National Library of Energy BETA

Sample records for 1634-04-4 methyl tert

  1. Manipulation of the HIFVegf 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 0.006255 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 HIFVegf 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 HippelLindau 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 HIFVegf 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.

  2. 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.

  3. Hydrogen Atom Reactivity toward Aqueous tert-Butyl Alcohol

    SciTech Connect (OSTI)

    Lymar S. V.; Schwarz, H.A.

    2012-02-09

    Through a combination of pulse radiolysis, purification, and analysis techniques, the rate constant for the H + (CH{sub 3}){sub 3}COH {yields} H{sub 2} + {sm_bullet}CH{sub 2}C(CH{sub 3}){sub 2}OH reaction in aqueous solution is definitively determined to be (1.0 {+-} 0.15) x 10{sup 5} M{sup -1} s{sup -1}, which is about half of the tabulated number and 10 times lower than the more recently suggested revision. Our value fits on the Polanyi-type, rate-enthalpy linear correlation ln(k/n) = (0.80 {+-} 0.05){Delta}H + (3.2 {+-} 0.8) that is found for the analogous reactions of other aqueous aliphatic alcohols with n equivalent abstractable H atoms. The existence of such a correlation and its large slope are interpreted as an indication of the mechanistic similarity of the H atom abstraction from {alpha}- and {beta}-carbon atoms in alcohols occurring through the late, product-like transition state. tert-Butyl alcohol is commonly contaminated by much more reactive secondary and primary alcohols (2-propanol, 2-butanol, ethanol, and methanol), whose content can be sufficient for nearly quantitative scavenging of the H atoms, skewing the H atom reactivity pattern, and explaining the disparity of the literature data on the H + (CH{sub 3}){sub 3}COH rate constant. The ubiquitous use of tert-butyl alcohol in pulse radiolysis for investigating H atom reactivity and the results of this work suggest that many other previously reported rate constants for the H atom, particularly the smaller ones, may be in jeopardy.

  4. Evidence of extra-telomeric effects of hTERT and its regulation involving a feedback loop

    SciTech Connect (OSTI)

    Lai, Serene R.; Cunningham, Amanda P.; Huynh, Vu Q.; Andrews, Lucy G.; Tollefsbol, Trygve O. . E-mail: trygve@uab.edu

    2007-01-15

    The human telomerase reverse transcriptase (hTERT) is the catalytic subunit of the enzyme telomerase which is responsible for telomeric maintenance and extension. Using RNA interference to knock down hTERT mRNA expression, we provide evidence that hTERT exerts extra-telomeric effects on the cell cycle and on its own regulatory proteins, specifically: p53 and p21. We tested our hypothesis that hTERT regulates its own expression through effects on upstream regulatory genes using transformed human embryonic kidney (HEK 293) cells, p53 and p16 {sup INK4a} null human ovarian cancer SKOV-3 cells, and p53-null MDA-MB-157 human mammary cancer cells. In HEK 293 cells, hTERT knockdown resulted in elevated p53 and p21 transcription and a decrease in cellular proliferation. Similar results were observed in the MDA-MB-157 cell line where p21 was upregulated, correlating with cell growth inhibition. In contrast, we observed a decrease in expression of p21 in SKOV-3 cells with hTERT knockdown and cell growth appeared to be unaffected. These findings suggest that hTERT may be involved in a feedback loop system, thereby playing a role in its own regulation.

  5. Controlling DNA Methylation

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

    Controlling DNA Methylation Though life on earth is composed of a diverse range of organisms, some with many different types of tissues and cells, all these are encoded by a molecule we call DNA. The information required to build a protein is stored in DNA within the cells. Not all the message in the DNA is used in each cell and not all the message is used all the time. During cell differentiation, the cells become dedicated for their specific function which involves selectively activating some

  6. Features of the spectral dependences of transmittance of organic semiconductors based on tert-butyl substituted lutetium phthalocyanine molecules

    SciTech Connect (OSTI)

    Belogorokhov, I. A.; Tikhonov, E. V.; Dronov, M. A.; Belogorokhova, L. I.; Ryabchikov, Yu. V.; Tomilova, L. G.; Khokhlov, D. R.

    2011-11-15

    Vibronic properties of organic semiconductors based on tert-butyl substituted phthalocyanine lutetium diphthalocyanine molecules are studied by IR and Raman spectroscopy. It is shown that substitution of several carbon atoms in initial phthalocyanine (Pc) ligands with {sup 13}C isotope atoms causes a spectral shift in the main absorption lines attributed to benzene, isoindol, and peripheral C-H groups. A comparison of spectral characteristics showed that the shift can vary from 3 to 1 cm{sup -1}.

  7. Functionalization/passivation of porous graphitic carbon with di-tert-amylperoxide

    SciTech Connect (OSTI)

    Jensen, David S.; Gupta, Vipul; Olsen, Rebecca E.; Miller, Alex T.; Davis, Robert C.; Ess, Daniel; Zhu, Zihua; Vail, Michael A.; Dadson, Andrew; Linford, Matthew R.

    2011-11-18

    Porous graphitic carbon (PGC) particles were functionalized/passivated in situ in packed beds at elevated temperature with neat di-tert-amylperoxide (DTAP) in a column oven. The performance of these particles for high performance liquid chromatography (HPLC) was assayed before and after this chemistry with the following analytes: benzene, toluene, ethyl benzene, n-propyl benzene, n-butyl benzene, p-xylene, phenol, 4-methylphenol, phenetole, 3,5-xylenol, and anisole. After the first functionalization/passivation, the retention factors, k, of these compounds decreased by about 5% and the number of theoretical plates (N) increased by ca. 15%. These values of k then remained roughly constant after a second functionalization/ passivation but a further increase in N was noticed. In addition, after each of the reactions, the peak asymmetries decreased by ca. 15%, for a total of ca. 30%. The columns were then subjected twice to methanol at 100 C for 5 h at 1 mL/min. After these stability tests, the values of k remained roughly constant, the number of plates increased, which is favorable, and the asymmetries rose and then declined, where they remained below the initial values for the unfunctionalized columns. Functionalized and unfunctionalized particles were characterized by scanning electron microscopy and BET measurements, which showed no difference between the functionalized and unfunctionalized materials, and X-ray photoelectron spectroscopy and time-of-flight secondary ion mass spectrometry (ToF-SIMS), where ToF-SIMS suggested some chemical differences between the functionalized and unfunctionalized materials. In particular ToF-SIMS suggested that the expected five-carbon fragments from DTAP exist at higher concentrations on DTAP-functionalized PGC. First principle calculations on model graphitic surfaces suggest that the first addition of a DTAP radical to the surface proceeds in an approximately isothermal or slightly favorable fashion, but that subsequent DTAP additions are then increasingly thermodynamically favorable. Thus, this analysis suggests that the direct functionalization/passivation of PGC with DTAP is plausible. Chemometric analyses of the chromatographic and ToF-SIMS data are also presented.

  8. 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.

  9. 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.

  10. Low temperature synthesis of methyl formate

    DOE Patents [OSTI]

    Mahajan, Devinder (Selden, NY); Slegeir, William A. (Hampton Bays, NY); Sapienza, Richard S. (Shoreham, NY); O'Hare, Thomas E. (Huntington Station, NY)

    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.

  11. 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 ...

  12. 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.

  13. 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...

  14. Production of methyl-vinyl ketone from levulinic acid

    DOE Patents [OSTI]

    Dumesic, James A. (Verona, WI); West; Ryan M. (Madison, WI)

    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.

  15. 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.

  16. 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.

  17. 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.

  18. Low-temperature CVD of iron, cobalt, and nickel nitride thin films from bis[di(tert-butyl)amido]metal(II) precursors and ammonia

    SciTech Connect (OSTI)

    Cloud, Andrew N.; Abelson, John R., E-mail: abelson@illinois.edu [Department of Materials Science and Engineering, University of Illinois at Urbana-Champaign, 201 Materials Science and Engineering Building, 1304 W. Green St., Urbana, Illinois 61801 (United States); Davis, Luke M.; Girolami, Gregory S., E-mail: girolami@scs.illinois.edu [School of Chemical Sciences, University of Illinois at Urbana-Champaign, 600 S. Mathews Ave., Urbana, Illinois 61801 (United States)

    2014-03-15

    Thin films of late transition metal nitrides (where the metal is iron, cobalt, or nickel) are grown by low-pressure metalorganic chemical vapor deposition from bis[di(tert-butyl)amido]metal(II) precursors and ammonia. These metal nitrides are known to have useful mechanical and magnetic properties, but there are few thin film growth techniques to produce them based on a single precursor family. The authors report the deposition of metal nitride thin films below 300?C from three recently synthesized M[N(t-Bu){sub 2}]{sub 2} precursors, where M?=?Fe, Co, and Ni, with growth onset as low as room temperature. Metal-rich phases are obtained with constant nitrogen content from growth onset to 200?C over a range of feedstock partial pressures. Carbon contamination in the films is minimal for iron and cobalt nitride, but similar to the nitrogen concentration for nickel nitride. X-ray photoelectron spectroscopy indicates that the incorporated nitrogen is present as metal nitride, even for films grown at the reaction onset temperature. Deposition rates of up to 18?nm/min are observed. The film morphologies, growth rates, and compositions are consistent with a gas-phase transamination reaction that produces precursor species with high sticking coefficients and low surface mobilities.

  19. 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

  20. 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.

  1. 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.

  2. 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.'

  3. 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.

  4. 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.

  5. 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

  6. 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.

  7. 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.

  8. 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.

  9. 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 ...

  10. Phase 1 Methyl Iodide Deep-Bed Adsorption Tests (Technical Report...

    Office of Scientific and Technical Information (OSTI)

    Phase 1 Methyl Iodide Deep-Bed Adsorption Tests Citation Details In-Document Search Title: Phase 1 Methyl Iodide Deep-Bed Adsorption Tests You are accessing a document from the...

  11. 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.

  12. 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.

  13. "Seeing" Mercury Methylation in Progress

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

    Mercury in the environment can easily reach toxic levels. In a process called methylation, Hg is transformed into a form that can be accumulated in the muscle and fatty tissue of fish. Accumulated levels of methylmercury become higher as the fish grow, and levels are magnified up the food web as larger fish eat smaller fish, a process called biomagnification. As a result, mercury concentrations in fish can be millions of times higher than in surrounding waters [1]. Fish advisories have been set

  14. Anion Partitioning and Ion-Pairing Behavior of Anions in the Extraction of Cesium Salts by 4,5?-bis(tert-octylbenzo)dibenzo-24-crown-8 in 1,2-Dichloroethane

    SciTech Connect (OSTI)

    Levitskaia, Tatiana G.; Maya, Leon; Van Berkel, Gary J.; Moyer, Bruce A.

    2007-01-01

    A systematic study of anion partitioning, anion selectivity, and ion-pairing was performed for an extraction of individual cesium salts into 1,2-dichloroethane (1,2-DCE) using 4,5?-bis(tert-octylbenzo)dibenzo-24-crown-8 host. Equilibrium constants corresponding to the extraction of ion pairs and dissociated ions, formation of the 1:1 cesium/crown complex, and dissociation of the ion pairs in water-saturated 1,2-DCE at 25 C were obtained from equilibrium modeling using the SXLSQI program. The standard Gibbs energy of partitioning between water and water-saturated 1,2-DCE was determined for picrate, permanganate, trifluoromethanesulfonate, methanesulfonate, trifluoroacetate, and acetate anions. The ion pairing behavior observed in the extraction experiments was shown to be consistent with the dissociation constant of the complex ion pair (Cs4,4?- bis(tert-octylbenzo)dibenzo-24-crown-8)+NO3 determined independently by conductance measurements. The cesium/crown complex cation exhibited a weak tendency toward ion pairing and no discrimination among the tested anions, as attributed to the large effective radius of the complex cation, in agreement with the Fuoss treatment of ion pairing. These results provide insight into the inclusion properties of the clefts formed by opposing arene rings of the crown ether upon encapsulation of the Cs+ ion, whose lack of anion recognition likely reflects the preferential inclusion of 1,2-DCE molecules in the clefts. Observed anion selectivity, which was ascribed to solvent-induced bias selectivity in preference of large charge-diffuse anions, was nearly the same whether cesium salts were extracted as dissociated ions or ion pairs.

  15. Anion Partitioning and Ion-Pairing Behavior of Anions in the Extraction of Cesium Salts by 4,5"-bix(tert-octylbenzo)dibenzo-24-crown-8 in 1,2-Dichloroethane

    SciTech Connect (OSTI)

    Levitskaia, Tatiana G.; Maya, Leon {nmn}; Van Berkel, Gary J; Moyer, Bruce A

    2007-01-01

    A systematic study of anion partitioning and ion-pairing was performed for an extraction of individual cesium salts into 1,2-dichloroethane (1,2-DCE) using 4,5"-bis(tert-octylbenzo)dibenzo-24-crown-8 as the cesium receptor. Equilibrium constants corresponding to the extraction of ion pairs and dissociated ions, formation of the 1:1 cesium/crown complex (confirmed by electrospray mass spectrometry), and dissociation of the ion pairs in water-saturated 1,2-DCE at 25 C were obtained from equilibrium modeling using the SXLSQI program. The standard Gibbs energy of partitioning between water and water-saturated 1,2-DCE was determined for picrate, permanganate, trifluoromethanesulfonate, methanesulfonate, trifluoroacetate, and acetate anions. The dissociation of the organic-phase complex ion pair [Cs(4,4"-bis(tert-octylbenzo)dibenzo-24-crown-8)]+NO3 observed in the extraction experiments was shown to be consistent with the dissociation constant determined independently by conductance measurements. As attributed to the large effective radius of the complex cation, the evident anion discrimination due to ion-pairing in the 1,2-DCE phase, was relatively small, by comparison only a tenth of the discrimination exhibited by the anion partitioning. Only chloride and picrate exhibit evidence for significantly greater-than-expected ion-pairing tendency. These results provide insight into the inclusion properties of the clefts formed by opposing arene rings of the crown ether upon encapsulation of the Cs+ ion, whose weak anion recognition likely reflects the preferential inclusion of 1,2-DCE molecules in the clefts. Observed anion extraction selectivity in this system, which may be ascribed predominantly to solvent-induced Hofmeister bias selectivity toward large charge-diffuse anions, was nearly the same whether cesium salts were extracted as dissociated ions or ion pairs.

  16. 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.

  17. 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.

  18. 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

  19. Phase 1 Methyl Iodide Deep-Bed Adsorption Tests (Technical Report...

    Office of Scientific and Technical Information (OSTI)

    Tests established detection limits, developed procedures for sample analysis with minimal analytical interferences, and confirmed earlier results that show that the methyl iodide ...

  20. 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 ?-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.

  1. 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.

  2. 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.

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

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

    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,moreand 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.less

  4. 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.

  5. 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)

  6. 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.

  7. 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.

  8. 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.

  9. 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

  10. 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.

  11. 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] ;

  12. 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

  13. 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) × You are accessing a document from the Department of Energy's (DOE) SciTech Connect.

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

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

    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

  15. 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.

  16. 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.

  17. 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.

  18. 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.

  19. 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)

  20. 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.

  1. Low Temperature Autoignition of C8H16O2 Ethyl and Methyl Esters in a

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

    Motored Engine | Department of Energy 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 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 PDF icon deer09_boehman.pdf More Documents & Publications Low

  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. 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. 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.

  5. 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.

  6. 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.

  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. 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).

  9. 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.

  10. 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.

  11. 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.

  12. 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.

  13. 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.

  14. 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)

  15. 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.

  16. 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.

  17. 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.

  18. 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

  19. 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.

  20. 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.

  1. 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.

  2. 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.

  3. 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.

  4. 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

  5. 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.

  6. 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.

  7. 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

  8. 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.

  9. 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.

  10. 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.

  11. 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.

  12. 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.

  13. 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)

  14. 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.

  15. 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).

  16. 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. Probing 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

  17. 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

  18. 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.

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

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

    Lipids as Fatty Acid Methyl Esters (FAME) by in situ Transesterification Laboratory Analytical Procedure (LAP) Issue Date: December 2, 2013 Revision Date: December 29, 2015 Stefanie Van Wychen, Kelsey Ramirez, and Lieve M.L. Laurens Technical Report NREL/TP-5100-60958 Revised December 2015 NREL is a national laboratory of the U.S. Department of Energy Office of Energy Efficiency & Renewable Energy Operated by the Alliance for Sustainable Energy, LLC This report is available at no cost from

  1. 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.

  2. 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.'

  3. 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.

  4. 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.

  5. 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.

  6. 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.

  7. (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.

  8. 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.

  9. 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 SiO 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 SiO 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.

  10. 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.

  11. 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.

  12. 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.

  13. 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.

  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. 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

  16. 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.

  17. 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.

  18. 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.

  19. 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.

  20. 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.

  1. 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.

  2. 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

  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. 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.

  5. 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 (

  6. 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.

  7. 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.

  8. 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.

  9. 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.

  10. 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.

  11. 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}.

  12. 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.

  13. 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. (Santa Fe, NM); Martinez, Rodolfo A. (Santa Fe, NM); Unkefer, Clifford J. (Los Alamos, NM)

    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.

  14. 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.

  15. 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.

  16. 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.

  17. 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.

  18. 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.

  19. 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.

  20. 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.

  1. 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)

  2. 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)...

  3. 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.

  4. 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 ...

  5. 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.

  6. High temperature concrete composites containing organosiloxane crosslinked copolymers

    DOE Patents [OSTI]

    Zeldin, Arkady; Carciello, Neal; Kukacka, Lawrence; Fontana, Jack

    1980-01-01

    This invention relates to high temperature polymer concrete composites comprising about 10-30% by weight of a liquid monomer mixture consisting essentially of an organosiloxane polymer crosslinked with an olefinically unsaturated monomer selected from the group consisting of styrene, methyl methacrylate, trimethylolpropane trimethacrylate, triallyl cyanurate, n-phenylmalimide, divinyl benzene and mixtures theroef; and about 70-90% by weight of an inert inorganic filler system containing silica sand and preferably a member selected from the group consisting of portland cement, Fe.sub.2 O.sub.3, carbon black and mixtures thereof; and optionally a free radical initiator such as di-tert-butyl peroxide, azobisisobutyronitrile, benzoyl peroxide, lauryl peroxide and other organic peroxides to initiate crosspolymerization of the monomer mixture in the presence of the inorganic filler.

  7. High temperature chemically resistant polymer concrete

    DOE Patents [OSTI]

    Sugama, T.; Kukacka, L.E.

    High temperature chemically resistant, non-aqueous polymer concrete composites consist of about 12 to 20% by weight of a water-insoluble polymer binder. The binder is polymerized in situ from a liquid vinyl-type monomer or mixture of vinyl containing monomers such as triallylcyanurate, styrene, acrylonitrile, acrylamide, methacrylamide, methyl-methacrylate, trimethylolpropane trimethacrylate and divinyl benzene. About 5 to 40% by weight of a reactive inorganic filler selected from the group consisting of tricalcium silicate and dicalcium silicate and mixtures containing less than 2% free lime, and about 48 to 83% by weight of silica sand/ and a free radical initiator such as di-tert-butyl peroxide, azobisisobutyronitrile, benzoyl peroxide, lauryl peroxide, other orgaic peroxides and combinations to initiate polymerization of the monomer in the presence of the inorganic filers are used.

  8. High temperature concrete composites containing organosiloxane crosslinked copolymers

    DOE Patents [OSTI]

    Zeldin, A.; Carciello, N.; Kukacka, L.; Fontana, J.

    High temperature polymer concrete composites comprising about 10 to 30% by weight of a liquid monomer mixture is described. It consists essentially of an organosiloxane polymer crosslinked with an olefinically unsaturated monomer selected from the group consisting of styrene, methyl methacrylate, trimethylolpropane trimethacrylate, triallyl cyanurate, n-phenylmalimide, divinyl benzene and mixtures thereof. About 70 to 90% by weight of an inert inorganic filler system containing silica sand and portland cement, Fe/sub 2/O/sub 3/, carbon black or mixtures thereof. Optionally a free radical initiator such as di-tert-butyl peroxide, azobisisobyutyronitrile, benzoyl peroxide, lauryl peroxide and other organic peroxides are used to initiate crosspolymerization of the monomer mixture in the presence of the inorganic filler.

  9. 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.

  10. 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.

  11. N-(N-[2-(3,5-Difluorophenyl)acetyl]-(S)-alanyl)-(S)-phenylglycine tert-butyl ester (DAPT): an inhibitor of ?-secretase, revealing fine electronic and hydrogen-bonding features

    SciTech Connect (OSTI)

    Czerwinski, Andrzej; Valenzuela, Francisco; Afonine, Pavel; Dauter, Miroslawa; Dauter, Zbigniew

    2010-12-01

    The title compound, C{sub 23}H{sub 26}F{sub 2}N{sub 2}O{sub 4}, is a dipeptidic inhibitor of ?-secretase, one of the enzymes involved in Alzheimers dis@@ease. The mol@@ecule adopts a compact conformation, without intra@@molecular hydrogen bonds. In the crystal structure, one of the amide N atoms forms the only inter@@molecular NH?O hydrogen bond; the second amide N atom does not form hydrogen bonds. High-resolution synchrotron diffraction data permitted the unequivocal location and refinement without restraints of all H atoms, and the identification of the characteristic shift of the amide H atom engaged in the hydrogen bond from its ideal position, resulting in a more linear hydrogen bond. Significant residual densities for bonding electrons were revealed after the usual SHELXL refinement, and modeling of these features as additional inter@@atomic scatterers (IAS) using the program PHENIX led to a significant decrease in the R factor from 0.0411 to 0.0325 and diminished the r.m.s. deviation level of noise in the final difference Fourier map from 0.063 to 0.037 e {sup ?3}.

  12. 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).

  13. 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.

  14. 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

  15. 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.

  16. 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.

  17. 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.

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

    Office of Scientific and Technical Information (OSTI)

    Authors: Nicoludis, John M. ; Miller, Stephen T. ; Jeffrey, Philip D. ; Barrett, Steven P. ; Rablen, Paul R. ; Lawton, Thomas J. ; Yatsunyk, Liliya A. 1 ; NWU) 2 ; Princeton) ...

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

    Office of Scientific and Technical Information (OSTI)

    the cell cycle and cell survival. Authors: Stanevich, Vitali ; Jiang, Li ; Satyshur, Kenneth A. ; Li, Yongfeng ; Jeffrey, Philip D. ; Li, Zhu ; Menden, Patrick ; Semmelhack, ...

  20. 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; Prez, Liliana; Corts, 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 ?g/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), 0.993.67), and 3.26 (1.766.04) (p-trend < 0.001). Corresponding odds ratios for bladder cancer were 1.00, 1.81 (1.063.11), and 2.02 (1.153.54) (p-trend < 0.001). In analyses confined to subjects only with arsenic water concentrations < 200 ?g/L (median = 60 ?g/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 (1.085.68) and 2.37 (1.015.57), 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 ?g/L.

  1. 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.

  2. 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.

  3. 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.

  4. 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.

  5. Conformations of organophosphine oxides

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

    De Silva, Nuwan; Zahariev, Federico; Hay, Benjamin P.; Gordon, Mark S.; Windus, Theresa L.

    2015-07-17

    The conformations of a series of organophosphine oxides, OP(CH3)2R, where R = methyl, ethyl, isopropyl, tert-butyl, vinyl, and phenyl, are predicted using the MP2/cc-pVTZ level of theory. Comparison of potential energy surfaces for rotation about P–C bonds with crystal structure data reveals a strong correlation between predicted location and energetics of minima and histograms of dihedral angle distributions observed in the solid state. In addition, the most stable conformers are those that minimize the extent of steric repulsion between adjacent rotor substituents, and the torsional barriers tend to increase with the steric bulk of the rotating alkyl group. MM3 forcemore » field parameters were adjusted to fit the MP2 results, providing a fast and accurate model for predicting organophosphine oxides shapes—an essential part of understanding the chemistry of these compounds. As a result, the predictive power of the modified MM3 model was tested against MP2/cc-pVTZ conformations for triethylphosphine oxide, OP(CH2CH3)3, and triphenylphosphine oxide, OP(Ph)3.« less

  6. 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.

  7. 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).

  8. 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)

  9. 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.

  10. 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.

  11. 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.

  12. 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.

  13. 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.

  14. 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.

  15. 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.

  16. Mixed N-Heterocyclic Carbene-Bis(oxazolinyl)borato Rhodium and Iridium Complexes in Photochemical and Thermal Oxidative Addition Reactions

    SciTech Connect (OSTI)

    Xu, Songchen; Manna, Kuntal; Ellern, Arkady; Sadow, Aaron D

    2014-12-08

    In order to facilitate oxidative addition chemistry of fac-coordinated rhodium(I) and iridium(I) compounds, carbenebis(oxazolinyl)phenylborate proligands have been synthesized and reacted with organometallic precursors. Two proligands, PhB(OxMe2)2(ImtBuH) (H[1]; OxMe2 = 4,4-dimethyl-2-oxazoline; ImtBuH = 1-tert-butylimidazole) and PhB(OxMe2)2(ImMesH) (H[2]; ImMesH = 1-mesitylimidazole), are deprotonated with potassium benzyl to generate K[1] and K[2], and these potassium compounds serve as reagents for the synthesis of a series of rhodium and iridium complexes. Cyclooctadiene and dicarbonyl compounds {PhB(OxMe2)2ImtBu}Rh(?4-C8H12) (3), {PhB(OxMe2)2ImMes}Rh(?4-C8H12) (4), {PhB(OxMe2)2ImMes}Rh(CO)2 (5), {PhB(OxMe2)2ImMes}Ir(?4-C8H12) (6), and {PhB(OxMe2)2ImMes}Ir(CO)2 (7) are synthesized along with ToMM(?4-C8H12) (M = Rh (8); M = Ir (9); ToM = tris(4,4-dimethyl-2-oxazolinyl)phenylborate). The spectroscopic and structural properties and reactivity of this series of compounds show electronic and steric effects of substituents on the imidazole (tert-butyl vs mesityl), effects of replacing an oxazoline in ToM with a carbene donor, and the influence of the donor ligand (CO vs C8H12). The reactions of K[2] and [M(?-Cl)(?2-C8H14)2]2 (M = Rh, Ir) provide {?4-PhB(OxMe2)2ImMes?CH2}Rh(?-H)(?-Cl)Rh(?2-C8H14)2 (10) and {PhB(OxMe2)2ImMes}IrH(?3-C8H13) (11). In the former compound, a spontaneous oxidative addition of a mesityl ortho-methyl to give a mixed-valent dirhodium species is observed, while the iridium compound forms a monometallic allyl hydride. Photochemical reactions of dicarbonyl compounds 5 and 7 result in CH bond oxidative addition providing the compounds {?4-PhB(OxMe2)2ImMes?CH2}RhH(CO) (12) and {PhB(OxMe2)2ImMes}IrH(Ph)CO (13). In 12, oxidative addition results in cyclometalation of the mesityl ortho-methyl similar to 10, whereas the iridium compound reacts with the benzene solvent to give a rare crystallographically characterized cis-[Ir](H)(Ph) complex. Alternatively, the rhodium carbonyl 5 or iridium isocyanide {PhB(OxMe2)2ImMes}Ir(CO)CNtBu (15) reacts with PhSiH3 in the dark to form the silyl compound {PhB(OxMe2)2ImMes}RhH(SiH2Ph)CO (14) or {PhB(OxMe2)2ImMes}IrH(SiH2Ph)CNtBu (17). These examples demonstrate the enhanced thermal reactivity of {PhB(OxMe2)2ImMes}-supported iridium and rhodium carbonyl compounds in comparison to tris(oxazolinyl)borate, tris(pyrazolyl)borate, and cyclopentadienyl-supported compounds.

  17. Numerical study of the effect of oxygenated blending compounds on soot formation in shock tubes

    SciTech Connect (OSTI)

    Boehm, H.; Braun-Unkhoff, M.

    2008-04-15

    This numerical study deals with the influence of blends on the amount of soot formed in shock tubes, which were simulated by assuming a homogeneous plug flow reactor model. For this purpose, first, the reaction model used here was validated against experimental results previously obtained in the literature. Then, the soot volume fractions of various mixtures of methyl tert-butyl ether (MTBE)-benzene, isobutene-benzene, methanol-benzene, and ethanol-benzene diluted in argon were simulated and compared to the results of benzene-argon pyrolysis at 1721 K and 5.4 MPa. For MTBE, isobutene, methanol, and ethanol, small amounts of additives to benzene-argon mixtures promoted soot formation, for the shock tube model assumed, while higher concentrations of these additives led to smaller soot volume fractions in comparison to pure benzene-argon pyrolysis. The most significant soot promotion effect was found for the additives MTBE and isobutene. The channel for MTBE decomposition producing isobutene and methanol is very effective at temperatures beyond 1200 K. Thus, both MTBE-benzene and isobutene-benzene mixtures diluted in argon showed rather similar behavior in regard to soot formation. Special emphasis was directed toward the causes for the concentration-dependent influence of the blends on the amount of soot formed. Aromatic hydrocarbons and acetylene were identified as key gas-phase species that determine the trends in the formation of soot of various mixtures. From reaction flux analysis for phenanthrene, it was deduced that the combinative routes including phenyl species play a major role in forming PAHs, especially at early reaction times. It is found that the additives play an important role in providing material to grow side chains, such as by reaction channels including phenylacetylene or benzyl, which are confirmed to form aromatic hydrocarbons and thus to influence the amount of soot formed, particularly when the concentrations of the blends are increased. (author)

  18. Solid-state polymerization of acrylamide and its derivatives complexed with some Lewis acids. II. Radiation-induced in-source polymerization

    SciTech Connect (OSTI)

    Zurakowska-Orszagh, J.; Mirowski, K.; Chajewski, A.

    1982-07-01

    Radiation-induced solid-state polymerizations of complexes of N-tert-butylacrylamide, N-tert-amylacrylamide, and N-tert-hexylacrylamide with zinc chloride and zinc bromide have been studied. An accelerating effect of temperature and an inhibiting effect of oxygen on the polymerization process were observed. The activation energies have been established. The influence of monomer structure as well as the halide used on the polymerization rate have been discussed and some regularities have been pointed out. The polymers obtained show good solubilities in common solvents, which proves that they are not crosslinked.

  19. Center for Energy Nanoscience at USC

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

    L. Improving open circuit potential in hybrid P3HT:CdSe bulk heterojunction solar cells via colloidal tert-butylthiol ligand exchange ACS Nano, 6(5), 4222-30 (2012). DOI:...

  20. I:PRCXFERZYSK9105691056R0F.PDF

    Office of Scientific and Technical Information (OSTI)

    ... is reversed in the case of 2-tert-butylnaphthalene. ... Table 6 shows some examples of the work where different ... The method for calculating the conversion of the aromatic ...

  1. 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.

  2. 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].

  3. 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. (Santa Fe, NM); Martinez, Rodolfo A. (Santa Fe, NM); Unkefer, Clifford J. (Los Alamos, NM)

    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.

  4. 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.

  5. Composition and method for encapsulating photovoltaic devices

    DOE Patents [OSTI]

    Pern, Fu-Jann

    2000-01-01

    A composition and method for encapsulating a photovoltaic device which minimizes discoloration of the encapsulant. The composition includes an ethylene-vinyl acetate encapsulant, a curing agent, an optional ultraviolet light stabilizer, and/or an optional antioxidant. The curing agent is preferably 1,1-di-(t-butylperoxy)-3,3,5-trimethylcyclohexane; the ultraviolet light stabilizer is bis-(N-octyloxy-tetramethyl) piperidinyl sebacate and the antioxidant is selected from the group consisting of tris (2,4-di-tert-butylphenyl) phosphite, tetrakis methylene (3,5-di-tert-butyl-4-hydroxyhydrocinnamate) methane, octadecyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate, and 2,2'-ethylidene bis(4,6-di-t-butylphenyl) fluorophosponite. The composition is applied to a solar cell then cured. The cured product contains a minimal concentration of curing-generated chromophores and resists UV-induced degradation.

  6. Leptin upregulates telomerase activity and transcription of human telomerase reverse transcriptase in MCF-7 breast cancer cells

    SciTech Connect (OSTI)

    Ren, He; Zhao, Tiansuo; Wang, Xiuchao; Gao, Chuntao; Wang, Jian; Yu, Ming; Hao, Jihui

    2010-03-26

    The aim was to analyze the mechanism of leptin-induced activity of telomerase in MCF-7 breast cancer cells. We found that leptin activated telomerase in a dose-dependent manner; leptin upregulated the expression of Human Telomerase Reverse Transcriptase (hTERT) at mRNA and protein levels; blockade of signal transducer and activator of transcription 3 (STAT3) phosphorylation significantly counteracted leptin-induced hTERT transcription and protein expression; chromatin immunoprecipitation analysis showed that leptin enhanced the binding of STAT3 to the hTERT promoter. This study uncovers a new mechanism of the proliferative effect of leptin on breast cancer cells and provides a new explanation of obesity-related breast cancer.

  7. EA-1157: Final Environmental Assessment

    Broader source: Energy.gov [DOE]

    Methyl Chloride via Oxyhydrochlorination of Methane: A Building Black for Chemicals and Fuels from Natural Gas

  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. Gas/solvent-induced transformation and expansion of a nonporous solid to 1:1 host guest form

    SciTech Connect (OSTI)

    Thallapally, Praveen K.; McGrail, B. Peter; Dalgarno, Scott J.; Atwood, Jerry L.

    2008-07-01

    Herein we report the gas (CO2, N2O and propane) and solvent (CS2 and acetone) induced transformation and expansion of guest free thermodynamic form of a p-tert-butylcalix [4]arene to 1:1 host guest form.

  10. Electrolyte Materials Available for Sampling | Argonne National...

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

    ANL-1S1M3 2,2-dimethyl-4,7,10,13-tetraoxa-2-silatetradecane Properties ANL-RS2 1,4-di-tert-butyl-2,5-bis(2-methoxyethoxy)benzene Properties ANL-RS5 (2,5-dimethoxy-1,4-phenyle...

  11. Variable dimensionality in the uranium fluoride/2-methyl-piperazine system: Synthesis and structures of UFO-5, -6, and -7; Zero-, one-, and two-dimensional materials with unprecedented topologies

    SciTech Connect (OSTI)

    Francis, R.J.; Halasyamani, P.S.; Bee, J.S.; O'Hare, D.

    1999-02-24

    Recently, low temperature (T < 300 C) hydrothermal reactions of inorganic precursors in the presence of organic cations have proven highly productive for the synthesis of novel solid-state materials. Interest in these materials is driven by the astonishingly diverse range of structures produced, as well as by their many potential materials chemistry applications. This report describes the high yield, phase pure hydrothermal syntheses of three new uranium fluoride phases with unprecedented structure types. Through the systematic control of the synthesis conditions the authors have successfully controlled the architecture and dimensionality of the phase formed and selectively synthesized novel zero-, one-, and two-dimensional materials.

  12. Detailed chemical kinetic mechanism for the oxidation of biodiesel fuels blend surrogate.

    SciTech Connect (OSTI)

    Herbinet, O; Pitz, W J; Westbrook, C K

    2009-07-21

    Detailed chemical kinetic mechanisms were developed and used to study the oxidation of two large unsaturated esters: methyl-5-decenoate and methyl-9-decenoate. These models were built from a previous methyl decanoate mechanism and were compared with rapeseed oil methyl esters oxidation experiments in a jet stirred reactor. A comparative study of the reactivity of these three oxygenated compounds was performed and the differences in the distribution of the products of the reaction were highlighted showing the influence of the presence and the position of a double bond in the chain. Blend surrogates, containing methyl decanoate, methyl-5-decenoate, methyl-9-decenoate and n-alkanes, were tested against rapeseed oil methyl esters and methyl palmitate/n-decane experiments. These surrogate models are realistic kinetic tools allowing the study of the combustion of biodiesel fuels in diesel and homogeneous charge compression ignition engines.

  13. Detailed chemical kinetic mechanism for the oxidation of biodiesel fuels blend surrogate

    SciTech Connect (OSTI)

    Herbinet, Olivier; Pitz, William J.; Westbrook, Charles K.

    2010-05-15

    Detailed chemical kinetic mechanisms were developed and used to study the oxidation of two large unsaturated esters: methyl-5-decenoate and methyl-9-decenoate. These models were built from a previous methyl decanoate mechanism and were compared with rapeseed oil methyl esters oxidation experiments in a jet-stirred reactor. A comparative study of the reactivity of these three oxygenated compounds was performed and the differences in the distribution of the products of the reaction were highlighted showing the influence of the presence and the position of a double bond in the chain. Blend surrogates, containing methyl decanoate, methyl-5-decenoate, methyl-9-decenoate and n-alkanes, were tested against rapeseed oil methyl esters and methyl palmitate/n-decane experiments. These surrogate models are realistic kinetic tools allowing the study of the combustion of biodiesel fuels in diesel and homogeneous charge compression ignition engines. (author)

  14. Brain Receptor Structures Key to Future Therapeutics

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

    AMPA, -amino-3-hydroxy-5-methyl-4-isoxazolepropionic acid; and NMDA, N-methyl-D-aspartate. The receptors used in the studies-from the Norwegian rat and the frog Xenopus...

  15. Slide 1

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

    Dr. Michele Pavone : NSF, A*STAR, DOE-BES See Victor Oyeyemi's poster today Common biodiesel derived from rapeseed oil and soybeans: Methyl esters (R(CO)OCH 3 ): methyl...

  16. Method for epoxy foam production using a liquid anhydride

    DOE Patents [OSTI]

    Celina, Mathias (Albuquerque, NM)

    2012-06-05

    An epoxy resin mixture with at least one epoxy resin of between approximately 50 wt % and 100 wt %, an anhydride cure agent of between approximately 0 wt % and approximately 50 wt %, a tert-butoxycarbonyl anhydride foaming agent of between proximately 0.1-20 wt %, a surfactant and an imidazole or similar catalyst of less than approximately 2 wt %, where the resin mixture is formed from at least one epoxy resin with a 1-10 wt % tert-butoxycarbonyl anhydride compound and an imidazole catalyst at a temperature sufficient to keep the resin in a suitable viscosity range, the resin mixture reacting to form a foaming resin which in the presence of an epoxy curative can then be cured at a temperature greater than 50.degree. C. to form an epoxy foam.

  17. 1

    Office of Environmental Management (EM)

    Tetrachloroethylene, Trichloroethylene, Trichloroflouromethane, Acetone, Ethyl ether, Methanol, Methyl isobutyl ketone, n-Butyl alcohol, Xylene, Cresols, Cresylic acid,...

  18. 1

    Office of Environmental Management (EM)

    Tetrachloroethylene; Trichloroethylene; Trichloroflouromethane; Acetone; Ethyl ether; Methanol; Methyl isobutyl ketone; n-Butyl alcohol; Xylene; Cresols; Cresylic acid;...

  19. 1

    Office of Environmental Management (EM)

    Tetrachloroethylene; Trichloroethylene; Trichloroflouromethane; Acetone; Ethyl ether; Methanol; Methyl isobutyl ketone; n-Butyl alcohol; Xylene; 2- Ethoxyethanol; 2-Nitropropane;...

  20. 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.

  1. Development of Effective Solvent Modifiers for the Solvent Extraction of Cesium from Alkaline High-Level Tank Waste.

    SciTech Connect (OSTI)

    Bonnesen, Peter V.; Delmau, Laetitia H.; Moyer, Bruce A.; Lumetta, Gregg J. )

    2003-01-01

    A series of novel alkylphenoxy fluorinated alcohols were prepared and investigated for their effectiveness as modifiers in solvents containing calix[4]arene-bis-(tert-octylbenzo)-crown-6 for extracting cesium from alkaline nitrate media. A modifier that contained a terminal 1,1,2,2-tetrafluoroethoxy group was found to decompose following long-term exposure to warm alkaline solutions. However, replacement of the tetrafluoroethoxy group with a 2,2,3,3-tetrafluoropropoxy group led to a series of modifiers that possessed the alkaline stability required for a solvent extraction process. Within this series of modifiers, the structure of the alkyl substituent (tert-octyl, tert-butyl, tert-amyl, and sec-butyl) of the alkylphenoxy moiety was found to have a profound impact on the phase behavior of the solvent in liquid-liquid contacting experiments, and hence on the overall suitability of the modifier for a solvent extraction process. The sec-butyl derivative[1-(2,2,3,3-tetrafluoropropoxy)-3-(4-sec-butylphenoxy)-2-propanol] (Cs-7SB) was found to possess the best overall balance of properties with respect to third phase and coalescence behavior, cleanup following degradation, resistance to solids formation, and cesium distribution behavior. Accordingly, this modifier was selected for use as a component of the solvent employed in the Caustic-Side Solvent Extraction (CSSX) process for removing cesium from high level nuclear waste (HLW) at the U.S. Department of Energy?s (DOE) Savannah River Site. In batch equilibrium experiments, this solvent has also been successfully shown to extract cesium from both simulated and actual solutions generated from caustic leaching of HLW tank sludge stored in tank B-110 at the DOE?s Hanford Site.

