National Library of Energy BETA

Sample records for denatured aliphatic alco

  1. Process for producing peracids from aliphatic hydroxy carboxylic acids

    DOE Patents [OSTI]

    Chum, H.L.; Palasz, P.D.; Ratcliff, M.A.

    1984-12-20

    A process is described for producing peracids from lactic acid-containing solutions derived from biomass processing systems. It consists of adjusting the pH of the solution to about 8 to 9 and removing alkaline residue fractions therefrom to form a solution comprised substantially of lower aliphatic hydroxy acids. The solution is oxidized to produce volatile lower aliphatic aldehydes. The aldehydes are removed as they are generated and converted to peracids.

  2. Process for producing peracids from aliphatic hydroxy carboxylic acids

    DOE Patents [OSTI]

    Chum, Helena L.; Ratcliff, Matthew A.; Palasz, Peter D.

    1986-01-01

    A process for producing peracids from lactic acid-containing solutions derived from biomass processing systems comprising: adjusting the pH of the solution to about 8-9 and removing alkaline residue fractions therefrom to form a solution comprised substantially of lower aliphatic hydroxy acids; oxidizing the solution to produce volatile lower aliphatic aldehydes; removing said aldehydes as they are generated; and converting said aldehydes to peracids.

  3. ROMP Crosslinkers for the Preparation of Aliphatic Aerogels (Journal

    Office of Scientific and Technical Information (OSTI)

    Article) | SciTech Connect ROMP Crosslinkers for the Preparation of Aliphatic Aerogels Citation Details In-Document Search Title: ROMP Crosslinkers for the Preparation of Aliphatic Aerogels Authors: Lenhardt, J M ; Kim, S ; Worsley, M A ; Leif, R N ; Baumann, T F ; Satcher, J H Publication Date: 2014-06-05 OSTI Identifier: 1227991 Report Number(s): LLNL-JRNL-655922 DOE Contract Number: AC52-07NA27344 Resource Type: Journal Article Resource Relation: Journal Name: Journal of Non-Crystalline

  4. Aerobic microorganism for the degradation of chlorinated aliphatic hydrocarbons

    DOE Patents [OSTI]

    Fliermans, Carl B.

    1989-01-01

    A chlorinated aliphatic hydrocarbon-degrading microorganism, having American Type Culture Collection accession numbers ATCC 53570 and 53571, in a biologically pure culture aseptically collected from a deep subsurface habitat and enhanced, mineralizes trichloroethylene and tetrachloroethylene to HCl, H.sub.2 O and Co.sub.2 under aerobic conditions stimulated by methane, acetate, methanol, tryptone-yeast extract, propane and propane-methane.

  5. Shape memory polymers based on uniform aliphatic urethane networks

    SciTech Connect (OSTI)

    Wilson, T S; Bearinger, J P; Herberg, J L; Marion III, J E; Wright, W J; Evans, C L; Maitland, D J

    2007-01-19

    Aliphatic urethane polymers have been synthesized and characterized, using monomers with high molecular symmetry, in order to form amorphous networks with very uniform supermolecular structures which can be used as photo-thermally actuable shape memory polymers (SMPs). The monomers used include hexamethylene diisocyanate (HDI), trimethylhexamethylenediamine (TMHDI), N,N,N{prime},N{prime}-tetrakis(hydroxypropyl)ethylenediamine (HPED), triethanolamine (TEA), and 1,3-butanediol (BD). The new polymers were characterized by solvent extraction, NMR, XPS, UV/VIS, DSC, DMTA, and tensile testing. The resulting polymers were found to be single phase amorphous networks with very high gel fraction, excellent optical clarity, and extremely sharp single glass transitions in the range of 34 to 153 C. Thermomechanical testing of these materials confirms their excellent shape memory behavior, high recovery force, and low mechanical hysteresis (especially on multiple cycles), effectively behaving as ideal elastomers above T{sub g}. We believe these materials represent a new and potentially important class of SMPs, and should be especially useful in applications such as biomedical microdevices.

  6. Process for the synthesis of aliphatic alcohol-containing mixtures

    DOE Patents [OSTI]

    Greene, Marvin I.; Gelbein, Abraham P.

    1984-01-01

    A process for the synthesis of mixtures which include saturated aliphatic alcohols is disclosed. In the first step of the process, the first catalyst activation stage, a catalyst, which comprises the oxides of copper, zinc, aluminum, potassium and one or two additional metals selected from the group consisting of chromium, magnesium, cerium, cobalt, thorium and lanthanum, is partially activated. In this step, a reducing gas stream, which includes hydrogen and at least one inert gas, flows past the catalyst at a space velocity of up to 5,000 liters (STP) per hour, per kilogram of catalyst. The partially activated catalyst is then subjected to the second step of the process, second-stage catalyst activation. In this step, the catalyst is contacted by an activation gas stream comprising hydrogen and carbon monoxide present in a volume ratio of 0.5:1 and 4:1, respectively, at a temperature of 200.degree. to 450.degree. C. and a pressure of between 35 and 200 atmospheres. The activation gas flows at a space velocity of from 1,000 to 20,000 liters (STP) per hour, per kilogram of catalyst. Second-stage activation continues until the catalyst is contacted with at least 500,000 liters (STP) of activation gas per kilogram of catalyst. The fully activated catalyst, in the third step of the process, contacts a synthesis gas stream comprising hydrogen and carbon monoxide.

  7. Process for the synthesis of aliphatic alcohol-containing mixtures

    DOE Patents [OSTI]

    Greene, M.I.; Gelbein, A.P.

    1984-10-16

    A process for the synthesis of mixtures which include saturated aliphatic alcohols is disclosed. In the first step of the process, the first catalyst activation stage, a catalyst, which comprises the oxides of copper, zinc, aluminum, potassium and one or two additional metals selected from the group consisting of chromium, magnesium, cerium, cobalt, thorium and lanthanum, is partially activated. In this step, a reducing gas stream, which includes hydrogen and at least one inert gas, flows past the catalyst at a space velocity of up to 5,000 liters (STP) per hour, per kilogram of catalyst. The partially activated catalyst is then subjected to the second step of the process, second-stage catalyst activation. In this step, the catalyst is contacted by an activation gas stream comprising hydrogen and carbon monoxide present in a volume ratio of 0.5:1 and 4:1, respectively, at a temperature of 200 to 450 C and a pressure of between 35 and 200 atmospheres. The activation gas flows at a space velocity of from 1,000 to 20,000 liters (STP) per hour, per kilogram of catalyst. Second-stage activation continues until the catalyst is contacted with at least 500,000 liters (STP) of activation gas per kilogram of catalyst. The fully activated catalyst, in the third step of the process, contacts a synthesis gas stream comprising hydrogen and carbon monoxide.

  8. Process for removing halogenated aliphatic and aromatic compounds from petroleum products

    DOE Patents [OSTI]

    Googin, John M.; Napier, John M.; Travaglini, Michael A.

    1983-01-01

    A process for removing halogenated aliphatic and aromatic compounds, e.g., polychlorinated biphenyls, from petroleum products by solvent extraction. The halogenated aliphatic and aromatic compounds are extracted from a petroleum product into a polar solvent by contacting the petroleum product with the polar solvent. The polar solvent is characterized by a high solubility for the extracted halogenated aliphatic and aromatic compounds, a low solubility for the petroleum product and considerable solvent power for polyhydroxy compound. The preferred polar solvent is dimethylformamide. A miscible compound, such as, water or a polyhydroxy compound, is added to the polar extraction solvent to increase the polarity of the polar extraction solvent. The halogenated aliphatic and aromatic compounds are extracted from the highly-polarized mixture of water or polyhydroxy compound and polar extraction solvent into a low polar or nonpolar solvent by contacting the water or polyhydroxy compound-polar solvent mixture with the low polar or nonpolar solvent. The halogenated aliphatic and aromatic compounds and the low polar or nonpolar solvent are separated by physical means, e.g., vacuum evaporation. The polar and nonpolar solvents are recovered from recycling. The process can easily be designed for continuous operation. Advantages of the process include that the polar solvent and a major portion of the nonpolar solvent can be recycled, the petroleum products are reclaimable and the cost for disposing of waste containing polychlorinated biphenyls is significantly reduced.

  9. Process for removing halogenated aliphatic and aromatic compounds from petroleum products

    DOE Patents [OSTI]

    Googin, J.M.; Napier, J.M.; Travaglini, M.A.

    1983-09-20

    A process is described for removing halogenated aliphatic and aromatic compounds, e.g., polychlorinated biphenyls, from petroleum products by solvent extraction. The halogenated aliphatic and aromatic compounds are extracted from a petroleum product into a polar solvent by contacting the petroleum product with the polar solvent. The polar solvent is characterized by a high solubility for the extracted halogenated aliphatic and aromatic compounds, a low solubility for the petroleum product and considerable solvent power for polyhydroxy compound. The preferred polar solvent is dimethylformamide. A miscible compound, such as, water or a polyhydroxy compound, is added to the polar extraction solvent to increase the polarity of the polar extraction solvent. The halogenated aliphatic and aromatic compounds are extracted from the highly-polarized mixture of water or polyhydroxy compound and polar extraction solvent into a low polar or nonpolar solvent by contacting the water or polyhydroxy compound-polar solvent mixture with the low polar or nonpolar solvent. The halogenated aliphatic and aromatic compounds and the low polar or nonpolar solvent are separated by physical means, e.g., vacuum evaporation. The polar and nonpolar solvents are recovered from recycling. The process can easily be designed for continuous operation. Advantages of the process include that the polar solvent and a major portion of the nonpolar solvent can be recycled, the petroleum products are reclaimable and the cost for disposing of waste containing polychlorinated biphenyls is significantly reduced. 1 fig.

  10. Gas phase heterogeneous catalytic oxidation of alkanes to aliphatic ketones and/or other oxygenates

    DOE Patents [OSTI]

    Lin, Manhua; Wang, Xiang; Yeom, Younghoon

    2015-09-29

    A catalyst, its method of preparation and its use for producing aliphatic ketones by subjecting alkanes C.sub.3 to C.sub.9 to a gas phase catalytic oxidation in the presence of air or oxygen, and, optionally, steam and/or one or more diluting gases. The catalyst comprises a catalytically active mixed metal oxide phase and a suitable support material onto and/or into which the active catalytic phase is dispersed.

  11. Gas phase heterogeneous catalytic oxidation of alkanes to aliphatic ketones and/or other oxygenates

    DOE Patents [OSTI]

    Lin, Manhua; Wang, Xiang; Yeom, Younghoon

    2015-03-17

    A catalyst, its method of preparation and its use for producing aliphatic ketones by subjecting alkanes C.sub.3 to C.sub.9 to a gas phase catalytic oxidation in the presence of air or oxygen, and, optionally, steam and/or one or more diluting gases. The catalyst comprises a catalytically active mixed metal oxide phase and a suitable support material onto and/or into which the active catalytic phase id dispersed.

  12. Conceptual design characteristics of a denatured molten-salt reactor with once-through fueling

    SciTech Connect (OSTI)

    Engel, J.R.; Bauman, H.F.; Dearing, J.F.; Grimes, W.R.; McCoy, H.E.; Rhoades, W.A.

    1980-07-01

    A study was made to examine the conceptual feasibility of a molten-salt power reactor fueled with denatured /sup 235/U and operated with a minimum of chemical processing. Because such a reactor would not have a positive breeding gain, reductions in the fuel conversion ratio were allowed in the design to achieve other potentially favorable characteristics for the reactor. A conceptual core design was developed in which the power density was low enough to allow a 30-year life expectancy of the moderator graphite with a fluence limit of 3 x 10/sup 26/ neutrons/m/sup 2/ (E > 50 keV). This reactor could be made critical with about 3450 kg of 20% enriched /sup 235/U and operated for 30 years with routine additions of denatured /sup 235/U and no chemical processing for removal of fission products. A review of the chemical considerations assoicated with the conceptual fuel cycle indicates that no substantial difficulties would be expected if the soluble fission products and higher actinides were allowed to remain in the fuel salt for the life of the plant.

  13. Process for removing halogenated aliphatic and aromatic compounds from petroleum products. [Polychlorinated biphenyls; methylene chloride; perchloroethylene; trichlorofluoroethane; trichloroethylene; chlorobenzene

    DOE Patents [OSTI]

    Googin, J.M.; Napier, J.M.; Travaglini, M.A.

    1982-03-31

    A process for removing halogenated aliphatic and aromatic compounds, e.g., polychlorinated biphenyls, from petroleum products by solvent extraction. The halogenated aliphatic and aromatic compounds are extracted from a petroleum product into a polar solvent by contracting the petroleum product with the polar solvent. The polar solvent is characterized by a high solubility for the extracted halogenated aliphatic and aromatic compounds, a low solubility for the petroleum product and considerable solvent power for polyhydroxy compound. The preferred polar solvent is dimethylformamide. A miscible polyhydroxy compound, such as, water, is added to the polar extraction solvent to increase the polarity of the polar extraction solvent. The halogenated aliphatic and aromatic compounds are extracted from the highly-polarized mixture of polyhydroxy compound and polar extraction solvent into a low polar or nonpolar solvent by contacting the polyhydroxy compound-polar solvent mixture with the low polar or nonpolar solvent. The halogenated aliphatic and aromatic compounds in the low polar or nonpolar solvent by physical means, e.g., vacuum evaporation. The polar and nonpolar solvents are recovered for recycling. The process can easily be designed for continuous operation. Advantages of the process include that the polar solvent and a major portion of the nonpolar solvent can be recycled, the petroleum products are reclaimable and the cost for disposing of waste containing polychlorinated biphenyls is significantly reduced. 2 tables.

  14. Amperometric detection and electrochemical oxidation of aliphatic amines and ammonia on silver-lead oxide thin-film electrodes

    SciTech Connect (OSTI)

    Ge, Jisheng

    1996-01-08

    This thesis comprises three parts: Electrocatalysis of anodic oxygen-transfer reactions: aliphatic amines at mixed Ag-Pb oxide thin-film electrodes; oxidation of ammonia at anodized Ag-Pb eutectic alloy electrodes; and temperature effects on oxidation of ethylamine, alanine, and aquated ammonia.

  15. The non-uniform early structural response of globular proteins to cold denaturing conditions: A case study with Yfh1

    SciTech Connect (OSTI)

    Chatterjee, Prathit; Bagchi, Sayan E-mail: s.bagchi@ncl.res.in; Sengupta, Neelanjana E-mail: s.bagchi@ncl.res.in

    2014-11-28

    The mechanism of cold denaturation in proteins is often incompletely understood due to limitations in accessing the denatured states at extremely low temperatures. Using atomistic molecular dynamics simulations, we have compared early (nanosecond timescale) structural and solvation properties of yeast frataxin (Yfh1) at its temperature of maximum stability, 292 K (T{sub s}), and the experimentally observed temperature of complete unfolding, 268 K (T{sub c}). Within the simulated timescales, discernible global level structural loss at T{sub c} is correlated with a distinct increase in surface hydration. However, the hydration and the unfolding events do not occur uniformly over the entire protein surface, but are sensitive to local structural propensity and hydrophobicity. Calculated infrared absorption spectra in the amide-I region of the whole protein show a distinct red shift at T{sub c} in comparison to T{sub s}. Domain specific calculations of IR spectra indicate that the red shift primarily arises from the beta strands. This is commensurate with a marked increase in solvent accessible surface area per residue for the beta-sheets at T{sub c}. Detailed analyses of structure and dynamics of hydration water around the hydrophobic residues of the beta-sheets show a more bulk water like behavior at T{sub c} due to preferential disruption of the hydrophobic effects around these domains. Our results indicate that in this protein, the surface exposed beta-sheet domains are more susceptible to cold denaturing conditions, in qualitative agreement with solution NMR experimental results.

  16. Essential roles of protein-solvent many-body correlation in solvent-entropy effect on protein folding and denaturation: Comparison between hard-sphere solvent and water

    SciTech Connect (OSTI)

    Oshima, Hiraku; Kinoshita, Masahiro

    2015-04-14

    In earlier works, we showed that the entropic effect originating from the translational displacement of water molecules plays the pivotal role in protein folding and denaturation. The two different solvent models, hard-sphere solvent and model water, were employed in theoretical methods wherein the entropic effect was treated as an essential factor. However, there were similarities and differences in the results obtained from the two solvent models. In the present work, to unveil the physical origins of the similarities and differences, we simultaneously consider structural transition, cold denaturation, and pressure denaturation for the same protein by employing the two solvent models and considering three different thermodynamic states for each solvent model. The solvent-entropy change upon protein folding/unfolding is decomposed into the protein-solvent pair (PA) and many-body (MB) correlation components using the integral equation theories. Each component is further decomposed into the excluded-volume (EV) and solvent-accessible surface (SAS) terms by applying the morphometric approach. The four physically insightful constituents, (PA, EV), (PA, SAS), (MB, EV), and (MB, SAS), are thus obtained. Moreover, (MB, SAS) is discussed by dividing it into two factors. This all-inclusive investigation leads to the following results: (1) the protein-water many-body correlation always plays critical roles in a variety of folding/unfolding processes; (2) the hard-sphere solvent model fails when it does not correctly reproduce the protein-water many-body correlation; (3) the hard-sphere solvent model becomes problematic when the dependence of the many-body correlation on the solvent number density and temperature is essential: it is not quite suited to studies on cold and pressure denaturating of a protein; (4) when the temperature and solvent number density are limited to the ambient values, the hard-sphere solvent model is usually successful; and (5) even at the ambient values, however, the many-body correlation plays significant roles in the β-sheet formation and argument of relative stabilities of very similar structures of a protein. These results are argued in detail with respect to the four physically insightful constituents and the two factors mentioned above. The relevance to the absence or presence of hydrogen-bonding properties in the solvent is also discussed in detail.

  17. Experimental and Modeling Study of the Flammability of Fuel Tank Headspace Vapors from Ethanol/Gasoline Fuels; Phase 3: Effects of Winter Gasoline Volatility and Ethanol Content on Blend Flammability; Flammability Limits of Denatured Ethanol

    SciTech Connect (OSTI)

    Gardiner, D. P.; Bardon, M. F.; Clark, W.

    2011-07-01

    This study assessed differences in headspace flammability for summertime gasolines and new high-ethanol content fuel blends. The results apply to vehicle fuel tanks and underground storage tanks. Ambient temperature and fuel formulation effects on headspace vapor flammability of ethanol/gasoline blends were evaluated. Depending on the degree of tank filling, fuel type, and ambient temperature, fuel vapors in a tank can be flammable or non-flammable. Pure gasoline vapors in tanks generally are too rich to be flammable unless ambient temperatures are extremely low. High percentages of ethanol blended with gasoline can be less volatile than pure gasoline and can produce flammable headspace vapors at common ambient temperatures. The study supports refinements of fuel ethanol volatility specifications and shows potential consequences of using noncompliant fuels. E85 is flammable at low temperatures; denatured ethanol is flammable at warmer temperatures. If both are stored at the same location, one or both of the tanks' headspace vapors will be flammable over a wide range of ambient temperatures. This is relevant to allowing consumers to splash -blend ethanol and gasoline at fueling stations. Fuels compliant with ASTM volatility specifications are relatively safe, but the E85 samples tested indicate that some ethanol fuels may produce flammable vapors.

  18. Denaturing of Molecules | GE Global Research

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

    Symposium and Exhibition Focuses on Materials, Surfaces and Interfaces IMG0475 Innovation 247: We're Always Open MunichinteriorV 10 Years ON: From the Lab to the...

  19. Materials Data on U2AlCo3 (SG:194) by Materials Project

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

    Kristin Persson

    2015-03-08

    Computed materials data using density functional theory calculations. These calculations determine the electronic structure of bulk materials by solving approximations to the Schrodinger equation. For more information, see https://materialsproject.org/docs/calculations

  20. Materials Data on U2AlCo2 (SG:127) by Materials Project

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

    Kristin Persson

    2015-03-08

    Computed materials data using density functional theory calculations. These calculations determine the electronic structure of bulk materials by solving approximations to the Schrodinger equation. For more information, see https://materialsproject.org/docs/calculations

  1. ROMP Crosslinkers for the Preparation of Aliphatic Aerogels ...

    Office of Scientific and Technical Information (OSTI)

    DOE Contract Number: AC52-07NA27344 Resource Type: Journal Article Resource Relation: Journal Name: Journal of Non-Crystalline Solids, vol. 408, na, January 15, 2014, pp. 98-101 ...

  2. Toward a Taxonomy of the Denatured State: Small Angle Scattering Studies of Unfolded Proteins

    SciTech Connect (OSTI)

    Millett, I.S.; Doniach, S.; Plaxco, K.W. (Stanford); (UCSB)

    2005-02-15

    Despite the critical role the unfolded state plays in defining protein folding kinetics and thermodynamics (Berg et al., 2002; Dunker, 2002; Shortle, 2002; Wright and Dyson, 2002), our understanding of its detailed structure remains rather rudimentary; the heterogeneity of the unfolded ensemble renders difficult or impossible its study by traditional, atomic-level structural methods. Consequently, recent years have seen a significant expansion of small-angle X-ray and neutron scattering (SAXS and SANS, respectively) techniques that provide direct, albeit rotationally and time-averaged, measures of the geometric properties of the unfolded ensemble. These studies have reached a critical mass, allowing us for the first time to define general observations regarding the nature of the geometry - and possibly the chemistry and physics - of unfolded proteins.

  3. Petroleum Supply Annual

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

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

  4. Table Definitions, Sources, and Explanatory Notes

    Gasoline and Diesel Fuel Update (EIA)

    percent denatured fuel ethanol. Conventional Gasoline, Greater than Ed 55 Finished conventional motor gasoline blended with denatured fuel ethanol where the volume percent of ...

  5. Table Definitions, Sources, and Explanatory Notes

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

    percent denatured fuel ethanol. Conventional Gasoline, Greater than Ed55 Finished conventional motor gasoline blended with denatured fuel ethanol where the volume percent of ...

  6. Deuterium separation by infrared-induced addition reaction

    DOE Patents [OSTI]

    Marling, John B.

    1977-01-01

    A method for deuterium enrichment by the infrared-induced addition reaction of a deuterium halide with an unsaturated aliphatic compound. A gaseous mixture of a hydrogen halide feedstock and an unsaturated aliphatic compound, particularly an olefin, is irradiated to selectively vibrationally excite the deuterium halide contained therein. The excited deuterium halide preferentially reacts with the unsaturated aliphatic compound to produce a deuterated addition product which is removed from the reaction mixture.

  7. TABLE33.CHP:Corel VENTURA

    Gasoline and Diesel Fuel Update (EIA)

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

  8. TABLE34.CHP:Corel VENTURA

    Gasoline and Diesel Fuel Update (EIA)

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

  9. Essential roles of protein-solvent many-body correlation in solvent-entropy

    Office of Scientific and Technical Information (OSTI)

    effect on protein folding and denaturation: Comparison between hard-sphere solvent and water (Journal Article) | SciTech Connect Essential roles of protein-solvent many-body correlation in solvent-entropy effect on protein folding and denaturation: Comparison between hard-sphere solvent and water Citation Details In-Document Search Title: Essential roles of protein-solvent many-body correlation in solvent-entropy effect on protein folding and denaturation: Comparison between hard-sphere

  10. Prospects for Simulating Macromolecular Surfactant Chemistry...

    Office of Scientific and Technical Information (OSTI)

    at the Ocean-Atmosphere Boundary Biogenic lipids and polymers are surveyed for their ... Lipids and denatured protein-like polymers dominate at the selected locations. The ...

  11. Ethanol and the Environment - Energy Explained, Your Guide To...

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

    ... Unlike gasoline, pure ethanol is nontoxic and biodegradable, and it quickly breaks down into harmless substances if spilled. Chemical denaturants are added to fuel ethanol (about ...

  12. Fuel Tables.indd

    Gasoline and Diesel Fuel Update (EIA)

    F4: Fuel ethanol consumption estimates, 2014 State Commercial Industrial Transportation ... a In estimating the Btu consumption of fuel ethanol, the Btu content of denaturant ...

  13. Metal-sulfur type cell having improved positive electrode

    DOE Patents [OSTI]

    DeJonghe, L.C.; Visco, S.J.; Mailhe, C.C.; Armand, M.B.

    1988-03-31

    A novel metal-sulfur type cell operable at a temperature of 200/degree/C or less with an energy density of 150 Whrs/Kg or better is disclosed characterized by an organo-sulfur cathode formed from an organic-sulfur compound having the general formula, in its charged state, of (R(S)/sub y/)n wherein y = 1 to 6; n = 2 to 20; and R is one or more different aliphatic or aromatic organic moieties having 1 to 20 carbon atoms, which may include one or more oxygen, sulfur, or nitrogen heteroatoms when R comprises one or more aromatic rings, or one or more oxygen, sulfur, nitrogen, or fluorine atoms associated with the chain when R comprises an aliphatic chain, wherein the aliphatic group may be linear or branched, saturated or unsaturated, and wherein either the aliphatic chain or the aromatic ring may have substituted groups thereon. 4 figs.

  14. Metal-sulfur type cell having improved positive electrode

    DOE Patents [OSTI]

    Dejonghe, Lutgard C.; Visco, Steven J.; Mailhe, Catherine C.; Armand, Michel B.

    1989-01-01

    An novel metal-sulfur type cell operable at a temperature of 200.degree. C. or less with an energy density of 150 Whrs/Kg or better is disclosed characterized by an organo-sulfur cathode formed from an organic-sulfur compound having the general formula, in its charged state, of (R(S).sub.y).sub.n wherein y=1 to 6; n=2 to 20; and R is one or more different aliphatic or aromatic organic moieties having 1 to 20 carbon atoms, which may include one or more oxygen, sulfur, or nitrogen heteroatoms when R comprisises one of more aromatic rings, or one or more oxygen, sulfur, nitrogen, or fluorine atoms associtated with the chain when R comprises an aliphatic chain, wherein the aliphatic group may be linear or branched, saturated or unsaturated, and wherein either the aliphatic chain or the aromatic ring may have substituted groups thereon.

  15. Decontamination performance of selected in situ technologies for jet fuel contamination. Master's thesis

    SciTech Connect (OSTI)

    Chesley, G.D.

    1993-01-01

    Specific study of jet fuel is warranted because of the quantitive and qualitative component differences between jet fuel and other hydrocarbon fuels. Quantitatively, jet fuel contains a larger aliphatic or saturate fraction and a smaller aromatic fraction than other fuels (i.e. heating oil and diesel oil) in the medium-boiling-point-distillate class of fuels. Since the aliphatic and aromatic fractions of fuel are not equally susceptible to biodegradation, jet fuel decontamination using biodegradation may be different from other fuels.

  16. Process for reducing organic compounds with calcium, amine, and alcohol

    DOE Patents [OSTI]

    Benkeser, R.A.; Laugal, J.A.; Rappa, A.

    1985-08-06

    Olefins are produced by contacting an organic compound having at least one benzene ring with calcium metal, ethylenediamine, a low molecular weight aliphatic alcohol, and optionally a low molecular weight aliphatic primary amine, and/or an inert, abrasive particulate substance. The reduction is conducted at temperatures ranging from about [minus]10 C to about 30 C or somewhat higher. Substantially all of the organic compounds are converted to corresponding cyclic olefins, primarily diolefins.

  17. Process for reducing organic compounds with calcium, amine, and alcohol

    DOE Patents [OSTI]

    Benkeser, Robert A.; Laugal, James A.; Rappa, Angela

    1985-01-01

    Olefins are produced by contacting an organic compound having at least one benzene ring with calcium metal, ethylenediamine, a low molecular weight aliphatic alcohol, and optionally a low molecular weight aliphatic primary amine, and/or an inert, abrasive particulate substance. The reduction is conducted at temperatures ranging from about -10.degree. C. to about 30.degree. C. or somewhat higher. Substantially all of the organic compounds are converted to corresponding cyclic olefins, primarily diolefins.

  18. Experimental and Modeling Study of the Flammability of Fuel Tank Headspace Vapors from High Ethanol Content Fuels

    SciTech Connect (OSTI)

    Gardiner, D.; Bardon, M.; Pucher, G.

    2008-10-01

    Study determined the flammability of fuel tank headspace vapors as a function of ambient temperature for seven E85 fuel blends, two types of gasoline, and denatured ethanol at a low tank fill level.

  19. Word Pro - Untitled1

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

    chemical compounds composed of carbon, hydrogen, and oxygen. The series of molecules vary in chain length and are composed of a hydrocarbon plus a hydroxyl group: CH 3 -(CH 2 )n-OH (e.g., metha- nol, ethanol, and tertiary butyl alcohol). See Fuel Ethanol. Alternative Fuel: Alternative fuels, for transportation applications, include the following: methanol; denatured ethanol, and other alcohols; fuel mixtures contain- ing 85 percent or more by volume of methanol, denatured ethanol, and other

  20. Synthesis of pore-variable mesoporous CdS and evaluation of its photocatalytic activity in degrading methylene blue

    SciTech Connect (OSTI)

    Zhang, Wei-Min; Jiang, Yao-Quan; Cao, Xiao-Yan; Chen, Meng; Ge, Dong-Lai; Sun, Zhong-Xi

    2013-10-15

    Graphical abstract: - Highlights: Self-templated synthesis of tubular CdS. Cadmium complexes of aliphatic acids sustain the network of mesoporous structures. Aliphatic acids affect the phase composition and particle size. Pore size and volume vary with aliphatic acids having different hydrocarbonyl. - Abstract: In this study, mesoporous CdS polycrystallites have been synthesized using aliphatic acids of hexanoic acid, octanoic acid, and oleic acid as coordinating and capping agents, respectively. The fibrous Cdfatty acid salts act as a template to form the tubular CdS. The organic species are found to be necessary for maintaining the network of mesoporous CdS. The characterization results indicate that the shorter carbon chain length in aliphatic acids favors the wurtzite phase and particle size growth the specific surface area, pore diameter and pore volume show a monotonic raise with increasing carbon chain. The photocatalytic activities of mesoporous CdS tubes exhibit much higher efficiency than those of nanosized CdS powders in decolorizing methylene blue under simulated visible light.

  1. Lithium/organosulfur redox cell having protective solid electrolyte barrier formed on anode and method of making same

    DOE Patents [OSTI]

    De Jonghe, Lutgard C.; Visco, Steven J.; Liu, Meilin; Mailhe, Catherine C.

    1990-01-01

    A lithium/organosulfur redox cell is disclosed which comprises a solid lium anode, a liquid organosulfur cathode, and a barrier layer formed adjacent a surface of the solid lithium anode facing the liquid organosulfur cathode consisting of a reaction product of the lithium anode with the organosulfur cathode. The organosulfur cathode comprises a material having the formula (R(S).sub.y).sub.N where y=1 to 6, n=2 to 20 and R is one or more different aliphatic or aromatic organic moieties having 1 to 20 carbon atoms, which may include one or more oxygen, sulfur, nitrogen, or fluorine atoms associated with the chain when R comprises an aliphatic chain, wherein the linear chain may be linear or branched, saturated or unsaturated, and wherein either the aliphatic chain or the aromatic ring may have substituted groups thereon.

  2. PRODUCTION OF FLUOROCARBONS

    DOE Patents [OSTI]

    Sarsfield, N.F.

    1949-06-21

    This patent pertains to a process for recovering fluorocarbons from a liquid mixture of hydrocarbons with partially and completely fluorinated products thereof. It consists of contacting the mxture in the cold with a liquid which is a solvent for the hydrocarbons and which is a nonsolvent for the fluorocarbons, extracting the hydrocarbons, separating the fluorocarbon-containing layer from the solvent-containing layer, and submitting the fluorocarbon layer to fractlonal distillation, to isolate the desired fluorocarbon fraction. Suitable solvents wnich may be used in the process include the lower aliphatic alcohols, and the lower aliphatic ketones.

  3. Flexible moldable conductive current-limiting materials

    DOE Patents [OSTI]

    Shea, John Joseph; Djordjevic, Miomir B.; Hanna, William Kingston

    2002-01-01

    A current limiting PTC device (10) has two electrodes (14) with a thin film of electric conducting polymer material (20) disposed between the electrodes, the polymer material (20) having superior flexibility and short circuit performance, where the polymer material contains short chain aliphatic diepoxide, conductive filler particles, curing agent, and, preferably, a minor amount of bisphenol A epoxy resin.

  4. Process and catalyst for carbonylating olefins

    DOE Patents [OSTI]

    Zoeller, J.R.

    1998-06-02

    Disclosed is an improved catalyst system and process for preparing aliphatic carbonyl compounds such as aliphatic carboxylic acids, alkyl esters of aliphatic carboxylic acids and anhydrides of aliphatic carboxylic acids by carbonylating olefins in the presence of a catalyst system comprising (1) a first component selected from at least one Group 6 metal, i.e., chromium, molybdenum, and/or tungsten and (2) a second component selected from at least one of certain halides and tertiary and quaternary compounds of a Group 15 element, i.e., nitrogen, phosphorus and/or arsenic, and (3) as a third component, a polar, aprotic solvent. The process employing the improved catalyst system is carried out under carbonylating conditions of pressure and temperature discussed herein. The process constitutes and improvement over known processes since it can be carried out at moderate carbonylation conditions without the necessity of using an expensive noble metal catalyst, volatile, toxic materials such as nickel tetracarbonyl, formic acid or a formate ester. Further, the addition of a polar, aprotic solvent to the catalyst system significantly increases, or accelerates, the rate at which the carbonylation takes place.

  5. Surface chemistry control for selective fossil resin flotation

    DOE Patents [OSTI]

    Miller, Jan D.; Yi, Ye; Yu, Qiang

    1994-01-01

    A froth flotation method is disclosed for separating fine particles of fossil resin from by use of frothing reagents which include an aliphatic organic compound having a polar group and containing not more than four carbon atoms. Butanol is an effective frothing reagent in this method.

  6. Surface chemistry control for selective fossil resin flotation

    DOE Patents [OSTI]

    Miller, J.D.; Yi, Y.; Yu, Q.

    1994-06-07

    A froth flotation method is disclosed for separating fine particles of fossil resin by use of frothing reagents which include an aliphatic organic compound having a polar group and containing not more than four carbon atoms. Butanol is an effective frothing reagent in this method. 12 figs.

  7. Process for the extraction of strontium from acidic solutions

    DOE Patents [OSTI]

    Horwitz, E.P.; Dietz, M.L.

    1994-09-06

    The invention is a process for selectively extracting strontium values from aqueous nitric acid waste solutions containing these and other fission product values. The extractant solution is a macrocyclic polyether in an aliphatic hydrocarbon diluent containing a phase modifier. The process will selectively extract strontium values from nitric acid solutions which are up to 6 molar in nitric acid. 4 figs.

  8. SOLVENT EXTRACTION PROCESS FOR PROTACTINIUM

    DOE Patents [OSTI]

    Hyde, E.K.; Katzin, L.I.; Wolf, M.J.

    1961-04-01

    A process is described for separating protactinium from thorium present together as the nitrates in a 0.1 to 10 N nitric acid solution. The separation is carried out by extraction with an aliphatic alcohol, ketone, and/or ester having at least six carbon atoms, such as n-amyl acetate, 2-ethyl hexanol, and diisopropyl ketone.

  9. Process for the extraction of strontium from acidic solutions

    DOE Patents [OSTI]

    Horwitz, E.P.; Dietz, M.L.

    1993-01-01

    The invention is a process for selectively extracting strontium values from aqueous nitric acid waste solutions containing these and other fission product values. The extractant solution is a macrocyclic polyether in an aliphatic hydrocarbon diluent containing a phase modifier. The process will selectively extract strontium values from nitric acid solutions which are up to 6 molar in nitric acid.

  10. Process for the extraction of strontium from acidic solutions

    DOE Patents [OSTI]

    Horwitz, E. Philip; Dietz, Mark L.

    1994-01-01

    The invention is a process for selectively extracting strontium values from aqueous nitric acid waste solutions containing these and other fission product values. The extractant solution is a macrocyclic polyether in an aliphatic hydrocarbon diluent containing a phase modifier. The process will selectively extract strontium values from nitric acid solutions which are up to 6 molar in nitric acid.

  11. Coal liquefaction process using pretreatment with a binary solvent mixture

    DOE Patents [OSTI]

    Miller, Robert N.

    1986-01-01

    An improved process for thermal solvent refining or hydroliquefaction of non-anthracitic coal at elevated temperatures under hydrogen pressure in a hydrogen donor solvent comprises pretreating the coal with a binary mixture of an aromatic hydrocarbon and an aliphatic alcohol at a temperature below 300.degree. C. before the hydroliquefaction step. This treatment generally increases both conversion of coal and yields of oil.

  12. Sprayable titanium composition

    DOE Patents [OSTI]

    Tracy, Chester E.; Kern, Werner; Vibronek, Robert D.

    1980-01-01

    The addition of 2-ethyl-1-hexanol to an organometallic titanium compound dissolved in a diluent and optionally containing a lower aliphatic alcohol spreading modifier, produces a solution that can be sprayed onto a substrate and cured to form an antireflection titanium oxide coating having a refractive index of from about 2.0 to 2.2.

  13. Next Release Date: August 2013

    Gasoline and Diesel Fuel Update (EIA)

    5. Biofuels overview, 2006 - 2010 (trillion Btu) Type 2006 2007 2008 2009 2010 Ethanol Feedstock 1 688 914 1300 1517 1839 Losses and Co-products 2 285 376 531 616 742 Denaturant 11 14 21 26 30 Production 3 414 553 790 928 1127 Net Imports 4 62 37 45 17 -32 Stock Change 5 11 6 13 8 5 Consumption 465 584 821 936 1090 Consumption minus Denaturant 453 569 800 910 1061 Biodiesel Feedstock 6 32 63 88 R67 44 Losses and Co-products 7 * 1 1 1 1 Production 8 32 62 87 R66 44 Net Imports 1 -17 -46 -24 -10

  14. Method and apparatus for cartilage reshaping by radiofrequency heating

    DOE Patents [OSTI]

    Wong, Brian J.; Milner, Thomas E.; Sobol, Emil N.; Keefe, Michael W.

    2003-07-08

    A method and apparatus for reshaping cartilage using radiofrequency heating. The cartilage temperature is raised sufficiently for stress relaxation to occur in the cartilage, but low enough so that significant denaturation of the cartilage does not occur. The RF electrodes may be designed to also function as molds, preses, clamps, or mandrills to deform the cartilage tissue. Changes in various properties of the cartilage associated with stress relaxation in the cartilage may be measured in order to provide the control signal to provide effective reshaping without denaturation.

  15. Land subsidence associated with hydrocarbon production, Texas Gulf Coast

    SciTech Connect (OSTI)

    Kreitler, C.W.; White, W.A.; Akhter, M.S.

    1988-01-01

    Although ground-water withdrawal has been the predominant cause of land subsidence in the Texas Gulf Coast, localized subsidence and faulting have also resulted from hydrocarbon production. Subsidence was documented as early as the 1920s over the Goose Creek field. Since then, subsidence and/or faulting have been identified over the Saxet, South Houston, Chocolate Bayou, Hastings, Alco-Mag, Clinton, Mykawa, Blue Ridge, Webster, and Caplen oil fields. Oil-production-related subsidence over these fields generally creates few environmental or engineering problems. One exception is the subsidence and faulting over the Caplen oil field on Bolivar Peninsula, where more than 1,000 ac of saltwater marsh has been replaced by subaqueous flats. Subsidence may be occurring over other fields but has not been identified because of limited releveled benchmark data. An evaluation of drill-stem and bottom-hole pressure data for the Frio Formation in Texas indicates extensive depressurization presumably from hydrocarbon production. Nearly 12,000 measurements from a pressure data base of 17,000 measurements indicate some depressurization. Some of the Frio zones have pressure declines of more than 1,500 psi from original hydrostatic conditions. Subsidence and faulting may be associated with these fields in the Frio as well as other Tertiary formations where extensive hydrocarbon production and subsequent depressurization have occurred.

  16. Land subsidence caused by withdrawal of oil and gas in the Gulf coastal plain - The Houston, Texas, case history

    SciTech Connect (OSTI)

    Holzer, T.L. )

    1990-09-01

    The extensive network of geodetic leveling lines in the Houston-Galveston, Texas, area, where at least 110 oil and gas fields have been developed, provides the most comprehensive opportunity in the Gulf Coast to search for the occurrence of land subsidence caused by withdrawal of oil and gas. Although the evaluation is complicated by regional subsidence caused by a decline of ground-water level in aquifers beneath the area, subsidence caused by oil and gas withdrawal can be examined by searching for local increases of subsidence at oil and gas fields crossed by leveling lines. Twenty-nine fields are crossed by lines with repeated leveling surveys. Subsidence profiles across these fields indicate local increases of subsidence at six fields-Alco-Mag, Chocolate Bayou, Goose Creek, Hastings, Mykawa, and South Houston. Although ground-water withdrawal is undoubtedly the most important factor contributing to the total subsidence at each field, oil and gas withdrawal may be partly responsible for the local increases. Except for Chocolate Bayou, the volume of petroleum production at each field was sufficient to account for the increase. The volume of petroleum production, however, in general is not a reliable index for predicting the local increase because land within many fields with significant production did not show local increases of subsidence. With the exception of the 1 m subsidence caused by petroleum withdrawal at Goose Creek (1917-1925), local increases of subsidence were less than 0.3 m.

