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Sample records for alkylated aromatics

  1. Alkylation of organic aromatic compounds

    DOEpatents

    Smith, L.A. Jr.; Arganbright, R.P.; Hearn, D.

    1993-09-07

    Aromatic compounds are alkylated in a catalytic distillation, wherein the catalyst structure also serves as a distillation component by contacting the aromatic compound with a C[sub 2] to C[sub 10] olefin in the catalyst bed under 0.25 to 50 atmospheres of pressure and at temperatures in the range of 80 C to 500 C, using as the catalyst a molecular sieve characterized as acidic or an acidic cation exchange resin. For example, ethyl benzene is produced by feeding ethylene to about the mid point of the catalyst bed while benzene is conveniently added through the reflux in molar excess to that required to react with ethylene, thereby reacting substantially all of the ethylene and recovering benzene as the principal overhead and ethyl benzene in the bottoms. 1 figures.

  2. Alkylation of organic aromatic compounds

    DOEpatents

    Smith, Jr., Lawrence A.; Arganbright, Robert P.; Hearn, Dennis

    1994-01-01

    Aromatic compounds are alkylated in a catalytic distillation, wherein the catalyst structure also serves as a distillation component by contacting the aromatic compound with a C.sub.2 to C.sub.10 olefin in the catalyst bed under 0.25 to 50 atmospheres of pressure and at temperatures in the range of 80.degree. C. to 500.degree. C., using as the catalyst a mole sieve characterized as acidic or an acidic cation exchange resin. For example, ethyl benzene is produced by feeding ethylene below the catalyst bed while benzene is conveniently added through the reflux in molar excess to that required to react with ethylene, thereby reacting substantially all of the ethylene and recovering benzene as the principal overhead and ethyl benzene in the bottoms.

  3. Alkylation of organic aromatic compounds

    DOEpatents

    Smith, L.A. Jr.; Arganbright, R.P.; Hearn, D.

    1994-06-14

    Aromatic compounds are alkylated in a catalytic distillation, wherein the catalyst structure also serves as a distillation component by contacting the aromatic compound with a C[sub 2] to C[sub 10] olefin in the catalyst bed under 0.25 to 50 atmospheres of pressure and at temperatures in the range of 80 C to 500 C, using as the catalyst a molecular sieve characterized as acidic or an acidic cation exchange resin. For example, ethyl benzene is produced by feeding ethylene below the catalyst bed while benzene is conveniently added through the reflux in molar excess to that required to react with ethylene, thereby reacting substantially all of the ethylene and recovering benzene as the principal overhead and ethyl benzene in the bottoms. 1 fig.

  4. Alkylation of organic aromatic compounds

    DOEpatents

    Smith, Jr., Lawrence A.

    1989-01-01

    Aromatic compounds are alkylated in a catalytic distillation, wherein the catalyst structure also serves as a distillation component by contacting the aromatic compound with a C.sub.2 to C.sub.10 olefin in the catalyst bed under 0.25 to 50 atmospheres of pressure and at temperatures in the range of 80.degree. C. to 500.degree. C., using as the catalyst a mole sieve characterized as acidic or an acidic cation exchange resin. For example, ethyl benzene is produced by feeding ethylene below the catalyst bed while benzene is conveniently added through the reflux in molar excess to that required to react with ethylene, thereby reacting substantially all of the ethylene and recovering benzene as the principal overhead and ethyl benzene in the bottoms.

  5. Alkylation of organic aromatic compounds

    DOEpatents

    Smith, Jr., Lawrence A.; Arganbright, Robert P.; Hearn, Dennis

    1993-01-01

    Aromatic compounds are alkylated in a catalytic distillation, wherein the catalyst structure also serves as a distillation component by contacting the aromatic compound with a C.sub.2 to C.sub.10 olefin in the catalyst bed under 0.25 to 50 atmospheres of pressure and at temperatures in the range of 80.degree. C. to 500.degree. C., using as the catalyst a mole sieve characterized as acidic or an acidic cation exchange resin. For example, ethyl benzene is produced by feeding ethylene to about the mid point of the catalyst bed while benzene is conveniently added through the reflux in molar excess to that required to react with ethylene, thereby reacting substantially all of the ethylene and recovering benzene as the principal overhead and ethyl benzene in the bottoms.

