National Library of Energy BETA

Sample records for aliphatic alco hol

  1. Verifying Test Hypotheses -HOL/TestGen Verifying Test Hypotheses -HOL/TestGen

    E-Print Network [OSTI]

    Verifying Test Hypotheses - HOL/TestGen Verifying Test Hypotheses - HOL/TestGen An Experiment in Test and Proof Thomas Malcher January 20, 2014 1 / 20 #12;Verifying Test Hypotheses - HOL/TestGen HOL/TestGen Outline Introduction Test Hypotheses HOL/TestGen - Demo Verifying Test Hypotheses Conclusion 2 / 20 #12

  2. http://hol.sagepub.com/ The Holocene

    E-Print Network [OSTI]

    Gilli, Adrian

    . 425547HOL22410.1177/095968 3611425547Elbert et al.The Holocene 1 University of Bern, Switzerland 2 PAGES International Project Office, Switzerland 3 Universidad de Concepción, Chile 4 University of Geneva, Switzerland 5 SURF-EAWAG, Switzerland 6 Geological Institute, ETH Zurich, Switzerland Received 1 April 2011

  3. Matching concepts across HOL libraries Thibault Gauthier and Cezary Kaliszyk

    E-Print Network [OSTI]

    Kaliszyk, Cezary

    Matching concepts across HOL libraries Thibault Gauthier and Cezary Kaliszyk University of Innsbruck, Austria {thibault.gauthier,cezary.kaliszyk}@uibk.ac.at Abstract. Many proof assistant libraries concepts, like natural num- bers, matching them between libraries is often straightforward, because

  4. Analysis of low-cost building material for the MixAlco process 

    E-Print Network [OSTI]

    Titzman, L. Clinton

    2009-05-15

    Engineering iii ABSTRACT Analysis of Low-cost Building Material for the MixAlco Process. (December 2006) L. Clinton Titzman, B.S., Texas A&M University Chair of Advisory Committee: Dr. Mark Holtzapple The development of biofuels... ............................................................................................................. 1 2 Quonset shape ............................................................................................................... 3 3 Tow mixer...

  5. The Semantics of Power and ARM Multiprocessor Machine The HOL Specification

    E-Print Network [OSTI]

    Sewell, Peter

    The Semantics of Power and ARM Multiprocessor Machine Code The HOL Specification Jade Alglave2 Contents i Full Contents ii i #12;BRIEF CONTENTS ii I common coretypes 1 II common types 3 III ppc arm axiomatic model 6 IV arm coretypes 14 V arm types 19 VI arm ast 21 VII arm opsem 24 VIII arm seq monad 36 IX

  6. The Semantics of Power and ARM Multiprocessor Machine The HOL Specification

    E-Print Network [OSTI]

    Sewell, Peter

    The Semantics of Power and ARM Multiprocessor Machine Code The HOL Specification Jade Alglave 2 III ppc arm axiomatic model 6 IV arm coretypes 14 V arm types 19 VI arm ast 21 VII arm opsem 24 VIII arm seq monad 36 IX arm event monad 43 X arm decoder 51 XI arm program 55 XII ppc coretypes 58 XIII

  7. 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.

  8. 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.

  9. ORGANIC GEOCHEMICAL STUDIES. II. THE DISTRIBUTION OF ALIPHATIC HYDROCARBONS IN ALGAE, BACTERIA, AND IN A RECENT LAKE SEDIMENT: A PRELIMINARY REPORT

    E-Print Network [OSTI]

    Han, Jerry; McCarthy, E.D.; Van Hoeven Jr., William; Calvin, Melvin; Bradley, W. H.

    2008-01-01

    significantly to the hydrocarbons of higher molecular weightDISTRIBUTION OF ALIPHATIC HYDROCARBONS IN ALGAE, BACTERIA,T E DISTRIBUTION O ALIPHATIC HYDROCARBONS H F A PRELIMINARY

  10. Reductive dechlorination of chlorinated aliphatic hydrocarbons by Fe(ii) in degradative solidification/stabilization 

    E-Print Network [OSTI]

    Jung, Bahng Mi

    2007-04-25

    This dissertation examines the applicability of the iron-based degradative solidification/stabilization (DS/S-Fe(II)) to various chlorinated aliphatic hydrocarbons (CAHs) that are common chemicals of concern at contaminated sites. The research...

  11. 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.

  12. 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.

  13. 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.

  14. 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.

  15. 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.

  16. aliphatic hydrocarbons constitute the largest fraction of cuticular wax in bees and cover

    E-Print Network [OSTI]

    Paris-Sud XI, Université de

    aliphatic hydrocarbons constitute the largest fraction of cuticular wax in bees and cover a highly hydrocarbons in the cuticular waxes of bees are widely assumed to func- tion as recognition cues (for nestmate discriminate cuticular waxes based on esters and polar components Birgit FRÖHLICHa, Markus RIEDERERa, Jürgen

  17. Palladium-Catalysed CH Activation of Aliphatic Amines! to give Strained Nitrogen Heterocycles !

    E-Print Network [OSTI]

    Jackson, Sophie

    Palladium-Catalysed C­H Activation of Aliphatic Amines! to give Strained Nitrogen Heterocycles. The University of Cambridge, Lensfield Road, Cambridge, CB2 1EW.! Palladium-Catalyzed C­H Activation Modes cyclopalladation complex N H palladium catalyst directed C­H activation oxidant C­Pd functionalization 4-membered

  18. Metal Catalyzed Formation of Aliphatic Polycarbonates Involving Oxetanes and Carbon Dioxide as Monomers 

    E-Print Network [OSTI]

    Moncada, Adriana I.

    2011-08-08

    OF THE COPOLYMERIZATION REACTION OF OXETANE AND CARBON DIOXIDE TO PROVIDE ALIPHATIC POLYCARBONATES CATALYZED BY (SALEN)CrX COMPLEXES ............................................................... 27 Introduction... OF OXETANE OR EPOXIDES AND CO2 CATALYZED BY (SALEN)CrX COMPLEXES .............. 66 Introduction .................................................................................... 66 Experimental Section...

  19. HOUSEHOLD AND STRUCTURAL INSECTS Mineral Oil and Aliphatic Alcohols: Toxicity and Analysis of Synergistic

    E-Print Network [OSTI]

    O'Brien, Timothy E.

    HOUSEHOLD AND STRUCTURAL INSECTS Mineral Oil and Aliphatic Alcohols: Toxicity and Analysis. Entomol. 104(5): 1680Ð1686 (2011); DOI: http://dx.doi.org/10.1603/EC10440 ABSTRACT Two mineral oils and 12 and some- times repeated applications. Mineral oils, and other petroleum distillates, are often used

  20. Matrixassisted laser desorption/ionization mass spectrometric analysis of aliphatic biodegradable photoluminescent polymers

    E-Print Network [OSTI]

    Yang, Jian

    photoluminescent polymers using new ionic liquid matrices Carlos A. Serrano1 , Yi Zhang2 , Jian Yang2 and Kevin A elucidation of recently developed aliphatic biodegradable polymers by matrixassisted laser desorption/ionization mass spectrometry (MALDIMS). The polymers, formed by a condensation reaction of three components

  1. THE UNUSUAL HYDROCARBON EMISSION FROM THE EARLY CARBON STAR HD 100764: THE CONNECTION BETWEEN AROMATICS AND ALIPHATICS

    E-Print Network [OSTI]

    Sloan, Gregory C.

    THE UNUSUAL HYDROCARBON EMISSION FROM THE EARLY CARBON STAR HD 100764: THE CONNECTION BETWEEN disk. The spectrum shows emission features from polycyclic aro- matic hydrocarbons (PAHs shifts are consistent with hydrocarbon mixtures containing both aromatic and aliphatic bonds. We propose

  2. IEEE TRANSACTIONS ON VEHICULAR TECHNOLOGY, VOL. 50, NO. 1, JANUARY 2001 125 The Application of Neural Networks to Fuel

    E-Print Network [OSTI]

    Stengel, Robert F.

    , IEEE Abstract--Passenger vehicles fueled by hydrocarbons or alco- hols and powered by proton exchange than, but retains the reliability and ease of use of, conventional industrial controllers. The proposed in parallel with a conventional proportional-integral-derivative (PID) controller. A computer simulation

  3. 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.

  4. Ligand-Enabled Catalytic C–H Arylation of Aliphatic Amines via a Four Membered Ring Cyclopalladation Pathway

    E-Print Network [OSTI]

    He, Chuan; Gaunt, Matthew J.

    2015-01-01

    A palladium-catalyzed C–H arylation of aliphatic amines with arylboronic esters is described via a four membered ring cyclopalladation pathway. Crucial to the successful outcome of this reaction is the action of an amino acid derived ligand. A range...

  5. 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.

  6. Unique gas and hydrocarbon adsorption in a highly porous metal-organic framework made of extended aliphatic ligandsw

    E-Print Network [OSTI]

    Li, Jing

    Unique gas and hydrocarbon adsorption in a highly porous metal-organic framework made of extended as an Advance Article on the web 15th October 2008 DOI: 10.1039/b814498b High and unique gas and hydrocarbon the corresponding carboxylates). Due to the aliphatic nature of these ligands, the gas and hydrocarbon adsorption

  7. Spatial variations and chronologies of aliphatic hydrocarbons in Lake Michigan sediments.

    SciTech Connect (OSTI)

    Doskey, P. V.; Environmental Research

    2001-01-15

    Four sediment cores were collected in fine-grained depositional areas of the southern basin of Lake Michigan. Spatial variations of aliphatic hydrocarbons in surficial sediments were consistent with a lakeward movement of riverine sediments in a series of resuspension-settling cycles in which an unresolved complex mixture (UCM) of hydrocarbons associated with dense sediments is deposited in nearshore areas, fine-grained sediments of terrestrial origin accumulate in the deep basin, and planktonic hydrocarbons are depleted by microbial degradation during transport to the deep basin. The rate of accumulation of the UCM (a marker of petroleum residues) in deep basin sediments has increased by more than an order of magnitude since 1880, from 60 {mu}g m{sup -2}{center_dot}a{sup -1} to approximately 960 {mu}g m{sup -2}{center_dot}a{sup -1} in 1980. Crude estimates of the atmospheric loading of the UCM (1100 {mu}g m{sup -2}{center_dot}a{sup -1}) indicate that accumulations in deep-basin sediments might be supported by atmospheric deposition. Agreement was poor between the atmospheric flux of the terrestrial n-alkanes ({Sigma}C{sub 25}, C{sub 27}, C{sub 29}, C{sub 31}) to the deep basin (3200 {mu}g m{sup -2}{center_dot}a{sup -1}) and the sediment accumulation rate (660 {mu}g m{sup -2}{center_dot}a{sup -1}). Understanding of atmospheric fluxes, estimated from the very few available data, would be improved by more frequent measurement of the levels of aliphatic hydrocarbons in air and precipitation and a better knowledge of the particle deposition velocities and precipitation scavenging coefficients.

  8. ORGANIC GEOCHEMICAL STUDIES. II. THE DISTRIBUTION OF ALIPHATIC HYDROCARBONS IN ALGAE, BACTERIA, AND IN A RECENT LAKE SEDIMENT: A PRELIMINARY REPORT

    E-Print Network [OSTI]

    Han, Jerry; McCarthy, E.D.; Van Hoeven Jr., William; Calvin, Melvin; Bradley, W. H.

    2008-01-01

    ALIPHATIC HYDROCARBONS IN ALGAE, BACTERIA, AND IN A RECENTH F A PRELIMINARY REPORT IN ALGAE, BACTERIA, AKD IN A RECENTrests on the finding that algae have less cellulose and a

  9. Composition and Digestibility of the Chloroform Extract of Hays and Fodders. 

    E-Print Network [OSTI]

    Fraps, G. S.; Rather, J. B.

    1913-01-01

    of Chloroform Extract and of Ether Extract. Period. 3 12 9 6 17 16 4 10 15 11 5 1413 7 18 2 Description. Alfalfa hay ..................... Bermuda hay ................. Buffalo grass hay.......... Burr clover..................... Corn...-73? 4665 Excrement, rice straw..................................... 115.0 72-73? The acetyl numbers of the crystals are near to that of myricyl alco? hol, which is 116.4. This corresponds to the crystals separated from the ether extract of burr clover...

  10. http://hol.sagepub.com/ The Holocene

    E-Print Network [OSTI]

    Anderson, R. Scott

    in the Americas by synthesizing char- coal series spanning the last 2000 years (2 kyr) from an updated version Northern Arizona University, USA 6 Georg-August University, Germany 7 Canadian Forest Service, Canada 8, University of Calgary, Canada 11 University of Tennessee, USA 12 Virginia Tech, USA 13 University of North C

  11. http://hol.sagepub.com/ The Holocene

    E-Print Network [OSTI]

    Bern, Universität

    decline in biomass burning in the Americas by synthesizing char- coal series spanning the last 2000 years, Canada 8 École Pratique des Hautes Études, France 9 University of Bern, Switzerland 10 Biogeoscience Institute, University of Calgary, Canada 11 University of Tennessee, USA 12 Virginia Tech, USA 13 University

  12. Conversion of MixAlco Process Sludge to Liquid Transportation Fuels 

    E-Print Network [OSTI]

    Teiseh, Eliasu 1973-

    2012-02-15

    gas using the process of pyrolysis. The hydrogen component of the product synthesis gas may be separated by pressure swing adsorption and used in the hydrogenation of ketones into fuels and chemicals. The synthesis gas may also be catalytically...

  13. Lemma Mining over HOL Light Cezary Kaliszyk and Josef Urban

    E-Print Network [OSTI]

    Kaliszyk, Cezary

    the pool of human-defined main (top-level) theorems in the large libraries with the most useful with its core library and the Flyspeck library. The various evaluation scenarios are defined and discussed Radboud University, Nijmegen Abstract. Large formal mathematical libraries consist of millions of atomic

  14. The conversion of corn stover and pig manure to carboxylic acids with the MixAlco process 

    E-Print Network [OSTI]

    Black, Amanda Spring

    2013-02-22

    into carboxylate salts (e. g. , calcium acetate, propionate, and butyrate). These carboxylate salts can be chemically manipulated to produce ketones or alcohols, both of which have a marketable value. Benefits of the process include the positive value of its..., it is necessary to specify an optimal combination of biomass types. Lime Treatment Much of the candidate biomass is lignocellulose, a material consisting of cellulose, lignin, and hemicellulose (Holtzapple, 1997). Lignocellulose has a characteristically low...

  15. Cite this: RSC Advances, 2013, 3, Synthesis of nano-sized spherical Mg3AlCO3 layered

    E-Print Network [OSTI]

    Guo, John Zhanhu

    properties and can potentially be used in a wide range of applications such as high-temperature CO2 capture,8 hydroxide as a high-temperature CO2 adsorbent Received 23rd October 2012, Accepted 19th December 2012 DOI amines, which are good low-temperature CO2 adsorbents, are normally supported on the mesoporous

  16. ---1, I I Paeudo#~&&&&ia * B m -HolWMsholkfirql@Mmtefiatic

    E-Print Network [OSTI]

    ~ t h e ~ t h e m w e r e ~ m t quite dam. WhanIcameverycbm the Zhh e ~ ~ y iutotheahe although recomed as "different".) The small elchlld lnnablUng the Lanistes shell was not P. Ndng8tail

  17. Synthesis of Aliphatic-Aromatic Copolyesters by a High Temperature

    E-Print Network [OSTI]

    Khan, Saad A.

    ceramic precur- sors, to supercritical CO2 under surface constraints yields microcellular polymeric foams(ferrocenylsilane) Ceramic Precursors Foamed in Supercritical CO2 D. J. Frankowski, S. Fournier-Bidoz, I. Manners,* G. A-constrained foaming of poly(ferrocenylsilane) ceramic precursor films with supercritical CO2 yields tunable

  18. Quantitative relationships between structure and reactivity of aliphatic esters 

    E-Print Network [OSTI]

    Yager, Billy Joe

    1960-01-01

    conducted, the re. . ct ion c end it iona vary vide ly from one study to another. Ihorofore& it ws felt th. t a conprehens ive study should bc n. ". de of c large nur. ber of rotors under 1 don! 1cal re". ct ion conditions co th . t ths v". ri. . t ion... const nto were obtsined. . 'icvevcr, in this rescorch 40 ~ diox ns v-o used with consistent rec its, (purthor work in this lcbor cr?hcs shotm c. -n "intent results o. . =. bc obtsinod wiih ~(1 ~ dioxnne by vol&no, ) 2:. . ~rc;f ~&0. diox:m by vol c:c...