  17. SEPARATION OF PLUTONIUM FROM ELEMENTS HAVING AN ATOMIC NUMBER NOT LESS THAN 92

    DOE Patents [OSTI]

    Fitch, F.T.; Russell, D.S.

    1958-09-16

    other elements having atomic numbers nnt less than 92, It has been proposed in the past to so separate plutonium by solvent extraction iato an organic solvent using triglycoldichlcride as the organic solvent. The improvement lies in the discovery that triglycoldichloride performs far more efflciently as an extractant, wher certain second organie compounds are added to it. Mentioned as satisfactory additive compounds are benzaldehyde, saturated aliphatic aldehydes containtng at least twc carbon atoms, and certain polyhydric phenols.

  18. Coal liquefaction process using pretreatment with a binary solvent mixture

    DOE Patents [OSTI]

    Miller, R.N.

    1986-10-14

    An improved process for thermal solvent refining or hydroliquefaction of non-anthracitic coal at elevated temperatures under hydrogen pressure in a hydrogen donor solvent comprises pretreating the coal with a binary mixture of an aromatic hydrocarbon and an aliphatic alcohol at a temperature below 300 C before the hydroliquefaction step. This treatment generally increases both conversion of coal and yields of oil. 1 fig.

  19. Polyestercarbonates which exhibit improved processibility

    DOE Patents [OSTI]

    Krabbenhoft, Herman Otto (Scotia, NY)

    1999-01-01

    The invention relates to a polyestercarbonate polymer which comprises repeating units of a mono-unsaturated aliphatic dicarboxylic acid having about 12 to about 20 carbon atoms. Preferred dicarboxylic acids for incorporation into the polymer are cis-octadec-9-enedioic acid or trans-octadec-9-enedioic acid. The use of these mono-unsaturated acids results in polymers with lower glass transition temperatures, and enhances processibility.

  20. Nanofluids and a method of making nanofluids for ground source heat pumps and other applications

    DOE Patents [OSTI]

    Olson, John Melvin

    2013-11-12

    This invention covers nanofluids. Nanofluids are a combination of particles between 1 and 100 nanometers, a surfactant and the base fluid. The nanoparticles for this invention are either pyrogenic nanoparticles or carbon nanotubes. These nanofluids improve the heat transfer of the base fluids. The base fluid can be ethylene glycol, or propylene glycol, or an aliphatic-hydrocarbon based heat transfer fluid. This invention also includes a method of making nanofluids. No surfactant is used to suspend the pyrogenic nanoparticles in glycols.

  1. PRODUCTION OF FLUORINE-CONTAINING HYDROCARBON

    DOE Patents [OSTI]

    Sarsfield, N.F.

    1949-08-01

    This patent relates to improvements in the production of fluorine- containing hydrocarbon derivatives. The process for increasing the degree of fluorination of a fluorochlorohydrocarbon comprises subjecting a highly fluorinated fluorochlorohydrocarbon to the action of a dehydrochlorinating agent, and treating the resulting unsaturated body with fluorine, cobalt trifluoride, or silver difluoride. A number of reagents are known as dehydrochlorinaling agents, including, for example, the caustic alkalies, either in an anhydrous condition or dissolved in water or a lower aliphatic alcohol.

  2. Molecular and crystal structure of n-hexyloxybenzoic anhydride at low and room temperatures

    SciTech Connect (OSTI)

    Konstantinov, I. I.; Churakov, A. V.; Kuz'mina, L. G.

    2010-09-15

    The crystal and molecular structures of n-hexyloxybenzoic anhydride, C{sub 6}H{sub 13}-O-C{sub 6}H{sub 4}-C(O)-O-C(O)-C{sub 6}H{sub 4}-C{sub 6}H{sub 13}, at low (120 K) and room (296 K) temperatures have been investigated. The molecule has an asymmetric bent structure. The dihedral angle between the benzene ring planes is 48.5 deg. The aliphatic chain on one side of the molecule has a transoid orientation with respect to the 'internal' C4 atom of the closest benzene ring, whereas the aliphatic chain on the other side has a cissoid orientation with respect to the analogous C(4A) atom. The crystal packing does not exhibit any pronounced separation of the crystal space into closely packed aromatic or loosely packed aliphatic regions. No weak directional interactions are observed in the packing; this fact explains the absence of liquid-crystal properties for this compound.

  3. Intrinsic and accelerated anaerobic biodegradation of perchloroethylene in groundwater

    SciTech Connect (OSTI)

    Buchanan, R.J. Jr.; Ellis, D.E.; Odom, J.M.; Lee, M.D.; Mazierski, P.F.

    1995-12-31

    The DuPont Niagara Falls Plant is located in a heavily industrialized area of Niagara Falls, New York, adjacent to the Niagara River. The plant has been in continuous operation since 1898 and manufactured various organic and inorganic chemicals. Chlorinated solvents were produced from 1930 to 1975 at the plant. Numerous hydrogeologic investigations have described the subsurface hydrogeology and indicated that the groundwater underlying the plant was impacted by a variety of chlorinated aliphatic hydrocarbons in a wide range of concentrations. DuPont initiated in-field evaluations to determine whether biological reductive anaerobic dechlorination was occurring naturally and, if so, whether such dechlorination could be enhanced in situ. A field program was subsequently implemented could be enhanced in situ. A field program was subsequently implemented in a preselected area of the plant through use of an in situ borehole bioreactor to attempt to stimulate indigenous biological reductive dechlorination of chlorinated aliphatics by the addition of yeast extract (substrate) and sulfate (electron acceptor). At this location, a very active microbial population developed, which reduced the in situ concentrations of chlorinated aliphatic compounds by more than 94%, but did not increase the typical biological degradation products. This may have been due to an alternative biological degradation pathway or to very rapid biological kinetics. Efforts to elucidate this mechanism have been initiated under a separate laboratory program.

  4. Kinder Morgan Central Florida Pipeline Ethanol Project

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

    KINDER MORGAN CENTRAL FLORIDA PIPELINE ETHANOL PROJECT  In December 2008, Kinder Morgan began transporting commercial batches of denatured ethanol along with gasoline shipments in its 16-inch Central Florida Pipeline (CFPL) from Tampa to Orlando, making CFPL the first transmarket gasoline pipeline in the United States to do so. The 16-inch pipeline previously only transported regular and premium gasoline.  Kinder Morgan invested approximately $10 million to modify the line for ethanol

  5. Liquid-metal fast-breeder reactors: Preliminary safety and environmental information document. Volume VI

    SciTech Connect (OSTI)

    Not Available

    1980-01-01

    Information is presented concerning LMFBR design characteristics; uranium-plutonium/uranium recycle homogeneous core; uranium-plutonium/uranium spiked recycle heterogeneous core; uranium-plutonium/uranium spiked recycle homogeneous core; uranium-plutonium/thorium spiked recycle heterogeneous core; uranium-plutonium/thorium spiked recycle homogeneous core; thorium-plutonium/thorium spiked recycle homogeneous core; denatured uranium-233/thorium cycle homogeneous core; safety consideration for the LMFBR; and environmental considerations.

  6. Ethanol Tolerant Yeast for Improved Production of Ethanol from Biomass -

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

    Ethanol Basics Ethanol is a widely used, domesti- cally produced renewable fuel made from corn and other plant materials. More than 96% of gasoline sold in the United States contains ethanol. Fuel ethanol contains the same chemical compound as beverage alcohol, but it is denatured with a small amount of gasoline or other chemicals during the production process, making it unsafe for human consumption. Ethanol's primary market drivers are the Federal Renewable Fuel Standard requiring its use and

  7. Study of polymer molecules and conformations with a nanopore

    DOE Patents [OSTI]

    Golovchenko, Jene A.; Li, Jiali; Stein, Derek; Gershow, Marc H.

    2013-03-12

    The invention features methods for evaluating the conformation of a polymer, for example, for determining the conformational distribution of a plurality of polymers and to detect binding or denaturation events. The methods employ a nanopore which the polymer, e.g., a nucleic acid, traverses. As the polymer traverses the nanopore, measurements of transport properties of the nanopore yield data on the conformation of the polymer.

  8. Study of polymer molecules and conformations with a nanopore

    DOE Patents [OSTI]

    Golovchenko, Jene A.; Li, Jiali; Stein, Derek; Gershow, Marc H.

    2010-12-07

    The invention features methods for evaluating the conformation of a polymer, for example, for determining the conformational distribution of a plurality of polymers and to detect binding or denaturation events. The methods employ a nanopore which the polymer, e.g., a nucleic acid, traverses. As the polymer traverses the nanopore, measurements of transport properties of the nanopore yield data on the conformation of the polymer.

  9. Study of polymer molecules and conformations with a nanopore

    DOE Patents [OSTI]

    Golovchenko, Jene A; Li, Jiali; Stein, Derek; Gershow, Marc H

    2015-03-03

    The invention features methods for evaluating the conformation of a polymer, for example, for determining the conformational distribution of a plurality of polymers and to detect binding or denaturation events. The methods employ a nanopore which the polymer, e.g., a nucleic acid, traverses. As the polymer traverses the nanopore, measurements of transport properties of the nanopore yield data on the conformation of the polymer.

  10. Alternative Fuels Data Center

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

    Alternative Fuel Labeling Requirements Alternative fuel dispensers must be labeled with information to help consumers make informed decisions about fueling a vehicle, including the name of the fuel and the minimum percentage of the main component of the fuel. Labels may also list the percentage of other fuel components. This requirement applies to, but is not limited to, the following fuel types: methanol, denatured ethanol, and/or other alcohols; mixtures containing 85% or more by volume of

  11. Alternative Fuels Data Center

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

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

  12. Ethanol Basics (Fact Sheet), Clean Cities, Energy Efficiency & Renewable Energy (EERE)

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

    Ethanol Basics Ethanol is a widely used, domesti- cally produced renewable fuel made from corn and other plant materials. More than 96% of gasoline sold in the United States contains ethanol. Fuel ethanol contains the same chemical compound as beverage alcohol, but it is denatured with a small amount of gasoline or other chemicals during the production process, making it unsafe for human consumption. Ethanol's primary market drivers are the Federal Renewable Fuel Standard requiring its use and

  13. Table Definitions, Sources, and Explanatory Notes

    Gasoline and Diesel Fuel Update (EIA)

    Net Production Definitions Key Terms Definition Barrel A unit of volume equal to 42 U.S. gallons. Conventional Gasoline Finished motor gasoline not included in the oxygenated or reformulated gasoline categories. Excludes reformulated gasoline blendstock for oxygenate blending (RBOB) as well as other blendstock. Conventional Gasoline, Ed55 and Lower Finished conventional motor gasoline blended with a maximum of 55 volume percent denatured fuel ethanol. Conventional Gasoline, Greater than Ed55

  14. Light-water reactors: preliminary safety and environmental information document. Volume I

    SciTech Connect (OSTI)

    Not Available

    1980-01-01

    Information is presented concerning the reference PWR reactor system; once-through, low-enrichment uranium-235 fuel, 30 MWD per kilogram (PWR LEU(5)-OT); once-through, low-enrichment, high-burnup uranium fuel (PWR LEU(5)-Mod OT); self-generated plutonium spiked recycle (PWR LEU(5)-Pu-Spiked Recycle); denatured uranium-233/thorium cycle (PWR DU(3)-Th Recycle DU(3)); and plutonium/thorium cycle (Pu/ThO/sub 2/ Burner).

  15. Heavy metal ions are potent inhibitors of protein folding

    SciTech Connect (OSTI)

    Sharma, Sandeep K. [Biochemisches Institut, Universitaet Zuerich, CH-8057 Zuerich (Switzerland); Departement de Biologie Moleculaire Vegetale, Universite de Lausanne, CH-1015 Lausanne (Switzerland); Goloubinoff, Pierre [Departement de Biologie Moleculaire Vegetale, Universite de Lausanne, CH-1015 Lausanne (Switzerland); Christen, Philipp [Biochemisches Institut, Universitaet Zuerich, CH-8057 Zuerich (Switzerland)], E-mail: christen@bioc.uzh.ch

    2008-07-25

    Environmental and occupational exposure to heavy metals such as cadmium, mercury and lead results in severe health hazards including prenatal and developmental defects. The deleterious effects of heavy metal ions have hitherto been attributed to their interactions with specific, particularly susceptible native proteins. Here, we report an as yet undescribed mode of heavy metal toxicity. Cd{sup 2+}, Hg{sup 2+} and Pb{sup 2+} proved to inhibit very efficiently the spontaneous refolding of chemically denatured proteins by forming high-affinity multidentate complexes with thiol and other functional groups (IC{sub 50} in the nanomolar range). With similar efficacy, the heavy metal ions inhibited the chaperone-assisted refolding of chemically denatured and heat-denatured proteins. Thus, the toxic effects of heavy metal ions may result as well from their interaction with the more readily accessible functional groups of proteins in nascent and other non-native form. The toxic scope of heavy metals seems to be substantially larger than assumed so far.

  16. Molecular Recognition: Preparation and Characterization of Two Tripodal Anion Receptors

    SciTech Connect (OSTI)

    Shokri, Alireza; Deng, Shihu; Wang, Xue B.; Kass, Steven R.

    2014-03-01

    Two new tripodal hydroxyl-based anion receptors (1 and 2) are reported and their molecular complexes with Cl, H2PO4 , and OAc along with the (M1) ion of 1 were characterized by negative ion photoelectron spectroscopy in the gas phase and by binding constant determinations in four solvents (i.e., CDCl3, CD2Cl2, CD3COCD3, and CD3CN). An intramolecular hydrogen bond network (HBN) in hexaol 1 was found to diminish its binding whereas the triol 2 is the strongest aliphatic hydroxyl-based receptor to date.

  17. Selective sorbents for purification of hydrocarbons

    DOE Patents [OSTI]

    Yang, Ralph T.; Hernandez-Maldonado, Arturo J.; Yang, Frances H.; Takahashi, Akira

    2006-08-22

    A method for removing thiophene and thiophene compounds from liquid fuel includes contacting the liquid fuel with an adsorbent which preferentially adsorbs the thiophene and thiophene compounds. The adsorption takes place at a selected temperature and pressure, thereby producing a non-adsorbed component and a thiophene/thiophene compound-rich adsorbed component. The adsorbent includes either a metal or a metal cation that is adapted to form .pi.-complexation bonds with the thiophene and/or thiophene compounds, and the preferential adsorption occurs by .pi.-complexation. A further method includes selective removal of aromatic compounds from a mixture of aromatic and aliphatic compounds.

  18. Selective sorbents for purification of hydrocarbons

    DOE Patents [OSTI]

    Yang, Ralph T.; Yang, Frances H.; Takahashi, Akira; Hernandez-Maldonado, Arturo J.

    2006-05-30

    A method for removing thiophene and thiophene compounds from liquid fuel includes contacting the liquid fuel with an adsorbent which preferentially adsorbs the thiophene and thiophene compounds. The adsorption takes place at a selected temperature and pressure, thereby producing a non-adsorbed component and a thiophene/thiophene compound-rich adsorbed component. The adsorbent includes either a metal or a metal cation that is adapted to form .pi.-complexation bonds with the thiophene and/or thiophene compounds, and the preferential adsorption occurs by .pi.-complexation. A further method includes selective removal of aromatic compounds from a mixture of aromatic and aliphatic compounds.

  19. Selective Sorbents For Purification Of Hydrocarbons

    DOE Patents [OSTI]

    Yang, Ralph T.; Yang, Frances H.; Takahashi, Akira; Hernandez-Maldonado, Arturo J.

    2006-04-18

    A method for removing thiophene and thiophene compounds from liquid fuel includes contacting the liquid fuel with an adsorbent which preferentially adsorbs the thiophene and thiophene compounds. The adsorption takes place at a selected temperature and pressure, thereby producing a non-adsorbed component and a thiophene/thiophene compound-rich adsorbed component. The adsorbent includes either a metal or a metal ion that is adapted to form p-complexation bonds with the thiophene and/or thiophene compounds, and the preferential adsorption occurs by p-complexation. A further method includes selective removal of aromatic compounds from a mixture of aromatic and aliphatic compounds.

  20. Selective sorbents for purification of hydrocartons

    DOE Patents [OSTI]

    Yang, Ralph T.; Yang, Frances H.; Takahashi, Akira; Hermandez-Maldonado, Arturo J.

    2006-12-12

    A method for removing thiophene and thiophene compounds from liquid fuel includes contacting the liquid fuel with an adsorbent which preferentially adsorbs the thiophene and thiophene compounds. The adsorption takes place at a selected temperature and pressure, thereby producing a non-adsorbed component and a thiophene/thiophene compound-rich adsorbed component. The adsorbent includes either a metal or a metal ion that is adapted to form .pi.-complexation bonds with the thiophene and/or thiophene compounds, and the preferential adsorption occurs by .pi.-complexation. A further method includes selective removal of aromatic compounds from a mixture of aromatic and aliphatic compounds.

  1. URANIUM SEPARATION PROCESS

    DOE Patents [OSTI]

    Hyde, E.K.; Katzin, L.I.; Wolf, M.J.

    1959-07-14

    The separation of uranium from a mixture of uranium and thorium by organic solvent extraction from an aqueous solution is described. The uranium is separrted from an aqueous mixture of uranium and thorium nitrates 3 N in nitric acid and containing salting out agents such as ammonium nitrate, so as to bring ihe total nitrate ion concentration to a maximum of about 8 N by contacting the mixture with an immiscible aliphatic oxygen containing organic solvent such as diethyl carbinol, hexone, n-amyl acetate and the like. The uranium values may be recovered from the organic phase by back extraction with water.

  2. Degradation problems with the solvent extraction organic at Roessing uranium

    SciTech Connect (OSTI)

    Munyungano, Brodrick; Feather, Angus; Virnig, Michael

    2008-07-01

    Roessing Uranium Ltd recovers uranium from a low-grade ore in Namibia. Uranium is recovered and purified from an ion-exchange eluate in a solvent-extraction plant. The solvent-extraction plant uses Alamine 336 as the extractant for uranium, with isodecanol used as a phase modifier in Sasol SSX 210, an aliphatic hydrocarbon diluent. Since the plant started in the mid 1970's, there have been a few episodes where the tertiary amine has been quickly and severely degraded when the plant was operated outside certain operating parameters. The Rossing experience is discussed in more detail in this paper. (authors)

  3. Shock temperature as a criterion for the detonability of LNG/LPG constituents

    SciTech Connect (OSTI)

    Michels, H.J. . Dept. of Chemical Engineering and Chemical Technology); Rashidi, F. )

    1992-12-01

    Detonation limit data obtained at ambient conditions for some aliphatic LNG/LNG constituents with oxygen and nitrogen (air) have been analyzed in search of a single critical parameter for detonation propagation. It was established the shock, rather than C-J reaction temperatures, provides a firm basis for marginal detonability prediction and that, furthermore, classical reaction mechanisms and relatively simple calculation methods can be used for their reliable evaluation. In this paper the result is used to formulate a criterion, for predicting composition limits to detonation. For the systems investigated, this criterion is accurate to within approximately 0.2% for fuel-lean and around 1% for fuel-rich mixtures.

  4. Kinetic data base for combustion modeling

    SciTech Connect (OSTI)

    Tsang, W.; Herron, J.T.

    1993-12-01

    The aim of this work is to develop a set of evaluated rate constants for use in the simulation of hydrocarbon combustion. The approach has been to begin with the small molecules and then introduce larger species with the various structural elements that can be found in all hydrocarbon fuels and decomposition products. Currently, the data base contains most of the species present in combustion systems with up to four carbon atoms. Thus, practically all the structural grouping found in aliphatic compounds have now been captured. The direction of future work is the addition of aromatic compounds to the data base.

  5. Selective aerobic alcohol oxidation method for conversion of lignin into simple aromatic compounds

    DOE Patents [OSTI]

    Stahl, Shannon S; Rahimi, Alireza

    2015-03-03

    Described is a method to oxidize lignin or lignin sub-units. The method includes oxidation of secondary benzylic alcohol in the lignin or lignin sub-unit to a corresponding ketone in the presence of unprotected primarily aliphatic alcohol in the lignin or lignin sub-unit. The optimal catalyst system consists of HNO.sub.3 in combination with another Bronsted acid, in the absence of a metal-containing catalyst, thereby yielding a selectively oxidized lignin or lignin sub-unit. The method may be carried out in the presence or absence of additional reagents including TEMPO and TEMPO derivatives.

  6. Aromatic and polycyclic aromatic hydrocarbon formation in a laminar premixed n-butane flame

    SciTech Connect (OSTI)

    Marinov, N.M.; Pitz, W.J.; Westbrook, C.K.; Vincitore, A.M.; Castaldi, M.J.; Senkan, S.M.; Melius, C.F.

    1998-07-01

    Experimental and detailed chemical kinetic modeling work has been performed to investigate aromatic and polycyclic aromatic hydrocarbon (PAH) formation pathways in a premixed, rich, sooting, n-butane-oxygen-argon burner stabilized flame. An atmospheric pressure, laminar flat flame operated at an equivalence ratio of 2.6 was used to acquire experimental data for model validation. Gas composition analysis was conducted by an on-line gas chromatograph/mass spectrometer technique. Measurements were made in the main reaction and post-reaction zones for a number of low molecular weight species, aliphatics, aromatics, and polycyclic aromatic hydrocarbons (PAHs) ranging from two to five-fused aromatic rings. Reaction flux and sensitivity analysis were used to help identify the important reaction sequences leading to aromatic and PAH growth and destruction in the n-butane flame. Reaction flux analysis showed the propargyl recombination reaction was the dominant pathway to benzene formation. The consumption of propargyl by H atoms was shown to limit propargyl, benzene, and naphthalene formation in flames as exhibited by the large negative sensitivity coefficients. Naphthalene and phenanthrene production was shown to be plausibly formed through reactions involving resonantly stabilized cyclopentadienyl and indenyl radicals. Many of the low molecular weight aliphatics, combustion by-products, aromatics, branched aromatics, and PAHs were fairly well simulated by the model. Additional work is required to understand the formation mechanisms of phenyl acetylene, pyrene, and fluoranthene in the n-butane flame. 73 refs.

  7. Computational Study of Bond Dissociation Enthalpies for Substituted $\\beta$-O-4 Lignin Model Compounds

    SciTech Connect (OSTI)

    Younker, Jarod M; Beste, Ariana; Buchanan III, A C

    2011-01-01

    The biopolymer lignin is a potential source of valuable chemicals. Phenethyl phenyl ether (PPE) is representative of the dominant $\\beta$-O-4 ether linkage. Density functional theory (DFT) is used to calculate the Boltzmann-weighted carbon-oxygen and carbon-carbon bond dissociation enthalpies (BDEs) of substituted PPE. These values are important in order to understand lignin decomposition. Exclusion of all conformers that have distributions of less than 5\\% at 298 K impacts the BDE by less than 1 kcal mol$^{-1}$. We find that aliphatic hydroxyl/methylhydroxyl substituents introduce only small changes to the BDEs (0-3 kcal mol$^{-1}$). Substitution on the phenyl ring at the $ortho$ position substantially lowers the C-O BDE, except in combination with the hydroxyl/methylhydroxyl substituents, where the effect of methoxy substitution is reduced by hydrogen bonding. Hydrogen bonding between the aliphatic substituents and the ether oxygen in the PPE derivatives has a significant influence on the BDE. CCSD(T)-calculated BDEs and hydrogen bond strengths of $ortho$-substituted anisoles when compared with M06-2X values confirm that the latter method is sufficient to describe the molecules studied and provide an important benchmark for lignin model compounds.

  8. Zinc ferrite nanoparticle as a magnetic catalyst: Synthesis and dye degradation

    SciTech Connect (OSTI)

    Mahmoodi, Niyaz Mohammad

    2013-10-15

    Graphical abstract: Photocatalytic degradation of Reactive Red 198 and Reactive Red 120 by the synthesized zinc ferrite nanoparticle. - Highlights: Magnetic zinc ferrite nanoparticle was synthesized and characterized. Photocatalytic dye degradation by magnetic nanoparticle was studied. Formate, acetate and oxalate were detected as dominant dye degradation aliphatic intermediates. Nitrate and sulfate ions were detected as mineralization products of dyes. Zinc ferrite nanoparticle was an effective magnetic photocatalyst to degrade dyes. - Abstract: In this paper, magnetic zinc ferrite (ZnFe{sub 2}O{sub 4}) nanoparticle was synthesized and its photocatalytic dye degradation ability from colored wastewater was studied. Reactive Red 198 (RR198) and Reactive Red 120 (RR120) were used as model dyes. The characteristics of ZnFe{sub 2}O{sub 4} were investigated using Fourier transform infrared (FTIR), X-ray diffraction (XRD) and scanning electron microscope (SEM). Photocatalytic dye degradation by ZnFe{sub 2}O{sub 4} was studied by UVvis spectrophotometer and ion chromatography (IC). The effects of ZnFe{sub 2}O{sub 4} dosage, initial dye concentration and salt on dye degradation were evaluated. Formate, acetate and oxalate anions were detected as dominant aliphatic intermediate. Inorganic anions (nitrate and sulfate anions) were detected as dye mineralization products. The results indicated that ZnFe{sub 2}O{sub 4} could be used as a magnetic photocatalyst to degrade dyes from colored wastewater.

  9. October 1999 Groundwater Sampling and Data Analysis, Distler Brickyard Site, Hardin County, Kentucky

    SciTech Connect (OSTI)

    J. P. Martin, L. N. Peterson; C. J. Taylor

    2000-03-01

    This report describes the results of a sampling event conducted at the Distler Brickyard Superfund Site, Hardin County, Kentucky, October 1999. The purpose of the sampling event was to evaluate the extent of natural biodegradation of chlorinated aliphatic hydrocarbons (CAH) occurring at the Site. Sampling locations were selected to evaluate three areas of the suspected CAH plume: the source area, an axial cross-section, and a downgradient transect. Due to inadequate recharge to and the poor physical condition of some monitoring wells at the Site, the sampling approach was modified to reflect wells that could be sampled. Results indicate that natural anaerobic degradation of chlorinated aliphatic hydrocarbons is occurring in the presumed source area around monitoring well GW-11. The primary contaminant of concern, trichloroethene, migrates downgradient from the source area into the Coarse Grained Alluvium Aquifer at concentrations slightly greater than the Maximum Contaminant Level (MCL). Based on the available, the following hypothesis is proposed: the source area has been remediated through soil removal activities and subsequent anaerobic reductive dechlorination. If this is the case, this Site may be a good candidate for implementation of a monitored natural attenuation remedy. However, more data are necessary before this hypothesis can be confirmed.

  10. Ionic Liquid–Solute Interactions Studied by 2D NOE NMR Spectroscopy

    SciTech Connect (OSTI)

    Khatun, Sufia; Castner, Edward W.

    2014-11-26

    Intermolecular interactions between a Ru²⁺(bpy)₃ solute and the anions and cations of four different ionic liquids (ILs) are investigated by 2D NMR nuclear Overhauser effect (NOE) techniques, including {¹H-¹⁹F} HOESY and {¹H-¹H} ROESY. Four ILs are studied, each having the same bis(trifluoromethylsulfonyl)amide anion in common. Two of the ILs have aliphatic 1-alkyl-1-methylpyrrolidinium cations, while the other two ILs have aromatic 1-alkyl-3-methylimidazolium cations. ILs with both shorter (butyl) and longer (octyl or decyl) cationic alkyl substituents are studied. NOE NMR results suggest that the local environment of IL anions and cations near the Ru²⁺(bpy)₃ solute is rather different from the bulk IL structure. The solute-anion and solute-cation interactions are significantly different both for ILs with short vs long alkyl tails and for ILs with aliphatic vs aromatic cation polar head groups. In particular, the solute-anion interactions are observed to be about 3 times stronger for the cations with shorter alkyl tails relative to the ILs with longer alkyl tails. The Ru²⁺(bpy)₃ solute interacts with both the polar head and the nonpolar tail groups of the 1- butyl-1-methylpyrrolidinium cation but only with the nonpolar tail groups of the 1-decyl-1-methylpyrrolidinium cation.

  11. Ionic Liquid–Solute Interactions Studied by 2D NOE NMR Spectroscopy

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

    Khatun, Sufia; Castner, Edward W.

    2014-11-26

    Intermolecular interactions between a Ru²⁺(bpy)₃ solute and the anions and cations of four different ionic liquids (ILs) are investigated by 2D NMR nuclear Overhauser effect (NOE) techniques, including {¹H-¹⁹F} HOESY and {¹H-¹H} ROESY. Four ILs are studied, each having the same bis(trifluoromethylsulfonyl)amide anion in common. Two of the ILs have aliphatic 1-alkyl-1-methylpyrrolidinium cations, while the other two ILs have aromatic 1-alkyl-3-methylimidazolium cations. ILs with both shorter (butyl) and longer (octyl or decyl) cationic alkyl substituents are studied. NOE NMR results suggest that the local environment of IL anions and cations near the Ru²⁺(bpy)₃ solute is rather different from the bulkmore » IL structure. The solute-anion and solute-cation interactions are significantly different both for ILs with short vs long alkyl tails and for ILs with aliphatic vs aromatic cation polar head groups. In particular, the solute-anion interactions are observed to be about 3 times stronger for the cations with shorter alkyl tails relative to the ILs with longer alkyl tails. The Ru²⁺(bpy)₃ solute interacts with both the polar head and the nonpolar tail groups of the 1- butyl-1-methylpyrrolidinium cation but only with the nonpolar tail groups of the 1-decyl-1-methylpyrrolidinium cation.« less

  12. Photodetachment and electron reactivity in 1-methyl-1-butyl-pyrrolidinium bis(trifluoromethylsulfonyl)amide

    SciTech Connect (OSTI)

    Molins i Domenech, Francesc; FitzPatrick, Benjamin; Healy, Andrew T.; Blank, David A.

    2012-07-21

    The transient absorption spectrum in the range 500 nm-1000 nm was measured with ultrafast time resolution on a flowing neat, aliphatic, room-temperature ionic liquid following anion photodetachment. In this region the spectrum was shown to be a combination of absorption from the electron and the hole. Spectrally-resolved electron quenching determined a bimodal shape for the hole spectrum in agreement with recent computational predictions on a smaller aliphatic ionic liquid [Margulis et al., J. Am. Chem. Soc. 133, 20186 (2011)]. For time delays beyond 15 ps, spectral evolution qualitatively agrees with recent radiolysis experiments [Wishart et al., Faraday Discuss. 154, 353 (2012)]. However, the shape of the spectrum is different, reflecting the contrast in ionization energy between the two methods. Previously unobserved reactivity of the electron was found with a time constant of 300 fs. The results demonstrate solvent control of the rate coefficient for reaction between the electron and proton, with a rapid decline in the rate within the first picosecond.

  13. Probing the molecular design of hyper-branched aryl polyesters towards lubricant applications

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

    Robinson, Joshua W.; Zhou, Yan; Bhattacharya, Priyanka; Erck, Robert; Qu, Jun; Bays, J. Timothy; Cosimbescu, Lelia

    2016-01-05

    We report novel polymeric materials that may be used as viscosity index improvers (VII) for lubricant applications. Our efforts included probing the comb-burst hyper-branched aryl polyester architecture for beneficial viscosity and friction behavior when utilized as an additive in a group I oil. The monomer was designed as to undergo polymerization via polycondensation within the architectural construct (AB2), typical of hyperbranched polymers. The monomer design was comprised of aliphatic arms (12 or 16 methylenes) to provide the necessary lipophilicity to achieve solubility in a non-polar medium. Once polymerized, via catalyst and heat, the surface alcohols were functionalized with fatty acidsmore » (lauric and palmitic). Controlling the aliphatic nature of the internal arms and peripheral end-groups provided four unique flexible polymer designs. Changing the reaction time and concentration provided opportunities to investigate the influence of molecular weight and branching density on oil-solubility, viscosity, and friction. Oil-solubility was found to decrease with fewer internal carbons, but the number of internal carbons appears to have little influence on the bulk solution viscosity. Increased branching and degree of polymerization, and thus molecular weight, were found to reduce the solubility of these systems in the base oil. At concentrations of 2 wt % in a group I base oil, these polymer additives demonstrated improved viscosity index and reduced friction coefficient, validating the basic approach.« less

  14. Crosslinked Polyamide

    DOE Patents [OSTI]

    Huang, Zhi H.; McDonald, William F.; Wright, Stacy C.; Taylor, Andrew C.

    2002-06-04

    A crosslinked polyamide material and a process for preparing the crosslinked polyamide material are disclosed. The crosslinked polyamide material comprises a crosslinked chemical combination of (1) a polyamide of the formula: ##STR1## wherein n is between about 50 and 10,000, wherein each R is between 1 and 50 carbon atoms alone and is optionally substituted with heteroatoms, oxygen, nitrogen, sulfur, or phosphorus and combinations thereof, wherein multiple of the R are in vertically aligned spaced relationship along a backbone forming the polyamide, and wherein two or more of the R contain an amino group; and (2) a crosslinking agent containing at least two functional groups capable of reacting with the amino groups of the polyamide. In one embodiment of the invention, the crosslinking agent is an aliphatic or aromatic isocyanate compound having 2 or more --N.dbd.C.dbd.O groups. In another embodiment of the invention, the crosslinking agent is an aliphatic aldehyde or aromatic aldehyde compound having 2 or more --CHO groups. In still another embodiment of the invention, the crosslinking agent is selected from a phosphine having the general formula (A).sub.2 P(B) and mixtures thereof, wherein A is hydroxyalkyl, and B is hydroxyalkyl, alkyl, or aryl. In yet another embodiment of the invention, the crosslinking agent is selected from the group consisting of epoxy resins having more than one epoxide group per molecule.

  15. The Influence of Process Conditions on the Chemical Composition of Pine Wood Catalytic Pyrolysis Oils

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

    Pereira, J.; Agblevor, F. A.; Beis, S. H.

    2012-01-01

    Pine wood samples were used as model feedstock to study the properties of catalytic fast pyrolysis oils. The influence of two commercial zeolite catalysts (BASF and SudChem) and pretreatment of the pine wood with sodium hydroxide on pyrolysis products were investigated. The pyrolysis oils were first fractionated using column chromatography and characterized using GC-MS. Long chain aliphatic hydrocarbons, levoglucosan, aldehydes and ketones, guaiacols/syringols, and benzenediols were the major compounds identified in the pyrolysis oils. The catalytic pyrolysis increased the polycyclic hydrocarbons fraction. Significant decreases in phthalate derivatives using SudChem and long chain aliphatics using BASF catalyst were observed. Significant amountsmore » of aromatic heterocyclic hydrocarbons and benzene derivatives were formed, respectively, using BASF and SudChem catalysts. Guaiacyl/syringyl and benzenediols derivatives were partly suppressed by the zeolite catalysts, while the sodium hydroxide treatment enriched phenolic derivatives. Zeolite catalyst and sodium hydroxide were employed together; they showed different results for each catalyst.« less

  16. Methods and kits for nucleic acid analysis using fluorescence resonance energy transfer

    DOE Patents [OSTI]

    Kwok, Pui-Yan; Chen, Xiangning

    1999-01-01

    A method for detecting the presence of a target nucleotide or sequence of nucleotides in a nucleic acid is disclosed. The method is comprised of forming an oligonucleotide labeled with two fluorophores on the nucleic acid target site. The doubly labeled oligonucleotide is formed by addition of a singly labeled dideoxynucleoside triphosphate to a singly labeled polynucleotide or by ligation of two singly labeled polynucleotides. Detection of fluorescence resonance energy transfer upon denaturation indicates the presence of the target. Kits are also provided. The method is particularly applicable to genotyping.

  17. Neutronics and safety characteristics of a 100% MOX fueled PWR using weapons grade plutonium

    SciTech Connect (OSTI)

    Biswas, D.; Rathbun, R.; Lee, Si Young; Rosenthal, P.

    1993-12-31

    Preliminary neutronics and safety studies, pertaining to the feasibility of using 100% weapons grade mixed-oxide (MOX) fuel in an advanced PWR Westinghouse design are presented in this paper. The preliminary results include information on boron concentration, power distribution, reactivity coefficients and xenon and control rode worth for the initial and the equilibrium cycle. Important safety issues related to rod ejection and steam line break accidents and shutdown margin requirements are also discussed. No significant change from the commercial design is needed to denature weapons-grade plutonium under the current safety and licensing criteria.

  18. Nanoscale topographical replication of graphene architecture by artificial DNA nanostructures

    SciTech Connect (OSTI)

    Moon, Y.; Seo, S.; Park, J.; Park, T.; Ahn, J. R., E-mail: jrahn@skku.edu [Department of Physics, Sungkyunkwan University, Suwon 440-746 (Korea, Republic of); Shin, J.; Dugasani, S. R. [Sungkyunkwan Advanced Institute of Nanotechnology (SAINT), Sungkyunkwan University, Suwon 440-746 (Korea, Republic of); Woo, S. H. [College of Pharmacy, Chungnam National University, Daejeon 305-764 (Korea, Republic of); Park, S. H., E-mail: sunghapark@skku.edu [Department of Physics, Sungkyunkwan University, Suwon 440-746 (Korea, Republic of); Sungkyunkwan Advanced Institute of Nanotechnology (SAINT), Sungkyunkwan University, Suwon 440-746 (Korea, Republic of)

    2014-06-09

    Despite many studies on how geometry can be used to control the electronic properties of graphene, certain limitations to fabrication of designed graphene nanostructures exist. Here, we demonstrate controlled topographical replication of graphene by artificial deoxyribonucleic acid (DNA) nanostructures. Owing to the high degree of geometrical freedom of DNA nanostructures, we controlled the nanoscale topography of graphene. The topography of graphene replicated from DNA nanostructures showed enhanced thermal stability and revealed an interesting negative temperature coefficient of sheet resistivity when underlying DNA nanostructures were denatured at high temperatures.

  19. Chip-based sequencing nucleic acids

    DOE Patents [OSTI]

    Beer, Neil Reginald

    2014-08-26

    A system for fast DNA sequencing by amplification of genetic material within microreactors, denaturing, demulsifying, and then sequencing the material, while retaining it in a PCR/sequencing zone by a magnetic field. One embodiment includes sequencing nucleic acids on a microchip that includes a microchannel flow channel in the microchip. The nucleic acids are isolated and hybridized to magnetic nanoparticles or to magnetic polystyrene-coated beads. Microreactor droplets are formed in the microchannel flow channel. The microreactor droplets containing the nucleic acids and the magnetic nanoparticles are retained in a magnetic trap in the microchannel flow channel and sequenced.

  20. Highly thermostable fluorescent proteins

    DOE Patents [OSTI]

    Bradbury, Andrew M.; Waldo, Geoffrey S.; Kiss, Csaba

    2011-03-22

    Thermostable fluorescent proteins (TSFPs), methods for generating these and other stability-enhanced proteins, polynucleotides encoding such proteins, and assays and method for using the TSFPs and TSFP-encoding nucleic acid molecules are provided. The TSFPs of the invention show extremely enhanced levels of stability and thermotolerance. In one case, for example, a TSFP of the invention is so stable it can be heated to 99.degree. C. for short periods of time without denaturing, and retains 85% of its fluorescence when heated to 80.degree. C. for several minutes. The invention also provides a method for generating stability-enhanced variants of a protein, including but not limited to fluorescent proteins.

  1. Highly thermostable fluorescent proteins

    DOE Patents [OSTI]

    Bradbury, Andrew M.; Waldo, Geoffrey S.; Kiss, Csaba

    2011-11-29

    Thermostable fluorescent proteins (TSFPs), methods for generating these and other stability-enhanced proteins, polynucleotides encoding such proteins, and assays and method for using the TSFPs and TSFP-encoding nucleic acid molecules are provided. The TSFPs of the invention show extremely enhanced levels of stability and thermotolerance. In one case, for example, a TSFP of the invention is so stable it can be heated to 99.degree. C. for short periods of time without denaturing, and retains 85% of its fluorescence when heated to 80.degree. C. for several minutes. The invention also provides a method for generating stability-enhanced variants of a protein, including but not limited to fluorescent proteins.

  2. Highly thermostable fluorescent proteins

    DOE Patents [OSTI]

    Bradbury, Andrew M.; Waldo, Geoffrey S.; Kiss, Csaba

    2012-05-01

    Thermostable fluorescent proteins (TSFPs), methods for generating these and other stability-enhanced proteins, polynucleotides encoding such proteins, and assays and method for using the TSFPs and TSFP-encoding nucleic acid molecules are provided. The TSFPs of the invention show extremely enhanced levels of stability and thermotolerance. In one case, for example, a TSFP of the invention is so stable it can be heated to 99.degree. C. for short periods of time without denaturing, and retains 85% of its fluorescence when heated to 80.degree. C. for several minutes. The invention also provides a method for generating stability-enhanced variants of a protein, including but not limited to fluorescent proteins.