  2. Diffusion of vaporous guests into a seemingly non-porous organic crystal

    SciTech Connect (OSTI)

    Herbert, Simon A.; Janiak, Agnieszka; Thallapally, Praveen K.; Atwood, Jerry L.; Barbour, Leonard J.

    2014-10-07

    In this research, the tetragonal apohost phase of p-tert-butyltetramethoxythiacalix[4]arene absorbs hydrochloric acid and iodine. These guest molecules occupy different sites in the solid-state structure -- either within the small intrinsic voids of the macrocycle or within the interstitial spaces between the host molecules. This study illustrates the dynamic deformation of the host, providing strong mechanistic insight into the diffusion of guests into this seemingly non-porous material.

  3. Diffusion of vaporous guests into a seemingly non-porous organic crystal

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

    Herbert, Simon A.; Janiak, Agnieszka; Thallapally, Praveen K.; Atwood, Jerry L.; Barbour, Leonard J.

    2014-10-07

    In this research, the tetragonal apohost phase of p-tert-butyltetramethoxythiacalix[4]arene absorbs hydrochloric acid and iodine. These guest molecules occupy different sites in the solid-state structure -- either within the small intrinsic voids of the macrocycle or within the interstitial spaces between the host molecules. This study illustrates the dynamic deformation of the host, providing strong mechanistic insight into the diffusion of guests into this seemingly non-porous material.

  4. Pseudo-hydroxide extraction in the separation of sodium hydroxide from aqueous solutions using alkyl phenols

    SciTech Connect (OSTI)

    Kang, Hyun Ah; Moyer, Bruce A

    2006-01-01

    Pseudo-hydroxide extraction of sodium hydroxide from aqueous solution using four alkyl phenols of nearly identical molecular weight in 1-octanol at 25 degrees C was examined to understand the effect of alkyl substituents. The order of extraction strength among the four alkyl phenols tested was 4-tert-octylphenol. 3,5-di-tertbutylphenol. 2,4-di-tert-butylphenol. 2,6-di-tert-butyl-4-methylphenol. A good correlation with phenol pK(a) was observed, indicating that extraction strength is determined by phenol acidity, as modified by steric effects in proximity to the phenol - OH group. The effective partition ratios (P-eff) of two phenols from 1 M NaOH solution were determined, showing that the phenols remain predominantly in the 1-octanol phase even when converted to their sodium salts. However, the hydrophobicity of the tested phenols may not be sufficient for process purposes. The equilibrium constants for the governing extraction equilibria were determined by modeling the data using the program SXLSQI, supporting the cation-exchange extraction mechanism. The proposed mechanism consists of two simple sets of equilibria for a. Ion-pair extraction to give Na+OH- ion pairs and corresponding free ions in 1-octanol the phase and b. Cation exchange by monomeric phenol molecules (HAs) to form monomeric organic-phase Na(+)A(-) ion pairs and corresponding free organic-phase ions.

  5. Epigenomics of Development in Populus

    SciTech Connect (OSTI)

    Strauss, Steve; Freitag, Michael; Mockler, Todd

    2013-01-10

    We conducted research to determine the role of epigenetic modifications during tree development using poplar (Populus trichocarpa), a model woody feedstock species. Using methylated DNA immunoprecipitation (MeDIP) or chromatin immunoprecipitation (ChIP), followed by high-throughput sequencing, we are analyzed DNA and histone methylation patterns in the P. trichocarpa genome in relation to four biological processes: bud dormancy and release, mature organ maintenance, in vitro organogenesis, and methylation suppression. Our project is now completed. We have 1) produced 22 transgenic events for a gene involved in DNA methylation suppression and studied its phenotypic consequences; 2) completed sequencing of methylated DNA from eleven target tissues in wildtype P. trichocarpa; 3) updated our customized poplar genome browser using the open-source software tools (2.13) and (V2.2) of the P. trichocarpa genome; 4) produced summary data for genome methylation in P. trichocarpa, including distribution of methylation across chromosomes and in and around genes; 5) employed bioinformatic and statistical methods to analyze differences in methylation patterns among tissue types; and 6) used bisulfite sequencing of selected target genes to confirm bioinformatics and sequencing results, and gain a higher-resolution view of methylation at selected genes 7) compared methylation patterns to expression using available microarray data. Our main findings of biological significance are the identification of extensive regions of the genome that display developmental variation in DNA methylation; highly distinctive gene-associated methylation profiles in reproductive tissues, particularly male catkins; a strong whole genome/all tissue inverse association of methylation at gene bodies and promoters with gene expression; a lack of evidence that tissue specificity of gene expression is associated with gene methylation; and evidence that genome methylation is a significant impediment to tissue dedifferentiation and redifferentiation in vitro.

  6. Synthesis and tribological behavior of silicon oxycarbonitride thin films

    Office of Scientific and Technical Information (OSTI)

    derived from poly(urea)methyl vinyl silazane. (Journal Article) | SciTech Connect Journal Article: Synthesis and tribological behavior of silicon oxycarbonitride thin films derived from poly(urea)methyl vinyl silazane. Citation Details In-Document Search Title: Synthesis and tribological behavior of silicon oxycarbonitride thin films derived from poly(urea)methyl vinyl silazane. No abstract prepared. Authors: Prasad, Somuri V. ; Tallant, David Robert ; Raj, Rishi [1] ; Cross, Tsali + Show

  7. Search for: All records | SciTech Connect

    Office of Scientific and Technical Information (OSTI)

    sequencing, we are analyzed DNA and histone methylation patterns in the P. trichocarpa genome in relation to four biological processes: bud dormancy and release, mature organ...

  8. 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.

  9. The Feasibility of Producing and Using Biomass-Based Diesel and...

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

    in demonstrational stage; others are still in the research and development phase. 2. Biodiesel, consisting of fatty acid methyl esters (FAME) produced from lipids (fats, oils, and...

  10. 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...

  11. 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...

  12. 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...

  13. 1

    Office of Environmental Management (EM)

    Ethyl benzene, Ethyl ether, Methyl Isobutyl Ketone, n-Butyl alcohol, Cyclohexanone, Methanol, Cresols, Cresylic acid, Nitrobenzene, Toluene, Carbon disulfide, Isobutanol,...

  14. Deep Bed Iodine Sorbent Testing FY 2011 Report (Technical Report...

    Office of Scientific and Technical Information (OSTI)

    prior testing, and due to a period of maintenance for the on-line GC. Each test consisted ... PRODUCTS; GASES; IODINE; ISOTHERMS; MAINTENANCE; MASS TRANSFER; METHYL IODIDE; NUCLEAR ...

  15. Transesterification: Laboratory Analytical Procedure (LAP) Van...

    Office of Scientific and Technical Information (OSTI)

    Wychen, S.; Laurens, L. M. L. 09 BIOMASS FUELS; 59 BASIC BIOLOGICAL SCIENCES BIOMASS; ALGAE; LABORATORY ANALYTICAL PROCEDURES; LAPS; TOTAL LIPIDS; FATTY ACID METHYL ESTERS; FAME;...

  16. "Title","Creator/Author","Publication Date","OSTI Identifier...

    Office of Scientific and Technical Information (OSTI)

    Bioenergy Technologies Office","09 BIOMASS FUELS; 59 BASIC BIOLOGICAL SCIENCES BIOMASS; ALGAE; LABORATORY ANALYTICAL PROCEDURES; LAPS; TOTAL LIPIDS; FATTY ACID METHYL ESTERS; FAME;...

  17. TITLE AUTHORS SUBJECT SUBJECT RELATED DESCRIPTION PUBLISHER AVAILABILI...

    Office of Scientific and Technical Information (OSTI)

    LAP Van Wychen S Laurens L M L BIOMASS FUELS BASIC BIOLOGICAL SCIENCES BIOMASS ALGAE LABORATORY ANALYTICAL PROCEDURES LAPS TOTAL LIPIDS FATTY ACID METHYL ESTERS FAME...

  18. 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...

  19. 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...

  20. The Y-12 Times, Vol. 9, No. 8, August 2009

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

    Infrastructure and Services; Engineering; Quality; Projects; Environment, Safety ... Because methyl mercury concentrations in fi sh tissue remain above the U.S. Environmental ...

  1. Prediction of epigenetically regulated genes in breast cancer cell lines

    SciTech Connect (OSTI)

    Loss, Leandro A; Sadanandam, Anguraj; Durinck, Steffen; Nautiyal, Shivani; Flaucher, Diane; Carlton, Victoria EH; Moorhead, Martin; Lu, Yontao; Gray, Joe W; Faham, Malek; Spellman, Paul; Parvin, Bahram

    2010-05-04

    Methylation of CpG islands within the DNA promoter regions is one mechanism that leads to aberrant gene expression in cancer. In particular, the abnormal methylation of CpG islands may silence associated genes. Therefore, using high-throughput microarrays to measure CpG island methylation will lead to better understanding of tumor pathobiology and progression, while revealing potentially new biomarkers. We have examined a recently developed high-throughput technology for measuring genome-wide methylation patterns called mTACL. Here, we propose a computational pipeline for integrating gene expression and CpG island methylation profles to identify epigenetically regulated genes for a panel of 45 breast cancer cell lines, which is widely used in the Integrative Cancer Biology Program (ICBP). The pipeline (i) reduces the dimensionality of the methylation data, (ii) associates the reduced methylation data with gene expression data, and (iii) ranks methylation-expression associations according to their epigenetic regulation. Dimensionality reduction is performed in two steps: (i) methylation sites are grouped across the genome to identify regions of interest, and (ii) methylation profles are clustered within each region. Associations between the clustered methylation and the gene expression data sets generate candidate matches within a fxed neighborhood around each gene. Finally, the methylation-expression associations are ranked through a logistic regression, and their significance is quantified through permutation analysis. Our two-step dimensionality reduction compressed 90% of the original data, reducing 137,688 methylation sites to 14,505 clusters. Methylation-expression associations produced 18,312 correspondences, which were used to further analyze epigenetic regulation. Logistic regression was used to identify 58 genes from these correspondences that showed a statistically signifcant negative correlation between methylation profles and gene expression in the panel of breast cancer cell lines. Subnetwork enrichment of these genes has identifed 35 common regulators with 6 or more predicted markers. In addition to identifying epigenetically regulated genes, we show evidence of differentially expressed methylation patterns between the basal and luminal subtypes. Our results indicate that the proposed computational protocol is a viable platform for identifying epigenetically regulated genes. Our protocol has generated a list of predictors including COL1A2, TOP2A, TFF1, and VAV3, genes whose key roles in epigenetic regulation is documented in the literature. Subnetwork enrichment of these predicted markers further suggests that epigenetic regulation of individual genes occurs in a coordinated fashion and through common regulators.

  2. Search for: All records | SciTech Connect

    Office of Scientific and Technical Information (OSTI)

    ... Tests established detection limits, developed procedures for sample analysis with minimal analytical interferences, and confirmed earlier results that show that the methyl iodide ...

  3. Microsoft Word - Stern_Sorek_Bioessays_revised.doc

    Office of Scientific and Technical Information (OSTI)

    ... Accordingly, all non-methylated DNA recognition sequences are recognized as foreign and are cleaved. Genetically, the minimal composition of RM systems consists of a ...

  4. DEVELOPMENT OF ALTERNATIVE FUELS AND CHEMICALS FROM SYNTHESIS GAS

    SciTech Connect (OSTI)

    Peter J. Tijrn

    2003-05-31

    This Final Report for Cooperative Agreement No. DE-FC22-95PC93052, the ''Development of Alternative Fuels and Chemicals from Synthesis Gas,'' was prepared by Air Products and Chemicals, Inc. (Air Products), and covers activities from 29 December 1994 through 31 July 2002. The overall objectives of this program were to investigate potential technologies for the conversion of synthesis gas (syngas), a mixture primarily of hydrogen (H{sub 2}) and carbon monoxide (CO), to oxygenated and hydrocarbon fuels and industrial chemicals, and to demonstrate the most promising technologies at the LaPorte, Texas Alternative Fuels Development Unit (AFDU). Laboratory work was performed by Air Products and a variety of subcontractors, and focused on the study of the kinetics of production of methanol and dimethyl ether (DME) from syngas, the production of DME using the Liquid Phase Dimethyl Ether (LPDME{trademark}) Process, the conversion of DME to fuels and chemicals, and the production of other higher value products from syngas. Four operating campaigns were performed at the AFDU during the performance period. Tests of the Liquid Phase Methanol (LPMEOH{trademark}) Process and the LPDME{trademark} Process were made to confirm results from the laboratory program and to allow for the study of the hydrodynamics of the slurry bubble column reactor (SBCR) at a significant engineering scale. Two campaigns demonstrated the conversion of syngas to hydrocarbon products via the slurry-phase Fischer-Tropsch (F-T) process. Other topics that were studied within this program include the economics of production of methyl tert-butyl ether (MTBE), the identification of trace components in coal-derived syngas and the means to economically remove these species, and the study of systems for separation of wax from catalyst in the F-T process. The work performed under this Cooperative Agreement has continued to promote the development of technologies that use clean syngas produced from any one of a variety of sources (including coal) for the production of a spectrum of alternative fuels (hydrocarbons and oxygenate fuels), octane enhancers, and chemicals and chemical intermediates. In particular, the data from the 1995 LPMEOH{trademark} campaign provided confirmation of assumptions used in the design of the catalyst reduction system at the Kingsport LPMEOH{trademark} Commercial Demonstration Project, and the alternate methanol catalyst has been in use there since late 1998. The kinetic model was also expanded to allow for more accurate prediction of methanol production and carbon dioxide (CO{sub 2}) conversion, and more accurate modeling of by-product formation for the alternate methanol catalyst. The outstanding performance results of the LPMEOH{trademark} Process at Kingsport can be attributed in large part to the body of work performed since 1981 in collaboration between the U.S. Department of Energy (DOE) and Air Products. In addition, a pilot-plant-tested LPDME{trademark} Process has been demonstrated, and the product cost of DME from coal-derived syngas can be competitive in certain locations and applications. The need for liquid fuels will continue to be a critical concern for this nation in the 21st century. Efforts are needed to ensure the development and demonstration of economically competitive, efficient, environmentally responsible technologies that produce clean fuels and chemicals from coal under DOE's Vision 21 concept. These liquids will be a component of the fuel mix that will provide the transition from the current reliance on carbon-based fuels to the ultimate use of H{sub 2} as a means of energy transport. Indirect liquefaction, which converts the syngas (H{sub 2} and CO) produced by the gasification of coal to sulfur- and nitrogen-free liquid products, is a key component of the Vision 21 initiative. The results from this current program provide continued support to the objectives for the conversion of domestic coal to electric power and co-produced clean liquid fuels and chemicals in an environmentally superior manner.

  5. Sol-spray preparation, particulate characteristics, and sintering of alumina powders

    SciTech Connect (OSTI)

    Varma, H.K.; Mani, T.V.; Damodaran, A.D.; Warrier, K.G.K.; Balachandran, U.

    1993-07-01

    Fine alumina powders of spherical morphology and narrow particle-size distribution have been synthesized by a technique that uses precipitation/peptization/spray drying of boehmite sol prepared from aluminum nitrate. The spray-dried powder was further washed with solvents of varying polarities, such as acetone, isopropanol, and tert-butanol. This post-spray-drying treatment changed the powder`s particle-size distribution, morphology, density, and compaction characteristics. Microstructure, dielectric properties, and effect of post-treatment on the boehmite-sol-derived alumina powders in reducing agglomeration are discussed.

  6. Crystalline mesoporous zirconia catalysts having stable tetragonal pore wall structure

    DOE Patents [OSTI]

    Sachtler, W.M.H.; Huang, Y.Y.

    1998-07-28

    Methods are disclosed for the preparation of new sulfated mesoporous zirconia materials/catalysts with crystalline pore walls of predominantly tetragonal crystal structure, characterized by nitrogen physical sorption measurement, X-ray diffraction, transmission electron microscopy and catalytic tests using n-butane isomerization to iso-butane and alkylation of 1-naphthol with 4-tert-butylstyrene as probe reactions. Sulfate deposition is preferred for the transformation of a mesoporous precursor with amorphous pore walls into a material with crystalline pore walls maintaining the mesoporous characteristics. 17 figs.

  7. Crystalline mesoporous zirconia catalysts having stable tetragonal pore wall structure

    DOE Patents [OSTI]

    Sachtler, Wolfgang M. H.; Huang, Yin-Yan

    1998-01-01

    Methods for the preparation of new sulfated mesoporous zirconia materials/catalysts with crystalline pore walls of predominantly tetragonal crystal structure, characterized by nitrogen physisorption measurement, X-ray diffraction, transmission electron microscopy and catalytic tests using n-butane isomerization to iso-butane and alkylation of 1-naphthol with 4-tert-butylstyrene as probe reactions. Sulfate deposition is preferred for the transformation of a mesoporous precursor with amorphous pore walls into a material with crystalline pore walls maintaining the mesoporous characteristics.

  8. Dye system for dye laser applications

    DOE Patents [OSTI]

    Hammond, Peter R.

    1991-01-01

    A dye of the DCM family, [2-methyl-6-[2-(1,2,3,4-tetrahydro-1-methyl-6-quinolinyl)ethenyl]-4H-pyran -4-ylidene]-propanedinitrile, dissolved in 2-phenoxyethanol, is non-mutagenic, stable and efficient, particularly in a pumped continuous wave laser system.

  9. Nonaqueous polypyrrole colloids

    DOE Patents [OSTI]

    Armes, Steven P. (Los Alamos, NM); Aldissi, Mahmoud (Santa Fe, NM)

    1991-01-01

    Processable conductive polymers including an oxidized, polymerized aromatic heterocyclic monomer, e.g., pyrrole, an stabilizing effective amount of a poly(vinyl acetate) and dopant anions, and a process of preparing said processable conductive polymers directly in a nonaqueous medium such as methyl acetate, methyl formate, ethyl formate, and propyl formate are disclosed.

  10. Spatiotemporal temperature and density characterization of high-power

    Office of Scientific and Technical Information (OSTI)

    atmospheric flashover discharges over inert poly(methyl methacrylate) and energetic pentaerythritol tetranitrate dielectric surfaces (Journal Article) | SciTech Connect Spatiotemporal temperature and density characterization of high-power atmospheric flashover discharges over inert poly(methyl methacrylate) and energetic pentaerythritol tetranitrate dielectric surfaces Citation Details In-Document Search Title: Spatiotemporal temperature and density characterization of high-power atmospheric

  11. Henry's law constants for paint solvents and their implications on volatile organic compound emissions from automotive painting

    SciTech Connect (OSTI)

    Kim, B.R.; Kalis, E.M.; DeWulf, T.; Andrews, K.M.

    2000-02-01

    This paper describes experimental results of equilibrium partitioning of several significant paint solvents and formaldehyde between air and water to quantify the potential for capturing and retaining the constituents in spraybooth scrubber water during automotive painting. The compounds studied are toluene, n-butanol, methyl ethyl ketone methyl propyl ketone, methyl isobutyl ketone, methyl amyl ketone, butyl cellosolve, butyl cellosolve acetate, butyl carbitol, and n-methyl-2-pyrrolidinone. A set of field data collected at a Ford Motor Company assembly plant was also analyzed to determine whether data were consistent with the equilibrium phenomenon. The primary findings include: (a) There were more than six orders of magnitude difference in the Henry's law constants among the solvents studied. A solvent with a smaller constant is less easily stripped from water. The Henry's law constants decrease in the following order: toluene and xylenes > methyl ethyl ketone > n-butanol > butyl cellosolve acetate > butyl cellosolve > formaldehyde > butyl carbitol > n-methyl-2-pyrrolidinone. (b) Field data showed accumulation of n-methyl-2-pyrrolidinone and stable concentrations of butyl carbitol, butyl cellosolve, and n-butanol in the paint-sludge pit water during a 2-month period. Stable concentrations indicate a continuous, balanced capture and stripping of the solvents. Data were consistent with measured Henry's law constants. (c) The low Henry's law constant for formaldehyde is the result of the fact that it is hydrated when dissolved in water.

  12. How the Membrane Protein AmtB Transports Ammonia

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

    were grown in the absence of any ammonium derivative and in the presence of ammonium sulfate or methyl ammonium sulfate. A stereo view of the monomeric ammonia channel viewed...

  13. Stanford Synchrotron Radiation Lightsource

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

    as a dissociative anesthetic acting as a noncompetitive antagonist on the N-methyl-D-aspartate (NMDA) receptor, it is also a potent inhibitor of neuronal nAChRs, and the sites of...

  14. Search for: All records | SciTech Connect

    Office of Scientific and Technical Information (OSTI)

    ... ; Anzai, Yojiro ; Kato, Fumio ; Sherman, David H. ; Smith, Janet L. ; Toho) O-linked ... The first methylation is catalyzed by MycE, a SAM- and metal-dependent MT. Crystal ...

  15. SSRL HEADLINES December 2009

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

    by Joy Andrews of SSRL studied mercury uptake and methylation in the rhizospheres of two common plant species in the San Francisco Bay. They used a combination of experiments to...

  16. This Week In Petroleum Printer-Friendly Version

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

    2, 2009 (Next Release on April 29, 2009) Accounting for Biodiesel Methyl Esters? No, it is not the name of the lead in a John Waters film, or of some gun-toting moll from 1940s...

  17. 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...

  18. Molecular Design of Near-IR Harvesting Unsymmetrical Squaraine Dyes

    SciTech Connect (OSTI)

    Kim, Sanghoon; Mor, Gopal K.; Paulose, Maggie; Varghese, Oomman K.; Baik, Chul; Grimes, Craig A.

    2010-08-17

    The functionalized unsymmetrical benzothiazole squaraine organic sensitizers 5-carboxy-2-({3-[(3-hexylbenzothiazol-2(3H)-ylidene)methyl]-2-hydroxy-4-oxo-2-cyclobuten-1-ylidene}methyl)-1-hexyl-3,3-dimethyl-3H-indolium (hereafter named as SK-11) and 5-carboxy-2-({3-[(3-hexyl-5-methoxybenzothiazol-2(3H)-ylidene)methyl]-2-hydroxy-4-oxo-2-cyclobuten-1-ylidene}methyl)-1-hexyl-3,3-dimethyl-3H-indolium (coded as SK-12) are designed and developed to observe an intense and wider absorption band in the red/NIR wavelength region. DFT/TDDFT calculations have been performed on the two unsymmetrical squaraine sensitizers to gain insight into their electronic and optical properties. The utility of these dyes in solid state dye sensitized solar cells (SS-DSSCs) is demonstrated.

  19. UCRL--53232

    Office of Scientific and Technical Information (OSTI)

    received f a r less scrutiny than t h e effects caused by t h e ingestion of foods (e+, fish and seed grains) contaminated with t h e methylated form of mercury. 63764...

  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. PULSE COLUMN DESIGN By Lawrence E. Burkhart R.W. Fahien

    Office of Scientific and Technical Information (OSTI)

    EXPERIMENTAL RESUITS 63 Hold-up Studies 63 The isoaiiyl alcohol-water system 63 The methyl isobutyl ketone-water system 72 Discussion of Hold-up Data 78 Extraction Studies 80 ...

  2. A Surprising Path for Proton Transfer Without Hydrogen Bonds

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

    9.0.2. To examine how the molecules were bonded, the team first created a gaseous molecular beam of methylated uracil monomers and dimers, then ionized them with vacuum...

  3. Monolignol 4-O-methyltransferases and uses thereof

    DOE Patents [OSTI]

    Liu, Chang-Jun; Bhuiya, Mohammad-Wadud; Zhang, Kewei

    2014-11-18

    Modified (iso)eugenol 4-O-methyltransferase enzymes having novel capacity for methylation of monolignols and reduction of lignin polymerization in plant cell wall are disclosed. Sequences encoding the modified enzymes are disclosed.

  4. Radical Compatibility with Nonaqueous Electrolytes and Its Impact on an All-Organic Redox Flow Battery

    SciTech Connect (OSTI)

    Wei, Xiaoliang; Xu, Wu; Huang, Jinhua; Zhang, Lu; Walter, Eric D.; Lawrence, Chad W.; Vijayakumar, M.; Henderson, Wesley A.; Liu, Tianbiao L.; Cosimbescu, Lelia; Li, Bin; Sprenkle, Vincent L.; Wang, Wei

    2015-07-20

    Nonaqueous redox flow batteries hold the promise to achieve higher energy density ascribed to the broader voltage window than their aqueous counterparts, but their current performance is limited by low redox material concentration, poor cell efficiency, and inferior cycling stability. We report a new nonaqueous total-organic flow battery based on high concentrations of 9-fluorenone as negative and 2,5-di-tert-butyl-1-methoxy-4-[2’-methoxyethoxy]benzene as positive redox materials. The supporting electrolytes are found to greatly affect the cycling stability of flow cells through varying chemical stabilities of the charged radical species, especially the 9-fluorenone radical anions, as confirmed by electron spin resonance. Such an electrolyte optimization sheds light on mechanistic understandings of capacity fading in flow batteries employing organic radical-based redox materials and demonstrates that rational design of supporting electrolyte is vital for stable cyclability.

  5. Polymer concrete composites for the production of high strength pipe and linings in high temperature corrosive environments

    DOE Patents [OSTI]

    Zeldin, A.; Carciello, N.; Fontana, J.; Kukacka, L.

    High temperature corrosive resistant, non-aqueous polymer concrete composites are described. They comprise about 12 to 20% by weight of a water-insoluble polymer binder polymerized in situ from a liquid monomer mixture consisting essentially of about 40 to 70% by weight of styrene, about 25 to 45% by weight acrylonitrile and about 2.5 to 7.5% by weight acrylamide or methacrylamide and about 1 to 10% by weight of a crosslinking agent. This agent is selected from the group consisting of trimethylolpropane trimethacrylate and divinyl benzene; and about 80 to 88% by weight of an inert inorganic filler system containing silica sand and portland cement, and optionally Fe/sub 2/O/sub 3/ or carbon black or mica. A free radical initiator such as di-tert-butyl peroxide, azobisisobutyronitrile, benzoyl peroxide, lauryl peroxide, other organic peroxides and combinations thereof to initiate crosspolymerization of the monomer mixture in the presence of said inorganic filler.

  6. Combined Extraction of Cesium and Strontium from Akaline Nitrate Solutions

    SciTech Connect (OSTI)

    Delmau, Laetitia Helene; Bonnesen, Peter V; Engle, Nancy L; Haverlock, Tamara; Sloop Jr, Frederick {Fred} V; Moyer, Bruce A

    2006-01-01

    The combined extraction of cesium and strontium from caustic wastes can be achieved by adding a crown ether and a carboxylic acid to the Caustic-Side Solvent Extraction (CSSX) solvent. The ligand 4,4'(5')-di(tert-butyl)cyclohexano-18-crown-6 and one of four different carboxylic acids were combined with the components of the CSSX solvent optimized for the extraction of cesium, allowing for the simultaneous extraction of cesium and strontium from alkaline nitrate media simulating alkaline high level wastes present at the U.S. Department of Energy Savannah River Site. Extraction and stripping experiments were conducted independently and exhibited adequate results for mimicking waste simulant processing through batch contacts. The promising results of these batch tests showed that the system could reasonably be tested on actual waste.

  7. High pressure chemistry of substituted acetylenes

    SciTech Connect (OSTI)

    Chellappa, Raja; Dattelbaum, Dana; Sheffield, Stephen; Robbins, David

    2011-01-25

    High pressure in situ synchrotron x-ray diffraction experiments were performed on substituted polyacetylenes: tert-butyl acetylene [TBA: (CH{sub 3}){sub 3}-C{triple_bond}CH] and ethynyl trimethylsilane [ETMS: (CH{sub 3}){sub 3}-Si{triple_bond}CH] to investigate pressure-induced chemical reactions. The starting samples were the low temperature crystalline phases which persisted metastably at room temperature and polymerized beyond 11 GPa and 26 GPa for TBA and ETMS respectively. These reaction onset pressures are considerably higher than what we observed in the shockwave studies (6.1 GPa for TBA and 6.6 GPa for ETMS). Interestingly, in the case of ETMS, it was observed with fluid ETMS as starting sample, reacts to form a semi-crystalline polymer (crystalline domains corresponding to the low-T phase) at pressures less than {approx}2 GPa. Further characterization using vibrational spectroscopy is in progress.

  8. Charge Retention by Gold Clusters on Surfaces Prepared Using Soft Landing of Mass Selected Ions

    SciTech Connect (OSTI)

    Johnson, Grant E.; Priest, Thomas A.; Laskin, Julia

    2012-01-24

    Monodisperse gold clusters have been prepared on surfaces in different charge states through soft landing of mass-selected ions. Ligand-stabilized gold clusters were prepared in methanol solution by reduction of chloro(triphenylphosphine)gold(I) with borane tert-butylamine complex in the presence of 1,3-bis(diphenylphosphino)propane. Electrospray ionization was used to introduce the clusters into the gas-phase and mass-selection was employed to isolate a single ionic cluster species (Au11L53+, L = 1,3-bis(diphenylphosphino)propane) which was delivered to surfaces at well controlled kinetic energies. Using in-situ time of flight secondary ion mass spectrometry (TOF-SIMS) it is demonstrated that the Au11L53+ cluster retains its 3+ charge state when soft landed onto the surface of a 1H,1H,2H,2H-

  9. Microwave Plasma Chemical Vapor Deposition of Nano-Structured Sn/C Composite Thin-Film Anodes for Li-ion Batteries

    SciTech Connect (OSTI)

    Stevenson, Cynthia; Marcinek, M.; Hardwick, L.J.; Richardson, T.J.; Song, X.; Kostecki, R.

    2008-02-01

    In this paper we report results of a novel synthesis method of thin-film composite Sn/C anodes for lithium batteries. Thin layers of graphitic carbon decorated with uniformly distributed Sn nanoparticles were synthesized from a solid organic precursor Sn(IV) tert-butoxide by a one step microwave plasma chemical vapor deposition (MPCVD). The thin-film Sn/C electrodes were electrochemically tested in lithium half cells and produced a reversible capacity of 440 and 297 mAhg{sup -1} at C/25 and 5C discharge rates, respectively. A long term cycling of the Sn/C nanocomposite anodes showed 40% capacity loss after 500 cycles at 1C rate.

  10. Modified cellulose synthase gene from Arabidopsis thaliana confers herbicide resistance to plants

    DOE Patents [OSTI]

    Somerville, Chris R. (Portola Valley, CA); Scheible, Wolf (Golm, DE)

    2007-07-10

    Cellulose synthase ("CS"), a key enzyme in the biosynthesis of cellulose in plants is inhibited by herbicides comprising thiazolidinones such as 5-tert-butyl-carbamoyloxy-3-(3-trifluromethyl)phenyl-4-thiazolidinone (TZ), isoxaben and 2,6-dichlorobenzonitrile (DCB). Two mutant genes encoding isoxaben and TZ-resistant cellulose synthase have been isolated from isoxaben and TZ-resistant Arabidopsis thaliana mutants. When compared with the gene coding for isoxaben or TZ-sensitive cellulose synthase, one of the resistant CS genes contains a point mutation, wherein glycine residue 998 is replaced by an aspartic acid. The other resistant mutation is due to a threonine to isoleucine change at amino acid residue 942. The mutant CS gene can be used to impart herbicide resistance to a plant; thereby permitting the utilization of the herbicide as a single application at a concentration which ensures the complete or substantially complete killing of weeds, while leaving the transgenic crop plant essentially undamaged.

  11. Alternative Fuels Data Center

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

    Ethanol and Methanol Tax Ethyl alcohol and methyl alcohol motor fuels are taxed at a rate of $0.14 per gallon when used as a motor fuel. Ethyl alcohol is defined as a motor fuel that is typically derived from agricultural products that have been denatured. Methyl alcohol is a motor fuel that is most commonly derived from wood products. (Reference Senate Bill 1, 2015, and South Dakota Statutes 10-47B-3 and 10-47B-4

  12. Process for the production of .sup.18 F-2-deoxy-2-fluoro-D-glucose

    DOE Patents [OSTI]

    Elmaleh, David R.; Levy, Shlomo; Shiue, Chyng-Yann; Wolf, Alfred P.

    1986-01-01

    Process for the production of 2-deoxy-2-fluoro-D-glucose and the corresponding .sup.18 F-compound in which methyl 4,6-O-benzylidine-3-O-methyl-2-O-trifluoromethanesulfonyl-.beta.-D-mannopy ranoside is reacted with a triflating reagent, the resulting compound reacted with CsHF.sub.2, RbF or the corresponding .sup.18 F-compounds, and thereafter the alkyl groups removed by hydrolysis.

  13. Detailed chemical kinetic oxidation mechanism for a biodiesel surrogate

    SciTech Connect (OSTI)

    Herbinet, O; Pitz, W J; Westbrook, C K

    2007-09-17

    A detailed chemical kinetic mechanism has been developed and used to study the oxidation of methyl decanoate, a surrogate for biodiesel fuels. This model has been built by following the rules established by Curran et al. for the oxidation of n-heptane and it includes all the reactions known to be pertinent to both low and high temperatures. Computed results have been compared with methyl decanoate experiments in an engine and oxidation of rapeseed oil methyl esters in a jet stirred reactor. An important feature of this mechanism is its ability to reproduce the early formation of carbon dioxide that is unique to biofuels and due to the presence of the ester group in the reactant. The model also predicts ignition delay times and OH profiles very close to observed values in shock tube experiments fueled by n-decane. These model capabilities indicate that large n-alkanes can be good surrogates for large methyl esters and biodiesel fuels to predict overall reactivity, but some kinetic details, including early CO2 production from biodiesel fuels, can be predicted only by a detailed kinetic mechanism for a true methyl ester fuel. The present methyl decanoate mechanism provides a realistic kinetic tool for simulation of biodiesel fuels.

  14. Detailed chemical kinetic oxidation mechanism for a biodiesel surrogate

    SciTech Connect (OSTI)

    Herbinet, O; Pitz, W J; Westbrook, C K

    2007-09-20

    A detailed chemical kinetic mechanism has been developed and used to study the oxidation of methyl decanoate, a surrogate for biodiesel fuels. This model has been built by following the rules established by Curran et al. for the oxidation of n-heptane and it includes all the reactions known to be pertinent to both low and high temperatures. Computed results have been compared with methyl decanoate experiments in an engine and oxidation of rapeseed oil methyl esters in a jet stirred reactor. An important feature of this mechanism is its ability to reproduce the early formation of carbon dioxide that is unique to biofuels and due to the presence of the ester group in the reactant. The model also predicts ignition delay times and OH profiles very close to observed values in shock tube experiments fueled by n-decane. These model capabilities indicate that large n-alkanes can be good surrogates for large methyl esters and biodiesel fuels to predict overall reactivity, but some kinetic details, including early CO{sub 2} production from biodiesel fuels, can be predicted only by a detailed kinetic mechanism for a true methyl ester fuel. The present methyl decanoate mechanism provides a realistic kinetic tool for simulation of biodiesel fuels.

  15. Detailed chemical kinetic oxidation mechanism for a biodiesel surrogate

    SciTech Connect (OSTI)

    Herbinet, Olivier; Pitz, William J.; Westbrook, Charles K.

    2008-08-15

    A detailed chemical kinetic mechanism has been developed and used to study the oxidation of methyl decanoate, a surrogate for biodiesel fuels. This model has been built by following the rules established by Curran and co-workers for the oxidation of n-heptane and it includes all the reactions known to be pertinent to both low and high temperatures. Computed results have been compared with methyl decanoate experiments in an engine and oxidation of rapeseed oil methyl esters in a jet-stirred reactor. An important feature of this mechanism is its ability to reproduce the early formation of carbon dioxide that is unique to biofuels and due to the presence of the ester group in the reactant. The model also predicts ignition delay times and OH profiles very close to observed values in shock tube experiments fueled by n-decane. These model capabilities indicate that large n-alkanes can be good surrogates for large methyl esters and biodiesel fuels to predict overall reactivity, but some kinetic details, including early CO{sub 2} production from biodiesel fuels, can be predicted only by a detailed kinetic mechanism for a true methyl ester fuel. The present methyl decanoate mechanism provides a realistic kinetic tool for simulation of biodiesel fuels. (author)

  16. Physicochemical properties and toxicities of hydrophobicpiperidinium and pyrrolidinium ionic liquids

    SciTech Connect (OSTI)

    Salminen, Justin; Papaiconomou, Nicolas; Kumar, R. Anand; Lee,Jong-Min; Kerr, John; Newman, John; Prausnitz, John M.

    2007-06-25

    Some properties are reported for hydrophobic ionic liquids (IL) containing 1-methyl-1-propyl pyrrolidinium [MPPyrro]{sup +}, 1-methyl-1-butyl pyrrolidinium [MBPyrro]{sup +}, 1-methyl-1-propyl piperidinium [MPPip]{sup +}, 1-methyl-1-butyl piperidinium [MBPip]{sup +}, 1-methyl-1-octylpyrrolidinium [MOPyrro]{sup +} and 1-methyl-1-octylpiperidinium [MOPip]{sup +} cations. These liquids provide new alternatives to pyridinium and imidazolium ILs. High thermal stability of an ionic liquid increases safety in applications like rechargeable lithium-ion batteries and other electrochemical devices. Thermal properties, ionic conductivities, viscosities, and mutual solubilities with water are reported. In addition, toxicities of selected ionic liquids have been measured using a human cancer cell-line. The ILs studied here are sparingly soluble in water but hygroscopic. We show some structure-property relationships that may help to design green solvents for specific applications. While ionic liquids are claimed to be environmentally-benign solvents, as yet few data have been published to support these claims.

  17. A roadmap to uranium ionic liquids: Anti-crystal engineering

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

    Yaprak, Damla; Spielberg, Eike T.; Bäcker, Tobias; Richter, Mark; Mallick, Bert; Klein, Axel; Mudring, Anja -Verena

    2014-04-15

    In the search for uranium-based ionic liquids, tris(N,N-dialkyldithiocarbamato)uranylates have been synthesized as salts of the 1-butyl-3-methylimidazolium (C4mim) cation. As dithiocarbamate ligands binding to the UO22+ unit, tetra-, penta-, hexa-, and heptamethylenedithiocarbamates, N,N-diethyldithiocarbamate, N-methyl-N-propyldithiocarbamate, N-ethyl-N-propyldithiocarbamate, and N-methyl-N-butyldithiocarbamate have been explored. X-ray single-crystal diffraction allowed unambiguous structural characterization of all compounds except N-methyl-N-butyldithiocarbamate, which is obtained as a glassy material only. In addition, powder X-ray diffraction as well as vibrational and UV/Vis spectroscopy, supported by computational methods, were used to characterize the products. Differential scanning calorimetry was employed to investigate the phase-transition behavior depending on the N,N-dialkyldithiocarbamato ligand with the aim tomore » establish structure–property relationships regarding the ionic liquid formation capability. Compounds with the least symmetric N,N-dialkyldithiocarbamato ligand and hence the least symmetric anions, tris(N-methyl-N-propyldithiocarbamato)uranylate, tris(N-ethyl-N-propyldithiocarbamato)uranylate, and tris(N-methyl-N-butyldithiocarbamato)uranylate, lead to the formation of (room-temperature) ionic liquids, which confirms that low-symmetry ions are indeed suitable to suppress crystallization. As a result, these materials combine low melting points, stable complex formation, and hydrophobicity and are therefore excellent candidates for nuclear fuel purification and recovery.« less

  18. Communication: Spectroscopic characterization of an alkyl substituted Criegee intermediate syn-CH{sub 3}CHOO through pure rotational transitions

    SciTech Connect (OSTI)

    Nakajima, Masakazu; Endo, Yasuki

    2014-01-07

    An alkyl-substituted Criegee intermediate syn-CH{sub 3}CHOO was detected in the gas phase through Fourier-transform microwave spectroscopy. Observed pure rotational transitions show a small splitting corresponding to the A/E components due to the threefold methyl internal rotation. The rotational constants and the barrier height of the hindered methyl rotation were determined to be A = 17?586.5295(15) MHz, B = 7133.4799(41) MHz, C = 5229.1704(40) MHz, and V{sub 3} = 837.1(17)cm{sup ?1}. High-level ab initio calculations which reproduce the experimentally determined values well indicate that the in-plane CH bond in the methyl moiety is trans to the CO bond, and other two protons are directed to the terminal oxygen atom for the most stable structure of syn-CH{sub 3}CHOO. The torsional barrier of the methyl top is fairly large in syn-CH{sub 3}CHOO, implying a significant interaction between the terminal oxygen and the protons of the methyl moiety, which may be responsible for the high production yields of the OH radical from energized alkyl-substituted Criegee intermediates.

