National Library of Energy BETA

Sample records for acid methyl ester

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

    Office of Scientific and Technical Information (OSTI)

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

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

    SciTech Connect (OSTI)

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

    2008-10-15

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

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

    SciTech Connect (OSTI)

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

    2013-12-01

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

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

    SciTech Connect (OSTI)

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

    2013-07-25

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

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

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

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

  6. 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.

  7. Photophysics and morphology of poly (3-dodecylthienylenevinylene)-[6,6]-phenyl-C{sub 61}-butyric acid methyl ester composite

    SciTech Connect (OSTI)

    Lafalce, E.; Toglia, P.; Jiang, X.; Zhang, C.

    2012-05-21

    A series of low band gap poly(3-dodecylthienylenevinylene) (PTV) with controlled morphological order have been synthesized and blended with the electron acceptor [6,6]-phenyl-C{sub 61}-butyric acid methyl ester (PCBM) for organic photovoltaic devices. Two polymers with the most and least side chain regioregularity were chosen in this work, namely the PTV010 and PTV55, respectively. Using photoluminescence, photo-induced absorption spectroscopy, and atomic force microscopy, we find no direct evidence of photoinduced charge transfer between the two constituents, independent of the bulk-heterojunction morphology of the film, although the possibility of formation of P{sup +}/C{sub 60}{sup -} charge transfer complex was not completely ruled out. The large exciton binding energy (E{sub b} = 0.6 eV) in PTV inhibits the photoinduced electron transfer from PTV to PCBM. In addition, excitons formed on polymer chains suffer ultrafast (

  8. Broadband gain in poly(3-hexylthiophene):phenyl-C{sub 61}-butyric-acid-methyl-ester photodetectors enabled by a semicontinuous gold interlayer

    SciTech Connect (OSTI)

    Melancon, Justin M.; Živanović, Sandra R.

    2014-10-20

    Substantial broadband photoconductive gain has been realized for organic, thin-film photodetectors with a poly(3-hexylthiophene):phenyl-C{sub 61}-butyric-acid-methyl-ester (P3HT:PCBM) active layer at low bias voltages. External quantum efficiencies upwards of 1500% were achieved when a semicontinuous gold layer was introduced at the anode interface. Significant gain was also observed in the sub-band gap, near infrared region where the external quantum efficiency approached 100% despite the lack of a sensitizer. The gain response was highly dependent on the thickness of the active layer of the photodetector with the best results achieved with the thinnest devices. The gain is the result of the injection of secondary electrons due to hole charge trapping at the semicontinuous gold layer.

  9. 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.

  10. Preparation of Propylene Glycol Fatty Acid Ester or Other Glycol...

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

    and more specifically uses methyl esters of vegetable oils that are referred to as "biodiesel" fuels. One particularly useful biodiesel is soybean oil biodiesel (methyl soyate)...

  11. 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 ...

  12. 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.

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

    Broader source: Energy.gov [DOE]

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

  14. Methods of refining and producing isomerized fatty acid esters and fatty acids from natural oil feedstocks

    DOE Patents [OSTI]

    Snead, Thomas E.; Cohen, Steven A.; Gildon, Demond L.; Beltran, Leslie V.; Kunz, Linda A.; Pals, Tessa M.; Quinn, Jordan R; Behrends, Jr., Raymond T.; Bernhardt, Randal J.

    2016-07-05

    Methods are provided for refining natural oil feedstocks and producing isomerized esters and acids. The methods comprise providing a C4-C18 unsaturated fatty ester or acid, and isomerizing the fatty acid ester or acid in the presence of heat or an isomerization catalyst to form an isomerized fatty ester or acid. In some embodiments, the methods comprise forming a dibasic ester or dibasic acid prior to the isomerizing step. In certain embodiments, the methods further comprise hydrolyzing the dibasic ester to form a dibasic acid. In certain embodiments, the olefin is formed by reacting the feedstock in the presence of a metathesis catalyst under conditions sufficient to form a metathesized product comprising olefins and esters, separating the olefins from the esters in the metathesized product, and transesterifying the esters in the presence of an alcohol to form a transesterified product having unsaturated esters.

  15. Preparation of {alpha},{beta}-unsaturated carboxylic acids and esters

    DOE Patents [OSTI]

    Gogate, M.R.; Spivey, J.J.; Zoeller, J.R.

    1998-09-15

    Disclosed is a process for the preparation of {alpha},{beta}-unsaturated carboxylic acids and esters thereof which comprises contacting formaldehyde or a source of formaldehyde with a carboxylic acid, ester or anhydride in the presence of a catalyst comprising an oxide of niobium.

  16. Preparation of .alpha.,.beta.-unsaturated carboxylic acids and esters

    DOE Patents [OSTI]

    Gogate, Makarand Ratnakar; Spivey, James Jerry; Zoeller, Joseph Robert

    1998-01-01

    Disclosed is a process for the preparation of .alpha.,.beta.-unsaturated carboxylic acids and esters thereof which comprises contacting formaldehyde or a source of formaldehyde with a carboxylic acid, ester or anhydride in the presence of a catalyst comprising an oxide of niobium.

  17. Process for the generation of .alpha., .beta.-unsaturated carboxylic acids and esters using niobium catalyst

    DOE Patents [OSTI]

    Gogate, Makarand Ratnakav; Spivey, James Jerome; Zoeller, Joseph Robert

    1999-01-01

    A process using a niobium catalyst includes the step of reacting an ester or carboxylic acid with oxygen and an alcohol in the presence a niobium catalyst to respectively produce an .alpha.,.beta.-unsaturated ester or carboxylic acid. Methanol may be used as the alcohol, and the ester or carboxylic acid may be passed over the niobium catalyst in a vapor stream containing oxygen and methanol. Alternatively, the process using a niobium catalyst may involve the step of reacting an ester and oxygen in the presence the niobium catalyst to produce an .alpha.,.beta.-unsaturated carboxylic acid. In this case the ester may be a methyl ester. In either case, niobium oxide may be used as the niobium catalyst with the niobium oxide being present on a support. The support may be an oxide selected from the group consisting of silicon oxide, aluminum oxide, titanium oxide and mixtures thereof. The catalyst may be formed by reacting niobium fluoride with the oxide serving as the support. The niobium catalyst may contain elemental niobium within the range of 1 wt % to 70 wt %, and more preferably within the range of 10 wt % to 30 wt %. The process may be operated at a temperature from 150 to 450.degree. C. and preferably from 250 to 350.degree. C. The process may be operated at a pressure from 0.1 to 15 atm. absolute and preferably from 0.5-5 atm. absolute. The flow rate of reactants may be from 10 to 10,000 L/kg.sub.(cat) /h, and preferably from 100 to 1,000 L/kg.sub.(cat) /h.

  18. Methods of refining and producing dibasic esters and acids from natural oil feedstocks

    DOE Patents [OSTI]

    Snead, Thomas E.; Cohen, Steven A.; Gildon, Demond L.

    2016-06-14

    Methods and systems for making dibasic esters and/or dibasic acids using metathesis are generally disclosed. In some embodiments, the methods comprise reacting a terminal olefin ester with an internal olefin ester in the presence of a metathesis catalyst to form a dibasic ester and/or dibasic acid. In some embodiments, the terminal olefin ester or the internal olefin ester are derived from a renewable feedstock, such as a natural oil feedstock. In some such embodiments, the natural oil feedstock, or a transesterified derivative thereof, is metathesized to make the terminal olefin ester or the internal olefin ester.

  19. Methods of refining and producing dibasic esters and acids from natural oil feedstocks

    DOE Patents [OSTI]

    Snead, Thomas E; Cohen, Steven A; Gildon, Demond L

    2015-04-07

    Methods are provided for refining natural oil feedstocks and producing dibasic esters and/or dibasic acids. The methods comprise reacting a terminal olefin with an internal olefin in the presence of a metathesis catalyst to form a dibasic ester and/or dibasic acid. In certain embodiments, the olefin esters are formed by reacting the feedstock in the presence of a metathesis catalyst under conditions sufficient to form a metathesized product comprising olefins and esters, separating the olefins from the esters in the metathesized product, and transesterifying the esters in the presence of an alcohol to form a transesterified product having olefin esters.

  20. Methods of refining and producing dibasic esters and acids from natural oil feedstocks

    DOE Patents [OSTI]

    Snead, Thomas E.; Cohen, Steven A.; Gildon, Demond L.

    2016-03-15

    Methods are provided for refining natural oil feedstocks and producing dibasic esters and/or dibasic acids. The methods comprise reacting a terminal olefin with an internal olefin in the presence of a metathesis catalyst to form a dibasic ester and/or dibasic acid. In certain embodiments, the olefin esters are formed by reacting the feedstock in the presence of a metathesis catalyst under conditions sufficient to form a metathesized product comprising olefins and esters, separating the olefins from the esters in the metathesized product, and transesterifying the esters in the presence of an alcohol to form a transesterified product having olefin esters.

  1. Production of methyl-vinyl ketone from levulinic acid

    DOE Patents [OSTI]

    Dumesic, James A.; West; Ryan M.

    2011-06-14

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

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

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

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

  3. Determination of Total Lipids as Fatty Acid Methyl Esters (FAME...

    Office of Scientific and Technical Information (OSTI)

    2, 2013 Research Org: National Renewable Energy Laboratory (NREL), Golden, CO. Sponsoring Org: USDOE Office of Energy Efficiency and Renewable Energy Bioenergy Technologies ...

  4. Synthesis of an acid addition salt of delta-aminolevulinic acid from 5-bromo levulinic acid esters

    DOE Patents [OSTI]

    Moens, Luc

    1999-01-01

    A process of preparing an acid addition salt of delta-aminolevulinic acid comprising: dissolving a lower alkyl 5-bromolevulinate and an alkali metal diformylamide in an organic solvent selected from the group consisting of acetonitrile, methanol, tetrahydrofuran, 2-methyltetrahydrofuran and methylformate or mixtures thereof to form a suspension of an alkyl 5-(N,N-diformylamino) levulinate ester; and hydrolyzing said alkyl 5-(N,N-diformylamino) levulinate with an inorganic acid to form an acid addition salt of delta-amino levulinic acid.

  5. Synthesis of an acid addition salt of delta-aminolevulinic acid from 5-bromo levulinic acid esters

    DOE Patents [OSTI]

    Moens, L.

    1999-05-25

    A process is disclosed for preparing an acid addition salt of delta-aminolevulinic acid comprising. The process involves dissolving a lower alkyl 5-bromolevulinate and an alkali metal diformylamide in an organic solvent selected from the group consisting of acetonitrile, methanol, tetrahydrofuran, 2-methyltetrahydrofuran and methylformate or mixtures to form a suspension of an alkyl 5-(N,N-diformylamino) levulinate ester; and hydrolyzing the alkyl 5-(N,N-diformylamino) levulinate with an inorganic acid to form an acid addition salt of delta-amino levulinic acid.

  6. Incorporating Amino Acid Esters into Catalysts for Hydrogen Oxidation: Steric and Electronic Effects and the Role of Water as a Base

    SciTech Connect (OSTI)

    Lense, Sheri; Ho, Ming-Hsun; Chen, Shentan; Jain, Avijita; Raugei, Simone; Linehan, John C.; Roberts, John A.; Appel, Aaron M.; Shaw, Wendy J.

    2012-10-08

    Four derivatives of a hydrogen oxidation catalyst, [Ni(PCy2NBn-R2)]2+ (Cy=cyclohexyl, Bn=benzyl, R= OMe, COOMe, CO-Alanine-methyl ester or CO-Phenylalanine-methyl ester), have been prepared to investigate steric and electronic effects on catalysis. Each complex was characterized spectroscopically and electrochemically, and thermodynamic data were determined. Crystal structures are also reported for the -OMe and -COOMe derivatives. All four catalysts were found to be active for H2 oxidation. The methyl ester (R = COOMe) and amino acid ester containing complexes (R = CO-Alanine-methyl ester or CO-Phenylalanine-methyl ester) had slower rates (4 s-1) than that of the parent complex (10 s-1), in which R = H, consistent with the lower amine pKa’s and less favorable GH2’s found for these electron-withdrawing substituents. Dynamic processes for the amino acid ester containing complexes were also investigated and found not to hinder catalysis. The electron-donating methoxy ether derivative (R = OMe) was prepared to compare electronic effects and has a similar catalytic rate as the parent complex. In the course of these studies, it was found that water could act as a weak base for H2 oxidation, although catalytic turnover requires a significantly higher potential and utilizes a different sequence of catalytic steps than when using a base with a higher pKa. Importantly, these catalysts provide a foundation upon which larger peptides can be attached to [Ni(PCy2NBn2)2]2+ hydrogen oxidation catalysts in order to more fully investigate and implement the effects of the outer-coordination sphere. This work was funded by the DOE Office of Science Early Career Research Program through the Office of Basic Energy Sciences (SL and WJS), by the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the US Department of Energy, Office of Science, Office of Basic Energy Sciences (JR), and by the US DOE Basic Energy Sciences, Chemical Sciences, Geoscience

  7. Synthesis of acid addition salt of delta-aminolevulinic acid from 5-bromo levulinic acid esters

    DOE Patents [OSTI]

    Moens, Luc

    2003-06-24

    A process of preparing an acid addition salt of delta-aminolevulinc acid comprising: a) dissolving a lower alkyl 5-bromolevulinate and hexamethylenetetramine in a solvent selected from the group consisting of water, ethyl acetate, chloroform, acetone, ethanol, tetrahydrofuran and acetonitrile, to form a quaternary ammonium salt of the lower alkyl 5-bromolevulinate; and b) hydrolyzing the quaternary ammonium salt with an inorganic acid to form an acid addition salt of delta-aminolevulinic acid.

  8. Integrated process of distillation with side reactors for synthesis of organic acid esters

    DOE Patents [OSTI]

    Panchal, Chandrakant B; Prindle, John C; Kolah, Aspri; Miller, Dennis J; Lira, Carl T

    2015-11-04

    An integrated process and system for synthesis of organic-acid esters is provided. The method of synthesizing combines reaction and distillation where an organic acid and alcohol composition are passed through a distillation chamber having a plurality of zones. Side reactors are used for drawing off portions of the composition and then recycling them to the distillation column for further purification. Water is removed from a pre-reactor prior to insertion into the distillation column. An integrated heat integration system is contained within the distillation column for further purification and optimizing efficiency in the obtaining of the final product.

  9. 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

  10. Method of making alkyl esters

    DOE Patents [OSTI]

    Elliott, Brian

    2010-09-14

    Methods of making alkyl esters are described herein. The methods are capable of using raw, unprocessed, low-cost feedstocks and waste grease. Generally, the method involves converting a glyceride source to a fatty acid composition and esterifying the fatty acid composition to make alkyl esters. In an embodiment, a method of making alkyl esters comprises providing a glyceride source. The method further comprises converting the glyceride source to a fatty acid composition comprising free fatty acids and less than about 1% glyceride by mass. Moreover, the method comprises esterifying the fatty acid composition in the presence of a solid acid catalyst at a temperature ranging firm about 70.degree. C. to about 120.degree. C. to produce alkyl esters, such that at least 85% of the free fatty acids are converted to alkyl esters. The method also incorporates the use of packed bed reactors for glyceride conversion and/or fatty acid esterification to make alkyl esters.

  11. 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.

  12. Chikusetsusaponin IVa methyl ester induces cell cycle arrest by the inhibition of nuclear translocation of β-catenin in HCT116 cells

    SciTech Connect (OSTI)

    Lee, Kyung-Mi; Yun, Ji Ho; Lee, Dong Hwa; Park, Young Gyun; Son, Kun Ho; Nho, Chu Won; Kim, Yeong Shik

    2015-04-17

    We demonstrate that chikusetsusaponin IVa methyl ester (CME), a triterpenoid saponin from the root of Achyranthes japonica, has an anticancer activity. We investigate its molecular mechanism in depth in HCT116 cells. CME reduces the amount of β-catenin in nucleus and inhibits the binding of β-catenin to specific DNA sequences (TCF binding elements, TBE) in target gene promoters. Thus, CME appears to decrease the expression of cell cycle regulatory proteins such as Cyclin D1, as a representative target for β-catenin, as well as CDK2 and CDK4. As a result of the decrease of the cell cycle regulatory proteins, CME inhibits cell proliferation by arresting the cell cycle at the G0/G1 phase. Therefore, we suggest that CME as a novel Wnt/β-catenin inhibitor can be a putative agent for the treatment of colorectal cancers. - Highlights: • CME inhibits cell proliferation in HCT116 cells. • CME increases cell cycle arrest at G0/G1 phase and apoptosis. • CME attenuates cyclin D1 and regulates cell cycle regulatory proteins. • CME inhibits β-catenin translocation to nucleus.

  13. 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.

  14. Guiding optimal biofuels : a comparative analysis of the biochemical production of ethanol and fatty acid ethyl esters from switchgrass.

    SciTech Connect (OSTI)

    Paap, Scott M.; West, Todd H.; Manley, Dawn Kataoka; Dibble, Dean C.; Simmons, Blake Alexander; Steen, Eric J.; Beller, Harry R.; Keasling, Jay D.; Chang, Shiyan

    2013-01-01

    In the current study, processes to produce either ethanol or a representative fatty acid ethyl ester (FAEE) via the fermentation of sugars liberated from lignocellulosic materials pretreated in acid or alkaline environments are analyzed in terms of economic and environmental metrics. Simplified process models are introduced and employed to estimate process performance, and Monte Carlo analyses were carried out to identify key sources of uncertainty and variability. We find that the near-term performance of processes to produce FAEE is significantly worse than that of ethanol production processes for all metrics considered, primarily due to poor fermentation yields and higher electricity demands for aerobic fermentation. In the longer term, the reduced cost and energy requirements of FAEE separation processes will be at least partially offset by inherent limitations in the relevant metabolic pathways that constrain the maximum yield potential of FAEE from biomass-derived sugars.

  15. Electrochemical method for producing a biodiesel mixture comprising fatty acid alkyl esters and glycerol

    DOE Patents [OSTI]

    Lin, YuPo J; St. Martin, Edward J

    2013-08-13

    The present invention relates to an integrated method and system for the simultaneous production of biodiesel from free fatty acids (via esterification) and from triglycerides (via transesterification) within the same reaction chamber. More specifically, one preferred embodiment of the invention relates to a method and system for the production of biodiesel using an electrodeionization stack, wherein an ion exchange resin matrix acts as a heterogeneous catalyst for simultaneous esterification and transesterification reactions between a feedstock and a lower alcohol to produce biodiesel, wherein the feedstock contains significant levels of free fatty acid. In addition, because of the use of a heterogeneous catalyst, the glycerol and biodiesel have much lower salt concentrations than raw biodiesel produced by conventional transesterification processes. The present invention makes it much easier to purify glycerol and biodiesel.