  6. Alkylation of organic aromatic compounds

    DOEpatents

    Smith, L.A. Jr.

    1989-07-18

    Aromatic compounds are alkylated in a catalytic distillation, wherein the catalyst structure also serves as a distillation component by contacting the aromatic compound with a C[sub 2] to C[sub 10] olefin in the catalyst bed under 0.25 to 50 atmospheres of pressure and at temperatures in the range of 80 C to 500 C, using as the catalyst a mole sieve characterized as acidic or an acidic cation exchange resin. For example, ethyl benzene is produced by feeding ethylene below the catalyst bed while benzene is conveniently added through the reflux in molar excess to that required to react with ethylene, thereby reacting substantially all of the ethylene and recovering benzene as the principal overhead and ethyl benzene in the bottoms. 1 fig.

  7. Alkylation of organic aromatic compounds

    DOEpatents

    Smith, L.A. Jr.; Arganbright, R.P.; Hearn, D.

    1993-01-05

    Aromatic compounds are alkylated in a combination reactor/distillation column comprising a vessel suitable for operating between 70 C and 500 C and from 0.5 to 20 atmospheres pressure; an inert distillation packing in the lower one-third of said vessel; solid acidic catalytic material such as zeolites or an acidic cation exchange resin supported in the middle one-third of said vessel; and inert distillation packing in the upper one-third of said vessel. A benzene inlet is located near the upper end of the vessel; an olefin inlet is juxtaposed with said solid acidic catalytic material; a bottoms outlet is positioned near the bottom of said vessel for removing said cumene and ethyl benzene; and an overhead outlet is placed at the top of said vessel for removing any unreacted benzene and olefin.

  8. Alkylation of organic aromatic compounds

    DOEpatents

    Smith, Jr., Lawrence A.; Arganbright, Robert P.; Hearn, Dennis

    1993-01-01

    Aromatic compounds are alkylated in a combination reactor/distillation column comprising a vessel suitable for operating between 70.degree. C. and 500.degree. C. and from 0.5 to 20 atmospheres pressure; an inert distillation packing in the lower one-third of said vessel; solid acidic catalytic material such as zeolites or an acidic cation exchange resin supported in the middle one-third of said vessel; and inert distillation packing in the upper one-third of said vessel. A benzene inlet is located near the upper end of the vessel; an olefin inlet is juxtaposed with said solid acidic catalytic material; a bottoms outlet is positioned near the bottom of said vessel for removing said cumene and ethyl benzene; and an overhead outlet is placed at the top of said vessel for removing any unreacted benzene and olefin.

  9. Palladium-Catalyzed, Ring-Forming Aromatic C–H Alkylations with Unactivated Alkyl Halides

    PubMed Central

    Venning, Alexander R. O.; Bohan, Patrick T.; Alexanian, Erik J.

    2015-01-01

    A catalytic C–H alkylation using unactivated alkyl halides and a variety of arenes and heteroarenes is described. This ring-forming process is successful with a variety of unactivated primary and secondary alkyl halides, including those with β-hydrogens. In contrast to standard polar or radical cyclizations of aromatic systems, electronic activation of the substrate is not required. The mild, catalytic reaction conditions are highly functional group tolerant and facilitate access to a diverse range of synthetically and medicinally important carbocyclic and heterocyclic systems. PMID:25746442

  10. Alkyl polycyclic aromatic hydrocarbons emissions in diesel/biodiesel exhaust

    NASA Astrophysics Data System (ADS)

    Casal, Carina S.; Arbilla, Graciela; Corrêa, Sergio M.