  3. Functional Stability of a Mixed Microbial Consortium Producing PHA From Waste Carbon Sources

    SciTech Connect (OSTI)

    David N. Thompson; Erik R. Coats; William A. Smith; Frank J. Loge; Michael P. Wolcott

    2006-04-01

    Polyhydroxyalkanoates (PHAs) represent an environmentally-effective alternative to synthetic thermoplastics; however, current production practices are not sustainable. In this study, PHA production was accomplished in sequencing batch bioreactors utilizing real wastewaters and mixed microbial consortia from municipal activated sludge as inoculum. Polymer production reached 85%, 53%, and 10% of the cell dry weight from methanol-enriched pulp-and-paper mill foul condensate, fermented municipal primary solids, and biodiesel wastewater, respectively. Employing denaturing gradient gel electrophoresis of 16S-rDNA from PCR-amplified DNA extracts, distinctly different communities were observed between and within wastewaters following enrichment. Most importantly, functional stability was maintained despite differing and contrasting microbial populations.

  4. Integrated multiplexed capillary electrophoresis system

    DOE Patents [OSTI]

    Yeung, Edward S.; Tan, Hongdong

    2002-05-14

    The present invention provides an integrated multiplexed capillary electrophoresis system for the analysis of sample analytes. The system integrates and automates multiple components, such as chromatographic columns and separation capillaries, and further provides a detector for the detection of analytes eluting from the separation capillaries. The system employs multiplexed freeze/thaw valves to manage fluid flow and sample movement. The system is computer controlled and is capable of processing samples through reaction, purification, denaturation, pre-concentration, injection, separation and detection in parallel fashion. Methods employing the system of the invention are also provided.

  5. Ethanol fuel modification for highway vehicle use. Final report

    SciTech Connect (OSTI)

    Not Available

    1980-01-01

    A number of problems that might occur if ethanol were used as a blending stock or replacement for gasoline in present cars are identified and characterized as to the probability of occurrence. The severity of their consequences is contrasted to those found with methanol in a previous contract study. Possibilities for correcting several problems are reported. Some problems are responsive to fuel modifications but others require or are better dealt with by modification of vehicles and the bulk fuel distribution system. In general, problems with ethanol in blends with gasoline were found to be less severe than those with methanol. Phase separation on exposure to water appears to be the major problem with ethanol/gasoline blends. Another potentially serious problem with blends is the illict recovery of ethanol for beverage usage, or bootlegging, which might be discouraged by the use of select denaturants. Ethanol blends have somewhat greater tendency to vapor lock than base gasoline but less than methanol blends. Gasoline engines would require modification to operate on fuels consisting mostly of ethanol. If such modifications were made, cold starting would still be a major problem, more difficult with ethanol than methanol. Startability can be provided by adding gasoline or light hydrocarbons. Addition of gasoline also reduces the explosibility of ethanol vapor and furthermore acts as denaturant.

  6. Relationship between ?-relaxation and structural stability of lysozyme: Microscopic insight on thermostabilization mechanism by trehalose from Raman spectroscopy experiments

    SciTech Connect (OSTI)

    Hdoux, Alain Paccou, Laurent; Guinet, Yannick

    2014-06-14

    Raman investigations were carried out in the low-frequency and amide I regions on lysozyme aqueous solutions in absence and presence of trehalose. Raman spectroscopy gives the unique opportunity to analyze the protein and solvent dynamics in the low-frequency range while monitoring the unfolding process by capturing the spectrum of the amide I band. From the analysis of the quasielastic intensity, a dynamic change is firstly observed in a highly hydrated protein, around 70?C, and interpreted in relation with the denaturation mechanism of the protein. The use of heavy water and partly deuterated trehalose gives clear information on proteintrehalose interactions in the native state of lysozyme (at room temperature) and during the thermal denaturation process of lysozyme. At room temperature, it was found that trehalose is preferentially excluded from the protein surface, and has a main effect on the tetrahedral local order of water molecules corresponding to a stiffening of the H-bond network in the solvent. The consequence is a significant reduction of the amplitude of fast relaxational motions, inducing a less marked dynamic transition shifted toward the high temperatures. Upon heating, interaction between trehalose and lysozyme is detected during the solvent penetration within the protein, i.e., while the native globular state softens into a molten globule (MG) state. Addition of trehalose reduces the protein flexibility in the MG state, improving the structural stability of the protein, and inhibiting the protein aggregation.

  7. Railroad accident report: Head-on collision between Iowa Interstate Railroad Extra 470 West and Extra 406 East with release of hazardous materials near Altoona, Iowa, on July 30, 1988. Irregular report

    SciTech Connect (OSTI)

    Not Available

    1989-07-06

    About 11:40 a.m. central daylight saving time on July 30, 1988, Iowa Interstate Railroad Ltd. (IAIS) freight trains Extra 470 West and Extra 406 East collided head on within the yard limits of Altoona, Iowa, about 10 miles east of Des Moines, Iowa. All 5 locomotive units from both trains; 11 cars of Extra 406 East; and 3 cars, including two tank cars containing denatured alcohol, of Extra 470 West derailed. The denatured alcohol, which was released through the pressure relief valves and the manway domes of the two derailed tank cars, was ignited by the fire resulting from the collision of the locomotives. Both crew members of Extra 470 West were fatally injured; the two crew members of Extra 406 East were only slightly injured. The estimated damage (including lading) as a result of this accident exceeded $1 million. The major safety issues in the accident include operational methods employed by the IAIS, training and selection of train and engine personnel, supervisory oversight by the IAIS, design of closure fittings on hazardous materials rail tanks, and oversight of regional railroads by the Federal Railroad Administration.

  8. Determining orientation and direction of DNA sequences

    DOE Patents [OSTI]

    Goodwin, Edwin H.; Meyne, Julianne

    2000-01-01

    Determining orientation and direction of DNA sequences. A method by which fluorescence in situ hybridization can be made strand specific is described. Cell cultures are grown in a medium containing a halogenated nucleotide. The analog is partially incorporated in one DNA strand of each chromatid. This substitution takes place in opposite strands of the two sister chromatids. After staining with the fluorescent DNA-binding dye Hoechst 33258, cells are exposed to long-wavelength ultraviolet light which results in numerous strand nicks. These nicks enable the substituted strand to be denatured and solubilized by heat, treatment with high or low pH aqueous solutions, or by immersing the strands in 2.times.SSC (0.3M NaCl+0.03M sodium citrate), to name three procedures. It is unnecessary to enzymatically digest the strands using Exo III or another exonuclease in order to excise and solubilize nucleotides starting at the sites of the nicks. The denaturing/solubilizing process removes most of the substituted strand while leaving the prereplication strand largely intact. Hybridization of a single-stranded probe of a tandem repeat arranged in a head-to-tail orientation will result in hybridization only to the chromatid with the complementary strand present.

  9. Molecular Siganture and Sources of Biochemical Recalcitrance of Organic C in Amozonian Dark Earths

    SciTech Connect (OSTI)

    Solomon,D.; Lehmann, J.; Thies, J.; Schafer, T.; Liang, B.; Kinyangi, J.; Neves, E.; Peterson, J.; Liuzao, F.; Skjemstad, J.

    2007-01-01

    Amazonian Dark Earths (ADE) are a unique type of soils developed through intense anthropogenic activities that transformed the original soils into Anthrosols throughout the Brazilian Amazon Basin. We conducted a comparative molecular-level investigation of soil organic C (SOC) speciation in ADE (ages between 600 and 8700 years B.P.) and adjacent soils using ultraviolet photo-oxidation coupled with {sup 13}C cross polarization-magic angle spinning nuclear magnetic resonance (CP-MAS NMR), synchrotron-based Fourier transform infrared-attenuated total reflectance (Sr-FTIR-ATR) and C (1s) near edge X-ray absorption fine structure (NEXAFS) spectroscopy to obtain deeper insights into the structural chemistry and sources of refractory organic C compounds in ADE. Our results show that the functional group chemistry of SOC in ADE was considerably different from adjacent soils. The SOC in ADE was enriched with: (i) aromatic-C structures mostly from H- and C-substituted aryl-C, (ii) O-rich organic C forms from carboxylic-C, aldehyde-C, ketonic-C and quinine-C, and (iii) diverse group of refractory aliphatic-C moieties. The SOC in adjacent soils was predominantly composed of O-alkyl-C and methoxyl-C/N-alkyl-C structures and elements of labile aliphatic-C functionalities. Our study suggests that the inherent molecular structures of organic C due to selective accumulation of highly refractory aryl-C structures seems to be the key factor for the biochemical recalcitrance and stability of SOC in ADE. Anthropogenic enrichment with charred carbonaceous residues from biomass-derived black C (BC) is presumed to be the precursor of these recalcitrant polyaromatic structures. Our results also highlight the complementary role that might be played by organic C compounds composed of O-containing organic C moieties and aliphatic-C structures that persisted for millennia in these anthropic soils as additional or secondary sources of chemical recalcitrance of SOC in ADE. These organic C compounds could be the products of: (i) primary recalcitrant biomolecules from non-BC sources or (ii) secondary processes involving microbial mediated oxidative or extracellular neoformation reactions of SOC from BC and non-BC sources; and stabilized through physical inaccessibility to decomposers due to sorption onto the surface or into porous structures of BC particles, selective preservation or through intermolecular interactions involving clay and BC particles.

  10. Nonhazardous solvent composition and method for cleaning metal surfaces

    DOE Patents [OSTI]

    Googin, John M.; Simandl, Ronald F.; Thompson, Lisa M.

    1993-01-01

    A solvent composition for displacing greasy and oily contaminants as well as water and/or aqueous residue from metallic surfaces, especially surfaces of radioactive materials so that such surfaces can be wiped clean of the displaced contaminants, water and/or aqueous residue. The solvent composition consists essentially of a blend of nonpolar aliphatic hydrocarbon solvent having a minimum flash point of about 140.degree. F. and 2 to 25 volume percent of a polar solvent having a flash point sufficiently high so as to provide the solvent composition with a minimum flash point of at least 140.degree. F. The solvent composition is nonhazardous so that when it is used to clean the surfaces of radioactive materials the waste in the form of paper or cloth wipes, lab coats and the like used in the cleaning operation is not considered to be mixed waste composed of a hazardous solvent and a radioactive material.

  11. Nonhazardous solvent composition and method for cleaning metal surfaces

    DOE Patents [OSTI]

    Googin, J.M.; Simandl, R.F.; Thompson, L.M.

    1993-05-04

    A solvent composition for displacing greasy and oily contaminants as well as water and/or aqueous residue from metallic surfaces, especially surfaces of radioactive materials so that such surfaces can be wiped clean of the displaced contaminants, water and/or aqueous residue. The solvent composition consists essentially of a blend of nonpolar aliphatic hydrocarbon solvent having a minimum flash point of about 140 F and 2 to 25 volume percent of a polar solvent having a flash point sufficiently high so as to provide the solvent composition with a minimum flash point of at least 140 F. The solvent composition is nonhazardous so that when it is used to clean the surfaces of radioactive materials the waste in the form of paper or cloth wipes, lab coats and the like used in the cleaning operation is not considered to be mixed waste composed of a hazardous solvent and a radioactive material.

  12. Interactions between silver nanoparticles and polyvinyl alcohol nanofibers

    SciTech Connect (OSTI)

    Chou, H. L.; Wu, C. M.; Lin, F. D.; Rick, J.

    2014-08-15

    The interaction of polyvinylalcohol (PVA) nanofibers with silver (Ag) nanoparticles (mean diameter 8nm) has been modeled using density functional theory (DFT) calculations. The physical adsorption of PVA through the hydroxyl group, to the Ag, and its corresponding molecular orientation was compared with experimental results obtained from surface-enhanced Raman scattering (SERS) studies of the same material. A good agreement was found between the computational model of the vibrational spectrum of the adsorbate and the experimentally observed SERS. In general, aliphatic capping molecules are used to passivate the surface of Ag{sub 55} nanocrystals (55 = atomic number of Ag). In this study, a DFT simulation was employed to show binding energies and electron contour map analyses of Ag{sub 55} with PVA. Here we show that the PVA interacts with the Ag nanoparticle's surface, through the OH group, thereby contributing significantly to the increase in SERS activity.

  13. Water soluble laser dyes

    DOE Patents [OSTI]

    Hammond, P.R.; Feeman, J.F.; Field, G.F.

    1998-08-11

    Novel water soluble dyes of the formula 1 are provided by the formula described in the paper wherein R{sup 1} and R{sup 4} are alkyl of 1 to 4 carbon atoms or hydrogen; or R{sup 1}--R{sup 2} or R{sup 2}--R{sup 4} form part of aliphatic heterocyclic rings; R{sup 2} is hydrogen or joined with R{sup 1} or R{sup 4} as described above; R{sup 3} is --(CH{sub 2}){sub m}--SO{sub 3}{sup {minus}}, where m is 1 to 6; X is N, CH or formula 2 given in paper where Y is 2 --SO{sub 3}{sup {minus}} ; Z is 3, 4, 5 or 6 --SO{sub 3}{sup {minus}}. The novel dyes are particularly useful as the active media in water solution dye lasers.

  14. Urethane-based stabilizers for radiation-crosslinked polyethylene. [Electron beams

    SciTech Connect (OSTI)

    Shkolnik, S.; Rajbenbach, L.A.

    1982-11-01

    Unsaturated urethane-based stabilizers for use in radiation-crosslinked polyethylene were synthesized. Aromatic amine moieties were attached to allylic and acrylic monomers by means of aromatic or aliphatic diisocyanates. The synthesized stabilizers were incorporated in high-density polyethylene films which were subjected to electron beam irradiation. The oxidative stability of the films prior to and after extraction was determined by DTA in the temperature range 185-210/sup 0/C and compared with samples treated with commercial amine-bearing antioxidants. Tensile strength and gel content were also determined. Best results were obtained with a stabilizer prepared from equimolecular amounts of allyl alcohol, tolylene-2,4-diisocyanate and N-phenyl-1,4-phenylenediamine. Estimated lifetimes at 70/sup 0/C of stabilized irradiated polyethylene samples were calculated.

  15. Protein Vivisection Reveals Elusive Intermediates in Folding

    SciTech Connect (OSTI)

    Zheng, Zhongzhou; Sosnick, Tobin R. (UC)

    2010-05-25

    Although most folding intermediates escape detection, their characterization is crucial to the elucidation of folding mechanisms. Here, we outline a powerful strategy to populate partially unfolded intermediates: A buried aliphatic residue is substituted with a charged residue (e.g., Leu {yields} Glu{sup -}) to destabilize and unfold a specific region of the protein. We applied this strategy to ubiquitin, reversibly trapping a folding intermediate in which the {beta}5-strand is unfolded. The intermediate refolds to a native-like structure upon charge neutralization under mildly acidic conditions. Characterization of the trapped intermediate using NMR and hydrogen exchange methods identifies a second folding intermediate and reveals the order and free energies of the two major folding events on the native side of the rate-limiting step. This general strategy may be combined with other methods and have broad applications in the study of protein folding and other reactions that require trapping of high-energy states.

  16. Method and apparatus for synthesizing hydrocarbons

    DOE Patents [OSTI]

    Colmenares, C.A.; Somorjai, G.A.; Maj, J.J.

    1985-04-16

    A method and apparatus for synthesizing a mixture of aliphatic alcohols having five carbons or less is disclosed. An equal molar ratio of CO and H/sub 2/ gases is caused to pass through a ThO/sub 2/ catalyst having a surface area of about 80 to 125 m/sup 2//g. The catalyst further optionally includes Na ions present as substitutional cations in an amount of about 5 to 10 atom %. At a temperature of about 570 to 630/sup 0/K, and at pressures of about 20 to 50 atm, methanol and isobutanol are the predominant products and are produced in amounts of about 90 wt % of the total hydrocarbon mixture. 6 figs.

  17. Field Sampling Plan for the Distler Brickyard Superfund Site, Hardin County, Kentucky

    SciTech Connect (OSTI)

    J. P. Martin; L. N. Peterson; C. J. Taylor

    1999-08-01

    This plan describes the field and analytical activities to be conducted at the Distler Brickyard Superfund Site, Hardin County, Kentucky, in order to evaluate natural attenuation processes within the aquifer system. Sampling will consist of a single round to take place in October 1999. Analytes will consist of the contaminants of concern (chlorinated aliphatic hydrocarbons), electron donors (non-chlorinated organic compounds), oxidation-reduction indicators, and water quality parameters. These activities are conducted in order to evaluate the water quality parameters. These activities are conducted in order to evaluate the extent to which natural attenuation processes, in the form of anaerobic reductive dechlorination, may be taking place in the aquifer system. These data will then be used to select the appropriate remediation technology for this site.

  18. Azacoumarin dye lasers

    DOE Patents [OSTI]

    Hammond, Peter R.; Atkins, Ronald L.; Henry, Ronald A.; Fletcher, Aaron N.

    1978-01-01

    A dye laser comprising a laser dye solution of a compound having the general structure: ##STR1## wherein at least one of the 5, 6 and 8 ring positions is occupied by a nitrogen atom in lieu of the corresponding CR group and X is OH, alkoxy, or amino including amino substituted by at least one of the following: alkyl, aryl, acyl, aracyl, a group which taken together with the nitrogen atom of the amino group forms a heterocyclic ring, or part of one or two 5 or 6 membered aliphatic heterocyclic rings attached to ring A at positions 6 or 8 or both depending on where the N in ring A is located. R.sub.3, R.sub.4, R.sub.5, R.sub.6 and R.sub.8 are hydrogen or other groups as defined below. The compounds lase in the blue-green to near ultraviolet region.

  19. Azaquinolone dye lasers

    DOE Patents [OSTI]

    Hammond, Peter R.; Atkins, Ronald L.; Henry, Ronald A.; Fletcher, Aaron N.

    1978-01-01

    A dye laser comprising a laser dye solution of a compound having the general structure: ##STR1## wherein at least one of the 5, 6 and 8 ring positions is occupied by a nitrogen atom in lieu of the corresponding CR group and X is OH, alkoxy, or amino including amino substituted by at least one of the following: alkyl, aryl, acyl, aracyl, a group which taken together with the nitrogen atom of the amino group forms a heterocyclic ring, or part of one or two 5 or 6 membered aliphatic heterocyclic rings attached to ring A at positions 6 or 8 or both depending on where the N in ring A is located. R.sub.1, R.sub.3, R.sub.4, R.sub.5, R.sub.6 and R.sub.8 are hydrogen or other groups as defined below. The compounds lase in the blue to near ultraviolet region.

  20. Method and composition for testing for the presence of an alkali metal

    DOE Patents [OSTI]

    Guon, Jerold

    1981-01-01

    A method and composition for detecting the presence of an alkali metal on the surface of a body such as a metal plate, tank, pipe or the like is provided. The method comprises contacting the surface with a thin film of a liquid composition comprising a light-colored pigment, an acid-base indicator, and a nonionic wetting agent dispersed in a liquid carrier comprising a minor amount of water and a major amount of an organic solvent selected from the group consisting of the lower aliphatic alcohols, ketones and ethers. Any alkali metal present on the surface in elemental form or as an alkali metal hydroxide or alkali metal carbonate will react with the acid-base indicator to produce a contrasting color change in the thin film, which is readily discernible by visual observation or automatic techniques.

  1. Substantially isotactic, linear, alternating copolymers of carbon monoxide and an olefin

    DOE Patents [OSTI]

    Sen, A.; Jiang, Z.

    1996-05-28

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

  2. FERRATES: SYNTHESIS, PROPERTIES AND APPLICATIONS IN WATER AND WASTEWATER TREATMENT.

    SciTech Connect (OSTI)

    CABELLI, D.E.; SHARMA, V.K.

    2006-05-19

    The higher oxidation states of iron (Fe(VI) and Fe(V) in particular) have been shown to be strongly oxidizing in enzymatic systems, where they can carry out aliphatic hydrogen abstraction. In addition, they have been postulated as intermediates in Fenton-type systems. Fe(VI) itself is relatively stable and has been shown to have potential as an oxidant in the so-called ''green'' treatment of polluted waters. By contrast, Fe(V) is a relatively short-lived transient when produced in aqueous solution in the absence of strongly bonding ligands other than hydroxide, a feature that has limited studies of its reactivity. Fe(VI) has been proposed to be useful in battery design and a very interesting study suggested that ferrate may be able to oxidize insoluble chromium to chromate and thus serve to remove chromium contamination in the Hanford radioactive waste tanks.

  3. Substantially isotactic, linear, alternating copolymers of carbon monoxide and an olefin

    DOE Patents [OSTI]

    Sen, Ayusman; Jiang, Zhaozhong

    1996-01-01

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

  4. N,N'-DICYCLOHEXYL-N"-ISOTRIDECYLGUANIDINE AS SUPPRESSOR FOR THE NEXT GENERATION CAUSTIC SIDE SOLVENT EXTRACTION (NG-CSSX) PROCESS

    SciTech Connect (OSTI)

    Duncan, Nathan C; Roach, Benjamin D; Williams, Neil J; Bonnesen, Peter V; Rajbanshi, Arbin; Moyer, Bruce A

    2012-01-01

    ABSTRACT The purity, concentration, and source of the N,N'-dicyclohexyl-N"-isotridecylguanidine (DCiTG) suppressor (guanidine) used in the NG-CSSX process were found to influence solvent performance. As the starting isotridecanol used in the preparation of DCiTG is comprised of a mixture of branched-chain aliphatic alcohols, varying in composition with manufacturer, the resulting DCiTG itself is a mixture. Thus, it is necessary to address how the solvent performance will be affected by the different preparations of the DCiTG solvent component. In this study, four preparations of DCiTG from three sources were analyzed and evaluated for purity and performance, both in the absence and presence of an anionic surfactant impurity.

  5. Clean, premium-quality chars: Demineralized and carbon enriched. [Quarterly] technical report, March 1, 1993--May 31, 1993

    SciTech Connect (OSTI)

    Smith, G.V.; Malhotra, V.M.; Wiltowski, T.; Myszka, E.

    1993-09-01

    The overall objective of this two-year project is to evaluate methods of preparing demineralized and carbon enriched chars from Illinois Basin coals. There are two processing steps: physical cleaning of the coal and devolatilization under different environments to form chars. Two differents techniques were used, in-situ Diffuse Reflectance FTIR measurements and BTU measurements. Experiments were performed with coals IBC-101, 102, and 104 as received and after cleaning. DR-FTIR spectrums helped to explain the possible existing chemical bonds in the coal structure as well as their changes during drying and mild pyrolysis. Drying coal causes hydrogen bonds between water and coal to be broken. Liquids produced above 500{degrees}C are much higher in aromatic content, thus, effectively reducing the concentration of aliphatic groups in the overall liquid yield. BTU values of coals after methane treatment are higher than after helium treatment.

  6. Reduction of Aromatic Hydrocarbons by Zero-Valent Iron and Palladium Catalyst

    SciTech Connect (OSTI)

    Kim, Young-Hun; Shin, Won Sik; Ko, Seok-Oh; Kim, Myung-Chul

    2004-03-31

    Permeable reactive barrier (PRB) is an alternative technology for soil and groundwater remediation. Zero valent iron, which is the most popular PRB material, is only applicable to halogenated aliphatic organics and some heavy metals. The objective of this study was to investigate reductive dechlorination of halogenated compounds and reduction of non-halogenated aromatic hydrocarbons using zero valent metals (ZVMs) and catalysts as reactive materials for PRBs. A group of small aromatic hydrocarbons such as monochlorophenols, phenol and benzene were readily reduced with palladium catalyst and zero valent iron. Poly-aromatic hydrocarbons (PAHs) were also tested with the catalysts and zero valent metal combinations. The aromatic rings were reduced and partly reduced PAHs were found as the daughter compounds. The current study demonstrates reduction of aromatic compounds by ZVMs and modified catalysts and implicates that PRB is applicable not only for halogenated organic compounds but nonhalogenated aromatic compounds such as PAHs.

  7. Water soluble laser dyes

    DOE Patents [OSTI]

    Hammond, Peter R.; Feeman, James F.; Field, George F.

    1998-01-01

    Novel water soluble dyes of the formula I are provided ##STR1## wherein R.sup.1 and R.sup.4 are alkyl of 1 to 4 carbon atoms or hydrogen; or R.sup.1 -R.sup.2 or R.sup.2 -R.sup.4 form part of aliphatic heterocyclic rings; R.sup.2 is hydrogen or joined with R.sup.1 or R.sup.4 as described above; R.sup.3 is --(CH.sub.2).sub.m --SO.sub.3.sup.-, where m is 1 to 6; X is N, CH or ##STR2## where Y is 2 --SO.sub.3.sup.- ; Z is 3, 4, 5 or 6 --SO.sub.3.sup.-. The novel dyes are particularly useful as the active media in water solution dye lasers.

  8. Reactor and method for hydrocracking carbonaceous material

    DOE Patents [OSTI]

    Duncan, Dennis A.; Beeson, Justin L.; Oberle, R. Donald; Dirksen, Henry A.

    1980-01-01

    Solid, carbonaceous material is cracked in the presence of hydrogen or other reducing gas to provide aliphatic and aromatic hydrocarbons of lower molecular weight for gaseous and liquid fuels. The carbonaceous material, such as coal, is entrained as finely divided particles in a flow of reducing gas and preheated to near the decomposition temperature of the high molecular weight polymers. Within the reactor, small quantities of oxygen containing gas are injected at a plurality of discrete points to burn corresponding amounts of the hydrogen or other fuel and elevate the mixture to high temperatures sufficient to decompose the high molecular weight, carbonaceous solids. Turbulent mixing at each injection point rapidly quenches the material to a more moderate bulk temperature. Additional quenching after the final injection point can be performed by direct contact with quench gas or oil. The reactions are carried out in the presence of a hydrogen-containing reducing gas at moderate to high pressure which stabilizes the products.

  9. Chemical changes to nonagrregtaed particulate soil organic matter following grassland-to woodland transition ina subtropical savanna.

    SciTech Connect (OSTI)

    Filley, T. R.; Boutton, T. W.; Liao, J. D.; Jastrow, J. D.; Gamblin, D. E.; Biosciences Division; Purdue Univ.; Texas A&M

    2008-07-19

    Encroachment of thorn woodlands into grasslands of southern Texas has resulted in greater aboveground and belowground biomass and greater soil organic carbon (SOC) stocks. Our previous studies showed that a large percentage of the SOC accrued under invading woody clusters was not stabilized within protective soil aggregates or on mineral-surfaces. Here we evaluated lignin and cutin- and suberin-derived substituted fatty acid (SFA) chemistry to determine if the accrual of nonaggregated particulate organic matter (POM) in woodlands was promoted by inherently greater recalcitrance of tissues from woody versus grass species, and if there was selective input of aboveground versus belowground plant carbon to POM. Woody clusters exhibited reduced concentrations of cutin-derived SFA and cinnamyl phenols within surface litter compared to fresh aboveground plant material. However, root litter exhibited relatively minor changes in biopolymer chemistry compared to fresh root tissue, suggesting it was either more stable or was refreshed at a greater rate. Between 14 and 105 years of woody plant encroachment, SFA in free POM fractions appeared to be consistently derived from root material while SFA within intraaggregate POM were increasingly derived from cutin sources. In addition, the shift from herbaceous to woody input was accompanied by enrichment in the amount of cutin and suberin-derived aliphatics with respect to lignin in both root and surface litter as well as nonaggregated POM. Woody plant encroachment at this site results in the rapid accrual of POM pools that are biochemically recalcitrant, providing a mechanism by which soil organic carbon can accumulate in this sandy soil system. Our results also lend further credence to the hypothesis that aliphatic biopolymers, particularly root-derived suberin, are important components of long-term soil organic carbon stabilization.

  10. 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.

  11. Metagenomics, metatranscriptomics and single cell genomics reveal functional response of active Oceanospirillales to Gulf oil spill

    SciTech Connect (OSTI)

    Mason, Olivia U.; Hazen, Terry C.; Borglin, Sharon; Chain, Patrick S. G.; Dubinsky, Eric A.; Fortney, Julian L.; Han, James; Holman, Hoi-Ying N.; Hultman, Jenni; Lamendella, Regina; Mackelprang, Rachel; Malfatti, Stephanie; Tom, Lauren M.; Tringe, Susannah G.; Woyke, Tanja; Zhou, Jizhong; Rubin, Edward M.; Jansson, Janet K.

    2012-06-12

    The Deepwater Horizon oil spill in the Gulf of Mexico resulted in a deep-sea hydrocarbon plume that caused a shift in the indigenous microbial community composition with unknown ecological consequences. Early in the spill history, a bloom of uncultured, thus uncharacterized, members of the Oceanospirillales was previously detected, but their role in oil disposition was unknown. Here our aim was to determine the functional role of the Oceanospirillales and other active members of the indigenous microbial community using deep sequencing of community DNA and RNA, as well as single-cell genomics. Shotgun metagenomic and metatranscriptomic sequencing revealed that genes for motility, chemotaxis and aliphatic hydrocarbon degradation were significantly enriched and expressed in the hydrocarbon plume samples compared with uncontaminated seawater collected from plume depth. In contrast, although genes coding for degradation of more recalcitrant compounds, such as benzene, toluene, ethylbenzene, total xylenes and polycyclic aromatic hydrocarbons, were identified in the metagenomes, they were expressed at low levels, or not at all based on analysis of the metatranscriptomes. Isolation and sequencing of two Oceanospirillales single cells revealed that both cells possessed genes coding for n-alkane and cycloalkane degradation. Specifically, the near-complete pathway for cyclohexane oxidation in the Oceanospirillales single cells was elucidated and supported by both metagenome and metatranscriptome data. The draft genome also included genes for chemotaxis, motility and nutrient acquisition strategies that were also identified in the metagenomes and metatranscriptomes. These data point towards a rapid response of members of the Oceanospirillales to aliphatic hydrocarbons in the deep sea.

  12. Flow cytometric measurement of total DNA and incorporated halodeoxyuridine

    DOE Patents [OSTI]

    Dolbeare, F.A.; Gray, J.W.

    1983-10-18

    A method for the simultaneous flow cylometric measurement of total cellular DNA content and of the uptake of DNA precursors as a measure of DNA synthesis during various phases of the cell cycle in normal and malignant cells in vitro and in vivo is described. The method comprises reacting cells with labelled halodeoxyuridine (HdU), partially denaturing cellular DNA, adding to the reaction medium monoclonal antibodies (mabs) reactive with HdU, reacting the bound mabs with a second labelled antibody, incubating the mixture with a DNA stain, and measuring simultaneously the intensity of the DNA stain as a measure of the total cellular DNA and the HdU incorporated as a measure of DNA synthesis. (ACR)

  13. Putting the Squeeze on Biology: Biomolecules Under Pressure

    ScienceCinema (OSTI)

    Sol Gruner

    2010-01-08

    Modest pressures encountered in the biosphere (i.e., below a few kbar) have extraordinary effects on biomembranes and proteins. These include pressure denaturation of proteins, dramatic changes in protein-protein association, substrate binding, membrane ion transport, DNA transcription, virus infectivity, and enzyme kinetics. Yet all of the biomaterials involved are highly incompressible. The challenge to the physicist is to understand the structural coupling between these effects and pressure to elucidate the relevant mechanisms. X-ray diffraction studies of membranes and proteins under pressure will be described. It is seen that it is not so much the magnitude of the changes, but rather the differential compressibilities of different parts of the structure that are responsible for effects.

  14. Tower reactors for bioconversion of lignocellulosic material

    DOE Patents [OSTI]

    Nguyen, Quang A.

    1998-01-01

    An apparatus for enzymatic hydrolysis and fermentation of pretreated lignocellulosic material, in the form of a tower bioreactor, having mixers to achieve intermittent mixing of the material. Precise mixing of the material is important for effective heat and mass transfer requirements without damaging or denaturing the enzymes or fermenting microorganisms. The pretreated material, generally in the form of a slurry, is pumped through the bioreactor, either upwards of downwards, and is mixed periodically as it passes through the mixing zones where the mixers are located. For a thin slurry, alternate mixing can be achieved by a pumping loop which also serves as a heat transfer device. Additional heat transfer takes place through the reactor heat transfer jackets.

  15. Tower reactors for bioconversion of lignocellulosic material

    DOE Patents [OSTI]

    Nguyen, Quang A.

    1999-01-01

    An apparatus for enzymatic hydrolysis and fermentation of pretreated lignocellulosic material, in the form of a tower bioreactor, having mixers to achieve intermittent mixing of the material. Precise mixing of the material is important for effective heat and mass transfer requirements without damaging or denaturing the enzymes or fermenting microorganisms. The pretreated material, generally in the form of a slurry, is pumped through the bioreactor, either upwards or downwards, and is mixed periodically as it passes through the mixing zones where the mixers are located. For a thin slurry, alternate mixing can be achieved by a pumping loop which also serves as a heat transfer device. Additional heat transfer takes place through the reactor heat transfer jackets.

  16. Tower reactors for bioconversion of lignocellulosic material

    DOE Patents [OSTI]

    Nguyen, Q.A.

    1998-03-31

    An apparatus is disclosed for enzymatic hydrolysis and fermentation of pretreated lignocellulosic material. The apparatus consists of a tower bioreactor which has mixers to achieve intermittent mixing of the material. Precise mixing of the material is important for effective heat and mass transfer requirements without damaging or denaturing the enzymes or fermenting microorganisms. The pretreated material, generally in the form of a slurry, is pumped through the bioreactor, either upwards or downwards, and is mixed periodically as it passes through the mixing zones where the mixers are located. For a thin slurry, alternate mixing can be achieved by a pumping loop which also serves as a heat transfer device. Additional heat transfer takes place through the reactor heat transfer jackets. 5 figs.

  17. Tower reactors for bioconversion of lignocellulosic material

    DOE Patents [OSTI]

    Nguyen, Q.A.

    1999-03-30

    An apparatus is described for enzymatic hydrolysis and fermentation of pretreated lignocellulosic material, in the form of a tower bioreactor, having mixers to achieve intermittent mixing of the material. Precise mixing of the material is important for effective heat and mass transfer requirements without damaging or denaturing the enzymes or fermenting microorganisms. The pretreated material, generally in the form of a slurry, is pumped through the bioreactor, either upwards or downwards, and is mixed periodically as it passes through the mixing zones where the mixers are located. For a thin slurry, alternate mixing can be achieved by a pumping loop which also serves as a heat transfer device. Additional heat transfer takes place through the reactor heat transfer jackets. 5 figs.

  18. ECB deacylase mutants

    DOE Patents [OSTI]

    Arnold, Frances H.; Shao, Zhixin; Zhao, Huimin; Giver, Lorraine J.

    2002-01-01

    A method for in vitro mutagenesis and recombination of polynucleotide sequences based on polymerase-catalyzed extension of primer oligonucleotides is disclosed. The method involves priming template polynucleotide(s) with random-sequences or defined-sequence primers to generate a pool of short DNA fragments with a low level of point mutations. The DNA fragments are subjected to denaturization followed by annealing and further enzyme-catalyzed DNA polymerization. This procedure is repeated a sufficient number of times to produce full-length genes which comprise mutants of the original template polynucleotides. These genes can be further amplified by the polymerase chain reaction and cloned into a vector for expression of the encoded proteins.

  19. Recombination of polynucleotide sequences using random or defined primers

    DOE Patents [OSTI]

    Arnold, Frances H.; Shao, Zhixin; Affholter, Joseph A.; Zhao, Huimin H; Giver, Lorraine J.

    2000-01-01

    A method for in vitro mutagenesis and recombination of polynucleotide sequences based on polymerase-catalyzed extension of primer oligonucleotides is disclosed. The method involves priming template polynucleotide(s) with random-sequences or defined-sequence primers to generate a pool of short DNA fragments with a low level of point mutations. The DNA fragments are subjected to denaturization followed by annealing and further enzyme-catalyzed DNA polymerization. This procedure is repeated a sufficient number of times to produce full-length genes which comprise mutants of the original template polynucleotides. These genes can be further amplified by the polymerase chain reaction and cloned into a vector for expression of the encoded proteins.

  20. Recombination of polynucleotide sequences using random or defined primers

    DOE Patents [OSTI]

    Arnold, Frances H.; Shao, Zhixin; Affholter, Joseph A.; Zhao, Huimin; Giver, Lorraine J.

    2001-01-01

    A method for in vitro mutagenesis and recombination of polynucleotide sequences based on polymerase-catalyzed extension of primer oligonucleotides is disclosed. The method involves priming template polynucleotide(s) with random-sequences or defined-sequence primers to generate a pool of short DNA fragments with a low level of point mutations. The DNA fragments are subjected to denaturization followed by annealing and further enzyme-catalyzed DNA polymerization. This procedure is repeated a sufficient number of times to produce full-length genes which comprise mutants of the original template polynucleotides. These genes can be further amplified by the polymerase chain reaction and cloned into a vector for expression of the encoded proteins.

  1. Elemental speciation in biomolecules by LC-ICP-MS with magnetic sector and collision cell instruments

    SciTech Connect (OSTI)

    Wang, Jin

    1999-11-08

    A methodology that can monitor and identify inorganic elements in biological and environmental systems was developed. Size exclusion chromatography (SEC) separates biomolecules, which are then nebulized by a microconcentric nebulizer. The resulting aerosol is desolved and introduced into either a high resolution ICP-MS device or a quadrupole device with a collision cell. Because of the high sensitivity and spectral resolution and high sample introduction efficiency, many unusual or difficult elements, such as Cr, Se, Cd and U, can be observed at ambient levels bound to proteins in human serum. These measurements are made in only a few minutes without preliminary isolation and preconcentration steps. Serum samples can be titrated with spikes of various elements to determine which proteins bind a given metal and oxidation state. Experiments concerning the effects of breaking disulfide linkages and denaturation on metal binding in proteins were also investigated. Elemental distribution in liver extract was also obtained.

  2. Structural and functional characterization of the hazelnut allergen Cor a 8

    SciTech Connect (OSTI)

    Offermann, Lesa R.; Bublin, Merima; Perdue, Makenzie L.; Pfeifer, Sabine; Dubiela, Pawel; Borowski, Tomasz; Chruszcz, Maksymilian; Hoffmann-Sommergruber, Karin

    2015-09-28

    Nonspecific lipid transfer proteins (nsLTPs) are basic proteins, stabilized by four disulfide bonds, and are expressed throughout the plant kingdom. These proteins are also known as important allergens in fruits and tree nuts. In this study, the nsLTP from hazelnuts, Cor a 8, was purified and its crystal structure determined. The protein is stable at low pH and refolds after thermal denaturation. Molecular dynamics simulations were used to provide an insight into conformational changes of Cor a 8 upon ligand binding. When known epitope areas from Pru p 3 were compared to those of Cor a 8, differences were obvious, which may contribute to limited cross-reactivity between peach and hazelnut allergens. The differences in epitope regions may contribute to limited cross-reactivity between Cor a 8 and nsLTPs from other plant sources. The structure of Cor a 8 represents the first resolved structure of a hazelnut allergen.

  3. Monitoring Biological Activity at Geothermal Power Plants

    SciTech Connect (OSTI)

    Peter Pryfogle

    2005-09-01

    The economic impact of microbial growth in geothermal power plants has been estimated to be as high as $500,000 annually for a 100 MWe plant. Many methods are available to monitor biological activity at these facilities; however, very few plants have any on-line monitoring program in place. Metal coupon, selective culturing (MPN), total organic carbon (TOC), adenosine triphosphate (ATP), respirometry, phospholipid fatty acid (PLFA), and denaturing gradient gel electrophoresis (DGGE) characterizations have been conducted using water samples collected from geothermal plants located in California and Utah. In addition, the on-line performance of a commercial electrochemical monitor, the BIoGEORGE?, has been evaluated during extended deployments at geothermal facilities. This report provides a review of these techniques, presents data on their application from laboratory and field studies, and discusses their value in characterizing and monitoring biological activities at geothermal power plants.

  4. Project report to STB/UO, Northern New Mexico Community College two- year college initiative: Biotechnology

    SciTech Connect (OSTI)

    1996-03-01

    This report summarizes the experiences gained in a project involving faculty direct undergraduate research focused on biotechnology and its applications. The biology program at Northern New Mexico Community College has been involved in screening for mutations in human DNA and has developed the ability to perform many standard and advanced molecular biology techniques. Most of these are based around the polymerase chain reaction (PCR) and include the use of single strand conformation polymorphism analysis (SSCP), denaturing gradient gel electrophoresis (DGGE) in the screening for mutant DNA molecules, and the capability to sequence PCR generated fragments of DNA using non-isotopic imaging. At Northern, these activities have a two-fold objective: (1) to bring current molecular biology techniques to the teaching laboratory, and (2) to support the training of minority undergraduates in research areas that stimulate them to pursue advanced degrees in the sciences.