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

    Office of Scientific and Technical Information (OSTI)

    AFDC Printable Version Share this resource Send a link to EERE: Alternative Fuels Data Center Home Page to someone by E-mail Share EERE: Alternative Fuels Data Center Home Page on Facebook Tweet about EERE: Alternative Fuels Data Center Home Page on Twitter Bookmark EERE: Alternative Fuels Data Center Homesum_a_epg0_fpd_mmcf_m.xls" ,"Available from WebQuantity of NaturalDukeWakefieldSulfateSciTech ConnectSpeedingConnect Pulse energy(Conference) |SciTechReport)RF-BasedArticle) |

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

    Office of Scientific and Technical Information (OSTI)

    AFDC Printable Version Share this resource Send a link to EERE: Alternative Fuels Data Center Home Page to someone by E-mail Share EERE: Alternative Fuels Data Center Home Page on Facebook Tweet about EERE: Alternative Fuels Data Center Home Page on Twitter Bookmark EERE: Alternative Fuels Data Center Homesum_a_epg0_fpd_mmcf_m.xls" ,"Available from WebQuantity of NaturalDukeWakefieldSulfateSciTech ConnectSpeedingConnect Pulse energy(Conference) |SciTechReport)RF-BasedArticle)

  1. Synthesis Gas Conversion to Aliphatic Alcohols: Study of MoS2 catalytic systems

    E-Print Network [OSTI]

    Baksh, Faisal

    2010-04-19

    ?Setup:?Catalyst?synthesis?&?evaluation?..................................................................................?46? 2.1? Reactor?Unit?..........................................................................................................................................................?46? 2.1.1? Modifications?to?original?reactor...?of?Volatile?Components?...................................................................................................?49? 2.1.1.3? Analysis?at?reactor?exit?......................................................................................................................?51? 2.1.1.4? Exit...

  2. Secondary Organic Aerosol Formation from Primary Aliphatic Amines with Nitrate Radical

    E-Print Network [OSTI]

    Malloy, Q G J; Qi, L; Warren, B; Cocker III, D R; Erupe, M E; Silva, P J

    2009-01-01

    Manahan, S. E. : Environmental Chemistry, 4th Ed. , Lewis,Environmental Research and Technology (CE-CERT), Riverside, CA, USA 3 Department of Chemistry

  3. A quantitative genetics and ecological model system: Understanding the aliphatic glucosinolate biosynthetic network via QTLs

    E-Print Network [OSTI]

    Kliebenstein, Daniel

    in secondary chemistry in wild plants. The easy detection of numerous secondary metabolites makes them with environmental changes rather than escape to more favorable sites. Secondary metabolites are a large and diverse,000 secondary metabolites probably represents a minority of the total (Wink, 1988) with this large chemical

  4. A kinetic study of the reactions of diphenyldiazomethane with some aliphatic carboxylic acids 

    E-Print Network [OSTI]

    Hoefelmeyer, Albert Bernard

    1954-01-01

    ," Chemical Rubber Publishing Co., - l o v e . l PD 5 Vd e d . , NAIKc c R* 2. Kirk and D. F. uthmer, rdlnuycddopi..did:- '.'d" dd;Kur:v; :\\C.. Technology," The Inter science Encyclopedia Inc,, '.nU\\rs\\v* ;ViV:;' :d:dd,/d:db;':r Inc., New York, N. Y., 19U7.... Kirk and D. F. Qthmer, "Encyclopedia of Chemical Technology," The Interscience Encyclopedia Inc., Interscience Publishers, Inc., New York, N. Y., 1950* Vol. V; j A. Forziati, ?. Research Natl. Bur. Standards* 36* 129 (19U6); ^ S. Young* J. Chem. Soc...

  5. A quantitative study of the effect of structure on the saponification rates of aliphatic esters 

    E-Print Network [OSTI]

    Gonzalez, Federico P

    1961-01-01

    . It has long been established that the basic hydrolyses of 1 eaters are second-order reactionsi The familiar study of rolanyi and Saabo has clearly shown that generally, acyl-oxygen bond 2 breakage occurs in the saponification reaction. In view... of these facts the following mechanism has been proposedt H C+ OH OR' 0 0 R C ? OH ~ k ? C ? OH+ OR' OR' ROOD + R' OH IA 1 ~ Fo Te Harder, Hero, 14 ' 1&61 (1881) ~ 2, H, P j yi d '. i. 8 b, T, ~td ' . , QO, 508 (1954). 5 ~ Xi S. Gould, "Nechanism ahd...

  6. foldal blogok frumok szavazsok HupWiki /frum friss

    E-Print Network [OSTI]

    Bencsáth, Boldizsár

    IRC A HUP hivatalos IRC csatornája, a #hup.hu Címlap Egy hónapja ismert a Kaminsky-DNS probléma - hol

  7. 1 Adagio q = 70 PETER BIRDMary's Hymn PETER BIRD

    E-Print Network [OSTI]

    Bird, Peter

    - with good things; and the rich He sent emp ty- a way.- E E 93 S. A. T. B. Org. hol pen- His ser vant- Is ra- el- in re mem- brance- of His mer cy;- - hol pen- His ser vant- Is ra- el- in re mem- brance- of His mer cy;- - He hath hol pen- His ser vant- Is ra- el- in His mer - - - He hath hol pen- His ser vant

  8. Mary's Hymn PETER BIRD Adagio q = 70

    E-Print Network [OSTI]

    Bird, Peter

    .- He hath hol pen- His ser vant- Is ra- el- in and the rich He sent emp ty- a way.- He hath hol pen- His ser vant- Is ra- el- in and the rich He sent emp ty- a way.- He hath hol pen- His ser vant mem- brance- of His mer cy;- - As He Is ra- el- in His mer cy.- - - As He hol pen- His ser vant- Is ra

  9. Environmental Chamber Studies of Reduced Nitrogen Compounds Observed in Anthropogenic Emissions

    E-Print Network [OSTI]

    Price, Derek Jason

    2015-01-01

    of Secondary Aliphatic Amines with Hydroxyl and Nitrateof aliphatic amines with hydroxyl and nitrate radicals.of aliphatic amines with hydroxyl and nitrate radicals.

  10. THE CHEMISTRY OF COAL MODEL COMPOUNDS -CLEAVAGE OF ALIPHATIC BRIDGES BETWEEN AROMATIC NUCLEI CATALYSED BY LEWIS ACIDS

    E-Print Network [OSTI]

    Taylor, Newell D.

    2011-01-01

    and Background I. II. III. IV. II. Coal Liquefaction . •Coal Structure • • . Lewis Acid Catalysts. Scope andOrganic Structure of Bituminous Coal", Proceedings, Stanford

  11. THE CHEMISTRY OF COAL MODEL COMPOUNDS -CLEAVAGE OF ALIPHATIC BRIDGES BETWEEN AROMATIC NUCLEI CATALYSED BY LEWIS ACIDS

    E-Print Network [OSTI]

    Taylor, Newell D.

    2011-01-01

    ~, 1 (955). Cited' in Chemical Abstracts, S'0,-1l2:9'7e:' G.Weingarten, Abstract of Papers, American Chemical Society,Chemical Engineering, University of California, Berkeley, California 94720 ABSTRACT

  12. Application of organolithium compounds for the preparation of some aliphatic and alicyclic phosphines, phosphine oxides and phosphine sulfides 

    E-Print Network [OSTI]

    Screttas, Constantinos G

    1961-01-01

    Rhe ?iehaeli~baae rearrasgeseat gieee tertiary rhea@hiss said&i ~ Rhia roaeties, ?hieh ia the hseaoriaatios af 4i~ 55e 56 albglyheaphisitea, eaa be ah)as bg the fellewiag eve etaa tieses ~PR') ~ R~~ X ~ R R~'Kl + R~X Qsates%4cf JlhoejlholII, Q...

  13. THE CHEMISTRY OF COAL MODEL COMPOUNDS -CLEAVAGE OF ALIPHATIC BRIDGES BETWEEN AROMATIC NUCLEI CATALYSED BY LEWIS ACIDS

    E-Print Network [OSTI]

    Taylor, Newell D.

    2011-01-01

    alkylation, acylation, and hydrocracking reactions. A briefwas necessary for coal hydrocracking, but that added HCl didlost to a combination of hydrocracking during reaction and

  14. THE CHEMISTRY OF COAL MODEL COMPOUNDS -CLEAVAGE OF ALIPHATIC BRIDGES BETWEEN AROMATIC NUCLEI CATALYSED BY LEWIS ACIDS

    E-Print Network [OSTI]

    Taylor, Newell D.

    2011-01-01

    and hydrogenolysis of coal. This type of reaction, however,types of liquid products that might be obtained from coal.types of aromatic rings present 1n short-contact time coal-

  15. THE CHEMISTRY OF COAL MODEL COMPOUNDS -CLEAVAGE OF ALIPHATIC BRIDGES BETWEEN AROMATIC NUCLEI CATALYSED BY LEWIS ACIDS

    E-Print Network [OSTI]

    Taylor, Newell D.

    2011-01-01

    of Solvent Refined Coal to Liquid Products, M.S. -Thesis,of Solvent Refined Coal to Liquid Products, M.S. The;is,Coal: Conversion of Coal into Liquids - Final Report,

  16. A review of "The Performance of Male Nobility in Moliere's Comedies-Ballets: Staging the Courtier" by Gretchen Elizabeth Smith 

    E-Print Network [OSTI]

    Smith, Jay M.

    2007-01-01

    Via mixed-culture fermentation, the MixAlcoTM produces carboxylic acids, which are chemically converted into industrial chemicals and hydrocarbon fuels. Using pilot fermentation data, The Continuum Particle Distribution ...

  17. Ketone Production from the Thermal Decomposition of Carboxylate Salts 

    E-Print Network [OSTI]

    Landoll, Michael 1984-

    2012-08-15

    The MixAlco process uses an anaerobic, mixed-culture fermentation to convert lignocellulosic biomass to carboxylate salts. The fermentation broth must be clarified so that only carboxylate salts, water, and minimal impurities remain. Carboxylate...

  18. Investigations of Biomass Pretreatment and Submerged Fixed-bed Fermentation 

    E-Print Network [OSTI]

    Meysing, Daniel

    2012-02-14

    To improve the MixAlco process and biomass pretreatment, five studies were conducted. Three studies related to fermentation, whereas the other two investigated the effectiveness of shock tube pretreatment (STP) coupled ...

  19. Instrumentation for Process Industries 

    E-Print Network [OSTI]

    Unknown

    2011-08-17

    The development of biofuels as an alternative fuel source highlights the MixAlco process as one method to convert organic waste into alcohol fuels. The pretreatment and fermentation of waste is integral to the process ...

  20. Oligomerization and Catalytic Ketonization in the Mixalco™ Process 

    E-Print Network [OSTI]

    Taco Vasquez, Sebastian

    2013-10-29

    and chicken manure into gasoline and jet fuel. In total, 100 L of jet fuel were obtained. Finally, an integrated approach to obtain gasoline and jet fuel in the MixAlco™ process using LINGO optimization software is presented....

  1. Outer membrane porin M35 of Moraxella catarrhalis mediates susceptibility to aminopenicillins

    E-Print Network [OSTI]

    Jetter, Marion; Heiniger, Nadja; Spaniol, Violeta; Troller, Rolf; Schaller, André; Aebi, Christoph

    2009-01-01

    E, Verhoef J, Fleer A, van Dijk H: Com- plement resistanceCM, Hol C, Fleer A, van Dijk H, van Belkum A: Moraxella

  2. Math.Comput.Sci. (2015) 9:522 DOI 10.1007/s11786-014-0182-0 Mathematics in Computer Science

    E-Print Network [OSTI]

    Middeldorp, Aart

    2015-01-01

    Math.Comput.Sci. (2015) 9:5­22 DOI 10.1007/s11786-014-0182-0 Mathematics in Computer Science HOL versions of the Flyspeck, Multivariate Analysis and Complex Analysis libraries. The service runs on a 48 assistants · Large-theory automated reasoning · HOL light Mathematics Subject Classification 68T15 · 68T05

  3. A novel copper(II)-Schiff base complex containing pyrrole ring: Synthesis, characterization and its modified electrodes applied in oxidation of aliphatic alcohols

    E-Print Network [OSTI]

    Boyer, Edmond

    , ethanol and benzyl alcohol. The electro-reduction of carbon dioxide was also examined. Keywords: Copper] and carbon dioxide [9]. So, in continuation of our recent papers [10], we have undertaken a covalent grafting. Thus, conducting polymeric films of polypyrrole were obtained on the surfaces of glassy carbon and ITO

  4. UNIVERSITY VIEW GLENN L. MARTIN HALL

    E-Print Network [OSTI]

    Daume III, Hal

    other parking lots are for use by PERMIT HOL HALL BENJAMIN BUILDING SCHOOL OF PUBLIC HEALTH ARCHITECTURE A.V. WILLIAMS TERRAPIN SOFTBALL COMPLEXVisitors: · Parking is primarily designated within cashier-attended facilities. Lots are marked with on map

  5. Veri?ed Planning by Deductive Synthesis in Intuitionistic Linear Logic 

    E-Print Network [OSTI]

    Dixon, L.; Bundy, Alan; Smaill, A.

    2009-01-01

    We describe a new formalisation in Isabelle/HOL of Intuitionistic Linear Logic and consider the support this provides for constructing plans by proving the achievability of given planning goals. The plans so found are ...

  6. Indistinguishability Obfuscation and UCEs: The Case of Computationally Unpredictable Sources

    E-Print Network [OSTI]

    International Association for Cryptologic Research (IACR)

    [x] = then if b = 1 then T[x] H.Ev(1 , hk, x) else T[x] $ {0, 1}H.ol() return T[x] Figure 2: Pseudocode

  7. Jules Verne Meister Zacharius

    E-Print Network [OSTI]

    Prodinger, Helmut

    ungeheure Krebsscheren, der Strom schäumte und brauste düster grollend im Schatten sei- ner Last zwischen, als sich auf der Insel, die wie eine hol- ländische Galiote2 in der Mitte des Stroms vor Anker 1 Wege

  8. Influence of Al doping on the critical fields and gap values in magnesium diboride single crystals T. Klein,1,2 L. Lyard,1 J. Marcus,1 C. Marcenat,3 P. Szab,4 Z. Hol'anov,4 P. Samuely,4 B. W. Kang,5 H-J. Kim,5

    E-Print Network [OSTI]

    Boyer, Edmond

    that MgB2 belongs to an origi- nal class of superconductors in which two weakly coupled bands with very the existence of two distinct superconducting gaps. One of the main consequence of this two-band superconduc of the superconducting gaps with Al doping remains controversial. Whereas Gonnelli et al.15 sug- gested that the small

  9. Assessing the Potential of Natural Microbial Communities to Improve a Second-Generation Biofuels Platform 

    E-Print Network [OSTI]

    Hammett, Amy Jo Macbey

    2012-10-19

    Naturally occurring microbial communities from high-salt and/or high-temperature environments were collected from sites across the United States and Puerto Rico and screened for their efficacy in the MixAlco biofuel production platform. The Mix...

  10. Timothy E John Dallas Department of Electrical and Computer Engineering

    E-Print Network [OSTI]

    Gelfond, Michael

    . of Microelectromechanical Systems 19, pp. 632-639 (2010). 9. "Design and Analysis of a Dual-Mode MEMS Micromirror," X. Xiong (Accepted, Journal of Electrostatics, 7/2012). 2. "The 18mm 2 Laboratory: Teaching MEMS Development-micromachined MEMS," Ashwin P. Vijayasai, Ganapathy Sivakumar, Matthew Mulsow, Shelby Lacouture, Alex Holness

  11. Hierarchical Verification of the Implementation of The IEEE754 TableDriven FloatingPoint Exponential

    E-Print Network [OSTI]

    Tahar, Sofiène

    verification system allows its use for the verification task over the whole design path of the circuitHierarchical Verification of the Implementation of The IEEE­754 Table­Driven Floating­Point Exponential Function using HOL Amr T. Abdel­Hamid 1 , Sofiâ?? ene Tahar 1 , John Harrison 2 1 Electrical

  12. Assessing the frictional and baroclinic contributions to stratified wake formation: a parameter space study 

    E-Print Network [OSTI]

    Smith, Jamie Brooke

    2006-08-16

    The baroclinic and surface-frictional contributions to stratified wake formation are considered as a function of the non-dimensional height ( = Nho/U) and aspect-ratio ( = ho/L) of the barrier. Numerical simulations are computed for a wide range...

