National Library of Energy BETA

Sample records for methyl tert butyl

  1. Accurate Computer Simulation of Phase Equilibrium for Complex Fluid Mixtures. Application to Binaries Involving Isobutene, Methanol, Methyl tert-Butyl Ether, and

    E-Print Network [OSTI]

    Lisal, Martin

    to Binaries Involving Isobutene, Methanol, Methyl tert-Butyl Ether, and n-Butane Martin Li´sal,*,, William R + methyl tert-butyl ether (MTBE) and the binaries formed by methanol with isobutene, MTBE, and n

  2. IDENTIFYING THE USAGE PATTERNS OF METHYL TERT-BUTYL ETHER (MTBE) AND OTHER OXYGENATES IN GASOLINE USING GASOLINE

    E-Print Network [OSTI]

    IDENTIFYING THE USAGE PATTERNS OF METHYL TERT-BUTYL ETHER (MTBE) AND OTHER OXYGENATES IN GASOLINE USING GASOLINE SURVEYS By Michael J. Moran, Rick M. Clawges, and John S. Zogorski U.S. Geological Survey 1608 Mt. View Rapid City, SD 57702 Methyl tert-butyl ether (MTBE) is commonly added to gasoline

  3. Methyl tert-butyl ether (MTBE) is a volatile organic com-pound (VOC) derived from natural gas that is added to gas-

    E-Print Network [OSTI]

    Methyl tert-butyl ether (MTBE) is a volatile organic com- pound (VOC) derived from natural gas Water in Urban and Agricultural Areas made from methanol, which is derived primarily from natural gas that is added to gas- oline either seasonally or year round in many parts of the United States to increase

  4. Whole-Genome Analysis of Methyl tert-Butyl Ether-Degrading Beta-Proteobacterium Methylibium petroleiphilum PM1

    E-Print Network [OSTI]

    2007-01-01

    Sato, and N. Kato. 2003. Propane monooxygenase and NAD + -alcohol dehydrogenase in propane metabolism by Gordonia sp.tert-butyl ether by propane-grown Mycobacterium vaccae JOB5.

  5. Control Study of Ethyl tert-Butyl Ether Reactive Distillation Muhammad A. Al-Arfaj

    E-Print Network [OSTI]

    Al-Arfaj, Muhammad A.

    -butyl ether (ETBE) for gasoline blending as a replacement for methyl tert-butyl ether (MTBE) because and be blended with ETBE in the gasoline pool. Even for neat operation, if the conversion is low, the unconverted

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

    SciTech Connect (OSTI)

    Bonventre, Josephine A., E-mail: josephine.bonventre@oregonstate.edu [Rutgers, The State University of New Jersey, Joint Graduate Program in Toxicology, 170 Frelinghuysen Road, Piscataway, NJ 08854 (United States); Rutgers, The State University of New Jersey, Department of Biochemistry and Microbiology, 76 Lipman Dr., New Brunswick, NJ 08901 (United States); Oregon State University, Department of Environmental and Molecular Toxicology, 1011 Agricultural and Life Sciences Bldg, Corvallis, OR 97331 (United States); Kung, Tiffany S., E-mail: tiffany.kung@rutgers.edu [Rutgers, The State University of New Jersey, Joint Graduate Program in Toxicology, 170 Frelinghuysen Road, Piscataway, NJ 08854 (United States); Rutgers, The State University of New Jersey, Department of Biochemistry and Microbiology, 76 Lipman Dr., New Brunswick, NJ 08901 (United States); White, Lori A., E-mail: lawhite@aesop.rutgers.edu [Rutgers, The State University of New Jersey, Joint Graduate Program in Toxicology, 170 Frelinghuysen Road, Piscataway, NJ 08854 (United States); Rutgers, The State University of New Jersey, Department of Biochemistry and Microbiology, 76 Lipman Dr., New Brunswick, NJ 08901 (United States); Cooper, Keith R., E-mail: cooper@aesop.rutgers.edu [Rutgers, The State University of New Jersey, Joint Graduate Program in Toxicology, 170 Frelinghuysen Road, Piscataway, NJ 08854 (United States); Rutgers, The State University of New Jersey, Department of Biochemistry and Microbiology, 76 Lipman Dr., New Brunswick, NJ 08901 (United States)

    2013-12-15

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

  7. he increasing frequency of detection of the widely used gasoline additive methyl tert-

    E-Print Network [OSTI]

    T he increasing frequency of detection of the widely used gasoline additive methyl tert- butyl, the September 15, 1999, Report of the Blue Ribbon Panel on Oxygenates in Gasoline (1) states that between 5 with large releases (e.g., LUFTs). Unprecedented growth in use Use of MTBE as a gasoline additive began

  8. Palladium/Tris(tert-butyl)phosphine-Catalyzed Suzuki Cross-Couplings in the Presence of Water

    E-Print Network [OSTI]

    Lou, Sha

    Dipalladiumtris(dibenzylideneacetone)/tris(tert-butyl)phosphonium tetrafluoroborate/potassium fluoride dihydrate [Pd2(dba)3/[HP(t-Bu)3]BF4/KF?2?H2O] serves as a mild, robust, and user-friendly method for the efficient ...

  9. 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}.

  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. 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.

  12. Determination of optical conductivity and different optical energy losses for non-crystalline Vanadyl tetra tert-butyl 2,3 Naphthalocyanine thinfilms

    SciTech Connect (OSTI)

    Dhanya, I.; Menon, C. S. [School of Pure and Applied Physics, Mahatma Gandhi University, Priyadarshini Hills, Kottayam, Kerala, 686 560 (India)

    2011-10-20

    Amorphous Vanadyl Tetra Tert Butyl 2, 3 naphthalocyanine thin films (VTTBNc) have been deposited using Physical Vapor Deposition technique. By analyzing the X-ray diffraction, the structure of as deposited films is found to be non-crystalline. Different optical properties of these thin films have been investigated by means of optical absorption and reflection spectra. Various optical constants like band gap energy, E{sub g} the width of band tails of localized states into the gap, E{sub U} and steepness parameter, {beta} gets calculated and the variation of different optical parameters like refractive index, extinction coefficient, dielectric constants, optical conductivity and surface and volume energy losses with photon energy are estimated.

  13. Treatment of Methyl tert-Butyl Ether Contaminated Water Using a Dense

    E-Print Network [OSTI]

    Dandy, David

    -massspectrometryandgaschromatography-thermal conductivity techniques. A rate law is developed for the removal of MTBE from an aqueous solution in the DMP of water in which alkyl groups have replaced both hydrogen atoms. In fact, the C-O-C bond angle is only, causing nationwide concern. Advanced oxidation technologies (AOTs) are techniques that involve an input

  14. Treatment of Methyl tert-Butyl Ether Vapors in Biotrickling Filters. 1.

    E-Print Network [OSTI]

    byproducts in either the gas or the liquid phase. They also exhibited a very high specific degradation and leaking pipe- lines. In the past few years, several studies have been conducted to determine if natural, ethyl benzene, and xylene (BTEX) plumes, with in most cases no clear signs of natural attenuation (2

  15. Impacts of Ethanol on Anaerobic Production of Tert-Butyl Alcohol (TBA) from Methyl Tert-Butyl Ether (MTBE) in Groundwater

    E-Print Network [OSTI]

    Scow, K M; MacKay, Douglas

    2008-01-01

    Project title: Impacts of Ethanol on Anaerobic Production oftert-butanol (TBA). As ethanol is being promoted as ainvestigate the effect of ethanol release on existing MTBE

  16. Supporting Information A scalable synthesis of the (S)-4-(tert-butyl)-2-(pyridin-2-yl)-4,5-dihydrooxazole

    E-Print Network [OSTI]

    Stoltz, Brian M.

    for flash chromatography. Analytical chiral SFC was performed utilizing an OB-H column (4.6 mm × 25 cm with a three-pitched curved blade, an internal thermometer, and a reflux condenser equipped with a two a steam of N2. The flask was charged with (S)-tert-leucine (15.08 g, 115.0 mmol, 1.00 equv, 99% ee

  17. Solvent extraction of technetium from alkaline waste media using bis-4,4{prime}(5{prime})[(tert-butyl)cyclohexano]-18-crown-6

    SciTech Connect (OSTI)

    Bonnesen, P.V.; Presley, D.J.; Moyer, B.A.

    1995-07-01

    The crown ether bis-4,4`(5`)[(tert-butyl)cyclohexano]-18-crown-6 can be utilized in a solvent-extraction process for the removal of technetium as pertechnetate ion, TcO{sub 4}{sup {minus}} from solutions simulating highly radioactive alkaline defense wastes (``tank wastes``) stored at several sites in the United States. The process employs non-halogenated and non-volatile diluents and modifiers and includes an efficient stripping procedure using only water. More than 95% of the pertechnetate present at 6 {times} 10{sup {minus}5} M in Melton Valley (Oak Ridge, TN) and Hanford (Washington) tank-waste simulants was removed following two cross-current extraction contacts using 0.02 M bis-4,4`(5`)[(tertbutyl)cyclohexano]- 18-crown-6 in 2:1 vol/vol TBP/Isopar{reg_sign} M diluent at 25 C. Similarly, for both simulants, more than 98% of the pertechnetate contained in the solvent was back-extracted following two cross-current stripping contacts using deionized water.

  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. Whole-Genome Analysis of Methyl tert-Butyl Ether-Degrading Beta-Proteobacterium Methylibium petroleiphilum PM1

    E-Print Network [OSTI]

    2007-01-01

    degradation pathways. PM1 contains an operon (mpeA0814-0821) likely encoding for conversion of benzene to phenol (

  20. Viscoelastic Properties and Phase Behavior of 12-tert-Butyl Ester Dendrimer/Poly(methyl methacrylate) Blends

    E-Print Network [OSTI]

    Harmon, Julie P.

    with bis- phenol A polycarbonate (PC), resulting in an in- crease in free volume with increasing dendrimer hyperbranched polyester/bisphenol A PC blends with respect to pure PC. Studies were conducted by Carr et al.24

  1. RELATIONS BETWEEN THE DETECTION OF METHYL TERT-BUTYL ETHER (MTBE) IN SURFACE AND GROUND WATER AND ITS CONTENT IN GASOLINE

    E-Print Network [OSTI]

    AND ITS CONTENT IN GASOLINE By Michael J. Moran, Mike J. Halde, Rick M. Clawges and John S. Zogorski U in the United States as an octane enhancer and oxygenate in gasoline. Octane enhancement began in the late 1970's with the phase-out of tetraethyl lead from gasoline. The use of oxygenates was expanded

  2. Organometallics 1994, 13, 4367-4376 4367 tert-Butyl-SubstitutedPoly(ferroceny1enepersulfides)

    E-Print Network [OSTI]

    Rauchfuss, Thomas B.

    . The trisulfides were converted to the polymers [(RC5H3)2FeS2Inupon desulfurization with Bu~P,which was shown by 31PNMR spectroscopy to be converted to Bu3PS. The rate of this desulfurization increases ferrocenylene persulfide polymers undergo reversible electrochemical oxidation in two steps, separated by 290 m

  3. Hydrocracking phenanthrene and 1-methyl naphthalene: Development of linear free energy relationships

    SciTech Connect (OSTI)

    Landau, R.N.; Korre, S.C.; Neurock, M.; Klein, M.T. [Univ. of Delaware, Newark, DE (United States); Quann, R.J. [Mobil Research and Development Corp., Paulsboro, NJ (United States)

    1994-12-31

    The catalytic hydrocracking reaction pathways, kinetics and mechanisms of 1-methyl naphthalene and phenanthrene were investigated in experiments at 350 C and 68.1 atm H{sub 2} partial pressure (190.6 atm total pressure), using a presulfided Ni/W on USY zeolite catalyst. 1-methyl naphthalene hydrocracking led to 2-methyl naphthalene, methyl tetralins, methyl decalins, pentyl benzene and tetralin. Phenanthrene hydrocracking led to dihydro, tetrahydro and octahydro phenanthrene, butyl naphthalene, tetralin to butyl tetralin and dibutyl benzene. The rate constants for the dealkylation of butyl tetralins produced in the phenanthrene hydrocracking network conform to a linear free energy relationship (LFER), with the heat of formation of the leaving alkyl carbenium ion as the reactivity index.

  4. Observational constraints on the global atmospheric budget of ethanol

    E-Print Network [OSTI]

    2010-01-01

    global atmospheric budget of ethanol V. Naik 1,2,* , A. M.nitrate formation from ethanol-fueled ve- hicular emissions,A. : Ambient concentrations of ethanol and methyl tert-butyl

  5. Phase Selectively Soluble Polystyrene-Supported Organocatalysts 

    E-Print Network [OSTI]

    Khamatnurova, Tatyana

    2014-08-10

    Alkane phase selectively soluble poly(4-alkylstyrene) supports have been developed. 4-Methyl-, 4-tert-butyl, 4-dodecyl-, and 4-octadecylstyrene were copolymerized with 5-10 mol % of 4-chloromethylstyrene to afford co- and ...

  6. 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.

  7. Synthesis and Application of Palladium Precatalysts that Accommodate Extremely Bulky Di-tert-butylphosphino Biaryl Ligands

    E-Print Network [OSTI]

    Bruno, Nicholas C.

    A series of palladacyclic precatalysts that incorporate electron-rich di-tert-butylphosphino biaryl ligands is reported. These precatalysts are easily prepared, and their use provides a general means of employing bulky ...

  8. Effects of bile salts and other carboxylates on the reactions of N-tert-butyl-2,4,6-trinitrobenzamide in dimethyl sulfoxide-water solutions 

    E-Print Network [OSTI]

    Koranek, David James

    1977-01-01

    incandescent bulb at a distance of 20 cm), [5] = 4x10 M: Curve 1 ( . ), initial spectrum; Curve Z ( ? ), after 2 hours; Curve 3 (---), after 10 days; Curve 4 (+-+), after 24 days. . . 92 2Z Absorption spectra of the complex in DMSO at 25. 0'C... of the absorbance at 535 nm vs. nitrite ion concentration using 1. 0 cm cells at 25. 0'C. 4 Absorption spectra of the complex generated in situ from Page 15 24 27 5 at 25. 0'C: 10 M NaOH; 10 M NaOH; -2 Curve 1 (---), in 99K/1% DMSO/H20 (v/v), Curve 2...

  9. Butyl Fuel LLC formerly Environmental Energy Inc | Open Energy Information

    Open Energy Info (EERE)

    AFDC Printable Version Share this resource Send a link to EERE: Alternative Fuels Data Center Home Page to someone by E-mail Share EERE: Alternative Fuels Data Center Home Page on Facebook Tweet about EERE: Alternative Fuels Data Center Home Page on Twitter Bookmark EERE: Alternative Fuels Data Center Home Page on Google Bookmark EERE: Alternative Fuels Data Center Home Page on QA:QA J-E-1 SECTION J APPENDIX E LISTStar Energy LLC JumpBiossenceBrunswick, Maine:IAEA CooperationSolarButyl Fuel LLC

  10. including cell-cycle regulation, and, along with hTERT, can immortalize human cells6

    E-Print Network [OSTI]

    Balibar, Sébastien

    including cell-cycle regulation, and, along with hTERT, can immortalize human cells6 . So it is possible that a central effect of these two pro- teins is to activate the cell-division machinery in chromosomes), thereby facilitating reprogramming. Are the iPS cells that Park et al. generated, or indeed

  11. 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.

  12. Enhanced anaerobic biodegradation of BTEX-ethanol mixtures in aquifer columns amended with sulfate, chelated ferric iron or nitrate

    E-Print Network [OSTI]

    Alvarez, Pedro J.

    -mail: alvarez@rice.edu) Key words: anaerobic biostimulation, bioremediation, BTEX, ethanol, natural attenuation and ground water contamination by methyl tert-butyl ether (MTBE) have made policy makers more cognizant approaches. BTEX bioremediation efforts often rely on the addition of oxygen and nutrients to stimulate

  13. Biotreatment of groundwater contaminated with MTBE: interaction of common environmental co-contaminants

    E-Print Network [OSTI]

    Biotreatment of groundwater contaminated with MTBE: interaction of common environmental co of groundwater with the gasoline additive methyl tert-butyl ether (MTBE) is often accompanied by many aromatic, a laboratory-scale biotrickling filter for groundwater treatment inoculated with a microbial consortium

  14. A kinetic investigation of the reaction of dibutyl sodiophosphonate with n-butyl bromide 

    E-Print Network [OSTI]

    Shaffer, James Howard

    1955-01-01

    LIBRARY A A N COLLEGE OF TEXAS A KINETIC INVESTIGATION OI" TIIE RFACTION OF DIBUTYL SODIOITIOSPHONATE II'ITH N BUTYL BROIIllDE A Thesis By James Howard Shaffer Submitted to the Oraduate School of the Agricultural and Mechanical College... of Texn~ in partial fulfillment of the requirements for the de ree of MASTER OF SCIENCE August 1955 Major Subject: Chemistry A KINETIC INVESTIGATION OF THE REACTION OF DIBUTYL SODIOPHOSPHONATE WITH N-BUTYL BROMIDE A Thesis By James Howard Shaffer...

  15. Conversion of methanol to hydrocarbons III. Methylation, ethylation, and propylation of benzene with methanol

    SciTech Connect (OSTI)

    Kaeding, W.W. (Mobil Chemical Company, Princeton, NJ (USA))

    1988-12-01

    Methanol is converted to hydrocarbons (and water) over HZSM-5 zeolite catalyst in the presence of 1-8M excesses of benzene. Methanol products are primarily aliphatic hydrocarbon gases and C{sub 1} to C{sub 4} aliphatic substituents on the aromatic ring. Methylation of benzene to produce toluene increases as the feed ratio of methanol/benzene decreases. Mild conditions minimize aromatic ring production from methanol. Molar distribution of the methylene group (-CH{sub 2}-) in the product, is tabulated according to carbon number. Methane plus methyl substituents on the aromatic ring measure C{sub 1}; ethane, ethylene, and ethyl ring substituents measure C{sub 2}, etc. At temperatures up to 325 C, methylene distribution in the product is methyl = ethyl > propyl {much gt} butyl. Above 350 C, methyl {much gt} ethyl > propyl. This distribution of the methylene group, under mild conditions, may be a measure of the early production of light olefins, from methanol, within the zeolite pores.

  16. An evaluation of the 3M Organic Vapor Monitor #3500 as a short term exposure limit sampling device for acetone, methyl ethyl ketone, and methyl iso butyl ketone 

    E-Print Network [OSTI]

    Andrew, Lloyd B.

    1982-01-01

    . Six (6) monitors were removed from 3M's resealable envelopes and labeled. The monitors were attached to the aluminum disc so the air movement would be perpendicular to and against the back of the monitor. dl '0 l 0 dt dl dt 0 td 0 IJ 0 0 0 0... the contaminant into the system. The F-values in Table 7 are all greater than 3. 0718 so the null hypothesis is rejected, or Equation 4 is rejected in support of Equation 5. This means there are three different slopes describing the relationship between...

  17. Batch polymerization of styrene and isoprene by n-butyl lithium initiator 

    E-Print Network [OSTI]

    Hasan, Sayeed

    1970-01-01

    BATCN ?OLYMERIZATION OF STYRENE AND ISO?RENE BY n-BUTYL LITHIUM INITIATOR A Thesis SAYEED IIASAV Submitted to the Graduate College of Texas A&M University in partial fulfillment of the requirement for the d pre of IJASTER OF SCIFNCE... ler) CP3 MV gse P . January 1970 9&ZS&8 ABSTRACT Batch Polymerization of Styrene and Isoprene By n-Butyl Lithium Initiator. (January 1970) Sayeed 1Iasan, B. Sc. , East Pakistan University of Engineering and Technology, Dacca Directed by: Dr...

  18. Batch polymerization of styrene initiated by n-butyl lithium in a cyclohexane solvent 

    E-Print Network [OSTI]

    Landon, Thomas Rodman

    1971-01-01

    Committee ea Depa tment Mem er Mem er em er August 1971 ABSTRACT Batch Polymerization of Styrene Initiated by N-Butyl Lithium in Cyclohexane Solvent. (August 19 71) Thomas Rodman Landon, B, S. , Te x as A (&M Un i ve rs i ty Directed by: Dr.... Rayford G. Anthony Styrene is polymerized by n-butyl lithium with cyclo- hexane as the solvent. The polymerization is carried out in an isothermal batch reactors at three temperature 30, 40, and 50'C. The proposed reaction proceeds by a homo- geneous...

  19. Vapor-liquid equilibrium for methanol + 1,1-dimethylpropyl methyl ether at (288.15, 308.15, and 328.15) K

    SciTech Connect (OSTI)

    Moessner, F.; Coto, B.; Pando, C.; Rubio, R.G.; Renuncio, J.A.R. [Universidad Complutense, Madrid (Spain). Departamento de Quimica Fisica 1] [Universidad Complutense, Madrid (Spain). Departamento de Quimica Fisica 1

    1996-05-01

    Oxygenated compounds are being used as additives to gasoline because of their antiknock effects. Vapor-liquid equilibria for methanol + 1,1-dimethylpropyl methyl ether (tert-amyl methyl ether or TAME) have been measured at (288.15, 308.15, and 328.15) K. A Gibbs-Van Ness type apparatus for total vapor pressure measurements has been used. The system shows positive deviations from Raoult`s law with an azeotrope, whose coordinates are reported at the three temperatures studied. Results have been analyzed in terms of the UNIQUAC model, several versions of the UNIFAC model, and the modified-Huron-Vidal second-order (MHV2) group contribution equation of state.

  20. Aging of Weapon Seals – An Update on Butyl O-ring Issues

    SciTech Connect (OSTI)

    Wilson, Mark H.

    2011-07-13

    During testing under the Enhanced Surveillance Campaign in 2001, preliminary data detected a previously unknown and potentially serious concern with recently procured butyl o-rings on several programs. All butyl o-rings molded from a proprietary formulation throughout the period circa 1999 through 2001 had less than a full cure. Engineering judgment was that under curing is detrimental and could possibly lead to sub-optimum performance or, in the worst case, premature seal failure. An aging study was undertaken to ensure that suspect o-rings installed in the stockpile will retain sufficient sealing force for a minimum ten-year service life. A new prediction model developed for this study indicates suspect o-rings do not need to be replaced before the ten-year service life. Long-term testing results are reported on a yearly basis to validate the prediction model. This report documents the aging results for the period September 2002 to January 2011.

  1. 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 Alzheimer’s 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 N—H?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 Å{sup ?3}.

  2. 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.

  3. Detailed Chemical Kinetic Reaction Mechanism for Biodiesel Components Methyl Stearate and Methyl Oleate

    SciTech Connect (OSTI)

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

    2010-01-22

    New chemical kinetic reaction mechanisms are developed for two of the five major components of biodiesel fuel, methyl stearate and methyl oleate. The mechanisms are produced using existing reaction classes and rules for reaction rates, with additional reaction classes to describe other reactions unique to methyl ester species. Mechanism capabilities were examined by computing fuel/air autoignition delay times and comparing the results with more conventional hydrocarbon fuels for which experimental results are available. Additional comparisons were carried out with measured results taken from jet-stirred reactor experiments for rapeseed methyl ester fuels. In both sets of computational tests, methyl oleate was found to be slightly less reactive than methyl stearate, and an explanation of this observation is made showing that the double bond in methyl oleate inhibits certain low temperature chain branching reaction pathways important in methyl stearate. The resulting detailed chemical kinetic reaction mechanism includes more approximately 3500 chemical species and more than 17,000 chemical reactions.

  4. The methylated component of the Neurospora crassa genome 

    E-Print Network [OSTI]

    Selker, Eric U; Tountas, Nikolaos A; Cross, Sally H; Margolin, Brian S; Murphy, Jonathan G; Bird, Adrian P; Freitag, Michael

    2003-04-24

    Cytosine methylation is common, but not ubiquitous, in eukaryotes. Mammals (1) and the fungus Neurospora crassa (2,3) have about 2–3% of cytosines methylated. In mammals, methylation is almost exclusively in the ...

  5. Assessing Global Terrestrial Sources of Methyl Halides - Ozone Regulating Gases 

    E-Print Network [OSTI]

    Gancarczyk, Maciej

    2010-11-24

    Methyl bromide (CH3Br) and methyl chloride (CH3Cl) play significant roles in the depletion of the stratospheric ozone layer. The vast portion of methyl halide sources and sinks sources and sinks are natural in origin. The ...

  6. Synthesis and characterization of three-layered zinc phosphites containing tert-octylamine molecules with template and ligand roles

    SciTech Connect (OSTI)

    Wang, Chih-Min, E-mail: twcmwang@gmail.com [Department of Chemistry, National Central University, Jhongli, Taiwan 320, Taiwan ROC (China); Chiu, Cheng-Wei; Lin, Hsiu-Mei [Institute of Optoelectronic Sciences, National Taiwan Ocean University, Keelung, Taiwan 202, Taiwan ROC (China); Lii, Kwang-Hwa, E-mail: liikh@cc.ncu.edu.tw [Department of Chemistry, National Central University, Jhongli, Taiwan 320, Taiwan ROC (China); Institute of Chemistry, Academia Sinica, Nankang, Taipei, Taiwan 115, Taiwan ROC (China)

    2013-08-15

    Three-layered zinc phosphites containing single monoamine molecules with different roles have been synthesized using hydro(solvo)thermal methods and characterized by single-crystal X-ray diffraction, thermogravimetric analysis, and infrared spectroscopy. Compound 1, (C{sub 8}H{sub 17}NH{sub 3}){sub 4}Zn{sub 3}(HPO{sub 3}){sub 5}·3H{sub 2}O, consists of 20-ring layer structures sandwiched by water molecules and protonated tert-octylamine molecules. The structure of Zn(C{sub 8}H{sub 17}NH{sub 2})(HPO{sub 3}) (compound 2) is composed of 4.8{sup 2} network structures, wherein the tert-octylamines are coordinated to the Zn atom as pendant groups. Compound 3, (C{sub 8}H{sub 17}NH{sub 3}){sub 2}Zn{sub 4}(C{sub 8}H{sub 17}NH{sub 2})(HPO{sub 3}){sub 5}, was prepared in which the amine plays a dual role as both a ligand and a countercation. In addition, compound 1 is the first layered metal phosphite with large 20-ring windows. This group of substances represents the first example of the preparation of compounds in which the reactivity of incorporated single amine molecules is varied by adjusting the synthesis conditions. - Graphical abstract: The first layered metal phosphite with large 20-ring windows, (C8H17NH3)4Zn3(HPO3)5·3H{sub 2}O (1), sandwiched by water molecules and protonated tert-octylamine molecules. Highlights: • The first example of zinc phosphites contains amine molecules with template and ligand roles. • The reactivity of single amine molecules is varied by adjusting the synthesis conditions. • Compound 1 contains the largest pore opening of 20-rings in known layered metal phosphites. • Compound 3 has dual roles of amine molecules in its structure.

  7. Green polymer electrolytes based on chitosan and 1-butyl-3-methylimidazolium acetate

    SciTech Connect (OSTI)

    Shamsudin, Intan Juliana [Chemistry Department, Centre for Defence Foundation Studies, National Defence University of Malaysia, 57000 Kuala Lumpur (Malaysia); Ahmad, Azizan; Hassan, Nur Hasyareeda [School of Chemical Sciences and Food Technology, Faculty of Science and Technology, Universiti Kebangsaan Malaysia, 43600, Bangi, Selangor Darul Ehsan (Malaysia)

    2014-09-03

    Green polymer electrolytes based on chitosan as the polymer matrix and ionic liquid 1-butyl-3-methylimidazolium acetate [Bmim][OAc] as charge carriers were prepared by solution casting technique. Complexes with various amount of ionic liquid loading were investigated as possible ionic conducting polymers. The ionic conductivity was found to increase with increasing weight percent of ionic liquid. The highest ionic conductivity of the charged chitosan-[Bmim][OAc] was 2.44 × 10{sup ?3} S cm{sup ?1} at 90 wt.% of [Bmim][OAc] content at ambient temperature. Attenuated Total Reflection Fourier Transform infrared (ATR-FTIR) spectroscopy has proven the interaction between chitosan and [Bmim][OAc]. X-ray Diffraction (XRD) has shown that the amorphosity of the complexes increase as the amount of [Bmim][OAc] increase.

  8. Dnmt1-Independent CG Methylation Contributes to Nucleosome Positioning

    E-Print Network [OSTI]

    , 2010). Methylation by chromomethylases in plants and green algae occurs at 50 -CNG-30 sites (treated

  9. Method for photochemical reduction of uranyl nitrate by tri-N-butyl phosphate and application of this method to nuclear fuel reprocessing

    DOE Patents [OSTI]

    De Poorter, Gerald L. (Los Alamos, NM); Rofer-De Poorter, Cheryl K. (Los Alamos, NM)

    1978-01-01

    Uranyl ion in solution in tri-n-butyl phosphate is readily photochemically reduced to U(IV). The product U(IV) may effectively be used in the Purex process for treating spent nuclear fuels to reduce Pu(IV) to Pu(III). The Pu(III) is readily separated from uranium in solution in the tri-n-butyl phosphate by an aqueous strip.

  10. Anhydrous aluminum chloride as an alkylation catalyst: identification of mono- and dialkyl-benzenes from the condensation of tertiary butyl alcohol with benzene. 

    E-Print Network [OSTI]

    Scoggins, Lacey E

    1959-01-01

    - alkyl and polyalkyl derivatives. The percentage yield, of monoalkyl derivatives is dependent upon the alcohol, dehydrating agent and. the activation of the aromatic nuclei Anhydrous ferric and alusdnum chloride, hydrogen fluoride with phosphorous...-butyl alcohol with 'benzene in the presence of i'erric chloride and. a 5g yield using aluminum chloride under the same conditions. Simons and. Archer5 reacted t-butyl alcohol with 'benzene using hydrogen fluoride as an alkylation catalyst, obtaining 4Q...

  11. De novo DNA methylation activity of METHYLTRANSFERASE 1 (MET1) partially restores body methylation in Arabidopsis

    E-Print Network [OSTI]

    Meyer, Peter

    targets cytosine residues in all sequence contexts (CG, CNG and CNN), and is controlled by three DNA methylation (RdDM) pathway (Xie et al., 2004). CNG methylation is predominantly controlled by the plant of genes accumulated H3K9me2 and CNG marks, which reflects the interplay between KYP and CMT3 (Inagaki et

  12. Growing season methyl bromide and methyl chloride fluxes at a sub-arctic wetland in Sweden 

    E-Print Network [OSTI]

    Hardacre, Catherine J.; Blei, Emanuel; Heal, Mathew R

    2009-01-01

    Methyl bromide and methyl chloride fluxes were measured at several sites in a sub-arctic wetland near Abisko, Sweden (68°28?N 18°49?E) throughout the 2008 growing season. Averaged over 92 flux measurements the sub-arctic ...

  13. 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.

  14. Ethyl-tertiary-butyl-ether (ETBE) as an aviation fuel: Eleventh international symposium on alcohol fuels

    SciTech Connect (OSTI)

    Maben, G.D.; Shauck, M.E.; Zanin, M.G.

    1996-12-31

    This paper discusses the preliminary flight testing of an aircraft using neat burning ethyl-tertiary-butyl-ether (ETBE) as a fuel. No additional changes were made to the fuel delivery systems which had previously been modified to provide the higher fuel flow rates required to operate the engine on neat ethanol. Air-fuel ratios were manually adjusted with the mixture control. This system allows the pilot to adjust the mixture to compensate for changes in air density caused by altitude, pressure and temperature. The engine was instrumented to measure exhaust gas temperatures (EGT), cylinder head temperatures (CHT), and fuel flows, while the standard aircraft instruments were used to collect aircraft performance data. Baseline engine data for ETBE and Avgas are compared. Preliminary data indicates the technical and economic feasibility of using ETBE as an aviation fuel for the piston engine fleet. Furthermore, the energy density of ETBE qualifies it as a candidate for a turbine engine fuel of which 16.2 billion gallons are used in the US each year.