  19. Modeling the Auto-Ignition of Biodiesel Blends with a Multi-Step Model

    SciTech Connect (OSTI)

    Toulson, Dr. Elisa; Allen, Casey M; Miller, Dennis J; McFarlane, Joanna; Schock, Harold; Lee, Tonghun

    2011-01-01

    There is growing interest in using biodiesel in place of or in blends with petrodiesel in diesel engines; however, biodiesel oxidation chemistry is complicated to directly model and existing surrogate kinetic models are very large, making them computationally expensive. The present study describes a method for predicting the ignition behavior of blends of n-heptane and methyl butanoate, fuels whose blends have been used in the past as a surrogate for biodiesel. The autoignition is predicted using a multistep (8-step) model in order to reduce computational time and make this a viable tool for implementation into engine simulation codes. A detailed reaction mechanism for n-heptane-methyl butanoate blends was used as a basis for validating the multistep model results. The ignition delay trends predicted by the multistep model for the n-heptane-methyl butanoate blends matched well with that of the detailed CHEMKIN model for the majority of conditions tested.

  20. Recent Advances in Detailed Chemical Kinetic Models for Large Hydrocarbon and Biodiesel Transportation Fuels

    SciTech Connect (OSTI)

    Westbrook, C K; Pitz, W J; Curran, H J; Herbinet, O; Mehl, M

    2009-03-30

    n-Hexadecane and 2,2,4,4,6,8,8-heptamethylnonane represent the primary reference fuels for diesel that are used to determine cetane number, a measure of the ignition property of diesel fuel. With the development of chemical kinetics models for these two primary reference fuels for diesel, a new capability is now available to model diesel fuel ignition. Also, we have developed chemical kinetic models for a whole series of large n-alkanes and a large iso-alkane to represent these chemical classes in fuel surrogates for conventional and future fuels. Methyl decanoate and methyl stearate are large methyl esters that are closely related to biodiesel fuels, and kinetic models for these molecules have also been developed. These chemical kinetic models are used to predict the effect of the fuel molecule size and structure on ignition characteristics under conditions found in internal combustion engines.

  1. A review of chromatographic characterization techniques for biodiesel and biodiesel blends.

    SciTech Connect (OSTI)

    Pauls, R. E.

    2011-05-01

    This review surveys chromatographic technology that has been applied to the characterization of biodiesel and its blends. Typically, biodiesel consists of fatty acid methyl esters produced by transesterification of plant or animal derived triacylglycerols. Primary attention is given to the determination of trace impurities in biodiesel, such as methanol, glycerol, mono-, di-, and triacylglycerols, and sterol glucosides. The determination of the fatty acid methyl esters, trace impurities in biodiesel, and the determination of the biodiesel content of commercial blends of biodiesel in conventional diesel are also addressed.

  2. A Stable Fluorinated and Alkylated Lithium Malonatoborate Salt for Lithium Ion Battery Application

    SciTech Connect (OSTI)

    Wan, Shun; Jiang, Xueguang; Guo, Bingkun; Dai, Sheng; Sun, Xiao-Guang

    2015-01-01

    A new fluorinated and alkylated lithium malonatoborate salt, lithium bis(2-methyl-2-fluoromalonato)borate (LiBMFMB), has been synthesized for lithium ion battery application. A 0.8 M LiBMFMB solution is obtained in a mixture of ethylene carbonate (EC) and ethyl methyl carbonate (EMC) (1:2 by wt.). The new LiBMFMB based electrolyte exhibits good cycling stability and rate capability in LiNi0.5Mn1.5O4 and graphite based half-cells.

  3. Apparatus and method for production of methanethiol

    DOE Patents [OSTI]

    Agarwal, Pradeep K.; Linjewile, Temi M.; Hull, Ashley S.; Chen, Zumao

    2006-02-07

    A method for the production of methyl mercaptan is provided. The method comprises providing raw feed gases consisting of methane and hydrogen sulfide, introducing the raw feed gases into a non-thermal pulsed plasma corona reactor, and reacting the raw feed gases within the non-thermal pulsed plasma corona reactor with the reaction CH4+H2S.fwdarw.CH3SH+H2. An apparatus for the production of methyl mercaptan using a non-thermal pulsed plasma corona reactor is also provided.

  4. 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.

  5. Carbocation Stability in H-ZSM5 at High Temperature

    SciTech Connect (OSTI)

    Ferguson, Glen A.; Cheng, Lei; Bu, Lintao; Kim, Seonah; Robichaud, David J.; Nimlos, Mark R.; Curtiss, Larry A.; Beckham, Gregg T.

    2015-10-26

    Zeolites are common catalysts for multiple industrial applications, including alcohol dehydration to produce olefins, and given their commercial importance, reaction mechanisms in zeolites have long been proposed and studied. Some proposed reaction mechanisms for alcohol dehydration exhibit noncyclic carbocation intermediates or transition states that resemble carbocations, and several previous studies suggest that the tert-butyl cation is the only noncyclic cation more stable than the corresponding chemisorbed species with the hydrocarbon bound to the framework oxygen (i.e., an alkoxide). To determine if carbocations can exist at high temperatures in zeolites, where these catalysts are finding new applications for biomass vapor-phase upgrading (~500 C), the stability of carbocations and the corresponding alkoxides were calculated with two ONIOM embedding methods (M06-2X/6-311G(d,p):M06-2X/3-21G) and (PBE-D3/6-311G(d,p):PBE-D3/3-21G) and plane-wave density functional theory (DFT) using the PBE functional corrected with entropic and TkatchenkoScheffler van der Waals corrections. Additionally, the embedding methods tested are unreliable at finding minima for primary carbocations, and only secondary or higher carbocations can be described with embedding methods consistent with the periodic DFT results. The relative energy between the carbocations and alkoxides differs significantly between the embedding and the periodic DFT methods. The difference is between ~0.23 and 14.30 kcal/mol depending on the molecule, the model, and the functional chosen for the embedding method. At high temperatures, the pw-DFT calculations predict that the allyl, isopropyl, and sec-butyl cations exhibit negligible populations while acetyl and tert-butyl cations exhibit significant populations (>10%). Furthermore, the periodic DFT results indicate that mechanisms including secondary and tertiary carbocations intermediates or carbocations stabilized by adjacent oxygen or double bonds are possible at high temperatures relevant to some industrial uses of zeolite catalysts, although as the minority species in most cases.

  6. Laminar burning velocities and flame instabilities of butanol isomers-air mixtures

    SciTech Connect (OSTI)

    Gu, Xiaolei; Huang, Zuohua; Wu, Si; Li, Qianqian [State Key Laboratory of Multiphase Flow in Power Engineering, Xi'an Jiaotong University, Xi'an 710049 (China)

    2010-12-15

    Laminar burning velocities and flame instabilities of the butanol-air premixed flames and its isomers are investigated using the spherically expanding flame with central ignition at initial temperature of 428 K and initial pressures of 0.10 MPa, 0.25 MPa, 0.50 MPa and 0.75 MPa. Laminar burning velocities and sensitivity factor of n-butanol-air mixtures are computed using a newly developed kinetic mechanism. Unstretched laminar burning velocity, adiabatic temperature, Lewis number, Markstein length, critical flame radius and Peclet number are obtained over a wide range of equivalence ratios. Effect of molecular structure on laminar burning velocity of the isomers of butanol is analyzed from the aspect of C-H bond dissociation energy. Study indicates that although adiabatic flame temperatures of the isomers of butanol are the same, laminar burning velocities give an obvious difference among the isomers of butanol. This indicates that molecular structure has a large influence on laminar burning velocities of the isomers of butanol. Branching (-CH3) will decrease laminar burning velocity. Hydroxyl functional group (-OH) attaching to the terminal carbon atoms gives higher laminar burning velocity compared to that attaching to the inner carbon atoms. Calculated dissociation bond energies show that terminal C-H bonds have larger bond energies than that of inner C-H bonds. n-Butanol, no branching and with hydroxyl functional group (-OH) attaching to the terminal carbon atom, gives the largest laminar burning velocity. tert-Butanol, with highly branching and hydroxyl functional group (-OH) attaching to the inner carbon atom, gives the lowest laminar burning velocity. Laminar burning velocities of iso-butanol and sec-butanol are between those of n-butanol and tert-butanol. The instant of transition to cellularity is experimentally determined for the isomers of butanol and subsequently interpreted on the basis of hydrodynamic and diffusion-thermal instabilities. Little effect on flame instability is observed for the isomers of butanol. Critical flame radii are the same for the isomers of butanol. Peclet number decreases with the increase in equivalence ratio. (author)

  7. Catalytic Routes for the Conversion of Biomass Derivatives to Hydrocarbons and/or Platform Chemicals

    SciTech Connect (OSTI)

    Silks, III, Louis A.

    2015-10-07

    Unprotected carbohydrates were reacted in amine-catalyzed cascade reactions with various methyl ketones to give a direct access to C-glycosides by an operationally simple protocol. As the reaction mechanism,an aldol condensation followed by an intramolecular conjugate addition is assumed.

  8. 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).

  9. Self-assembly and photophysical properties of lanthanide dinuclear triple-helical complexes

    SciTech Connect (OSTI)

    Piguet, C.; Bernardinelli, G.; Williams, A.F. ); Buenzli, J.C.G. ); Hopfgartner, G. )

    1993-09-08

    The dinucleating ligand bis[1-methyl-2-(6[prime]-[1[double prime]-(3,5-dimethoxybenzyl)benzimidazol-2[double prime]-yl]pyrid-2[prime]-yl)benzimidazol-5-yl]methane (L) reacts with lanthanide perchlorates to give dinuclear 2:3 complexes [Ln[sub 2](L)[sub 3

  10. Solvent Extraction of Chemical Attribution Signature Compounds from Painted Wall Board: Final Report

    SciTech Connect (OSTI)

    Wahl, Jon H.; Colburn, Heather A.

    2009-10-29

    This report summarizes work that developed a robust solvent extraction procedure for recovery of chemical attribution signature (CAS) compound dimethyl methyl phosphonate (DMMP) (as well as diethyl methyl phosphonate (DEMP), diethyl methyl phosphonothioate (DEMPT), and diisopropyl methyl phosphonate (DIMP)) from painted wall board (PWB), which was selected previously as the exposed media by the chemical attribution scientific working group (CASWG). An accelerated solvent extraction approach was examined to determine the most effective method of extraction from PWB. Three different solvent systems were examined, which varied in solvent strength and polarity (i.e., 1:1 dichloromethane : acetone,100% methanol, and 1% isopropanol in pentane) with a 1:1 methylene chloride : acetone mixture having the most robust and consistent extraction for four original target organophosphorus compounds. The optimum extraction solvent was determined based on the extraction efficiency of the target analytes from spiked painted wallboard as determined by gas chromatography x gas chromatography mass spectrometry (GCxGC-MS) analysis of the extract. An average extraction efficiency of approximately 60% was obtained for these four compounds. The extraction approach was further demonstrated by extracting and detecting the chemical impurities present in neat DMMP that was vapor-deposited onto painted wallboard tickets.

  11. Structure and Function of the Glycopeptide N-methyltransferase MtfA, a Tool for the Biosynthesis of Modified Glycopeptide Antibiotics

    SciTech Connect (OSTI)

    Shi, Rong; Lamb, Sherry S.; Zakeri, Bijan; Proteau, Ariane; Cui, Qizhi; Sulea, Traian; Matte, Allan; Wright, Gerard D.; Cygler, Miroslaw

    2009-06-01

    There is a considerable interest in the modification of existing antibiotics to generate new antimicrobials. Glycopeptide antibiotics (GPAs) are effective against serious Gram-positive bacterial pathogens including methicillin-resistant Staphylococcus aureus. However, resistance to these antibiotics is becoming a serious problem requiring new strategies. We show that the Amycolatopsis orientalis (S)-adenosyl-L-methionine-dependent methyltransferase MtfA, from the vancomycin-class GPA chloroeremomycin biosynthetic pathway, catalyzes in vivo and in vitro methyl transfer to generate methylated GPA derivatives of the teicoplanin class. The crystal structure of MtfA complexed with (S)-adenosyl-L-methionine, (S)-adenosylhomocysteine, or sinefungin inhibitor, coupled with mutagenesis, identified His228 as a likely general base required for methyl transfer to the N terminus of the glycopeptide. Computational docking and molecular dynamics simulations were used to model binding of demethyl-vancomycin aglycone to MtfA. These results demonstrate its utility as a tool for engineering methylated analogs of GPAs.

  12. Biodiesel fuel from animal fat. Ancillary studies on transesterification of beef tallow

    SciTech Connect (OSTI)

    Ma, F.; Clements, L.D.; Hanna, M.A.

    1998-09-01

    Transesterification of beef tallow was investigated. The solubility of ethanol in beef tallow was much higher than that of methanol. At 100 C the solubility of methanol was 19% (w/w). The solubility of ethanol in beef tallow reached 100% (w/w) at about 68 C. For the distribution of methanol between beef tallow methyl esters (BTME) and glycerol, the percentage of total methanol in the glycerol phase was higher than that in the fatty acid methyl ester (FAME) phase in a simulated system at room temperature. At 65--80 C, however, the percentage of total methanol in FAME (60% (w/w)) was higher than that in glycerol (40% (w/w)) in a 90:10 (w/w) blend of FAME and glycerol. This coincided with the methanol distribution in the transesterified product. The process for making beef tallow methyl esters should recover methanol using vacuum distillation, separate the ester and glycerol phases, and then wash the beef tallow methyl esters with warm water. At neutral pH, the separation of ester and glycerol and water washing was easier because it reduced emulsion formation.

  13. Continuous wasteless ecologically safe technology of propylenecarbonate production in presence of phthalocyanine catalysts

    DOE Patents [OSTI]

    Afanasiev, Vladimir Vasilievich (Moscow, RU); Zefirov, Nikolai Serafimovich (Moscow, RU); Zalepugin, Dmitry Yurievich (Moscow, RU); Polyakov, Victor Stanislavovich (Moscow, RU); Tilkunova,Nataliya Alexandrovna (Moscow, RU); Tomilova, Larisa Godvigovna (Moscow, RU)

    2009-09-08

    A continuous method of producing propylenecarbonate includes carboxylation of propylene oxide with carbon dioxide in presence of phthalocyanine catalyst on an inert carrier, using as the phthalocyanine catalyst at least one catalyst selected from the group consisting of not-substituted, methyl, ethyl, butyl, and tret butyl-substituted phthalocyanines of metals, including those containing counterions, and using as the carrier a hydrophobic carrier.

  14. Impact of Solvent on Photocatalytic Mechanisms: Reactions of Photodesorption Products with Ice Overlayers on the TiO2(110) Surface

    SciTech Connect (OSTI)

    Shen, Mingmin; Henderson, Michael A.

    2011-04-07

    The effects of water and methanol ice overlayers on the photodecomposition of acetone on rutile TiO2(110) were evaluated in ultrahigh vacuum (UHV) using photon stimulated desorption (PSD) and temperature programmed desorption (TPD). In the absence of ice overlayers, acetone photodecomposed on TiO2(110) at 95 K by ejection of a methyl radical into the gas phase and formation of acetate on the surface. With ice overlayers, the methyl radicals are trapped at the interface between TiO2(110) and the ice. When water ice was present, these trapped methyl radicals reacted either with each other to form ethane or with other molecules in the ice (e.g., water or displaced acetone) to form methane (CH4), ethane (CH3CH3) and other products (e.g., methanol), with all of these products trapped in the ice. The new products were free to revisit the surface or depart during desorption of the ice. When methanol ice was present, methane formation came about only from reaction of trapped methyl radicals with the methanol ice. Methane and ethane slowly leaked through methanol ice overlayers into vacuum at 95 K, but not through water ice overlayers. Different degrees of site competition between water and acetone, and between methanol and acetone led to different hydrogen abstraction pathways in the two ices. These results provide new insights into product formation routes and solution-phase radical formation mechanisms that are important in heterogeneous photocatalysis.

  15. 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.

  16. Metal resistance sequences and transgenic plants

    DOE Patents [OSTI]

    Meagher, Richard Brian (Athens, GA); Summers, Anne O. (Athens, GA); Rugh, Clayton L. (Athens, GA)

    1999-10-12

    The present invention provides nucleic acid sequences encoding a metal ion resistance protein, which are expressible in plant cells. The metal resistance protein provides for the enzymatic reduction of metal ions including but not limited to divalent Cu, divalent mercury, trivalent gold, divalent cadmium, lead ions and monovalent silver ions. Transgenic plants which express these coding sequences exhibit increased resistance to metal ions in the environment as compared with plants which have not been so genetically modified. Transgenic plants with improved resistance to organometals including alkylmercury compounds, among others, are provided by the further inclusion of plant-expressible organometal lyase coding sequences, as specifically exemplified by the plant-expressible merB coding sequence. Furthermore, these transgenic plants which have been genetically modified to express the metal resistance coding sequences of the present invention can participate in the bioremediation of metal contamination via the enzymatic reduction of metal ions. Transgenic plants resistant to organometals can further mediate remediation of organic metal compounds, for example, alkylmetal compounds including but not limited to methyl mercury, methyl lead compounds, methyl cadmium and methyl arsenic compounds, in the environment by causing the freeing of mercuric or other metal ions and the reduction of the ionic mercury or other metal ions to the less toxic elemental mercury or other metals.

  17. Ultraviolet absorbing copolymers

    DOE Patents [OSTI]

    Gupta, Amitava (Pasadena, CA); Yavrouian, Andre H. (La Crescenta, CA)

    1982-01-01

    Photostable and weather stable absorping copolymers have been prepared from acrylic esters such as methyl methacrylate containing 0.1 to 5% of an 2-hydroxy-allyl benzophenone, preferably the 4,4' dimethoxy derivative thereof. The pendant benzophenone chromophores protect the acrylic backbone and when photoexcited do not degrade the ester side chain, nor abstract hydrogen from the backbone.

  18. 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.

  19. Chemistry: Theory - Combustion Energy Frontier Research Center

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

    Theory Chemistry: Theory Presentations from 2010 CEFRC First Annual Conference MultireferenceCorrelated WavefunctionCalculations and Reaction Flux Analyses of Methyl Ester Combustion Emily A. Carter, Princeton University Constructing Accurate Combustion Chemistry Models William H. Green, MIT Theoretical Gas Phase Chemical Kinetics Stephen J. Klippenstein, Argonne National Laboratory Theoretical Chemical Kinetics and Combustion Modeling James A. Miller, Argonne National Laboratory Computation of

  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. 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.

  2. Hydridomethyl iridium complex

    DOE Patents [OSTI]

    Bergman, Robert G. (P.O. Box 7141, San Francisco, CA 94120-7141); Buchanan, J. Michael (P.O. Box 7141, San Francisco, CA 94120-7141); Stryker, Jeffrey M. (P.O. Box 7141, San Francisco, CA 94120-7141); Wax, Michael J. (P.O. Box 7141, San Francisco, CA 94120-7141)

    1989-01-01

    A process for functionalizing methane comprising: (a) reacting methane with a hydridoalkyl metal complex of the formula: CpIr[P(R.sub.1).sub.3 ]H(R.sub.2) wherein Cp represents a cyclopentadienyl or alkylcyclopentadienyl radical having from 1 to 5 carbon atoms; Ir represents an iridium atom; P represents a phosphorus atom; R.sub.1 represents an alkyl group; R.sub.2 represents an alkyl group having at least two carbon atoms; and H represents a hydrogen atom, in the presence of a liquid alkane R.sub.3 H having at least three carbon atoms to form a hydridomethyl complex of the formula: CpIr[P(R.sub.1).sub.3 ]HMe where Me represents a methyl radical. (b) reacting said hydridomethyl complex with an organic halogenating agent such as a tetrahalomethane or a haloform of the formulas: CX'X"X'"X"" or CHX'X"X'"; wherein X', X", X"', and X"" represent halogens selected from bromine, iodine and chlorine, to halomethyl complex of step (a) having the formula: CpIr[P(R.sub.1).sub.3 ]MeX: (c) reacting said halomethyl complex with a mercuric halide of the formula HgX.sub.2 to form a methyl mercuric halide of the formula HgMeX; and (d) reacting said methyl mercuric halide with a molecular halogen of the formula X.sub.2 to form methyl halide.

  3. Alkane functionalization at ([mu]-Oxo)diiron(III) centers

    SciTech Connect (OSTI)

    Leising, R.A.; Kim, J.; Perez, M.A.; Que, L. Jr. )

    1993-10-20

    The reactivity of ([mu]-oxo)diferric complexes with [sup t]BuOOH (TBHP) for the functionalization of alkanes in CH[sub 3]CN has been investigated as part of our efforts to model dinuclear sites in nonheme iron enzymes. [Fe[sub 2](TPA)[sub 2]O(OAc)](CIO[sub 4])[sub 3] (1) (TPA = tris(2-pyridylmethyl)amine, OAc = acetate) is an efficient catalyst for cyclohexane oxidation, affording cyclohexanol (A, 9 equiv), cyclohexanone (K, 11 equiv), and (tert-butylperoxy)cyclohexane (P, 16 equiv) in 0.25 h at ambient temperature and pressure under an argon atmosphere. The catalyst is remarkably robust, as indicated by the [sup 1]H NMR and UV-vis spectra of the reaction mixture during the catalytic reaction and by its ability to maintain its turnover efficiency with subsequent additions of oxidant. The catalytic mechanism for TBHP utilization was explored by observing the effects of varying the tripodal ligands on the ([mu]-oxo)([mu]-carboxylato)diferric catalysts and varying the bridge on Fe[sub 2]O(TPA)[sub 2] catalysts. The (A + K)/P ratio increased as the ligands became more electron donating. Solvent also played an important role in determining the partitioning of products between A + K and P, with benzonitrile favoring hydroxylated products at the expense of P and pyridine having the opposite effect. 49 refs., 2 figs., 3 tabs.

  4. Exome sequencing of hepatocellular carcinomas identifies new mutational signatures and potential therapeutic targets

    SciTech Connect (OSTI)

    Schulze, Kornelius; Imbeaud, Sandrine; Letouz, Eric; Alexandrov, Ludmil B.; Calderaro, Julien; Rebouissou, Sandra; Couchy, Gabrielle; Meiller, Clment; Shinde, Jayendra; Soysouvanh, Frederic; Calatayud, Anna-Line; Pinyol, Roser; Pelletier, Laura; Balabaud, Charles; Laurent, Alexis; Blanc, Jean-Frederic; Mazzaferro, Vincenzo; Calvo, Fabien; Villanueva, Augusto; Nault, Jean-Charles; Bioulac-Sage, Paulette; Stratton, Michael R.; Llovet, Josep M.; Zucman-Rossi, Jessica

    2015-03-30

    Our genomic analyses promise to improve tumor characterization to optimize personalized treatment for patients with hepatocellular carcinoma (HCC). Exome sequencing analysis of 243 liver tumors identified mutational signatures associated with specific risk factors, mainly combined alcohol and tobacco consumption and exposure to aflatoxin B1. We identified 161 putative driver genes associated with 11 recurrently altered pathways. Associations of mutations defined 3 groups of genes related to risk factors and centered on CTNNB1 (alcohol), TP53 (hepatitis B virus, HBV) and AXIN1. These analyses according to tumor stage progression identified TERT promoter mutation as an early event, whereasFGF3, FGF4, FGF19 or CCND1 amplification and TP53 and CDKN2A alterations appeared at more advanced stages in aggressive tumors. In 28% of the tumors, we identified genetic alterations potentially targetable by US Food and Drug Administration (FDA)approved drugs. Finally, we identified risk factorspecific mutational signatures and defined the extensive landscape of altered genes and pathways in HCC, which will be useful to design clinical trials for targeted therapy.

  5. Solvent Extraction of Sodium Hydroxide Using Alkylphenols and Fluorinated Alcohols: Understanding the Extraction Mechanism by Equilibrium Modeling

    SciTech Connect (OSTI)

    Kang, Hyun-Ah; Engle, Nancy L.; Bonnesen Peter V.; Delmau, Laetitia H.; Haverlock, Tamara J.; Moyer, Bruce A.

    2004-03-29

    In the present work, it has been the aim to examine extraction efficiencies of nine proton-ionizable alcohols (HAs) in 1-octanol and to identify both the controlling equilibria and predominant species involved in the extraction process within a thermochemical model. Distribution ratios for sodium (DNa) extraction were measured as a function of organic-phase HA and aqueous-phase NaOH molarity at 25 C. Extraction efficiency follows the expected order of acidity of the HAs, 4-(tert-octyl) phenol (HA 1a) and 4-noctyl- a,a-bis-(trifluoromethyl)benzyl alcohol (HA 2a) being the most efficient extractants among the compounds tested. By use of the equilibrium-modeling program SXLSQI, a model for the extraction of NaOH has been advanced based on an ion-pair extraction by the diluent to give organic-phase Na+OH- and corresponding free ions and cation exchange by the weak acids to form monomeric organic-phase Na+A- and corresponding free organic-phase ions.

  6. Solvent Hold Tank Sample Results For MCU-13-814, MCU-13-815, MCU-13-816, MCU-13,817, MCU-13-818 And MCU-13-819: Quarterly Sample From May 2013

    SciTech Connect (OSTI)

    Fondeur, F. F.; Taylor-Pashow, K. M.

    2013-08-13

    Savannah River National Laboratory (SRNL) analyzed solvent samples from Modular Caustic-Side Solvent Extraction Unit (MCU) in support of continuing operations. A quarterly analysis of the solvent is required to maintain solvent composition within specifications. Analytical results of the analyses of Solvent Hold Tank (SHT) samples MCU-13-814, MCU-13-815, MCU-13-816, MCU-13-817, MCU-13-818 and MCU-13-819 received May 28, 2013 are reported. The results show that the solvent at MCU does not require an Isopar L addition, but it will require addition of trioctylamine despite of the 272 g of TOA that was added to the solvent on June 5, 2013 based on the solvent containing a TOA level of 45% of nominal. A new TOA analysis method (HCl titration) has been used and its output was statistically similar to the results from the SVOA-TOA method. This method provides an independent method for measuring TOA and TiDG in MCU-NG solvent. An impurity containing a tert-butyl group was detected in the solvent and further analytical analysis is needed to identify it. SRNL recommends determining the impact of this impurity on the mass transfer ability of the solvent. SRNL also analyzed the SHT sample for {sup 137}Cs content and determined the measured value is above the results observed from the January 2013.

  7. Gas chromatographic determination of residual solvents in lubricating oils and waxes

    SciTech Connect (OSTI)

    De Andrade Bruening, I.M.R.

    1983-10-01

    A direct gas-liquid chromatographic analysis of residual solvents is described, using tert-butylbenzene as an internal standard. The lube oils and waxes were prevented from contaminating the chromatographic column by injecting the samples directly into a precolumn containing a silicone stationary phase. The samples of lube oils and waxes were injected directly into the chromatographic column containing another stationary phase, 1,2,3-tris(2-cyanoethoxy)propane. (The waxy samples were dissolved in a light neutral oil). With proper operating conditions, analysis time was 7 min. The procedure has been applied in the control of a lube oil dewaxing plant; the chromatographic column showed no sign of deterioration after 1 h when the precolumn was removed. Known amounts of toluene and methylethyl ketone were added to the solvent-free lubricating oils and wax, and these mixtures were analyzed to evaluate the accuracy of the procedure. Precision and accuracy of these data are comparable to those of methods previously described. 1 figure, 1 table.

  8. Catalytic conversion of light alkanes, Phase 3. Topical report, January 1990--December 1992

    SciTech Connect (OSTI)

    1992-12-31

    The mission of this work is to devise a new catalyst which can be used in the first simple, economic process to convert the light alkanes in natural gas to an alcohol-rich oxygenated product which can either be used as an environmentally friendly, high-performance liquid fuel, or a precursor to a liquid hydrocarbon transportation fuel. The authors have entered the proof-of-concept stage for converting isobutane to tert butyl alcohol in a practical process and are preparing to enter proof-of-concept of a propane to isopropyl alcohol process in the near future. Methane and ethane are more refractory and thus more difficult to oxidize than the C{sub 3} and C{sub 4} hydrocarbons. Nonetheless, advances made in this area indicate that further research progress could achieve the goal of their direct conversion to alcohols. Progress in Phase 3 catalytic vapor phase methane and ethane oxidation over metals in regular oxidic lattices are the subject of this topical report.

  9. 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.

  10. 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.

  11. The photocatalysis of Bi{sub 2}MoO{sub 6} under the irradiation of blue LED

    SciTech Connect (OSTI)

    Sun, Yuanyuan; Wang, Wenzhong Zhang, Ling; Sun, Songmei

    2013-10-15

    Graphical abstract: - Highlights: • ·OH trap and hole sink were involved to investigate the active radicals. • Holes play a more important role in the degradation of RhB. • The ·OH were related to the decomposition of phenol. • The ·O{sub 2}-played a leading role in the photodegradation of phenol. • Blue LED is competitive and promising alternative for the future application. - Abstract: Bi{sub 2}MoO{sub 6} has been reported as a promising photocatalyst in wastewater treatment. The active radicals generated over the Bi{sub 2}MoO{sub 6} during the photocatalytic process were thought to be hydroxyl radical (·OH) but have not been proved. Herein, Bi{sub 2}MoO{sub 6} with nanoplate like morphology was synthesized and its photocatalytic performances in the degradation of rhodamine B (RhB) and phenol as colored and colorless model pollutants respectively were evaluated under the irradiation of blue light emitting diode (LED). The tert-butyl alcohol (TBA) as a ·OH trap and ethylene diamine tetraacetic acid (EDTA) as a hole sink were involved to investigate the main active groups that are generated on Bi{sub 2}MoO{sub 6} and function during the photodegradation of RhB and phenol. In addition, it is a competitive and promising alternative plan to use blue LED as light source for the future practical application in environmental remediation.

  12. In silico identification of anthropogenic chemicals as ligands of zebrafish sex hormone binding globulin

    SciTech Connect (OSTI)

    Thorsteinson, Nels; Ban, Fuqiang; Santos-Filho, Osvaldo; Tabaei, Seyed M.H. [Prostate Centre at the Vancouver General Hospital, University of British Columbia, 2660 Oak Street, Vancouver, BC, V6H 3Z6 (Canada); Miguel-Queralt, Solange; Underhill, Caroline [Department of Obstetrics and Gynecology, University of British Columbia, Child and Family Research Institute, 950 West 28th Avenue, Vancouver, BC, V5Z 4H4 (Canada); Cherkasov, Artem [Prostate Centre at the Vancouver General Hospital, University of British Columbia, 2660 Oak Street, Vancouver, BC, V6H 3Z6 (Canada)], E-mail: artc@interchange.ubc.ca; Hammond, Geoffrey L. [Department of Obstetrics and Gynecology, University of British Columbia, Child and Family Research Institute, 950 West 28th Avenue, Vancouver, BC, V5Z 4H4 (Canada)

    2009-01-01

    Anthropogenic compounds with the capacity to interact with the steroid-binding site of sex hormone binding globulin (SHBG) pose health risks to humans and other vertebrates including fish. Building on studies of human SHBG, we have applied in silico drug discovery methods to identify potential binders for SHBG in zebrafish (Danio rerio) as a model aquatic organism. Computational methods, including; homology modeling, molecular dynamics simulations, virtual screening, and 3D QSAR analysis, successfully identified 6 non-steroidal substances from the ZINC chemical database that bind to zebrafish SHBG (zfSHBG) with low-micromolar to nanomolar affinities, as determined by a competitive ligand-binding assay. We also screened 80,000 commercial substances listed by the European Chemicals Bureau and Environment Canada, and 6 non-steroidal hits from this in silico screen were tested experimentally for zfSHBG binding. All 6 of these compounds displaced the [{sup 3}H]5{alpha}-dihydrotestosterone used as labeled ligand in the zfSHBG screening assay when tested at a 33 {mu}M concentration, and 3 of them (hexestrol, 4-tert-octylcatechol, and dihydrobenzo(a)pyren-7(8H)-one) bind to zfSHBG in the micromolar range. The study demonstrates the feasibility of large-scale in silico screening of anthropogenic compounds that may disrupt or highjack functionally important protein:ligand interactions. Such studies could increase the awareness of hazards posed by existing commercial chemicals at relatively low cost.

  13. Activation of Nrf2 by arsenite and monomethylarsonous acid is independent of Keap1-C151: enhanced Keap1-Cul3 interaction

    SciTech Connect (OSTI)

    Wang Xiaojun; Sun Zheng; Chen Weimin; Li Yanjie; Villeneuve, Nicole F.; Zhang, Donna D.

    2008-08-01

    Drinking water contaminated with arsenic, a human carcinogen, is a worldwide health issue. An understanding of cellular signaling events in response to arsenic exposure and rational designing of strategies to reduce arsenic damages by modulating signaling events are important to fight against arsenic-induced diseases. Previously, we reported that activation of the Nrf2-mediated cellular defense pathway confers protection against toxic effects induced by sodium arsenite [As(III)] or monomethylarsonous acid [MMA(III)]. Paradoxically, arsenic has been reported to induce the Nrf2-dependent signaling pathway. Here, we report the unique mechanism of Nrf2 induction by arsenic. Similar to tert-butylhydroquinone (tBHQ) or sulforaphane (SF), arsenic induced the Nrf2-dependent response through enhancing Nrf2 protein levels by inhibiting Nrf2 ubiquitination and degradation. However, the detailed action of arsenic in Nrf2 induction is different from that of tBHQ or SF. Arsenic markedly enhanced the interaction between Keap1 and Cul3, subunits of the E3 ubiquitin ligase for Nrf2, which led to impaired dynamic assembly/disassembly of the E3 ubiquitin ligase and thus decreased its ligase activity. Furthermore, induction of Nrf2 by arsenic is independent of the previously identified C151 residue in Keap1 that is required for Nrf2 activation by tBHQ or SF. Distinct mechanisms of Nrf2 activation by seemingly harmful and beneficial reagents provide a molecular basis to design Nrf2-activating agents for therapeutic intervention.

  14. Catalytic conversion of light alkanes. Final report, January 1, 1990--October 31, 1994

    SciTech Connect (OSTI)

    1998-12-31

    During the course of the first three years of the Cooperative Agreement (Phase I-III), we uncovered a family of metal perhaloporphyrin complexes which had unprecedented activity for the selective air-oxidation of fight alkanes to alcohols. The reactivity of fight hydrocarbon substrates with air or oxygen was in the order: isobutane>propane>ethane>methane, in accord with their homolytic bond dissociation energies. Isobutane was so reactive that the proof-of concept stage of a process for producing tert-butyl alcohol from isobutane was begun (Phase V). It was proposed that as more active catalytic systems were developed (Phases IV, VI), propane, then ethane and finally methane oxidations will move into this stage (Phases VII through IX). As of this writing, however, the program has been terminated during the later stages of Phases V and VI so that further work is not anticipated. We made excellent progress during 1994 in generating a class of less costly new materials which have the potential for high catalytic activity. New routes were developed for replacing costly perfluorophenyl groups in the meso-position of metalloporphyrin catalysts with far less expensive and lower molecular weight perfluoromethyl groups.

  15. Homoleptic Ce(III) and Ce(IV) Nitroxide Complexes: Significant Stabilization of the 4+ Oxidation State

    SciTech Connect (OSTI)

    Bogart, Justin A.; Lewis, Andrew J.; Medling, Scott A.; Piro, Nicholas A.; Carroll, Patrick J.; Booth, Corwin H.; Schelter, Eric J.

    2014-06-25

    Electrochemical experiments performed on the complex Ce-IV[2-((BuNO)-Bu-t)py](4), where [2-((BuNO)-Bu-t)py](-) = N-tert-butyl-N-2-pyridylnitroxide, indicate a 2.51 V stabilization of the 4+ oxidation state of Ce compared to [(Bu4N)-Bu-n](2)[Ce(NO3)(6)] in acetonitrile and a 2.95 V stabilization compared to the standard potential for the ion under aqueous conditions. Density functional theory calculations suggest that this preference for the higher oxidation state is a result of the tetrakis(nitroxide) ligand framework at the Ce cation, which allows for effective electron donation into, and partial covalent overlap with, vacant 4f orbitals with delta symmetry. The results speak to the behavior of CeO2 and related solid solutions in oxygen uptake and transport applications, in particular an inherent local character of bonding that stabilizes the 4+ oxidation state. The results indicate a cerium(IV) complex that has been stabilized to an unprecedented degree through tuning of its ligand-field environment.

  16. Mimicking Conjugated Polymer Thin Film Photophysics with a Well-Defined Triblock Copolymer in Solution

    SciTech Connect (OSTI)

    Brazard, Johanna; Ono, Robert J.; Bielawski, Christopher W.; Barbara, Paul F.; Vanden Bout, David A.

    2013-04-25

    Conjugated polymers (CPs) are promising materials for use in electronic applications, such as low-cost, easily processed organic photovoltaic (OPV) devices. Improving OPV efficiencies is hindered by a lack of a fundamental understanding of the photophysics in CP-based thin films that is complicated by their heterogeneous nanoscale morphologies. Here, we report on a poly(3-hexylthiophene)-block-poly(tert-butyl acrylate)-block-poly(3-hexylthiophene) rodcoilrod triblock copolymer. In good solvents, this polymer resembles solutions of P3HT; however, upon the addition of a poor solvent, the two P3HT chains within the triblock copolymer collapse, affording a material with electronic spectra identical to those of a thin film of P3HT. Using this new system as a model for thin films of P3HT, we can attribute the low fluorescence quantum yield of films to the presence of a charge-transfer state, providing fundamental insights into the condensed phase photophysics that will help to guide the development of the next generation of materials for OPVs.

  17. Exome sequencing of hepatocellular carcinomas identifies new mutational signatures and potential therapeutic targets

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

    Schulze, Kornelius; Imbeaud, Sandrine; Letouzé, Eric; Alexandrov, Ludmil B.; Calderaro, Julien; Rebouissou, Sandra; Couchy, Gabrielle; Meiller, Clément; Shinde, Jayendra; Soysouvanh, Frederic; et al

    2015-03-30

    Our genomic analyses promise to improve tumor characterization to optimize personalized treatment for patients with hepatocellular carcinoma (HCC). Exome sequencing analysis of 243 liver tumors identified mutational signatures associated with specific risk factors, mainly combined alcohol and tobacco consumption and exposure to aflatoxin B1. We identified 161 putative driver genes associated with 11 recurrently altered pathways. Associations of mutations defined 3 groups of genes related to risk factors and centered on CTNNB1 (alcohol), TP53 (hepatitis B virus, HBV) and AXIN1. These analyses according to tumor stage progression identified TERT promoter mutation as an early event, whereasFGF3, FGF4, FGF19 or CCND1more » amplification and TP53 and CDKN2A alterations appeared at more advanced stages in aggressive tumors. In 28% of the tumors, we identified genetic alterations potentially targetable by US Food and Drug Administration (FDA)–approved drugs. Finally, we identified risk factor–specific mutational signatures and defined the extensive landscape of altered genes and pathways in HCC, which will be useful to design clinical trials for targeted therapy.« less

  18. Metabolic changes and DNA hypomethylation in cerebellum are associated with behavioral alterations in mice exposed to trichloroethylene postnatally

    SciTech Connect (OSTI)

    Blossom, Sarah J.; Cooney, Craig A.; Melnyk, Stepan B.; Rau, Jenny L.; Swearingen, Christopher J.; Wessinger, William D.