    2014-10-01

    Polycyclic aromatic hydrocarbons (PAHs) are widely studied in environmental matrices, such as air, water, soil and sediment, because of their toxicity, mutagenicity and carcinogenicity. Because of these properties, the environmental agencies of developed countries have listed sixteen PAHs as priority pollutants. Few countries have limits for these compounds for ambient air, but they only limit emissions from stationary and mobile sources and occupational areas. There are several studies to specifically address the 16 priority PAHs and very little for the alkyl PAHs. These compounds are more abundant, more persistent and frequently more toxic than the non-alkylated PAHs, and the toxicity increases with the number of alkyl substitutions on the aromatic ring. In this study, a method was developed for the analysis of PAHs and alkyl PAHs by using a GC-MS and large injection volume injection coupled with program temperature vaporisation, which allows for limits of detection below 1.0 ng μL-1. Several variables were tested, such as the injection volume, injection velocity, injector initial temperature, duration of the solvent split and others. This method was evaluated in samples from particulate matter from the emissions of engines employing standard diesel, commercial diesel and biodiesel B20. Samples were collected on a dynamometer bench for a diesel engine cycle and the results ranged from 0.5 to 96.9 ng mL-1, indicating that diesel/biodiesel makes a significant contribution to the formation of PAHs and alkyl PAHs.

  11. Cracking of long-chain alkyl aromatics on USY zeolite catalysts

    SciTech Connect

    Corma, A. ); Miguel, P.J.; Orchilles, A.V. ); Koermer, G.S. )

    1992-05-01

    Long-chain alkyl aromatics are important precursors for FCC gasoline. It is well known that for short-chain alkyl aromatics like cumene the dominant cracking process is simple alkyl aryl cleavage. In contrast the authors have found that for long-chain alkyl aromatics like 1-phenylheptane, cracking over in situ USY catalysts is much more complex. Cracking in a long alkyl side chain results in a carbenium ion that isomerizes easily and gives self-alkylation of the aromatic ring. Self-alkylation produces coke precursors and heavy gasoline aromatics. Product selectivities vary with zeolite unit cell size in ways that are rationalized on the basis of decreasing acid site density and zeolite adsorption properties.

  12. 40 CFR 721.3845 - Alkyl substituted aromatic glycidyl ether (generic).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... ether (generic). 721.3845 Section 721.3845 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.3845 Alkyl substituted aromatic glycidyl ether (generic). (a) Chemical... as alkyl substituted aromatic glycidyl ether (PMN P-97-661) is subject to reporting under...

  13. 40 CFR 721.3845 - Alkyl substituted aromatic glycidyl ether (generic).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... ether (generic). 721.3845 Section 721.3845 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.3845 Alkyl substituted aromatic glycidyl ether (generic). (a) Chemical... as alkyl substituted aromatic glycidyl ether (PMN P-97-661) is subject to reporting under...

  14. 40 CFR 721.950 - Sodium salt of an alkylated, sulfonated aromatic (generic name).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ..., sulfonated aromatic (generic name). 721.950 Section 721.950 Protection of Environment ENVIRONMENTAL... Significant New Uses for Specific Chemical Substances § 721.950 Sodium salt of an alkylated, sulfonated... chemical substance identified generically as a sodium salt of an alkylated, sulfonated aromatic (PMN...

  15. 40 CFR 721.950 - Sodium salt of an alkylated, sulfonated aromatic (generic name).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Sodium salt of an alkylated... Significant New Uses for Specific Chemical Substances § 721.950 Sodium salt of an alkylated, sulfonated... chemical substance identified generically as a sodium salt of an alkylated, sulfonated aromatic (PMN...

  16. Polycyclic Aromatic Acids Are Primary Metabolites of Alkyl-PAHs-A Case Study with Nereis diversicolor.

    PubMed

    Malmquist, Linus M V; Selck, Henriette; Jørgensen, Kåre B; Christensen, Jan H

    2015-05-01

    Although concentrations of alkylated polycyclic aromatic hydrocarbons (alkyl-PAHs) in oil-contaminated sediments are higher than those of unsubstituted PAHs, only little attention has been given to metabolism and ecotoxicity of alkyl-PAHs. In this study we demonstrated that metabolism of alkyl-PAHs primarily forms polycyclic aromatic acids (PAAs). We generalize this to other alkyl-PAHs, based on literature and the present study of the metabolism of 1-methylphenanthrene, 3,6-dimethylphenanthrene, and 1-, 2-, 3-, and 6-methylchrysene related to their unsubstituted parent PAHs. Also, we observed that body burdens and production of PAAs was related to the position of the methyl group, showing the same isomer specific preferences as for microbial degradation of alkyl-PAHs. We detected a high production of PAAs, and larger metabolism of alkyl-PAHs than their unsubstituted parent PAHs. We therefore propose that carboxylic acid metabolites of alkyl-PAHs have the potential of constituting a new class of contaminants in marine waters that needs attention in relation to ecological risk assessments. PMID:25827176