  16. Novel class of amino acid antagonists at non-N-methyl-D-aspartic acid excitatory amino acid receptors. Synthesis, in vitro and in vivo pharmacology, and neuroprotection

    SciTech Connect (OSTI)

    Krogsgaard-Larsen, P.; Ferkany, J.W.; Nielsen, E.O.; Madsen, U.; Ebert, B.; Johansen, J.S.; Diemer, N.H.; Bruhn, T.; Beattie, D.T.; Curtis, D.R. )

    1991-01-01

    The isoxazole amino acid 2-amino-3-(3-hydroxy-5-methylisoxazol-4-yl) propionic acid (AMPA) (1), which is a highly selective agonist at the AMPA subtype of excitatory amino acid (EAA) receptors, has been used as a lead for the development of two novel EAA receptor antagonists. One of the compounds, 2-amino-3-(3-(carboxymethoxy)-5-methylisoxazol-4-yl)propionic acid (AMOA, 7), was synthesized via O-alkylation by ethyl chloroacetate of the amino acid protected AMPA derivative 4. The other compound, 2-amino-3-(2-(3-hydroxy-5-methylisoxazol-4-yl)-methyl-5-methyl-3-+ ++oxoisoxazolin -4-yl)propionic acid (AMNH, 14) was synthesized with use of 4-(chloromethyl)-3-methoxy-5-methylisoxazole (8) as the starting material. The intermediate 4-(chloromethyl)-2-(3-methoxy-5-methylisoxazol-4-yl)methyl-5-me thylisoxazolin- 3-one (11) was converted into the acetamidomalonate (12), which was stepwise deprotected to give 14. Compounds 7 and 14 were stable in aqueous solution at pH values close to physiological pH. Neither 7 nor 14 showed detectable affinities for the receptor, ion channel, or modulatory sites of the N-methyl-D-aspartic acid (NMDA) receptor complex. Quantitative receptor autoradiographic and conventional binding techniques were used to study the affinities of 7 and 14 for non-NMDA receptor sites. Both compounds were inhibitors of the binding of (3H)AMPA (IC50 = 90 and 29 microM, respectively). Compounds 14 and 7 were both very weak inhibitors of the high-affinity binding of radioactive kainic acid ((3H)KAIN). Compound 14, but not 7, was, however, shown to be an inhibitor of low-affinity (3H)KAIN binding as determined in the presence of 100 mM calcium chloride. In the rat cortical slice preparation, 7 was shown to antagonize excitation induced by 1 with some selectivity, whereas 14 proved to be a rather selective antagonist of KAIN-induced excitation.

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

    SciTech Connect (OSTI)

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

    2010-08-15

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

  18. Methods of making alkyl esters

    DOE Patents [OSTI]

    Elliott, Brian

    2010-08-03

    A method comprising contacting an alcohol, a feed comprising one or more glycerides and equal to or greater than 2 wt % of one or more free fatty acids, and a solid acid catalyst, a nanostructured polymer catalyst, or a sulfated zirconia catalyst in one or more reactors, and recovering from the one or more reactors an effluent comprising equal to or greater than about 75 wt % alkyl ester and equal to or less than about 5 wt % glyceride.

  19. Caffeic acid phenethyl ester inhibits 3-MC-induced CYP1A1 expression through induction of hypoxia-inducible factor-1α

    SciTech Connect (OSTI)

    Kim, Hyung Gyun; Han, Eun Hee; Im, Ji Hye; Lee, Eun Ji; Jin, Sun Woo; Jeong, Hye Gwang

    2015-09-25

    Caffeic acid phenethyl ester (CAPE), a natural component of propolis, is reported to have anticarcinogenic properties, although its precise chemopreventive mechanism remains unclear. In this study, we examined the effects of CAPE on 3-methylcholanthrene (3-MC)-induced CYP1A1 expression and activities. CAPE reduced the formation of the benzo[a]pyrene-DNA adduct. Moreover, CAPE inhibited 3-MC-induced CYP1A1 activity, mRNA expression, protein level, and promoter activity. CAPE treatment also decreased 3-MC-inducible xenobiotic-response element (XRE)-linked luciferase, aryl hydrocarbons receptor (AhR) transactivation and nuclear localization. CAPE induced hypoxia inducible factor-1α (HIF-1α) protein level and HIF-1α responsible element (HRE) transcriptional activity. CAPE-mediated HIF-1α reduced 3-MC-inducible CYP1A1 protein expression. Taken together, CAPE decreases 3-MC-mediated CYP1A1 expression, and this inhibitory response is associated with inhibition of AhR and HIF-1α induction. - Highlights: • CAPE reduced the formation of the benzo[a]pyrene-DNA adduct. • CAPE inhibited 3-MC-induced CYP1A1 expression. • CAPE induced HIF-1α induction. • CAPE-mediated HIF-1α reduced 3-MC-inducible CYP1A1 expression.

  20. LRD-22, a novel dual dithiocarbamatic acid ester, inhibits Aurora-A kinase and induces apoptosis and cell cycle arrest in HepG2 cells

    SciTech Connect (OSTI)

    Wang, Huiling; Li, Ridong; Li, Li; Ge, Zemei; Zhou, Rouli; Li, Runtao

    2015-02-27

    In this study we investigated the antitumor activity of the novel dual dithiocarbamatic acid ester LRD-22 in vitro and in vivo. Several cancer cell lines were employed to determine the effect of LRD-22 on cell growth, and the MTT assay showed there was a significant decrease in viable tumor cell numbers in the presence of LRD-22, especially in the HepG2 cell line. Colony formation assay also showed LRD-22 strongly inhibits HepG2 cell growth. Evaluation of the mechanism involved showed that inhibitory effects of LRD-22 on cell growth are due to induction of apoptosis and G2/M arrest. LRD-22 inhibited Aurora-A phosphorylation at Thr{sub 288} and subsequently impaired p53 phosphorylation at Ser{sub 315} which was associated with the proteasome degradation pathway. Tumor suppressor protein p53 is stabilized by this mechanism and accumulates through inhibition of Aurora-A kinase activity via treatment with LRD-22. In vivo study of HepG2 xenograft in nude mice also shows LRD-22 suppresses tumor growth at a concentration of 5 mg/kg without animals suffering loss of body weight. In conclusion, our results demonstrate LRD-22 acts as an Aurora-A kinase inhibitor to induce apoptosis and inhibit proliferation in HepG2 cells, and should be considered as a promising targeting agent for HCC therapy. - Highlights: • LRD-22 significantly inhibits cancer cell growth, especially in the HepG2 cell line. • The inhibitory effect of LRD-22 is due to induction of apoptosis and cell cycle arrest. • LRD-22 inhibits Aurora-A phosphorylation which results in subsequent impairment of the p53 pathway. • LRD-22 suppresses tumor growth in xenograft mice without body weight loss.

  1. Acid-base properties, deactivation, and in situ regeneration of condensation catalysts for synthesis of methyl methacrylate

    SciTech Connect (OSTI)

    Gogate, M.R.; Spivey, J.J.; Zoeller, J.R.

    1996-12-31

    Condensation reaction of a propionate with formaldehyde is a novel route for synthesis of methyl methacrylate (MMA). The reaction mechanism involves a proton abstraction from the propionate on the basic sites and activation of the aliphatic aldehyde on the acidic sites of the catalyst. The acid-base properties of ternary V-Si-P oxide catalysts and their relation to the NWA yield in the vapor phase condensation of formaldehyde with propionic anhydride has been studied for the first time. Five different V-Si-P catalysts with different atomic ratios of vanadium, silicon, and phosphorous were synthesized, characterized, and tested in a fixed-bed microreactor system. A V-Si-P 1:10:2.8 catalyst gave the maximum condensation yield of 56% based on HCHO fed at 300{degrees}C and 2 atm and at a space velocity of 290 cc/g cat{center_dot}h. A parameter called the ``q-ratio`` has been defined to correlate the condensation yields to the acid-base properties. The correlation of q-ratio with the condensation yield shows that higher q-ratios are more desirable. The long-term deactivation studies on the V-Si-P 1: 10:2.8 catalyst at 300{degrees}C and 2 atm and at a space velocity of 290 cc/g cat{center_dot}h show that the catalyst activity drops by a factor of nearly 20 over a 180 h period. The activity can be restored to about 78% of the initial activity by a mild oxidative regeneration at 300{degrees}C and 2 atm. The performance of V-Si-P catalyst has been compared to a Ta/SiO{sub 2} catalyst. The Ta- catalyst is more stable and has a higher on-stream catalyst life.

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

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

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

    2016-04-07

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

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

    DOE Patents [OSTI]

    Seaborg, G.T.

    1961-08-01

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

  4. Multiply Methyl-Branched Fatty Acids and Diacids in the Polar Lipids of a Microaerophilic Subsurface Microbial Community

    SciTech Connect (OSTI)

    Hedrick, David B.; Peacock, Aaron D.; Long, Philip E.; White, David C.

    2008-09-01

    A previously unreported series of di- and trimethylated fatty acids, as well as saturated and monounsaturated diacids were identified in polar lipids isolated from environmental subsurface sediment samples. Mechanisms are proposed for their formation, but their origin and role in cell membranes remains unknown.

  5. Synthesis of [.sup.13C] and [.sup.2H] substituted methacrylic acid, [.sup.13C] and [.sup.2H] substituted methyl methacrylate and/or related compounds

    DOE Patents [OSTI]

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

    2008-01-22

    The present invention is directed to labeled compounds of the formulae ##STR00001## wherein Q is selected from the group consisting of --S--, --S(.dbd.O)--, and --S(.dbd.O).sub.2--, Z is selected from the group consisting of 1-naphthyl, substituted 1-naphthyl, 2-naphthyl, substituted 2-naphthyl, and phenyl groups with the structure ##STR00002## wherein R.sub.1, R.sub.2, R.sub.3, R.sub.4 and R.sub.5 are each independently selected from the group consisting of hydrogen, a C.sub.1-C.sub.4 lower alkyl, a halogen, and an amino group selected from the group consisting of NH.sub.2, NHR and NRR' where R and R' are each independently selected from the group consisting of a C.sub.1-C.sub.4 lower alkyl, an aryl, and an alkoxy group, and X is selected from the group consisting of hydrogen, a C.sub.1-C.sub.4 lower alkyl group, and a fully-deuterated C.sub.1-C.sub.4 lower alkyl group. The present invention is also directed to a process of preparing labeled compounds, e.g., process of preparing [.sup.13C]methacrylic acid by reacting a (CH.sub.3CH.sub.2O--.sup.13C(O)--.sup.13CH.sub.2)-- aryl sulfone precursor with .sup.13CHI to form a (CH.sub.3CH.sub.2O--.sup.13C(O)--.sup.13C(.sup.13CH.sub.3).sub.2)-- aryl sulfone intermediate, and, reacting the (CH.sub.3CH.sub.2O--.sup.13C(O)--.sup.13C(.sup.13CH.sub.3).sub.2)-- aryl sulfone intermediate with sodium hydroxide, followed by acid to form [.sup.13C]methacrylic acid. The present invention is further directed to a process of preparing [.sup.2H.sub.8]methyl methacrylate by reacting a (HOOC--C(C.sup.2H.sub.3).sub.2-- aryl sulfinyl intermediate with CD.sub.3I to form a (.sup.2H.sub.3COOC--C(C.sup.2H.sub.3).sub.2)-- aryl sulfinyl intermediate, and heating the(.sup.2H.sub.3COOC--C(C.sup.2H.sub.3).sub.2)-- aryl sulfinyl intermediate at temperatures and for time sufficient to form [.sup.2H.sub.8]methyl methacrylate.

  6. RECOVERY OF LACTIC ACID FROM AMERICAN CRYSTAL SUGAR COMPANY WASTEWATER

    SciTech Connect (OSTI)

    Daniel J. Stepan; Edwin S. Olson; Richard E. Shockey; Bradley G. Stevens; John R. Gallagher

    2001-04-30

    This project has shown that the recovery of several valuable lactic acid products is both technically feasible and economically viable. One of the original objectives of this project was to recover lactic acid. However, the presence of a variety of indigenous bacteria in the wastewater stream and technical issues related to recovery and purification have resulted in the production of lactic acid esters. These esters could by hydrolyzed to lactic acid, but only with unacceptable product losses that would be economically prohibitive. The developed process is projected to produce approximately 200,000 lb per day of lactate esters from wastewater at a single factory at costs that compete with conventional solvents. The lactate esters are good solvents for polymers and resins and could replace acetone, methyl ethyl ketone, MIBK, and other polar solvents used in the polymer industry. Because of their low volatility and viscosity-lowering properties, they will be especially useful for inks for jet printers, alkyl resins, and high-solid paints. Owing to their efficiency in dissolving salts and flux as well as oils and sealants, lactate esters can be used in cleaning circuit boards and machine and engine parts. Unlike conventional solvents, lactate esters exhibit low toxicity, are biodegradable, and are not hazardous air pollutants. Another application for lactate esters is in the production of plasticizers. Severe health problems have been attributed to widely used phthalate ester plasticizers. The U.S. Department of Agriculture showed that replacement of these with inexpensive lactate esters is feasible, owing to their superior polymer compatibility properties. A very large market is projected for polymers prepared from lactic acid. These are called polylactides and are a type of polyester. Thermoplastics of this type have a variety of uses, including moldings, fibers, films, and packaging of both manufactured goods and food products. Polylactides form tough, orientable

  7. Two new coordination polymers constructed by naphthalene-1,4-dicarboxylic acid and 2,4-diamino-6-methyl-triazine

    SciTech Connect (OSTI)

    Li, Yamin; Xiao, Changyu; Zhang, Xudong; Xu, Yanhui; Li, Junrui; Lun, Huijie; Chen, Qi

    2013-08-15

    Two new transition metal coordination complexes, ([MnO(nda)](H{sub 2}dmt)(H{sub 2}O)){sub n} (1), [Ag{sub 5}(nda){sub 2.5}(dmt)]{sub n} (2), (H{sub 2}nda=naphthalene-1,4-dicarboxylic acid, dmt=2,4-diamine-6-methyl-1,3,5-triazine) have been hydrothermally synthesized by the reactions of H{sub 2}nda and dmt with the homologous MnCl{sub 2}·4H{sub 2}O and AgNO{sub 3}, respectively, and characterized by single-crystal X-ray diffraction, IR spectra, elemental analysis, thermogravimetric analysis (TGA). The compound 1 exhibits a 3D network comprising 1D metal chain (MnO(CO{sub 2}){sub 2}){sub n} connected by the ligand nda{sup 2−}, featuring a four-connected uninodal diamond -like topology. In compound 2, it is firstly observed that decanuclear silver units as secondary building units to construct 3D network by the ligands dmt and nda{sup 2−}, with a rare 2-nodal (3,8)-connected tfz-d topology ((4{sup 3}){sub 2}(4{sup 6}.6{sup 18}.8{sup 4})). The interactions within each Mn(II)—Mn(II) pair of compound 1 are antiferromagnetic (g=2.07, J=−1.42(1) cm{sup −1}, zj′=−0.73(2) cm{sup −1}). In addition, compound 2 exhibits photoluminescent property at about 472 nm (λ{sub ex}=394 nm). - Graphical abstract: Two new transition metal coordination complexes 1–2 have been hydrothermally synthesized and characterized by single-crystal X-ray diffraction, IR spectra, elemental analysis thermogravimetric analysis (TGA). Highlights: • The compound 1 exhibits a 3D network with four-connected uninodal diamond-like topology. • The first 3D network of 2 with a rare tfz-d topology consists of decanuclear silver clusters as secondary building units. • The magnetic measurement indicates the compound 1 shows antiferromagnetic interactions. • The photoluminescent property of 2 has been measured.

  8. Direct esterification of ammonium salts of carboxylic acids

    DOE Patents [OSTI]

    Halpern, Yuval

    2003-06-24

    A non-catalytic process for producing esters, the process comprising reacting an ammonium salt of a carboxylic acid with an alcohol and removing ammonia from the reaction mixture. Selectivities for the desired ester product can exceed 95 percent.

  9. Ether and ester derivatives of the perborate icosahedron

    DOE Patents [OSTI]

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

    2003-12-16

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

  10. Method of making a cyanate ester foam

    DOE Patents [OSTI]

    Celina, Mathias C.; Giron, Nicholas Henry

    2014-08-05

    A cyanate ester resin mixture with at least one cyanate ester resin, an isocyanate foaming resin, other co-curatives such as polyol or epoxy compounds, a surfactant, and a catalyst/water can react to form a foaming resin that can be cured at a temperature greater than 50.degree. C. to form a cyanate ester foam. The cyanate ester foam can be heated to a temperature greater than 400.degree. C. in a non-oxidative atmosphere to provide a carbonaceous char foam.

  11. Effects of Light and Temperature on Fatty Acid Production in Nannochloropsis Salina

    SciTech Connect (OSTI)

    Van Wagenen, Jonathan M.; Miller, Tyler W.; Hobbs, Samuel J.; Hook, Paul W.; Crowe, Braden J.; Huesemann, Michael H.

    2012-03-12

    Accurate prediction of algal biofuel yield will require empirical determination of physiological responses to the climate, particularly light and temperature. One strain of interest, Nannochloropsis salina, was subjected to ranges of light intensity (5-850 {mu}mol m{sup -2} s{sup -1}) and temperature (13-40 C); exponential growth rate, total fatty acids (TFA) and fatty acid composition were measured. The maximum acclimated growth rate was 1.3 day{sup -1} at 23 C and 250 {mu}mol m{sup -2} s{sup -1}. Fatty acids were detected by gas chromatography with flame ionization detection (GC-FID) after transesterification to corresponding fatty acid methyl esters (FAME). A sharp increase in TFA containing elevated palmitic acid (C16:0) and palmitoleic acid (C16:1) during exponential growth at high light was observed, indicating likely triacylglycerol accumulation due to photo-oxidative stress. Lower light resulted in increases in the relative abundance of unsaturated fatty acids; in thin cultures, increases were observed in palmitoleic and eicosapentaenoeic acids (C20:5{omega}3). As cultures aged and the effective light intensity per cell converged to very low levels, fatty acid profiles became more similar and there was a notable increase of oleic acid (C18:1{omega}9). The amount of unsaturated fatty acids was inversely proportional to temperature, demonstrating physiological adaptations to increase membrane fluidity. This data will improve prediction of fatty acid characteristics and yields relevant to biofuel production.

  12. Synthesis and characterization of ester and amide derivatives of titanium(IV) carboxymethylphosphonate

    SciTech Connect (OSTI)

    Melánová, Klára; Beneš, Ludvík; Trchová, Miroslava; Svoboda, Jan; Zima, Vítězslav

    2013-06-15

    A set of layered ester and amide derivatives of titanium(IV) carboxymethylphosphonate was prepared by solvothermal treatment of amorphous titanium(IV) carboxymethylphosphonate with corresponding 1-alkanols, 1,ω-alkanediols, 1-aminoalkanes, 1,ω-diaminoalkanes and 1,ω-amino alcohols and characterized by powder X-ray diffraction, IR spectroscopy and thermogravimetric analysis. Whereas alkyl chains with one functional group form bilayers tilted to the layers, 1,ω-diaminoalkanes and most of 1,ω-alkanediols form bridges connecting the adjacent layers. In the case of amino alcohols, the alkyl chains form bilayer and either hydroxyl or amino group is used for bonding. This simple method for the synthesis of ester and amide derivatives does not require preparation of acid chloride derivative as a precursor or pre-intercalation with alkylamines and can be used also for the preparation of ester and amide derivatives of titanium carboxyethylphosphonate and zirconium carboxymethylphosphonate. - Graphical abstract: Ester and amide derivatives of layered titanium carboxymethylphosphonate were prepared by solvothermal treatment of amorphous solid with alkanol or alkylamine. - Highlights: • Ester and amide derivatives of titanium carboxymethylphosphonate. • Solvothermal treatment of amorphous solid with alkanol or alkylamine. • Ester and amide formation confirmed by IR spectroscopy.

  13. Production of Succinic Acid for Lignocellulosic Hydrolysates

    SciTech Connect (OSTI)

    Davison, B.H.; Nghiem, J.