    2013-06-15

    Previous studies demonstrated that low-level postnatal and early life exposure to the environmental contaminant, trichloroethylene (TCE), in the drinking water of MRL +/+ mice altered glutathione redox homeostasis and increased biomarkers of oxidative stress indicating a more oxidized state. Plasma metabolites along the interrelated transmethylation pathway were also altered indicating impaired methylation capacity. Here we extend these findings to further characterize the impact of TCE exposure in mice exposed to water only or two doses of TCE in the drinking water (0, 2, and 28 mg/kg/day) postnatally from birth until 6 weeks of age on redox homeostasis and biomarkers of oxidative stress in the cerebellum. In addition, pathway intermediates involved in methyl metabolism and global DNA methylation patterns were examined in cerebellar tissue. Because the cerebellum is functionally important for coordinating motor activity, including exploratory and social approach behaviors, these parameters were evaluated in the present study. Mice exposed to 28 mg/kg/day TCE exhibited increased locomotor activity over time as compared with control mice. In the novel object exploration test, these mice were more likely to enter the zone with the novel object as compared to control mice. Similar results were obtained in a second test when an unfamiliar mouse was introduced into the testing arena. The results show for the first time that postnatal exposure to TCE causes key metabolic changes in the cerebellum that may contribute to global DNA methylation deficits and behavioral alterations in TCE-exposed mice. - Highlights: We exposed male mice to low-level trichloroethylene from postnatal days 1 through 42. This exposure altered redox potential and increased oxidative stress in cerebellum. This exposure altered metabolites important in cellular methylation in cerebellum. This exposure promoted DNA hypomethylation in cerebellum. This exposure enhanced locomotor activity and exploratory behavior.

  19. Regulation of MDA-MB-231 cell proliferation by GSK-3? involves epigenetic modifications under high glucose conditions

    SciTech Connect (OSTI)

    Gupta, Chanchal; Kaur, Jasmine; Tikoo, Kulbhushan

    2014-05-15

    Hyperglycemia is a critical risk factor for development and progression of breast cancer. We have recently reported that high glucose induces phosphorylation of histone H3 at Ser 10 as well as de-phosphorylation of GSK-3? at Ser 9 in MDA-MB-231 cells. Here, we elucidate the mechanism underlying hyperglycemia-induced proliferation in MDA-MB-231 breast cancer cells. We provide evidence that hyperglycemia led to increased DNA methylation and DNMT1 expression in MDA-MB-231 cells. High glucose condition led to significant increase in the expression of PCNA, cyclin D1 and decrease in the expression of PTPN 12, p21 and PTEN. It also induced hypermethylation of DNA at the promoter region of PTPN 12, whereas hypomethylation at Vimentin and Snail. Silencing of GSK-3? by siRNA prevented histone H3 phosphorylation and reduced DNMT1 expression. We show that chromatin obtained after immunoprecipitation with phospho-histone H3 was hypermethylated under high glucose condition, which indicates a cross-talk between DNA methylation and histone H3 phosphorylation. ChIP-qPCR analysis revealed up-regulation of DNMT1 and metastatic genes viz. Vimentin, Snail and MMP-7 by phospho-histone H3, which were down-regulated upon GSK-3? silencing. To the best of our knowledge, this is the first report which shows that interplay between GSK-3? activation, histone H3 phosphorylation and DNA methylation directs proliferation of breast cancer cells. - Highlights: High glucose induces phosphorylation of histone H3 and dephosphorylation of GSK-3?. Moreover, hyperglycemia also leads to increased DNA methylation in MDA-MB-231 cells. Inhibition of GSK-3? prevented histone H3 phosphorylation and reduced DNMT1 levels. Interplay exists between GSK-3?, histone H3 phosphorylation and DNA methylation.

  20. TECHNICAL REPORT

    SciTech Connect (OSTI)

    ADAMS, RICHARD D., PhD.

    2011-04-06

    Cadmium selenide nanoparticles and nanoclusters were prepared and added to polymer solar cells to improve their photon capture ability. These nanoparticles did exhibit some beneficial effects on the photon conversion efficiencies of selected polymer solar cells. Ternary bulk heterojunction systems based on composites of methyl viologen-doped, CdSe nanoparticles blended with poly (3-hexothiopene) (P3HT) and 6, 6-phenyl C{sub 61}-butyric acid methyl ester (PCBM) were also tested. It was found that the devices with methyl viologen-doped CdSe nanoparticles do produce more photocurrent in a region surrounding the absorption peak of the particles (560 to 660nm) when compared to pristine P3HT:PCBM devices. Gold nanorods were also prepared and tested in some solar cells. These nanorods did produce a very small enhancement in photon absorbance, but the observed increase the photon conversion efficiency was not sufficient to make the effort worthwhile. Our goals were (1) to prepare cadmium sulfide and cadmium selenide clusters and nanoparticles to be tested as photon absorbers to enhance the photon conversion efficiency of polymer solar polymer solar cells and (2) to prepare gold and silver nanorods to be added to polymer solar cells to enhance their photon capture capability. The cadmium sulfide and cadmium selenide nanoparticles and some new nanoclusters were prepared. The cadmium selenide nanoparticles were also tested in solar cells and did exhibit some positive effects when they were combined with certain co-absorbing polymers. Due to solubility problems that were not solved in the available time, the new nanoclusters were not tested in solar cells. Ternary bulk heterojunction systems based on composites of methyl viologen doped, CdSe nanoparticles blended with poly (3-hexothiopene) (P3HT) and 6, 6-phenyl C61-butyric acid methyl ester (PCBM) have been examined in detail. The methyl viologen was added to promote charge separation of the initially formed excitons. It was found that the devices with CdSe produce more photocurrent in a region surrounding the absorption peak of the particles (560 to 660nm) when compared to a pristine P3HT:PCBM device. Gold nanorods were prepared and tested in some solar cells. These did show a very small enhancement in photon absorbance. However, the increase in short circuit current was negligible, which suggests that this antenna effect produces no significant increase in photocurrent generation. Efforts to synthesize niobium-doped zinc oxide nanoparticles for use in polymer solar polymer solar cells were also made. The nanoparticles were prepared, but they were not tested in the cells before the termination of the funding of the project.

  1. Low Dose Radiation-Induced Genome and Epigenome Instability Symposium and Epigenetic Mechanisms, DNA Repair, and Chromatin Symposium at the EMS 2008 Annual Meeting - October 2008

    SciTech Connect (OSTI)

    Morgan, William F.; Kovalchuk, Olga; Dolinoy, Dana C.; Dubrova, Yuri E.; Coleman, Matthew A.; Schr, Primo; Pogribny, Igor; Hendzel, Michael

    2010-02-19

    The Low Dose Radiation Symposium thoughtfully addressed ionizing radiation non-mutational but transmissable alterations in surviving cells. Deregulation of epigenetic processes has been strongly implicated in carcinogenesis, and there is increasing realization that a significant fraction of non-targeted and adaptive mechanisms in response to ionizing radiation are likely to be epigenetic in nature. Much remains to be learned about how chromatin and epigenetic regulators affect responses to low doses of radiation, and how low dose radiation impacts other epigenetic processes. The Epigenetic Mechanisms Symposium focused on on epigenetic mechanisms and their interplay with DNA repair and chromatin changes. Addressing the fact that the most well understood mediators of epigenetic regulation are histone modifications and DNA methylation. Low levels of radiation can lead to changes in the methylation status of certain gene promoters and the expression of DNA methyltransferases, However, epigenetic regulation can also involve changes in higher order chromosome structure.

  2. Light-emitting block copolymers composition, process and use

    DOE Patents [OSTI]

    Ferraris, John P.; Gutierrez, Jose J.

    2006-11-14

    Generally, and in one form, the present invention is a composition of light-emitting block copolymer. In another form, the present invention is a process producing a light-emitting block copolymers that intends polymerizing a first di(halo-methyl) aromatic monomer compound in the presence of an anionic initiator and a base to form a polymer and contacting a second di(halo-methyl) aromatic monomer compound with the polymer to form a homopolymer or block copolymer wherein the block copolymer is a diblock, triblock, or star polymer. In yet another form, the present invention is an electroluminescent device comprising a light-emitting block copolymer, wherein the electroluminescent device is to be used in the manufacturing of optical and electrical devices.

  3. Process for the synthesis of unsaturated alcohols

    DOE Patents [OSTI]

    Maughon, Bob R.; Burdett, Kenneth A.; Lysenko, Zenon

    2007-02-13

    A process of preparing an unsaturated alcohol (olefin alcohol), such as, a homo-allylic mono-alcohol or homo-allylic polyol, involving protecting a hydroxy-substituted unsaturated fatty acid or fatty acid ester, such as methyl ricinoleate, derived from a seed oil, to form a hydroxy-protected unsaturated fatty acid or fatty acid ester; homo-metathesizing or cross-metathesizing the hydroxy-protected unsaturated fatty acid or fatty acid ester to produce a product mixture containing a hydroxy-protected unsaturated metathesis product; and deprotecting the hydroxy-protected unsaturated metathesis product under conditions sufficient to prepare the unsaturated alcohol. Preferably, methyl ricinoleate is converted by cross-metathesis or homo-metathesis into the homo-allylic mono-alcohol 1-decene-4-ol or the homo-allylic polyol 9-octadecene-7,12-diol, respectively.

  4. Consumers' Gas lays coiled steel tubing in Lake Erie

    SciTech Connect (OSTI)

    Not Available

    1980-10-01

    Forty-four miles of polypropylene-coated, coiled steel tubing have been laid underwater by the Consumers' Gas Co. of Toronto. Laid in 33,000-ft sections from a giant reel, the tubing is used for the remote control of subsea hydraulically operated line valves and the distribution of methyl alcohol to subsea gas wells. The installation is the first of long, continuous tubing underwater using this technology in Canada. The line was installed in conjunction with a newly completed gas well gathering system and processing plant that is expected to yield more than 35 billion cu ft of fuel over the next 15 yr. The new system under W.-Central Lake Erie provides consumers with a cost-effective method for remotely controlling underwater hydraulic valves and distributing methyl alcohol to eliminate hydrate build-up in the gas gathering lines.

  5. Geochemical, Genetic, and Community Controls on Mercury

    SciTech Connect (OSTI)

    Wall, Judy D.

    2014-11-10

    The sulfate-reducing bacteria (SRB) are soil bacteria that share two common characteristics, strict anaerobiosis and the ability to respire sulfate. The metabolic activities of these bacteria play significant roles in the global sulfur cycle, anaerobic degradation of biomass, biological metal corrosion in the environment and, recently, degradation of toxic compounds. The accumulation of evidence suggests these bacteria are also key to the production of the neurotoxin methylmercury in environmental settings. We propose to use our experience with the development of genetics in sulfate-reducing bacteria of the genus Desulfovibrio to create mutations that will eliminate the methylation of mercury, thereby identifying the genes essential for this process. This information may allow the environmental monitoring of the mercury methylation potential to learn the location and quantity of the production this toxin. From these data, more accurate predictive models of mercury cycling can be generated.

  6. Acute aquatic toxicity of biodiesel fuels

    SciTech Connect (OSTI)

    Wright, B.; Haws, R.; Little, D.; Reese, D.; Peterson, C.; Moeller, G.

    1995-12-31

    This study develops data on the acute aquatic toxicity of selected biodiesel fuels which may become subject to environmental effects test regulations under the US Toxic Substances Control Act (TSCA). The test substances are Rape Methyl Ester (RME), Rape Ethyl Ester (REE), Methyl Soyate (MS), a biodiesel mixture of 20% REE and 80% Diesel, a biodiesel mixture of 50% REE and diesel, and a reference substance of Phillips D-2 Reference Diesel. The test procedure follows the Daphnid Acute Toxicity Test outlined in 40 CFR {section} 797.1300 of the TSCA regulations. Daphnia Magna are exposed to the test substance in a flow-through system consisting of a mixing chamber, a proportional diluter, and duplicate test chambers. Novel system modifications are described that accommodate the testing of oil-based test substances with Daphnia. The acute aquatic toxicity is estimated by an EC50, an effective concentration producing immobility in 50% of the test specimen.

  7. Mercury residues in south Florida apple snails (Pomacea paludosa)

    SciTech Connect (OSTI)

    Eisemann, J.D.; Beyer, W.N.; Morton, A.; Bennetts, R.E.

    1997-05-01

    Mercury concentrations in the sediments of south Florida wetlands have increased three fold in the last century. Because south Florida is home to many endemic and endangered species, it is important to understand the potential impacts of mercury in this ecosystem`s food web. Recent research by Malley et al. has shown mollusks to be sensitive indicators of methyl mercury which can reflect small differences in background methyl mercury concentrations. In this study, we attempted to determine if the apple snail (Pomacea paludosa) or its eggs are good indicators of bioavailable mercury. Then, using the apple snail as an indicator, we attempted to determine geographic differences in the concentrations of mercury in south Florida. 12 refs., 1 fig., 1 tab.

  8. Luminescent lanthanide chelates and methods of use

    DOE Patents [OSTI]

    Selvin, Paul R. (Berkeley, CA); Hearst, John (Berkeley, CA)

    1997-01-01

    The invention provides lanthanide chelates capable of intense luminescence. The celates comprise a lanthanide chelator covalently joined to a coumarin-like or quinolone-like sensitizer. Exemplary sensitzers include 2- or 4-quinolones, 2- or 4-coumarins, or derivatives thereof e.g. carbostyril 124 (7-amino-4-methyl-2-quinolone), coumarin 120 (7-amino-4-methyl-2-coumarin), coumarin 124 (7-amino-4-(trifluoromethyl)-2-coumarin), aminomethyltrimethylpsoralen, etc. The chelates form high affinity complexes with lanthanides, such as terbium or europium, through chelator groups, such as DTPA. The chelates may be coupled to a wide variety of compounds to create specific labels, probes, diagnostic and/or therapeutic reagents, etc. The chelates find particular use in resonance energy transfer between chelate-lanthanide complexes and another luminescent agent, often a fluorescent non-metal based resonance energy acceptor. The methods provide useful information about the structure, conformation, relative location and/or interactions of macromolecules.

  9. Catalytic Ionic Hydrogenation of Ketones by {[Cp*Ru(CO)2]2(? H)}+

    SciTech Connect (OSTI)

    Fagan, Paul J.; Voges, Mark H.; Bullock, R. Morris

    2010-02-22

    {[Cp*Ru(CO)2]2(? H)}+OTf functions as a homogeneous catalyst precursor for hydrogenation of ketones to alcohols, with hydrogenations at 1 mol % catalyst loading at 90 C under H2 (820 psi) proceeding to completion and providing >90% yields. Hydrogenation of methyl levulinate generates ?-valerolactone, presumably by ring-closing of the initially formed alcohol with the methyl ester. Experiments in neat Et2C=O show that the catalyst loading can be <0.1 mole %, and that at least 1200 turnovers of the catalyst can be obtained. These reactions are proposed to proceed by an ionic hydrogenation pathway, with the highly acidic dihydrogen complex [Cp*Ru(CO)2(?2-H2)]+OTf- being formed under the reaction conditions from reaction of H2 with {[Cp*Ru(CO)2]2(? H)}+OTf .

  10. Synthesis and single crystal x-ray diffraction study of a Schiff base derived from 4-acylpyrazolone and 2-aminophenol

    SciTech Connect (OSTI)

    Sharma, Naresh; Kant, Rajni Gupta, Vivek K.; Jadeja, R. N.

    2014-04-24

    The title compound, (Z)-1-(3-chlorophenyl)-4[1((2hydroxyphenyl)amino)propylidene] -3-methyl-1H-pyrazol-5(4H)-one was synthesized by refluxing compound 1-(m-chlorophenyl)-3-methyl-4-propionyl-5-pyrazolone, with 2-aminophenol in ethanol. The compound crystallizes in the orthorhombic crystal system with space group Pca2{sub 1} having unit cell parameters: a = 26.2993(8), b = 7.0724(2) and c = 18.7170(5)Å. The structure contains two crystallographically independent molecules, A, and, B, in the asymmetric unit cell. The crystal structure was solved by direct method using single crystal X-ray diffraction data collected at room temperature and refined by full-matrix least-squares procedures to a final R- value of 0.049 for 5207 observed reflections.

  11. Final Report - Epigenetics of low dose radiation effects in an animal model

    SciTech Connect (OSTI)

    Kovalchuk, Olga

    2014-10-22

    This project sought mechanistic understanding of the epigenetic response of tissues as well as the consequences of those responses, when induced by low dose irradiation in a well-established model system (mouse). Based on solid and extensive preliminary data we investigated the molecular epigenetic mechanisms of in vivo radiation responses, particularly effects of low, occupationally relevant radiation exposures on the genome stability and adaptive response in mammalian tissues and organisms. We accumulated evidence that low dose irradiation altered epigenetic profiles and impacted radiation target organs of the exposed animals. The main long-term goal was to dissect the epigenetic basis of induction of the low dose radiation-induced genome instability and adaptive response and the specific fundamental roles of epigenetic changes (i.e. DNA methylation, histone modifications and miRNAs) in their generation. We hypothesized that changes in global and regional DNA methylation, global histone modifications and regulatory microRNAs played pivotal roles in the generation and maintenance low-dose radiation-induced genome instability and adaptive response. We predicted that epigenetic changes influenced the levels of genetic rearrangements (transposone reactivation). We hypothesized that epigenetic responses from low dose irradiation were dependent on exposure regimes, and would be greatest when organisms are exposed in a protracted/fractionated manner: fractionated exposures > acute exposures. We anticipated that the epigenetic responses were correlated with the gene expression levels. Our immediate objectives were: To investigate the exact nature of the global and locus-specific DNA methylation changes in the LDR exposed cells and tissues and dissect their roles in adaptive response To investigate the roles of histone modifications in the low dose radiation effects and adaptive response To dissect the roles of regulatory microRNAs and their targets in low dose radiation effects and adaptive response To correlate the levels of epigenetic changes with genetic rearrangement levels and gene expression patterns. In sum, we determined the precise global and locus-specific DNA methylation patterns in the LDR-exposed cells and tissues of mice, and to correlated DNA methylation changes with the gene expression patterns and manifestations of genome instability. We also determined the alterations of global histone modification pattern in the LDR exposed tissues. Additionally, we established the nature of microRNAome changes in the LDR exposed tissue. In this study we for the first time found that LDR exposure caused profound tissue-specific epigenetic changes in the exposed tissues. We established that LDR exposure affect methylation of repetitive elements in the murine genome, causes changes in histone methylation, acetylation and phosphorylation. Importantly, we found that LDR causes profound and persistent effects on small RNA profiles and gene expression, and that miRNAs are excellent biomarkers of LDR exposure. Furthermore, we extended our analysis and studied LDR effects in rat tissues and human tissues and cell lines. There we also analyzed LDR-induced gene expression, DNA methylation and miRNA changes. Our datasets laid foundation for several new research projects aimed to understand molecular underpinnings of low dose radiation responses, and biological repercussions of low dose radiation effects and radiation carcinogenesis.

  12. 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.

  13. Chemical Shuttle Additives in Lithium Ion Batteries

    SciTech Connect (OSTI)

    Patterson, Mary

    2013-03-31

    The goals of this program were to discover and implement a redox shuttle that is compatible with large format lithium ion cells utilizing LiNi{sub 1/3}Mn{sub 1/3}Co{sub 1/3}O{sub 2} (NMC) cathode material and to understand the mechanism of redox shuttle action. Many redox shuttles, both commercially available and experimental, were tested and much fundamental information regarding the mechanism of redox shuttle action was discovered. In particular, studies surrounding the mechanism of the reduction of the oxidized redox shuttle at the carbon anode surface were particularly revealing. The initial redox shuttle candidate, namely 2-(pentafluorophenyl)-tetrafluoro-1,3,2-benzodioxaborole (BDB) supplied by Argonne National Laboratory (ANL, Lemont, Illinois), did not effectively protect cells containing NMC cathodes from overcharge. The ANL-RS2 redox shuttle molecule, namely 1,4-bis(2-methoxyethoxy)-2,5-di-tert-butyl-benzene, which is a derivative of the commercially successful redox shuttle 2,5-di-tert-butyl-1,4-dimethoxybenzene (DDB, 3M, St. Paul, Minnesota), is an effective redox shuttle for cells employing LiFePO{sub 4} (LFP) cathode material. The main advantage of ANL-RS2 over DDB is its larger solubility in electrolyte; however, ANL-RS2 is not as stable as DDB. This shuttle also may be effectively used to rebalance cells in strings that utilize LFP cathodes. The shuttle is compatible with both LTO and graphite anode materials although the cell with graphite degrades faster than the cell with LTO, possibly because of a reaction with the SEI layer. The degradation products of redox shuttle ANL-RS2 were positively identified. Commercially available redox shuttles Li{sub 2}B{sub 12}F{sub 12} (Air Products, Allentown, Pennsylvania and Showa Denko, Japan) and DDB were evaluated and were found to be stable and effective redox shuttles at low C-rates. The Li{sub 2}B{sub 12}F{sub 12} is suitable for lithium ion cells utilizing a high voltage cathode (potential that is higher than NMC) and the DDB is useful for lithium ion cells with LFP cathodes (potential that is lower than NMC). A 4.5 V class redox shuttle provided by Argonne National Laboratory was evaluated which provides a few cycles of overcharge protection for lithium ion cells containing NMC cathodes but it is not stable enough for consideration. Thus, a redox shuttle with an appropriate redox potential and sufficient chemical and electrochemical stability for commercial use in larger format lithium ion cells with NMC cathodes was not found. Molecular imprinting of the redox shuttle molecule during solid electrolyte interphase (SEI) layer formation likely contributes to the successful reduction of oxidized redox shuttle species at carbon anodes. This helps to understand how a carbon anode covered with an SEI layer, that is supposed to be electrically insulating, can reduce the oxidized form of a redox shuttle.

  14. Reactive formulations for a neutralization of toxic industrial chemicals

    DOE Patents [OSTI]

    Tucker, Mark D.; Betty, Rita G.

    2006-10-24

    Decontamination formulations for neutralization of toxic industrial chemicals, and methods of making and using same. The formulations are effective for neutralizing malathion, hydrogen cyanide, sodium cyanide, butyl isocyanate, carbon disulfide, phosgene gas, capsaicin in commercial pepper spray, chlorine gas, anhydrous ammonia gas; and may be effective at neutralizing hydrogen sulfide, sulfur dioxide, formaldehyde, ethylene oxide, methyl bromide, boron trichloride, fluorine, tetraethyl pyrophosphate, phosphorous trichloride, arsine, and tungsten hexafluoride.

  15. Electron Solvation Dynamics and Reactivity in Ionic Liquids Observed by Picosecond RadiolysisTechniques

    SciTech Connect (OSTI)

    Wishart J. F.; Funston, A.M.; Szreder, T.; Cook, A.R.; Gohdo, M.

    2012-01-01

    On time scales of a nanosecond or less, radiolytically-generated excess electrons in ionic liquids undergo solvation processes and reactions that determine all subsequent chemistry and the accumulation of radiolytic damage. Using picosecond pulse radiolysis detection methods, we observed and quantified the solvation response of the electron in 1-methyl-1-butyl-pyrrolidinium bis(trifluoromethylsulfonyl)amide and used it to understand electron scavenging by a typical solute, duroquinone.

  16. Photovoltaic switching mechanism in lateral structure hybrid perovskite solar cells

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

    Yuan, Yongbo; Chae, Jungseok; Shao, Yuchuan; Wang, Qi; Xiao, Zhengguo; Centrone, Andrea; Huang, Jinsong

    2015-06-05

    In this study, long range electromigration of methylammonium ions (MA+) in methyl ammonium lead tri-iodide (MAPbI3) film is observed directly using the photo­thermal induced resonance technique. The electromigration of MA+ leads to the formation of a lateral p-i-n structure, which is the origin of the switchable photovoltaic effect in MAPbI3 perovskite devices.

  17. Electrochromic salts, solutions, and devices

    DOE Patents [OSTI]

    Burrell, Anthony K. (Los Alamos, NM); Warner, Benjamin P. (Los Alamos, NM); McClesky,7,064,212 T. Mark (Los Alamos, NM)

    2006-06-20

    Electrochromic salts. Electrochromic salts of dicationic viologens such as methyl viologen and benzyl viologen associated with anions selected from bis(trifluoromethylsulfonyl)imide, bis(perfluoroethylsulfonyl)imide, and tris(trifluoromethylsulfonyl)methide are produced by metathesis with the corresponding viologen dihalide. They are highly soluble in molten quarternary ammonium salts and together with a suitable reductant provide electrolyte solutions that are used in electrochromic windows.

  18. A conformational transition in the structure of a 2'-thiomethyl-modified DNA visualized at high resolution

    SciTech Connect (OSTI)

    Pallan, Pradeep S.; Prakash, Thazha P.; Li, Feng; Eoff, Robert L.; Manoharan, Muthiah; Egli, Martin

    2009-06-17

    Crystal structures of A-form and B-form DNA duplexes containing 2'-S-methyl-uridines reveal that the modified residues adopt a RNA-like C3'-endo pucker, illustrating that the replacement of electronegative oxygen at the 2'-carbon of RNA by sulfur does not appear to fundamentally alter the conformational preference of the sugar in the oligonucleotide context and sterics trump stereoelectronics.

  19. Oxidative DNA damage and repair in children exposed to low levels of arsenic in utero and during early childhood: Application of salivary and urinary biomarkers

    SciTech Connect (OSTI)

    Hinhumpatch, Pantip; Navasumrit, Panida; Chaisatra, Krittinee; Promvijit, Jeerawan; Mahidol, Chulabhorn; Ruchirawat, Mathuros

    2013-12-15

    The present study aimed to assess arsenic exposure and its effect on oxidative DNA damage and repair in young children exposed in utero and continued to live in arsenic-contaminated areas. To address the need for biological specimens that can be acquired with minimal discomfort to children, we used non-invasive urinary and salivary-based assays for assessing arsenic exposure and early biological effects that have potentially serious health implications. Levels of arsenic in nails showed the greatest magnitude of difference between exposed and control groups, followed by arsenic concentrations in saliva and urine. Arsenic levels in saliva showed significant positive correlations with other biomarkers of arsenic exposure, including arsenic accumulation in nails (r = 0.56, P < 0.001) and arsenic concentration in urine (r = 0.50, P < 0.05). Exposed children had a significant reduction in arsenic methylation capacity indicated by decreased primary methylation index and secondary methylation index in both urine and saliva samples. Levels of salivary 8-OHdG in exposed children were significantly higher (? 4-fold, P < 0.01), whereas levels of urinary 8-OHdG excretion and salivary hOGG1 expression were significantly lower in exposed children (? 3-fold, P < 0.05), suggesting a defect in hOGG1 that resulted in ineffective cleavage of 8-OHdG. Multiple regression analysis results showed that levels of inorganic arsenic (iAs) in saliva and urine had a significant positive association with salivary 8-OHdG and a significant negative association with salivary hOGG1 expression. - Highlights: The effects of arsenic exposure in utero and through early childhood were studied. Arsenic-exposed children had a reduction in arsenic methylation capacity. Exposed children had more DNA damage, observed as elevated salivary 8-OHdG. Lower salivary hOGG1 in exposed children indicated impairment of 8-OHdG repair. Salivary and urinary 8-OHdG levels were discordant.

  20. Low toxicity method of inhibiting sickling of sickle erythrocytes

    DOE Patents [OSTI]

    Packer, Lester; Bymun, Edwin N.

    1977-01-01

    A low toxicity method of inhibiting sickling of sickle erythrocytes which comprises intermixing the erythrocytes with an effective anti-sickling amount of a water-soluble imidoester of the formula RC(=NH)OR' wherein R is an alkyl group of 1 - 8 carbon atoms, particularly 1 - 4 carbon atoms, and R' is an alkyl group of 1 - 4 carbon atoms, specifically methyl or ethyl acetimidate.

  1. 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.

  2. 33rd International Symposium on Combustion Hottel Lecture Applications of Quantitative Laser Sensors to Kinetics, Propulsion and Practical Combustion Systems Ronald K. Hanson Department of Mechanical Engineering Stanford University, Stanford CA, 94305

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

    for Combustion Science Stanford University Contribution R. K. Hanson and D. F. Davidson Department of Mechanical Engineering Stanford University 1 * Butanol Studies * Ignition Delay Times * Species Time-Histories * Reaction Rate Constants * Methyl Ester Studies * Ignition Delay Times Long-Term Objectives * Generate high-quality fundamental kinetics database using shock tube/laser absorption methods Leading to: * Improved detailed mechanisms for next-generation fuels First Targets: * Isomers of

  3. Separation of the isotopes of boron by chemical exchange reactions

    DOE Patents [OSTI]

    McCandless, Frank P. (Bozeman, MT); Herbst, Ronald S. (Idaho Falls, ID)

    1995-01-01

    The isotopes of boron, .sup.10 B and .sup.11 B, are separated by means of a gas-liquid chemical exchange reaction involving the isotopic equilibrium between gaseous BF.sub.3 and a liquid BF.sub.3 . donor molecular addition complex formed between BF.sub.3 gas and a donor chosen from the group consisting of: nitromethane, acetone, methyl isobutyl ketone, or diisobutyl ketone.

  4. Separation of the isotopes of boron by chemical exchange reactions

    DOE Patents [OSTI]

    McCandless, F.P.; Herbst, R.S.

    1995-05-30

    The isotopes of boron, {sup 10}B and {sup 11}B, are separated by means of a gas-liquid chemical exchange reaction involving the isotopic equilibrium between gaseous BF{sub 3} and a liquid BF{sub 3} donor molecular addition complex formed between BF{sub 3} gas and a donor chosen from the group consisting of: nitromethane, acetone, methyl isobutyl ketone, or diisobutyl ketone. 1 Fig.

  5. Spherical nitroguanidine process

    DOE Patents [OSTI]

    Sanchez, John A. (Los Alamos, NM); Roemer, Edward L. (Los Alamos, NM); Stretz, Lawrence A. (Los Alamos, NM)

    1990-01-01

    A process of preparing spherical high bulk density nitroguanidine by dissing low bulk density nitroguanidine in N-methyl pyrrolidone at elevated temperatures and then cooling the solution to lower temperatures as a liquid characterized as a nonsolvent for the nitroguanidine is provided. The process is enhanced by inclusion in the solution of from about 1 ppm up to about 250 ppm of a metal salt such as nickel nitrate, zinc nitrate or chromium nitrate, preferably from about 20 to about 50 ppm.

  6. Photovoltaic switching mechanism in lateral structure hybrid perovskite solar cells

    SciTech Connect (OSTI)

    Yuan, Yongbo; Chae, Jungseok; Shao, Yuchuan; Wang, Qi; Xiao, Zhengguo; Centrone, Andrea; Huang, Jinsong

    2015-06-05

    In this study, long range electromigration of methylammonium ions (MA+) in methyl ammonium lead tri-iodide (MAPbI3) film is observed directly using the photothermal induced resonance technique. The electromigration of MA+ leads to the formation of a lateral p-i-n structure, which is the origin of the switchable photovoltaic effect in MAPbI3 perovskite devices.

  7. An assessment of alternatives and technologies for replacing ozone- depleting substances at DOE facilities

    SciTech Connect (OSTI)

    Purcell, C.W.; Miller, K.B.; Friedman, J.R.; Rapoport, R.D.; Conover, D.R.; Hendrickson, P.L.; Koss, T.C.

    1992-10-01

    Title VI of the Clean Air Act, as amended, mandates a production phase-out for ozone-depleting substances (ODSs). These requirements will have a significant impact on US Department of Energy (DOE) facilities. Currently, DOE uses ODSs in three major activities: fire suppression (halon), refrigeration and cooling (chlorofluorocarbons [CFCs]), and cleaning that requires solvents (CFCs, methyl chloroform, and carbon tetrachloride). This report provides basic information on methods and strategies to phase out use of ODSs at DOE facilities.

  8. Table Definitions, Sources, and Explanatory Notes

    Gasoline and Diesel Fuel Update (EIA)

    Imports & Exports Definitions Key Terms Definition All Other Motor Gasoline Blending Components Naphthas (e.g. straight-run gasoline, alkylate, reformate, benzene, toluene, xylene) used for blending or compounding into finished motor gasoline. Includes receipts and inputs of Gasoline Treated as Blendstock (GTAB). Excludes conventional blendstock for oxygenate blending (CBOB), reformulated blendstock for oxygenate blending, oxygenates (e.g. fuel ethanol and methyl tertiary butyl ether),

  9. Table Definitions, Sources, and Explanatory Notes

    Gasoline and Diesel Fuel Update (EIA)

    Ethanol Plant Production Definitions Key Terms Definition Barrel A unit of volume equal to 42 U.S. gallons. Fuel Ethanol An anhydrous alcohol (ethanol with less than 1% water) intended for gasoline blending as described in the Oxygenates definition. Oxygenates Substances which, when added to gasoline, increase the amount of oxygen in that gasoline blend. Ethanol, Methyl Tertiary Butyl Ether (MTBE), Ethyl Tertiary Butyl Ether (ETBE), and methanol are common oxygenates. Fuel Ethanol: Blends of up

  10. Table Definitions, Sources, and Explanatory Notes

    Gasoline and Diesel Fuel Update (EIA)

    Total Stocks Definitions Key Terms Definition All Other Motor Gasoline Blending Components Naphthas (e.g. straight-run gasoline, alkylate, reformate, benzene, toluene, xylene) used for blending or compounding into finished motor gasoline. Includes receipts and inputs of Gasoline Treated as Blendstock (GTAB). Excludes conventional blendstock for oxygenate blending (CBOB), reformulated blendstock for oxygenate blending, oxygenates (e.g. fuel ethanol and methyl tertiary butyl ether), butane, and

  11. Table Definitions, Sources, and Explanatory Notes

    Gasoline and Diesel Fuel Update (EIA)

    Weekly Supply Estimates Definitions Key Terms Definition All Other Motor Gasoline Blending Components Naphthas (e.g. straight-run gasoline, alkylate, reformate, benzene, toluene, xylene) used for blending or compounding into finished motor gasoline. Includes receipts and inputs of Gasoline Treated as Blendstock (GTAB). Excludes conventional blendstock for oxygenate blending (CBOB), reformulated blendstock for oxygenate blending, oxygenates (e.g. fuel ethanol and methyl tertiary butyl ether),

  12. Total Crude Oil and Petroleum Products Exports

    Gasoline and Diesel Fuel Update (EIA)

    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

  13. Next Generation Sequencing at the University of Chicago Genomics Core

    Office of Scientific and Technical Information (OSTI)

    (Conference) | SciTech Connect Next Generation Sequencing at the University of Chicago Genomics Core Citation Details In-Document Search Title: Next Generation Sequencing at the University of Chicago Genomics Core The University of Chicago Genomics Core provides University of Chicago investigators (and external clients) access to State-of-the-Art genomics capabilities: next generation sequencing, Sanger sequencing / genotyping and micro-arrays (gene expression, genotyping, and methylation).

  14. Lanthanide coordination polymers: Synthesis, diverse structure and

    Office of Scientific and Technical Information (OSTI)

    luminescence properties (Journal Article) | SciTech Connect Lanthanide coordination polymers: Synthesis, diverse structure and luminescence properties Citation Details In-Document Search Title: Lanthanide coordination polymers: Synthesis, diverse structure and luminescence properties The new semirigid exo-bidentate ligand incorporating furfurysalicylamide terminal groups, namely, 1,4-bis([(2'-furfurylaminoformyl)phenoxyl]methyl)-2,5-bismethylbenzene (L) was synthesized and used as building

  15. Chlorine atom-initiated low-temperature oxidation of prenol and isoprenol: The effect of C=C double bonds on the peroxy radical chemistry in alcohol oxidation

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

    Welz, Oliver; Savee, John D.; Osborn, David L.; Taatjes, Craig A.

    2014-07-04

    The chlorine atom-initiated oxidation of two unsaturated primary C5 alcohols, prenol (3-methyl-2-buten-1-ol, (CH3)2CCHCH2OH) and isoprenol (3-methyl-3-buten-1-ol, CH2C(CH3)CH2CH2OH), is studied at 550 K and low pressure (8 Torr). The time- and isomer-resolved formation of products is probed with multiplexed photoionization mass spectrometry (MPIMS) using tunable vacuum ultraviolet ionizing synchrotron radiation. The peroxy radical chemistry of the unsaturated alcohols appears much less rich than that of saturated C4 and C5 alcohols. The main products observed are the corresponding unsaturated aldehydes – prenal (3-methyl-2-butenal) from prenol oxidation and isoprenal (3-methyl-3-butenal) from isoprenol oxidation. No significant products arising from QOOH chemistry are observed. Thesemore » results can be qualitatively explained by the formation of resonance stabilized allylic radicals via H-abstraction in the Cl + prenol and Cl + isoprenol initiation reactions. The loss of resonance stabilization upon O2 addition causes the energies of the intermediate wells, saddle points, and products to increase relative to the energy of the initial radicals and O2. These energetic shifts make most product channels observed in the peroxy radical chemistry of saturated alcohols inaccessible for these unsaturated alcohols. The experimental findings are underpinned by quantum-chemical calculations for stationary points on the potential energy surfaces for the reactions of the initial radicals with O2. Under our conditions, the dominant channels in prenol and isoprenol oxidation are the chain-terminating HO2-forming channels arising from radicals, in which the unpaired electron and the –OH group are on the same carbon atom, with stable prenal and isoprenal co-products, respectively. These results suggest that the presence of C=C double bonds in alcohols will reduce low-temperature reactivity during autoignition.« less

  16. Method for producing hydrophobic aerogels

    DOE Patents [OSTI]

    Hrubesh, Lawrence W. (Pleasanton, CA); Poco, John F. (Livermore, CA); Coronado, Paul R. (Livermore, CA)

    1999-01-01

    A method for treating a dried monolithic aerogel containing non-dispersed particles, with an organometallic surface modifying agent to produce hydrophobic aerogels. The dried, porous hydrophobic aerogels contain a protective layer of alkyl groups, such as methyl groups, on the modified surfaces of the pores of the aerogel. The alkyl groups at the aerogel surface typically contain at least one carbon-metal bond per group.

  17. Apparatus for use in sulfide chemiluminescence detection

    DOE Patents [OSTI]

    Spurlin, S.R.; Yeung, E.S.

    1987-01-06

    A method is described for chemiluminescently determining a sulfide which is either hydrogen sulfide or methyl mercaptan by reacting the sulfide with chlorine dioxide at low pressure and under conditions which allow a longer reaction time in emission of a single photon for every two sulfide containing species, and thereafter, chemiluminescently detecting and determining the sulfide. The invention also relates not only to the detection method, but the novel chemical reaction and a specifically designed chemiluminescence detection cell for the reaction. 4 figs.

  18. Electrochemical components employing polysiloxane-derived binders

    DOE Patents [OSTI]

    Delnick, Frank M.

    2013-06-11

    A processed polysiloxane resin binder for use in electrochemical components and the method for fabricating components with the binder. The binder comprises processed polysiloxane resin that is partially oxidized and retains some of its methyl groups following partial oxidation. The binder is suitable for use in electrodes of various types, separators in electrochemical devices, primary lithium batteries, electrolytic capacitors, electrochemical capacitors, fuel cells and sensors.

  19. Electrochromic Salts, Solutions, and Devices

    DOE Patents [OSTI]

    Burrell, Anthony K. (Los Alamos, NM); Warner, Benjamin P. (Los Alamos, NM); McClesky, T. Mark (Los Alamos, NM)

    2008-10-14

    Electrochromic salts. Electrochromic salts of dicationic viologens such as methyl viologen and benzyl viologen associated with anions selected from bis(trifluoromethylsulfonyl)imide, bis(perfluoroethylsulfonyl)imide, and tris(trifluoromethylsulfonyl)methide are produced by metathesis with the corresponding viologen dihalide. They are highly soluble in molten quarternary ammonium salts and together with a suitable reductant provide electrolyte solutions that are used in electrochromic windows.

  20. Electrochromic Salts, Solutions, and Devices

    DOE Patents [OSTI]

    Burrell, Anthony K. (Los Alamos, NM); Warner, Benjamin P. (Los Alamos, NM); McClesky, T. Mark (Los Alamos, NM)

    2008-11-11

    Electrochromic salts. Electrochromic salts of dicationic viologens such as methyl viologen and benzyl viologen associated with anions selected from bis(trifluoromethylsulfonyl)imide, bis(perfluoroethylsulfonyl)imide, and tris(trifluoromethylsulfonyl)methide are produced by metathesis with the corresponding viologen dihalide. They are highly soluble in molten quarternary ammonium salts and together with a suitable reductant provide electrolyte solutions that are used in electrochromic windows.