  15. Multiprobe Spectroscopic Evidence for "Hyperpolarity" within 1-Butyl-3-methylimidazolium Hexafluorophosphate Mixtures with Tetraethylene Glycol

    SciTech Connect (OSTI)

    Sarkar, Abhra [Indian Institute of Technology, Delhi; Trivedi, Shruti [Indian Institute of Technology, Delhi; Baker, Gary A [ORNL; Pandey, Siddharth [Indian Institute of Technology, Delhi

    2008-01-01

    A hybrid, potentially green solvent system composed of tetraethylene glycol (TEG) and the ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate ([bmim][PF6]) was investigated across all mole fractions with regard to the solvent properties of the mixture. For this purpose, a suite of absorbance- and fluorescence-based solvatochromic probes were utilized to explore solute-solvent and solvent-solvent interactions existing within the [bmim][PF6] + TEG system. These studies revealed an interesting and unusual synergistic solvent effect. In particular, a remarkable hyperpolarity was observed in which the ET value, comprising dipolarity/polarizability and hydrogen bond donor (HBD) acidity contributions, at intermediate mole fractions of the binary mixture well exceeded that of the most polar pure component (i.e., [bmim][PF6]). Independently determined dipolarity/polarizability ( *) and HBD acidity (R) Kamlet-Taft values for the [bmim][PF6] + TEG mixtures were also observed to be anomalously high at intermediate mole fractions, whereas hydrogen bond acceptor (HBA) basicities ( values) were much more in line with the ideal arithmetic values predicted on a mole fraction basis.

  16. N-butyl Cyanoacrylate Glue Embolization of Arterial Networks to Facilitate Hepatic Arterial Skeletonization before Radioembolization

    SciTech Connect (OSTI)

    Samuelson, Shaun D.; Louie, John D.; Sze, Daniel Y.

    2013-06-15

    Purpose. Avoidance of nontarget microsphere deposition via hepatoenteric anastomoses is essential to the safety of yttrium-90 radioembolization (RE). The hepatic hilar arterial network may remain partially patent after coil embolization of major arteries, resulting in persistent risk. We retrospectively reviewed cases where n-butyl cyanoacrylate (n-BCA) glue embolization was used to facilitate endovascular hepatic arterial skeletonization before RE. Methods. A total of 543 RE procedures performed between June 2004 and March 2012 were reviewed, and 10 were identified where n-BCA was used to embolize hepatoenteric anastomoses. Arterial anatomy, prior coil embolization, and technical details were recorded. Outcomes were reviewed to identify subsequent complications of n-BCA embolization or nontarget RE. Results. The rate of complete technical success was 80 % and partial success 20 %, with one nontarget embolization complication resulting in a minor change in treatment plan. No evidence of gastrointestinal or biliary ischemia or infarction was identified, and no microsphere-related gastroduodenal ulcerations or other evidence of nontarget RE were seen. Median volume of n-BCA used was <0.1 ml. Conclusion. n-BCA glue embolization is useful to eliminate hepatoenteric networks that may result in nontarget RE, especially in those that persist after coil embolization of major vessels such as the gastroduodenal and right gastric arteries.

  17. 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.

  18. DNA Methylation as a Biomarker for Preeclampsia

    SciTech Connect (OSTI)

    Anderson, Cindy M.; Ralph, Jody L.; Wright, Michelle L.; Linggi, Bryan E.; Ohm, Joyce E.

    2014-10-01

    Background: Preeclampsia contributes significantly to pregnancy-associated morbidity and mortality as well as future risk of cardiovascular disease in mother and offspring, and preeclampsia in offspring. The lack of reliable methods for early detection limits the opportunities for prevention, diagnosis, and timely treatment. Purpose: The purpose of this study was to explore distinct DNA methylation patterns associated with preeclampsia in both maternal cells and fetal-derived tissue that represent potential biomarkers to predict future preeclampsia and inheritance in children. Method: A convenience sample of nulliparous women (N = 55) in the first trimester of pregnancy was recruited for this prospective study. Genome-wide DNA methylation was quantified in first-trimester maternal peripheral white blood cells and placental chorionic tissue from normotensive women and those with preeclampsia (n = 6/group). Results: Late-onset preeclampsia developed in 12.7% of women. Significant differences in DNA methylation were identified in 207 individual linked cytosine and guanine (CpG) sites in maternal white blood cells collected in the first trimester (132 sites with gain and 75 sites with loss of methylation), which were common to approximately 75% of the differentially methylated CpG sites identified in chorionic tissue of fetal origin. Conclusion: This study is the first to identify maternal epigenetic targets and common targets in fetal-derived tissue that represent putative biomarkers for early detection and heritable risk of preeclampsia. Findings may pave the way for diagnosis of preeclampsia prior to its clinical presentation and acute damaging effects, and the potential for prevention of the detrimental long-term sequelae.

  19. Spectroscopic Investigations of Solvent Effect on Chiral Interactions Chieu D. Tran* and Shaofang Yu

    E-Print Network [OSTI]

    Reid, Scott A.

    the mechanism of chiral interactions between a known chiral selector, tert-butyl carbamoylated quinine (t in liquid chromatography and capillary electrophoresis. Carbamoylated derivatives of quinine are effective

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

    SciTech Connect (OSTI)

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

    2009-12-04

    Biodiesel is a mixture of long chain fatty acid methyl esters derived from fats and oils. This research study presents opposed-flow diffusion flame data for one large fatty acid methyl ester, methyl decanoate, and uses the experiments to validate an improved skeletal mechanism consisting of 648 species and 2998 reactions. The results 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.

  1. Ureteric Embolization for Lower Urinary Tract Fistulae: Use of Two Amplatzer Vascular Plugs and N-Butyl Cyanoacrylate Employing the 'Sandwich' Technique

    SciTech Connect (OSTI)

    Saad, Wael E. A., E-mail: ws6r@virginia.edu; Kalagher, S.; Turba, U. C.; Sabri, S. S.; Park, A.-W.; Stone, J.; Angle, J. F.; Matsumoto, A. H. [University of Virginia Health System, Department of Radiology and Medical Imaging, Division of Vascular Interventional Radiology (United States)

    2013-08-01

    PurposeThis study describes and evaluated the effectiveness of occluding distal ureters in the clinical setting of urinary vaginal (vesicovaginal or enterovesicovaginal) fistulae utilizing a new technique which combines Amplatzer vascular plugs and N-butyl cyanoacrylate.MaterialsThis is a retrospective study (January 2007-December 2010) of patients with urinary-vaginal fistulae undergoing distal ureter embolization utilizing an Amplatzer- N-butyl cyanoacrylate-Amplatzer sandwich technique. An 8-12-mm type-I or type-II Amplatzer vascular plug was delivered using the sheath and deployed in the ureter distal to the pelvic brim. Instillation of 0.8-1.5 cc of N-butyl cyanoacrylate into ureter proximal to the Amplatzer plug was performed. This was followed by another set of 8-12-mm type-I or type-II Amplatzer vascular plugs in a technique referred to as the 'sandwich technique.'ResultsFive ureters in three patients were occluded utilizing the above-described technique during the 4-year study period. Mean maximum size Amplatzer used per ureter was 10.8 mm (range, 8-12). One ureter required three Amplatzer plugs and the rest required two. Two patients (3 ureters) were clinically successful with complete resolution of symptoms in 36-48 h. The third patient (2 ureters) was partly successful and required a second Amplatzer- N-butyl cyanoacrylate sandwich technique embolization. The mean clinical follow-up was 11.3 months (range, 1.7-29.2).ConclusionsThe Amplatzer- N-butyl cyanoacrylate-Amplatzer sandwich technique for occluding the distal ureter is safe and effective with a quick (probably due to the N-butyl cyanoacrylate) and durable (probably due to the Amplatzer plugs) clinical response.

  2. Molecular Simulation of Water Extraction into a Tri-n-Butyl-Phosphate/n-Dodecane Solution

    SciTech Connect (OSTI)

    de Almeida, Valmor F [ORNL] [ORNL; Ye, Xianggui [ORNL] [ORNL; Cui, Shengting [ORNL] [ORNL; Khomami, Bamin [ORNL] [ORNL

    2013-01-01

    Abstract: Molecular dynamics simulations were performed to investigate water extraction into a solution of 30 vol% tri-n-butyl-phosphate (TBP) in n-dodecane. This solvent extraction mixture is commonly used in hydrometallurgical and nuclear fuel recycling operations for recovering metals from aqueous streams. It is known that water is coextracted in the organic phase and that it competes with metal ions for the available extractant agent (TBP). Therefore investigating pure water extraction provides a realistic prototype to test molecular simulation methods for the first time in this area. Our computational results indicate that the TBP electric dipole moment has a significant effect on the predicted water solubility. A larger TBP dipole moment decreases the aqueous-organic interfacial tension, leading to increased roughness of the aqueous-organic interface. Interfacial roughness has a significant effect on disrupting the interfacial water hydrogen bonding structure, resulting in a greater number of dangling water molecules at the interface. This enhances the probability of water molecules to break away from the aqueous phase and to migrate into the bulk of the organic phase. Therefore, the magnitude of the TBP dipole moment is a crucial factor in controlling water hydrogen bond breaking at the aqueous-organic interface. By slightly lowering the atomic partial charges of the TBP atoms, to produce a dipole moment that better agrees with experimental data, we were able to predict water solubility in close agreement with experimental measurements. Hence we demonstrate that a molecular modeling and simulation approach may provide quantitative support to experimental programs in this area. In addition, our simulation results shed light into the molecular mechanism of water extraction, the critical role of TBP, and the structural forms of water molecules both at the interface and in the bulk of the organic phase. Specifically, it is found that water molecules are extracted either as single molecules or as clusters. Furthermore, within the organic phase, the extracted water forms clusters with up to 20 water molecules, however, more than 70% of these water clusters contain less than 5 water molecules when the water extraction process reaches saturation.

  3. 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.

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

    Office of Scientific and Technical Information (OSTI)

    LIFE SCIENCES; ARGININE; CARCINOGENS; CHROMIUM; DNA DAMAGES; GENES; HUMAN POPULATIONS; LUNGS; LYSINE; METHYLATION; NEOPLASMS; OCCUPATIONAL EXPOSURE; PROMOTERS Word Cloud More Like...

  5. Investigation of the Atmospheric Ozone Impacts of Methyl Iodide

    E-Print Network [OSTI]

    Carter, W P L

    2007-01-01

    comparable to that for ethane. It is concluded that methylmethyl iodide and ethane. 32 Table A-of methyl iodide and ethane in the atmospheric reactivity

  6. Binary total pressure measurements for methanol with 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, 2-methyl-2-butanol, 3-methyl-1-butanol, and 3-methyl-2-butanol at 313.15 K

    SciTech Connect (OSTI)

    Barton, D.P.; Bhethanabotla, V.R.; Campbell, S.W. [Univ. of South Florida, Tampa, FL (United States). Dept. of Chemical Engineering] [Univ. of South Florida, Tampa, FL (United States). Dept. of Chemical Engineering

    1996-09-01

    Total pressure measurements at 313.15 K are reported for binary systems of methanol with each of seven pentanol isomers: 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, 2-methyl-2-butanol, 3-methyl-1-butanol, and 3-methyl-2-butanol. The results were obtained using a Van Ness apparatus and were fitted to the four-suffix Margules equation using Barker`s method. The four-suffix Margules equation represents the data to within an average of approximately 0.02 kPa.

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

    Office of Scientific and Technical Information (OSTI)

    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...

  8. RNAi, DRD1, and Histone Methylation Actively Target Developmentally Important Non-CG DNA

    E-Print Network [OSTI]

    Jacobsen, Steve

    cluster [8]. DNA methylation is found at cytosines in three different sequence contexts, CG, CNG (where N signals to continually target regions of DNA for methylation [12]. In the case of CNG methylation

  9. 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. (Berkeley, CA); Keasling, Jay D. (Berkeley, CA)

    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.

  10. Elucidate the mechanism(s) of Hg uptake in methylating bacteria and effects on Hg methylation in nature.

    E-Print Network [OSTI]

    Post, Wilfred M.

    Objective · Elucidate the mechanism(s) of Hg uptake in methylating bacteria and effects on Hg, suggesting a possible detoxification mechanism for the formation and export of methylmercury. 1 BER Overview A New Mechanism of Mercury Uptake and Methylation in Anaerobic Bacteria Contact: Jeffra Schaefer

  11. 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.

  12. 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.

  13. Identification of volatile butyl rubber thermal-oxidative degradation products by cryofocusing gas chromatography/mass spectrometry (cryo-GC/MS).

    SciTech Connect (OSTI)

    Smith, Jonell Nicole; White, Michael Irvin; Bernstein, Robert; Hochrein, James Michael

    2013-02-01

    Chemical structure and physical properties of materials, such as polymers, can be altered as aging progresses, which may result in a material that is ineffective for its envisioned intent. Butyl rubber formulations, starting material, and additives were aged under thermal-oxidative conditions for up to 413 total days at up to 124 %C2%B0C. Samples included: two formulations developed at Kansas City Plant (KCP) (%236 and %2310), one commercially available formulation (%2321), Laxness bromobutyl 2030 starting material, and two additives (polyethylene AC-617 and Vanax MBM). The low-molecular weight volatile thermal-oxidative degradation products that collected in the headspace over the samples were preconcentrated, separated, and detected using cryofocusing gas chromatography mass spectrometry (cryo-GC/MS). The majority of identified degradation species were alkanes, alkenes, alcohols, ketones, and aldehydes. Observations for Butyl %2310 aged in an oxygen-18 enriched atmosphere (18O2) were used to verify when the source of oxygen in the applicable degradation products was from the gaseous environment rather than the polymeric mixture. For comparison purposes, Butyl %2310 was also aged under non-oxidative thermal conditions using an argon atmosphere.

  14. Regulation of yeast development by mRNA methylation

    E-Print Network [OSTI]

    Agarwala, Sudeep D

    2012-01-01

    The internal methylation of mRNA post-transcriptionally is an essential component of the mRNA editing machinery in virtually every eukaryotic system. Despite this ubiquity, little is known about the relevance, consequences ...

  15. Methyl arsenic adsorption and desorption behavior on iron oxides 

    E-Print Network [OSTI]

    Lafferty, Brandon James

    2005-08-29

    been conducted regarding interactions of the methyl-arsenic forms. The objective of this study was to compare the adsorption and desorption behavior of methylarsonate (MMAsV), methylarsonous acid (MMAsIII), dimethylarsinate (DMAsV), dimethylarsinous...

  16. Methyl bromide emissions to the atmosphere from temperate woodland ecosystems 

    E-Print Network [OSTI]

    Drewer, Julia; Heal, Kate V; Smith, Keith A; Heal, Mathew R

    2008-01-01

    The environmental importance of methyl bromide (CH3Br) arises from its contribution to stratospheric ozone loss processes and, as a consequence, its emissions from anthropogenic sources are subject to the Montreal Protocol. ...

  17. 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 2–12 kJ?mol{sup ?1} range.

  18. 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.

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

    SciTech Connect (OSTI)

    Hohl, G.H.

    1995-12-31

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

  20. Phytoremediation of ionic and methyl mercury pollution

    SciTech Connect (OSTI)

    Meagher, R.B.

    1998-06-01

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

  1. Characterization of the influence of 1-butyl-3-methylimidazolium chloride on the structure and thermal stability of green fluorescent protein

    SciTech Connect (OSTI)

    Heller, William T [ORNL; O'Neill, Hugh Michael [ORNL; Zhang, Qiu [ORNL; Baker, Gary A [ORNL

    2010-01-01

    Ionic liquids (ILs) are finding a vast array of applications as novel solvents for a wide variety of processes that include enzymatic chemistry, particularly as more biocompatible ILs are designed and discovered. While it is assumed that a native or near-native structure is required for enzymatic activity, there is some evidence that ILs alter protein structure and oligomerization states in a manner than can negatively impact function. The IL 1-butyl-3-methylimidazolium chloride, [bmim]Cl, is a well-studied, water-miscible member of the popular 1-alkyl-3-methylimidazolium IL family. To improve our understanding of the impact of water-miscible ILs on proteins, we have characterized the structure and oligomerization state of green fluorescent protein (GFP) in aqueous solutions containing 25 and 50 vol % [bmim]Cl using a combination of optical spectroscopy and small-angle neutron scattering (SANS). Measurements were also performed as a function of temperature to provide insight into the effect of the IL on the thermal stability of GFP. While GFP exists as a dimer in water, the presence of 25 vol % [bmim]Cl causes GFP to transition to a monomeric state. The SANS data indicate that GFP is a great deal less compact in 50 vol % [bmim]Cl than in neat water, indicative of unfolding from the native structure. The oligomerization state of the protein in IL-containing aqueous solution changes from a dimer to a monomer in response to the IL, but does not change as a function of temperature in the IL-containing solution. The SANS and spectroscopic results also demonstrate that the addition of [bmim]Cl to the solution decreases the thermal stability of GFP, allowing the protein to unfold at lower temperatures than in aqueous solution.

  2. Portal Vein Embolization before Right Hepatectomy: Improved Results Using n-Butyl-Cyanoacrylate Compared to Microparticles Plus Coils

    SciTech Connect (OSTI)

    Guiu, Boris Bize, Pierre; Gunthern, Daniel; Demartines, Nicolas; Halkic, Nermin; Denys, Alban

    2013-10-15

    Background: There is currently no consensus in the literature on which embolic agent induces the greatest degree of liver hypertrophy after portal vein embolization (PVE). Only experimental results in a pig model have demonstrated an advantage of n-butyl-cyanoacrylate (NBCA) over 3 other embolic materials (hydrophilic gel, small and large polyvinyl alcohol particles) for PVE. Therefore, the aim of this human study was to retrospectively compare the results of PVE using NBCA with those using spherical microparticles plus coils. Methods: A total of 34 patients underwent PVE using either NBCA (n = 20), or spherical microparticles plus coils (n = 14). PVE was decided according to preoperative volumetry on the basis of contrast-enhanced CT. Groups were compared for age, sex, volume of the left lobe before PVE and future remnant liver ratio (FRL) (volume of the left lobe/total liver volume - tumor volume). The primary end point was the increase in left lobe volume 1 month after PVE. Secondary end points were procedure complications and biological tolerance. Results: Both groups were similar in terms of age, sex ratio, left lobe volume, and FRL before PVE. NBCA induced a greater increase in volume after PVE than did microparticles plus coils (respectively, +74 {+-} 69 % and +23 {+-} 14 %, p < 0.05). The amount of contrast medium used for the procedure was significantly larger when microparticles and coils rather than NBCA were used (respectively, 264 {+-} 43 ml and 162 {+-} 34 ml, p < 0.01). The rate of PVE complications as well as the biological tolerance was similar in both groups. Conclusion: NBCA seems more effective than spherical microparticles plus coils to induce left-lobe hypertrophy.

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

    DOE Patents [OSTI]

    Belinsky, Steven A. (Albuquerque, NM); Palmisano, William A. (Edgewood, NM)

    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.

  4. 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.

  5. 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.

  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. 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...

  8. Role of CpG island methylation and MBD2 in immune cell gene regulation 

    E-Print Network [OSTI]

    Deaton, Aimée M.

    2010-01-01

    The phenomenon of cell type-specific DNA methylation has received much attention in recent years and a number of DNA methylation differences have been described between cells of the immune system. Of particular interest ...

  9. Investigating the association between BRAFV600E and methylation in sporadic colon cancer 

    E-Print Network [OSTI]

    Baxter, Eva Louise

    2012-06-30

    Aberrant methylation of CpG island promoters is a frequent observation in cancer and is known to affect many genes, including tumour suppressor genes. Genes with methylated promoters are usually repressed and inactive, ...

  10. 2,000-year record of atmospheric methyl bromide from a South Pole ice core

    E-Print Network [OSTI]

    Saltzman, Eric S; Aydin, Murat; Tatum, Cheryl; Williams, Margaret B

    2008-01-01

    air from firn at the South Pole, Nature, 383, 231 – 235. 5METHYL BROMIDE FROM SOUTH POLE ICE CORE Butler, J. H. , M.of methyl chloride from a South Pole ice core: Evidence for

  11. 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.

  12. OUTLOOK: Specialty crops and methyl bromide alternatives: Taking stock after 7 years

    E-Print Network [OSTI]

    Browne, Greg T

    2013-01-01

    finding alternatives to Outlook Specialty crops and methylNumber 3 Steve Fennimore Outlook Non-fumigant approaches to

  13. S0S1 transition of trans--methyl styrene: Vibronic structure and dynamics

    E-Print Network [OSTI]

    Haas, Yehuda

    S0S1 transition of trans- -methyl styrene: Vibronic structure and dynamics Y. Haas, S. Kendler, E; accepted 28 March 1995 The fluorescence excitation and emission spectra of trans- -methyl styrene have been of styrene and of trans- -methyl styrene BMS is reported. The BMS molecule is calculated to be essentially

  14. An Arabidopsis thaliana methyltransferase capable of methylating farnesoic acid q

    E-Print Network [OSTI]

    Pichersky, Eran

    : Plant biochemistry; Secondary metabolism; Plant defense; Methyl farnesoate; Terpenes; Insect juvenile Arbor, MI 48109-1048, USA b Department of Plant Sciences, 2431 Joe Johnson Drive, University reported the identification of a new family of plant methyltransferases (MTs), named the SABATH family

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

    SciTech Connect (OSTI)

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

    1987-04-29

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

  16. Synthesis of 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.

  17. Gold(I)-Mediated Nucleophilic Additions to Allenes: from Enantioselective Catalysis to Supramolecular Chemistry

    E-Print Network [OSTI]

    Wang, Zhan

    2012-01-01

    the N-X bond in hydroxyl-amine and hydrazine nucleophilesHydroamination with hydroxyl amine substrates: Tert-butyl 4-hydroxyl nitriles, hydroxyphosphates, azido alcohols and amines

  18. Modulators of Toll-like Receptors-4 and -2

    E-Print Network [OSTI]

    Wu, Wenyan

    2009-08-31

    ?OEt2 – boron trifluoride diethyl etherate BnBr – benzyl bromide br - broad Boc – di-tert-butyl carbonate BPI – bactericidal permeability increasing protein CH3CN – acetonitrile C15H31COCl – palmitoyl chloride CTL – cytotoxic T lymphocyte DAB...

  19. 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.

  20. Durability of Poly (Methyl Methacrylate) Lenses Used in Concentrating Photovoltaics (Presentation)

    SciTech Connect (OSTI)

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

    2010-10-21

    This presentation reports the findings of NREL's screen test to characterize the durability of poly (methyl methacrylate) lenses used in concentrated photovoltaics.

  1. REVERSIBLE METAL-TO-METAL METHYL TRANSFER IN n5-CYCLOPENTADIENYL(TRIPHENYLPHOSPHINE)DIMETHYLCOBALT(III)

    E-Print Network [OSTI]

    Bryndza, Henry E.

    2013-01-01

    transfer between transition metals which is assisted by aJournal of the American Chemical Society REVERSIBLE METAL-TO-METAL METHYL TRANSFER IN n 5-CYCLOPENTAOIENYL(

  2. Arsenic Methylation and Bladder Cancer Risk in CaseControl Studies in Argentina and the

    E-Print Network [OSTI]

    California at Berkeley, University of

    Arsenic Methylation and Bladder Cancer Risk in Case­Control Studies in Argentina and the United's susceptibility to bladder cancer. Methods: Urinary methylation products were measured in subjects from Argentina (114 cases and 114 controls) and the United States (23 cases and 49 controls). Results: In Argentina

  3. Methyl Bromide o Bromomethane, monobromomethane, isobrome, Brom-o-Gas, Bromomethane, Celume,

    E-Print Network [OSTI]

    Toohey, Darin W.

    Methyl Bromide What o Bromomethane, monobromomethane, isobrome, Brom-o-Gas, Bromomethane, Celume, Embafume, Haltox, MB, MeBr, Profume, Terr-o-Gas, Zytox, and methyl fume o Oder less and colorless gas, up times heavier than air, accumulates in poorly ventilated and low-lying areas Uses o Pesticide

  4. Molecular Dynamics of Methylamine, Methanol, and Methyl Fluoride Cations in Intense 7 Micron Laser Fields

    E-Print Network [OSTI]

    Schlegel, H. Bernhard

    Molecular Dynamics of Methylamine, Methanol, and Methyl Fluoride Cations in Intense 7 Micron Laser of methylamine (CH3NH2 + ), methanol (CH3OH+ ), and methyl fluoride (CH3F+ ) cations by short, intense laser 7 m laser pulses. This work is motivated by recent studies of methanol cations by Yamanouchi and co

  5. New insight into the mechanism of methyl transfer during the biosynthesis of fosfomycin{

    E-Print Network [OSTI]

    Zhao, Huimin

    New insight into the mechanism of methyl transfer during the biosynthesis of fosfomycin{ Ryan D shown in Scheme 1A.4­11 Yet, the mechanism of an unprecedented methyl transfer step in the biosynthesis in combina- tion with bioinformatics analysis lead to a radically different mechanism

  6. Arsenic methylation and lung and bladder cancer in a case-control study in northern Chile

    E-Print Network [OSTI]

    California at Berkeley, University of

    Arsenic methylation and lung and bladder cancer in a case-control study in northern Chile Dawit Accepted 20 November 2013 Available online 1 December 2013 Keywords: Arsenic Cancer Methylation Lung about its role in lung cancer, the most common cause of arsenic-related death, or about its impacts

  7. Experimental and Computational Thermochemical Study of 2-and 3-Thiopheneacetic Acid Methyl Esters

    E-Print Network [OSTI]

    Chickos, James S.

    Experimental and Computational Thermochemical Study of 2- and 3-Thiopheneacetic Acid Methyl Esters an experimental and computational thermochemical study on the relative stabilities of 2- and 3-thiopheneacetic acid methyl esters. The enthalpies of combustion and vaporization were measured by a rotating

  8. 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 (Cs•4,4?- 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.

  9. 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.

  10. 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.

  11. The synthesis of some N-methylated aminoalkylphosphonic acids 

    E-Print Network [OSTI]

    Eikenberry, Jon Nathan

    1966-01-01

    with a Beckman, Model IR-8 double 20 N. A. L 0, H dh k f~Ch* ' t, 10th d. , td G -H'tf Book Co. , Inc. , New York, N. Y. , 1961, p. 1391. 21 G. M. Kosolapoff and R. M. Watson, J. Am, Chem. Soc. , 73, 4101 (1951). 32 beam spectrophotometer. Spectra... 80. 2 g. (53. 8%) of l-dimethylamino-2-methyl-l-propene, b. p. 85-86, n l. 4195, d 0. 7360; M calcd. 33. 54, found 34. 09. o 25 25 o 19. 6 Tiollais and assoc&ates reported 64% yield, b. p. 87, n ' l. 4212, D 19. 6 5 13c 4 1-Dimethylamino-1-butene...

  12. 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.

  13. Current Biology 17, 379384, February 20, 2007 2007 Elsevier Ltd All rights reserved DOI 10.1016/j.cub.2007.01.009 The SRA Methyl-Cytosine-Binding Domain

    E-Print Network [OSTI]

    Jacobsen, Steve

    . In Arabidopsis, DNA methylation (5-methyl cytosine) occurs not only at CG residues, but also at CNG methylation at CG residues [7, 8], whereas CHROMOMETHYLASE3 (CMT3) maintains the majority of CNG methylation of CNG methylation and is also required for de novo methylation of cytosines in all sequence contexts [2

  14. 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.

  15. High temperature concrete composites containing organosiloxane crosslinked copolymers

    DOE Patents [OSTI]

    Zeldin, Arkady (Rego Park, NY); Carciello, Neal (Patchogue, NY); Kukacka, Lawrence (Port Jefferson, NY); Fontana, Jack (Shoreham, NY)

    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.

  16. Co-treatment of VOCs in low-pH sulfide biofilters

    SciTech Connect (OSTI)

    Devinny, J.S.; Chitwood, D.E.; Choi, D.S.

    1999-07-01

    Biofiltration of off-gases from wastewater treatment plants requires removal of sulfides and volatile organic compounds. Sulfides are readily removed in low-pH biofilters filled with inorganic media. If the same biofilter could simultaneously remove the volatile organic compounds, an efficient single-step system would be possible. Laboratory work on co-treatment of toluene and sulfides, and fieldwork on several volatile compounds indicate that this is possible. Removals of over 90% of toluene, xylene, acetone, methanol, and ethylbenzene should be possible with an empty bed contact time of 60 s. Methyl tert-butyl ether, isopentane, chloroform and methylene chloride were removed with lower but still substantial efficiencies. Biofilters operated at steady state but non-neutral pHs represent a promising avenue of research.

  17. ENVIRONMENTAL ENGINEERING SCIENCE Volume 20, Number 5, 2003

    E-Print Network [OSTI]

    Chu, Kung-Hui "Bella"

    -butyl ether (MTBE) is the most widely used oxygenate in gasoline, followed by ethanol. Widespread use in certain urban regions to reduce air pollution from motor vehi- cles. To meet the requirements of the CAAA), and diisopropyl ether (DIPE). Alcohol oxy- genates include ethanol (EtOH), tert-butyl alcohol (TBA), and methanol

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

    SciTech Connect (OSTI)

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

    2015-01-01

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

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

    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,more »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.« less

  20. Conformational free energies of methyl-$\\alpha$-L-iduronic and methyl-$\\beta$-D-glucuronic acids in water

    E-Print Network [OSTI]

    Babin, Volodymyr

    2009-01-01

    We present a simulation protocol that allows for efficient sampling of the degrees of freedom of a solute in explicit solvent. The protocol involves using a non-equilibrium umbrella sampling method, in this case the recently developed adaptively biased molecular dynamics method, to compute an approximate free energy for the slow modes of the solute in explicit solvent. This approximate free energy is then used to set up a Hamiltonian replica exchange scheme that samples both from biased and unbiased distributions. The final accurate free energy is recovered via the WHAM technique applied to all the replicas, and equilibrium properties of the solute are computed from the unbiased trajectories. We illustrate the approach by means of applying it to the study of the puckering landscapes of the methyl glycosides of $\\alpha$-L-iduronic acid and its C5 epimer $\\beta$-D-glucuronic acid in water. Big savings in computational resources are gained in comparison to the standard parallel tempering method.

  1. Anti-inflammatory and antifibrotic effects of methyl palmitate

    SciTech Connect (OSTI)

    El-Demerdash, Ebtehal, E-mail: ebtehal_dm@yahoo.com

    2011-08-01

    Methyl palmitate (MP) has been shown earlier to inhibit Kupffer cells and rat peritoneal macrophages. To evaluate the potential of MP to inhibit the activation of other macrophages, RAW cells (macrophages of alveolar origin) were treated with varying concentrations of MP (0.25, 0.5, 1 mM). Assessment of cytotoxicity using MTT assay revealed that 0.25 and 0.5 mM are not toxic to RAW cells. MP was able to inhibit the phagocytic function of RAW cells. Treatment of cells with MP 24 hours prior to LPS stimulation significantly decreased nitric oxide release and altered the pattern of cytokines release; there was a significant decrease in TNF-{alpha} and a significant increase in IL-10 compared to the controls. However, there is a non-significant change in IL-6 level. Furthermore, phosphorylation of inhibitory kappa B (I{kappa}B{alpha}) protein was significantly decreased in RAW cells treated with 0.5 mM MP after LPS stimulation. Based upon the in-vitro results, it was examined whether MP treatment will be effective in preventing bleomycin-induced lung inflammation and fibrosis in-vivo. Bleomycin given by itself caused destruction of the lung architecture characterized by pulmonary fibrosis with collapse of air alveoli and emphysematous. Bleomycin induced a significant increase in hydroxyproline level and activated NF-{kappa}B, p65 expression in the lung. MP co-treatment significantly ameliorated bleomycin effects. These results suggest that MP has a potential of inhibiting macrophages in general. The present study demonstrated for the first time that MP has anti-inflammatory and antifibrotic effect that could be through NF-kB inhibition. Thus MP like molecule could be a promising anti-inflammatory and antifibrotic drug. - Research Highlights: >Methyl palmitate is a universal macrophage inhibitor. >It could be a promising nucleus of anti-inflammatory and antifibrotic drugs. >The underlying mechanism of these effects could be through NF-kB inhibition.

