate to the total carbon surface area available for reaction allowed for the definition of a single reaction rate with constant activation energy (112.5 {+-} 5.8 kJ/mol) for the oxidation of PM, independent of its fuel source. A kinetic model incorporating the surface area dependence of fixed carbon oxidation rate and the impact of the mobile carbon fraction was constructed and validated against experimental data.

  17. Structure of trans-methyl 2-phenylhexahydro-2H-isoxazolo (2,3-a)-pyridine-3-carboxylate

    SciTech Connect (OSTI)

    Ul-Haque, M.; Horne, W.; Ali, S.A. )

    1993-02-01

    The title compound, a 1,3-dipolar cycloaddition product, crystallizes in the monoclinic space group P2[sub 1]/c, with a = 8.199(3), b = 16.908(1), c = 10.248(2) [angstrom],[beta] = 93.58(2)[degrees] and Z = 4. The structure was solved by direct methods and refined by full matrix least squares methods to R = 0.038 for 1687 observed reflections. The stereochemistry of this compound was found to have the [open quotes]ee[close quotes] conformation in the solid state as well as in solution. The piperidine ring in the molecule is in the chair form and the isoxazolidine ring adopts an envelope conformation.

  18. Translational and internal energy distributions of methyl and hydroxyl radicals produced by 157 nm photodissociation of amorphous solid methanol

    SciTech Connect (OSTI)

    Hama, Tetsuya; Yokoyama, Masaaki; Yabushita, Akihiro; Kawasaki, Masahiro; Wickramasinghe, Piyumie; Guo Wei; Loock, Hans-Peter; Ashfold, Michael N. R.; Western, Colin M.

    2009-12-14

    Methanol is typically observed within water-rich interstellar ices and is a source of interstellar organic species. Following the 157 nm photoexcitation of solid methanol at 90 K, desorbed CH{sub 3}(v=0) and OH(v=0,1) radicals have been observed in situ, near the solid surface, using resonance-enhanced multiphoton ionization (REMPI) detection methods. Time-of-flight and rotationally resolved REMPI spectra of the desorbed species were measured, and the respective fragment internal energy and kinetic energy distributions were obtained. Photoproduction mechanisms for CH{sub 3} and OH radicals from solid methanol are discussed. The formation of O({sup 1}D and {sup 3}P) atoms and H{sub 2}O was investigated, but the yield of these species was found to be negligible. CH{sub 3} products arising following the photoexcitation of water-methanol mixed ice showed similar kinetic and internal energy distributions to those from neat methanol ice.

  19. Low Temperature Autoignition of C8H16O2 Ethyl and Methyl Esters in a Motored Engine

    Broader source: Energy.gov [DOE]

    The alkyl chain of fatty acid esters experience the typical paraffin-like low temperature oxidation sequence; the alkyl chain length of fatty acid esters has a crucial impact on the ignition behavior of fatty acid esters

  20. Multiply Methyl-Branched Fatty Acids and Diacids in the Polar Lipids of a Microaerophilic Subsurface Microbial Community

    SciTech Connect (OSTI)

    Hedrick, David B.; Peacock, Aaron D.; Long, Philip E.; White, David C.

    2008-09-01

    A previously unreported series of di- and trimethylated fatty acids, as well as saturated and monounsaturated diacids were identified in polar lipids isolated from environmental subsurface sediment samples. Mechanisms are proposed for their formation, but their origin and role in cell membranes remains unknown.

  1. Initial Effects of NOx on Idodine and Methyl Iodine Loading of AgZ and Aerogels

    SciTech Connect (OSTI)

    Bruffey, Stephanie H.; Jubin, Robert Thomas

    2015-03-31

    This initial evaluation provides insight into the effect of NO on the adsorption of both I2 and CH3I onto reduced silver-exchanged mordenite (Ag0Z). It was determined that adsorption of CH3I onto Ag0Z occurs at approximately 50% of the rate of I2 adsorption onto Ag0Z, although total iodine capacities are comparable. Addition of 1% NO to the simulated off-gas stream results in very similar loading behaviors and iodine capacities for both iodine species. This is most likely an effect of CH3I oxidation to I2 by NO prior to contact with the sorbent bed. Completion of tests including NO2 in the simulated off-gas stream was delayed due to vendor NO2 production schedules. A statistically designed test matrix is partially completed, and upon conclusion of the suggested experiments, the effects of temperature, NO, NO2, and water vapor on the sorption of CH3I and I2 onto Ag0Z will be able to be statistically resolved. This work represents progress towards that aim.

  2. Synthesis of 6-Methyl-9-propyldibenzothiophene-4-ol. Technical progress report No. 2, October 25, 1990--January 25, 1991

    SciTech Connect (OSTI)

    Eisenbraun, E.J.

    1991-02-15

    The synthesis route for preparing the title compound, has been carried out on a small scale for the preparation of a mixture of isomers. Alternative routes for the cyclization are being explored. (DLC)

  3. Synthesis and crystal structure studies of ethyl 5-methyl-1, 3-diphenyl-1H-pyrazole-4-carboxylate

    SciTech Connect (OSTI)

    Chandra,; Babu, E. A. Jithesh; Mahendra, M.; Srikantamurthy, N.; Umesha, K. B.

    2014-04-24

    The title compound, C{sub 19}H{sub 18}N{sub 2}O{sub 2}, was investigated by single crystal X-ray diffraction method. It crystallizes in monoclinic class under the space group P2{sub 1}/c with cell parameters a= 8.4593(4) Å, b=15.6284(6) Å, c=12.4579(5) Å, α=90°, β=98.241(3)°, γ=90° and Z=2. The ethoxycarbonyl group is slightly twisted from the pyrazole ring, and adopts syn-periplanar conformation. The crystal structure is stabilized by intermolecular C-H….O hydrogen bonds, which help in stabilizing the crystal structure.

  4. EA-1157: Methyl Chloride via Oxyhydrochlorination of Methane: A Building Black for Chemicals and Fuels from Natural Gas, Carrollton, Kentucky

    Broader source: Energy.gov [DOE]

    This EA evaluates the environmental impacts for the proposal to advance Oxyhydrochlorination technology to an integrated engineering-scale process.

  5. CATALYST ACTIVITY MAINTENANCE FOR THE LIQUID PHASE SYNTHESIS GAS-TO-DIMETHYL ETHER PROCESS PART II: DEVELOPMENT OF ALUMINUM PHOSPHATE AS THE DEHYDRATION CATALYST FOR THE SINGLE-STEP LIQUID PHASE SYNGAS-TO-DME PROCESS

    SciTech Connect (OSTI)

    Xiang-Dong Peng

    2002-05-01

    At the heart of the single-step liquid phase syngas-to-DME process (LPDME{trademark}) is a catalyst system that can be active as well as stable. In the Alternative Fuels I program, a dual-catalyst system containing a Cu-based commercial methanol synthesis catalyst (BASF S3-86) and a commercial dehydration material ({gamma}-alumina) was demonstrated. It provided the productivity and selectivity expected from the LPDME process. However, the catalyst system deactivated too rapidly to warrant a viable commercial process [1]. The mechanistic investigation in the early part of the DOE's Alternative Fuels II program revealed that the accelerated catalyst deactivation under LPDME conditions is due to detrimental interaction between the methanol synthesis catalyst and methanol dehydration catalyst [2,3]. The interaction was attributed to migration of Cu- and/or Zn-containing species from the synthesis catalyst to the dehydration catalyst. Identification of a dehydration catalyst that did not lead to this detrimental interaction while retaining adequate dehydration activity was elusive. Twenty-nine different dehydration materials were tested, but none showed the desired performance [2]. The search came to a turning point when aluminum phosphate was tested. This amorphous material is prepared by precipitating a solution containing Al(NO{sub 3}){sub 3} and H{sub 3}PO{sub 4} with NH{sub 4}OH, followed by washing, drying and calcination. The aluminum phosphate catalyst has adequate dehydration activity and good stability. It can co-exist with the Cu-based methanol synthesis catalyst without negatively affecting the latter catalyst's stability. This report documents the details of the development of this catalyst. These include initial leads, efforts in improving activity and stability, investigation and development of the best preparation parameters and procedures, mechanistic understanding and resulting preparation guidelines, and the accomplishments of this work.