  5. Engineering and Characterization of a Superfolder Green Fluorescent Protein

    SciTech Connect (OSTI)

    Pedelacq,J.; Cabantous, S.; Tran, T.; Terwilliger, T.; Waldo, G.

    2006-01-01

    Existing variants of green fluorescent protein (GFP) often misfold when expressed as fusions with other proteins. We have generated a robustly folded version of GFP, called 'superfolder' GFP, that folds well even when fused to poorly folded polypeptides. Compared to 'folding reporter' GFP, a folding-enhanced GFP containing the 'cycle-3' mutations and the 'enhanced GFP' mutations F64L and S65T, superfolder GFP shows improved tolerance of circular permutation, greater resistance to chemical denaturants and improved folding kinetics. The fluorescence of Escherichia coli cells expressing each of eighteen proteins from Pyrobaculum aerophilum as fusions with superfolder GFP was proportional to total protein expression. In contrast, fluorescence of folding reporter GFP fusion proteins was strongly correlated with the productive folding yield of the passenger protein. X-ray crystallographic structural analyses helped explain the enhanced folding of superfolder GFP relative to folding reporter GFP.

  6. Cellulosome: a discrete cell surface organelle of Clostridium thermocellum which exhibits separate antigenic, cellulose-binding and various cellulolytic activities

    SciTech Connect (OSTI)

    Lamed, R.; Setter, E.; Kenig, R.; Bayer, E.A.

    1983-01-01

    A cellulose-binding, cellulase-containing factor, previously demonstrated to be responsible for the adherence of Clostridium thermocellum to cellulose, has been partly purified from cellulose-grown cells of this organism. The biochemical properties of the cell-associated factor were compared to those of the previously isolated extracellular factor, and a high degree of similarity was found in the properties and behavior of the two forms. Partial denaturation of the purified extracellular factor by treatment with sodium dodecyl sulfate at 25/sup 0/C, broke the complex into a reproducible pattern of smaller subcomplexes which were analyzed for their respective cellulolytic activities and corresponding subunit composition. The data indicate that a defined arrangement of endo- and exo-cellulases are organized in the parent complex. The term cellulosome is proposed for the cell-associated, cellulose-binding, multicellulase complex. 20 references, 8 figures, 2 tables.

  7. Alternatives to traditional transportation fuels 1994. Volume 1

    SciTech Connect (OSTI)

    1996-02-01

    In this report, alternative and replacement fuels are defined in accordance with the EPACT. Section 301 of the EPACT defines alternative fuels as: methanol, denatured ethanol, and other alcohols; mixtures containing 85% or more (or such other percentage, but not less than 70%, as determined by the Secretary of Energy, by rule, to provide for requirements relating to cold start, safety, or vehicle functions) by volume of methanol, denatured ethanol, and other alcohols with gasoline or other fuels; natural gas; liquefied petroleum gas; hydrogen; coal-derived liquid fuels; fuels (other than alcohol) derived from biological materials; electricity (including electricity from solar energy); and any other fuel the Secretary determines, by rule, is substantially not petroleum and would yield substantial energy security benefits and substantial environmental benefits. The EPACT defines replacement fuels as the portion of any motor fuel that is methanol, ethanol, or other alcohols, natural gas, liquefied petroleum gas, hydrogen, coal-derived liquid fuels, fuels (other than alcohol) derived from biological materials, electricity (including electricity from solar energy), ethers, or any other fuel the Secretary of Energy determines, by rule, is substantially not petroleum and would yield substantial energy security benefits and substantial environmental benefits. This report covers only those alternative and replacement fuels cited in the EPACT that are currently commercially available or produced in significant quantities for vehicle demonstration purposes. Information about other fuels, such as hydrogen and biodiesel, will be included in later reports as those fuels become more widely used. Annual data are presented for 1992 to 1996. Data for 1996 are based on plans or projections for 1996.

  8. Total internal reflection fluorescence spectrometer to study dynamic adsorption phenomena at liquid/liquid interfaces

    SciTech Connect (OSTI)

    Tupy, M.J.; Blanch, H.W.; Radke, C.J.

    1998-08-01

    Adsorption at oil/water interfaces affects the performance of many industrial systems including oil recovery, extraction processes, cosmetic products, and food technology. However, no technique currently available can monitor adsorption dynamics using molecularly sensitive methods. The authors have constructed a novel total internal reflection fluorescence spectrometer (TIRFS) to follow dynamic adsorption events at the oil/water interface. The TIRFS monitors changes in fluorescence intensity and fluorescence spectra over time by maintaining an optical focus on the fluid interface during adsorption and desorption processes. Kinetic adsorption phenomena are examined by altering the composition of the aqueous phase and recording surface fluorescence response without mechanically disturbing the fluid/fluid interface. The spectrometer captures changes in the fluorescence intensity over tenths of seconds and maintains optical focus for periods of days. Mass transport of fluorescing surface-active material to and from the oil/water interface is accurately modeled using the simple one-dimensional diffusion equation. The geometry designed for this apparatus can be applied to other light-based techniques studying adsorption at liquid/liquid interfaces. Here, the authors apply the TIRFS apparatus to the study of {beta}-casein adsorption and desorption at an aliphatic oil/water interface. The observed increase in interfacial fluorescence due to {beta}-casein adsorption is slower than the diffusive flux, and desorption is found to be very slow if not irreversible. The TIRF spectrum indicates interaction of sorbed {beta}-casein with the oil phase and subsequent rearrangement of the native structure.

  9. Detection of high molecular weight organic tracers in vegetation smoke samples by high-temperature gas chromatography-mass spectrometry

    SciTech Connect (OSTI)

    Elias, V.O.; Simoneit, B.R.T. ); Pereira, A.S.; Cardoso, J.N. ); Cabral, J.A. )

    1999-07-15

    High-temperature high-resolution gas chromatography (HTGC) is an established technique for the separation of complex mixtures of high molecular weight (HMW) compounds which do not elute when analyzed on conventional GC columns. The combination of this technique with mass spectrometry is not so common and application to aerosols is novel. The HTGC and HTGC-MS analyses of smoke samples taken by particle filtration from combustion of different species of plants provided the characterization of various classes of HMW compounds reported to occur for the first time in emissions from biomass burning. Among these components are a series of wax esters with up to 58 carbon numbers, aliphatic hydrocarbons, triglycerides, long chain methyl ketones, alkanols and a series of triterpenyl fatty acid esters which have been characterized as novel natural products. Long chain fatty acids with more than 32 carbon numbers are not present in the smoke samples analyzed. The HMW compounds in smoke samples from the burning of plants from Amazonia indicate the input of directly volatilized natural products in the original plants during their combustion. However, the major organic compounds extracted from smoke consist of a series of lower molecular weight polar components, which are not natural products but the result of the thermal breakdown of cellulose and lignin. In contrast, the HMW natural products may be suitable tracers for specific sources of vegetation combustion because they are emitted as particles without thermal alternation in the smoke and can thus be related directly to the original plant material.

  10. Biofiltration control of VOC and air toxic emissions: n-Butane and benzene

    SciTech Connect (OSTI)

    Allen, E.R.

    1996-12-31

    n-Butane and benzene vapors are routinely observed in urban atmospheres. Their presence in urban airsheds is of concern because of their ozone production potential as volatile organic compounds (VOCs) and/or potential toxicity. Also, these saturated hydrocarbons are representative of airborne aliphatic and aromatic compounds. Separate laboratory studies have been conducted on the biological elimination of n-butane (n-C{sub 4}H{sub 10}) and benzene (C{sub 6}H{sub 6}) from airstreams using treated compost biofilters. The removal efficiencies were found to exceed 90% for a conditioned biofilter medium and pollutant low concentrations (< 25 ppm) and zeroth order kinetics at higher concentrations (> 100 ppm), whereas benzene vapor elimination followed zeroth order kinetics at concentrations up to 200 ppm. The maximum n-butane and benzene elimination capacities observed for the compost biofilters and conditions employed were 25 and 70 g pollutant m{sup -3} h{sup -1}, respectively. 13 refs., 6 figs., 2 tabs.

  11. Chemical Characterization and Water Content Determination of Bio-Oils Obtained from Various Biomass Species using 31P NMR Spectroscopy

    SciTech Connect (OSTI)

    David, K.; Ben, H.; Muzzy, J.; Feik, C.; Iisa, K.; Ragauskas, A.

    2012-03-01

    Pyrolysis is a promising approach to utilize biomass for biofuels. One of the key challenges for this conversion is how to analyze complicated components in the pyrolysis oils. Water contents of pyrolysis oils are normally analyzed by Karl Fischer titration. The use of 2-chloro-4,4,5,5,-tetramethyl-1,3,2-dioxaphospholane followed by {sup 31}P NMR analysis has been used to quantitatively analyze the structure of hydroxyl groups in lignin and whole biomass. Results: {sup 31}P NMR analysis of pyrolysis oils is a novel technique to simultaneously characterize components and analyze water contents in pyrolysis oils produced from various biomasses. The water contents of various pyrolysis oils range from 16 to 40 wt%. The pyrolysis oils obtained from Loblolly pine had higher guaiacyl content, while that from oak had a higher syringyl content. Conclusion: The comparison with Karl Fischer titration shows that {sup 31}P NMR could also reliably be used to measure the water content of pyrolysis oils. Simultaneously with analysis of water content, quantitative characterization of hydroxyl groups, including aliphatic, C-5 substituted/syringyl, guaiacyl, p-hydroxyl phenyl and carboxylic hydroxyl groups, could also be provided by {sup 31}P NMR analysis.

  12. Molecular Characterization of Organosulfates in Organic Aerosols from Shanghai and Los Angeles Urban Areas by Nanospray-Desorption Electrospray Ionization High-Resolution Mass Spectrometry

    SciTech Connect (OSTI)

    Tao, Shikang; Lu, Xiaohui; Levac, Nicole A.; Bateman, Adam P.; Nguyen, Tran B.; Bones, David L.; Nizkorodov, Sergey; Laskin, Julia; Laskin, Alexander; Yang, Xin

    2014-08-21

    Aerosol samples collected in the urban areas of Shanghai and Los Angeles were analyzed by nanospray-desorption electrospray ionization mass spectrometry (nano-DESI MS) with high mass resolution (m/?m=100,000). Solvent mixtures of acetonitrile/water and acetonitrile/toluene were used to extract and ionize polar and non-polar compounds, respectively. A diverse mixture of oxygenated hydrocarbons, organosulfates, organonitrates, and organics with reduced nitrogen were detected in the Los Angeles sample. Majority of the organics in the Shanghai sample were detected as organosulfates. The dominant organosulfates in the two samples have distinctly different molecular characteristics. Specifically, organosulfates in the Los Angeles sample were dominated by isoprene- or monoterpene-derived products, while organosulfates of yet unknown origin in the Shanghai sample had distinctive characteristics of long aliphatic carbon chains and low degree of oxidation and unsaturation. The use of acetonitrile/toluene solvent facilitated identification of this type of organosulfates, suggesting they could be missed in previous studies relying on sample extraction using common polar solvents. The high molecular weight and low degree of unsaturation and oxidization of the organosulfates detected in the Shanghai sample suggest that they may act as surfactants, and plausibly affect the surface tension and hygroscopicity of the atmospheric particulate matter. We propose that direct esterification of carbonyl or hydroxyl compounds by sulfates or sulfuric acid in liquid phase could be the formation pathway of these special organosulfates. Long-chain alkanes from vehicle emissions might be their precursors.

  13. Synthesis and characterization of interfacially polymerized films of tetraphenylporphyrin derivatives

    SciTech Connect (OSTI)

    Li, W.; Wamser, C.C.

    1995-10-01

    Thin films of polymeric porphyrins have been made by interfacial polymerization of derivatives of tetraphenyl porphyrins, in particular by condensation of a dichloromethane solution of the acid chloride derivative (TCCPP) with a buffered aqueous solution of either the amine derivative (TAPP) or the phenol derivative (THPP). Spectroscopic and other studies are consistent with cross-linked polyamide or polyester network structures. The polyamide and polyester films display a novel asymmetry of functional groups on opposite sides of the film; excess amine (or hydroxyl) groups appear on one side of the film and excess carboxyl groups on the other. Film thickness can be correlated with the intensity of the UV-visible absorption spectrum, x (in nm) = 120 A{sub max} (at the Soret peak), with typical thicknesses in the range 10-500 nm, easily controlled by reaction time and conditions. Significantly thicker films (up to several {mu}m) can be prepared using an aliphatic diamine orpolyamine as the comonomer with TCCPP. Addition of 2, 6-lutidine to the organic phase substantially increases the rate of polymerization, which is especially useful for TAPP reactions. In addition, control experiments show that TCCPP with lutidine in CH{sub 2}Cl{sub 2} reacts at the interface with an aqueous pH 3 buffer, giving a very thin, easily hydrolyzed film, apparently due to anhydride linkages formed by condensation reactions with partially hydrolyzed TCCPP. 56 refs., 11 figs., 4 tabs.

  14. Linkages and aromatic clusters in a bituminous coal: Final report, September 1, 1985--September 30, 1988

    SciTech Connect (OSTI)

    Chung, K.E.

    1988-10-01

    The distribution and arrangement of aromatic clusters, oxygen functional groups, and linkages in an Illinois No. 6 bituminous coal were determined by controlled solubilization of the coal, followed by solvent fractionation of the soluble product and detailed analyses of the product fractions. The solubilization was carried out in reactions with NaOH/ethanol/H/sub 2/O at temperatures of 260/degree/, 300/degree/ and 320/degree/C. Elemental balance and spectroscopic data revealed that the oxygen functional groups of the coal were attacked selectively in the solubilization process, resulting in an orderly definable diminution of the complex coal structure. Also aliphatic linkages present in selected solubilized product fractions were subjected to a transalkylation reaction. A molecular structural model specific to the Illinois coal was constructed, and the hydroliquefaction behavior of the coal was evaluated in terms of potential product distribution and hydrogen consumption. The structural characteristics are compared with those of a Wyoming subbituminous coal in our previous study. 9 refs., 16 figs., 11 tabs.

  15. Peptide affinity labels for thrombin and other trypsin-like proteases

    DOE Patents [OSTI]

    Shaw, E.N.; Kettner, C.A.

    1982-03-09

    A peptide affinity label is disclosed of the formula (I): as given in the patent wherein X is a radical capable of acting as a leaving group in a nucleophilic substitution reaction; A is an aromatic amino acid residue; B is H, or a C[sub 1]--C[sub 4] alkyl group, or aryl; Y is selected from the group consisting of hydrogen, aroyl, C[sub 1]--C[sub 6] acyl, and Q--(A)--[sub n], wherein Q = hydrogen, aroyl, or C[sub 1]--C[sub 6] acyl, n = 1--10, A is an amino acid residue selected from the aliphatic, hydroxy-containing, carboxylic acid group, and amide-thereofcontaining, aromatic, sulfur-containing and imino-containing amino acids; and wherein J is selected from the group consisting of --CH[sub 2]--, --CH[sub 2]--CH[sub 2]--, --CH[sub 2]--CH[sub 2]--CH[sub 2]--, --CH[double bond]CH-- and --CH(OH)--CH[sub 2]. The affinity label is useful for irreversibly inactivating thrombin and trypsin-like enzymes and may be used as a potential anticlotting agent. 2 figs.

  16. Ras-GTP dimers activate the mitogen-activated protein kinase (MAPK) pathway

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

    Nan, Xiaolin; Tamgüney, Tanja M.; Collisson, Eric A.; Lin, Li -Jung; Pitt, Cameron; Galeas, Jacqueline; Lewis, Sophia; Gray, Joe W.; McCormick, Frank; Chu, Steven

    2015-06-16

    Rat sarcoma (Ras) GTPases regulate cell proliferation and survival through effector pathways including Raf-MAPK, and are the most frequently mutated genes in human cancer. Although it is well established that Ras activity requires binding to both GTP and the membrane, details of how Ras operates on the cell membrane to activate its effectors remain elusive. Efforts to target mutant Ras in human cancers to therapeutic benefit have also been largely unsuccessful. Here we show that Ras-GTP forms dimers to activate MAPK. We used quantitative photoactivated localization microscopy (PALM) to analyze the nanoscale spatial organization of PAmCherry1-tagged KRas 4B (hereafter referredmore » to KRas) on the cell membrane under various signaling conditions. We found that at endogenous expression levels KRas forms dimers, and KRasG12D, a mutant that constitutively binds GTP, activates MAPK. Overexpression of KRas leads to formation of higher order Ras nanoclusters. Conversely, at lower expression levels, KRasG12D is monomeric and activates MAPK only when artificially dimerized. Moreover, dimerization and signaling of KRas are both dependent on an intact CAAX (C, cysteine; A, aliphatic; X, any amino acid) motif that is also known to mediate membrane localization. These results reveal a new, dimerization-dependent signaling mechanism of Ras, and suggest Ras dimers as a potential therapeutic target in mutant Ras-driven tumors.« less

  17. TALSPEAK CURVE: AN ILLUSTRATION OF A SEE-SAW EFFECT IN SEPARATIONS

    SciTech Connect (OSTI)

    Peter Zalupski; Leigh Martin

    2010-11-01

    A superbly balanced thermodynamic struggle for metal ion coordination by aqueous aminopolycarboxylate reagent, DTPA, and non-aqueous organophosphorous phase transfer reagent, HDEHP, affords the separation of trivalent actinides from trivalent lanthanides under the umbrella of the Talspeak liquid-liquid distribution process. This thermodynamic relationship has been linked to an analogous see-saw behavior, where the balance is distorted when either of the key complexing players is subject to adverse conditions that interfere with their optimal operation. The thermodynamic balance is tipped in favour of HDEHP whenever increased acidity of the aqueous solution out-competes the metal ion complexation by aqueous complexing agent. Also enhanced steric crowding may switch-off efficient coordination of the metal ion. When HDEHP is depolymerised due to the presence of aliphatic alcohol in the organic phase its phase transferring power is diminished. Such complication paves way for DTPA to establish its dominance on the distribution of trivalent metal ions in the 2-phase system. The illustrated sensitivity of the thermodynamic balance between DTPA and HDEHP in Talspeak-type systems may serve as informative tool when studying less-predictable realms of Talspeak chemistry.

  18. Metal catalyzed synthesis of hyperbranched ethylene and/or .alpha.-olefin polymers

    DOE Patents [OSTI]

    Sen, Ayusman; Kim, Jang Sub; Pawlow, James H.; Murtuza, Shahid; Kacker, Smita; Wojcinski, III, Louis M.

    2001-01-01

    Oily hyperbranched polymers derived from ethylene, propylene, butene and/or a C.sub.5 -C.sub.24 .alpha.-olefin, and a method for their synthesis, are disclosed. The polymers have non-regular microstructures and are characterized by a ratio ({character pullout})of methyl hydrogens centered around 0.85 ppm on the 1H-NMR spectra of the polymers relative to total aliphatic hydrogens of from about 0.40 to about 0.65 for polymers derived from ethylene or butene, and a ratio ({character pullout})of from greater than 0.50 to about 0.65 for polymers derived from propylene. A method for grafting hyperbranched polymers derived from ethylene, propylene, butene and/or a C.sub.5 -C.sub.24 .alpha.-olefin onto aromatic rings in organic molecules and polymers, and the resulting grafted materials, are also disclosed. The hyperbranched polymers and grafted materials are useful, for example, as lubricants and lubricant additives.

  19. The Molecular Structure of a Phosphatidylserine Bilayer Determined by Scattering and Molecular Dynamics Simulations

    SciTech Connect (OSTI)

    Pan, Jianjun [University of South Florida, Tampa (USF)] [University of South Florida, Tampa (USF); Cheng, Xiaolin [ORNL] [ORNL; Monticelli, Luca [Institut National de la Sant et de la Recherche Mdicale (INSERM) and INTS, France] [Institut National de la Sant et de la Recherche Mdicale (INSERM) and INTS, France; Heberle, Frederick A [ORNL] [ORNL; Kucerka, Norbert [Atomic Energy of Canada Limited (AECL), Canadian Neutron Beam Centre (CNBC) and Comenius University,] [Atomic Energy of Canada Limited (AECL), Canadian Neutron Beam Centre (CNBC) and Comenius University,; Tieleman, D. Peter [University of Calgary, ALberta, Canada] [University of Calgary, ALberta, Canada; Katsaras, John [ORNL] [ORNL

    2014-01-01

    Phosphatidylserine (PS) lipids play essential roles in biological processes, including enzyme activation and apoptosis. We report on the molecular structure and atomic scale interactions of a fluid bilayer composed of 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphatidylserine (POPS). A scattering density profile model, aided by molecular dynamics (MD) simulations, was developed to jointly refine different contrast small-angle neutron and X-ray scattering data, which yielded a lipid area of 62.7 A2 at 25 C. MD simulations with POPS lipid area constrained at different values were also performed using all-atom and aliphatic united-atom models. The optimal simulated bilayer was obtained using a model-free comparison approach. Examination of the simulated bilayer, which agrees best with the experimental scattering data, reveals a preferential interaction between Na+ ions and the terminal serine and phosphate moieties. Long-range inter-lipid interactions were identified, primarily between the positively charged ammonium, and the negatively charged carboxylic and phosphate oxygens. The area compressibility modulus KA of the POPS bilayer was derived by quantifying lipid area as a function of surface tension from area-constrained MD simulations. It was found that POPS bilayers possess a much larger KA than that of neutral phosphatidylcholine lipid bilayers. We propose that the unique molecular features of POPS bilayers may play an important role in certain physiological functions.

  20. Time-resolved fluorometric determination of terbium in aqueous solution

    SciTech Connect (OSTI)

    Hemmilae, I.

    1985-07-01

    The fluorescent properties of water-soluble binary and ternary complexes of terbium(III) were studied and their applications in time-resolved fluorometric analysis were tested. Solutions composed of different ..beta..-diketones, tri-n-octylphosphine oxide as the synergistic agent, and Triton X-100 as the detergent were optimized to maximize fluorescence emission in Tb measurement. The results were then compared with seven published methods which included the use of the following respective solutions, ethylenediamine-N,N'-bis((o-hydroxy-phenyl)acetic acid), dipicolinic acid, iminodiacetic acid with Tiron, EDTA with Tiron, EDTA with 2,3-dihydroxynaphthalene, EDTA with sulfosalicylic acid, and EDTA with salicylate. Fluorinated aliphatic ..beta..-diketones showed the most promising properties in acidic solution. They were especially suitable for use in time-resolved fluorometric analyses where Tb was used as the label after being conjugated to the analyte via bifunctional complexones. An acidic pH is required for Tb release before conversion into a fluorescent chelate. The applicability of the developed measurement solutions to the measurement of Eu was also tested. 22 references, 3 figures, 7 tables.

  1. Composition and method for removing photoresist materials from electronic components

    DOE Patents [OSTI]

    Davenhall, Leisa B.; Rubin, James B.

    2002-01-01

    The invention is a combination of at least one dense phase fluid and at least one dense phase fluid modifier which can be used to contact substrates for electronic parts such as semiconductor wafers or chips to remove photoresist materials which are applied to the substrates during manufacture of the electronic parts. The dense phase fluid modifier is one selected from the group of cyclic, aliphatic or alicyclic compounds having the functional group: ##STR1## wherein Y is a carbon, oxygen, nitrogen, phosphorus or sulfur atom or a hydrocarbon group having from 1 to 10 carbon atoms, a halogen or halogenated hydrocarbon group having from 1 to 10 carbon atoms, silicon or a fluorinated silicon group; and wherein R.sub.1 and R.sub.2 can be the same or different substituents; and wherein, as in the case where X is nitrogen, R.sub.1 or R.sub.2 may not be present. The invention compositions generally are applied to the substrates in a pulsed fashion in order to remove the hard baked photoresist material remaining on the surface of the substrate after removal of soft baked photoresist material and etching of the barrier layer.

  2. BIOTIGER, A NATURAL MICROBIAL PRODUCT FOR ENHANCED HYDROCARBON RECOVERY FROM OIL SANDS.

    SciTech Connect (OSTI)

    Brigmon, R; Topher Berry, T; Whitney Jones, W; Charles Milliken, C

    2008-05-27

    BioTiger{trademark} is a unique microbial consortia that resulted from over 8 years of extensive microbiology screening and characterization of samples collected from a century-old Polish waste lagoon. BioTiger{trademark} shows rapid and complete degradation of aliphatic and aromatic hydrocarbons, produces novel surfactants, is tolerant of both chemical and metal toxicity and shows good activity at temperature and pH extremes. Although originally developed and used by the U.S. Department of Energy for bioremediation of oil-contaminated soils, recent efforts have proven that BioTiger{trademark} can also be used to increase hydrocarbon recovery from oil sands. This enhanced ex situ oil recovery process utilizes BioTiger{trademark} to optimize bitumen separation. A floatation test protocol with oil sands from Ft. McMurray, Canada was used for the BioTiger{trademark} evaluation. A comparison of hot water extraction/floatation test of the oil sands performed with BioTiger{trademark} demonstrated a 50% improvement in separation as measured by gravimetric analysis in 4 h and a five-fold increase at 25 hr. Since BioTiger{trademark} performs well at high temperatures and process engineering can enhance and sustain metabolic activity, it can be applied to enhance recovery of hydrocarbons from oil sands or other complex recalcitrant matrices.

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

    SciTech Connect (OSTI)

    Waller, F.J.

    1997-11-01

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

  4. α, α', α", α'"-meso-tetrahexyltetramethyl-calix[4]pyrrole: An easy-to-prepare, isomerically pure anion extractant with enhanced solubility in organic solvents

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

    Williams, Neil J.; Bryantsev, Vyacheslav S.; Custelcean, Radu; Seipp, Charles A.; Moyer, Bruce A.

    2016-01-29

    α, α', α", α'"-meso-Tetrahexyltetramethyl-calix[4]pyrrole is easily obtained as a single diastereomer in a one-pot reaction. It exhibits enhanced solubility in organic solvents, including aliphatic solvents, relative to its parent meso-octamethylcalix[4]pyrrole (1). Somewhat surprisingly, the tetrahexyl derivative 2 complexes with tributylmethylammonium chloride in chloroform more strongly than does 1 as shown by NMR titrations. However, 1 and 2 exhibit comparable complexation strength in extraction experiments, the difference between the NMR and extraction results being attributed to the effect of organic-phase water in the extraction systems. Mass-action analysis indicates the formation of the predominant complex TBMA+(1 or 2)Cl– in both NMR andmore » extraction systems, and equilibrium constants are reported. x-Ray crystal structures were obtained for the free ligand 2 and its complex with tetramethylammonium chloride. In addition, the free ligand crystallises in the 1,3-alt conformation with equatorial hexyl arms. In the chloride complex with 2 in its cone conformation, the hexyl arms adopt an axial orientation, enveloping the anion. DFT calculations show this binding conformation to be the most stable, mostly owing to destabilising steric interactions involving the pyrrole C–H and alkyl C–H groups positioned equatorially.« less

  5. Theoretical Study of the Thermal Decomposition of Carboxylic Acids at Pyrolysis Temperature

    SciTech Connect (OSTI)

    Clark, J. M.; Robichaud, D. J.; Nimlos, M. R.

    2013-01-01

    Carboxylic acids are important in the processing of biomass into renewable fuels and chemicals. They are formed from the pretreatment and pyrolysis of hemicellulose biopolymers and are released from the decomposition of sugars. They result from the deconstruction of polyhydroxyalkanoates (bacterial carbon storage polymers) from fatty acids derived from algae, bacteria, and oil crops. The thermal deoxygenation of carboxylic acids is an important step in the conversion of biomass into aliphatic hydrocarbons suitable for use in renewable biofuels and as petrochemical replacements. Decarboxylation, a primary decomposition pathway under pyrolysis conditions, represents an ideal conversion process, because it eliminates two atoms of oxygen for every carbon atom removed. Problematically, additional deoxygenation processes exist (e.g. dehydration) that are in direct competition with decarboxylation and result in the formation of reactive and more fragmented end products. To better understand the competition between decarboxylation and other deoxygenation processes and to gain insight into possible catalysts that would favor decarboxylation, we have investigated the mechanisms and thermochemistry of the various unimolecular and bimolecular deoxygenation pathways for a family of C1-C4 organic acids using electronic structure calculations at the M06-2X/6-311++G(2df,p) level of theory.

  6. Defective Pollen Wall is Required for Anther and Microspore Development in Rice and Encodes a Fatty Acyl Carrier Protein Reductase

    SciTech Connect (OSTI)

    Shi, J.; Shanklin, J.; Tan, H.; Yu, X.-H.; Liu, Y.; Liang, W.; Ranathunge, K.; Franke, R. B.; Schreiber, L.; Wang, Y.; Kai, G.; Ma, H.; Zhang, D.

    2011-06-01

    Aliphatic alcohols naturally exist in many organisms as important cellular components; however, their roles in extracellular polymer biosynthesis are poorly defined. We report here the isolation and characterization of a rice (Oryza sativa) male-sterile mutant, defective pollen wall (dpw), which displays defective anther development and degenerated pollen grains with an irregular exine. Chemical analysis revealed that dpw anthers had a dramatic reduction in cutin monomers and an altered composition of cuticular wax, as well as soluble fatty acids and alcohols. Using map-based cloning, we identified the DPW gene, which is expressed in both tapetal cells and microspores during anther development. Biochemical analysis of the recombinant DPW enzyme shows that it is a novel fatty acid reductase that produces 1-hexadecanol and exhibits >270-fold higher specificity for palmiltoyl-acyl carrier protein than for C16:0 CoA substrates. DPW was predominantly targeted to plastids mediated by its N-terminal transit peptide. Moreover, we demonstrate that the monocot DPW from rice complements the dicot Arabidopsis thaliana male sterile2 (ms2) mutant and is the probable ortholog of MS2. These data suggest that DPWs participate in a conserved step in primary fatty alcohol synthesis for anther cuticle and pollen sporopollenin biosynthesis in monocots and dicots.

  7. Yellow phosphorus process to convert toxic chemicals to non-toxic products

    DOE Patents [OSTI]

    Chang, S.G.

    1994-07-26

    The present invention relates to a process for generating reactive species for destroying toxic chemicals. This process first contacts air or oxygen with aqueous emulsions of molten yellow phosphorus. This contact results in rapid production of abundant reactive species such as O, O[sub 3], PO, PO[sub 2], etc. A gaseous or liquid aqueous solution organic or inorganic chemicals is next contacted by these reactive species to reduce the concentration of toxic chemical and result in a non-toxic product. The final oxidation product of yellow phosphorus is phosphoric acid of a quality which can be recovered for commercial use. A process is developed such that the byproduct, phosphoric acid, is obtained without contamination of toxic species in liquids treated. A gas stream containing ozone without contamination of phosphorus containing species is also obtained in a simple and cost-effective manner. This process is demonstrated to be effective for destroying many types of toxic organic, or inorganic, compounds, including polychlorinated biphenyls (PCB), aromatic chlorides, amines, alcohols, acids, nitro aromatics, aliphatic chlorides, polynuclear aromatic compounds (PAH), dyes, pesticides, sulfides, hydroxyamines, ureas, dithionates and the like. 20 figs.

  8. Yellow phosphorus process to convert toxic chemicals to non-toxic products

    DOE Patents [OSTI]

    Chang, Shih-Ger

    1994-01-01

    The present invention relates to a process for generating reactive species for destroying toxic chemicals. This process first contacts air or oxygen with aqueous emulsions of molten yellow phosphorus. This contact results in rapid production of abundant reactive species such as O, O.sub.3, PO, PO.sub.2, etc. A gaseous or liquid aqueous solution organic or inorganic chemicals is next contacted by these reactive species to reduce the concentration of toxic chemical and result in a non-toxic product. The final oxidation product of yellow phosphorus is phosphoric acid of a quality which can be recovered for commercial use. A process is developed such that the byproduct, phosphoric acid, is obtained without contamination of toxic species in liquids treated. A gas stream containing ozone without contamination of phosphorus containing species is also obtained in a simple and cost-effective manner. This process is demonstrated to be effective for destroying many types of toxic organic, or inorganic, compounds, including polychlorinated biphenyls (PCB), aromatic chlorides, amines, alcohols, acids, nitro aromatics, aliphatic chlorides, polynuclear aromatic compounds (PAH), dyes, pesticides, sulfides, hydroxyamines, ureas, dithionates and the like.

  9. Ras-GTP dimers activate the mitogen-activated protein kinase (MAPK) pathway

    SciTech Connect (OSTI)

    Nan, Xiaolin; Tamgney, Tanja M.; Collisson, Eric A.; Lin, Li -Jung; Pitt, Cameron; Galeas, Jacqueline; Lewis, Sophia; Gray, Joe W.; McCormick, Frank; Chu, Steven

    2015-06-16

    Rat sarcoma (Ras) GTPases regulate cell proliferation and survival through effector pathways including Raf-MAPK, and are the most frequently mutated genes in human cancer. Although it is well established that Ras activity requires binding to both GTP and the membrane, details of how Ras operates on the cell membrane to activate its effectors remain elusive. Efforts to target mutant Ras in human cancers to therapeutic benefit have also been largely unsuccessful. Here we show that Ras-GTP forms dimers to activate MAPK. We used quantitative photoactivated localization microscopy (PALM) to analyze the nanoscale spatial organization of PAmCherry1-tagged KRas 4B (hereafter referred to KRas) on the cell membrane under various signaling conditions. We found that at endogenous expression levels KRas forms dimers, and KRasG12D, a mutant that constitutively binds GTP, activates MAPK. Overexpression of KRas leads to formation of higher order Ras nanoclusters. Conversely, at lower expression levels, KRasG12D is monomeric and activates MAPK only when artificially dimerized. Moreover, dimerization and signaling of KRas are both dependent on an intact CAAX (C, cysteine; A, aliphatic; X, any amino acid) motif that is also known to mediate membrane localization. These results reveal a new, dimerization-dependent signaling mechanism of Ras, and suggest Ras dimers as a potential therapeutic target in mutant Ras-driven tumors.

  10. Single gene insertion drives bioalcohol production by a thermophilic archaeon

    SciTech Connect (OSTI)

    Basen, M; Schut, GJ; Nguyen, DM; Lipscomb, GL; Benn, RA; Prybol, CJ; Vaccaro, BJ; Poole, FL; Kelly, RM; Adams, MWW

    2014-12-09

    Bioethanol production is achieved by only two metabolic pathways and only at moderate temperatures. Herein a fundamentally different synthetic pathway for bioalcohol production at 70 degrees C was constructed by insertion of the gene for bacterial alcohol dehydrogenase (AdhA) into the archaeon Pyrococcus furiosus. The engineered strain converted glucose to ethanol via acetate and acetaldehyde, catalyzed by the host-encoded aldehyde ferredoxin oxidoreductase (AOR) and heterologously expressed AdhA, in an energy-conserving, redox-balanced pathway. Furthermore, the AOR/AdhA pathway also converted exogenously added aliphatic and aromatic carboxylic acids to the corresponding alcohol using glucose, pyruvate, and/or hydrogen as the source of reductant. By heterologous coexpression of a membrane-bound carbon monoxide dehydrogenase, CO was used as a reductant for converting carboxylic acids to alcohols. Redirecting the fermentative metabolism of P. furiosus through strategic insertion of foreign genes creates unprecedented opportunities for thermophilic bioalcohol production. Moreover, the AOR/AdhA pathway is a potentially game-changing strategy for syngas fermentation, especially in combination with carbon chain elongation pathways.

  11. Effect of Ligands on Characteristics of (CdSe)13 Quantum Dot

    SciTech Connect (OSTI)

    Gao, Yang; Zhou, Bo; Kang, Seung-gu; Xin, Minsi; Yang, Ping; Dai, Xing; Wang, Zhigang; Zhou, Ruhong

    2014-01-01

    The widespread applications of quantum dots (QDs) have spurred an increasing interest in the study of their coating ligands, which can not only protect the electronic structures of the central QDs, but also control their permeability through biological membranes with both size and shape. In this work, we have used density functional theory (DFT) to investigate the electronic structures of (CdSe)13 passivated by OPMe2(CH2)nMe ligands with different lengths and various numbers of branches (Me=methyl group, n = 0, 1-3). Our results show that the absorption peak in the ultraviolet-visible (UV-vis) spectra displays a clear blue-shift, on the scale of ~100 nm, upon the binding of ligands. Once the total number of ligands bound with (CdSe)13 reached a saturated number (9 or 10), no more blue-shift occurred in the absorption peak in the UV-vis spectra. On the other hand, the aliphatic chain length of ligands has a negligible effect on the optical properties of the QD core. Analyses of the bonding characteristics confirm that optical transitions are dominantly governed by the central QD core rather than the organic passivation. Interestingly, the density of states (DOS) share similar characteristics as vibrational spectra, even though there is no coordination vibration mode between the ligands and the central QD. These findings might provide insights on the material design for the passivation of quantum dots for biomedical applications.

  12. Mechanisms, Chemistry, and Kinetics of Anaerobic Biodegradation of cis-Dichloroethene and Vinyl Chloride

    SciTech Connect (OSTI)

    McCarty, P.L.; Spormann, A.M.

    2000-12-01

    Anaerobic biological processes can result in PCE and TCE destruction through conversion to cis-dichloroethene (cDCE) then to vinyl chloride (VC), and finally to ethene. Here, the chlorinated aliphatic hydrocarbons (CAHs) serve as electron acceptors in energy metabolism, requiring electron donors such as hydrogen from an external source. The purpose of this study was to learn more about the biochemistry of cDCE and VC conversion to ethene, to better understand the requirements for electron donors, and to determine factors affecting the rates of CAH degradation and organism growth. The biochemistry of reductive dehalogenation of VC was studied with an anaerobic mixed culture enriched on VC. In other studies on electron donor needs for dehalogenation of cDCE and VC, competition for hydrogen was found to occur between the dehalogenators and other microorganisms such as methanogens and homoacetogens in a benzoate-acclimated dehalogenating methanogenic mixed culture. Factors affecting the relative rates of destruction of the solvents and their intermediate products were evaluated. Studies using a mixed PCE-dehalogenating culture as well as the VC enrichment for biochemical studies suggested that the same species was involved in both cDCE and VC dechlorination, and that cDCE and VC competitively inhibited each other's dechlorination rate.

  13. Experimental and modeling investigation of aromatic and polycyclic aromatic hydrocarbon formation in a premixed ethylene flame

    SciTech Connect (OSTI)

    Castaldi, M.J.; Marinov, N.M.; Melius, C.F.

    1996-02-01

    Experimental and detailed chemical kinetic modeling has been performed to investigate aromatic and polyaromatic hydrocarbon formation pathways in a rich, sooting, ethylene-oxygen-argon premixed flame. An atmospheric pressure, laminar flat flame operated at an equivalence ratio of 2.5 was used to acquire experimental data for model validation. Gas composition analysis was conducted by an on-line gas chromatograph/mass spectrometer (GC/MS) technique. Measurements were made in the flame and post-flame zone for a number of low molecular weight species, aliphatics, aromatics and polycyclic aromatic hydrocarbons (PAHs) ranging from two to five-aromatic fused rings. The modeling results show the key reaction sequences leading to aromatic and polycyclic aromatic hydrocarbon growth involve the combination of resonantly stabilized radicals. In particular, propargyl and 1-methylallenyl combination reactions lead to benzene and methyl substituted benzene formation, while polycyclic aromatics are formed from cyclopentadienyl radicals and fused rings that have a shared C{sub 5} side structure. Naphthalene production through the reaction step of cyclopentadienyl self-combination and phenanthrene formation from indenyl and cyclopentadienyl combination were shown to be important in the flame modeling study. The removal of phenyl by O{sub 2} leading to cyclopentadienyl formation is expected to play a pivotal role in the PAH or soot precursor growth process under fuel-rich oxidation conditions.

  14. Structural Transformation of Isolated Poplar and Switchgrass Lignins from Dilute Acid Pretreatment

    SciTech Connect (OSTI)

    Sun, Qining; Pu, Yunqiao; Meng, Xianzhi; Wells, Tyrone; Ragauskas, Arthur J.

    2015-08-27

    A key step in conversion of cellulosic biomass into sustainable fuels and chemicals is thermochemical pretreatment to reduce plant cell wall recalcitrance. Obtaining an improved understanding of the fundamental chemistry of lignin, the most recalcitrant component of biomass, during pretreatment is critical to the continued development of renewable biofuel production. To examine the intrinsic chemistry of lignin during dilute acid pretreatment (DAP), lignin was isolated from poplar and switchgrass using a cellulolytic enzyme system and then treated under DAP conditions. These results highlight that lignin is subjected to depolymerization reactions within the first 2 min of dilute acid pretreatment and these changes are accompanied by increased generation of aliphatic and phenolic hydroxyl groups of lignin. This is followed by a competing set of depolymerization and repolymerization reactions that lead to a decrease in the content of guaiacyl lignin units and an increase in condensed lignin units as the reaction residence time is extended beyond 5 min. Finally, we showed that a detailed comparison of changes in functional groups and molecular weights of cellulolytic enzyme lignins with different structural parameters, related to the recalcitrant properties of lignin, could be successfully altered during DAP conditions.