  2. Selective Monoarylation of Acetate Esters and Aryl Methyl Ketones Using Aryl Chlorides

    E-Print Network [OSTI]

    Biscoe, Mark R.

    Simple, efficient procedures for the monoarylation of acetate esters and aryl methyl ketones using aryl chlorides are presented. Previously, no general method was available to ensure the highly selective monoarylation of ...

  3. Mechanisms Regulating Mercury Bioavailability for Methylating Microorganisms in the Aquatic Environment: A Critical Review

    E-Print Network [OSTI]

    Mechanisms Regulating Mercury Bioavailability for Methylating Microorganisms in the Aquatic by anaerobic bacteria. In this Review, we evaluate the current state of knowledge regarding the mechanisms the uptake of inorganic mercury to these microorganisms. Our understanding of the mechanisms behind

  4. Palladium-catalyzed substitution of (coumarinyl)methyl acetates with C-, N-, and S-nucleophiles

    E-Print Network [OSTI]

    Chattopadhyay, Kalicharan; Fenster, Erik; Grenning, Alexander James; Tunge, Jon A.

    2012-07-27

    The palladium-catalyzed nucleophilic substitution of (coumarinyl)methyl acetates is described. The reaction proceeds though a palladium ?-benzyl-like complex and allows for many different types of C-, N-, and S-nucleophiles to be regioselectively...

  5. Thermomechanical properties of polyhedral oligomeric silsequioxane- poly(methyl methacrylate) nanocomposites

    E-Print Network [OSTI]

    Kopesky, Edward Thomas

    2005-01-01

    Poly(methyl methacrylate)s (PMMA) containing polyhedral oligomeric silsesquioxane (POSS) nanoparticles (d [approx.] 1.5 nm) were subjected to heological, mechanical, and morphological tests to determine the effects that ...

  6. Halogenated 1'-methyl-1,2'-bipyrroles (MBPs) in the Norwestern Atlantic

    E-Print Network [OSTI]

    Pangallo, Kristin C

    2009-01-01

    Halogenated 1'-methyl-1,2'-bipyrroles (MBPs) are a distinctive class of marine organic compounds. They are naturally produced, they have a unique carbon structure, they are highly halogenated, and they bioaccumulate in ...

  7. Heavy-atom isotope effects on the acid-catalyzed hydrolysis of methyl benzoate

    SciTech Connect (OSTI)

    Marlier, J.F.; O'Leary, M.H.

    1981-05-08

    Results of the use of a previously reported technique of four-heavy atom isotope effects for study of the acid-catalyzed hydrolysis of methyl benzoate are reported. Ether oxygen and methyl carbon isotope effects on the reaction were measured by the usual natural-abundance isotope-ratio technique. The carbonyl oxygen isotope effect was measured by the pseudo-natural-abundance double-label method as was the carbonyl carbon isotope effect. The results led to the assumption that the hydrolysis of methyl benzoate proceeds by way of a tetrahedral intermediate. The small amount of oxygen exchange with the solvent that accompanies the hydrolysis indicated that it is intermediate formation rather than decomposition that is rate determining. The small magnitude of the observed carbon isotope effect on the acid-catalyzed hydrolysis of methyl benzoate compared to carbon isotope effects on other reactions of this compound indicate that the transition state is relatively reactant-like. (BLM)

  8. Bioremediation of the organophosphate methyl parathion using genetically engineered and native organisms 

    E-Print Network [OSTI]

    Diaz Casas, Adriana Z.

    2005-11-01

    to remediate hazardous substances at significantly higher rates than found with natural systems. Specifically, degradation of methyl parathion (MP) by hydrolysis with a genetically engineered Escherichia coli was investigated along with degradation of one...

  9. A global inventory of ecosystem sources of methyl bromide, an ozone destroying gas 

    E-Print Network [OSTI]

    Fenney, Gareth

    2008-12-11

    Stratospheric ozone depletion is affected by halogen radicals, such as bromine, which is 40 times more effective at depleting ozone than chlorine. Methyl bromide, the largest contributor of bromine to the stratosphere is ...

  10. Temporal and spatial variation in methyl bromide emissions from a salt marsh 

    E-Print Network [OSTI]

    Drewer, Julia; Heal, Mathew R; Heal, Kate V; Smith, Keith A

    2006-01-01

    Methyl bromide (CH3Br) is a trace gas involved in stratospheric ozone depletion with both anthropogenic and natural sources. Estimates of natural source strengths are highly uncertain. In this study, >320 highly temporally ...

  11. Evaluating the sensitivity of hybridization-based epigenotyping using a methyl binding domain protein

    E-Print Network [OSTI]

    Shatova, Tatyana A.

    Hypermethylation of CpG islands in gene promoter regions has been shown to be a predictive biomarker for certain diseases. Most current methods for methylation profiling are not well-suited for clinical analysis. Here, we ...

  12. 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.

  13. 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.

  14. 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.

  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. Identification of methyl violet 2B as a novel blocker of focal adhesion kinase signaling pathway in cancer cells

    SciTech Connect (OSTI)

    Kim, Hwan [Chemical Kinomics Research Center, Korea Institute of Science and Technology, 39-1, Hawolgok-dong, Seongbuk-gu, Seoul 136-791 (Korea, Republic of) [Chemical Kinomics Research Center, Korea Institute of Science and Technology, 39-1, Hawolgok-dong, Seongbuk-gu, Seoul 136-791 (Korea, Republic of); Translational Research Center for Protein Function Control (TRCP), Department of Biotechnology and Department of Biomedical Sciences (WCU Program), Yonsei University, Seodaemun-gu, Seoul 120-752 (Korea, Republic of); Kim, Nam Doo [Daegu-Gyeongbuk Medical Innovation Foundation, 2387 Dalgubeol-daero, Suseong-gu, Daegu 706-010 (Korea, Republic of)] [Daegu-Gyeongbuk Medical Innovation Foundation, 2387 Dalgubeol-daero, Suseong-gu, Daegu 706-010 (Korea, Republic of); Lee, Jiyeon [Chemical Kinomics Research Center, Korea Institute of Science and Technology, 39-1, Hawolgok-dong, Seongbuk-gu, Seoul 136-791 (Korea, Republic of)] [Chemical Kinomics Research Center, Korea Institute of Science and Technology, 39-1, Hawolgok-dong, Seongbuk-gu, Seoul 136-791 (Korea, Republic of); Han, Gyoonhee [Translational Research Center for Protein Function Control (TRCP), Department of Biotechnology and Department of Biomedical Sciences (WCU Program), Yonsei University, Seodaemun-gu, Seoul 120-752 (Korea, Republic of)] [Translational Research Center for Protein Function Control (TRCP), Department of Biotechnology and Department of Biomedical Sciences (WCU Program), Yonsei University, Seodaemun-gu, Seoul 120-752 (Korea, Republic of); Sim, Taebo, E-mail: tbsim@kist.re.kr [Chemical Kinomics Research Center, Korea Institute of Science and Technology, 39-1, Hawolgok-dong, Seongbuk-gu, Seoul 136-791 (Korea, Republic of) [Chemical Kinomics Research Center, Korea Institute of Science and Technology, 39-1, Hawolgok-dong, Seongbuk-gu, Seoul 136-791 (Korea, Republic of); KU-KIST Graduate School of Converging Science and Technology, 145, Anam-ro, Seongbuk-gu, Seoul 136-713 (Korea, Republic of)

    2013-07-26

    Highlights: •FAK signaling cascade in cancer cells is profoundly inhibited by methyl violet 2B. •Methyl violet 2B identified by virtual screening is a novel allosteric FAK inhibitor. •Methyl violet 2B possesses extremely high kinase selectivity. •Methyl violet 2B suppresses strongly the proliferation of cancer cells. •Methyl violet 2B inhibits focal adhesion, invasion and migration of cancer cells. -- Abstract: The focal adhesion kinase (FAK) signaling cascade in cancer cells was profoundly inhibited by methyl violet 2B identified with the structure-based virtual screening. Methyl violet 2B was shown to be a non-competitive inhibitor of full-length FAK enzyme vs. ATP. It turned out that methyl violet 2B possesses extremely high kinase selectivity in biochemical kinase profiling using a large panel of kinases. Anti-proliferative activity measurement against several different cancer cells and Western blot analysis showed that this substance is capable of suppressing significantly the proliferation of cancer cells and is able to strongly block FAK/AKT/MAPK signaling pathways in a dose dependent manner at low nanomolar concentration. Especially, phosphorylation of Tyr925-FAK that is required for full activation of FAK was nearly completely suppressed even with 1 nM of methyl violet 2B in A375P cancer cells. To the best of our knowledge, it has never been reported that methyl violet possesses anti-cancer effects. Moreover, methyl violet 2B significantly inhibited FER kinase phosphorylation that activates FAK in cell. In addition, methyl violet 2B was found to induce cell apoptosis and to exhibit strong inhibitory effects on the focal adhesion, invasion, and migration of A375P cancer cells at low nanomolar concentrations. Taken together, these results show that methyl violet 2B is a novel, potent and selective blocker of FAK signaling cascade, which displays strong anti-proliferative activities against a variety of human cancer cells and suppresses adhesion/migration/invasion of tumor cells.

  17. Acute toxicity of smoke screen materials to aquatic organisms, white phosphorus-felt, red phosphorus-butyl rubber and SGF No. 2 fog oil. Final report

    SciTech Connect (OSTI)

    Poston, T.M.; McFadden, K.M.; Bean, R.M.; Clark, M.L.; Thomas, B.L.; Killand, B.W.; Prohammer, L.A.; Kalkwarf, D.R.

    1986-04-01

    The acute toxicity of three obscurants was determined for nine freshwater organisms. The materials tested were white phosphorus-felt smoke, red phosphorus-butyl rubber (RP-BR) smoke, and smoke generator fuel (SGF) No. 2 fog oil (bulk and vaporized). The chemistry of WP-F and RP-BR smoke in water and the resulting effects on aquatic organisms are similar. Combustion of these two obscurants and their deposition in water leads to the formation of many complex oxy-phosphoric acids. Rates of hydrolysis of these complex products to ortho-phosphate were inconsistent and unpredictable over time. These products acidify water and produce toxic effects after exhausting the buffering capacity of the water. Acute 96 hr tests using Daphnia magna with neutralized and nonneutralized exposure solutions indicated that the presence of unidentified toxic component(s) acted independently of pH. At pH levels of 6.0 to 7.0, phosphorus combustion products precipitated out of solution leading to a bimodal toxic response in extended 96-hr tests with Daphnia magna. Most components of fog oil had low solubility in water. Saturation was apparent at approximately 0.1 to 0.3 mg/L total oil. Vaporization had no demonstrable effect on the chemistry or toxicity of the fog oil. Neither the bulk fog oil nor the vaporized fog oil was acutely toxic to freshwater animals at concentrations less than 10 mg/L total oil. In oil-water mixes in excess of 1.0 mg/L total oil, fog oil quickly separated and floated to the surface. The primary hazard associated with vaporized and bulk fog oil was the physical effect of oil fouling the organisms. Photolysis increased the concentration of water-soluble components of the fog oil. Acute toxicity was demonstrated in oil-water mixes (approx.10 mg/L total oil) of photolyzed bulk and vaporized fog oil. No difference in toxicity was observed between photolyzed and non-photolyzed dilutions of OWM at comparable levels of total oil.

  18. journal homepage: www.elsevier.com/locate/nanoenergy Available online at www.sciencedirect.com

    E-Print Network [OSTI]

    -methyl-N-propylpiperidinium bis(fluorosulfonyl)imide (PIP13-FSI) and N-butyl-N- methylpyrrolidinium bis(fluorosulfonyl)imide (PYR

  19. 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.

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

    SciTech Connect (OSTI)

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

    2012-11-15

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

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

    DOE Patents [OSTI]

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

    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.

  2. 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)

  3. Crystal structures of nitrato-4-bromo-2-[(2-hydroxyethylimino)methyl]phenolatoimidazolecopper and nitrato-4-chloro-2-[(2-Hydroxyethylimino)methyl]phenolatoimidazolecopper

    SciTech Connect (OSTI)

    Chumakov, Yu. M. [Academy of Sciences of Moldova, Institute of Applied Physics (Moldova, Republic of); Tsapkov, V. I., E-mail: vtsapkov@gmail.com [Moldova State University (Moldova, Republic of); Antosyak, B. Ya. [Academy of Sciences of Moldova, Institute of Applied Physics (Moldova, Republic of); Popovschi, L. G. [Moldova State University (Moldova, Republic of); Bocelli, G. [Institute of Materials for Electronics and Magnetism (Italy); Guly, A. P. [Academy of Sciences of Moldova, Institute of Applied Physics (Moldova, Republic of); Palomares-Sanchez, S. A. [Autonomous University of San Luis Potosi (Mexico)

    2012-03-15

    Nitrato-4-bromo-2-[(2-hydroxyethylimino)methyl]phenolatoimidazolecopper and nitrato-4-chloro-2-[(2-hydroxyethylimino)methyl]phenolatoimidazolecopper were synthesized and studied by X-ray diffraction. The crystals are isostructural. The coordination polyhedron of the copper atom can be described as a distorted square pyramid whose basal plane is formed by the phenolic and alcoholic oxygen atoms and the nitrogen atom of the monodeprotonated tridentate azomethine molecule and the imidazole nitrogen atom. The apex of the copper polyhedron is occupied by the oxygen atom of the nitrato group. The complexes are linked together by hydrogen bonds with the participation of the nitrato groups to form a three-dimensional framework.

  4. 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) Å, ? = 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.

  5. 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.

  6. Acid strength and solvation effects on methylation, hydride transfer, and isomerization rates during catalytic homologation of C1 species

    E-Print Network [OSTI]

    Iglesia, Enrique

    Acid strength and solvation effects on methylation, hydride transfer, and isomerization rates,b, a Department of Chemical and Biomolecular Engineering, University of California at Berkeley, USA b Division, FAU, MFI) via methylation and hydride transfer steps that favor isobutane and triptane formation

  7. Ab initio study of styrene and -methyl styrene in the ground and in the two lowest excited singlet states

    E-Print Network [OSTI]

    Haas, Yehuda

    Ab initio study of styrene and -methyl styrene in the ground and in the two lowest excited singlet; accepted 28 March 1995 The structure and vibrational frequencies of styrene and trans- -methyl styrene treating molecules as large as styrene. High resolution fluorescence excitation and resonant en- hanced

  8. Oxidation Kinetics of Pure and Blended Methyl Octanoate/n-Nonane/Methylcyclohexane: Measurements and Modeling of OH*/CH* Chemiluminescence, Ignition Delay Times and Laminar Flame Speeds 

    E-Print Network [OSTI]

    Rotavera, Brandon Michael

    2012-07-16

    trends between methyl octanoate and n-nonane exhibited overlap at temperatures below 1350 K, below which the trends diverged with methyl octanoate having shorter ignition delay times. Similar behavior was observed under fuel-rich conditions, yet...

  9. Methylation patterns and mathematical models reveal dynamics of stem cell turnover in the human colon

    E-Print Network [OSTI]

    renewal while the daughter stem cell remains in the niche; each stem cell is ``immortal'' under this modelCommentary Methylation patterns and mathematical models reveal dynamics of stem cell turnover in diseases such as cancer, it is essential to understand the process of somatic cell development and renewal

  10. Intraindividual Variability in Arsenic Methylation in a U.S. Population

    E-Print Network [OSTI]

    California at Berkeley, University of

    , large interindividual variations exist (18). For example, in a study in Chile, the proportion of urinary intraindividual variation in methylation capacity in 81 subjects with low to moderate arsenic exposures. Multiple (ICC) for the proportion of urinary arsenic as inorganic arsenic, monomethylarsonate

  11. Thermochemistry of radicals formed by hydrogen abstraction from 1-butanol, 2-methyl-1-propanol, and butanal

    E-Print Network [OSTI]

    Truhlar, Donald G

    , and butanal Ewa Papajak, Prasenjit Seal, Xuefei Xu, and Donald G. Truhlar Citation: J. Chem. Phys. 137, 104314 abstraction from 1-butanol, 2-methyl-1-propanol, and butanal Ewa Papajak, Prasenjit Seal, Xuefei Xu- propanol, and butanal. Electronic structure calculations for all conformers of the radicals were car- ried

  12. 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.

  13. Supplemental Data S1 The SRA Methyl-Cytosine-Binding Domain

    E-Print Network [OSTI]

    Jacobsen, Steve

    of 4 CG, 7 CNG, and 33 CNN residues. Ten to twelve independent clones were sequenced, and the average number of methylated CG, CNG, or CNN was deter- mined (see Table S1 for all primer sequences). At AtCOPIA4, there are a total of 25 CG, 18 CNG, and 116 CNN residues. Seven to twelve independent clones were

  14. Partial demethylation of oligogalacturonides by pectin methyl esterase 1 is required for eliciting defence

    E-Print Network [OSTI]

    Málaga, Universidad de

    defence responses in wild strawberry (Fragaria vesca) Sonia Osorio1 , Cristina Castillejo1, , Miguel A methyl esterase FaPE1 in the wild strawberry Fragaria vesca. Pectin from transgenic ripe fruits differed esterification is necessary to elicit defence responses in strawberry. The transgenic F. vesca lines had

  15. Hybrid Energy Cell for Degradation of Methyl Orange by Self-Powered Electrocatalytic Oxidation

    E-Print Network [OSTI]

    Wang, Zhong L.

    -effective, renewable and green energy sources to meet the global energy demands of the future is one of the most urgentHybrid Energy Cell for Degradation of Methyl Orange by Self- Powered Electrocatalytic Oxidation Ya of superoxidative hydroxyl radical on the anode. Here, we report a hybrid energy cell that is used for a self

  16. Solvent Effects on Methyl Transfer Reactions. 2. The Reaction of Amines with Trimethylsulfonium Salts

    E-Print Network [OSTI]

    Sklenak, Stepan

    Solvent Effects on Methyl Transfer Reactions. 2. The Reaction of Amines with Trimethylsulfonium the effect of cyclohexane and dimethyl sulfoxide as the solvent on the energy changes. The effect of water as the solvent was studied using the Monte Carlo free energy perturbation method. The reaction with both ammonia

  17. Steric Effects on Silene Reactivity. The Effects of ortho-Methyl Substituents on the Kinetics and

    E-Print Network [OSTI]

    Leigh, William J.

    , Tamara C. S. Pace, and William J. Leigh* Department of Chemistry, McMaster University, 1280 Main Street,1-diarylsilenes bearing ortho-methyl substituents in various numbers and positions on the aryl rings. The five in systems bearing simple, nonbulky alkyl or aryl substit- uents at one or both atoms of the MdC bond;1 thus

  18. Active transport, substrate specificity, and methylation of Hg(II) in anaerobic bacteria

    SciTech Connect (OSTI)

    Schasfer, Jeffra [Princeton University; Rocks, Sara [Princeton University; Zheng, Wang [ORNL; Liang, Liyuan [ORNL; Gu, Baohua [ORNL; Morel, Francois M [ORNL

    2011-01-01

    The formation of methylmercury (MeHg), which is biomagnified in aquatic food chains and poses a risk to human health, is effected by some iron- and sulfate-reducing bacteria (FeRB and SRB) in anaerobic environments. However, very little is known regarding the mechanism of uptake of inorganic Hg by these organisms, in part because of the inherent difficulty in measuring the intracellular Hg concentration. By using the FeRB Geobacter sulfurreducens and the SRB Desulfovibrio desulfuricans ND132 as model organisms, we demonstrate that Hg(II) uptake occurs by active transport. We also establish that Hg(II) uptake by G. sulfurreducens is highly dependent on the characteristics of the thiols that bind Hg(II) in the external medium, with some thiols promoting uptake and methylation and others inhibiting both. The Hg(II) uptake system of D. desulfuricans has a higher affinity than that of G. sulfurreducens and promotes Hg methylation in the presence of stronger complexing thiols. We observed a tight coupling between Hg methylation and MeHg export from the cell, suggesting that these two processes may serve to avoid the build up and toxicity of cellular Hg. Our results bring up the question of whether cellular Hg uptake is specific for Hg(II) or accidental, occurring via some essential metal importer. Our data also point at Hg(II) complexation by thiols as an important factor controlling Hg methylation in anaerobic environments.

  19. Polymer surface and thin film vibrational dynamics of poly,,methyl methacrylate..., polybutadiene,

    E-Print Network [OSTI]

    Sibener, Steven

    Polymer surface and thin film vibrational dynamics of poly,,methyl methacrylate..., polybutadiene atom scattering has been used to investigate the vibrational dynamics at the polymer vacuum interface polymers. The broad multiphonon feature that arises in the inelastic scattering spectra at surface

  20. Highly Selective Condensation of Biomass-Derived Methyl Ketones as a Source of Aviation Fuel

    E-Print Network [OSTI]

    Toste, Dean

    Highly Selective Condensation of Biomass-Derived Methyl Ketones as a Source of Aviation Fuel Eric R,[b] and Alexis T. Bell*[a] Introduction Aviation fuels must meet a number of stringent specifications, the most by branched and cyclic hydrocar- bons, and, consequently, these types of fuels are not likely to be displaced

  1. Understanding chemical reactions of CO{sub 2} and its isoelectronic molecules with 1-butyl-3-methylimidazolium acetate by changing the nature of the cation: The case of CS{sub 2} in 1-butyl-1-methylpyrrolidinium acetate studied by NMR spectroscopy and density functional theory calculations

    SciTech Connect (OSTI)

    Cabaço, M. Isabel, E-mail: isabelcabaco@ist.utl.pt [Departamento de Física, Instituto Superior Técnico, UTL, Av. Rovisco Pais 1049-001 Lisboa (Portugal); Centro de Física Atómica da UL, Av. Prof. Gama Pinto 2, 1649-003 Lisboa (Portugal); Besnard, Marcel; Danten, Yann [GSM Institut des Sciences Moléculaires, CNRS (UMR 5255), Université de Bordeaux, 351, Cours de la Libération 33405 Talence Cedex (France); Chávez, Fabián Vaca [Centro de Física da Matéria Condensada da UL, Av. Prof. Gama Pinto 2, 1694-003 Lisboa (Portugal); Pinaud, Noël [CESAMO Institut des Sciences Moléculaires, CNRS (UMR 5255), Université de Bordeaux, 351, Cours de la Libération 33405 Talence Cedex (France); Sebastião, Pedro J. [Departamento de Física, Instituto Superior Técnico, UTL, Av. Rovisco Pais 1049-001 Lisboa (Portugal); Centro de Física da Matéria Condensada da UL, Av. Prof. Gama Pinto 2, 1694-003 Lisboa (Portugal); Coutinho, João A. P. [CICECO, Departamento de Química, Universidade de Aveiro 3810-193 Aveiro (Portugal)

    2014-06-28

    NMR spectroscopy ({sup 1}H, {sup 13}C, {sup 15}N) shows that carbon disulfide reacts spontaneously with 1-butyl-1-methylpyrrolidinium acetate ([BmPyrro][Ac]) in the liquid phase. It is found that the acetate anions play an important role in conditioning chemical reactions with CS{sub 2} leading, via coupled complex reactions, to the degradation of this molecule to form thioacetate anion (CH{sub 3}COS{sup ?}), CO{sub 2}, OCS, and trithiocarbonate (CS{sub 3}{sup 2?}). In marked contrast, the cation does not lead to the formation of any adducts allowing to conclude that, at most, its role consists in assisting indirectly these reactions. The choice of the [BmPyrro]{sup +} cation in the present study allows disentangling the role of the anion and the cation in the reactions. As a consequence, the ensemble of results already reported on CS{sub 2}-[Bmim][Ac] (1), OCS-[Bmim][Ac] (2), and CO{sub 2}-[Bmim][Ac] (3) systems can be consistently rationalized. It is argued that in system (1) both anion and cation play a role. The CS{sub 2} reacts with the acetate anion leading to the formation of CH{sub 3}COS{sup ?}, CO{sub 2}, and OCS. After these reactions have proceeded the nascent CO{sub 2} and OCS interact with the cation to form imidazolium-carboxylate ([Bmim] CO{sub 2}) and imidazolium-thiocarboxylate ([Bmim] COS). The same scenario also applies to system (2). In contrast, in the CO{sub 2}-[Bmim] [Ac] system a concerted cooperative process between the cation, the anion, and the CO{sub 2} molecule takes place. A carbene issued from the cation reacts to form the [Bmim] CO{sub 2}, whereas the proton released by the ring interacts with the anion to produce acetic acid. In all these systems, the formation of adduct resulting from the reaction between the solute molecule and the carbene species originating from the cation is expected. However, this species was only observed in systems (2) and (3). The absence of such an adduct in system (1) has been theoretically investigated using DFT calculations. The values of the energetic barrier of the reactions show that the formation of [Bmim] CS{sub 2} is unfavoured and that the anion offers a competitive reactive channel via an oxygen-sulphur exchange mechanism with the solute in systems (1) and (2)

  2. 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.

  3. Soluble, High Molecular Weight Polysilsesquioxanes with Carboxylate Functionalities

    SciTech Connect (OSTI)

    RAHIMIAN,KAMYAR; LOY,DOUGLAS A.; WHEELER,DAVID R.

    2000-07-14

    Trialkoxysilyl-containing monomers of the type (RO){sub 3}Si(CH{sub 2}){sub 3}C(O)OtBu (R = Me, Et) were prepared by hydrosilation of the corresponding vinylic tert-butyl esters CH{sub 3}CHCH{sub 2}C(O)OtBu. Acid- or base-catalyzed polymerization of the monomers leads to very high molecular weight polymers with relatively narrow polydispersities. The polymerization results in complete condensation of the alkoxy groups while the tert-butyl ester functionality remains fully intact. Partial or full deprotection of the tert-butyl group can easily be achieved to yield the corresponding carboxylic acid polymers. The ester and carboxylic acid functionalities of these new materials allow for their potential use in a variety of applications such as scavenging of heavy metals.

  4. Mild and General Palladium-Catalyzed Synthesis of Methyl Aryl Ethers Enabled by the Use of a Palladacycle Precatalyst

    E-Print Network [OSTI]

    Cheung, Chi Wai

    A general method for the Pd-catalyzed coupling of methanol with (hetero)aryl halides is described. The reactions proceed under mild conditions with a wide range of aryl and heteroaryl halides to give methyl aryl ethers in ...

  5. Daphnetin Methylation by a Novel O-Methyltransferase Is Associated with Cold Acclimation and Photosystem II Excitation

    E-Print Network [OSTI]

    Sarhan, Fathey

    , University of Western Ontario, London, Ontario N6A 5B7, Canada In plants, O-methylation of phenolic compounds biosynthesis have been identified. We report here the molecular and biochemical characterization of a gene

  6. Feasibility of reconstructing paleoatmospheric records of selected alkanes, methyl halides, and sulfur gases from Greenland ice cores

    E-Print Network [OSTI]

    Aydin, M.; Williams, M. B; Saltzman, E. S

    2007-01-01

    Hemispheric air. 4.1.3. n-Butane [ 26 ] n-C 4 H 10 levels inH 6 ; propane, C 3 H 8 ; n-butane, n-C 4 H 10 ), two methyl

  7. Experimental investigation of size effect on thermal conductivity for ultra-thin amorphous poly(methyl methacrylate) (PMMA) films 

    E-Print Network [OSTI]

    Kim, Ick Chan

    2009-05-15

    An investigation was conducted to determine whether a “size effect” phenomenon for one particular thermophysical property, thermal conductivity, actually exists for amorphous poly(methyl methacrylate) (PMMA) films with thicknesses ranging from 40 nm...

  8. Infra red spectroscopy, flash pyrolysis, thermally assisted hydrolysis and methylation (THM) in the presence of tetramethylammonium hydroxide

    E-Print Network [OSTI]

    Infra red spectroscopy, flash pyrolysis, thermally assisted hydrolysis and methylation (THM to sporopollenin or algaenan. This is in agreement with flash pyrolysis­gas chromatography­mass spectrometry (py

  9. 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.

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

    SciTech Connect (OSTI)

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

    2012-01-01

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

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

    SciTech Connect (OSTI)

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

    2015-03-01

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

  12. 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.

  13. 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.; O’Leary, 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.

  14. The Regulation of Dendritic Spine Plasticity by EphB and N-methyl-D-aspartate Receptors Through Spatial Control Over Cofilin Activity in Mature Hippocampal Neurons

    E-Print Network [OSTI]

    Pontrello, Crystal G.

    2010-01-01

    Plasticity by EphB and N-methyl-D-aspartate Receptors Through Spatial Control Over Cofilin Activity in Mature Hippocampal Neurons by Crystal

  15. Storage effects on desorption efficiencies of methyl ethyl ketone and styrene collected on activated charcoal 

    E-Print Network [OSTI]

    Dommer, Richard Alvin

    1978-01-01

    STORAGE EFf ECTS ON DESORP'TIC'N EFFICIENCIES OF METHYL ETHYL KF10NE AND STYRENE COLLECTED ON ACTIVATED CHARCOAL A Thesis by RICHARD ALVIN DONiNiER Approved as to style and content by: ( ha1ris a of Coll'Jn1 t tee Nay l978 QQZSGH ABSTRACT... Storage Effects on Desorption Efficiercies of i&lethyl Ethyl Ketone and Styrene Colleci-. ed on Activated Charcoal (liay 1978) Richard A. Dommer, B. S. , Central !'iichigan D&nivers ity Directed by: Dr, Ralph J. Vernon The effects on the desorption...

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

    SciTech Connect (OSTI)

    Trachsel, Maria A.; Lobsiger, Simon; Schär, 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 32 252 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.

  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. 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)

  19. 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.

  20. UNCORRECTEDPROOF Please cite this article in press as: D. Lipkind et al., The vaporization enthalpies and vapor pressures of a series of unsaturated fatty acids methyl

    E-Print Network [OSTI]

    Chickos, James S.

    enthalpies and vapor pressures of a series of unsaturated fatty acids methyl esters by correlation gas­8 Thermochimica Acta xxx (2007) xxx­xxx The vaporization enthalpies and vapor pressures of a series of unsaturated- vonate (methyl Z 15-tetracosenoate) are evaluated at T = 298.15 and vapor pressures are evaluated over

  1. On the Interaction of Methyl Azide (CH3N3) Ices with Ionizing Radiation: Formation of Methanimine (CH2NH), Hydrogen Cyanide (HCN), and Hydrogen Isocyanide (HNC)

    E-Print Network [OSTI]

    Kaiser, Ralf I.

