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Sample records for anhydrous denatured aliphatic

  1. Project Profile: Thermochemical Storage with Anhydrous Ammonia: Optimizing

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

    the Synthesis Reactor for Direct Production of Supercritical Steam | Department of Energy Project Profile: Thermochemical Storage with Anhydrous Ammonia: Optimizing the Synthesis Reactor for Direct Production of Supercritical Steam Project Profile: Thermochemical Storage with Anhydrous Ammonia: Optimizing the Synthesis Reactor for Direct Production of Supercritical Steam UCLA Logo The University of California, Los Angeles (UCLA), through the Concentrating Solar Power: Efficiently Leveraging

  2. Production of anhydrous aluminum chloride composition

    DOE Patents [OSTI]

    Vandergrift, G.F. III; Krumpelt, M.; Horwitz, E.P.

    1981-10-08

    A process is described for producing an anhydrous aluminum chloride composition from a water-based aluminous material such as a slurry of aluminum hydroxide in a multistage extraction process in which the aluminum ion is first extracted into an organic liquid containing an acidic extractant and then extracted from the organic phase into an alkali metal chloride or chlorides to form a melt containing a mixture of chlorides of alkali metal and aluminum. In the process, the organic liquid may be recycled. In addition, the process advantageously includes an electrolysis cell for producing metallic aluminum and the alkali metal chloride or chlorides may be recycled for extraction of the aluminum from the organic phase.

  3. A Review Of Water Contents Of Nominally Anhydrous Natural Minerals...

    Open Energy Info (EERE)

    Of Water Contents Of Nominally Anhydrous Natural Minerals In The Mantles Of Earth, Mars And The Moon Jump to: navigation, search OpenEI Reference LibraryAdd to library Journal...

  4. Method and apparatus for synthesizing anhydrous HNO.sub.3

    DOE Patents [OSTI]

    Coon, Clifford L. (Fremont, CA); Harrar, Jackson E. (Castro Valley, CA); Pearson, Richard K. (Pleasanton, CA); McGuire, Raymond R. (Brentwood, CA)

    1984-01-01

    A method and apparatus for electrochemically synthesizing anhydrous HNO.sub.3 from an aqueous solution of HNO.sub.3 includes oxidizing a solution of N.sub.2 O.sub.4 /aqueous HNO.sub.3 at an anode, while maintaining a controlled potential between the N.sub.2 O.sub.4 /aqueous HNO.sub.3 solution and the anode. A potential of about 1.80V vs. SCE is preferred. Anhydrous or aqueous HNO.sub.3 may be disposed at the cathode within the electrochemical cell. Aqueous HNO.sub.3 having a water content of up to about 12% by weight is utilized to synthesize anhydrous HNO.sub.3.

  5. Compact anhydrous HCl to aqueous HCl conversion system

    DOE Patents [OSTI]

    Grossman, Mark W. (Belmont, MA); Speer, Richard (S. Hamilton, MA)

    1993-01-01

    The present invention is directed to an inexpensive and compact apparatus adapted for use with a .sup.196 Hg isotope separation process and the conversion of anhydrous HCl to aqueous HCl without the use of air flow to carry the HCl vapor into the converter system.

  6. Compact anhydrous HCl to aqueous HCl conversion system

    DOE Patents [OSTI]

    Grossman, M.W.; Speer, R.

    1993-06-01

    The present invention is directed to an inexpensive and compact apparatus adapted for use with a [sup 196]Hg isotope separation process and the conversion of anhydrous HCl to aqueous HCl without the use of air flow to carry the HCl vapor into the converter system.

  7. Method of synthesis of anhydrous thorium(IV) complexes

    DOE Patents [OSTI]

    Kiplinger, Jaqueline L; Cantat, Thibault

    2013-04-30

    Method of producing anhydrous thorium(IV) tetrahalide complexes, utilizing Th(NO.sub.3).sub.4(H.sub.2O).sub.x, where x is at least 4, as a reagent; method of producing thorium-containing complexes utilizing ThCl.sub.4(DME).sub.2 as a precursor; method of producing purified ThCl.sub.4(ligand).sub.x compounds, where x is from 2 to 9; and novel compounds having the structures: ##STR00001##

  8. 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.

  9. Process for producing peracids from aliphatic hydroxy carboxylic acids

    DOE Patents [OSTI]

    Chum, Helena L. (Arvada, CO); Ratcliff, Matthew A. (Lakewood, CO); Palasz, Peter D. (Lakewood, CO)

    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.

  10. Method and apparatus for synthesizing anhydrous HNO/sub 3/. [Patent application

    DOE Patents [OSTI]

    Coon, C.L.; Harrar, J.E.; Pearson, R.K.; McGuire, R.R.

    1982-07-20

    A method and apparatus for electrochemically synthesizing anhydrous HNO/sub 3/ from an aqueous solution of HNO/sub 3/- includes oxidizing a solution of N/sub 2/O/sub 4//aqueous HNO/sub 3/ at an anode, while maintaining a controlled potential between the N/sub 2/O/sub 4//aqueous HNO/sub 3/ solution and the anode. A potential of about 1.80V vs. SCE is preferred. Anhydrous or aqueous HNO/sub 3/ may be disposed at the cathode within the electrochemical cell. Aqueous HNO/sub 3/ having a water content of up to about 12% by weight is utilized to synthesize anhydrous HNO/sub 3/.

  11. 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

  12. Aerobic microorganism for the degradation of chlorinated aliphatic hydrocarbons

    DOE Patents [OSTI]

    Fliermans, Carl B. (Augusta, GA)

    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.

  13. Production of anhydrous aluminum chloride composition and process for electrolysis thereof

    DOE Patents [OSTI]

    Vandegrift, George F. (Bolingbrook, Naperville, IL); Krumpelt, Michael (Naperville, IL); Horwitz, E. Philip (Hinsdale, IL)

    1983-01-01

    A process for producing an anhydrous aluminum chloride composition from a water-based aluminous material such as a slurry of aluminum hydroxide in a multistage extraction process in which the aluminum ion is first extracted into an organic liquid containing an acidic extractant and then extracted from the organic phase into an alkali metal chloride or chlorides to form a melt containing a mixture of chlorides of alkali metal and aluminum. In the process, the organic liquid may be recycled. In addition, the process advantageously includes an electrolysis cell for producing metallic aluminum and the alkali metal chloride or chlorides may be recycled for extraction of the aluminum from the organic phase.

  14. Large-scale production of anhydrous nitric acid and nitric acid solutions of dinitrogen pentoxide

    DOE Patents [OSTI]

    Harrar, Jackson E. (Castro Valley, CA); Quong, Roland (Oakland, CA); Rigdon, Lester P. (Livermore, CA); McGuire, Raymond R. (Brentwood, CA)

    2001-01-01

    A method and apparatus are disclosed for a large scale, electrochemical production of anhydrous nitric acid and N.sub.2 O.sub.5. The method includes oxidizing a solution of N.sub.2 O.sub.4 /aqueous-HNO.sub.3 at the anode, while reducing aqueous HNO.sub.3 at the cathode, in a flow electrolyzer constructed of special materials. N.sub.2 O.sub.4 is produced at the cathode and may be separated and recycled as a feedstock for use in the anolyte. The process is controlled by regulating the electrolysis current until the desired products are obtained. The chemical compositions of the anolyte and catholyte are monitored by measurement of the solution density and the concentrations of N.sub.2 O.sub.4.

  15. 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.

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

    DOE Patents [OSTI]

    Greene, Marvin I. (Oradell, NJ); Gelbein, Abraham P. (Morristown, NJ)

    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.

  17. 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.

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

    DOE Patents [OSTI]

    Googin, John M. (Oak Ridge, TN); Napier, John M. (Oak Ridge, TN); Travaglini, Michael A. (Oliver Springs, TN)

    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.

  19. 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.

  20. Table Definitions, Sources, and Explanatory Notes

    Gasoline and Diesel Fuel Update (EIA)

    Input Definitions Key Terms Definition Barrel A unit of volume equal to 42 U.S. gallons. Blending Plant A facility which has no refining capability but is either capable of producing finished motor gasoline through mechanical blending or blends oxygenates with motor gasoline. Conventional Blendstock for Oxygenate Blending (CBOB) Motor gasoline blending components intended for blending with oxygenates to produce finished conventional motor gasoline. Fuel Ethanol An anhydrous denatured aliphatic

  1. Table Definitions, Sources, and Explanatory Notes

    Gasoline and Diesel Fuel Update (EIA)

    Oxygenate Production Definitions Key Terms Definition Barrel A unit of volume equal to 42 U.S. gallons. Captive Refinery Oxygenate Plants Oxygenate production facilities located within or adjacent to a refinery complex. Fuel Ethanol An anhydrous denatured aliphatic alcohol intended for gasoline blending as described in Oxygenates definition. Gasohol A blend of finished motor gasoline containing alcohol (generally ethanol but sometimes methanol) at a concentration of 10 percent or less by volume.

  2. 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.

  3. 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.

  4. 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.

  5. 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.

  6. 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.

  7. 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.

  8. Recovery of anhydrous hydrogen iodide

    DOE Patents [OSTI]

    O'Keefe, Dennis R. (San Diego, CA); McCorkle, Jr., Kenneth H. (Del Mar, CA); de Graaf, Johannes D. (The Hague, NL)

    1982-01-01

    Relatively dry hydrogen iodide can be recovered from a mixture of HI, I.sub.2 and H.sub.2 O. After the composition of the mixture is adjusted so that the amounts of H.sub.2 O and I.sub.2 do not exceed certain maximum limits, subjection of the mixture to superatmospheric pressure in an amount equal to about the vapor pressure of HI at the temperature in question causes distinct liquid phases to appear. One of the liquid phases contains HI and not more than about 1 weight percent water. Often the adjustment in the composition will include the step of vaporization, and the distinct layers appear following the increase in pressure of the vapor mixture. Adjustment in the composition may also include the addition of an extraction agent, such as H.sub.3 PO.sub.4, and even though the adjusted composition mixture contains a significant amount of such an agent, the creation of the distinct liquid phases is not adversely affected.

  9. 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.

  10. Project Profile: Thermochemical Storage with Anhydrous Ammonia...

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

    One of the key aims of the research is to design and build a synthesis reactor that is optimized for the direct production of supercritical steam at 650C. Approach Ammonia ...

  11. 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.

  12. Denaturing of Molecules | GE Global Research

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

    Do Molecules Get Old? Click to email this to a friend (Opens in new window) Share on Facebook (Opens in new window) Click to share (Opens in new window) Click to share on LinkedIn (Opens in new window) Click to share on Tumblr (Opens in new window) Do Molecules Get Old? 2012.07.03 Chief Scientist Jim Bray explains how molecules degrade over various time periods, not unlike human aging. 0 Comments Comment Name Email Submit Comment You Might Also Like Vin_Smentlowski_AVS_Registration AVS 61st

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

    Office of Scientific and Technical Information (OSTI)

    Laboratory (LLNL), Livermore, CA Sponsoring Org: USDOE Country of Publication: United States Language: English Subject: 37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY...

  14. Accident prevention and Clean Air Act Amendments of 1990 with particular reference to anhydrous hydrogen fluoride

    SciTech Connect (OSTI)

    Kaiser, G.D. (Science Applications International Corp., McLean, VA (United States))

    1993-07-01

    The sections of the Clean Air Act Amendments (CAAA) of 1990 that refer to accident prevention are to be found in Title III. Two significant requirements of the CAAA in this respect relate to the responsibilities of the Occupational Safety and Health Administration (OSHA), which has promulgated a new Process Safety Management (PSM) standard and the Environmental Protection Agency (EPA), which at the time of writing, is developing Risk Management Program (RMP) regulations. The focus of this paper is on how the requirements of the CAAA may affect the reasons for performing a Quantitative Risk Assessment (QRA) or may affect the results of QRA. In order to limit the discussion, this paper focuses on HF. First, the CAAA requires that the EPA assess the hazards associated with HF; the EPA's current draft report is discussed. Second, a generic assessment of the risks associated with the use of HF is given, with emphasis on alkylation units in refineries. The principal contributors to risk are listed. Finally, an assessment of OSHA's PSM standard 29 CFR 1910.119, the related requirements of state laws such as California's Risk Management and Prevention Program and the potential requirement of EPA's Risk Management Program are given, including an assessment of how these requirements may influence quantitative estimates of risk. 13 refs., 1 fig.

  15. 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.

  16. Equations of state of anhydrous AlF{sub 3} and AlI{sub 3}: Modeling of extreme condition halide chemistry

    SciTech Connect (OSTI)

    Stavrou, Elissaios; Zaug, Joseph M. Bastea, Sorin; Crowhurst, Jonathan C.; Radousky, Harry B.; Armstrong, Michael R.; Roberts, Sarah K.; Plaue, Jonathan W.; Goncharov, Alexander F.

    2015-06-07

    Pressure dependent angle-dispersive x-ray powder diffraction measurements of alpha-phase aluminum trifluoride (?-AlF{sub 3}) and separately, aluminum triiodide (AlI{sub 3}) were conducted using a diamond-anvil cell. Results at 295 K extend to 50 GPa. The equations of state of AlF{sub 3} and AlI{sub 3} were determined through refinements of collected x-ray diffraction patterns. The respective bulk moduli and corresponding pressure derivatives are reported for multiple orders of the Birch-Murnaghan (B-M), finite-strain (F-f), and higher pressure finite-strain (G-g) EOS analysis models. Aluminum trifluoride exhibits an apparent isostructural phase transition at approximately 12 GPa. Aluminum triiodide also undergoes a second-order atomic rearrangement: applied stress transformed a monoclinically distorted face centered cubic (fcc) structure into a standard fcc structural arrangement of iodine atoms. Results from semi-empirical thermochemical computations of energetic materials formulated with fluorine containing reactants were obtained with the aim of predicting the yield of halogenated products.

  17. Semipermeable polymers and method for producing the same

    DOE Patents [OSTI]

    Buschmann, Wayne E

    2014-04-01

    A polyamide membrane including reaction product of an anhydrous solution comprising an anhydrous solvent, at least one polyfunctional secondary amine and a pre-polymer deposition catalyst, and an anhydrous, organic solvent solution comprising a polyfunctional aromatic amine-reactive reactant having one ring. A composite semipermeable membrane including the polyamide membrane on a porous support.

  18. 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...

  19. 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...

  20. Development of a surface acoustic wave sensor for in-situ monitoring...

    Office of Scientific and Technical Information (OSTI)

    Polymers were optimized and chosen based on their response to chlorinated aliphatic hydrocarbons (e.g., trichloroethylene), which are common groundwater contaminants. Initial ...

  1. Ab Initio Thermodynamic Study of the CO2 Capture Properties of...

    Office of Scientific and Technical Information (OSTI)

    Compared to anhydrous K2CO3, K2CO3*1.5H2O requires less energy for regeneration. Authors: Duan, Yuhua ; Luebkes,David R. ; Pennline, Henry W ; Li, Bingyun Li ; Janik, Michael J. ; ...

  2. CX-012111: Categorical Exclusion Determination

    Broader source: Energy.gov [DOE]

    Thermochemical Storage with Anhydrous Ammonia: Optimizing the Synthesis Reactor for Direct Production of Supercritical Steam CX(s) Applied: A9 Date: 05/06/2014 Location(s): California Offices(s): Golden Field Office

  3. Method to Produce Highly Digestible, Pretreated Lignocellulosic Biomass

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

    Using Anhydrous Liquid Ammonia - Energy Innovation Portal Method to Produce Highly Digestible, Pretreated Lignocellulosic Biomass Using Anhydrous Liquid Ammonia Inventors: Shishir Chundawat, Leonardo Sousa, Albert Cheh, Venkatesh Balan, Bruce Dale Great Lakes Bioenergy Research Center Contact GLBRC About This Technology Technology Marketing SummaryIn the continuing push to develop alternative fuels, bioethanol is clearly a viable option. However, if it is to become a truly economical

  4. Semipermeable polymers and method for producing same

    DOE Patents [OSTI]

    Buschmann, Wayne E. (Boulder, CO)

    2012-04-03

    A polyamide membrane comprising reaction product of an anhydrous solution comprising an anhydrous solvent, at least one polyfunctional secondary amine and a pre-polymer deposition catalyst; and an anhydrous, organic solvent solution comprising a polyfunctional aromatic amine-reactive reactant comprising one ring. A composite semipermeable membrane comprising the polyamide membrane on a porous support. A method of making a composite semipermeable membrane by coating a porous support with an anhydrous solution comprising an anhydrous solvent, a polyfunctional secondary amine and a pre-polymer deposition catalyst, to form an activated pre-polymer layer on the porous support and contacting the activated pre-polymer layer with an anhydrous, organic solvent solution comprising a polyfunctional amine-reactive reactant to interfacially condense the amine-reactive reactant with the polyfunctional secondary amine, thereby forming a cross-linked, interfacial polyamide layer on the porous support. A method of impregnating a composite semipermeable membrane with nanoparticles selected from heavy metals and/or oxides of heavy metals.

  5. 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

  6. Word Pro - S2

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

    ... tion sector fuel ethanol (minus denaturant) consumption; minus refinery and blender net inputs of renewable fuels (excluding fuel ethanol) from U.S. Energy Information ...