  15. Application of /sup 13/C, /sup 2/H, /sup 1/H NMR and GPC to the study of structural evolution of subbituminous coal in tetralin at 427/sup 0/C

    SciTech Connect (OSTI)

    Franz, J.A.; Camaioni, D.M.; Skiens, W.E.

    1981-01-01

    The products from the treatment of subbituminous coal at 427/sup 0/C in tetralin or 1,1-d/sub 2/-tetralin for times varying from 2.5 to 120 min were examined by /sup 13/C, /sup 2/H, and /sup 1/H Fourier transform nuclear magnetic resonance (FTNMR), gel permeation chromatography (GPC), and elemental and hydroxyl group analysis. NMR and elemental analysis revealed that the flash hydroliquefaction products contained about 10% of aromatic ether carbon and phenolic carbon in roughly equal amounts, but no aliphatic ether, carboxyl, or quinine carbon. The combined asphaltenes and preasphaltenes from a 10-min reaction exhibited 68% carbon, 30% hydrogen, and 30% deuterium aromaticity, with aromaticity slowly increasing at longer reaction times. GPC analysis revealed that approximately 10% of the products were greater than 1500 mol wt, with number-average molecular weights reduced from 840 to 500 over a 2-hr reaction. Deuterium NMR revealed that the majority of deuterium transferred to coal appeared at benzylic carbons.

  16. Identification of sulfur heterocycles in coal liquids and shale oils. Technical progress report, August 1, 1980-May 1, 1981

    SciTech Connect (OSTI)

    Lee, M. L.; Castle, R. N.

    1981-01-01

    The sulfur heterocycle separation scheme which was described in the last progress report was evaluated for quantitative recovery of individual components. The results indicate that recoveries can range from 10% to approx. 30% depending on the structure of the compound. During this period, 23 unsubstituted sulfur-containing heterocyclic ring systems were synthesized in oder to confirm GC/MS identifications and for biological testing. The four possible 3-ring heterocycles and the thirteen possible 4-ring heterocycles were tested for mutagenic activity in the histidine reversion (Ames assay) system. One of the 3-ring isomers, naphtho(1,2-b)-thiophene, and six of the 4-ring isomers induced mutations in Salmonella test strains. One of these compounds, phenanthro(3,4-b)thiophene, displayed approximately the same mutagenic activity as benzo(a)pyrene. A two-step adsorption chromatographic procedure was developed in order to fractionate synthetic fuels into various chemical-type classes for studying the relative concentrations and mutagenic activities of the various types. An SRC-II Heavy Distillate was fractionated into aliphatic hydrocarbons, polycyclic aromatic hydrocarbons, sulfur heterocycles, indoles and carbazoles, azaarenes, and amino polycyclic aromatic hydrocarbons. It was found that the amino-PAH fraction contained most of the mutagenic activity. A survey was made for compounds containing both nitrogen and sulfur heteroatoms in their structures. A number of these compounds were detected by GC using nitrogen- and sulfur-selective detection.

  17. Process for hydrocracking carbonaceous material in liquid carrier

    DOE Patents [OSTI]

    Duncan, Dennis A.

    1980-01-01

    Solid carbonaceous material is hydrocracked to provide aliphatic and aromatic hydrocarbons for use as gaseous and liquid fuels or chemical feed stock. Particulate carbonaceous material such as coal in slurry with recycled product oil is preheated in liquid state to a temperature of 600.degree.-1200.degree. F. in the presence of hydrogen gas. The product oil acts as a sorbing agent for the agglomerating bitumins to minimize caking within the process. In the hydrocracking reactor, the slurry of oil and carbonaceous particles is heated within a tubular passageway to vaporize the oil and form a gas-solid mixture which is further heated to a hydropyrolysis temperature in excess of 1200.degree. F. The gas-solid mixture is quenched by contact with additional oil to condense normally liquid hydrocarbons for separation from the gases. A fraction of the hydrocarbon liquid product is recycled for quenching and slurrying with the carbonaceous feed. Hydrogen is recovered from the gas for recycle and additional hydrogen is produced by gasification of residual char.

  18. Clean, premium-quality chars: Demineralized and carbon enriched. Final technical report, 1 September, 1992--31 August, 1993

    SciTech Connect (OSTI)

    Smith, G.V.; Malhotra, V.M.; Wiltowski, T.

    1993-12-31

    The overall objective of this two-year project was to evaluate methods of preparing demineralized and carbon enriched chars from Illinois Basin coals. The two processing steps, physical cleaning and devolatilization under different environments, led to the following results. Cleaning coal incompletely removes mineral matter which decreases catalytic activity and increases micropore structure. Water forms hydrogen bonds to oxygen functional groups in coal, and during drying, coals undergo structural changes which affect mild gasification. When methane reacts wit coal, devolatilization and carbon deposition occur, the rates of which depend on temperature and amount of ash. Thermal decomposition of IBC-101 coal starts at 300 C, which is much lower than previously believed, but maximum yields of liquids occur at 500 C for IBC-101 coal and at 550 C for IBC-102 coal. Aliphatic-to-aromatic ratios increase with increasing pyrolysis temperatures to 300 C and then decrease; therefore, liquids formed during gasification of 550 C or higher contain mainly aromatic compounds. Btu values of chars are higher after methane treatment than after helium treatment.

  19. Energetics and dynamics of solvent reorganization in charge-transfer excited states

    SciTech Connect (OSTI)

    Kozik, M.; Sutin, N.; Winkler, J.R.

    1989-01-01

    The dynamics of solvation of the Ru(bpy){sub 2}(CN){sub 2} metal-to-ligand charge-transfer excited state have been examined in a series of aliphatic alcohols. Steady-state emission spectra recorded at low temperature ({approx} 10 K) and at room temperature were used to resolve internal-mode and solvent contributions to the emission bandshape. Time-resolved emission spectra were fit to a model that takes into account internal-mode distortions as well as time-dependent broadening and shifts in emission maxima. A single- exponential solvent relaxation function does not adequately describe the temporal development of the emission profile of Ru(bpy){sub 2}(CN){sub 2} in alcohols. The evolution of the emission spectrum is clearly biphasic, and can be reasonably fit with a biexponential function. The slower of the two relaxation times is comparable to the longest longitudinal relaxation time reported for the bulk solvent. These slower components, however, represent less than half of the overall approach to equilibrium. Local heating due to above-threshold excitation, and local solvent relaxation are two likely sources of the faster dynamics. 25 refs., 3 figs., 2 tabs.

  20. High resolution capillary column development for selective separations in gas chromatography

    SciTech Connect (OSTI)

    Przybyciel, M.

    1985-01-01

    A review of techniques for the preparation of high resolution capillary columns for gas chromatography is presented. Surface roughing, surface deactivation, stationary phase coating, and stationary phase crosslinking are discussed. Criteria for the selection of GC stationary phases and procedures for column evaluation are presented. A method is proposed for the isolation and determination of crude oil contamination in tropical plants and sediments. The method uses Florisil (TM) chromatography for the simultaneous clean-up and fractionation of aliphatic and aromatic hydrocarbons. Crosslinked SE-54 fused silica capillary columns prepared in our laboratory were employed for all GC separations. Mass spectrometry was used to help locate and identify specific oil components despite the intense background of the chromatogram. Crude oil components were identified in extracts of mangrove plant samples collected from the Peck Slip oil spill site at Media Munda, Puerto Rico. Crude oil components were also identified in sediment samples from controlled oil spill of Prudhoe Bay oil at Laguna de Chiriqui, Panama.

  1. Molecular and crystal structures of p-heptyloxyphenyl p-hexyloxybenzoate and p-butyloxyphenyl p-heptyloxybenzoate: Mesophase design

    SciTech Connect (OSTI)

    Kuz'mina, L. G. Gunina, M. A.; Churakov, A. V.; Pestov, S. M.

    2013-03-15

    Two aromatic esters with the formulas C{sub 6}H{sub 13}-O-C{sub 6}H{sub 4}-C(O)O-C{sub 6}H{sub 4}-O-C{sub 7}H{sub 15} (1) and C{sub 7}H{sub 15}-O-C{sub 6}H{sub 4}-C(O)O-C{sub 6}H{sub 4}-O-C{sub 4}H{sub 9} (2) belonging to nematic liquid-crystal compounds were studied by X-ray diffraction. Compound 1 crystallizes in two modifications: monoclinic (1-m) and triclinic (1-tr). The crystal packing of 1 and 2 is built from alternating loosely packed aliphatic regions and closely packed aromatic regions. In crystal structures 1-m and 2, the aromatic regions are linked into chains by hydrogen bonds with the participation of the carbonyl oxygen atom of the ester group and the C-H fragment of the benzene ring, but these hydrogen bonds in 1-m are much weaker than in 2. In 1-m there are {pi}-stacking interactions between the molecules, resulting in the formation of centrosymmetric dimers with an interplanar distance of 3.45 A. In 1-tr, the aromatic fragments form a herringbone packing motif favorable for a two-dimensional network of directional C-H...{pi}-system interactions.

  2. Nitrous oxide production from radiolysis of simulted high-level nuclear waste solutions

    SciTech Connect (OSTI)

    Walker, D.D.; Hobbs, D.T.; Tiffany, J.B.; Bibler, N.E.; Meisel, D.

    1992-07-01

    Nitrous oxide gas (N{sub 2}O) is produced by the radiolysis of aqueous nitrate or nitrite solutions in the presence of organic compounds. When ethylenediaminetetraacetic acid (EDTA) or N- (2-hydroxyethyl)-ethylenediaminetriacetic acid (HEDTA) is present, the G-value for hydrogen increases and N{sub 2}O become the major gaseous product (G=0.54). A survey of organic compounds indicates the amount of N{sub 2}O formed depends on the structure of the organic. With highly oxidized organics (carbonate, formate, acetate and oxalate), little or no N{sub 2}O is formed. Aromatic and aliphatic organics (sodium tetraphenylborate, benzene, phenol, n-paraffin, and tributylphosphate) produce small amounts of N{sub 2}O. Water soluble, easily oxidized organics (methanol, ethanol, isopropanol, n-butanol, acetone, and ethylene glycol) produce large amounts of N{sub 2}O relative to the previous two categories. Nitrous oxide production is not greatly affected by pH between neutral and pH=13, but increases significantly in acid solution. The G-value for N{sub 2}O production in 10 wt% potassium tetraphenylborate slurries has been measured under process conditions important at the Savannah River Site.

  3. Nitrous oxide production from radiolysis of simulted high-level nuclear waste solutions

    SciTech Connect (OSTI)

    Walker, D.D.; Hobbs, D.T.; Tiffany, J.B.; Bibler, N.E. ); Meisel, D. )

    1992-01-01

    Nitrous oxide gas (N{sub 2}O) is produced by the radiolysis of aqueous nitrate or nitrite solutions in the presence of organic compounds. When ethylenediaminetetraacetic acid (EDTA) or N- (2-hydroxyethyl)-ethylenediaminetriacetic acid (HEDTA) is present, the G-value for hydrogen increases and N{sub 2}O become the major gaseous product (G=0.54). A survey of organic compounds indicates the amount of N{sub 2}O formed depends on the structure of the organic. With highly oxidized organics (carbonate, formate, acetate and oxalate), little or no N{sub 2}O is formed. Aromatic and aliphatic organics (sodium tetraphenylborate, benzene, phenol, n-paraffin, and tributylphosphate) produce small amounts of N{sub 2}O. Water soluble, easily oxidized organics (methanol, ethanol, isopropanol, n-butanol, acetone, and ethylene glycol) produce large amounts of N{sub 2}O relative to the previous two categories. Nitrous oxide production is not greatly affected by pH between neutral and pH=13, but increases significantly in acid solution. The G-value for N{sub 2}O production in 10 wt% potassium tetraphenylborate slurries has been measured under process conditions important at the Savannah River Site.

  4. The effect of feedstock additives on FCC catalyst deactivation

    SciTech Connect (OSTI)

    Hughes, R.; Koon, C.L.; McGhee, B.

    1995-12-31

    Fluid catalytic cracking is a major petroleum refining process and because of this the deactivation of FCC catalysts by coke deposition has been the subject of considerable investigation during the past 50 years. Nevertheless, a lack of understanding of the fundamental understanding of processes leading to coke formation still exists. Basic studies using Zeolites have usually involved excessively high levels of coke deposits compared to normal FCC operation. The present study addresses coke formation at realistic levels of 0.5 to 1.0% w/w using a standard MAT reactor in which concentrations of 1% and 10% of various additives were added to the n-hexadecane feedstock. These additives included, quinoline, phenanthrene, benzofuran, thianaphthene and indene. The coke formed was characterised by mass spectrometry and was significantly aliphatic in nature, the amount formed increasing in the order quinoline, phenanthrene, thianaphthene, benzofuran, indene. Quinoline acts primarily as a poison, whereas the other additives tend to promote coke formation in n-hexadecane cracking.

  5. Chemical tagging of chlorinated phenols for their facile detection and analysis by NMR spectroscopy

    SciTech Connect (OSTI)

    Valdez, Carlos A.; Leif, Roald N.

    2015-03-22

    A derivatization method that employs diethyl (bromodifluoromethyl) phosphonate (DBDFP) to efficiently tag the endocrine disruptor pentachlorophenol (PCP) and other chlorinated phenols (CPs) along with their reliable detection and analysis by NMR is presented. The method accomplishes the efficient alkylation of the hydroxyl group in CPs with the difluoromethyl (CF2H) moiety in extremely rapid fashion (5 min), at room temperature and in an environmentally benign manner. The approach proved successful in difluoromethylating a panel of 18 chlorinated phenols, yielding derivatives that displayed unique 1H, 19F NMR spectra allowing for the clear discrimination between isomerically related CPs. Due to its biphasic nature, the derivatization can be applied to both aqueous and organic mixtures where the analysis of CPs is required. Furthermore, the methodology demonstrates that PCP along with other CPs can be selectively derivatized in the presence of other various aliphatic alcohols, underscoring the superiority of the approach over other general derivatization methods that indiscriminately modify all analytes in a given sample. The present work demonstrates the first application of NMR on the qualitative analysis of these highly toxic and environmentally persistent species.

  6. Inhalation developmental toxicology studies: Teratology study of acetone in mice and rats: Final report

    SciTech Connect (OSTI)

    Mast, T.J.; Evanoff, J.J.; Rommereim, R.L.; Stoney, K.H.; Weigel, R.J.; Westerberg, R.B.

    1988-11-01

    Acetone, an aliphatic ketone, is a ubiquitous industrial solvent and chemical intermediate; consequently, the opportunity for human exposure is high. The potential for acetone to cause developmental toxicity was assessed in Sprague-Dawley rats exposed to 0, 440, 2200, or 11000 ppm, and in Swiss (CD-1) mice exposed to 0, 440, 2200, and 6600 ppm acetone vapors, 6 h/day, 7 days/week. Each of the four treatment groups consisted of 10 virgin females (for comparison), and approx.32 positively mated rats or mice. Positively mated mice were exposed on days 6-17 of gestation (dg), and rats on 6-19 dg. The day of plug or sperm detection was designated as 0 dg. Body weights were obtained throughout the study period, and uterine and fetal body weights were obtained at sacrifice (rats, 20 dg; mice, 18 dg). Implants were enumerated and their status recorded. Live fetuses were sexed and examined for gross, visceral, skeletal, and soft-tissue craniofacial defects. 46 refs., 6 figs., 27 tabs.

  7. Structural Transformation of Isolated Poplar and Switchgrass Lignins from Dilute Acid Pretreatment

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

    Sun, Qining; Pu, Yunqiao; Meng, Xianzhi; Wells, Tyrone; Ragauskas, Arthur J.

    2015-08-27

    A key step in conversion of cellulosic biomass into sustainable fuels and chemicals is thermochemical pretreatment to reduce plant cell wall recalcitrance. Obtaining an improved understanding of the fundamental chemistry of lignin, the most recalcitrant component of biomass, during pretreatment is critical to the continued development of renewable biofuel production. To examine the intrinsic chemistry of lignin during dilute acid pretreatment (DAP), lignin was isolated from poplar and switchgrass using a cellulolytic enzyme system and then treated under DAP conditions. These results highlight that lignin is subjected to depolymerization reactions within the first 2 min of dilute acid pretreatment andmore » these changes are accompanied by increased generation of aliphatic and phenolic hydroxyl groups of lignin. This is followed by a competing set of depolymerization and repolymerization reactions that lead to a decrease in the content of guaiacyl lignin units and an increase in condensed lignin units as the reaction residence time is extended beyond 5 min. Finally, we showed that a detailed comparison of changes in functional groups and molecular weights of cellulolytic enzyme lignins with different structural parameters, related to the recalcitrant properties of lignin, could be successfully altered during DAP conditions.« less

  8. Superfund Record of Decision (EPA Region 7): Vogel Paint and Wax, Maurice, IA. (First remedial action), September 1989. Final report

    SciTech Connect (OSTI)

    Not Available

    1989-09-20

    The Vogel Paint and Wax (VPW) site is an approximately two-acre disposal area two miles southwest of the town of Maurice, in Sioux County, Iowa. Adjacent land uses are primarily agricultural; however, several private residences are within one-quarter mile of the site. A surficial sand and gravel aquifer underlies the site and supplies nearby private wells and the Southern Sioux County Rural Water System, located a mile and one half southeast of the site. Paint sludge, resins, solvents, and other paint-manufacturing wastes were disposed of at the site between 1971 and 1979. VPW records indicate that approximately 43,000 gallons of aliphatic and aromatic hydrocarbons and 6,000 pounds of metals waste were buried at the site. The primary contaminants of concern affecting the soil and ground water are VOCs including benzene, toluene, and xylenes; and metals including chromium and lead. The selected remedial action for this site includes excavation of contaminated soil and separation of solid and liquid wastes; onsite bioremediation of 3,000 cubic yards of the contaminated soil in a fully contained surface impoundment unit, or onsite thermal treatment if soil contains high metal content; and stabilization of treated soil, if necessary to prevent leaching of metals, followed by disposal in the excavated area.

  9. Solid-state organometallic chemistry of molecular metal oxide clusters: C-H activation by an iridium polyoxometalate

    SciTech Connect (OSTI)

    Siedle, A.R.; Newmark, R.A.; Brown-Wensley, K.A.; Skarjune, R.P.; Haddad, L.C.; Hodgson, K.O.; Roe, A.L.

    1988-09-01

    Hydrogenation of ((Ph/sub 3/P)/sub 2/Ir(C/sub 8/H/sub 12/))/sub 3/PW/sub 12/O/sub 40/ in a solid-gas reaction produces ((Ph/sub 3/P)/sub 2/IrH/sub 2/)/sub 3/PW/sub 12/O/sub 40/. EXAFS studies of the molybdenum analogue indicate the presence of isolated, lattice-stabilized (Ph/sub 3/P)/sub 2/IrH/sub 2//sup +/ ions. H/emdash/D exchange with CD/sub 3/CH/double bond/CH/sub 2/ occurs via a reversible C/emdash/H addition reaction that also produces ((Ph/sub 3/P)/sub 2/IrH(/pi/-C/sub 3/H/sub 5/))/sub 3/PW/sub 12/O/sub 40/ and scrambles the C/sub 3/D/sub 3/H/sub 3/ deuterium label. Exchange with toluene is selective and involves activation of aromatic but not aliphatic C-H bonds. Slow exchange with c-C/sub 6/D/sub 12/ also occurs.

  10. Complexation of N4-Tetradentate Ligands with Nd(III) and Am(III)

    SciTech Connect (OSTI)

    Ogden, Mark D.; Sinkov, Sergey I.; Meier, G. Patrick; Lumetta, Gregg J.; Nash, Kenneth L.

    2012-12-06

    To improve understanding of aza-complexants in trivalent actinidelanthanide separations, a series of tetradentate N-donor ligands have been synthesized and their complexation of americium(III) and neodymium(III) investigated by UVvisible spectrophotometry in methanolic solutions. The six pyridine/alkyl amine/imine ligands are N,N0-bis(2-methylpyridyl)-1,2-diaminoethane, N,N0-bis(2-methylpyridyl)-1,3-diaminopropane, trans-N,N-bis(2-pyridylmethyl)-1,2-diaminocyclohexane (BPMDAC), N,N-bis(2-pyridylmethyl)piperazine, N,N-bis-[pyridin-2-ylmethylene]ethane-1,2-diamine, and trans-N,Nbis-([pyridin-2-ylmethylene]-cyclohexane-1,2-diamine. Each ligand has two pyridine groups and two aliphatic amine/imine N-donor atoms arranged with different degrees of preorganization and structural backbone rigidity. Conditional stability constants for the complexes of Am(III) and Nd(III) by these ligands establish the selectivity patterns. The overall selectivity of Am(III) over Nd(III) is similar to that reported for the terdentate bis(dialkyltriazinyl)pyridine molecules. The cyclohexane amine derivative (BPMDAC) is the strongest complexant and shows the highest selectivity for Am(III) over Nd(III) while the imines appear to prefer a bridging arrangement between two cations. These results suggest that this series of ligands could be employed to develop an enhanced actinide(III) lanthanide(III) separation system.

  11. Peptide affinity labels for thrombin and other trypsin-like proteases

    DOE Patents [OSTI]

    Shaw, Elliott N.; Kettner, Charles A.

    1982-03-09

    A peptide affinity label of the formula (I): ##STR1## wherein X is a radical capable of acting as a leaving group in a nucleophilic substitution reaction; A is an aromatic amino acid residue; B is H, or a C.sub.1 -C.sub.4 alkyl group, or aryl; Y is selected from the group consisting of hydrogen, aroyl, C.sub.1 -C.sub.6 acyl, and Q--(A)--.sub.n, wherein Q=hydrogen, aroyl, or C.sub.1 -C.sub.6 acyl, n=1-10, A is an amino acid residue selected from the aliphatic, hydroxy-containing, carboxylic acid group, and amide-thereof-containing, aromatic, sulfur-containing and imino-containing amino acids; and wherein J is selected from the group consisting of --CH.sub.2 --, --CH.sub.2 --CH.sub.2 --,--CH.sub.2 --CH.sub.2 --CH.sub.2 --, --CH.dbd.CH-- and --CH(OH)--CH.sub.2. The affinity label is useful for irreversibly inactivating thrombin and trypsin-like enzymes and may be used as a potential anticlotting agent.

  12. Microheterogeneous Thoria-Urania Fuels for Pressurized Water Reactors

    SciTech Connect (OSTI)

    Shwageraus, Eugene; Zhao Xianfeng; Driscoll, Michael J.; Hejzlar, Pavel; Kazimi, Mujid S.; Herring, J. Stephen

    2004-07-15

    A thorium-based fuel cycle for light water reactors will reduce the plutonium generation rate and enhance the proliferation resistance of the spent fuel. However, priming the thorium cycle with {sup 235}U is necessary, and the {sup 235}U fraction in the uranium must be limited to below 20% to minimize proliferation concerns. Thus, a once-through thorium-uranium dioxide (ThO{sub 2}-UO{sub 2}) fuel cycle of no less than 25% uranium becomes necessary for normal pressurized water reactor (PWR) operating cycle lengths. Spatial separation of the uranium and thorium parts of the fuel can improve the achievable burnup of the thorium-uranium fuel designs through more effective breeding of {sup 233}U from the {sup 232}Th. Focus is on microheterogeneous fuel designs for PWRs, where the spatial separation of the uranium and thorium is on the order of a few millimetres to a few centimetres, including duplex pellet, axially microheterogeneous fuel, and a checkerboard of uranium and thorium pins. A special effort was made to understand the underlying reactor physics mechanisms responsible for enhancing the achievable burnup at spatial separation of the two fuels. The neutron spectral shift was identified as the primary reason for the enhancement of burnup capabilities. Mutual resonance shielding of uranium and thorium is also a factor; however, it is small in magnitude. It is shown that the microheterogeneous fuel can achieve higher burnups, by up to 15%, than the reference all-uranium fuel. However, denaturing of the {sup 233}U in the thorium portion of the fuel with small amounts of uranium significantly impairs this enhancement. The denaturing is also necessary to meet conventional PWR thermal limits by improving the power share of the thorium region at the beginning of fuel irradiation. Meeting thermal-hydraulic design requirements by some of the microheterogeneous fuels while still meeting or exceeding the burnup of the all-uranium case is shown to be potentially feasible. However, the large power imbalance between the uranium and thorium regions creates several design challenges, such as higher fission gas release and cladding temperature gradients. A reduction of plutonium generation by a factor of 3 in comparison with all-uranium PWR fuel using the same initial {sup 235}U content was estimated. In contrast to homogeneously mixed U-Th fuel, microheterogeneous fuel has a potential for economic performance comparable to the all-UO{sub 2} fuel provided that the microheterogeneous fuel incremental manufacturing costs are negligibly small.

  13. Structural and functional characterization of the hazelnut allergen Cor a 8

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

    Offermann, Lesa R.; Bublin, Merima; Perdue, Makenzie L.; Pfeifer, Sabine; Dubiela, Pawel; Borowski, Tomasz; Chruszcz, Maksymilian; Hoffmann-Sommergruber, Karin

    2015-09-28

    Nonspecific lipid transfer proteins (nsLTPs) are basic proteins, stabilized by four disulfide bonds, and are expressed throughout the plant kingdom. These proteins are also known as important allergens in fruits and tree nuts. In this study, the nsLTP from hazelnuts, Cor a 8, was purified and its crystal structure determined. The protein is stable at low pH and refolds after thermal denaturation. Molecular dynamics simulations were used to provide an insight into conformational changes of Cor a 8 upon ligand binding. When known epitope areas from Pru p 3 were compared to those of Cor a 8, differences were obvious,more » which may contribute to limited cross-reactivity between peach and hazelnut allergens. The differences in epitope regions may contribute to limited cross-reactivity between Cor a 8 and nsLTPs from other plant sources. The structure of Cor a 8 represents the first resolved structure of a hazelnut allergen.« less

  14. Progressive structural changes of Avicel, bleached softwood, and bacterial cellulose during enzymatic hydrolysis

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

    Kafle, Kabindra; Shin, Heenae; Lee, Christopher M.; Park, Sunkyu; Kim, Seong H.

    2015-10-14

    A comprehensive picture of structural changes of cellulosic biomass during enzymatic hydrolysis is essential for a better understanding of enzymatic actions and development of more efficient enzymes. In this study, a suite of analytical techniques including sum frequency generation (SFG) spectroscopy, infrared (IR) spectroscopy, x-ray diffraction (XRD), and x-ray photoelectron spectroscopy (XPS) were employed for lignin-free model biomass samples—Avicel, bleached softwood, and bacterial cellulose—to find correlations between the decrease in hydrolysis rate over time and the structural or chemical changes of biomass during the hydrolysis reaction. The results showed that the decrease in hydrolysis rate over time appears to correlatemore » with the irreversible deposition of non-cellulosic species (either reaction side products or denatured enzymes, or both) on the cellulosic substrate surface. The crystallinity, degree of polymerization, and meso-scale packing of cellulose do not seem to positively correlate with the decrease in hydrolysis rate observed for all three substrates tested in this study. Moreover, it was also found that the cellulose Iα component of the bacterial cellulose is preferentially hydrolyzed by the enzyme than the cellulose Iβ component.« less

  15. Method for introducing unidirectional nested deletions

    DOE Patents [OSTI]

    Dunn, J.J.; Quesada, M.A.; Randesi, M.

    1999-07-27

    Disclosed is a method for the introduction of unidirectional deletions in a cloned DNA segment. More specifically, the method comprises providing a recombinant DNA construct comprising a DNA segment of interest inserted in a cloning vector. The cloning vector has an f1 endonuclease recognition sequence adjacent to the insertion site of the DNA segment of interest. The recombinant DNA construct is then contacted with the protein pII encoded by gene II of phage f1 thereby generating a single-stranded nick. The nicked DNA is then contacted with E. coli Exonuclease III thereby expanding the single-stranded nick into a single-stranded gap. The single-stranded gapped DNA is then contacted with a single-strand-specific endonuclease thereby producing a linearized DNA molecule containing a double-stranded deletion corresponding in size to the single-stranded gap. The DNA treated in this manner is then incubated with DNA ligase under conditions appropriate for ligation. Also disclosed is a method for producing single-stranded DNA probes. In this embodiment, single-stranded gapped DNA, produced as described above, is contacted with a DNA polymerase in the presence of labeled nucleotides to fill in the gap. This DNA is then linearized by digestion with a restriction enzyme which cuts outside the DNA segment of interest. The product of this digestion is then denatured to produce a labeled single-stranded nucleic acid probe. 1 fig.

  16. Method for producing labeled single-stranded nucleic acid probes

    DOE Patents [OSTI]

    Dunn, John J.; Quesada, Mark A.; Randesi, Matthew

    1999-10-19

    Disclosed is a method for the introduction of unidirectional deletions in a cloned DNA segment. More specifically, the method comprises providing a recombinant DNA construct comprising a DNA segment of interest inserted in a cloning vector, the cloning vector having an f1 endonuclease recognition sequence adjacent to the insertion site of the DNA segment of interest. The recombinant DNA construct is then contacted with the protein pII encoded by gene II of phage f1 thereby generating a single-stranded nick. The nicked DNA is then contacted with E. coli Exonuclease III thereby expanding the single-stranded nick into a single-stranded gap. The single-stranded gapped DNA is then contacted with a single-strand-specific endonuclease thereby producing a linearized DNA molecule containing a double-stranded deletion corresponding in size to the single-stranded gap. The DNA treated in this manner is then incubated with DNA ligase under conditions appropriate for ligation. Also disclosed is a method for producing single-stranded DNA probes. In this embodiment, single-stranded gapped DNA, produced as described above, is contacted with a DNA polymerase in the presence of labeled nucleotides to fill in the gap. This DNA is then linearized by digestion with a restriction enzyme which cuts outside the DNA segment of interest. The product of this digestion is then denatured to produce a labeled single-stranded nucleic acid probe.

  17. Method for introducing unidirectional nested deletions

    DOE Patents [OSTI]

    Dunn, John J.; Quesada, Mark A.; Randesi, Matthew

    1999-07-27

    Disclosed is a method for the introduction of unidirectional deletions in a cloned DNA segment. More specifically, the method comprises providing a recombinant DNA construct comprising a DNA segment of interest inserted in a cloning vector, the cloning vector having an f1 endonuclease recognition sequence adjacent to the insertion site of the DNA segment of interest. The recombinant DNA construct is then contacted with the protein pII encoded by gene II of phage f1 thereby generating a single-stranded nick. The nicked DNA is then contacted with E. coli Exonuclease III thereby expanding the single-stranded nick into a single-stranded gap. The single-stranded gapped DNA is then contacted with a single-strand-specific endonuclease thereby producing a linearized DNA molecule containing a double-stranded deletion corresponding in size to the single-stranded gap. The DNA treated in this manner is then incubated with DNA ligase under conditions appropriate for ligation. Also disclosed is a method for producing single-stranded DNA probes. In this embodiment, single-stranded gapped DNA, produced as described above, is contacted with a DNA polymerase in the presence of labeled nucleotides to fill in the gap. This DNA is then linearized by digestion with a restriction enzyme which cuts outside the DNA segment of interest. The product of this digestion is then denatured to produce a labeled single-stranded nucleic acid probe.

  18. A zinc complex of heparan sulfate destabilises lysozyme and alters its conformation

    SciTech Connect (OSTI)

    Hughes, Ashley J. [Institute of Integrative Biology, University of Liverpool, Liverpool L69 7ZB (United Kingdom) [Institute of Integrative Biology, University of Liverpool, Liverpool L69 7ZB (United Kingdom); Diamond Light Source Ltd., Diamond House, Didcot, Oxfordshire OX11 0DE (United Kingdom); Hussain, Rohanah [Diamond Light Source Ltd., Diamond House, Didcot, Oxfordshire OX11 0DE (United Kingdom)] [Diamond Light Source Ltd., Diamond House, Didcot, Oxfordshire OX11 0DE (United Kingdom); Cosentino, Cesare; Guerrini, Marco [Istituto di Chimica e Biochimica 'G. Ronzoni', Via G. Colombo 81, Milano 20133 (Italy)] [Istituto di Chimica e Biochimica 'G. Ronzoni', Via G. Colombo 81, Milano 20133 (Italy); Siligardi, Giuliano [Diamond Light Source Ltd., Diamond House, Didcot, Oxfordshire OX11 0DE (United Kingdom)] [Diamond Light Source Ltd., Diamond House, Didcot, Oxfordshire OX11 0DE (United Kingdom); Yates, Edwin A., E-mail: eayates@liv.ac.uk [Institute of Integrative Biology, University of Liverpool, Liverpool L69 7ZB (United Kingdom); Rudd, Timothy R., E-mail: trudd@liv.ac.uk [Institute of Integrative Biology, University of Liverpool, Liverpool L69 7ZB (United Kingdom); Istituto di Chimica e Biochimica 'G. Ronzoni', Via G. Colombo 81, Milano 20133 (Italy)

    2012-09-07

    Highlights: Black-Right-Pointing-Pointer Zinc-heparan sulfate complex destabilises lysozyme, a model amyloid protein. Black-Right-Pointing-Pointer Addition of zinc, without heparan sulfate, stabilises lysozyme. Black-Right-Pointing-Pointer Heparan sulfate cation complexes provide alternative protein folding routes. -- Abstract: The naturally occurring anionic cell surface polysaccharide heparan sulfate is involved in key biological activities and is implicated in amyloid formation. Following addition of Zn-heparan sulfate, hen lysozyme, a model amyloid forming protein, resembled {beta}-rich amyloid by far UV circular dichroism (increased {beta}-sheet: +25%), with a significantly reduced melting temperature (from 68 to 58 Degree-Sign C) by fluorescence shift assay. Secondary structure stability of the Zn-heparan sulfate complex with lysozyme was also distinct from that with heparan sulfate, under stronger denaturation conditions using synchrotron radiation circular dichroism. Changing the cation associated with heparan sulfate is sufficient to alter the conformation and stability of complexes formed between heparan sulfate and lysozyme, substantially reducing the stability of the protein. Complexes of heparan sulfate and cations, such as Zn, which are abundant in the brain, may provide alternative folding routes for proteins.

  19. The HPr Proteins from the Thermophile Bacillus stearothermophilus Can Form Domain-swapped Dimers

    SciTech Connect (OSTI)

    Sridharan, Sudharsan; Razvi, Abbas; Scholtz, J. Martin; Sacchettini, James C. (TAM)

    2010-07-20

    The study of proteins from extremophilic organisms continues to generate interest in the field of protein folding because paradigms explaining the enhanced stability of these proteins still elude us and such studies have the potential to further our knowledge of the forces stabilizing proteins. We have undertaken such a study with our model protein HPr from a mesophile, Bacillus subtilis, and a thermophile, Bacillus stearothermophilus. We report here the high-resolution structures of the wild-type HPr protein from the thermophile and a variant, F29W. The variant proved to crystallize in two forms: a monomeric form with a structure very similar to the wild-type protein as well as a domain-swapped dimer. Interestingly, the structure of the domain-swapped dimer for HPr is very different from that observed for a homologous protein, Crh, from B. subtilis. The existence of a domain-swapped dimer has implications for amyloid formation and is consistent with recent results showing that the HPr proteins can form amyloid fibrils. We also characterized the conformational stability of the thermophilic HPr proteins using thermal and solvent denaturation methods and have used the high-resolution structures in an attempt to explain the differences in stability between the different HPr proteins. Finally, we present a detailed analysis of the solution properties of the HPr proteins using a variety of biochemical and biophysical methods.

  20. Mechanism and kinetics of peptide partitioning into membranes

    SciTech Connect (OSTI)

    Ulmschneider, Martin [University of Oxford; Killian, J Antoinette [University of Utrecht; Doux, Jacques P. F. [University of Utrecht; Smith, Jeremy C [ORNL; Ulmschneider, Jakob [University of Heidelberg

    2010-02-01

    Partitioning properties of transmembrane (TM) polypeptide segments directly determine membrane protein folding, stability, and function, and their understanding is vital for rational design of membrane active peptides. However, direct determination of water-to-bilayer transfer of TM peptides has proved difficult. Experimentally, sufficiently hydrophobic peptides tend to aggregate, while atomistic computer simulations at physiological temperatures cannot yet reach the long time scales required to capture partitioning. Elevating temperatures to accelerate the dynamics has been avoided, as this was thought to lead to rapid denaturing. However, we show here that model TM peptides (WALP) are exceptionally thermostable. Circular dichroism experiments reveal that the peptides remain inserted into the lipid bilayer and are fully helical, even at 90 C. At these temperatures, sampling is 50 500 times faster, sufficient to directly simulate spontaneous partitioning at atomic resolution. A folded insertion pathway is observed, consistent with three-stage partitioning theory. Elevated temperature simulation ensembles further allow the direct calculation of the insertion kinetics, which is found to be first-order for all systems. Insertion barriers are Hin = 15 kcal/mol for a general hydrophobic peptide and 23 kcal/mol for the tryptophan-flanked WALP peptides. The corresponding insertion times at room temperature range from 8.5 s to 163 ms. High-temperature simulations of experimentally validated thermostable systems suggest a new avenue for systematic exploration of peptide partitioning properties.

  1. Probing the mechanism of rubredoxin thermal unfolding in the absence of salt bridges by temperature jump experiments

    SciTech Connect (OSTI)

    Henriques, Barbara J. [Instituto Tecnologia Quimica e Biologica, Universidade Nova de Lisboa, Oeiras (Portugal); Saraiva, Ligia M. [Instituto Tecnologia Quimica e Biologica, Universidade Nova de Lisboa, Oeiras (Portugal); Gomes, Claudio M. [Instituto Tecnologia Quimica e Biologica, Universidade Nova de Lisboa, Oeiras (Portugal)]. E-mail: gomes@itqb.unl.pt

    2005-08-05

    Rubredoxins are the simplest type of iron-sulphur proteins and in recent years they have been used as model systems in protein folding and stability studies, especially the proteins from thermophilic sources. Here, we report our studies on the rubredoxin from the hyperthermophile Methanococcus jannaschii (T {sub opt} = 85 deg C), which was investigated in respect to its thermal unfolding kinetics by temperature jump experiments. Different spectroscopic probes were used to monitor distinct structural protein features during the thermal transition: the integrity of the iron-sulphur centre was monitored by visible absorption spectroscopy, whereas tertiary structure was followed by intrinsic tryptophan fluorescence and exposure of protein hydrophobic patches was sensed by 1-anilinonaphthalene-8-sulphonate fluorescence. The studies were performed at acidic pH conditions in which any stabilising contributions from salt bridges are annulled due to protonation of protein side chain groups. In these conditions, M. jannaschii rubredoxin assumes a native-like, albeit more flexible and open conformation, as indicated by a red shift in the tryptophan emission maximum and 1-anilinonaphthalene-8-sulphonate binding. Temperature jumps were monitored by the three distinct techniques and showed that the protein undergoes thermal denaturation via a simple two step mechanism, as loss of tertiary structure, hydrophobic collapse, and disintegration of the iron-sulphur centre are concomitant processes. The proposed mechanism is framed with the multiphasic one proposed for Pyrococcus furiosus rubredoxin, showing that a common thermal unfolding mechanism is not observed between these two closely related thermophilic rubredoxins.

  2. Structure of the prolyl-tRNA synthetase from the eukaryotic pathogen Giardia lamblia

    SciTech Connect (OSTI)

    Larson, Eric T.; Kim, Jessica E.; Napuli, Alberto J.; Verlinde, Christophe L. M. J.; Fan, Erkang; Zucker, Frank H.; Van Voorhis, Wesley C.; Buckner, Frederick S.; Hol, Wim G. J.; Merritt, Ethan A.

    2012-09-01

    The structure of Giardia prolyl-tRNA synthetase cocrystallized with proline and ATP shows evidence for half-of-the-sites activity, leading to a corresponding mixture of reaction substrates and product (prolyl-AMP) in the two active sites of the dimer. The genome of the human intestinal parasite Giardia lamblia contains only a single aminoacyl-tRNA synthetase gene for each amino acid. The Giardia prolyl-tRNA synthetase gene product was originally misidentified as a dual-specificity Pro/Cys enzyme, in part owing to its unexpectedly high off-target activation of cysteine, but is now believed to be a normal representative of the class of archaeal/eukaryotic prolyl-tRNA synthetases. The 2.2 Å resolution crystal structure of the G. lamblia enzyme presented here is thus the first structure determination of a prolyl-tRNA synthetase from a eukaryote. The relative occupancies of substrate (proline) and product (prolyl-AMP) in the active site are consistent with half-of-the-sites reactivity, as is the observed biphasic thermal denaturation curve for the protein in the presence of proline and MgATP. However, no corresponding induced asymmetry is evident in the structure of the protein. No thermal stabilization is observed in the presence of cysteine and ATP. The implied low affinity for the off-target activation product cysteinyl-AMP suggests that translational fidelity in Giardia is aided by the rapid release of misactivated cysteine.