    2002-06-01

    The purpose of this Cooperative Research and Development Agreement (CRADA) is to add and test new metabolic activities to existing microbial catalysts for the production of succinic acid from renewables. In particular, they seek to add to the existing organism the ability to utilize xylose efficiently and simultaneously with glucose in mixtures of sugars or to add succinic acid production to another strain and to test the value of this new capability for production of succinic acid from industrial lignocellulosic hydrolyasates. The Contractors and Participant are hereinafter jointly referred to as the 'Parties'. Research to date in succinic acid fermentation, separation and genetic engineering has resulted in a potentially economical process based on the use of an Escherichia coli strain AFP111 with suitable characteristics for the production of succinic acid from glucose. Economic analysis has shown that higher value commodity chemicals can be economically produced from succinic acid based on repliminary laboratory findings and predicted catalytic parameters. The initial target markets include succinic acid itself, succinate salts, esters and other derivatives for use as deicers, solvents and acidulants. The other commodity products from the succinic acid platform include 1,4-butanediol, {gamma}-butyrolactone, 2-pyrrolidinone and N-methyl pyrrolidinone. Current economic analyses indicate that this platform is competitive with existing petrochemical routes, especially for the succinic acid and derivatives. The report presents the planned CRADA objectives followed by the results. The results section has a combined biocatalysis and fermentation section and a commercialization section. This is a nonproprietary report; additional proprietary information may be made available subject to acceptance of the appropriate proprietary information agreements.

  14. Preparation of 3R- and 3S-methyl isomers of the myocardial imaging agent 15-(p-IODOPHENYL)-3-methylpentadecanoic acid ({open_quotes}BMIPP{close_quotes})

    SciTech Connect (OSTI)

    Lin, Q. |; Luo, J.; Mokler, F.

    1996-10-01

    Iodine-123-labeled racemic BMIPP is used for clinical evaluation of heart disease. To evaluate the expected importance of configuration of the asymmetric C-3 center, we have synthesized the 3R-isomer. 6-Phenylhexanoyl chloride was condensed with thiophene (Friedel-Crafts), followed by Wolff-Kishner reduction and subsequent acylation with the ethyl-3-R-methylglutaroyl chloride, Wolff-Kishner reduction and Raney-Ni ring opening. Para Thallation (TTFA)/KI provided 3R-BMIPP, m.p. 51-52{degrees}C, [{alpha}{sub D}] = +0.74{degrees}. The diastereomeric amide mixture was prepared by reaction of racemic 3-R,S-BMIPP with (S)-(-)-{alpha}-methylbenzylamine. Chromatographic separation and HCl hydrolysis (at 175{degrees}C) provided the 3R- and 3S- (m.p. 45-46{degrees}C, [{alpha}{sub D}] = -1.67{degrees}) BMIPP isomers. The more polar amide (m.p. 93-94{degrees}C) was identical with the amide from the synthetic 3R-BMIPP (m.p., HPLC, NMR). Availability of the 3R- and 3S-BMIPP isomers will permit preparation of the radioiodinated isomers and animal evaluation to determine the effects of the methyl group configuration on myocardial uptake and metabolism.

  15. Process for the preparation of an energetic nitrate ester

    DOE Patents [OSTI]

    Chavez, David E; Naud, Darren L; Hiskey, Michael A

    2013-12-17

    A process for the preparation of an energetic nitrate ester compound and related intermediates is provided.

  16. Synthesis of a new energetic nitrate ester

    SciTech Connect (OSTI)

    Chavez, David E

    2008-01-01

    Nitrate esters have been known as useful energetic materials since the discovery of nitroglycerin by Ascanio Sobrero in 1846. The development of methods to increase the safety and utility of nitroglycerin by Alfred Nobel led to the revolutionary improvement in the utility of nitroglycerin in explosive applications in the form of dynamite. Since then, many nitrate esters have been prepared and incorporated into military applications such as double-based propellants, detonators and as energetic plasticizers. Nitrate esters have also been shown to have vasodilatory effects in humans and thus have been studied and used for treatments of ailments such as angina. The mechanism of the biological response towards nitrate esters has been elucidated recently. Interestingly, many of the nitrate esters used for military purposes are liquids (ethylene glycol dinitrate, propylene glycol dinitrate, etc). Pentaerythritol tetranitrate (PETN) is one of the only solid nitrate esters, besides nitrocellulose, that is used in any application. Unfortunately, PETN melting point is above 100 {sup o}C, and thus must be pressed as a solid for detonator applications. A more practical material would be a melt-castable explosive, for potential simplification of manufacturing processes. Herein we describe the synthesis of a new energetic nitrate ester (1) that is a solid at ambient temperatures, has a melting point of 85-86 {sup o}C and has the highest density of any known nitrate ester composed only of carbon, hydrogen, nitrogen and oxygen. We also describe the chemical, thermal and sensitivity properties of 1 as well as some preliminary explosive performance data.

  17. Nucleophilic substitutions of 1-alkenylcyclopropyl esters and 1-alkynylcyclopropyl chlorides catalyzed by palladium (0)

    SciTech Connect (OSTI)

    Stolle, A. |; Ollivier, J.; Salauen, J.

    1992-05-20

    The 1-ethenylcyclopropylsulfonates 2e,f and 2-cyclopropylideneethyl esters 10b,c, readily available from cyclopropanone hemiacetal 1, undergo regioselective Pd(0) catalyzed nucleophilic substitution via the unsymmetric 1,1-dimethylene-{pi}-allyl complex 23. With stabilized anions (enolates of malonic ester, {beta}-dicarbonyl compounds, {beta}-sulfonyl ester, and Schiff bases as well as acetate anion, sulfonamide anion, etc.) the nucleophilic substitution occurs at the terminal vinylic position exclusively, providing cyclopropylideneethyl derivatives as building blocks of high synthetic potential. Competition experiments have disclosed that 1-ethenylcyclopropyl tosylate (2e) and cyclopropylideneethyl acetate (10b) are more reactive than dimethylallyl acetates 19 and 22, respectively. Use of chiral phosphines as ligands in the palladium catalyst can provide optically active methylenecyclopropane derivatives. With phenyl-, methyl-, and even n-butylzinc chloride as nucleophiles, the reaction apparently proceeds with initial transfer of the organic residue to palladium, followed by reductive elimination entailing tertiary substitution on the cyclopropane ring exclusively; the same type of product is obtained with azide and bis(trimethylsilyl)amide. But the site of hydride attack to yield reduction products depends on the hydride source. 1-Alkynylcyclopropyl chlorides 12, 13, and 14 react only with organozinc chlorides (nonstabilized nucleophiles) to provide mixtures of ethenylidenecyclopropanes 65 and alkynylcyclopropanes 66, via the {sigma}-palladium complexes 69 and 70, while chloride 15 undergoes mainly reduction. Other transition metal catalysts (Ni, Mo) also induce substitutions, but with poorer regioselectivity. 81 refs., 9 figs., 3 tabs.

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

    SciTech Connect (OSTI)

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

    2012-01-01

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

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

    SciTech Connect (OSTI)

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

    2012-10-01

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

  20. Zinc oxide modified with benzylphosphonic acids as transparent electrodes in regular and inverted organic solar cell structures

    SciTech Connect (OSTI)

    Lange, Ilja; Reiter, Sina; Kniepert, Juliane; Piersimoni, Fortunato; Brenner, Thomas; Neher, Dieter; Pätzel, Michael; Hildebrandt, Jana; Hecht, Stefan

    2015-03-16

    An approach is presented to modify the work function of solution-processed sol-gel derived zinc oxide (ZnO) over an exceptionally wide range of more than 2.3 eV. This approach relies on the formation of dense and homogeneous self-assembled monolayers based on phosphonic acids with different dipole moments. This allows us to apply ZnO as charge selective bottom electrodes in either regular or inverted solar cell structures, using poly(3-hexylthiophene):phenyl-C71-butyric acid methyl ester as the active layer. These devices compete with or even surpass the performance of the reference on indium tin oxide/poly(3,4-ethylenedioxythiophene) polystyrene sulfonate. Our findings highlight the potential of properly modified ZnO as electron or hole extracting electrodes in hybrid optoelectronic devices.

  1. 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)

  2. Recovery of organic acids

    DOE Patents [OSTI]

    Verser, Dan W. (Menlo Park, CA); Eggeman, Timothy J. (Lakewood, CO)

    2011-11-01

    A method is disclosed for the recovery of an organic acid from a dilute salt solution in which the cation of the salt forms an insoluble carbonate salt. A tertiary amine and CO.sub.2 are introduced to the solution to form the insoluble carbonate salt and a complex between the acid and an amine. A water immiscible solvent, such as an alcohol, is added to extract the acid/amine complex from the dilute salt solution to a reaction phase. The reaction phase is continuously dried and a product between the acid and the solvent, such as an ester, is formed.

  3. Recovery of organic acids

    DOE Patents [OSTI]

    Verser, Dan W. (Golden, CO); Eggeman, Timothy J. (Lakewood, CO)

    2009-10-13

    A method is disclosed for the recovery of an organic acid from a dilute salt solution in which the cation of the salt forms an insoluble carbonate salt. A tertiary amine and CO.sub.2 are introduced to the solution to form the insoluble carbonate salt and a complex between the acid and an amine. A water immiscible solvent, such as an alcohol, is added to extract the acid/amine complex from the dilute salt solution to a reaction phase. The reaction phase is continuously dried and a product between the acid and the solvent, such as an ester, is formed.

  4. 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.

  5. Structure–activity relationships of imidazole-derived 2-[N-carbamoylmethyl-alkylamino]acetic acids, dual binders of human insulin-degrading enzyme

    SciTech Connect (OSTI)

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

    2015-10-30

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

  6. 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.

  7. Microbial production of wax esters from highly branched alkanes

    DOE Patents [OSTI]

    Bogan, William W.; Sullivan, Wendy R.; Paterek, James R.

    2005-02-01

    A microbial culture and method for producing wax esters using highly branched alkanes. In accordance with one embodiment, the highly branched alkane is squalane.

  8. The use of novel biodegradable, optically active and nanostructured poly(amide-ester-imide) as a polymer matrix for preparation of modified ZnO based bionanocomposites

    SciTech Connect (OSTI)

    Abdolmaleki, Amir; Nanotechnology and Advanced Materials Institute, Isfahan University of Technology, Isfahan 84156-83111, Islamic Republic of Iran ; Mallakpour, Shadpour; Nanotechnology and Advanced Materials Institute, Isfahan University of Technology, Isfahan 84156-83111, Islamic Republic of Iran ; Borandeh, Sedigheh

    2012-05-15

    Highlights: Black-Right-Pointing-Pointer A novel biodegradable and nanostructured PAEI based on two amino acids, was synthesized. Black-Right-Pointing-Pointer ZnO nanoparticles were modified via two different silane coupling agents. Black-Right-Pointing-Pointer PAEI/modified ZnO BNCs were synthesized through ultrasound irradiation. Black-Right-Pointing-Pointer ZnO particles were dispersed homogeneously in PAEI matrix on nanoscale. Black-Right-Pointing-Pointer The effect of ZnO nanoparticles on the properties of synthesized polymer was examined. -- Abstract: A novel biodegradable and nanostructured poly(amide-ester-imide) (PAEI) based on two different amino acids, was synthesized via direct polycondensation of biodegradable N,N Prime -bis[2-(methyl-3-(4-hydroxyphenyl)propanoate)]isophthaldiamide and N,N Prime -(pyromellitoyl)-bis-L-phenylalanine diacid. The resulting polymer was characterized by FT-IR, {sup 1}H NMR, specific rotation, elemental analysis, thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), X-ray diffraction (XRD) and field emission scanning electron microscopy (FE-SEM) analysis. The synthesized polymer showed good thermal stability with nano and sphere structure. Then PAEI/ZnO bionanocomposites (BNCs) were fabricated via interaction of pure PAEI and ZnO nanoparticles. The surface of ZnO was modified with two different silane coupling agents. PAEI/ZnO BNCs were studied and characterized by FT-IR, XRD, UV/vis, FE-SEM and TEM. The TEM and FE-SEM results indicated that the nanoparticles were dispersed homogeneously in PAEI matrix on nanoscale. Furthermore the effect of ZnO nanoparticle on the thermal stability of the polymer was investigated with TGA and DSC technique.

  9. Optimization of esterification of oleic acid and trimethylolpropane (TMP) and pentaerythritol (PE)

    SciTech Connect (OSTI)

    Mahmud, Hamizah Ammarah; Salimon, Jumat

    2014-09-03

    Vegetable oil (VO) is the most potential alternative to replace mineral oil for lubricant due to better lubricating properties and great physicochemical properties. Chemical modification has to be done to overcome low temperature performance and low oxidation instability due to the presence of β-hydrogen atoms of glycerol molecule. The optimization of esterification of oleic acid and polyhydric alcohol with sulfuric acid catalyst was carried out to find the optimum conditions with the highest yield. Reeaction variables such as; molar ratio, temperature, duration and catalyst concentration. Two types of polyhydric alcohol have been used; TMP and PE. The optimum results showed oleic acid successfully converted 91.2% ester TMP and 92.7% ester PE at duration: 5 hours (Ester TMP), 6 hours (Ester PE); temperature: 150°C (ester TMP), 180°C (Ester PE); catalyst concentration: 1.5% (w/w); and mol ratio: 3.9:1 (ester TMP), 4.9:1 (ester PE). From the data obtained, mole ratio showed most influenced factors to the increasing yields of ester conversions.. The TMP/PE ester was confirmed using gas chromatography (GC-FID), Fourier Transform Infrared Spectroscopy (FTIR) and Nuclear Magnetic Resonance (NMR)

  10. Production of high molecular weight polylactic acid

    DOE Patents [OSTI]

    Bonsignore, Patrick V.

    1995-01-01

    A degradable high molecular weight poly(lactic acid). A poly(lactic acid) has a terminal end group of one of carboxyl or hydroxyl groups with low molecular weight poly(lactic acid) units coupled with linking agents of di-isocyanates, bis-epoxides, bis-oxazolines and bis-ortho esters. The resulting high molecular weight poly(lactic acid) can be used for applications taking advantage of the improved physical properties.

  11. Production of high molecular weight polylactic acid

    DOE Patents [OSTI]

    Bonsignore, P.V.

    1995-11-28

    A degradable high molecular weight poly(lactic acid) is described. The poly(lactic acid) has a terminal end group of one of carboxyl or hydroxyl groups with low molecular weight poly(lactic acid) units coupled with linking agents of di-isocyanates, bis-epoxides, bis-oxazolines and bis-ortho esters. The resulting high molecular weight poly(lactic acid) can be used for applications taking advantage of the improved physical properties.

  12. 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.

  13. Controlling DNA Methylation

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

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

  14. Determination of Free Fatty Acids and Triglycerides by Gas Chromatography Using Selective Esterification Reactions

    SciTech Connect (OSTI)

    Kail, Brian W.; Link, Dirk D.; Morreale, Bryan D

    2012-11-01

    A method for selectively determining both free fatty acids (FFA) and triacylglycerides (TAGs) in biological oils was investigated and optimized using gas chromatography after esterification of the target species to their corresponding fatty acid methyl esters (FAMEs). The method used acid catalyzed esterification in methanolic solutions under conditions of varying severity to achieve complete conversion of more reactive FFAs while preserving the concentration of TAGs. Complete conversion of both free acids and glycerides to corresponding FAMEs was found to require more rigorous reaction conditions involving heating to 120C for up to 2 h. Method validation was provided using gas chromatographyflame ionization detection, gas chromatographymass spectrometry, and liquid chromatographymass spectrometry. The method improves on existing methods because it allows the total esterified lipid to be broken down by FAMEs contributed by FFA compared to FAMEs from both FFA and TAGs. Single and mixed-component solutions of pure fatty acids and triglycerides, as well as a sesame oil sample to simulate a complex biological oil, were used to optimize the methodologies. Key parameters that were investigated included: HCl-to-oil ratio, temperature and reaction time. Pure free fatty acids were found to esterify under reasonably mild conditions (10 min at 50C with a 2.1:1 HCl to fatty acid ratio) with 97.6 2.3% recovery as FAMEs, while triglycerides were largely unaffected under these reaction conditions. The optimized protocol demonstrated that it is possible to use esterification reactions to selectively determine the free acid content, total lipid content, and hence, glyceride content in biological oils. This protocol also allows gas chromatography analysis of FAMEs as a more ideal analyte than glyceride species in their native state.

  15. Carboxylic acid accelerated formation of diesters

    DOE Patents [OSTI]

    Tustin, Gerald Charles; Dickson, Todd Jay

    1998-01-01

    This invention pertains to accelerating the rate of formation of 1,1-dicarboxylic esters from the reaction of an aldehyde with a carboxylic acid anhydride or a ketene in the presence of a non-iodide containing a strong Bronsted acid catalyst by the addition of a carboxylic acid at about one bar pressure and between about 0.degree. and 80.degree. C. in the substantial absence of a hydrogenation or carbonylation catalyst.

  16. Carboxylic acid accelerated formation of diesters

    DOE Patents [OSTI]

    Tustin, G.C.; Dickson, T.J.

    1998-04-28

    This invention pertains to accelerating the rate of formation of 1,1-dicarboxylic esters from the reaction of an aldehyde with a carboxylic acid anhydride or a ketene in the presence of a non-iodide containing a strong Bronsted acid catalyst by the addition of a carboxylic acid at about one bar pressure and between about 0 and 80 C in the substantial absence of a hydrogenation or carbonylation catalyst.

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

    SciTech Connect (OSTI)

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

    2009-04-15

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

  18. Esterification of fermentation-derived acids via pervaporation

    DOE Patents [OSTI]

    Datta, R.; Tsai, S.P.

    1998-03-03

    A low temperature method for esterifying ammonium- and amine-containing salts is provided whereby the salt is reacted with an alcohol in the presence of heat and a catalyst and then subjected to a dehydration and deamination process using pervaporation. The invention also provides for a method for producing esters of fermentation derived, organic acid salt comprising first cleaving the salt into its cationic part and anionic part, mixing the anionic part with an alcohol to create a mixture; heating the mixture in the presence of a catalyst to create an ester; dehydrating the now heated mixture; and separating the ester from the now-dehydrated mixture. 2 figs.

  19. Esterification of fermentation-derived acids via pervaporation

    DOE Patents [OSTI]

    Datta, Rathin; Tsai, Shih-Perng

    1998-01-01

    A low temperature method for esterifying ammonium- and amine-containing salts is provided whereby the salt is reacted with an alcohol in the presence of heat and a catalyst and then subjected to a dehydration and deamination process using pervaporation. The invention also provides for a method for producing esters of fermentation derived, organic acid salt comprising first cleaving the salt into its cationic part and anionic part, mixing the anionic part with an alcohol to create a mixture; heating the mixture in the presence of a catalyst to create an ester; dehydrating the now heated mixture; and separating the ester from the now-dehydrated mixture.

  20. Reactive Distillation for Esterification of Bio-based Organic Acids

    SciTech Connect (OSTI)

    Fields, Nathan; Miller, Dennis J.; Asthana, Navinchandra S.; Kolah, Aspi K.; Vu, Dung; Lira, Carl T.

    2008-09-23

    The following is the final report of the three year research program to convert organic acids to their ethyl esters using reactive distillation. This report details the complete technical activities of research completed at Michigan State University for the period of October 1, 2003 to September 30, 2006, covering both reactive distillation research and development and the underlying thermodynamic and kinetic data required for successful and rigorous design of reactive distillation esterification processes. Specifically, this project has led to the development of economical, technically viable processes for ethyl lactate, triethyl citrate and diethyl succinate production, and on a larger scale has added to the overall body of knowledge on applying fermentation based organic acids as platform chemicals in the emerging biorefinery. Organic acid esters constitute an attractive class of biorenewable chemicals that are made from corn or other renewable biomass carbohydrate feedstocks and replace analogous petroleum-based compounds, thus lessening U.S. dependence on foreign petroleum and enhancing overall biorefinery viability through production of value-added chemicals in parallel with biofuels production. Further, many of these ester products are candidates for fuel (particularly biodiesel) components, and thus will serve dual roles as both industrial chemicals and fuel enhancers in the emerging bioeconomy. The technical report from MSU is organized around the ethyl esters of four important biorenewables-based acids: lactic acid, citric acid, succinic acid, and propionic acid. Literature background on esterification and reactive distillation has been provided in Section One. Work on lactic acid is covered in Sections Two through Five, citric acid esterification in Sections Six and Seven, succinic acid in Section Eight, and propionic acid in Section Nine. Section Ten covers modeling of ester and organic acid vapor pressure properties using the SPEAD (Step Potential

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

    Office of Scientific and Technical Information (OSTI)

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

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

    Office of Scientific and Technical Information (OSTI)

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

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

    Office of Scientific and Technical Information (OSTI)

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

  4. Slide 0

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

    compensate for the effects of different injection sizes and sample concentration *The peak ... of Fatty Acid Methyl Esters (FAMEs) Methanol content * The methanol content of the ...