  1. Biodiesel - Combustion Energy Frontier Research Center

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

    Biodiesel Biodiesel Goals Develop accurate multi-scale models and experimental methods for quantitative combustion modeling of methyl esters and biodiesels at current and future engine conditions. Deliverables Obtain new experiment data of elementary reaction rates, ignition delay times, extinction limits, and speciation in broad temperature and pressure ranges. Develop quantum computational schemes for chemically accurate prediction of elementary reaction rates, activation energies, and bond

  2. Frontiers of Combustion: From Microgravity to Microengines

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

    University FLAME CHEMISTRY, DYNAMICS AND MODEL REDUCTION Sanghee Won, Wenting Sung, Michael Burke and Yiguang Ju Princeton University Collaborators: Stephen Dooley and Fredrick Dryer Xiaolong Gou, Zheng Chen Princeton University Research summary 1. Fuels * H 2 /CH 4 /CO/O 2 flame speed (25 atm) * Methyl-butanoate (extinction & transport) * t-butanol (extinction) 2. Model reduction * Dynamic multi-timescale * Multi-generation path flux analysis * Adaptive chemistry 3. Theory and modeling *

  3. Refinery Stocks of Crude Oil and Petroleum Products

    Gasoline and Diesel Fuel Update (EIA)

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

  4. Currently used pesticides and their mixtures affect the function of sex hormone receptors and aromatase enzyme activity

    SciTech Connect (OSTI)

    Kjeldsen, Lisbeth Stigaard; Ghisari, Mandana; Bonefeld-Jrgensen, Eva Cecilie, E-mail: ebj@mil.au.dk

    2013-10-15

    The endocrine-disrupting potential of pesticides is of health concern, since they are found ubiquitously in the environment and in food items. We investigated in vitro effects on estrogen receptor (ER) and androgen receptor (AR) transactivity, and aromatase enzyme activity, of the following pesticides: 2-methyl-4-chlorophenoxyacetic acid (MCPA), terbuthylazine, iodosulfuron-methyl-sodium, mesosulfuron-methyl, metsulfuron-methyl, chlormequat chloride, bitertanol, propiconazole, prothioconazole, mancozeb, cypermethrin, tau fluvalinate, malathion and the metabolite ethylene thiourea (ETU). The pesticides were analyzed alone and in selected mixtures. Effects of the pesticides on ER and AR function were assessed in human breast carcinoma MVLN cells and hamster ovary CHO-K1 cells, respectively, using luciferase reporter gene assays. Effects on aromatase enzyme activity were analyzed in human choriocarcinoma JEG-3 cells, employing the classical [{sup 3}H]{sub 2}O method. Five pesticides (terbuthylazine, propiconazole, prothioconazole, cypermethrin and malathion) weakly induced the ER transactivity, and three pesticides (bitertanol, propiconazole and mancozeb) antagonized the AR activity in a concentration-dependent manner. Three pesticides (terbuthylazine, propiconazole and prothioconazole) weakly induced the aromatase activity. In addition, two mixtures, consisting of three pesticides (bitertanol, propiconazole, cypermethrin) and five pesticides (terbuthylazine, bitertanol, propiconazole, cypermethrin, malathion), respectively, induced the ER transactivity and aromatase activity, and additively antagonized the AR transactivity. In conclusion, our data suggest that currently used pesticides possess endocrine-disrupting potential in vitro which can be mediated via ER, AR and aromatase activities. The observed mixture effects emphasize the importance of considering the combined action of pesticides in order to assure proper estimations of related health effect risks. - Highlights: Currently used pesticides possess endocrine-disrupting (ED) potential in vitro. ED effects can be mediated via sex hormone receptors and/or the aromatase enzyme. Additive mixture effects on androgen receptor transactivity were observed.

  5. Refinery & Blenders Net Input of Crude Oil

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

    Input Product: Total Crude Oil & Petroleum Products Crude Oil Natural Gas Plant Liquids and Liquefied Refinery Gases Pentanes Plus Liquefied Petroleum Gases Ethane Normal Butane Isobutane Other Liquids Hydrogen/Oxygenates/Renewables/Other Hydrocarbons Hydrogen Oxygenates (excl. Fuel Ethanol) Methyl Tertiary Butyl Ether (MTBE) All Other Oxygenates Renewable Fuels (incl. Fuel Ethanol) Fuel Ethanol Renewable Diesel Fuel Other Renewable Fuels Other Hydrocarbons Unfinished Oils (net) Unfinished

  6. Strategies for Electrooptic Film Fabrication. Influence of Pyrrole-Pyridine-Based Dibranched Chromophore Architecture on Covalent Self-Assembly, Thin-Film Microstructure, and Nonlinear Optical Response

    SciTech Connect (OSTI)

    Facchetti,A.; Beverina, L.; van der Boom, M.; Shukla, A.; Dutta, P.; Evmenenko, G.; Marks, T.; Pagani, G.

    2006-01-01

    The new dibranched, heterocyclic 'push-pull' chromophores bis{l_brace}1-(pyridin-4-yl)-2-[2-(N-methylpyrrol-5-yl)]ethane{r_brace}methane (1), 1-(pyrid-4-yl)-2-(N-methyl-5-formylpyrrol-2-yl)ethylene (2), {l_brace}1-(N-methylpyridinium-4-yl)-2-[2-(N-methylpyrrol-5-yl)]ethane{r_brace}{l_brace}[1-(pyridin-4-yl)-2-[2-(N-methylpyrrol-5-yl)]ethane]{r_brace}methane (3), N-methyl-2-[1-(N-methylpyrid-4-yl)ethen-2-yl]-5-[pyrid-4-yl]ethen-2-yl-pyrrole iodide (4), bis{l_brace}1-(N-methyl-4-pyridinio)-2-[2-(N-methylpyrrol-5-yl)]ethane{r_brace}methane iodide (5), and N-methyl-2,5-[1-(N-methylpyrid-4-yl)ethen-2-yl]pyrrole iodide (6) have been synthesized and characterized. The neutral (1 and 2) and monomethyl salts (3 and 4) undergo chemisorptive reaction with iodobenzyl-functionalized surfaces to afford chromophore monolayers SA-1/SA-2 and SA-3/SA-4, respectively. Molecular structures and other physicochemical properties have been defined by 1H NMR, optical spectroscopy, and XRD. Thin-film characterization by a variety of techniques (optical spectroscopy, specular X-ray reflectivity, atomic force microscopy, X-ray photoelectron spectroscopy, and angle-dependent polarized second harmonic generation) underscore the importance of the chromophore molecular architecture as well as film growth method on film microstructure and optical/electrooptic response.

  7. LLNL Chemical Kinetics Modeling Group

    SciTech Connect (OSTI)

    Pitz, W J; Westbrook, C K; Mehl, M; Herbinet, O; Curran, H J; Silke, E J

    2008-09-24

    The LLNL chemical kinetics modeling group has been responsible for much progress in the development of chemical kinetic models for practical fuels. The group began its work in the early 1970s, developing chemical kinetic models for methane, ethane, ethanol and halogenated inhibitors. Most recently, it has been developing chemical kinetic models for large n-alkanes, cycloalkanes, hexenes, and large methyl esters. These component models are needed to represent gasoline, diesel, jet, and oil-sand-derived fuels.

  8. Direct conversion of algal biomass to biofuel

    SciTech Connect (OSTI)

    Deng, Shuguang; Patil, Prafulla D; Gude, Veera Gnaneswar

    2014-10-14

    A method and system for providing direct conversion of algal biomass. Optionally, the method and system can be used to directly convert dry algal biomass to biodiesels under microwave irradiation by combining the reaction and combining steps. Alternatively, wet algae can be directly processed and converted to fatty acid methyl esters, which have the major components of biodiesels, by reacting with methanol at predetermined pressure and temperature ranges.

  9. Method for producing hydrophobic aerogels

    SciTech Connect (OSTI)

    Hrubesh, L.W.; Poco, J.F.; Coronado, P.R.

    1999-12-21

    A method is described for treating a dried monolithic aerogel containing non-dispersed particles, with an organometallic surface modifying agent to produce hydrophobic aerogels. The dried, porous hydrophobic aerogels contain a protective layer of alkyl groups, such as methyl groups, on the modified surfaces of the pores of the aerogel. The alkyl groups at the aerogel surface typically contain at least one carbon-metal bond per group.

  10. Floral Benzenoid Carboxyl Methyltransferases: From in Vitro to in Planta Function

    SciTech Connect (OSTI)

    Effmert,U.; Saschenbrecker, S.; Ross, J.; Negre, F.; Fraser, C.; Noel, J.; Dudareva, N.; Piechulla, B.

    2005-01-01

    Benzenoid carboxyl methyltransferases synthesize methyl esters (e.g., methyl benzoate and methyl salicylate), which are constituents of aromas and scents of many plant species and play important roles in plant communication with the surrounding environment. Within the past five years, eleven such carboxyl methyltransferases were isolated and most of them were comprehensively investigated at the biochemical, molecular and structural level. Two types of enzymes can be distinguished according to their substrate preferences: the SAMT-type enzymes isolated from Clarkia breweri, Stephanotis floribunda, Antirrhinum majus, Hoya carnosa, and Petunia hybrida, which have a higher catalytic efficiency and preference for salicylic acid, while BAMT-type enzymes from A. majus, Arabidopsis thaliana, Arabidopsis lyrata, and Nicotiana suaveolens prefer benzoic acid. The elucidation of C. breweri SAMT's three-dimensional structure allowed a detailed modelling of the active sites of the carboxyl methyltransferases and revealed that the SAM binding pocket is highly conserved among these enzymes while the methyl acceptor binding site exhibits some variability, allowing a classification into SAMT-type and BAMT-type enzymes. The analysis of expression patterns coupled with biochemical characterization showed that these carboxyl methyltransferases are involved either in floral scent biosynthesis or in plant defense responses. While the latter can be induced by biotic or abiotic stress, the genes responsible for floral scent synthesis exhibit developmental and rhythmic expression pattern. The nature of the product and efficiency of its formation in plants depend on the availability of substrates, the catalytic efficiency of the enzyme toward benzoic acid and/or salicylic acid, and the transcriptional, translational, and post-translational regulation at the enzyme level. The biochemical properties of benzenoid carboxyl methyltransferases suggest that the genes involved in plant defenses might represent the ancestor for the presently existing floral genes which during evolution gained different expression profiles and encoded enzymes with the ability to accept structurally similar substrates.

  11. EA-1157: Finding of No Significant Impact | Department of Energy

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

    57: Finding of No Significant Impact EA-1157: Finding of No Significant Impact Methyl Chloride via Oxyhydrochlorination of Methane: A Building Black for Chemicals and Fuels from Natural Gas The proposed Federal action, to provide cost-shared financial assistance for demonstration of the OHC process in an engineering scale facility, does not constitute a major Federal action that would significantly affect the quality of the human environment as defined by NEPA. This conclusion is based on the

  12. Sulfide chemiluminescence detection

    DOE Patents [OSTI]

    Spurlin, Stanford R. (Ames, IA); Yeung, Edward S. (Ames, IA)

    1985-01-01

    A method of chemiluminescently determining a sulfide which is either hydrogen sulfide or methyl mercaptan by reacting the sulfide with chlorine dioxide at low pressure and under conditions which allow a longer reaction time in emission of a single photon for every two sulfide containing species, and thereafter, chemiluminescently detecting and determining the sulfide. The invention also relates not only to the detection method, but the novel chemical reaction and a specifically designed chemiluminescence detection cell for the reaction.

  13. Apparatus for use in sulfide chemiluminescence detection

    DOE Patents [OSTI]

    Spurlin, Stanford R. (Ames, IA); Yeung, Edward S. (Ames, IA)

    1987-01-01

    A method of chemiluminescently determining a sulfide which is either hydrogen sulfide or methyl mercaptan by reacting the sulfide with chlorine dioxide at low pressure and under conditions which allow a longer reaction time in emission of a single photon for every two sulfide containing species, and thereafter, chemiluminescently detecting and determining the sulfide. The invention also relates not only to the detection method, but the novel chemical reaction and a specifically designed chemiluminescence detection cell for the reaction.

  14. Method of generating chemiluminescent light

    DOE Patents [OSTI]

    Spurlin, Stanford R. (Ames, IA); Yeung, Edward S. (Ames, IA)

    1986-01-01

    A method of chemiluminescently determining a sulfide which is either hydrogen sulfide or methyl mercaptan by reacting the sulfide with chlorine dioxide at low pressure and under conditions which allow a longer reaction time in emission of a single photon for every two sulfide containing species, and thereafter, chemiluminescently detecting and determining the sulfide. The invention also relates not only to the detection method, but the novel chemical reaction that generates chemiluminescent light and a specifically designed chemiluminescence detection cell for the reaction.

  15. Sulfide chemiluminescence detection

    DOE Patents [OSTI]

    Spurlin, S.R.; Yeung, E.S.

    1985-11-26

    A method is described for chemiluminescently determining a sulfide which is either hydrogen sulfide or methyl mercaptan by reacting the sulfide with chlorine dioxide at low pressure and under conditions which allow a longer reaction time in emission of a single photon for every two sulfide containing species, and thereafter, chemiluminescently detecting and determining the sulfide. The invention also relates not only to the detection method, but the novel chemical reaction and a specifically designed chemiluminescence detection cell for the reaction. 4 figs.

  16. MTBE Production Economics

    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

  17. MTBE, Oxygenates, and Motor Gasoline

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

    MTBE, Oxygenates, and Motor Gasoline Contents * Introduction * Federal gasoline product quality regulations * What are oxygenates? * Who gets gasoline with oxygenates? * Which areas get MTBE? * How much has been invested in MTBE production capacity? * What does new Ethanol capacity cost? * What would an MTBE ban cost? * On-line information resources * Endnotes * Summary of revisions to this analysis Introduction The blending of methyl tertiary butyl ether (MTBE) into motor gasoline has increased

  18. Effect of Accelerated Aging Rate on the Capture of Fuel-Borne Metal Impurities by Emissions Control Devices

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

    INTRODUCTION Metallic fuel contaminants such as sodium (Na), potassium (K), calcium (Ca) and magnesium (Mg) may be introduced into diesel fuel through a number of different sources. As one example, biodiesel production relies on sodium hydroxide or potassium hydroxide to catalyze the reaction of vegetable oils with methanol to form methyl esters. In this process, residual amounts of Na or K can be left behind. In addition, small amounts of Ca or Mg can be added to the fuel from the purifcation

  19. Synthesis and characterization of a series of Group 4 phenoxy-thiol derivatives

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

    Boyle, Timothy J.; Neville, Michael L.; Parkes, Marie V.

    2016-02-11

    In this study, a series of Group 4 phenoxy-thiols were developed from the reaction products of a series of metal tert-butoxides ([M(OBut)4]) with four equivalents of 4-mercaptophenol (H-4MP). The products were found by single crystal X-ray diffraction to adopt the general structure [(HOBut)(4MP)3M(μ-4MP)]2 [where M = Ti (1), Zr (2), Hf (3)] from toluene and [(py)2M(4MP)] where M = Ti (4), Zr (5) and [(py)(4MP)3Hf(μ-4MP)]2 (6) from pyridine (py). Varying the [Ti(OR)4] precursors (OR = iso-propoxide (OPri) or neo-pentoxide (ONep)) in toluene led to [(HOR)(4MP)3Ti(μ-4MP)]2 (OR = OPri (7), ONep (8)), which were structurally similar to 1. Lower stoichiometric reactionsmore » in toluene led to partial substitution by the 4MP ligands yielding [H][Ti(μ-4MP)(4MP)(ONep)3]2 (9). Independent of the stoichiometry, all of the Ti derivatives were found to be red in color, whereas the heavier congeners were colorless. Attempts to understand this phenomenon led to investigation with a series of varied –SH substituted phenols. From the reaction of H-2MP and H-3MP (2-mercaptophenol and 3-mercaptophenol, respectively), the isolated products had identical arrangements: [(ONep)2(2MP)Ti(μ,η2-2MP)]2 (10) and [(HOR)(3MP)M(μ-3MP)]2 (M/OR = Ti/ONep (11); Zr/OBut (12)) with a similar red color. Based on the simulated and observed UV–Vis spectra, it was reasoned that the color was generated due to a ligand-to-metal charge transfer for Ti that was not available for the larger congeners.« less

  20. Investigating the Synthesis of Ligated Metal Clusters in Solution Using a Flow Reactor and Electrospray Ionization Mass Spectrometry

    SciTech Connect (OSTI)

    Olivares, Astrid M.; Laskin, Julia; Johnson, Grant E.

    2014-09-18

    The scalable synthesis of subnanometer metal clusters containing an exact number of atoms is of interest due to the highly size-dependent catalytic, electronic and optical properties of these species. While significant research has been conducted on the batch preparation of clusters through reduction synthesis in solution, the processes of metal complex reduction as well as cluster nucleation, growth and post-reduction etching are still not well understood. Herein, we demonstrate a temperature-controlled flow reactor for studying cluster formation in solution at well-defined conditions. Employing this technique methanol solutions of a chloro(triphenylphosphine)gold precursor, 1,4-bis(diphenylphosphino)butane capping ligand and borane-tert-butylamine reducing agent were combined in a mixing tee and introduced into a heated capillary with an adjustable length. In this manner, the temperature dependence of the relative abundance of different ionic reactants, intermediates and products synthesized in real time was characterized using online mass spectrometry. A wide distribution of doubly and triply charged cationic gold clusters was observed as well as smaller singly charged metal-ligand complexes. The results demonstrate that temperature plays a crucial role in determining the relative population of cationic gold clusters and, in general, that higher temperature promotes the formation of doubly charged clusters and singly charged metal-ligand complexes while hindering the growth of triply charged clusters. Moreover, the distribution of clusters observed at elevated temperatures is found to be consistent with that obtained at longer reaction times at room temperature, thereby demonstrating that heating may be used to access cluster distributions characteristic of different stages of reduction synthesis in solution.

  1. Developing and Testing an Alkaline-Side Solvent Extraction Process for Technetium Separation from Tank Waste

    SciTech Connect (OSTI)

    Leonard, Ralph A.; Conner, Cliff; Liberatore, Matthew W.; Bonnesen, Peter V.; Presley, Derek J.; Moyer, Bruce A.; Lumetta, Gregg J. )

    1998-11-01

    Engineering development and testing of the SRTALK solvent extraction process are discussed in this paper. This process provides a way to carry out alkaline-side removal and recovery of technetium in the form of pertechnetate anion from nuclear waste tanks within the DOE complex. The SRTALK extractant consists of a crown ether, bis-4,4'(5')[(tert-butyl)cyclohexano]-18-crown-6, in a modifier, tributyl phosphate, and a diluent, Isopar-L. The SRTALK flowsheet given here separates technetium form the waste and concentrates it by a factor of ten to minimize the load on downstream evaporator for the technetium effluent. In this work, we initially generated and correlated the technetium extraction data, measured the dispersion number for various processing conditions, and determined hydraulic performance in a single-stage 2-cm centrifugal contactor. Then we used extraction-factor analysis, single-stage contactor tests, and stage-to-stage process calculations to develop a SRTALK flowsheet . Key features of the flowsheet are (1) a low organic-to-aqueous (O/A) flow ratio in the extraction section and a high O/A flow ratio in the strip section to concentrate the technetium and (2) the use of a scrub section to reduce the salt load in the concentrated technetium effluent. Finally, the SRTALK process was evaluated in a multistage test using a synthetic tank waste. This test was very successful. Initial batch tests with actual waste from the Hanford nuclear waste tanks show the same technetium extractability as determined with the synthetic waste feed. Therefore, technetium removal from actual tank wastes should also work well using the SRTALK process.

  2. Low and High Temperature Combustion Chemistry of Butanol Isomers in Premixed Flames and Autoignition Systems

    SciTech Connect (OSTI)

    Sarathy, S M; Pitz, W J; Westbrook, C K; Mehl, M; Yasunaga, K; Curran, H J; Tsujimura, T; Osswald, P; Kohse-Hoinghaus, K

    2010-12-12

    Butanol is a fuel that has been proposed as a bio-derived alternative to conventional petroleum derived fuels. The structural isomer in traditional 'bio-butanol' fuel is n-butanol, but newer conversion technologies produce iso-butanol as a fuel. In order to better understand the combustion chemistry of bio-butanol, this study presents a comprehensive chemical kinetic model for all the four isomers of butanol (e.g., 1-, 2-, iso- and tert-butanol). The proposed model includes detailed high temperature and low temperature reaction pathways. In this study, the primary experimental validation target for the model is premixed flat low-pressure flame species profiles obtained using molecular beam mass spectrometry (MBMS). The model is also validated against previously published data for premixed flame velocity and n-butanol rapid compression machine and shock tube ignition delay. The agreement with these data sets is reasonably good. The dominant reaction pathways at the various pressures and temperatures studied are elucidated. At low temperature conditions, we found that the reaction of alphahydroxybutyl with O{sub 2} was important in controlling the reactivity of the system, and for correctly predicting C{sub 4} aldehyde profiles in low pressure premixed flames. Enol-keto isomerization reactions assisted by HO{sub 2} were also found to be important in converting enols to aldehydes and ketones in the low pressure premixed flames. In the paper, we describe how the structural features of the four different butanol isomers lead to differences in the combustion properties of each isomer.

  3. Conditionally immortalized human pancreatic stellate cell lines demonstrate enhanced proliferation and migration in response to IGF-I

    SciTech Connect (OSTI)

    Rosendahl, Ann H.; Gundewar, Chinmay; Said Hilmersson, Katarzyna; Ni, Lan; Saleem, Moin A.; Andersson, Roland

    2015-01-15

    Pancreatic stellate cells (PSCs) play a key role in the dense desmoplastic stroma associated with pancreatic ductal adenocarcinoma. Studies on human PSCs have been minimal due to difficulty in maintaining primary PSC in culture. We have generated the first conditionally immortalized human non-tumor (NPSC) and tumor-derived (TPSC) pancreatic stellate cells via transformation with the temperature-sensitive SV40 large T antigen and human telomerase (hTERT). These cells proliferate at 33C. After transfer to 37C, the SV40LT is switched off and the cells regain their primary PSC phenotype and growth characteristics. NPSC contained cytoplasmic vitamin A-storing lipid droplets, while both NPSC and TPSC expressed the characteristic markers ?SMA, vimentin, desmin and GFAP. Proteome array analysis revealed that of the 55 evaluated proteins, 27 (49%) were upregulated ?3-fold in TPSC compared to NPSC, including uPA, pentraxin-3, endoglin and endothelin-1. Two insulin-like growth factor binding proteins (IGFBPs) were inversely expressed. Although discordant IGFBP-2 and IGFBP-3 levels, IGF-I was found to stimulate proliferation of both NPSC and TPSC. Both basal and IGF-I stimulated motility was significantly enhanced in TPSC compared to NPSC. In conclusion, these cells provide a unique resource that will facilitate further study of the active stroma compartment associated with pancreatic cancer. - Highlights: Generation of human conditionally immortalized human pancreatic stellate cell lines. Temperature-sensitive SV40LT allows switch to primary PSC phenotype characteristics. Proteome profiling revealed distinct expression patterns between TPSC and NPSC. Enhanced IGF-I-stimulated proliferation and motility by TPSC compared to NPSC.

  4. Fundamental Study of the Oxidation Characteristics and Pollutant Emissions of Model Biodiesel Fuels

    SciTech Connect (OSTI)

    Feng, Q.; Wang, Y. L.; Egolfopoulos, Fokion N.; Tsotsis, T. T.

    2010-07-18

    In this study, the oxidation characteristics of biodiesel fuels are investigated with the goal of contributing toward the fundamental understanding of their combustion characteristics and evaluating the effect of using these alternative fuels on engine performance as well as on the environment. The focus of the study is on pure fatty acid methyl-esters (FAME,) that can serve as surrogate compounds for real biodiesels. The experiments are conducted in the stagnation-flow configuration, which allows for the systematic evaluation of fundamental combustion and emission characteristics. In this paper, the focus is primarily on the pollutant emission characteristics of two C{sub 4} FAMEs, namely, methyl-butanoate and methyl-crotonate, whose behavior is compared with that of n-butane and n-pentane. To provide insight into the mechanisms of pollutant formation for these fuels, the experimental data are compared with computed results using a model with consistent C1-C4 oxidation and NOx formation kinetics.

  5. Neutral monosaccharides from a hypersaline tropical environment: Applications to the characterization of modern and ancient ecosystems

    SciTech Connect (OSTI)

    Moers, M.E.C.; Larter, S.R. )

    1993-07-01

    Surficial and buried sediment samples from a hypersaline lagoon-sabkha system (Abu Dhabi, United Arab Emirates) were analyzed for carbohydrates (as neutral monosaccharides) to distinguish and characterize various types of recent and ancient tropical ecosystems on a molecular level. The samples consisted of surficial and buried microbial mats, lagoonal sediments containing seagrass (Halodule uninervis), and mangrove (Avicennia marine) paleosoils and handpicked mangrove leaves, ranging in age from contemporary to ca. 6000 yr BP. Analysis of quantitative neutral monosaccharide data by multivariate techniques shows that various groups can be distinguished: intact vascular plant material (mangrove leaf) contains high amounts of arabinose and glucose and hardly any partially methylated monosaccharides, whereas microbial mats in general and lagoonal seagrass sediments show high contributions of fucose, ribose, mannose, galactose, and partially methylated monosaccharides. Moreover, surficial microbial mats consisting of filamentous cyanobacteria (Microcoleus chtonoplastes, Lyngbya aestuarii) can be distinguished from other mats and sediments containing coccoid cyanobacteria (Entophysalis major) and/or fermenting, sulphate reducing, and methanogenic bacteria on the basis of high contributions of specific groups of partially methylated monosaccharides and other [open quotes]minor[close quotes] saccharides. The neutral monosaccharides present in mangrove paleosoils are for a substantial part derived from microorganisms. 22 refs., 4 figs., 4 tabs.

  6. Polysilane positive photoresist materials and methods for their use

    DOE Patents [OSTI]

    Harrah, Larry A.; Zeigler, John M.

    1986-01-01

    New polysilane copolymers comprise recurring units of --Si(X)(Y)-- and Si(A)(B)--, Si(X)(Y) being different from Si(A)(B), wherein X and Y together have 1-13 carbon atoms, and X and Y each independently is hydrogen, alkyl, cycloalkyl, phenyl, alkylphenyl, or phenylalkyl, with the proviso that only one of X and Y contains a phenyl moiety, or together X and Y are an alkylene group forming a ring with the adjoining Si atom, and wherein A and B together have 3-13 carbon atoms, and A and B each independently is alkyl or cycloalkyl, with the proviso (a) that when one of A and B is ethyl, the other is not methyl or ethyl, and (b) that when one of A and B is n-propyl and the other is methyl, X and Y are not both methyl. Corresponding homopolysilanes are also provided. Upon ultraviolet irradiation, they photodepolymerize to form volatile products. As a result, they represent a new class of photoresists which enable direct formation of a positive image eliminating the heretofore required development step.

  7. Method of using polysilane positive photoresist materials

    DOE Patents [OSTI]

    Harrah, Larry A.; Zeigler, John M.

    1986-01-01

    New polysilane copolymers comprise recurring units of --Si(X)(Y)-- and Si(A)(B)--, Si(X)(Y) being different from Si(A)(B), wherein X and Y together have 1-13 carbon atoms, and X and Y each independently is hydrogen, alkyl, cycloalkyl, phenyl, alkylphenyl, or phenylalkyl, with the proviso that only one of X and Y contains a phenyl moiety, or together X and Y are an alkylene group forming a ring with the adjoining Si atom, and wherein A and B together have 3-13 carbon atoms, and A and B each independently is alkyl or cycloalkyl, with the proviso (a) that when one of A and B is ethyl, the other is not methyl or ethyl, and (b) that when one of A ad B is n-propyl and the other is methyl, X and Y are not both methyl. Corresponding homopolysilanes are also provided. Upon ultraviolet irradiation, they photodepolymerize to form volatile products. As a result, they represent a new class of photoresists which enable direct formation of a positive image eliminating the heretofore required development step.

  8. Polysilane positive photoresist materials and methods for their use

    DOE Patents [OSTI]

    Harrah, L.A.; Zeigler, J.M.

    1984-04-05

    New polysilane copolymers comprise recurring units of -Si(X)(Y)- and Si(A)(B)-, Si(X)(Y) being different from Si(A)(B). X and Y together have 1 to 13 carbon atoms, and X and Y each independently is hydrogen, alkyl, cycloalkyl, phenyl, alkylphenyl, or phenylalkyl, with the proviso that only one of X and Y contains a phenyl moiety, or together X and Y are an alkylene group forming a ring with the adjoining Si atom. A and B together have 3 to 13 carbon atoms, and A and B each independently is alkyl or cycloalkyl, with the proviso that when one of A and B is ethyl, the other is not methyl or ethyl, and that when one of A and B is n-propyl and the other is methyl, X and Y are not both methyl. Corresponding homopolysilanes are also provided. Upon ultraviolet irradiation, they photodepolymerize to form volatile products. As a result, they represent a new class of photoresists which enable direct formation of a positive image eliminating the heretofore required development step.

  9. Mesophase stabilization in ionic liquid crystals through pairing equally shaped mesogenic cations and anions

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

    Stappert, Kathrin; Lipinski, Gregor; Kopiec, Gabriel; Spielberg, Eike T.; Mudring, Anja -Verena

    2015-07-23

    The synthesis and properties of a set of novel ionic liquid crystals with congruently shaped cations and anions are reported to check whether pairing mesogenic cations with mesogenic anions leads to a stabilization of a liquid crystalline phase. To that avail 1-alkyl-3-methyl-triazolium cations with an alkyl chain length of 10, 12, and 14 carbon atoms have been combined with p-alkyloxy-benzenesulfonate anions with different alkyl chain lengths (n = 10, 12, and 14). The corresponding triazolium iodides have been synthesized as reference compounds where the cation and anion have strong size and shape mismatch. The mesomorphic behavior of all compounds ismore » studied by differential scanning calorimetry and polarizing optical microscopy. All compounds except 1-methyl-3-decyltriazolium iodide, which qualifies as an ionic liquid, are thermotropic ionic liquid crystals. All other compounds adopt smectic A phases. As a result, a comparison of the thermal phase behavior of the 1-methyl-3-decyltriazolium bromides to the corresponding p-alkoxy-benzensulfonates reveals that definitely the mesophase is stabilized by pairing the rod-shaped 1-alkyl-3-methyltriazolium cation with a rod-like anion of similar size.« less

  10. Method of using polysilane positive photoresist materials

    DOE Patents [OSTI]

    Harrah, L.A.; Zeigler, J.M.

    1986-05-06

    New polysilane copolymers comprise recurring units of --Si(X)(Y)-- and Si(A)(B)--, Si(X)(Y) being different from Si(A)(B), wherein X and Y together have 1-13 carbon atoms, and X and Y each independently is hydrogen, alkyl, cycloalkyl, phenyl, alkylphenyl, or phenylalkyl, with the proviso that only one of X and Y contains a phenyl moiety, or together X and Y are an alkylene group forming a ring with the adjoining Si atom, and wherein A and B together have 3-13 carbon atoms, and A and B each independently is alkyl or cycloalkyl, with the proviso (a) that when one of A and B is ethyl, the other is not methyl or ethyl, and (b) that when one of A ad B is n-propyl and the other is methyl, X and Y are not both methyl. Corresponding homopolysilanes are also provided. Upon ultraviolet irradiation, they photodepolymerize to form volatile products. As a result, they represent a new class of photoresists which enable direct formation of a positive image eliminating the heretofore required development step.

  11. Metathesis process for preparing an alpha, omega-functionalized olefin

    DOE Patents [OSTI]

    Burdett, Kenneth A. (Midland, MI); Mokhtarzadeh, Morteza (Charleston, WV); Timmers, Francis J. (Midland, MI)

    2010-10-12

    A cross-metathesis process for preparing an .alpha.,.omega.-functionalized olefin, such as methyl 9-decenoate, and an .alpha.-olefin having three or more carbon atoms, such as 1-decene. The process involves contacting in a first reaction zone an .alpha.-functionalized internal olefin, such as methyl oleate, and an .alpha.-olefinic monomer having three or more carbon atoms, such as 1-decene, with a first metathesis catalyst to prepare an effluent stream containing the .alpha.,.omega.-functionalized olefin, such as methyl 9-decenoate, an unfunctionalized internal olefin, such as 9-octadecene, unconverted reactant olefins, and optionally, an .alpha.,.omega.-difunctionalized internal olefinic dimer, such as dimethyl 9-octadecen-1,18-dioate; separating said effluent streams; then contacting in a second reaction zone the unfunctionalized internal olefin with ethylene in the presence of a second metathesis catalyst to obtain a second product effluent containing the .alpha.-olefinic monomer having three or more carbon atoms; and cycling a portion of the .alpha.-olefinic monomer stream(s) to the first zone.

  12. High efficient ZnO nanowalnuts photocatalyst: A case study

    SciTech Connect (OSTI)

    Yan, Feng; Zhang, Siwen; Liu, Yang; Liu, Hongfeng; Qu, Fengyu; Cai, Xue; Wu, Xiang

    2014-11-15

    Highlights: Walnut-like ZnO nanostructures are synthesized through a facile hydrothermal method. Morphologies and microstructures of the as-obtained ZnO products were investigated. The photocatalytic results demonstrate that methyl orange (MO) aqueous solution can be degraded over 97% after 45 min under UV light irradiation. - Abstract: Walnut-like ZnO nanostructures are successfully synthesized through a facile hydrothermal method. The structure and morphology of the as-synthesized products were characterized by X-ray diffraction (XRD) and scanning electron microscope (SEM). The photocatalytic properties of ZnO nanowalnuts are investigated by photodegradating several organic dyes, such as Congo red (CR), methyl orange (MO) and eosin red aqueous solutions under UV irradiation, respectively. The results demonstrate that methyl orange (MO) aqueous solution can be degraded over 97% after 45 min under UV light irradiation. In addition, eosin red and Congo red (CR) aqueous solution degradation experiments are also conducted in the same condition, respectively. It showed that ZnO nanowalnuts represent high photocatalytic activities with a degradation efficiency of 87% for CR with 115 min of irradiation and 97% for eosin red with 55 min of irradiation. The reported ZnO products may be promising candidates as the photocatalysts in waste water treatment.

  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. Imprinted genes and transpositions: epigenomic targets for low dose radiation effects. Final report

    SciTech Connect (OSTI)

    Jirtle, Randy L.

    2012-10-11

    The overall hypothesis of this grant application is that low dose ionizing radiation (LDIR) elicits adaptive responses in part by causing heritable DNA methylation changes in the epigenome. This novel postulate was tested by determining if the level of DNA methylation at the Agouti viable yellow (A{sup vy}) metastable locus is altered, in a dose-dependent manner, by low dose radiation exposure (<10 cGy) during early gestation. This information is particularly important to ascertain given the increased use of CT scans in disease diagnosis, increased number of people predicted to live and work in space, and the present concern about radiological terrorism. We showed for the first time that LDIR significantly increased DNA methylation at the A{sup vy} locus in a sex-specific manner (p=0.004). Average DNA methylation was significantly increased in male offspring exposed to doses between 0.7 cGy and 7.6 cGy with maximum effects at 1.4 cGy and 3.0 cGy (p<0.01). Offspring coat color was concomitantly shifted towards pseudoagouti (p<0.01). Maternal dietary antioxidant supplementation mitigated both the DNA methylation changes and coat color shift in the irradiated offspring (p<0.05). Thus, LDIR exposure during gestation elicits epigenetic alterations that lead to positive adaptive phenotypic changes that are negated with antioxidants, indicating they are mediated in part by oxidative stress. These findings provide evidence that in the isogenic Avy mouse model epigenetic alterations resulting from LDIR play a role in radiation hormesis, bringing into question the assumption that every dose of radiation is harmful. Our findings not only have significant implications concerning the mechanism of hormesis, but they also emphasize the potential importance of this phenomenon in determining human risk at low radiation doses. Since the epigenetic regulation of genes varies markedly between species, the effect of LDIR on other epigenetically labile genes (e.g. imprinted genes) in animals and humans needs to be defined.

  15. Molecular Markers of Lung Cancer in MAYAK Workers

    SciTech Connect (OSTI)

    Steven A. Belinsky, PhD

    2007-02-15

    The molecular mechanisms that result in the elevated risk for lung cancer associated with exposure to radiation have not been well characterized. Workers from the MAYAK nuclear enterprise are an ideal cohort in which to study the molecular epidemiology of cancer associated with radiation exposure and to identify the genes targeted for inactivation that in turn affect individual risk for radiation-induced lung cancer. Epidemiology studies of the MAYAK cohort indicate a significantly higher frequency for adenocarcinoma and squamous cell carcinoma (SCC) in workers than in a control population and a strong correlation between these tumor types and plutonium exposure. Two hypotheses will be evaluated through the proposed studies. First, radiation exposure targets specific genes for inactivation by promoter methylation. This hypothesis is supported by our recent studies with the MAYAK population that demonstrated the targeting of the p16 gene for inactivation by promoter methylation in adenocarcinomas from workers (1). Second, genes inactivated in tumors can serve as biomarkers for lung cancer risk in a cancer-free population of workers exposed to plutonium. Support for this hypothesis is based on exciting preliminary results of our nested, case-control study of persons from the Colorado cohort. In that study, a panel of methylation markers for predicting lung cancer risk is being evaluated in sputum samples from incident lung cancer cases and controls. The first hypothesis will be tested by determining the prevalence for promoter hypermethylation of a panel of genes shown to play a critical role in the development of either adenocarcinoma and/or SCC associated with tobacco. Our initial studies on adenocarcinoma in MAYAK workers will be extended to evaluate methylation of the PAX5 {alpha}, PAX5 {beta}, H-cadherin, GATA5, and bone morphogenesis 3B (BMP3B) genes in the original sample set described under Preliminary studies. In addition, studies will be initiated in SCC from workers and controls to identify genes targeted for inactivation by plutonium in this other common histologic form of lung cancer. We will examine methylation of the p16, O{sup 6}-methylguanine-DNA methyl-transferase (MGMT), and death associated protein kinase genes ([DAP-K], evaluated previously in adenocarcinomas) as well as the new genes being assessed in the adenocarcinomas. The second hypothesis will be tested in a cross-sectional study of cancer-free workers exposed to plutonium and an unexposed population. A cohort of 700 cancer-free workers and 700 unexposed persons is being assembled, exposures are being defined, and induced sputum collected at initial entry into the study and approximately 1-year later. Exposed and unexposed persons will be matched by 5-year age intervals and smoking status (current and former). The frequency for methylation of four genes that show the greatest difference in prevalence in tumors from workers and controls will be determined in exfoliated cells within sputum. These studies will extend those in primary tumors to determine whether difference in prevalence for individual or multiple genes are detected in sputum samples from high-risk subjects exposed to plutonium. Follow-up of this cohort offers the opportunity to validate these endpoints and future biomarkers as true markers for lung cancer risk.

  16. UTILIZING WATER EMULSIFICATION TO REDUCE NOX AND PARTICULATE EMISSIONS ASSOCIATED WITH BIODIESEL

    SciTech Connect (OSTI)

    Kass, Michael D; Lewis Sr, Samuel Arthur; Lee, Doh-Won; Huff, Shean P; Storey, John Morse; Swartz, Matthew M; Wagner, Robert M

    2009-01-01

    A key barrier limiting extended utilization of biodiesel is higher NOx emissions compared to petrodiesel fuels. The reason for this effect is unclear, but various researchers have attributed this phenomena to the higher liquid bulk modulus associated with biodiesel and the additional heat released during the breaking of C-C double bonds in the methyl ester groups. In this study water was incorporated into neat biodiesel (B100) as an emulsion in an attempt to lower NOx and particulate matter (PM) emissions. A biodiesel emulsion containing 10wt% water was formulated and evaluated against an ultra-low sulfur petroleum diesel (ULSD) and neat biodiesel (B100) in a light-duty diesel engine operated at 1500RPM and at loads of 68Nm (50ft-lbs) and 102Nm (75ft-lbs). The influence of exhaust gas recirculation (EGR) was also examined. The incorporation of water was found to significantly lower the NOx emissions of B100, while maintaining fuel efficiency when operating at 0 and 27% EGR. The soot fraction of the particulates (as determined using an opacity meter) was much lower for the B100 and B100-water emulsion compared ULSD. In contrast, total PM mass (for the three fuel types) was unchanged for the 0% EGR condition but was significantly lower for the B100 and B100-emulsion during the 27% EGR condition compared to the ULSD fuel. Analysis of the emissions and heat release data indicate that water enhances air-fuel premixing to maintain fuel economy and lower soot formation. The exhaust chemistry of the biodiesel base fuels (B100 and water-emulsified B100) was found to be unique in that they contained measurable levels of methyl alkenoates, which were not found for the ULSD. These compounds were formed by the partial cracking of the methyl ester groups during combustion.