  13. Released on receipt but intended f o r use

    E-Print Network [OSTI]

    &-Hol*tein earth walls are thrown up and shrubbery is planted upon them, since forest trees cannot be made t o grow- protected portions of the groves AS i n those sheltered by the windbreak. p s e r i e s of anemometers

  14. Time Repor*ng Codes 3/1/15 TRC Description TRC Description TRC Description

    E-Print Network [OSTI]

    Barrash, Warren

    HHS Holiday Pay - Temp - Salary OTA Overtime Accrued 1.5 CBK Call Back Pay HLS Holiday Pay - Reg-Salary.0 CPT Comp Time Taken - Reg HOH Holiday Pay - Temp-Hourly REG Regular - Hourly/Salary DNO Organ Donation - Temp - Salary HOL Holiday Pay - Reg-Hourly RET Regular - Temp-Hourly/Salary DNR Organ Donation - Reg

  15. FREE ACTIVITIES UNIVERSITY OF OXFORD MUSEUMS & COLLECTIONS

    E-Print Network [OSTI]

    Wallace, Mark

    ,Sun and Bank Hols 11am­4pm FREE ENTRY FOR CHILDREN FREE ENTRY FREE ENTRY FOR CHILDREN PITT RIVERS MUSEUM PITT.mhs.ox.ac.uk 01865 277280 OPEN Tuesday ­ Sunday 12 ­ 5pm FREE ENTRY FREE ENTRY FREE ENTRY FREE ENTRY Brilliant bugs for all · 10am-4pm Subject to availability Available from Information Point Every Sunday FAMILY FRIENDLY

  16. Int. J. , Vol. x, No. x, xxxx 1 Modelling and Analysis of Service Parts Logistics Systems

    E-Print Network [OSTI]

    Rossetti, Manuel D.

    Int. J. , Vol. x, No. x, xxxx 1 Modelling and Analysis of Service Parts Logistics Systems Fernando, the behaviour of the service parts logistics system (SPLS) is approximated with a modified M/G/1 HOL queuing policy. Keywords: Service parts logistics, optimisation, genetic algorithms, M/G/1 queuing model

  17. STATE RESTORATION IN DISTRIBUTED SYSTEMS Philip M. MERLIN

    E-Print Network [OSTI]

    Newcastle upon Tyne, University of

    Technion - Israel institute of Technology Haifa, Israel Brian RANDELL Computing Laboratory The University to continue normal processing,, Such backward error recovery © 1978 IEEE. Personal use of this material;2 graphs are similar to the Occurrence Nets (also called Causal Nets) described in [HOL68, PET76, PET77

  18. Theory of Genetic Algorithms ---extended abstract---

    E-Print Network [OSTI]

    de Graaf, Jeannette

    , Joost N. Kok and Walter A. Kosters Leiden University, Department of Computer Science P.O. Box 9512, 2300 some methods for examining the fundamental properties of genetic algorithms ([Hol75, Jon75, Gol89, Mit computation. For a good overview of evolutionary computation one may consult the Handbook of Evolutionary

  19. SOCIOLOGICAL WORK ON ENERGY: THE OPPORTUNITY AND SOME PRESCRIPTIONS

    E-Print Network [OSTI]

    Lacy, Michael G.

    1982-04-01

    and relatively low technology," and are matched in scale, location, and "energy quality to end use needs" (Lovins, 1977: 38-39). Examples, as given in the text, would be solar heating, wind­ powered generators, and the conversion of organic waste to fuel alco....g., the windmill, watermill, steam engine, electric generator), along with estimates of their physical efficiencies. A noteworthy element of the energy primer is the consideration of how energy underlies culture and society, as in Cook's (1976:6) Man, Energy...

  20. The impact of meteorological conditions and variation in chemical composition of aerosols on regional cloud formation

    E-Print Network [OSTI]

    Creamean, Jessie Marie

    2012-01-01

    modelling: a review, Atmospheric Chemistry and Physics, 5,aliphatic amines, Atmospheric Chemistry and Physics, 7 (9),of carbon monoxide, Atmospheric Chemistry and Physics,

  1. This article appeared in a journal published by Elsevier. The attached copy is furnished to the author for internal non-commercial research

    E-Print Network [OSTI]

    Semprini, Lewis

    of groundwater plumes with contaminant con- centrations above the drinking water standards (Semprini, 1997 cometabolism of chlorinated aliphatic hydrocarbons (CAHs) is a promising technology for the remediation

  2. INDEX TO VOLUME 144 This index provides coverage for both the Initial Reports and Scientific Results

    E-Print Network [OSTI]

    of individuals, and routine front and back matter. The Subject Index follows a standard format. Geographic, authigenesis, B:465­466 aliphatic aci

  3. Molecular signature and sources of biochemical recalcitrance of organic C in Amazonian Dark Earths

    E-Print Network [OSTI]

    Lehmann, Johannes

    -C, aldehyde-C, ketonic-C and quinine-C, and (iii) diverse group of refractory aliphatic-C moieties. The SOC

  4. A Case for Safer Building Materials: Lifecycle Concerns, Data Gaps, and

    E-Print Network [OSTI]

    Lee, Seung-Wuk

    ;Conventional Building Materials · Wood · Stone · Cement · Metal · Glass · Straw · Ceramics #12;Synthetic;Volatile organic compounds (VOCs) · Aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons

  5. Curriculum Vitae Abdulaziz Ahmed Bagabas

    E-Print Network [OSTI]

    Yaghi, Omar M.

    -investigator). IX. Synthesis of carbon nanotubes using chemical vapor deposition (CVD), characterization receiving the chemicals: I. Novel iron, cobalt, and nickel complexes based on aliphatic nitrogen ligands

  6. Molybdenum alkylidene complexes : syntheses and applications to olefin metathesis reactions

    E-Print Network [OSTI]

    Pilyugina, Tatiana

    2007-01-01

    Chapter 1. Alkylimido Molybdenum Complexes: Synthesis, Characterization and Activity as Chiral Olefin Metathesis Catalysts. Molybdenum olefin metathesis catalysts that contain previously unexplored aliphatic 1- ...

  7. Crinoids of the Francis Shale (Missourian) of Oklahoma

    E-Print Network [OSTI]

    Strimple, H. L.; Moore, R. C.

    1971-11-30

    the possibility of collecting more speci- mens at the brick pit just south of Ada, Pontotoc County, Oklahoma, and was joined by ALLEN GRAFFHAM and one of us (STRimpLE) in excavat- ing a large colony or pocket of crinoids. A few rather large concretions..., Missourian, Pontotoc Coun- ty, Oklahoma; T. progressus STRIMP LE, 1952, Barnsdall Formation, Missourian, Osage County, Oklahoma; T. associatus STRIMP LE, 1952, Oolo- gah Limestone, Desmoinesian, Tulsa County, Oklahoma; T. coniformis STRIMP LE, 1961, Hol- deny...

  8. Ammonia fiber explosion (AFEX) pretreatment of municipal solid waste components 

    E-Print Network [OSTI]

    Lundeen, Joseph Eric

    1991-01-01

    AMMONIA FIBER EXPLOSION (AFEX) PRETREATMENT OF MUNICIPAL SOLID WASTE COMPONENTS A Thesis by JOSEPH ERIC LUNDEEN Submitted to the Oflice of Graduate Studies of Texas A&M University in partial fulfdlment of the requirements for the degree... of MASTER OF SCIENCE December 1991 Major Subject: Chemical Engineering AMMONIA FIBER EXPLOSION (AFEX) PRETREATMENT OF MUNICIPAL SOLID WASTE COMPONENTS A Thesis Joseph Eric Lundeen Approved as to style and content by: Mark Hol pie ( tte R. W...

  9. Interfacial assembly of dendritic microcapsules with host-guest chemistry

    E-Print Network [OSTI]

    Zheng, Yu; Yu, Ziyi; Parker, Richard M.; Wu, Yuchao; Abell, Chris; Scherman, Oren A.

    2014-12-16

    subsequent etching under relatively harsh conditions to obtain a hol- low structure, lowering encapsulation and loading effi- ciencies. Droplets-in-droplet based double or multiple emulsion strategies28,29, although powerful, depend on ingenious microfluidic... ,34, micelles35, hydro- gels36,37, colloids38 and more recently by our group, mi- crocapsules39. In this supramolecular system, cucur- bit[8]uril (CB[8]) was exploited to crosslink a naphthol- modified poly(acrylamide) copolymer and methyl viologen...

  10. Compositional differences in biomarker constituents of the hydrocarbon, resin, asphaltene and kerogen fractions

    E-Print Network [OSTI]

    Mills, Allen P.

    Compositional differences in biomarker constituents of the hydrocarbon, resin, asphaltene fraction, so biomarker parameters measured for different fractions are not directly comparable. The samples- tion are of equal magnitude to the quantities that are present in the extractable aliphatic hydrocarbon

  11. Contact: Clifford K. Ho, (505) 844-2384, ckho@sandia.gov 1 Updated 6/21/2002 Sandia National Laboratories--LDRD Fact Sheet

    E-Print Network [OSTI]

    Ho, Cliff

    -concentrator for enhanced detection capabilities. · Develop robust packaging system that allows the sensor to operate in wet), aliphatic hydrocarbons (e.g., hexane, octane), alcohols, ketones. Manual soil sampling, such as this hand

  12. Synthesis, characterization and X-ray crystal structures of chiral ferrocene-containing -diketones

    E-Print Network [OSTI]

    Paris-Sud XI, Université de

    mono-condensation with aliphatic and aromatic diamines [4-6], as well as for the design of transition variety of synthetic transformations [13]; its solubility in organic solvents such as methanol

  13. Design and manipulation of 1-D rugate photonic crystals of porous silicon for chemical sensing applications

    E-Print Network [OSTI]

    King, Brian Henry

    2010-01-01

    diglycidyl ether of bisphenol-A) was provided by Reichhold,354 diglycidyl ether of bisphenol-F) and Novolac (D.E.N 438using a partially cured Bisphenol A epoxy/modified aliphatic

  14. Manipulation of surface chemistry and nanostructure in porous silicon-based chemical sensors

    E-Print Network [OSTI]

    Ruminski, Anne Marie

    2009-01-01

    diglycidyl ether of bisphenol-A) was provided by Reichhold,partially cured mixture of bisphenol A epoxy and modifiedusing a partially cured bisphenol A epoxy/modified aliphatic

  15. Microbial dynamics during intrinsic remediation of oil contaminated coastal wetland sediments (a microcosm study) 

    E-Print Network [OSTI]

    Thornburg, Nathaniel David

    2001-01-01

    was observed throughout the experiment, illustrating that oil was being intrinsically remediated. Kinetic analysis showed that the aliphatic and aromatic hydrocarbons had a half-life of 18 and 56 days, respectively. While MPN and GC-MS analysis showed...

  16. Kinetics of Ion Removal from an Iron-Rich Industrial Coproduct: H. Sulfate Yigal Salingar, Donald L. Sparks,* and John D. Pesek

    E-Print Network [OSTI]

    Sparks, Donald L.

    of water quality, often yielding high acidity and concentrations of metals and SO4.Such pyrite weathering (1990) investigated the influence of naturally occurring aliphatic acids on the kinetics of A1and SO4

  17. 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.

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

    DOE Patents [OSTI]

    Benkeser, Robert A. (West Lafayette, IN); Laugal, James A. (Lostant, IL); Rappa, Angela (Baltimore, MD)

    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.

  19. 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.

  20. Yeast Breads: Made at Home. 

    E-Print Network [OSTI]

    Reasonover, Frances

    1971-01-01

    ~rc,~wd 1 pound loaf pans. Let rise until doubled. pit ,it 400? I;. about 50 minutes. When loaves shrink .nm s~des of pan, are a golden brown and give a hol- 1~ sound when tapped, the bread is done. As soon I \\ lalres are taken from the oven, turn... wanted, remove dough from refrigerator and punch down. Mold at once in any desired shape. Or, if preferred, let dough stand in warm room an hour before molding. Place in greased pans and let rise until doubled in size, about 1 hour. Bake at 425' F...

  1. An economic evaluation of selected tenure arrangements for a representative farm in the northern high plains of Texas 

    E-Print Network [OSTI]

    Harwell, R. Lynn

    1970-01-01

    'frixfxttee) ~ ~~yg/J Jeff:axxy 1970 ABSTRACT An Economic Evaluation of Selected Tenure Arrangements For A Representative Farm in the Northern Sigh Plains of Texas. (January 1970) Richard Lynn Sarwell; B. B. S. , The University of Texas Directed by: Dr. J. S... thar three-fourths of the annual noisture falls during the growing season [27]. LLANO M E'yg ~VI P@ I CO HARFvvv EHERSAV tiooRF HolCHINsoN Study Area vs% Figure 1. Distribution of Hardlands Soils, Texas bligh Pla111S Souro: [57 J !!ind !mi...

  2. Commercial Feeding Stuffs, September 1, 1924 to August 31, 1925. 

    E-Print Network [OSTI]

    Youngblood, B. (Bonney); Fuller, F. D. (Frederick Driggs); Pearce, S. D.

    1925-01-01

    T. 0 WALTON, President STATION STAFFf- -'r ADMINISTRATION: B YOUNGBLOOD M S Ph. D Director A: B. CONNER, M. s.. 't'ice-~i;lctor R. E. KARPER, B. S., Asszstani Dlrector A S WARE Secretary W. H. HOL~MANN Chief Clerk M. P HOLLEMAN 'JR Assistant... A Chief H.'NESS, M. s.', ~krry'~reeder RANGE ANIMAL HUSBANDRY: J. M. JONES, 4. M., Chief; Sheep and Goat Invest[gatrons J. L. LUSH? Ph. D., Animal Husbandman; Breedzng Investzgatzons J. J. HUNT, Wool Grader ENTOMOLOGY: F. L. THOMAS? Ph. D...

  3. Breed and environmental factors influencing the performance of crossbred cattle for milk production in a tropical environment 

    E-Print Network [OSTI]

    Contreras Duran, Ricardo Eligio

    1977-01-01

    'ber on lactation performance. Plain dairy- ing characterist'c= of these farms are: most of the cows are Bos . indicos-Bos taurus crossbreds, , cows a!0 '1~cd-m. Ikcd and no concentrate is fed to the animals. The experimental material consisted of 1888 lactation... records from Hol. tein, Brown Hwiss, Criollo, Zebu and Brahman crossbred cows. 1'dil k yield was estimated from monthly weights. Calvir!g number, lactation length, calving interval and previous dry pe iod were also recorded. Analyses we e conducted...

  4. Magnetic Quadrupole Decay of (1s2s2p) 4p05/2-(1s)22s2se1/2 Transition of Lithium Isoelectronic Sequence 

    E-Print Network [OSTI]

    Onello, J. S.; Ford, A. Lewis.

    1975-01-01

    of electron decay-in-flight spectra from autoionizing states of the lithium s eries' and x-ray emission from foil -excited beams' have prompted a systematic study of the magnetic quadrupole decay rates for the sequence by means of a nuclear-charge-expansion... the expansion eigenval- ues of the lithium sequence from I.iI through ArXVI and compares them to the variational estimates of HolOien and Geltman. ' For 0 VI the energy from the Z expansion differs from the variational energy obtained with the 41-term...

  5. Hammering towards QED

    E-Print Network [OSTI]

    Blanchette, Jasmin C.; Kaliszyk, Cezary; Paulson, Lawrence C.; Urban, Josef

    2015-01-01

    algorithms have led to visible suc- cess. Fully automated procedures can prove 40% of the theorems in the Mizar math library, 47% of the HOL Light/Flyspeck libraries, with com- parable rates in Isabelle. These automation rates represent an enormous savings... the automatic proof of the Robbins conjecture by William McCune’s EQP system in 1996 [91]. ATPs have solved some open equational algebraic problems—for example, in quasigroup and loop theory [109]—finding proofs consisting of thousands of inferences. Linking...

  6. 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 Cd–fatty 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.

  7. HAPPENING THIS WEEK NEWSLETTER FOR NOVEMBER 18th-NOVEMBER 25

    E-Print Network [OSTI]

    Lawrence, Rick L.