  5. Drop In Fuels: Where the Road Leads

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

    ... Algal Oil 8 Biomass-based Diesel: Biodiesel-ester Standalone Renewable Diesel ... 3 OC(CH 2 ) 7 CHCH(CH 2 ) 7 CH 3 O Biodiesel or Fatty Acid Methyl Ester (FAME) CH 3 ...

  6. ESTER, Enel integrated System for TEsts on stoRage (Smart Grid...

    Open Energy Info (EERE)

    ESTER, Enel integrated System for TEsts on stoRage (Smart Grid Project) Jump to: navigation, search Project Name ESTER, Enel integrated System for TEsts on stoRage Country Italy...

  7. Rheinische Bio Ester GmbH Co KG | Open Energy Information

    Open Energy Info (EERE)

    Rheinische Bio Ester GmbH Co KG Jump to: navigation, search Name: Rheinische Bio Ester GmbH & Co.KG Place: Neuss, North Rhine-Westphalia, Germany Zip: 41460 Product: Rheinische Bio...

  8. Viscosity of aqueous and cyanate ester suspensions containing alumina nanoparticles

    SciTech Connect (OSTI)

    Lawler, Katherine

    2009-08-05

    The viscosities of both aqueous and cyanate ester monomer (BECy) based suspensions of alumina nanoparticle were studied. The applications for these suspensions are different: aqueous suspensions of alumina nanoparticles are used in the production of technical ceramics made by slip casting or tape casting, and the BECy based suspensions are being developed for use in an injection-type composite repair resin. In the case of aqueous suspensions, it is advantageous to achieve a high solids content with low viscosity in order to produce a high quality product. The addition of a dispersant is useful so that higher solids content suspensions can be used with lower viscosities. For BECy suspensions, the addition of nanoparticles to the BECy resin is expected to enhance the mechanical properties of the cured composite. The addition of saccharides to aqueous suspensions leads to viscosity reduction. Through DSC measurements it was found that the saccharide molecules formed a solution with water and this resulted in lowering the melting temperature of the free water according to classic freezing point depression. Saccharides also lowered the melting temperature of the bound water, but this followed a different rule. The shear thinning and melting behaviors of the suspensions were used to develop a model based on fractal-type agglomeration. It is believed that the structure of the particle flocs in these suspensions changes with the addition of saccharides which leads to the resultant viscosity decrease. The viscosity of the BECy suspensions increased with solids content, and the viscosity increase was greater than predicted by the classical Einstein equation for dilute suspensions. Instead, the Mooney equation fits the viscosity behavior well from 0-20 vol% solids. The viscosity reduction achieved at high particle loadings by the addition of benzoic acid was also investigated by NMR. It appears that the benzoic acid interacts with the surface of the alumina particle which may

  9. SYNTHESIS OF METHYL METHACRYLATE FROM COAL-DERIVED SYNGAS

    SciTech Connect (OSTI)

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

    1999-04-21

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

  10. Kinetic Model Development for the Combustion of Particulate Matter from Conventional and Soy Methyl Ester Diesel Fuels

    SciTech Connect (OSTI)

    Strzelec, Andrea

    2009-12-01

    The primary objective of this research has been to investigate how the oxidation characteristics of diesel particulate matter (PM) are affected by blending soy-based biodiesel fuel with conventional ultra low sulfur diesel (ULSD) fuel. PM produced in a light duty engine from different biodiesel-conventional fuel blends was subjected to a range of physical and chemical measurements in order to better understand the mechanisms by which fuel-related changes to oxidation reactivity are brought about. These observations were then incorporated into a kinetic model to predict PM oxidation. Nanostructure of the fixed carbon was investigated by HR-TEM and showed that particulates from biodiesel had a more open structure than particulates generated from conventional diesel fuel, which was confirmed by BET surface area measurements. Surface area evolution with extent of oxidation reaction was measured for PM from ULSD and biodiesel. Biodiesel particulate has a significantly larger surface area for the first 40% of conversion, at which point the samples become quite similar. Oxidation characteristics of nascent PM and the fixed carbon portion were measured by temperature programmed oxidation (TPO) and it was noted that increased biodiesel blending lowered the light-off temperature as well as the temperature where the peak rate of oxidation occurred. A shift in the oxidation profiles of all fuels was seen when the mobile carbon fraction was removed, leaving only the fixed carbon, however the trend in temperature advantage of the biofuel blending remained. The mobile carbon fraction was measured by temperature programmed desorption found to generally increase with increasing biodiesel blend level. The relative change in the light-off temperatures for the nascent and fixed carbon samples was found to be related to the fraction of mobile carbon. Effective Arrhenius parameters for fixed carbon oxidation were directly measured with isothermal, differential oxidation experiments. Normalizing the reaction rate to the total carbon surface area available for reaction allowed for the definition of a single reaction rate with constant activation energy (112.5 {+-} 5.8 kJ/mol) for the oxidation of PM, independent of its fuel source. A kinetic model incorporating the surface area dependence of fixed carbon oxidation rate and the impact of the mobile carbon fraction was constructed and validated against experimental data.

  11. 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.

  12. Carbomethoxyethylation of aryl and alkyl bromides catalyzed by nickel complexes

    SciTech Connect (OSTI)

    Lebedev, S.A.; Lopatina, V.S.; Berestova, S.S.; Petrov, E.S.; Beletskaya, I.P.

    1986-12-10

    The reaction of aryl and alkyl bromides with methyl acrylate in the presence of water, pyridine, and a nickel catalyst results in the formation of saturated conjugate-addition products, viz. methyl esters of aryl- and alkyl-propionic acids.

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

    DOE Patents [OSTI]

    Filby, Evan E.

    1977-01-01

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

  14. 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.

  15. Transesterification process to manufacture ethyl ester of rape oil

    SciTech Connect (OSTI)

    Korus, R.A.; Hoffman, D.S.; Bam, N.; Peterson, C.L.; Drown, D.C.

    1993-12-31

    A process for the production of the ethyl ester of winter rape [EEWR] for use as a biodiesel fuel has been studied. The essential part of the process is the transesterification of rape oil with ethanol, in the presence of a catalyst, to yield the ethyl ester of rape oil as a product and glycerin as a by-product. Experiments have been performed to determine the optimum conditions for the preparation of EEWR. The process variables were: (1) temperature, (2) catalyst, (3) rate of agitation, (4) water content of the alcohol used, and (5) the amount of excess alcohol used. The optimum conditions were: (1) room temperature, (2) 0.5% sodium methoxide or 1% potassium hydroxide catalyst by weight of rapeseed oil, (3) extremely vigorous agitation with some splashing during the initial phase of the reaction and agitation was not necessary after the reaction mixture became homogeneous, (4) absolute ethanol was necessary for high conversion, and (5) 50% excess ethanol with NaOCH{sub 3} or 100% excess with KOH gave a maximum conversion. Viscosity, cloud point and pour point of the EEWR were measured. A preliminary break-even cost for the commercial production of EEWR was found to be $0.55/liter [$2.08/US gallon].

  16. Evaluation of alternate routes for the synthesis of methyl methacrylate

    SciTech Connect (OSTI)

    Spivey, J.J.; Gogate, M.R.; Zoeller, J.R.; Colberg, R.D.; Choi, G.N.

    1998-12-31

    The use of coal-derived syngas to produce high value chemicals is an important means of upgrading this resource. One example of a chemical that can be produced from coal-derived syngas is methyl methacrylate (MMA). Poly-methyl methacrylate is widely used in coatings and in various industrial molded products. The most widely practiced commercial technology for the synthesis of MMA is the acetone cyanohydrin (ACH) process. This process requires handling of large quantities of toxic hydrogen cyanide and generates one mole of ammonium bisulfate waste per mole of MMA. This bisulfate must either be regenerated or discarded, either of which substantially increases the cost. The ACH technology is thus environmentally and economically untenable for any new MMA plant expansions that would be needed to meet increasing demand. The RTI-Eastman-Bechtel research team is developing an alternative, environmentally benign route to MMA consisting of three steps; (step 1) synthesis of a propionate from ethylene, carbon monoxide, and steam, (step 2) condensation of this propionate with formaldehyde, and (step 3) esterification of resulting methacrylic acid with methanol to form MMA. This paper describes the preliminary economics of the overall process compared to other emerging processes, and focuses on step 2, including long term testing of catalysts for the condensation of propionic acid with formaldehyde to form MAA.

  17. Mild partial deoxygenation of esters catalyzed by an oxazolinylborate-coordinated rhodium silylene

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

    Xu, Songchen; Boschen, Jeffery S.; Biswas, Abhranil; Kobayashi, Takeshi; Pruski, Marek; Windus, Theresa L.; Sadow, Aaron D.

    2015-08-17

    An electrophilic, coordinatively unsaturated rhodium complex supported by borate-linked oxazoline, oxazoline-coordinated silylene, and N-heterocyclic carbene donors [{κ³-N,Si,C-PhB(OxMe²)(OxMe²SiHPh)ImMes}Rh(H)CO][HB(C₆F₅)₃] (2, OxMe² = 4,4-dimethyl-2-oxazoline; ImMes = 1-mesitylimidazole) is synthesized from the neutral rhodium silyl {PhB(OxMe²)₂ImMes}RhH(SiH2Ph)CO (1) and B(C6F5)3. The unusual oxazoline-coordinated silylene structure in 2 is proposed to form by rearrangement of an unobserved isomeric cationic rhodium silylene species [{PhB(OxMe²)₂ImMes}RhH(SiHPh)CO][HB(C₆F₅)₃] generated by H abstraction. Complex 2 catalyzes reductions of organic carbonyl compounds with silanes to give hydrosilylation products or deoxygenation products. The pathway to these reactions is primarily influenced by the degree of substitution of the organosilane. Reactions with primary silanes give deoxygenationmore » of esters to ethers, amides to amines, and ketones and aldehydes to hydrocarbons, whereas tertiary silanes react to give 1,2-hydrosilylation of the carbonyl functionality. In contrast, the strong Lewis acid B(C₆F₅)₃ catalyzes the complete deoxygenation of carbonyl compounds to hydrocarbons with PhSiH₃ as the reducing agent.« less

  18. Structural Interactions within Lithium Salt Solvates: Cyclic Carbonates and Esters

    SciTech Connect (OSTI)

    Seo, D. M.; Afroz, Taliman; Allen, Joshua L.; Boyle, Paul D.; Trulove, Paul C.; De Long, Hugh C.; Henderson, Wesley A.

    2014-11-13

    Only limited information is available regarding the manner in which cyclic carbonate and ester solvents coordinate Li+ cations in electrolyte solutions for lithium batteries. One approach to gleaning significant insight into these interactions is to examine crystalline solvate structures. To this end, eight new solvate structures are reported with ethylene carbonate, ?-butyrolactone and ?-valerolactone: (EC)3:LiClO4, (EC)2:LiClO4, (EC)2:LiBF4, (GBL)4:LiPF6, (GBL)1:LiClO4, (GVL)1:LiClO4, (GBL)1:LiBF4 and (GBL)1:LiCF3SO3. The crystal structure of (EC)1:LiCF3SO3 is also re-reported for comparison. These structures enable the factors which govern the manner in which the ions are coordinated and the ion/solvent packingin the solid-stateto be scrutinized in detail.

  19. Advanced Biocatalytic Processing of Heterogeneous Lignocellulosic Feedstocks to a Platform Chemical Intermediate (Lactic acid Ester)

    SciTech Connect (OSTI)

    Dr. Sharon Shoemaker

    2004-09-03

    The development of commercial boi-based processes and products derived from agricultural waste biomass has the potential for significant impact on the economy and security of our nation. Adding value, rather than disposing of the waste of agriculture, can solve an environmental problem and reduce our dependence on foreign sources of fossil fuel for production of chemicals, materials and fuels.

  20. 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.

  1. 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.

  2. Novel syngas-based process for methyl methacrylate

    SciTech Connect (OSTI)

    Gogate, M.R.; Spivey, J.J.; Zoeller, J.R.; Choi, G.N.; Tam, S.S.; Tischer, R.E.; Srivastava, R.D.

    1996-12-31

    Research Triangle Institute (RTI), Eastman Chemical Company, and Bechtel are developing a novel process for synthesis of methyl methacrylate (MMA) from coal-derived syngas, under a contract from the U.S. Department of Energy, Pittsburgh Energy Technology Center. This three-step process consists of synthesis of a propionate, its condensation with formaldehyde, and esterification of resulting methacrylic acid (MAA) with methanol to produce MMA. Eastman has focused on the research on propionate synthesis step. The resultant Mo catalysts work efficiently at much less severe conditions (170{degrees}C and 30 atm) than the conventional Ni catalysts (270{degrees}C and 180 atm). Bechtel has performed an extensive cost analysis, which shows that Eastman`s propionate synthesis process is competitive with other technologies to produce the anhydride. In the second step, RTI and Eastman have developed active and stable V-SI-P and Ta metal oxide catalysts for condensation reactions of propionates with formaldehyde. RTI has demonstrated a novel correlation among the catalyst acid-base properties, condensation reaction yield, and long-term catalyst activity. Current research focuses on enhancing the condensation reaction yields, acid-base properties, in situ condensation in a high- temperature, high-pressure (HTHP) slurry reactor, and alternate formaldehyde feedstocks. Based on Eastman and RTI laboratory reactor operating data, a cost estimate is also being developed for the integrated process.

  3. Structural Interactions within Lithium Salt Solvates: Acyclic Carbonates and Esters

    SciTech Connect (OSTI)

    Afroz, Taliman; Seo, D. M.; Han, Sang D.; Boyle, Paul D.; Henderson, Wesley A.

    2015-03-06

    Solvate crystal structures serve as useful models for the molecular-level interactions within the diverse solvates present in liquid electrolytes. Although acyclic carbonate solvents are widely used for Li-ion battery electrolytes, only three solvate crystal structures with lithium salts are known for these and related solvents. The present work, therefore, reports six lithium salt solvate structures with dimethyl and diethyl carbonate: (DMC)2:LiPF6, (DMC)1:LiCF3SO3, (DMC)1/4:LiBF4, (DEC)2:LiClO4, (DEC)1:LiClO4 and (DEC)1:LiCF3SO3 and four with the structurally related methyl and ethyl acetate: (MA)2:LiClO4, (MA)1:LiBF4, (EA)1:LiClO4 and (EA)1:LiBF4.

  4. Novel catalysts for the environmentally friendly synthesis of methyl methacrylate

    SciTech Connect (OSTI)

    Spivey, J.J.; Gogate, M.R.; Zoeller, J.R.; Colberg, R.D.

    1997-11-01

    The development of a process for the synthesis of methyl methacrylate (MMA) from coal-derived syngas can alleviate the environmental hazards associated with the current commercial MMA technology, the acetone cyanohydrin (ACH) process. A three-step syngas-based process consisted of synthesis of a propionic acid, its condensation with formaldehyde, and esterification of resulting methacrylic acid (MAA) to form MMA. The first two steps, propionic acid synthesis and condensation, are discussed here. The low-temperature, low-pressure process for single-step hydrocarbonylation of ethylene to propionic acid is carried out using a homogeneous iodine-promoted Mo(CO){sub 6} catalyst at pressures (30--70 atm) and temperatures (150--200 C) lower than those reported for other catalysts. Mechanistic investigations suggest that catalysis is initiated by a rate-limiting CO dissociation from Mo(CO){sub 6}. This dissociation appears to be followed by an inner electron-transfer process of an I atom from EtI to the coordinately unsaturated Mo(CO){sub 5}. This homogeneous catalyst for propionate synthesis represents the first case of an efficient carbonylation process based on Cr group metals. The condensation of formaldehyde with propionic acid is carried out by acid-base bifunctional catalysts. As a result of screening over 80 catalytic materials, group V metals supported on an amorphous silica are found to be most effective. A 20% Nb/SiO{sub 2} catalyst appears to be the most active and stable catalyst thus far. Preliminary relations among the reaction yield and catalyst properties indicate that a high surface area and a low overall surface acidity (<50 = mol of NH{sub 3}/g), with a high proportion of the acidity being weak (<350 C desorption of NH{sub 3}), are desirable. Long-term deactivation of V-Si-P, Nb-Si, and Ta-Si catalysts suggests that carbon deposition is the primary cause for activity decay, and the catalyst activity is partially restorable by oxidative regeneration.

  5. Low temperature synthesis of methyl formate

    DOE Patents [OSTI]

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

    1986-01-01

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

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

    Office of Scientific and Technical Information (OSTI)

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

  7. Lubricant return comparison of naphthenic and polyol ester oils in R-134a household refrigeration applications

    SciTech Connect (OSTI)

    Reyes-Gavilan, J.L.; Flak, G.T.; Tritcak, T.R.

    1996-12-31

    This paper presents mineral oils and polyol esters as possible lubricant options for domestic refrigeration applications employing R-134a as the heat exchange fluid. A performance comparison, based on data presented, is made between the mineral oils and polyol esters evaluated. To more closely examine lubricant return with N-70 and R-134a and ensure that the oil is not contributing to any deterioration in efficiency due to its accumulation in evaporators, a special test unit was designed with a difficult oil return configuration and its performance carefully monitored. Oil return with a hydrofluorocarbon-miscible polyol ester, R-133-O was also evaluated in this setup and its performance results compared to those obtained with the naphthenic refrigeration oil.

  8. Chronic toxicity of 14 phthalate esters to Daphnia magna and rainbow trout (Oncorhynchus mykiss)

    SciTech Connect (OSTI)

    Rhodes, J.E.; Adams, W.J.; Biddinger, G.R.; Robillard, K.A.; Gorsuch, J.W.

    1995-11-01

    Chronic toxicity studies were performed with commercial phthalate esters and Daphnia magna (14 phthalates) and rainbow trout (Oncorhynchus mykiss) (six phthalates). For the lower-molecular-weight phthalate esters--dimethyl phthalate (DMP), diethyl phthalate (DEP), di-n-butyl phthalate (DBP), and butylbenzyl phthalate (BBP)--the results of the studies indicated a general trend in which toxicity for both species increased as water solubility decreased. The geometric mean maximum acceptable toxicant concentration(GM-MATC) for D. magna ranged from 0.63 to 34.8 mg/L. For the higher-molecular-weight phthalate esters--dihexyl phthalate (DHP), butyl 2-ethylhexyl phthalate (BOP), di-(n-hexyl, n-octyl, n-decyl) phthalate (610P), di-(2-ethylhexyl) phthalate (DEHP), diisooctyl phthalate (DIOP), diisononyl phthalate (DINP), di-(heptyl, nonyl, undecyl) phthalate (711P), diisodecyl phthalate (DIDP), diundecyl phthalate (DUP), and ditridecyl phthalate (DTDP)--the GM-MATC values ranged from 0.042 to 0.15 mg/L. Survival was equally sensitive and sometimes more sensitive than reproduction. The observed toxicity to daphnids with most of the higher-molecular-weight phthalate esters appeared to be due to surface entrapment or a mode of toxicity that is not due to exposure to dissolved aqueous-phase chemical. Early life-stage toxicity studies with rainbow trout indicated that survival (DMP) and growth (DBP) were affected at 24 and 0.19 mg/L, respectively. This pattern of observed toxicity with the lower-molecular-weight phthalate esters and not the higher-molecular-weight phthalate esters is consistent with previously reported acute toxicity studies for several aquatic species.