  6. Inquiring Minds - Questions About Physics

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Concept of ether in explaining forces You asked: Will there be any research carried out in the near or distant future to find a physical relationship between gravity, mass, light, matter/antimatter through something like the idea of ether hundred years ago? The concept of ether surfaced decades before scientists knew of quantum mechanics and some very fundamental symmetry principles of the microscopic world. Because of the huge change in knowledge, the historic word ether is not used anymore

  7. Advanced membrane separation technology for biosolvents. Final CRADA report.

    SciTech Connect (OSTI)

    Snyder, S. W.; Energy Systems

    2010-02-08

    Argonne and Vertec Biosolvents investigated the stability and perfonnance for a number of membrane systems to drive the 'direct process' for pervaporation-assisted esterification to produce lactate esters. As outlined in Figure 1, the target is to produce ammonium lactate by fennentation. After purification and concentration, ammonium lactate is reacted with ethanol to produce the ester. Esterification is a reversible reaction so to drive the reaction forward, the produced ammonia and water must be rapidly separated from the product. The project focused on selecting pervaporation membranes with (1) acid functionality to facilitate ammonia separation and (2) temperature stability to be able to perform that reaction at as high a temperature as possible (Figure 2). Several classes of commercial membrane materials and functionalized membrane materials were surveyed. The most promising materials were evaluated for scale-up to a pre-commercial application. Over 4 million metric tons per year of solvents are consumed in the U.S. for a wide variety of applications. Worldwide the usage exceeds 10 million metric tons per year. Many of these, such as the chlorinated solvents, are environmentally unfriendly; others, such as the ethylene glycol ethers and N Methyl Pyrrolidone (NMP), are toxic or teratogenic, and many other petroleum-derived solvents are coming under increasing regulatory restrictions. High performance, environmentally friendly solvents derived from renewable biological resources have the potential to replace many of the chlorinated and petrochemical derived solvents. Some of these solvents, such as ethyl lactate; d-limonene, soy methyl esters, and blends ofthese, can give excellent price/perfonnance in addition to the environmental and regulatory compliance benefits. Advancement of membrane technologies, particularly those based on pervaporation and electrodialysis, will lead to very efficient, non-waste producing, and economical manufacturing technologies for production of ethyl lactate and other esters.

  8. COMPLEX ORGANIC MOLECULES AT HIGH SPATIAL RESOLUTION TOWARD ORION-KL. I. SPATIAL SCALES

    SciTech Connect (OSTI)

    Widicus Weaver, Susanna L.; Friedel, Douglas N. E-mail: friedel@astro.illinois.edu

    2012-08-01

    Here we present high spatial resolution (<1'') observations of molecular emission in Orion-KL conducted using the Combined Array for Research in Millimeter-wave Astronomy. This work was motivated by recent millimeter continuum imaging studies of this region conducted at a similarly high spatial resolution, which revealed that the bulk of the emission arises from numerous compact sources, rather than the larger-scale extended structures typically associated with the Orion Hot Core and Compact Ridge. Given that the spatial extent of molecular emission greatly affects the determination of molecular abundances, it is important to determine the true spatial scale for complex molecules in this region. Additionally, it has recently been suggested that the relative spatial distributions of complex molecules in a source might give insight into the chemical mechanisms that drive complex chemistry in star-forming regions. In order to begin to address these issues, this study seeks to determine the spatial distributions of ethyl cyanide [C{sub 2}H{sub 5}CN], dimethyl ether [(CH{sub 3}){sub 2}O], methyl formate [HCOOCH{sub 3}], formic acid [HCOOH], acetone [(CH{sub 3}){sub 2}CO], SiO, methanol [CH{sub 3}OH], and methyl cyanide [CH{sub 3}CN] in Orion-KL at {lambda} = 3 mm. We find that for all observed molecules, the molecular emission arises from multiple components of the cloud that include a range of spatial scales and physical conditions. Here, we present the results of these observations and discuss the implications for studies of complex molecules in star-forming regions.

  9. Composition and process for separating cesium ions from an acidic aqueous solution also containing other ions

    DOE Patents [OSTI]

    Dietz, Mark L.; Horwitz, E. Philip; Bartsch, Richard A.; Barrans, Jr., Richard E.; Rausch, David

    1999-01-01

    A crown ether cesium ion extractant is disclosed as is its synthesis. The crown ether cesium ion extractant is useful for the selective purification of cesium ions from aqueous acidic media, and more particularly useful for the isolation of radioactive cesium-137 from nuclear waste streams. Processes for isolating cesium ions from aqueous acidic media using the crown ether cesium extractant are disclosed as are processes for recycling the crown ether cesium extractant and processes for recovering cesium from a crown ether cesium extractant solution.

  10. Composition and process for separating cesium ions from an acidic aqueous solution also containing other ions

    DOE Patents [OSTI]

    Dietz, M.L.; Horwitz, E.P.; Bartsch, R.A.; Barrans, R.E. Jr.; Rausch, D.

    1999-03-30

    A crown ether cesium ion extractant is disclosed as is its synthesis. The crown ether cesium ion extractant is useful for the selective purification of cesium ions from aqueous acidic media, and more particularly useful for the isolation of radioactive cesium-137 from nuclear waste streams. Processes for isolating cesium ions from aqueous acidic media using the crown ether cesium extractant are disclosed as are processes for recycling the crown ether cesium extractant and processes for recovering cesium from a crown ether cesium extractant solution. 4 figs.

  11. Shock tube ignition of ethanol, isobutene and MTBE: Experiments and modeling

    SciTech Connect (OSTI)

    Curran, H.J.; Dunphy, M.P.; Simmie, J.M.; Westbrook, C.K.; Pitz, W.J.

    1991-11-22

    The ignition of ethanol, isobutene and methyl tert-butyl ether (MTBE) has been studied experimentally in a shock tube and computationally with a detailed chemical kinetic model. Experimental results, consisting of ignition delay measurements, were obtained for a range of fuel/oxygen mixtures diluted in Argon, with temperatures varying over a range of 1100--1900 K. The numerical model consisted of a detailed kinetic reaction mechanism with more than 400 elementary reactions, chosen to describe reactions of each fuel and the smaller hydrocarbon and other species produced during their oxidation. The overall agreement between experimental and computed results was excellent, particularly for mixtures with greater than 0.3% fuel. The greatest sensitivity in the computed results was found to falloff parameters in the dissociation reactions of isobutene, ethane, methane, and ethyl and vinyl radicals, to the C{sub 3}H{sub 4} and C{sub 3}H{sub 5} reaction submechanisms in the model, and to the reactions in the H{sub 2}-O{sub 2}-Co submechanism.