    ENERgy aNd SuSTaiNaBiLiTy WiLL pRESENT ThEiR pOSTERS ON TOpicS Such aS BiOMaSS FuELS, ENERgy EFFiciENcy, MSu ENERgy aNd SuSTaiNaBiLiTy EFFORTS, SOLaR ThERMaL ENERgy, SuSTaiNaBLE FOOd SySTEMS aNd ag FOR SuSTaiNaBLE FOOd pROducTiON. GET A HolD oF uS ThE MSu OFFicE OF SuSTaiNaBiLiTy ThE MSu OFFicE OF SuSTaiNaBiLiTy

  8. arXiv:hepex/0109015 CLNS 01/1754

    E-Print Network [OSTI]

    -end sig- nal processing chips, with a combined power output of #24;360 W. The drift chamber's heat sources coolant-control platforms provides independent and regulated heat removal from four recently upgraded: the suitability of using the aliphatic-hydrocarbon solvent PF TM -200IG as a heat-transfer uid, the sensor

  9. APPLIED AND ENVIRONMENTAL MICROBIOLOGY, Aug. 1993, p. 2380-2387 Vol. 59, No. 8 0099-2240/93/082380-08$02.00/0

    E-Print Network [OSTI]

    Hazen, Terry

    was degraded at various rates by most of the sMMO-producing isolates, whereas PCE was not degraded. Savannah of indigenous methanotrophic communities can be efficacious for removal of chlorinated aliphatic hydrocarbons, subsurface microorganisms carry out the cycling of carbon, nitrogen, sulfur, manganese, iron, and phosphorus

  10. Acetylene Inhibition of Trichloroethene and Vinyl Chloride

    E-Print Network [OSTI]

    Semprini, Lewis

    the biological transformation of VC to ethene. Introduction Chlorinated aliphatic hydrocarbons (CAHs lost their ability to degrade PCE. These results suggested that more than two dehalogenating microorganisms were responsible for the complete transformation of PCE to ethene (4). By examining anaerobic

  11. Identification of the Wax Ester Synthase/Acyl-Coenzyme A:Diacylglycerol Acyltransferase WSD1 Required for

    E-Print Network [OSTI]

    Kunst, Ljerka

    Identification of the Wax Ester Synthase/Acyl-Coenzyme A:Diacylglycerol Acyltransferase WSD1 Required for Stem Wax Ester Biosynthesis in Arabidopsis1,2[W][OA] Fengling Li, Xuemin Wu, Patricia Lam Columbia, Canada V6T 1Z1 (R.J.) Wax esters are neutral lipids composed of aliphatic alcohols and acids

  12. PHONON DISPERSION CURVES OF ORDERED PHASES OF T.B.B.A. Abstract. --The lattice dynamics of a deuterated single crystal of T.B.B.A. have been measured

    E-Print Network [OSTI]

    Boyer, Edmond

    of a deuterated single crystal of T.B.B.A. have been measured by mean of inelastic neutron scattering of the molecules. Previous neutron inelastic scattering measurements have been done on non-deuterated single of a melting of the terminal aliphatic chains. So neutron coherent inelastic scattering measure- ments have

  13. Evaluation of biological treatment for the degradation of petroleum hydrocarbons in a wastewater treatment plant 

    E-Print Network [OSTI]

    Basu, Pradipta Ranjan

    2005-08-29

    . Samples were taken for two seasons, winter (Nov 03 ?? Jan 03) and summer (Jun 04 ?? Aug 04), from each of the four treatment units: the inlet tank, equalization tank, aeration tank and the outfall tank. The population of aliphatic hydrocarbon degraders...

  14. Nanoindentation of Biodegradable Cellulose Diacetate-graft-Poly(L-lactide) Copolymers: Effect

    E-Print Network [OSTI]

    Wang, Siqun

    - degradable polymers, for example, aliphatic poly- esters and copoly(ester-carbonate)s, have been actively 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 1114­1121, 2007 Keywords: cellulose'' concepts, copolymerization and polymer blending of cellulose and its derivatives with synthetic bio

  15. 4858 J. Am. Chem. SOC.1994, 116, 4858-4865 Lanthanide-Cyclodextrin Complexes as Probes for Elucidating

    E-Print Network [OSTI]

    Bogyo, Matthew

    of phenyl and naphthyl rings in aqueous solutions' and hydrophobic aliphatic chains.2 Cyclo- dextrin the formation of hydrogen bonds between the substrate and cyclodextrin. The proximity of hydrogen of determining enantiomeric excess.613 Abstract published in Advance ACS Abstracts, May 1, 1994. (1) Armstrong

  16. 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.

  17. Correlated microanalysis of cometary organic grains returned by Stardust Bradley T. De GREGORIO1,2*

    E-Print Network [OSTI]

    Nittler, Larry R.

    of this chemical variety may be due to contamination or alteration during particle capture in aerogel. We matter infilling densified silica aerogel. Aliphatic organic matter from Track 16 was also observed not be clearly distinguished from carbonaceous contaminants known to be present in the Stardust aerogel collector

  18. 934 / JOURNAL OF ENVIRONMENTAL ENGINEERING / OCTOBER 2000 CHLORINATED SOLVENT COMETABOLISM BY BUTANE-GROWN

    E-Print Network [OSTI]

    Semprini, Lewis

    BY BUTANE-GROWN MIXED CULTURE By Young Kim,1 Daniel J. Arp,2 and Lewis Semprini3 ABSTRACT: A survey of aerobic cometabolism of chlorinated aliphatic hydrocarbons by a butane-grown mixed culture was performed and was inhibited by butane and inactivated by acetylene, indicating that a monooxygenase enzyme was likely involved

  19. 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.

  20. An experimental and theoretical study of the reaction of ethynyl radicals with nitrogen dioxide ,,HCCCNO2...

    E-Print Network [OSTI]

    Nguyen, Minh Tho

    ; accepted 18 March 2003 A pulsed laser photolysis/chemiluminescence PLP/CL technique was used to determine known to play a major role in the high-temperature chemistry of combustion,13,14 where it is linked precursors of soot particles in aliphatic hydrocarbon fuel combustion. Besides C2H formation in flames by H

  1. Seasonal and diurnal variations of submicron organic aerosol in Tokyo observed using the Aerodyne aerosol mass spectrometer

    E-Print Network [OSTI]

    Jimenez, Jose-Luis

    with carbon monoxide (CO) and fragments of aliphatic and oxygenated organic compounds in the AMS mass spectra. Combustion-related organic aerosol (combustion OA) is defined as the primary organic aerosol (POA) fraction the combustion OA and the background OA from the total OA. The combustion OA and excess OA show good correlation

  2. Pressure-controlled injection of guar gum stabilized microscale zerovalent iron for groundwater remediation

    E-Print Network [OSTI]

    Cirpka, Olaf Arie

    project AQUAREHAB in a site in Belgium contaminated by chlorinated aliphatic hydrocarbons (CAHs in the laboratory based on several tests (reactivity tests towards contaminants, sedimentation tests and rheological injection step rate tests, one performed with water and the other one with guar gum. Based on laboratory

  3. Biochemical Engineering Journal 38 (2008) 219225 Bioavailability of PCBs in biphasic bioreactors

    E-Print Network [OSTI]

    Daugulis, Andrew J.

    2008-01-01

    to their widespread use in industrial applications, often found at PCB contaminated sites [8]. These hydrocarbons can and physiochem- ical factors. Short chain aliphatic hydrocarbons are significantly more soluble in water than PCB 2007 Abstract Polychlorinated biphenyls (PCBs) are xenobiotic and toxic contaminants of soil

  4. Utilization of Cathodic Hydrogen as Electron Donor for Chloroform

    E-Print Network [OSTI]

    Alvarez, Pedro J.

    bacteria may have significant practical implica- tions. Introduction Chlorinated aliphatic hydrocarbons (CAHs) are frequent groundwater contaminants (1). They are susceptible to biotransformations catalyzed existwithregardtotheuseofhydrogenduetoitslowsolubility in water, about 1.6 mg/L at 20 °C, based on a Henry's constant of 6.83 × 104 atm/mol (16). One way

  5. Anaerobic Reductive Dechlorination of 1-Chloro-1-fluoroethene To Track

    E-Print Network [OSTI]

    Semprini, Lewis

    surrogate for evaluating the rates of VC transformation. Introduction Chlorinated aliphatic hydrocarbons observed in CAH-contaminated groundwater, and this limits the usefulness of anaerobic biotransformation carcinogen and has the lowest drinking water standard (2 µg/L) (3). VC transformation to ethene is generally

  6. Treatment of Chlorinated Solvents by Nitrogen-Fixing and

    E-Print Network [OSTI]

    Chu, Kung-Hui "Bella"

    ). Therefore, effective contaminant destruction approaches such as in-situ vadose zone bioremediation or above of ground- water contaminants including aliphatic, aromatic, and halogenated hydrocarbons (3 bioremediation for the treatment of chlorinated solvents at Savannah River (6, 7). At this site, nitrogen

  7. Nanoparticles designed from low pressure plasmas as identification tool for astrophysical observations

    E-Print Network [OSTI]

    Paris-Sud XI, Université de

    interstellar media. The particles were polymerised in a low pressure capacitively coupled radio-frequency molecule production and reprocesses UV and optical radiation. The C-H stretch vibration of aliphatic coupled the radiofrequency discharge in argon/acetylene mixtures [Kovacevic submitted]. The particles

  8. "Humic Coverage Index" as a Determining Factor Governing

    E-Print Network [OSTI]

    Muzzio, Fernando J.

    "Humic Coverage Index" as a Determining Factor Governing Strain-Specific Hydrocarbon Availability, the "humic coverage index" (HCI), provides a measurement of the relative spatial extents and/or thicknesses to modeling biodegradation of aromatic and aliphatic hydrocarbons (phenanthrene, pyrene, and hexadecane

  9. Biomolecular Dynamic Article Links

    E-Print Network [OSTI]

    Silverman, Scott K.

    the serine (Ser) aliphatic hydroxyl side chain was extremely poor (only ~0.2% yield), and reactivity of the lysine (Lys) amine side chain was not observed. Lys side chain reactivity has never previously been) available: Assays of un- cloned pools and 13LS3 deoxyribozyme; reductive amination assay of 13LS3 ligation

  10. Synthesis of Rigid Cyclodextrin-Containing Polymeric Resins for Adsorption TINGYUE GU1,

    E-Print Network [OSTI]

    Gu, Tingyue

    . Adsorption isotherms for three small aromatic com- pounds, namely phenylalanine, tryptophan and aspartame, aromatic compounds, aliphatic alcohols, biomolecules with bulky side chains including antibiotics to provide selectivity [9, 10]. An aqueous alcohol, such as methanol, solution is often used as the mobile

  11. Vaporization Enthalpy and Vapor Pressure of Valproic Acid by Correlation Gas Chromatography

    E-Print Network [OSTI]

    Chickos, James S.

    Vaporization Enthalpy and Vapor Pressure of Valproic Acid by Correlation Gas Chromatography Joe A-propylpentanoic acid) is reported, and the vapor pressures of a series on aliphatic carboxylic acids are used to evaluate its vapor pressure as a function of temperature. The vaporization enthalpy was derived

  12. 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.

  13. A KINETIC STUDY OF AEROBIC PROPANE UPTAKE AND COMETABOLIC DEGRADATION OF CHLOROFORM,

    E-Print Network [OSTI]

    Semprini, Lewis

    A KINETIC STUDY OF AEROBIC PROPANE UPTAKE AND COMETABOLIC DEGRADATION OF CHLOROFORM, CIS the behavior of different consortiums of aerobic propane-utilizing microorganisms, with respect to both the lag time for growth after exposure to propane, and their ability to transform three chlorinated aliphatic

  14. IUPAC-NIST Solubility Data Series. 81. Hydrocarbons with Water and Seawater Revised and Updated. Part 7. C8H12C8H18 Hydrocarbons

    E-Print Network [OSTI]

    IUPAC-NIST Solubility Data Series. 81. Hydrocarbons with Water and Seawater Revised and Updated. Part 7. C8H12­C8H18 Hydrocarbons with Water Volume Editors David G. Shawa... University of Alaska on the evaluation of the all experimental data for a given homologous series of aliphatic and aromatic hydrocarbons

  15. Coarse-grained Molecular-level Analysis of Polyurea Properties and Shock-mitigation Potential

    E-Print Network [OSTI]

    Grujicic, Mica

    Coarse-grained Molecular-level Analysis of Polyurea Properties and Shock-mitigation Potential M-phenyl methane); (b) R¢ represents an aromatic/aliphatic long chain functional group (e.g., Poly. This enables the application of conventional spraying technol- ogies for in situ production of PU coatings

  16. Theoretical kinetic study of thermal unimolecular decomposition of cyclic alkyl radicals

    E-Print Network [OSTI]

    Paris-Sud XI, Université de

    : While many studies have been reported on the reactions of aliphatic hydrocarbons, the chemistry of cyclic hydrocarbons has not been explored extensively. In the present work, a theoretical study However, cycloalkanes and alkylcycloalkanes (in particular C5 and C6) are usually present in conventional

  17. ORIGINAL CONTRIBUTION Rheological characterization of asphalt

    E-Print Network [OSTI]

    Mather, Patrick T.

    compared favorably with those obtained using conventional parallel-plate torsional flow in a commercial and are aggregates of polar aromatic compounds (Maruska and Rao 1987). Maltenes are nonpolar aliphatic hydrocarbons time (Anderson and Marasteanu 1999). Because of their codification, the conventional tests

  18. 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.

  19. 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.

  20. 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.

  1. Stabilization of Water-in-Oil Emulsions by Naphthenic Acids and Their Salts: Model Compounds, Role of pH, and Soap : Acid Ratio#

    E-Print Network [OSTI]

    Kilpatrick, Peter K.

    Stabilization of Water-in-Oil Emulsions by Naphthenic Acids and Their Salts: Model Compounds, Role cyclic and branched aliphatic carboxylic acids, are interfacially active and adsorb at water­oil in petroleum production is the resulting stabilization of water-in-oil emulsions, which can cause problems

  2. Frequently asked questions about MFCs and our replies (Logan lab, Penn State) 1. In the paper by Liu, H., Cheng, S. and Logan, B.E. (2005b) Env. Sci. Tech., Vol. 39(14), pp.

    E-Print Network [OSTI]

    Nafion perfluorinated ion-exchange resin, 5% solution in low aliphatic alcohols/H2Omix, contains 15.5 mm diameter, 5 meters length, $264.60 USD, Manufacturer - Alfa Aesar 3. What is the difference technology. 5. Can you tell us costs and where to get anion exchange membranes (AEM) and cation exchange

  3. Neem extract as an inhibitor for biocorrosion influenced by sulfate reducing bacteria: A preliminary investigation

    E-Print Network [OSTI]

    hydrogen as an electron donor for metabolic life [1,2], (2) use O2 and Fe3+ as a terminal electron acceptor [3], (3) utilize aliphatic and aromatic hydrocarbons as a carbon source [4], (4) use very low levels linepipe steel by a sulfate- reducing bacterial (SRB) consortium. The SRB consortium used in this study

  4. Superallowed Fermi Decay of Ga-62 

    E-Print Network [OSTI]

    Davids, C. N.; Gagliardi, Carl A.; Murphy, M. J.; Norman, E. B.

    1979-01-01

    the copolymerization of CO2 and epoxide to form aliphatic polycarbonates. A new chromium(III) Schiff base complex has been synthesized and evaluated for its ability to catalyze the formation of polymer. The ligand employed bears an N2O2 coordination sphere identical...

  5. doi:10.1016/j.gca.2004.09.009 Alkylation of polycyclic aromatic hydrocarbons in carbonaceous chondrites

    E-Print Network [OSTI]

    Zare, Richard N.

    doi:10.1016/j.gca.2004.09.009 Alkylation of polycyclic aromatic hydrocarbons in carbonaceous hydrocarbons (PAHs) in the free organic material of 20 carbonaceous chondrites. These meteorites represent, is in a solvent-extractable form containing aromatic and aliphatic hydrocarbons, amino acids, and other compounds

  6. A novel biodegradable nanocomposite based on poly (3-hydroxybutyrate-co-3-hydroxyhexanoate) and silylated kaolinite/silica

    E-Print Network [OSTI]

    Mark, James E.

    The Procter & Gamble Company, 8611 Beckett Road, West Chester, OH 45069, USA a b s t r a c ta r t i c l e i n, with the aim to solve the environmental problem caused by the disposal of large volumes of non promising biodegradable semi- crystalline aliphatic polyesters of the polyhydroxyalkanoate family (Choi

  7. X-ray photoelectron emission spectromicroscopic analysis of arborescent lycopsid cell wall composition and Carboniferous coal ball preservation

    E-Print Network [OSTI]

    Boyce, C. Kevin

    composition and Carboniferous coal ball preservation C. Kevin Boyce a, , Mike Abrecht b , Dong Zhou b , P that were canopy dominants of many Pennsylvanian coal swamp forests. Its periderm or bark--the single greatest biomass contributor to many Late Paleozoic coals--is found to have a greater aliphatic content

  8. 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.