  17. 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

  18. Decomposition and vibrational relaxation in CH{sub 3}I and self-reaction of CH{sub 3} radicals.

    SciTech Connect (OSTI)

    Yang, X.; Goldsmith, C. F.; Tranter, R. S.

    2009-07-01

    Vibrational relaxation and dissociation of CH{sub 3}I, 2-20% in krypton, have been investigated behind incident shock waves in a diaphragmless shock tube at 20, 66, 148, and 280 Torr and 630-2200 K by laser schlieren densitometry. The effective collision energy obtained from the vibrational relaxation experiments has a small, positive temperature dependence, {Delta}E{sub down} = 63 x (T/298){sup 0.56} cm{sup -1}. First-order rate coefficients for dissociation of CH{sub 3}I show a strong pressure dependence and are close to the low-pressure limit. Restricted-rotor Gorin model RRKM calculations fit the experimental results very well with {Delta}E{sub down} = 378 x (T/298){sup 0.457} cm{sup -1}. The secondary chemistry of this reaction system is dominated by reactions of methyl radicals and the reaction of the H atom with CH{sub 3}I. The results of the decomposition experiments are very well simulated with a model that incorporates methyl recombination and reactions of methylene. Second-order rate coefficients for ethane dissociation to two methyl radicals were derived from the experiments and yield k = (4.50 {+-} 0.50) x 10{sup 17} exp(-32709/T) cm{sup 3} mol{sup -1} s{sup -1}, in good agreement with previous measurements. Rate coefficients for H + CH{sub 3}I were also obtained and give k = (7.50 {+-} 1.0) x 10{sup 13} exp(-601/T) cm{sup 3} mol{sup -1} s{sup -1}, in reasonable agreement with a previous experimental value.

  19. TiO2 nanotube arrays for photocatalysis: Effects of crystallinity, local order, and electronic structure

    SciTech Connect (OSTI)

    Liu, Jing; Hosseinpour, Pegah M.; Luo, Si; Heiman, Don; Menon, Latika; Arena, Dario A.; Lewis, Laura H.

    2014-11-19

    To furnish insight into correlations of electronic and local structure and photoactivity, arrays of short and long TiO? nanotubes were synthesized by electrochemical anodization of Ti foil, followed by thermal treatment in O? (oxidizing), Ar (inert), and H? (reducing) environments. The physical and electronic structures of these nanotubes were probed with x-ray diffraction, scanning electron microscopy, and synchrotron-based x-ray absorption spectroscopy, and correlated with their photocatalytic properties. The photocatalytic activity of the nanotubes was evaluated by monitoring the degradation of methyl orange under UV-VIS light irradiation. Results show that upon annealing at 350 C all as-anodized amorphous TiO? nanotube samples partially transform to the anatase structure, with variations in the degree of crystallinity and in the concentration of local defects near the nanotubes' surface (~5 nm) depending on the annealing conditions. Degradation of methyl orange was not detectable for the as-anodized TiO? nanotubes regardless of their length. The annealed long nanotubes demonstrated detectable catalytic activity, which was more significant with the H?-annealed nanotubes than with the Ar- and O?-annealed nanotube samples. This enhanced photocatalytic response of the H?-annealed long nanotubes relative to the other samples is positively correlated with the presence of a larger concentration of lattice defects (such as Ti3+ and anticipated oxygen vacancies) and a slightly lower degree of crystallinity near the nanotube surface. These physical and electronic structural attributes impact the efficacy of visible light absorption; moreover, the increased concentration of surface defects is postulated to promote the generation of hydroxyl radicals and thus accelerate the photodegradation of the methyl orange. The information obtained from this study provides unique insight into the role of the near-surface electronic and defect structure, crystal structure, and the local chemical environment on the photocatalytic activity and may be employed for tailoring the materials' properties for photocatalysis and other energy-related applications.

  20. Enhancement of photocatalytic properties of Bi{sub 2}WO{sub 6} nanoparticles by Pt deposition

    SciTech Connect (OSTI)

    Mohamed, R.M.; Aazam, E.S.

    2013-09-01

    Graphical abstract: - Highlights: Pt/Bi{sub 2}WO{sub 6} was used for photocatalytic degradation of methyl orange dye. Photocatalytic degradation was dependent on wt% of Pt reaction time, and weight of catalyst. Kinetic study revealed that the photocatalytic degradation of methyl orange dye followed the first order. Catalyst re-use revealed the present photocatalyst remain effective and active after five cycles. - Abstract: Bi{sub 2}WO{sub 6} nanoparticles were prepared using a hydrothermal method, and Pt was immobilized on the surface of Bi{sub 2}WO{sub 6} via a photo-assisted deposition (PAD) method. The samples produced were characterized using X-ray diffraction, ultraviolet and visible spectroscopy, photoluminescence emission spectra, transmission electron microscopy, extended X-ray absorption fine structure, and surface area measurements. Furthermore, the catalytic performance of the Bi{sub 2}WO{sub 6} and Pt/Bi{sub 2}WO{sub 6} samples was examined in the degradation of methyl orange dye (MO) under visible light. The extended X-ray absorption fine structure (EXAFS) results, which showed the presence of peaks assigned to the PtPt at approximately 2.50 ?, indicate the formation of nanoscale Pt features. The UVvis spectral analysis detected a red shift after loading the Pt into the Bi{sub 2}WO{sub 6}. The maximum degradation efficiency achieved was 100% with 0.3 Pt/Bi{sub 2}WO{sub 6} as the photocatalyst after a 30-min reaction time. The catalyst could be reused without any loss in activity for the first five cycles.

  1. Ag@AgHPW as a plasmonic catalyst for visible-light photocatalytic degradation of environmentally harmful organic pollutants

    SciTech Connect (OSTI)

    Zhou, Wenhui; Cao, Minhua Li, Na; Su, Shuangyue; Zhao, Xinyu; Wang, Jiangqiang; Li, Xianghua; Hu, Changwen

    2013-06-01

    Graphical abstract: Ag@Ag{sub x}H{sub 3?x}PW12O40 (Ag@AgHPW) nanoparticles (NPs), a new visible-light driven plasmonic photocatalyst, are prepared by a green photoreduction strategy without the addition of any surfactant, which show a high activity and stability for the degradation of methyl blue (MB) under visible light irradiation. - Highlights: A new visible-light driven photocatalyst Ag@Ag{sub x}H{sub 3?x}PW{sub 12}O{sub 40} was designed. The photocatalyst shows a high activity for the degradation of methyl blue. The high activity can be ascribed to the synergy of photoexcited AgHPW and Ag. - Abstract: Ag@Ag{sub x}H{sub 3?x}PW{sub 12}O{sub 40} (Ag@AgHPW) nanoparticles (NPs), a new visible-light driven plasmonic photocatalyst, are prepared by a green photoreduction strategy without the addition of any surfactant. They show strong absorption in the visible region because of the localized surface plasmon resonance (LSPR) of Ag NPs. This plasmonic photocatalyst shows a high activity and stability for the degradation of methyl blue (MB) under visible light irradiation, which could be attributed to the highly synergy of photoexcited Ag{sub x}H{sub 3?x}PW{sub 12}O{sub 40} (AgHPW) and plasmon-excited Ag NPs and the confinement effects at interfaces between polyoxometalates (POMs) and silver. POM anions have redox ability and high photocatalytic activity, whereas Ag NPs could effectively accelerate the separation of electrons and holes, both of which contribute to their high activity.

  2. The South Karelia Air Pollution Study. The effects of malodorous sulfur compounds from pulp mills on respiratory and other symptoms

    SciTech Connect (OSTI)

    Jaakkola, J.J.; Vilkka, V.; Marttila, O.; Jaeppinen, P.H.; Haahtela, T. )

    1990-12-01

    The paper mills in South Karelia, the southeast part of Finland, are responsible for releasing a substantial amount of malodorous sulfur compounds such as hydrogen sulfide (H2S), methyl mercaptan (CH3SH), and methyl sulfides ((CH3)2S and (CH3)2S2), into ambient air. In the most polluted residential area the annual mean concentrations of hydrogen sulfide and methyl mercaptan are estimated to be 8 and 2 to 5 micrograms/m3 and the highest daily average concentration 100 and 50 micrograms/m3. The annual mean and highest daily concentrations of sulfur dioxide (SO2) are very low. We studied the effects of malodorous sulfur compounds on eye, nasal and respiratory symptoms, and headache in adults. A cross-sectional self-administered questionnaire was distributed in February 1987 and responded to by 488 adults living in a severely (n = 198), a moderately (n = 204), and a nonpolluted community (n = 86). This included questions about occurrence of the symptoms of interest during the previous 4 wk and 12 months and individual, behavioral, and other environmental determinants of the symptoms. The response rate was 83%. The odds ratios (OR) for symptoms experienced often or constantly in severely versus nonpolluted and moderately versus nonpolluted communities were estimated in logistic regression analysis controlling potential confounders. The odds ratios for eye (moderate exposure OR 11.70, Cl95% 2.33 to 58.65; severe exposure OR 11.78, Cl95% 2.35 to 59.09) and nasal symptoms (OR 2.01, Cl95% 0.97 to 4.15; OR 2.19, Cl95% 1.06 to 4.55) and cough (OR 1.89, Cl95% 0.61 to 5.86; OR 3.06, Cl95% 1.02 to 9.29) during the previous 12 months were increased, with a dose-response pattern.

  3. Hybrid sol-gel optical materials

    DOE Patents [OSTI]

    Zeigler, John M. (Albuquerque, NM)

    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.

  4. Hybrid sol-gel optical materials

    DOE Patents [OSTI]

    Zeigler, John M. (Albuquerque, NM)

    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. Simplified models of growth, defect formation, and thermal conductivity in diamond chemical vapor deposition

    SciTech Connect (OSTI)

    Coltrin, M.E.; Dandy, D.S.

    1996-04-01

    A simplified surface reaction mechanism is presented for the CVD of diamond thin films. The mechanism also accounts for formation of point defects in the diamond lattice, an alternate, undesirable reaction pathway. Both methyl radicals and atomic C are considered as growth precursors. While not rigorous in all details, the mechanism is useful in describing the CVD diamond process over a wide range of reaction conditions. It should find utility in reactor modeling studies, for example in optimizing diamond growth rate while minimizing defect formation. This report also presents a simple model relating the diamond point-defect density to the thermal conductivity of the material.

  6. Recent progress in the morphology of bulk heterojunction photovoltaics

    SciTech Connect (OSTI)

    Brady, Michael A.; Su, Gregory M.; Chabinyc, Michael L.

    2011-10-06

    A review of current research in the characterization of the morphology of semiconducting polymer:fullerene bulk heterojunctions (BHJs) is presented. BHJs are complex blends of polymers and fullerenes with nanostructures that are highly dependent on materials, processing conditions, and post-treatments to films. Recent work on the study of the morphology of BHJs is surveyed. Emphasis is placed on emerging work on BHJs of poly(3-hexylthiophene), P3HT, and [6,6]-phenyl-C61-butyric acid methyl ester, PCBM, along with BHJs of donoracceptor polymers that have high power conversion efficiency.

  7. Franck-Condon transitions in a system with large-amplitude anharmonic vibrations coupled to a harmonic-oscillator bath: Application to the C 1s photoelectron spectrum of ethanol

    SciTech Connect (OSTI)

    Abu-samha, M.; Boerve, K. J.

    2006-10-15

    A vibrational adiabatic approach to Franck-Condon analysis is presented for systems with a few highly displaced oscillators coupled to a bath of harmonic oscillators. The model reduces the many-coupled-oscillator problem to few-body problems, albeit with corrections due to coupling to harmonic modes. The theory is applied with very good results to the carbon 1s photoelectron spectrum of ethanol, which is strongly influenced by change in conformation from gauche to anti when ethanol is ionized at the methyl site.

  8. Enhanced performance of polymer:fullerene bulk heterojunction solar cells upon graphene addition

    SciTech Connect (OSTI)

    Robaeys, Pieter Dierckx, Wouter; Dexters, Wim; Spoltore, Donato; Drijkoningen, Jeroen; Bonaccorso, Francesco; Bourgeois, Emilie; D'Haen, Jan; Haenen, Ken; Manca, Jean V.; Nesladek, Milos; Liesenborgs, Jori; Van Reeth, Frank; Lombardo, Antonio; Ferrari, Andrea C.

    2014-08-25

    Graphene has potential for applications in solar cells. We show that the short circuit current density of P3HT (Poly(3-hexylthiophene-2,5-diyl):PCBM((6,6)-Phenyl C61 butyric acid methyl ester) solar cells is enhanced by 10% upon the addition of graphene, with a 15% increase in the photon to electric conversion efficiency. We discuss the performance enhancement by studying the crystallization of P3HT, as well as the electrical transport properties. We show that graphene improves the balance between electron and hole mobilities with respect to a standard P3HT:PCBM solar cell.

  9. Isolated spinach ribulose-1,5-bisphosphate carboxylase/oxgenase large subunit .epsilon. n-methyltransferase and method of inactivating ribulose-1,5-bishosphatase .epsilon. n-methyltransferase activity

    DOE Patents [OSTI]

    Houtz, Robert L. (Lexington, KY)

    2001-01-01

    The gene sequence for ribulose-1,5-bisphosphate carboxylase/oxygenase (Rubisco) large subunit (LS) .sup..epsilon. N-methyltansferase (protein methylase III or Rubisco LSMT) from a plant which has a des(methyl) lysyl residue in the LS is disclosed. In addition, the full-length cDNA clones for Rubisco LSMT are disclosed. Transgenic plants and methods of producing same which have the Rubisco LSMT gene inserted into the DNA are also provided. Further, methods of inactivating the enzymatic activity of Rubisco LSMT are also disclosed.

  10. Isolated spinach ribulose-1,5-bisphosphate carboxylase/oxygenase large subunit .sup..epsilon. N-methyltransferase and method of inactivating ribulose-1,5-bisphosphatase carboxylase/oxygenase large subunit .sup..epsilon. N-methyltransferase activity

    DOE Patents [OSTI]

    Houtz, Robert L. (Lexington, KY)

    1999-01-01

    The gene sequence for ribulose-1,5-bisphosphate carboxylase/oxygenase (Rubisco) large subunit (LS) .sup..epsilon. N-methyltransferase (protein methylase III or Rubisco LSMT) from a plant which has a des(methyl) lysyl residue in the LS is disclosed. In addition, the full-length cDNA clones for Rubisco LSMT are disclosed. Transgenic plants and methods of producing same which have the Rubisco LSMT gene inserted into the DNA are also provided. Further, methods of inactivating the enzymatic activity of Rubisco LSMT are also disclosed.

  11. Method for making carbon super capacitor electrode materials

    DOE Patents [OSTI]

    Firsich, D.W.; Ingersoll, D.; Delnick, F.M.

    1998-07-07

    A method is described for making near-net-shape, monolithic carbon electrodes for energy storage devices. The method includes the controlled pyrolysis and activation of a pressed shape of methyl cellulose powder with pyrolysis being carried out in two stages; pre-oxidation, preferably in air at a temperature between 200--250 C, followed by carbonization under an inert atmosphere. An activation step to adjust the surface area of the carbon shape to a value desirable for the application being considered, including heating the carbon shape in an oxidizing atmosphere to a temperature of at least 300 C, follows carbonization. 1 fig.

  12. Clostridium thermocellum DSM 1313 transcriptional responses to redox perturbation

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

    Sander, Kyle B.; Wilson, Charlotte M.; M. Rodriquez, Jr.; Klingeman, Dawn Marie; Davison, Brian H.; Brown, Steven D.; Rydzak, T.

    2015-12-12

    Clostridium thermocellum is a promising consolidated bioprocessing candidate organism capable of directly converting lignocellulosic biomass to ethanol. Current ethanol yields, productivities, and growth inhibitions are industrial deployment impediments for commodity fuel production by this bacterium. Redox imbalance under certain conditions and in engineered strains may contribute to incomplete substrate utilization and may direct fermentation products to undesirable overflow metabolites. As a result, towards a better understanding of redox metabolism in C. thermocellum, we established continuous growth conditions and analyzed global gene expression during addition of two stress chemicals (methyl viologen and hydrogen peroxide) which changed the fermentation redox potential.

  13. Nanometer-scale ablation using focused, coherent extreme ultraviolet/soft x-ray light

    DOE Patents [OSTI]

    Menoni, Carmen S. (Fort Collins, CO); Rocca, Jorge J. (Fort Collins, CO); Vaschenko, Georgiy (San Diego, CA); Bloom, Scott (Encinitas, CA); Anderson, Erik H. (El Cerrito, CA); Chao, Weilun (El Cerrito, CA); Hemberg, Oscar (Stockholm, SE)

    2011-04-26

    Ablation of holes having diameters as small as 82 nm and having clean walls was obtained in a poly(methyl methacrylate) on a silicon substrate by focusing pulses from a Ne-like Ar, 46.9 nm wavelength, capillary-discharge laser using a freestanding Fresnel zone plate diffracting into third order is described. Spectroscopic analysis of light from the ablation has also been performed. These results demonstrate the use of focused coherent EUV/SXR light for the direct nanoscale patterning of materials.

  14. Science Summary

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

    Hg Methylation » Links Scientific Highlight BL2-3 BL6-2C BL9-3 BL10-2 » Share this Article Laboratree Ologeez SciLink LabSpaces Imaging Mercury in the Rhizosphere of Wetland Plants summary written by Raven Hanna High levels of mercury in our diets can have adverse effects on our health, and fish are a major source of dietary mercury. Because of a process called biomagnification, mercury levels in fish can build up to be at a much higher concentration than in the surrounding water. The mercury

  15. Low density, microcellular foams, preparation, and articles

    DOE Patents [OSTI]

    Young, A.T.

    1982-03-03

    A microcellular low-density foam of poly(4-methyl-1-pentene) particularly useful for forming targets for inertial confinement fusion has been developed. Articles made from the foam have been machined to tolerances of 0.0001 inch, although the densities of the fragile foam are low (about 10 to about 100 mg/cc) and the cell sizes are small (about 10 to about 30 ..mu..m). Methods for forming the foam and articles are given. The yield strength of the foam of the invention is higher than was obtained in other structures of this same material.

  16. Mound activities in chemical and physical research: July-December 1982

    SciTech Connect (OSTI)

    Not Available

    1983-06-20

    Research is reported in the following areas: low-temperature research (kinetics of DT formation in D/sub 2/ + T/sub 2/ mixtures, calculation of charged particle density in tritium containing CT/sub 4/, deuterium triple point cell), separation research (liquid thermal diffusion of methyl chloride and bromine-81 in bromobenzene, separation of Ca and Zr isotopes, triple-pumped detector, magnesium two-phase chemical exchange, extraction columns for Ca isotope enrichment, reflux-electrochemical NO-HNO/sub 3/ chemical exchange for /sup 15/N enrichment, testing of boron phosphate for Pu adsorption), and metal hydride studies (prediction of nonmagnetic Kondo effect in metal hydrides). (DLC)

  17. (U) A Gruneisen Equation of State for TPX. Application in FLAG

    SciTech Connect (OSTI)

    Fredenburg, David A.; Aslam, Tariq Dennis; Bennett, Langdon Stanford

    2015-11-02

    A Gruneisen equation of state (EOS) is developed for the polymer TPX (poly 4-methyl-1-pentene) within the LANL hydrocode FLAG. Experimental shock Hugoniot data for TPX is fit to a form of the Gruneisen EOS, and the necessary parameters for implementing the TPX EOS in FLAG are presented. The TPX EOS is further validated through one-dimensional simulations of recent double-shock experiments, and a comparison is made between the new Gruneisen EOS for TPX and the EOS representation for TPX used in the LANL Common Model.

  18. Challenges in Catalytic Manufacture of Renewable Pyrrolidinones from Fermentation Derived Succinate

    SciTech Connect (OSTI)

    White, James F.; Holladay, Johnathan E.; Zacher, Alan H.; Frye, John G.; Werpy, Todd A.

    2014-09-05

    Fermentation derived succinic acid ammonium salt is an ideal precursor for manufacture of renewable N-methyl pyrrolidinone (NMP) or 2-pyrrolidinone (2P) via heterogeneous catalysis. However, there are many challenges to making this a practical reality. Chief among the challenges is avoiding catalyst poisoning by fermentation by- and co-products. Battelle / Pacific Northwest National Laboratory (PNNL) have developed an economically effective technology strategy for this purpose. The technology is a combination of purely thermal processing, followed by simple catalytic hydrogenation that together avoids catalyst poisoning from fermentation impurities and provides high selectivity and yields of NMP or 2P.

  19. 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.

  20. Fabrication and characterization of inverted organic solar cells using shuttle cock-type metal phthalocyanine and PCBM:P3HT

    SciTech Connect (OSTI)

    Suzuki, Atsushi Furukawa, Ryo Akiyama, Tsuyoshi Oku, Takeo

    2015-02-27

    Inverted organic solar cells using shuttle cock-type phthalocyanine, semiconducting polymer and fullerenes were fabricated and characterized. Photovoltaic and optical properties of the solar cells with inverted structures were investigated by optical absorption, current density-voltage characteristics. The photovoltaic properties of the tandem organic solar cell using titanyl phthalocyanine, vanadyl phthalocyanine, poly(3-hexylthiophene) (P3HT) and [6, 6]-phenyl C{sub 61}-butyric acid methyl ester (PCBM) were improved. Effect of annealing and solvent treatment on surface morphologies of the active layer was investigated. The photovoltaic mechanisms, energy levels and band gap of active layers were discussed for improvement of the photovoltaic performance.

  1. Proposed Molecular Beam Determination of Energy Partition in the Photodissociation of Polyatomic Molecules

    DOE R&D Accomplishments [OSTI]

    Zare, P. N.; Herschbach, D. R.

    1964-01-29

    Conventional photochemical experiments give no information about the partitioning of energy between translational recoil and internal excitation of the fragment molecules formed in photodissociation of a polyatomic molecule. In a molecular beam experiment, it becomes possible to determine the energy partition from the form of the laboratory angular distribution of one of the photodissociation products. A general kinematic analysis is worked out in detail, and the uncertainty introduced by the finite angular resolution of the apparatus and the velocity spread in the parent beam is examined. The experimental requirements are evaluated for he photolysis of methyl iodide by the 2537 angstrom Hg line.

  2. Word Pro - Untitled1

    Gasoline and Diesel Fuel Update (EIA)

    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

  3. 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.

  4. Wide bandgap OPV polymers based on pyridinonedithiophene unit with efficiency >5%

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

    Schneider, Alexander M.; Lu, Luyao; Manley, Eric F.; Zheng, Tianyue; Sharapov, Valerii; Xu, Tao; Marks, Tobin J.; Chen, Lin X.; Yu, Luping

    2015-06-04

    We report the properties of a new series of wide band gap photovoltaic polymers based on the N-alkyl 2-pyridone dithiophene (PDT) unit. These polymers are effective bulk heterojunction solar cell materials when blended with phenyl-C71-butyric acid methyl ester (PC71BM). They achieve power conversion efficiencies (up to 5.33%) high for polymers having such large bandgaps, ca. 2.0 eV (optical) and 2.5 eV (electrochemical). As a result, grazing incidence wide-angle X-ray scattering (GIWAXS) reveals strong correlations between ?? stacking distance and regularity, polymer backbone planarity, optical absorption maximum energy, and photovoltaic efficiency.

  5. Nanopatterns by phase separation of patterned mixed polymer monolayers

    DOE Patents [OSTI]

    Huber, Dale L; Frischknecht, Amalie

    2014-02-18

    Micron-size and sub-micron-size patterns on a substrate can direct the self-assembly of surface-bonded mixed polymer brushes to create nanoscale patterns in the phase-separated mixed polymer brush. The larger scale features, or patterns, can be defined by a variety of lithographic techniques, as well as other physical and chemical processes including but not limited to etching, grinding, and polishing. The polymer brushes preferably comprise vinyl polymers, such as polystyrene and poly(methyl methacrylate).

  6. pH-sensitive methacrylic copolymer gels and the production thereof

    DOE Patents [OSTI]

    Mallapragada, Surya K. (Ames, IA); Anderson, Brian C. (Lake Bluff, IA)

    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.

  7. Fullerene Cyanation Does Not Always Increase Electron Affinity: Experimental and Theoretical Study

    SciTech Connect (OSTI)

    Clikeman, Tyler T.; Deng, Shihu; Popov, Alexey A.; Wang, Xue B.; Strauss, Steven H.; Boltalina, Olga V.

    2015-01-01

    The electron affinities of C70 derivatives with trifluoromethyl, methyl and cyano groups were studied experimentally and theoretically using low-temperature photoelectron spectroscopy (LT PES) and density functional theory (DFT). The electronic effects of these functional groups were determined and found to be highly dependent on the addition patterns. Substitution of CF3 for CN for the same addition pattern increases the experimental electron affinity by 70 meV per substitution. The synthesis of a new fullerene derivative, C70(CF3)10(CN)2, is reported for the first time

  8. 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

  9. Method for measuring surface temperature

    DOE Patents [OSTI]

    Baker, Gary A. (Los Alamos, NM); Baker, Sheila N. (Los Alamos, NM); McCleskey, T. Mark (Los Alamos, NM)

    2009-07-28

    The present invention relates to a method for measuring a surface temperature using is a fluorescent temperature sensor or optical thermometer. The sensor includes a solution of 1,3-bis(1-pyrenyl)propane within a 1-butyl-1-1-methyl pyrrolidinium bis(trifluoromethylsulfonyl)imide ionic liquid solvent. The 1,3-bis(1-pyrenyl)propane remains unassociated when in the ground state while in solution. When subjected to UV light, an excited state is produced that exists in equilibrium with an excimer. The position of the equilibrium between the two excited states is temperature dependent.

  10. Tellurium-Containing Conjugated Materials for Solar Cells: From Sulfur to Tellurium

    SciTech Connect (OSTI)

    Park Y. S.; Kale, T.; Wu, Q.; Ocko, B.M.; Black, C.T., Grubbs, R.B.

    2013-04-03

    A series of diketopyrrolopyrrole(DPP)-based small molecules have been synthesized by palladium-catalyzed coupling reactions. Electron-donating moieties (benzothiophene, benzoselenophene, and benzotellurophene) are bridged by an electron-withdrawing DPP unit to generate donor-acceptor-donor (D-A-D) type molecules. We observe red-shifts in absorption spectra of these compounds by varying heteroatoms from sulfur to tellurium. In bulk heterojunction solar cells with [6,6]phenyl-C61-butyric acid methyl ester (PC61BM) as acceptor, we obtain power conversion efficiencies of 2.4% (benzothiophene), 4.1% (benzoselenophene), and 3.0% (benzotellurophene), respectively.

  11. A New Structural Form in the SAM/Metal-Dependent O;#8209;Methyltransferase

    Office of Scientific and Technical Information (OSTI)

    Family: MycE from the Mycinamicin Biosynthetic Pathway (Journal Article) | SciTech Connect A New Structural Form in the SAM/Metal-Dependent O;#8209;Methyltransferase Family: MycE from the Mycinamicin Biosynthetic Pathway Citation Details In-Document Search Title: A New Structural Form in the SAM/Metal-Dependent O;#8209;Methyltransferase Family: MycE from the Mycinamicin Biosynthetic Pathway O-linked methylation of sugar substituents is a common modification in the biosynthesis of many

  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. Method for making carbon super capacitor electrode materials

    DOE Patents [OSTI]

    Firsich, David W.; Ingersoll, David; Delnick, Frank M.

    1998-01-01

    A method for making near-net-shape, monolithic carbon electrodes for energy storage devices. The method includes the controlled pyrolysis and activation of a pressed shape of methyl cellulose powder with pyrolysis being carried out in two stages; pre-oxidation, preferably in air at a temperature between 200.degree.-250.degree. C., followed by carbonization under an inert atmosphere. An activation step to adjust the surface area of the carbon shape to a value desirable for the application being considered, including heating the carbon shape in an oxidizing atmosphere to a temperature of at least 300.degree. C., follows carbonization.

  14. Method of generating chemiluminescent light

    DOE Patents [OSTI]

    Spurlin, S.R.; Yeung, E.S.

    1986-03-11

    A method of chemiluminescently determining a sulfide which is either hydrogen sulfide or methyl mercaptan by reacting the sulfide with chlorine dioxide at low pressure and under conditions which allow a longer reaction time in emission of a single photon for every two sulfide containing species, and thereafter, chemiluminescently detecting and determining the sulfide. The invention also relates not only to the detection method, but the novel chemical reaction that generates chemiluminescent light and a specifically designed chemiluminescence detection cell for the reaction. 4 figs.

  15. Synthesis of CdS nanoparticles for photocatalytic application of methyleneblue degradation

    SciTech Connect (OSTI)

    Muthuraj, V.; Umadevi, M.; Sankarasubramanian, K.; Kajamuhideen, M. S.

    2014-04-24

    CdS nanoparticles were prepared by the reaction of cadmium acetate with thiourea in the presence and absence of methylene blue dye (MB). The nanoparticles were characterized by, XRD, FT-IR, UV-Vis. XRD study shows the presence of hexagonal phase for the nanoparticles whereas in case of the bulk samples only the hexagonal phase is observed. Fourier transform infrared spectroscopy (FT-IR) showed a strong interaction of methyl groups with CdS nanoparticles. The degradation of methylene blue was analysed using UV-Vis absorbance spectrum. Thus the results authenticate that methylene blue dye influences the structural and optical properties of the CdS nanoparticles.

  16. Production of super-smooth articles

    DOE Patents [OSTI]

    Duchane, David V. (Los Alamos, NM)

    1983-01-01

    Super-smooth rounded or formed articles made of thermoplastic materials including various poly(methyl methacrylate) or acrylonitrile-butadiene-styrene copolymers are produced by immersing the articles into a bath, the composition of which is slowly changed with time. The starting composition of the bath is made up of at least one solvent for the polymer and a diluent made up of at least one nonsolvent for the polymer and optional materials which are soluble in the bath. The resulting extremely smooth articles are useful as mandrels for laser fusion and should be useful for a wide variety of other purposes, for example lenses.

  17. Light-controlled electric Freedericksz threshold in dye doped liquid crystals

    SciTech Connect (OSTI)

    Lucchetti, L.; Catani, L.; Simoni, F.

    2014-05-28

    We report the results of measurements of the threshold of Freedericksz transition in a nematic liquid crystal doped by Methyl-red. We show that in case of dc field the threshold voltage can decrease or increase depending on the light dose, due to the light-induced desorption and adsorption of charge complexes from and on the irradiated surface, that has been recently demonstrated. This effect has the potential to be exploited in optical devices such as liquid crystal microlenses and spatial light modulators.

  18. Composite Synthesis Methodology Development: Nanocrvstalline SiC and Ti3SiC2 Alloys for Reactory Materials Outline of initial synthesis capabilities M4CT-13PN0405034

    SciTech Connect (OSTI)

    Henager, Charles H.; Alvine, Kyle J.; Shin, Yongsoon; Jiang, Weilin; Nguyen, Ba Nghiep

    2013-03-29

    We have identified three initial preceramic polymers to help produce the SiC-based alloys for this project and have developed simple processing steps to make SiC-based alloy ceramics. The use of unfilled SMP-10 (Polycarbosilane) or SMP-877 (Methyl-Polycarbosilane) is not feasible due to the large mass losses that occur during pyrolysis. The pre-gelling steps below save time when those two polymers are filled with powders. The use of SL-MS30 provides us with a SiC-filled polymer that can be used to test out the CNT mats without further complications due to other powders.

  19. Low density, microcellular foams, preparation, and articles

    DOE Patents [OSTI]

    Young, Ainslie T. (Los Alamos, NM); Marsters, Robert G. (Jemez Springs, NM); Moreno, Dawn K. (Espanola, NM)

    1984-01-01

    A microcellular low density foam of poly(4-methyl-1-pentene) which is particularly useful for forming targets for inertial confinement fusion has been developed. Articles made from the foam have been machined to tolerances of 0.0001 inch, although the densities of the fragile foam are low (about 10 to about 100 mg/cc) and the cell sizes are small (about 10 to about 30 .mu.m). Methods for forming the foam and articles are given; and the yield strength of the foam of the invention is higher than was obtained in other structures of this same material.

  20. 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.

  1. Characteristics of alumina powders prepared by spray-drying of boehmite sol

    SciTech Connect (OSTI)

    Varma, H.K.; Mani, T.V.; Damodaran, A.D.; Warrier, K.G. ); Balachandran, U. . Energy Technology Div.)

    1994-06-01

    Boehmite sol prepared from aluminum nitrate has been spray-dried to obtain micrometer-size spherical particles consisting of submicrometer crystallites. The spray-dried powder was further washed with solvents of varying polarities such as acetone, 2-propanol, and 2-methyl-2-propanol. Particle-size distribution, morphology, density, compaction, and sintering characteristics of powders washed with different solvents are reported. The effect of post treatments on the boehmite-sol-derived powders toward reducing agglomeration and obtaining high-density bodies is discussed.

  2. Fuel Ethanol Oxygenate Production

    Gasoline and Diesel Fuel Update (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 Annual-Thousand Barrels per Day Download Series History Download Series History Definitions, Sources & Notes Definitions, Sources & Notes Show Data By: Product Area Jul-15 Aug-15 Sep-15 Oct-15 Nov-15 Dec-15 View History U.S. 30,256 29,621 28,543 30,139 29,594 31,075 1981-2015 East Coast (PADD 1) 876 854 692 664 664

  3. 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.

  4. The effect of electron induced hydrogenation of graphene on its electrical transport properties

    SciTech Connect (OSTI)

    Woo, Sung Oh [Department of Physics and Astronomy, Texas A and M University, College Station, Texas 77843 (United States)] [Department of Physics and Astronomy, Texas A and M University, College Station, Texas 77843 (United States); Teizer, Winfried [Department of Physics and Astronomy, Texas A and M University, College Station, Texas 77843 (United States) [Department of Physics and Astronomy, Texas A and M University, College Station, Texas 77843 (United States); WPI-Advanced Institute for Materials Research, Tohoku University, Sendai (Japan)

    2013-07-22

    We report a deterioration of the electrical transport properties of a graphene field effect transistor due to energetic electron irradiation on a stack of Poly Methyl Methacrylate (PMMA) on graphene (PMMA/graphene bilayer). Prior to electron irradiation, we observed that the PMMA layer on graphene does not deteriorate the carrier transport of graphene but improves its electrical properties instead. As a result of the electron irradiation on the PMMA/graphene bilayer, the Raman D band appears after removal of PMMA. We argue that the degradation of the transport behavior originates from the binding of hydrogen generated during the PMMA backbone secession process.

  5. A molecular dynamics study of polymer/graphene interfacial systems

    SciTech Connect (OSTI)

    Rissanou, Anastassia N.; Harmandaris, Vagelis

    2014-05-15

    Graphene based polymer nanocomposites are hybrid materials with a very broad range of technological applications. In this work, we study three hybrid polymer/graphene interfacial systems (polystyrene/graphene, poly(methyl methacrylate)/graphene and polyethylene/graphene) through detailed atomistic molecular dynamics (MD) simulations. Density profiles, structural characteristics and mobility aspects are being examined at the molecular level for all model systems. In addition, we compare the properties of the hybrid systems to the properties of the corresponding bulk ones, as well as to theoretical predictions.

  6. 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.

  7. Elastomeric organic material for switching application

    SciTech Connect (OSTI)

    Shiju, K. E-mail: pravymon@gmail.com Praveen, T. E-mail: pravymon@gmail.com Preedep, P. E-mail: pravymon@gmail.com

    2014-10-15

    Organic Electronic devices like OLED, Organic Solar Cells etc are promising as, cost effective alternatives to their inorganic counterparts due to various reasons. However the organic semiconductors currently available are not attractive with respect to their high cost and intricate synthesis protocols. Here we demonstrate that Natural Rubber has the potential to become a cost effective solution to this. Here an attempt has been made to fabricate iodine doped poly isoprene based switching device. In this work Poly methyl methacrylate is used as dielectric layer and Aluminium are employed as electrodes.

  8. Synthesis and Structural Flexibility of a Series of Copper(II)

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

    Azolate-Based Metal-Organic Frameworks | Center for Gas SeparationsRelevant to Clean Energy Technologies | Blandine Jerome Synthesis and Structural Flexibility of a Series of Copper(II) Azolate-Based Metal-Organic Frameworks Previous Next List Kenji Sumida, Maw Lin Foo, Satoshi Horike, Jeffrey R. Long, Eur. J. Inorg. Chem., (24), 3739-3744 (2010) DOI: 10.1002/ejic.201000490 nfigure2.jpg Abstract: The reaction of CuCl2*2H2O with three novel ditopic ligands, 2-methyl-1,4-benzeneditetrazolate

  9. Rotary engine

    SciTech Connect (OSTI)

    Leas, A. M.; Leas, L. E.

    1985-02-12

    Disclosed are an engine system suitable for use with methyl alcohol and hydrogen and a rotary engine particularly suited for use in the engine system. The rotary engine comprises a stator housing having a plurality of radially directed chamber dividers, a principal rotor, a plurality of subordinate rotors each having an involute gear in its periphery mounted on the principal rotor, and means for rotating the subordinate rotors so that their involute gears accept the radially directed dividers as the subordinate rotors move past them.

  10. 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.

  11. 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.

  12. 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.

  13. Search for: All records | SciTech Connect

    Office of Scientific and Technical Information (OSTI)

    Switch to Detail View for this search SciTech Connect Search Results Page 1 of 1 Search for: All records Creators/Authors contains: "Xing, Yongna" × Sort by Relevance Sort by Date (newest first) Sort by Date (oldest first) Sort by Relevance « Prev Next » Everything4 Electronic Full Text0 Citations4 Multimedia0 Datasets0 Software0 Filter Results Filter by Subject applied life sciences (1) basic biological sciences (1) cell cycle (1) crystal structure (1) enzymes (1) methylation (1)

  14. Tracers for monitoring the activity of sodium/glucose cotransporters in health and disease

    DOE Patents [OSTI]

    Wright, Ernest M; Barrio, Jorge R; Hirayama, Bruce A; Kepe, Vladimir

    2014-09-30

    Radiolabeled tracers for sodium/glucose cotransporters (SGLTs), their synthesis, and their use are provided. The tracers are methyl or ethyl pyranosides having an equatorial hydroxyl group at carbon-2 and a C 1 preferred conformation, radiolabeled with .sup.18F, .sup.123I, or .sup.124I, or free hexoses radiolabeled with .sup.18F, .sup.123I, or .sup.124. Also provided are in vivo and in vitro techniques for using these and other tracers as analytical and diagnostic tools to study glucose transport, in health and disease, and to evaluate therapeutic interventions.

  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. Separation of actinides from lanthanides

    DOE Patents [OSTI]

    Smith, B.F.; Jarvinen, G.D.; Ryan, R.R.

    1988-03-31

    An organic extracting solution and an extraction method useful for separating elements of the actinide series of the periodic table from elements of the lanthanide series, where both are in trivalent form is described. The extracting solution consists of a primary ligand and a secondary ligand, preferably in an organic solvent. The primary ligand is a substituted monothio-1,3-dicarbonyl, which includes a substituted 4-acyl-2-pyrazolin-5-thione, such as 4-benzoyl-2,4- dihydro-5-methyl-2-phenyl-3H-pyrazol-3-thione (BMPPT). The secondary ligand is a substituted phosphine oxide, such as trioctylphosphine oxide (TOPO).

  17. Separation of actinides from lanthanides

    DOE Patents [OSTI]

    Smith, Barbara F.; Jarvinen, Gordon D.; Ryan, Robert R.

    1989-01-01

    An organic extracting solution and an extraction method useful for separating elements of the actinide series of the periodic table from elements of the lanthanide series, where both are in trivalent form. The extracting solution consists of a primary ligand and a secondary ligand, preferably in an organic solvent. The primary ligand is a substituted monothio-1,3-dicarbonyl, which includes a substituted 4-acyl-2-pyrazolin-5-thione, such as 4-benzoyl-2,4-dihydro-5-methyl-2-phenyl-3H-pyrazol-3-thione (BMPPT). The secondary ligand is a substituted phosphine oxide, such as trioctylphosphine oxide (TOPO).