  17. Asymmetric Intramolecular Alkylation of Chiral Aromatic Imines via Catalytic C-H Bond Activation

    SciTech Connect

    Watzke, Anja; Wilson, Rebecca; O'Malley, Steven; Bergman, Robert; Ellman, Jonathan

    2007-04-16

    The asymmetric intramolecular alkylation of chiral aromatic aldimines, in which differentially substituted alkenes are tethered meta to the imine, was investigated. High enantioselectivities were obtained for imines prepared from aminoindane derivatives, which function as directing groups for the rhodium-catalyzed C-H bond activation. Initial demonstration of catalytic asymmetric intramolecular alkylation also was achieved by employing a sterically hindered achiral imine substrate and catalytic amounts of a chiral amine.

  18. 40 CFR 721.3845 - Alkyl substituted aromatic glycidyl ether (generic).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... as alkyl substituted aromatic glycidyl ether (PMN P-97-661) is subject to reporting under this... in § 721.125 (a), (b), (c),(d),(e), (f), (g), (h),(i), and (k) are applicable to manufacturers... (CONTINUED) TOXIC SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses...

  19. 40 CFR 721.3845 - Alkyl substituted aromatic glycidyl ether (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... as alkyl substituted aromatic glycidyl ether (PMN P-97-661) is subject to reporting under this... in § 721.125 (a), (b), (c),(d),(e), (f), (g), (h),(i), and (k) are applicable to manufacturers... (CONTINUED) TOXIC SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses...

  20. 40 CFR 721.10058 - Reaction product of alkylphenol, aromatic cyclicamine, alkyl diglycidyl dibenzene, and...

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Reaction product of alkylphenol... SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.10058 Reaction product of alkylphenol, aromatic cyclicamine, alkyl diglycidyl dibenzene, and...

  1. 40 CFR 721.10058 - Reaction product of alkylphenol, aromatic cyclicamine, alkyl diglycidyl dibenzene, and...

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Reaction product of alkylphenol... SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.10058 Reaction product of alkylphenol, aromatic cyclicamine, alkyl diglycidyl dibenzene, and...

  2. 40 CFR 721.10058 - Reaction product of alkylphenol, aromatic cyclicamine, alkyl diglycidyl dibenzene, and...

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Reaction product of alkylphenol... SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.10058 Reaction product of alkylphenol, aromatic cyclicamine, alkyl diglycidyl dibenzene, and...

  3. 40 CFR 721.10058 - Reaction product of alkylphenol, aromatic cyclicamine, alkyl diglycidyl dibenzene, and...

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Reaction product of alkylphenol... SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.10058 Reaction product of alkylphenol, aromatic cyclicamine, alkyl diglycidyl dibenzene, and...

  4. 40 CFR 721.10058 - Reaction product of alkylphenol, aromatic cyclicamine, alkyl diglycidyl dibenzene, and...

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Reaction product of alkylphenol... SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.10058 Reaction product of alkylphenol, aromatic cyclicamine, alkyl diglycidyl dibenzene, and...

  5. 40 CFR 721.7200 - Perfluoroalkyl aromatic carbamate modified alkyl methacrylate copolymer.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Perfluoroalkyl aromatic carbamate modified alkyl methacrylate copolymer. 721.7200 Section 721.7200 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) TOXIC SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific...