  9. Synthesis of Methyl Methacrylate From Coal-Derived Syngas

    SciTech Connect (OSTI)

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

    1998-07-27

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

  10. SYNTHESIS OF METHYL METHACRYLATE FROM COAL-DERIVED SYNGAS

    SciTech Connect (OSTI)

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

    1999-07-19

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

  11. Method for high specific bioproductivity of .alpha.,.omega.-alkanedicarboxylic acids

    DOE Patents [OSTI]

    Mobley, David Paul; Shank, Gary Keith

    2000-01-01

    This invention provides a low-cost method of producing .alpha.,.omega.-alkanedicarboxylic acids. Particular bioconversion conditions result in highly efficient conversion of fatty acid, fatty acid ester, or alkane substrates to diacids. Candida tropicalis AR40 or similar yeast strains are grown in a medium containing a carbon source and a nitrogen source at a temperature of 31.degree. C. to 38.degree. C., while additional carbon source is continuously added, until maximum cell growth is attained. Within 0-3 hours of this point, substrate is added to the culture to initiate conversion. An .alpha.,.omega.-alkanedicarboxylic acid made according to this method is also provided.

  12. In-tube heat transfer and pressure drop of R-134a and ester lubricant mixtures in a smooth tube and a micro-fin tube. Part 1: Evaporation

    SciTech Connect (OSTI)

    Eckels, S.J.; Doerr, T.M.; Pate, M.B.

    1994-12-31

    In-tube heat transfer coefficients and pressure drops during evaporation are reported for mixtures of refrigerant R-134a and a penta erythritol ester mixed-acid lubricant. The ester lubricant was tested at viscosities of 169 SUS and 369 SUS over a lubricant concentration range of 0% to 5% in both a smooth tube and a micro-fine tube. The average saturation temperature used was 1 C (33.8 F). Measurements were taken for the refrigerant-lubricant mixture over a mass flux range of 85 kg/m{sup 2}{center_dot}s (62,700 lb/ft{sup 2}{center_dot}h) to 375 kg/m{sup 2}{center_dot}s (276,640 lb/ft{sup 2}{center_dot}h) in test tubes with an outer diameter of 9.52 mm (3/8 in.). Heat transfer coefficients during evaporation increased at low concentrations of the 169-SUS ester lubricant and then dropped off at high lubricant concentrations in both the smooth tube and the micro-fin tube. The higher viscosity 369-SUS lubricant decreased the heat transfer coefficients in both tubes over the range of lubricant concentrations tested. Pressure drops during evaporation increased in both the smooth tube and the micro-fin tube with the addition of ester lubricant of either viscosity. The heat transfer coefficients for the micro-fin tube were 100% to 50% higher than those for the smooth tube, with the higher values occurring at low mass fluxes. Pressure drops in the micro-fin tube were 10% to 20% higher than those in the smooth tube.

  13. SYNTHESIS OF METHYL METHACRYLATE FROM COAL-DERIVED SYNGAS

    SciTech Connect (OSTI)

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

    1998-10-20

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

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

    Office of Scientific and Technical Information (OSTI)

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

  16. Organic Carbon Transformation and Mercury Methylation in Tundra Soils from Barrow Alaska

    DOE Data Explorer [Office of Scientific and Technical Information (OSTI)]

    Liang, L.; Wullschleger, Stan; Graham, David; Gu, B.; Yang, Ziming

    2016-04-20

    This dataset includes information on soil labile organic carbon transformation and mercury methylation for tundra soils from Barrow, Alaska. The soil cores were collected from high-centered polygon (trough) at BEO and were incubated under anaerobic laboratory conditions at both freezing and warming temperatures for up to 8 months. Soil organic carbon including reducing sugars, alcohols, and organic acids were analyzed, and CH4 and CO2 emissions were quantified. Net production of methylmercury and Fe(II)/Fe(total) ratio were also measured and provided in this dataset.

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

    SciTech Connect (OSTI)

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

    2014-09-14

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

  18. SYNTHESIS OF METHYL METHACRYLATE FROM COAL-DERIVED SYNGAS

    SciTech Connect (OSTI)

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

    1999-01-20

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

  19. Evaluation of bisphenol E cyanate ester for the resin-injection repair of advanced composites

    SciTech Connect (OSTI)

    Wilber Yaote Lio

    2009-12-19

    This thesis is a compilation of a general introduction and literature review that ties together the subsequent chapters which consist of two journal articles that have yet to be submitted for publication. The overall topic relates to the evaluation and application of a new class of cyanate ester resin with unique properties that lend it applicable to use as a resin for injection repair of high glass transition temperature polymer matrix composites. The first article (Chapter 2) details the evaluation and optimization of adhesive properties of this cyanate ester and alumina nanocomposites under different conditions. The second article (Chapter 3) describes the development and evaluation of an injection repair system for repairing delaminations in polymer matrix composites.

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

    DOE Patents [OSTI]

    Chou, Howard H.; Keasling, Jay D.

    2011-07-26

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

  1. Role of acid catalysis in dimethyl ether conversion processes

    SciTech Connect (OSTI)

    Tartamella, T.L.; Lee, S.

    1996-12-31

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

  2. Amino acid modified Ni catalyst exhibits reversible H2 oxidation/production over a broad pH range at elevated temperatures

    SciTech Connect (OSTI)

    Dutta, Arnab; DuBois, Daniel L.; Roberts, John A.; Shaw, Wendy J.

    2014-11-18

    Hydrogenases interconvert H2 and protons at high rates and with high energy efficiencies, providing inspiration for the development of molecular catalysts. Studies designed to determine how the protein scaffold can influence a catalytically active site has led to the synthesis of amino acid derivatives, [Ni(PCy2NAmino acid2)2]2+ (CyAA), of [Ni(PR2NR'2)2]2+ complexes. It is shown that these CyAA derivatives can catalyze fully reversible H2 production/oxidation, a feature reminiscent of enzymes. The reversibility is achieved in acidic aqueous solutions, 0.25% H2/Ar, and elevated temperatures (tested up to 348 K) for the glycine (CyGly), arginine (CyArg), and arginine methyl ester (CyArgOMe) derivatives. As expected for a reversible process, the activity is dependent upon H2 and proton concentration. CyArg is significantly faster in both directions than the other two derivatives (~300 s-1 H2 production and 20 s-1 H2 oxidation; pH=1, 348 K). The significantly slower rates for CyArgOMe (35 s-1 production and 7 s-1 oxidation) compared to CyArg suggests an important role for the COOH group during catalysis. That CyArg is faster than CyGly (3 s-1 production and 4 s-1 oxidation under the same conditions) suggests that the additional structural features imparted by the guanidinium groups facilitate fast and reversible H2 addition/release. These observations demonstrate that appended, outer coordination sphere amino acids work in synergy with the active site and can play an equally important role for synthetic molecular electrocatalysts as the protein scaffold does for redox active enzymes. This work was funded by the Office of Science Early Career Research Program through the US DOE, BES (AD, WJS), and the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the US DOE, BES (DLD, JASR). PNNL is operated by Battelle for the US DOE.

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

    SciTech Connect (OSTI)

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

    2012-01-01

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

  4. 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.

  5. Gamma-radiolytic stability of new methylated TODGA derivatives for minor actinide recycling

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

    Galan, Hitos; Zarzana, Christopher A.; Wilden, Andreas; Nunez, Ana; Schmidt, Holger; Egberink, Richard J. M.; Leoncini, Andrea; Cobos, Joaquin; Verboom, Willem; Modolo, Giuseppe; et al

    2015-09-15

    The stability against gamma radiation of MeTODGA (methyl tetraoctyldiglycolamide) and Me2TODGA (dimethyl tetraoctyldiglycolamide), derivatives from the well-known extractant TODGA (N,N,N',N';-tetraoctyldiglycolamide), were studied and compared. Solutions of MeTODGA and Me2TODGA in alkane diluents were subjected to 60Co γ-irradiation in the presence and absence of nitric acid and analyzed using LC-MS to determine their rates of radiolytic concentration decrease, as well as to identify radiolysis products. The results of product identification from three different laboratories are compared and found to be in good agreement. The diglycolamide (DGA) concentrations decreased exponentially with increasing absorbed dose. The MeTODGA degradation rate constants (dose constants) weremore » uninfluenced by the presence of nitric acid, but the acid increased the rate of degradation for Me2TODGA. The degradation products formed by irradiation are also initially produced in greater amounts in acid-contacted solution, but products may also be degraded by continued radiolysis. As a result, the identified radiolysis products suggest that the weakest bonds are those in the diglycolamide center of these molecules.« less

  6. 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.

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

    SciTech Connect (OSTI)

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

    2013-11-28

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

  8. 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.'

  9. 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.

  10. On the Dissociation of Methyl Orange: Spectrophotometric Investigation in Aqueous Solutions from 10 to 90ºC and Theoretical Evidence for Intramolecular Dihydrogen Bonding

    SciTech Connect (OSTI)

    Boily, Jean F.; Seward, Terry M.

    2005-12-01

    The dissociation of methyl orange was investigated by spectrophotometry in aqueous solutions from 10 to 90°C and by quantum chemical calculations. Combined chemometric and thermodynamic analyses of the spectrophotometric data were used to simultaneously extract the thermodynamic stabilities and the spectrophotometric attributes of the dominant methyl orange species in solutions containing less than 20.00 mmol kg-1 perchloric acid and submicromolal concentrations of methyl orange. The analyses revealed the presence of only one monomeric deprotonated and one monomeric protonated species. The spectra did not reveal any evidence for the presence of tautomeric equilibria between the protonated azo and ammonium species in the experimental range studied. Thermodynamic analyses of the temperature dependent dissociation constants showed the reactions to be endothermic and enthalpy driven reaction with increasing acidity and increasing temperature. All molar absorption coefficients in the 275-375 nm range can be adequately reproduced in the 10-90°C range with a set of Gauss-Lorentz parameters and used to predict the absorption spectra for any desired condition. The dominant features of the spectrophotometric attributes of the methyl orange species could also be retrieved in Time Dependent-Density Functional Theory (TD-DFT) calculations. Topological analyses of the electron density also revealed the formation of a dihydrogen bond between the azo proton and an adjacent phenyl ring hydridic hydrogen which increases the stability of the azo molecules relative to the ammonium molecule.

  11. Hydroxycarboxylic acids and salts

    SciTech Connect (OSTI)

    Kiely, Donald E; Hash, Kirk R; Kramer-Presta, Kylie; Smith, Tyler N

    2015-02-24

    Compositions which inhibit corrosion and alter the physical properties of concrete (admixtures) are prepared from salt mixtures of hydroxycarboxylic acids, carboxylic acids, and nitric acid. The salt mixtures are prepared by neutralizing acid product mixtures from the oxidation of polyols using nitric acid and oxygen as the oxidizing agents. Nitric acid is removed from the hydroxycarboxylic acids by evaporation and diffusion dialysis.

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

    DOE Patents [OSTI]

    Belinsky, Steven A.; Palmisano, William A.

    2007-05-08

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

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

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

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

  14. Catalysis by heteropoly compounds. XXII. Reactions of esters and esterification catalyzed by heteropolyacids in a homogeneous liquid phase - effects of the central atom of heteropolyanions having tungsten as the addenda atom

    SciTech Connect (OSTI)

    Hu, Changwen; Hashimoto, Masato; Okuhara, Toshio; Misono, Makoto )

    1993-10-01

    Decomposition of isobutyl propionate (IBP) (Reaction (1)), ester exchange of IBP with acetic acid (Reaction (2)), ester exchange of IBP with n-propyl alcohol (Reaction (3)), and esterification of propionic acid with isobutyl alcohol (Reaction (4)) have been studied in a homogeneous liquid phase using heteropolyacids H[sub m]XW[sub 12]O[sub 40] (X = P, Si, Ge, B, and Co) having the Keggin structure and H[sub 6]P[sub 2]W[sub 18]O[sub 62] having the Dawson structure. The results clearly indicated that the catalytic behavior of heteropolyacids remarkably depended on the kind of reaction system, namely, the basicity of reactants. For Reaction (1), the catalytic activities of the heteropolyacids were 60-100 times higher than those of H[sub 2]SO[sub 4] and p-toluenesulfonic acid. Among the heteropolyacids, the activity was in the order H[sub 3]PW[sub 12]O[sub 40] > H[sub 4]SiW[sub 12]O[sub 40] [approximately] H[sub 4]GeW[sub 12]O[sub 40] > H[sub 5]BW[sub 12]O[sub 40] > H[sub 6]CoW[sub 12]O[sub 40]. This order suggests that the activity follows the order of the acid strength of the solutions of heteropolyacids, which increases with the decrease in the negative charge of the polyanion. H[sub 6]P[sub 2]W[sub 18]O[sub 62] showed an activity between those of H[sub 5]BW[sub 12]O[sub 40] and H[sub 6]CoW[sub 12]O[sub 40]. Water molecules in the system retarded Reaction 1. For Reaction 2, the activity order was similar to that for Reaction 1 in the absence of water. However, contrary to Reaction 1, the addition of water greatly accelerated Reaction 2. It was presumed that, in the presence of water, Reaction 2 proceeds via the hydrolysis of IBP to propionic acid and isobutyl alcohol, followed by the esterification of isobutyl alcohol with acetic acid. 28 refs., 8 figs., 4 tabs.

  15. Heat transfer coefficients and pressure drops for R-134a and an ester lubricant mixture in a smooth tube and a micro-fin tube

    SciTech Connect (OSTI)

    Eckels, S.J.; Doerr, T.M.; Pate, M.B.

    1998-10-01

    This paper reports average heat transfer coefficients and pressure drops during the evaporation and condensation of mixtures of R-134a and a 150 SUS penta erythritol ester branched-acid lubricant. The smooth tube and micro-fin tube tested in this study had outer diameters of 9.52 mm (3/8 in.). The micro-fin tube had 60 fins, a fin height of 0.2 mm (0.008 in), and a spiral angle of 18{degree}. The objective of this study is to evaluate the effectiveness of the micro-fin tube with R-134a and to determine the effect of circulating lubricant. The experimental results show that the micro-fin tube has distinct performance advantages over the smooth tube. For example, the average heat transfer coefficients during evaporation and condensation in the micro-fin tube were 50--200% higher than those for the smooth tube, while the average pressure drops were on average only 10--50% higher. The experimental results indicate that the presence of a lubricant degrades the average heat transfer coefficients during both evaporation and condensation at high lubricant concentrations. Pressure drops during evaporation increased with the addition of a lubricant in both tubes. For condensation, pressure drops were unaffected by the addition of a lubricant.

  16. 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.

  17. 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.

  18. 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.

  19. Injection repair of carbon fiber/bismaleimide composite panels with bisphenol E cyanate ester resin

    SciTech Connect (OSTI)

    Thunga, Mahendra; Bauer, Amy; Obusek, Kristine; Meilunas, Ray; Akinc, Mufit; Kessler, Michael R

    2014-08-01

    Resin injection of bisphenol E cyanate ester, a low viscosity resin that cures into a high temperature thermoset polymer, is investigated as a reliable repair method to restore strength and stiffness in delaminated carbon fiber/bismaleimide composites used in aircraft panels. The influence of temperature on the viscosity of the uncured resin was measured to optimize the injection conditions for high resin infiltration into the delaminations. The repair efficiency of the resin was evaluated by varying the panel thickness and the method by which the delamination damage was created in the composite specimens. Ultrasonic scanning (C-scan), flash thermography images, and cross-section analysis of repaired panels revealed excellent resin infiltration into the damaged region. Evaluation of mechanical repair efficiency using both bending stiffness and in-plain compressive strength of the composite panels as the repair metrics showed values exceeding 100%.

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

    SciTech Connect (OSTI)

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

    2015-04-15

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

  1. Phase 1 Methyl Iodide Deep-Bed Adsorption Tests

    SciTech Connect (OSTI)

    Nick Soelberg; Tony Watson

    2014-08-01

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

  2. Low contaminant formic acid fuel for direct liquid fuel cell

    DOE Patents [OSTI]

    Masel, Richard I.; Zhu, Yimin; Kahn, Zakia; Man, Malcolm

    2009-11-17

    A low contaminant formic acid fuel is especially suited toward use in a direct organic liquid fuel cell. A fuel of the invention provides high power output that is maintained for a substantial time and the fuel is substantially non-flammable. Specific contaminants and contaminant levels have been identified as being deleterious to the performance of a formic acid fuel in a fuel cell, and embodiments of the invention provide low contaminant fuels that have improved performance compared to known commercial bulk grade and commercial purified grade formic acid fuels. Preferred embodiment fuels (and fuel cells containing such fuels) including low levels of a combination of key contaminants, including acetic acid, methyl formate, and methanol.

  3. 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.

  4. Tropospheric oxidation mechanism of dimethyl ether and methyl formate

    SciTech Connect (OSTI)

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

    2000-02-17

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

  5. Process for the synthesis of unsaturated alcohols

    DOE Patents [OSTI]

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

    2007-02-13

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

  6. PERFORMANCE ENHANCEMENT OF COMPRESSION MOLDED KENAF FIBER REINFORCED VINYL ESTER COMPOSITES THROUGH RESIN ADDITIVE

    SciTech Connect (OSTI)

    Fifield, Leonard S.; Simmons, Kevin L.; Laddha, Sachin; Kafentzis, Tyler A.

    2010-05-17

    Plant-based bio-fiber has the potential to achieve weight and cost savings over glass fiber in automotive polymer composites if moisture stability and fiber-resin compatibility issues can be solved. This paper describes the compression molding of 50vol% 2 inch random nonwoven mat kenaf fiber vinyl ester composites with and without chemical resin additives intended to improve moisture stability and resin compatibility. The 2wt% addition of n-undecanoyl chloride or 10-undecenoyl chloride to the styrene-based resin prior to molding of the kenaf composites was observed to decrease the 24hr, 25oC moisture uptake of the molded panels by more than 50%. The tensile stiffness and flexural stiffness of the soaked panels containing these additives were seen to increase by more than 30% and 70%, respectively, relative to panels made with no additives. While dry panel (50% relative humidity at 25oC) strengths did not significantly change in the presence of the additives, tensile strength was observed to increase by more than 40% and flexural strength more than doubled for the soaked panels.

  7. Landfarming of phthalate ester-contaminated soil: Two years of bioremediation results

    SciTech Connect (OSTI)

    Kunze, C.M.; Yu, J.; Wilson, S.; Rezin, J.L.; Andronico, A.

    1995-12-31

    Biorem Technologies Inc. collaborated with Regal Plastics Corporation over 2 years to clean up approximately 600 cubic yards of soil contaminated with di-2-ethylhexyl phthalate ester (DEHP) and No. 2 fuel oil using a landfarming bioremediation process. The contaminated soils consisted of sandy backfill material which had been excavated during the removal of two underground storage tanks (USTs). In 1994, the initial average DEHP concentration was 4,551 ppm while the TPH concentration was 7,252 ppm. In 1995, the initial DEHP concentration was 1067 ppm while TPH was 3,733 ppm. Prior to the implementation of the project, Biorem Technologies completed a laboratory biofeasibility study to demonstrate that a bacterial culture isolated from the site had the capacity to efficiently degrade DEBP in the soil. It was determined during this study that nitrogen and phosphorus nutrient amendments were needed to promote the bioremediation process. In 1994, the soils were loaded on to a lined treatment bed to a depth of 14--16 in. The bed was covered with a greenhouse structure to eliminate stormwater runoff concerns associated with the contaminated soil. To optimize biodegradation, soil moisture and nutrient levels were adjusted. In 1995, a windrow turner replaced the 1994 tilling system. Tarps were used to cover the piles in place of the greenhouse. A leachate collection system was implemented to contain stormwater and leachate.