    On the Interaction of Methyl Azide (CH3N3) Ices with Ionizing Radiation: Formation of Methanimine in solar system analogue ices. Introduction Methyl azide (CH3N3) is an organic compound suggested to be present in Titan's atmosphere.1 To date, the Voyager Infrared Radiometer and Infrared Spectrometer (IRIS

  2. Reactions of methyl groups on a non-reducible metal oxide: The reaction of iodomethane on stoichiometric ?-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 ?-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. 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

  3. Current Biology, Vol. 15, 154159, January 26, 2005, 2005 Elsevier Ltd All rights reserved. DOI 10.1016/j.cub.2005.01.008 DNA Methylation Profiling Identifies

    E-Print Network [OSTI]

    Jacobsen, Steve

    Summary the Msp I restriction endonuclease, which cleaves CCGG and is blocked by CNG methylation. We had-typically found in CG, CNG, and asymmetric contexts. ferase. To identify other classes of sites, we have perreplication. Methylation of CNG and asymmetric sites [4­6]. Two methyl-sensitive restriction

  4. High-energy mechanical milling of poly(methyl methacrylate), polyisoprene and poly(ethylene-alt-propylene)

    E-Print Network [OSTI]

    High-energy mechanical milling of poly(methyl methacrylate), polyisoprene and poly November 1999; accepted 5 November 1999 Abstract High-energy mechanical milling has been performed on poly and subsequently narrows with increasing milling time. Solid-state mechanical milling promotes comparable decreases

  5. Transparent Poly(methyl methacrylate)/Single-Walled Carbon Nanotube (PMMA/SWNT) Composite Films with Increased

    E-Print Network [OSTI]

    Harmon, Julie P.

    to conventional polymer composites due to the stronger interac- tions between polymer and filler phases. CarbonTransparent Poly(methyl methacrylate)/Single-Walled Carbon Nanotube (PMMA/SWNT) Composite Films Meyyappan, Timofey G. Gerasimov, and Julie P. Harmon* 1. Introduction Polymer nanocomposites are a novel

  6. Class I Chitinase and -1,3-Glucanase Are Differentially Regulated by Wounding, Methyl Jasmonate, Ethylene, and

    E-Print Network [OSTI]

    Bradford, Kent

    Class I Chitinase and -1,3-Glucanase Are Differentially Regulated by Wounding, Methyl Jasmonate of Vegetable Crops, University of California, Davis, California 95616­8631 Class I chitinase (Chi9) and -1 that class I -1,3-glucanase (EC 3.2.1.39) mRNA accumu- lation, enzyme activity, and protein content in

  7. THE JOURNAL OF CHEMICAL PHYSICS 138, 054301 (2013) Photodissociation dynamics of the methyl perthiyl radical at 248 nm

    E-Print Network [OSTI]

    Neumark, Daniel M.

    2013-01-01

    -phase chemistry and photochemistry of alkyl disulfides, with dimethyl disulfide (DMDS) at the forefront of many investigations.3­17 Depending on the wave- length used, the competing dissociation pathways for DMDS observed both the methyl perthiyl radical and S2 fragments from the 193 nm photodis- sociation of DMDS

  8. Analysis of 14-3-3? methylation and associated changes in gene expression and function in colorectal carcinoma 

    E-Print Network [OSTI]

    Roberts, Kirsty Anne

    2010-01-01

    that overexpression of 14-3-3? in SW480 cells (14-3-3? methylated) delayed the apoptotic response to UV-C, compared to control SW480 cells. This suggests that 14-3-3? may protect colorectal cancer cells from apoptosis. MTT assays showed that overexpression of 14-3-3?...

  9. Simultaneous optimization and heat integration for the co-production of diesel substitutes

    E-Print Network [OSTI]

    Grossmann, Ignacio E.

    consumption of the resulting process. The production of glycerol ethers increases the yield of diesel1 Simultaneous optimization and heat integration for the co-production of diesel substitutes the integration of the etherification of glycerol for the production of tert butyl glycerol with the production

  10. Rev. Date: June 6, 2013 1 Particularly Hazardous Substances Class SOP Chemical Class Standard Operating Procedures

    E-Print Network [OSTI]

    Cohen, Ronald C.

    -Butadiene diepoxide 2. Synthesis of di-hydroxyl di-nitrate from 1,3-butadiene diepoxide. Chemical(s) Use(s) Isoprene 1. Making 5 ppm isoprene gas mixture in N2 1,3. Used as an NMR solvent pyrromethene 597 (2,6-di-tert- butyl-8-nonyl-1,3

  11. Appendix: Bibliography of Technical Reports of the National Cancer Institute/ National Toxicology Program

    E-Print Network [OSTI]

    Gold, Lois Swirsky

    95 108 1978 1,3-Butadiene 288 1984 1,3-Butadiene 434 1993 2-Butoxyethanol 484 2000 tert-Butyl alcohol(bromomethyl)-1,3-propanediol 452 1996 Bis(2-chloro-1-methylethyl) ether 191 1979 #12;--2-- Bis(2-chloro-1

  12. J.Org. Chem. 1991,56,4435-4439 4435 themally equilibrated reaction solutioncontained in the cwette

    E-Print Network [OSTI]

    Collum, David B.

    constant with potasaium chloride (I = 1.0M), had their pHs adjusted with HC1and sodium acetate (1X l0-l, W. E.J. Chem. Educ. 1966,42,96. On the Structure and Reactivity of Lithium Diisopropylamide (LDA-1301 Received January 9, 1991 Enolizations of ketones, tert-butyl esters, and carboxamidesby solventfree lithium

  13. Heterogeneous Catalysis DOI: 10.1002/anie.200503898

    E-Print Network [OSTI]

    Iglesia, Enrique

    , as in the reactions of isobutane on sulfated zirconia[14] and tert-butyl alcohol[5,7,8] on acidic ZSM5, MOR, BEA of Chemical Engineering University of California at Berkeley Berkeley, CA 94720 (USA) Fax: (+1)510-642-4778 E

  14. 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.

  15. 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.

  16. 3-Methyl-1,2-BN-Cyclopentane: A Promising H2 Storage Material?

    SciTech Connect (OSTI)

    Luo, Wei; Neiner, Doinita; Karkamkar, Abhijeet J.; Parab, Kshitij; Garner, Edward B.; Dixon, David A.; Matson, Dean W.; Autrey, Thomas; Liu, Shih-Yuan

    2013-01-21

    We provide detailed characterization of properties for 3-methyl-1,2-BN-cyclopentane 1 that are relevant to H2 storage applications such as viscosity, thermal stability, H2 gas stream purity, and polarity. The viscosity of 1 at room temperature is 25±5 cP, about one fourth the viscosity of olive oil. TGA/MS analysis indicates that liquid carrier 1 is thermally stable at 30 °C but decomposes slowly at 50 °C. RGA data suggest that the H2 desorption from 1 is a clean process, producing relatively pure H2 gas. Compound 1 is a polar zwitterionic type liquid consistent with theoretical predictions and solvatochromic studies. "T.A. acknowledges support from the Fuel Cell Technology Program at U.S. DOE, Office of Energy Efficiency 65 and Renewable Energy. Pacific Northwest National Laboratory is operated by Battelle."

  17. 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.

  18. 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.

  19. 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.

  20. 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.

  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. Crystallization of iysozyme 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

  3. 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

  4. 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.

  5. Conductive methyl blue-functionalized reduced graphene oxide with excellent stability and solubility in water

    SciTech Connect (OSTI)

    Cai, Xiang [Department of Chemistry, Jinan University, Guangzhou 510632 (China)] [Department of Chemistry, Jinan University, Guangzhou 510632 (China); Tan, Shaozao, E-mail: shaozao@tom.com [Department of Chemistry, Jinan University, Guangzhou 510632 (China)] [Department of Chemistry, Jinan University, Guangzhou 510632 (China); Xie, Agui; Lin, Minsong; Liu, Yingliang [Department of Chemistry, Jinan University, Guangzhou 510632 (China)] [Department of Chemistry, Jinan University, Guangzhou 510632 (China); Zhang, Xiuju; Lin, Zhidan [Department of Material Science and Engineering, Jinan University, Guangzhou 510632 (China)] [Department of Material Science and Engineering, Jinan University, Guangzhou 510632 (China); Wu, Ting [Department of Chemistry, Jinan University, Guangzhou 510632 (China)] [Department of Chemistry, Jinan University, Guangzhou 510632 (China); Mai, Wenjie, E-mail: wenjiemai@gmail.com [Department of Physics, Jinan University, Guangzhou 510632 (China)] [Department of Physics, Jinan University, Guangzhou 510632 (China)

    2011-12-15

    Graphical abstract: MB-rGO was synthesized by making use of {pi} stacking and water-solubility of MB to assist the hydrazine mediated reduction of graphene oxide (GO) in aqueous solution. The resulting MB-rGO shows excellent solubility and stability in aqueous solution, and the electrical conductivity of MB-rGO is almost two orders of magnitude larger than that of GO. Highlights: Black-Right-Pointing-Pointer Methyl blue (MB) stacks onto the plane of reduced graphene oxide (rGO) by strong {pi}-{pi} interactions. Black-Right-Pointing-Pointer Sulfo groups of MB prevent rGO from aggregating by electrostatic and steric repulsions. Black-Right-Pointing-Pointer MB-functionalized rGO (MB-rGO) shows excellent solubility and stability in aqueous solution. Black-Right-Pointing-Pointer Electrical conductivity of MB-rGO is almost two orders of magnitude larger than that of GO. -- Abstract: {pi} stacking and water-solubility of methyl blue (MB) are expected to facilitate the hydrazine mediated reduction of graphene oxide (GO) in aqueous environment. Our newly obtained MB-functionalized reduced graphene oxide (MB-rGO) exhibited excellent solubility and stability in water. The results showed that the MB molecules stacked non-covalently onto the basal plane of rGO while the sulfo groups of MB prevented the rGO from aggregation. In addition, the better electrical conductivity of MB-rGO than that of GO was analyzed. This novel conductive MB-rGO should have promising applications in diverse nanotechnological areas, such as electronic and optoelectronic devices, photovoltaics, sensors, and microfabrication.

  6. Composition and method for encapsulating photovoltaic devices

    DOE Patents [OSTI]

    Pern, Fu-Jann (Golden, CO)

    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.

  7. LANXESS Global Butyl Rubber Research Facility

    E-Print Network [OSTI]

    Denham, Graham

    or improve existing petrochemical products. They're then used for plastics, fragrance and cosmetics," Hartmann said.BioAmber's process is cheaper than conventional petroleum-based routes, he said. It

  8. 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)

  9. Evaluation of the Thermophysical Properties of Poly(MethylMethacrylate): A Reference Material for the Development of a flammability Test for Micro-Gravity Environments 

    E-Print Network [OSTI]

    Steinhaus, Thomas

    1999-01-01

    A study has been conducted using PMMA (Poly(methyl methacrylate)) as a reference material in the development process of the Forced Flow and flame Spread Test (FIST). This test attempts to establish different criteria for ...

  10. 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 air–n-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.

  11. 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).

  12. 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 amore »new 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

  13. 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

    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 archaeon Haloferax volcanii as a model. Indicative of phosphorylation, phosphatase-sensitive isoforms of ? 1 and ? 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). Usingmore »this approach, several phosphosites were mapped including ? 1 Thr147, ? 2 Thr13/Ser14 and PAN-A Ser340. Multiple methylation sites were also mapped to ? 1 , thus, revealing a new type of proteasomal modification. Probing the biological role of ? 1 and PAN-A phosphorylation by site-directed mutagenesis revealed dominant negative phenotypes for cell viability and/or pigmentation for ? 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 ? 1 . The ? 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

  14. 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.

  15. 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.

  16. 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.

  17. Dissolution of monoaromatic hydrocarbons into groundwater from gasoline-oxygenate mixtures

    SciTech Connect (OSTI)

    Poulsen, M.; Lemon, L.; Barker, J.F. (Univ. of Waterloo, Ontario (Canada))

    1992-12-01

    The effects of the [open quotes]oxygenate[close quotes] additives methanol and methyl tert-butyl ether (MTBE) on the aqueous solubility of benzene, toluene, ethylbenzene, and xylenes (BTEX) from gasoline were evaluated through equilibrium batch experiments. For a gasoline:water ratio of 1:10 (v/v), up to 15% MTBE or up to 85% methanol in gasoline produced no enhanced BTEX solubility. However, at higher gasoline:water ratios, aqueous methanol concentrations above 10% enhanced BTEX solubility. The initial methanol content of the gasoline and the equilibrating gasoline- to water-phase ratio controlled the aqueous methanol concentration. Partitioning theory and the experimental results were used to calculate aqueous benzene and methanol concentrations in successive batches of fresh groundwater equilibrating with the fuel and subsequent residuals. These successive batches simulated formation of a plume of contaminated groundwater. The front of the plume generated from high-methanol gasoline equilibrating with groundwater at a gasoline:water ratio of more than 1 had high methanol content and elevated BTEX concentrations. Thus, release of high-methanol fuels could have a more serious, initial impact on groundwater than do releases of methanol-free gasoline. 22 refs., 4 figs., 3 tabs.

  18. 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.

    2015-07-29

    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. 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

  19. 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. [East China University of Chemical Technology, Shanghai (China)

    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.

  20. 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.

  1. Crystal structures of bis-ligand complexes of copper(II) with 2-[(2-hydroxyethylamino)-methyl]-4,6-dinitrophenol, 2,4-dichloro-6-[(2-hydroxyethylamino)-methyl]phenol, and 2,4-dibromo-6-[(2-hydroxyethylamino)-methyl]phenol

    SciTech Connect (OSTI)

    Chumakov, Yu. M. [Academy of Sciences of Moldova, Institute of Applied Physics (Moldova, Republic of)], E-mail: chumakov.xray@phys.asm.md; Tsapkov, V. I. [State University of Moldova (Moldova, Republic of); Bocelli, G. [National Research Council (IMEM-CNR), Institute of Materials for Electronics and Magnetism (Italy); Palomares-Sanchez, S. A.; Ortiz, R. S. [Universidad Autonoma de San Luis Potosi, Facultad de Ciencias (Mexico); Gulea, A. P. [State University of Moldova (Moldova, Republic of)

    2007-02-15

    The crystal structures of bis{l_brace}2,4-dibromo-6-[(2-hydroxyethylamino)-methyl]phenolato{r_brace}copper (I), bis{l_brace}2,4-dichloro-6-[(2-hydroxyethylamino)-methyl]phenolato{r_brace}copper (II), and bis{l_brace}2-[(2-hydroxyethylamino)-methyl]-4,6-dinitrophenolato{r_brace}copper (III) in which the metal atom is located at the center of symmetry are determined using X-ray diffraction. Crystals of compounds I and II are isostructural. The copper atom in the structures of compounds I and I coordinates two singly deprotonated bidentate molecules of the ligand through the phenol oxygen atoms and the azomethine nitrogen atoms with the formation of a distorted planar square. In the crystals, complexes I and II form one-dimensional infinite chains along the b axis. In the structure of compound III, the coordination polyhedron of the central atom is an elongated tetragonal bipyramid with the base formed by the azomethine nitrogen atoms and the phenol oxygen atoms. Both vertices of the bipyramid are occupied by the oxygen atoms of the amino alcohol groups of the neighboring complexes, which are related to the initial complex through the center of symmetry. In turn, the oxygen atoms of the alcohol groups of the initial complex are located at the vertices of the coordination bipyramids of the metal atoms of the neighboring centrosymmetric complexes, thus forming infinite polymer chains along the a axis.

  2. 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.

  3. Labdanolic acid methyl ester (LAME) exerts anti-inflammatory effects through inhibition of TAK-1 activation

    SciTech Connect (OSTI)

    Cuadrado, Irene [Departamento de Farmacología, Facultad de Farmacia, Universidad Complutense, Plaza Ramón y Cajal s/n, 28040 Madrid (Spain)] [Departamento de Farmacología, Facultad de Farmacia, Universidad Complutense, Plaza Ramón y Cajal s/n, 28040 Madrid (Spain); Cidre, Florencia; Herranz, Sandra [Unidad de Inflamación y Cáncer. Área de Biología Celular y Desarrollo. Centro Nacional de Microbiología, Instituto de Salud Carlos III, Madrid (Spain)] [Unidad de Inflamación y Cáncer. Área de Biología Celular y Desarrollo. Centro Nacional de Microbiología, Instituto de Salud Carlos III, Madrid (Spain); Estevez-Braun, Ana [Instituto Universitario de Bio-Orgánica “Antonio González”. Universidad de La Laguna. Avda. Astrofísico Fco. Sánchez 2. 38206. La Laguna, Tenerife (Spain) [Instituto Universitario de Bio-Orgánica “Antonio González”. Universidad de La Laguna. Avda. Astrofísico Fco. Sánchez 2. 38206. La Laguna, Tenerife (Spain); Instituto Canario de Investigaciones del Cáncer (ICIC) (Spain); Heras, Beatriz de las, E-mail: lasheras@farm.ucm.es [Departamento de Farmacología, Facultad de Farmacia, Universidad Complutense, Plaza Ramón y Cajal s/n, 28040 Madrid (Spain); Hortelano, Sonsoles, E-mail: shortelano@isciii.es [Unidad de Inflamación y Cáncer. Área de Biología Celular y Desarrollo. Centro Nacional de Microbiología, Instituto de Salud Carlos III, Madrid (Spain)] [Unidad de Inflamación y Cáncer. Área de Biología Celular y Desarrollo. Centro Nacional de Microbiología, Instituto de Salud Carlos III, Madrid (Spain)

    2012-01-01

    Labdane derivatives obtained from the diterpenoid labdanediol suppressed NO and PGE{sub 2} production in LPS-stimulated RAW 264.7 macrophages. However, mechanisms involved in these inhibitory effects are not elucidated. In this study, we investigated the signaling pathways involved in the anti-inflammatory effects of labdanolic acid methyl ester (LAME) in peritoneal macrophages and examined its therapeutic effect in a mouse endotoxic shock model. LAME reduced the production of NO and PGE{sub 2} in LPS-activated macrophages. This effect involved the inhibition of NOS-2 and COX-2 gene expression, acting at the transcription level. Examination of the effects of the diterpene on NF-?B signaling showed that LAME inhibits the phosphorylation of I?B? and I?B?, preventing their degradation and the nuclear translocation of the NF-?B p65 subunit. Moreover, inhibition of MAPK signaling was also observed. A further experiment revealed that LAME inhibited the phosphorylation of transforming growth factor-? (TGF-?)-activated kinase 1 (TAK1), an upstream signaling molecule required for IKK and mitogen-activated protein kinases (MAPKs) activation. Inflammatory cytokines such as IL-6, TNF-? and IP-10 were downregulated in the presence of this compound after stimulation with LPS. Additionally, LAME also improved survival in a mouse model of endotoxemia and reduced the circulatory levels of cytokines (IL-6, TNF-?). In conclusion, these results indicate that labdane diterpene LAME significantly attenuates the pro-inflammatory response induced by LPS both in vivo and in vitro. Highlights: ? LAME reduced the production of NO and PGE{sub 2} in LPS-activated macrophages. ? IL-6, TNF-? and IP-10 were also inhibited by LAME. ? Inhibition of TAK-1 activation is the mechanism involved in this process. ? LAME improved survival in a mouse model of endotoxemia. ? LAME reduced the circulatory levels of cytokines (IL-6, TNF-?).

  4. 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.'

  5. 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.

  6. 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 1275–1935 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 0.8–1.6, 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.

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

    DOE Patents [OSTI]

    Martinez, Rodolfo A. (Santa Fe, NM); Alvarez, Marc A. (Santa Fe, NM); Silks, III, Louis A. (Los Alamos, NM); Unkefer, Clifford J. (Los Alamos, NM); Schmidt, Jurgen G. (Los Alamos, NM)

    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.

  8. Determination of optimal conditions for obtaining 1,3-dimethoxy-1-phenyl-propane by addition of methylal to styrene

    SciTech Connect (OSTI)

    Brudnik, I.M.; Akhmatdinov, R.T.; Kantor, E.A.; Rakhmankulov, D.L.

    1988-02-10

    The reaction of styrene with methylal was investigated in order to reveal the regularities of the reaction and determine the conditions for obtaining acceptable yields of 1,3-dimethoxy-1-phenylpropane. Earlier, boron trifluoride was recommended as catalyst of the reaction. However, the necessity of working at low temperatures or under pressure makes this catalyst inconvenient for quantitative syntheses. The primary task of the investigation was determination of the possibility of using some other acidic catalysts, particularly sulfuric acid, para toluenesulfonic acid monohydrate, KU-2 cation-exchanger, zinc chloride, and boron trifluoride etherate. The most effective and selective of the investigated catalysts is boron trifluoride etherate.

  9. Polymorphism of inflammatory genes and arsenic methylation capacity are associated with urothelial carcinoma

    SciTech Connect (OSTI)

    Wu, Chia-Chang [School of Public Health, College of Public Health and Nutrition, Taipei Medical University, Taipei, Taiwan (China); Department of Urology, Taipei Medical University—Shuang Ho Hospital, Taipei, Taiwan (China); Huang, Yung-Kai [School of Oral Hygiene, College of Oral Medicine, Taipei Medical University, Taipei, Taiwan (China); Chung, Chi-Jung [Department of Health Risk Management, College of Public Health, China Medical University and Hospital, Taichung, Taiwan (China); Department of Medical Research, China Medical University Hospital, Taichung, Taiwan (China); Huang, Chao-Yuan; Pu, Yeong-Shiau [Department of Urology, National Taiwan University Hospital, College of Medicine National Taiwan University, Taipei, Taiwan (China); Shiue, Horng-Sheng [Department of Chinese Medicine, Chang Gung Memorial Hospital, Taipei, Taiwan (China); Lai, Li-An [School of Public Health, College of Public Health and Nutrition, Taipei Medical University, Taipei, Taiwan (China); Lin, Ying-Chin [Department of Family Medicine, Shung Ho Hospital, Taipei Medical University, Taipei, Taiwan (China); Department of Health Examination, Wan Fang Hospital, Taipei Medical University, Taipei, Taiwan (China); Su, Chien-Tien [Department of Family Medicine, Taipei Medical University Hospital, Taipei, Taiwan (China); Hsueh, Yu-Mei, E-mail: ymhsueh@tmu.edu.tw [School of Public Health, College of Public Health and Nutrition, Taipei Medical University, Taipei, Taiwan (China); Department of Public Health, School of Medicine, College of Medicine, Taipei Medical University, Taipei, Taiwan (China)

    2013-10-01

    Chronic exposure to arsenic can generate reactive oxidative species, which can induce certain proinflammatory cytokines such as tumor necrosis factor-alpha (TNF-?), interleukin-6 (IL-6) and interleukin-8 (IL-8). TNF-?, IL-6 and IL-8 have been shown to be involved in the development and progression of various cancers, including bladder cancer. This study aimed to investigate the joint effect of the polymorphism of TNF-? ? 308 G/A, IL-6 ? 174 G/C, IL-8 ? 251 T/A and urinary arsenic profiles on urothelial carcinoma (UC) risk. This study evaluated 300 pathologically-confirmed cases of UC and 594 cancer-free controls. Urinary arsenic species were detected using high-performance liquid chromatography-linked hydride generator and atomic absorption spectrometry. The polymorphism of TNF-? ? 308 G/A, IL-6 ? 174 G/C and IL-8 ? 251 T/A was determined using polymerase chain reaction-restriction fragment length polymorphism. The joint effects on UC risk were estimated by odds ratios and 95% confidence intervals using unconditional logistic regression. We found that the TNF-? ? 308 A/A and IL-8 ? 251 T/T polymorphisms were significantly associated with UC. Moreover, significant dose–response joint effect of TNF-? ? 308 A/A or IL-8 ? 251 T/T genotypes and arsenic methylation indices were seen to affect UC risk. The present results also showed a significant increase in UC risk in subjects with the IL-8 ? 251 T/T genotype for each SD increase in urinary total arsenic and MMA%. In contrast, a significant decrease in UC risk was found in subjects who carried the IL-8 ? 251 T/T genotype for each SD increase in DMA%. - Highlights: • Joint effect of the TNF-? -308 A/A genotype and urinary total arsenic affected UC. • Joint effect of the IL-8 -251 T/T genotype and urinary total arsenic affected UC. • Urinary total arsenic level, TNF-? -308 A/A and IL-8 -251 T/T genotype affected UC.

  10. The flow of liquid PDMS (10:1 v/v base to cross-linker ratio) in open, rectangular silicon micro channels, with and without a hexa-methyl-di-silazane (HMDS) or poly-tetra-fluoro-ethylene (PTFE) (120 nm) coat,

    E-Print Network [OSTI]

    channels, with and without a hexa-methyl-di-silazane (HMDS) or poly-tetra-fluoro-ethylene (PTFE) (120 nm

  11. Theoretical Study of Chain Transfer to Solvent Reactions of Alkyl Nazanin Moghadam,

    E-Print Network [OSTI]

    Rappe, Andrew M.

    to the oxygen atom in n-butanol, from the methylene group in MEK, and from a methyl group in p-xylene by a live(d,p), 6-311G(d), and 6-311G(d,p)) is investigated. Among n-butanol, sec-butanol, and tert- butanol, tert of chain transfer to n-butanol reactions compared to those of chain transfer to MEK and p-xylene reactions

  12. TpPtMe(H)2: Why Is There H/D Scrambling of the Methyl Group but Not Methane Loss?

    E-Print Network [OSTI]

    Keinan, Ehud

    TpPtMe(H)2: Why Is There H/D Scrambling of the Methyl Group but Not Methane Loss? Mark A. Iron, H ) hydrido-tris(pyrazolyl)borate) was investigated. This complex is remarkably resistant to methane loss; heating it in methanol at 55 °C does not lead to either methane or hydrogen loss. When CD3OD is used

  13. Statistical thermodynamics of 1-butanol, 2-methyl-1-propanol, and butanal Prasenjit Seal, Ewa Papajak, Tao Yu, and Donald G. Truhlar

    E-Print Network [OSTI]

    Truhlar, Donald G

    Statistical thermodynamics of 1-butanol, 2-methyl-1-propanol, and butanal Prasenjit Seal, Ewa-body decomposition of ethanedial, propanal, propenal, n-butane, 1-butene, and 1,3-butadiene J. Chem. Phys. 136, and butanal Prasenjit Seal, Ewa Papajak, Tao Yu, and Donald G. Truhlara) Department of Chemistry

  14. 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.

  15. Excited State Processes of 2-Butylamino-6-methyl-4-nitropyridine N-oxide in Nonpolar Solvents. A Transient Absorption Spectroscopy Study

    E-Print Network [OSTI]

    van Stokkum, Ivo

    Excited State Processes of 2-Butylamino-6-methyl-4-nitropyridine N-oxide in Nonpolar Solvents undergo fast excited-state intramolecular proton transfer (ESIPT). In a nonpolar solvent such as n­6. A strong solvent dependency of the emission spectra of 2B6M was observed. Poo´r et al. noted a Stokes

  16. The SO++S1transition of Pans-p-methyl styrene W. Drescher, S. Kendler, S. Zilberg, E. Zingher, H. Zuckermann, and Y. Haas

    E-Print Network [OSTI]

    Haas, Yehuda

    NOTES The SO++S1transition of Pans-p-methyl styrene W. Drescher, S. Kendler, S. Zilberg, E. Zingher August 1994) The Sa++S' transition of styrene and its derivatives has been extensively discussed applied to the ground state of styrene.`-12 According to these calculations and contrary to experimental

  17. Long-term high frequency measurements of ethane, benzene and methyl chloride at Ragged Point, Barbados: Identification of long-range transport events.

    E-Print Network [OSTI]

    Archibald, A. T.; Witham, C. S.; Ashfold, M. J.; Manning, A. J.; O'Doherty, S.; Greally, B. R.; Young, D.; Shallcross, D. E.

    2015-01-01

    Here we present high frequency long-term observations of ethane, benzene and methyl chloride from the AGAGE Ragged Point, Barbados, monitoring station made using a custom built GC-MS system. Our analysis focuses on the first three years of data...

  18. (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.

  19. 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.

  20. 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.

  1. Synthetic Metals 162 (2012) 352355 Contents lists available at SciVerse ScienceDirect

    E-Print Network [OSTI]

    Demir, Hilmi Volkan

    2012-01-01

    ,4-dihydro-2H-pyrazol-3-yl)-phenol (HPhP)/3,6-Di(9-carbazolyl)-9-(2- ethylhexyl) carbazole (TCz1)/Ca degradation of electroluminescent structure [14,15]. It was also reported [15] that the use of 2,6-di-tert.-butyl-4-(2,5-diphenyl-3,4-dihydro-2H- pyrazol-3-yl)-phenol (HPhP) (Fig. 1 (left)) as a hole-t

  2. J. Am. Chem. SOC.1988, 110, 3829-3835 3829 between I3CCP/MAS spectra of amorphous starches and V-type

    E-Print Network [OSTI]

    Smith, Bradley D.

    -ethyl-, 2-n-propyl-, 2-isopropyl-, 2-tert-butyl-, 2-(methoxymethyl), 3,5-dimethyl-,3,5-dimethyl-4-methoxy-,4-chloro-3,5-dimethyI-, 3,5-diethyl-, and 3,5-dimethoxyphenolates in solution in weakly polar-') are found for 2 dimer *tetramer: lithium 4-bromophenolate (THF), 4.4 f 0.5,24 & 2; 3,5-dimethylphenolate

  3. 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.

  4. -1 -Supporting information belonging to the paper entitled

    E-Print Network [OSTI]

    Hofstad, Remco van der

    ) and simulated (bottom) MALDI-ToF-MS spectrum of: Figure S3. Copolymer of styrene/methyl acrylate. 12 Figure S4. Copolymer of styrene/ethyl acrylate. 12 Figure S5. Copolymer of styrene/butyl acrylate. 13 Figure S6. Copolymer of styrene/methyl methacrylate. 13 Figure S7. Copolymer of styrene/ethyl methacrylate. 14 Figure S

  5. 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, Montréal, Québec, Canada H3T 1E2 (Canada) [Lady Davis Institute for Medical Research, Jewish General Hospital, 3755 chemin Cote Ste Catherine, Montréal, Québec, Canada H3T 1E2 (Canada); Division of Experimental Medicine, Department of Medicine, McGill University, 850 Sherbrooke Street, Montréal, Québec, 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, Montréal, Québec, Canada H3T 1E2 (Canada)] [Lady Davis Institute for Medical Research, Jewish General Hospital, 3755 chemin Cote Ste Catherine, Montréal, Québec, 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, Montréal, Québec, Canada H3T 1E2 (Canada) [Lady Davis Institute for Medical Research, Jewish General Hospital, 3755 chemin Cote Ste Catherine, Montréal, Québec, Canada H3T 1E2 (Canada); Division of Experimental Medicine, Department of Medicine, McGill University, 850 Sherbrooke Street, Montréal, Québec, Canada H3A 1A2 (Canada); Sebag, Igal A., E-mail: igal.sebag@mcgill.ca [Division of Cardiology, Jewish General Hospital, 3755 chemin Cote Ste Catherine, Montréal, Québec, 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 11.5–14.5. 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.

  6. 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.

  7. 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.

  8. Sol–gel 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 sol–gel 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 sol–gel 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 10–400 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 Stoner–Wohlfarth model.

  9. 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 (SH–NH2) 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 P–S containing pesticides and provides a promising strategy to construct a robust biosensor.