  6. Physico-chemical properties and toxicity of alkylated polycyclic aromatic hydrocarbons.

    PubMed

    Kang, Hyun-Joong; Lee, So-Young; Kwon, Jung-Hwan

    2016-07-15

    Crude oil and refined petroleum products contain many polycyclic and heterocyclic aromatic hydrocarbons, in particular, alkylated PAHs. Although alkylated PAHs are found in significantly higher quantities than their corresponding unsubstituted PAHs, the most studies on the physico-chemical properties and toxicities of these compounds have been conducted on unsubstituted PAHs. In this study, we measured crucial physico-chemical properties (i.e., water solubility, partition coefficients between polydimethylsiloxane and water (KPDMSw), and partition coefficient between liposomes and water (Klipw)) of selected alkylated PAHs, and evaluated their toxicity using the luminescence inhibition of Aliivibrio fischeri and growth inhibition of Raphidocelis subcapitata. In general, the logarithms of these properties for alkylated PAHs showed good linear correlations with log Kow, as did those for unsubstituted PAHs. Changes in molecular symmetry on the introduction of alkyl groups on aromatic ring structure significantly altered water solubility. The inhibition of bacterial luminescence and algal growth by alkylated PAHs can be explained well by the baseline toxicity hypothesis, and good linear relationships between log Kow or log Klipw and log (1/EC50) were found. PMID:27037474

  7. Retention behavior of alkyl-substituted polycyclic aromatic sulfur heterocycles in reversed-phase liquid chromatography.

    PubMed

    Wilson, Walter B; Sander, Lane C; de Alda, Miren Lopez; Lee, Milton L; Wise, Stephen A

    2016-08-26

    Retention indices for 79 alkyl-substituted polycyclic aromatic sulfur heterocycles (PASHs) were determined by using reversed-phase liquid chromatography (LC) on a monomeric and polymeric octadecylsilane (C18) stationary phase. Molecular shape parameters [length, breadth, thickness (T), and length-to-breadth ratio (L/B)] were calculated for all the compounds studied. Based on separations of isomeric methylated polycyclic aromatic hydrocarbons on polymeric C18 phases, alkyl-substituted PASHs are expected to elute based on increasing L/B ratios. However, the correlation coefficients had a wide range of values from r=0.43 to r=0.93. Several structural features besides L/B ratios were identified to play an important role in the separation mechanism of PASHs on polymeric C18 phases. First, the location of the sulfur atom in a bay-like-region results in alkylated-PASHs being more retentive than non-bay-like-region alkylated-PASHs, and they elute later than expected based on L/B value. Second, the placement of the alkyl group in the k region of the structure resulted in a later elution than predicted by L/B. Third, highly nonplanar methyl-PASHs (i.e., 1-Me and 11-MeBbN12T) elute prior to the parent PASH (BbN12T). PMID:27477517

  8. Production of alkyl-aromatics from light oxygenates over zeolite catalysts for bio-oil refining

    NASA Astrophysics Data System (ADS)

    Hoang, Trung Q.

    in aromatic yield. Further improvement of aromatization and catalyst lifetime was also found with ZnHZSM-5 wherein the Zn evidently modifies the acidity. These model compound results show that the optimized use of zeolites for production of alkyl aromatics from light oxygenates at mild conditions may be effective for bio-oil refining.

  9. Selective and Serial Suzuki-Miyaura Reactions of Polychlorinated Aromatics with Alkyl Pinacol Boronic Esters.

    PubMed

    Laulhé, Sébastien; Blackburn, J Miles; Roizen, Jennifer L

    2016-09-01

    Among cross-coupling reactions, the Suzuki-Miyaura transformation stands out because of its practical advantages, including the commercial availability and low toxicity of the required reagents, mild reaction conditions, and functional group compatibility. Nevertheless, few conditions can be used to cross-couple alkyl boronic acids or esters with aryl halides, especially 2-pyridyl halides. Herein, we describe two novel Suzuki-Miyaura protocols that enable selective conversion of polychlorinated aromatics, with a focus on reactions to convert 2,6-dichloropyridines to 2-chloro-6-alkylpyridines or 2-aryl-6-alkylpyridines. PMID:27537216