  18. Extractant composition

    DOE Patents [OSTI]

    Smith, Barbara F.; Jarvinen, Gordon D.; Ryan, Robert R.

    1990-01-01

    An organic extracting solution useful for separating elements of the actinide series of the periodic table from elements of the lanthanide series, where both are in trivalent form. The extracting solution consists of a primary ligand and a secondary ligand, preferably in an organic solvent. The primary ligand is a substituted monothio-1,3-dicarbonyl, which includes a substituted 4-acyl-2-pyrazolin-5-thione, such as 4-benzoyl-2,4-dihydro-5-methyl-2-phenyl-3H-pyrazol-3-thione (BMPPT). The secondary ligand is a substituted phosphine oxide, such as trioctylphosphine oxide (TOPO).

  19. Testing of a model to estimate vapor concentration of various organic chemicals. Master's thesis

    SciTech Connect (OSTI)

    Bakalyar, S.M.

    1990-01-01

    A model developed by Dr. Parker C. Reist to predict the build-up and decay rates of vapor concentrations following a chemical spill and clean-up was tested. The chemicals tested were: acetone, butyl acetate, ethyl acetate, hexane, methylene chloride, methyl ethyl ketone, and toluene. The evaporation rates of these chemicals were determined both by prediction, using a model developed by I. Kawamura and D. Mackay, and empirically and these rates were used in the Reist model. Chamber experiments were done to measure actual building-up and decay of vapor concentrations for simulated spills and simulated clean-up.

  20. New Palladium-Catalyzed Approaches to Heterocycles and Carbocycles

    SciTech Connect (OSTI)

    Qinhua Huang

    2004-12-19

    The tert-butylimines of o-(1-alkynyl)benzaldehydes and analogous pyridinecarbaldehydes have been cyclized under very mild reaction conditions in the presence of I{sub 2}, ICl, PhSeCl, PhSCl and p-O{sub 2}NC{sub 6}H{sub 4}SCl to give the corresponding halogen-, selenium- and sulfur-containing disubstituted isoquinolines and naphthyridines, respectively. Monosubstituted isoquinolines and naphthyridines have been synthesized by the metal-catalyzed ring closure of these same iminoalkynes. This methodology accommodates a variety of iminoalkynes and affords the anticipated heterocycles in moderate to excellent yields. The Pd(II)-catalyzed cyclization of 2-(1-alkynyl)arylaldimines in the presence of various alkenes provides an efficient way to synthesize a variety of 4-(1-alkenyl)-3-arylisoquinolines in moderate to excellent yields. The introduction of an ortho-methoxy group on the arylaldimine promotes the Pd-catalyzed cyclization and stabilizes the resulting Pd(II) intermediate, improving the yields of the isoquinoline products. Highly substituted naphthalenes have been synthesized by the palladium-catalyzed annulation of a variety of internal alkynes, in which two new carbon-carbon bonds are formed in a single step under relatively mild reaction conditions. This method has also been used to synthesize carbazoles, although a higher reaction temperature is necessary. The process involves arylpalladation of the alkyne, followed by intramolecular Heck olefination and double bond isomerization. This method accommodates a variety of functional groups and affords the anticipated highly substituted naphthalenes and carbazoles in good to excellent yields. Novel palladium migratiodarylation methodology for the synthesis of complex fused polycycles has been developed, in which one or more sequential Pd-catalyzed intramolecular migration processes involving C-H activation are employed. The chemistry works best with electron-rich aromatics, which is in agreement with the idea that these palladium-catalyzed C-H activation reactions parallel electrophilic aromatic substitution. A relatively efficient synthesis of cyclopropanes has been developed using palladium-catalyzed C-H activation chemistry, in which two new carbon-carbon bonds are formed in a single step. This method involves the palladium-catalyzed activation of relatively unreactive C-H bonds, and provides a very efficient way to synthesize cyclopropapyrrolo[1,2-a]indoles, analogues of the mitomycin antibiotics.

  1. Alternatives to Nitric Acid Stripping in the Caustic-Side Solvent Extraction (CSSX) Process for Cesium Removal from Alkaline High-Level Waste

    SciTech Connect (OSTI)

    Delmau, Laetitia Helene; Haverlock, Tamara; Bazelaire, Eve; Bonnesen, Peter V; Ditto, Mary E; Moyer, Bruce A

    2009-01-01

    Effective alternatives to nitric acid stripping in the Caustic-Side Solvent Extraction (CSSX) solvent have been demonstrated in this work. The CSSX solvent employs calix[4]arene-bis(tert-octylbenzo-18-crown-6) (BOBCalixC6) as the cesium extractant in a modified alkane diluent for decontamination of alkaline high-level wastes. Results reported in this paper support the idea that replacement of the nitrate anion by a much more hydrophilic anion like borate can substantially lower cesium distribution ratios on stripping. Without any other change in the CSSX flowsheet, however, the use of a boric acid stripping solution in place of the 1 mM nitric acid solution used in the CSSX process marginally, though perhaps still usefully, improves stripping. The less-than-expected improvement was explained by the carryover of nitrate from scrubbing into stripping. Accordingly, more effective stripping is obtained after a scrub of the solvent with 0.1 M sodium hydroxide. Functional alternatives to boric acid include sodium bicarbonate or cesium hydroxide as strip solutions. Profound stripping improvement is achieved when trioctylamine, one of the components of the CSSX solvent, is replaced with a commercial guanidine reagent (LIX 79). The more basic guanidine affords greater latitude in selection of aqueous conditions in that it protonates even at mildly alkaline pH values. Under process-relevant conditions, cesium distributions on stripping are decreased on the order of 100-fold compared with current CSSX performance. The extraction properties of the solvent were preserved unchanged over three successive extract-scrub-strip cycles. From the point of view of compatibility with downstream processing, boric acid represents an attractive stripping agent, as it is also a potentially ideal feed for borosilicate vitrification of the separated 137Cs product stream. Possibilities for use of these results toward a dramatically better next-generation CSSX process, possibly one employing the more soluble cesium extractant calix[4]arene-bis(2 ethylhexylbenzo-18-crown-6) (BEHBCalixC6) are discussed.

  2. Development of a novel solvent for the simultaneous separation of strontium and cesium from dissolved Spent Nuclear Fuel solutions

    SciTech Connect (OSTI)

    Catherine L. Riddle; John D. Baker; Jack D. Law; Christopher A. McGrath; David H. Meikrantz; Bruce J. Mincher; Dean R. Peterman; Terry A. Todd

    2004-10-01

    The recovery of Cs and Sr from acidic solutions by solvent extraction has been investigated. The goal of this project was to develop an extraction process to remove Cs and Sr from high-level waste in an effort to reduce the heat loading in storage. Solvents for the extraction of Cs and Sr separately have been used on both caustic and acidic spent nuclear fuel waste in the past. The objective of this research was to find a suitable solvent for the extraction of both Cs and Sr simultaneously from acidic nitrate media. The solvents selected for this research possess good stability and extraction behavior when mixed together. The extraction experiments were performed with 4 ,4,(5 )-Di-(tbutyldicyclohexano)- 18-crown-6 {DtBuCH18C6}, Calix[4]arene-bis-(tert-octylbenzocrown-6) {BOBCalixC6} and 1-(2,2,3,3-tetrafluoropropoxy)-3-(4-sec-butylphenoxy)-2-propanol {Cs-7SB modifier} in a branched aliphatic kerosene {Isopar L}. The BOBCalixC6 and Cs-7SB modifier were developed at Oak Ridge National Laboratory (ORNL) by Bonnesen et al. [1]. The values obtained from the SREX solvent for DSr in 1 M nitric acid ranged from 0.7 to 2.2 at 25oC and 10oC respectively. The values for DCs in 1 M nitric acid with the CSSX solvent ranged from 8.0 to 46.0 at 25oC and 10oC respectively. A new mixed solvent, developed at the Idaho National Engineering and Environmental Laboratory (INEEL) by Riddle et al. [2], showed distributions for Sr ranging from 8.8 to 17.4 in 1 M nitric acid at 25oC and 10oC respectively. The DCs for the mixed solvent ranged from 7.7 to 20.2 in 1 M nitric acid at 25oC to 10oC respectively. The unexpectedly high distributions for Sr at both 25oC and 10oC show a synergy in the mixed solvent. The DCs, although lower than with CSSX solvent, still showed good extraction behavior.

  3. Atomic layer deposited lithium aluminum oxide: (In)dependency of film properties from pulsing sequence

    SciTech Connect (OSTI)

    Miikkulainen, Ville Nilsen, Ola; Fjellvg, Helmer; Li, Han; King, Sean W.; Laitinen, Mikko; Sajavaara, Timo

    2015-01-01

    Atomic layer deposition (ALD) holds markedly high potential of becoming the enabling method for achieving the three-dimensional all-solid-state thin-film lithium ion battery (LiB). One of the most crucial components in such a battery is the electrolyte that needs to hold both low electronic conductivity and at least fair lithium ion conductivity being at the same time pinhole free. To obtain these desired properties in an electrolyte film, one necessarily has to have a good control over the elemental composition of the deposited material. The present study reports on the properties of ALD lithium aluminum oxide (Li{sub x}Al{sub y}O{sub z}) thin films. In addition to LiB electrolyte applications, Li{sub x}Al{sub y}O{sub z} is also a candidate low dielectric constant (low-k) etch stop and diffusion barrier material in nanoelectronics applications. The Li{sub x}Al{sub y}O{sub z} films were deposited employing trimethylaluminum-O{sub 3} and lithium tert-butoxide-H{sub 2}O for Al{sub 2}O{sub 3} and Li{sub 2}O/LiOH, respectively. The composition was aimed to be controlled by varying the pulsing ratio of those two binary oxide ALD cycles. The films were characterized by several methods for composition, crystallinity and phase, electrical properties, hardness, porosity, and chemical environment. Regardless of the applied pulsing ratio of Al{sub 2}O{sub 3} and Li{sub 2}O/LiOH, all the studied ALD Li{sub x}Al{sub y}O{sub z} films of 200 and 400 nm in thickness were polycrystalline in the orthorhombic ?-LiAlO{sub 2} phase and also very similar to each other with respect to composition and other studied properties. The results are discussed in the context of both fundamental ALD chemistry and applicability of the films as thin-film LiB electrolytes and low-k etch stop and diffusion barriers.

  4. A role for glutathione, independent of oxidative stress, in the developmental toxicity of methanol

    SciTech Connect (OSTI)

    Siu, Michelle T.; Shapiro, Aaron M.; Wiley, Michael J.; Wells, Peter G.

    2013-12-15

    Oxidative stress and reactive oxygen species (ROS) have been implicated in the teratogenicity of methanol (MeOH) in rodents, both in vivo and in embryo culture. We explored the ROS hypothesis further in vivo in pregnant C57BL/6J mice. Following maternal treatment with a teratogenic dose of MeOH, 4 g/kg via intraperitoneal (ip) injection on gestational day (GD) 12, there was no increase 6 h later in embryonic ROS formation, measured by 2?,7?-dichlorodihydrofluorescin diacetate (DCFH-DA) fluorescence, despite an increase observed with the positive control ethanol (EtOH), nor was there an increase in embryonic oxidatively damaged DNA, quantified as 8-oxo-2?-deoxyguanosine (8-oxodG) formation. MeOH teratogenicity (primarily ophthalmic anomalies, cleft palate) also was not altered by pre- and post-treatment with varying doses of the free radical spin trapping agent alpha-phenyl-N-tert-butylnitrone (PBN). In contrast, pretreatment with L-buthionine-(S,R)-sulfoximine (BSO), an inhibitor of glutathione (GSH) synthesis, depleted maternal hepatic and embryonic GSH, and enhanced some new anomalies (micrognathia, agnathia, short snout, fused digits, cleft lip, low set ears), but not the most common teratogenic effects of MeOH (ophthalmic anomalies, cleft palate) in this strain. These results suggest that ROS did not contribute to the teratogenic effects of MeOH in this in vivo mouse model, in contrast to results in embryo culture from our laboratory, and that the protective effect of GSH in this model may arise from its role as a cofactor for formaldehyde dehydrogenase in the detoxification of formaldehyde. - Highlights: In vivo, a free radical scavenger did not block methanol (MeOH) teratogenesis. MeOH did not increase embryonic reactive oxygen species formation or DNA oxidation. MeOH teratogenesis was enhanced by glutathione (GSH) depletion. GSH may protect as the cofactor for formaldehyde dehydrogenase (ADH3). Formaldehyde may be a ROS-independent proximate teratogenic species in vivo.

  5. Development of a SREX flowsheet for the separation of strontium from dissolved INEEL zirconium calcine

    SciTech Connect (OSTI)

    Law, J.D.; Wood, D.J.; Todd, T.A.

    1999-01-01

    Laboratory experimentation has indicated that the SREX process is effective for partitioning {sup 90}Sr from acidic radioactive waste solutions located at the Idaho Nuclear Technology and Engineering Center. These laboratory results were used to develop a flowsheet for countercurrent testing of the SREX process with dissolved pilot plant calcine. Testing was performed using 24 stages of 2-cm diameter centrifugal contactors which are installed in the Remote Analytical Laboratory hot cell. Dissolved Run No.64 pilot plant calcine spiked with {sup 85}Sr was used as feed solution for the testing. The flowsheet tested consisted of an extraction section (0.15 M 4{prime},4{prime}(5{prime})-di-(tert-butylcyclohexo)-18-crown-6 and 1.5 M TBP in Isopar-L.), a 1.0 M NaNO{sub 3} scrub section to remove extracted K from the SREX solvent, a 0.01 M HNO{sub 3} strip section for the removal of Sr from the SREX solvent, a 0.25 M Na2CO{sub 3} wash section to remove degradation products from the solvent, and a 0.1 M HNO{sub 3} rinse section. The behavior of {sup 85}Sr, Na, K, Al, B, Ca, Cr, Fe, Ni, and Zr was evaluated. The described flowsheet successfully extracted {sup 85}Sr from the dissolved pilot plant calcine with a removal efficiency of 99.6%. Distribution coefficients for {sup 85}Sr ranged from 3.6 to 4.5 in the extraction section. With these distribution coefficients a removal efficiency of approximately >99.99% was expected. It was determined that the lower than expected removal efficiency can be attributed to a stage efficiency of only 60% in the extraction section. Extracted K was effectively scrubbed from the SREX solvent with the 1.0 M NaNO{sub 3} resulting in only 6.4% of the K in the HLW strip product. Sodium was not extracted from the dissolved calcine by the SREX solvent; however, the use of a 1.0 M NaNO{sub 3} scrub solution resulted in a Na concentration of 70 mg/L (12.3% of the feed concentration) in the HLW strip product. Al, B, Ca, Cr, Fe, Ni, and Zr were determined to be essentially inextractable.

  6. Development of a SREX Flowsheet for the Separation of Strontium from Dissolved INEEL Zirconium Calcine

    SciTech Connect (OSTI)

    Law, Jack Douglas; Wood, David James; Todd, Terry Allen

    1999-02-01

    Laboratory experimentation has indicated that the SREX process is effective for partitioning 90 Sr from acidic radioactive waste solutions located at the Idaho Nuclear Technology and Engineering Center. These laboratory results were used to develop a flowsheet for countercurrent testing of the SREX process with dissolved pilot plant calcine. Testing was performed using 24 stages of 2-cm diameter centrifugal contactors which are installed in the Remote Analytical Laboratory hot cell. Dissolved Run #64 pilot plant calcine spiked with 85 Sr was used as feed solution for the testing. The flowsheet tested consisted of an extraction section (0.15 M 4',4'(5')-di-(tert-butylcyclohexo)-18-crown-6 and 1.5 M TBP in Isopar-L.), a 1.0 M NaNO3 scrub section to remove extracted K from the SREX solvent, a 0.01 M HNO3 strip section for the removal of Sr from the SREX solvent, a 0.25 M Na2CO3 wash section to remove degradation products from the solvent, and a 0.1 M HNO3 rinse section. The behavior of 85 Sr, Na, K, Al, B, Ca, Cr, Fe, Ni, and Zr was evaluated. The described flowsheet successfully extracted 85 Sr from the dissolved pilot plant calcine with a removal efficiency of 99.6%. Distribution coefficients for 85 Sr ranged from 3.6 to 4.5 in the extraction section. With these distribution coefficients a removal efficiency of approximately >99.99% was expected. It was determined that the lower than expected removal efficiency can be attributed to a stage efficiency of only 60% in the extraction section. Extracted K was effectively scrubbed from the SREX solvent with the 1.0 M NaNO3 resulting in only 6.4% of the K in the HLW strip product. Sodium was not extracted from the dissolved calcine by the SREX solvent; however, the use of a 1.0 M NaNO3 scrub solution resulted in a Na concentration of 70 mg/L (12.3% of the feed concentration) in the HLW strip product. Al, B, Ca, Cr, Fe, Ni, and Zr were determined to be essentially inextractable.

  7. Iron Complexes Bearing Diphosphine Ligands with Positioned Pendant Amines as Electrocatalysts for the Oxidation of H2

    SciTech Connect (OSTI)

    Liu, Tianbiao L.; Liao, Qian; O'Hagan, Molly J.; Hulley, Elliott; DuBois, Daniel L.; Bullock, R. Morris

    2015-06-22

    The synthesis and spectroscopic characterization of CpC5F4NFe(PtBu2NBn2)Cl, [3-Cl] (where C5F4N is the tetrafluorpyridyl substituent and PtBu2NBn2 = 1,5-di(tert-butyl)-3,7-di(benzyl)-1,5-diaza-3,7-diphosphacyclooctane) are reported. Complex 3-Cl and previously reported [CpC5F4NFe(PtBu2NtBu2)Cl], 4-Cl, are precursors to intermediates in the catalytic oxidation of H2, including CpC5F4NFe(PtBu2NBn2)H (3-H), CpC5F4NFe(PtBu2NtBu2)H (4-H), [CpC5F4NFe(PtBu2NBn2)]BArF4 ([3](BArF4), [CpC5F4NFe(PtBu2NtBu2)]BArF4 ([4](BArF4), [CpC5F4NFe(PtBu2NBn2)(H2)]BArF4 ([3-H2]BArF4), and [CpC5F4NFe(PtBu2NtBu2H)H]BArF4 ([4-FeH(NH)]BArF4). All of these complexes were characterized by spectroscopic and electrochemical studies; 3-Cl, 3-H and 4-Cl were also characterized by single crystal diffraction studies. 3-H and 4-H are electrocatalysts for H2 (1.0 atm) oxidation in the presence of a excess of the amine base N-methylpyrrolidine, with turnover frequencies at 22 °C of 2.5 s-1 and 0.5 s-1, and overpotentials at Ecat/2 of 235 mV and 95 mV, respectively. Studies of individual chemical and/or electrochemical reactions of the various intermediates provide important insights into the factors governing the overall catalytic activity for H2 oxidation, and provide important insights into the role of the pendant base of the [FeFe] hydrogenase active site. This work was supported by the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences. Pacific Northwest National Laboratory is operated by Battelle for the U.S. Department of Energy.

  8. Cobalt Complexes Containing Pendant Amines in the Second Coordination Sphere as Electrocatalysts for H2 Production

    SciTech Connect (OSTI)

    Fang, Ming; Wiedner, Eric S.; Dougherty, William G.; Kassel, W. S.; Liu, Tianbiao L.; DuBois, Daniel L.; Bullock, R. Morris

    2014-10-27

    A series of heteroleptic 17e- cobalt complexes, [CpCoII(PtBu2NPh2)](BF4), [CpC6F5CoII(PtBu2NPh2)](BF4), [CpC5F4NCoII(PtBu2NPh2)](BF4), [where P2tBuN2Ph = 1,5-diphenyl-3,7-di(tert-butyl)-1,5-diaza-3,7-diphosphacyclooctane, CpC6F5 = C5H4(C6F5), and CpC5F4N = C5H4(C5F4N)] were synthesized, and structures of all three were determined by X-ray crystallography. Electrochemical studies showed that the CoIII/II couple of [CpC5F4NCoII(PtBu2NPh2)]+ appears 250 mV positive of the CoIII/II couple of [CpCoII(PtBu2NPh2)] as a result of the strongly electron-withdrawing perfluorpyridyl substituent on the Cp ring. Reduction of these paramagnetic CoII complexes by KC8 led to the diamagnetic 18e- complexes CpICo(PtBu2NPh2), CpC6F5CoI(PtBu2NPh2), CpC5F4NCoI(PtBu2NPh2), which were also characterized by crystallography. Protonation of these neutral CoI complexes led to the cobalt hydrides [CpCoIII(PtBu2NPh2)H](BF4), [CpC6F5CoIII(PtBu2NPh2)H](BF4), and [CpC5F4NCoIII(PtBu2NPh2)H](BF4). The cobalt hydride with the most electron-withdrawing Cp ligand, [CpC5F4NCoIII(PtBu2NPh2)H]+ is an electrocatalyst for production of H2 using 4-MeOC6H4NH3BF4 (pKaMeCN = 11.86) with a turnover frequency of 350 s-1 and an overpotential of 0.75 V. Experimental measurement of thermochemical data provided further insights into the thermodynamics of H2 elimination. This research was supported as part of the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences. Pacific Northwest National Laboratory is operated by Battelle for the U.S. Department of Energy.

  9. 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.

  10. Electrode films of porous agarose: The effects of physical structure on electron transport processes. [Impregnated with Nafion; immobilized electroactive species

    SciTech Connect (OSTI)

    Moran, K.D.

    1988-02-01

    Potential use of chemically modified electrodes in electrocatalysis has stimulated interest in creation and characterization of electrode films for reagent immobilization. We have created two highly porous electrocatalyst support matrices, with high rates of electron transport. Both are based on immobilization of reagents in agarose gel. In one case, Nafion was impregnated into agarose gel films. Diffusion of methyl viologen in Nafionagarose matrices are higher than in Nafion. In Nafion, the diffusion coefficient decreases with increasing methyl viologen concentration, while in Nafionagarose, the opposite dependence is observed. The faster rate of electron transport in Nafionagarose films is related to the heterogeneous structure and the coupling of the diffusion pathways. In the second application of agarose gels as an electrode coating material, agarose hydroxyl groups were activated in 1,1'carbonyldiimidazole and subsequently reacted with amine derivatives of electroactive mediators. Electron transport between the electroactive sites in the gel is very rapid (on the order of 10/sup -7/ cm/sup 2/s. Interpreting the data in light of the Dahms-Ruff description of electron transport shows that the rate of electron transport through both ferrocene and viologen derivatized gels is limited by the rate of electron self-exchange of the species. 22 figs., 15 tabs

  11. Structureactivity relationships of imidazole-derived 2-[N-carbamoylmethyl-alkylamino]acetic acids, dual binders of human insulin-degrading enzyme

    SciTech Connect (OSTI)

    Charton, Julie; Dumont, Julie; Liang, Wenguang G.; Leroux, Florence; Deprez, Benoit

    2015-10-30

    Insulin degrading enzyme (IDE) is a zinc metalloprotease that degrades small amyloid peptides such as amyloid- and insulin. So far the dearth of IDE-specific pharmacological inhibitors impacts the understanding of its role in the physiopathology of Alzheimer's disease, amyloid- clearance, and its validation as a potential therapeutic target. Hit 1 was previously discovered by high-throughput screening. Here we describe the structure-activity study, that required the synthesis of 48 analogues. We found that while the carboxylic acid, the imidazole and the tertiary amine were critical for activity, the methyl ester was successfully optimized to an amide or a 1,2,4-oxadiazole. Along with improving their activity, compounds were optimized for solubility, lipophilicity and stability in plasma and microsomes. The docking or co-crystallization of some compounds at the exosite or the catalytic site of IDE provided the structural basis for IDE inhibition. The pharmacokinetic properties of best compounds 44 and 46 were measured in vivo. As a result, 44 (BDM43079) and its methyl ester precursor 48 (BDM43124) are useful chemical probes for the exploration of IDE's role.

  12. Inhibition of angiogenesis by S-adenosylmethionine

    SciTech Connect (OSTI)

    Sahin, Mehmet; Sahin, Emel; Guemueslue, Saadet; Erdogan, Abdullah; Gueltekin, Meral

    2011-04-29

    Highlights: {yields} Effects of S-adenosylmethionine (SAM) were investigated in endothelial cells. {yields} Our results showed that SAM decreased proliferation of endothelial cells. {yields} SAM influentially inhibited the percentage of cell migration. {yields} SAM probably stopped migration as independent from its effects on proliferation. {yields} SAM was shown to suppress in vitro angiogenesis. -- Abstract: Metastasis is a leading cause of mortality and morbidity in cancer. One of the steps in metastasis process is the formation of new blood vessels. Aberrant DNA methylation patterns are common in cancer cells. In recent studies, S-adenosylmethionine (SAM), which is a DNA methylating agent, has been found to have inhibitory effects on some carcinoma cells in vivo and in vitro. In the present study, we have used SAM to investigate whether it is effective against angiogenesis in vitro. Our results have shown that SAM can reduce the formation and organization of capillary-like structures of endothelial cells in tumoral environment. Besides, we have found SAM can block endothelial cell proliferation and the migration of cells towards growth factors-rich media. In conclusion, our study suggests that SAM may be used against angiogenesis as a natural bio-product.

  13. Soft ionization of thermally evaporated hypergolic ionic liquid aerosols

    SciTech Connect (OSTI)

    University of California; ERC, Incorporated, Edwards Air Force Base; Air Force Research Laboratory, Edwards Air Force Base; National Synchrotron Radiation Research Center; Koh, Christine J.; Liu, Chen-Lin; Harmon, Christopher W.; Strasser, Daniel; Golan, Amir; Kostko, Oleg; Chambreau, Steven D.; L.Vaghjiani, Ghanshyam; Leone, Stephen R.

    2012-03-16

    Isolated ion pairs of a conventional ionic liquid, 1-Ethyl-3-Methyl-Imidazolium Bis(trifluoromethylsulfonyl)imide ([Emim+][Tf2N?]), and a reactive hypergolic ionic liquid, 1- Butyl-3-Methyl-Imidazolium Dicyanamide ([Bmim+][Dca?]), are generated by vaporizing ionic liquid submicron aerosol particles for the first time; the vaporized species are investigated by dissociative ionization with tunable vacuum ultraviolet (VUV) light, exhibiting clear intact cations, Emim+ and Bmim+, presumably originating from intact ion pairs. Mass spectra of ion pair vapor from an effusive source of the hypergolic ionic liquid show substantial reactive decomposition due to the internal energy of the molecules emanating from the source. Photoionization efficiency curves in the near threshold ionization region of isolated ion pairs of [Emim+][Tf2N?] ionic liquid vapor are compared for an aerosol source and an effusive source, revealing changes in the appearance energy due to the amount of internal energy in the ion pairs. The aerosol source has a shift to higher threshold energy (~;;0.3 eV), attributed to reduced internal energy of the isolated ion pairs. The method of ionic liquid submicron aerosol particle vaporization, for reactive ionic liquids such as hypergolic species, is a convenient, thermally ?cooler? source of isolated intact ion pairs in the gas phase compared to effusive sources.

  14. Soft ionization of thermally evaporated hypergolic ionic liquid aerosols

    SciTech Connect (OSTI)

    University of California; ERC, Incorporated, Edwards Air Force Base; Air Force Research Laboratory, Edwards Air Force Base; National Synchrotron Radiation Research Center; Institute of Chemistry, Hebrew University; Koh, Christine J.; Liu, Chen-Lin; Harmon, Christopher W.; Strasser, Daniel; Golan, Amir; Kostko, Oleg; Chambreau, Steven D.; Vaghjiani, Ghanshyam L.; Leone, Stephen R.

    2011-07-19

    Isolated ion pairs of a conventional ionic liquid, 1-Ethyl-3-Methyl-Imidazolium Bis(trifluoromethylsulfonyl)imide ([Emim+][Tf2N?]), and a reactive hypergolic ionic liquid, 1-Butyl-3-Methyl-Imidazolium Dicyanamide ([Bmim+][Dca?]), are generated by vaporizing ionic liquid submicron aerosol particles for the first time; the vaporized species are investigated by dissociative ionization with tunable vacuum ultraviolet (VUV) light, exhibiting clear intact cations, Emim+ and Bmim+, presumably originating from intact ion pairs. Mass spectra of ion pair vapor from an effusive source of the hypergolic ionic liquid show substantial reactive decomposition due to the internal energy of the molecules emanating from the source. Photoionization efficiency curves in the near threshold ionization region of isolated ion pairs of [Emim+][Tf2N?]ionic liquid vapor are compared for an aerosol source and an effusive source, revealing changes in the appearance energy due to the amount of internal energy in the ion pairs. The aerosol source has a shift to higher threshold energy (~;;0.3 eV), attributed to reduced internal energy of the isolated ion pairs. The method of ionic liquid submicron aerosol particle vaporization, for reactive ionic liquids such as hypergolic species, is a convenient, thermally ?cooler? source of isolated intact ion pairs in the gas phase compared to effusive sources.

  15. Physical and chemical comparison of soot in hydrocarbon and biodiesel fuel diffusion flames: A study of model and commercial fuels

    SciTech Connect (OSTI)

    Matti Maricq, M.

    2011-01-15

    Data are presented to compare soot formation in both surrogate and practical fatty acid methyl ester biodiesel and petroleum fuel diffusion flames. The approach here uses differential mobility analysis to follow the size distributions and electrical charge of soot particles as they evolve in the flame, and laser ablation particle mass spectrometry to elucidate their composition. Qualitatively, these soot properties exhibit a remarkably similar development along the flames. The size distributions begin as a single mode of precursor nanoparticles, evolve through a bimodal phase marking the onset of aggregate formation, and end in a self preserving mode of fractal-like particles. Both biodiesel and hydrocarbon fuels yield a common soot composition dominated by C{sub x}H{sub y}{sup +} ions, stabilomer PAHs, and fullerenes in the positive ion mass spectrum, and C{sub x}{sup -} and C{sub 2x}H{sup -} in the negative ion spectrum. These ion intensities initially grow with height in the diffusion flames, but then decline during later stages, consistent with soot carbonization. There are important quantitative differences between fuels. The surrogate biodiesel fuel methyl butanoate substantially reduces soot levels, but soot formation and evolution in this flame are delayed relative to both soy and petroleum fuels. In contrast, soots from soy and hexadecane flames exhibit nearly quantitative agreement in their size distribution and composition profiles with height, suggesting similar soot precursor chemistry. (author)

  16. 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

  17. Stratospheric ozone protection: The Montreal Protocol and Title VI of the Clean Air Act Amendments of 1990

    SciTech Connect (OSTI)

    Babst, C.R. III

    1993-08-01

    The stratospheric ozone layer protects the surface of the Earth from harmful ultraviolet (UV-B) radiation, which has been causally linked to skin cancer and cataracts, suppression of the human immune system, damage to crops and aquatic organisms, the formation of ground-level zone and the rapid weathering of outdoor plastics. In recent years, scientists have observed a significant deterioration of the ozone layer, particularly over the poles, but increasingly over populated regions as well. This deterioration has been attributed to the atmospheric release of certain man-made halocarbons, including chlorofluorocarbons (CFCs), halons, methyl chloroform and carbon tetrachloride. Once used extensively as propellants for aerosol sprays (but generally banned for such purposes since 1978), CFCs are widely used today as refrigerants, foams and solvents. All of these chlorinated (CFC, methyl chloroform and carbon tetrachloride) and brominated (halon) compounds are classified for regulatory purposes as Class I substances because of their significant ozone-depleting potential. Hydrochlorofluorocarbons (HCFCs), developed as alternatives to CFCs and halons for many different applications, have been classified for regulatory purposes as Class II substances because of their relatively less destructive impact on stratospheric ozone. This paper describes the following regulations to reduce destruction of the ozone layer: the Montreal Protocol; Title VI of the Clean air Act Amendments of 1990; Accelerated Phase-out schedules developed by the countries which signed the Montreal Protocol; Use restrictions; Recycling and Emission reduction requirements; Servicing of motor vehicle air conditions; ban on nonessential products; labeling requirements; safe alternatives. 6 refs.

  18. Synthesis of labeled oxalic acid derivatives

    DOE Patents [OSTI]

    Martinez, Rodolfo A.; Unkefer, Clifford J.; Alvarez, Marc A.

    2004-06-22

    The present invention is directed to labeled compounds, specifically ##STR1## where each C* is selected from the group consisting of a carbon-12, i.e., .sup.12 C, or a carbon-13, i.e., .sup.13 C and at least one C* is .sup.13 C, R.sup.1 is selected from the group of C.sub.1 -C.sub.4 lower alkyl and aryl, and X is selected from the group of --NR.sup.2 R.sup.3 where R.sup.2 and R.sup.3 are each independently selected from the group of C.sub.1 -C.sub.4 lower alkyl, alkoxy and aryl, --SR.sup.4 where R.sup.4 is selected from the group of C.sub.1 -C.sub.4 lower alkyl, alkoxy and aryl, and --OR.sup.5 where R.sup.5 is selected from the group of C.sub.1 -C.sub.4 lower alkyl, alkoxy and aryl with the proviso that when R.sup.1 is methyl then R.sup.5 is other than methyl, when R.sup.1 is ethyl then R.sup.5 is other than ethyl, and when R.sup.1 is benzyl then R.sup.5 is other than benzyl.

  19. Comprehensive chemical kinetic modeling of the oxidation of C8 and larger n-alkanes and 2-methylalkanes

    SciTech Connect (OSTI)

    Sarathy, S M; Westbrook, C K; Pitz, W J; Mehl, M; Togbe, C; Dagaut, P; Wang, H; Oehlschlaeger, M; NIemann, U; Seshadri, K; Veloo, P S; Ji, C; Egolfopoulos, F; Lu, T

    2011-03-16

    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 and reduced chemical kinetic mechanism for singly methylated iso-alkanes (i.e., 2-methylalkanes) ranging from C{sub 8} to C{sub 20}. The mechanism also includes an updated version of our previously published C{sub 8} to C{sub 16} n-alkanes model. The complete detailed mechanism contains approximately 7,200 species 31,400 reactions. The proposed model is validated against new experimental data from a variety of fundamental combustion devices including premixed and nonpremixed flames, perfectly stirred reactors and shock tubes. This new model is used to show how the presence of a methyl branch affects important combustion properties such as laminar flame propagation, ignition, and species formation.

  20. 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.

  1. Modifications to toxic CUG RNAs induce structural stability, rescue mis-splicing in a myotonic dystrophy cell model and reduce toxicity in a myotonic dystrophy zebrafish model

    SciTech Connect (OSTI)

    deLorimier, Elaine; Coonrod, Leslie A.; Copperman, Jeremy; Taber, Alex; Reister, Emily E.; Sharma, Kush; Todd, Peter K.; Guenza, Marina G.; Berglund, J. Andrew

    2014-10-10

    In this study, CUG repeat expansions in the 3' UTR of dystrophia myotonica protein kinase (DMPK) cause myotonic dystrophy type 1 (DM1). As RNA, these repeats elicit toxicity by sequestering splicing proteins, such as MBNL1, into proteinRNA aggregates. Structural studies demonstrate that CUG repeats can form A-form helices, suggesting that repeat secondary structure could be important in pathogenicity. To evaluate this hypothesis, we utilized structure-stabilizing RNA modifications pseudouridine (?) and 2'-O-methylation to determine if stabilization of CUG helical conformations affected toxicity. CUG repeats modified with ? or 2'-O-methyl groups exhibited enhanced structural stability and reduced affinity for MBNL1. Molecular dynamics and X-ray crystallography suggest a potential water-bridging mechanism for ?-mediated CUG repeat stabilization. ? modification of CUG repeats rescued mis-splicing in a DM1 cell model and prevented CUG repeat toxicity in zebrafish embryos. This study indicates that the structure of toxic RNAs has a significant role in controlling the onset of neuromuscular diseases.

  2. Coincidence ion imaging with a fast frame camera

    SciTech Connect (OSTI)

    Lee, Suk Kyoung; Cudry, Fadia; Lin, Yun Fei; Lingenfelter, Steven; Winney, Alexander H.; Fan, Lin; Li, Wen

    2014-12-15

    A new time- and position-sensitive particle detection system based on a fast frame CMOS (complementary metal-oxide semiconductors) camera is developed for coincidence ion imaging. The system is composed of four major components: a conventional microchannel plate/phosphor screen ion imager, a fast frame CMOS camera, a single anode photomultiplier tube (PMT), and a high-speed digitizer. The system collects the positional information of ions from a fast frame camera through real-time centroiding while the arrival times are obtained from the timing signal of a PMT processed by a high-speed digitizer. Multi-hit capability is achieved by correlating the intensity of ion spots on each camera frame with the peak heights on the corresponding time-of-flight spectrum of a PMT. Efficient computer algorithms are developed to process camera frames and digitizer traces in real-time at 1 kHz laser repetition rate. We demonstrate the capability of this system by detecting a momentum-matched co-fragments pair (methyl and iodine cations) produced from strong field dissociative double ionization of methyl iodide.

  3. Spectroscopic analysis of H{sub 2}/CH{sub 4} microwave plasma and fast growth rate of diamond single crystal

    SciTech Connect (OSTI)

    Derkaoui, N.; Rond, C. Hassouni, K.; Gicquel, A.

    2014-06-21

    One of the best ways to increase the diamond growth rate is to couple high microwave power to the plasma. Indeed, increasing the power density leads to increase gas temperature the atomic hydrogen density in the plasma bulk, and to produce more hydrogen and methyl at the diamond surface. Experimental and numerical approaches were used to study the microwave plasma under high power densities conditions. Gas temperature was measured by optical emission spectroscopy and H-atom density using actinometry. CH{sub 3}-radical density was obtained using a 1D model that describes temperatures and plasma composition from the substrate to the top of the reactor. The results show that gas temperature in the plasma bulk, atomic hydrogen, and methyl densities at the diamond surface highly increase with the power density. As a consequence, measurements have shown that diamond growth rate also increases. At very high power density, we measured a growth rate of 40??m/h with an H-atom density of 5 10{sup 17} cm{sup ?3} which corresponds to a H{sub 2} dissociation rate higher than 50%. Finally, we have shown that the growth rate can be framed between a lower and an upper limit as a function depending only on the maximum of H-atom density measured or calculated in the plasma bulk. The results also demonstrated that increasing fresh CH{sub 4} by an appropriate injection into the boundary layer is a potential way to increase the diamond growth rates.

  4. Site-Specific Scaling Relations for Hydrocarbon Adsorption on Hexagonal Transition Metal Surfaces

    SciTech Connect (OSTI)

    Montemore, Matthew M.; Medlin, James W.

    2013-10-03

    Screening a large number of surfaces for their catalytic performance remains a challenge, leading to the need for simple models to predict adsorption properties. To facilitate rapid prediction of hydrocarbon adsorption energies, scaling relations that allow for calculation of the adsorption energy of any intermediate attached to any symmetric site on any hexagonal metal surface through a carbon atom were developed. For input, these relations require only simple electronic properties of the surface and of the gas-phase reactant molecules. Determining adsorption energies consists of up to four steps: (i) calculating the adsorption energy of methyl in the top site using density functional theory or by simple relations based on the electronic structure of the surface; (ii) using modified versions of classical scaling relations to scale between methyl in the top site and C? species with more metal-surface bonds (i.e., C, CH, CH?) in sites that complete adsorbate tetravalency; (iii) using gas-phase bond energies to predict adsorption energies of longer hydrocarbons (i.e., CR, CR?, CR?); and (iv) expressing energetic changes upon translation of hydrocarbons to various sites in terms of the number of agostic interactions and the change in the number of carbon-metal bonds. Combining all of these relations allows accurate scaling over a wide range of adsorbates and surfaces, resulting in efficient screening of catalytic surfaces and a clear elucidation of adsorption trends. The relations are used to explain trends in methane reforming, hydrocarbon chain growth, and propane dehydrogenation.