  8. 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.

  9. "Seeing" Mercury Methylation in Progress

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

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

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

    SciTech Connect (OSTI)

    Soelberg, Nicholas Ray; Watson, Tony Leroy

    2015-09-30

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

  11. Acid distribution in phosphoric acid fuel cells

    SciTech Connect (OSTI)

    Okae, I.; Seya, A.; Umemoto, M.

    1996-12-31

    Electrolyte acid distribution among each component of a cell is determined by capillary force when the cell is not in operation, but the distribution under the current load conditions had not been clear so far. Since the loss of electrolyte acid during operation is inevitable, it is necessary to store enough amount of acid in every cell. But it must be under the level of which the acid disturbs the diffusion of reactive gases. Accordingly to know the actual acid distribution during operation in a cell is very important. In this report, we carried out experiments to clarify the distribution using small single cells.

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

    SciTech Connect (OSTI)

    Singerman, G.M.

    1980-11-01

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

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

    SciTech Connect (OSTI)

    Pauls, R. E.

    2011-05-01

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

  14. Two Dimensional Polyamides Prepared From Unsaturated Carboxylic Acids And Amines.

    DOE Patents [OSTI]

    McDonald, William F.; Huang, Zhi Heng; Wright, Stacy C.; Danzig, Morris; Taylor, Andrew C.

    2002-07-17

    A polyamide and a process for preparing the polyamide are disclosed. The process comprises reacting in a reaction mixture a monomer selected from unsaturated carboxylic acids, esters of unsaturated carboxylic acids, anhydrides of unsaturated carboxylic acids, and mixtures thereof, and a first amine to form an intermediate reaction product in the reaction mixture, wherein the first amine is selected from RR.sub.1 NH, RNH.sub.2, RR.sub.1 NH.sub.2.sup.+, RNH.sub.3.sup.+ and mixtures thereof, wherein R and R.sub.1 can be the same or different and each contain between about 1 and 50 carbon atoms and are optionally substituted with heteroatoms oxygen, nitrogen, sulfur, and phosphorus and combinations thereof, and reacting the intermediate reaction product and a second amine to form a polyamide, wherein the second amine is selected from R.sub.2 R.sub.3 NH, R.sub.2 NH.sub.2, R.sub.2 R.sub.3 NH.sub.2.sup.+, R.sub.2 NH.sub.3.sup.+ and mixtures thereof wherein R.sub.2 and R.sub.3 can be the same or different and each contain between about 1 and 50 carbon atoms and are optionally substituted with heteroatoms oxygen, nitrogen, sulfur, and phosphorus and combinations thereof, wherein multiple of the R, R.sub.1, R.sub.2, and R.sub.3 are in vertically aligned spaced relationship along a backbone formed by the polyamide. In one version of the invention, the monomer is selected from maleic anhydride, maleic acid esters, and mixtures thereof. In another version of the invention, the first amine is an alkylamine, such as tetradecylamine, and the second amine is a polyalkylene polyamine, such as pentaethylenehexamine. In yet another version of the invention, the first amine and the second amine are olefinic or acetylenic amines, such as the reaction products of an alkyldiamine and an acetylenic carboxylic acid. The first amine and the second amine may be the same or different depending on the desired polyamide polymer structure.

  15. 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.

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

    Office of Scientific and Technical Information (OSTI)

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

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

    SciTech Connect (OSTI)

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

    2013-08-30

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

  18. A study of perfluorocarboxylate ester solvents for lithium ion battery electrolytes

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

    Fears, Tyler M; Sacci, Robert L; Winiarz, Jeffrey; Kaiser, Helmut; Taub, H.; Veith, Gabriel M

    2015-01-01

    Several high-purity methyl perfluorocarboxylates were prepared (>99.5% purity by mole) and investigated as potential fluorine-rich electrolyte solvents in Li-ion batteries. The most conductive electrolyte, 0.1 M lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) in dimethyl perfluoroglutarate (PF5M2) (ionic conductivity 1.87 102 mS cm1), is investigated in Si thin-film half-cells. The solid-electrolyteinterphase (SEI) formed by the PF5M2 electrolyte is composed of similar organic and inorganic moieties and at comparable concentrations as those formed by ethylene carbonate/dimethyl carbonate electrolytes containing LiPF6 and LiTFSI salts. However, the SEI formed by the PF5M2 electrolyte undergoes reversible electrochemical defluorination, contributing to the reversible capacity of the cell and compensatingmore » in part for capacity fade in the Si electrode. While far from ideal these electrolytes provide an opportunity to further develop predictions of suitable fluorinated molecules for use in battery solvents.« less

  19. Fatty acid analogs

    DOE Patents [OSTI]

    Elmaleh, David R.; Livni, Eli

    1985-01-01

    In one aspect, a radioactively labeled analog of a fatty acid which is capable of being taken up by mammalian tissue and which exhibits an in vivo beta-oxidation rate below that with a corresponding radioactively labeled fatty acid.

  20. Mixed Acid Oxidation

    SciTech Connect (OSTI)

    Pierce, R.A.

    1999-10-26

    Several non-thermal processes have been developed to destroy organic waste compounds using chemicals with high oxidation potentials. These efforts have focused on developing technologies that work at low temperatures, relative to incineration, to overcome many of the regulatory issues associated with obtaining permits for waste incinerators. One such technique with great flexibility is mixed acid oxidation. Mixed acid oxidation, developed at the Savannah River Site, uses a mixture of an oxidant (nitric acid) and a carrier acid (phosphoric acid). The carrier acid acts as a non-volatile holding medium for the somewhat volatile oxidant. The combination of acids allows appreciable amounts of the concentrated oxidant to remain in the carrier acid well above the oxidant''s normal boiling point.

  1. PRODUCTION OF TRIFLUOROACETIC ACID

    DOE Patents [OSTI]

    Haworth, W.N.; Stacey, M.

    1949-07-19

    A method is given for the production of improved yields of trifluoroacetic acid. The compound is prepared by oxidizing m-aminobenzotrifluoride with an alkali metal or alkaline earth metal permanganate at a temperature in the range of 80 deg C to 100 deg C while dissolved ln a mixture of water with glacial acetic acid and/or trifluoroacetic acid. Preferably a mixture of water and trifluoroacetic acid ls used as the solvent.

  2. Plant fatty acid hydroxylases

    DOE Patents [OSTI]

    Somerville, Chris; Broun, Pierre; van de Loo, Frank

    2001-01-01

    This invention relates to plant fatty acyl hydroxylases. Methods to use conserved amino acid or nucleotide sequences to obtain plant fatty acyl hydroxylases are described. Also described is the use of cDNA clones encoding a plant hydroxylase to produce a family of hydroxylated fatty acids in transgenic plants. In addition, the use of genes encoding fatty acid hydroxylases or desaturases to alter the level of lipid fatty acid unsaturation in transgenic plants is described.

  3. Multifunctional Properties of Cyanate Ester Composites with SiO2 Coated Fe3O4 Fillers

    SciTech Connect (OSTI)

    Sun, Weixing; Sun, Wuzhu; Kessler, Michael R.; Bowler, Nicola; Dennis, Kevin W.; McCallum, R. William; Li, Qi; Tan, Xiaoli

    2013-02-22

    SiO2 coated Fe3O4 submicrometer spherical particles (a conducting core/insulating shell configuration) are fabricated using a hydrothermal method and are loaded at 10 and 20 vol % into a bisphenol E cyanate ester matrix for synthesis of multifunctional composites. The dielectric constant of the resulting composites is found to be enhanced over a wide frequency and temperature range while the low dielectric loss tangent of the neat cyanate ester polymer is largely preserved up to 160 ?C due to the insulating SiO2 coating on individual conductive Fe3O4 submicrometer spheres. These composites also demonstrate high dielectric breakdown strengths at room temperature. Dynamic mechanical analysis indicates that the storage modulus of the composite with a 20 vol % filler loading is twice as high as that of neat resin, but the glass transition temperature considerably decreases with increasing filler content. Magnetic measurements reveal a large saturation magnetization and negligibly low coercivity and remanent magnetization in these composites.

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

    SciTech Connect (OSTI)

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

    2015-01-14

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

  5. Cleavage of nucleic acids

    DOE Patents [OSTI]

    Prudent, James R.; Hall, Jeff G.; Lyamichev, Victor I.; Brow, Mary Ann D.; Dahlberg, James E.

    2000-01-01

    The present invention relates to means for the detection and characterization of nucleic acid sequences, as well as variations in nucleic acid sequences. The present invention also relates to methods for forming a nucleic acid cleavage structure on a target sequence and cleaving the nucleic acid cleavage structure in a site-specific manner. The structure-specific nuclease activity of a variety of enzymes is used to cleave the target-dependent cleavage structure, thereby indicating the presence of specific nucleic acid sequences or specific variations thereof.

  6. Cleavage of nucleic acids

    DOE Patents [OSTI]

    Prudent, James R.; Hall, Jeff G.; Lyamichev, Victor L.; Brow, Mary Ann D.; Dahlberg, James E.

    2007-12-11

    The present invention relates to means for the detection and characterization of nucleic acid sequences, as well as variations in nucleic acid sequences. The present invention also relates to methods for forming a nucleic acid cleavage structure on a target sequence and cleaving the nucleic acid cleavage structure in a site-specific manner. The structure-specific nuclease activity of a variety of enzymes is used to cleave the target-dependent cleavage structure, thereby indicating the presence of specific nucleic acid sequences or specific variations thereof.

  7. Nucleic acid detection assays

    DOE Patents [OSTI]

    Prudent, James R.; Hall, Jeff G.; Lyamichev, Victor I.; Brow, Mary Ann; Dahlberg, James E.

    2005-04-05

    The present invention relates to means for the detection and characterization of nucleic acid sequences, as well as variations in nucleic acid sequences. The present invention also relates to methods for forming a nucleic acid cleavage structure on a target sequence and cleaving the nucleic acid cleavage structure in a site-specific manner. The structure-specific nuclease activity of a variety of enzymes is used to cleave the target-dependent cleavage structure, thereby indicating the presence of specific nucleic acid sequences or specific variations thereof.

  8. Nucleic acid detection compositions

    DOE Patents [OSTI]

    Prudent, James R.; Hall, Jeff G.; Lyamichev, Victor I.; Brow, Mary Ann; Dahlberg, James L.

    2008-08-05

    The present invention relates to means for the detection and characterization of nucleic acid sequences, as well as variations in nucleic acid sequences. The present invention also relates to methods for forming a nucleic acid cleavage structure on a target sequence and cleaving the nucleic acid cleavage structure in a site-specific manner. The structure-specific nuclease activity of a variety of enzymes is used to cleave the target-dependent cleavage structure, thereby indicating the presence of specific nucleic acid sequences or specific variations thereof.

  9. Cleavage of nucleic acids

    DOE Patents [OSTI]

    Prudent, James R.; Hall, Jeff G.; Lyamichev, Victor I.; Brow; Mary Ann D.; Dahlberg, James E.

    2010-11-09

    The present invention relates to means for the detection and characterization of nucleic acid sequences, as well as variations in nucleic acid sequences. The present invention also relates to methods for forming a nucleic acid cleavage structure on a target sequence and cleaving the nucleic acid cleavage structure in a site-specific manner. The structure-specific nuclease activity of a variety of enzymes is used to cleave the target-dependent cleavage structure, thereby indicating the presence of specific nucleic acid sequences or specific variations thereof.

  10. Determination of organic acids (C/sub 1/-C/sub 10/) in the atmosphere, motor exhaust, and engine oils

    SciTech Connect (OSTI)

    Kawamura, K.; Ng, L.L.; Kaplan, I.R.

    1985-11-01

    A method is described for the determination of volatile organic acids in the atmosphere, motor exhausts, and engine oils. Atmospheric organic acids were collected on a KOH impregnated quartz filter and derivatized to p-bromophenacyl esters. The derivatives were analyzed by high-resolution capillary gas chromatography and gas chromatography-mass spectrometry. C/sub 1/-C/sub 10/ aliphatic organic acids and benzoic acid were detected in Los Angeles air. Acetic and formic acids are dominant followed by propionic acids. Total concentrations measured were 0.37-7.45 ppb. Organic acids (C/sub 1/-C/sub 10/) were also detected in the motor exhaust from a single automobile at idle conditions and showed that the distribution of individual acids was similar to that in the air, but the concentration was 17 times higher than for the average atmospheric content. Formic, acetic, and benzoic acids were detected as major species of used engine oil, but their content is negligible in new oil.

  11. Nucleic acid detection kits

    DOE Patents [OSTI]

    Hall, Jeff G.; Lyamichev, Victor I.; Mast, Andrea L.; Brow, Mary Ann; Kwiatkowski, Robert W.; Vavra, Stephanie H.

    2005-03-29

    The present invention relates to means for the detection and characterization of nucleic acid sequences, as well as variations in nucleic acid sequences. The present invention also relates to methods for forming a nucleic acid cleavage structure on a target sequence and cleaving the nucleic acid cleavage structure in a site-specific manner. The structure-specific nuclease activity of a variety of enzymes is used to cleave the target-dependent cleavage structure, thereby indicating the presence of specific nucleic acid sequences or specific variations thereof. The present invention further relates to methods and devices for the separation of nucleic acid molecules based on charge. The present invention also provides methods for the detection of non-target cleavage products via the formation of a complete and activated protein binding region. The invention further provides sensitive and specific methods for the detection of nucleic acid from various viruses in a sample.

  12. 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.

  13. Process for the preparation of lactic acid and glyceric acid

    DOE Patents [OSTI]

    Jackson, James E [Haslett, MI; Miller, Dennis J [Okemos, MI; Marincean, Simona [Dewitt, MI

    2008-12-02

    Hexose and pentose monosaccharides are degraded to lactic acid and glyceric acid in an aqueous solution in the presence of an excess of a strongly anionic exchange resin, such as AMBERLITE IRN78 and AMBERLITE IRA400. The glyceric acid and lactic acid can be separated from the aqueous solution. Lactic acid and glyceric acid are staple articles of commerce.

  14. Microorganisms for producing organic acids

    SciTech Connect (OSTI)

    Pfleger, Brian Frederick; Begemann, Matthew Brett

    2014-09-30

    Organic acid-producing microorganisms and methods of using same. The organic acid-producing microorganisms comprise modifications that reduce or ablate AcsA activity or AcsA homolog activity. The modifications increase tolerance of the microorganisms to such organic acids as 3-hydroxypropionic acid, acrylic acid, propionic acid, lactic acid, and others. Further modifications to the microorganisms increase production of such organic acids as 3-hydroxypropionic acid, lactate, and others. Methods of producing such organic acids as 3-hydroxypropionic acid, lactate, and others with the modified microorganisms are provided. Methods of using acsA or homologs thereof as counter-selectable markers are also provided.

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

    SciTech Connect (OSTI)

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

    1998-09-01

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

  16. 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.; Soren, Allyson; Brown, Steven D.; Crable, Bryan R.; Palumbo, Anthony Vito; Somenahally, Anil C.; Elias, Dwayne A.

    2015-01-01

    Mercury methylation produces the neurotoxic, highly bioaccumulative methylmercury (MeHg). Recent identification of the methylation genes (hgcAB) provides the foundation for broadly evaluating microbial Hg-methylation potential in nature without making explicit rate measurements. We first queried hgcAB diversity and distribution in all available microbial metagenomes, encompassing most environments. The genes were found in nearly all anaerobic, but not in aerobic, environments including oxygenated layers of the open ocean. Critically, hgcAB was effectively absent in ~1500 human microbiomes, suggesting a low risk of endogenous MeHg production. New potential methylation habitats were identified, including invertebrate guts, thawing permafrost, coastal dead zones, soils, sediments,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 then begin to address long-standing evolutionary questions about Hg-methylation and ancient carbon fixation mechanisms while generating a new global view of Hg-methylation potential.« less

  17. 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.

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

    SciTech Connect (OSTI)

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

    2015-01-01

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

  19. Reversible Acid Gas Capture

    ScienceCinema (OSTI)

    Dave Heldebrant

    2012-12-31

    Pacific Northwest National Laboratory scientist David Heldebrant demonstrates how a new process called reversible acid gas capture works to pull carbon dioxide out of power plant emissions.

  20. Catalytic Upgrading of bio-oil using 1-octene and 1-butanol over sulfonic acid resin catalysts

    SciTech Connect (OSTI)

    Zhang, Zhijun; Wang, Qingwen; Tripathi, Prabhat; Pittman, Charles U.

    2011-02-04

    Raw bio-oil from fast pyrolysis of biomass must be refined before it can be used as a transporation fuel, a petroleum refinery feed or for many other fuel uses. Raw bio-oil was upgraded with the neat model olefin, 1-octene, and with 1-octene/1-butanol mixtures over sulfonic acid resin catalysts frin 80 to 150 degrees celisus in order to simultaneously lower water content and acidity and to increase hydrophobicity and heating value. Phase separation and coke formation were key factors limiting the reaction rate during upgrading with neat 1-octene although octanols were formed by 1-octene hydration along with small amounts of octyl acetates and ethers. GC-MS analysis confirmed that olefin hydration, carboxylic acid esterification, acetal formation from aldehydes and ketones and O- and C-alkylations of phenolic compounds occurred simultaneously during upgrading with 1-octene/1-butanol mixtures. Addition of 1-butanol increased olefin conversion dramatically be reducing mass transfer restraints and serving as a cosolvent or emulsifying agent. It also reacted with carboxylic acids and aldehydes/ketones to form esters, and acetals, respectively, while also serving to stabilize bio-oil during heating. 1-Butanol addition also protected the catalysts, increasing catalyst lifetime and reducing or eliminationg coking. Upgrading sharply increased ester content and decreased the amounts of levoglucosan, polyhydric alcohols and organic acids. Upgrading lowered acidity (pH value rise from 2.5 to >3.0), removed the uppleasant ordor and increased hydrocarbon solubility. Water content decreased from 37.2% to < 7.5% dramatically and calorific value increased from 12.6 MJ kg to about 30.0 MJ kg.

  1. Factors affecting the retention of methyl iodide by iodide-impregnated carbon

    SciTech Connect (OSTI)

    Hyder, M.L.; Malstrom, R.A.

    1990-12-31

    Iodide-impregnated activated carbon that had been in use for up to 30 months was studied to characterize those factors that affect its interaction with and retention of methyl iodide. Humidity and competing organic sorbents were observed to decrease the residence time of the methyl iodide on the carbon bed. Additionally, changes in the effective surface area and the loss of iodide from the surface are both important in determining the effectiveness of the carbon for retaining radioactive iodine from methyl iodide. A simple model incorporating both factors gave a fairly good fit to the experimental data.

  2. Factors affecting the retention of methyl iodide by iodide-impregnated carbon

    SciTech Connect (OSTI)

    Hyder, M.L.; Malstrom, R.A.

    1990-01-01

    Iodide-impregnated activated carbon that had been in use for up to 30 months was studied to characterize those factors that affect its interaction with and retention of methyl iodide. Humidity and competing organic sorbents were observed to decrease the residence time of the methyl iodide on the carbon bed. Additionally, changes in the effective surface area and the loss of iodide from the surface are both important in determining the effectiveness of the carbon for retaining radioactive iodine from methyl iodide. A simple model incorporating both factors gave a fairly good fit to the experimental data.