  9. Kinetic and Inhibition Studies for the Aerobic Cometabolism of

    E-Print Network [OSTI]

    Semprini, Lewis

    ,1-Dichloroethylene, and 1,1-Dichloroethane by a Butane-Grown Mixed Culture Young Kim,1 Daniel J. Arp,2 Lewis Semprini), and 1,1-dichloroethane (1,1-DCA) by a butane- grown mixed culture. These chlorinated aliphatic hydro. The highest kmax was obtained for butane (2.6 µmol/mg TSS/ h) followed by 1,1-DCE (1.3 µmol/mg TSS/h), 1,1-DCA

  10. Kinetic and inhibition studies for the aerobic cometabolism of 1,1,1-trichloroethane, 1,1-dichloroethylene, and 1,1-dichloroethane by a butane-grown mixed culture

    E-Print Network [OSTI]

    Semprini, Lewis

    ,1-dichloroethylene, and 1,1-dichloroethane by a butane-grown mixed culture Kim Y, Arp DJ, Semprini L BIOTECHNOLOGY,1- dichloroethane (1,1-DCA) by a butane-grown mixed culture. These chlorinated aliphatic hydrocarbons (CAHs for butane (2.6 mumol/mg TSS/ h) followed by 1,1-DCE (1.3 mumol/mg TSS/h), 1,1-DCA (0.49 mumol/mg TSS

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

    SciTech Connect (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.

  12. 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.

  13. Accurate measurements of {sup 13}C-{sup 13}C distances in uniformly {sup 13}C-labeled proteins using multi-dimensional four-oscillating field solid-state NMR spectroscopy

    SciTech Connect (OSTI)

    Straasø, Lasse Arnt; Nielsen, Jakob Toudahl; Bjerring, Morten; Nielsen, Niels Chr., E-mail: ncn@inano.au.dk [Center for Insoluble Protein Structures (inSPIN), Interdisciplinary Nanoscience Center (iNANO) and Department of Chemistry, Aarhus University, DK-8000 Aarhus C (Denmark); Khaneja, Navin [Division of Applied Sciences, Harvard University, Cambridge, Massachusetts 02138 (United States)

    2014-09-21

    Application of sets of {sup 13}C-{sup 13}C internuclear distance restraints constitutes a typical key element in determining the structure of peptides and proteins by magic-angle-spinning solid-state NMR spectroscopy. Accurate measurements of the structurally highly important {sup 13}C-{sup 13}C distances in uniformly {sup 13}C-labeled peptides and proteins, however, pose a big challenge due to the problem of dipolar truncation. Here, we present novel two-dimensional (2D) solid-state NMR experiments capable of extracting distances between carbonyl ({sup 13}C?) and aliphatic ({sup 13}C{sub aliphatic}) spins with high accuracy. The method is based on an improved version of the four-oscillating field (FOLD) technique [L. A. Straasø, M. Bjerring, N. Khaneja, and N. C. Nielsen, J. Chem. Phys. 130, 225103 (2009)] which circumvents the problem of dipolar truncation, thereby offering a base for accurate extraction of internuclear distances in many-spin systems. The ability to extract reliable accurate distances is demonstrated using one- and two-dimensional variants of the FOLD experiment on uniformly {sup 13}C,{sup 15}N-labeled-L-isoleucine. In a more challenging biological application, FOLD 2D experiments are used to determine a large number of {sup 13}C?-{sup 13}C{sub aliphatic} distances in amyloid fibrils formed by the SNNFGAILSS fibrillating core of the human islet amyloid polypeptide with uniform {sup 13}C,{sup 15}N-labeling on the FGAIL fragment.

  14. 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.

  15. I-Love-Q relations for gravastars and the approach to the black-hole limit

    E-Print Network [OSTI]

    Pani, Paolo

    2015-01-01

    The multipole moments and the tidal Love numbers of neutron stars and quark stars satisfy certain relations which are almost insensitive to the star's internal structure. A natural question is whether the same relations hold for different compact objects and how they possibly approach the black-hole limit. Here we consider "gravastars," which are hypothetical compact objects sustained by their internal vacuum energy. Such solutions have been proposed as exotic alternatives to the black-hole paradigm because they can be as compact as black holes and exist in any mass range. By constructing slowly-rotating, thin-shell gravastars to quadratic order in the spin, we compute the moment of inertia $I$, the mass quadrupole moment $Q$, and the tidal Love number $\\lambda$ in exact form. When suitably normalized, these quantities are nonanalytical functions of the compactness of the object. The $I$-$\\lambda$-$Q$ relations of a gravastar are dramatically different from those of an ordinary compact star, but the black-hol...

  16. Development of an integrated, in-situ remediation technology. Draft topical report for task No. 9. Part II. Entitled: TCE degradation using non-biological methods, September 26, 1994--May 25, 1996

    SciTech Connect (OSTI)

    Orth, R.G.; McKenzie, D.E.

    1997-04-01

    Contamination in low permeability soils poses a significant technical challenge to in-situ remediation efforts. Poor accessibility to the contaminants and difficulty in delivery of treatment reagents have rendered existing in-situ treatments such as bioremediation, vapor extraction, pump and treat rather ineffective when applied to low permeability soils present at many contaminated sites. The technology is an integrated in-situ treatment in which established geotechnical methods are used to install degradation zones directly in the contaminated soil and electro-osmosis is utilized to move the contaminants back and forth through those zones until the treatment is completed. The use of zero valence iron for reductive dechlorination of aliphatic chlorinated hydrocarbons is currently under investigation by a number of research groups as a potential method of in-situ treatment of contaminated ground water. The reaction appears to involve the transfer of electrons to chloro-aliphatic compounds by the oxidation of zero valence iron to ferrous iron (Fe{sup +2}). Our studies have indicated that this reaction is consistent with those of corrosion, and as such, can be influenced or increased by the presence of small amounts of metals (5% by weight) such as copper, tin, silver, gold and palladium coated on the iron surface. Incomplete coverage of the iron surface with a more electropositive metal results in an open galvanic cell, which increases the oxidation of iron and facilitates and increases the concurrent reduction of trichloroethylene and other chlorinated aliphatic compounds to the corresponding alkenes and alkanes. Our results show that plating more electropositive metals onto certain iron surfaces results in approximately a factor of ten increase in the dechlorination rate of small organochlorine compounds such as TCE.

  17. Kinetic data base for combustion modeling

    SciTech Connect (OSTI)

    Tsang, W.; Herron, J.T. [National Institute of Standards and Technology, Gaithersburg, MD (United States)

    1993-12-01

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

  18. Mechanistic and Structural Studies of Phenylalanine Hydroxylase from Chromobacterium violaceum 

    E-Print Network [OSTI]

    Panay Escobar, Aram Joel

    2011-10-21

    intermediate. iv Kinetic isotope effects were used to study the hydroxylation of the aliphatic substrate cyclohexylalanine. The Dkcat value with [1,2,2,3,3,4,4,5,5,6,6-2H11]- cyclohexylalanine is unity with wild-type CvPheH, suggesting that chemistry... Page 4.2 Chemical mechanism of aromatic amino acid hydroxylation .................... 60 4.3 Time course at 5 ?C for the formation of tyrosine from the reaction of CvPheH (1.6 mM):Fe(II) (1.5 mM):6-MePH4 (5 mM):Phe (5 mM): with an equal...

  19. Atomic Structures of Graphene, Benzene and Methane with Bond Lengths as Sums of the Single, Double and Resonance Bond Radii of Carbon

    E-Print Network [OSTI]

    Raji Heyrovska

    2008-04-25

    Two dimensional layers of graphene are currently drawing a great attention in fundamental and applied nanoscience. Graphene consists of interconnected hexagons of carbon atoms as in graphite. This article presents for the first time the structures of graphene at the atomic level and shows how it differs from that of benzene, due to the difference in the double bond and resonance bond based radii of carbon. The carbon atom of an aliphatic compound such as methane has a longer covalent single bond radius as in diamond. All the atomic structures presented here have been drawn to scale.

  20. 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 (M–1)– 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.

  1. 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)

  2. Reuse of Drill Cutting Ash as a Stabilizing Agent for Niger Delta Soils

    E-Print Network [OSTI]

    Alayaki, F. M.; Al-Tabbaa, A.; Ayotamuno, M. J.

    2015-01-01

    operations. The waste product is a mixture of drilling mud (type depends on the crude oil company), base fluid (water, oil, or synthetic-oil), and crude oil. The waste product is stock-piled according to source/company and treated accordingly... . This was followed by clean-up and separation into aliphatic and aromatic fractions in a 10mm chromatographic column. The aromatic fraction was then concentrated to 1ml, transferred into the vials and analysed using Agilent 6890N/5975C GC/MS previously calibrated...

  3. The peculiar dust shell of Nova DZ Cru (2003).

    SciTech Connect (OSTI)

    Evans, A.; Gehrz, R. D.; Woodward, C. E.; Helton, L. A.; Rushton, M. T.; Bode, M. F.; Krautter, J.; Lyke, J.; Lynch, D. K.; Ness, J.-U.; Starrfield, S.; Truran, J. W.; Wagner, R. M.; Physics; Keele Univ.; Univ. of Minnesota; Univ. of Central Lancashire; Liverpool John Moores Univ.; Zentrum fur Astronomie der Univ. Heidelberg; M. W. Keck Observatory; The Aerospace Corp.; European Space Astronomy Centre; Arizona State Univ.; Univ. of Chicago; Large Binocular Telscope Observatory

    2010-01-01

    We present Spitzer Space Telescope observations of the 'peculiar variable' DZ Cru, identified by Rushton et al. as a classical nova. A dust shell, on which are superimposed a number of features, is prominent in the 5-35 {micro}m range some 4 yr after eruption. We suggest that the dust in DZ Cru is primarily hydrogenated amorphous carbon in which aliphatic bands currently predominate and which may become either predominantly aromatic as the dust is photoprocessed by ultraviolet radiation from the stellar remnant or more likely completely destroyed.

  4. R.W. Winters- The Texas Aggie 

    E-Print Network [OSTI]

    Unknown

    2011-08-17

    Sciences College of Pharmacy Chairman of' Advisory Committee: Mr. Charles L. Gilmore The effects of' shipment on recovery was investigated for three aliphatic hydrocarbons adsorbed on the 3M Company's $3500 Organic Vapor Monitor and the Scientific Kit... the course of this research. Their help and friendship has been invaluable. I would like to thank Dr's. Leon Anders and Frank Snowden of the 3M Company for the help they have given me. A special thanks must also go to Mr. Rod Simmons and Dr . Alan Hanks...

  5. Anodic polymerization of vinyl ethylene carbonate in Li-Ion battery electrolyte

    SciTech Connect (OSTI)

    Chen, Guoying; Zhuang, Guorong V.; Richardson, Thomas J.; Gao, Liu; Ross Jr., Philip N.

    2005-02-28

    A study of the anodic oxidation of vinyl ethylene carbonate (VEC) was conducted with post-mortem analysis of reaction products by ATR-FTIR and gel permeation chromatography (GPC). The half-wave potential (E1/2) for oxidation of VEC is ca. 3.6 V producing a resistive film on the electrode surface. GPC analysis of the film on a gold electrode produced by anodization of a commercial Li-ion battery electrolyte containing 2 percent VEC at 4.1 V showed the presence of a high molecular weight polymer. IR analysis indicated polycarbonate with alkyl carbonate rings linked by aliphatic methylene and methyl branches.

  6. 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)? solute and the anions and cations of four different ionic liquids (ILs) are investigated by 2D NMR nuclear Overhauser effect (NOE) techniques, including {¹H-¹?F} 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)? 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)? 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

  7. 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.

  8. The Transit Transmission Spectrum of a Cold Gas Giant Planet

    E-Print Network [OSTI]

    Dalba, Paul A; Fortney, Jonathan J; Hedman, Matthew M; Nicholson, Philip D; Veyette, Mark J

    2015-01-01

    We use solar occultations observed by the Visual and Infrared Mapping Spectrometer aboard the Cassini Spacecraft to extract the 1 to 5 micron transmission spectrum of Saturn, as if it were a transiting exoplanet. We detect absorption from methane, ethane, acetylene, aliphatic hydrocarbons, and possibly carbon monoxide with peak-to-peak features of up to 90 parts-per-million despite the presence of ammonia clouds. We also find that atmospheric refraction, as opposed to clouds or haze, determines the minimum altitude that could be probed during mid-transit. Self-consistent exoplanet atmosphere models show good agreement with Saturn's transmission spectrum but fail to reproduce a large absorption feature near 3.4 microns likely caused by gaseous ethane and a C-H stretching mode of an unknown aliphatic hydrocarbon. This large feature is located in one of the Spitzer Space Telescope bandpasses and could alter interpretations of transmission spectra if not properly modeled. The large signal in Saturn's transmission...

  9. Safe epoxy encapsulant for high voltage magnetics

    SciTech Connect (OSTI)

    Sanchez, R.O.; Archer, W.E.

    1998-01-01

    This paper describes the use of Formula 456, an aliphatic amine cured epoxy for impregnating coils and high voltage transformers. Sandia has evaluated a number of MDA-free epoxy encapsulants which relied on either anhydride or other aromatic amine curing agents. The use of aliphatic amine curing agents was more recently evaluated and has resulted in the definition of Formula 456 resin. Methylene dianiline (MDA) has been used for more than 20 years as the curing agent for various epoxy formulations throughout the Department of Energy and much of industry. Sandia National Laboratories began the process of replacing MDA with other formulations because of regulations imposed by OSHA on the use of MDA. OSHA has regulated MDA because it is a suspect carcinogen. Typically the elimination of OSHA-regulated materials provides a rare opportunity to qualify new formulations in a range of demanding applications. It was important to take full advantage of that opportunity, although the associated materials qualification effort was costly. Small high voltage transformers are one of those demanding applications. The successful implementation of the new formulation for high reliability transformers will be described. The test results that demonstrate the parts are qualified for use in DOE weapon systems will be presented.

  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. 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

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

    SciTech Connect (OSTI)

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

    1988-12-01

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

  13. First-Principles Studies of Photoinduced Charge Transfer in Noncovalently Functionalized Carbon Nanotubes

    E-Print Network [OSTI]

    Chu, Iek-Heng; Cheng, Hai-Ping

    2013-01-01

    We have studied the energetics, electronic structure, optical excitation, and electron relaxation of dinitromethane molecules (CH$_{2}$N$_{2}$O$_{4}$) adsorbed on semiconducting carbon nanotubes (CNTs) of chiral index (n,0) (n=7, 10, 13, 16, 19). Using first-principles density functional theory (DFT) with generalized gradient approximations and van der Waals corrections, we have calculated adsorption energies of dinitropentylpyrene, in which the dinitromethane is linked to the pyrene via an aliphatic chain, on a CNT. A 75.26 kJ/mol binding energy has been found, which explains why such aliphatic chain-pyrene units can be and have been used in experiments to bind functional molecules to CNTs. The calculated electronic structures show that the dinitromethane introduces a localized state inside the band gap of CNT systems of n=10, 13, 16 and 19; such a state can trap an electron when the CNT is photoexcited. We have therefore investigated the dynamics of intra-band relaxations using the reduced density matrix fo...

  14. Characterization of the surface properties of Illinois basin coals. Final technical report, September 1, 1991--August 31, 1992

    SciTech Connect (OSTI)

    Demir, I.; Harvey, R.D.; Lizzio, A.A. [Illinois State Geological Survey, Champaign, IL (United States)

    1992-12-31

    Surface area and pore volume distributions, surface charge, and surface chemical structure of the eight coals in the Illinois Basin Coal Sample Program (IBCSP) were determined. The IBC-101 coal has the lowest total and micropore (3.5-20.0 {Angstrom}) surface areas. The IBC-103 coal has the lowest mesopore (20-500 {Angstrom}) surface area. The mesopore surface areas of IBC-101, IBC-102, and IBC-107 coals are higher than the other four coals. Pore volume in pores <1800 {Angstrom} in diameter varies almost five-fold with IBC-103 coal having the lowest value. These differences may affect the reactivity of these coals during cleaning, conversion, and combustion processes. Surface charge and isoelectric points vary among the samples. The isoelectric point, where processes such as agglomeration and dewatering is most efficient, shifted to higher pH values for some of the samples upon exposure to air oxidation at room temperature. Diffuse reflectance infrared spectroscopy (DRIS) data indicate that the surfaces of the IBCSP coals contain aromatic hydrocarbon components, aliphatic hydrocarbons, and an aldehyde group. Ball-mill grinding reduced the organic hydroxyls and thus enriched relative concentrations of nonpolar aliphatic functional groups in the samples. The room temperature air oxidation did not cause any significant change on the surface chemical structure of the coals.

  15. Evaluation of control strategies for volatile organic compounds in indoor air (journal article)

    SciTech Connect (OSTI)

    Ramanathan, K.; Debler, V.L.