  12. Advanced quadrupole ion trap instrumentation for low level vehicle emissions measurements. CRADA final report for number ORNL93-0238

    SciTech Connect (OSTI)

    McLuckey, S.A.; Buchanan, M.V.; Asano, K.G.; Hart, K.J.; Goeringer, D.E.; Dearth, M.A.

    1997-09-01

    Quadrupole ion trap mass spectrometry has been evaluated for its potential use in vehicle emissions measurements in vehicle test facilities as an analyzer for the top 15 compounds contributing to smog generation. A variety of ionization methods were explored including ion trap in situ chemical ionization, atmospheric sampling glow discharge ionization, and nitric oxide chemical ionization in a glow discharge ionization source coupled with anion trap mass spectrometer. Emphasis was placed on the determination of hydrocarbons and oxygenated hydrocarbons at parts per million to parts per billion levels. Ion trap in situ water chemical ionization and atmospheric sampling glow discharge ionization were both shown to be amenable to the analysis of arenes, alcohols, aldehydes and, to some degree, alkenes. Atmospheric sampling glow discharge also generated molecular ions of methyl-t-butyl ether (MTBE). Neither of these ionization methods, however, were found to generate diagnostic ions for the alkanes. Nitric oxide chemical ionization, on the other hand, was found to yield diagnostic ions for alkanes, alkenes, arenes, alcohols, aldehydes, and MTBE. The ability to measure a variety of hydrocarbons present at roughly 15 parts per billion at measurement rates of 3 Hz was demonstrated. These results have demonstrated that the ion trap has an excellent combination of sensitivity, specificity, speed, and flexibility with respect to the technical requirements of the top 15 analyzer.

  13. Alkali or alkaline earth metal promoted catalyst and a process for methanol synthesis using alkali or alkaline earth metals as promoters

    DOE Patents [OSTI]

    Tierney, John W.; Wender, Irving; Palekar, Vishwesh M.

    1995-01-01

    The present invention relates to a novel route for the synthesis of methanol, and more specifically to the production of methanol by contacting synthesis gas under relatively mild conditions in a slurry phase with a heterogeneous catalyst comprising reduced copper chromite impregnated with an alkali or alkaline earth metal. There is thus no need to add a separate alkali or alkaline earth compound. The present invention allows the synthesis of methanol to occur in the temperature range of approximately 100.degree.-160.degree. C. and the pressure range of 40-65 atm. The process produces methanol with up to 90% syngas conversion per pass and up to 95% methanol selectivity. The only major by-product is a small amount of easily separated methyl formate. Very small amounts of water, carbon dioxide and dimethyl ether are also produced. The present catalyst combination also is capable of tolerating fluctuations in the H.sub.2 /CO ratio without major deleterious effect on the reaction rate. Furthermore, carbon dioxide and water are also tolerated without substantial catalyst deactivation.

  14. Alkali or alkaline earth metal promoted catalyst and a process for methanol synthesis using alkali or alkaline earth metals as promoters

    DOE Patents [OSTI]

    Tierney, J.W.; Wender, I.; Palekar, V.M.

    1995-01-31

    The present invention relates to a novel route for the synthesis of methanol, and more specifically to the production of methanol by contacting synthesis gas under relatively mild conditions in a slurry phase with a heterogeneous catalyst comprising reduced copper chromite impregnated with an alkali or alkaline earth metal. There is thus no need to add a separate alkali or alkaline earth compound. The present invention allows the synthesis of methanol to occur in the temperature range of approximately 100--160 C and the pressure range of 40--65 atm. The process produces methanol with up to 90% syngas conversion per pass and up to 95% methanol selectivity. The only major by-product is a small amount of easily separated methyl formate. Very small amounts of water, carbon dioxide and dimethyl ether are also produced. The present catalyst combination also is capable of tolerating fluctuations in the H[sub 2]/CO ratio without major deleterious effect on the reaction rate. Furthermore, carbon dioxide and water are also tolerated without substantial catalyst deactivation.

  15. Synthesis of acrylates. Quarterly report, 1996

    SciTech Connect (OSTI)

    1996-10-01

    Eastman has completed its experimental work in the generation of propionate derivatives. Over the last quarter, Eastman has primarily devoted its time to completing the documentation and developing the potential extension of the oxidative condensation to dimethyl ether. Eastman has completed internal invention reports covering two patents and is working on the third with RTI which they expect to complete within the month. Becthel has also completed its work on the cost analysis of the propionate synthesis work (Task 1). RTI is continuing to develop active and stable catalysts for the condensation of propionic acid and formaldehyde. A total of 74 acid-base catalysts have been tested so far. Two invention reports have been completed based on RTI and Eastman`s work. A third invention report is currently being prepared for Eastman`s review on a novel methodology of methyl propionate activation. RTI is continuing to synthesize more acid-base catalysts with a goal of developing a catalyst which exhibits stable activity over a 200 h test period. Over the last quarter, RTI has also completed its initial tests on the slurry reactor system.

  16. Selecting activated carbon for water and wastewater treatability studies

    SciTech Connect (OSTI)

    Zhang, W.; Chang, Q.G.; Liu, W.D.; Li, B.J.; Jiang, W.X.; Fu, L.J.; Ying, W.C.

    2007-10-15

    A series of follow-up investigations were performed to produce data for improving the four-indicator carbon selection method that we developed to identify high-potential activated carbons effective for removing specific organic water pollutants. The carbon's pore structure and surface chemistry are dependent on the raw material and the activation process. Coconut carbons have relatively more small pores than large pores; coal and apricot nutshell/walnut shell fruit carbons have the desirable pore structures for removing adsorbates of all sizes. Chemical activation, excessive activation, and/or thermal reactivation enlarge small pores, resulting in reduced phenol number and higher tannic acid number. Activated carbon's phenol, iodine, methylene blue, and tannic acid numbers are convenient indicators of its surface area and pore volume of pore diameters < 10, 10-15, 15-28, and > 28 angstrom, respectively. The phenol number of a carbon is also a good indicator of its surface acidity of oxygen-containing organic functional groups that affect the adsorptive capacity for aromatic and other small polar organics. The tannic acid number is an indicator of carbon's capacity for large, high-molecular-weight natural organic precursors of disinfection by-products in water treatment. The experimental results for removing nitrobenzene, methyl-tert-butyl ether, 4,4-bisphenol, humic acid, and the organic constituents of a biologically treated coking-plant effluent have demonstrated the effectiveness of this capacity-indicator-based method of carbon selection.