  5. The Role of Comprehensive Detailed Chemical Kinetic Reaction Mechanisms in Combustion Research

    SciTech Connect (OSTI)

    Westbrook, C K; Pitz, W J; Curran, H J; Mehl, M

    2008-07-16

    Recent developments by the authors in the field of comprehensive detailed chemical kinetic reaction mechanisms for hydrocarbon fuels are reviewed. Examples are given of how these mechanisms provide fundamental chemical insights into a range of combustion applications. Practical combustion consists primarily of chemical heat release from reactions between a fuel and an oxidizer, and computer simulations of practical combustion systems have become an essential tool of combustion research (Westbrook et al., 2005). At the heart of most combustion simulations, the chemical kinetic submodel frequently is the most detailed, complex and computationally costly part of a system model. Historically, the chemical submodel equations are solved using time-implicit numerical algorithms, due to the extreme stiffness of the coupled rate equations, with a computational cost that varies roughly with the cube of the number of chemical species in the model. While early mechanisms (c. 1980) for apparently simple fuels such as methane (Warnatz, 1980) or methanol (Westbrook and Dryer, 1979) included perhaps 25 species, current detailed mechanisms for much larger, more complex fuels such as hexadecane (Fournet et al., 2001; Ristori et al., 2001; Westbrook et al., 2008) or methyl ester methyl decanoate (Herbinet et al., 2008) have as many as 2000 or even 3000 species. Rapid growth in capabilities of modern computers has been an essential feature in this rapid growth in the size and complexity of chemical kinetic reaction mechanisms.

  6. EDDY RESOLVING NUTRIENT ECODYNAMICS IN THE GLOBAL PARALLEL OCEAN PROGRAM AND CONNECTIONS WITH TRACE GASES IN THE SULFUR, HALOGEN AND NMHC CYCLES

    SciTech Connect (OSTI)

    S. CHU; S. ELLIOTT

    2000-08-01

    Ecodynamics and the sea-air transfer of climate relevant trace gases are intimately coupled in the oceanic mixed layer. Ventilation of species such as dimethyl sulfide and methyl bromide constitutes a key linkage within the earth system. We are creating a research tool for the study of marine trace gas distributions by implementing coupled ecology-gas chemistry in the high resolution Parallel Ocean Program (POP). The fundamental circulation model is eddy resolving, with cell sizes averaging 0.15 degree (lat/long). Here we describe ecochemistry integration. Density dependent mortality and iron geochemistry have enhanced agreement with chlorophyll measurements. Indications are that dimethyl sulfide production rates must be adjusted for latitude dependence to match recent compilations. This may reflect the need for phytoplankton to conserve nitrogen by favoring sulfurous osmolytes. Global simulations are also available for carbonyl sulfide, the methyl halides and for nonmethane hydrocarbons. We discuss future applications including interaction with atmospheric chemistry models, high resolution biogeochemical snapshots and the study of open ocean fertilization.

  7. Temperature effects on nanostructure and mechanical properties of single-nanoparticle thick membranes.

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

    Salerno, Kenneth Michael; Grest, Gary S.

    2015-04-30

    In this study, the properties of mechanically stable single-nanoparticle (NP)-thick membranes have largely been studied at room temperature. How these membranes soften as nanoparticle ligands disorder with increasing temperature is unknown. Molecular dynamics simulations are used to probe the temperature dependence of the mechanical and nanostructural properties of nanoparticle membranes made of 6 nm diameter Au nanoparticles coated with dodecanethiol ligands and terminated with either methyl (CH3) or carboxyl (COOH) terminal groups. For methyl-terminated ligands, interactions along the alkane chain provide mechanical stiffness, with a Young's modulus of 1.7 GPa at 300 K. For carboxyl-terminated chains, end-group interactions are significant,more » producing stiffer membranes at all temperatures, with a Young's modulus of 3.8 GPa at 300 K. For both end-group types, membrane stiffness is reduced to zero at about 400 K. Ligand structure and mechanical properties of membranes at 300 K that have been annealed at 400 K are comparable to samples that do not undergo thermal annealing.« less

  8. The dissociation of diacetyl : a shock-tube and theoretical study.

    SciTech Connect (OSTI)

    Yang, X.; Jasper, A. W.; Kiefer, J. H.; Tranter, R. S.

    2009-07-01

    The dissociation of diacetyl dilute in krypton has been studied in a shock tube using laser schlieren densitometry at 1200-1800 K and reaction pressures of 55 {+-} 2, 120 {+-} 3, and 225 {+-} 5 Torr. The experimentally determined rate coefficients show falloff and an ab initio/Master Equation/VRC-TST analysis was used to determine pressure-dependent rate coefficient expressions that are in good agreement with the experimental data. From the theoretical calculations k{sub {infinity}} (T) = 5.029 x 10{sup 19} (T/298 K){sup -3.40} exp(-37665/T) s{sup -1} for 300 < T < 2000 K. The laser schlieren profiles were simulated using a model for methyl recombination with appropriate additions for diacetyl. From the simulations rate coefficients were determined for CH{sub 3} + CH{sub 3} = C{sub 2}H{sub 6} and CH{sub 3} + C{sub 4}H{sub 6}O{sub 2} = CH{sub 3}CO + CH{sub 2}CO + CH{sub 4} (k(T) = 2.818T{sup 4.00} exp(-5737/T) cm{sup 3} mol{sup -1} s{sup -1}). Excellent agreement is found between the simulations and experimental profiles, and Troe type parameters have been calculated for the dissociation of diacetyl and the recombination of methyl radicals.

  9. Modifications to toxic CUG RNAs induce structural stability, rescue mis-splicing in a myotonic dystrophy cell model and reduce toxicity in a myotonic dystrophy zebrafish model

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

    deLorimier, Elaine; Coonrod, Leslie A.; Copperman, Jeremy; Taber, Alex; Reister, Emily E.; Sharma, Kush; Todd, Peter K.; Guenza, Marina G.; Berglund, J. Andrew

    2014-10-10

    In this study, CUG repeat expansions in the 3' UTR of dystrophia myotonica protein kinase (DMPK) cause myotonic dystrophy type 1 (DM1). As RNA, these repeats elicit toxicity by sequestering splicing proteins, such as MBNL1, into protein–RNA aggregates. Structural studies demonstrate that CUG repeats can form A-form helices, suggesting that repeat secondary structure could be important in pathogenicity. To evaluate this hypothesis, we utilized structure-stabilizing RNA modifications pseudouridine (Ψ) and 2'-O-methylation to determine if stabilization of CUG helical conformations affected toxicity. CUG repeats modified with Ψ or 2'-O-methyl groups exhibited enhanced structural stability and reduced affinity for MBNL1. Molecular dynamicsmore » and X-ray crystallography suggest a potential water-bridging mechanism for Ψ-mediated CUG repeat stabilization. Ψ modification of CUG repeats rescued mis-splicing in a DM1 cell model and prevented CUG repeat toxicity in zebrafish embryos. This study indicates that the structure of toxic RNAs has a significant role in controlling the onset of neuromuscular diseases.« less

  10. 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.

  11. Synthesis of [1-.sup.13C]pyruvic acid], [2-.sup.13C]pyruvic acid], [3-.sup.13C]pyruvic acid] and combinations thereof

    DOE Patents [OSTI]

    Martinez, Rodolfo A. (Santa Fe, NM), Unkefer; Clifford J. (Los Alamos, NM), Alvarez; Marc A. (Santa Fe, NM)

    2012-06-12

    The present invention is directed to the labeled compounds, ##STR00001## wherein C* is each either .sup.13C and .sup.12C where at least one C* is .sup.13C, each hydrogen of the methylene group is hydrogen or deuterium, the methyl group includes either zero or three deuterium atoms, Q is sulfide, sulfinyl, or sulfone, Z is an aryl group such as 1-naphthyl, substituted 1-naphthyl, 2-naphthyl, substituted 2-naphthyl, or a phenyl group ##STR00002## wherein R.sub.1, R.sub.2, R.sub.3, R.sub.4 and R.sub.5 are each independently either hydrogen, a C.sub.1-C.sub.4 lower alkyl, a halogen, and an amino group such as NH.sub.2, NHR and NRR' where R and R' are each independently either a C.sub.1-C.sub.4 lower alkyl, a phenyl, and an alkoxy group, and the methyl group can include either zero or three deuterium atoms. The present invention is also directed to the labeled compounds ##STR00003##

  12. Synthesis of [1-.sup.13C]pyruvic acid], [2-.sup.13C]pyruvic acid], [3-.sup.13C]pyruvic acid] and combinations thereof

    DOE Patents [OSTI]

    Martinez, Rodolfo A. (Santa Fe, NM); Unkefer, Clifford J. (Los Alamos, NM); Alvarez, Marc A. (Santa Fe, NM)

    2009-09-01

    The present invention is directed to labeled compounds, of the formulae ##STR00001## wherein C* is each independently selected from the group consisting of .sup.13C and .sup.12C with the proviso that at least one C* is .sup.13C, each hydrogen of the methylene group can independently be either hydrogen or deuterium, the methyl group includes either zero or three deuterium atoms, Q is from the group of sulfide, sulfinyl, and sulfone, Z is an aryl group from the group 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 from the group of hydrogen, a C.sub.1-C.sub.4 lower alkyl, a halogen, and an amino group from the group of NH.sub.2, NHR and NRR' where R and R' are each independently from the group of a C.sub.1-C.sub.4 lower alkyl, a phenyl, and an alkoxy group, and the methyl group can include either zero or three deuterium atoms.

  13. Phase Behavior of Neat Triblock Copolymers and Copolymer/Homopolymer Blends Near Network Phase Windows

    SciTech Connect (OSTI)

    M Tureau; L Rong; B Hsiao; T Epps

    2011-12-31

    The phase behavior of poly(isoprene-b-styrene-b-methyl methacrylate) (ISM) copolymers near the styrene-rich network phase window was examined through the use of neat triblock copolymers and copolymer/homopolymer blends. Both end-block and middle-block blending protocols were employed using poly(isoprene) (PI), poly(methyl methacrylate) (PMMA), and poly(styrene) (PS) homopolymers. Blended specimens exhibited phase transformations to well-ordered nanostructures (at homopolymer loadings up to 26 vol % of the total blend volume). Morphological consistency between neat and blended specimens was established at various locations in the ISM phase space. Copolymer/homopolymer blending permitted the refinement of lamellar, hexagonally packed cylinder, and disordered melt phase boundaries as well as the identification of double gyroid (Q{sup 230}), alternating gyroid (Q{sup 214}), and orthorhombic (O{sup 70}) network regimes. Additionally, the experimental phase diagram exhibited similar trends to those found in a theoretical ABC triblock copolymer phase diagram with symmetric interactions and statistical segments lengths generated by Tyler et al.

  14. Catalytic Ionic Hydrogenation of Ketones by {[Cp*Ru(CO)2]2(-H)}+

    SciTech Connect (OSTI)

    Bullock, R.M.; Fagan, P.J.; Voges, M.H.

    2010-02-22

    {l_brace}[Cp*Ru(CO){sub 2}]{sub 2}({mu}-H){r_brace}{sup +}OTf{sup -} functions as a homogeneous catalyst precursor for hydrogenation of ketones to alcohols, with hydrogenations at 1 mol % catalyst loading at 90 C under H{sub 2} (820 psi) proceeding to completion and providing >90% yields. Hydrogenation of methyl levulinate generates {gamma}-valerolactone, presumably by ring-closing of the initially formed alcohol with the methyl ester. Experiments in neat Et{sub 2}C=O show that the catalyst loading can be <0.1 mol % and that at least 1200 turnovers of the catalyst can be obtained. These reactions are proposed to proceed by an ionic hydrogenation pathway, with the highly acidic dihydrogen complex [Cp*Ru(CO){sub 2}({eta}{sup 2}-H{sub 2})]{sup +}OTf{sup -} being formed under the reaction conditions from reaction of H2 with {l_brace}[Cp*Ru(CO){sub 2}]{sub 2}({mu}-H){r_brace}{sup +}OTf{sup -}.

  15. Synthesis of novel photocatalytic RGO-InVO{sub 4} nanocomposites with visible light photoactivity

    SciTech Connect (OSTI)

    Shen, Jianfeng; Li, Xianfu; Huang, Weishi; Li, Na; Ye, Mingxin

    2013-09-01

    Graphical abstract: A facile method for preparation of reduced graphene oxide (RGO) sheets supported indium vanadate (InVO{sub 4}) photocatalysts is reported. The visible light response and adsorption ability of RGO-InVO{sub 4} nanocomposites is greatly improved, which can effectively remove methyl orange and Cr (VI) from water. - Highlights: Supramolecular photocatalyst of RGO-InVO{sub 4} was achieved. Reduction of GO and preparation of RGO-InVO{sub 4} was simultaneous. The prepared RGO-InVO{sub 4} shows high photocatalytic activity and adsorption capacity under visible light. In situ growth of uniform InVO{sub 4} particles on RGO sheets is facile and efficient - Abstract: In this study, we report a facile method for preparation of reduced graphene oxide (RGO) sheets supported indium vanadate (InVO{sub 4}) photocatalysts. A wide range of characterization techniques, such as Fourier transform infrared spectroscopy, Raman spectroscopy, X-ray diffraction, Thermogravimetric analysis and Transmission electron microscopy were applied to characterize the obtained composites. The results indicated that the composites consist of uniformly dispersed InVO{sub 4} nanocrystals on RGO sheets. Visible light responses of RGO-InVO{sub 4} nanocomposites are greatly improved as compared with the bulk InVO{sub 4}. The as-prepared RGO-InVO{sub 4} nanocomposites can effectively remove methyl orange and Cr (VI) from water under visible light irradiation, which can be used as novel photocatalysts for environmental protection.

  16. The Morphology of Emulsion Polymerized Latex Particles

    DOE R&D Accomplishments [OSTI]

    Wignall, G. D.; Ramakrishnan, V. R.; Linne, M. A.; Klein, A.; Sperling, L. H.; Wai, M. P.; Gelman, R. A.; Fatica, M. G.; Hoerl, R. H.; Fisher, L. W.

    1987-11-01

    Under monomer starved feed conditions, emulsion polymerization of perdeuterated methyl methacrylate and styrene in the presence of preformed polymethylmethacrylate latexes resulted in particles with a core-shell morphology, as determined by small-angle neutron scattering (SANS) analysis for a hollow sphere. The locus of polymerization of the added deuterated monomer is therefore at the particle surface. In similar measurements a statistical copolymer of styrene and methyl methacrylate was used as seed particles for further polymerization of trideuteromethyl methacrylate. The resulting polymer latex was again shown to have a core-shell morphological structure as determined by SANS. SANS experiments were also undertaken on polystyrene latexes polymerized by equilibrium swelling methods, with deuterated polymer forming the first or second step. The experiments covered a molecular weight range of 6 x 10{sup 4} 10{sup 6} the molecular weights are consistent with the experimental errors, indicating that the deuterium labeled molecules are randomly distributed in the latex. These results led to the finding that the polymer chains were constrained in the latex particles by factors of 2 to 4 from the relaxed coil dimensions. For M < 10{sup 6} g/mol SANS gave zero angle scattering intensities much higher than expected on the basis of a random distribution of labeled molecules. Several models were examined, including the possible development of core-shell structures at lower molecular weights.

  17. LARG at chromosome 11q23 has functional characteristics of a tumor suppressor in human breast cancer

    SciTech Connect (OSTI)

    Ong, Danny C.T.; Rudduck, Christina; Chin, Koei; Kuo, Wen-Lin; Lie, Daniel K.H.; Chua, Constance L.M.; Wong, Chow Yin; Hong, Ga Sze; Gray, Joe; Lee, Ann S.G.

    2008-05-06

    Deletion of 11q23-q24 is frequent in a diverse variety of malignancies, including breast and colorectal carcinoma, implicating the presence of a tumor suppressor gene at that chromosomal region. We show here that LARG, from 11q23, has functional characteristics of a tumor suppressor. We examined a 6-Mb region on 11q23 by high-resolution deletion mapping, utilizing both loss of heterozygosity (LOH) analysis and microarray comparative genomic hybridization (CGH). LARG (also called ARHGEF12), identified from the analyzed region, was underexpressed in 34% of primary breast carcinomas and 80% of breast cancer cell lines including the MCF-7 line. Multiplex ligation-dependent probe amplification on 30 primary breast cancers and six breast cancer cell lines showed that LARG had the highest frequency of deletion compared to the BCSC-1 and TSLC1 genes, two known candidate tumor suppressor genes from 11q. In vitro analysis of breast cancer cell lines that underexpress LARG showed that LARG could be reactivated by trichostatin A, a histone deacetylase inhibitor, but not by 5-Aza-2{prime}-deoxycytidine, a demethylating agent. Bisulfite sequencing and quantitative high-throughput analysis of DNA methylation confirmed the lack of CpG island methylation in LARG in breast cancer. Restoration of LARG expression in MCF-7 cells by stable transfection resulted in reduced proliferation and colony formation, suggesting that LARG has functional characteristics of a tumor suppressor gene.

  18. Reconciling macro- with nano- carrier mobility measurements in organic photovoltaic blends

    SciTech Connect (OSTI)

    Omar, Yamila M.; Maragliano, Carlo; Chiesa, Matteo; Al Ghaferi, Amal; Stefancich, Marco

    2014-04-28

    Conductive atomic force microscopy (CAFM) is a valuable tool for electrical characterization of organic photovoltaics. However, the quantitative interpretation of the data is complicated by an apparent disagreement between the carrier mobilities calculated by CAFM and those determined by macroscopic measurements, with no apparent physical explanation for the discrepancy. In the present work, the space charge limited current model (specifically Mott-Gurney law) and its assumptions are assessed, and a physical model reconciling this discrepancy is proposed. Its applicability on the tip-sample system used in CAFM measurements is discussed, by accounting for the high electric fields arising around the tip of the CAFM probe and affecting carrier mobility. Charge carrier mobility is calculated from current-voltage curves obtained from conductive atomic force microscopy spectroscopy scans done on Poly(3-hexylthiophene-2,5-diyl): 95% PC{sub 70}BM ([6,6]-Phenyl-C71-butyric acid methyl ester)/5% PC{sub 60}BM ([6,6]-Phenyl-C61-butyric acid methyl ester) samples for different concentration ratios of donor and acceptor. We show that charge carrier mobilities obtained with this model are in satisfactory agreement with macroscopic measurements available in literature.

  19. Bioremediation of contaminated groundwater: A turnkey approach

    SciTech Connect (OSTI)

    Shivjiani, D.M.; Rudy, R.J.; Burns, B.; Heuler, G.

    1994-12-31

    The Silvex Corporation Site is a Florida state funded remedial action site in St. Augustine, Florida, that, prior to 1980, was a silver smelting facility that accepted waste materials from the Naval Air Station-Jacksonville. Fuels, reportedly consisting of waste paint, cold carbon removers, and solvent degreasers that were stored in a 25,000-gallon tank, spilled onto the property. The assessment concluded that the surficial aquifer in the spill area and the area hydrologically down-gradient of the spill were contaminated by elevated levels of ketones (acetone, methyl-ethyl ketone, and methyl-isobutyl ketone), phenols, and toluene. Subsequently, a risk assessment/feasibility study and groundwater bench-scale and pilot-scale studies were performed to determine the technical feasibility/cost-effectiveness of the recommended alternative, submerged fixed-film bioremediation. The on-site pilot study, which was conducted at three flow rates (0.5, 1, and 2 gallons per minute [gpm]), demonstrated a greater than 99% contaminant removal efficiency from the three-stage bioreactor. Due to the impact of site contamination on a nearby creek that flows into the St. Johns River, an interim remedial deign was developed and implemented to reduce the potential for migration of contaminated groundwater into the creek.

  20. Anaerobic cometabolic transformation of polycyclic and heterocyclic aromatic hydrocarbons: evidence from laboratory and field studies

    SciTech Connect (OSTI)

    Michael Safinowski; Christian Griebler; Rainer U. Meckenstock

    2006-07-01

    The sulfate-reducing enrichment culture N47 can grow on naphthalene or 2-methylnaphthalene as the sole carbon and energy source. The study reported shows that the culture can furthermore cometabolically transform a variety of polycyclic and heteroaromatic compounds with naphthalene or methylnaphthalene as the auxiliary substrate. Most of the cosubstrates were converted to the corresponding carboxylic acids, frequently to several isomers. The mass spectra of specific metabolites that were extracted from supernatants of cultures containing the cosubstrates benzothiophene, benzofuran, and 1-methylnaphthalene resembled known intermediates of the anaerobic naphthalene and 2-methylnaphthalene degradation pathways. This indicates that some of the tested compounds were first methylated and then transformed to the corresponding methylsuccinic acids by a fumarate addition to the methyl group. For some of the cosubstrates, a partial or total inhibition of growth on the auxiliary substrate was observed. This was caused by a specific combination of auxiliary substrate and cosubstrate. None of the cosubstrates tested could be utilized as the sole carbon source and electron donor by the enrichment culture N47. Field investigations at the tar-oil-contaminated aquifer (at a former gasworks in southwest Germany), where strain N47 originated, revealed the presence of metabolites similar to the ones identified in batch culture supernatants. The findings suggest that aromatic hydrocarbons and heterocyclic compounds can be converted by aquifer organisms and produce a variety of polar compounds that become mobile in groundwater. 51 refs., 4 figs., 2 tabs.

  1. Process for the preparation of benozotriazoles and their polymers, and 2(2-hydroxy-5-isopropenylphenyl)2H-benzotriazole produced thereby

    DOE Patents [OSTI]

    Vogl, Otto (Brooklyn, NY); Nir, Zohar (Beer Sheva, IL)

    1989-03-14

    The compound 2(2-hydroxy-5-isopropenylphenyl)2H-benzotriazole (2H5P) is produced by azo coupling of o-nitrophenyl diazonium chloride with p-hydroxyacetophenone, subjecting the resulting isolated azo compound to reductive cyclization with zinc in the presence of sodium hydroxide at a temperature of about 50.degree.-70.degree. C., acidifying the resulting mixture so as to produce (2(2-hydroxy-5-acetylphenyl)2H-benzotriazole (2H5A), acetylating the isolated 2(2-hydroxy-5-acetylphenyl)2H-benzotriazole (2H5A), so as to produce 2(2-acetoxy-5-acetylphenyl)2H-benzotriazole (2A5A), methylating the isolated 2(2-acetoxy-5-acetylphenyl(2H-benzotriazole (2A5A) with a methyl Grignard reagent and dehydrating the isolated reaction product with potassium hydrogen sulfate so as to produce 2(2-hydroxy-5-isopropenylphenyl)2H-benzotriazole (2H5P). The compound is used as a polymerizable ultra violet light stabilizer.

  2. 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.

  3. 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.

  4. 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.

  5. 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.

  6. X-ray survival characteristics and genetic analysis for nine saccharomyces deletion mutants that show altered radiation sensitivity

    SciTech Connect (OSTI)

    Game, John C.; Williamson, Marsha S.; Baccari, Clelia

    2004-01-07

    The availability of a genome-wide set of Saccharomyces deletion mutants provides a chance to identify all the yeast genes involved in DNA repair. Using X-rays, we are screening these mutants to identify additional genes that show increased sensitivity to the lethal effects of ionizing radiation. For each mutant identified as sensitive, we are confirming that the sensitivity phenotype co-segregates with the deletion allele and are obtaining multipoint survival-versus-dose assays in at least two haploid and one homozygous diploid strains. We present data for deletion mutants involving the genes DOT1, MDM20, NAT3, SPT7, SPT20, GCN5, HFI1, DCC1 and VID21/EAF1, and discuss their potential roles in repair. Eight of these genes have a clear radiation-sensitive phenotype when deleted, but the ninth, GCN5, has at most a borderline phenotype. None of the deletions confer substantial sensitivity to ultra-violet radiation, although one or two may confer marginal sensitivity. The DOT1 gene is of interest because its only known function is to methylate one lysine residue in the core of the histone H3 protein. We find that histone H3 mutants (supplied by K. Struhl) in which this residue is replaced by other amino-acids are also X-ray sensitive, seeming to confirm that methylation of the lysine-79 residue is required for effective repair of radiation damage.

  7. Chemical characterization of biogenic SOA generated from plant emissions under baseline and stressed conditions: inter- and intra-species variability for six coniferous species

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

    Faiola, C. L.; Wen, M.; VanReken, T. M.

    2014-10-01

    The largest global source of secondary organic aerosol in the atmosphere is derived from the oxidation of biogenic emissions. Plant stressors associated with a changing environment can alter both the quantity and composition of the compounds that are emitted. Alterations to the biogenic VOC profile could impact the characteristics of the SOA formed from those emissions. This study investigated the impacts of one global change stressor, increased herbivory, on the composition of SOA derived from real plant emissions. Herbivory was simulated via application of methyl jasmonate, a proxy compound. Experiments were repeated under pre- and post-treatment conditions for six differentmore » coniferous plant types. VOCs emitted from the plants were oxidized to form SOA via dark ozone-initiated chemistry. The SOA particle size distribution and chemical composition were measured using a scanning mobility particle sizer (SMPS) and Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-AMS), respectively. The aerosol mass spectra of pre-treatment biogenic SOA from all plant types tended to be similar with correlations usually greater than or equal to 0.90. The presence of a stressor produced characteristic differences in the SOA mass spectra. Specifically, the following m/z were identified as a possible biogenic stress AMS marker with the corresponding HR ion(s) shown in parentheses: m/z 31 (CH3O+), m/z 58 (C2H2O2+, C3H6O+) m/z 29 (C2H5+), m/z 57 (C3H5O+), m/z 59 (C2H3O2+, C3H7O+), m/z 71 (C3H3O2+, C4H7O+), and m/z 83 (C5H7O+). The first aerosol mass spectrum of SOA generated from the oxidation of the plant stress hormone, methyl jasmonate, is also presented. Elemental analysis results demonstrated an O:C range of baseline biogenic SOA between 0.3–0.47. The O:C of standard methyl jasmonate SOA was 0.52. Results presented here could be used to help identify a biogenic plant stress marker in ambient datasets collected in forest environments.« less

  8. TiO2 nanotube arrays for photocatalysis: Effects of crystallinity, local order, and electronic structure

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

    Liu, Jing; Hosseinpour, Pegah M.; Luo, Si; Heiman, Don; Menon, Latika; Arena, Dario A.; Lewis, Laura H.

    2014-11-19

    To furnish insight into correlations of electronic and local structure and photoactivity, arrays of short and long TiO₂ nanotubes were synthesized by electrochemical anodization of Ti foil, followed by thermal treatment in O₂ (oxidizing), Ar (inert), and H₂ (reducing) environments. The physical and electronic structures of these nanotubes were probed with x-ray diffraction, scanning electron microscopy, and synchrotron-based x-ray absorption spectroscopy, and correlated with their photocatalytic properties. The photocatalytic activity of the nanotubes was evaluated by monitoring the degradation of methyl orange under UV-VIS light irradiation. Results show that upon annealing at 350 °C all as-anodized amorphous TiO₂ nanotube samplesmore » partially transform to the anatase structure, with variations in the degree of crystallinity and in the concentration of local defects near the nanotubes' surface (~5 nm) depending on the annealing conditions. Degradation of methyl orange was not detectable for the as-anodized TiO₂ nanotubes regardless of their length. The annealed long nanotubes demonstrated detectable catalytic activity, which was more significant with the H₂-annealed nanotubes than with the Ar- and O₂-annealed nanotube samples. This enhanced photocatalytic response of the H₂-annealed long nanotubes relative to the other samples is positively correlated with the presence of a larger concentration of lattice defects (such as Ti3+ and anticipated oxygen vacancies) and a slightly lower degree of crystallinity near the nanotube surface. These physical and electronic structural attributes impact the efficacy of visible light absorption; moreover, the increased concentration of surface defects is postulated to promote the generation of hydroxyl radicals and thus accelerate the photodegradation of the methyl orange. The information obtained from this study provides unique insight into the role of the near-surface electronic and defect structure, crystal structure, and the local chemical environment on the photocatalytic activity and may be employed for tailoring the materials' properties for photocatalysis and other energy-related applications.« less

  9. Organo-Lewis acids of enhanced utility, uses thereof, and products based thereon

    DOE Patents [OSTI]

    Marks, Tobin J. (Evanston, IL); Chen, You-Xian (Midland, MI)

    2002-01-01

    The organo-Lewis acids are novel triarylboranes which are are highly fluorinated. Triarylboranes of one such type contain at least one ring substituent other than fluorine. These organoboranes have a Lewis acid strength essentially equal to or greater than that of the corresponding organoborane in which the substituent is replaced by fluorine, or have greater solubility in organic solvents. Another type of new organoboranes have 1-3 perfluorinated fused ring groups and 2-0 perfluorophenyl groups. When used as a cocatalyst in the formation of novel catalytic complexes with d- or f-block metal compounds having at least one leaving group such as a methyl group, these triorganoboranes, because of their ligand abstracting properties, produce corresponding anions which are capable of only weakly, if at all, coordinating to the metal center, and thus do not interfere in various polymerization processes such as are described.

  10. Simple, rapid method for the preparation of isotopically labeled formaldehyde

    DOE Patents [OSTI]

    Hooker, Jacob Matthew; Schonberger, Matthias; Schieferstein, Hanno; Fowler, Joanna S.

    2011-10-04

    Isotopically labeled formaldehyde (*C.sup..sctn.H.sub.2O) is prepared from labeled methyl iodide (*C.sup..sctn.H.sub.3I) by reaction with an oxygen nucleophile having a pendant leaving group. The mild and efficient reaction conditions result in good yields of *C.sup..sctn.H.sub.2O with little or no *C isotopic dilution. The simple, efficient production of .sup.11CH.sub.2O is described. The use of the .sup.11CH.sub.2O for the formation of positron emission tomography tracer compounds is described. The reaction can be incorporated into automated equipment available to radiochemistry laboratories. The isotopically labeled formaldehyde can be used in a variety of reactions to provide radiotracer compounds for imaging studies as well as for scintillation counting and autoradiography.

  11. Precursor polymer compositions comprising polybenzimidazole

    DOE Patents [OSTI]

    Klaehn, John R.; Peterson, Eric S.; Orme, Christopher J.

    2015-07-14

    Stable, high performance polymer compositions including polybenzimidazole (PBI) and a melamine-formaldehyde polymer, such as methylated, poly(melamine-co-formaldehyde), for forming structures such as films, fibers and bulky structures. The polymer compositions may be formed by combining polybenzimidazole with the melamine-formaldehyde polymer to form a precursor. The polybenzimidazole may be reacted and/or intertwined with the melamine-formaldehyde polymer to form the polymer composition. For example, a stable, free-standing film having a thickness of, for example, between about 5 .mu.m and about 30 .mu.m may be formed from the polymer composition. Such films may be used as gas separation membranes and may be submerged into water for extended periods without crazing and cracking. The polymer composition may also be used as a coating on substrates, such as metal and ceramics, or may be used for spinning fibers. Precursors for forming such polymer compositions are also disclosed.

  12. Polymer compositions, polymer films and methods and precursors for forming same

    DOE Patents [OSTI]

    Klaehn, John R; Peterson, Eric S; Orme, Christopher J

    2013-09-24

    Stable, high performance polymer compositions including polybenzimidazole (PBI) and a melamine-formaldehyde polymer, such as methylated, poly(melamine-co-formaldehyde), for forming structures such as films, fibers and bulky structures. The polymer compositions may be formed by combining polybenzimidazole with the melamine-formaldehyde polymer to form a precursor. The polybenzimidazole may be reacted and/or intertwined with the melamine-formaldehyde polymer to form the polymer composition. For example, a stable, free-standing film having a thickness of, for example, between about 5 .mu.m and about 30 .mu.m may be formed from the polymer composition. Such films may be used as gas separation membranes and may be submerged into water for extended periods without crazing and cracking. The polymer composition may also be used as a coating on substrates, such as metal and ceramics, or may be used for spinning fibers. Precursors for forming such polymer compositions are also disclosed.

  13. Influence of hydroxyl contents on photocatalytic activities of polymorphic titania nanoparticles

    SciTech Connect (OSTI)

    kaewguna, Sujaree; Nolpha, Christopher A.; Lee, Burtrand I.; Wang, Li Q.

    2009-03-15

    Polymorphic titania nanoparticles, prepared by a Water-based Ambient Condition Sol (WACS) process, were post-treated by a Solvent-based Ambient Condition Sol (SACS) process in sec-butanol. All samples were characterized for phase composition, surface area, lattice hydroxyl contamination, and particle morphology by X-ray diffraction, N2 physisorption, FT-IR, solid state Magic Angle Spinning (MAS) 1H NMR and scanning electron microscopy. The resultswerecompared to acommercial titania, Degussa P25. Evaluation of methyl orange degradation under UV irradiation results showed that the lower lattice hydroxyl content in SACS titania nanoparticles enhances photocatalytic activity. As-prepared titania and post-treated SACS samples, which have similar surface areas and crystallinity, were compared in order to prove that the superior photocatalytic activity came from a reduction in lattice hydroxyl content.

  14. Reactive triblock polymers from tandem ring-opening polymerization for nanostructured vinyl thermosets

    SciTech Connect (OSTI)

    Amendt, Mark A.; Pitet, Louis M.; Moench, Sarah; Hillmyer, Marc A.

    2013-03-07

    Multiply functional hydroxyl telechelic poly(cyclooctene-s-5-norbornene-2-methylene methacrylate) was synthesized by ring opening metathesis (co)polymerization of cis-cyclooctene and 5-norbornene-2-methylene methacrylate using the second generation Grubbs catalyst in combination with a symmetric chain transfer agent bearing hydroxyl functionality. The resulting hydroxyl-telechelic polymer was used as a macroinitiator for the ring opening transesterification polymerization of d,l-lactide to form reactive poly(lactide)-b-poly(cyclooctene-s-5-norbornene-2-methylene methacrylate)-b-poly(lactide) triblock polymers. Subsequently, the triblocks were crosslinked by free radical copolymerization with several vinyl monomers including styrene, divinylbenzene, methyl methacrylate, and ethyleneglycol dimethacrylate. Certain conditions led to optically transparent thermosets with mesoscale phase separation as evidenced by small angle X-ray scattering, differential scanning calorimetry and transmission electron microscopy. Disordered, bicontinuous structures with nanoscopic domains were generated in several cases, rendering the samples attractive for size-selective membrane applications.

  15. Molecular Hydrogen Formation from Proximal Glycol Pairs on TiO2(110)

    SciTech Connect (OSTI)

    Chen, Long; Li, Zhenjun; Smith, R. Scott; Kay, Bruce D.; Dohnalek, Zdenek

    2014-04-16

    Understanding hydrogen formation on TiO2 surfaces is of great importance as it could provide fundamental insight into water splitting for hydrogen production using solar energy. In this work, hydrogen formation from glycols having different numbers of methyl end-groups have been studied using temperature pro-grammed desorption on reduced, hydroxylated, and oxidized TiO2(110) surfaces. The results from OD-labeled glycols demon-strate that gas-phase molecular hydrogen originates exclusively from glycol hydroxyl groups. The yield is controlled by a combi-nation of glycol coverage, steric hindrance, TiO2(110) order and the amount of subsurface charge. Combined, these results show that proximal pairs of hydroxyl aligned glycol molecules and subsurface charge are required to maximize the yield of this redox reaction. These findings highlight the importance of geometric and electronic effects in hydrogen formation from adsorbates on TiO2(110).

  16. Frequency and patterns of abnormality detected by iodine-123 amine emission CT after cerebral infarction

    SciTech Connect (OSTI)

    Brott, T.G.; Gelfand, M.J.; Williams, C.C.; Spilker, J.A.; Hertzberg, V.S.

    1986-03-01

    Single photon emission computed tomography (SPECT) was performed in 31 patients with cerebral infarction and 13 who had had transient ischemic attacks, using iodine-123-labeled N,N,N'-trimethyl-N'-(2-hydroxyl-3-methyl-5-iodobenzyl)-1,3-propanediamin e (I-123-HIPDM) as the radiopharmaceutical. SPECT scans were compared with computed tomographic (CT) scans. SPECT was as sensitive as CT in detecting cerebral infarction (94% vs. 84%). The abnormalities were larger on the SPECT scans than on the CT scans in 19 cases, equal in seven, and smaller in five (SPECT abnormalities greater than or equal to CT abnormalities in 86% of cases). Fifteen of 30 patients with hemispheric infarction had decreased perfusion (decreased uptake of I-123-HIPDM) to the cerebellar hemisphere contralateral to the cerebral hemisphere involved by the infarction (crossed cerebellar diaschisis). Nine of these 15 patients had major motor deficits, while only one of the 15 without crossed cerebellar diaschisis had a major motor deficit.

  17. Patterned functional arrays by selective de-wetting

    SciTech Connect (OSTI)

    FAN,HONGYOU; DOSHI,DHAVAL; LU,YUNFENG; BRINKER,C. JEFFREY

    2000-05-11

    Using a micro-Contact Printing ({mu}-CP) technique, substrates are prepared with patterns of hydrophilic, hydroxyl-terminated SAMS and hydrophobic methyl-terminated SAMS. Beginning with a homogeneous solution of silica, surfactant, ethanol, water, and functional silane, preferential ethanol evaporation during dip-coating, causes water enrichment and selective de-wetting of the hydrophobic SAMS. Correspondingly, film deposition occurs exclusively on the patterned hydrophilic SAMS. In addition, by co-condensation of tetrafunctional silanes (Si(OR){sub 4}) with tri-functional organosilanes ((RO){sub 3}Si(CH{sub 2}){sub 3}NH{sub 2}), the authors have selectively derived the silica framework with functional amine NH{sub 2} groups. A pH sensitive, micro-fluidic system was formed by further conjugation reactions with pH sensitive dye molecules.

  18. Functional Diversification of Maize RNA Polymerase IV and V subtypes via Alternative Catalytic Subunits

    SciTech Connect (OSTI)

    Haag, Jeremy R.; Brower-Toland, Brent; Krieger, Elysia K.; Sidorenko, Lyudmila; Nicora, Carrie D.; Norbeck, Angela D.; Irsigler, Andre; LaRue, Huachun; Brzeski, Jan; Mcginnis, Karen A.; Ivashuta, Sergey; Pasa-Tolic, Ljiljana; Chandler, Vicki L.; Pikaard, Craig S.

    2014-10-01

    Unlike nuclear multisubunit RNA polymerases I, II, and III, whose subunit compositions are conserved throughout eukaryotes, plant RNA polymerases IV and V are nonessential, Pol II-related enzymes whose subunit compositions are still evolving. Whereas Arabidopsis Pols IV and V differ from Pol II in four or five of their 12 subunits, respectively, and differ from one another in three subunits, proteomic ana- lyses show that maize Pols IV and V differ from Pol II in six subunits but differ from each other only in their largest subunits. Use of alternative catalytic second subunits, which are nonredundant for development and paramutation, yields at least two sub- types of Pol IV and three subtypes of Pol V in maize. Pol IV/Pol V associations with MOP1, RMR1, AGO121, Zm_DRD1/CHR127, SHH2a, and SHH2b extend parallels between paramutation in maize and the RNA-directed DNA methylation pathway in Arabidopsis.

  19. Delayed cure bismaleimide resins

    DOE Patents [OSTI]

    Adams, Johnnie E. (Grandview, MO); Jamieson, Donald R. (Merriam, KS)

    1984-08-07

    Polybismaleimides prepared by delayed curing of bis-imides having the formula ##STR1## wherein R.sub.1 and R.sub.2 each independently is H, C.sub.1-4 -alkyl, C.sub.1-4 -alkoxy, Cl or Br, or R.sub.1 and R.sub.2 together form a fused 6-membered hydrocarbon aromatic ring, with the proviso that R.sub.1 and R.sub.2 are not t-butyl or t-butoxy; X is O, S or Se; n is 1-3; and the --(CH.sub.2).sub.n -- group, optionally, is substituted by 1-3 methyl groups or by fluorine.

  20. Bismaleimide compounds

    DOE Patents [OSTI]

    Adams, Johnnie E. (Grandview, MO); Jamieson, Donald R. (Merriam, KS)

    1986-01-14

    Bismaleimides of the formula ##STR1## wherein R.sub.1 and R.sub.2 each independently is H, C.sub.1-4 -alkyl, C.sub.1-4 -alkoxy, C1 or Br, or R.sub.1 and R.sub.2 together form a fused 6-membered hydrocarbon aromatic ring, with the proviso that R.sub.1 and R.sub.2 are not t-butyl or t-butoxy; X is O, S or Se; n is 1-3; and the alkylene bridging group, optionally, is substituted by 1-3 methyl groups or by fluorine, form polybismaleimide resins which have valuable physical properties. Uniquely, these compounds permit extended cure times, i.e., they remain fluid for a time sufficient to permit the formation of a homogeneous melt prior to curing.