  10. Polymerization of aniline and alkyl ring-substituted anilines in the presence of aromatic additives

    SciTech Connect

    Wei, Yen; Jang, Guangway; Chan, Chicheung; Hsueh, K.F.; Hariharan, R.; Patel, S.A.; Whitecar, C.K. )

    1990-09-20

    A new synthetic method for the preparation of electrically conductive polyaniline and alkyl ring-substituted polyanilines is presented, in which a small amount of aromatic additives is introduced into both chemical and electrochemical polymerization systems. In the presence of the additives, such as p-aminodiphenylamine, benzidine, and p-phenoxyaniline, the rate of polyaniline formation increases greatly; and lower applied potentials, e.g., 0.55 V vs SCE, or milder oxidants, e.g., O{sub 2}, can be effectively employed in the polymerization. All of these additives have lower oxidation potentials than the aniline monomers and at least one sterically accessible aromatic amino group which allow their incorporation into polymer chains as a part of the structural backbones. In contrast, addition of N,N-diphenylamine or hydroquinone to the polymerization system reduces the rate of polymer formation. The results are consistent with the proposed mechanism of polymerization.

  11. Selective iridium-catalyzed alkylation of (hetero)aromatic amines and diamines with alcohols under mild reaction conditions.

    PubMed

    Blank, Benoît; Michlik, Stefan; Kempe, Rhett

    2009-01-01

    A P,N-ligand-coordinated iridium complex has been employed as an efficient catalyst for the selective monoalkylation of (hetero)aromatic amines with alcohols. A significant improvement of this alkylation method has been achieved, such that it can be performed at a temperature of 70 degrees C and with catalyst loadings as low as 0.1 mol % Ir, while still affording excellent yields of secondary amines. Furthermore, the high selectivity of this catalyst for the monoalkylation of aromatic amino functions has been successfully exploited for the alkylation of diamines in both symmetric and nonsymmetric fashions, providing a novel and very efficient synthetic tool for the preparation of N,N'-dialkylated aromatic diamines. PMID:19219878

  12. Co(II) PCP Pincer Complexes as Catalysts for the Alkylation of Aromatic Amines with Primary Alcohols.

    PubMed

    Mastalir, Matthias; Tomsu, Gerald; Pittenauer, Ernst; Allmaier, Günter; Kirchner, Karl

    2016-07-15

    Efficient alkylations of amines by alcohols catalyzed by well-defined Co(II) complexes are described that are stabilized by a PCP ligand (N,N'-bis(diisopropylphosphino)-N,N'-dimethyl-1,3-diaminobenzene) based on the 1,3-diaminobenzene scaffold. This reaction is an environmentally benign process implementing inexpensive, earth-abundant nonprecious metal catalysts and is based on the acceptorless alcohol dehydrogenation concept. A range of primary alcohols and aromatic amines were efficiently converted into mono-N-alkylated amines in good to excellent isolated yields. PMID:27356282

  13. A new spectral deconvolution - selected ion monitoring method for the analysis of alkylated polycyclic aromatic hydrocarbons in complex mixtures.

    PubMed

    Robbat, Albert; Wilton, Nicholas M

    2014-07-01

    A new gas chromatography/mass spectrometry (GC/MS) method is proffered for the analysis of polycyclic aromatic hydrocarbons (PAH) and their alkylated homologs in complex samples. Recent work elucidated the fragmentation pathways of alkylated PAH, concluding that multiple fragmentation patterns per homolog (MFPPH) are needed to correctly identify all isomers. Programming the MS in selected ion monitoring (SIM) mode to detect homolog-specific MFPPH ions delivers the selectivity and sensitivity that the conventional SIM and/or full scan mass spectrometry methods fail to provide. New spectral deconvolution software eliminates the practice of assigning alkylated homolog peaks via pattern recognition within laboratory-defined retention windows. Findings show that differences in concentration by SIM/molecular ion detection of C1-C4 PAH, now the standard, yield concentration differences compared to SIM/MFPPH of thousands of percent for some homologs. The SIM/MFPPH methodology is also amenable to the analysis of polycyclic aromatic sulfur heterocycles (PASH) and their alkylated homologs, since many PASH have the same m/z ions as those of PAH and, thus, are false positives in SIM/1-ion PAH detection methods. PMID:24840423