  17. Understanding the impact of ionic liquid pretreatment on eucalyptus

    SciTech Connect (OSTI)

    Centikol, Ozgul; Dibble, Dean; Cheng, Gang; Kent, Michael S; Knierim, Manfred; Melnichenko, Yuri B

    2010-01-01

    The development of cost-competitive biofuels necessitates the realization of advanced biomass pretreatment technologies. Ionic liquids provide a basis for one of the most promising pretreatment technologies and are known to allow effective processing of cellulose and some biomass species. Here, we demonstrate that the ionic liquid 1-ethyl-3-methyl imidazolium acetate, [C2mim][OAc], induces structural changes at the molecular level in the cell wall of Eucalyptus globulus. Deacetylation of xylan, acetylation of the lignin units, selective removal of guaiacyl units (increasing the syringyl:guaiacyl ratio) and decreased {beta}-ether content were the most prominent changes observed. Scanning electron microscopy images of the plant cell wall sections reveal extensive swelling during [C2mim][OAc] pretreatment. X-ray diffraction measurements indicate a change in cellulose crystal structure from cellulose I to cellulose II after [C2mim][OAc] pretreatment. Enzymatic saccharification of the pretreated material produced increased sugar yields and improved hydrolysis kinetics after [C2mim][OAc] pretreatment. These results provide new insight into the mechanism of ionic liquid pretreatment and reaffirm that this approach may be promising for the production of cellulosic biofuels from woody biomass.

  18. Silver-Mordenite for Radiologic Gas Capture from Complex Streams: Dual Catalytic CH3I Decomposition and I Confinement

    SciTech Connect (OSTI)

    Tina M. Nenoff; Mark Rodriguez; Nick Soelberg; Karena W. Chapman

    2014-12-01

    The effective capture and storage of radiological iodine (129I) remains a strong concern for safe nuclear waste storage and safe nuclear energy. Silver-containing mordenite (MOR) is a longstanding benchmark for iodine capture. In nuclear fuel reprocessing scenarios, complex gas streams will be present and the need for high selectivity of all iodine containing compounds is of the utmost importance for safety and the environment. In particular, a molecular level understanding of the sorption of organic iodine compounds is not well understood. Here we probe the structure and distribution of methyl iodide sorbed by silver-containing MOR using a combination of crystallographic and materials characterization techniques including: infrared spectroscopy, thermogravimetric analysis with mass spectrometry, Micro-X-ray Fluorescence, powder X-ray diffraction analysis, and pair distribution function analysis. The iodine is captured inside the MOR pore in the form of AgI nanoparticles, that is consistent with the pores sizes of the MOR, indicating that the molecule is both physically and chemically captured in the Ag-MOR. The organic component is surface catalyzed by the zeolite via the formation of Surface Methoxy Species (SMS) that result in downstream organics of dimethyl ether and methanol formation.

  19. Six-Membered-Ring Malonatoborate-Based Lithium Salts as Electrolytes for Lithium Ion Batteries

    SciTech Connect (OSTI)

    Yang, Li; Zhang, Hanjun; Driscoll, Peter; Lucht, Brett; Kerr, John

    2011-09-30

    A new class of lithium salts of malonatoborate anions has been synthesized. These six-membered-ring salts provided slightly lower ionic conductivity than that of LiBOB and LiBF4. Nevertheless, compared with LiBOB and LiPF6, the lowered ring strains in the malonatoborate structures and reduced numbers of fluorine atoms in the molecules was found to enhance the thermal and water stabilities and compatibilities of these salts with ether solvents. Small amount LiDMMDFB when used as an additive, was found to stabilize LiPF6 in carbonate electrolytes at 80°C for one month. Employing LiMDFB as the electrolyte in Li/Li cells and full cells, large interfacial impedances were observed on lithium metal and the cathode. Moreover, the large impedances are at least partially attributed to the acidic hydrogen atoms in the malonate structure. This issue can be addressed by replacing the acidic atoms with methyl groups.

  20. REACTIVE DESORPTION AND RADIATIVE ASSOCIATION AS POSSIBLE DRIVERS OF COMPLEX MOLECULE FORMATION IN THE COLD INTERSTELLAR MEDIUM

    SciTech Connect (OSTI)

    Vasyunin, A. I.; Herbst, Eric E-mail: eh2ef@virginia.edu

    2013-05-20

    The recent discovery of terrestrial-type organic species such as methyl formate and dimethyl ether in the cold interstellar gas has proved that the formation of organic matter in the Galaxy begins at a much earlier stage of star formation than was previously thought. This discovery represents a challenge for astrochemical modelers. The abundances of these molecules cannot be explained by the previously developed ''warm-up'' scenario, in which organic molecules are formed via diffusive chemistry on surfaces of interstellar grains starting at 30 K, and then released to the gas at higher temperatures during later stages of star formation. In this article, we investigate an alternative scenario in which complex organic species are formed via a sequence of gas-phase reactions between precursor species formed on grain surfaces and then ejected into the gas via efficient reactive desorption, a process in which non-thermal desorption occurs as a result of conversion of the exothermicity of chemical reactions into the ejection of products from the surface. The proposed scenario leads to reasonable if somewhat mixed results at temperatures as low as 10 K and may be considered as a step toward the explanation of abundances of terrestrial-like organic species observed during the earliest stages of star formation.

  1. A combustion model for IC engine combustion simulations with multi-component fuels

    SciTech Connect (OSTI)

    Ra, Youngchul; Reitz, Rolf D.

    2011-01-15

    Reduced chemical kinetic mechanisms for the oxidation of representative surrogate components of a typical multi-component automotive fuel have been developed and applied to model internal combustion engines. Starting from an existing reduced mechanism for primary reference fuel (PRF) oxidation, further improvement was made by including additional reactions and by optimizing reaction rate constants of selected reactions. Using a similar approach to that used to develop the reduced PRF mechanism, reduced mechanisms for the oxidation of n-tetradecane, toluene, cyclohexane, dimethyl ether (DME), ethanol, and methyl butanoate (MB) were built and combined with the PRF mechanism to form a multi-surrogate fuel chemistry (MultiChem) mechanism. The final version of the MultiChem mechanism consists of 113 species and 487 reactions. Validation of the present MultiChem mechanism was performed with ignition delay time measurements from shock tube tests and predictions by comprehensive mechanisms available in the literature. A combustion model was developed to simulate engine combustion with multi-component fuels using the present MultiChem mechanism, and the model was applied to simulate HCCI and DI engine combustion. The results show that the present multi-component combustion model gives reliable performance for combustion predictions, as well as computational efficiency improvements through the use of reduced mechanism for multi-dimensional CFD simulations. (author)

  2. A facile and scalable route to nano-crystallized kesterite Cu{sub 2}ZnSnS{sub 4} fibers via electrospinning/sulfurization

    SciTech Connect (OSTI)

    Song, Yuanqiang Liu, Aifang; Mu, Chunhong; Huo, Weirong; Lv, Weiqiang; He, Weidong

    2015-01-15

    Detailed characterization of the microstructure and its properties have been done on the nanocrystallized CZTS nanofibers fabricated via electrospinning following sulfurization. The fiber growth mechanism is proposed to explain the spontaneous reaction and crystallization of CZTS, as confirmed by the thermodynamic calculations. - Abstract: In this work, we report facile route to quaternary kesterite Cu{sub 2}ZnSnS{sub 4} (CZTS) microfibers through electrospinning method. Precursor fibers are electrospun from the solution composed of Cu(CH{sub 3}COO){sub 2}, Zn(CH{sub 3}COO){sub 2{sup ,}} and SnCl{sub 4} as the solutes, ethylene glycol methyl ether as the solvent, and polyvinylpyrrolidone (PVP) as the plasticizer. CZTS fibers are obtained after annealing at 773 K for 40 min in a sulfur ambient. Characterization including scanning electron microscopy (SEM), energy-dispersive spectroscopy (EDS), X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and Raman spectra, confirm the formation of single-phased, well-crystallized CZTS fibers, with a band gap of about 1.48 eV estimated from the optical absorption curve. In addition, the fiber growth mechanism is proposed to explain the spontaneous reaction and crystallization of CZTS, as confirmed by the thermodynamic calculations.