  3. Mutant fatty acid desaturase

    DOE Patents [OSTI]

    Shanklin, John; Cahoon, Edgar B.

    2004-02-03

    The present invention relates to a method for producing mutants of a fatty acid desaturase having a substantially increased activity towards fatty acid substrates with chains containing fewer than 18 carbons relative to an unmutagenized precursor desaturase having an 18 carbon atom chain length substrate specificity. The method involves inducing one or more mutations in the nucleic acid sequence encoding the precursor desaturase, transforming the mutated sequence into an unsaturated fatty acid auxotroph cell such as MH13 E. coli, culturing the cells in the absence of supplemental unsaturated fatty acids, thereby selecting for recipient cells which have received and which express a mutant fatty acid desaturase with an elevated specificity for fatty acid substrates having chain lengths of less than 18 carbon atoms. A variety of mutants having 16 or fewer carbon atom chain length substrate specificities are produced by this method. Mutant desaturases produced by this method can be introduced via expression vectors into prokaryotic and eukaryotic cells and can also be used in the production of transgenic plants which may be used to produce specific fatty acid products.

  4. Subcritical water extraction of lipids from wet algal biomass

    DOE Patents [OSTI]

    Deng, Shuguang; Reddy, Harvind K.; Schaub, Tanner; Holguin, Francisco Omar

    2016-05-03

    Methods of lipid extraction from biomass, in particular wet algae, through conventionally heated subcritical water, and microwave-assisted subcritical water. In one embodiment, fatty acid methyl esters from solids in a polar phase are further extracted to increase biofuel production.

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

    Office of Scientific and Technical Information (OSTI)

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

  6. 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.

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

    DOE Patents [OSTI]

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

    2014-08-12

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

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

    DOE Patents [OSTI]

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

    2014-08-05

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

  9. Analytical Methodologies for Detection of Gamma-Valerolactone, Delta-Valerolactone, Acephate and Azinphos Methyl and Their Associated Metabolites in Complex Biological Matrices

    SciTech Connect (OSTI)

    Zink, E.; Clark, R.; Grant, K.; Campbell, J.; Hoppe, E.

    2005-01-01

    Non-invasive biomonitoring for chemicals of interest in law enforcement and similar monitoring of pesticides, together with their metabolites, can not only save money but can lead to faster medical attention for individuals exposed to these chemicals. This study describes methods developed for the analysis of gamma-valerolactone (GVL), delta-valerolactone (DVL), acephate, and azinphos methyl in saliva and serum. Liquid chromatography/mass spectrometry (LC/MS) operated in the negative and positive ion mode and gas chromatography/mass spectrometry (GC/MS) were used to analyze GVL and DVL. Although both analytical techniques worked well, lower detection limits were obtained with GC/MS. The lactones and their corresponding sodium salts were spiked into both saliva and serum. The lactones were isolated from saliva or serum using newly developed extraction techniques and then subsequently analyzed using GC/MS. The sodium salts of the lactones are nonvolatile and require derivatization prior to analysis by this method. N-methyl-N-(t-butyldimethylsilyl)-trifluoroacetamide (MTBSTFA) was ultimately selected as the reagent for derivatization because the acidic conditions required for reactions with diazomethane caused the salts to undergo intramolecular cyclization to the corresponding lactones. In vitro studies were conducted using rat liver microsomes to determine other metabolites associated with these compounds. Azinphos methyl and acephate are classified as organophosphate pesticides, and are known to be cholinesterase inhibitors in humans and insects, causing neurotoxicity. For this reason they have both exposure and environmental impact implications. These compounds were spiked into serum and saliva and prepared for analysis by GC/MS. Continuation of this research would include analysis by GC/MS under positive ion mode to determine the parent ions of the unknown metabolites. Further research is planned through an in vivo analysis of the lactones and pesticides. These

  10. Method for isolating nucleic acids

    SciTech Connect (OSTI)

    Hurt, Jr., Richard Ashley; Elias, Dwayne A.

    2015-09-29

    The current disclosure provides methods and kits for isolating nucleic acid from an environmental sample. The current methods and compositions further provide methods for isolating nucleic acids by reducing adsorption of nucleic acids by charged ions and particles within an environmental sample. The methods of the current disclosure provide methods for isolating nucleic acids by releasing adsorbed nucleic acids from charged particles during the nucleic acid isolation process. The current disclosure facilitates the isolation of nucleic acids of sufficient quality and quantity to enable one of ordinary skill in the art to utilize or analyze the isolated nucleic acids for a wide variety of applications including, sequencing or species population analysis.

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

    SciTech Connect (OSTI)

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

    1994-10-01

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

  12. Membrane Stresses Induced by Overproduction of Free Fatty Acids in Escherichia coli.

    SciTech Connect (OSTI)

    Lennen, Rebecca M.; Kruziki, Max A.; Kumar, Kritika; Zinkel, Robert A.; Burnum, Kristin E.; Lipton, Mary S.; Hoover, Spencer W.; Ranatunga, Don Ruwan; Wittkopp, Tyler M.; Marner II, Wesley D.; Pfleger, Brian F.

    2011-11-01

    Microbially produced fatty acids are potential precursors to high energy density biofuels, including alkanes and alkyl ethyl esters by either catalytic conversion of free fatty acids (FFAs) or enzymatic conversions of acyl-acyl carrier protein or acyl-coenzyme A intermediates. Metabolic engineering efforts aimed at overproducing FFAs in Escherichia coli have achieved less than 30% of the maximum theoretical yield on the supplied carbon source. In this work, the viability, morphology, transcript levels, and protein levels of a strain of E. coli that overproduces medium chain length FFAs was compared to an engineered control strain. By early stationary phase, an 85% reduction in viable cell counts and exacerbated loss of inner membrane integrity were observed in the FFA overproducing strain. These effects were enhanced in strains endogenously producing FFAs compared to strains exposed to exogenously fed FFAs. Under two sets of cultivation conditions, long chain unsaturated fatty acid content greatly increased and the expression of genes and proteins required for unsaturated fatty acid biosynthesis were significantly decreased. Membrane stresses were further implicated by increased expression of genes and proteins of the phage shock response, the MarA/Rob/SoxS regulon, and the nuo and cyo operons of aerobic respiration. Gene deletion studies confirmed the importance of the phage shock proteins and Rob for maintaining cell viability, however little to no change in FFA titers was observed after 24 h cultivation. The results of this study serve as a baseline for future targeted attempts to improve FFA yields and titers in E. coli.

  13. Optical high acidity sensor

    DOE Patents [OSTI]

    Jorgensen, B.S.; Nekimken, H.L.; Carey, W.P.; O`Rourke, P.E.

    1997-07-22

    An apparatus and method for determining acid concentrations in solutions having acid concentrations of from about 0.1 Molar to about 16 Molar is disclosed. The apparatus includes a chamber for interrogation of the sample solution, a fiber optic light source for passing light transversely through the chamber, a fiber optic collector for receiving the collimated light after transmission through the chamber, a coating of an acid resistant polymeric composition upon at least one fiber end or lens, the polymeric composition in contact with the sample solution within the chamber and having a detectable response to acid concentrations within the range of from about 0.1 Molar to about 16 Molar, a measurer for the response of the polymeric composition in contact with the sample solution, and a comparer of the measured response to predetermined standards whereby the acid molarity of the sample solution within the chamber can be determined. Preferably, a first lens is attached to the end of the fiber optic light source, the first lens adapted to collimate light from the fiber optic light source, and a second lens is attached to the end of the fiber optic collector for focusing the collimated light after transmission through the chamber. 10 figs.

  14. Optical high acidity sensor

    DOE Patents [OSTI]

    Jorgensen, Betty S.; Nekimken, Howard L.; Carey, W. Patrick; O'Rourke, Patrick E.

    1997-01-01

    An apparatus and method for determining acid concentrations in solutions having acid concentrations of from about 0.1 Molar to about 16 Molar is disclosed. The apparatus includes a chamber for interrogation of the sample solution, a fiber optic light source for passing light transversely through the chamber, a fiber optic collector for receiving the collimated light after transmission through the chamber, a coating of an acid resistant polymeric composition upon at least one fiber end or lens, the polymeric composition in contact with the sample solution within the chamber and having a detectable response to acid concentrations within the range of from about 0.1 Molar to about 16 Molar, a measurer for the response of the polymeric composition in contact with the sample solution, and, a comparer of the measured response to predetermined standards whereby the acid molarity of the sample solution within the chamber can be determined. Preferably, a first lens is attached to the end of the fiber optic light source, the first lens adapted to collimate light from the fiber optic light source, and a second lens is attached to the end of the fiber optic collector for focusing the collimated light after transmission through the chamber.

  15. Redox buffered hydrofluoric acid etchant for the reduction of galvanic attack during release etching of MEMS devices having noble material films

    SciTech Connect (OSTI)

    Hankins, Matthew G.

    2009-10-06

    Etchant solutions comprising a redox buffer can be used during the release etch step to reduce damage to the structural layers of a MEMS device that has noble material films. A preferred redox buffer comprises a soluble thiophosphoric acid, ester, or salt that maintains the electrochemical potential of the etchant solution at a level that prevents oxidation of the structural material. Therefore, the redox buffer preferentially oxidizes in place of the structural material. The sacrificial redox buffer thereby protects the exposed structural layers while permitting the dissolution of sacrificial oxide layers during the release etch.

  16. 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.

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

    DOE Patents [OSTI]

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

    2004-03-30

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

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

    SciTech Connect (OSTI)

    Martello, Mark T.; Hillmyer, Marc A.

    2012-11-14

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

  19. Isomerization and dissociation in competition: The two-component dissociation rates of methyl propionate ions

    SciTech Connect (OSTI)

    Mazyar, O.A.; Baer, T.

    1999-03-04

    Threshold photoelectron-photoion coincidence (TPEPICO) spectroscopy has been used to investigate the unimolecular chemistry of gas-phase methyl propionate ions. This ion undergoes isomerization to a lower energy enol structure, CH{sub 3}CHC(OH)OCH{sub 3}{sup {sm_bullet}+}, via two different pathways involving two distonic isomers, {sup {sm_bullet}}CH{sub 2}CH{sub 2}C{sup +}(OH)OCH{sub 3} and CH{sub 3}CH{sub 2}C{sup +}(OH)OCH{sub 2}{sup {sm_bullet}}. This isomerization reaction is in competition with the direct CH{sub 3}O{sup {sm_bullet}} loss reaction, which leads to two-component dissociation rates of the methyl propionate ions. Detailed modeling of this complex reaction permitted the extraction of the dissociative photoionization threshold for methyl propionate, which at 0 K is 10.83 {+-} 0.01 eV, as well as the isomerization barrier between the distonic CH{sub 3}CH{sub 2}C{sup +}(OH)OCH{sub 2}{sup {sm_bullet}} and enol CH{sub 3}CHC(OH)OCH{sub 3}{sup {sm_bullet}+} ions of 8.5 kcal/mol (relative to the methyl propionate ion). By combining this with the 0 K heats of formation of methyl propionate and the methoxy radical, the authors derive a 0 K heat of formation of the product propanoyl ion of 147 kcal/mol. Also measured was the adiabatic ionization energy of methyl propionate, 10.03 {+-} 0.05 eV.

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

    SciTech Connect (OSTI)

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

    2013-12-15

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

  1. Plant fatty acid hydroxylase

    DOE Patents [OSTI]

    Somerville, Chris; van de Loo, Frank

    2000-01-01

    The present invention relates to the identification of nucleic acid sequences and constructs, and methods related thereto, and the use of these sequences and constructs to produce genetically modified plants for the purpose of altering the composition of plant oils, waxes and related compounds.

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

    SciTech Connect (OSTI)

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

    1994-06-01

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

  3. Fatty acid-producing hosts

    DOE Patents [OSTI]

    Pfleger, Brian F; Lennen, Rebecca M

    2013-12-31

    Described are hosts for overproducing a fatty acid product such as a fatty acid. The hosts include an exogenous nucleic acid encoding a thioesterase and, optionally, an exogenous nucleic acid encoding an acetyl-CoA carboxylase, wherein an acyl-CoA synthetase in the hosts are functionally delected. The hosts prefereably include the nucleic acid encoding the thioesterase at an intermediate copy number. The hosts are preferably recominantly stable and growth-competent at 37.degree. C. Methods of producing a fatty acid product comprising culturing such hosts at 37.degree. C. are also described.

  4. Acid diffusion through polyaniline membranes

    SciTech Connect (OSTI)

    Su, T.M.; Huang, S.C.; Conklin, J.A.

    1995-12-01

    Polyaniline membranes in the undoped (base) and doped (acid) forms are studied for their utility as pervaporation membranes. The separation of water from mixtures of propionic acid, acetic acid and formic acid have been demonstrated from various feed compositions. Doped polyaniline displays an enhanced selectivity of water over these organic acids as compared with undoped polyaniline. For as-cast polyaniline membranes a diffusion coefficient (D) on the order of 10{sup -9} cm{sup 2}/sec has been determined for the flux of protons through the membranes using hydrochloric acid.

  5. Stepwise DNA Methylation Changes Are Linked to Escape from Defined Proliferation Barriers and Mammary Epithelial Cell Immortalization

    SciTech Connect (OSTI)

    Novak, Petr; Jensen, Taylor J.; Garbe, James C.; Stampfer, Martha R.; Futscher, Bernard W.

    2009-04-20

    The timing and progression of DNA methylation changes during carcinogenesis are not completely understood. To develop a timeline of aberrant DNA methylation events during malignant transformation, we analyzed genome-wide DNA methylation patterns in an isogenic human mammary epithelial cell (HMEC) culture model of transformation. To acquire immortality and malignancy, the cultured finite lifespan HMEC must overcome two distinct proliferation barriers. The first barrier, stasis, is mediated by the retinoblastoma protein and can be overcome by loss of p16(INK4A) expression. HMEC that escape stasis and continue to proliferate become genomically unstable before encountering a second more stringent proliferation barrier, telomere dysfunction due to telomere attrition. Rare cells that acquire telomerase expression may escape this barrier, become immortal, and develop further malignant properties. Our analysis of HMEC transitioning from finite lifespan to malignantly transformed showed that aberrant DNA methylation changes occur in a stepwise fashion early in the transformation process. The first aberrant DNA methylation step coincides with overcoming stasis, and results in few to hundreds of changes, depending on how stasis was overcome. A second step coincides with immortalization and results in hundreds of additional DNA methylation changes regardless of the immortalization pathway. A majority of these DNA methylation changes are also found in malignant breast cancer cells. These results show that large-scale epigenetic remodeling occurs in the earliest steps of mammary carcinogenesis, temporally links DNA methylation changes and overcoming cellular proliferation barriers, and provides a bank of potential epigenetic biomarkers that mayprove useful in breast cancer risk assessment.

  6. 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.

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

    DOE Patents [OSTI]

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

    1983-01-01

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

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

    DOE Patents [OSTI]

    Smith, L.A. Jr.

    1983-03-01

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

  9. Lubrication with boric acid additives

    DOE Patents [OSTI]

    Erdemir, Ali

    2000-01-01

    Self-lubricating resin compositions including a boric acid additive and a synthetic polymer including those thermoset materials.

  10. Carboxylic acid sorption regeneration process

    DOE Patents [OSTI]

    King, C.J.; Poole, L.J.

    1995-05-02

    Carboxylic acids are sorbed from aqueous feedstocks into an organic liquid phase or onto a solid adsorbent. The acids are freed from the sorbent phase by treating it with aqueous alkylamine thus forming an alkylammonium carboxylate which is dewatered and decomposed to the desired carboxylic acid and the alkylamine. 10 figs.

  11. Carboxylic acid sorption regeneration process

    DOE Patents [OSTI]

    King, C. Judson; Poole, Loree J.

    1995-01-01

    Carboxylic acids are sorbed from aqueous feedstocks into an organic liquid phase or onto a solid adsorbent. The acids are freed from the sorbent phase by treating it with aqueous alkylamine thus forming an alkylammonium carboxylate which is dewatered and decomposed to the desired carboxylic acid and the alkylamine.

  12. Pantothenic acid biosynthesis in zymomonas

    DOE Patents [OSTI]

    Tao, Luan; Tomb, Jean-Francois; Viitanen, Paul V.

    2014-07-01

    Zymomonas is unable to synthesize pantothenic acid and requires this essential vitamin in growth medium. Zymomonas strains transformed with an operon for expression of 2-dehydropantoate reductase and aspartate 1-decarboxylase were able to grow in medium lacking pantothenic acid. These strains may be used for ethanol production without pantothenic acid supplementation in seed culture and fermentation media.

  13. 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.

  14. Composition for nucleic acid sequencing

    DOE Patents [OSTI]

    Korlach, Jonas; Webb, Watt W.; Levene, Michael; Turner, Stephen; Craighead, Harold G.; Foquet, Mathieu

    2008-08-26

    The present invention is directed to a method of sequencing a target nucleic acid molecule having a plurality of bases. In its principle, the temporal order of base additions during the polymerization reaction is measured on a molecule of nucleic acid, i.e. the activity of a nucleic acid polymerizing enzyme on the template nucleic acid molecule to be sequenced is followed in real time. The sequence is deduced by identifying which base is being incorporated into the growing complementary strand of the target nucleic acid by the catalytic activity of the nucleic acid polymerizing enzyme at each step in the sequence of base additions. A polymerase on the target nucleic acid molecule complex is provided in a position suitable to move along the target nucleic acid molecule and extend the oligonucleotide primer at an active site. A plurality of labelled types of nucleotide analogs are provided proximate to the active site, with each distinguishable type of nucleotide analog being complementary to a different nucleotide in the target nucleic acid sequence. The growing nucleic acid strand is extended by using the polymerase to add a nucleotide analog to the nucleic acid strand at the active site, where the nucleotide analog being added is complementary to the nucleotide of the target nucleic acid at the active site. The nucleotide analog added to the oligonucleotide primer as a result of the polymerizing step is identified. The steps of providing labelled nucleotide analogs, polymerizing the growing nucleic acid strand, and identifying the added nucleotide analog are repeated so that the nucleic acid strand is further extended and the sequence of the target nucleic acid is determined.

  15. Degradation of CYANEX 301 in Contact with Nitric Acid Media

    SciTech Connect (OSTI)

    Philippe Marc; Radu Custelcean; Gary S. Groenewold; John R. Klaehn; Dean R. Peterman; Laetitia H. Delmau

    2012-10-01

    The nature of the degradation product obtained upon contacting CYANEX 301 (bis(2,4,4-trimethylpentyl)dithiophosphinic acid) with nitric acid has been elucidated and found to be a disulfide derivative. The first step to the degradation of CYANEX 301 in toluene has been studied using 31P{1H} NMR after being contacted with nitric acid media. The spectrum of the degradation product exhibits a complex multiplet around dP = 80 ppm. A succession of purifications of CYANEX 301 has resulted in single crystals of the acidic form and the corresponding ammonium salt. Unlike the original CYANEX 301, which consists of a complex diastereomeric mixture displaying all possible combinations of chiral orientations at the 2-methyl positions, the purified crystals were shown by single-crystal X-ray diffraction to be racemates, containing 50:50 mixtures of the [R;R] and [S;S] diastereomers. The comparison between the 31P {1H} NMR spectra of the degradation products resulting from the diastereomerically pure CYANEX 301 and the original diastereomeric mixture has elucidated the influence of the isomeric composition on the multiplicity of the 31P {1H} NMR peak. These NMR data indicate the initial degradation leads to a disulfide-bridged condensation product displaying multiple resonances due to phosphorusphosphorus coupling, which is caused by the inequivalence of the two P atoms as a result of their different chirality. A total of nine different NMR resonances, six of which display phosphorusphosphorus coupling, could be assigned, and the identity of the peaks corresponding to phosphorus atoms coupled to each other was confirmed by 31P {1H} homodecoupled NMR analysis.