  7. Transformation and Crystallization Energetics of Synthetic and Biogenic Amorphous Calcium Carbonate

    SciTech Connect (OSTI)

    Radha, A. V.; Forbes, Tori Z.; Killian, Christopher E.; Gilbert, P.U.P.A; Navrotsky, Alexandra

    2010-01-01

    Amorphous calcium carbonate (ACC) is a metastable phase often observed during low temperature inorganic synthesis and biomineralization. ACC transforms with aging or heating into a less hydrated form, and with time crystallizes to calcite or aragonite. The energetics of transformation and crystallization of synthetic and biogenic (extracted from California purple sea urchin larval spicules, Strongylocentrotus purpuratus) ACC were studied using isothermal acid solution calorimetry and differential scanning calorimetry. Transformation and crystallization of ACC can follow an energetically downhill sequence: more metastable hydrated ACC ? less metastable hydrated ACC?anhydrous ACC ~ biogenic anhydrous ACC?vaterite ? aragonite ? calcite. In a given reaction sequence, not all these phases need to occur. The transformations involve a series of ordering, dehydration, and crystallization processes, each lowering the enthalpy (and free energy) of the system, with crystallization of the dehydrated amorphous material lowering the enthalpy the most. ACC is much more metastable with respect to calcite than the crystalline polymorphs vaterite or aragonite. The anhydrous ACC is less metastable than the hydrated, implying that the structural reorganization during dehydration is exothermic and irreversible. Dehydrated synthetic and anhydrous biogenic ACC are similar in enthalpy. The transformation sequence observed in biomineralization could be mainly energetically driven; the first phase deposited is hydrated ACC, which then converts to anhydrous ACC, and finally crystallizes to calcite. The initial formation of ACC may be a first step in the precipitation of calcite under a wide variety of conditions, including geological CO? sequestration.

  8. 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.

  9. 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.

  10. Effects of torrefaction and densification on switchgrass pyrolysis products

    SciTech Connect (OSTI)

    Yang, Zixu; Sarkar, Madhura; Kumar, Ajay; Tumuluru, Jaya Shankar; Huhnke, Raymond L.

    2014-12-01

    Abstract The pyrolysis behaviors of four types of pretreated switchgrass (torrefied at 230 and 270 C, densification, and torrefaction at 270 C followed by densification) were studied at three temperatures (500, 600, 700 C) using a pyroprobe attached to a gas chromatogram mass spectroscopy (Py-GC/MS). The torrefaction of switchgrass improved its oxygen to carbon ratio and energy content. Contents of anhydrous sugars and phenols in pyrolysis products of torrefied switchgrass were higher than those in pyrolysis products of raw switchgrass. As the torrefaction temperature increased from 230 to 270 C, the contents of anhydrous sugars and phenols in pyrolysis products increased whereas content of guaiacols decreased. High pyrolysis temperature (600 and 700 C as compared to 500 C) enhanced decomposition of lignin and anhydrous sugars, leading to increase in phenols, aromatics and furans. Densification enhanced depolymerization of cellulose and hemicellulose during pyrolysis.

  11. 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.

  12. 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.

  13. 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.

  14. Dehydration of plutonium or neptunium trichloride hydrate

    DOE Patents [OSTI]

    Foropoulos, Jr., Jerry (Los Alamos, NM); Avens, Larry R. (Los Alamos, NM); Trujillo, Eddie A. (Espanola, NM)

    1992-01-01

    A process of preparing anhydrous actinide metal trichlorides of plutonium or neptunium by reacting an aqueous solution of an actinide metal trichloride selected from the group consisting of plutonium trichloride or neptunium trichloride with a reducing agent capable of converting the actinide metal from an oxidation state of +4 to +3 in a resultant solution, evaporating essentially all the solvent from the resultant solution to yield an actinide trichloride hydrate material, dehydrating the actinide trichloride hydrate material by heating the material in admixture with excess thionyl chloride, and recovering anhydrous actinide trichloride is provided.

  15. Dehydration of plutonium or neptunium trichloride hydrate

    DOE Patents [OSTI]

    Foropoulos, J. Jr.; Avens, L.R.; Trujillo, E.A.

    1992-03-24

    A process is described for preparing anhydrous actinide metal trichlorides of plutonium or neptunium by reacting an aqueous solution of an actinide metal trichloride selected from the group consisting of plutonium trichloride or neptunium trichloride with a reducing agent capable of converting the actinide metal from an oxidation state of +4 to +3 in a resultant solution, evaporating essentially all the solvent from the resultant solution to yield an actinide trichloride hydrate material, dehydrating the actinide trichloride hydrate material by heating the material in admixture with excess thionyl chloride, and recovering anhydrous actinide trichloride.

  16. CX-100438 Categorical Exclusion Determination

    Broader source: Energy.gov [DOE]

    Thermochemical Storage with Anhydrous Ammonia: Optimizing the Synthesis Reactor for Direct Production of Supercritical Steam Award Number: DE-EE0006536 CX(s) Applied: B3.6 Solar Energy Technology Office Date: 12/22/15 Location(s): CA Office(s): Golden Field Office

  17. Essential roles of protein-solvent many-body correlation in solvent...

    Office of Scientific and Technical Information (OSTI)

    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 ...

  18. Search for: All records | SciTech Connect

    Office of Scientific and Technical Information (OSTI)

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

  19. 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.

  20. EIA - Gulf of Mexico Energy Data

    Gasoline and Diesel Fuel Update (EIA)

    of Mexico Federal Offshore share of U.S. crude oil production 23% 1. Accounts for non-biofuel oxygenates, denaturants, other hydrocarbons, hydrogen, and crude oil adjustment. 2. ...

  1. Word Pro - S1

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

    ... minus fuel ethanol (minus denaturant) consumption from Table 10.3; minus refinery and blender net inputs of renew- able fuels (excluding fuel ethanol) from U.S. Energy Informa- ...

  2. Alternative Fuels Data Center

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

    High Occupancy Vehicle (HOV) Lane Exemption States are allowed to exempt certified alternative fuel vehicles (AFVs) and plug-in electric vehicles (PEVs) from HOV lane requirements within the state. Eligible AFVs are defined as vehicles operating solely on methanol, denatured ethanol, or other alcohols; a mixture containing at least 85% methanol, denatured ethanol, or other alcohols; natural gas, propane, hydrogen, or coal derived liquid fuels; or fuels derived from biological materials. PEVs are

  3. 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.

  4. 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.

  5. Process for the treatment of lignocellulosic biomass

    DOE Patents [OSTI]

    Dale, Bruce E.; Lynd, Lee R.; Laser, Mark

    2013-03-12

    A process for the treatment of biomass to render structural carbohydrates more accessible and/or digestible using concentrated ammonium hydroxide with or without anhydrous ammonia addition, is described. The process preferably uses steam to strip ammonia from the biomass for recycling. The process yields of monosaccharides from the structural carbohydrates are good, particularly as measured by the enzymatic hydrolysis of the structural carbohydrates. The monosaccharides are used as animal feeds and energy sources for ethanol production.

  6. Process for the treatment of lignocellulosic biomass

    DOE Patents [OSTI]

    Dale, Bruce E.

    2014-07-08

    A process for the treatment of biomass to render structural carbohydrates more accessible and/or digestible using concentrated ammonium hydroxide with or without anhydrous ammonia addition, is described. The process preferably uses steam to strip ammonia from the biomass for recycling. The process yields of monosaccharides from the structural carbohydrates are good, particularly as measured by the enzymatic hydrolysis of the structural carbohydrates. The monosaccharides are used as animal feeds and energy sources for ethanol production.

  7. Reactive formulations for a neutralization of toxic industrial chemicals

    DOE Patents [OSTI]

    Tucker, Mark D.; Betty, Rita G.

    2006-10-24

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

  8. Method for the synthesis of chlorosilanes

    DOE Patents [OSTI]

    Wheeler, D.R.; Pollagi, T.P.

    1999-08-17

    A novel method is described for the synthesis of chlorinated or partially chlorinated organosilanes and organopolysilanes. The chlorination is effected by contacting an organosilanes or organopolysilanes with anhydrous CuCl{sub 2} in a nonpolar alkane solvent, preferably pentane or hexadecane, without the use of a catalyst. Copper metal, which is easily filtered, is a reaction product. The filtrate containing the chlorinated organosilane or organopolysilane can be used directly as a reactant to produce, for example, aminoorganosilanes.

  9. Table Definitions, Sources, and Explanatory Notes

    Gasoline and Diesel Fuel Update (EIA)

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

  10. Process for the treatment of lignocellulosic biomass (Patent) | SciTech

    Office of Scientific and Technical Information (OSTI)

    Connect Process for the treatment of lignocellulosic biomass Citation Details In-Document Search Title: Process for the treatment of lignocellulosic biomass A process for the treatment of biomass to render structural carbohydrates more accessible and/or digestible using concentrated ammonium hydroxide with or without anhydrous ammonia addition, is described. The process preferably uses steam to strip ammonia from the biomass for recycling. The process yields of monosaccharides from the

  11. Process for the treatment of lignocellulosic biomass (Patent) | SciTech

    Office of Scientific and Technical Information (OSTI)

    Connect Process for the treatment of lignocellulosic biomass Citation Details In-Document Search Title: Process for the treatment of lignocellulosic biomass A process for the treatment of biomass to render structural carbohydrates more accessible and/or digestible using concentrated ammonium hydroxide with or without anhydrous ammonia addition, is described. The process preferably uses steam to strip ammonia from the biomass for recycling. The process yields of monosaccharides from the

  12. Interface Induced Carbonate Mineralization: A Fundamental Geochemical

    Office of Scientific and Technical Information (OSTI)

    Process Relevant to Carbon Sequestration (Technical Report) | SciTech Connect Interface Induced Carbonate Mineralization: A Fundamental Geochemical Process Relevant to Carbon Sequestration Citation Details In-Document Search Title: Interface Induced Carbonate Mineralization: A Fundamental Geochemical Process Relevant to Carbon Sequestration We have approached the long-standing geochemical question why anhydrous high-Mg carbonate minerals (i.e., magnesite and dolomite) cannot be formed at

  13. BN Bonded BN fiber article and method of manufacture

    DOE Patents [OSTI]

    Hamilton, Robert S. (Youngstown, NY)

    1981-08-18

    A boron nitride bonded boron nitride fiber article and the method for its manufacture which comprises forming a shaped article with a composition comprising a bonding compound selected from boron oxide and boric acid and a structural fiber selected from the group consisting of boron oxide, boron nitride and partially nitrided boron oxide fibers, heating the composition in an anhydrous gas to a temperature above the melting point of the compound and nitriding the resulting article in ammonia gas.

  14. Quasielastic neutron scattering with in situ humidity control: Water dynamics in uranyl fluoride

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

    Miskowiec, A.; Kirkegaard, M. C.; Herwig, K. W.; Trowbridge, L.; Mamontov, E.; Anderson, B.

    2016-03-04

    The authors confirm that water vapor pressure is the driving thermodynamic force for the conversion of the anhydrous structure to [(UO2F2)(H2O)]7 ? (H2O)4, and they demonstrate the feasibility of extending this approach to aqueous forms of UO2F2+ xH2O. This method has general applicability to systems in which water content itself is a driving variable for structural or dynamical phase transitions.

  15. Fluorination utilizing thermodynamically unstable fluorides and fluoride salts thereof

    DOE Patents [OSTI]

    Bartlett, Neil (Orinda, CA); Whalen, J. Marc (Corning, NY); Chacon, Lisa (Corning, NY)

    2000-12-12

    A method for fluorinating a carbon compound or cationic carbon compound utilizes a fluorination agent selected from thermodynamically unstable nickel fluorides and salts thereof in liquid anhydrous hydrogen fluoride. The desired carbon compound or cationic organic compound to undergo fluorination is selected and reacted with the fluorination agent by contacting the selected organic or cationic organic compound and the chosen fluorination agent in a reaction vessel for a desired reaction time period at room temperature or less.

  16. George Andrew Olah - Patents

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

    Patents - George Andrew Olah Olah Page * Resources with Additional Information US 4,394,247 LIQUEFACTION OF COALS USING RECYCLABLE SUPERACID CATALYST - Olah, George A.; July 19, 1983 This invention discloses a process for the liquefaction of coals and other predominantly hydrocarbonaceous materials by treating the same with a superacidic catalyst system consisting of anhydrous hydrogen fluoride and boron trifluoride in the presence of super-atmospheric hydrogen. US 4,433,192 CONDENSATION OF

  17. Nonaqueous purification of mixed nitrate heat transfer media

    DOE Patents [OSTI]

    Fiorucci, Louis C.; Morgan, Michael J.

    1983-12-20

    A nonaqueous, in-line method for removing carbonate and hydroxide contamination from a molten mixed sodium nitrate/potassium nitrate heat transfer salt. The method comprises dissolving a stoichiometric quantity of anhydrous Ca(NO.sub.3).sub.2 in the melt whereby an insoluble CaCO.sub.3 and Ca(OH).sub.2 precipitate is formed. The precipitate can be removed by settling, filtration or floatation techniques.

  18. Method of preparing nuclear wastes for tansportation and interim storage

    DOE Patents [OSTI]

    Bandyopadhyay, Gautam (Naperville, IL); Galvin, Thomas M. (Darien, IL)

    1984-01-01

    Nuclear waste is formed into a substantially water-insoluble solid for temporary storage and transportation by mixing the calcined waste with at least 10 weight percent powdered anhydrous sodium silicate to form a mixture and subjecting the mixture to a high humidity environment for a period of time sufficient to form cementitious bonds by chemical reaction. The method is suitable for preparing an interim waste form from dried high level radioactive wastes.

  19. Alcohol injection cuts diesel consumption on turbocharged tractors

    SciTech Connect (OSTI)

    Edson, D.V.

    1980-07-21

    M and W Gear Co. of Gibson City, IL, are marketing a new alcohol- injection system that permits turbocharged diesel engines to burn alcohol and claims to cut diesel consumption by 30% and more. The alcohol fuel, a blend of alcohol and water, does not meet the diesel fuel until the alcohol has been atomized and sprayed through the intake manifold into the cylinders. It permits farmers to use home- still-produced ethanol without the added expense of refining to anhydrous composition.

  20. Method for the synthesis of chlorosilanes

    DOE Patents [OSTI]

    Wheeler, David R. (Albuquerque, NM); Pollagi, Timothy P. (Dayton, OH)

    1999-01-01

    A novel method for the synthesis of chlorinated or partially chlorinated organosilanes and organopolysilanes. The chlorination is effected by contacting an organosilanes or organopolysilanes with anhydrous CuCl.sub.2 in a nonpolar alkane solvent, preferably pentane or hexadecane, without the use of a catalyst. Copper metal, which is easily filtered, is a reaction product. The filtrate containing the chlorinated organosilane or organopolysilane can be used directly as a reactant to produce, for example, aminoorganosilanes.

  1. 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.

  2. Surface chemistry control for selective fossil resin flotation

    DOE Patents [OSTI]

    Miller, Jan D. (1886 Atkin Ave., Salt Lake City, UT 84106); Yi, Ye (2875 E. Wander Way, Salt Lake City, UT 84117); Yu, Qiang (224 University Village, Salt Lake City, UT 84108)

    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.

  3. 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.

  4. 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.

  5. 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.

  6. Sprayable titanium composition

    DOE Patents [OSTI]

    Tracy, Chester E. (South River, NJ); Kern, Werner (Belle Mead, NJ); Vibronek, Robert D. (Sayreville, NJ)

    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.

  7. 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.

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

    DOE Patents [OSTI]

    Miller, Robert N. (Allentown, PA)

    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.

  9. Flexible moldable conductive current-limiting materials

    DOE Patents [OSTI]

    Shea, John Joseph (Pittsburgh, PA); Djordjevic, Miomir B. (Milwaukee, WI); Hanna, William Kingston (Pittsburgh, PA)

    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.

  10. Effects of torrefaction and densification on switchgrass pyrolysis products

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

    Yang, Zixu; Sarkar, Madhura; Kumar, Ajay; Tumuluru, Jaya Shankar; Huhnke, Raymond L.

    2014-12-01

    Abstract The pyrolysis behaviors of four types of pretreated switchgrass (torrefied at 230 and 270 °C, densification, and torrefaction at 270 ºC followed by densification) were studied at three temperatures (500, 600, 700 ºC) using a pyroprobe attached to a gas chromatogram mass spectroscopy (Py-GC/MS). The torrefaction of switchgrass improved its oxygen to carbon ratio and energy content. Contents of anhydrous sugars and phenols in pyrolysis products of torrefied switchgrass were higher than those in pyrolysis products of raw switchgrass. As the torrefaction temperature increased from 230 to 270 °C, the contents of anhydrous sugars and phenols in pyrolysis productsmore » increased whereas content of guaiacols decreased. High pyrolysis temperature (600 and 700 °C as compared to 500 °C) enhanced decomposition of lignin and anhydrous sugars, leading to increase in phenols, aromatics and furans. Densification enhanced depolymerization of cellulose and hemicellulose during pyrolysis.« less

  11. Process for the encapsulation and stabilization of radioactive, hazardous and mixed wastes

    DOE Patents [OSTI]

    Colombo, Peter (Patchogue, NY); Kalb, Paul D. (Wading River, NY); Heiser, III, John H. (Bayport, NY)

    1997-11-14

    The present invention provides a method for encapsulating and stabilizing radioactive, hazardous and mixed wastes in a modified sulfur cement composition. The waste may be incinerator fly ash or bottom ash including radioactive contaminants, toxic metal salts and other wastes commonly found in refuse. The process may use glass fibers mixed into the composition to improve the tensile strength and a low concentration of anhydrous sodium sulfide to reduce toxic metal solubility. The present invention preferably includes a method for encapsulating radioactive, hazardous and mixed wastes by combining substantially anhydrous wastes, molten modified sulfur cement, preferably glass fibers, as well as anhydrous sodium sulfide or calcium hydroxide or sodium hydroxide in a heated double-planetary orbital mixer. The modified sulfur cement is preheated to about 135.degree..+-.5.degree. C., then the remaining substantially dry components are added and mixed to homogeneity. The homogeneous molten mixture is poured or extruded into a suitable mold. The mold is allowed to cool, while the mixture hardens, thereby immobilizing and encapsulating the contaminants present in the ash.

  12. 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.

  13. 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.

  14. 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.

  15. 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.

  16. 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.

  17. 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.

  18. 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.