  3. Effects of temperature and acidic pre-treatment on Fenton-driven oxidation of MTBE-spent granular activated carbon

    SciTech Connect (OSTI)

    Kan, E.; Huling, S.G.

    2009-03-01

    The effects of temperature and acidic pretreatment on Fenton-driven chemical oxidation of methyl tert-butyl ether (MTBE)-spent granular activated carbon (GAC, derived from bituminous coal) were investigated. Limiting factors in MTBE removal in GAC include the heterogeneous distribution of amended Fe, and slow intraparticle diffusive transport of MTBE and hydrogen peroxide (H{sub 2}O{sub 2}) into the 'reactive zone'. Acid pretreatment of GAC before Fe amendment altered the surface chemistry of the GAC, lowered the pH point of zero charge, and resulted in greater penetration and more uniform distribution of Fe in GAC. This led to a condition where Fe, MTBE, and H{sub 2}O{sub 2} coexisted over a larger volume of the GAC contributing to greater MTBE oxidation and removal. H{sub 2}O{sub 2} reaction and MTBE removal in GAC increased with temperature. Modeling H{sub 2}O{sub 2} transport and reaction in GAC indicated that H{sub 2}O{sub 2} penetration was inversely proportional with temperature and tortuosity, and occurred over a larger fraction of the total volume of small GAC particles (0.3 mm diameter) relative to large particles (1.2 mm diameter). Acidic pretreatment of GAC, Fe-amendment, elevated reaction temperature, and use of small GAC particles are operational parameters that improve Fenton-driven oxidation of MTBE in GAC. 29 refs., 6 figs., 1 tab.

  4. A class of polysulfide catholytes for lithium-sulfur batteries: energy density, cyclability, and voltage enhancement

    SciTech Connect (OSTI)

    Yu, XW; Manthiram, A

    2015-01-01

    Liquid-phase polysulfide catholytes are attracting much attention in lithium-sulfur (Li-S) batteries as they provide a facile dispersion and homogeneous distribution of the sulfur active material in the conductive matrix. However, the organic solvents used in lithium-polysulfide (Li-PS) batteries play an important role and have an impact on the physico-chemical characteristics of polysulfides. For instance, significantly higher voltages (similar to 2.7 V) of the S/S-n(2-) (4 <= n <= 8) redox couple are observed in Li-PS batteries with dimethyl sulfoxide (DMSO) and N-methyl-2-pyrrolidone (NMP) solvents. Accordingly, high power Li-PS batteries are presented here with the catholyte prepared with NMP solvent and operated with the highly reversible sulfur/long-chain polysulfide redox couple. On the other hand, a remarkable cyclability enhancement of the Li-PS battery is observed with the long-chain, ether-based tetraglyme (TEGDME) solvent. The voltage enhancement and the cyclability enhancement of the Li-PS batteries are attributed to the solvation effect, viscosity, and volatility of the solvents. Finally, highly concentrated polysulfide catholytes are successfully synthesized, with which high energy density Li-PS batteries are demonstrated by employing a multi-walled carbon nanotube (MWCNT) fabric electrode.

  5. Investigation of Oxidative Degradation in Polymers Using (17)O NMR Spectroscopy

    SciTech Connect (OSTI)

    Alam, Todd M.; Celina, Mathew; Assink, Roger A.; Clough, Roger L.; Gillen, Kenneth T.; Wheeler David R.

    1999-07-20

    The thermal oxidation of pentacontane (C{sub 50}H{sub 102}), and of the homopolymer polyisoprene, has been investigated using {sup 17}O NMR spectroscopy. By performing the oxidation using {sup 17}O labeled O{sub 2} gas, it is possible to easily identify degradation products, even at relatively low concentrations. It is demonstrated that details of the degradation mechanism can be obtained from analysis of the {sup 17}O NMR spectra as a function of total oxidation. Pentacontane reveals the widest variety of reaction products, and exhibits changes in the relative product distributions with increasing O{sub 2} consumption. At low levels of oxygen incorporation, peroxides are the major oxidation product, while at later stages of degradation these species are replaced by increasing concentrations of ketones, alcohols, carboxylic acids and esters. Analyzing the product distribution can help in identification of the different free-radical decomposition pathways of hydroperoxides, including recombination, proton abstraction and chain scission, as well as secondary reactions. The {sup 17}O NMR spectra of thermally oxidized polyisoprene reveal fewer degradation functionalities, but exhibit an increased complexity in the type of observed degradation species due to structural features such as unsaturation and methyl branching. Alcohols and ethers formed from hydrogen abstraction and free radical termination.

  6. Low temperature (550-700 K) oxidation pathways of cyclic ketones: Dominance of HO2-elimination channels yielding conjugated cyclic coproducts

    SciTech Connect (OSTI)

    Scheer, Adam M.; Welz, Oliver; Vasu, Subith S.; Osborn, David L.; Taatjes, Craig A.

    2015-04-13

    The low-temperature oxidation of three cyclic ketones, cyclopentanone (CPO; C5H8O), cyclohexanone (CHO; C6H10 O), and 2-methyl-cyclopentanone (2-Me-CPO; CH3–C5H7 O), is studied between 550 and 700 K and at 4 or 8 Torr total pressure. Initial fuel radicals R are formedvia fast H-abstraction from the ketones by laser-photolytically generated chlorine atoms. Intermediates and products from the subsequent reactions of these radicals in the presence of excess O2 are probed with time and isomeric resolution using multiplexed photoionization mass spectrometry with tunable synchrotron ionizing radiation. For CPO and CHO the dominant product channel in the R + O2 reactions is chain-terminating HO2-elimination yielding the conjugated cyclic coproducts 2-cyclopentenone and 2-cyclohexenone, respectively. Results on oxidation of 2-Me-CPO also show a dominant contribution from HO2-elimination. Moreover, the photoionization spectrum of the co-product suggests formation of 2-methyl-2-cyclopentenone and/or 2-cyclohexenone, resulting from a rapid Dowd–Beckwith rearrangement, preceding addition to O2, of the initial (2-oxocyclopentyl)methyl radical to 3-oxocyclohexyl. Cyclic ethers, markers for hydroperoxyalkyl radicals (QOOH), key intermediates in chain-propagating and chain-branching low-temperature combustion pathways, are only minor products. The interpretation of the experimental results is supported by stationary point calculations on the potential energy surfaces of the associated R + O2 reactions at the CBS-QB3 level. Furthermore, the calculations indicate that HO2-elimination channels are energetically favored and product formation via QOOH is disfavored. Lastly, the prominence of chain-terminating pathways linked with HO2 formation in low-temperature oxidation of cyclic ketones suggests little low-temperature reactivity of these species as fuels in internal combustion engines.