  14. Transducer influence of polycyclic aromatic hydrocarbons (PAHs) on photoisomerisation of 1-alkyl-2-(arylazo)imidazoles

    NASA Astrophysics Data System (ADS)

    Gayen, Pallab; Sinha, Chittaranjan

    2013-03-01

    The UV light irradiation to a solution of 1-alkyl-2-(arylazo)imidazole (L) in toluene shows transformation of trans to cis configuration about sbnd Ndbnd Nsbnd bond. The rate of photo-isomerisation and quantum yields are influenced by internal parameters like - nature of substituents, coordination to metal ions, steric and electronic effect, protonation etc. and the external factors like solvent (polarity, viscosity, dipole moment etc.), presence of innocent (to be chemically noninteracting) and noninnocent (chemically interacting) ions or molecules. In this work the influence of polycyclic aromatic hydrocarbons (PAH) such as - napththalene, anthracene, phenanthrene, pyrene - an innocent system, on the photochromic efficiency of L has been examined. The PAHs are π-donor and may form a π-π continuum with L which can significantly affect the motional (vibration, rotation) properties of the analyte and hence the photochromic activity. The rate and quantum yield of trans-to-cis isomerisation of L decrease with increasing [PAH] and also with increasing number of the fused phenyl ring(s) in PAH. Thus the photoisomerisation follows the rate sequence: no PAH > napththalene > anthracene-phenanthrene > pyrene. The reverse change, cis-to-trans is very slow upon light irradiation while appreciably fast in thermal process at dark. The activation energy (Ea) also decreases with [PAH] and number of fused phenyl rings.

  15. Post-source decay of alkylated and functionalized polycyclic aromatic compounds.

    PubMed

    Frache, Gilles; Krier, Gabriel; Vernex-Loset, Lionel; Muller, Jean-François; Manuelli, Pascal

    2007-01-01

    Post-source decay (PSD) is a valuable tool for providing structural information from large molecules by time-of-flight mass spectrometry (TOFMS). We used PSD to obtain this type of data from small molecules in the laser desorption/ionization (LDI) study of diesel engine exhaust particles. As the original nitrogen laser (lambda = 337 nm, E = 3.5 eV/photon) of our TOF mass spectrometer does not yield sufficient energy to ionize polycyclic aromatic hydrocarbons (PAHs), a second laser with a shorter wavelength has been coupled to the instrument. The fourth harmonic of a Nd:YAG laser (lambda = 266 nm, 4.6 eV/photon) has been chosen to achieve two-photon single-step desorption/ionization of PAHs. The PSD fragmentation of functionalized, alkylated and sulfur PAHs is discussed. Diesel engine exhaust particles are also studied as an example of a real complex sample. This technique is presented herein as a way to identify small molecules in environmental samples. Information provided by LDI-PSD-TOFMS can be a way to distinguish pollutants with very close molecular weights even if the resolving power of a TOF mass spectrometer is not sufficient. PMID:17639565

  16. Carbon, hydrogen, and nitrogen isotope fractionation associated with oxidative transformation of substituted aromatic N-alkyl amines.

    PubMed

    Skarpeli-Liati, Marita; Pati, Sarah G; Bolotin, Jakov; Eustis, Soren N; Hofstetter, Thomas B