    1988-01-01

    The paper discusses research which evaluates the application of adsorption techniques to the control of indoor organic vapors. The adsorption on activated carbon of three compounds representing three classes of organic species was studied at 30 C in the concentration range zero to 200 ppb using a microbalance. The three were benzene (aromatic), acetaldehyde (oxygenated aliphatic), and 1,1,1-trichloroethane (halogenated aliphatic). Three sorbents (a wood base carbon, a coal base carbon, and a coconut shell base carbon) were examined. Uptakes for all the compounds on all the carbons were low (on the order of 10 to the minus 7th power gmol/g carbon). Simulation of a packed bed of carbon indicated that carbon adsorption may not be practical for continuous removal, but may be applicable to sudden releases (e.g., spills). Potential alternatives to activated carbon adsorption are discussed. Potentially toxic organic vapors are emitted from a wide variety of building materials, consumer products, and human activities. Control of indoor organic vapors generally involves removing the source and/or increasing the ventilation rate. The ubiquitous nature of sources of organic vapors generally makes source removal impractical. Increased ventilation causes increased energy usage with its resultant economic penalties. Therefore, practical removal methods are needed.

  16. Far- and mid-infrared spectroscopy of complex organic matter of astrochemical interest: coal, heavy petroleum fractions, and asphaltenes

    E-Print Network [OSTI]

    Cataldo, F; Manchado, A

    2012-01-01

    The coexistence of a large variety of molecular species (i.e., aromatic, cycloaliphatic and aliphatic) in several astrophysical environments suggests that unidentified IR emission (UIE) occurs from small solid particles containing a mix of aromatic and aliphatic structures (e.g., coal, petroleum, etc.), renewing the astronomical interest on this type of materials. A series of heavy petroleum fractions namely DAE, RAE, BQ-1, and asphaltenes derived from BQ-1 were used together with anthracite coal and bitumen as model compounds in matching the band pattern of the emission features of proto-planetary nebulae (PPNe). All the model materials were examined in the mid-infrared (2.5-16.7 um) and for the first time in the far-infrared (16.7-200 um), and the IR bands were compared with the UIE from PPNe. The best match of the PPNe band pattern is offered by the BQ-1 heavy aromatic oil fraction and by its asphaltenes fraction. Particularly interesting is the ability of BQ-1 to match the band pattern of the aromatic-ali...

  17. Crosslinked Polyamide

    DOE Patents [OSTI]

    Huang, Zhi H. (East Lansing, MI); McDonald, William F. (Utica, OH); Wright, Stacy C. (Lansing, MI); Taylor, Andrew C. (Ann Arbor, MI)

    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.

  18. 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.

  19. 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.

  20. 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.

  1. 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.

  2. 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).

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

    DOE Patents [OSTI]

    Sen, Ayusman (State College, PA); Jiang, Zhaozhong (State College, PA)

    1996-01-01

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

  4. 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.

  5. 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.

  6. 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.

  7. Nonhazardous solvent composition and method for cleaning metal surfaces

    DOE Patents [OSTI]

    Googin, John M. (Oak Ridge, TN); Simandl, Ronald F. (Farragut, TN); Thompson, Lisa M. (Knoxville, TN)

    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.

  8. 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.

  9. Bending elasticity of a curved amphiphilic film decorated anchored copolymers: a small angle neutron scattering study

    E-Print Network [OSTI]

    Jacqueline Appell; Christian Ligoure; Gregoire Porte

    2004-06-30

    Microemulsion droplets (oil in water stabilized by a surfactant film) are progressively decorated with increasing amounts of poly ethylene- oxide (PEO) chains anchored in the film by the short aliphatic chain grafted at one end of the PEO chain . The evolution of the bending elasticity of the surfactant film with increasing decoration is deduced from the evolution in size and polydispersity of the droplets as reflected by small angle neutron scattering. The optimum curvature radius decreases while the bending rigidity modulus remains practically constant. The experimental results compare well with the predictions of a model developed for the bending properties of a curved film decorated by non-adsorbing polymer chains, which takes into account, the finite curvature of the film and the free diffusion of the chains on the film.

  10. Reactor and method for hydrocracking carbonaceous material

    DOE Patents [OSTI]

    Duncan, Dennis A. (Downers Grove, IL); Beeson, Justin L. (Clarendon Hills, IL); Oberle, R. Donald (Hammond, IN); Dirksen, Henry A. (Harvey, IL)

    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.

  11. On the origin of the 11.3 micron unidentified infrared emission feature

    E-Print Network [OSTI]

    Sadjadi, SeyedAbdolreza; Kwok, Sun

    2015-01-01

    The 11.3 $\\mu$m emission feature is a prominent member of the family of unidentified infrared emission (UIE) bands and is frequently attributed to out-of-plane bending modes of polycyclic aromatic hydrocarbon (PAH) molecules. We have performed quantum mechanical calculations of 60 neutral PAH molecules and found that it is difficult to reconcile the observed astronomical feature with any or a mix of these PAH molecules. We have further analyzed the fitting of spectra of several astronomical objects by the NASA PAH database program and found that reasonable fittings to the observed spectra are only possible by including significant contributions from oxygen and/or magnesium containing molecules in the mix. A mixed of pure PAH molecules, even including units of different sizes, geometry and charged states, is unable to fit the astronomical spectra. Preliminary theoretical results on the vibrational spectra of simple molecules with mixed aromatic/aliphatic structures show that these structures have consistent bu...

  12. Systematic modulation and enhancement of CO{sub 2} : N{sub 2} selectivity and water stability in an isoreticular series of bio-MOF-11 analogues

    SciTech Connect (OSTI)

    Li, Tao; Chen, De-Li; Sullivan, Jeanne E.; Kozlowski, Mark T.; Johnson, J. Karl; Rosi, Nathaniel L.

    2013-02-01

    An isoreticular series of cobalt-adeninate bio-MOFs (bio-MOFs 11-14) is reported. The pores of bio-MOFs 11-14 are decorated with acetate, propionate, butyrate, and valerate, respectively. The nitrogen (N{sub 2}) and carbon dioxide (CO{sub 2}) adsorption properties of these materials are studied and compared. The isosteric heats of adsorption for CO{sub 2} are calculated, and the CO{sub 2}:N{sub 2} selectivities for each material are 10 determined. As the lengths of the aliphatic chains decorating the pores in bio-MOFs 11-14 increase, the BET surface areas decrease from 1148 m{sup 2}/g to 17 m{sup 2}/g while the CO{sub 2}:N{sub 2} selectivities predicted from ideal adsorbed solution theory at 1 bar and 273 K for a 10:90 CO{sub 2}:N{sub 2} mixture range from 73:1 for bio-MOF-11 to 123:1 for bio-MOF-12 and finally to 107:1 for bio-MOF-13. At 298 K, the selectivities are 43:1 for bio-MOF-11, 52:1 for bio-MOF-12, and 40:1 for bio-MOF-13. Additionally, it is shown that 15 bio-MOF-14 exhibits a unique molecular sieving property that allows it to adsorb CO{sub 2} but not N{sub 2} at 273 and 298 K. Finally, the water stability of bio-MOFs 11-14 increases with increasing aliphatic chain length. Bio-MOF-14 exhibits no loss of crystallinity or porosity after soaking in water for one month.

  13. Fluoroalkyl and Alkyl Chains Have Similar Hydrophobicities in Binding to the “Hydrophobic Wall” of Carbonic Anhydrase

    SciTech Connect (OSTI)

    J Mecinovic; P Snyder; K Mirica; S Bai; E Mack; R Kwant; D Moustakas; A Heroux; G Whitesides

    2011-12-31

    The hydrophobic effect, the free-energetically favorable association of nonpolar solutes in water, makes a dominant contribution to binding of many systems of ligands and proteins. The objective of this study was to examine the hydrophobic effect in biomolecular recognition using two chemically different but structurally similar hydrophobic groups, aliphatic hydrocarbons and aliphatic fluorocarbons, and to determine whether the hydrophobicity of the two groups could be distinguished by thermodynamic and biostructural analysis. This paper uses isothermal titration calorimetry (ITC) to examine the thermodynamics of binding of benzenesulfonamides substituted in the para position with alkyl and fluoroalkyl chains (H{sub 2}NSO{sub 2}C{sub 6}H{sub 4}-CONHCH{sub 2}(CX{sub 2}){sub n}CX{sub 3}, n = 0-4, X = H, F) to human carbonic anhydrase II (HCA II). Both alkyl and fluoroalkyl substituents contribute favorably to the enthalpy and the entropy of binding; these contributions increase as the length of chain of the hydrophobic substituent increases. Crystallography of the protein-ligand complexes indicates that the benzenesulfonamide groups of all ligands examined bind with similar geometry, that the tail groups associate with the hydrophobic wall of HCA II (which is made up of the side chains of residues Phe131, Val135, Pro202, and Leu204), and that the structure of the protein is indistinguishable for all but one of the complexes (the longest member of the fluoroalkyl series). Analysis of the thermodynamics of binding as a function of structure is compatible with the hypothesis that hydrophobic binding of both alkyl and fluoroalkyl chains to hydrophobic surface of carbonic anhydrase is due primarily to the release of nonoptimally hydrogen-bonded water molecules that hydrate the binding cavity (including the hydrophobic wall) of HCA II and to the release of water molecules that surround the hydrophobic chain of the ligands. This study defines the balance of enthalpic and entropic contributions to the hydrophobic effect in this representative system of protein and ligand: hydrophobic interactions, here, seem to comprise approximately equal contributions from enthalpy (plausibly from strengthening networks of hydrogen bonds among molecules of water) and entropy (from release of water from configurationally restricted positions).

  14. Chemical analysis and biological testing of materials from the EDS coal liquefaction process: a status report

    SciTech Connect (OSTI)

    Later, D.W.; Pelroy, R.A.; Wilson, B.W.

    1984-05-01

    Representative process materials were obtained from the EDS pilot plant for chemical and biological analyses. These materials were characterized for biological activity and chemical composition using a microbial mutagenicity assay and chromatographic and mass spectrometric analytical techniques. The two highest boiling distillation cuts, as well as process solvent (PS) obtained from the bottoms recycle mode operation, were tested for initiation of mouse skin tumorigenicity. All three materials were active; the crude 800/sup 0 +/F cut was substantially more potent than the crude bottoms recycle PS or 750 to 800/sup 0/F distillate cut. Results from chemical analyses showed the EDS materials, in general, to be more highly alkylated and have higher hydroaromatic content than analogous SRC II process materials (no in-line process hydrogenation) used for comparison. In the microbial mutagenicity assays the N-PAC fractions showed greater activity than did the aliphatic hydrocarbon, hydroxy-PAH, or PAH fractions, although mutagenicity was detected in certain PAH fractions by a modified version of the standard microbial mutagenicity assay. Mutagenic activities for the EDS materials were lower, overall, than those for the corresponding materials from the SRC II process. The EDS materials produced under different operational modes had distinguishable differences in both their chemical constituency and biological activity. The primary differences between the EDS materials studied here and their SRC II counterparts used for comparison are most likely attributable to the incorporation of catalytic hydrogenation in the EDS process. 27 references, 28 figures, 27 tables.

  15. Complexation of Am(III) and Nd(III) by 1,10-Phenanthroline-2,9-Dicarboxylic Acid

    SciTech Connect (OSTI)

    Ogden, Mark D.; Sinkov, Sergey I.; Nilsson, Mikael; Lumetta, Gregg J.; Hancock, Robert D.; Nash, Ken L.

    2013-01-01

    The complexant 1,10-phenanthroline-2,9-dicarboxylic acid (PDA) is a planar tetradentate ligand that is more preorganized for metal complexation than its unconstrained analogue ethylendiiminodiacetic acid (EDDA). Furthermore, the backbone nitrogen atoms of PDA are aromatic, hence are softer than the aliphatic amines of EDDA. It has been hypothesized that PDA will selectively bond to trivalent actinides over lanthanides. In this report, the results of spectrophotometric studies of the complexation of Nd(III) and Am(III) by PDA are reported. Because the complexes are moderately stable, it was necessary to conduct these titrations using competitive equilibrium methods, competitive cation omplexing between PDA and diethylenetriaminepentaacetic acid, and competition between ligand protonation and complex formation. Stability constants and ligand protonation constants were determined at 0.1 mol/L ionic strength and at 0.5 mol/L ionic strength nitrate media at 21 ± 1 C. The stability constants are lower than those predicted from first principles and speciation calculations indicate that Am(III) selectivity over Nd(III) is less than that exhibited by 1,10-phenanthroline.

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

    SciTech Connect (OSTI)

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

    1981-01-01

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

  17. Analysis of volatile contaminants in US Navy fleet soda lime. Technical report, August 1992-May 1995

    SciTech Connect (OSTI)

    Lillo, R.S.; Ruby, R.; Gummin, D.D.; Porter, W.R.; Caldwell, J.M.

    1995-06-01

    Contamination was suspected of U.S. Navy Fleet soda lime (High Performance Sodasorb(R)) when an ammonia-like odor was reported during its use in August 1992. This material contained indicator dye and was used for carbon dioxide absorption during diving. This incident had a major impact on the U.S Navy diving program when the Navy temporarily banned use of Sodasorb(R) and authorized Sofnolime(R) as an interim replacement. The Naval Medical Research Institute was immediately assigned to investigate. Testing involved sampling from the headspace (gas space) inside closed buckets and from an apparatus simulating conditions during operational diving. Volatile organic compounds were analyzed by gas chromatography and mass spectrometry; ammonia and amines were measured by infrared spectroscopy. Significant amounts of ammonia (up to 30 ppm), ethyl and diethyl amines (up to several ppm), and various aliphatic hydrocarbons (up to 60 ppm) were detected during testing of both Sodasorb(R) and Sofnolime(R). Contaminants were slowly removed by gas flow and did not return. The source(s) of the ammonia and amines are unknown, although they may result from the breakdown of the indicator dye. Hydrocarbon contamination appeared to result from the materials of which the bucket is constructed. Based on these findings, the U.S. Navy is expected to phase in non-indicating soda lime that will be required to meet defined contaminant limits.

  18. CHARACTERIZATION AND EVALUATION OF CAUSTIC WASH TANK AND SOLVENT HOLD TANK SAMPLES FROM MCU FROM AUGUST TO SEPTEMBER 2011

    SciTech Connect (OSTI)

    Fondeur, F.; Fink, S.

    2012-08-01

    During processing of Salt Batches 3 and 4 in the Modular Caustic-Side Solvent Extraction Unit (MCU), the decontamination efficiency for cesium declined from historical values and from expectations based on laboratory testing. This report documents efforts to analyze samples of solvent and process solutions from MCU in an attempt to understand the cause of the reduced performance and to recommend mitigations. CWT Solutions from MCU from the time period of variable decontamination factor (DF) performance which covers from April 2011 to September 2011 (during processing of Salt Batch 4) were examined for impurities using chromatography and spectroscopy. The results indicate that impurities were found to be of two types: aromatic containing impurities most likely from Modifier degradation and aliphatic type impurities most likely from Isopar{reg_sign} L and tri-n-octylamine (TOA) degradation. Caustic washing the Solvent Hold Tank (SHT) solution with 1M NaOH improved its extraction ability as determined from {sup 22}Na uptake tests. Evidence from this work showed that pH variance in the aqueous solutions within the range of 1M nitric acid to 1.91M NaOH that contacted the solvent samples does not influence the analytical determination of the TOA concentration by GC-MS.

  19. 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.

  20. Non-Ideal Behavior in Solvent Extraction

    SciTech Connect (OSTI)

    Peter Zalupski

    2011-09-01

    This report presents a summary of the work performed to meet FCR&D level 3 milestone M31SW050801, 'Complete the year-end report summarizing FY11 experimental and modeling activities.' This work was carried out under the auspices of the Non-Ideality in Solvent Extraction Systems FCR&D work package. The report summarizes our initial considerations of potential influences that non-ideal chemistry may impose on computational prediction of outcomes in solvent extraction systems. The report is packaged into three separate test cases where a robustness of the prediction by SXFIT program is under scrutiny. The computational exercises presented here emphasize the importance of accurate representation of both an aqueous and organic mixtures when modeling liquid-liquid distribution systems. Case No.1 demonstrates that non-ideal behavior of HDEHP in aliphatic diluents, such as n-dodecane, interferes with the computation. Cases No.2 and No.3 focus on the chemical complexity of aqueous electrolyte mixtures. Both exercises stress the need for an improved thermodynamic model of an aqueous environment present in the europium distribution experiments. Our efforts for year 2 of this project will focus on the improvements of aqueous and non-aqueous solution models using fundamental physical properties of mixtures acquired experimentally in our laboratories.