  19. Liquefied Gaseous Fuels Safety and Environmental Control Assessment Program: second status report

    SciTech Connect (OSTI)

    1980-10-01

    This document is arranged in three volumes and reports on progress in the Liquefied Gaseous Fuels (LGF) Safety and Environmental Control Assessment Program made in fiscal Year (FY)-1979 and early FY-1980. Volume 3 contains reports from 6 government contractors on LPG, anhydrous ammonia, and hydrogen energy systems. Report subjects include: simultaneous boiling and spreading of liquefied petroleum gas (LPG) on water; LPG safety research; state-of-the-art of release prevention and control technology in the LPG industry; ammonia: an introductory assessment of safety and environmental control information; ammonia as a fuel, and hydrogen safety and environmental control assessment.

  20. System and process for capture of H.sub.2S from gaseous process streams and process for regeneration of the capture agent

    DOE Patents [OSTI]

    Heldenbrant, David J; Koech, Phillip K; Rainbolt, James E; Bearden, Mark D; Zheng, Feng

    2014-02-18

    A system and process are disclosed for selective removal and recovery of H.sub.2S from a gaseous volume, e.g., from natural gas. Anhydrous organic, sorbents chemically capture H.sub.2S gas to form hydrosulfide salts. Regeneration of the capture solvent involves addition of an anti-solvent that releases the captured H.sub.2S gas from the capture sorbent. The capture sorbent and anti-solvent are reactivated for reuse, e.g., by simple distillation.

  1. Method and system for ethanol production

    DOE Patents [OSTI]

    Feder, H.M.; Chen, M.J.

    1980-05-21

    A transition metal carbonyl and a tertiary amine are employed as a homogeneous catalytic system in methanol or a less volatile solvent to react methanol with carbon monoxide and hydrogen gas producing ethanol and carbon dioxide. The gas contains a high carbon monoxide to hydrogen ratio as is present in a typical gasifier product. The reaction has potential for anhydrous ethanol production as carbon dioxide rather than water is produced. The only other significant by-product is methane. Selected transition metal carbonyls include those of iron, ruthenium and possibly manganese and osmium. Selected amines include trimethylamine, N-Methylpyrrolidine, 24-diazabicyclooctane, dimethyneopentylamine and 2-pryidinol.

  2. Method and system for ethanol production

    DOE Patents [OSTI]

    Feder, H.M.; Chen, M.J.

    1981-09-24

    A transition metal carbonyl and a tertiary amine are employed as a homogeneous catalytic system in methanol or a less volatile solvent to react methanol with carbon monoxide and hydrogen gas producing ethanol and carbon dioxide. The gas contains a high carbon monoxide to hydrogen ratio as is present in a typical gasifier product. The reaction has potential for anhydrous ethanol production as carbon dioxide rather than water is produced. Selected transition metal carbonyls include those of iron, rhodium, ruthenium, manganese in combination with iron and possibly osmium. Selected amines include trimethylamine, N-Methylpyrrolidine, 2,4-diazabicyclooctane, dimethylneopentylamine, N-methylpiperidine and derivatives of N-methylpiperidine.

  3. Method and system for ethanol production

    DOE Patents [OSTI]

    Feder, Harold M. (Darien, IL); Chen, Michael J. (Darien, IL)

    1983-01-01

    A transition metal carbonyl and a tertiary amine are employed as a homogeneous catalytic system in methanol or a less volatile solvent to react methanol with carbon monoxide and hydrogen gas producing ethanol and carbon dioxide. The gas contains a high carbon monoxide to hydrogen ratio as is present in a typical gasifier product. The reaction has potential for anhydrous ethanol production as carbon dioxide rather than water is produced. Selected transition metal carbonyls include those of iron, rhodium ruthenium, manganese in combination with iron and possibly osmium. Selected amines include trimethylamine, N-Methylpyrrolidine, 2,4-diazabicyclooctane, dimethylneopentylamine, N-methylpiperidine and derivatives of N-methylpiperidine.

  4. Platinum-group element abundance patterns in different mantle environments

    SciTech Connect (OSTI)

    Rehkaemper, M.; Halliday, A.N.; Barfod, D.; Fitton, J.G.; Dawson, J.B.

    1997-11-28

    Mantle-derived xenoliths from the Cameroon Line and northern Tanzania display differences in their platinum-group element (PGE) abundance patterns. The Cameroon Line lherzolites have uniform PGE patterns indicating a homogeneous upper mantle over several hundreds of kilometers, with approximately chondritic PGE ratios. The PGE patterns of the Tanzanian peridotites are similar to the PGE systematics of ultramafic rocks from ophiolites. The differences can be explained if the northern Tanzanian lithosphere developed in a fluid-rich suprasubduction zone environment, whereas the Cameroon Line lithosphere only experienced melt extraction from anhydrous periodotites. 32 refs., 2 figs., 1 tab.

  5. Composition and process for the encapsulation and stabilization of radioactive, hazardous and mixed wastes

    DOE Patents [OSTI]

    Kalb, P.D.; Colombo, P.

    1999-07-20

    The present invention provides a composition and process for disposal of radioactive, hazardous and mixed wastes. The present invention preferably includes a process for multibarrier encapsulation of radioactive, hazardous and mixed wastes by combining substantially simultaneously dry waste powder, a non-biodegradable thermoplastic polymer and an anhydrous additive in an extruder to form a homogeneous molten matrix. The molten matrix may be directed in a clean'' polyethylene liner, allowed to cool, thus forming a monolithic waste form which provides a multibarrier to the dispersion of wastes into the environment. 2 figs.

  6. Process for converting magnesium fluoride to calcium fluoride

    DOE Patents [OSTI]

    Kreuzmann, A.B.; Palmer, D.A.

    1984-12-21

    This invention is a process for the conversion of magnesium fluoride to calcium fluoride whereby magnesium fluoride is decomposed by heating in the presence of calcium carbonate, calcium oxide or calcium hydroxide. Magnesium fluoride is a by-product of the reduction of uranium tetrafluoride to form uranium metal and has no known commercial use, thus its production creates a significant storage problem. The advantage of this invention is that the quality of calcium fluoride produced is sufficient to be used in the industrial manufacture of anhydrous hydrogen fluoride, steel mill flux or ceramic applications.

  7. Zinc phosphate conversion coatings

    DOE Patents [OSTI]

    Sugama, Toshifumi

    1997-01-01

    Zinc phosphate conversion coatings for producing metals which exhibit enhanced corrosion prevention characteristics are prepared by the addition of a transition-metal-compound promoter comprising a manganese, iron, cobalt, nickel, or copper compound and an electrolyte such as polyacrylic acid, polymethacrylic acid, polyitaconic acid and poly-L-glutamic acid to a phosphating solution. These coatings are further improved by the incorporation of Fe ions. Thermal treatment of zinc phosphate coatings to generate .alpha.-phase anhydrous zinc phosphate improves the corrosion prevention qualities of the resulting coated metal.

  8. Zinc phosphate conversion coatings

    DOE Patents [OSTI]

    Sugama, T.

    1997-02-18

    Zinc phosphate conversion coatings for producing metals which exhibit enhanced corrosion prevention characteristics are prepared by the addition of a transition-metal-compound promoter comprising a manganese, iron, cobalt, nickel, or copper compound and an electrolyte such as polyacrylic acid, polymethacrylic acid, polyitaconic acid and poly-L-glutamic acid to a phosphating solution. These coatings are further improved by the incorporation of Fe ions. Thermal treatment of zinc phosphate coatings to generate {alpha}-phase anhydrous zinc phosphate improves the corrosion prevention qualities of the resulting coated metal. 33 figs.

  9. Composition and process for the encapsulation and stabilization of radioactive, hazardous and mixed wastes

    DOE Patents [OSTI]

    Kalb, P.D.; Colombo, P.

    1998-03-24

    The present invention provides a composition and process for disposal of radioactive, hazardous and mixed wastes. The present invention preferably includes a process for multibarrier encapsulation of radioactive, hazardous and mixed wastes by combining substantially simultaneously dry waste powder, a non-biodegradable thermoplastic polymer and an anhydrous additive in an extruder to form a homogeneous molten matrix. The molten matrix may be directed in a ``clean`` polyethylene liner, allowed to cool, thus forming a monolithic waste form which provides a multibarrier to the dispersion of wastes into the environment. 2 figs.

  10. Composition and process for the encapsulation and stabilization of radioactive hazardous and mixed wastes

    DOE Patents [OSTI]

    Kalb, P.D.; Colombo, P.

    1997-07-15

    The present invention provides a composition and process for disposal of radioactive, hazardous and mixed wastes. The present invention preferably includes a process for multibarrier encapsulation of radioactive, hazardous and mixed wastes by combining substantially simultaneously dry waste powder, a non-biodegradable thermoplastic polymer and an anhydrous additive in an extruder to form a homogeneous molten matrix. The molten matrix may be directed in a ``clean`` polyethylene liner, allowed to cool, thus forming a monolithic waste form which provides a multibarrier to the dispersion of wastes into the environment. 2 figs.

  11. Method and system for ethanol production

    DOE Patents [OSTI]

    Feder, Harold M. (Darien, IL); Chen, Michael J. (Darien, IL)

    1981-01-01

    A transition metal carbonyl and a tertiary amine are employed as a homogeneous catalytic system in methanol or a less volatile solvent to react methanol with carbon monoxide and hydrogen gas producing ethanol and carbon dioxide. The gas contains a high carbon monoxide to hydrogen ratio as is present in a typical gasifier product. The reaction has potential for anhydrous ethanol production as carbon dioxide rather than water is produced. The only other significant by product is methane. Selected transition metal carbonyls include those of iron, ruthenium and possibly manganese and osmium. Selected amines include trimethylamine, N-Methylpyrrolidine, 24-diazabicyclooctane, dimethyneopentylamine and 2-pryidinol.

  12. Production of the ammonium salt of 3,5-dinitro-1,2,4-triazole by solvent extraction

    DOE Patents [OSTI]

    Lee, Kien Y. (Los Alamos, NM); Ott, Donald G. (Los Alamos, NM)

    1980-01-01

    The ammonium salt of 3,5-dinitro-1,2,4-triazole has utility as a chemical explosive. In accordance with the present invention, it may readily be produced by solvent extraction using high-molecular weight, water-insoluble amines followed by amination with anhydrous ammonia gas. The aqueous reaction mixture produced in the synthesis of the parent compound, 3,5-dinitro-1,2,4-triazole, is quite suitable--and indeed is preferred--for use as the feed material in the process of the invention.

  13. Composition and process for the encapsulation and stabilization of radioactive hazardous and mixed wastes

    DOE Patents [OSTI]

    Kalb, Paul D. (21 Barnes Road, Wading River, NY 11792); Colombo, Peter (44 N. Pinelake Dr., Patchogue, NY 11772)

    1997-01-01

    The present invention provides a composition and process for disposal of radioactive, hazardous and mixed wastes. The present invention preferably includes a process for multibarrier encapsulation of radioactive, hazardous and mixed wastes by combining substantially simultaneously dry waste powder, a non-biodegradable thermoplastic polymer and an anhydrous additive in an extruder to form a homogenous molten matrix. The molten matrix may be directed in a "clean" polyethylene liner, allowed to cool, thus forming a monolithic waste form which provides a multibarrier to the dispersion of wastes into the environment.

  14. Composition and process for the encapsulation and stabilization of radioactive, hazardous and mixed wastes

    DOE Patents [OSTI]

    Kalb, Paul D. (Wading River, NY); Colombo, Peter (Patchogue, NY)

    1998-03-24

    The present invention provides a composition and process for disposal of radioactive, hazardous and mixed wastes. The present invention preferably includes a process for multibarrier encapsulation of radioactive, hazardous and mixed wastes by combining substantially simultaneously dry waste powder, a non-biodegradable thermoplastic polymer and an anhydrous additive in an extruder to form a homogenous molten matrix. The molten matrix may be directed in a "clean" polyethylene liner, allowed to cool, thus forming a monolithic waste form which provides a multibarrier to the dispersion of wastes into the environment.

  15. Composition and process for the encapsulation and stabilization of radioactive, hazardous and mixed wastes

    DOE Patents [OSTI]

    Kalb, Paul D. (Wading River, NY); Colombo, Peter (Patchogue, NY)

    1999-07-20

    The present invention provides a composition and process for disposal of radioactive, hazardous and mixed wastes. The present invention preferably includes a process for multibarrier encapsulation of radioactive, hazardous and mixed wastes by combining substantially simultaneously dry waste powder, a non-biodegradable thermoplastic polymer and an anhydrous additive in an extruder to form a homogenous molten matrix. The molten matrix may be directed in a "clean" polyethylene liner, allowed to cool, thus forming a monolithic waste form which provides a multibarrier to the dispersion of wastes into the environment.

  16. Hygroscopicity Evaluation of Halide Scintillators

    SciTech Connect (OSTI)

    Zhuravleva, M; Stand, L; Wei, H; Hobbs, C. L.; Boatner, Lynn A; Ramey, Joanne Oxendine; Burger, Arnold; Rowe, E; Bhattacharya, P.; Tupitsyn, E; Melcher, Charles L

    2014-01-01

    A collaborative study of relative hygroscopicity of anhydrous halide scintillators grown at various laboratories is presented. We have developed a technique to evaluate moisture sensitivity of both raw materials and grown crystals, in which the moisture absorption rate is measured using a gravimetric analysis. Degradation of the scintillation performance was investigated by recording gamma-ray spectra and monitoring the photopeak position, count rate and energy resolution. The accompanying physical degradation of the samples exposed to ambient atmosphere was photographically recorded as well. The results were compared with ben

  17. STATES GOVERNMENT S. R. Sapirle~, Manager, Oak Ridge Operations

    Office of Legacy Management (LM)

    oh&- 1) +9-y l "UNITED STATES GOVERNMENT S. R. Sapirle~, Manager, Oak Ridge Operations NOVEMBER 2.3 1954 S : J. C. Clarke, Acting Manager, New York . . SUBJXT: REQUEST FOR URMWJM TEm-CHLORIDE SYMBOL: AM:% "& ATTENTION: Mr.N. Woodruff The Frankford Arsenal, Philadelphia, Pennsylvania has under date .of October 26, 1954; requested that we arrange for the shipment of approximately one kilogram of normal uranium tetra-chloride, preferably anhydrous to Mr. C. C> Fawcett, S. F.

  18. Coolside waste management demonstration OCDO grant agreement No. CDO/D-902-9. Final report

    SciTech Connect (OSTI)

    Wu, M.; Winschel, R.A.

    1997-10-01

    The objectives of this project were to evaluate the potential utilization in road construction of wastes produced from the Coolside, LIMB (limestone injection multi-stage burner) and FBC (fluidized-bed combustion) processes, and to specify criteria for landfill disposal of waste from the Coolside process. These three processes are considered to be clean coal technologies. The Coolside process involves injecting an aqueous slurry of hydrated lime into the ductwork downstream of the air preheater in a coal-fired boiler. The hydrated lime captures sulfur dioxide from the flue gas producing anhydrous calcium sulfite and calcium sulfate, which are collected along with the unused hydrated lime and fly ash. The LIMB process involves injection of lime or hydrated lime directly into the furnace to capture sulfur dioxide. The waste consists principally of anhydrous calcium sulfate, lime, and fly ash. Both processes were demonstrated successfully at the Edgewater Station of Ohio Edison in Lorrain, OH, from 1989 to 1992. Circulating fluidized-bed combustion (FBC) is a commercial technology which combines steam generation with SO{sub 2} control by burning coal in a circulating bed of limestone. The waste, chemically similar to LIMB waste, is produced by bleed-off of the bed material and by collection of the flue dust. All three processes produce a dry solid waste, which must either be used or disposed of and managed to ensure environmental compliance and economic feasibility. The project was completed in June 1996.

  19. Molecular simulation of structure and diffusion at smectite-water interfaces: Using expanded clay interlayers as model nanopores

    SciTech Connect (OSTI)

    Greathouse, Jeffery A.; Hart, David; Bowers, Geoffrey M.; Kirkpatrick, R. James; Cygan, Randall Timothy

    2015-07-20

    In geologic settings relevant to a number of extraction and potential sequestration processes, nanopores bounded by clay mineral surfaces play a critical role in the transport of aqueous species. Solution structure and dynamics at claywater interfaces are quite different from their bulk values, and the spatial extent of this disruption remains a topic of current interest. We have used molecular dynamics simulations to investigate the structure and diffusion of aqueous solutions in clay nanopores approximately 6 nm thick, comparing the effect of clay composition with model Na-hectorite and Na-montmorillonite surfaces. In addition to structural properties at the interface, water and ion diffusion coefficients were calculated within each aqueous layer at the interface, as well as in the central bulk-like region of the nanopore. The results show similar solution structure and diffusion properties at each surface, with subtle differences in sodium adsorption complexes and water structure in the first adsorbed layer due to different arrangements of layer hydroxyl groups in the two clay models. Interestingly, the extent of surface disruption on bulk-like solution structure and diffusion extends to only a few water layers. Additionally, a comparison of sodium ion residence times confirms similar behavior of inner-sphere and outer-sphere surface complexes at each clay surface, but ~1% of sodium ions adsorb in ditrigonal cavities on the hectorite surface. Thus, the presence of these anhydrous ions is consistent with highly immobile anhydrous ions seen in previous nuclear magnetic resonance spectroscopic measurements of hectorite pastes.