  7. Radionuclide-binding compound, a radionuclide delivery system, a method of making a radium complexing compound, a method of extracting a radionuclide, and a method of delivering a radionuclide

    DOE Patents [OSTI]

    Fisher, Darrell R.; Wai, Chien M.; Chen, Xiaoyuan

    2000-01-01

    The invention pertains to compounds which specifically bind radionuclides, and to methods of making radionuclide complexing compounds. In one aspect, the invention includes a radionuclide delivery system comprising: a) a calix[n]arene-crown-[m]-ether compound, wherein n is an integer greater than 3, and wherein m is an integer greater than 3, the calix[n]arene-crown-[m]-ether compound comprising at least two ionizable groups; and b) an antibody attached to the calix[n]arene-crown-[m]-ether compound. In another aspect, the invention includes a method of making a radium complexing compound, comprising: a) providing a calix[n]arene compound, wherein n is an integer greater than 3, the calix[n]arene compound comprising n phenolic hydroxyl groups; b) providing a crown ether precursor, the crown ether precursor comprising a pair of tosylated ends; c) reacting the pair of tosylated ends with a pair of the phenolic hydroxyl groups to convert said pair of phenolic hydroxyl groups to ether linkages, the ether linkages connecting the crown ether precursor to the calix[n]arene to form a calix[n]arene-crown-[m]-ether compound, wherein m is an integer greater than 3; d) converting remaining phenolic hydroxyl groups to esters; e) converting the esters to acids, the acids being proximate a crown-[m]-ether portion of the calix[n]arene-crown-[m]-ether compound; and f) providing a Ra.sup.2+ ion within the crown-[m]-ether portion of the calix[n]arene-crown-[m]-ether compound.

  8. Aza compounds as anion receptors

    DOE Patents [OSTI]

    Lee, Hung Sui; Yang, Xiao-Qing; McBreen, James

    1998-01-06

    A family of aza-ether based compounds including linear, multi-branched and aza-crown ethers is provided. When added to non-aqueous battery electrolytes, the family of aza-ether based compounds acts as neutral receptors to complex the anion moiety of the electrolyte salt thereby increasing the conductivity and the transference number of Li.sup.+ ion in alkali metal batteries.

  9. Aza compounds as anion receptors

    DOE Patents [OSTI]

    Lee, H.S.; Yang, X.Q.; McBreen, J.

    1998-01-06

    A family of aza-ether based compounds including linear, multi-branched and aza-crown ethers is provided. When added to non-aqueous battery electrolytes, the family of aza-ether based compounds acts as neutral receptors to complex the anion moiety of the electrolyte salt thereby increasing the conductivity and the transference number of Li{sup +} ion in alkali metal batteries. 3 figs.

  10. Anion receptor compounds for non-aqueous electrolytes

    DOE Patents [OSTI]

    Lee, Hung Sui; Yang, Xiao-Oing; McBreen, James

    2000-09-19

    A new family of aza-ether based compounds including linear, multi-branched and aza-crown ethers is provided. When added to non-aqueous battery electrolytes, the new family of aza-ether based compounds acts as neutral receptors to complex the anion moiety of the electrolyte salt thereby increasing the conductivity and the transference number of LI.sup.+ ion in alkali metal batteries.

  11. Synthesis of [.sup.13C] and [.sup.2H] substituted methacrylic acid, [.sup.13C] and [.sup.2H] substituted methyl methacrylate and/or related compounds

    DOE Patents [OSTI]

    Alvarez, Marc A.; Martinez, Rodolfo A.; Unkefer, Clifford J.

    2010-02-16

    The present invention is directed to labeled compounds of the formulae ##STR00001## wherein Q is selected from the group consisting of --S(.dbd.O)--, and --S(.dbd.O).sub.2--, Z is selected from the group consisting of 1-naphthyl, substituted 1-naphthyl, 2-naphthyl, substituted 2-naphthyl, and phenyl groups with the structure ##STR00002## wherein R.sub.1, R.sub.2, R.sub.3, R.sub.4 and R.sub.5 are each independently selected from the group consisting of hydrogen, a C.sub.1-C.sub.4 lower alkyl, a halogen, and an amino group selected from the group consisting of NH.sub.2, NHR and NRR' where R and R' are each independently selected from the group consisting of a C.sub.1-C.sub.4 lower alkyl, an aryl, and an alkoxy group, and X is selected from the group consisting of hydrogen, a C.sub.1-C.sub.4 lower alkyl group, and a fully-deuterated C.sub.1-C.sub.4 lower alkyl group.

  12. Crystal structure of 4-[benzylideneamino]-3-thiophen-2-yl-methyl-4,5-dihydro-1H-[1,2,4] triazole-5-one

    SciTech Connect (OSTI)

    Tanak, H.

    2013-12-15

    The crystal structure of the title compound C{sub 14}H{sub 12}N{sub 4}OS was determined by the X-ray diffraction method. The compound crystallizes in the triclinic space group P-bar1 with Z = 2. The molecule is not planar: the dihedral angle between the triazole and thiophene rings is 73.98(2)°, and that between the triazole and benzene rings is 4.05(2)°. The thiophene ring is disordered over two positions, which are approximately parallel and oppositely oriented. The major component refined to a site-occupancy factor of 0.573(3). An intramolecular C-H...O hydrogen bond generates an S(6) ring motif. In the crystal, molecules are linked together by two pairs of N-H...O interactions (to the same O atom as acceptor), forming inversion dimers. The crystal packing is also stabilized by π-π interactions [centroid-centroid distance is 3.978 Å].

  13. L-[METHYL-{sup 11}C] Methionine Positron Emission Tomography for Target Delineation in Malignant Gliomas: Impact on Results of Carbon Ion Radiotherapy

    SciTech Connect (OSTI)

    Mahasittiwat, Pawinee; Mizoe, Jun-etsu Hasegawa, Azusa; Ishikawa, Hiroyuki; Yoshikawa, Kyosan; Mizuno, Hideyuki; Yanagi, Takeshi; Takagi, Ryou D.D.S.; Pattaranutaporn, Pittayapoom; Tsujii, Hirohiko

    2008-02-01

    Purpose: To assess the importance of {sup 11}C-methionine (MET)-positron emission tomography (PET) for clinical target volume (CTV) delineation. Methods and Materials: This retrospective study analyzed 16 patients with malignant glioma (4 patients, anaplastic astrocytoma; 12 patients, glioblastoma multiforme) treated with surgery and carbon ion radiotherapy from April 2002 to Nov 2005. The MET-PET target volume was compared with gross tumor volume and CTV, defined by using computed tomography/magnetic resonance imaging (MRI). Correlations with treatment results were evaluated between positive and negative extended volumes (EVs) of the MET-PET target for CTV. Results: Mean volumes of the MET-PET targets, CTV1 (defined by means of high-intensity volume on T2-weighted MRI), and CTV2 (defined by means of contrast-enhancement volume on T1-weighted MRI) were 6.35, 264.7, and 117.7 cm{sup 3}, respectively. Mean EVs of MET-PET targets for CTV1 and CTV2 were 0.6 and 2.2 cm{sup 3}, respectively. The MET-PET target volumes were included in CTV1 and CTV2 in 13 (81.3%) and 11 patients (68.8%), respectively. Patients with a negative EV for CTV1 had significantly greater survival rate (p = 0.0069), regional control (p = 0.0047), and distant control time (p = 0.0267) than those with a positive EV. Distant control time also was better in patients with a negative EV for CTV2 than those with a positive EV (p = 0.0401). Conclusions: For patients with malignant gliomas, MET-PET has a possibility to be a predictor of outcome in carbon ion radiotherapy. Direct use of MET-PET fused to planning computed tomography will be useful and yield favorable results for the therapy.