  3. Optimizing immobilized enzyme performance in cell-free environments to produce liquid fuels.

    SciTech Connect (OSTI)

    Kumar, Sanat

    2015-02-05

    The overall goal of this project was to optimize enzyme performance for the production of bio-diesel fuel. Enzyme immobilization has attracted much attention as a means to increase productivity. Mesorporous silica materials have been known to be best suited for immobilizing enzymes. A major challenge is to ensure that the enzymatic activity is retained after immobilization. Two major factors which drive enzymatic deactivation are protein-surface and inter-protein interactions. Previously, we studied protein stability inside pores and how to optimize protein-surface interactions to minimize protein denaturation. In this work we studied eh effect of surface curvature and chemistry on inter-protein interactions. Our goal was to find suitable immobilization supports which minimize these inter-protein interactions. Our studies carried out in the frame work of Hydrophobic-Polar (HP) model showed that enzymes immobilized inside hydrophobic pores of optimal sizes are best suited to minimize these inter-protein interactions. Besides, this study is also of biological importance to understand the role of chaperonins in protein disaggregation. Both of these aspects profited immensely with collaborations with our experimental colleague, Prof. Georges Belfort (RPI), who performed the experimental analog of our theoretical works.

  4. Characterization of the BVEST waste tanks located at ORNL

    SciTech Connect (OSTI)

    Keller, J.M.; Giaquinto, J.M.; Meeks, A.M.

    1997-01-01

    During the fall of 1996 there was a major effort to sample and analyze the Active Liquid Low-Level Waste (LLLW) tanks at ORNL which include the Melton Valley Storage Tanks (MVST) and the Bethel Valley Evaporator Service Tanks (BVEST). The characterization data summarized in this report was needed to address waste processing options, address concerns dealing with the performance assessment (PA) data for the Waste Isolation Pilot Plant (WIPP), evaluate the waste characteristics with respect to the waste acceptance criteria (WAC) for WIPP and Nevada Test Site (NTS), address criticality concerns, and meet DOT requirements for transporting the waste. This report discusses the analytical characterization data for the supernatant and sludge in the BVEST waste tanks W-21, W-22, and W-23. The isotopic data presented in this report supports the position that fissile isotopes of uranium and plutonium were denatured as required by the administrative controls stated in the ORNL LLLW waste acceptance criteria (WAC). In general, the BVEST sludge was found to be hazardous based on RCRA characteristics and the transuranic alpha activity was well above the 100 nCi/g limit for TRU waste. The characteristics of the BVEST sludge relative to the WIPP WAC limits for fissile gram equivalent, plutonium equivalent activity, and thermal power from decay heat were estimated from the data in this report and found to be far below the upper boundary for any of the remote-handled transuranic waste (RH-TRU) requirements for disposal of the waste in WIPP.

  5. Multivariable optimization of fusion reactor blankets

    SciTech Connect (OSTI)

    Meier, W.R.

    1984-04-01

    The optimization problem consists of four key elements: a figure of merit for the reactor, a technique for estimating the neutronic performance of the blanket as a function of the design variables, constraints on the design variables and neutronic performance, and a method for optimizing the figure of merit subject to the constraints. The first reactor concept investigated uses a liquid lithium blanket for breeding tritium and a steel blanket to increase the fusion energy multiplication factor. The capital cost per unit of net electric power produced is minimized subject to constraints on the tritium breeding ratio and radiation damage rate. The optimal design has a 91-cm-thick lithium blanket denatured to 0.1% /sup 6/Li. The second reactor concept investigated uses a BeO neutron multiplier and a LiAlO/sub 2/ breeding blanket. The total blanket thickness is minimized subject to constraints on the tritium breeding ratio, the total neutron leakage, and the heat generation rate in aluminum support tendons. The optimal design consists of a 4.2-cm-thick BeO multiplier and 42-cm-thick LiAlO/sub 2/ breeding blanket enriched to 34% /sup 6/Li.

  6. Degradative capacities and bioaugmentation potential of an anaerobic benzene-degrading bacterium strain DN11

    SciTech Connect (OSTI)

    Yuki Kasai; Yumiko Kodama; Yoh Takahata; Toshihiro Hoaki; Kazuya Watanabe

    2007-09-15

    Azoarcus sp. strain DN11 is a denitrifying bacterium capable of benzene degradation under anaerobic conditions. The present study evaluated strain DN11 for its application to bioaugmentation of benzene-contaminated underground aquifers. Strain DN11 could grow on benzene, toluene, m-xylene, and benzoate as the sole carbon and energy sources under nitrate-reducing conditions, although o- and p-xylenes were transformed in the presence of toluene. Phenol was not utilized under anaerobic conditions. Kinetic analysis of anaerobic benzene degradation estimated its apparent affinity and inhibition constants to be 0.82 and 11 {mu}M, respectively. Benzene-contaminated groundwater taken from a former coal-distillation plant site in Aichi, Japan was anaerobically incubated in laboratory bottles and supplemented with either inorganic nutrients (nitrogen, phosphorus, and nitrate) alone, or the nutrients plus strain DN11, showing that benzene was significantly degraded only when DN11 was introduced. Denaturing gradient gel electrophoresis of PCR-amplified 16S rRNA gene fragments, and quantitative PCR revealed that DN11 decreased after benzene was degraded. Following the decrease in DN11 16S rRNA gene fragments corresponding to bacteria related to Owenweeksia hongkongensis and Pelotomaculum isophthalicum, appeared as strong bands, suggesting possible metabolic interactions in anaerobic benzene degradation. Results suggest that DN11 is potentially useful for degrading benzene that contaminates underground aquifers at relatively low concentrations. 50 refs., 6 figs., 1 tab.

  7. Santa Clara County Planar Solid Oxide Fuel Cell Demonstration Project

    SciTech Connect (OSTI)

    Fred Mitlitsky; Sara Mulhauser; David Chien; Deepak Shukla; David Weingaertner

    2009-11-14

    The Santa Clara County Planar Solid Oxide Fuel Cell (PSOFC) project demonstrated the technical viability of pre-commercial PSOFC technology at the County 911 Communications headquarters, as well as the input fuel flexibility of the PSOFC. PSOFC operation was demonstrated on natural gas and denatured ethanol. The Santa Clara County Planar Solid Oxide Fuel Cell (PSOFC) project goals were to acquire, site, and demonstrate the technical viability of a pre-commercial PSOFC technology at the County 911 Communications headquarters. Additional goals included educating local permit approval authorities, and other governmental entities about PSOFC technology, existing fuel cell standards and specific code requirements. The project demonstrated the Bloom Energy (BE) PSOFC technology in grid parallel mode, delivering a minimum 15 kW over 8760 operational hours. The PSOFC system demonstrated greater than 81% electricity availability and 41% electrical efficiency (LHV net AC), providing reliable, stable power to a critical, sensitive 911 communications system that serves geographical boundaries of the entire Santa Clara County. The project also demonstrated input fuel flexibility. BE developed and demonstrated the capability to run its prototype PSOFC system on ethanol. BE designed the hardware necessary to deliver ethanol into its existing PSOFC system. Operational parameters were determined for running the system on ethanol, natural gas (NG), and a combination of both. Required modeling was performed to determine viable operational regimes and regimes where coking could occur.

  8. Functional Stability Of A Mixed Microbial Consortia Producing PHA From Waste Carbon Sources

    SciTech Connect (OSTI)

    David N. Thompson; Erik R. Coats; William A. Smith; Frank J. Loge; Michael P. Wolcott

    2006-04-01

    Polyhydroxyalkanoates (PHAs), naturally-occurring biological polyesters that are microbially synthesized from a myriad of carbon sources, can be utilized as biodegradable substitutes for petroleum-derived thermoplastics. However, current PHA commercialization schemes are limited by high feedstock costs, the requirement for aseptic reactors, and high separation and purification costs. Bacteria indigenous to municipal waste streams can accumulate large quantities of PHA under environmentally controlled conditions; hence, a potentially more environmentally-effective method of production would utilize these consortia to produce PHAs from inexpensive waste carbon sources. In this study, PHA production was accomplished in sequencing batch bioreactors utilizing mixed microbial consortia from municipal activated sludge as inoculum, in cultures grown on real wastewaters. PHA production averaged 85%, 53%, and 10% of the cell dry weight from methanol-enriched pulp-and-paper mill foul condensate, fermented municipal primary solids, and biodiesel wastewater, respectively. The PHA-producing microbial consortia were examined to explore the microbial community changes that occurred during reactor operations, employing denaturing gradient gel electrophoresis (DGGE) of 16S-rDNA from PCR-amplified DNA extracts. Distinctly different communities were observed both between and within wastewaters following enrichment. More importantly, stable functions were maintained despite the differing and contrasting microbial populations.

  9. Structure-Based Design of Robust Glucose Biosensors using a Thermotoga maritima Periplasmic Glucose-Binding Protein

    SciTech Connect (OSTI)

    Tian,Y.; Cunco, M.; Changela, A.; Hocker, B.; Beese, L.; Hellinga, H.

    2007-01-01

    We report the design and engineering of a robust, reagentless fluorescent glucose biosensor based on the periplasmic glucose-binding protein obtained from Thermotoga maritima (tmGBP). The gene for this protein was cloned from genomic DNA and overexpressed in Escherichia coli, the identity of its cognate sugar was confirmed, ligand binding was studied, and the structure of its glucose complex was solved to 1.7 Angstroms resolution by X-ray crystallography. TmGBP is specific for glucose and exhibits high thermostability (midpoint of thermal denaturation is 119 {+-} 1 C and 144 {+-} 2 C in the absence and presence of 1 mM glucose, respectively). A series of fluorescent conjugates was constructed by coupling single, environmentally sensitive fluorophores to unique cysteines introduced by site-specific mutagenesis at positions predicted to be responsive to ligand-induced conformational changes based on the structure. These conjugates were screened to identify engineered tmGBPs that function as reagentless fluorescent glucose biosensors. The Y13C Cy5 conjugate is bright, gives a large response to glucose over concentration ranges appropriate for in vivo monitoring of blood glucose levels (1-30 mM), and can be immobilized in an orientation-specific manner in microtiter plates to give a reversible response to glucose. The immobilized protein retains its response after long-term storage at room temperature.

  10. Edge effects in propagation of terahertz radiation in subwavelength periodic structures

    SciTech Connect (OSTI)

    Gelmont, B. Parthasarathy, R.; Globus, T.

    2008-08-15

    Improving detection sensitivity of biological molecules with low absorption characteristics in the terahertz gap still remains an important issue in terahertz vibrational resonance spectroscopy. One possible way to increase coupling of incident terahertz radiation to molecules is to exploit local enhancement of electromagnetic field in periodic slot arrays. In this work, we show that periodic arrays of rectangular slots with subwavelength widths provide for local electromagnetic field enhancements due to edge effects in our low frequency range of interest, 10-25 cm{sup -1}. Periodic structures of Au doped Si and InSb were studied. The half power enhancement width is {approx}500 nm or less around the slot, edges in all cases, thereby possibly bringing terahertz sensing to the nanoscale. InSb is confirmed to offer the highest results with local power enhancements on the order of 1100 at frequency 14 cm{sup -1}. InSb and Si have large skin depths in our frequency range of interest and so the analysis of their structures was done through the Fourier expansion method of field diffracted from gratings. Surface impedance boundary conditions were employed to model the Au structure. The applications possibly include development of novel biosensors, and monitoring biophysical processes such as DNA denaturation.

  11. Sources of Technical Variability in Quantitative LC-MS Proteomics: Human Brain Tissue Sample Analysis.

    SciTech Connect (OSTI)

    Piehowski, Paul D.; Petyuk, Vladislav A.; Orton, Daniel J.; Xie, Fang; Moore, Ronald J.; Ramirez Restrepo, Manuel; Engel, Anzhelika; Lieberman, Andrew P.; Albin, Roger L.; Camp, David G.; Smith, Richard D.; Myers, Amanda J.

    2013-05-03

    To design a robust quantitative proteomics study, an understanding of both the inherent heterogeneity of the biological samples being studied as well as the technical variability of the proteomics methods and platform is needed. Additionally, accurately identifying the technical steps associated with the largest variability would provide valuable information for the improvement and design of future processing pipelines. We present an experimental strategy that allows for a detailed examination of the variability of the quantitative LC-MS proteomics measurements. By replicating analyses at different stages of processing, various technical components can be estimated and their individual contribution to technical variability can be dissected. This design can be easily adapted to other quantitative proteomics pipelines. Herein, we applied this methodology to our label-free workflow for the processing of human brain tissue. For this application, the pipeline was divided into four critical components: Tissue dissection and homogenization (extraction), protein denaturation followed by trypsin digestion and SPE clean-up (digestion), short-term run-to-run instrumental response fluctuation (instrumental variance), and long-term drift of the quantitative response of the LC-MS/MS platform over the 2 week period of continuous analysis (instrumental stability). From this analysis, we found the following contributions to variability: extraction (72%) >> instrumental variance (16%) > instrumental stability (8.4%) > digestion (3.1%). Furthermore, the stability of the platform and its suitability for discovery proteomics studies is demonstrated.

  12. Progressive structural changes of Avicel, bleached softwood, and bacterial cellulose during enzymatic hydrolysis

    SciTech Connect (OSTI)

    Kafle, Kabindra; Shin, Heenae; Lee, Christopher M.; Park, Sunkyu; Kim, Seong H.

    2015-10-14

    A comprehensive picture of structural changes of cellulosic biomass during enzymatic hydrolysis is essential for a better understanding of enzymatic actions and development of more efficient enzymes. In this study, a suite of analytical techniques including sum frequency generation (SFG) spectroscopy, infrared (IR) spectroscopy, x-ray diffraction (XRD), and x-ray photoelectron spectroscopy (XPS) were employed for lignin-free model biomass samples—Avicel, bleached softwood, and bacterial cellulose—to find correlations between the decrease in hydrolysis rate over time and the structural or chemical changes of biomass during the hydrolysis reaction. The results showed that the decrease in hydrolysis rate over time appears to correlate with the irreversible deposition of non-cellulosic species (either reaction side products or denatured enzymes, or both) on the cellulosic substrate surface. The crystallinity, degree of polymerization, and meso-scale packing of cellulose do not seem to positively correlate with the decrease in hydrolysis rate observed for all three substrates tested in this study. Moreover, it was also found that the cellulose Iα component of the bacterial cellulose is preferentially hydrolyzed by the enzyme than the cellulose Iβ component.

  13. The cost of ethanol production from lignocellulosic biomass -- A comparison of selected alternative processes. Final report

    SciTech Connect (OSTI)

    Grethlein, H.E.; Dill, T.

    1993-04-30

    The purpose of this report is to compare the cost of selected alternative processes for the conversion of lignocellulosic biomass to ethanol. In turn, this information will be used by the ARS/USDA to guide the management of research and development programs in biomass conversion. The report will identify where the cost leverages are for the selected alternatives and what performance parameters need to be achieved to improve the economics. The process alternatives considered here are not exhaustive, but are selected on the basis of having a reasonable potential in improving the economics of producing ethanol from biomass. When other alternatives come under consideration, they should be evaluated by the same methodology used in this report to give fair comparisons of opportunities. A generic plant design is developed for an annual production of 25 million gallons of anhydrous ethanol using corn stover as the model substrate at $30/dry ton. Standard chemical engineering techniques are used to give first order estimates of the capital and operating costs. Following the format of the corn to ethanol plant, there are nine sections to the plant; feed preparation, pretreatment, hydrolysis, fermentation, distillation and dehydration, stillage evaporation, storage and denaturation, utilities, and enzyme production. There are three pretreatment alternatives considered: the AFEX process, the modified AFEX process (which is abbreviated as MAFEX), and the STAKETECH process. These all use enzymatic hydrolysis and so an enzyme production section is included in the plant. The STAKETECH is the only commercially available process among the alternative processes.

  14. Energy recovery from the effluent of plants anaerobically digesting cellulosic urban solid waste. Final technical report, September 1978-September 1980

    SciTech Connect (OSTI)

    Doerr-Bullock, L.; Higgins, G.M.; Long, K.; Smith, R.B.; Swartzbaugh, J.T.

    1981-06-03

    The program objective was to study the parameters of concentration, time, temperature, and pH to find optimum conditions for enzymatically converting unreacted cellulose in the effluent of an anaerobic digester to glucose for ultimate conversion to methane, and then to project the economics to a 100 tons per day (TPD) plant. The data presented illustrate the amount of cellulose hydrolysis (in percent solubilized mass) for enzyme concentrations from 5 to 1000 C/sub 1/U/gram of substrate using either filter paper or anaerobically digested municipal solid waste (MSW) reacted over periods of time of from 0 to 72 hours. With an active bacterial culture present, the optimum temperature for the hydrolysis reaction was found to be 40/sup 0/C. The feasibility of recycling enzymes by ultrafilter capture was studied and shows that the recovered enzyme is not denatured by any of several possible enzyme loss mechanisms, either chemical, physical, or biological. Although rather stable enzyme-substrate complexes seem to be formed, various techniques permit a 55% enzyme recovery. Posttreatment of digested MSW by cellulase enzymes produces nearly a three-fold increase in biomethanation. However, the value of the additional methane produced in the process as studied is not sufficient to support the cost of enzymes. The feasibility of enzymatic hydrolysis as a biomethanation process step requires further process optimization or an entirely different process concept.

  15. Microbiology and physiology of anaerobic fermentation of cellulose. Progress report (4/30/91--4/30/92) and outline of work for the period 9/1/92--9/1/93

    SciTech Connect (OSTI)

    Ljungdahl, L.G.

    1992-12-31

    The authors are continuing their efforts to partly dissociate the cellulolytic enzyme complex of C. thermocellum. This complex named cellulosome (also existing as polycellulosome) consists of perhaps as many as 26 different subunits. It is extremely resistant to dissociation and denaturation. Treatments with urea and SDS have little effect unless the latter treatment is at high temperature. Significantly, some of the subunits after SDS dissociation have CMCase (endoglucanase) activity but no activity toward crystalline cellulose. The only reported success of hydrolysis of crystalline cellulose by cellulosomal subunits is by Wu et al. who isolated two protein fractions labeled SL and SS which when combined exhibit a low (about 1% of the original cellulosome) activity toward crystalline cellulose. The long standing goal is still to determine the activities of the individual subunits, to characterize them, to find out how they are associated in the cellulosome, and to establish the minimum number of subunits needed for efficient hydrolysis of crystalline cellulose. This report also presents the results of experiments on cellulose hydrolysis in aerobic fungi, as well as other anaerobic bacteria.

  16. Subcellulosome preparation with high cellulase activity from Clostridium thermocellum

    SciTech Connect (OSTI)

    Kobayashi, T.; Romaniec, M.P.M.; Fauth, U.; DeMain, A.L. )

    1990-10-01

    The authors have prepared a much simpler cellulase preparation than that of cellulosomes from the extracellular broth of Clostridium thermocellum. This subcellulosome preparation from C. thermocellum was obtained by column chromatography on CM-Bio-Gel A and then on a lectin-affinity material (Jacalin). The subcellulosome preparation is a macromolecular complex, composed of six main protein subunits (molecular weight, 210,000 to 58,000) revealed on sodium dodecyl sulfate-polyacrylamide gel electrophoresis. The specific activities of carboxymethylcellulase (CMCase) and Avicelase are 15- and 8-fold-higher, respectively, than those of crude extracellular cellulase. They could not further fractionate this preparation without denaturing it. The optimum pH and temperature of the subcellulosome preparation are 5.5 to 7.0 and 70{degree}C for CMCase and 5.5 to 7.0 and 65{degree}C for Avicelase. The subcellulosome preparation acted on various types of carboxymethyl cellulose, cellulose, and p-nitrophenyl-{beta}-D-cellobioside but not on p-nitrophenyl-{beta}-D-glucoside. Sulfhydryl reagents and N-bromosuccinimide inhibited both CMCase and Avicelase activities, whereas EDTA and o-phenanthroline inhibited Avicelase activity only.

  17. Improving Power Production in Acetate-Fed Microbial Fuel Cells via Enrichment of Exoelectrogenic Organisms in Flow-Through Systems

    SciTech Connect (OSTI)

    Borole, Abhijeet P; Hamilton, Choo Yieng; Vishnivetskaya, Tatiana A; Leak, David; Andras, Calin

    2009-01-01

    An exoelectrogenic, biofilm-forming microbial consortium was enriched in an acetate-fed microbial fuel cell (MFC) using a flow-through anode coupled to an air-cathode. Multiple parameters known to improve MFC performance were integrated in one design including electrode spacing, specific electrode surface area, flow-through design, minimization of dead volume within anode chamber, and control of external resistance. In addition, continuous feeding of carbon source was employed and the MFC was operated at intermittent high flows to enable removal of non-biofilm forming organisms over a period of six months. The consortium enriched using the modified design and operating conditions resulted in a power density of 345 W m-3 of net anode volume (3650 mW m-2), when coupled to a ferricyanide cathode. The enriched consortium included -, -, -Proteobacteria, Bacteroidetes and Firmicutes. Members of the order Rhodocyclaceae and Burkholderiaceae (Azospira spp. (49%), Acidovorax spp. (11%) and Comamonas spp. (7%)), dominated the microbial consortium. Denaturing gradient gel electrophoresis (DGGE) analysis based on primers selective for Archaea suggested a very low abundance of methanogens. Limiting the delivery of the carbon source via continuous feeding corresponding to the maximum cathodic oxidation rates permitted in the flow-through, air-cathode MFC resulted in coulombic efficiencies reaching 88 5.7%.

  18. Pyrolysis of waste tyres: A review

    SciTech Connect (OSTI)

    Williams, Paul T.

    2013-08-15

    Graphical abstract: - Highlights: Pyrolysis of waste tyres produces oil, gas and char, and recovered steel. Batch, screw kiln, rotary kiln, vacuum and fluidised-bed are main reactor types. Product yields are influenced by reactor type, temperature and heating rate. Pyrolysis oils are complex and can be used as chemical feedstock or fuel. Research into higher value products from the tyre pyrolysis process is reviewed. - Abstract: Approximately 1.5 billion tyres are produced each year which will eventually enter the waste stream representing a major potential waste and environmental problem. However, there is growing interest in pyrolysis as a technology to treat tyres to produce valuable oil, char and gas products. The most common reactors used are fixed-bed (batch), screw kiln, rotary kiln, vacuum and fluidised-bed. The key influence on the product yield, and gas and oil composition, is the type of reactor used which in turn determines the temperature and heating rate. Tyre pyrolysis oil is chemically very complex containing aliphatic, aromatic, hetero-atom and polar fractions. The fuel characteristics of the tyre oil shows that it is similar to a gas oil or light fuel oil and has been successfully combusted in test furnaces and engines. The main gases produced from the pyrolysis of waste tyres are H{sub 2}, C{sub 1}C{sub 4} hydrocarbons, CO{sub 2}, CO and H{sub 2}S. Upgrading tyre pyrolysis products to high value products has concentrated on char upgrading to higher quality carbon black and to activated carbon. The use of catalysts to upgrade the oil to a aromatic-rich chemical feedstock or the production of hydrogen from waste tyres has also been reported. Examples of commercial and semi-commercial scale tyre pyrolysis systems show that small scale batch reactors and continuous rotary kiln reactors have been developed to commercial scale.

  19. Self-Assembly, Molecular Ordering, and Charge Mobility in Solution-Processed Ultrathin Oligothiophene Films

    SciTech Connect (OSTI)

    Murphy,A.; Chang, P.; VanDyke, P.; Liu, J.; Frechet, J.; Subramanian, V.; Delongchamp, D.; Sambasivan, S.; Fischer, D.; Lin, E.

    2005-01-01

    Symmetrical {alpha}, {omega}-substituted quarter-(T4), penta-(T5), sexi-(T6), and heptathiophene (T7) oligomers containing thermally removable aliphatic ester solubilizing groups were synthesized, and their UV-vis and thermal characteristics were compared. Spun-cast thin films of each oligomer were examined with atomic force microscopy and near-edge X-ray absorption fine structure spectroscopy to evaluate the ability of the material to self-assemble from a solution-based process while maintaining complete surface coverage. Films of the T5-T7 oligomers self-assemble into crystalline terraces after thermal annealing with higher temperatures required to affect this transformation as the size of the oligomers increases. A symmetrical {alpha}, {omega}-substituted sexithiophene (T6-acid) that reveals carboxylic acids after thermolysis was also prepared to evaluate the effect of the presence of hydrogen-bonding moieties. The charge transport properties for these materials evaluated in top-contact thin film transistor devices were found to correlate with the observed morphology of the films. Therefore, the T4 and the T6-acid performed poorly because of incomplete surface coverage after thermolysis, while T5-T7 exhibited much higher performance as a result of molecular ordering. Increases in charge mobility correlated to increasing conjugation length with measured mobilities ranging from 0.02 to 0.06 cm2/(V{center_dot}s). The highest mobilities were measured when films of each oligomer had an average thickness between one and two monolayers, indicating that the molecules become exceptionally well-ordered during the thermolysis process. This unprecedented ordering of the solution-cast molecules results in efficient charge mobility rarely seen in such ultrathin films.

  20. Synthetic fuel aromaticity and staged combustion

    SciTech Connect (OSTI)

    Longanbach, J. R.; Chan, L. K.; Levy, A.

    1982-11-15

    Samples of middle and heavy SRC-II distillates were distilled into 50 C boiling point range fractions. These were characterized by measurements of their molecular weight, elemental analysis and basic nitrogen content and calculation of average molecular structures. The structures typically consisted of 1 to 3 aromatic rings fused to alicyclic rings with short, 1 to 3 carbon aliphatic side chains. The lower boiling fractions contained significant amounts (1 atom/molecule) of oxygen while the heavier fractions contained so few heteroatoms that they were essentially hydrocarbons. Laboratory scale oxidative-pyrolysis experiments were carried out at pyrolysis temperatures of 500 to 1100 C and oxygen concentrations from 0 to 100 percent of stoichiometry. Analysis of liquid products, collected in condensers cooled with liquid nitrogen showed that aromatization is a major reaction in the absence of oxygen. The oxygen-containing materials (phenolics) seem to be more resistant to thermal pyrolysis than unsubstituted aromatics. Nitrogen converts from basic to nonbasic forms at about 500 C. The nonbasic nitrogen is more stable and survives up to 700 C after which it is slowly removed. A recently constructed 50,000 Btu/hr staged combustor was used to study the chemistry of the nitrogen and aromatics. SRC II combustion was studied under fuel-rich, first-stage conditions at air/fuel ratios from 0.6 to 1.0 times stoichiometric. The chemistry of the fuel during combustion calls for further investigation in order to examine the mechanism by which HCN is evolved as a common intermediate for the formation of the nitrogen-containing gaseous combustion products. 25 references, 45 figures, 25 tables.

  1. 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.

  2. Studies of Human 2,4-Dienoyl CoA Reductase Shed New Light on Peroxisomal ?-Oxidation of Unsaturated Fatty Acids

    SciTech Connect (OSTI)

    Hua, Tian; Wu, Dong; Ding, Wei; Wang, Jiangyun; Shaw, Neil; Liu, Zhi-Jie

    2012-10-15

    Peroxisomes play an essential role in maintaining fatty acid homeostasis. Although mitochondria are also known to participate in the catabolism of fatty acids via ?-oxidation, differences exist between the peroxisomal and mitochondrial ?-oxidation. Only peroxisomes, but not mitochondrion, can shorten very long chain fatty acids. Here, we describe the crystal structure of a ternary complex of peroxisomal 2,4-dienoyl CoA reductases (pDCR) with hexadienoyl CoA and NADP, as a prototype for comparison with the mitochondrial 2,4-dienoyl CoA reductase (mDCR) to shed light on the differences between the enzymes from the two organelles at the molecular level. Unexpectedly, the structure of pDCR refined to 1.84 resolution reveals the absence of the tyrosine-serine pair seen in the active site of mDCR, which together with a lysine and an asparagine have been deemed a hallmark of the SDR family of enzymes. Instead, aspartate hydrogen-bonded to the C? hydroxyl via a water molecule seems to perturb the water molecule for protonation of the substrate. Our studies provide the first structural evidence for participation of water in the DCR-catalyzed reactions. Biochemical studies and structural analysis suggest that pDCRs can catalyze the shortening of six-carbon-long substrates in vitro. However, the Km values of pDCR for short chain acyl CoAs are at least 6-fold higher than those for substrates with 10 or more aliphatic carbons. Unlike mDCR, hinge movements permit pDCR to process very long chain polyunsaturated fatty acids.

  3. New organically templated photoluminescence iodocuprates(I)

    SciTech Connect (OSTI)

    Hou Qin; Zhao Jinjing; Zhao Tianqi; Jin Juan; Yu Jiehui; Xu Jiqing

    2011-07-15

    Two types of organic cyclic aliphatic diamine molecules piperazine (pip) and 1,3-bis(4-piperidyl)propane (bpp) were used, respectively, to react with an inorganic mixture of CuI and KI in the acidic CH{sub 3}OH solutions under the solvothermal conditions, generating finally three new organically templated iodocuprates as 2-D layered [(Hpip)Cu{sub 3}I{sub 4}] 1, 1-D chained [tmpip][Cu{sub 2}I{sub 4}] 2 (tmpip=N,N,N',N'-tetramethylpiperazinium) and dinuclear [H{sub 2}bpp]{sub 2}[Cu{sub 2}I{sub 5}] I.2H{sub 2}O 3. Note that the templating agent tmpip{sup 2+} in compound 2 originated from the in situ N-alkylation reaction between the pip molecule and the methanol solvent. The photoluminescence analysis indicates that the title compounds emit the different lights: yellow for 1, blue for 2 and yellow-green for 3, respectively. - Graphical abstract: The solvothermal self-assemblies of CuI, KI and pip/bpp in acidic CH{sub 3}OH solutions created three iodocuprates 2-D layered [(Hpip)Cu{sub 3}I{sub 4}] 1, 1-D chained [tmpip][Cu{sub 2}I{sub 4}] 2 and dinuclear [H{sub 2}bpp]{sub 2}[Cu{sub 2}I{sub 5}] I.2H{sub 2}O 3. Highlights: > A new layered iodocuprate(I) with 20-membered rings was hydrothermally prepared. > A simple approach to prepare the new organic templating agent was reported. > Photoluminescence analysis indicates the emission for iodocuprate(I) is associated with the Cu...Cu interactions.

  4. Identification and characterization of conservative organic tracers for use as hydrologic tracers for the Yucca Mountain site characterization study. Final report

    SciTech Connect (OSTI)

    Stetzenbach, K.; Farnham, I.

    1996-06-01

    Extensive tracer testing is expected to take place at the C-well complex in the Nevada Test Site as part of the Yucca Mountain Site Characterization Project. The C-well complex consists of one pumping well, C3, and two injection wells, C1 and C2 into which tracer will be introduced. The goal of this research was to provide USGS with numerous tracers to completed these tests. Several classes of fluorinated organic acids have been evaluated. These include numerous isomers of fluorinated benzoic acids, cinnamic acids, and salicylic acids. Also several derivatives of 2-hydroxy nicotinic acid (pyridone) have been tested. The stability of these compounds was determined using batch and column tests. Ames testing (mutagenicity/carcinogenicity) was conducted on the fluorinated benzoic acids and a literature review of toxicity of the fluorobenzoates and three perfluoro aliphatic acids was prepared. Solubilities were measured and method development work was performed to optimize the detection of these compounds. A Quality Assurance (QA) Program was developed under existing DOE and USGS guidelines. The program includes QA procedures and technical standard operating procedures. A tracer test, using sodium iodide, was performed at the C-well complex. HRC chemists performed analyses on site, to provide real time data for the USGS hydrologists and in the laboratories at UNLV. Over 2,500 analyses were performed. This report provides the results of the laboratory experiments and literature reviews used to evaluate the potential tracers and reports on the results of the iodide C-well tracer test.

  5. Solvent extraction of thorium(IV), uranium(VI), and europium(III) with lipophilic alkyl-substituted pyridinium salts. Final report for subcontract 9-XZ2-1123E-1, June 1, 1992--December 1, 1995

    SciTech Connect (OSTI)

    Ensor, D.D.

    1997-01-01

    In the treatment of high level nuclear wastes, aromatic pyridinium salts which are radiation-resistant are desired for the extraction of actinides and lanthanides. The solvent extraction of Th{sup +4}, UO{sub 2}{sup +2}, and Eu{sup +3} by three aromatic extractants, 3,5-didodecylpyridinium nitrate (35PY), 2,6-didodecylpyridinium nitrate (26PY), and 1-methyl-3,5-didodecyl-pyridinium iodide (1M35PY) has been studied in nitric acid media. The general order of extractability of the three extractants in toluene was 1M35PY>> 26PY > 35PY. The overall extraction efficiency of the metal ions was Th{sup +4} >UO{sub 2}{sup +2} > Eu{sup +3}. The extraction of HNO{sub 3}, which was competitive with the extraction of metal ions, was quantitatively investigated by NaOH titration and UV spectrometry. The loading capacity suggested that the extracted species in the organic phase for thorium was (R{sub 4}N{sup +}){sub 2}Th(NO{sub 3}{sup -}){sub 6}, where R{sub 4}N{sup +} denotes 1M35PY. A comparison of 1M35PY to the well-characterized extractant, Aliquat-336, an aliphatic ammonium salt was made. At the same extractant concentration, 1M35PY extracted thorium more efficiently than Aliquat-336 at high acidity. Thorium could be readily stripped with dilute nitric acid from 1M35PY. After irradiation of 0.1M 1M35PY with {sup 60}Co at 40R/min for 48 hours, no change in the extraction efficiency of thorium was observed.

  6. Carbon-Type Analysis and Comparison of Original and Reblended FACE Diesel Fuels (FACE 2, FACE 4, and FACE 7)

    SciTech Connect (OSTI)

    Bays, J. Timothy; King, David L.; O'Hagan, Molly J.

    2012-10-01

    This report summarizes the carbon-type analysis from 1H and 13C{1H} nuclear magnetic resonance spectroscopy (NMR) of Fuels for Advanced Combustion Engines (FACE) diesel blends, FD-2B, FD 4B, and FD-7B, and makes comparison of the new blends with the original FACE diesel blends, FD 2A, FD 4A, and FD-7A, respectively. Generally, FD-2A and FD-2B are more similar than the A and B blends of FD-4 and FD-7. The aromatic carbon content is roughly equivalent, although the new FACE blends have decreased monoaromatic content and increased di- and tri-cycloaromatic content, as well as a higher overall aromatic content, than the original FACE blends. The aromatic components of the new FACE blends generally have a higher alkyl substitution with longer alkyl substituents. The naphthenic and paraffinic contents remained relatively consistent. Based on aliphatic methyl and methylene carbon ratios, cetane numbers for FD-2A and -2B, and FD-7A and -7B are predicted to be consistent, while the cetane number for FD-4B is predicted to be higher than FD-4A. Overall, the new FACE fuel blends are fairly consistent with the original FACE fuel blends, but there are observable differences. In addition to providing important comparative compositional information on reformulated FACE diesel blends, this report also provides important information about the capabilities of the team at Pacific Northwest National Laboratory in the use of NMR spectroscopy for the detailed characterization and comparison of fuels and fuel blends.

  7. Hydrogen Atom Reactivity toward Aqueous tert-Butyl Alcohol

    SciTech Connect (OSTI)

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

    2012-02-09

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

  8. Occupational hygiene in terms of volatile organic compounds (VOCs) and bioaerosols at two solid waste management plants in Finland

    SciTech Connect (OSTI)

    Lehtinen, Jenni; Tolvanen, Outi; Nivukoski, Ulla; Veijanen, Anja; Hnninen, Kari

    2013-04-15

    Highlights: ? Odorous VOCs: acetic acid, 2,3-butanedione, ethyl acetate, alpha-pinene and limonene. ? VOC concentrations did not exceed occupational exposure limit concentrations. ? 2,3-Butanedione as the health effecting compound is discussed. ? Endotoxin concentrations may cause health problems in waste treatment. - Abstract: Factors affecting occupational hygiene were measured at the solid waste transferring plant at Hyvink and at the optic separation plant in Hmeenlinna. Measurements consisted of volatile organic compounds (VOCs) and bioaerosols including microbes, dust and endotoxins. The most abundant compounds in both of the plants were aliphatic and aromatic hydrocarbons, esters of carboxylic acids, ketones and terpenes. In terms of odour generation, the most important emissions were acetic acid, 2,3-butanedione, ethyl acetate, alpha-pinene and limonene due to their low threshold odour concentrations. At the optic waste separation plant, limonene occurred at the highest concentration of all single compounds of identified VOCs. The concentration of any single volatile organic compound did not exceed the occupational exposure limit (OEL) concentration. However, 2,3-butanedione as a health risk compound is discussed based on recent scientific findings linking it to lung disease. Microbe and dust concentrations were low at the waste transferring plant. Only endotoxin concentrations may cause health problems; the average concentration inside the plant was 425 EU/m{sup 3} which clearly exceeded the threshold value of 90 EU/m{sup 3}. In the wheel loader cabin the endotoxin concentrations were below 1 EU/m{sup 3}. High microbial and endotoxin concentrations were measured in the processing hall at the optic waste separation plant. The average concentration of endotoxins was found to be 10,980 EU/m{sup 3}, a concentration which may cause health risks. Concentrations of viable fungi were quite high in few measurements in the control room. The most problematic factor was endotoxins whose average measured concentrations was 4853 EU/m{sup 3}.

  9. Iron(II) catalysis in oxidation of hydrocarbons with ozone in acetonitrile

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

    Bataineh, Hajem; Pestovsky, Oleg; Bakac, Andreja

    2015-02-11

    Oxidation of alcohols, ethers, and sulfoxides by ozone in acetonitrile is catalyzed by submillimolar concentrations of Fe(CH3CN)62+. The catalyst provides both rate acceleration and greater selectivity toward the less oxidized products. For example, Fe(CH3CN)62+-catalyzed oxidation of benzyl alcohol yields benzaldehyde almost exclusively (>95%), whereas the uncatalyzed reaction generates a 1:1 mixture of benzaldehyde and benzoic acid. Similarly, aliphatic alcohols are oxidized to aldehydes/ketones, cyclobutanol to cyclobutanone, and diethyl ether to a 1:1 mixture of ethanol and acetaldehyde. The kinetics of oxidation of alcohols and diethyl ether are first-order in [Fe(CH3CN)62+] and [O3] and independent of [substrate] at concentrations greater thanmore » ~5 mM. In this regime, the rate constant for all of the alcohols is approximately the same, kcat = (8 ± 1) × 104 M–1 s–1, and that for (C2H5)2O is (5 ± 0.5) × 104 M–1 s–1. In the absence of substrate, Fe(CH3CN)62+ reacts with O3 with kFe = (9.3 ± 0.3) × 104 M–1 s–1. The similarity between the rate constants kFe and kcat strongly argues for Fe(CH3CN)62+/O3 reaction as rate-determining in catalytic oxidation. The active oxidant produced in Fe(CH3CN)62+/O3 reaction is suggested to be an Fe(IV) species in analogy with a related intermediate in aqueous solutions. As a result, this assignment is supported by the similarity in kinetic isotope effects and relative reactivities of the two species toward substrates.« less

  10. Prospects for Simulating Macromolecular Surfactant Chemistry at the Ocean-Atmosphere Boundary

    SciTech Connect (OSTI)

    Elliott, S.; Burrows, Susannah M.; Deal, C.; Liu, Xiaohong; Long, M.; Ogunro, O.; Russell, Lynn M.; Wingenter, O.

    2014-05-01

    Biogenic lipids and polymers are surveyed for their ability to adsorb at the water-air interfaces associated with bubbles, marine microlayers and particles in the overlying boundary layer. Representative ocean biogeochemical regimes are defined in order to estimate local concentrations for the major macromolecular classes. Surfactant equilibria and maximum excess are then derived based on a network of model compounds. Relative local coverage and upward mass transport follow directly, and specific chemical structures can be placed into regional rank order. Lipids and denatured protein-like polymers dominate at the selected locations. The assigned monolayer phase states are variable, whether assessed along bubbles or at the atmospheric spray droplet perimeter. Since oceanic film compositions prove to be irregular, effects on gas and organic transfer are expected to exhibit geographic dependence as well. Moreover, the core arguments extend across the sea-air interface into aerosol-cloud systems. Fundamental nascent chemical properties including mass to carbon ratio and density depend strongly on the geochemical state of source waters. High surface pressures may suppress the Kelvin effect, and marine organic hygroscopicities are almost entirely unconstrained. While bubble adsorption provides a well-known means for transporting lipidic or proteinaceous material into sea spray, the same cannot be said of polysaccharides. Carbohydrates tend to be strongly hydrophilic so that their excess carbon mass is low despite stacked polymeric geometries. Since sugars are abundant in the marine aerosol, gel-based mechanisms may be required to achieve uplift. Uncertainties in the surfactant logic distill to a global scale dearth of information regarding two dimensional kinetics and equilibria. Nonetheless simulations are recommended, to initiate the process of systems level quantification.