  20. Molecular Simulation of Structure and Diffusion at Smectite-Water Interfaces: Using Expanded Clay Interlayers as Model Nanopores

    SciTech Connect (OSTI)

    Greathouse, Jeffery A.; Hart, David; Bowers, Geoffrey M.; Kirkpatrick, R. James; Cygan, Randall Timothy

    2015-07-20

    In geologic settings relevant to a number of extraction and potential sequestration processes, nanopores bounded by clay mineral surfaces play a critical role in the transport of aqueous species. Solution structure and dynamics at claywater interfaces are quite different from their bulk values, and the spatial extent of this disruption remains a topic of current interest. We have used molecular dynamics simulations to investigate the structure and diffusion of aqueous solutions in clay nanopores approximately 6 nm thick, comparing the effect of clay composition with model Na-hectorite and Na-montmorillonite surfaces. In addition to structural properties at the interface, water and ion diffusion coefficients were calculated within each aqueous layer at the interface, as well as in the central bulk-like region of the nanopore. The results show similar solution structure and diffusion properties at each surface, with subtle differences in sodium adsorption complexes and water structure in the first adsorbed layer due to different arrangements of layer hydroxyl groups in the two clay models. Interestingly, the extent of surface disruption on bulk-like solution structure and diffusion extends to only a few water layers. Additionally, a comparison of sodium ion residence times confirms similar behavior of inner-sphere and outer-sphere surface complexes at each clay surface, but ~1% of sodium ions adsorb in ditrigonal cavities on the hectorite surface. Thus, the presence of these anhydrous ions is consistent with highly immobile anhydrous ions seen in previous nuclear magnetic resonance spectroscopic measurements of hectorite pastes.

  1. Word Pro - Untitled1

    Gasoline and Diesel Fuel Update (EIA)

    a Petroleum and Other Liquids Overview Overview, 1949-2011 Overview, 2011 Production, 1949-2011 Production and Net Imports, Share of Estimated Consumption, 1949-2011 118 U.S. Energy Information Administration / Annual Energy Review 2011 Note: Production includes production of crude oil (including lease condensate), natural gas plant liquids, fuel ethanol (minus denaturant), and biodiesel; and processing gain. Source: Table 5.1a. 1950 1960 1970 1980 1990 2000 2010 0 5 10 15 20 25 Million Barrels

  2. 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.

  3. 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.

  4. 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.

  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. 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

  7. Alternative Fuels Data Center

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

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

  8. 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

  9. 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

  10. 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.

  11. 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.

  12. 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)

  13. 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.

  14. 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.

  15. 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.

  16. 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.

  17. 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.

  18. 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.

  19. L-asparagine crystals with wide gap semiconductor features: Optical absorption measurements and density functional theory computations

    SciTech Connect (OSTI)

    Zanatta, G.; Gottfried, C.; Silva, A. M.; Caetano, E. W. S.; Sales, F. A. M.; Freire, V. N.

    2014-03-28

    Results of optical absorption measurements are presented together with calculated structural, electronic, and optical properties for the anhydrous monoclinic L-asparagine crystal. Density functional theory (DFT) within the generalized gradient approximation (GGA) including dispersion effects (TS, Grimme) was employed to perform the calculations. The optical absorption measurements revealed that the anhydrous monoclinic L-asparagine crystal is a wide band gap material with 4.95 eV main gap energy. DFT-GGA+TS simulations, on the other hand, produced structural parameters in very good agreement with X-ray data. The lattice parameter differences ?a, ?b, ?c between theory and experiment were as small as 0.020, 0.051, and 0.022, respectively. The calculated band gap energy is smaller than the experimental data by about 15%, with a 4.23 eV indirect band gap corresponding to Z???? and Z???? transitions. Three other indirect band gaps of 4.30 eV, 4.32 eV, and 4.36 eV are assigned to ?3 ???, ?1 ???, and ?2 ??? transitions, respectively. ?-sol computations, on the other hand, predict a main band gap of 5.00 eV, just 50 meV above the experimental value. Electronic wavefunctions mainly originating from O 2pcarboxyl, C 2pside chain, and C 2pcarboxyl orbitals contribute most significantly to the highest valence and lowest conduction energy bands, respectively. By varying the lattice parameters from their converged equilibrium values, we show that the unit cell is less stiff along the b direction than for the a and c directions. Effective mass calculations suggest that hole transport behavior is more anisotropic than electron transport, but the mass values allow for some charge mobility except along a direction perpendicular to the molecular layers of L-asparagine which form the crystal, so anhydrous monoclinic L-asparagine crystals could behave as wide gap semiconductors. Finally, the calculations point to a high degree of optical anisotropy for the absorption and complex dielectric function, with more structured curves for incident light polarized along the 100 and 101 directions.

  20. Aspects of uranium chemistry pertaining to UF{sub 6} cylinder handling

    SciTech Connect (OSTI)

    Ritter, R.L.; Barber, E.J.

    1991-12-31

    Under normal conditions, the bulk of UF{sub 6} in storage cylinders will be in the solid state with an overpressure of gaseous UF{sub 6} well below one atmosphere. Corrosion of the interior of the cylinder will be very slow, with formation of a small amount of reduced fluoride, probably U{sub 2}F{sub 9}. The UO{sub 3}-HF-H{sub 2}O phase diagram indicates that reaction of any inleaking water vapor with the solid UF{sub 6} will generate the solid material [H{sub 3}O]{sub 2}(U(OH){sub 4}F{sub 4}) in equilibrium with an aqueous HF solution containing only small amounts of uranium. The corrosion of the steel cylinder by these materials may be enhanced over that observed with gaseous anhydrous UF{sub 6}.

  1. Aluminum phosphate ceramics for waste storage

    SciTech Connect (OSTI)

    Wagh, Arun; Maloney, Martin D

    2014-06-03

    The present disclosure describes solid waste forms and methods of processing waste. In one particular implementation, the invention provides a method of processing waste that may be particularly suitable for processing hazardous waste. In this method, a waste component is combined with an aluminum oxide and an acidic phosphate component in a slurry. A molar ratio of aluminum to phosphorus in the slurry is greater than one. Water in the slurry may be evaporated while mixing the slurry at a temperature of about 140-200.degree. C. The mixed slurry may be allowed to cure into a solid waste form. This solid waste form includes an anhydrous aluminum phosphate with at least a residual portion of the waste component bound therein.

  2. Structural and thermal studies of H{sub 2}La{sub 2/3}Ta{sub 2}O{sub 7}, a protonated layered perovskite

    SciTech Connect (OSTI)

    Le Berre, F.; Crosnier-Lopez, M.P.; Fourquet, J.L.

    2006-04-13

    We have synthesised the new protonated layered perovskite H{sub 2}La{sub 2/3}Ta{sub 2}O{sub 7} which is related to the Ruddlesden-Popper family. This compound is obtained by ionic exchange starting from Li{sub 2}La{sub 2/3}Ta{sub 2}O{sub 7} maintained in dilute HNO{sub 3} at 60 deg. C. Thermal X-ray diffraction and DTA/TGA revealed interesting dehydration properties with formation of a layered anhydrous phase leading at higher temperature (1550 deg. C) to La{sub 1/3}TaO{sub 3}. This latter compound exhibits the original lanthanum ordering expected similarly to that of the Li form, while at 900 deg. C a metastable form, presenting a disordered La distribution, is observed.

  3. Actinide Dioxides in Water: Interactions at the Interface

    SciTech Connect (OSTI)

    Alexandrov, Vitaly; Shvareva, Tatiana Y.; Hayun, Shmuel; Asta, Mark; Navrotsky, Alexandra

    2011-12-15

    A comprehensive understanding of chemical interactions between water and actinide dioxide surfaces is critical for safe operation and storage of nuclear fuels. Despite substantial previous research, understanding the nature of these interactions remains incomplete. In this work, we combine accurate calorimetric measurements with first-principles computational studies to characterize surface energies and adsorption enthalpies of water on two fluorite-structured compounds, ThO? and CeO?, that are relevant for understanding the behavior of water on actinide oxide surfaces more generally. We determine coverage-dependent adsorption enthalpies and demonstrate a mixed molecular and dissociative structure for the first hydration layer. The results show a correlation between the magnitude of the anhydrous surface energy and the water adsorption enthalpy. Further, they suggest a structural model featuring one adsorbed water molecule per one surface cation on the most stable facet that is expected to be a common structural signature of water adsorbed on actinide dioxide compounds.

  4. Nucleophilic fluorination of aromatic compounds

    DOE Patents [OSTI]

    Satyamurthy, Nagichettiar; Barrio, Jorge R

    2014-03-18

    Iodylbenzene derivatives substituted with electron donating as well as electron withdrawing groups on the aromatic ring are used as precursors in aromatic nucleophilic substitution reactions. The iodyl group (IO.sub.2) is regiospecifically substituted by nucleophilic fluoride to provide the corresponding fluoroaryl derivatives. No-carrier-added [F-18]fluoride ion derived from anhydrous [F-18](F/Kryptofix, [F-18]CsF or a quaternary ammonium fluoride (e.g., Me.sub.4NF, Et.sub.4NF, n-Bu.sub.4NF, (PhCH.sub.2).sub.4NF) exclusively substitutes the iodyl moiety in these derivatives and provides high specific activity F-18 labeled fluoroaryl analogs. Iodyl derivatives of a benzothiazole analog and 6-iodyl-L-dopa derivatives have been synthesized as precursors and have been used in the preparation of no-carrier-added [F-18]fluorobenzothiazole as well as 6-[F-18]fluoro-L-dopa.

  5. Simultaneous Thermal Analysis of WIPP and LANL Waste Drum Samples: A Preliminary Report

    SciTech Connect (OSTI)

    Wayne, David M.

    2015-10-19

    On Friday, February 14, 2014, an incident in P7R7 of the WIPP underground repository released radioactive material into the environment. The direct cause of the event was a breached transuranic (TRU) waste container, subsequently identified as Drum 68660. Photographic and other evidence indicates that the breach of 68660 was caused by an exothermic event. Subsequent investigations (Britt, 2015; Clark and Funk, 2015; Wilson et al., 2015; Clark, 2015) indicate that the combination of nitrate salts, pH neutralizing chemicals, and organic-based adsorbent represented a potentially energetic mixture. The materials inside the breached steel drum consisted of remediated, 30- to 40-year old, Pu processing wastes from LANL. The contents were processed and repackaged in 2014. Processing activities at LANL included: 1) neutralization of acidic liquid contents, 2) sorption of the neutralized liquid, and 3) mixing of acidic nitrate salts with an absorber to meet waste acceptance criteria. The contents of 68660 and its sibling, 68685, were derived from the same parent drum, S855793. Drum S855793 originally contained ten plastic bags of acidic nitrate salts, and four bags of mixed nitrate and oxalate salts generated in 1985 by Pu recovery operations. These salts were predominantly oxalic acid, hydrated nitrate salts of Mg, Ca, and Fe, anhydrous Na(NO3), and minor amounts of anhydrous and hydrous nitrate salts of Pb, Al, K, Cr, and Ni. Other major components include sorbed water, nitric acid, dissolved nitrates, an absorbent (Swheat Scoop) and a neutralizer (KolorSafe). The contents of 68660 are described in greater detail in Appendix E of Wilson et al. (2015)

  6. Solid-state thermal behavior and stability studies of theophylline-citric acid cocrystals prepared by neat cogrinding or thermal treatment

    SciTech Connect (OSTI)

    Hsu, Po-Chun; Lin, Hong-Liang; Wang, Shun-Li; Lin, Shan-Yang

    2012-08-15

    To investigate the thermal behavior of cocrystal formed between anhydrous theophylline (TP) and anhydrous citric acid (CA) by neat manual cogrinding or thermal treatment, DSC and FTIR microspectroscopy with curve-fitting analysis were applied. The physical mixture and 60-min ground mixture were stored at 55{+-}0.5 Degree-Sign C/40{+-}2% RH condition to determine their stability behavior. Typical TP-CA cocrystals were prepared by slow solvent evaporation method. Results indicate that the cogrinding process could gradually induce the cocrystal formation between TP and CA. The IR spectral peak shift from 3495 to 3512 cm{sup -1} and the stepwise appearance of several new IR peaks at 1731, 1712, 1676, 1651, 1557 and 1265 cm{sup -1} with cogrinding time suggest that the mechanism of TP-CA cocrystal formation was evidenced by interacting TP with CA through the intermolecular O-H{center_dot}{center_dot}{center_dot}O hydrogen bonding. The stability of 60-min ground mixture of TP-CA was confirmed at 55{+-}0.5 Degree-Sign C/40{+-}2% RH condition over a storage time of 60 days. - Garphical abstract: Cogrinding, thermal and solvent-evaporation methods might easily induce the theophylline-citric acid cocrystal formation. Highlights: Black-Right-Pointing-Pointer Cogrinding process could gradually induce the cocrystal formation between TP and CA. Black-Right-Pointing-Pointer The TP-CA cocrystal was formed through the intermolecular O-H{center_dot}{center_dot}{center_dot}O hydrogen bonding. Black-Right-Pointing-Pointer The 60-min TP-CA ground mixture was similar to the solvent-evaporated cocrystal. Black-Right-Pointing-Pointer The thermal-induced TP-CA cocrystal formation was confirmed by pre-heating the physical mixture to 152 Degree-Sign C. Black-Right-Pointing-Pointer The 60-min TP-CA ground mixture was stable at accelerated condition over a storage time of 60 days.

  7. Molecular simulation of structure and diffusion at smectite-water interfaces: Using expanded clay interlayers as model nanopores

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

    Greathouse, Jeffery A.; Hart, David; Bowers, Geoffrey M.; Kirkpatrick, R. James; Cygan, Randall Timothy

    2015-07-20

    In geologic settings relevant to a number of extraction and potential sequestration processes, nanopores bounded by clay mineral surfaces play a critical role in the transport of aqueous species. Solution structure and dynamics at clay–water interfaces are quite different from their bulk values, and the spatial extent of this disruption remains a topic of current interest. We have used molecular dynamics simulations to investigate the structure and diffusion of aqueous solutions in clay nanopores approximately 6 nm thick, comparing the effect of clay composition with model Na-hectorite and Na-montmorillonite surfaces. In addition to structural properties at the interface, water andmore » ion diffusion coefficients were calculated within each aqueous layer at the interface, as well as in the central bulk-like region of the nanopore. The results show similar solution structure and diffusion properties at each surface, with subtle differences in sodium adsorption complexes and water structure in the first adsorbed layer due to different arrangements of layer hydroxyl groups in the two clay models. Interestingly, the extent of surface disruption on bulk-like solution structure and diffusion extends to only a few water layers. Additionally, a comparison of sodium ion residence times confirms similar behavior of inner-sphere and outer-sphere surface complexes at each clay surface, but ~1% of sodium ions adsorb in ditrigonal cavities on the hectorite surface. Thus, the presence of these anhydrous ions is consistent with highly immobile anhydrous ions seen in previous nuclear magnetic resonance spectroscopic measurements of hectorite pastes.« less

  8. 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

  9. 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.

  10. 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.

  11. 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.

  12. 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

  13. 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.

  14. 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

  15. 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.

  16. Integrated multiplexed capillary electrophoresis system

    DOE Patents [OSTI]

    Yeung, Edward S. (Ames, IA); Tan, Hongdong (Ames, IA)

    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.

  17. Highly thermostable fluorescent proteins

    DOE Patents [OSTI]

    Bradbury, Andrew M. (Santa Fe, NM); Waldo, Geoffrey S. (Santa Fe, NM); Kiss, Csaba (Los Alamos, NM)

    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.

  18. Highly thermostable fluorescent proteins

    DOE Patents [OSTI]

    Bradbury, Andrew M. (Santa Fe, NM); Waldo, Geoffrey S. (Santa Fe, NM); Kiss, Csaba (Los Alamos, NM)

    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.

  19. Highly thermostable fluorescent proteins

    DOE Patents [OSTI]

    Bradbury, Andrew M. (Santa Fe, NM); Waldo, Geoffrey S. (Santa Fe, NM); Kiss, Csaba (Los Alamos, NM)

    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.

  20. 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.

  1. Word Pro - S10

    Gasoline and Diesel Fuel Update (EIA)

    5 Table 10.3 Fuel Ethanol Overview Feed- stock a Losses and Co- products b Dena- turant c Production d Trade d Stocks d,f Stock Change d,g Consumption d Consump- tion Minus Denaturant h Net Imports e TBtu TBtu Mbbl Mbbl MMgal TBtu Mbbl Mbbl Mbbl Mbbl MMgal TBtu TBtu 1981 Total .................. 13 6 40 1,978 83 7 NA NA NA 1,978 83 7 7 1985 Total .................. 93 42 294 14,693 617 52 NA NA NA 14,693 617 52 51 1990 Total .................. 111 49 356 17,802 748 63 NA NA NA 17,802 748 63 62

  2. 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.

  3. 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.

  4. 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.

  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. 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.

  7. Determining orientation and direction of DNA sequences

    DOE Patents [OSTI]

    Goodwin, Edwin H. (Los Alamos, NM); Meyne, Julianne (Los Alamos, NM)

    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.

  8. 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.

  9. 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.

  10. 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.

  11. 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.

  12. 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.

  13. 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.

  14. 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).

  15. 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)

  16. 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.

  17. 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.

  18. 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.

  19. 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.

  20. 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.

  1. 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.

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

    DOE Patents [OSTI]

    Guon, Jerold (Canoga Park, CA)

    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.

  3. 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.

  4. 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.

  5. 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.

  6. 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.

  7. 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.

  8. 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.

  9. New high pressure rare earth tantalates RE{sub x}Ta{sub 2}O{sub 5+1.5x} (RE=La, Eu, Yb)

    SciTech Connect (OSTI)

    Zibrov, Igor P.; Filonenko, Vladimir P.; Zakharov, Nikolai D.; Nikishina, Elena E.; Lebedeva, Elena N.