  14. Synthesis of 2'-deoxy-2'-[.sup.18F]fluoro-5-methyl-1-B-D-arabinofuranosyluracil (.sup.18F-FMAU)

    DOE Patents [OSTI]

    Li, Zibo; Cai, Hancheng; Conti, Peter S

    2014-12-16

    The present invention relates to methods of synthesizing .sup.18F-FMAU. In particular, .sup.18F-FMAU is synthesized using one-pot reaction conditions in the presence of Friedel-Crafts catalysts. The one-pot reaction conditions are incorporated into a fully automated cGMP-compliant radiosynthesis module, which results in a reduction in synthesis time and simplifies reaction conditions. The one-pot reaction conditions are also suitable for the production of 5-substituted thymidine or cytidine analogs. The products from the one-pot reaction (e.g. the labeled thymidine or cytidine analogs) can be used as probes for imaging tumor proliferative activity. More specifically, these [.sup.18F]-labeled thymidine or cytidine analogs can be used as a PET tracer for certain medical conditions, including, but not limited to, cancer disease, autoimmunity inflammation, and bone marrow transplant.

  15. DOE Selects 16 Transformational Carbon Capture Technologies Projects...

    Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site

    Corporation (Woburn, MA), and Trimeric Corporation (Buda, TX) - will combine a graphene oxide (GO) membrane unit with the polyether ether ketone (PEEK) hollow fiber membrane...

  16. Newsletter

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    create expertly carved jack-o-lanterns, and enjoy this year's selection. Hear ethereal music performed by vibrating strings. Check out creepy, crawly critters like snakes,...

  17. Special Lecture:

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    create expertly carved jack-o-lanterns, and enjoy this year's selection. Hear ethereal music performed by vibrating strings. Check out creepy, crawly critters like snakes,...

  18. Sandia Energy Research & Capabilities

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    CRF Experiment Confirms Accepted Oxidation Scheme of Proposed Diesel Alternative: Dimethyl Ether http:energy.sandia.govcrf-experiment-confirms-accepted-oxidation-scheme-of-propo...

  19. Search for: All records | DOE Patents

    Office of Scientific and Technical Information (OSTI)

    lacking ether groups in the polymer may be used as membranes and binders for electrocatalysts in preparation of anodes for electrochemical cells such as solid alkaline fuel cells. ...

  20. Search for: All records | SciTech Connect

    Office of Scientific and Technical Information (OSTI)

    ... of syngas to methanol, methanol dehydration to dimethyl ether (DME), and the homologation of DME over a zeolite catalyst to high-octane gasoline-range hydrocarbon products. ...

  1. Dr. Googin and his early days at Y-12, part 10 ? Googin, a valuable...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    first processing building for the Beta intermediate and final product cycles, where solvent extraction with diethyl ether was used to purify and recover the uranium instead of...

  2. CRF Experiment Confirms Accepted Oxidation Scheme of Proposed...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    EnergyWater History Water Monitoring & Treatment Technology Decision Models for ... generally accepted dimethyl ether (DME) oxidation scheme at low temperature (540 K, 267 C). ...

  3. 2014 | U.S. DOE Office of Science (SC)

    Office of Science (SC) Website

    Crown Ethers Flatten in Graphene for Strong, Specific Binding External link ORNL discovery holds potential for separations, sensors, batteries, biotech and more. Read More External ...

  4. Thermodynamic Evaluation of Low-Global Warming Potential Refrigerants

    Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site

    device ...and a variety of applications: cooling (T evap 10 C, T cond 40 C) ... Halogenated oxygenates (e.g., ethers) Nitrogen & sulfur compounds 12 | Building ...

  5. Crude Oil and Petroleum Products Movements by Tanker and Barge...

    U.S. Energy Information Administration (EIA) Indexed Site

    Components MGBC - Reformulated MGBC - Reformulated RBOB MGBC - RBOB for Blending w Alcohol* MGBC - RBOB for Blending w Ether* MGBC - Reformulated GTAB* MGBC - Conventional MGBC ...

  6. Total Blender Net Input of Petroleum Products

    U.S. Energy Information Administration (EIA) Indexed Site

    - Reformulated, RBOB for Blending w Alcohol MGBC - Reformulated, RBOB for Blending w ... Notes: RBOB with Ether, RBOB with Alcohol, and Reformulated GTAB Motor Gasoline Blending ...

  7. Refinery Stocks of Crude Oil and Petroleum Products

    U.S. Energy Information Administration (EIA) Indexed Site

    MGBC - Reformulated MGBC - Reformulated - RBOB MGBC - RBOB for Blending with Alcohol* MGBC - RBOB for Blending with Ether* MGBC - Conventional MGBC - Conventional CBOB ...

  8. Total Imports

    U.S. Energy Information Administration (EIA) Indexed Site

    Components, RBOB Imports - Motor Gasoline Blend. Components, RBOB w Ether Imports - Motor Gasoline Blend. Components, RBOB w Alcohol Imports - Motor Gasoline Blend. Components, ...

  9. U.S. Crude Oil and Petroleum Products Stocks by Type

    U.S. Energy Information Administration (EIA) Indexed Site

    (MGBC) MGBC - Reformulated MGBC - Reformulated, RBOB MGBC - Reformulated, RBOB w Alcohol MGBC - Reformulated, RBOB w Ether MGBC - Reformulated, GTAB MGBC - Conventional MGBC ...

  10. East Coast (PADD 1) Total Crude Oil and Petroleum Products Net...

    U.S. Energy Information Administration (EIA) Indexed Site

    Comp. (MGBC) MGBC - Reformulated MGBC - Reformulated RBOB MGBC - RBOB for Blending w Alcohol* MGBC - RBOB for Blending w Ether* MGBC - Reformulated GTAB* MGBC - Conventional MGBC ...

  11. Refinery & Blenders Net Input of Crude Oil

    U.S. Energy Information Administration (EIA) Indexed Site

    - Reformulated, RBOB for Blending w Alcohol MGBC - Reformulated, RBOB for Blending w ... Notes: RBOB with Ether, RBOB with Alcohol, and Reformulated GTAB Motor Gasoline Blending ...

  12. Search for: All records | SciTech Connect

    Office of Scientific and Technical Information (OSTI)

    ... Filter Results Filter by Subject chemistry (2) crown ethers (2) energy conservation, consumption, and utilization (2) isotope separation (2) asymmetry (1) bangladesh (1) biology ...

  13. Scientific Achievement

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    convert furans to alcohols via hydrogenation through the MPV mechanism and then to ethers. Combined with metal catalysts (RuC), synergetic hydrogenolysis occurs. Catalytic...

  14. Zelenay named Electrochemical Society Fellow

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    including non-precious metalprecious metal electrocatalysis of oxygen reduction and methanol and dimethyl ether oxidation; hydrogen, direct methanol, and direct dimethyl...

  15. Highly Active and Selective Metal-modified Zeolite Catalysts...

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Active and Selective Metal-modified Zeolite Catalysts for Low Temperature Conversion of Methanol and Dimethyl Ether to Gasoline-range Branched Hydrocarbons National Renewable...

  16. ALSNews Vol. 319

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    molecules mimic double slits Secrets of a Precision Protein Machine One "Cool Tool" That's Helping Repair Your DNA AFRD's Leemans Surfs the Ether in a Scientists' Soccer Match...

  17. An a priori DNS study of the shadow-position mixing model

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Zhao, Xin -Yu; Bhagatwala, Ankit; Chen, Jacqueline H.; Haworth, Daniel C.; Pope, Stephen B.