  1. 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.

  2. 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.

  3. Spectropolarimetry of the 3.4 micron Feature in the Diffuse ISM toward the Galactic Center Quintuplet Cluster

    E-Print Network [OSTI]

    J. E. Chiar; A. J. Adamson; D. C. B. Whittet; A. Chrysostomou; J. H. Hough; T. H. Kerr; R. E. Mason; P. F. Poche; G. Wright

    2006-07-12

    Aliphatic hydrocarbons exhibit an absorption feature at 3.4 micron observed toward sources that sample diffuse regions of the interstellar medium. The absorbers responsible for this feature are assumed to reside in some component of interstellar dust, but the physical nature of the particles (size, shape, structure, etc.) is uncertain. Observations of interstellar polarization provide discrimination. Since the grains that carry the silicate absorption feature are known to be aligned, polarization across the 3.4 micron hydrocarbon feature can be used to test the silicate core-organic refractory mantle grain theory. Although the 3.4 micron feature has been observed to be devoid of polarization for one line of sight toward the Galactic center, a corresponding silicate polarization measurement for the same line of sight was not available. Here, we present spectropolarimetric observations toward GCS 3-II and GCS 3-IV toward the Galactic center, where the 9.7 micron silicate polarization has been previously observed. We show that polarization is not detected across the 3.4 micron feature to a limit of 0.06 +/- 0.13% (GCS 3-II) and 0.15 +/- 0.31% (GCS 3-IV), well below the lowest available prediction of polarization on the basis of the core-mantle model. We conclude that the hydrocarbons in the diffuse ISM do not reside on the same grains as the silicates and likely form a separate population of small grains.

  4. Interfacial activity of phosphonated-polyethylene glycol functionalized cerium oxide nanoparticles

    E-Print Network [OSTI]

    L. Qi; J. Fresnais; P. Muller; O. Theodoly; J. -F. Berret; J. -P. Chapel

    2013-05-04

    In a recent publication, we have highlighted the potential of phosphonic acid terminated PEG oligomers to functionalize strong UV absorption cerium oxide nanoparticles[1], which yield suspensions that are stable in aqueous or organic solvents and are redispersible in different solvent after freeze-drying. In the present work, we highlight the interfacial activity of the functional ceria nanoparticles and their potential to modify hydrophobic surfaces. We first investigated Phosphonated-PEG amphiphilic oligomers behavior as strong surface active species forming irreversibly adsorbed layers. We then show that the oligomers interfacial properties translate to the functional nanoparticles. In particular, the addition of a small fraction of phosphonated-PEG oligomers with an extra C16 aliphatic chain (stickers) into the formulation enabled the tuning of i) the nanoparticles adsorption at the air/water, polystyrene/water, oil/water interfaces and ii) the particle/particle interaction in aqueous solutions. We also found that dense and closely packed two dimensional monolayers of nanoceria can be formed by spontaneous adsorption or surface compression using a Langmuir trough. A hexagonal organization controlled by reversible and repulsive repulsion has been characterized by GISAXS. Mono- or multilayers can also be stably formed or transferred on solid surfaces. Our results are key features in the field of polymer surface modification, solid stabilized emulsions (Pickering) or supracolloidal assemblies.

  5. 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.

  6. 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 actinide–lanthanide separations, a series of tetradentate N-donor ligands have been synthesized and their complexation of americium(III) and neodymium(III) investigated by UV–visible 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.

  7. 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.

  8. Process for hydrocracking carbonaceous material in liquid carrier

    DOE Patents [OSTI]

    Duncan, Dennis A. (Downers Grove, IL)

    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.

  9. 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.

  10. 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.

  11. 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.

  12. 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 Santé et de la Recherche Médicale (INSERM) and INTS, France] [Institut National de la Santé et de la Recherche Médicale (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.

  13. 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.

  14. 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.

  15. 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.

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

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

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

    2015-06-16

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

  17. 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.

  18. Complex Organic and Inorganic Compounds in Shells of Lithium-rich K Giant Stars

    E-Print Network [OSTI]

    de la Reza, Ramiro; Oliveira, Isa; Rengaswamy, Sridharan

    2015-01-01

    Hydrocarbon organic material, as found in the interstellar medium, exists in complex mixtures of aromatic and aliphatic forms. It is considered to be originated from carbon enriched giant stars during their final stages of evolution, when very strong mass loss occurs in a few thousand years on their way to become planetary nebulae. We show here that the same organic compounds appear to be formed in previous stages of the evolution of giant stars. More specifically, during the first ascending giant branch K-type stars. According to our model this happens only when these stars are being abruptly enriched with lithium together with the formation of a circumstellar shell with a strong mass loss during just a few thousand years. This sudden mass loss is, on an average, a thousand times larger than that of normal Li-poor K giant stars. This shell would later be detached, specially when the star stops its Li enrichment and a rapid photospheric Li depletion occurs. In order to gain extra carbon-based material to form...

  19. 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.

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

    SciTech Connect (OSTI)

    Hemmilae, I.

    1985-07-01

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

  1. 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.

  2. 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.

  3. 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.

  4. 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.

  5. Absolute hydrogen determination in coal-derived heavy distillate samples

    SciTech Connect (OSTI)

    Kottenstette, R.J.; Schneider, D.A.; Loy, D.A.

    1994-06-01

    Organic elemental hydrogen analysis is routinely performed with an automated analyzer having a high temperature combustion zone that is connected to a detector which measures the response of the product water. With the advent of instrumental electronics, automated microanalysis gradually replaced the gravimetric techniques mainly because of increased analysis speed. Modern automated organic elemental analysis consists of combusting the sample in the presence of a solid oxidant and sweeping the products into a thermal conductivity of infrared detector [4,5]. An alternative technique for the detection of hydrogen is to react the product water with carbonyldiimidazole to generate a quantitative amount of carbon dioxide which is measured by a coulometric tritration [6]. The development of Proton Nuclear Magnetic Nuclear Resonance Spectroscopy has led to the description and qualitative classification of hydrogen in organic compounds. These techniques have been especially helpful in describing hydrogen as it is classified into aliphatic, aromatic and hydroaromatic groupings [1,2,3]. In addition, low resolution proton {sup 1}H-NMR has been sucessfully used to determine absolute amounts of hydrogen in a variety of petroleum fractions [7,8]. Our technique involves simple integration of high resolution {sup 1}H-NMR spectra with careful attention given to sample preparation and spectral integration.

  6. 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.

  7. 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.

  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. Influence of pressure on coal pyrolysis and char gasification

    SciTech Connect (OSTI)

    Haiping Yang; Hanping Chen; Fudong Ju; Rong Yan; Shihong Zhang [Huazhong University of Science and Technology, Wuhan (China). State Key Laboratory of Coal Combustion

    2007-12-15

    Coal char structure varied greatly with pyrolysis pressure, which has a significant influence on the gasification reactivity. In this study, the influence of pressure on the behavior of coal pyrolysis and physicochemical structure and gasification characteristics of the resultant coal char was investigated using a pressurized thermogravimetric analyzer combined with an ambient thermogravimetric analyzer. First, the pyrolysis of Shenfu (SF) bituminous coal was performed in a pressurized thermogravimetric analyzer (TGA) at different pressures (0.1, 0.8, 1.5, 3, and 5 MPa). The volatile mainly evolved out at 400-800{sup o}C. The gas products are mainly CO{sub 2}, CO, CH{sub 4}, and light aliphatics with some water. It was observed that the pyrolysis of coal was shifted to lower temperature (50{sup o}C) with pressure increasing from ambient to 5 MPa, and the devolatilization rate of coal pyrolysis was decreased and the coal char yield was increased slightly. The structure of solid coal char was analyzed using FTIR, ASAP2020, and CNHS. In the solid char, the main organic functional groups are mainly CO, C-C (alkane), C-H ar, C-O-C, and C=C ar. The carbon content was increased while H content decreased. Finally, the gasification of the solid char was preformed at ambient pressure with CO{sub 2} as gasify agent. The gasification process of coal char can be divided into postpyrolysis and char gasification. Higher pressure accelerated the initial stage of char gasification, and higher gasification reactivity was observed for char derived at 5 MPa. 23 refs., 8 figs., 5 tabs.

  10. 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

  11. 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.

  12. 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.

  13. Desulfurization of organic sulfur from a subbituminous coal by electron-transfer process with K{sub 4}(Fe(CN){sub 6})

    SciTech Connect (OSTI)

    Dipu Borah [Pragjyotika J College, Titabar (India). Department of Chemistry

    2006-02-01

    The desulfurization reaction involving direct electron transfer from potassium ferrocyanide, K{sub 4}(Fe(CN){sub 6}), successfully removed organic sulfur from a subbituminous coal. The temperature variation of desulfurization revealed that increase of temperature enhanced the level of sulfur removal. Moreover, the desulfurization reaction was found to be dependent on the concentration of K{sub 4}(Fe(CN){sub 6}). Gradual increase in the concentration of K{sub 4}(Fe(CN){sub 6}) raised the magnitude of desulfurization, but at higher concentration the variation was not significant. The removal of organic sulfur from unoxidized coal slightly increased with reduced particle size. Desulfurization from oxidized coals (prepared by aerial oxidation) revealed a higher level of sulfur removal in comparison to unoxidized coal. Highest desulfurization of 36.4 wt % was obtained at 90{sup o}C and 0.1 M concentration of K{sub 4}(Fe(CN){sub 6}) in the 100-mesh size oxidized coal prepared at 200{sup o}C. Model sulfur compound study revealed that aliphatic types of sulfur compounds are primarily responsible for desulfurization. Because of higher stability, thiophene and condensed thiophene-type of compounds perhaps remained unaffected by the electron-transfer agent. Infrared study revealed the formation of oxidized sulfur compounds (sulfoxide, sulfone, sulfonic acid, etc.) in the oxidized coals. The desulfurization reaction in different systems is well-represented by the pseudo-first-order kinetic model. Application of the transition state theory indicated that the desulfurization reaction proceeds with the absorption of heat (endothermic reaction) and is nonspontaneous in nature. 53 refs., 6 figs., 3 tabs.

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

    SciTech Connect (OSTI)

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

    2012-10-01

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

  15. 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; Hänninen, 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 Hyvinkää and at the optic separation plant in Hämeenlinna. 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}.

  16. Hydrocarbon biomarkers, thermal maturity, and depositional setting of tasmanite oil shales from Tasmania, Australia

    SciTech Connect (OSTI)

    Revill, A.T.; Volkman, J.K.; O'Leary, T. (CSIRO Division of Oceanography, Tasmania (Australia)); Summons, R.E.; Boreham, C.J. (Australian Geological Survey Organisation, Canberra (Australia)); Banks, M.R.; Denwer, K. (Univ. of Tasmania (Australia))

    1994-09-01

    This study represents the first geological and organic geochemical investigation of samples of tasmanite oil shale representing different thermal maturities from three separate locations in Tasmania, Australia. The most abundant aliphatic hydrocarbon in the immature oil shale from Latrobe is a C[sub 19] tricyclic alkane, whereas in the more mature samples from Oonah and Douglas River low molecular weight n-alkanes dominate the extractable hydrocarbon distribution. The aromatic hydrocarbons are predominantly derivatives of tricyclic compounds, with 1,2,8-trimethylphenanthrene increasing in relative abundance with increasing maturity. Geological and geochemical evidence suggests that the sediments were deposited in a marine environment of high latitude with associated cold waters and seasonal sea-ice. It is proposed that the organism contributing the bulk of the kerogen, Tasmanites, occupied an environmental niche similar to that of modern sea-ice diatoms and that bloom conditions coupled with physical isolation from atmospheric CO[sub 2] led to the distinctive [open quotes]isotopically heavy[close quotes] [delta][sup 13]C values for the kerogen. [delta][sup 13]C data from modern sea-ice diatoms supports this hypothesis. Isotopic analysis of n-alkanes in the bitumen suggests a multiple source from bacteria and algae. On the other hand, the n-alkanes generated from closed-system pyrolysis of the kerogen are mainly derived from the preserved Tasmanites biopolymer algaenan. The tricyclic compounds (mean -8[per thousand]) both in the bitumen and pyrolysate, have a common precursor. They are consistently enriched in [sup 13]C compared with the kerogen and probably have a different source from the n-alkanes. The identification of a location where the maturity of the tasmanite oil shale approaches the [open quotes]oil window[close quotes] raises the possibility that it may be a viable petroleum source rock.

  17. 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.

  18. Behavior of sulfur and chlorine in coal during combustion and boiler corrosion. [Quarterly] technical report, March 1, 1992--May 31, 1992

    SciTech Connect (OSTI)

    Chou, C.L.; Hackley, K.C.; Donnals, G.L.; Cao, J.; Ruch, R.R. [Illinois State Geological Survey, Champaign, IL (United States); Pan, W.P.; Shao, D. [Western Kentucky Univ., Bowling Green, KY (United States)

    1992-10-01

    Four replicate experiments of pyrolysis with quadrupole gas analyzer and ion selective electrode were conducted to monitor the release of chlorine and sulfur from a high-chlorine Illinois coal IBC-109 (0.42% chlorine on dry basis). The chlorine in coal is released solely as HCl, and the HCl release profile shows a broad peak between 250{degree}C and 600{degree}C with a maximum at 445{degree}C. In contrast, the sulfur release profile shows three peaks; the sulfur released around 370{degree}C may be derived from a labile (possibly aliphatic) component of organic sulfur, the main peak at 475{degree}C corresponds to the release of the main component (thiophenic) of organic sulfur, and the third peak at 600{degree} results from the decomposition of pyrite. Sulfur dioxide (SO{sub 2}) is the major sulfur species under an oxidizing condition in the combustion gas; additional gaseous sulfur species (COS and H{sub 2}S) are observed when the atmosphere is changed to a reducing condition. Sodium and chlorine contents in char residues determined by neutron activation analysis showed that 98% of chlorine in coal was volatilized during pyrolysis to 800{degree}C, and all the sodium is retained in the chars. The thermogravimetry-Fourier transform infrared (FTIR) spectroscopy experiments were carried out to characterize gaseous species during pyrolysis of four Illinois coals (IBC-103, -105, -106, and -109). Gas evolution profiles of sulfur (H{sub 2}S, S0{sub 2}, and COS), chlorine (HCl), and nitrogen (NH{sub 3} and HCN) species were determined. Similar release profiles of HCl and NH{sub 3} supported an interpretation that chlorine and nitrogen are closely associated in coal. COS may be formed by reaction of CO with H{sub 2}S in the gas phase.

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

    SciTech Connect (OSTI)

    Ensor, D.D.

    1997-01-01

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

  20. Evolution of Substrate Specificity within a Diverse Family of [beta/alpha]-Barrel-fold Basic Amino Acid Decarboxylases X-ray Structure Determination of Enzymes with Specificity for L-Arginine and Carboxynorspermidine

    SciTech Connect (OSTI)

    Deng, Xiaoyi; Lee, Jeongmi; Michael, Anthony J.; Tomchick, Diana R.; Goldsmith, Elizabeth J.; Phillips, Margaret A. (Sungkyunkwan); (UTSMC)

    2010-08-26

    Pyridoxal 5{prime}-phosphate (PLP)-dependent basic amino acid decarboxylases from the {beta}/{alpha}-barrel-fold class (group IV) exist in most organisms and catalyze the decarboxylation of diverse substrates, essential for polyamine and lysine biosynthesis. Herein we describe the first x-ray structure determination of bacterial biosynthetic arginine decarboxylase (ADC) and carboxynorspermidine decarboxylase (CANSDC) to 2.3- and 2.0-{angstrom} resolution, solved as product complexes with agmatine and norspermidine. Despite low overall sequence identity, the monomeric and dimeric structures are similar to other enzymes in the family, with the active sites formed between the {beta}/{alpha}-barrel domain of one subunit and the {beta}-barrel of the other. ADC contains both a unique interdomain insertion (4-helical bundle) and a C-terminal extension (3-helical bundle) and it packs as a tetramer in the asymmetric unit with the insertions forming part of the dimer and tetramer interfaces. Analytical ultracentrifugation studies confirmed that the ADC solution structure is a tetramer. Specificity for different basic amino acids appears to arise primarily from changes in the position of, and amino acid replacements in, a helix in the {beta}-barrel domain we refer to as the 'specificity helix.' Additionally, in CANSDC a key acidic residue that interacts with the distal amino group of other substrates is replaced by Leu{sup 314}, which interacts with the aliphatic portion of norspermidine. Neither product, agmatine in ADC nor norspermidine in CANSDC, form a Schiff base to pyridoxal 5{prime}-phosphate, suggesting that the product complexes may promote product release by slowing the back reaction. These studies provide insight into the structural basis for the evolution of novel function within a common structural-fold.