    2013-07-15

    Rare earth tantalates La{sub 0.075}Ta{sub 2}O{sub 5.113}, Eu{sub 0.089}Ta{sub 2}O{sub 5.134} and Yb{sub 0.051}Ta{sub 2}O{sub 5.077} have been prepared by solid state reaction at P=7.0 GPa and T=10501100 C and studied by X-ray diffraction, thermal analysis and electron microscopy. Low hydrated amorphous tantalum, lanthanum, europium and ytterbium hydroxides were used as starting materials. Aqueous as well as anhydrous compounds were obtained. Title tantalates are crystallized in the structure type of FTa{sub 2}O{sub 5} [Zibrov et al. Russ. J. Inorg. Chem. 48 (2003) 464471] [5]. The structure was refined by the Rietveld method from X-ray powder diffractometer data: La{sub 0.075}Ta{sub 2}O{sub 5.113}, a=10.5099(2), b=7.2679(1), c=6.9765(1) , V=532.90(1) {sup 3}, Z=6, space group Ibam; Eu{sub 0.089}Ta{sub 2}O{sub 5.134}, a=10.4182(3), b=7.2685(1), c=6.9832(1) , V=528.80(2) {sup 3}, Z=6, space group Ibam; Yb{sub 0.051}Ta{sub 2}O{sub 5.077}, a=10.4557(2), b=7.3853(1), c=6.8923(1) , V=532.21(1) {sup 3}, Z=6, space group Ibam. RE atoms do not replace the tantalum in its positions but the only water in the channels of the structure. Highly charged cations RE{sup +3} compress the unit cell so that its volume becomes less than that of FTa{sub 2}O{sub 5}. Significant decrease of the unit cell volume after water removal from the structure is possible due to the puckering of pentagonal bipyramid layers and change of the corrugation angle in the layer. - Graphical abstract: The structure of RE{sub x}Ta{sub 2}O{sub 5+1.5x} and its HRTEM image (A arrows show empty channel, B arrows show filled channel). - Highlights: We synthesized new tantalates of RE under high pressure high temperature conditions. RE atoms replace water molecules in the channels of the structure. Aqueous as well as anhydrous tantalates were obtained. Highly charged cations RE{sup +3} compress the unit cell decreasing REO distances.

  10. Ground-state proton-transfer tautomer of the salicylate anion

    SciTech Connect (OSTI)

    Friedrich, D.M.; Wang, Z.; Joly, A.G.; Peterson, K.A.; Callis, P.R.

    1999-12-02

    Solutions of sodium salicylate in anhydrous polar solvents exhibit a weak, temperature-dependent absorption band ({lambda}{sub max} {approx} 325 nm) lying in the Stokes gap between the main absorption (296 nm) and the fluorescence band (396 nm, acetonitrile). This weak, longer wavelength absorption band is hardly observable in aqueous solution, but its intensity increases with temperature and increases with polarity in anhydrous organic solvents in the order of ethanol < acetonitrile < dimethyl sulfoxide at room temperature. After correction for solvent thermal contraction, the temperature-dependent absorption spectrum of salicylate in acetonitrile solutions reveals a clear isosbestic point ({epsilon}{sub 310}= 2,000 M{sup {minus}1} cm{sup {minus}1}) characteristic of an equilibrium between two salicylate species with band-maximum extinction coefficients of {epsilon}{sub 325} = 3,400 M{sup {minus}1} cm{sup {minus}1} and {epsilon}{sub 296} = 3,586 M{sup {minus}1} cm{sup {minus}1}. In acetonitrile at room temperature (298 K) the concentration equilibrium constant (minor/major) for the interconversion reaction between the two species is K{sub 298} = 0.11, with {Delta}H = 1.6 kcal mol{sup {minus}1} and {Delta}S = 0.97 cal{center{underscore}dot}mol{sup {minus}1} K{sup {minus}1}. The fluorescence lifetime (4.8 ns in acetonitrile) and the shape of the fluorescence spectrum are independent of excitation wavelength. The fluorescence quantum yield for excitation in the long-wavelength shoulder (340 nm) is approximately 60% larger than the yield for excitation in the main band at 296 nm ({phi}{sub 340} = 0.29, {phi}{sub 296} = 0.18) in acetonitrile at room temperature. These results are consistent with assignment of the shoulder band to the proton-transfer tautomer of the salicylate anion. Electronic structure calculations support assignment of the 325 nm absorption band to the ground-state tautomer (phenoxide anion form) of the salicylate anion. Absorption transition moments for both the normal and tautomer forms are parallel to the emission transition moment, are electronically allowed, and are consistent with {sup 1}L{sub b} assignment for both absorbing and emitting transitions. The static dipole moments are in the order of {mu}(N*) {ge} {mu}(N) > {mu}(T*) > {mu}(T) for the normal (N) and tautomer (T) ground and electronic excited states.

  11. A gas-loading system for LANL two-stage gas guns

    SciTech Connect (OSTI)

    Gibson, Lloyd Lee; Bartram, Brian Douglas; Dattelbaum, Dana Mcgraw; Lang, John Michael; Morris, John Scott

    2015-09-01

    A novel gas loading system was designed for the specific application of remotely loading high purity gases into targets for gas-gun driven plate impact experiments. The high purity gases are loaded into well-defined target configurations to obtain Hugoniot states in the gas phase at greater than ambient pressures.The small volume of the gas samples is challenging, as slight changing in the ambient temperature result in measurable pressure changes. Therefore, the ability to load a gas gun target and continually monitor the sample pressure prior to firing provides the most stable and reliable target fielding approach. We present the design and evaluation of a gas loading system built for the LANL 50 mm bore two-stage light gas gun. Targets for the gun are made of 6061 Al or OFHC Cu, and assembled to form a gas containment cell with a volume of approximately 1.38 cc. The compatibility of materials was a major consideration in the design of the system, particularly for its use with corrosive gases. Piping and valves are stainless steel with wetted seals made from Kalrez® and Teflon®. Preliminary testing was completed to ensure proper flow rate and that the proper safety controls were in place. The system has been used to successfully load Ar, Kr, Xe, and anhydrous ammonia with purities of up to 99.999 percent. The design of the system and example data from the plate impact experiments will be shown.

  12. Timescales and settings for alteration of chondritic meteorites

    SciTech Connect (OSTI)

    Krot, A N; Hutcheon, I D; Brearley, A J; Pravdivtseva, O V; Petaev, M I; Hohenberg, C M

    2005-11-16

    Most groups of chondritic meteorites experienced diverse styles of secondary alteration to various degrees that resulted in formation of hydrous and anhydrous minerals (e.g., phyllosilicates, magnetite, carbonates, ferrous olivine, hedenbergite, wollastonite, grossular, andradite, nepheline, sodalite, Fe,Ni-carbides, pentlandite, pyrrhotite, Ni-rich metal). Mineralogical, petrographic, and isotopic observations suggest that the alteration occurred in the presence of aqueous solutions under variable conditions (temperature, water/rock ratio, redox conditions, and fluid compositions) in an asteroidal setting, and, in many cases, was multistage. Although some alteration predated agglomeration of the final chondrite asteroidal bodies (i.e. was pre-accretionary), it seems highly unlikely that the alteration occurred in the solar nebula, nor in planetesimals of earlier generations. Short-lived isotope chronologies ({sup 26}Al-{sup 26}Mg, {sup 53}Mn-{sup 53}Cr, {sup 129}I-{sup 129}Xe) of the secondary minerals indicate that the alteration started within 1-2 Ma after formation of the Ca,Al-rich inclusions and lasted up to 15 Ma. These observations suggest that chondrite parent bodies must have accreted within the first 1-2 Ma after collapse of the protosolar molecular cloud and provide strong evidence for an early onset of aqueous activity on these bodies.

  13. Dessicant materials screening for backfill in a salt repository

    SciTech Connect (OSTI)

    Simpson, D.R.

    1980-10-01

    Maintaining an anhydrous environment around nuclear waste stored in a salt repository is a concern which can be alleviated by using a desiccant material for backfilling. Such a desiccant should desiccate a brine yet be non deliquescent, the hydrated product should have moderate thermal stability, and the desiccant should have a high capacity and be readily available. From a literature search MgO and CaO were identified for detailed study. These oxides, and an intimate mixture of the two obtained by calcining dolomite, were used in experiments to further determine their suitability. They proved to be excellent desiccants with a high water capacity. The hydrates of both have moderate thermal stability and a high water content. Both MgO and CaO react in an alkaline chloride brine forming oxychloride compounds with different waters of crystallization. Some of these compounds are the Sorel Cements. CaO hydrates to Ca(OH)/sub 2/ which carbonates with CO/sub 2/ in air to form CaCO/sub 3/ and release the hydrated water. Thus the intimate mixture of CaO and MgO from calcined dolomite may serve as a desiccant and remove CO/sub 2/ from the repository atmosphere.

  14. Facile synthesis of lithium sulfide nanocrystals for use in advanced rechargeable batteries

    SciTech Connect (OSTI)

    Li, Xuemin; Wolden, Colin A.; Ban, Chunmei; Yang, Yongan

    2015-12-03

    This work reports a new method of synthesizing anhydrous lithium sulfide (Li2S) nanocrystals and demonstrates their potential as cathode materials for advanced rechargeable batteries. Li2S is synthesized by reacting hydrogen sulfide (H2S) with lithium naphthalenide (Li-NAP), a thermodynamically spontaneous reaction that proceeds to completion rapidly at ambient temperature and pressure. The process completely removes H2S, a major industrial waste, while cogenerating 1,4-dihydronaphthalene, itself a value-added chemical that can be used as liquid fuel. The phase purity, morphology, and homogeneity of the resulting nanopowders were confirmed by X-ray diffraction and scanning electron microscopy. The synthesized Li2S nanoparticles (100 nm) were assembled into cathodes, and their performance was compared to that of cathodes fabricated using commercial Li2S micropowders (15 ?m). As a result, electrochemical analyses demonstrated that the synthesized Li2S were superior in terms of (dis)charge capacity, cycling stability, output voltage, and voltage efficiency.

  15. Structural and magnetic properties of triethylene glycol stabilized Zn{sub x}Co{sub 1?x}Fe{sub 2}O{sub 4} nanoparticles

    SciTech Connect (OSTI)

    Sozeri, H.; Durmus, Z.; Baykal, A.

    2012-09-15

    Highlights: ? Monodispersed TREG stabilized Zn{sub x}Co{sub 1?x}Fe{sub 2}O{sub 4} NP's were prepared via hydrothermal method. ? Zn{sub x0.6}Co{sub 0.4}Fe{sub 2}O{sub 4} NP's has superparamagnetic behavior like absence of saturation at high fields. ? The lattice parameter (a{sub o}) increases linearly with the addition of Zn and follows Vegard's law. -- Abstract: Zn substituted cobalt ferrite nanoparticles having formula of Zn{sub x}Co{sub 1?x}Fe{sub 2}O{sub 4} (x = 0.01.0) were prepared by hydrothermal technique. In this process, triethylene glycol was used as a solvent and surfactant, anhydrous sodium hydroxide was used as an alkalinity additive. Investigation of the structural, morphological and thermal properties were carried out using X-ray diffraction (XRD), infrared spectroscopy (FT-IR), transmission electron spectroscopy (TEM) and thermal analysis (TGA) respectively. The X-ray diffraction study reveals that the lattice constant of cobalt ferrite increases with the increase of Zn content. Magnetization measurements showed that as zinc concentration increases saturation magnetization initially stays constant and then decreases monotically. Samples having high zinc concentration (x ? 0.6) have superparamagnetic behavior like absence of saturation at high fields, low saturation magnetization values and immeasurable coercivity. These features were explained by surface spin disorder and canted spins.

  16. Liquefied Gaseous Fuels Safety and Environmental Control Assessment Program: second status report

    SciTech Connect (OSTI)

    Not Available

    1980-10-01

    The Assistant Secretary for Environment has responsibility for identifying, characterizing, and ameliorating the environmental, health, and safety issues and public concerns associated with commercial operation of specific energy systems. The need for developing a safety and environmental control assessment for liquefied gaseous fuels was identified by the Environmental and Safety Engineering Division as a result of discussions with various governmental, industry, and academic persons having expertise with respect to the particular materials involved: liquefied natural gas, liquefied petroleum gas, hydrogen, and anhydrous ammonia. This document is arranged in three volumes and reports on progress in the Liquefied Gaseous Fuels (LGF) Safety and Environmental Control Assessment Program made in Fiscal Year (FY)-1979 and early FY-1980. Volume 1 (Executive Summary) describes the background, purpose and organization of the LGF Program and contains summaries of the 25 reports presented in Volumes 2 and 3. Annotated bibliographies on Liquefied Natural Gas (LNG) Safety and Environmental Control Research and on Fire Safety and Hazards of Liquefied Petroleum Gas (LPG) are included in Volume 1.

  17. Enhancing Magnesite Formation at Low Temperature and High CO2 Pressure: The Impact of Seed Crystals and Minor Components

    SciTech Connect (OSTI)

    Felmy, Andrew R.; Qafoku, Odeta; Arey, Bruce W.; Kovarik, Libor; Liu, Jia; Perea, Daniel E.; Ilton, Eugene S.

    2015-02-24

    The formation of magnesite was followed in aqueous solution containing initially added Mg(OH)2 equilibrated with supercritical carbon dioxide (90 atm pressure, 50C) in the presence of introduced magnesite particles and minor components, Co(II). As expected, the introduction of magnesite particles accelerated the formation of magnesite from solution. However, the formation rate of magnesite was even greater when small concentrations of Co(II) were introduced, indicating that the increased rate of magnesite formation in the presence of Co(II) was not solely due to the addition of a growth promoting surface. Detailed analysis of the magnesite particles by scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive spectroscopy (EDS), and atom probe tomography (APT) revealed that the originally added Co(II) was concentrated in the center but also present throughout the growing magnesite particles. Addition of the Co(II) in different chemical forms (i.e. as solid phase CoCO3 or Co(OH)2) could alter the growth rate of magnesite depending upon the addition of bicarbonate to the starting solution. Geochemical modeling calculations indicate that this difference is related to the thermodynamic stability of these different phases in the initial solutions. More broadly, these results indicate that the presence of even small concentrations of foreign ions that form carbonate compounds with a similar structure as magnesite can be incorporated into the magnesite lattice, accelerating the formation of anhydrous carbonates in natural environments.

  18. Facile synthesis of lithium sulfide nanocrystals for use in advanced rechargeable batteries

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

    Li, Xuemin; Wolden, Colin A.; Ban, Chunmei; Yang, Yongan

    2015-12-03

    This work reports a new method of synthesizing anhydrous lithium sulfide (Li2S) nanocrystals and demonstrates their potential as cathode materials for advanced rechargeable batteries. Li2S is synthesized by reacting hydrogen sulfide (H2S) with lithium naphthalenide (Li-NAP), a thermodynamically spontaneous reaction that proceeds to completion rapidly at ambient temperature and pressure. The process completely removes H2S, a major industrial waste, while cogenerating 1,4-dihydronaphthalene, itself a value-added chemical that can be used as liquid fuel. The phase purity, morphology, and homogeneity of the resulting nanopowders were confirmed by X-ray diffraction and scanning electron microscopy. The synthesized Li2S nanoparticles (100 nm) were assembledmore » into cathodes, and their performance was compared to that of cathodes fabricated using commercial Li2S micropowders (1–5 μm). As a result, electrochemical analyses demonstrated that the synthesized Li2S were superior in terms of (dis)charge capacity, cycling stability, output voltage, and voltage efficiency.« less

  19. The nature of the active phase in the heteropolyacid catalyst H{sub 4}PVMo{sub 11}O{sub 40} {center_dot} 32H{sub 2}O used for the selective oxidation of isobutyric acid

    SciTech Connect (OSTI)

    Ilkenhans, T.; Herzog, B.; Braun, T.

    1995-05-01

    The structural changes of the title compound during heating and under conditions of catalytic conversion of isobutyric acid to methacrylic acid were followed in situ by powder X-ray diffraction under continuous control of its activity. The results were verified by a postmortem phase analysis of practical supported catalyst samples used in kinetic reactors. The activity of the catalyst is correlated with its dehydrated form. A new cubic phase of a water-free vanadyl salt of the heteropolyacid (HPA) was found to be connected to a maximum conversion. This phase is isostructural to the unsubstituted anhydrous alkali-3-HPA salts and is metastable at ambient conditions with respect to rehydration. The catalyst material as a whole is metastable at any temperature above the onset of conversion with respect to a partially reversible decomposition into MoO{sub 3} and amorphous other components. Restructuring into crystalline forms of HPA is possible from the deactivated material upon dissolution and recrystallization at 323 K. In Situ UV-VIS data and X-ray diffraction show the complete self-reorganization of the MoO{sub 3} phase and the amorphous V and P compounds into new Keggin anions indicating the possible living nature of the catalyst under reaction conditions which enable extended lifetimes beyond the stability limits found in the present in situ X-ray diffraction experiments. 32 refs., 16 figs., 3 tabs.

  20. PRODUCTION OF URANIUM HEXAFLUORIDE

    DOE Patents [OSTI]

    Fowler, R.D.

    1957-08-27

    A process for the production of uranium hexafluoride from the oxides of uranium is reported. In accordance with the method, the higher oxides of uranium may be reduced to uranium dioxide (UO/sub 2/), the latter converted into uranium tetrafluoride by reaction with hydrogen fluoride, and the UF/sub 4/ converted to UF/sub 6/ by reaction with a fluorinating agent, such as CoF/sub 3/. The UO/sub 3/ or U/sub 3/O/sub 8/ is placed in a reac tion chamber in a copper boat or tray enclosed in a copper oven, and heated to 500 to 650 deg C while hydrogen gas is passed through the oven. After nitrogen gas is used to sweep out the hydrogen and the water vapor formed, and while continuing to inaintain the temperature between 400 deg C and 600 deg C, anhydrous hydrogen fluoride is passed through. After completion of the conversion of UO/sub 2/ to UF/sub 4/ the temperature of the reaction chamber is lowered to about 400 deg C or less, the UF/sub 4/ is mixed with the requisite quantity of CoF/sub 3/, and after evacuating the chamber, the mixture is heated to 300 to 400 deg C, and the resulting UF/sub 6/ is led off and delivered to a condenser.

  1. Coal combustion products: trash or treasure?

    SciTech Connect (OSTI)

    Hansen, T.