  10. 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 ?-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

  11. Facile synthesis of graphene by pyrolysis of poly(methyl methacrylate) on nickel particles in the confined microzones

    SciTech Connect (OSTI)

    Hong, Ningning [State Key Laboratory of Fire Science, University of Science and Technology of China, Hefei, Anhui 230026 (China)] [State Key Laboratory of Fire Science, University of Science and Technology of China, Hefei, Anhui 230026 (China); Yang, Wei [State Key Laboratory of Fire Science, University of Science and Technology of China, Hefei, Anhui 230026 (China) [State Key Laboratory of Fire Science, University of Science and Technology of China, Hefei, Anhui 230026 (China); Suzhou Key Laboratory of Urban Public Safety, Suzhou Institute of University of Science and Technology of China, Suzhou, Jiangsu, 215123 (China); Bao, Chenlu; Jiang, Saihua; Song, Lei [State Key Laboratory of Fire Science, University of Science and Technology of China, Hefei, Anhui 230026 (China)] [State Key Laboratory of Fire Science, University of Science and Technology of China, Hefei, Anhui 230026 (China); Hu, Yuan, E-mail: yuanhu@ustc.edu.cn [State Key Laboratory of Fire Science, University of Science and Technology of China, Hefei, Anhui 230026 (China) [State Key Laboratory of Fire Science, University of Science and Technology of China, Hefei, Anhui 230026 (China); Suzhou Key Laboratory of Urban Public Safety, Suzhou Institute of University of Science and Technology of China, Suzhou, Jiangsu, 215123 (China)

    2012-12-15

    Graphical abstract: Display Omitted Highlights: ? The GNWs with few defects were synthesized by pyrolyzing PMMA on nickel particles. ? PMMA as carbon source was easily prepared and safe to handle. ? Nickel microparticles were directly used as catalysts without any pre-treatment. ? The method can be used for the low cost and bulk production of graphene. -- Abstract: In this work, multi-layer graphene has been prepared by pyrolyzing poly(methyl methacrylate) (PMMA) on nickel microparticles in the confined microzones formed by organophilic montmorillonite (OMT). Gram-scale of product can be obtained per day by using this method. The obtained graphene was evaluated by scanning and transmission electron microscopy, X-ray diffraction, Raman spectroscopy, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy and thermogravimetric analysis. Pyrolytic conditions such as the system composition of the composites, reaction temperature and the size of catalyst are important parameters affecting the morphology and yield of the final product. Based on the experimental observations and reported literatures, a possible formation process is discussed. The synthesis method of graphene is simple, low-cost, and scalable, which is promising for the application in many fields.

  12. Durability testing of a diesel fuel, methyl tallowate, and ethanol blend in a Cummins N14-410 diesel engine

    SciTech Connect (OSTI)

    Ali, Y.; Hanna, M.A. [Univ. of Nebraska, Lincoln, NE (United States)

    1996-05-01

    A Cummins N14-410 diesel engine was operated on an 80:13:7% (v/v) blend of diesel fuel: methyl tallowate: ethanol. The standard 200-h Engine Manufacturers Association (EMA) test procedure was followed to test engine durability. Engine performance was evaluated in terms of power produced at rated speed, peak torque produced at a speed of 1200 rpm, and brake specific fuel consumption at both speeds. Engine exhaust emissions analyses were performed, and the engine oil was analyzed for accumulation of heavy metals at 45 h intervals. It was observed that engine performance was satisfactory for 148 h at which time the injector in cylinder 2 failed. The injector was changed, and after an additional 11 h (159 h total) of operation the injector in cylinder 5 failed. That injector was also replaced, and the 200-h procedure was continued. The test was discontinued after 197 h when the supply of the fuel blend was exhausted. The injectors were removed and the injector in cylinder 1 was observed to be coked. This injector was sent to the Cummins Engine Co. for analysis. It was found that failure of this injector was not because of the fuel used, but because of a crack had developed across the tip due to an excessively tight overhead adjustment. Engine oil analyses performed for accumulation of wear metals did not reveal any excessive wear on the engine parts. 12 refs., 4 figs., 3 tabs.

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

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

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

    2011-01-01

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

  14. Isomerization of xylene and methylation of toluene on zeolite H-ZSM-5 compound kinetics and selectivity

    SciTech Connect (OSTI)

    Beschmann, K; Riekert, L. (Institute fuer Chemische Verfahrenstechnik der Universitaet Karlsruhe (Germany))

    1993-06-01

    The alkylation of toluene with methanol and the isomerization of xylene were investigated separately and in detail on zeolite H-ZSM-5 as catalyst. The influence of crystal size alone on rates and product distributions was studied for two Si/Al ratios in the zeolite at 573 and 723 K in a gradientless batch-reactor. The isomer distribution in the xylene resulting from toluene methylation is constant from zero up to at least 50% conversion of the methanol in a stoichiometric mixture, H-ZSM-5 being always para-selective. para-Xylene prevails increasingly in the products when either crystal size, temperature, or Al content in the zeolite increase; essentially pure p-xylene can be obtained in the limit with unmodified H-ZSM-5 as catalyst. The rate of isomerization of xylene alone to an equilibrium mixture of isomers was found to be roughly proportional to the extent of the (external) surface of the zeolite crystals, the ratios of the rates of different reactions in the triangular scheme of isomerization being nearly independent of crystal size. The observations can be understood as resulting from the interaction of reaction an diffusion in the volume of the crystals. 34 refs., 11 figs., 4 tabs.

  15. 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 2–10 ?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}.

  16. Infrared spectra of methyl-, and nitrogen-modified void coronene; modeling a carrier of interstellar polycyclic aromatic hydrocarbon

    E-Print Network [OSTI]

    Ota, Norio

    2015-01-01

    Void induced coronene C23H12++ was suggested to be a possible carrier of the astronomically observed polycyclic aromatic hydrocarbon (PAH), which shows unique molecular structure with carbon two pentagons connected with five hexagons. Well observed astronomical infrared spectrum from 3-15 micron could be almost reproduced based on density functional theory. However, there remain several discrepancies with observed spectra, especially on 11-15 micron band weaker intensity. Observed 11.2 micron intensity is comparable to 7.6-7.8 micron one. Methyl-modified molecule C24H14++ revealed that calculated peak height of 11.4 micron show fairly large intensity up to 70-90% compared with that of 7.6-7.8 micron band. Also, nitrogen atom was substituted to peripheral C-H site of void coronene to be C22H11N1++. Pentagon site substituted case show 60% peak height. This molecule also reproduced well 12-15 micron peak position and relative intensity. Vibration mode analysis demonstrated that 11.3 micron mode comes from C-H ou...

  17. {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, Cécile; Bergin, Edwin A.; Crockett, Nathan R.; Neill, Justin L.; Carvajal, Miguel; Field, David; Jørgensen, Jes K.; Bisschop, Suzanne E.; Brouillet, Nathalie; Despois, Didier; Baudry, Alain; Kleiner, Isabelle; Margulès, Laurent; Huet, Thérèse 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 283.4-287.4 GHz. 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), NGC 6334 IRS 1, W51 e2, and G19.61-0.23. In addition, we have used the 1 mm 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.

  18. 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.

  19. 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)

  20. Which oxygenates is right for you?

    SciTech Connect (OSTI)

    Chang, E.J. [SRI International, Menlo Park, CA (United States)

    1994-12-31

    Recent announcements of additional sources of oxygenates have generated considerable interest. Increasing demand for methyl tert-butyl ether (MTBE) worldwide, especially in the United States for oxygenated fuel and reformulated gasoline (RFG), provides the primary incentive for technologies that produce additional raw material (namely isobutene) and/or alternative oxygenate compounds. Normal butene isomerization and diisopropyl ether (DIPE) are two new processes introduced in 1992 to meet the oxygenate demand. The U.S. Clean Air Act Amendments of 1990 (CAAA) have created a huge demand for capital. Between 1991 and 2000, the U.S. refining industry will need to make capital expenditures of about $37 billion (1990 dollars) to meet refinery regulatory requirements, and to manufacture reformulated gasoline and ultra-low sulfur diesel fuel. To obtain financing, whether internally or from external sources, projects must provide sound economics and pose minimal technological risks. These concerns have prevented several large MTBE projects, involving both established and new technologies, from going forward. The introduction of normal butene isomerization and DIPE processes has generated a great deal of enthusiasm, but neither process had been licensed by the third quarter of 1993. Technology risk is a major barrier to obtaining financing inasmuch as lenders arc unlikely to finance the first commercial application of any technology. Currently, Texas Olefins/Phillips Petroleum and Lyondell have demonstrated normal butene isomerization on a commercial scale in their plants. However, Mobil has not demonstrated the DIPE process beyond the pilot plant stage. In this paper, we assess the technological aspects of normal butene isomerization and DIPE processes, and compare their economics with existing etherification processes.

  1. Controlling DNA Methylation

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

    AFDC Printable Version Share this resource Send a link to EERE: Alternative Fuels Data Center Home Page to someone by E-mail Share EERE: Alternative Fuels Data Center Home Page on Facebook Tweet about EERE: Alternative Fuels Data Center Home Page on Twitter Bookmark EERE: Alternative Fuels Data Center Homesum_a_epg0_fpd_mmcf_m.xls" ,"Available from WebQuantityBonneville Power Administration would like submit the followingConcentrating

  2. 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.

  3. Reactivity of the Quinone Methide of Butylated hydroxytoluene in Solution

    E-Print Network [OSTI]

    Willcockson, Maren Gulsrud

    2011-08-31

    8 pH Measurements 9 High Performance Liquid Chromatography (HPLC) Analysis 9 Ultra Violet-Visible Spectrophotometry (UV-Vis) Analysis 9 Kinetic Studies 10 Generation of Standard Curves 10 Calculation of Mole... at 285 nm and Dionex Chromeleon analysis software (Sunnyvale, CA) was used to integrate peak area. Ultra Violet-Visible Spectrophotometry (UV-Vis) Analysis Shimadzu UV-1700 (Japan) Ultra Violet-Visible Spectrophotometer (UV-Vis) equipped...

  4. Butyl acetate replaces toluene to remove phenol from water

    SciTech Connect (OSTI)

    Hodel, A.E.

    1993-03-01

    Plastics Engineering Co. manufactures phenol formaldehyde resins and molding compounds at a plant in Sheboygan, WI. Process water from the plant, containing 7% phenol and 1% methanol, requires treatment prior to discharge to the sewer. Toluene was used as a solvent in a countercurrent liquid-liquid extraction column. A vacuum distillation of the extract separated the phenol and toluene. The raffinate (1% methanol, 98% water and 1% toluene) was stripped to recover the toluene and remove methanol from the bottoms prior to discharge. Methanol was not recovered. Disposal costs for the waste methanol (with about 10% toluene as an azeotrope) were high.

  5. Conversion of Lignocellulosic Biomass to Ethanol Butyl Acrylate

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

    AFDC Printable Version Share this resource Send a link to EERE: Alternative Fuels Data Center Home Page to someone by E-mail Share EERE: Alternative Fuels Data Center Home Page on Facebook Tweet about EERE: Alternative Fuels Data Center Home Page on Twitter Bookmark EERE: Alternative Fuels Data Center Home Page on Google Bookmark EERE: Alternative Fuels Data Center Home Page on Delicious Rank EERE:FinancingPetroleum Based Fuels|ProgramsLakeDepartment of Energy3-1Department of

  6. 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.

  7. MEMBRANES FOR THE CONTROL OF NATURAL ORGANIC MATTER FROM SURFACE WATERS

    E-Print Network [OSTI]

    Ryan, Joe

    , Boulder Reservoir Water; CHFP, chloral hydrate formation potential; Dalton, indicative of membrane pore, heterotrophic plate count; LSI, Langelier saturation index; MWCO, molecular weight cuto; MTBE, methyl tert.0), silt density index SDI ` 3), and Langelier saturation index LSI ` 0). A potential major role

  8. | FLORIDA GROWER | NOVEMBER 2006 | 37 D r. L a r r y P a r s o n s

    E-Print Network [OSTI]

    Etxeberria, Edgardo

    is great, and Florida is already moving toward some ethanol production. Besides high gasoline prices additive, ethanol can increase octane levels in gasoline. In some cases, ethanol is replacing Methyl tert- ing ground-water contamination. Demand On The Rise Several speakers from petroleum companies talked

  9. The relative reactivity of formic esters with aromatic amines

    E-Print Network [OSTI]

    Markley, Max C.

    1922-01-01

    at 100° are as follows- Ester used Percent yield Methyl formate ' 3% Ethyl M 81 Propyl " 92 Butyl " 80 Sec,octyl n 10 ( 15 ) PROPYL P OREATE W ITH SEVERAL A MINES The next move was to secure data on the relative reactivity of the amines... at 100° are as follows- Ester used Percent yield Methyl formate ' 3% Ethyl M 81 Propyl " 92 Butyl " 80 Sec,octyl n 10 ( 15 ) PROPYL P OREATE W ITH SEVERAL A MINES The next move was to secure data on the relative reactivity of the amines...

  10. Current Biology 20, R780R785, September 14, 2010 2010 Elsevier Ltd All rights reserved DOI 10.1016/j.cub.2010.07.007 MinireviewEvolution of Eukaryotic DNA Methylation

    E-Print Network [OSTI]

    all of life with almost invariant consistency, but imagine, for a moment, if this were not so. After. Methylation of the fifth carbon of cytosine, the subject of this article, is mediated by the same enzymatic are directly applicable to mammals, which will be useful for distantly related crop plants, and which

  11. A novel, single-isomer, sulfated cyclodextrin for use as a chiral resolving agent in capillary electrophoresis: the sodium salt of octakis(2,3-di-O-methyl-6-O-sulfo)-?-cyclodextrin 

    E-Print Network [OSTI]

    Busby, Michael Brent

    2002-01-01

    A novel, single-isomer, sulfated cyclodextrin, the sodium salt of octakis(2,3-di-O-methyl-6-O-sulfo)cyclomaltooctaose (ODMS) was used as a chiral resolving agent in both aqueous and non-aqueous chiral mediated electrophoretic ...

  12. 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}.

  13. 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.

  14. 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.

  15. 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.

  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, carbene–bis(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 C–H 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. 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.

  18. The Influence of Linker Geometry on Uranyl Complexation by Rigidly-Linked Bis(3-hydroxy-N-methyl-pyridin-2-one)

    SciTech Connect (OSTI)

    Szigethy, Geza; Raymond, Kenneth

    2010-04-22

    A series of bis(3-hydroxy-N-methyl-pyridin-2-one) ligands was synthesized, and their respective uranyl complexes were characterized by single crystal X-ray diffraction analyses. These structures were inspected for high-energy conformations and evaluated using a series of metrics to measure co-planarity of chelating moieties with each other and the uranyl coordination plane, as well as to measure coordinative crowding about the uranyl dication. Both very short (ethyl, 3,4-thiophene and o-phenylene) and very long ({alpha},{alpha}{prime}-m-xylene and 1,8-fluorene) linkers provide optimal ligand geometries about the uranyl cation, resulting in planar, unstrained molecular arrangements. The planarity of the rigid linkers also suggests there is a degree of pre-organization for a planar coordination mode that is ideal for uranyl-selective ligand design. Comparison of intramolecular N{sub amide}-O{sub phenolate} distances and {sup 1}H NMR chemical shifts of amide protons supports earlier results that short linkers provide the optimal geometry for intramolecular hydrogen bonding.

  19. 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.

  20. Auto Template Assembly of CaCO3-Chitosan Hybrid Nanoboxes and Nanoframes in Ionic Liquid Medium 

    E-Print Network [OSTI]

    Chen, Hsingming Anna

    2012-07-16

    . The purpose of this thesis is to describe a method for forming hollow inorganic-organic hybrid nanoboxes and nanoframes. This approach relies upon ionic liquid (1-butyl-3-methyl-imidazolium chloride) mediated auto-templating assembly of CaCO3 and chitosan...

  1. 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).

  2. 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.

  3. An Examination of the Thermodynamics of Fusion, Vaporization, and Sublimation of Several Parabens by Correlation Gas

    E-Print Network [OSTI]

    Chickos, James S.

    on their thermochemical properties. A number of studies have reported measurements of their phase change enthalpies.com). DOI 10.1002/jps.22423 ABSTRACT: The vaporization, fusion, and sublimation enthalpies of methyl, ethyl, propyl, and butyl paraben are reported and compared with literature values. The vaporization enthalpies

  4. 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.

  5. 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.

  6. Total Syntheses of Linear Poly-Thiazole/Oxazole Plantazolicin A and its biosynthetic precursor Plantazolicin B

    E-Print Network [OSTI]

    Wilson, Zoe E.; Fenner, Sabine; Ley, Steven V.

    2014-11-25

    stream_source_info Wilson et al 2015 Angewandte Chemie International Edition.pdf.txt stream_content_type text/plain stream_size 18368 Content-Encoding UTF-8 stream_name Wilson et al 2015 Angewandte Chemie International Edition... Et, CH 2 Cl 2 , RT, 48 h, 35% 4a, 13% 28. Boc 2 O=di-tert-butyl dicarbonate. Angewandte Chemie 1285Angew. Chem. Int. Ed. 2015, 54, 1284 –1288 Ó 2015 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim www.angewandte.org cysteine ethyl...

  7. Miscibility of blends of poly(methyl methacrylate) and oligodiols based on a bisphenol A nucleus and ethylene oxide or propylene oxide branches

    E-Print Network [OSTI]

    B. Jaffrennou; E. R. Soule; F. Mechin; J. Borrajo; J. P. Pascault; R. J. J. Williams

    2013-11-21

    Cloud-point curves of blends of poly(methyl methacrylate) (PMMA) with a series of oligodiols based on a bisphenol A nucleus and short branches of poly(ethylene oxide) or poly(propylene oxide) (BPA-EO or BPA-PO), and with PEO and PPO oligomers, were obtained using a light transmission device. Experimental results were fitted with the Flory- Huggins model using an interaction parameter depending on both temperature and composition. For PMMA/PEO and PMMA/PPO blends, the miscibility increased when increasing the size of the diol, due to the significant decrease in the entropic and enthalpic terms contributing to the interaction parameter. This reflected the decrease in the selfassociation of solvent molecules and in the contribution of terminal OH groups to the mismatching of solubility parameters. For PMMA/BPA-EO blends, a decrease of the entropic contribution to the interaction parameter when increasing the size of the oligodiol was also found. However, the effect was counterbalanced by the opposite contribution of combinatorial terms leading to cloud-point curves located in approximately the same temperature range. For PMMA/BPA-PO blends, the interaction parameter exhibited a very low value. In this case, the effect of solvent size was much more important on combinatorial terms than on the interaction parameter, leading to an increase in miscibility when decreasing the oligodiol size. For short BPA-PO oligodiols no phase separation was observed. The entropic contribution of the interaction parameter exhibited an inverse relationship with the size of the oligodiols, independent of the nature of the chains bearing the hydroxyls and the type of OH groups (primary or secondary). This indicates that the degree of self-association of solvent molecules through their OH terminal groups, was mainly determined by their relative sizes.

  8. Conducting polymer blends: Polypyrrole and polythiophene blends with polystyrene, polycarbonate resin, poly(vinyl alcohol) and poly(vinyl methyl ketone)

    SciTech Connect (OSTI)

    Wang, H.L.

    1992-01-01

    Various aromatic compounds can be polymerized by electrochemical oxidation in solution containing a supporting electrolyte. Most studies have been devoted to polypyrrole and polythiophene. In situ doping during electrochemical polymerization yields free standing conductive polymer film. One major approach to making conducting polymer blends is electrochemical synthesis after coating the host polymer on a platinum electrode. In the electrolysis of pyrrole or thiophene monomer, using (t-Bu[sub 4]N)BF[sub 4] as supporting electrolyte, and acetonitrile as solvent, monomer can diffuse through the polymer film, to produce a polypyrrole or polythiophene blend in the film. Doping occurs along with polymerization to form a conducting polymer alloy. The strongest molecular interaction in polymers, and one that is central to phase behavior, is hydrogen bonding. This mixing at the molecular level enhances the degree of miscibility between two polymers and results in macroscopic properties indicative of single phase behavior. In this dissertation, the authors describes the syntheses of conducting polymer blends: polypyrrole and polythiophene blends with polystyrene, poly(bisphenol-A-carbonate), polyvinyl alcohol and poly(vinyl methyl ketone). The syntheses are performed both electrochemically and chemically. Characterization of these blends was carried out by Fourier Transform Infrared spectroscopy, Differential Scanning Calorimetry, Thermogravimetric Analysis, Scanning Electron Microscopy, and X-ray diffraction. Percolating threshold conductivities occur from 7% to 20% for different polymer blends. The low threshold conductivity is attributed to blend homogeneity enhanced by hydrogen bonding between the carbonyl group in the insulating polymer and the N-H group in polypyrrole. Thermal stability, environmental stability, mechanical properties, crystallinity and morphological structure are also discussed. The authors have also engaged in the polymerization of imidazoles.

  9. 1) Methyl Acrylate, h 2) Methyl Orthoformate, Amberlyst-15

    E-Print Network [OSTI]

    -CPBA, NaHCO3 42) K2CO3, MeOH 35) SO3 * py, DMSO-Et3N 36) 1N aq HCl 37) Sc(OTf)3 34-36 O O H H OH OTES TIPSO

  10. 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.

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

    SciTech Connect (OSTI)

    Tseng, Hsiao-Ling, E-mail: lily1001224@gmail.com [Department of Life Sciences, Tzu Chi University, Hualien, Taiwan (China)] [Department of Life Sciences, Tzu Chi University, Hualien, Taiwan (China); Li, Chia-Jung, E-mail: 97751101@stmail.tcu.edu.tw [Institute of Medical Sciences, Tzu Chi University, Hualien, Taiwan (China)] [Institute of Medical Sciences, Tzu Chi University, Hualien, Taiwan (China); Huang, Lin-Huang, E-mail: yg1236@yahoo.com.tw [School of Medicine, Institute of Traditional Medicine, National Yang-Ming University, Taipei, Taiwan (China)] [School of Medicine, Institute of Traditional Medicine, National Yang-Ming University, Taipei, Taiwan (China); Chen, Chun-Yao, E-mail: cychen@mail.tcu.edu.tw [Department of Life Sciences, Tzu Chi University, Hualien, Taiwan (China)] [Department of Life Sciences, Tzu Chi University, Hualien, Taiwan (China); Tsai, Chun-Hao, E-mail: 100726105@stmail.tcu.edu.tw [Department of Life Sciences, Tzu Chi University, Hualien, Taiwan (China)] [Department of Life Sciences, Tzu Chi University, Hualien, Taiwan (China); Lin, Chun-Nan, E-mail: lincna@cc.kmu.edu.tw [Faculty of Pharmacy, College of Pharmacy, Kaohsiung Medical University, Kaohsiung, Taiwan (China) [Faculty of Pharmacy, College of Pharmacy, Kaohsiung Medical University, Kaohsiung, Taiwan (China); Department of Biological Science and Technology, School of Medicine, China Medical University, Taichung, Taiwan (China); Hsu, Hsue-Yin, E-mail: hsueyin@mail.tcu.edu.tw [Department of Life Sciences, Tzu Chi University, Hualien, Taiwan (China)] [Department of Life Sciences, Tzu Chi University, Hualien, Taiwan (China)

    2012-10-01

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

  12. Spin Equilibria in Monomeric Manganocenes: Solid State Magnetic and EXAFS Studies

    SciTech Connect (OSTI)

    Walter, M. D.; Sofield, C. D.; Booth, C. H.; Andersen, R. A.

    2009-02-09

    Magnetic susceptibility measurements and X-ray data confirm that tert-butyl-substituted manganocenes [(Me{sub 3}C){sub n}C{sub 5}H{sub 5?n}]{sub 2}Mn (n = 1, 2) follow the trend previously observed with the methylated manganocenes; that is, electron-donating groups attached to the Cp ring stabilize the low-spin (LS) electronic ground state relative to Cp{sub 2}Mn and exhibit higher spin-crossover (SCO) temperatures. However, introducing three CMe{sub 3} groups on each ring gives a temperature-invariant high-spin (HS) state manganocene. The origin of the high-spin state in [1,2,4-(Me{sub 3}C){sub 3}C{sub 5}H{sub 2}]{sub 2}Mn is due to the significant bulk of the [1,2,4-(Me{sub 3}C){sub 3}C{sub 5}H{sub 2}]{sup -} ligand, which is sufficient to generate severe inter-ring steric strain that prevents the realization of the low-spin state. Interestingly, the spin transition in [1,3-(Me{sub 3}C){sub 2}C{sub 5}H{sub 3}]{sub 2}Mn is accompanied by a phase transition resulting in a significant irreversible hysteresis ({Delta}T{sub c} = 16 K). This structural transition was also observed by extended X-ray absorption fine-structure (EXAFS) measurements. Magnetic susceptibility studies and X-ray diffraction data on SiMe{sub 3}-substituted manganocenes [(Me{sub 3}Si){sub n}C{sub 5}H{sub 5-n}]{sub 2}Mn (n = 1, 2, 3) show high-spin configurations in these cases. Although tetra- and hexasubstituted manganocenes are high-spin at all accessible temperatures, the disubstituted manganocenes exhibit a small low-spin admixture at low temperature. In this respect it behaves similarly to [(Me{sub 3}C)(Me{sub 3}Si)C{sub 5}H{sub 3}]{sub 2}Mn, which has a constant low-spin admixture up to 90 K and then gradually converts to high-spin. Thermal spin-trapping can be observed for [(Me{sub 3}C)(Me{sub 3}Si)C{sub 5}H{sub 3}]{sub 2}Mn on rapid cooling.

  13. Modeling of the oxidation of methyl esters--Validation for methyl hexanoate, methyl heptanoate, and methyl decanoate in a

    E-Print Network [OSTI]

    Paris-Sud XI, Université de

    conditions, at a pressure of 1.06 bar and for a residence time of 1.5 s: more than 30 reaction products change and the impending scarcity of oil resources have led to increasing interest in shifting from toxic by-products such as aldehydes [5]. Therefore, a deeper understanding of oxygenate biofuel

  14. 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.

  15. 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.

  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. Effects of oxygenate concentration on species mole fractions in premixed n-heptane flames

    E-Print Network [OSTI]

    Senkan, Selim M.

    -heptane/oxygenate mixtures were 2.7 and 3.4. Three different fuel oxygenates (i.e. MTBE, methanol, and ethanol) were tested in these emissions is the improvement in motor vehicle fuel properties. Fuel oxygenates were first used as an octane.e. oxygenates) such as alcohols (e.g. methanol, ethanol, and tertiary butyl alcohol) and ethers (e.g. methyl

  18. Reactive formulations for a neutralization of toxic industrial chemicals

    DOE Patents [OSTI]

    Tucker, Mark D. (Albuqueruqe, NM); Betty, Rita G. (Rio Rancho, NM)

    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.

  19. Direct exfoliation of natural graphite into micrometer size few layers graphene sheets using ionic liquids

    SciTech Connect (OSTI)

    Wang, X.; Fulvio, P. F.; Baker, G. A.; Veith, G. M.; Unocic, R. R.; Mahurin, S., M.; Chi, M.; Dai, S.

    2010-01-01

    Stable high-concentration suspensions (up to 0.95 mg mL{sup ?1}) of non-oxidized few layer graphene (FLG), five or less sheets, with micrometre-long edges were obtained via direct exfoliation of natural graphite flakes in ionic liquids, such as 1-butyl-3-methyl-imidazolium bis(trifluoro-methane-sulfonyl)imide ([Bmim]-[Tf{sub 2}N]), by tip ultrasonication.

  20. Index of Subjects Abbreviations ix,203-6

    E-Print Network [OSTI]

    Hall, Christopher

    (acrylic acid) and Poly(methyl methacrylate) PMMA Acrylonitrile-butadiene copolymer (nitrile rubber NBR) 2 Acrylonitrile-styrene-butadiene ABS 2-5, 41-2,76, 78,136,154,156, 203, 209-10, 224 Addition reaction 23-5, 33 modulus 57,70,92 Bulk polymerisation 31 Butadiene 5,167,169,217 Butane 11 Butene 219 Butyl acetate 181

  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. Saponification rates of isomeric butyl esters in aqueous 1,4-dioxane 

    E-Print Network [OSTI]

    Ruhnke, Edward Vincent

    1954-01-01

    stranded RNA ligands with overhangs or a 5’ triphosphate group. The Cys951 residue was shown to disrupt stability of the MDA5 RD-RNA complex. Binding analyses were performed using a combination of SDS-PAGE, gel filtration analysis, and nondenaturing gel...

  3. Use of ethyl-t-butyl ether (ETBE) as a gasoline blending component

    SciTech Connect (OSTI)

    Shiblom, C.M.; Schoonveld, G.A.; Riley, R.K.; Pahl, R.H.

    1990-01-01

    The U.S. Treasury Department recently ruled that the ethanol blenders tax credit applies to ethanol used to make ETBE for blending with gasoline. As a result, ETBE may soon become a popular gasoline blending component. Like MTBE ETBE adds oxygen to the fuel while contributing to other performance properties of the gasoline. Phillips Petroleum Company has completed limited driveability and material compatibility studies on gasolines containing ETBE and has determined the effect on various performance parameters such as octane, volatility, and distillation of ETBE in gasoline. Levels of ETBE ranging from 0.0 to 23.5 volume percent (3.7 weight percent oxygen) in gasoline were included in the investigation. Use in gasoline is currently limited to only 12.7 volume percent (2.0 weight percent oxygen) by the gasoline substantially similar rule. No detrimental effects of the ETBE on metal or elastomeric parts common to gasoline delivery and fueling system were found. Also, several favorable blending properties of eTBE in gasoline are apparent as compared to either MTBE or ethanol. This paper presents details of these results.

  4. Exchange Reactions Between a Molten Salt and a Solution of Tri-Butyl

    Office of Scientific and Technical Information (OSTI)

    AFDC Printable Version Share this resource Send a link to EERE: Alternative Fuels Data Center Home Page to someone by E-mail Share EERE: Alternative Fuels Data Center Home Page on Facebook Tweet about EERE: Alternative Fuels Data Center Home Page on Twitter Bookmark EERE: Alternative Fuels Data Center Homesum_a_epg0_fpd_mmcf_m.xls" ,"Available from WebQuantity of NaturalDukeWakefieldSulfate Reducing(Journal Article) | SciTech(Journal(Patent)pressure inrepeats (Journal(Journal

  5. A STUDY OF FUNDAMENTAL REACTION PATHWAYS FOR TRANSITION METAL ALKYL COMPLEXES. I. THE REACTION OF A NICKEL METHYL COMPLEX WITH ALKYNES. II. THE MECHANISM OF ALDEHYDE FORMATION IN THE REACTION OF A MOLYBDENUM HYDRIDE WITH MOLYBDENUM ALKYLS

    SciTech Connect (OSTI)

    Huggins, John Mitchell

    1980-06-01

    I. This study reports the rapid reaction under mild conditions of internal or terminal alkynes with methyl (acetyl~ acetonato) (triphenylphosphine) nickel (1) in either aromatic or ether solvents. In all cases vinylnickel products 2 are formed by insertion of the alkyne into the nickel=methyl bond. These complexes may be converted into a variety of organic products (e.g. alkenes, esters, vinyl halides) by treatment with appropriate reagents. Unsymmetrical alkynes give selectively the one regioisomer with the sterically largest substituent next to the nickel atom. In order to investigate the stereochemistry of the initial insertion, a x-ray diffraction study of the reaction of 1 with diphenylacetylene was carried out. This showed that the vinylnickel complex formed by overall trans insertion was the product of the reaction. Furthermore, subsequent slow isomerization of this complex, to a mixture of it and the corresponding cis isomer, demonstrated that this trans addition product is the kinetic product of the reaction. In studies with other alkynes, the product of trans addition was not always exclusively (or even predominantly) formed, but the ratio of the stereoisomers formed kinetically was substantially different from the thermodynamic ratio. Isotope labeling, added phosphine, and other experiments have allowed us to conclude that the mechanism of this reaction does involve initial cis addition. However, a coordinatively unsaturated vinylnickel complex is initially formed which can undergo rapid, phosphine-catalyzed cis-trans isomerization in competition with its conversion to the isolable phosphine-substituted kinetic reaction products. II. The reaction of CpMo(CO){sub 3}H (1a) with CpMo(CO){sub 3}R (2, R= CH{sub 3}, C{sub 2}H{sub 5}) at 50{degrees} C in THF gives the aldehyde RCHO and the dimers [CpMo(CO){sub 3}]{sub 2} (3a) and [CpMo(CO){sub 2}]{sub 2} (4a). Labeling one of the reactants with a methylcyclopentadienyl ligand it was possible to show that the mixed dimers MeCpMo(CO){sub 3}-(CO){sub 3}MoCp (3b) and MeCpMo(CO){sub 2}{triple_bond}(CO){sub 2}MoCp (4b) are the predominant kinetic products of the reaction. Additionally labeling the carbonyl ligands of 1a with {sup 13}CO led to the conclusion that all three of the carbonyl ligands in 1a end up in the tetracarbonyl dimers 4a if the reaction is carried out under a continuous purge of argon Trapping studies failed to find any evidence for the intermediacy of either [CpMo(CO){sub 3}]{sup -} or [CpMo(CO){sub 3}]{sup +} in this reaction. A mechanism is proposed that involves the initial migration of the alkyl ligand in 2 to CO forming an unsaturated acyl complex which reacts with 1a to give a binuclear complex containing a three center-two electron Mo-H-Mo bond. This complex then selectively looses a carbonyl from the acyl molybdenum, migrates the hydride to that same metal, and forms a metal-metal bond. This binuclear complex with the hydride and acyl ligands on one metal reductively eliminates aldehyde, and migrates a carbonyl ligand, to give 4a directly. The other product 3a is formed by addition of two molecules of free CO to 4a.