  11. Non-lethal heat treatment of cells results in reduction of tumor initiation and metastatic potential

    SciTech Connect (OSTI)

    Kim, Yoo-Shin; Lee, Tae Hoon; O'Neill, Brian E.

    2015-08-14

    Non-lethal hyperthermia is used clinically as adjuvant treatment to radiation, with mixed results. Denaturation of protein during hyperthermia treatment is expected to synergize with radiation damage to cause cell cycle arrest and apoptosis. Alternatively, hyperthermia is known to cause tissue level changes in blood flow, increasing the oxygenation and radiosensitivity of often hypoxic tumors. In this study, we elucidate a third possibility, that hyperthermia alters cellular adhesion and mechanotransduction, with particular impact on the cancer stem cell population. We demonstrate that cell heating results in a robust but temporary loss of cancer cell aggressiveness and metastatic potential in mouse models. In vitro, this heating results in a temporary loss in cell mobility, adhesion, and proliferation. Our hypothesis is that the loss of cellular adhesion results in suppression of cancer stem cells and loss of tumor virulence and metastatic potential. Our study suggests that the metastatic potential of cancer is particularly reduced by the effects of heat on cellular adhesion and mechanotransduction. If true, this could help explain both the successes and failures of clinical hyperthermia, and suggest ways to target treatments to those who would most benefit. - Highlights: • Non-lethal hyperthermia treatment of cancer cells is shown to cause a reduction in rates of tumor initiation and metastasis. • Dynamic imaging of cells during heat treatment shows temporary changes in cell shape, cell migration, and cell proliferation. • Loss of adhesion may lead to the observed effect, which may disproportionately impact the tumor initiating cell fraction. • Loss or suppression of the tumor initiating cell fraction results in the observed loss of metastatic potential in vivo. • This result may lead to new approaches to synergizing hyperthermia with surgery, radiation, and chemotherapy.

  12. Recurrent nonsense mutations within the type VII collagen gene in patients with severe recessive dystrophic epidermolysis bullosa

    SciTech Connect (OSTI)

    Hovnanian, A.; Hilal, L.; Goossens, M. ); Blanchet-Bardon, C.; Prost, Y. de ); Christiano, A.M.; Uitto, J. )

    1994-08-01

    The generalized mutilating form of recessive dystrophic epidermolysis bullosa (i.e., the Hallopeau-Siemens type; HS-RDEB) is a life-threatening disease characterized by extreme mucocutaneous fragility associated with absent or markedly altered anchoring fibrils (AF). Recently, the authors reported linkage between HS-RDEB and the type VII collagen gene (COL7A1), which encodes the major component of AF. In this study, they investigated 52 unrelated HS-RDEB patients and 2 patients with RDEB inversa for the presence, at CpG dinucleotides, of mutations changing CGA arginine codons to premature stop codons TGA within the COL7A1 gene. Eight exons containing 10 CGA codons located in the amino-terminal domain of the COL7A1 gene were studied. Mutation analysis was performed using denaturing gradient gel electrophoresis of PCR-amplified genomic fragments. Direct sequencing of PCR-amplified products with altered electrophoretic mobility led to the characterization of three premature stop codons, each in a single COL7A1 allele, in four patients. Two patients (one affected with HS-RDEB and the other with RDEB inversa) have the same C-to-T transition at arginine codon 109. Two other HS-RDEB patients have a C-to-T transition at arginine 1213 and 1216, respectively. These nonsense mutations predict the truncation of [approximately]56%-92% of the polypeptide, including the collagenous and the noncollagenous NC-2 domains. On the basis of linkage analysis, which showed no evidence for locus heterogeneity in RDEB, it is expected that these patients are compound heterozygotes and have additional mutations on the other COL7A1 allele, leading to impaired AF formation. These results indicate that stop mutations within the COL7A1 gene can underlie both HS-RDEB and RDEB inversa, thus providing further evidence for the implication of this gene in RDEB. 46 refs., 3 figs., 1 tab.

  13. Chapter 11. Community analysis-based methods

    SciTech Connect (OSTI)

    Cao, Y.; Wu, C.H.; Andersen, G.L.; Holden, P.A.

    2010-05-01

    Microbial communities are each a composite of populations whose presence and relative abundance in water or other environmental samples are a direct manifestation of environmental conditions, including the introduction of microbe-rich fecal material and factors promoting persistence of the microbes therein. As shown by culture-independent methods, different animal-host fecal microbial communities appear distinctive, suggesting that their community profiles can be used to differentiate fecal samples and to potentially reveal the presence of host fecal material in environmental waters. Cross-comparisons of microbial communities from different hosts also reveal relative abundances of genetic groups that can be used to distinguish sources. In increasing order of their information richness, several community analysis methods hold promise for MST applications: phospholipid fatty acid (PLFA) analysis, denaturing gradient gel electrophoresis (DGGE), terminal restriction fragment length polymorphism (TRFLP), cloning/sequencing, and PhyloChip. Specific case studies involving TRFLP and PhyloChip approaches demonstrate the ability of community-based analyses of contaminated waters to confirm a diagnosis of water quality based on host-specific marker(s). The success of community-based MST for comprehensively confirming fecal sources relies extensively upon using appropriate multivariate statistical approaches. While community-based MST is still under evaluation and development as a primary diagnostic tool, results presented herein demonstrate its promise. Coupled with its inherently comprehensive ability to capture an unprecedented amount of microbiological data that is relevant to water quality, the tools for microbial community analysis are increasingly accessible, and community-based approaches have unparalleled potential for translation into rapid, perhaps real-time, monitoring platforms.

  14. Structural basis of the heterodimerization of the MST and RASSF SARAH domains in the Hippo signalling pathway

    SciTech Connect (OSTI)

    Hwang, Eunha; Cheong, Hae-Kap; Mushtaq, Ameeq Ul; Kim, Hye-Yeon; Yeo, Kwon Joo; Kim, Eunhee; Lee, Woo Cheol; Hwang, Kwang Yeon; Cheong, Chaejoon; Jeon, Young Ho

    2014-07-01

    The heterodimeric structure of the MST1 and RASSF5 SARAH domains is presented. A comparison of homodimeric and heterodimeric interactions provides a structural basis for the preferential association of the SARAH heterodimer. Despite recent progress in research on the Hippo signalling pathway, the structural information available in this area is extremely limited. Intriguingly, the homodimeric and heterodimeric interactions of mammalian sterile 20-like (MST) kinases through the so-called ‘SARAH’ (SAV/RASSF/HPO) domains play a critical role in cellular homeostasis, dictating the fate of the cell regarding cell proliferation or apoptosis. To understand the mechanism of the heterodimerization of SARAH domains, the three-dimensional structures of an MST1–RASSF5 SARAH heterodimer and an MST2 SARAH homodimer were determined by X-ray crystallography and were analysed together with that previously determined for the MST1 SARAH homodimer. While the structure of the MST2 homodimer resembled that of the MST1 homodimer, the MST1–RASSF5 heterodimer showed distinct structural features. Firstly, the six N-terminal residues (Asp432–Lys437), which correspond to the short N-terminal 3{sub 10}-helix h1 kinked from the h2 helix in the MST1 homodimer, were disordered. Furthermore, the MST1 SARAH domain in the MST1–RASSF5 complex showed a longer helical structure (Ser438–Lys480) than that in the MST1 homodimer (Val441–Lys480). Moreover, extensive polar and nonpolar contacts in the MST1–RASSF5 SARAH domain were identified which strengthen the interactions in the heterodimer in comparison to the interactions in the homodimer. Denaturation experiments performed using urea also indicated that the MST–RASSF heterodimers are substantially more stable than the MST homodimers. These findings provide structural insights into the role of the MST1–RASSF5 SARAH domain in apoptosis signalling.

  15. Ligand-induced conformational changes in a thermophilic ribose-binding protein

    SciTech Connect (OSTI)

    Cuneo, Matthew J.; Beese, Lorena S.; Hellinga, Homme W.

    2009-05-21

    Members of the periplasmic binding protein (PBP) superfamily are involved in transport and signaling processes in both prokaryotes and eukaryotes. Biological responses are typically mediated by ligand-induced conformational changes in which the binding event is coupled to a hinge-bending motion that brings together two domains in a closed form. In all PBP-mediated biological processes, downstream partners recognize the closed form of the protein. This motion has also been exploited in protein engineering experiments to construct biosensors that transduce ligand binding to a variety of physical signals. Understanding the mechanistic details of PBP conformational changes, both global (hinge bending, twisting, shear movements) and local (rotamer changes, backbone motion), therefore is not only important for understanding their biological function but also for protein engineering experiments. Here we present biochemical characterization and crystal structure determination of the periplasmic ribose-binding protein (RBP) from the hyperthermophile Thermotoga maritima in its ribose-bound and unliganded state. The T. maritima RBP (tmRBP) has 39% sequence identity and is considerably more resistant to thermal denaturation (appTm value is 108 C) than the mesophilic Escherichia coli homolog (ecRBP) (appTm value is 56 C). Polar ligand interactions and ligand-induced global conformational changes are conserved among ecRBP and tmRBP; however local structural rearrangements involving side-chain motions in the ligand-binding site are not conserved. Although the large-scale ligand-induced changes are mediated through similar regions, and are produced by similar backbone movements in tmRBP and ecRBP, the small-scale ligand-induced structural rearrangements differentiate the mesophile and thermophile. This suggests there are mechanistic differences in the manner by which these two proteins bind their ligands and are an example of how two structurally similar proteins utilize different mechanisms to form a ligand-bound state.

  16. End-to-end gene fusions and their impact on the production of multifunctional biomass degrading enzymes

    SciTech Connect (OSTI)

    Rizk, Mazen; Antranikian, Garabed; Elleuche, Skander

    2012-11-09

    Highlights: Black-Right-Pointing-Pointer Multifunctional enzymes offer an interesting approach for biomass degradation. Black-Right-Pointing-Pointer Size and conformation of separate constructs play a role in the effectiveness of chimeras. Black-Right-Pointing-Pointer A connecting linker allows for maximal flexibility and increased thermostability. Black-Right-Pointing-Pointer Genes with functional similarities are the best choice for fusion candidates. -- Abstract: The reduction of fossil fuels, coupled with its increase in price, has made the search for alternative energy resources more plausible. One of the topics gaining fast interest is the utilization of lignocellulose, the main component of plants. Its primary constituents, cellulose and hemicellulose, can be degraded by a series of enzymes present in microorganisms, into simple sugars, later used for bioethanol production. Thermophilic bacteria have proven to be an interesting source of enzymes required for hydrolysis since they can withstand high and denaturing temperatures, which are usually required for processes involving biomass degradation. However, the cost associated with the whole enzymatic process is staggering. A solution for cost effective and highly active production is through the construction of multifunctional enzyme complexes harboring the function of more than one enzyme needed for the hydrolysis process. There are various strategies for the degradation of complex biomass ranging from the regulation of the enzymes involved, to cellulosomes, and proteins harboring more than one enzymatic activity. In this review, the construction of multifunctional biomass degrading enzymes through end-to-end gene fusions, and its impact on production and activity by choosing the enzymes and linkers is assessed.

  17. Effect of cosolvent on protein stability: A theoretical investigation

    SciTech Connect (OSTI)

    Chalikian, Tigran V.

    2014-12-14

    We developed a statistical thermodynamic algorithm for analyzing solvent-induced folding/unfolding transitions of proteins. The energetics of protein transitions is governed by the interplay between the cavity formation contribution and the term reflecting direct solute-cosolvent interactions. The latter is viewed as an exchange reaction in which the binding of a cosolvent to a solute is accompanied by release of waters of hydration to the bulk. Our model clearly differentiates between the stoichiometric and non-stoichiometric interactions of solvent or co-solvent molecules with a solute. We analyzed the urea- and glycine betaine (GB)-induced conformational transitions of model proteins of varying size which are geometrically approximated by a sphere in their native state and a spherocylinder in their unfolded state. The free energy of cavity formation and its changes accompanying protein transitions were computed based on the concepts of scaled particle theory. The free energy of direct solute-cosolvent interactions were analyzed using empirical parameters previously determined for urea and GB interactions with low molecular weight model compounds. Our computations correctly capture the mode of action of urea and GB and yield realistic numbers for (??G/?a{sub 3}){sub T,P} which are related to the m-values of protein denaturation. Urea is characterized by negative values of (??G/?a{sub 3}){sub T,P} within the entire range of urea concentrations analyzed. At concentrations below ?1 M, GB exhibits positive values of (??G/?a{sub 3}){sub T,P} which turn positive at higher GB concentrations. The balance between the thermodynamic contributions of cavity formation and direct solute-cosolvent interactions that, ultimately, defines the mode of cosolvent action is extremely subtle. A 20% increase or decrease in the equilibrium constant for solute-cosolvent binding may change the sign of (??G/?a{sub 3}){sub T,P} thereby altering the mode of cosolvent action (stabilizing to destabilizing or vice versa)

  18. The anchorage function of CipA (CelL), a scaffolding protein of the Clostridium thermocellum cellulosome

    SciTech Connect (OSTI)

    Kruus, K.; Wu, J.H.D.; Lua, A.C.

    1995-09-26

    Enzymatic cellulose degradation is a heterogeneous reaction requiring binding of soluble cellulase molecules to the solid substrate. Based on our studies of the cellulase complex of Clostridium thermocellum (the cellulosome), we have previously proposed that such binding can be brought about by a special {open_quotes}anchorage subunit.{close_quotes} In this {open_quotes}anchor-enzyme{close_quotes} model, CipA (a major subunit of the cellulosome) enhances the activity of CelS (the most abundant catalytic subunit of the cellulosome) by anchoring it to the cellulose surface. We have subsequently reported that CelS contains a conserved duplicated sequence at its C terminus and the CipA contains nine repeated sequences with a cellulose binding domain (CBD) in between the second and third repeats. In this work, we reexamined the anchor-enzyme mechanism by using recombinant CelS (rCelS) and various CipA domains, CBD, R3 (the repeat next to CBD), and CBD/R3, expressed in Escherichia coli. As analyzed by non-denaturing gel electrophoresis, rCelS, through its conserved duplicated sequence, formed a stable complex with R3 or CBD/R3 but not with CBD. Although R3 or CBD alone did not affect the binding of rCelS to cellulose, such binding was dependent on CBD/R3, indicating the anchorage role of CBD/R3. Such anchorage apparently increased the rCelS activity toward crystalline cellulose. These results substantiate the proposed anchor-enzyme model and the expected roles of individual CipA domains and the conserved duplicated sequence of CelS.

  19. Designer synthetic media for studying microbial-catalyzed biofuel production

    SciTech Connect (OSTI)

    Tang, Xiaoyu [Biogas Inst. of Ministry of Agriculture, Chengdu (China); da Costa Sousa, Leonardo [Michigan State Univ., East Lansing, MI (United States); Jin, Mingjie [Michigan State Univ., East Lansing, MI (United States); Chundawat, Shishir [Michigan State Univ., East Lansing, MI (United States); State Univ. of New Jersey, Piscataway, NJ (United States); Chambliss, Charles [Baylor Univ., Waco, TX (United States); Lau, Ming W [Michigan State Univ., East Lansing, MI (United States); Xiao, Zeyi [Sichuan Univ., Chengdu (China); Dale, Bruce E [Michigan State Univ., East Lansing, MI (United States); Balan, Venkatesh [Michigan State Univ., East Lansing, MI (United States)

    2015-01-01

    Background: The fermentation inhibition of yeast or bacteria by lignocellulose-derived degradation products, during hexose/pentose co-fermentation, is a major bottleneck for cost-effective lignocellulosic biorefineries. To engineer microbial strains for improved performance, it is critical to understand the mechanisms of inhibition that affect fermentative organisms in the presence of major components of a lignocellulosic hydrolysate. The development of a synthetic lignocellulosic hydrolysate (SH) media with a composition similar to the actual biomass hydrolysate will be an important advancement to facilitate these studies. In this work, we characterized the nutrients and plant-derived decomposition products present in AFEX pretreated corn stover hydrolysate (ACH). The SH was formulated based on the ACH composition and was further used to evaluate the inhibitory effects of various families of decomposition products during Saccharomyces cerevisiae 424A (LNH-ST) fermentation. Results: The ACH contained high levels of nitrogenous compounds, notably amides, pyrazines, and imidazoles. In contrast, a relatively low content of furans and aromatic and aliphatic acids were found in the ACH. Though most of the families of decomposition products were inhibitory to xylose fermentation, due to their abundance, the nitrogenous compounds showed the most inhibition. From these compounds, amides (products of the ammonolysis reaction) contributed the most to the reduction of the fermentation performance. However, this result is associated to a concentration effect, as the corresponding carboxylic acids (products of hydrolysis) promoted greater inhibition when present at the same molar concentration as the amides. Due to its complexity, the formulated SH did not perfectly match the fermentation profile of the actual hydrolysate, especially the growth curve. However, the SH formulation was effective for studying the inhibitory effect of various compounds on yeast fermentation. Conclusions: The formulation of SHs is an important advancement for future multi-omics studies and for better understanding the mechanisms of fermentation inhibition in lignocellulosic hydrolysates. The SH formulated in this work was instrumental for defining the most important inhibitors in the ACH. Major AFEX decomposition products are less inhibitory to yeast fermentation than the products of dilute acid or steam explosion pretreatments; thus, ACH is readily fermentable by yeast without any detoxification.

  20. Use of thermal analysis techniques (TG-DSC) for the characterization of diverse organic municipal waste streams to predict biological stability prior to land application

    SciTech Connect (OSTI)

    Fernandez, Jose M.; Plaza, Cesar; Polo, Alfredo; Plante, Alain F.

    2012-01-15

    Highlights: Black-Right-Pointing-Pointer Thermal analysis was used to assess stability and composition of organic matter in three diverse municipal waste streams. Black-Right-Pointing-Pointer Results were compared with C mineralization during 90-day incubation, FTIR and {sup 13}C NMR. Black-Right-Pointing-Pointer Thermal analysis reflected the differences between the organic wastes before and after the incubation. Black-Right-Pointing-Pointer The calculated energy density showed a strong correlation with cumulative respiration. Black-Right-Pointing-Pointer Conventional and thermal methods provide complimentary means of characterizing organic wastes. - Abstract: The use of organic municipal wastes as soil amendments is an increasing practice that can divert significant amounts of waste from landfill, and provides a potential source of nutrients and organic matter to ameliorate degraded soils. Due to the high heterogeneity of organic municipal waste streams, it is difficult to rapidly and cost-effectively establish their suitability as soil amendments using a single method. Thermal analysis has been proposed as an evolving technique to assess the stability and composition of the organic matter present in these wastes. In this study, three different organic municipal waste streams (i.e., a municipal waste compost (MC), a composted sewage sludge (CS) and a thermally dried sewage sludge (TS)) were characterized using conventional and thermal methods. The conventional methods used to test organic matter stability included laboratory incubation with measurement of respired C, and spectroscopic methods to characterize chemical composition. Carbon mineralization was measured during a 90-day incubation, and samples before and after incubation were analyzed by chemical (elemental analysis) and spectroscopic (infrared and nuclear magnetic resonance) methods. Results were compared with those obtained by thermogravimetry (TG) and differential scanning calorimetry (DSC) techniques. Total amounts of CO{sub 2} respired indicated that the organic matter in the TS was the least stable, while that in the CS was the most stable. This was confirmed by changes detected with the spectroscopic methods in the composition of the organic wastes due to C mineralization. Differences were especially pronounced for TS, which showed a remarkable loss of aliphatic and proteinaceous compounds during the incubation process. TG, and especially DSC analysis, clearly reflected these differences between the three organic wastes before and after the incubation. Furthermore, the calculated energy density, which represents the energy available per unit of organic matter, showed a strong correlation with cumulative respiration. Results obtained support the hypothesis of a potential link between the thermal and biological stability of the studied organic materials, and consequently the ability of thermal analysis to characterize the maturity of municipal organic wastes and composts.

  1. Systematic analysis of proteindetergent complexes applying dynamic light scattering to optimize solutions for crystallization trials

    SciTech Connect (OSTI)

    Meyer, Arne [University of Hamburg, c/o DESY, Building 22a, Notkestrasse 85, 22603 Hamburg (Germany); Dierks, Karsten [University of Hamburg, c/o DESY, Building 22a, Notkestrasse 85, 22603 Hamburg (Germany); XtalConcepts, Marlowring 19, 22525 Hamburg (Germany); Hussein, Rana [University of Hamburg, c/o DESY, Building 22a, Notkestrasse 85, 22603 Hamburg (Germany); Brillet, Karl [ESBS, Ple API, 300 Boulevard Sbastien Brant, CS10413, 67412 Illkirch CEDEX (France); Brognaro, Hevila [So Paulo State University, UNESP/IBILCE, Caixa Postal 136, So Jos do Rio Preto-SP, 15054 (Brazil); Betzel, Christian, E-mail: christian.betzel@uni-hamburg.de [University of Hamburg, c/o DESY, Building 22a, Notkestrasse 85, 22603 Hamburg (Germany)

    2015-01-01

    Application of in situ dynamic light scattering to solutions of proteindetergent complexes permits characterization of these complexes in samples as small as 2 l in volume. Detergents are widely used for the isolation and solubilization of membrane proteins to support crystallization and structure determination. Detergents are amphiphilic molecules that form micelles once the characteristic critical micelle concentration (CMC) is achieved and can solubilize membrane proteins by the formation of micelles around them. The results are presented of a study of micelle formation observed by in situ dynamic light-scattering (DLS) analyses performed on selected detergent solutions using a newly designed advanced hardware device. DLS was initially applied in situ to detergent samples with a total volume of approximately 2 l. When measured with DLS, pure detergents show a monodisperse radial distribution in water at concentrations exceeding the CMC. A series of all-transn-alkyl-?-d-maltopyranosides, from n-hexyl to n-tetradecyl, were used in the investigations. The results obtained verify that the application of DLS in situ is capable of distinguishing differences in the hydrodynamic radii of micelles formed by detergents differing in length by only a single CH{sub 2} group in their aliphatic tails. Subsequently, DLS was applied to investigate the distribution of hydrodynamic radii of membrane proteins and selected water-insoluble proteins in presence of detergent micelles. The results confirm that stable proteindetergent complexes were prepared for (i) bacteriorhodopsin and (ii) FetA in complex with a ligand as examples of transmembrane proteins. A fusion of maltose-binding protein and the Duck hepatitis B virus X protein was added to this investigation as an example of a non-membrane-associated protein with low water solubility. The increased solubility of this protein in the presence of detergent could be monitored, as well as the progress of proteolytic cleavage to separate the fusion partners. This study demonstrates the potential of in situ DLS to optimize solutions of proteindetergent complexes for crystallization applications.

  2. FY-2011 Status Report for Thermodynamics and Kinetics of Advanced Separations Systems

    SciTech Connect (OSTI)

    Leigh R. Martin; Peter R. Zalupski; Travis S. Grimes

    2011-09-01

    This report presents a summary of the work performed in the area of thermodynamics and kinetics of advanced separations systems under the Fuel Cycle Research and Development (FCR&D) program during FY 2011 at the INL. On the thermodynamic front, investigations of liquid-liquid distribution of lanthanides at TALSPEAK-related conditions continued in FY11. It has been determined that a classical ion-exchanging phase transfer mechanism, where three HDEHP dimers solvate the metal ion in the organic phase, dominates metal extraction for systems that contain up to 0.1 M free lactate in solution. The correct graphical interpretation of the observed data in those regions relied on incorporating corrections for non-ideal behavior of HDEHP dimer in aliphatic diluents as well as sodium extraction equilibria. When aqueous conditions enter the complex regions of high lactate concentrations, slope analysis is no longer possible. When normalized metal distribution ratios were studied along the increasing concentration of free lactate, a slope of -1 was apparent. Such dependency either indicates aqueous complexing competition from lactate, or, a more likely scenario, a participation of lactate in the extracted metal complex. This finding agrees with our initial assessment of postulated changes in the extraction mechanism as a source of the lactate-mediated loss of extraction efficiency. The observed shape in the lanthanide distribution curve in our studies of TALSPEAK systems was the same for solutions containing no lactate or 2.3 M lactate. As such we may conclude that the mechanism of phase transfer is not altered dramatically and remains similarly sensitive to effective charge density of the metal ion. In addition to these thermodynamics studies, this report also summarizes the first calorimetric determination of heat of extraction of 248Cm in a bi-phasic system. The heat of extraction measured by isothermal titration calorimetry is compared to that determined using van't Hoff calculations. Further investigations on the kinetics of extraction in TALSPEAK with macro quantities of lanthanides present in the initial aqueous phase composition have been performed. These results have been summarized and compared to previous work performed for FCR&D. In addition, the effects of HDEHP concentration in the organic phase on europium extraction have been studied.

  3. Iron(II) catalysis in oxidation of hydrocarbons with ozone in acetonitrile

    SciTech Connect (OSTI)

    Bataineh, Hajem; Pestovsky, Oleg; Bakac, Andreja

    2015-02-11

    Oxidation of alcohols, ethers, and sulfoxides by ozone in acetonitrile is catalyzed by submillimolar concentrations of Fe(CH3CN)62+. The catalyst provides both rate acceleration and greater selectivity toward the less oxidized products. For example, Fe(CH3CN)62+-catalyzed oxidation of benzyl alcohol yields benzaldehyde almost exclusively (>95%), whereas the uncatalyzed reaction generates a 1:1 mixture of benzaldehyde and benzoic acid. Similarly, aliphatic alcohols are oxidized to aldehydes/ketones, cyclobutanol to cyclobutanone, and diethyl ether to a 1:1 mixture of ethanol and acetaldehyde. The kinetics of oxidation of alcohols and diethyl ether are first-order in [Fe(CH3CN)62+] and [O3] and independent of [substrate] at concentrations greater than ~5 mM. In this regime, the rate constant for all of the alcohols is approximately the same, kcat = (8 ± 1) × 104 M–1 s–1, and that for (C2H5)2O is (5 ± 0.5) × 104 M–1 s–1. In the absence of substrate, Fe(CH3CN)62+ reacts with O3 with kFe = (9.3 ± 0.3) × 104 M–1 s–1. The similarity between the rate constants kFe and kcat strongly argues for Fe(CH3CN)62+/O3 reaction as rate-determining in catalytic oxidation. The active oxidant produced in Fe(CH3CN)62+/O3 reaction is suggested to be an Fe(IV) species in analogy with a related intermediate in aqueous solutions. As a result, this assignment is supported by the similarity in kinetic isotope effects and relative reactivities of the two species toward substrates.

  4. Development of Advanced Membranes Technology Platform for Hydrocarbon Separations

    SciTech Connect (OSTI)

    Kalthod, Dr Dilip

    2010-03-01

    Virtually all natural gas is dehydrated during its production, transmission and storage, mostly by absorption processes. Membranes offer many potential advantages over absorption, including smaller footprints, lighter-weight packages, packaging flexibility, minimal electrical power duty, amenability to expansion due to system modularity, reduced maintenance costs, reduced emissions of heavy hydrocarbons, no liquid waste streams, and amenability to unmanned operation. The latter is particularly valuable because new natural gas sources are generally located in remote onshore and offshore sites. Most commercially-available membranes for natural gas upgrading involve high capital costs, high methane loss and performance degradation from operational upsets – all of which are barriers to their widespread adoption by the industry. The original focus of the project was to develop and demonstrate robust, high-performance membranes for natural gas dehydration. The first task completed was a user needs-and-wants study to 1) clarify the expectations of system fabricators and end users of the new separations equipment, and 2) establish the required technical and commercial targets for the membrane products. Following this, membrane system modeling and membrane development in the lab proceeded in parallel. Membrane module diameter and length, as well as and the fiber outer and inner fiber diameter, were optimized from a mathematical model that accounts for the relevant fluid dynamics and permeation phenomena. Module design was evaluated in the context of overall system design, capital costs and energy consumption, including the process scheme (particularly sweep generation), feed pretreatment, system layout, and process control. This study provided targets for membrane permeation coefficients and membrane geometry in a commercial offering that would be competitive with absorption systems. A commercially-available polymer with good tensile strength and chemical resistance was selected for membrane development. A novel dope composition and spinning process were developed, which provide a new approach to controlling membrane porosity and wall and skin morphology. A hollow-fiber membrane with an external dense “skin” was produced that has a high water vapor permeation coefficient and selectivity, durability when in operation at 1000 psig and 70°C, and the ability to withstand aromatic and aliphatic hydrocarbon vapors for an extended period. The fiber meets the technical requirements for a commercial product offering in gas dehydration. It can be readily manufactured with some changes in process equipment and process conditions, and is an excellent candidate for scale-up to full-size membrane modules.

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

    SciTech Connect (OSTI)

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

    2004-10-01

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

  6. SUBTASK 3.11 – PRODUCTION OF CBTL-BASED JET FUELS FROM BIOMASS-BASED FEEDSTOCKS AND MONTANA COAL

    SciTech Connect (OSTI)

    Sharma, Ramesh

    2014-06-01

    The Energy & Environmental Research Center (EERC), in partnership with the U.S. Department of Energy (DOE) and Accelergy Corporation, an advanced fuels developer with technologies exclusively licensed from Exxon Mobil, undertook Subtask 3.11 to use a recently installed bench-scale direct coal liquefaction (DCL) system capable of converting 45 pounds/hour of pulverized, dried coal to a liquid suitable for upgrading to fuels and/or chemicals. The process involves liquefaction of Rosebud mine coal (Montana coal) coupled with an upgrading scheme to produce a naphthenic fuel. The upgrading comprises catalytic hydrotreating and saturation to produce naphthenic fuel. A synthetic jet fuel was prepared by blending equal volumes of naphthenic fuel with similar aliphatic fuel derived from biomass and 11 volume % of aromatic hydrocarbons. The synthetic fuel was tested using standard ASTM International techniques to determine compliance with JP-8 fuel. The composite fuel thus produced not only meets but exceeds the military aviation fuel-screening criteria. A 500-milliliter synthetic jet fuel sample which met internal screening criteria was submitted to the Air Force Research Laboratory (AFRL) at Wright–Patterson Air Force Base, Dayton, Ohio, for evaluation. The sample was confirmed by AFRL to be in compliance with U.S. Air Force-prescribed alternative aviation fuel initial screening criteria. The results show that this fuel meets or exceeds the key specification parameters for JP-8, a petroleum-based jet fuel widely used by the U.S. military. JP-8 specifications include parameters such as freeze point, density, flash point, and others; all of which were met by the EERC fuel sample. The fuel also exceeds the thermal stability specification of JP-8 fuel as determined by the quartz crystalline microbalance (QCM) test also performed at an independent laboratory as well as AFRL. This means that the EERC fuel looks and acts identically to petroleum-derived jet fuel and can be used interchangeably without any special requirements and thus provides a pathway to energy security to the U.S. military and the entire nation. This subtask was funded through the EERC–DOE Joint Program on Research and Development for Fossil Energy-Related Resources Cooperative Agreement No. DE-FC26- 08NT43291. Nonfederal funding was provided by Accelergy Corporation.

  7. Designer synthetic media for studying microbial-catalyzed biofuel production

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

    Tang, Xiaoyu; da Costa Sousa, Leonardo; Jin, Mingjie; Chundawat, Shishir; Chambliss, Charles; Lau, Ming W; Xiao, Zeyi; Dale, Bruce E; Balan, Venkatesh

    2015-01-01

    Background: The fermentation inhibition of yeast or bacteria by lignocellulose-derived degradation products, during hexose/pentose co-fermentation, is a major bottleneck for cost-effective lignocellulosic biorefineries. To engineer microbial strains for improved performance, it is critical to understand the mechanisms of inhibition that affect fermentative organisms in the presence of major components of a lignocellulosic hydrolysate. The development of a synthetic lignocellulosic hydrolysate (SH) media with a composition similar to the actual biomass hydrolysate will be an important advancement to facilitate these studies. In this work, we characterized the nutrients and plant-derived decomposition products present in AFEX™ pretreated corn stover hydrolysate (ACH). Themore » SH was formulated based on the ACH composition and was further used to evaluate the inhibitory effects of various families of decomposition products during Saccharomyces cerevisiae 424A (LNH-ST) fermentation. Results: The ACH contained high levels of nitrogenous compounds, notably amides, pyrazines, and imidazoles. In contrast, a relatively low content of furans and aromatic and aliphatic acids were found in the ACH. Though most of the families of decomposition products were inhibitory to xylose fermentation, due to their abundance, the nitrogenous compounds showed the most inhibition. From these compounds, amides (products of the ammonolysis reaction) contributed the most to the reduction of the fermentation performance. However, this result is associated to a concentration effect, as the corresponding carboxylic acids (products of hydrolysis) promoted greater inhibition when present at the same molar concentration as the amides. Due to its complexity, the formulated SH did not perfectly match the fermentation profile of the actual hydrolysate, especially the growth curve. However, the SH formulation was effective for studying the inhibitory effect of various compounds on yeast fermentation. Conclusions: The formulation of SHs is an important advancement for future multi-omics studies and for better understanding the mechanisms of fermentation inhibition in lignocellulosic hydrolysates. The SH formulated in this work was instrumental for defining the most important inhibitors in the ACH. Major AFEX decomposition products are less inhibitory to yeast fermentation than the products of dilute acid or steam explosion pretreatments; thus, ACH is readily fermentable by yeast without any detoxification.« less

  8. Hydrotreating Pyrolytic Lignin to Produce a Refinery Feedstock (Poster)

    SciTech Connect (OSTI)

    French, R. J.

    2013-09-01

    Fast pyrolysis of biomass followed by water separation to produce pyrolytic lignin and hydrotreating of the lignin could be used to produce a stable volatile low-oxygen intermediate liquid. Such a liquid could be converted into a finished motor-fuel in a refinery, taking advantage of the existing infrastructure and economies of scale of refineries. Hydrotreating just the lignin would consume less hydrogen while preserving about half of the energy of the original oil. The aqueous by-products could be reformed to produce the needed hydrogen and would contain much of the unwanted acids and unstable oxygenates. To assess such intermediate liquids, several pyrolytic lignins were prepared by mixing pyrolysis oil with water at 1:1 and 3:1 ratios. The carboxylic acidity in the pyrolytic lignin was reduced to 24 and 10 mg-KOH/g-lignin compared to 81 in the whole oil. These lignins were hydrotreated using Ni-Mo(S)/alumina, Pt/char, or Pd/C(activated) in a semi-batch 1 L stirred autoclave. The oil was stabilized under hydrogen at 150-280 degrees C, then water and light organics were removed by partial depressurization. Hydrodeoxygenation was then performed at 340-400 degrees C. Total pressure was controlled at 70 or 170 bar with hydrogen gas. Organic liquid yields of 39-56% were obtained. For many experiments the organic oxygen content was <7%, acidity was < 7 mg-KOH/g-oil, the volatility was greater than or equal to 94% and, on a carbon basis, the total yield of organic products miscible in hydrocarbons at a 1:10 ratio was over 50%. These properties are probably acceptable to a refinery.The residual liquids left in the reactor at the end of the experiment comprised 60-85% of the organic-phase product while the rest was condensate. 13C-NMR of the residual liquids showed that they were 50-80% aliphatic. 13C-NMR coupled with GC-MS identified phenolic compounds as the main oxygenates in most residual liquids.

  9. AS-2, a novel inhibitor of p53-dependent apoptosis, prevents apoptotic mitochondrial dysfunction in a transcription-independent manner and protects mice from a lethal dose of ionizing radiation

    SciTech Connect (OSTI)

    Morita, Akinori; Ariyasu, Shinya; Wang, Bing; Asanuma, Tetsuo; Onoda, Takayoshi; Sawa, Akiko; Tanaka, Kaoru; Takahashi, Ippei; Togami, Shotaro; Nenoi, Mitsuru; Inaba, Toshiya; Aoki, Shin

    2014-08-08

    Highlights: A bidentate HQ derivative, AS-2, suppresses p53-dependent apoptosis by DNA damage. AS-2 does not significantly affect nuclear p53 response. UV-excited blue emission of AS-2 clearly showed its extranuclear localization. AS-2 prevents mitochondrial dysfunction despite the increase of mitochondrial p53. AS-2 protects mice from a radiation dose that causes lethal hematopoietic syndrome. - Abstract: In a previous study, we reported that some tetradentate zinc(II) chelators inhibit p53 through the denaturation of its zinc-requiring structure but a chelator, Bispicen, a potent inhibitor of in vitro apoptosis, failed to show any efficient radioprotective effect against irradiated mice because the toxicity of the chelator to mice. The unsuitability of using tetradentate chelators as radioprotectors prompted us to undertake a more extensive search for p53-inhibiting agents that are weaker zinc(II) chelators and therefore less toxic. Here, we show that an 8-hydroxyquinoline (8HQ) derivative, AS-2, suppresses p53-dependent apoptosis through a transcription-independent mechanism. A mechanistic study using cells with different p53 characteristics revealed that the suppressive effect of AS-2 on apoptosis is specifically mediated through p53. In addition, AS-2 was less effective in preventing p53-mediated transcription-dependent events than pifithrin-? (PFT?), an inhibitor of transcription-independent apoptosis by p53. Fluorescence visualization of the extranuclear distribution of AS-2 also supports that it is ineffective on the transcription-dependent pathway. Further investigations revealed that AS-2 suppressed mitochondrial apoptotic events, such as the mitochondrial release of intermembrane proteins and the loss of mitochondrial membrane potential, although AS-2 resulted in an increase in the mitochondrial translocation of p53 as opposed to the decrease of cytosolic p53, and did not affect the apoptotic interaction of p53 with Bcl-2. AS-2 also protected mice that had been exposed to a lethal dose of ionizing radiation. Our findings indicate that some types of bidentate 8HQ chelators could serve as radioprotectors with no substantial toxicity in vivo.

  10. Osmoregulation in Methanogens (and Other Interesting Organisms)

    SciTech Connect (OSTI)

    Roberts, Mary Fedarko

    2014-12-03

    Our research has been aimed at (i) identifying, (ii) determining mode of regulation, and (iii) understanding how different classes of compatible solutes (also termed osmolytes) affect macromolecular stability in response to osmotic and thermal stress. For solutes we have identified (e.g., di-inositol-1,1-phosphate (DIP)), we used NMR to elucidate biosynthetic pathways and then cloned suspected enzymes in the pathway to explore how they are regulated. Compatible solutes are thought to protect proteins from thermal and osmotic stresses by being excluded from the surface, allowing critical water molecules to interact with the protein. This implies there are no specific binding interactions between osmolytes and proteins. However, we and others have often observed very specific solute effects for proteins that suggest a more direct interaction between solute and protein is likely can occur. Measuring such a weak interaction is extremely difficult. We have developed a solution NMR method, high-resolution field cycling relaxometry, that can measure spin-lattice relaxation rates as a function of magnetic field from 11.7 (the field of a 500 MHz spectrometer) to 0.003 T. The methodology is ideal for nuclei in small molecules with moderately long relaxation times at high fields phosphate groups (31P), enriched carbonyls (13C), or methyl groups (1H). The protein of interest is spin-labeled to introduce a large dipole on it that will dominate the relaxation of nuclei on any small molecules that bind transiently. The key is to measure relaxation below 1-2 T (and extract nuclei-spin label distances in the bound complex) where the small molecule relaxation will be dominated by dipolar mechanisms with a correlation time indicative of the large protein complex. Our explorations of an inositol monophosphatase (the last step in DIP generation) localized four discrete binding sides for the thermoprotectant ?-glutamate. This is a novel approach, and while the work did not fully explain how this solute protected the IMPase from thermal denaturation, it did showcase a new and exciting method to monitor weak binding in biological systems.