    2006-07-15

    Coal combustion by-products can be a valuable resource to various industries. The American Coal Ash Association (ACAA) collects data on production and uses of coal combustion products (CCPs). 122.5 million tons of CCPs were produced in 2004. The article discusses the results of the ACCA's 2004 survey. Fly ash is predominantly used as a substitute for Portland cement; bottom ash for structural fill, embankments and paved road cases. Synthetic gypsum from the FGD process is commonly used in wallboard. Plant owners are only likely to have a buyer for a portion of their CCPs. Although sale of hot water (from Antelope Valley Station) from condensers for use in a fish farm to raise tilapia proved unviable, the Great Plains Synfuels Plant which manufactures natural gas from lignite produces a wide range of products including anhydrous ammonia, phenol, krypton, carbon dioxide (for enhanced oil recovery), tar oils and liquid nitrogen. ACCA's goal is to educate people about CCPs and how to make them into useful products, and market them, in order to reduce waste disposal and enhance revenue. The article lists members of the ACCA. 2 photos., 1 tab.

  2. Process for removing thorium and recovering vanadium from titanium chlorinator waste

    DOE Patents [OSTI]

    Olsen, Richard S.; Banks, John T.

    1996-01-01

    A process for removal of thorium from titanium chlorinator waste comprising: (a) leaching an anhydrous titanium chlorinator waste in water or dilute hydrochloric acid solution and filtering to separate insoluble minerals and coke fractions from soluble metal chlorides; (b) beneficiating the insoluble fractions from step (a) on shaking tables to recover recyclable or otherwise useful TiO.sub.2 minerals and coke; and (c) treating filtrate from step (a) with reagents to precipitate and remove thorium by filtration along with acid metals of Ti, Zr, Nb, and Ta by the addition of the filtrate (a), a base and a precipitant to a boiling slurry of reaction products (d); treating filtrate from step (c) with reagents to precipitate and recover an iron vanadate product by the addition of the filtrate (c), a base and an oxidizing agent to a boiling slurry of reaction products; and (e) treating filtrate from step (d) to remove any remaining cations except Na by addition of Na.sub.2 CO.sub.3 and boiling.

  3. Breckinridge Project, initial effort. Report VII, Volume I. Introduction and background. [Storage losses of 28 products and by-products

    SciTech Connect (OSTI)

    none,

    1982-01-01

    The proposed plant site consists of 1594 acres along the Ohio River in Breckinridge County, Kentucky. An option to purchase the site has been secured on behalf of the Breckinridge Project by the Commonwealth of Kentucky Department of Energy. Figure 1 is an area map locating the site with respect to area cities and towns. The nearest communities to the site are the hamlet of Stephensport, Kentucky, about 3-1/2 miles northeast and Cloverport, Kentucky, which is 6 miles to the southwest. The nearest major cities are Owensboro, Kentucky, 45 road miles to the west and Louisville, Kentucky, 65 miles to the northeast. The Breckinridge facility will convert about 23,000 TPD of run-of-mine (ROM) coal into a nominal 50,000 BPD of hydrocarbon liquids including a significant quantity of transportation fuels. Major products refined for marketing include pipeline gas, propane, butane, 105 RONC gasoline reformate, middle distillate and heavy distillate. By-products include sulfur, anhydrous ammonia, and commercial-grade phenol. Care is being taken to minimize the impact of the facility operations on the environment. Water and wastewater treatment systems have been designed to achieve zero discharge. Waste solids will be disposed of in a carefully designed and well-monitored landfill operation. Also, special design features have been included to minimize air emissions.

  4. Multilayer heterostructures and their manufacture

    DOE Patents [OSTI]

    Hammond, Scott R; Reese, Matthew; Rupert, Benjamin; Miedaner, Alexander; Curtis, Clavin; Olson, Dana; Ginley, David S

    2015-11-04

    A method of synthesizing multilayer heterostructures including an inorganic oxide layer residing on a solid substrate is described. Exemplary embodiments include producing an inorganic oxide layer on a solid substrate by a liquid coating process under relatively mild conditions. The relatively mild conditions include temperatures below 225.degree. C. and pressures above 9.4 mb. In an exemplary embodiment, a solution of diethyl aluminum ethoxide in anhydrous diglyme is applied to a flexible solid substrate by slot-die coating at ambient atmospheric pressure, and the diglyme removed by evaporation. An AlO.sub.x layer is formed by subjecting material remaining on the solid substrate to a relatively mild oven temperature of approximately 150.degree. C. The resulting AlO.sub.x layer exhibits relatively high light transmittance and relatively low vapor transmission rates for water. An exemplary embodiment of a flexible solid substrate is polyethylene napthalate (PEN). The PEN is not substantially adversely affected by exposure to 150.degree. C

  5. Preparation and application of zirconium sulfate supported on SAPO-34 molecular sieve as solid acid catalyst for esterification

    SciTech Connect (OSTI)

    Xu, Dongyan Ma, Hong; Cheng, Fei

    2014-05-01

    Graphical abstract: - Highlights: SAPO-34 supported zirconium sulfate solid acid catalyst was prepared. Esterification of acetic acid with ethanol can be catalyzed by ZS/SAPO-34. The hydration of ZS is vital to the acidic property and catalytic performance. The ZS/SAPO-34 catalyst treated at 200 C shows good reusability. - Abstract: Zirconium sulfate (ZS) was supported on SAPO-34 molecular sieve by using an incipient wetness impregnation method with zirconium sulfate as the precursor. The as-prepared catalysts were used as solid acid catalyst for esterification reaction of acetic acid with ethanol. The influence of calcination temperature on the acidic property, catalytic activity, and reusability of ZS/SAPO-34 catalysts were mainly investigated. FT-IR, SEM, EDS and TG analysis have been carried out to demonstrate the characteristics of ZS/SAPO-34 catalysts. It was found that the 30 wt%ZS/SAPO-34 catalysts display the property of superacid irrespective of calcination temperature. The ZS/SAPO-34 catalyst treated at 200 C can enhance the interaction between the supported ZS and SAPO-34 and keep the catalyst remaining substantially active after several reaction cycles. However, further increasing calcination temperature will cause the transfer of ZS from hydrate to anhydrous phase, and thus the decrease of activity.

  6. Innovative technologies on fuel assemblies cleaning for sodium fast reactors: First considerations on cleaning process

    SciTech Connect (OSTI)

    Simon, N.; Lorcet, H.; Beauchamp, F.; Guigues, E.; Lovera, P.; Fleche, J. L.; Lacroix, M.; Carra, O.; Prele, G.

    2012-07-01

    Within the framework of Sodium Fast Reactor development, innovative fuel assembly cleaning operations are investigated to meet the GEN IV goals of safety and of process development. One of the challenges is to mitigate the Sodium Water Reaction currently used in these processes. The potential applications of aqueous solutions of mineral salts (including the possibility of using redox chemical reactions) to mitigate the Sodium Water Reaction are considered in a first part and a new experimental bench, dedicated to this study, is described. Anhydrous alternative options based on Na/CO{sub 2} interaction are also presented. Then, in a second part, a functional study conducted on the cleaning pit is proposed. Based on experimental feedback, some calculations are carried out to estimate the sodium inventory on the fuel elements, and physical methods like hot inert gas sweeping to reduce this inventory are also presented. Finally, the implementation of these innovative solutions in cleaning pits is studied in regard to the expected performances. (authors)

  7. Chemistry control and corrosion mitigation of heat transfer salts for the fluoride salt reactor (FHR)

    SciTech Connect (OSTI)

    Kelleher, B. C.; Sellers, S. R.; Anderson, M. H.; Sridharan, K.; Scheele, R. D.

    2012-07-01

    The Molten Salt Reactor Experiment (MSRE) was a prototype nuclear reactor which operated from 1965 to 1969 at Oak Ridge National Laboratory. The MSRE used liquid fluoride salts as a heat transfer fluid and solvent for fluoride based {sup 235}U and {sup 233}U fuel. Extensive research was performed in order to optimize the removal of oxide and metal impurities from the reactor's heat transfer salt, 2LiF-BeF{sub 2} (FLiBe). This was done by sparging a mixture of anhydrous hydrofluoric acid and hydrogen gas through the FLiBe at elevated temperatures. The hydrofluoric acid reacted with oxides and hydroxides, fluorinating them while simultaneously releasing water vapor. Metal impurities such as iron and chromium were reduced by hydrogen gas and filtered out of the salt. By removing these impurities, the corrosion of reactor components was minimized. The Univ. of Wisconsin - Madison is currently researching a new chemical purification process for fluoride salts that make use of a less dangerous cleaning gas, nitrogen trifluoride. Nitrogen trifluoride has been predicted as a superior fluorinating agent for fluoride salts. These purified salts will subsequently be used for static and loop corrosion tests on a variety of reactor materials to ensure materials compatibility for the new FHR designs. Demonstration of chemistry control methodologies along with potential reduction in corrosion is essential for the use of a fluoride salts in a next generator nuclear reactor system. (authors)

  8. Rising from the ashes: Coal ash in recycling and construction

    SciTech Connect (OSTI)

    Naquin, D.

    1998-02-01

    Beneficial Ash Management (BAM, Clearfield, Pa.) has won an environmental award for its use of ash and other waste to fight acid mine drainage. The company`s workers take various waste materials, mainly fly ash from coal-burning plants, to make a cement-like material or grouting, says Ernest Roselli, BAM president. The grouting covers the soil, which helps prevent water from contacting materials. This, in turn, helps control chemical reactions, reducing or eliminating formation of acid mine drainage. The company is restoring the 1,400-acre Bark Camp coal mine site near Penfield in Clearfield County, Pa. Under a no-cost contract with the state of Pennsylvania, BAM is using boiler slag, causticizing byproducts (lime) and nonreclaimable clarifier sludge from International Paper Co. (Erie, Pa.). The mine reclamation techniques developed and monitored at the site include using man-made wetlands to treat acid mine drainage and testing anhydrous ammonia as a similar treatment agent. BAM researches and tests fly ash mixed with lime-based activators as fill material for land reclamation, and develops and uses artificial soil material from paper mill and tannery biosolids.

  9. Synthesis and CO{sub 2} adsorption study of modified MOF-5 with multi-wall carbon nanotubes and expandable graphite

    SciTech Connect (OSTI)

    Ullah, Sami E-mail: azmibustam@petronas.com.my E-mail: lkhlfh@gmail.com E-mail: nadiariazz@gmail.com; Bustam, M. A. E-mail: azmibustam@petronas.com.my E-mail: lkhlfh@gmail.com E-mail: nadiariazz@gmail.com; Shariff, A. M. E-mail: azmibustam@petronas.com.my E-mail: lkhlfh@gmail.com E-mail: nadiariazz@gmail.com; Elkhalifah, Ali E. I. E-mail: azmibustam@petronas.com.my E-mail: lkhlfh@gmail.com E-mail: nadiariazz@gmail.com; Murshid, G. E-mail: azmibustam@petronas.com.my E-mail: lkhlfh@gmail.com E-mail: nadiariazz@gmail.com; Riaz, Nadia E-mail: azmibustam@petronas.com.my E-mail: lkhlfh@gmail.com E-mail: nadiariazz@gmail.com

    2014-10-24

    MOF-5 was synthesized by solvothermal method and its reactivation under anhydrous conditions. This research is conducted to investigate the effect of MOF-5 and MOF-5 modified with multi-wall carbon nanotubes (MWCNTs) and expandable graphite (EG) on the performance of CO{sub 2} adsorption. The synthesized MOFs were characterized using Field emission scanning electron microscopy (FESEM) for surface morphology, Thermogravimetric analysis (TGA) for thermal stability, X-ray diffraction (XRD) for crystals plane, Brunauer-Emmet-Teller (BET) for surface area and CO{sub 2} adsorption. The result had showed that the modified MOF-5 enhanced the CO{sub 2} adsorption compared to the pure MOF-5. The increment in the CO{sub 2} uptake capacities of MOF materials was attributed to the decrease in the pore size and enhancement of micropore volume of MOF-5 by multi-walled carbon nanotube and EG incorporation. The BET surface area of the synthesized MOF-5@MWCNTs is more than MOF-5. The CO{sub 2} sorption capacities of MOF-5 and MOF-5@MWCNTs were observed to increase from 0.00008 to 0.00048 mol g-1 at 298 K and 1 bar. The modified MOF-5@MWCNTs resulted in the highest CO{sub 2} adsorption followed by the modified MOF-5@ EG and lastly, MOF-5.

  10. Reduction experiment of FeO-bearing amorphous silicate: application to origin of metallic iron in GEMS

    SciTech Connect (OSTI)

    Matsuno, Junya; Tsuchiyama, Akira; Miyake, Akira [Department of Geology and Mineralogy, Graduate School of Science, Kyoto University, Kitashirakawa-Oiwake, Sakyo-ku, Kyoto 606-8502 (Japan); Noguchi, Ryo [Department of Earth and Space Science, Graduate School of Science, Osaka University, 1-1 Machikaneyama, Toyonaka, Osaka 560-0043 (Japan); Ichikawa, Satoshi, E-mail: jmatsuno@kueps.kyoto-u.ac.jp [Institute for Nano-science Design, Osaka University, 1-3 Machikaneyama, Toyonaka, Osaka 560-8531 (Japan)

    2014-09-10

    Glass with embedded metal and sulfides (GEMS) are amorphous silicates included in anhydrous interplanetary dust particles (IDPs) and can provide information about material evolution in our early solar system. Several formation processes for GEMS have been proposed so far, but these theories are still being debated. To investigate a possible GEMS origin by reduction of interstellar silicates, we synthesized amorphous silicates with a mean GEMS composition and performed heating experiments in a reducing atmosphere. FeO-bearing amorphous silicates were heated at 923 K and 973 K for 3 hr, and at 1023 K for 1-48 hr at ambient pressure in a reducing atmosphere. Fe grains formed at the interface between the silicate and the reducing gas through a reduction. In contrast, TEM observations of natural GEMS show that metallic grains are uniformly embedded in amorphous silicates. Therefore, the present study suggests that metallic inclusions in GEMS could not form as reduction products and that other formation process such as condensation or irradiation are more likely.

  11. Method of extracting iodine from liquid mixtures of iodine, water and hydrogen iodide

    DOE Patents [OSTI]

    Mysels, Karol J.

    1979-01-01

    The components of a liquid mixture consisting essentially of HI, water and at least about 50 w/o iodine are separated in a countercurrent extraction zone by treating with phosphoric acid containing at least about 90 w/o H.sub.3 PO.sub.4. The bottom stream from the extraction zone is substantially completely molten iodine, and the overhead stream contains water, HI, H.sub.3 PO.sub.4 and a small fraction of the amount of original iodine. When the water and HI are present in near-azeotropic proportions, there is particular advantage in feeding the overhead stream to an extractive distillation zone wherein it is treated with additional concentrated phosphoric acid to create an anhydrous HI vapor stream and bottoms which contain at least about 85 w/o H.sub.3 PO.sub.4. Concentration of these bottoms provides phosphoric acid infeed for both the countercurrent extraction zone and for the extractive distillation zone.

  12. Method for directly recovering fluorine from gas streams

    DOE Patents [OSTI]

    Orlett, Michael J.; Saraceno, Anthony J.

    1981-01-01

    This invention is a process for the direct recovery of gaseous fluorine from waste-gas streams or the like. The process comprises passing the gas stream through a bed of anhydrous K.sub.3 NiF.sub.6 pellets to fluorinate the same to K.sub.3 NiF.sub.7 and subsequently desorbing the fluorine by heating the K.sub.3 NiF.sub.7 pellets to a temperature re-converting them to K.sub.3 NiF.sub.6. The efficiency of the fluorine-absorption step is maximized by operating in a selected and conveniently low temperature. The desorbed fluorine is highly pure and is at a pressure of several atmospheres. Preferably, the K.sub.3 NiF.sub.6 pellets are prepared by a method including the steps of forming agglomerates of hydrated K.sub.3 NiF.sub.5, sintering the agglomerates to form K.sub.3 NiF.sub.5 pellets of enhanced reactivity with respect to fluorine, and fluorinating the sintered pellets to K.sub.3 NiF.sub.6.

  13. ECB deacylase mutants

    DOE Patents [OSTI]

    Arnold, Frances H. (Pasadena, CA); Shao, Zhixin (Penzberg, DE); Zhao, Huimin (San Diego, CA); Giver, Lorraine J. (Sunnyvale, CA)

    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.

  14. Recombination of polynucleotide sequences using random or defined primers

    DOE Patents [OSTI]

    Arnold, Frances H. (Pasadena, CA); Shao, Zhixin (Pasadena, CA); Affholter, Joseph A. (Midland, MI); Zhao, Huimin H (San Diego, CA); Giver, Lorraine J. (Sunnyvale, CA)

    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.

  15. 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.

  16. 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.

  17. 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.

  18. 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.

  19. 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.

  20. 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.

  1. Tower reactors for bioconversion of lignocellulosic material

    DOE Patents [OSTI]

    Nguyen, Quang A. (16458 W. 1st Ave., Golden, CO 80401)

    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.

  2. Tower reactors for bioconversion of lignocellulosic material

    DOE Patents [OSTI]

    Nguyen, Quang A. (16458 W. 1st Ave., Golden, CO 80401)

    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.

  3. 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.

  4. Recombination of polynucleotide sequences using random or defined primers

    DOE Patents [OSTI]

    Arnold, Frances H. (Pasadena, CA); Shao, Zhixin (Pasadena, CA); Affholter, Joseph A. (Midland, MI); Zhao, Huimin (Pasadena, CA); Giver, Lorraine J. (Pasadena, CA)

    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.

  5. 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)

  6. 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.