  6. 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.

  7. 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.

  8. 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.

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

    SciTech Connect (OSTI)

    Somerville, Chris R.; Scieble, Wolf

    2000-10-11

    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.

  10. Exploring the Potential of Fulvalene Dimetals as Platforms for Molecular Solar Thermal Energy Storage: Computations, Syntheses, Structures, Kinetics, and Catalysis

    SciTech Connect (OSTI)

    Borjesson, K; Coso, D; Gray, V; Grossman, JC; Guan, JQ; Harris, CB; Hertkorn, N; Hou, ZR; Kanai, Y; Lee, D; Lomont, JP; Majumdar, A; Meier, SK; Moth-Poulsen, K; Myrabo, RL; Nguyen, SC; Segalman, RA; Srinivasan, V; Tolman, WB; Vinokurov, N; Vollhardt, KPC; Weidman, TW

    2014-10-03

    A study of the scope and limitations of varying the ligand framework around the dinuclear core of FvRu(2) in its function as a molecular solar thermal energy storage framework is presented. It includes DFT calculations probing the effect of substituents, other metals, and CO exchange for other ligands on Delta H-storage. Experimentally, the system is shown to be robust in as much as it tolerates a number of variations, except for the identity of the metal and certain substitution patterns. Failures include 1,1',3,3'-tetra-tert-butyl (4), 1,2,2',3'-tetraphenyl (9), diiron (28), diosmium (24), mixed iron-ruthenium (27), dimolybdenum (29), and di-tungsten (30) derivatives. An extensive screen of potential catalysts for the thermal reversal identified AgNO3-SiO2 as a good candidate, although catalyst decomposition remains a challenge.

  11. New Methods for the Synthesis of alpha-Amino Acid Derivatives From N-tert-Butanesulfinyl Imines AND The Synthesis and Application of Novel Amino Acid Based N-tert-Butanesulfinyl Amide Organocatalysts

    E-Print Network [OSTI]

    Herbage, Melissa Ann

    2009-01-01

    products were obtained in ? 98:2 dr. This chemistry will be1.27c 1.27b S S O method A: R = Me; 90%, 98:2 dr method B:R = Et; 65%, 98:2 dr O S method B: 73%, 95:5 dr O NH S NH

  12. Copper Catalyzed Oceanic Methyl Halide Production

    E-Print Network [OSTI]

    Robin Kim, Jae Yun; Rhew, Robert

    2014-01-01

    gas exchange between the water and air. After each samplehalides from the water to the air, representing productionhalides from the water to the air. Possible drivers of this

  13. Histone methylation marks play important roles in predicting the methylation status of CpG islands

    E-Print Network [OSTI]

    and Bioinformatics Division, TNLIST/Department of Automation, Tsinghua University, FIT Building 1-107, Beijing 100084, China b School of Automation Engineering, University of Electronic Science and Technology of China

  14. The Role of the Ocean in the Atmospheric Budgets of Methyl Bromide, Methyl Chloride and Methane 

    E-Print Network [OSTI]

    Hu, Lei

    2012-10-19

    , which was 700 (490 to 920) Gg yr^-1 and -370 (-440 to -280) Gg yr^-1, respectively. The ocean accounts for 10 - 19 % in the global CH3Cl emission and 6 - 9 % in its global sinks. Methane (CH4) is a potent greenhouse gas, which has a warming potential...

  15. Detailed chemical kinetic reaction mechanism for biodiesel components methyl stearate and methyl oleate

    E-Print Network [OSTI]

    Paris-Sud XI, Université de

    with more conventional hydrocarbon fuels for which experimental results are available. Additional;1. Introduction Biofuels have the potential to supplement conventional petroleumbased transportation fuels emissions of CO, unburned hydrocarbons, and soot [14]. The principal components of both soy and rapeseed

  16. 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.

  17. Polymer Brushes on Single-Walled Carbon Nanotubes by Atom Transfer Radical Polymerization of n-Butyl Methacrylate

    E-Print Network [OSTI]

    Resasco, Daniel

    Polymer Brushes on Single-Walled Carbon Nanotubes by Atom Transfer Radical Polymerization of n-mail: wtford@okstate.edu Abstract: Polymer brushes with single-walled carbon nanotubes (SWNT) as backbones were-walled carbon nanotubes (SWNT) are leading to the development of new nanotechnologies because of their out

  18. A search for mode-selective chemistry: The unimolecular dissociation of I-butyl hydroperoxide induced by

    E-Print Network [OSTI]

    rate over the thermal energy distribution of the photoactivated molecules is included. At pressures of thermal unimolecular processes. 1 The ergodic theories were very successful in rationaliZing the bulk rate. The excess chemical energy released through the addition process is initially localized

  19. Fetal germ cell development in the rat testis and the impact of di (n-Butyl) phthalate exposure 

    E-Print Network [OSTI]

    Jobling, Matthew S.

    2010-01-01

    During gonad development and fetal life, the germ cells (GC) undergo a range of different developmental processes necessary for correct postnatal gametogenesis and the production of the next generation. If these fetal ...

  20. On the structural and impedance characteristics of Li- doped PEO, using n-butyl lithium in hexane as dopant

    SciTech Connect (OSTI)

    Anand, P. B., E-mail: anandputhirath@gmail.com, E-mail: jayalekshmi@cusat.ac.in; Jayalekshmi, S., E-mail: anandputhirath@gmail.com, E-mail: jayalekshmi@cusat.ac.in [Division for Research in Advanced Materials Department of Physics Cochin University of Science and Technology Cochin 22, Kerala (India)

    2014-01-28

    Nowadays polymer based solid state electrolytes for applications in rechargeable battery systems are highly sought after materials, pursued extensively by various research groups worldwide. Numerous methods are discussed in literature to improve the fundamental properties like electrical conductivity, mechanical stability and interfacial stability of polymer based electrolytes. The application of these electrolytes in Li-ion cells is still in the amateur state, due to low ionic conductivity, low lithium transport number and the processing difficulties. The present work is an attempt to study the effects of Li doping on the structural and transport properties of the polymer electrolyte, poly-ethelene oxide (PEO) (Molecular weight: 200,000). Li doped PEO was obtained by treating PEO with n-Butyllithium in hexane for different doping concentrations. Structural characterization of the samples was done by XRD and FTIR techniques. Impedance measurements were carried out to estimate the ionic conductivity of Li doped PEO samples. It is seen that, the crystallinity of the doped PEO decreases on increasing the doping concentration. XRD and FTIR studies support this observation. It is inferred that, ionic conductivity of the sample is increasing on increasing the doping concentration since less crystallinity permits more ionic transport. Impedance measurements confirm the results quantitatively.

  1. Kinetic study of acid-catalyzed cellulose hydrolysis in 1-butyl-3-methylimidazolium Zehui Zhang a,d,1

    E-Print Network [OSTI]

    Li, Weixue

    . Zhao a,c, a Division of Biotechnology, Dalian Institute of Chemical Physics, CAS, 457 Zhongshan Road, Dalian 116023, China b The State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, CAS, 457 Zhongshan Road, Dalian 116023, China c Dalian National Laboratory for Clean Energy, Dalian 116023

  2. An experimental system for the n-butyl-lithium initiated polymerization of styrene in a multi-sampled batch reactor 

    E-Print Network [OSTI]

    Cox, James Harvey

    1974-01-01

    AN EXPERIMENTAL SYSTEM FOR THE n-BUTYLLITHIUM INITIATED POLYMERIZATION OF STYRENE IN A MULTI-SAMPLED BATCH REACTOR A Thesis by JAMES HARVEY COX, JR. Submitted to the Graduate College of Texas A&M University in partial fulfillment... of the requirement for the degree of MASTER OF SCIENCE May 1974 Ma]or Subject: Chemical Engineering AN EXPERIMENTAL SYSTEM FOR THE n-BUTYLLITHIUM INITIATED POLYMERIZATION OF STYRENE IN A MULTI-SAMPLED BATCH REACTOR A Thesis by JAMES HARVEY COX, JR. Approved...

  3. 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.

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

    Reports and Publications (EIA)

    2009-01-01

    In Annual Energy Outlook 2009, (AEO) E10–a gasoline blend containing 10% ethanol–is 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.

  5. 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.

  6. 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.

  7. 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.

  8. Coordination Compounds of Strontium. Syntheses, Characterizations, and Crystal Structures of [Sr(u-ONc)(2)(HONc(4))]2 and Sr(5)(u(4)-O)(u(3)-ONep)(4)(u-ONep)(4)(HONep)(solv)(4) (ONc=O(2)CCH(2)CMe(3));Nep=CH(2)CMe(3); solv=tetrahydrofuran or 1-methyl-imida

    SciTech Connect (OSTI)

    Boyle, Timothy J.; Tafoya, Cory J.; Scott, Brian L.; Ziller, Joseph W.

    1999-07-21

    The authors have synthesized and characterized two novel Sr compounds: [Sr({mu}-ONc){sub 2}(HONc){sub 4}]{sub 2} (1, ONc = O{sub 2}CCH{sub 2}CMe{sub 3}), and Sr{sub 5}({mu}{sub 4}-O)({mu}{sub 3}-ONep){sub 4}({mu}-ONep){sub 4}(HONep)(solv){sub 4} [ONep = OCH{sub 2}CMe{sub 3}, solv = tetrahydrofuran (THF), 2a; 1-methyl-imidazole (MeIm), (2b)], that demonstrate increased solubility in comparison to the commercially available Sr precursors. The two metal centers of 1 share 4 unidentate bridging {mu}-ONc ligands and complete their octahedral geometry through the coordination of 4 monodentate terminal HONc ligands. The structure arrangement of the central core of 2a and b are identical, wherein 4 octahedral Sr atoms are arranged in a square geometry around a {mu}{sub 4}-O ligand. An additional 7-coordinated Sr atom sits directly atop the {mu}{sub 4}-O to form a square base pyramidal arrangement of the Sr atoms but the apical Sr-O distance is too long to be considered a bond. In solution, compound 1 is disrupted forming a monomer but 2a and b retain their structures.

  9. Study of optimal sequences and energy requirements of integrated processing systems

    SciTech Connect (OSTI)

    Al-Enezi, G.A.

    1986-01-01

    The increased demand for high quality unleaded gasoline produced from a refinery has caused an increased in developing processing alternatives for producing high-octane gasoline components. The production of methyl tertiary butyl ether is currently considered one of the most practical alternatives. The production of methyl tertiary butyl ether is based mainly on the availability of light hydrocarbons as a feed, such as isobutane from a refinery. The availability of isobutane is increased by isomerization of normal butanes. Even though distillation processes are widely used to separate mixtures of light hydrocarbons, they are highly energy intensive. A steady-state design of several configurations of distillation columns were studied for separating light hydrocarbon mixtures. A number of energy conservation alternatives were evaluated for the distillation process integrated with an isomerization unit. A modified form of the Complex Method of Box was used for optimizing the design and operating conditions of these energy conservation alternatives. The use of vapor recompression with distillation columns was evaluated as one of the alternatives. Despite the more complex processing scheme required, this alternative used only about 30% of the external energy required in a conventional distillation process for the same separation. The operating conditions of the multi-effect distillation columns were optimized as another alternative. Reduction in energy consumption for this case was about 40% compared to conventional distillation columns.

  10. Signaling networks in Eric L. Greer1,2

    E-Print Network [OSTI]

    Brunet, Anne

    /prevents longevity jcs.biologists.org Protein gene Resveratrol? TERT Promotes longevity Promotes aging C

  11. Application of a palladium/tri-tert-butylphosphine catalyst system towards mild and general methods for carbon-carbon bond formation

    E-Print Network [OSTI]

    Littke, Adam F. (Adam Francis), 1974-

    2002-01-01

    Our research over the last four years has been focused on the development of mild and general methods for conducting palladium-catalyzed carbon-carbon bond forming reactions utilizing the bulky and electron-rich ...

  12. Candidate locus analysis of the TERT–CLPTM1L cancer risk region on chromosome 5p15 identifies multiple independent variants associated with endometrial cancer risk

    E-Print Network [OSTI]

    Carvajal-Carmona, Luis G.; O’Mara, Tracy A.; Painter, Jodie N.; Lose, Felicity A.; Dennis, Joe; Michailidou, Kyriaki; Tyrer, Jonathan P.; Ahmed, Shahana; Ferguson, Kaltin; Healey, Catherine S.; Pooley, Karen; Beesley, Jonathan; Cheng, Timothy; Jones, Angela; Howarth, Kimberley; Martin, Lynn; Gorman, Maggie; Hodgson, Shirley; National Study of Endometrial Cancer Genetics Group (NSECG); The Australian National Endometrial Cancer Study Group (ANECS); Wentzensen, Nicholas; Fasching, Peter A.; Hein, Alexander; Beckmann, Matthias W.; Renner, Stefan P.; Dörk, Thilo; Hillemanns, Peter; Dürst, Matthias; Runnebaum, Ingo; Lambrechts, Diether; Coenegrachts, Lieve; Schrauwen, Stefanie; Amant, Frederic; Winterhoff, Boris; Dowdy, Sean C.; Goode, Ellen L.; Teoman, Attila; Salvesen, Helga B.; Trovik, Jone; Njolstad, Tormund S.; Werner, Henrica M. J.; Scott, Rodney J.; Ashton, Katie; Proietto, Tony; Otton, Geoffrey; Tzortzatos, Gerasimos; Mints, Miriam; Tham, Emma; RENDOCAS; Hall, Per; Czene, Kamila; Liu, Jianjun; Li, Jingmei; Hopper, John L.; Southey, Melissa C.; Australian Ovarian Cancer Study (AOCS); Ekici, Arif B.; Ruebner, Matthias; Johnson, Nichola; Peto, Julian; Burwinkel, Barbara; Marme, Frederik; Brenner, Hermann; Dieffenbach, Aida K.; Meindl, Alfons; Brauch, Hiltrud; The GENICA Network; Lindblom, Annika; Depreeuw, Jeroen; Moisse, Matthieu; Chang-Claude, Jenny; Rudolph, Anja; Couch, Fergus J.; Olson, Janet E.; Giles, Graham G.; Bruinsma, Fiona; Cunningham, Julie M.; Fridley, Brooke L.; Børresen-Dale, Anne-Lise; Kristensen, Vessela N.; Cox, Angela; Swerdlow, Anthony; Orr, Nicholas; Bolla, Manjeet K.; Wang, Qin; Weber, Rachel Palmieri; Chen, Zhihua; Shah, Mitul; Pharoah, Paul D. P.; Dunning, Alison M.; Tomlinson, Ian; Easton, Douglas F.; Spurdle, Amanda B.; Thompson, Deborah J.

    2014-12-09

    , Sweden J. Liu · J. Li Human Genetics, Genome Institute of Singapore, Singapore, Singapore J. L. Hopper · G. G. Giles Centre for Epidemiology and Biostatistics, Melbourne School of Population and Global Health, The University of Melbourne, Melbourne... 2010 release of the 1000 Genomes Project (2012). These included all known SNPs with MAF >0.02 in Europeans and r2 > 0.1 with the then-known cancer-associated SNPs [rs402710 (McKay et al. 2008)] and/or rs3816659 (Shen et al. 2010), plus a tagging set...

  13. Vanadyl tert-Butoxy Orthosilicate, OV[OSi(OtBu)3]3: A Model for Isolated Vanadyl Sites on Silica and a

    E-Print Network [OSTI]

    Iglesia, Enrique

    performance for propane oxidative dehydrogenation. Introduction The direct oxidation of organic compounds combustion. For this reason, studies on the selective oxidation of hydrocar- bons have focused on metal oxide

  14. Influence of the host cell factors CK2, hTERT, and PML, on the antiviral response to herpes simplex virus type I infection

    E-Print Network [OSTI]

    Smith, Miles Christian

    2013-08-31

    Herpes simplex virus type I (HSV-1) is a significant human pathogen that infects a large portion of the human population. As an obligate intracellular parasite, HSV-1 requires certain cellular factors for its replication; ...

  15. Evaluation of Candidate Stromal Epithelial Cross-Talk Genes Identifies Association between Risk of Serous Ovarian Cancer and TERT, a Cancer Susceptibility â??Hot-Spotâ?

    E-Print Network [OSTI]

    2010-01-01

    and susceptibility to serous ovarian cancer in three studygenetic risk associations for ovarian cancer throughthe international Ovarian Cancer Association Consortium. Br

  16. Chemical Hygiene and Safety Plan

    E-Print Network [OSTI]

    Ricks Editor, R.

    2009-01-01

    NICKEL ARSENIDE SULFIDE NICKEL CARBONYL NICKEL REFINERY DUSTsulfide iodine pentafluoride methyl bromide methyl chloride methyl silane nickel carbonylsulfide iodine pentafluoride methyl bromide methyl chloride methyl silane nickel carbonyl

  17. Supporting Information Microbial methylation of mercury sulfide nanoparticles

    E-Print Network [OSTI]

    with selected area electron diffraction (SAED) to assess crystal structure of the particles (Figure S4a through 0.025 m pore size mixed cellulose ester membranes (Millipore). The material that deposited on the filter membrane was analyzed for crystallographic structure by synchrotron XRD performed at the Stanford

  18. 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)

  19. DNA methylation arrays as surrogate measures of cell mixture distribution

    E-Print Network [OSTI]

    2012-01-01

    but non-negligible proportion of total variation (systematicrepresents the proportion of sys- tematic variation in S 1

  20. 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)...

  1. The Genetics of de novo Methylation in Arabidopsis thaliana

    E-Print Network [OSTI]

    Greenberg, Maxim Van Cleef

    2012-01-01

    V transcription is dependent on the DDR complex (DRD1, DMS3,V is dependent on the DDR complex: the putative chromatinbegs: what recruits the DDR complex and Pol V? Is it based

  2. Investigation of the Atmospheric Ozone Impacts of Methyl Iodide

    E-Print Network [OSTI]

    Carter, W P L

    2007-01-01

    ethylene, propylene, n-butane and trans-2-butene werepropane, propylene, n-butane, n-hexane, toluene, n-octaneas ethylene, propylene, n-butane and trans-2-butene and 30 m

  3. Synthetic approaches to the activation of substituted 2-methyl pyridines 

    E-Print Network [OSTI]

    Cancanon, Fernadina de la Caridad

    1993-01-01

    dichloromethane/hexanes giving ethyl-6-(N-acetyiamino)-2-pyridyl pyruvate (38) (2. 92g, 58'/o). mp (CHzClz/hexanes) 138-141'C (dec). 1H nmr (CDCls, 200MHz), 5: 1. 36 (3H, t, J1=7. 1Hz, OCHzCHs); 2. 50 (3H, s, CHsCONH); 4. 36 (2H, q, Jf =7. 1Hz, OCHzCHs); 6. 10... of the requirements for the degree of MASTER OF SCIENCE Approved as to style and content by: QQ YjM Derek H. R. Barton (Chair of Committee) Jeffery W. Kelly (Member) o M. Member) Michael B. Hall (Head of Departm t) December 1993 Major Subject: Chemistry...

  4. Engineering of bacterial methyl ketone synthesis for biofuels

    E-Print Network [OSTI]

    Goh, Ee-Been

    2012-01-01

    2003. Tools for genetic engineering in the amino acid-thioesterase by protein engineering. Proc. Natl. Acad. Sci.coli via metabolic engineering. Metab. Eng. 11:192-8. Zhou,

  5. Engineering of bacterial methyl ketone synthesis for biofuels

    E-Print Network [OSTI]

    Goh, Ee-Been

    2012-01-01

    All other glass and PTFE surfaces were also rigorouslycontacted only glass or PTFE surfaces, whenever possible.a polytetrafluoroethylene (PTFE)-lined septum for the 1-ml

  6. High-throughput sequencing of cytosine methylation in plant DNA

    E-Print Network [OSTI]

    Hardcastle, Thomas J.

    2013-06-07

    . Genome Res 2008, 18(7):1051–1063. 66. Bormann Chung CA, Boyd VL, McKernan KJ, Fu Y, Monighetti C, Peckham HE, Barker M: Whole methylome analysis by ultra-deep sequencing using two-base encoding. PloS One 2010, 5(2):e9320. 67. Ondov BD, Cochran C, Landers... reads. Bioinformatics 2013, 29(2):268–270. 70. Minoche AE, Dohm JC, Himmelbauer H: Evaluation of genomic high-throughput sequencing data generated on Illumina HiSeq and genome analyzer systems. Genome Biol 2011, 12(11):R112. 71. Wang XV, Blades N, Ding J...

  7. Statistical algorithms in the study of mammalian DNA methylation

    E-Print Network [OSTI]

    Singer, Meromit

    2012-01-01

    non-overlapping CCGIs: the algorithm 2.2.6 Running time andI Statistical algorithms in the study of mammalian DNAof the result of the CCGI algorithm. Nodes marked along the

  8. Validation in Genomics: CpG Island Methylation Revisited

    E-Print Network [OSTI]

    Segal, Mark R

    2006-01-01

    analysis. In: Functional Genomics: Methods and Protocols, M.Segal: Validation in Genomics: CpG Island Methylationpackage and applications to genomics. Bioinformatics and

  9. Engineering of bacterial methyl ketone synthesis for biofuels

    E-Print Network [OSTI]

    Goh, Ee-Been

    2012-01-01

    ketone synthesis for biofuels Ee-Been Goh†† 1,3 , Edward E.microbes for use as biofuels, such as fatty acid ethylother fatty acid-derived biofuels, such as fatty acid ethyl

  10. ORIGINAL ARTICLE -Aminolevulinic acid and its methyl ester induce

    E-Print Network [OSTI]

    Lübbert, Hermann

    tumours, psoriasis and related conditions (MacCormack 2008). PpIX can be generated inside target cells

  11. Some sympathomimetic activities of N-methyl-tyramine 

    E-Print Network [OSTI]

    Blankenship, James William

    1967-01-01

    , 1950) and Acacia berlandieri, a toxic range plant (Adams and Camp, 1966). It was found by Barger and Dale (1910) to have sympathomimetic activity in cats. The major objectives of the present study were: 1. To determine the blood pressure changes...). In 1910, Barger and Dale studied the physiological activity of N-methyltyramine as a member of the 8-phenylethylamine series, They found that the compound when injected into cats caused a rise in arterial blood pressure, and that it also had inhibitory...

  12. Sub-millimeter sized methyl butanoate droplet combustion: Microgravity experiments

    E-Print Network [OSTI]

    Walter, M.Todd

    grown and deployed onto the intersection of two 14 lm silicon carbide fibers in a cross agreement with the measurements. The average burning rates and flame temperatures for both fuels were found to the presence of additional oxygen atoms in the parent fuel. Important differences in the diffusion flame

  13. The contribution of oceanic methyl iodide to stratospheric iodine

    E-Print Network [OSTI]

    2013-01-01

    CH 3 I transport from the surface to the cold point (giventhe vertical transport from the surface to the cold point atCH 3 I transport from the ocean surface to the cold point in

  14. Optical constants of methyl-pentaphenylsilole by spectroscopic ellipsometry

    E-Print Network [OSTI]

    Organic light-emitting diodes OLEDs have attracted a great deal of attention because of their great capability.1 OLEDs are also relatively easy to manufacture and package. The most commonly used emitter. Conventional undoped small-molecule OLED using Alq3 can achieve a high external quantum efficiency QE of 1

  15. Conversion of Levulinic Acid to Methyl Tetrahydrofuran - Energy Innovation

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

    AFDC Printable Version Share this resource Send a link to EERE: Alternative Fuels Data Center Home Page to someone by E-mail Share EERE: Alternative Fuels Data Center Home Page on Facebook Tweet about EERE: Alternative Fuels Data Center Home Page on Twitter Bookmark EERE: Alternative Fuels Data Center Homesum_a_epg0_fpd_mmcf_m.xls" ,"Available from WebQuantityBonneville Power Administration would like submit the followingConcentratingPortal ControllingConvection feedbacks in

  16. "Seeing" Mercury Methylation in Progress

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

    AFDC Printable Version Share this resource Send a link to EERE: Alternative Fuels Data Center Home Page to someone by E-mail Share EERE: Alternative Fuels Data Center Home Page on Facebook Tweet about EERE: Alternative Fuels Data Center Home Page on Twitter Bookmark EERE: Alternative Fuels Data Center Homesum_a_epg0_fpd_mmcf_m.xls" ,"Available from WebQuantity ofkandz-cm11 Outreach Home RoomPreservationBio-Inspired SolarAboutXuRod Hunt (208)

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

    Office of Scientific and Technical Information (OSTI)

    AFDC Printable Version Share this resource Send a link to EERE: Alternative Fuels Data Center Home Page to someone by E-mail Share EERE: Alternative Fuels Data Center Home Page on Facebook Tweet about EERE: Alternative Fuels Data Center Home Page on Twitter Bookmark EERE: Alternative Fuels Data Center Homesum_a_epg0_fpd_mmcf_m.xls" ,"Available from WebQuantity of NaturalDukeWakefieldSulfateSciTechtail. (Conference)Feedback System inStatus ofSmall GTPasesmirror (Journalinsights on the

  18. Kinetic and mechanistic study of methyl transfer from methylcobalamin (methyl vitamin B??) to mercuric ion in aqueous and micellar environments 

    E-Print Network [OSTI]

    Robinson, Glenn Clarke

    1976-01-01

    degrees by aqueous and reverse micelles, it was concluded that a micellar environment could possibly affect the reaction of methylcobalamin and mercuric ion. The study of the effect of the surfactant, sodium dodecyl sulfate, on the rate of reaction... between methylcobalamin and mercuric ion has contributed additional evidence for the proposed two ? step reaction mechanism. By shifting the pKa of the benzimidazole on the methylcobalamin to a higher value than in aqueous solution, sodium dodecyl...

  19. 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.

  20. 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.

  1. 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.

  2. 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.

  3. 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.

  4. A study of the condensation of primary, secondary, and tertiary butyl alcohols with benzene in the presence of anhydrous ferric chloride 

    E-Print Network [OSTI]

    Dodson, Ralph Jordan

    1939-01-01

    with aresatio hg4rosoxboas aeso those shish ooataiao4 the QK greay aituate4 aloes be a 4oohlo boa4 (4) yatosse oa4 yileti, Xloyfer, 8K ~ 5I 5btV (1899) (V) 8ohlaa ao4 Kleyfor, Sar, , ~58 5150 (1899) ~ (8} Khstisoht ao4 PoLaositeh, ~, ~ 5104 (1909} (9...) Huetoa oa4 yx4o4ssouai ~ 5995 (1954) ~ Bootes, sosis, oa4 0roh~at, ibb4, ~ 1555 (195t) g Raelea oa4 Lssis, ~. ~ ~55 SSty (1951) g Rsstca os4 Boat, ~, ~ 1505 (1955}} ~ oa4 stsisuoe, ~b. , ~ 481' (1955} g Bustoa 0eamteat ea4 sasOaL11+ ibbL, ~58 4484...

  5. 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.

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

    SciTech Connect (OSTI)

    Singh, M.; McNutt, B.

    1993-10-01

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

  7. Low-temperature superacid catalysis: Reactions of n-butane catalyzed by iron- and manganese-promoted sulfated zirconia

    SciTech Connect (OSTI)

    Cheung, T.K.; D`Itri, J.L.; Gates, B.C.

    1995-02-01

    Environmental concerns are leading to the replacement of aromatic hydrocarbons in gasoline with high-octane-number branched paraffins and oxygenated compounds such as methyl t-butyl ether, which is produced from methanol and isobutylene. The latter can be formed from n-butane by isomerization followed by dehydrogenation. To meet the need for improved catalysts for isomerization of n-butane and other paraffins, researchers identified solid acids that are noncorrosive and active at low temperatures. Sulfated zirconia catalyzes the isomerization of n-butane even at 25{degrees}C, and the addition of Fe and Mn promoters increases its activity by three orders of magnitude. Little is known about this new catalyst. Here the authors provide evidence of its performance for n-butane conversion, demonstrating that isomerization is accompanied by disproportionation and other, less well understood, acid-catalyzed reactions and undergoes rapid deactivation associated with deposition of carbonaceous material. 10 refs., 3 figs.

  8. Catalytic distillation process

    DOE Patents [OSTI]

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

    1982-01-01

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

  9. Bis(fluoromalonato)borate (BFMB) Anion Based Ionic Liquid As an Additive for Lithium-Ion Battery Electrolytes

    SciTech Connect (OSTI)

    Sun, Xiao-Guang [ORNL] [ORNL; Liao, Chen [ORNL] [ORNL; Baggetto, Loic [ORNL] [ORNL; Guo, Bingkun [ORNL] [ORNL; Unocic, Raymond R [ORNL] [ORNL; Veith, Gabriel M [ORNL] [ORNL; Dai, Sheng [ORNL] [ORNL

    2014-01-01

    Propylene carbonate (PC) is a good solvent for lithium ion battery applications due to its low melting point and high dielectric constant. However, PC is easily intercalated into graphite causing it to exfoliate, killing its electrochemical performance. Here we report on the synthesis of a new ionic liquid electrolyte based on partially fluorinated borate anion, 1-butyl-1,2-dimethylimidazolium bis(fluoromalonato)borate (BDMIm.BFMB), which can be used as an additive in 1 M LiPF6/PC electrolyte to suppress graphite exfoliation and improve cycling performance. In addition, both PC and BDMIm.BFMB can be used synergistically as additive to 1.0M LiPF6/methyl isopropyl sulfone (MIPS) to dramatically improve its cycling performance. It is also found that the chemistry nature of the ionic liquids has dramatic effect on their role as additive in PC based electrolyte.

  10. Variables affecting the yields of fatty esters from transesterified vegetable oils

    SciTech Connect (OSTI)

    Freedman, B.; Pryde, E.H.; Mounts, T.L.