    2016-01-15

    In this study, the modeling of mixing by molecular diffusion is a central aspect for transported probability density function (tPDF) methods. In this paper, the newly-proposed shadow position mixing model (SPMM) is examined, using a DNS database for a temporally evolving di-methyl ether slot jet flame. Two methods that invoke different levels of approximation are proposed to extract the shadow displacement (equivalent to shadow position) from the DNS database. An approach for a priori analysis of the mixing-model performance is developed. The shadow displacement is highly correlated with both mixture fraction and velocity, and the peak correlation coefficient of themore » shadow displacement and mixture fraction is higher than that of the shadow displacement and velocity. This suggests that the composition-space localness is reasonably well enforced by the model, with appropriate choices of model constants. The conditional diffusion of mixture fraction and major species from DNS and from SPMM are then compared, using mixing rates that are derived by matching the mixture fraction scalar dissipation rates. Good qualitative agreement is found, for the prediction of the locations of zero and maximum/minimum conditional diffusion locations for mixture fraction and individual species. Similar comparisons are performed for DNS and the IECM (interaction by exchange with the conditional mean) model. The agreement between SPMM and DNS is better than that between IECM and DNS, in terms of conditional diffusion iso-contour similarities and global normalized residual levels. It is found that a suitable value for the model constant c that controls the mixing frequency can be derived using the local normalized scalar variance, and that the model constant a controls the localness of the model. A higher-Reynolds-number test case is anticipated to be more appropriate to evaluate the mixing models, and stand-alone transported PDF simulations are required to more fully enforce localness and to assess model performance.« less

  18. Superacid catalysis of light hydrocarbon conversion. Final report, August 26, 1993--August 26, 1996

    SciTech Connect (OSTI)

    Gates, B.C.

    1996-12-31

    Motivated by the goal of finding improved catalysts for low- temperature conversion of light alkanes into fuel components or precursors of fuel components, the researchers have investigated sulfated zirconia and promoted sulfated zirconia for conversion of butane, propane, and ethane. Catalyst performance data for sulfated zirconia promoted with iron and manganese show that it is the most active noncorrosive, nonhalide catalyst known for n-butane isomerization, and it is an excellent candidate catalyst for new low- temperature n-butane isomerization processes to make isobutane, which can be converted by established technology into methyl t-butyl ether (MTBE). Various transition metals have been found to work as promoters of sulfated zirconia for n-butane isomerization. The combination of iron and manganese is the best known combination of promoters yet discovered. The iron- and manganese-promoted sulfated zirconia is also a catalyst for conversion of propane and of ethane. Ethane is converted into ethylene and butanes in the presence of the iron- and manganese-promoted sulfated zirconia; propane is also converted into butane, among other products. However, the activities of the catalyst for these reactions are orders of magnitude less than the activity for n-butane conversion, and there is no evidence that the catalyst would be of practical value for conversion of alkanes lighter than butane. The product distribution data for ethane and propane conversion provide new insights into the nature of the catalyst and its acidity. These data suggest the involvement of Olah superacid chemistry, whereby the catalyst protonates the alkane itself, giving carbonium ions (as transition states). The mechanism of protonation of the alkane may also pertain to the conversion of butane, but there is good evidence that the butane conversion also proceeds via alkene intermediates by conventional mechanisms of carbenium ion formation and rearrangement.

  19. Predicted concentrations in new relocatable classrooms of volatile organic compounds emitted from standard and alternate interior finish materials

    SciTech Connect (OSTI)

    Hodgson, Alfred T.; Fisk, William J.; Shendell, Derek G.; Apte, Michael G.

    2001-07-01

    Relocatable classrooms (RCs) are widely employed by California school districts to satisfy rapidly expanding space requirements due to population growth and class size reduction policies. There is public concern regarding indoor environmental quality (IEQ) in schools, particularly in RCs, but very little data to support or dispel these concerns. Several studies are investigating various aspects of IEQ in California schools. This laboratory-based study focused on evaluating the emissions of toxic and/or odorous volatile organic compounds (VOCs), including formaldehyde and acetaldehyde, from materials used to finish the interiors of new RCs. Furthermore, the study implemented a procedure for VOC source reduction by testing and selecting lower-emitting materials as substitutes for standard materials. In total, 17 standard and alternate floor coverings, wall panels and ceiling panels were quantitatively tested for emissions of VOCs using smallscale environmental chambers. Working with the largest northern California manufacturer of conventional RCs and two school districts, specifications were developed for four new RCs to be produced in early summer 2001. Two of these will be predominantly finished with standard materials. Alternate carpet systems, an alternate wall panel covering and an alternate ceiling panel were selected for the two other RCs based on the results of the laboratory study and considerations of cost and anticipated performance and maintenance. Particular emphasis was placed on reducing the concentrations of VOCs on California agency lists of toxic compounds. Indoor concentrations of toxic and odorous VOCs were estimated for the four classrooms by mass balance using the measured VOC emission factors, exposed surface areas of the materials in the RCs, and three ventilation rate scenarios. Results indicate that reductions in the concentrations of formaldehyde, acetaldehyde phenol, di(ethylene glycol) butyl ether, vinyl acetate, 1,2,4-trimethylbenzene and 1-methyl-2-pyrrolidinone should be achieved as the result of the source reduction procedure.

  20. Amphiphilic Surface Active Triblock Copolymers with Mixed Hydrophobic and Hydrophilic Side Chains for Tuned Marine Fouling-Release Properties

    SciTech Connect (OSTI)

    Park, D.; Weinman, C; Finlay, J; Fletcher, B; Paik, M; Sundaram, H; Dimitriou, M; Sohn, K; Callow, M; et al.

    2010-01-01

    Two series of amphiphilic triblock surface active block copolymers (SABCs) were prepared through chemical modification of two polystyrene-block-poly(ethylene-ran-butylene)-block-polyisoprene ABC triblock copolymer precursors. The methyl ether of poly(ethylene glycol) [M{sub n} {approx} 550 g/mol (PEG550)] and a semifluorinated alcohol (CF{sub 3}(CF{sub 2}){sub 9}(CH{sub 2}){sub 10}OH) [F10H10] were attached at different molar ratios to impart both hydrophobic and hydrophilic groups to the isoprene segment. Coatings on glass slides consisting of a thin layer of the amphiphilic SABC deposited on a thicker layer of an ABA polystyrene-block-poly(ethylene-ran-butylene)-block-polystyrene thermoplastic elastomer were prepared for biofouling assays with algae. Dynamic water contact angle analysis, X-ray photoelectron spectroscopy (XPS) and near-edge X-ray absorption fine structure (NEXAFS) measurements were utilized to characterize the surfaces. Clear differences in surface structure were realized as the composition of attached side chains was varied. In biofouling assays, the settlement (attachment) of zoospores of the green alga Ulva was higher for surfaces incorporating a large proportion of the hydrophobic F10H10 side chains, while surfaces with a large proportion of the PEG550 side chains inhibited settlement. The trend in attachment strength of sporelings (young plants) of Ulva did not show such an obvious pattern. However, amphiphilic SABCs incorporating a mixture of PEG550 and F10H10 side chains performed the best. The number of cells of the diatom Navicula attached after exposure to flow decreased as the content of PEG550 to F10H10 side chains increased.