  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. In situ dehydration behavior of zeolite-like pentagonite: A single-crystal X-ray study

    SciTech Connect (OSTI)

    Danisi, Rosa Micaela; Armbruster, Thomas; Lazic, Biljana

    2013-01-15

    The structural modifications upon heating of pentagonite, Ca(VO)(Si{sub 4}O{sub 10}){center_dot}4H{sub 2}O (space group Ccm2{sub 1}, a=10.3708(2), b=14.0643(2), c=8.97810(10) A, V=1309.53(3) A{sup 3}) were investigated by in situ temperature dependent single-crystal X-ray structure refinements. Diffraction data of a sample from Poona district (India) have been measured in steps of 25 up to 250 Degree-Sign C and in steps of 50 Degree-Sign C between 250 and 400 Degree-Sign C. Pentagonite has a porous framework structure made up by layers of silicate tetrahedra connected by V{sup 4+}O{sub 5} square pyramids. Ca and H{sub 2}O molecules are extraframework occupants. Room temperature diffraction data allowed refinement of H positions. The hydrogen-bond system links the extraframework occupants to the silicate layers and also interconnects the H{sub 2}O molecules located inside the channels. Ca is seven-fold coordinated forming four bonds to O of the tetrahedral framework and three bonds to extraframework H{sub 2}O. The H{sub 2}O molecule at O9 showing a high displacement parameter is not bonded to Ca. The dehydration in pentagonite proceeds in three steps. At 100 Degree-Sign C the H{sub 2}O molecule at O8 was released while O9 moved towards Ca. As a consequence the displacement parameter of H{sub 2}O at O9 halved compared to that at room temperature. The unit-cell volume decreased to 1287.33(3) A{sup 3} leading to a formula with 3H{sub 2}O per formula unit (pfu). Ca remained seven-fold coordinated. At 175 Degree-Sign C Ca(VO)(Si{sub 4}O{sub 10}){center_dot}3H{sub 2}O transformed into a new phase with 1H{sub 2}O molecule pfu characterized by doubling of the c axis and the monoclinic space group Pn. Severe bending of specific T--O--T angles led to contraction of the porous three-dimensional framework. In addition, H{sub 2}O at O9 was expelled while H{sub 2}O at O7 approached a position in the center of the channel. The normalized volume decreased to 1069.44(9) A{sup 3}. The Ca coordination reduced from seven- to six-fold. At 225 Degree-Sign C a new anhydrous phase with space group Pna2{sub 1} but without doubling of c had formed. Release of H{sub 2}O at O7 caused additional contraction of T--O--T angles and volume reduction (V=1036.31(9) A{sup 3}). Ca adopted five-fold coordination. During heating excursion up to 400 Degree-Sign C this anhydrous phase remained preserved. Between room temperature and 225 Degree-Sign C the unit-cell volume decreased by 21% due to dehydration. The dehydration steps compare well with the thermo-gravimetric data reported in the literature. - Graphical abstract: Pentagonite structure at room temperature and at 225 Degree-Sign C. Highlights: Black-Right-Pointing-Pointer We investigate the relationship between the removal of H{sub 2}O molecules and structural modifications of the framework of pentagonite. Black-Right-Pointing-Pointer Pentagonite undergoes phase transitions upon heating. Black-Right-Pointing-Pointer We analyze similarities and differences between pentagonite and related structures.

  9. Screening Hofmann Compounds as CO{sub 2} Sorbents: Nontraditional Synthetic Route to Over 40 Different Pore-Functionalized and Flexible Pillared Cyanonickelates

    SciTech Connect (OSTI)

    Culp, Jeffrey T.; Madden, Catherine; Kauffman, Kristi; Shi, Fan; Matranga, Christopher

    2013-04-15

    A simple reaction scheme based on the heterogeneous intercalation of pillaring ligands (HIPLs) provides a convenient method for systematically tuning pore size, pore functionality, and network flexibility in an extended series of pillared cyanonickelates (PICNICs), commonly referred to as Hofmann compounds. The versatility of the approach is demonstrated through the preparation of over 40 different PICNICs containing pillar ligands ranging from ?4 to ?15 in length and modified with a wide range of functional groups, including fluoro, aldehyde, alkylamine, alkyl, aryl, trifluoromethyl, ester, nitro, ether, and nonmetalated 4,4?-bipyrimidine. The HIPL method involves reaction of a suspension of preformed polymeric sheets of powdered anhydrous nickel cyanide with an appropriate pillar ligand in refluxing organic solvent, resulting in the conversion of the planar [Ni{sub 2}(CN){sub 4}]{sub n} networks into polycrystalline three-dimensional porous frameworks containing the organic pillar ligand. Preliminary investigations indicate that the HIPL reaction is also amenable to forming Co(L)Ni(CN){sub 4}, Fe(L)Ni(CN){sub 4}, and Fe(L)Pd(CN){sub 4} networks. The materials show variable adsorption behavior for CO{sub 2} depending on the pillar length and pillar functionalization. Several compounds show structurally flexible behavior during the adsorption and desorption of CO{sub 2}. Interestingly, the newly discovered flexible compounds include two flexible Fe(L)Ni(CN){sub 4} derivatives that are structurally related to previously reported porous spin-crossover compounds. The preparations of 20 pillar ligands based on ring-functionalized 4,4?-dipyridyls, 1,4-bis(4- pyridyl)benzenes, and N-(4-pyridyl)isonicotinamides are also described.

  10. Ionic Liquids: Breakthrough Absorption Technology for Post-Combustion CO{sub 2} Capture

    SciTech Connect (OSTI)

    Maginn, Edward

    2012-09-30

    This is the final report for DE-FC26-07NT43091 ??Ionic Liquids: Breakthrough Absorption Technology for Post-Combustion CO{sub 2} Capture?. A detailed summary is provided of the ionic liquid (IL) discovery process, synthesis and testing results, process / systems modeling, lab-scale operational testing, corrosion testing and commercialization possibilities. The work resulted in the discovery of a new class of ionic liquids (ILs) that efficiently react with CO{sub 2} in a 1:1 stoichiometry with no water present and no increase in viscosity. The enthalpy of reaction was tuned to optimize process economics. The IL was found to have excellent corrosion behavior with and without CO{sub 2} present. In lab-scale tests, the IL was able to effectively remove CO{sub 2} from a simulated flue gas stream, although mass transfer was slower than with aqueous monoethanolamine (MEA) due to higher viscosities. The non-volatile nature of the solvent and its high thermal stability, however, make it an intriguing option. An independent systems analysis indicates that the economics of using the best IL discovered to date (NDIL0157), are at least comparable to ?? and potentially slightly better than -?? the Fluor Econamine FG PlusTM process (DOE Case 12). Further work should be directed at improving mass transfer / lowering viscosity and developing commercial synthesis routes to make these ILs at scale in an inexpensive manner. Demonstration of the process at larger scales is also warranted, as is the exploration of other process configurations that leverage the anhydrous nature of the solvent and its extremely low volatility.

  11. Synthesis metal nanoparticle

    DOE Patents [OSTI]

    Bunge, Scott D.; Boyle, Timothy J.

    2005-08-16

    A method for providing an anhydrous route for the synthesis of amine capped coinage-metal (copper, silver, and gold) nanoparticles (NPs) using the coinage-metal mesityl (mesityl=C.sub.6 H.sub.2 (CH.sub.3).sub.3 -2,4,6) derivatives. In this method, a solution of (Cu(C.sub.6 H.sub.2 (CH.sub.3).sub.3).sub.5, (Ag(C.sub.6 H.sub.2 (CH.sub.3).sub.3).sub.4, or (Au(C.sub.6 H.sub.2 (CH.sub.3).sub.3).sub.5 is dissolved in a coordinating solvent, such as a primary, secondary, or tertiary amine; primary, secondary, or tertiary phosphine, or alkyl thiol, to produce a mesityl precursor solution. This solution is subsequently injected into an organic solvent that is heated to a temperature greater than approximately 100.degree. C. After washing with an organic solvent, such as an alcohol (including methanol, ethanol, propanol, and higher molecular-weight alcohols), oxide free coinage NP are prepared that could be extracted with a solvent, such as an aromatic solvent (including, for example, toluene, benzene, and pyridine) or an alkane (including, for example, pentane, hexane, and heptane). Characterization by UV-Vis spectroscopy and transmission electron microscopy showed that the NPs were approximately 9.2.+-.2.3 nm in size for Cu.degree., (no surface oxide present), approximately 8.5.+-.1.1 nm Ag.degree. spheres, and approximately 8-80 nm for Au.degree..

  12. Chemical properties of the heavier actinides and transactinides

    SciTech Connect (OSTI)

    Hulet, E.K.

    1981-01-01

    The chemical properties of each of the elements 99 (Es) through 105 are reviewed and their properties correlated with the electronic structure expected for 5f and 6d elements. A major feature of the heavier actinides, which differentiates them from the comparable lanthanides, is the increasing stability of the divalent oxidation state with increasing atomic number. The divalent oxidation state first becomes observable in the anhydrous halides of californium and increases in stability through the series to nobelium, where this valency becomes predominant in aqueous solution. In comparison with the analogous 4f electrons, the 5f electrons in the latter part of the series are more tightly bound. Thus, there is a lowering of the 5f energy levels with respect to the Fermi level as the atomic number increases. The metallic state of the heavier actinides has not been investigated except from the viewpoint of the relative volatility among members of the series. In aqueous solutions, ions of these elements behave as a normal trivalent actinides and lanthanides (except for nobelium). Their ionic radii decrease with increasing nuclear charge which is moderated because of increased screening of the outer 6p electrons by the 5f electrons. The actinide series of elements is completed with the element lawrencium (Lr) in which the electronic configuration is 5f/sup 14/7s/sup 2/7p. From Mendeleev's periodicity and Dirac-Fock calculations, the next group of elements is expected to be a d-transition series corresponding to the elements Hf through Hg. The chemical properties of elements 104 and 105 only have been studied and they indeed appear to show the properties expected of eka-Hf and eka-Ta. However, their nuclear lifetimes are so short and so few atoms can be produced that a rich variety of chemical information is probably unobtainable.

  13. Dynamics of Magnesite Formation at Low-Temperature and High pCO2 in Aqueous Solution

    SciTech Connect (OSTI)

    Qafoku, Odeta; Dixon, David A.; Rosso, Kevin M.; Schaef, Herbert T.; Bowden, Mark E.; Arey, Bruce W.; Felmy, Andrew R.

    2015-09-17

    Like many metal carbonate minerals, despite conditions of supersaturation, precipitation of magnesite from aqueous solution is kinetically hindered at low temperatures, for reasons that remain poorly understood. The present study examines precipitation products from reaction of Mg(OH)2 in aqueous solutions saturated with supercritical CO2 at high pressures (90 atm and 110 atm) and low temperatures (35 C and 50 C). Traditional bulk characterization (X-ray diffraction) of the initial solid formed indicated the presence of hydrated magnesium carbonates (hydromagnesite and nesquehonite), thermodynamically metastable phases that were found to slowly react during ageing to the more stable anhydrous form, magnesite, at temperatures as low as 35 C (135-140 days) and at a faster rate at 50 C (56 days). Undetected by bulk measurements, detailed examination of the precipitates by scanning electron microscopy (SEM) showed that magnesite is present as a minor component at relatively early reaction times (7 days) at 50 C. In addition to magnesite dominating the solid phases over time, we find that mangesite nucleation and growth occurs more quickly with increasing partial pressure of CO2, and in electrolyte solutions with high bicarbonate content. Furthermore, formation of magnesite was found to be enhanced in sulfate-rich solutions, compared to chloride-rich solutions. We speculate that much of this behavior is possibly due to sulfate serving as sink of protons generated during carbonation reactions. These results support the importance of integrating magnesite as an equilibrium phase in reactive transport calculations of the effects of carbon dioxide sequestration on subsurface formations at long time scales.

  14. A combined experimental and computational study of the molecular interactions between anionic ibuprofen and water

    SciTech Connect (OSTI)

    Zapata-Escobar, Andy; Manrique-Moreno, Marcela; Guerra, Doris; Hadad, C. Z.; Restrepo, Albeiro

    2014-05-14

    In this work, we report a detailed study of the microsolvation of anionic ibuprofen, Ibu{sup ?}. Stochastic explorations of the configurational spaces for the interactions of Ibu{sup ?} with up to three water molecules at the DFT level lead to very rich and complex potential energy surfaces. Our results suggest that instead of only one preponderant structure, a collection of isomers with very similar energies would have significant contributions to the properties of the solvated drug. One of these properties is the shift on the vibrational frequencies of the asymmetric stretching band of the carboxylate group in hydrated Ibu{sup ?} with respect to the anhydrous drug, whose experimental values are nicely reproduced using the weighted contribution of the structures. We found at least three types of stabilizing interactions, including conventional CO {sub 2}{sup ?}?H{sub 2}O, H{sub 2}O?H{sub 2}O charge assisted hydrogen bonds (HBs), and less common H{sub 2}O?HC and H{sub 2}O?? interactions. Biological water molecules, those in direct contact with Ibu{sup ?}, prefer to cluster around the carboxylate oxygen atoms via cyclic or bridged charge assisted hydrogen bonds. Many of those interactions are strongly affected by the formal carboxylate charge, resulting in enhanced HBs with increased strengths and degree of covalency. We found striking similarities between this case and the microsolvation of dymethylphosphate, which lead us to hypothesize that since microsolvation of phosphatidylcholine depends mainly on the formal charge of its ionic PO {sub 2}{sup ?} group in the polar head, then microsolvation of anionic ibuprofen and interactions of water molecules with eukaryotic cell membranes are governed by the same types of physical interactions.

  15. Growth and properties of Lithium Salicylate single crystals

    SciTech Connect (OSTI)

    Zaitseva, N; Newby, J; Hull, G; Saw, C; Carman, L; Cherepy, N; Payne, S

    2009-02-13

    An attractive feature of {sup 6}Li containing fluorescence materials that determines their potential application in radiation detection is the capture reaction with slow ({approx}< 100 keV) neutrons: {sup 6}Li + n = {sup 4}He + {sup 3}H + 4.8MeV. The use of {sup 6}Li-salicylate (LiSal, LiC{sub 6}H{sub 5}O{sub 3}) for thermal neutron detection was previously studied in liquid and polycrystalline scintillators. The studies showed that both liquid and polycrystalline LiSal scintillators could be utilized in pulse shape discrimination (PSD) techniques that enable separation of neutrons from the background gamma radiation. However, it was found that the efficiency of neutron detection using LiSal in liquid solutions was severely limited by its low solubility in commonly used organic solvents like, for example, toluene or xylene. Better results were obtained with neutron detectors containing the compound in its crystalline form, such as pressed pellets, or microscopic-scale (7-14 micron) crystals dispersed in various media. The expectation drown from these studies was that further improvement of pulse height, PSD, and efficiency characteristics could be reached with larger and more transparent LiSal crystals, growth of which has not been reported so far. In this paper, we present the first results on growth and characterization of relatively large, a cm-scale size, single crystals of LiSal with good optical quality. The crystals were grown both from aqueous and anhydrous (methanol) media, mainly for neutron detection studies. However, the results on growth and structural characterization may be interesting for other fields where LiSal, together with other alkali metal salicylates, is used for biological, medical, and chemical (as catalyst) applications.

  16. The production of fuels and chemicals from food processing wastes using a novel fermenter separator. Annual progress report, January 1991--December 1991

    SciTech Connect (OSTI)

    Dale, M.C.; Venkatesh, K.V.; Choi, Hojoon; Moelhman, M.; Saliceti, L.; Okos, M.R.; Wankat, P.C.

    1991-12-01

    During 1991, considerable progress was made on the waste utilization project. Two small Wisconsin companies have expressed an interest in promoting and developing the ICRS technology. Pilot plant sites at (1) Hopkinton, IA, for a sweet whey plant, and Beaver Dam WI, for an acid whey site have been under development siting ICRS operations. The Hopkinton, IA site is owned and operated by Permeate Refining Inc., who have built a batch ethanol plant across the street from Swiss Valley Farms cheddar cheese operations. Permeate from Swiss Valley is piped across to PRI. PRI has signed a contract to site a 300--500,000 gallon/yr to ICRS pilot plant. They feel that the lower labor, lower energy, continuous process offered by the ICRS will substantially improve their profitability. Catalytics, Inc, is involved with converting whey from a Kraft cream cheese operation to ethanol and yeast. A complete project including whey concentration, sterilization, and yeast growth has been designed for this site. Process design improvements with the ICRS focussed on ethanol recovery techniques during this year`s project. A solvent absorption/extractive distillation (SAED) process has been developed which offers the capability of obtaining an anhydrous ethanol product from vapors off 3 to 9% ethanol solutions using very little energy for distillation. Work on products from waste streams was also performed. a. Diacetyl as a high value flavor compound was very successfully produced in a Stirred Tank Reactor w/Separation. b. Yeast production from secondary carbohydrates in the whey, lactic acid, and glycerol was studied. c. Lactic acid production from cellulose and lactose studies continued. d. Production of anti-fungal reagents by immobilized plant cells; Gossypol has antifungal properties and is produced by G. arboretum.

  17. The production of fuels and chemicals from food processing wastes using a novel fermenter separator

    SciTech Connect (OSTI)

    Dale, M.C.; Venkatesh, K.V.; Choi, Hojoon; Moelhman, M.; Saliceti, L.; Okos, M.R.; Wankat, P.C.

    1991-12-01

    During 1991, considerable progress was made on the waste utilization project. Two small Wisconsin companies have expressed an interest in promoting and developing the ICRS technology. Pilot plant sites at (1) Hopkinton, IA, for a sweet whey plant, and Beaver Dam WI, for an acid whey site have been under development siting ICRS operations. The Hopkinton, IA site is owned and operated by Permeate Refining Inc., who have built a batch ethanol plant across the street from Swiss Valley Farms cheddar cheese operations. Permeate from Swiss Valley is piped across to PRI. PRI has signed a contract to site a 300--500,000 gallon/yr to ICRS pilot plant. They feel that the lower labor, lower energy, continuous process offered by the ICRS will substantially improve their profitability. Catalytics, Inc, is involved with converting whey from a Kraft cream cheese operation to ethanol and yeast. A complete project including whey concentration, sterilization, and yeast growth has been designed for this site. Process design improvements with the ICRS focussed on ethanol recovery techniques during this year's project. A solvent absorption/extractive distillation (SAED) process has been developed which offers the capability of obtaining an anhydrous ethanol product from vapors off 3 to 9% ethanol solutions using very little energy for distillation. Work on products from waste streams was also performed. a. Diacetyl as a high value flavor compound was very successfully produced in a Stirred Tank Reactor w/Separation. b. Yeast production from secondary carbohydrates in the whey, lactic acid, and glycerol was studied. c. Lactic acid production from cellulose and lactose studies continued. d. Production of anti-fungal reagents by immobilized plant cells; Gossypol has antifungal properties and is produced by G. arboretum.