    1984-10-01

    Transesterification reaction variables that affect yield and purity of the product esters from cottonseed, peanut, soybean and sunflower oils include molar ratio of alcohol to vegetable oil, type of catalyst (alkaline vs acidic), temperature and degree of refinement of the vegetable oil. With alkaline catalysts (either sodium hydroxide or methoxide), temperatures of 60 degrees C or higher, molar ratios of at least 6 to 1 and with fully refined oils, conversion to methyl, ethyl and butyl esters was essentially complete in 1 hr. At moderate temperatures (32 degrees C), vegetable oils were 99% transesterified in ca. 4 hr with an alkaline catalyst. Transesterification by acid catalysis was much slower than by alkali catalysis. Although the crude oils could be transesterified, ester yields were reduced because of gums and extraneous material present in the crude oils. 30 references.

  11. The efficient use of natural gas in transportation

    SciTech Connect (OSTI)

    Stodolsky, F.; Santini, D.J.

    1992-04-01

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

  12. The efficient use of natural gas in transportation

    SciTech Connect (OSTI)

    Stodolsky, F.; Santini, D.J.

    1992-01-01

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

  13. Ordered, microphase-separated, noncharged-charged diblock copolymers via the sequential ATRP of styrene and styrenic imidazolium monomers

    SciTech Connect (OSTI)

    Shi, ZX; Newell, BS; Bailey, TS; Gin, DL

    2014-12-15

    A series of imidazolium-based noncharged-charged diblock copolymers (1) was synthesized by the direct, sequential ATRP of styrene and styrenic imidazolium bis(trifluoromethyl)sulfonamide monomers with methyl, n-butyl, and n-decyl side-chains. Small-angle X-ray scattering studies on initial examples of 1 with a total of 50 repeat units and styrene:imidazolium-styrene repeat unit ratios of 25:25, 20:30, and 15:35 showed that their ability to form ordered nanostructures (i.e., sphere and cylinder phases) in their neat states depends on both the block ratio and the length of the alkyl side-chain on the imidazolium monomer. To our knowledge, the synthesis of imidazolium-based BCPs that form ordered, phase-separated nanostructures via direct ATRP of immiscible co-monomers is unprecedented. (C) 2014 Elsevier Ltd. All rights reserved.

  14. Development of a partition function for polymer systems 

    E-Print Network [OSTI]

    Oliver-Labra, Pedro Aurelio

    1967-01-01

    of the Reduced Pressure, Reduced Temperature, and Calculated Reduced Vol- ume i'or Mixtures of Heptane and Butyl Rubber 19 III. Values for Mixtures of Octane and Butyl Rubber 19 IV. Values for Mixtures of Nonane and Butyl Rubber 20 V. Values for Mixtures... of Decane and Butyl Rubber 20 VI. Values Obtained Using the Formulation Derived in this Thesis for Heptane and Butyl Rubber 23 VII. Values for Mixtures of Octane and Butyl Rubber 23 VIII. Values for Mixtures of Nonane and Butyl Rubber 24 IX. Values...

  15. Nitroxides: Profluorescent Sensors and Functionalized Alkoxyamine Initiators for Nitroxide Mediated Radical Polymerization

    E-Print Network [OSTI]

    TANSAKUL, CHITTREEYA

    2012-01-01

    Sigma-Aldrich, 99%), styrene (Fisher, 99.9%) and tert-butylpolymerization (NMRP) of styrene using TIPNO-based initiatorScheme 5.8 Polymerization of styrene and tert-butylacrylate

  16. Efficacy of the investigational mTOR kinase inhibitor MLN0128 / INK128 in models of B-cell acute lymphoblastic leukemia

    E-Print Network [OSTI]

    2012-01-01

    and xenograft experiments with human leukemia samples NIH-PAculture experiments, hTERT-immortalized human marrow stromal

  17. Synthesis, Structure, and Molecular Orbital Studies of Yttrium, Erbium, and Lutetium Complexes Bearing 2-Pyrazolato Ligands: Development of a New Class of Precursors for

    E-Print Network [OSTI]

    Schlegel, H. Bernhard

    Synthesis, Structure, and Molecular Orbital Studies of Yttrium, Erbium, and Lutetium Complexes-tert-butylpyrazole)erbium(III) (59%), respectively. Treatment of tris(cyclopentadienyl)lutetium(III) or tris temperature for 24 h afforded tris(3,5-di-tert- butylpyrazolato)bis(4-tert-butylpyridine)lutetium(III) (83

  18. 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.

  19. 5570 J.Org. Chem. 1987,52, 5570-5574 597-49-9; phenol, 108-95-2; 2,6-di-tert-butylphenol,128-39-2;

    E-Print Network [OSTI]

    Keinan, Ehud

    , 111-85-3; 1-bromooctane, 111-83-1;1-iodooctane, 629-27-6;2-bromooctane, 557-35-7;cyclohexyl bromide developed for reductive dehalogenation of a-halo carbonyl compounds include (a) reducing agents such as zinc

  20. 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.

  1. 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).

  2. 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.

  3. 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.

  4. Detailed comparisons of airborne formaldehyde measurements with box models during the 2006 INTEX-B and MILAGRO campaigns: potential evidence for significant impacts of unmeasured and multi-generation volatile organic carbon compounds

    E-Print Network [OSTI]

    2011-01-01

    of 2-butyl nitrate to butane, as dis- cussed by Bertman ethereafter be referred to as butane time or photochemicalof 2-butyl nitrate to butane (see Perring et al. , 2010)

  5. Enhanced photodegradation of methyl orange with TiO nanoparticles using a triboelectric

    E-Print Network [OSTI]

    Wang, Zhong L.

    creatures. Consequently, a green, energy-saving and low cost method for purifying water sources is desired triboelectric nanogenerator (TENG) whose electric power output can be used for enhancing the photodegradation of MO with the presence of TiO2 nanoparticles, because the TENG generated electric field can effectively

  6. Recent trends in atmospheric methyl bromide: analysis of post-Montreal Protocol variability

    E-Print Network [OSTI]

    Yvon-Lewis, S. A; Saltzman, E. S; Montzka, S. A

    2009-01-01

    and validate current models of oceanic cycling. Atmos. Chem.condi- tions to validate current models of oceanic cycling.oceanic CH 3 Br saturation anomalies, to provide a comparison of pre-phaseout and current

  7. DNA methylation map of mouse and human brain identifies target genes in Alzheimer's disease

    E-Print Network [OSTI]

    2013-01-01

    Institute of Oncology of Asturias (IUOPA), HUCA, Universidada del Principado de Asturias (IUOPA), HUCA, Universidad de

  8. Contribution of Iron-Reducing Bacteria to Mercury Methylation in Marine Sediments

    E-Print Network [OSTI]

    Fleming, Emily J.; Nelson, D C

    2006-01-01

    sediments. Environmental Toxicology and Chemistry 18: 1362-pH lakes. Environmental Toxicology and Chemistry 9: 853-69.Nevada, USA. Environmental Toxicology and Chemistry 15: 677-

  9. Backbiting and b-Scission Reactions in Free-Radical Polymerization of Methyl Acrylate

    E-Print Network [OSTI]

    Rappe, Andrew M.

    decade, stringent environmental regula- tions have lowered the volatile organic content in paint of acrylates is used to manufacture a wide variety of paints, coatings, and adhe- sives.[1,2] In the last

  10. Absorption Spectra and Photolysis of Methyl Peroxide in Liquid and Frozen Water

    E-Print Network [OSTI]

    Nizkorodov, Sergey

    from the gas phase, and they do not change upon freezing. Between -12 and 43 °C, the quantum yield narrowing and shifting to the blue under cryogenic conditions because of constrained dihedral motion around

  11. Intradimer and interdimer methylation response by bacterial chemoreceptors to attractant stimulus 

    E-Print Network [OSTI]

    Bormans, Arjan Frank

    2007-04-25

    of the current concentration with the concentration in the recent (a few seconds) past. The current concentration is measured as the percent occupancy of the extracellular ligand-binding domain of the receptor, and the past is represented by the extent...

  12. Reprogramming DNA Methylation in Bovine Cells by Knocking Down DNA Methyltransferase-1 with RNA Interference 

    E-Print Network [OSTI]

    Stroud, Todd

    2010-01-20

    fluorescent protein (GFP) that will allow us to identify cells expressing the hairpin as well as a region coding for neomycin resistance so we could select for a pure population of transgenic cells to use for analysis. Infecting bovine fetal fibroblast cells...

  13. Determinants of Unique DNA Methylation, Histone Modification, and Nucleosome Occupany at CpG Islands

    E-Print Network [OSTI]

    Langerman, Justin Bryon

    2014-01-01

    ammonium acetate and precipitated with 2mg yeast tRNA. Bisulfite-ammonium acetate and precipitated with 2mg yeast tRNA. Bisulfite-

  14. Cysteine Dioxygenase 1 Is a Tumor Suppressor Gene Silenced by Promoter Methylation in Multiple Human Cancers

    E-Print Network [OSTI]

    2012-01-01

    Construction and Stable Cell Lines Full-length CDO1 wasof full-length CDO1 in human cancer cells markedly decreased

  15. Global sea-to-air flux climatology for bromoform, dibromomethane and methyl iodide

    E-Print Network [OSTI]

    2013-01-01

    cess Atmospheric Chemistry and Physics Open Accessvon Glasow, R. : Atmospheric chemistry – sun, sea and ozoneUK 4 Marine and Atmospheric Chemistry, Rosenstiel School of

  16. 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.

  17. Methyl jasmonate elicits rapid changes in carbon and nitrogen dynamics in tomato

    E-Print Network [OSTI]

    Orians, Colin

    et al., 1995; Mahanil et al., 2008), phenolic compounds (Stamp & Yang, 1996), glycoalkaloids (Duffey associated costs, related to the biosynthesis, maintenance, storage and construction of structures, as well

  18. Aging effects on DNA methylation modules in human brain and blood tissue

    E-Print Network [OSTI]

    2012-01-01

    error Total variation Proportion of total F variancecan determine what proportion of the variation in eigengene-of variation Source ave.kME.green, total proportion of

  19. Catalytic Hydrodeoxygenation of Methyl-Substituted Phenols: Correlations of Kinetic Parameters with Molecular Properties

    E-Print Network [OSTI]

    Simons, Jack

    with Molecular Properties F. E. Massoth, P. Politzer,,§ M. C. Concha,,§ J. S. Murray,,§ J. Jakowski,, and Jack reactant- molecule properties, a reaction mechanism is proposed for each pathway, and it is suggested to remove them to preserve the catalyst's lifetime. The potential use of synthetic oils derived from coal

  20. Selective Methylation Changes on the Bacillus subtilis Chemotaxis Receptor McpB Promote Adaptation*

    E-Print Network [OSTI]

    Ordal, George W.

    . McpB(Q371D,E630D,E637D) in a (mcpA mcpB tlpA tlpB)101::cat mcpC4::erm background failed to release

  1. DNA methylation map of mouse and human brain identifies target genes in Alzheimer's disease

    E-Print Network [OSTI]

    2013-01-01

    PLoS One 2009; 2: e895. Song CX, Szulwach KE, Fu Y, Dai Q,Szulwach KE, Li X, Li Y, Song CX, Wu H, Dai Q, et al. 5-hmC-cells), cerebral cortex (CX, CA1, CA3 and den- tate gyrus)

  2. 2?-O Methylation of Internal Adenosine by Flavivirus NS[subscript 5] Methyltransferase

    E-Print Network [OSTI]

    Dong, Hongping

    RNA modification plays an important role in modulating host-pathogen interaction. Flavivirus NS5 protein encodes N-7 and 2?-O methyltransferase activities that are required for the formation of 5? type I cap (m[superscript ...

  3. DNA methylation map of mouse and human brain identifies target genes in Alzheimer's disease

    E-Print Network [OSTI]

    2013-01-01

    putamen, substantia nigra, hypothalamus, globus pallidus andÀ 0.90 to À 0.95), hypothalamus ( À 0.82), globus pallidus (

  4. Disruption of DNA methylation induces genome-specific changes in gene expression in Arabidopsis allotetraploids 

    E-Print Network [OSTI]

    Chen, Meng

    2007-04-25

    Allopolyploids are formed by the combination of evolutionarily-diverged genomes, the union of which leads to dynamic changes in gene expression and genome organization. Expression patterns of orthologous genes are rapidly and stochastically...

  5. Costs of 2001 methyl bromide rules estimated for California strawberry industry

    E-Print Network [OSTI]

    Carter, Colin A.; Chalfant, James A.; Goodhue, Rachael E.; McKee, Gregory J.

    2005-01-01

    requirements. California strawberry industry California’sfresh and processed strawberry sales were $805.8 millionCalif. strawberry acreage using MBr MBr applied per acre to

  6. Instrument intercomparison of glyoxal, methyl glyoxal and NO2 under simulated atmospheric conditions

    E-Print Network [OSTI]

    2015-01-01

    to an unheated 1/8 inch OD PTFE line (? 1 m length), whichoutside diameter), 1/4 inch ID (inside diameter) PTFE tube.Halfway along the cavity, a PTFE tee was used as an inlet

  7. Toward Organic Photohydrides: Excited-State Behavior of 10-Methyl-9-phenyl-9,10-dihydroacridine

    E-Print Network [OSTI]

    Krylov, Anna I.

    , and these reactions are driven by the stabilization of the aromatized NAD+ product.1 Given its biological significance fuels, by reducing protons to hydrogen12-18 or carbon dioxide to methanol,19 via simple earth cleavage to generate the aromatic PhAcr+ product upon excitation. In the absence of protic solvation, Ph

  8. Fungal inoculation and methyl jasmonate application induce highly variable terpene accumulation in Norway spruce

    E-Print Network [OSTI]

    in Norway spruce Tao Zhao 1, Paal Krokene 2, Niklas Björklund 3, Nadir Erbilgin 4 , Erik Christiansen 2 Bo of Chemistry, KTH, SE-100 44 Stockholm, Sweden 2 Norwegian Forest and Landscape Institute, N-1431 Ås, Norway 3 healthy forests. With the aims of characterizing the defensive chemical induction in Norway spruce Picea

  9. 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 [Stony Brook Univ., NY (United States). School of Medicine; Brookhaven National Lab. (BNL), Upton, NY (United States); Fowler, Joanna S. [Brookhaven National Lab. (BNL), Upton, NY (United States); State University of New York, Stony Brook, NY (United States); Alexoff, David L. [Brookhaven National Lab. (BNL), Upton, NY (United States); Kim, Sung Won [National Institute on Alcoholism and Alcohol Abuse, Bethesda, MD (United States); Logan, Jean [New York University Langone Medical Center, New York, NY (United States); Pareto, Deborah [Institut de Recerca Hospital Universitari Vall d'Hebron, Universitat Autònoma de Barcelona, Alta Tecnologia, Barcelona (Spain); Schlyer, David [Brookhaven National Lab. (BNL), Upton, NY (United States); Wang, Gene-Jack [National Institute on Alcoholism and Alcohol Abuse, Bethesda, MD (United States)

    2015-04-01

    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.

  10. Effect of thermal history on the molecular orientation in polystyrene/poly(vinyl methyl ether) blends

    E-Print Network [OSTI]

    Pezolet, Michel

    volume and mechanical deformation of polyimides and polycarbonate [16,17]. Wang et al. have reported

  11. Genome-wide conserved consensus transcription factor binding motifs are hyper-methylated

    E-Print Network [OSTI]

    Choy, Mun-Kit; Movassagh, Mehregan; Goh, Hock-Guan; Bennett, Martin; Down, Thomas A.; Foo, Roger S.-Y.

    2010-09-27

    M: Epigenetic differences arise during the lifetime of monozygotic twins. Proc Natl Acad Sci USA 2005, 102:10604-10609. 6. Christensen BC, Houseman EA, Marsit CJ, Zheng S, Wrensch MR, Wiemels JL, Nelson HH, Karagas MR, Padbury JF, Bueno R, Sugarbaker...

  12. Regulation of DNA Methylation and Hydroxymethylation in Postmitotic Neurons and Other Mammalian Cells

    E-Print Network [OSTI]

    Le, Thuc Minh

    2013-01-01

    ion source (Agilent Jet Stream) connected to a tripleion source (Agilent Jet Stream) connected to a triple

  13. Sorption/Desorption Kinetics and Equilibria of Atrazine, Diuron, And Bensulfuron Methyl on Selected Soils

    E-Print Network [OSTI]

    Sparks, Donald L.

    Soils M. Zhou, R. K. Trubey, T. M. Priester and T. H. Carski Sorption/desorption isotherm equilibria soils. Results indicated that the content of organic matter was the major variable contributing that both pesticides were not readily desorbed from the soils tested. The rates of sorption were more rapid

  14. Theoretical Study of Zeolite-Catalyzed Dimethoxymethane Carbonylation to Methyl Methoxyacetate

    E-Print Network [OSTI]

    Bell, Alexis

    be obtained by gasification of a variety of carbon sources, such as methane, coal, and biomass. One potential materials. A potentially attractive candidate is synthesis gas, a mixture of CO and H2, which can route for the production of MEG from syngas is shown in Figure 1. In the first step, methanol

  15. Genome-Wide Quantitative Identification of DNA Differentially Methylated Sites in Arabidopsis Seedlings

    E-Print Network [OSTI]

    Jones, Alan M.

    the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and Biosciences, Office of Basic Energy Sciences of the United States Department of Energy through the grant DE

  16. Arsenic methylation and lung and bladder cancer in a case-control study in northern Chile

    SciTech Connect (OSTI)

    Melak, Dawit; Ferreccio, Catterina; Kalman, David; Parra, Roxana; Acevedo, Johanna; Pérez, Liliana; Cortés, Sandra; Smith, Allan H.; Yuan, Yan; Liaw, Jane; Steinmaus, Craig

    2014-01-15

    In humans, ingested inorganic arsenic is metabolized to monomethylarsenic (MMA) then to dimethylarsenic (DMA), although this process is not complete in most people. The trivalent form of MMA is highly toxic in vitro and previous studies have identified associations between the proportion of urinary arsenic as MMA (%MMA) and several arsenic-related diseases. To date, however, relatively little is known about its role in lung cancer, the most common cause of arsenic-related death, or about its impacts on people drinking water with lower arsenic concentrations (e.g., < 200 ?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), 0.99–3.67), and 3.26 (1.76–6.04) (p-trend < 0.001). Corresponding odds ratios for bladder cancer were 1.00, 1.81 (1.06–3.11), and 2.02 (1.15–3.54) (p-trend < 0.001). In analyses confined to subjects only with arsenic water concentrations < 200 ?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 (1.08–5.68) and 2.37 (1.01–5.57), respectively. Overall, these findings provide evidence that inter-individual differences in arsenic metabolism may be an important risk factor for arsenic-related lung cancer, and may play a role in cancer risks among people exposed to relatively low arsenic water concentrations. - Highlights: • Urine arsenic metabolites were measured in cancer cases and controls from Chile. • Higher urine %MMA values were associated with increased lung and bladder cancer. • %MMA-cancer associations were seen at drinking water arsenic levels < 200 ?g/L.

  17. Solution Spraying of Poly(methyl methacrylate) Blends to Fabricate Micro-textured, Superoleophobic

    E-Print Network [OSTI]

    and electrospinning processes. In melt spinning, a polymer melt is extruded through a spinneret and is taken up resulting in fibers of 0.5-2 m [8]. In contrast, electrospinning involves the application of a strong (submicron) fibers. The electrospinning process is limited by the slow rate of fiber production

  18. Molecular detection of B-cell neoplasms by specific DNA methylation biomarkers

    E-Print Network [OSTI]

    2010-01-01

    Blast % in bone marrow Karyotype DLC-1 M/7 Complex Pos M/2Complex Pos F/10Complex Pos F/13 Complex Pos M/6 47, XY, +21 Pos F/22 t(9;

  19. Biogenic 2-methyl-3-buten-2-ol increases regional ozone and HOx sources

    E-Print Network [OSTI]

    Goldstein, Allen

    similar daily maxima of about 5 mg mÀ2 hrÀ1 . MBO oxidation causes an increase in ozone, formaldehyde, acetone and consequently hydrogen radical production (PHOx). The addition of MBO increases the daily in the Central Valley. Formaldehyde concentrations increase by as much as 1 ppb (40%) over the Sierra Nevada

  20. A neutron diffraction study of bis(cyclopentadienyl)(methyl)(methylene)tantalum(V) at 15 K

    E-Print Network [OSTI]

    Takusagawa, Fusao

    1988-01-01

    ORNL-TM-305. Oak Ridge National Laboratory, Oak Ridge, Tennessee, USA. CARDIN, D. J. , CETINKAYA, B., DOYLE, M. J. & LAPPERT, M. F. (1973). Chem. Soc. Rev. 2, 99-144. CLARK, G . R., ROPER, W . R. & WRIGHT, A . H . (1984). J. Organomet. Chem. 273, C... . & SCHROCK, R. R. (1982). J. Am. Chem. Soc. 104, 6322-6329. IVIN, K. J. (1983). Olefin Metathesis. London: Academic Press. JOHNSON, C. K. (1976). ORTEPll. Report ORNL-5138. Oak Ridge National Laboratory, Oak Ridge, Tennessee, USA. KOESTER, L. (1977...

  1. Temperature dependence of the vapour tension of methyl-substituted phenol derivatives

    SciTech Connect (OSTI)

    S.G. Gagarin [Institute of Mineral Fuels (Russian Federation)

    2007-05-15

    Notable among the coking products of coal are phenol and its derivatives, derived for the coal tar and water layer above ht tar. Given that phenol an its derivatives are mainly extracted from coal tar fractions by rectification, information on how the vapor tension of the individual components depends on the temperature is of great importance. For phenol and various substituted alkylphenols there are tabular data. In the pre-computer era these data were sufficient for the separation of phenol mixtures. However, the development and introduction of information technology in the coal industry and in the design process demands the mathematical description of the physicochemical processes of coking products. The temperature dependence of the saturated vapor pressure for organic compounds is commonly described by the Antoine equation.

  2. Methyl Chloride Adsorption on Si(001)-Electronic Structure M. Preuss,* W. G. Schmidt, and F. Bechstedt

    E-Print Network [OSTI]

    Schmidt, Wolf Gero

    reactions with metals, hydrogen, oxygen, and halogens have been intensively studied in the past.1 Fueled found interest in the context of silicon carbide film growth. The CH3Cl/Si interface has been

  3. Contribution of Iron-Reducing Bacteria to Mercury Methylation in Marine Sediments

    E-Print Network [OSTI]

    Fleming, Emily J.; Nelson, D C

    2006-01-01

    iron, which is characteristic of acid weathering of exposed miningexposed mining areas, a suite of other metals (such as iron,

  4. Crystal structures of 2-formyl-6-methyl- and 6-bromo-2-formylpyridine 4-phenylthiosemicarbazones

    SciTech Connect (OSTI)

    Chumakov, Yu. M. [Academy of Sciences of Moldova, Institute of Applied Physics (Moldova, Republic of); Tsapkov, V. I., E-mail: vtsapkov@gmail.com [Moldova State University (Moldova, Republic of); Antosyak, B. Ya.; Simonov, Yu. A. [Academy of Sciences of Moldova, Institute of Applied Physics (Moldova, Republic of); Ianelli, S. [National Research Council, Institute of Materials for Electronics and Magnetism (Italy); Bairac, N. N.; Gulea, A. P. [Moldova State University (Moldova, Republic of); Palomares-Sanchez, S. A. [Autonomous University of San Luis Potosi (Mexico)

    2011-01-15

    New thiosemicarbazones-2-formyl-6-methylpyridine 4-phenylthiosemicarbazone (I) and 6-bromo-2-formylpyridine 4-phenylthiosemicarbazone hydrate (II)-were synthesized and their structures were determined. Molecules I and II are nonplanar, the phenyl moiety at the terminal nitrogen atom being rotated by 19.9 Degree-Sign and 39.5 Degree-Sign , respectively. The water molecule is the main factor determining the crystal packing of molecules II.

  5. Intermediate-Valence Tautomerism in Decamethylytterbocene Complexes of Methyl-Substituted Bipyridines

    E-Print Network [OSTI]

    Booth, Corwin H.

    2011-01-01

    enthalpy (or energy) and favored by the entropy. The computational studies therefore illuminate the thermochemical

  6. Methyl chloride variability in the Taylor Dome ice core during the Holocene

    E-Print Network [OSTI]

    Verhulst, Kristal R; Aydin, Murat; Saltzman, Eric S

    2013-01-01

    in the Taylor Dome ice core during the Holocene Kristal R.2005GB002680. Lee-Taylor, J. , and K. R. Redeker (2005),

  7. 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; Brookhaven National Lab.; Fowler, Joanna S.; State University of New York, Stony Brook, NY; 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

  8. Essential versus potentially toxic dietary substances: A seasonal comparison of essential fatty acids and methyl mercury

    E-Print Network [OSTI]

    Mazumder, Asit

    to storage lipids that represent the primary source of metabolic energy in zooplankton during periods of low supply of essential fatty acids, while MeHg bioaccumulates with zooplankton size. Abstract We significantly with increasing plankton size and were independent of plankton taxonomy. However, total EFA

  9. The dimethyl sulfide reaction with atomic chlorine and its implications for the budget of methyl chloride

    E-Print Network [OSTI]

    Langer, Sarka; McGovney, Brian T; Finlayson-Pitts, Barbara J; Moore, Robert M

    1996-01-01

    of dimethyl disulfide (DMDS,-0.4%) and ethyl methylchloride. Since EMS and DMDS were observed as impurities inwhether the CI-EMS and CI-DMDS reactions produced CH3CI. No

  10. Forest nurseries face critical choices with the loss of methyl bromide fumigation

    E-Print Network [OSTI]

    Weiland, Jerry E; Littke, Will R; Haase, Diane L

    2013-01-01

    Pic), dimethyl disulfide (DMDS), and 1,3-dichloropropene (store in California (CDPR 2011). Dimethyl disulfide (DMDS).The fumi- gant DMDS also holds promise if odor issues can be

  11. Carbon-Sulfur Bond Cleavage of Methyl-Substituted Thiophenes with Iridium(III)

    E-Print Network [OSTI]

    Jones, William D.

    polluting sulfur compounds are removed during the hydroprocessing of crude oil. Unrefined petroleum contains of a hydrogen acceptor, the thiophene was desulfurized (eq 2).4 Also, in the heterogeneous CoMo system it has

  12. Genes methylated by DNA methyltransferase 3b are similar in mouse intestine and human colon cancer

    E-Print Network [OSTI]

    Steine, Eveline J.

    Human cancer cells frequently have regions of their DNA hypermethylated, which results in transcriptional silencing of affected genes and promotion of tumor formation. However, it is still unknown whether cancer-associated ...

  13. Methylation analysis and diagnostics of Beckwith-Wiedemann syndrome in 1,000 subjects

    E-Print Network [OSTI]

    Ibrahim, Abdulla; Kirby, Gail; Hardy, Carol; Dias, Renuka P.; Tee, Louise; Lim, Derek; Berg, Jonathan; MacDonald, Fiona; Nightingale, Peter; Maher, Eamonn R.

    2014-06-04

    of BWS, in comparison to current clinical diagnostic criteria, for any given sensitivity it has the highest specificity and vice versa, thus improving the overall diagnosis of the disorder. Moreover, in view of the tumour risk to a missed diagnosis of BWS... the diagnostic testing service was approved by the Birmingham Women’s Hospital Research and Devel- opment Office.that the ratio of normalised peak intensities was compared between the reference and the sample trace; ratios of ?0.75 and ?1.25 for each of the four...

  14. Contribution of Iron-Reducing Bacteria to Mercury Methylation in Marine Sediments

    E-Print Network [OSTI]

    Fleming, Emily J.; Nelson, D C

    2006-01-01

    in continental margin sediments off central Chile. Limnologyof microbial iron reduction in sediments of the Baltic-Northreducing bacteria from sediments of an acid stressed lake.

  15. Sublethal Effects of Chlorpyrifos-Methyl on Reproduction in Female German Cockroaches (Dictyoptera: Blattellidae)

    E-Print Network [OSTI]

    [1969] and Haynes [1988]). The German cockroach, Blattella germanica (L.), is a major pest of economic of organophosphate or carbamate insecticides to female cockroaches before they produce oothecae have not been studied of female German cockroaches. Materials and Methods Insects used in this study were from an estab- lished

  16. Genomic DNA methylation in various developmental stages of two plant pathogenic fungi 

    E-Print Network [OSTI]

    Schliesing, Laura Jo

    1990-01-01

    showing Southern hybridization of pRW614a to a blot of S. rolfsii mycelial DNA digested with HpaII and Mspl. Autoradiogram showing Southern hybridization of pRW614a to a blot of P. omnivorum mycelial and sclerotial DNA digested with Sau3AI and Mbo...I. Autoradiogram showing Southern hybridization of pRW614a to a blot of S. rolfsii mycelial and sclerotial DNA digested with Sau3AI and MboI. Page 27 28 29 31 34 I. INTRODUCTION To date, the molecular mechanisms responsible for the activity of genes...

  17. Isolation, Determination of Absolute Stereochemistry, and Asymmetric Synthesis of Insect Methyl-Branched Hydrocarbons

    E-Print Network [OSTI]

    Bello, Jan Edgar

    2014-01-01

    d’Ettore, P. In Insect Hydrocarbons: Biology, Biochemistry,A.G. In Insect Hydrocarbons: Biology, Biochemistry, ChemicalMillar, J.G. In Insect Hydrocarbons: Biology, Biochemistry,

  18. Aging effects on DNA methylation modules in human brain and blood tissue

    E-Print Network [OSTI]

    2012-01-01

    changes in chromosomes cause aging? Cell 1996, 86:9-12. 2.M: Cross-Talk between Aging and Cancer. Annals of the NewMF, Esteller M: Epigenetics and aging: the targets and the

  19. Catalytic Transformation of C7-C9 Methyl Benzenes over USY-based FCC Zeolite Catalyst

    E-Print Network [OSTI]

    Al-Khattaf, Sulaiman

    in the petrochemical market. Most of the currently working isomerization plants are using zeolite based catalysts. One) and the diphenyl methane mechanism. It was shown that toluene disproportionation does not require Brönsted acid

  20. Methyl halide and biogenic volatile organic compound fluxes from perennial bioenergy crops and annual arable crops 

    E-Print Network [OSTI]

    Morrison, Eilidh Christina

    2013-11-28

    The depletion of fossil fuel resources, pollution concerns and the challenge of energy security are driving the search for renewable energy sources. The use of lignocellulosic plant biomass as an energy source is increasing ...

  1. A study of the mixed association of cholesterol with methyl cholate by vapor pressure osmometry 

    E-Print Network [OSTI]

    Foster, Bruce William

    1981-01-01

    ) is rearranged as follows: * k g k b(c? ) A2 g 82 k c ~ 0 0 0 2MA 28 MB MAB AB A 8 g Bg then obviously the l. h. s. of eq. (28) should be equal for every (28) value of 8 at which the experiment is conducted (assuming experi- g mental conditions... outlined assuming the same model d1scussed 1n section 3. 1. and represented by eqs. (18), The stoichiometr1c equations wh1ch apply are: 2 A t A A A AB A B AB 2 2qAqB (5oa) 2 3 2 Bt qB 5 B B ABAqB ABqqB 2 3 2 ? qA qB B qA B qB B B eq eq 2 2 3 2 2 3...