  16. Invasive cleavage of nucleic acids

    DOE Patents [OSTI]

    Prudent, James R.; Hall, Jeff G.; Lyamichev, Victor I.; Brow, Mary Ann D.; Dahlberg, James E.

    2002-01-01

    The present invention relates to means for the detection and characterization of nucleic acid sequences, as well as variations in nucleic acid sequences. The present invention also relates to methods for forming a nucleic acid cleavage structure on a target sequence and cleaving the nucleic acid cleavage structure in a site-specific manner. The structure-specific nuclease activity of a variety of enzymes is used to cleave the target-dependent cleavage structure, thereby indicating the presence of specific nucleic acid sequences or specific variations thereof.

  17. Invasive cleavage of nucleic acids

    DOE Patents [OSTI]

    Prudent, James R.; Hall, Jeff G.; Lyamichev, Victor I.; Brow, Mary Ann D.; Dahlberg, James E.

    1999-01-01

    The present invention relates to means for the detection and characterization of nucleic acid sequences, as well as variations in nucleic acid sequences. The present invention also relates to methods for forming a nucleic acid cleavage structure on a target sequence and cleaving the nucleic acid cleavage structure in a site-specific manner. The structure-specific nuclease activity of a variety of enzymes is used to cleave the target-dependent cleavage structure, thereby indicating the presence of specific nucleic acid sequences or specific variations thereof.

  18. Synthesis of amino acids

    DOE Patents [OSTI]

    Davis, J.W. Jr.

    1979-09-21

    A method is described for synthesizing amino acids preceding through novel intermediates of the formulas: R/sub 1/R/sub 2/C(OSOC1)CN, R/sub 1/R/sub 2/C(C1)CN and (R/sub 1/R/sub 2/C(CN)O)/sub 2/SO wherein R/sub 1/ and R/sub 2/ are each selected from hydrogen and monovalent hydrocarbon radicals of 1 to 10 carbon atoms. The use of these intermediates allows the synthesis steps to be exothermic and results in an overall synthesis method which is faster than the synthesis methods of the prior art.

  19. Evaluation of inter-laminar shear strength of GFRP composed of bonded glass/polyimide tapes and cyanate-ester/epoxy blended resin for ITER TF coils

    SciTech Connect (OSTI)

    Hemmi, T.; Matsui, K.; Koizumi, N.; Nishimura, A.; Nishijima, S.; Shikama, T.

    2014-01-27

    The insulation system of the ITER TF coils consists of multi-layer glass/polyimide tapes impregnated a cyanate-ester/epoxy resin. The ITER TF coils are required to withstand an irradiation of 10 MGy from gamma-ray and neutrons since the ITER TF coils is exposed by fast neutron (>0.1 MeV) of 10{sup 22} n/m{sup 2} during the ITER operation. Cyanate-ester/epoxy blended resins and bonded glass/polyimide tapes are developed as insulation materials to realize the required radiation-hardness for the insulation of the ITER TF coils. To evaluate the radiation-hardness of the developed insulation materials, the inter-laminar shear strength (ILSS) of glass-fiber reinforced plastics (GFRP) fabricated using developed insulation materials is measured as one of most important mechanical properties before/after the irradiation in a fission reactor of JRR-3M. As a result, it is demonstrated that the GFRPs using the developed insulation materials have a sufficient performance to apply for the ITER TF coil insulation.

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

    SciTech Connect (OSTI)

    Not Available

    1986-01-01

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

  1. Nucleic Acid Detection Methods

    DOE Patents [OSTI]

    Smith, Cassandra L.; Yaar, Ron; Szafranski, Przemyslaw; Cantor, Charles R.

    1998-05-19

    The invention relates to methods for rapidly determining the sequence and/or length a target sequence. The target sequence may be a series of known or unknown repeat sequences which are hybridized to an array of probes. The hybridized array is digested with a single-strand nuclease and free 3'-hydroxyl groups extended with a nucleic acid polymerase. Nuclease cleaved heteroduplexes can be easily distinguish from nuclease uncleaved heteroduplexes by differential labeling. Probes and target can be differentially labeled with detectable labels. Matched target can be detected by cleaving resulting loops from the hybridized target and creating free 3-hydroxyl groups. These groups are recognized and extended by polymerases added into the reaction system which also adds or releases one label into solution. Analysis of the resulting products using either solid phase or solution. These methods can be used to detect characteristic nucleic acid sequences, to determine target sequence and to screen for genetic defects and disorders. Assays can be conducted on solid surfaces allowing for multiple reactions to be conducted in parallel and, if desired, automated.

  2. Nucleic acid detection methods

    DOE Patents [OSTI]

    Smith, C.L.; Yaar, R.; Szafranski, P.; Cantor, C.R.

    1998-05-19

    The invention relates to methods for rapidly determining the sequence and/or length a target sequence. The target sequence may be a series of known or unknown repeat sequences which are hybridized to an array of probes. The hybridized array is digested with a single-strand nuclease and free 3{prime}-hydroxyl groups extended with a nucleic acid polymerase. Nuclease cleaved heteroduplexes can be easily distinguish from nuclease uncleaved heteroduplexes by differential labeling. Probes and target can be differentially labeled with detectable labels. Matched target can be detected by cleaving resulting loops from the hybridized target and creating free 3-hydroxyl groups. These groups are recognized and extended by polymerases added into the reaction system which also adds or releases one label into solution. Analysis of the resulting products using either solid phase or solution. These methods can be used to detect characteristic nucleic acid sequences, to determine target sequence and to screen for genetic defects and disorders. Assays can be conducted on solid surfaces allowing for multiple reactions to be conducted in parallel and, if desired, automated. 18 figs.

  3. Ozone and acid rain

    SciTech Connect (OSTI)

    Not Available

    1987-10-09

    The roles of ozone and other oxidizing agents are discussed. The major polluting emissions are SO/sub 2/, NO, and volatile organic chemicals. In the usual ambient concentrations, these substances are relatively harmless. However, when SO/sub 2/ and NO are oxidized, they are converted into more acid, more toxic, substances. Oxidants, including OH, H/sub 2/O/sub 2/, HO/sub 2/, and organic peroxides, arise out of complex photochemistry that involves the ozone, the nitrogen oxides, and volatile organic chemicals. Were SO/sub 2/ the only pollutant, most of it would escape unchanged to the western Atlantic Ocean where it would be so diluted as to have no effect. At present about 35 percent of the SO/sub 2/ produced in the United States leaves the continent. In contrast, because of higher rates of reaction with oxidants, most of the NO is converted into nitric acid and deposited on land. The nitrogen oxides are involved in the production of ozone, some of which is naturally present. But particularly in urban settings where concentrations of NO/sub x/ are elevated and volatile organic chemicals such as those in gasoline are present, ozone concentrations may rise to levels deleterious to health. The Environmental Protection Agency has set standards for levels not to be exceeded, but nearly half of urban communities are not in compliance. The NO/sub x/ involved in the formation of urban ozone comes mostly from vehicular emissions.

  4. Search | OpenEI Community

    Open Energy Info (EERE)

    Propane Propane Market Propane Market Forecast Propane Market Growth Propane Market Size Propane Market Trends Propionic Acid Ethyl Ester Market Propionic Acid Ethyl Ester Market...

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

    DOE Patents [OSTI]

    Marks, Tobin J.; Chen, You-Xian

    2002-01-01

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

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

    DOE Patents [OSTI]

    Marks, Tobin J.; Chen, You-Xian

    2001-01-01

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

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

    SciTech Connect (OSTI)

    Hougen, J.T.

    1993-12-01

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

  8. Electrochemical destruction of organic acids

    SciTech Connect (OSTI)

    Gendes, J.D.; Hartsough, D.; Super, J.D.

    1994-12-31

    An electrochemical process for removing organic acids from an aqueous waste stream has been characterized. Biological treatment of aqueous organic acid waste streams has been the typical means of degrading organic acids, and the resultant biosludge is landfilled. In the electrochemical approach, aqueous organic acids may be efficiently converted to useful fuel in a one or two electron process. The possible reactions occurring are outlined here. The electrolysis of the sodium salts of acetic, propionic, and butyric acids has been studied both as single component solutions and mixtures. The reaction products as well as relative rates of destruction of the acid salts were measured. The effect of experimental variables such as current density, temperature, and anode material on the current efficiency and product distribution was investigated. Electrode stability due to platinum corrosion was identified as the major limitation to the process.

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

    DOE Patents [OSTI]

    Deitz, Victor R.; Blachly, Charles H.

    1977-01-01

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

  10. 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. Acidic gas capture by diamines

    DOE Patents [OSTI]

    Rochelle, Gary; Hilliard, Marcus

    2011-05-10

    Compositions and methods related to the removal of acidic gas. In particular, the present disclosure relates to a composition and method for the removal of acidic gas from a gas mixture using a solvent comprising a diamine (e.g., piperazine) and carbon dioxide. One example of a method may involve a method for removing acidic gas comprising contacting a gas mixture having an acidic gas with a solvent, wherein the solvent comprises piperazine in an amount of from about 4 to about 20 moles/kg of water, and carbon dioxide in an amount of from about 0.3 to about 0.9 moles per mole of piperazine.

  12. 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.

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

    SciTech Connect (OSTI)

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

    2008-11-17

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

  14. Carbonic Acid Pretreatment of Biomass

    SciTech Connect (OSTI)

    G. Peter van Walsum; Kemantha Jayawardhana; Damon Yourchisin; Robert McWilliams; Vanessa Castleberry

    2003-05-31

    This project sought to address six objectives, outlined below. The objectives were met through the completion of ten tasks. 1) Solidify the theoretical understanding of the binary CO2/H2O system at reaction temperatures and pressures. The thermodynamics of pH prediction have been improved to include a more rigorous treatment of non-ideal gas phases. However it was found that experimental attempts to confirm theoretical pH predictions were still off by a factor of about 1.8 pH units. Arrhenius experiments were carried out and the activation energy for carbonic acid appears to be substantially similar to sulfuric acid. Titration experiments have not yet confirmed or quantified the buffering or acid suppression effects of carbonic acid on biomass. 2) Modify the carbonic acid pretreatment severity function to include the effect of endogenous acid formation and carbonate buffering, if necessary. It was found that the existing severity functions serve adequately to account for endogenous acid production and carbonate effects. 3) Quantify the production of soluble carbohydrates at different reaction conditions and severity. Results show that carbonic acid has little effect on increasing soluble carbohydrate concentrations for pretreated aspen wood, compared to pretreatment with water alone. This appears to be connected to the release of endogenous acids by the substrate. A less acidic substrate such as corn stover would derive benefit from the use of carbonic acid. 4) Quantify the production of microbial inhibitors at selected reaction conditions and severity. It was found that the release of inhibitors was correlated to reaction severity and that carbonic acid did not appear to increase or decrease inhibition compared to pretreatment with water alone. 5) Assess the reactivity to enzymatic hydrolysis of material pretreated at selected reaction conditions and severity. Enzymatic hydrolysis rates increased with severity, but no advantage was detected for the use of carbonic

  15. Carbonic Acid Retreatment of Biomass

    SciTech Connect (OSTI)

    Baylor university

    2003-06-01

    This project sought to address six objectives, outlined below. The objectives were met through the completion of ten tasks. (1) Solidify the theoretical understanding of the binary CO{sub 2}/H{sub 2}O system at reaction temperatures and pressures. The thermodynamics of pH prediction have been improved to include a more rigorous treatment of non-ideal gas phases. However it was found that experimental attempts to confirm theoretical pH predictions were still off by a factor of about 1.8 pH units. Arrhenius experiments were carried out and the activation energy for carbonic acid appears to be substantially similar to sulfuric acid. Titration experiments have not yet confirmed or quantified the buffering or acid suppression effects of carbonic acid on biomass. (2) Modify the carbonic acid pretreatment severity function to include the effect of endogenous acid formation and carbonate buffering, if necessary. It was found that the existing severity functions serve adequately to account for endogenous acid production and carbonate effects. (3) Quantify the production of soluble carbohydrates at different reaction conditions and severity. Results show that carbonic acid has little effect on increasing soluble carbohydrate concentrations for pretreated aspen wood, compared to pretreatment with water alone. This appears to be connected to the release of endogenous acids by the substrate. A less acidic substrate such as corn stover would derive benefit from the use of carbonic acid. (4) Quantify the production of microbial inhibitors at selected reaction conditions and severity. It was found that the release of inhibitors was correlated to reaction severity and that carbonic acid did not appear to increase or decrease inhibition compared to pretreatment with water alone. (5) Assess the reactivity to enzymatic hydrolysis of material pretreated at selected reaction conditions and severity. Enzymatic hydrolysis rates increased with severity, but no advantage was detected for

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

    SciTech Connect (OSTI)

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

    2012-08-15

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

  17. Functional nucleic acid probes and uses thereof

    DOE Patents [OSTI]

    Nilsen-Hamilton, Marit

    2006-10-03

    The present invention provides functional nucleic acid probes, and methods of using functional nucleic acid probes, for binding a target to carry out a desired function. The probes have at least one functional nucleic acid, at least one regulating nucleic acid, and at least one attenuator. The functional nucleic acid is maintained in an inactive state by the attenuator and activated by the regulating nucleic acid only in the presence of a regulating nucleic acid target. In its activated state the functional nucleic acid can bind to its target to carry out a desired function, such as generating a signal, cleaving a nucleic acid, or catalyzing a reaction.

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

    SciTech Connect (OSTI)

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

    2014-07-14

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

  19. Comparison of silatrane, phosphonic acid, and carboxylic acid...

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

    cells Authors: Brennan, B.J., Llansola Portoles, M.J., Liddell, P.A., Moore, T.A., Moore, A.L., and Gust, D. Title: Comparison of silatrane, phosphonic acid, and...

  20. PRODUCTION OF TRIFLUOROACETIC ACID COMPOUNDS

    DOE Patents [OSTI]

    Haworth, W.N.; Stacey, M.

    1949-08-30

    A process is described for the preparation of trifluoroacetic acid. Acetone vapor diluted wlth nitrogen and fluorine also diluted with nltrogen are fed separately at a temperature of about 210 deg C into a reaction vessel containing a catalyst mass selected from-the group consisting of silver and gold. The temperature in the reaction vessel is maintained in the range of 200 deg to 250 deg C. The reaction product, trifluoroacetyl fluoride, is absorbed in aqueous alkali solution. Trifluoroacetic acid is recovered from the solution by acidification wlth an acid such as sulfuric followed by steam distillation.

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

    SciTech Connect (OSTI)

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

    1980-01-01

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

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

    SciTech Connect (OSTI)

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

    1985-03-01

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

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

    SciTech Connect (OSTI)

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

    2014-01-28

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

  4. Phosphonic acid based exchange resins

    DOE Patents [OSTI]

    Horwitz, E.P.; Alexandratos, S.D.; Gatrone, R.C.; Chiarizia, R.

    1995-09-12

    An ion exchange resin is described for extracting metal ions from a liquid waste stream. An ion exchange resin is prepared by copolymerizing a vinylidene diphosphonic acid with styrene, acrylonitrile and divinylbenzene. 10 figs.

  5. Phosphonic acid based exchange resins

    DOE Patents [OSTI]

    Horwitz, E. Philip; Alexandratos, Spiro D.; Gatrone, Ralph C.; Chiarizia, Ronato

    1995-01-01

    An ion exchange resin for extracting metal ions from a liquid waste stream. An ion exchange resin is prepared by copolymerizing a vinylidene diphosphonic acid with styrene, acrylonitrile and divinylbenzene.

  6. Cytotoxic and DNA-damaging effects of methyl tert-butyl ether and its metabolites on HL-60 cells in vitro

    SciTech Connect (OSTI)

    Tang, G.H.; Shen, Y.; Shen, H.M.

    1996-12-31

    Methyl tert-butyl ether (MTBE) is a widely used oxygenate in unleaded gasoline; however, few studies have been conducted on the toxicity of this compound. This study evaluates the cytotoxic and DNA-damaging effects of MTBE and its metabolites in a human haemopoietic cell line, HL-60. The metabolites of MTBE studied include tertiary butyl alcohol (TBA), {alpha}-hydroxyisobutyric acid (HIBA), and formaldehyde. Comet assay is used to assess DNA damage, and the cytotoxicity is investigated by lactate dehydrogenease (LDH) release. The results show no significant cytotoxic effects of MTBE, TBA, and HIBA over a concentration ranging from 1 to 30 mM. Formaldehyde, in contrast, causes a substantial LDH release at a concentration of 5 {mu}M. Hydrogen peroxide, a known oxidative agent, at concentrations ranging from 10 to 100 {mu}M, produces a significant dose-related increase in DNA damage, whereas a much higher concentration of MTBE (1 to 30 mM) is required to produce a similar observation. The genotoxic effects of TBA and HIBA appear to be identical to that of MTBE. Conversely, DNA damage is observed for formaldehyde at a relatively low concentration range (5 to 100 {mu}M). These findings suggest that MTBE and its metabolites, except formaldehyde, have relatively low cytotoxic and genotoxic effects. 16 refs., 4 figs.

  7. Nucleic acid arrays and methods of synthesis

    DOE Patents [OSTI]

    Sabanayagam, Chandran R.; Sano, Takeshi; Misasi, John; Hatch, Anson; Cantor, Charles

    2001-01-01

    The present invention generally relates to high density nucleic acid arrays and methods of synthesizing nucleic acid sequences on a solid surface. Specifically, the present invention contemplates the use of stabilized nucleic acid primer sequences immobilized on solid surfaces, and circular nucleic acid sequence templates combined with the use of isothermal rolling circle amplification to thereby increase nucleic acid sequence concentrations in a sample or on an array of nucleic acid sequences.

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

    SciTech Connect (OSTI)

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

    2015-01-28

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

  9. Photodissociation dynamics of hydroxybenzoic acids

    SciTech Connect (OSTI)

    Yang Yilin; Dyakov, Yuri; Lee, Y. T.; Ni, Chi-Kung; Sun Yilun; Hu Weiping

    2011-01-21

    Aromatic amino acids have large UV absorption cross-sections and low fluorescence quantum yields. Ultrafast internal conversion, which transforms electronic excitation energy to vibrational energy, was assumed to account for the photostability of amino acids. Recent theoretical and experimental investigations suggested that low fluorescence quantum yields of phenol (chromophore of tyrosine) are due to the dissociation from a repulsive excited state. Radicals generated from dissociation may undergo undesired reactions. It contradicts the observed photostability of amino acids. In this work, we explored the photodissociation dynamics of the tyrosine chromophores, 2-, 3- and 4-hydroxybenzoic acid in a molecular beam at 193 nm using multimass ion imaging techniques. We demonstrated that dissociation from the excited state is effectively quenched for the conformers of hydroxybenzoic acids with intramolecular hydrogen bonding. Ab initio calculations show that the excited state and the ground state potential energy surfaces change significantly for the conformers with intramolecular hydrogen bonding. It shows the importance of intramolecular hydrogen bond in the excited state dynamics and provides an alternative molecular mechanism for the photostability of aromatic amino acids upon irradiation of ultraviolet photons.

  10. Beyond Ketonization: Selective Conversion of Carboxylic Acids...

    Office of Scientific and Technical Information (OSTI)

    Title: Beyond Ketonization: Selective Conversion of Carboxylic Acids to Olefins over Balanced Lewis Acid-base Pairs Dwindling petroleum reserves combined with increased energy ...