  11. In contrast to conventional inactivated influenza vaccines, 4xM2e.HSP70c fusion protein fully protected mice against lethal dose of H1, H3 and H9 influenza A isolates circulating in Iran

    SciTech Connect (OSTI)

    Ebrahimi, Seyyed Mahmoud, E-mail: smebrahimi@shirazu.ac.ir [Applied Biotechnology Research Center, Baqiyatallah University of Medical Sciences, P.O. Box 14155-3651,Tehran (Iran, Islamic Republic of); Research Center of Virus and Vaccine, Baqiyatallah University of Medical Science, P.O.Box 14155-3651, Tehran (Iran, Islamic Republic of); Dabaghian, Mehran [Department of Pathobiology, University of Tehran, Faculty of Veterinary Medicine, P.O. Box 14155-6453, Tehran (Iran, Islamic Republic of)] [Department of Pathobiology, University of Tehran, Faculty of Veterinary Medicine, P.O. Box 14155-6453, Tehran (Iran, Islamic Republic of); Tebianian, Majid [Department of Biotechnology, Razi Vaccine and Serum Research Institute (RVSRI), P.O. Box 31975/148, Karaj, Tehran (Iran, Islamic Republic of)] [Department of Biotechnology, Razi Vaccine and Serum Research Institute (RVSRI), P.O. Box 31975/148, Karaj, Tehran (Iran, Islamic Republic of); Zabeh Jazi, Mohammad Hossein [Department of Pathobiology, University of Tehran, Faculty of Veterinary Medicine, P.O. Box 14155-6453, Tehran (Iran, Islamic Republic of)] [Department of Pathobiology, University of Tehran, Faculty of Veterinary Medicine, P.O. Box 14155-6453, Tehran (Iran, Islamic Republic of)

    2012-08-15

    Ideal vaccines against influenza viruses should elicit not only a humoral response, but also a cellular response. Mycobacterium tuberculosis HSP70 (mHSP70) have been found to promote immunogenic APCs function, elicit a strong cytotoxic T lymphocyte (CTL) response, and prevent the induction of tolerance. Moreover, it showed linkage of antigens to the C-terminus of mHSP70 (mHSP70c) can represent them as vaccines resulted in more potent, protective antigen specific responses in the absence of adjuvants or complex formulations. Hence, recombinant fusion protein comprising C-terminus of mHSP70 genetically fused to four tandem repeats of the ectodomain of the conserved influenza matrix protein M2 (M2e) was expressed in Escherichia coli, purified under denaturing condition, refolding, and then confirmed by SDS-PAGE, respectively. The recombinant fusion protein, 4xM2e.HSP70c, retained its immunogenicity and displayed the protective epitope of M2e by ELISA and FITC assays. A prime-boost administration of 4xM2e.HSP70c formulated in F105 buffer by intramuscular route in mice (Balb/C) provided full protection against lethal dose of mouse-adapted H1N1, H3N2, or H9N2 influenza A isolates from Iran compared to 0-33.34% survival rate of challenged unimmunized and immunized mice with the currently in use conventional vaccines designated as control groups. However, protection induced by immunization with 4xM2e.HSP70c failed to prevent weight loss in challenged mice; they experienced significantly lower weight loss, clinical symptoms and higher lung viral clearance in comparison with protective effects of conventional influenza vaccines in challenged mice. These data demonstrate that C-terminal domain of mHSP70 can be a superior candidate to deliver the adjuvant function in M2e-based influenza A vaccine in order to provide significant protection against multiple influenza A virus strains.

  12. WHERE MULTIFUNCTIONAL DNA REPAIR PROTEINS MEET: MAPPING THE INTERACTION DOMAINS BETWEEN XPG AND WRN

    SciTech Connect (OSTI)

    Rangaraj, K.; Cooper, P.K.; Trego, K.S.

    2009-01-01

    The rapid recognition and repair of DNA damage is essential for the maintenance of genomic integrity and cellular survival. Multiple complex and interconnected DNA damage responses exist within cells to preserve the human genome, and these repair pathways are carried out by a specifi c interplay of protein-protein interactions. Thus a failure in the coordination of these processes, perhaps brought about by a breakdown in any one multifunctional repair protein, can lead to genomic instability, developmental and immunological abnormalities, cancer and premature aging. This study demonstrates a novel interaction between two such repair proteins, Xeroderma pigmentosum group G protein (XPG) and Werner syndrome helicase (WRN), that are both highly pleiotropic and associated with inherited genetic disorders when mutated. XPG is a structure-specifi c endonuclease required for the repair of UV-damaged DNA by nucleotide excision repair (NER), and mutations in XPG result in the diseases Xeroderma pigmentosum (XP) and Cockayne syndrome (CS). A loss of XPG incision activity results in XP, whereas a loss of non-enzymatic function(s) of XPG causes CS. WRN is a multifunctional protein involved in double-strand break repair (DSBR), and consists of 3’–5’ DNA-dependent helicase, 3’–5’ exonuclease, and single-strand DNA annealing activities. Nonfunctional WRN protein leads to Werner syndrome, a premature aging disorder with increased cancer incidence. Far Western analysis was used to map the interacting domains between XPG and WRN by denaturing gel electrophoresis, which separated purifi ed full length and recombinant XPG and WRN deletion constructs, based primarily upon the length of each polypeptide. Specifi c interacting domains were visualized when probed with the secondary protein of interest which was then detected by traditional Western analysis using the antibody of the secondary protein. The interaction between XPG and WRN was mapped to the C-terminal region of XPG as well as the C-terminal region of WRN. The physical interaction between XPG and WRN links NER, (made evident by the disease XP) with DSBR, which imparts additional knowledge of the overlapping nature of these two proteins and the previously distinct DNA repair pathways they are associated with. Since genomic integrity is constantly threatened by both endogenous and exogenous (internal and external) damage, understanding the roles of these proteins in coordinating DNA repair processes with replication will signifi cantly further understanding how defects instigate physiological consequences in response to various DNA damaging sources. This ultimately contributes to our understanding of cancer and premature aging.

  13. Mesoporous silica nanoparticles for biomedical and catalytical applications

    SciTech Connect (OSTI)

    Sun, Xiaoxing

    2011-05-15

    Mesoporous silica materials, discovered in 1992 by the Mobile Oil Corporation, have received considerable attention in the chemical industry due to their superior textual properties such as high surface area, large pore volume, tunable pore diameter, and narrow pore size distribution. Among those materials, MCM-41, referred to Mobile Composition of Matter NO. 41, contains honeycomb liked porous structure that is the most common mesoporous molecular sieve studied. Applications of MCM-41 type mesoporous silica material in biomedical field as well as catalytical field have been developed and discussed in this thesis. The unique features of mesoporous silica nanoparticles were utilized for the design of delivery system for multiple biomolecules as described in chapter 2. We loaded luciferin into the hexagonal channels of MSN and capped the pore ends with gold nanoparticles to prevent premature release. Luciferase was adsorbed onto the outer surface of the MSN. Both the MSN and the gold nanoparticles were protected by poly-ethylene glycol to minimize nonspecific interaction of luciferase and keep it from denaturating. Controlled release of luciferin was triggered within the cells and the enzymatic reaction was detected by a luminometer. Further developments by varying enzyme/substrate pairs may provide opportunities to control cell behavior and manipulate intracellular reactions. MSN was also served as a noble metal catalyst support due to its large surface area and its stability with active metals. We prepared MSN with pore diameter of 10 nm (LP10-MSN) which can facilitate mass transfer. And we successfully synthesized an organo silane, 2,2'-Bipyridine-amide-triethoxylsilane (Bpy-amide-TES). Then we were able to functionalize LP10-MSN with bipyridinyl group by both post-grafting method and co-condensation method. Future research of this material would be platinum complexation. This Pt (II) complex catalyst has been reported for a C-H bond activation reaction as an alternative of the traditional Friedel-Crafts reaction. And we will compare the turnover numbers of MSN supported material with homogenous catalyst to evaluate the catalytical efficiency of our material.

  14. Selective Extraction of Uranium from Liquid or Supercritical Carbon Dioxide

    SciTech Connect (OSTI)

    Farawila, Anne F.; O'Hara, Matthew J.; Wai, Chien M.; Taylor, Harry Z.; Liao, Yu-Jung

    2012-07-31

    Current liquid-liquid extraction processes used in recycling irradiated nuclear fuel rely on (1) strong nitric acid to dissolve uranium oxide fuel, and (2) the use of aliphatic hydrocarbons as a diluent in formulating the solvent used to extract uranium. The nitric acid dissolution process is not selective. It dissolves virtually the entire fuel meat which complicates the uranium extraction process. In addition, a solvent washing process is used to remove TBP degradation products, which adds complexity to the recycling plant and increases the overall plant footprint and cost. A liquid or supercritical carbon dioxide (l/sc -CO2) system was designed to mitigate these problems. Indeed, TBP nitric acid complexes are highly soluble in l/sc -CO2 and are capable of extracting uranium directly from UO2, UO3 and U3O8 powders. This eliminates the need for total acid dissolution of the irradiated fuel. Furthermore, since CO2 is easily recycled by evaporation at room temperature and pressure, it eliminates the complex solvent washing process. In this report, we demonstrate: (1) A reprocessing scheme starting with the selective extraction of uranium from solid uranium oxides into a TBP-HNO3 loaded Sc-CO2 phase, (2) Back extraction of uranium into an aqueous phase, and (3) Conversion of recovered purified uranium into uranium oxide. The purified uranium product from step 3 can be disposed of as low level waste, or mixed with enriched uranium for use in a reactor for another fuel cycle. After an introduction on the concept and properties of supercritical fluids, we first report the characterization of the different oxides used for this project. Our extraction system and our online monitoring capability using UV-Vis absorbance spectroscopy directly in sc-CO2 is then presented. Next, the uranium extraction efficiencies and kinetics is demonstrated for different oxides and under different physical and chemical conditions: l/sc -CO2 pressure and temperature, TBP/HNO3 complex used, reductant or complexant used for selectivity, and ionic liquids used as supportive media. To complete the extraction and recovery cycle, we then demonstrate uranium back extraction from the TBP loaded sc-CO2 phase into an aqueous phase and the characterization of the uranium complex formed at the end of this process. Another aspect of this project was to limit proliferation risks by either co-extracting uranium and plutonium, or by leaving plutonium behind by selectively extracting uranium. We report that the former is easily achieved, since plutonium is in the tetravalent or hexavalent oxidation state in the oxidizing environment created by the TBP-nitric acid complex, and is therefore co-extracted. The latter is more challenging, as a reductant or complexant to plutonium has to be used to selectively extract uranium. After undertaking experiments on different reducing or complexing systems (e.g., AcetoHydroxamic Acid (AHA), Fe(II), ascorbic acid), oxalic acid was chosen as it can complex tetravalent actinides (Pu, Np, Th) in the aqueous phase while allowing the extraction of hexavalent uranium in the sc-CO2 phase. Finally, we show results using an alternative media to commonly used aqueous phases: ionic liquids. We show the dissolution of uranium in ionic liquids and its extraction using sc-CO2 with and without the presence of AHA. The possible separation of trivalent actinides from uranium is also demonstrated in ionic liquids using neodymium as a surrogate and diglycolamides as the extractant.

  15. Stable isotopic investigations of in-situ bioremediation of chlorinated organic solvents. 1998 annual progress report

    SciTech Connect (OSTI)

    Sturchio, N.C.

    1998-06-01

    'Contamination of soils and groundwaters with chlorinated aliphatic hydrocarbons (CAHs) is one of the most serious environmental problems in the DOE system and in the nation at large. These compounds are designated as priority pollutants by the US Environmental Protection Agency (EPA) and are known or suspected to be carcinogenic or mutagenic in humans. These compounds are readily transported by groundwater and are not reduced to acceptable concentrations for human consumption by most municipal water supply treatments; thus the compounds represent a significant hazard to a large portion of the human population. In situ bioremediation is an emerging technology that shows great promise for mitigation of CAH contamination at many sites. One of the most severe limitations of in-situ bioremediation is the difficulty of proving when it is working at a given site. The concentrations of CAHs and their degradation products in plumes may be difficult to relate to the efficiency of the remediation process because of dilution effects, but this problem is mitigated to a large extent by measuring isotope ratios. If there is a significant isotopic fractionation between CAHs and derivative chlorine-bearing products, then the fraction of CAH that is dechlorinated can be inferred from the {sup 37}Cl/{sup 35}Cl and {sup 13}C/{sup 12}C isotope ratios of the residual CAH. It is important to point out that there is currently no published information available on the magnitude of chlorine and carbon isotopic fractionation associated with biological degradation of CAHs. The authors plan to help eliminate this important gap in the knowledge with the work being performed here. This work is relevant to EMSP goals because it will provide a new and cost-effective means of evaluating and monitoring the effectiveness of in-situ bioremediation. It will employ newly developed techniques to characterize isotopic fractionation (of chlorine and carbon) associated with biotic and abiotic degradation of CAHs in laboratory microcosms. These techniques and the data acquired by using them in laboratory studies will form the fundamental basis for quantitative assessment of the mechanisms, rates, and efficiencies of various in-situ bioremediation schemes for CAHs. This report summarizes work as of 21 months into a 36-month project. First, the author has developed methods for precise measurement of stable carbon and chlorine isotope ratios of micromolar amounts of CAHs. He has also developed methods for quantitative extraction of CAHs from water and air. He has applied these methods in laboratory experiments, to investigate isotopic fractionation caused by microbial degradation and by abiotic processes such as evaporation and chemical reduction. He has also applied these methods to field investigations of contaminated groundwater aquifers at the Paducah Gaseous Diffusion Plant, Kentucky and at several manufacturing plants in the Chicago and Kansas City metropolitan areas. Results of much of this work have already been incorporated into four manuscripts that have been published, accepted for publication, or are in review.'

  16. Expedited Synthesis of Fluorine-18 Labeled Phenols. A Missing Link in PET Radiochemistry

    SciTech Connect (OSTI)

    Katzenellenbogen, John A.; Zhou, Dong

    2015-03-26

    Fluorine-18 (F-18) is arguably the most valuable radionuclide for positron emission tomographic (PET) imaging. However, while there are many methods for labeling small molecules with F-18 at aliphatic positions and on electron-deficient aromatic rings, there are essentially no reliable and practical methods to label electron-rich aromatic rings such as phenols, with F-18 at high specific activity. This is disappointing because fluorine-labeled phenols are found in many drugs; there are also many interesting plant metabolites and hormones that contain either phenols or other electron-rich aromatic systems such as indoles whose metabolism, transport, and distribution would be interesting to study if they could readily be labeled with F-18. Most approaches to label phenols with F-18 involve the labeling of electron-poor precursor arenes by nucleophilic aromatic substitution, followed by subsequent conversion to phenols by oxidation or other multi-step sequences that are often inefficient and time consuming. Thus, the lack of good methods for labeling phenols and other electron-rich aromatics with F-18 at high specific activity represents a significant methodological gap in F-18 radiochemistry that can be considered a “Missing Link in PET Radiochemistry”. The objective of this research project was to develop and optimize a series of unusual synthetic transformations that will enable phenols (and other electron-rich aromatic systems) to be labeled with F-18 at high specific activity, rapidly, reliably, and conveniently, thereby bridging this gap. Through the studies conducted with support of this project, we have substantially advanced synthetic methodology for the preparation of fluorophenols. Our progress is presented in detail in the sections below, and much has been published or presented publication; other components are being prepared for publication. In essence, we have developed a completely new method to prepare o-fluorophenols from non-aromatic precursors (diazocyclohexenones) by a novel reaction sequence that uses fluoride ion as a precursor and various activating electrophiles, and we have improved methods for the preparation of heterodiaryl iodonium salts. Both methods have been used to prepare interesting potential radiotracers. Other advances have been made in labeling dendrimeric nanoparticle structures of increasing interest for multimodal imaging and in advancing labeling through fluorosilane bonds. Thus, the progress we have made substantially fills the significant gap in PET radiochemistry that we originally identified, and it provides for the field new methodology that can be applied to a number of current challenges, including the preparation of several molecules of interest as radiotracers, such as 2-[18F]Fluoroestradiol (2-FES) and m-fluorotyrosine, which we have illustrated. These methods can be used by any skilled radiochemist interesting in preparing these agents or similar fluorine-18 labeled electron-rich arene systems of interested for PET biological imaging in the most general sense.

  17. Group 4 Metalloporphyrin diolato Complexes and Catalytic Application of Metalloporphyrins and Related Transition Metal Complexes

    SciTech Connect (OSTI)

    Guodong Du

    2004-12-19

    In this work, the first examples of group 4 metalloporphyrin 1,2-diolato complexes were synthesized through a number of strategies. In general, treatment of imido metalloporphyrin complexes, (TTP)M=NR, (M = Ti, Zr, Hf), with vicinal diols led to the formation of a series of diolato complexes. Alternatively, the chelating pinacolate complexes could be prepared by metathesis of (TTP)MCl{sub 2} (M = Ti, Hf) with disodium pinacolate. These complexes were found to undergo C-C cleavage reactions to produce organic carbonyl compounds. For titanium porphyrins, treatment of a titanium(II) alkyne adduct, (TTP)Ti({eta}{sup 2}-PhC{triple_bond}CPh), with aromatic aldehydes or aryl ketones resulted in reductive coupling of the carbonyl groups to produce the corresponding diolato complexes. Aliphatic aldehydes or ketones were not reactive towards (TTP)Ti({eta}{sup 2}-PhC{triple_bond}CPh). However, these carbonyl compounds could be incorporated into a diolato complex on reaction with a reactive precursor, (TTP)Ti[O(Ph){sub 2}C(Ph){sub 2}O] to provide unsymmetrical diolato complexes via cross coupling reactions. In addition, an enediolato complex (TTP)Ti(OCPhCPhO) was obtained from the reaction of (TTP)Ti({eta}{sup 2}-PhC{triple_bond}CPh) with benzoin. Titanium porphyrin diolato complexes were found to be intermediates in the (TTP)Ti=O-catalyzed cleavage reactions of vicinal diols, in which atmospheric oxygen was the oxidant. Furthermore, (TTP)Ti=O was capable of catalyzing the oxidation of benzyl alcohol and {alpha}-hydroxy ketones to benzaldehyde and {alpha}-diketones, respectively. Other high valent metalloporphyrin complexes also can catalyze the oxidative diol cleavage and the benzyl alcohol oxidation reactions with dioxygen. A comparison of Ti(IV) and Sn(IV) porphyrin chemistry was undertaken. While chelated diolato complexes were invariably obtained for titanium porphyrins on treatment with 1,2-diols, the reaction of vicinal diols with tin porphyrins gave a number of products, including mono-, bis-alkoxo, and chelating diolato complexes, depending on the identity of diols and the stoichiometry employed. It was also found that tin porphyrin complexes promoted the oxidative cleavage of vicinal diols and the oxidation of {alpha}-ketols to {alpha}-diketones with dioxygen. In extending the chemistry of metalloporphyrins and analogous complexes, a series of chiral tetraaza macrocyclic ligands and metal complexes were designed and synthesized. Examination of iron(II) complexes showed that they were efficient catalysts for the cyclopropanation of styrene by diazo reagents. Good yields and high diastereoselectivity were obtained with modest enantioselectivity. A rationalization of the stereoselectivity was presented on the basis of structural factors in a carbene intermediate.

  18. Mill Designed Bio bleaching Technologies

    SciTech Connect (OSTI)

    Institute of Paper Science Technology

    2004-01-30

    A key finding of this research program was that Laccase Mediator Systems (LMS) treatments on high-kappa kraft could be successfully accomplished providing substantial delignification (i.e., > 50%) without detrimental impact on viscosity and significantly improved yield properties. The efficiency of the LMS was evident since most of the lignin from the pulp was removed in less than one hour at 45 degrees C. Of the mediators investigated, violuric acid was the most effective vis-a-vis delignification. A comparative study between oxygen delignification and violuric acid revealed that under relatively mild conditions, a single or a double LMS{sub VA} treatment is comparable to a single or a double O stage. Of great notability was the retention of end viscosity of LMS{sub VA} treated pulps with respect to the end viscosity of oxygen treated pulps. These pulps could then be bleached to full brightness values employing conventional ECF bleaching technologies and the final pulp physical properties were equal and/or better than those bleached in a conventional ECF manner employing an aggressively O or OO stage initially. Spectral analyses of residual lignins isolated after LMS treated high-kappa kraft pulps revealed that similar to HBT, VA and NHA preferentially attack phenolic lignin moieties. In addition, a substantial decrease in aliphatic hydroxyl groups was also noted, suggesting side chain oxidation. In all cases, an increase in carboxylic acid was observed. Of notable importance was the different selectivity of NHA, VA and HBT towards lignin functional groups, despite the common N-OH moiety. C-5 condensed phenolic lignin groups were overall resistant to an LMS{sub NHA, HBT} treatments but to a lesser extent to an LMS{sub VA}. The inactiveness of these condensed lignin moieties was not observed when low-kappa kraft pulps were biobleached, suggesting that the LMS chemistry is influenced by the extent of delignification. We have also demonstrated that the current generation of laccase has a broad spectrum of operating parameters. Nonetheless, the development of future genetically engineered laccases with enhanced temperature, pH and redox potentials will dramatically improve the overall process. A second challenge for LMS bleaching technologies is the need to develop effective, catalytic mediators. From the literature we already know this is feasible since ABTS and some inorganic mediators are catalytic. Unfortunately, the mediators that exhibit catalytic properties do not exhibit significant delignification properties and this is a challenge for future research studies. Potential short-term mill application of laccase has been recently reported by Felby132 and Chandra133 as they have demonstrated that the physical properties of linerboard can be improved when exposed to laccase without a chemical mediator. In addition, xxx has shown that the addition of laccase to the whitewater of the paper machine has several benefits for the removal of colloidal materials. Finally, this research program has presented important features on the delignification chemistry of LMS{sub NHA} and LMS{sub VA} that, in the opinion of the author, are momentous contributions to the overall LMS chemistry/biochemistry knowledge base which will continue to have future benefits.

  19. A comprehensive review of the lipid cubic phase or in meso method for crystallizing membrane and soluble proteins and complexes

    SciTech Connect (OSTI)

    Caffrey, Martin, E-mail: martin.caffrey@tcd.ie [Trinity College Dublin, Dublin (Ireland)

    2015-01-01

    A comprehensive and up-to-date review of the lipid cubic phase or in meso method for crystallizing membrane and soluble proteins and complexes is reported. Recent applications of the method for in situ serial crystallography at X-ray free-electron lasers and synchrotrons are described. The lipid cubic phase or in meso method is a robust approach for crystallizing membrane proteins for structure determination. The uptake of the method is such that it is experiencing what can only be described as explosive growth. This timely, comprehensive and up-to-date review introduces the reader to the practice of in meso crystallogenesis, to the associated challenges and to their solutions. A model of how crystallization comes about mechanistically is presented for a more rational approach to crystallization. The possible involvement of the lamellar and inverted hexagonal phases in crystallogenesis and the application of the method to water-soluble, monotopic and lipid-anchored proteins are addressed. How to set up trials manually and automatically with a robot is introduced with reference to open-access online videos that provide a practical guide to all aspects of the method. These range from protein reconstitution to crystal harvesting from the hosting mesophase, which is noted for its viscosity and stickiness. The sponge phase, as an alternative medium in which to perform crystallization, is described. The compatibility of the method with additive lipids, detergents, precipitant-screen components and materials carried along with the protein such as denaturants and reducing agents is considered. The powerful host and additive lipid-screening strategies are described along with how samples that have low protein concentration and cell-free expressed protein can be used. Assaying the protein reconstituted in the bilayer of the cubic phase for function is an important element of quality control and is detailed. Host lipid design for crystallization at low temperatures and for large proteins and complexes is outlined. Experimental phasing by heavy-atom derivatization, soaking or co-crystallization is routine and the approaches that have been implemented to date are described. An overview and a breakdown by family and function of the close to 200 published structures that have been obtained using in meso-grown crystals are given. Recommendations for conducting the screening process to give a more productive outcome are summarized. The fact that the in meso method also works with soluble proteins should not be overlooked. Recent applications of the method for in situ serial crystallography at X-ray free-electron lasers and synchrotrons are described. The review ends with a view to the future and to the bright prospects for the method, which continues to contribute to our understanding of the molecular mechanisms of some of natures most valued proteinaceous robots.

  20. YEAR 2 BIOMASS UTILIZATION

    SciTech Connect (OSTI)

    Christopher J. Zygarlicke

    2004-11-01

    This Energy & Environmental Research Center (EERC) Year 2 Biomass Utilization Final Technical Report summarizes multiple projects in biopower or bioenergy, transportation biofuels, and bioproducts. A prototype of a novel advanced power system, termed the high-temperature air furnace (HITAF), was tested for performance while converting biomass and coal blends to energy. Three biomass fuels--wood residue or hog fuel, corn stover, and switchgrass--and Wyoming subbituminous coal were acquired for combustion tests in the 3-million-Btu/hr system. Blend levels were 20% biomass--80% coal on a heat basis. Hog fuel was prepared for the upcoming combustion test by air-drying and processing through a hammer mill and screen. A K-Tron biomass feeder capable of operating in both gravimetric and volumetric modes was selected as the HITAF feed system. Two oxide dispersion-strengthened (ODS) alloys that would be used in the HITAF high-temperature heat exchanger were tested for slag corrosion rates. An alumina layer formed on one particular alloy, which was more corrosion-resistant than a chromia layer that formed on the other alloy. Research activities were completed in the development of an atmospheric pressure, fluidized-bed pyrolysis-type system called the controlled spontaneous reactor (CSR), which is used to process and condition biomass. Tree trimmings were physically and chemically altered by the CSR process, resulting in a fuel that was very suitable for feeding into a coal combustion or gasification system with little or no feed system modifications required. Experimental procedures were successful for producing hydrogen from biomass using the bacteria Thermotoga, a deep-ocean thermal vent organism. Analytical procedures for hydrogen were evaluated, a gas chromatography (GC) method was derived for measuring hydrogen yields, and adaptation culturing and protocols for mutagenesis were initiated to better develop strains that can use biomass cellulose. Fly ash derived from cofiring coal with waste paper, sunflower hulls, and wood waste showed a broad spectrum of chemical and physical characteristics, according to American Society for Testing and Materials (ASTM) C618 procedures. Higher-than-normal levels of magnesium, sodium, and potassium oxide were observed for the biomass-coal fly ash, which may impact utilization in cement replacement in concrete under ASTM requirements. Other niche markets for biomass-derived fly ash were explored. Research was conducted to develop/optimize a catalytic partial oxidation-based concept for a simple, low-cost fuel processor (reformer). Work progressed to evaluate the effects of temperature and denaturant on ethanol catalytic partial oxidation. A catalyst was isolated that had a yield of 24 mole percent, with catalyst coking limited to less than 15% over a period of 2 hours. In biodiesel research, conversion of vegetable oils to biodiesel using an alternative alkaline catalyst was demonstrated without the need for subsequent water washing. In work related to biorefinery technologies, a continuous-flow reactor was used to react ethanol with lactic acid prepared from an ammonium lactate concentrate produced in fermentations conducted at the EERC. Good yields of ester were obtained even though the concentration of lactic acid in the feed was low with respect to the amount of water present. Esterification gave lower yields of ester, owing to the lowered lactic acid content of the feed. All lactic acid fermentation from amylose hydrolysate test trials was completed. Management activities included a decision to extend several projects to December 31, 2003, because of delays in receiving biomass feedstocks for testing and acquisition of commercial matching funds. In strategic studies, methods for producing acetate esters for high-value fibers, fuel additives, solvents, and chemical intermediates were discussed with several commercial entities. Commercial industries have an interest in efficient biomass gasification designs but are waiting for economic incentives. Utility, biorefinery, pulp and paper, or other industries are interested in lignin as a potential fuel or feedstock but need more information on properties.

  1. Genetic analysis of the regulation of TCH gene expression, Final Report

    SciTech Connect (OSTI)

    Braam, Janet

    2008-10-28

    The Arabidopsis TCH genes, originally isolated as a consequence of their upregulation in response to the mechanical stimulus of touch, are also upregulated by a variety of seemingly disparate environmental and hormonal stimuli. To gain insight into the complexities of TCH gene regulation, a number of approaches were taken. Regulatory elements responsible for regulation were identified and characteristics of the regulation were evaluated. Reporter genes were used to monitor expression localization and dynamics. Microarray analyses of genome-wide expression behavior indicated that touch-inducible gene expression is more widespread than generally appreciated. Identification of all touch-regulated genes shed light on the types of cellular processes that may be altered in response to mechanical stress perturbations. Expression of the TCH2 gene, also called CML24, encoding a calmodulin (CaM)-like (CML) protein, was evaluated. CML24 shares over 40% amino acid sequence identity with CaM, has 4 EF hands and undergoes a Ca2+-dependent change in migration rate through denaturing gel electrophoresis, indicating that CML24 binds Ca2+ and, as a consequence, undergoes conformational changes. CML24 expression occurs in all major organs and is induced from 2- to 15-fold in plants subjected to touch, darkness, heat, cold, hydrogen peroxide, abscisic acid (ABA) and indole-3-acetic acid. The putative CML24 regulatory region confers reporter expression at sites of predicted mechanical stress, in regions undergoing growth, in vascular tissues and various floral organs and in stomata, trichomes and hydathodes. CML24 underexpressing transgenics are resistant to ABA inhibition of germination and seedling growth, defective in long-day induction of flowering, and have enhanced tolerance to CoCl2, molybdic acid, ZnSO4 and MgCl2. These data present evidence that CML24 encodes a potential Ca2+ sensor that may function to enable responses to ABA, day length and presence of various salts. Further investigation of CML24 function and regulation led to the finding that CML24 has a critical role in nitric oxide regulation. Distinct tilling mutant alleles demonstrated that CML24 can act as a switch in the response to day length perception. Because of potential redundancy with the related CML23 gene, CML23 T-DNA insertion mutants were identified and characterized. Together, CML23 and CML24 impact the autonomous regulatory pathway of the transition to flowering. Nitric oxide levels are elevated in cml23/cml24 double mutants. Therefore, CML23 and CML24 are potential calcium sensors regulate nitric oxide accumulation. In collaboration with Drs. McCann and Carpita, fourier transform infrared spectroscopy (FTIR) was used to assess, verify and classify wall architectural changes that occur as a result of single XTH insertion mutations. Thirty-four homozygous mutant lines of Arabidopsis representing 21 members of the xyloglucan endotransglucosylase/hydrolase gene family provided a set of mutants to characterize. Kohonen networks classified cell wall architectures of xth mutant lines and previously characterized cell wall mutants. The xth mutants were found to have chemical changes in their cell walls not detectable as phenotypic growth and development changes, consistent with the existence of feed-back loops that modify wall composition in response to a life-long deficiency of a cell wall enzyme. To gain insight into the potential physiological relevance of the distinct members of the XTH family, GUS reporter fusion genes were constructed, and plants expressing these transgenes were characterized to reveal spatial and temporal patterns of expression. In addition, Genevestigator sources were mined for comprehensive and comparative XTH expression regulation analysis. These data revealed that the Arabidopsis XTHs are likely expressed in every developmental stage from seed germination through flowering. All organs showed XTH::GUS expression and most, if not all, are found to express multiple XTH::GUS genes suggesting that XTHs may contribute to morphogenesis at every d

  2. Subunits of highly Fluorescent Protein R-Phycoerythrin as Probes for Cell Imaging and Single-Molecule Detection

    SciTech Connect (OSTI)

    Dragan Isailovic

    2005-12-17

    The purposes of our research were: (1) To characterize subunits of highly fluorescent protein R-Phycoerythrin (R-PE) and check their suitability for single-molecule detection (SMD) and cell imaging, (2) To extend the use of R-PE subunits through design of similar proteins that will be used as probes for microscopy and spectral imaging in a single cell, and (3) To demonstrate a high-throughput spectral imaging method that will rival spectral flow cytometry in the analysis of individual cells. We first demonstrated that R-PE subunits have spectroscopic and structural characteristics that make them suitable for SMD. Subunits were isolated from R-PE by high-performance liquid chromatography (HPLC) and detected as single molecules by total internal reflection fluorescence microscopy (TIRFM). In addition, R-PE subunits and their enzymatic digests were characterized by several separation and detection methods including HPLC, capillary electrophoresis, sodium dodecyl sulfate-polyacrilamide gel electrophoresis (SDS-PAGE) and HPLC-electrospray ionization mass spectrometry (ESI-MS). Favorable absorption and fluorescence of the R-PE subunits and digest peptides originate from phycoerythrobilin (PEB) and phycourobilin (PUB) chromophores that are covalently attached to cysteine residues. High absorption coefficients and strong fluorescence (even under denaturing conditions), broad excitation and emission fluorescence spectra in the visible region of electromagnetic spectrum, and relatively low molecular weights make these molecules suitable for use as fluorescence labels of biomolecules and cells. We further designed fluorescent proteins both in vitro and in vivo (in Escherichia coli) based on the highly specific attachment of PEB chromophore to genetically expressed apo-subunits of R-PE. In one example, apo-alpha and apo-beta R-PE subunits were cloned from red algae Polisiphonia boldii (P. boldii), and expressed in E. coli. Although expressed apo-subunits formed inclusion bodies, fluorescent holo-subunits were formed after incubation of E. coli cells with PEB. Spectroscopic characterization of holo-subunits confirmed that the attachment of PEB chromophore to apo-subunits yielded holo-subunits containing both PEB and urobilin (UB). Fluorescence and differential interference contrast (DIC) microscopy showed polar location of holo-subunit inclusion bodies in E. coli cells. In another example, R-PE apo-subunits were genetically fused to cytoplasmic and periplasmic versions of E. coli maltose binding protein (MBP). Fluorescent proteins formed after attachment of PEB to MBP-subunit fusions in vitro and in vivo contained PEB as the sole chromophore, were soluble, and displayed high orange fluorescence. Fluorescence microscopy showed that fusions are located either throughout cells or at cell poles. In addition, cells containing fluorescent holo-subunits or MBP-subunit fusions were up to ten times brighter than control cells as measured by flow cytometry. Results show that the fluorescent proteins formed after non-enzymatic attachment of PEB to R-PE subunit fusions could be used as reporters of gene expression and protein localization in cells as well as fluorescence labels in flow cytometry. Finally, we demonstrated a high-throughput method able to record emission fluorescence spectra of individual cells containing fluorescent proteins. Upon excitation with a 488 mn argon-ion laser many bacterial cells were imaged by a 20X microscope objective while they moved through a capillary tube. Fluorescence was dispersed by a transmission diffraction grating, and an intensified charge-coupled device (ICCD) camera simultaneously recorded the zero and the first orders of the fluorescence from each cell. Single-cell fluorescence spectra were reconstructed from the distance between zero-order and first-order maxima as well as the length and the pixel intensity distribution of the first-order images. By using this approach, the emission spectrum of E. coli cells expressing green fluorescent protein (GFP) was reconstructed. Also, fluorescence spectra of E

  3. Bulk gold catalyzed oxidation reactions of amines and isocyanides and iron porphyrin catalyzed N-H and O-H bond insertion/cyclization reactions of diamines and aminoalcohols

    SciTech Connect (OSTI)

    Klobukowski, Erik

    2011-12-29

    This work involves two projects. The first project entails the study of bulk gold as a catalyst in oxidation reactions of isocyanides and amines. The main goal of this project was to study the activation and reactions of molecules at metal surfaces in order to assess how organometallic principles for homogeneous processes apply to heterogeneous catalysis. Since previous work had used oxygen as an oxidant in bulk gold catalyzed reactions, the generality of gold catalysis with other oxidants was examined. Amine N-oxides were chosen for study, due to their properties and use in the oxidation of carbonyl ligands in organometallic complexes. When amine N-oxides were used as an oxidant in the reaction of isocyanides with amines, the system was able to produce ureas from a variety of isocyanides, amines, and amine N-oxides. In addition, the rate was found to generally increase as the amine N-oxide concentration increased, and decrease with increased concentrations of the amine. Mechanistic studies revealed that the reaction likely involves transfer of an oxygen atom from the amine N-oxide to the adsorbed isocyanide to generate an isocyanate intermediate. Subsequent nucleophilic attack by the amine yields the urea. This is in contrast to the bulk gold-catalyzed reaction mechanism of isocyanides with amines and oxygen. Formation of urea in this case was proposed to proceed through a diaminocarbene intermediate. Moreover, formation of the proposed isocyanate intermediate is consistent with the reactions of metal carbonyl ligands, which are isoelectronic to isocyanides. Nucleophilic attack at coordinated CO by amine N-oxides produces CO{sub 2} and is analogous to the production of an isocyanate in this gold system. When the bulk gold-catalyzed oxidative dehydrogenation of amines was examined with amine N-oxides, the same products were afforded as when O{sub 2} was used as the oxidant. When the two types of oxidants were directly compared using the same reaction system and conditions, it was found that the oxidative dehydrogenation of dibenzylamine to Nbenzylidenebenzylamine, with N-methylmorpholine N-oxide (NMMO), was nearly quantitative (96%) within 24 h. However, the reaction with oxygen was much slower, with only a 52% yield of imine product over the same time period. Moreover, the rate of reaction was found to be influenced by the nature of the amine N-oxide. For example, the use of the weakly basic pyridine N-oxide (PyNO) led to an imine yield of only 6% after 24 h. A comparison of amine N-oxide and O2 was also examined in the oxidation of PhCH{sub 2}OH to PhCHO catalyzed by bulk gold. In this reaction, a 52% yield of the aldehyde was achieved when NMMO was used, while only a 7% product yield was afforded when O{sub 2} was the oxidant after 48 h. The bulk gold-catalyzed oxidative dehydrogenation of cyclic amines generates amidines, which upon treatment with Aerosil and water were found to undergo hydrolysis to produce lactams. Moreover, 5-, 6-, and 7-membered lactams could be prepared through a one-pot reaction of cyclic amines by treatment with oxygen, water, bulk gold, and Aerosil. This method is much more atom economical than industrial processes, does not require corrosive acids, and does not generate undesired byproducts. Additionally, the gold and Aerosil catalysts can be readily separated from the reaction mixture. The second project involved studying iron(III) tetraphenylporphyrin chloride, Fe(TPP)Cl, as a homogeneous catalyst for the generation of carbenes from diazo reagents and their reaction with heteroatom compounds. Fe(TPP)Cl, efficiently catalyzed the insertion of carbenes derived from methyl 2-phenyldiazoacetates into O-H bonds of aliphatic and aromatic alcohols. Fe(TPP)Cl was also found to be an effective catalyst for tandem N-H and O-H insertion/cyclization reactions when 1,2-diamines and 1,2-alcoholamines were treated with diazo reagents. This approach provides a one-pot process for synthesizing piperazinones and morpholinones and related analogues such as quinoxalinones and benzoxazin-2-ones.

  4. E85 Optimized Engine through Boosting, Spray-Optimized DIG, VCR and Variable Valvetrain

    SciTech Connect (OSTI)

    Keith Confer; Harry Husted

    2011-05-31

    The use of biofuels for internal combustion engines has several well published advantages. The biofuels, made from biological sources such as corn or sugar cane, are renewable resources that reduce the dependence on fossil fuels. Fuels from agricultural sources can therefore reduce a countries energy dependency on other nations. Biofuels also have been shown to reduce CO2 emissions into the atmosphere compared to traditional fossil based fuels. Because of these benefits several countries have set targets for the use of biofuels, especially ethanol, in their transportation fuels. Small percentages of ethanol are common place in gasoline but are typically limited to 5 to 8% by volume. Greater benefits are possible from higher concentrations and some countries such as the US and Sweden have encouraged the production of vehicles capable of operating on E85 (85% denatured ethanol and 15% gasoline). E85 capable vehicles are normally equipped to run the higher levels of ethanol by employing modified fuel delivery systems that can withstand the highly corrosive nature of the alcohol. These vehicles are not however equipped to take full advantage of ethanol's properties during the combustion process. Ethanol has a much higher blend research octane number than gasoline. This allows the use of higher engine compression ratios and spark advance which result in more efficient engine operation. Ethanol's latent heat of vaporization is also much higher that gasoline. This higher heat of vaporization cools the engine intake charge which also allows the engine compression ratio to be increased even further. An engine that is optimized for operation on high concentrations of ethanol therefore will have compression ratios that are too high to avoid spark knock (pre-ignition) if run on gasoline or a gasoline/ethanol blend that has a low percentage alcohol. An engine was developed during this project to leverage the improved evaporative cooling and high octane of E85 to improve fuel economy and offset E85's lower energy content. A 2.0 L production Direct Injection gasoline, (DIg) engine employing Dual Independent Cam Phasing, (DICP) and turbo charging was used as the base engine. Modified pistons were used to increase the geometric compression ratio from 9.2:1 to 11.85:1 by modifying the pistons and adding advanced valvetrain to proved control of displacement and effective compression ratio through valve timing control. The advanced valvetrain utilized Delphi's two step valvetrain hardware and intake cam phaser with increased phasing authority of 80 crank angle degrees. Using this hardware the engine was capable of operating knock free on all fuels tested from E0-E85 by controlling effective compression ratio using a Late Intake Valve Closing, (LIVC) strategy. The LIVC strategy results in changes in the trapped displacement such that knock limited torque for gasoline is significantly lower than E85. The use of spark retard to control knock enables higher peak torque for knock limited fuels, however a loss in efficiency results. For gasoline and E10 fuels, full effective displacement could not be reached before spark retard produced a net loss in torque. The use of an Early Intake Valve Closing, (EIVC) strategy resulted in an improvement of engine efficiency at low to mid loads for all fuels tested from E0- E85. Further the use of valve deactivation, to a single intake valve, improved combustion stability and enabled throttle-less operation down to less than 2 bar BMEP. Slight throttling to trap internal residual provided additional reductions in fuel consumption. To fully leverage the benefits of E85, or ethanol blends above E10, would require a vehicle level approach that would take advantage of the improved low end torque that is possible with E85. Operating the engine at reduced speeds and using advanced transmissions (6 speeds or higher) would provide a responsive efficient driving experience to the customer. The vehicle shift and torque converter lockup points for high ethanol blends could take advantage of the significant efficiency advantage of down-speeding and operating at higher loads to deliver the required power.