  18. 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.

  19. 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.

  20. 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.

  1. 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.

  2. 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.

  3. 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.

  4. 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.

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

    DOE Patents [OSTI]

    Shaw, Elliott N. (Shoreham, NY); Kettner, Charles A. (Yaphank, NY)

    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.

  6. 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.

  7. 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.

  8. 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.

  9. 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.

  10. 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.

  11. 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.

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

    DOE Patents [OSTI]

    Sen, Ayusman (State College, PA); Kim, Jang Sub (State College, PA); Pawlow, James H. (Gainesville, FL); Murtuza, Shahid (State College, PA); Kacker, Smita (Annandale, NJ); Wojcinski, III, Louis M. (State College, PA)

    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.

  13. 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.

  14. 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.

  15. 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.

  16. 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.

  17. 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.

  18. 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.

  19. 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.

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

    DOE Patents [OSTI]

    Davenhall, Leisa B. (Santa Fe, NM); Rubin, James B. (Los Alamos, NM)

    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.

  1. 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.

  2. 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

  3. 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.

  4. 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.

  5. 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.

  6. 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.

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

    DOE Patents [OSTI]

    Chang, Shih-Ger (El Cerrito, CA)

    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.

  8. 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.

  9. 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.

  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. 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.

  12. 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.

  13. 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

  14. 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.

  15. 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.

  16. 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.

  17. 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.

  18. 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.

  19. 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

  20. 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.

  1. 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.

  2. 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 samplesAvicel, bleached softwood, and bacterial celluloseto 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 I? component of the bacterial cellulose is preferentially hydrolyzed by the enzyme than the cellulose I? component.

  3. 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.

  4. 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.

  5. 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.

  6. 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.

  7. 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.

  8. 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.

  9. 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.

  10. 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.

  11. 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

  12. 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.

  13. 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.

  14. 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%.

  15. 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

  16. 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.

  17. 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.

  18. Method for introducing unidirectional nested deletions

    DOE Patents [OSTI]

    Dunn, John J. (Bellport, NY); Quesada, Mark A. (Middle Island, NY); Randesi, Matthew (Upton, NY)

    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.

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

    DOE Patents [OSTI]

    Dunn, John J. (Bellport, NY); Quesada, Mark A. (Middle Island, NY); Randesi, Matthew (Upton, NY)

    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.

  20. 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.

  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. 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

  4. 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.

  5. 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.

  6. 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.

  7. 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.

  8. 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.

  9. 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}.

  10. Structure and dynamics of complexes of the uranyl ion with nonamethylimidodiphosphoramide (NIPA). 2. NMR studies of complexes (UO/sub 2/(NIPA)/sub 2/X)(CIO/sub 4/)/sub 2/ with X = H/sub 2/O, MeOH, EtOH, or Me/sub 2/CO

    SciTech Connect (OSTI)

    Rodehueser, L.; Rubini, P.R.; Bokolo, K.; Delpuech, J.J.

    1982-03-01

    The /sup 31/P and /sup 1/H spectra at -90/sup 0/C of the title uranyl complex ions (prepared as solutions of the solid perchlorates in inert anhydrous organic solvents (CH/sub 3/NO/sub 2/, CH/sub 2/Cl/sub 2/)) reveal a pentacoordinated arrangement of two symmetrically doubly bonded NIPA molecules and one solvent molecule about the uranyl group. In the case of (UO/sub 2/(NIPA)/sub 2/(EtOH))(ClO/sub 4/)/sub 2/, an intermolecular exchange between bound and free ethanol molecules is observed above -75/sup 0/C upon addition of ethanol to a solution of the complex. The observed rate law, k/sub inter/ = kK(EtOH)/(1 + K(EtOH) is accounted for by the existence of an outer-sphere complex (UO/sub 2//sup 2 +/(NIPA)/sub 2/(EtOH))EtOH in fast equilibrium (K) with the initial complex and free ethanol. The rate-determining step (k) consists of an outer-sphere to inner-sphere interchange of ethanol molecules. The thermodynamic and kinetic parameters are K(25/sup 0/C) = 15.8 dm/sup 3/ mol/sup -1/, k(25/sup 0/C) = 1.0 x 10/sup 4/s/sup -1/, ..delta..H and ..delta..H/sub inter//sup + +/ = -4.8 and 7.6 kcal mol/sup -1/, and ..delta..S and ..delta..S/sub inter//sup + +/ = 10.7 and -14.7 eu. A second exchange takes place at higher temperatures (above -30/sup 0/C) yielding full dynamic equivalence of the phosphorus nuclei of the coordinated NIPA molecules. The observed rate law k/sub intra/ = k/sub ex/(1 + K(EtOH)) reveals that the internal rearrangement of NIPA molecules occurs on the complex ion (UO/sub 2/(NIPA)/sub 2/(EtOH))/sup 2 +/ but not on the outer-sphere complex: k/sub ex/(25/sup 0/C) = 0.91 x 10/sup 3/s/sup -1/, ..delta..H/sub intra//sup + +/ = 10.6 kcal mol/sup -1/ and ..delta..S/sub intra//sup + +/ = -9.4 eu. Possible mechanisms for this exchange are discussed. 5 figures, 2 tables.

  11. Process for converting sodium nitrate-containing, caustic liquid radioactive wastes to solid insoluble products

    DOE Patents [OSTI]

    Barney, Gary S.; Brownell, Lloyd E.

    1977-01-01

    A method for converting sodium nitrate-containing, caustic, radioactive wastes to a solid, relatively insoluble, thermally stable form is provided and comprises the steps of reacting powdered aluminum silicate clay, e.g., kaolin, bentonite, dickite, halloysite, pyrophyllite, etc., with the sodium nitrate-containing radioactive wastes which have a caustic concentration of about 3 to 7 M at a temperature of 30.degree. C to 100.degree. C to thereby entrap the dissolved radioactive salts in the aluminosilicate matrix. In one embodiment the sodium nitrate-containing, caustic, radioactive liquid waste, such as neutralized Purex-type waste, or salts or oxide produced by evaporation or calcination of these liquid wastes (e.g., anhydrous salt cake) is converted at a temperature within the range of 30.degree. C to 100.degree. C to the solid mineral form-cancrinite having an approximate chemical formula 2(NaAlSiO.sub.4) .sup.. xSalt.sup.. y H.sub.2 O with x = 0.52 and y = 0.68 when the entrapped salt is NaNO.sub.3. In another embodiment the sodium nitrate-containing, caustic, radioactive liquid is reacted with the powdered aluminum silicate clay at a temperature within the range of 30.degree. C to 100.degree. C, the resulting reaction product is air dried eitheras loose powder or molded shapes (e.g., bricks) and then fired at a temperature of at least 600.degree. C to form the solid mineral form-nepheline which has the approximate chemical formula of NaAlSiO.sub.4. The leach rate of the entrapped radioactive salts with distilled water is reduced essentially to that of the aluminosilicate lattice which is very low, e.g., in the range of 10.sup.-.sup.2 to 10.sup.-.sup.4 g/cm.sup.2 -- day for cancrinite and 10.sup.-.sup.3 to 10.sup.-.sup.5 g/cm.sup.2 -- day for nepheline.

  12. CO2-Binding Organic Liquids Gas Capture with Polarity-Swing-Assisted Regeneration Full Technology Feasibility Study B1 - Solvent-based Systems

    SciTech Connect (OSTI)

    Heldebrant, David J

    2014-08-31

    PNNL, Fluor Corporation and Queens University (Kingston, ON) successfully completed a three year comprehensive study of the CO2BOL water-lean solvent platform with Polarity Swing Assisted Regeneration (PSAR). This study encompassed solvent synthesis, characterization, environmental toxicology, physical, thermodynamic and kinetic property measurements, Aspen Plus™ modeling and bench-scale testing of a candidate CO2BOL solvent molecule. Key Program Findings The key program findings are summarized as follows: • PSAR favorably reduced stripper duties and reboiler temperatures with little/no impact to absorption column • >90% CO2 capture was achievable at reasonable liquid-gas ratios in the absorber • High rich solvent viscosities (up to 600 cP) were successfully demonstrated in the bench-scale system. However, the projected impacts of high viscosity to capital cost and operational limits compromised the other levelized cost of electricity benefits. • Low thermal conductivity of organics significantly increased the required cross exchanger surface area, and potentially other heat exchange surfaces. • CO2BOL had low evaporative losses during bench-scale testing • There was no evidence of foaming during bench scale testing • Current CO2BOL formulation costs project to be $35/kg • Ecotoxicity (Water Daphnia) was comparable between CO2BOL and MEA (169.47 versus 103.63 mg/L) • Full dehydration of the flue gas was determined to not be economically feasible. However, modest refrigeration (13 MW for the 550 MW reference system) was determined to be potentially economically feasible, and still produce a water-lean condition for the CO2BOLs (5 wt% steady-state water loading). • CO2BOLs testing with 5 wt% water loading did not compromise anhydrous performance behavior, and showed actual enhancement of CO2 capture performance. • Mass transfer of CO2BOLs was not greatly impeded by viscosity • Facile separation of antisolvent from lean CO2BOL was demonstrated on the bench cart • No measurable solvent degradation was observed over 4 months of testing – even with 5 wt% water present

  13. Water-enhanced solvation of organics

    SciTech Connect (OSTI)

    Lee, J.H.

    1993-07-01

    Water-enhanced solvation (WES) was explored for Lewis acid solutes in Lewis base organic solvents, to develop cheap extract regeneration processes. WES for solid solutes was determined from ratios of solubilities of solutes in water-sat. and low-water solvent; both were determined from solid-liquid equilibrium. Vapor-headspace analysis was used to determine solute activity coefficients as function of organic phase water concentration. WES magnitudes of volatile solutes were normalized, set equal to slope of log {gamma}{sub s} vs x{sub w}/x{sub s} curve. From graph shape {Delta}(log {gamma}{sub s}) represents relative change in solute activity coefficient. Solutes investigated by vapor-headspace analysis were acetic acid, propionic acid, ethanol, 1,2-propylene glycol, 2,3-butylene glycol. Monocarboxylic acids had largest decrease in activity coefficient with water addition followed by glycols and alcohols. Propionic acid in cyclohexanone showed greatest water-enhancement {Delta} (log {gamma}{sub acid})/{Delta}(x{sub w}/x{sub acid}) = {minus}0.25. In methylcyclohexanone, the decrease of the activity coefficient of propionic acid was {minus}0.19. Activity coefficient of propionic acid in methylcyclohexanone stopped decreasing once the water reached a 2:1 water to acid mole ratio, implying a stoichiometric relation between water, ketone, and acid. Except for 2,3-butanediol, activity coefficients of the solutes studied decreased monotonically with water content. Activity coefficient curves of ethanol, 1,2-propanediol and 2,3-butanediol did not level off at large water/solute mole ratio. Solutes investigated by solid-liquid equilibrium were citric acid, gallic acid, phenol, xylenols, 2-naphthol. Saturation concentration of citric acid in anhydrous butyl acetate increased from 0.0009 to 0.087 mol/L after 1.3 % (g/g) water co-dissolved into organic phase. Effect of water-enhanced solvation for citric acid is very large but very small for phenol and its derivatives.

  14. Compilation of Requirements for Safe Handling of Fluorine and Fluorine-Containing Products of Uranium Hexafluoride Conversion

    SciTech Connect (OSTI)

    Ferrada, J.J.

    2000-04-03

    Public Law (PL) 105-204 requires the U.S. Department of Energy to develop a plan for inclusion in the fiscal year 2000 budget for conversion of the Department's stockpile of depleted uranium hexafluoride (DUF{sub 6}) to a more stable form over an extended period. The conversion process into a more stable form will produce fluorine compounds (e.g., elemental fluorine or hydrofluoric acid) that need to be handled safely. This document compiles the requirements necessary to handle these materials within health and safety standards, which may apply in order to ensure protection of the environment and the safety and health of workers and the public. Fluorine is a pale-yellow gas with a pungent, irritating odor. It is the most reactive nonmetal and will react vigorously with most oxidizable substances at room temperature, frequently with ignition. Fluorine is a severe irritant of the eyes, mucous membranes, skin, and lungs. In humans, the inhalation of high concentrations causes laryngeal spasm and broncospasms, followed by the delayed onset of pulmonary edema. At sublethal levels, severe local irritation and laryngeal spasm will preclude voluntary exposure to high concentrations, unless the individual is trapped or incapacitated. A blast of fluorine gas on the shaved skin of a rabbit causes a second degree burn. Lower concentrations cause severe burns of insidious onset, resulting in ulceration, similar to the effects produced by hydrogen fluoride. Hydrofluoric acid is a colorless, fuming liquid or gas with a pungent odor. It is soluble in water with release of heat. Ingestion of an estimated 1.5 grams produced sudden death without gross pathological damage. Repeated ingestion of small amounts resulted in moderately advanced hardening of the bones. Contact of skin with anhydrous liquid produces severe burns. Inhalation of AHA or aqueous hydrofluoric acid mist or vapors can cause severe respiratory tract irritation that may be fatal. Based on the extreme chemical properties of these chemicals as noted above, fluorine or fluorine compounds must be handled appropriately within the boundaries of many safety requirements for the protection of the environment and the public. This report analyzes the safety requirements that regulatory agencies have issued to handle fluorine or fluorine compounds and lists them in Table 1. Table 1 lists the source of the requirements, the specific section of the source document, and a brief description of the requirements.

  15. 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.

  16. 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.

  17. 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.

  18. 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)

  19. 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.

  20. 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

  1. 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.

  2. 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.

  3. 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.

  4. 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.

  5. 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 M1 s1, and that for (C2H5)2O is (5 0.5) 104 M1 s1. In the absence of substrate, Fe(CH3CN)62+ reacts with O3 with kFe = (9.3 0.3) 104 M1 s1. 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.

  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. 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 70C, 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.

  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. 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.

  10. NOx Control Options and Integration for US Coal Fired Boilers

    SciTech Connect (OSTI)

    Mike Bockelie; Marc Cremer; Kevin Davis; Martin Denison; Adel Sarofim; Connie Senior; Hong-Shig Shim; Dave Swenson; Bob Hurt; Eric Suuberg; Eric Eddings; Kevin Whitty; Larry Baxter; Calvin Bartholomew; William Hecker

    2006-06-30

    This is the Final Report for DOE Cooperative Agreement No: DE-FC26-00NT40753. The goal of the project was to develop cost-effective analysis tools and techniques for demonstrating and evaluating low-NOx control strategies and their possible impact on boiler performance for boilers firing US coals. The Electric Power Research Institute (EPRI) provided co-funding for this program. This project included research on: (1) In furnace NOx control; (2) Impacts of combustion modifications on boiler operation; (3) Selective Catalytic Reduction (SCR) catalyst testing and (4) Ammonia adsorption/removal on fly ash. Important accomplishments were achieved in all aspects of the project. Rich Reagent Injection (RRI), an in-furnace NOx reduction strategy based on injecting urea or anhydrous ammonia into fuel rich regions in the lower furnace, was evaluated for cyclone-barrel and PC fired utility boilers. Field tests successfully demonstrated the ability of the RRI process to significantly reduce NOx emissions from a staged cyclone-fired furnace operating with overfire air. The field tests also verified the accuracy of the Computational Fluid Dynamic (CFD) modeling used to develop the RRI design and highlighted the importance of using CFD modeling to properly locate and configure the reagent injectors within the furnace. Low NOx firing conditions can adversely impact boiler operation due to increased waterwall wastage (corrosion) and increased soot production. A corrosion monitoring system that uses electrochemical noise (ECN) corrosion probes to monitor, on a real-time basis, high temperature corrosion events within the boiler was evaluated. Field tests were successfully conducted at two plants. The Ohio Coal Development Office provided financial assistance to perform the field tests. To investigate soot behavior, an advanced model to predict soot production and destruction was implemented into an existing reacting CFD modeling tool. Comparisons between experimental data collected in a pilot scale furnace and soot behavior predicted by the CFD model showed good agreement. Field and laboratory tests were performed for SCR catalysts used for coal and biomass co-firing applications. Fundamental laboratory studies were performed to better understand mechanisms involved with catalyst deactivation. Field tests with a slip stream reactor were used to create catalyst exposed to boiler flue gas for firing coal and for co-firing coal and biomass. The field data suggests the mechanisms leading to catalyst deactivation are, in order of importance, channel plugging, surface fouling, pore plugging and poisoning. Investigations were performed to better understand the mechanisms involved with catalyst regeneration through mechanical or chemical methods. A computer model was developed to predict NOx reduction across the catalyst in a SCR. Experiments were performed to investigate the fundamentals of ammonia/fly ash interactions with relevance to the operation of advanced NOx control technologies such as selective catalytic reduction. Measurements were performed for ammonia adsorption isotherms on commercial fly ash samples subjected to a variety of treatments and on the chemistry of dry and semi-dry ammonia removal processes. This work resulted in the first fundamental ammonia isotherms on carbon-containing fly ash samples. This work confirms industrial reports that aqueous solution chemistry takes place upon the introduction of even very small amounts of water, while the ash remains in a semi-dry state.

  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. 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.

  13. 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.

  14. 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.

  15. 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.

  16. 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.

  17. 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.'

  18. 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.

  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. 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

  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. 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.

  3. 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 ad