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

    Office of Scientific and Technical Information (OSTI)

    AFDC Printable Version Share this resource Send a link to EERE: Alternative Fuels Data Center Home Page to someone by E-mail Share EERE: Alternative Fuels Data Center Home Page on Facebook Tweet about EERE: Alternative Fuels Data Center Home Page on Twitter Bookmark EERE: Alternative Fuels Data Center Homesum_a_epg0_fpd_mmcf_m.xls" ,"Available from WebQuantity of NaturalDukeWakefield MunicipalTechnical Report: Achievements ofCOMPOSITION OF VAPORSSeries)SupportedDavidA - L

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

    Office of Scientific and Technical Information (OSTI)

    AFDC Printable Version Share this resource Send a link to EERE: Alternative Fuels Data Center Home Page to someone by E-mail Share EERE: Alternative Fuels Data Center Home Page on Facebook Tweet about EERE: Alternative Fuels Data Center Home Page on Twitter Bookmark EERE: Alternative Fuels Data Center Homesum_a_epg0_fpd_mmcf_m.xls" ,"Available from WebQuantity of NaturalDukeWakefieldSulfate Reducing(Journal Article) | SciTech(Journal Article) | SciTech Connect Effects of nickel,

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

    Office of Scientific and Technical Information (OSTI)

    AFDC Printable Version Share this resource Send a link to EERE: Alternative Fuels Data Center Home Page to someone by E-mail Share EERE: Alternative Fuels Data Center Home Page on Facebook Tweet about EERE: Alternative Fuels Data Center Home Page on Twitter Bookmark EERE: Alternative Fuels Data Center Homesum_a_epg0_fpd_mmcf_m.xls" ,"Available from WebQuantity of NaturalDukeWakefieldSulfate Reducing(JournalspectroscopyReport)Fermentative ActivitySciTech Connect

  5. Phase 1 Methyl Iodide Deep-Bed Adsorption Tests (Technical Report) |

    Office of Scientific and Technical Information (OSTI)

    AFDC Printable Version Share this resource Send a link to EERE: Alternative Fuels Data Center Home Page to someone by E-mail Share EERE: Alternative Fuels Data Center Home Page on Facebook Tweet about EERE: Alternative Fuels Data Center Home Page on Twitter Bookmark EERE: Alternative Fuels Data Center Homesum_a_epg0_fpd_mmcf_m.xls" ,"Available from WebQuantity of NaturalDukeWakefieldSulfateSciTech ConnectSpeeding accessusers' guide. V1.0.0. Citation DetailsSciTech Connect Phase

  6. Phase 1 Methyl Iodide Deep-Bed Adsorption Tests (Technical Report) |

    Office of Scientific and Technical Information (OSTI)

    AFDC Printable Version Share this resource Send a link to EERE: Alternative Fuels Data Center Home Page to someone by E-mail Share EERE: Alternative Fuels Data Center Home Page on Facebook Tweet about EERE: Alternative Fuels Data Center Home Page on Twitter Bookmark EERE: Alternative Fuels Data Center Homesum_a_epg0_fpd_mmcf_m.xls" ,"Available from WebQuantity of NaturalDukeWakefieldSulfateSciTech ConnectSpeeding accessusers' guide. V1.0.0. Citation DetailsSciTech Connect

  7. 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)

    AFDC Printable Version Share this resource Send a link to EERE: Alternative Fuels Data Center Home Page to someone by E-mail Share EERE: Alternative Fuels Data Center Home Page on Facebook Tweet about EERE: Alternative Fuels Data Center Home Page on Twitter Bookmark EERE: Alternative Fuels Data Center Homesum_a_epg0_fpd_mmcf_m.xls" ,"Available from WebQuantityBonneville Power Administration would likeUniverse (Journalvivo Low-Dose Low LET Ionizing RadiationSNACGeography

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

    E-Print Network [OSTI]

    Marcinek, M.

    2008-01-01

    Microwave Plasma Chemical Vapor Deposition of Nano-tert-butoxide by a one step microwave plasma chemical vaporBatteries; Anode; Plasma; Microwave Corresponding author. E-

  9. Fourth National Report on Human Exposure to Environmental Chemicals Fourth National Report on Human Exposure to

    E-Print Network [OSTI]

    Bisphenol A(2,2-bis[4-Hydroxyphenyl] propane) 30 4-tert-Octylphenol (4-[1,1,3,3- Tetramethylbutyl] phenol

  10. Fluorine-Containing ABC Linear Triblock Terpolymers: Synthesis and Self-assembly in Solution

    SciTech Connect (OSTI)

    He, Lihong [ORNL; Hinestrosa Salazar, Juan P [ORNL; Pickel, Joseph M [ORNL; Kilbey, II, S Michael [ORNL; Mays, Jimmy [ORNL; Zhang, Shanju [Georgia Institute of Technology; Bucknall, David G. [Georgia Institute of Technology; Hong, Kunlun [ORNL

    2011-01-01

    In this paper a fluorine-containing monomer, 2-fluroroethyl methacrylate (2FEMA) was used to synthesize the linear triblock terpolymer poly(n-butyl methacrylate)-poly(methyl methacrylate)-poly(2-fluoroethyl methacrylate) (PnBMA-PMMA-P2FEMA). A kinetic study of the homopolymerization of 2FEMA by reversible addition-fragmentation chain transfer (RAFT) polymerization showed that it demonstrates living character and produces well defined polymers with reasonably narrow polydispersities (~1.30). Triblock terpolymers were prepared sequentially using a purified Macro-CTA at 70 oC, resulting in final terpolymers with high Dp for each block (>150) and with polydispersities between 1.6 and 2.1. The structure and molecular weights of the resultant PnBMA-PMMA-P2FEMA triblock terpolymers were characterized via 1H NMR, 19F NMR, and gel permeation chromatography (GPC). Self-assembly of these polymers was carried out in a selective solvent and the micellar aggregates (MAs) thereby formed were analyzed using scanning electron microscopy (SEM) and dynamic light scattering (DLS). It was confirmed from SEM that these copolymers could directly self-organize into large compound micelles in tetrahydrofuran/methanol with different diameters, depending on polymer composition.

  11. Antiandrogenic properties of parabens and other phenolic containing small molecules in personal care products

    SciTech Connect (OSTI)

    Chen Jiangang; Ahn, Ki Chang; Gee, Nancy A.; Gee, Shirley J.; Hammock, Bruce D.; Lasley, Bill L. . E-mail: bllasley@ucdavis.edu

    2007-06-15

    To identify the androgenic potency of commonly used antimicrobials, an in vitro androgen receptor-mediated transcriptional activity assay was employed to evaluate the androgenic/antiandrogenic activity of parabens and selected other antimicrobials containing a phenolic moiety. This cell-based assay utilizes a stably transfected cell line that lacks critical steroid metabolizing enzymes and is formatted in a 96-well format. At a concentration of 10 {mu}M, methyl-, propyl- and butyl-4-hydroxybenzoate (parabens) inhibited testosterone (T)-induced transcriptional activity by 40%, 33% and 19%, respectively (P < 0.05), while 4-hydroxybenzoic acid, the major metabolite of parabens, had no effect on T-induced transcriptional activity. Triclosan inhibited transcriptional activity induced by T by more than 92% at a concentration of 10 {mu}M, and 38.8% at a concentration of 1.0 {mu}M (P < 0.05). Thirty-four percent of T-induced transcriptional activity was inhibited by thymol at 10 {mu}M (P < 0.05). Cell proliferation and/or cytotoxicity were not observed in any of the treatments. None of the compounds appeared to be androgenic when tested individually without T. The data presented in this report demonstrate that some widely used antimicrobial compounds have antiandrogenic properties and warrant further investigation to fully understand their potential impact on human reproductive health.

  12. Advanced quadrupole ion trap instrumentation for low level vehicle emissions measurements. CRADA final report for number ORNL93-0238

    SciTech Connect (OSTI)

    McLuckey, S.A.; Buchanan, M.V.; Asano, K.G.; Hart, K.J.; Goeringer, D.E.; Dearth, M.A.

    1997-09-01

    Quadrupole ion trap mass spectrometry has been evaluated for its potential use in vehicle emissions measurements in vehicle test facilities as an analyzer for the top 15 compounds contributing to smog generation. A variety of ionization methods were explored including ion trap in situ chemical ionization, atmospheric sampling glow discharge ionization, and nitric oxide chemical ionization in a glow discharge ionization source coupled with anion trap mass spectrometer. Emphasis was placed on the determination of hydrocarbons and oxygenated hydrocarbons at parts per million to parts per billion levels. Ion trap in situ water chemical ionization and atmospheric sampling glow discharge ionization were both shown to be amenable to the analysis of arenes, alcohols, aldehydes and, to some degree, alkenes. Atmospheric sampling glow discharge also generated molecular ions of methyl-t-butyl ether (MTBE). Neither of these ionization methods, however, were found to generate diagnostic ions for the alkanes. Nitric oxide chemical ionization, on the other hand, was found to yield diagnostic ions for alkanes, alkenes, arenes, alcohols, aldehydes, and MTBE. The ability to measure a variety of hydrocarbons present at roughly 15 parts per billion at measurement rates of 3 Hz was demonstrated. These results have demonstrated that the ion trap has an excellent combination of sensitivity, specificity, speed, and flexibility with respect to the technical requirements of the top 15 analyzer.

  13. Vicarious nucleophilic substitution to prepare 1,3-diamino-2,4,6-trinitrobenzene or 1,3,5-triamino-2,4,6-trinitrobenzene

    DOE Patents [OSTI]

    Mitchell, Alexander R. (Livermore, CA); Pagoria, Philip F. (Livermore, CA); Schmidt, Robert D. (Livermore, CA)

    1996-01-01

    The present invention relates to a process to produce 1,3-diamino-2,4,6-trinitrobenzene (DATB) or 1,3,5-triamino-2,4,6,-trinitrobenzene (TATB) by: (a) reacting at ambient pressure and a temperature of between about 0.degree. and 50.degree. C. for between about 0.1 and 24 hr, a trinitroaromatic compound of structure V: ##STR1## wherein X, Y, and Z are each independently selected from --H, or --NH.sub.2, with the proviso that at least 1 or 2 of X, Y, and Z are hydrogen, with an amount effective to produce DATB or TATB of 1,1,1-trialkylhydrazinium halide wherein alkyl is selected from methyl, ethyl, propyl or butyl and halide is selected from chloride, bromide or iodide. in the presence of a strong base selected from sodium butoxide, potassium butoxide, potassium propoxide, sodium propoxide, sodium ethoxide, potassium ethoxide, sodium methoxide, potassium methoxide, and combinations thereof; in a solvent selected from the group consisting of methanol, ethanol, propanol, butanol, dimethylsulphoxide, N-methylpyrrolidone, hexamethylphosphoramide, dimethylformide, dimethylacetamide and mixtures thereof, provided that when alcohols are present primarily DATB and picramide is formed; and (b) isolating the DATB or TATB produced. DATB and TATB are useful specialty explosives. TATB is also used for the preparation of benzenehexamine, a starting material for the synthesis of novel materials (optical imaging devices, liquid crystals, ferromagnetic compounds).

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

    SciTech Connect (OSTI)

    Dombek, B.D.

    1996-03-01

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

  15. 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.

  16. 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).

  17. The role of mismatch repair in mediating cellular sensitivity to cisplatin : the Escherichia coli methyl-directed repair paradigm

    E-Print Network [OSTI]

    Robbins, Jennifer L

    2006-01-01

    The anticancer drug cisplatin is in widespread use but its mechanism of action is only poorly understood. Moreover, human cancers acquire resistance to the drug, which limits its clinical utility. A paradox in the field ...

  18. Feasibility of reconstructing paleoatmospheric records of selected alkanes, methyl halides, and sulfur gases from Greenland ice cores

    E-Print Network [OSTI]

    Aydin, M.; Williams, M. B; Saltzman, E. S

    2007-01-01

    budget of atmospheric carbonyl sulfide: Temporal and spatialyear atmospheric history for carbonyl sulfide inferred fromterm measurement record of carbonyl sulfide (COS) in two

  19. Sub-10-nm half-pitch electron-beam lithography by using poly(methyl methacrylate) as a negative resist

    E-Print Network [OSTI]

    Berggren, Karl K.

    Developing high-resolution resists and processes for electron-beam lithography is of great importance for high-density magnetic storage, integrated circuits, and nanoelectronic and nanophotonic devices. Until now, hydrogen ...

  20. A determination of the heats of combustion of the five-carbon fatty acids and their methyl and ethyl esters 

    E-Print Network [OSTI]

    Gilby, Ralph F

    1952-01-01

    in the sehcsl dateasdmtdccw ef ths haste of oosbccstico ef tks sccLds scsL ef their ostace? In this wsy& ~ of the oonstsnt errorsi ssoh sec hest incest frcsc stirring? the hest fer elaotrio cnrrent ~sry te Tbs eaayls ef hsnseio scdd to bs cceed wss weighed...

  1. 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, ?=90°, ?=98.241(3)°, ?=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.

  2. Synthesis of 6-Methyl-9-propyldibenzothiophene-4-ol. Technical progress report No. 2, October 25, 1990--January 25, 1991

    SciTech Connect (OSTI)

    Eisenbraun, E.J.

    1991-02-15

    The synthesis route for preparing the title compound, has been carried out on a small scale for the preparation of a mixture of isomers. Alternative routes for the cyclization are being explored. (DLC)

  3. Selective, On-Resin N-Methylation of Cyclic Peptides and Implications for the Discovery of Membrane Permeable Scaffolds

    E-Print Network [OSTI]

    White, Tina Renea

    2012-01-01

    amino acid was combined with BTC and collidine, which wastrichloromethyl) carbonate, BTC, has been used to form N-

  4. A 2000 year atmospheric history of methyl chloride from a South Pole ice core: Evidence for climate-controlled variability

    E-Print Network [OSTI]

    Williams, Margaret B; Aydin, Murat; Tatum, Cheryl; Saltzman, Eric S

    2007-01-01

    M. B. Williams, Atmospheric Chemistry and Dynamics Branch,California, USA. Now at Atmospheric Chemistry and Dynamics

  5. 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.

  6. Low Temperature Autoignition of C8H16O2 Ethyl and Methyl Esters in a Motored Engine

    Office of Energy Efficiency and Renewable Energy (EERE)

    The alkyl chain of fatty acid esters experience the typical paraffin-like low temperature oxidation sequence; the alkyl chain length of fatty acid esters has a crucial impact on the ignition behavior of fatty acid esters

  7. CORRELATION OF DNA METHYLATION WITH MERCURY CONTAMINATION IN MARINE ORGANISMS: A CASE STUDY OF NOAA MUSSEL WATCH TISSUE SAMPLES 

    E-Print Network [OSTI]

    Brinkmeyer, Robin; Taylor, Robert; Germ, Kaylyn E.

    2011-08-04

    contamination (measured by NOAA) and from sites with little to no measurable mercury. Assessment of anthropogenic stressors such as mercury in the coastal environment has traditionally relied upon species diversity indices or assays to determine lethal doses...

  8. Sub-10-nm half-pitch electron-beam lithography by using poly,,methyl methacrylate... as a negative resist

    E-Print Network [OSTI]

    Berggren, Karl K.

    is of great importance for high-density magnetic storage, integrated circuits, and nanoelectronic and nanophotonic devices. Until now, hydrogen silsesquioxane HSQ and calixarene were the only two reported negative, the authors report that 10-nm half-pitch dense nanostructures can also be readily fabricated using the well

  9. 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.

  10. Feasibility of reconstructing paleoatmospheric records of selected alkanes, methyl halides, and sulfur gases from Greenland ice cores

    E-Print Network [OSTI]

    Aydin, M.; Williams, M. B; Saltzman, E. S

    2007-01-01

    study of ethane and propane oxidation in the tropo- sphere,alkanes (ethane, C 2 H 6 ; propane, C 3 H 8 ; n-butane, n-Cfluid contamination. 4.1.2. Propane [ 24 ] Propane levels in

  11. Polystyrene/Poly(methyl methacrylate) Blends in the Presence of Cyclohexane: Selective Solvent Washing or Equilibrium Adsorption?

    E-Print Network [OSTI]

    . Using near-edge X-ray absorption fine structure spectroscopy and inverse gas chromatography, coupled adsorption and DNA separation,9,10 more recent investigations have also focused on adsorption at so-called "soft" surfaces, where the substrate is an organic material such as a polymer or lipid membrane.11

  12. Feasibility of reconstructing paleoatmospheric records of selected alkanes, methyl halides, and sulfur gases from Greenland ice cores

    E-Print Network [OSTI]

    Aydin, M.; Williams, M. B; Saltzman, E. S

    2007-01-01

    production is responsible for this scatter, the processes responsible do not appear to be continuous and

  13. The effect of methyl silicone upon feedlot performance digestibility of nutrients and prevention of bloat in beef cattle 

    E-Print Network [OSTI]

    Wythe, Landon Douglas

    1955-01-01

    WA~ ~~ e! as' WA ~ ~ a~~MS &! aM!!!IM 4M~% ~ MQ AAINN@ NINN Rig/ M3p ~ ~ W, ~ . W !!! . 4, :: . 88, alfalfa hay '. . . 7, Johnson, grass hay 2. '. =. , silage 1. 1. Feed costs per ton: cottonseed. meal 'j75. 00, milo grain 50 F 00, cottonseed...'i i j i e e 'o i i 'e y' j s i' i e em'i'w s iy e i si i' ii e w'i ?' i'. " 7l ~~~~~~ye~~yeys~~~~~~~p~+?aey~e~jr~e'@~eea~we, ?~eeyao~. F7 1' if+~44e~ iiaeei'eeeeeieeii eiiqwi equi je'e'i++%veiese~4i+e'iei+%4 ' 8 9i ~ ~ ~:~~:M. ~p. 383~4 i'i, iiji...

  14. Transcriptional response of O?-methylguanine methyltransferase deficient yeast to methyl-N-nitro-N-nitrosoguanidine (MNNG)

    E-Print Network [OSTI]

    Rao, Anoop, 1977-

    2004-01-01

    (cont.) of transcription factors and subsequently, induction of RNA processing (35% of genes incrementally induced) and kinases involved in protein phosphorylation. In the WT, the response was restricted to a transient ...

  15. Molecular Cell, Vol. 6, 349360, August, 2000, Copyright 2000 by Cell Press RNA Methylation under Heat Shock Control

    E-Print Network [OSTI]

    Bardwell, James

    Heat Shock Control results will be applicable to homologs found in a wideHans Bu¨ gl,* Eric B. Fauman promoter of this operon is positively regulated by the Biophysics Research Division heat shock transcription factor 32 . Upon heat treatment, Department of Biological Chemistry ftsJ mRNA levels increase

  16. Atmospheric variability of methyl chloride during the last 300 years from an Antarctic ice core and firn air

    E-Print Network [OSTI]

    Saltzman, Eric

    as a low-pass filter, smoothing variations in the atmospheric composition of a gas over decadal time scales core measurements from Siple Dome provide evidence for a cyclic natural variability on the order of 10 increase measured in firn air may largely be a result of natural processes, which may continue to affect

  17. Effect of Amino Acid Subsititution in Set1 on Histone H3 Methylation and Gene Silencing in Saaccharomyces Cerevisiae 

    E-Print Network [OSTI]

    Chateau, Morgan

    2008-08-24

    -1231 4. Robzyk, K., and Kassir, Y. A. (1992) Nucleic Acids Research 20, 3790 5. Huang, Y. (2002) Nucleic Acids Research 30, 1465-1482 6. Bryk, M., Banerjee, M., Murphy, M., Knudsen, K. E., Garfinkel, D. J., and Curcio, M. J. (1997) Genes...

  18. Bisulfite Genomic DNA Sequencing -for high-resolution mapping of methylated cytosines in a DNA region of interest-

    E-Print Network [OSTI]

    Pikaard, Craig

    in an ice-water bath and cool at 0°C for 1 min. Quick chilling minimizes duplex formation, keeping in the thermocycler to maintain temperaature). Overlay the reaction mixture with mineral oil to prevent evaporation). Be sure to spread enough plates to be sure you will get enough clones for your analyses (we typically

  19. Adsorption of As(V), As(III) and methyl arsenic by calcite and the impact of some groundwater species 

    E-Print Network [OSTI]

    Jones, Robert Garret

    2009-05-15

    on arsenic solubility, adsorption and precipitation phenomena. Adsorption kinetics of iAsV, evaluated at a low and high concentration, was a relatively rapid process, with a fast initial reaction rate within the first few minutes and a subsequent slower...

  20. Structures and Properties of Zirconia-Supported Ruthenium Oxide Catalysts for the Selective Oxidation of Methanol to Methyl Formate

    E-Print Network [OSTI]

    Iglesia, Enrique

    Structures and Properties of Zirconia-Supported Ruthenium Oxide Catalysts for the Selective Species, College of Chemistry and Molecular Engineering, Green Chemistry Center, Peking UniVersity, Beijing 100871, China, and Department of Chemical Engineering, UniVersity of California at Berkeley

  1. Molecular Dynamic Simulation of Thermo-Mechanical Properties of Ultra-Thin Poly(methyl methacrylate) Films 

    E-Print Network [OSTI]

    Silva Hernandez, Carlos Ardenis A.

    2011-08-08

    The thermal conductivity of PMMA films with thicknesses from 5 to 50 nanometers and layered over a treated silicon substrate is explored numerically by the application of the reverse non-equilibrium molecular dynamics (NEMD) technique...

  2. Highly efficient deep blue organic electroluminescent device based on 1-methyl-9,10-di,,1-naphthyl...anthracene

    E-Print Network [OSTI]

    So, Shu K.

    .1063/1.2409367 In recent years, there has been considerable interest in developing blue organic light emitting diodes OLEDs-color OLED Ref. 2 and also be uti- lized to generate light of other colors by energy cascade to a suitable light emitting device which produces electroluminescence efficiencies of 3.3 cd/A and 1.3 lm

  3. Histone H3 lysine 4 methylation is associated with the transcriptional reprogramming efficiency of somatic nuclei by oocytes

    E-Print Network [OSTI]

    Murata, Kazutaka; Kouzarides, Tony; Bannister, Andrew J.; Gurdon, John

    2010-02-04

    reprogramming. Results Reverse transcription polymerase chain reaction analysis shows that the transcriptional reprogramming of pluripotency genes, such as Sox2 and Oct4, takes place in transplanted nuclei from C3H10T1/2 cells and from newly differentiated mouse...

  4. Chemical Hygiene and Safety Plan

    E-Print Network [OSTI]

    Ricks Editor, R.

    2009-01-01

    andor pyrophoric gases. 1,3 butadiene arsenic pentafluorideof highly toxic and/or 1,3-butadiene arsenic pentafluoridebracken fern 1,3-butadiene butylated hydroxyanisole (BHA)

  5. Nanostructure Control of Biologically Inspired Polymers

    E-Print Network [OSTI]

    Rosales, Adrianne

    2013-01-01

    Block-Random Copolymers of Styrene, 4-Acetoxystyrene, and 4-Random Copolymers of Styrene and Hydrogenated Isoprene.Phase Behavior of Styrene/n-Butyl Acrylate Block and

  6. TABLE33.CHP:Corel VENTURA

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

    products are reported by the PAD District of entry. b Includes crude oil imported for storage in the Strategic Petroleum Reserve. c Includes ethyl tertiary butyl ether (ETBE),...

  7. TABLE34.CHP:Corel VENTURA

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

    products are reported by the PAD District of entry. b Includes crude oil imported for storage in the Strategic Petroleum Reserve. c Includes ethyl tertiary butyl ether (ETBE),...

  8. Biomass IBR Fact Sheet: Archer Daniels Midland

    Broader source: Energy.gov [DOE]

    Archer Daniels Midland will develop a pilot plant to demonstrate the continuous production of cellulosic ethanol and butyl acrylate from densified corn stover.

  9. Cooperative activity of DNA methyltransferases for maintenance of symmetrical and non-symmetrical cytosine

    E-Print Network [OSTI]

    Meyer, Peter

    methylation types, CG, CNG and CNN methylation, which are regulated by three DNA methylation functions. DNMT1). CHROMOMETHYLASE 3 (CMT3) is the main enzyme controlling methylation at CNG sites Re-use of this article

  10. The mono-chlor, mono-iodo derivatives of toluene

    E-Print Network [OSTI]

    Long, Henry Johnson

    1922-01-01

    -iodo benzene. .......... 5 l-Methyl-2-amino-4-iodo benzene. 6 l-Methyl-2-benzoyl amino-4-iodo benzene. ...... 7 1-Methyl-2-acetyl amino-4-iodo benzene 7 l-Methyl-2-benzal araino-4-iodo benzene ••••••• 8 0-Tolyl, 2-iodo-6-methyl phenyl, thiourea 8... 1-Methyl-2-amino-4-iodo benzene hydrochloride. ... 9 1-METHYL-2-CH10R-5-I0D0 BENZEHE. .11 l-Methyl-2-chlor-5-acetyl amino benzene. ...... 11 l-Methyl-2-chlor-5-iodo-?-nitro benzene 13 l-Methyl-2-amino-5-iodo benzene. . . 14 1-METHYL - 2 -1ODO- 3...

  11. 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.

  12. Polymer International Polym Int 55:292298 (2006) DOI: 10.1002/pi.1951

    E-Print Network [OSTI]

    Wang, Siqun

    2006-01-01

    Polymer International Polym Int 55:292­298 (2006) DOI: 10.1002/pi.1951 Crystallization behaviour of cellulose acetate butylate/poly(butylene succinate)-co-(butylene carbonate) blends Seung-Hwan Lee and Siqun(butylene succinate)-co-(butylene carbonate) (PBS-co-BC) and its blends with cellulose acetate butylate (CAB) (10

  13. Antioxidant, color and sensory properties of sorghum bran in pre-cooked ground beef patties varying in fat and iron content 

    E-Print Network [OSTI]

    Shin, Dae Keun

    2009-05-15

    each fat level, ground beef portions were weighed and randomly assigned to control, butylated hydroxanisole (BHA) and butylated hydroxytoluene (BHT) (0.001%), rosemary (0.25%) or sorghum bran (0.25, 0.5 or 1.0%). After mixing in the appropriate...

  14. Enhancing the Catalytic Activity of Site-Isolated Heterogeneous Transition Metal Expoxidation Catalysts Prepared via the Thermolytic Molecular Precursor Method

    E-Print Network [OSTI]

    Cordeiro, Paul Joseph

    2010-01-01

    applied to a variety of catalytic oxidation reactions. 11-1548 h. Table 3. Catalytic 1-octene oxidation with tert-butylcatalysts. Table 4. Catalytic 1-octene oxidation with H 2 O

  15. Photoredox Vinylation of Amino Acids and NAryl Amines Adam Noble and David W. C. MacMillan*

    E-Print Network [OSTI]

    MacMillan, David W. C.

    -tert- butoxycarbonyl (N-Boc) -amino acids,7,8 a CO2-extrusion mechanism that has implications for the use of biomass feedstocks in conjugate additions and organometallic couplings. Allylic amines have long been attractive

  16. 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:...

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

    SciTech Connect (OSTI)

    Tyson, K.S.

    1993-11-01

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

  18. Leaching behavior of copper from waste printed circuit boards with Brønsted acidic ionic liquid

    SciTech Connect (OSTI)

    Huang, Jinxiu; Chen, Mengjun Chen, Haiyan; Chen, Shu; Sun, Quan

    2014-02-15

    Highlights: • A Brønsted acidic ILs was used to leach Cu from WPCBs for the first time. • The particle size of WPCBs has significant influence on Cu leaching rate. • Cu leaching rate was higher than 99% under the optimum leaching conditions. • The leaching process can be modeled with shrinking core model, and the E{sub a} was 25.36 kJ/mol. - Abstract: In this work, a Brønsted acidic ionic liquid, 1-butyl-3-methyl-imidazolium hydrogen sulfate ([bmim]HSO{sub 4}), was used to leach copper from waste printed circuit boards (WPCBs, mounted with electronic components) for the first time, and the leaching behavior of copper was discussed in detail. The results showed that after the pre-treatment, the metal distributions were different with the particle size: Cu, Zn and Al increased with the increasing particle size; while Ni, Sn and Pb were in the contrary. And the particle size has significant influence on copper leaching rate. Copper leaching rate was higher than 99%, almost 100%, when 1 g WPCBs powder was leached under the optimum conditions: particle size of 0.1–0.25 mm, 25 mL 80% (v/v) ionic liquid, 10 mL 30% hydrogen peroxide, solid/liquid ratio of 1/25, 70 °C and 2 h. Copper leaching by [bmim]HSO{sub 4} can be modeled with the shrinking core model, controlled by diffusion through a solid product layer, and the kinetic apparent activation energy has been calculated to be 25.36 kJ/mol.

  19. LOW POWER UPCONVERSION FOR SOLAR FUELS PHOTOCHEMISTRY

    SciTech Connect (OSTI)

    Castellano, Felix N.

    2013-08-05

    Earth abundant copper(I) diimine complexes represent a renewable and economically feasible alternative to commonly used heavy metal containing chromophores. In the metal-to-ligand charge transfer (MLCT) excited state, copper(I) diimine complexes typically undergo a significant structural rearrangement, leading to molecules with large Stokes shifts and very short excited state lifetimes, thereby limiting their usefulness as sensitizers in bimolecular electron and triplet energy transfer reactions. Strategically placed bulky substituents on the coordinating phenanthroline ligands have proven useful in restricting the transiently produced excited state Jahn-Teller distortion, leading to longer-lived excited states. By combining bulky sec-butyl groups in the 2- and 9- positions with methyl groups in the 3-,4-, 7-, and 8- positions, a remarkably long-lived (2.8 ?s in DCM) copper(I) bis-phenanthroline complex, [Cu(dsbtmp)2]+, has been synthesized and characterized. Unlike other copper(I) diimine complexes, [Cu(dsbtmp)2]+ also retains a ?s lifetime in coordinating solvents such as acetonitrile and water as a result of the cooperative sterics inherent in the molecular design. Preliminary results on the use of this complex in hydrogen-forming homogeneous photocatalysis is presented. Photon upconversion based on sensitized triplet-triplet annihilation (TTA) represents a photochemical means to generate high-energy photons (or high-energy chemical products) from low-energy excitation, having potential applications in solar energy conversion and solar fuels producing devices. For the first time, synthetically facile and earth abundant Cu(I) MLCT sensitizers have been successfully incorporated into two distinct photochemical upconversion schemes, affording both red-to-green and orange-to-blue wavelength conversions. Preliminary results on aqueous-based photochemical upconversion as well as intramolecular Sn(IV) porphyrins containing axially coordinated aromatic hydrocarbon chromophores poised for upconversion photochemistry are also presented.

  20. Superacid catalysis of light hydrocarbon conversion. DOE PETC third quarterly report, February 25, 1994--May 24, 1994

    SciTech Connect (OSTI)

    Gates, B.C.

    1995-12-31

    Environmental concerns are leading to the replacement of aromatic hydrocarbons in gasoline by high-octane-number branched paraffins and oxygenated compounds such as methyl t-butyl ether. The ether is produced from methanol and isobutylene, and the latter can be formed from n-butane by isomerization followed by dehydrogenation. Paraffin isomerization reactions are catalyzed by very strong acids such as aluminum chloride supported on alumina. The aluminum chloride-containing catalysts are corrosive, and their disposal is expensive. Alternatively, hydroisomerization is catalyzed by zeolite-supported metals at high temperatures, but high temperatures do not favor branched products at equilibrium. Thus there is a need for improved catalysts and processes for the isomerization of n-butane and other straight-chain paraffins. Consequently, researchers have sought for solid acids that are noncorrosive and active enough to catalyze isomerization of paraffins at low temperatures. For example, sulfated zirconia catalyzes isomerization of n-butane at temperatures as low as 25{degrees}C. The addition of iron and manganese promoters has been reported to increase the activity of sulfated zirconia for n-butane isomerization by three orders of magnitude. Although the high activity of this catalyst is now established, the reaction network is not known, and the mechanism has not been investigated. The goal of this work is to investigate low-temperature reactions of light paraffins catalyzed by solid superacids of the sulfated zirconia type. The present report is concerned with catalysis of n-butane conversion catalyzed by the Fe- and Mn- promoted sulfated zirconia described in the previous report in this series.