  1. A unified algorithm for predicting partition coefficients for PBPK modeling of drugs and environmental chemicals

    SciTech Connect (OSTI)

    Peyret, Thomas [DSEST, Universite de Montreal, Canada H3T 1A8 (Canada); Poulin, Patrick [Consultant, 4009 rue Sylvia Daoust, Quebec City, Quebec, G1X 0A6 (Canada); Krishnan, Kannan, E-mail: kannan.krishnan@umontreal.ca [DSEST, Universite de Montreal, H3T 1A8 (Canada)

    2010-12-15

    The algorithms in the literature focusing to predict tissue:blood PC (P{sub tb}) for environmental chemicals and tissue:plasma PC based on total (K{sub p}) or unbound concentration (K{sub pu}) for drugs differ in their consideration of binding to hemoglobin, plasma proteins and charged phospholipids. The objective of the present study was to develop a unified algorithm such that P{sub tb}, K{sub p} and K{sub pu} for both drugs and environmental chemicals could be predicted. The development of the unified algorithm was accomplished by integrating all mechanistic algorithms previously published to compute the PCs. Furthermore, the algorithm was structured in such a way as to facilitate predictions of the distribution of organic compounds at the macro (i.e. whole tissue) and micro (i.e. cells and fluids) levels. The resulting unified algorithm was applied to compute the rat P{sub tb}, K{sub p} or K{sub pu} of muscle (n = 174), liver (n = 139) and adipose tissue (n = 141) for acidic, neutral, zwitterionic and basic drugs as well as ketones, acetate esters, alcohols, aliphatic hydrocarbons, aromatic hydrocarbons and ethers. The unified algorithm reproduced adequately the values predicted previously by the published algorithms for a total of 142 drugs and chemicals. The sensitivity analysis demonstrated the relative importance of the various compound properties reflective of specific mechanistic determinants relevant to prediction of PC values of drugs and environmental chemicals. Overall, the present unified algorithm uniquely facilitates the computation of macro and micro level PCs for developing organ and cellular-level PBPK models for both chemicals and drugs.

  2. 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.

  3. 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.

  4. Distribution Behavior of U(VI), Pu(IV), Am(III), and Zr(IV) with N,N-Dihexyl Octanamide Under Uranium-Loading Conditions

    SciTech Connect (OSTI)

    Manchanda, V.K.; Ruikar, P.B.; Sriram, S.; Nagar, M.S.; Pathak, P.N.; Gupta, K.K.; Singh, R.K.; Chitnis, R.R.; Dhami, P.S.; Ramanujam, A. [Bhabha Atomic Research Centre (India)

    2001-06-15

    While the tri-n-butyl phosphate (TBP)-based PUREX process has been the workhorse of the nuclear fuel reprocessing industry for the last four and a half decades, a few drawbacks associated with the use of TBP have caused concern to the separation scientists and technologists. These shortcomings may pose a serious challenge particularly during the reprocessing of (a) short cooled thermal reactor fuels, (b) fast reactor fuels with the larger Pu content and significantly higher burn up, and (c) while treating various waste streams for their disposal to the environment. The N,N-dialkyl aliphatic amides have received particular attention as alternate potential extractants for the reprocessing of spent nuclear fuels in view of (a) the innocuous nature of their degradation products, namely, carboxylic acids/amines and (b) the possibility to incinerate the used solvent leading to reduced volume of secondary waste. The physical and chemical properties of these amides are influenced strongly by the nature of alkyl groups. The extractant N,N-dihexyl octanamide (DHOA) was found to be a promising candidate among a large number of extractants studied. Laboratory batch studies as well as mixer settler studies were performed under process conditions with DHOA and compared with those of TBP. DHOA was found to extract Pu(IV) more efficiently than TBP, both at trace-level concentration as well as under uranium loading conditions. In addition, the extraction behavior of Am(III) and Zr(IV) was studied at varying nitric acid concentrations (1 to 6 M). Extraction behavior of uranium at macroconcentrations (9.9 to 157.7 g/l) was carried out at different temperatures, and it was observed that D{sub U} decreased with the increase in U loading as well as with the increase of temperature (in the range 25 to 45 deg. C) and that the two-phase reaction was exothermic in nature. Mixer settler studies on U(VI) revealed that DHOA is similar to TBP during the extraction cycle but better than TBP during the stripping cycle.

  5. Development of Advanced Membranes Technology Platform for Hydrocarbon Separations

    SciTech Connect (OSTI)

    Kalthod, Dr Dilip

    2010-03-01

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

  6. 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.

  7. 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.

  8. Systematic analysis of protein–detergent 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, Pôle API, 300 Boulevard Sébastien Brant, CS10413, 67412 Illkirch CEDEX (France); Brognaro, Hevila [São Paulo State University, UNESP/IBILCE, Caixa Postal 136, São José 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 protein–detergent complexes permits characterization of these complexes in samples as small as 2 µl 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 µl. 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 protein–detergent 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 protein–detergent complexes for crystallization applications.

  9. 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

  10. Mechanistic, Mutational, and Structural Evaluation of a Taxus Phenylalanine Aminomutase

    SciTech Connect (OSTI)

    Feng, Lei; Wanninayake, Udayanga; Strom, Susan; Geiger, James; Walker, Kevin D. (MSU)

    2014-10-02

    The structure of a phenylalanine aminomutase (TcPAM) from Taxus canadensis has been determined at 2.4 {angstrom} resolution. The active site of the TcPAM contains the signature 4-methylidene-1H-imidazol-5(4H)-one prosthesis, observed in all catalysts of the class I lyase-like family. This catalyst isomerizes (S)-{alpha}-phenylalanine to the (R)-{beta}-isomer by exchange of the NH{sub 2}/H pair. The stereochemistry of the TcPAM reaction product is opposite of the (S)-{beta}-tyrosine made by the mechanistically related tyrosine aminomutase (SgTAM) from Streptomyces globisporus. Since TcPAM and SgTAM share similar tertiary- and quaternary-structures and have several highly conserved aliphatic residues positioned analogously in their active sites for substrate recognition, the divergent product stereochemistries of these catalysts likely cannot be explained by differences in active site architecture. The active site of the TcPAM structure also is in complex with (E)-cinnamate; the latter functions as both a substrate and an intermediate. To account for the distinct (3R)-{beta}-amino acid stereochemistry catalyzed by TcPAM, the cinnamate skeleton must rotate the C{sub 1}-C{sub {alpha}} and C{sub ipso}-C{sub {beta}} bonds 180{sup o} in the active site prior to exchange and rebinding of the NH{sub 2}/H pair to the cinnamate, an event that is not required for the corresponding acrylate intermediate in the SgTAM reaction. Moreover, the aromatic ring of the intermediate makes only one direct hydrophobic interaction with Leu-104. A L104A mutant of TcPAM demonstrated an 1.5-fold increase in k{sub cat} and a decrease in K{sub M} values for sterically demanding 3'-methyl-{alpha}-phenylalanine and styryl-{alpha}-alanine substrates, compared to the kinetic parameters for TcPAM. These parameters did not change significantly for the mutant with 4'-methyl-{alpha}-phenylalanine compared to those for TcPAM.

  11. 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.

  12. 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.

  13. Manganese Porphyrins Catalyze Selective C-H Bond Halogenations

    SciTech Connect (OSTI)

    Liu, Wei; Groves, John T

    2010-01-01

    We report a manganese porphyrin mediated aliphatic C?H bond chlorination using sodium hypochlorite as the chlorine source. In the presence of catalytic amounts of phase transfer catalyst and manganese porphyrin Mn(TPP)Cl 1, reaction of sodium hypochlorite with different unactivated alkanes afforded alkyl chlorides as the major products with only trace amounts of oxygenation products. Substrates with strong C?H bonds, such as neopentane (BDE =?100 kcal/mol) can be also chlorinated with moderate yield. Chlorination of a diagnostic substrate, norcarane, afforded rearranged products indicating a long-lived carbon radical intermediate. Moreover, regioselective chlorination was achieved by using a hindered catalyst, Mn(TMP)Cl, 2. Chlorination of trans-decalin with 2 provided 95% selectivity for methylene-chlorinated products as well as a preference for the C2 position. This novel chlorination system was also applied to complex substrates. With 5?-cholestane as the substrate, we observed chlorination only at the C2 and C3 positions in a net 55% yield, corresponding to the least sterically hindered methylene positions in the A-ring. Similarly, chlorination of sclareolide afforded the equatorial C2 chloride in a 42% isolated yield. Regarding the mechanism, reaction of sodium hypochlorite with the Mn{sup III} porphyrin is expected to afford a reactive Mn{sup V}?O complex that abstracts a hydrogen atom from the substrate, resulting in a free alkyl radical and a Mn{sup IV}—OH complex. We suggest that this carbon radical then reacts with a Mn{sup IV}—OCl species, providing the alkyl chloride and regenerating the reactive Mn{sup V}?O complex. The regioselectivity and the preference for CH{sub 2} groups can be attributed to nonbonded interactions between the alkyl groups on the substrates and the aryl groups of the manganese porphyrin. The results are indicative of a bent [Mn{sup v}?O---H---C] geometry due to the C—H approach to the Mn{sup v}?O (d??p?)* frontier orbital.

  14. Ion Exchange and Solvent Extraction: Supramolecular Aspects of Solvent Exchange Volume 21

    SciTech Connect (OSTI)

    Gloe, Karsten [Technischen Universität Dresden] [Technischen Universität Dresden; Tasker, Peter A [ORNL] [ORNL; Oshima, Tatsuya [University of Miyazaki] [University of Miyazaki; Watarai, Hitoshi [Institute for NanoScience Design at Osaka University] [Institute for NanoScience Design at Osaka University; Nilsson, Mikael [University of California, Irvine] [University of California, Irvine

    2013-01-01

    Preface The theme of supramolecular chemistry (SC), entailing the organization of multiple species through noncovalent interactions, has permeated virtually all aspects of chemical endeavor over the past several decades. Given that the observed behavior of discrete molecular species depends upon their weak interactions with one another and with matrix components, one would have to conclude that SC must indeed form part of the fabric of chemistry itself. A vast literature now serves to categorize SC phenomena within a body of consistent terminology. The word supramolecular itself appears in the titles of dozens of books, several journals, and a dedicated encyclopedia. Not surprisingly, the theme of SC also permeates the field of solvent extraction (SX), inspiring the framework for this volume of Ion Exchange and Solvent Extraction. It is attempted in the six chapters of this volume to identify both how supramolecular behavior occurs and is studied in the context of SX and how SC is influencing the current direction of SX. Researchers and practitioners have long dealt with supramolecular interactions in SX. Indeed, the use of polar extractant molecules in nonpolar media virtually assures that aggregative interactions will dominate the solution behavior of SX. Analytical chemists working in the 1930s to the 1950s with simple mono- and bidentate chelating ligands as extractants noted that extraction of metal ions obeyed complicated mass-action equilibria involving complex stoichiometries. As chemists and engineers developed processes for nuclear and hydrometallurgical applications in the 1950s and 1960s, the preference for aliphatic diluents only enhanced the complexity and supramolecular nature of extraction chemistry. Use of physical techniques such as light scattering and vapor-pressure measurements together with various spectroscopic methods revealed organic-phase aggregates from well-defined dimers to small aggregates containing a few extractant molecules to large inverse micelles swollen with water molecules. Extraction systems involving long-chain cations such as alkylammonium species or long-chain anions such as sulfonates or carboxylates proved especially prone to extensive aggregate formation. The related phenomenon of third-phase formation in SX systems, long misunderstood, is now yielding to spectroscopic and scattering techniques showing extensive long-range organization. Over the last 50 years, tools for studying the structure and thermodynamics of aggregation have grown increasingly sophisticated, leading to a rich and detailed understanding of what we can now recognize as SC phenomena in SX. In the 1970s and 1980s, the rapid growth of SC elicited a paradigm shift in SX. The influence of SC principles had two major effects on the course of SX research. First, it provided a framework for understanding the supramolecular behavior that was already well appreciated in the field of SX, though earlier without the SC terminology. Second, it provided the conceptual tools to control supramolecular behavior in SX, direct it for intended functionality, and to simplify it. Extraction by designed reagents has been steadily progressing ever since, with commercial applications emerging to successfully validate this approach. With the discovery of crown ethers in the late 1960s, the advancement of extractant design has fruitfully employed the concept of inclusion. While considerable initial progress occurred with such molecules, especially because of their affinity and selectivity for alkali and alkaline earth metals, other molecular platforms such as calixarenes have proven more versatile. Multidentate receptors for partial to full inclusion of cations, anions, ion pairs, as well as neutral species, have now become commonplace for selective extraction. This volume of Ion Exchange and Solvent Extraction examines how the principles of SC are being employed both in advancing the design of new highly selective SX systems and in understanding aggregation phenomena in SX systems. Chapter 1 discusses the nature and definition of SC

  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. 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.

  17. 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.

  18. 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.

  19. IMPROVED ANTIFOAM AGENT STUDY END OF YEAR REPORT, EM PROJECT 3.2.3

    SciTech Connect (OSTI)

    Lambert, D.; Koopman, D.; Newell, J.

    2011-09-30

    Antifoam 747 is added to minimize foam produced by process gases and water vapor during chemical processing of sludge in the Defense Waste Processing Facility (DWPF). This allows DWPF to maximize acid addition and evaporation rates to minimize the cycle time in the Chemical Processing Cell (CPC). Improvements in DWPF melt rate due to the addition of bubblers in the melter have resulted in the need for further reductions in cycle time in the CPC. This can only be accomplished with an effective antifoam agent. DWPF production was suspended on March 22, 2011 as the result of a Flammable Gas New Information/(NI) Potential Inadequacy in the Safety Analysis (PISA). The issue was that the DWPF melter offgas flammability strategy did not take into account the H and C in the antifoam, potentially flammable components, in the melter feed. It was also determined the DWPF was using much more antifoam than anticipated due to a combination of longer processing in the CPC due to high Hg, longer processing due to Actinide Removal Process (ARP)/Modular Caustic Side Solvent Extraction Unit (MCU) additions, and adding more antifoam than recommended. The resolution to the PISA involved and assessment of the impact of the antifoam on melter flammability and the implementation of a strategy to control additions within acceptable levels. This led to the need to minimize the use of Antifoam 747 in processing beginning in May 2011. DWPF has had limited success in using Antifoam 747 in caustic processing. Since starting up the ARP facility, the ARP product (similar chemically to caustic sludge) is added to the Sludge Receipt and Adjustment Tank (SRAT) at boiling and evaporated to maintain a constant SRAT volume. Although there is very little offgas generated during caustic boiling, there is a large volume of water vapor produced which can lead to foaming. High additions and more frequent use of antifoam are used to mitigate the foaming during caustic boiling. The result of these three issues above is that DWPF had three antifoam needs in FY2011: (1) Determine the cause of the poor Antifoam 747 performance during caustic boiling; (2) Determine the decomposition products of Antifoam 747 during CPC processing; and (3) Improve the effectiveness of Antifoam 747, in order to minimize the amount used. Testing was completed by Illinois Institute of Technology (IIT) and Savannah River National Laboratory (SRNL) researchers to address these questions. The testing results reported were funded by both DWPF and DOE/EM 31. Both sets of results are reported in this document for completeness. The results of this research are summarized: (1) The cause for the poor Antifoam 747 performance during caustic boiling was the high hydrolysis rate, cleaving the antifoam molecule in two, leading to poor antifoam performance. In testing with pH solutions from 1 to 13, the antifoam degraded quickly at a pH < 4 and pH > 10. As the antifoam decomposed it lost its spreading ability (wetting agent performance), which is crucial to its antifoaming performance. During testing of a caustic sludge simulants, there was more foam in tests with added Antifoam 747 than in tests without added antifoam. (2) Analyses were completed to determine the composition of the two antifoam components and Antifoam 747. In addition, the decomposition products of Antifoam 747 were determined during CPC processing of sludge simulants. The main decomposition products were identified primarily as Long Chain Siloxanes, boiling point > 400 C. Total antifoam recovery was 33% by mass. In a subsequent study, various compounds potentially related to antifoam were found using semi-volatile organic analysis and volatile organic analysis on the hexane extractions and hexane rinses. These included siloxanes, trimethyl silanol, methoxy trimethyl silane, hexamethyl disiloxane, aliphatic hydrocarbons, dioctyl phthalate, and emulsifiers. Cumulatively, these species amounted to less than 3% of the antifoam mass. The majority of the antifoam was identified using carbon analysis of the SRAT product (40-80% by ma