    2012-07-01

    We investigated the mechanisms and isotope effects associated with the N-dealkylation and N-atom oxidation of substituted N-methyl- and N,N-dimethylanilines to identify isotope fractionation trends for the assessment of oxidations of aromatic N-alkyl moieties by compound-specific isotope analysis (CSIA). In laboratory batch model systems, we determined the C, H, and N isotope enrichment factors for the oxidation by MnO(2) and horseradish peroxidase (HRP), derived apparent (13)C-, (2)H-, and (15)N-kinetic isotope effects (AKIEs), and characterized reaction products. The N-atom oxidation pathway leading to radical coupling products typically exhibited inverse (15)N-AKIEs (up to 0.991) and only minor (13)C- and (2)H-AKIEs. Oxidative N-dealkylation, in contrast, was subject to large normal (13)C- and (2)H-AKIEs (up to 1.019 and 3.1, respectively) and small (15)N-AKIEs. Subtle changes of the compound's electronic properties due to different types of aromatic and/or N-alkyl substituents resulted in changes of reaction mechanisms, rate-limiting step(s), and thus isotope fractionation trends. The complex sequence of electron and proton transfers during the oxidative transformation of substituted aromatic N-alkyl amines suggests highly compound- and mechanism-dependent isotope effects precluding extrapolations to other organic micropollutants reacting along the same degradation pathways. PMID:22681573

  17. One-pot synthesis of 4′-alkyl-4-cyanobiaryls on the basis of the terephthalonitrile dianion and neutral aromatic nitrile cross-coupling

    PubMed Central

    Peshkov, Roman Yu; Chunyan, Wang; Tretyakov, Evgeny V; Shteingarts, Vitalij D

    2016-01-01

    Summary A convenient one-pot approach to alkylcyanobiaryls is described. The method is based on biaryl cross-coupling between the sodium salt of the terephthalonitrile dianion and a neutral aromatic nitrile in liquid ammonia, and successive alkylation of the long-lived anionic intermediate with alkyl bromides. The reaction is compatible with benzonitriles that contain methyl, methoxy and phenyl groups, fluorine atoms, and a 1-cyanonaphthalene residue. The variety of ω-substituted alkyl bromides, including an extra bromine atom, a double bond, cyano and ester groups, as well as a 1,3-dioxane fragment are suitable as alkylation reagents. PMID:27559409

  18. One-pot synthesis of 4'-alkyl-4-cyanobiaryls on the basis of the terephthalonitrile dianion and neutral aromatic nitrile cross-coupling.

    PubMed

    Peshkov, Roman Yu; Panteleeva, Elena V; Chunyan, Wang; Tretyakov, Evgeny V; Shteingarts, Vitalij D

    2016-01-01

    A convenient one-pot approach to alkylcyanobiaryls is described. The method is based on biaryl cross-coupling between the sodium salt of the terephthalonitrile dianion and a neutral aromatic nitrile in liquid ammonia, and successive alkylation of the long-lived anionic intermediate with alkyl bromides. The reaction is compatible with benzonitriles that contain methyl, methoxy and phenyl groups, fluorine atoms, and a 1-cyanonaphthalene residue. The variety of ω-substituted alkyl bromides, including an extra bromine atom, a double bond, cyano and ester groups, as well as a 1,3-dioxane fragment are suitable as alkylation reagents. PMID:27559409

  19. pi-Selective stationary phases: (II) Adsorption behavior of substituted aromatic compounds on n-alkyl-phenyl stationary phases

    SciTech Connect

    Gritti, Fabrice; Guiochon, Georges A; Mayfield, Kirsty; Dennis, Gary; Shalliker, R. Andrew

    2010-01-01

    The frontal analysis method was used to measure the adsorption isotherms of phenol, 4-chlorophenol, p-cresol, 4-methoxyphenol and caffeine on a series of columns packed with home-made alkyl-phenyl bonded silica particles. These ligands consist of a phenyl ring tethered to the silica support via a carbon chain of length ranging from 0 to 4 atoms. The adsorption isotherm models that fit best to the data account for solute-solute interactions that are likely caused by p-p interactions occurring between aromatic compounds and the phenyl group of the ligand. These interactions are the dominant factor responsible for the separation of low molecular weight aromatic compounds on these phenyl-type stationary phases. The saturation capacities depend on whether the spacer of the ligands have an even or an odd number of carbon atoms, with the even alkyl chain lengths having a greater saturation capacity than the odd alkyl chain lengths. The trends in the adsorption equilibrium constant are also significantly different for the even and the odd chain length ligands.

  20. Unresolved complex mixtures (UCMs) of aromatic hydrocarbons: branched alkyl indanes and branched alkyl tetralins are present in UCMs and accumulated by and toxic to, the mussel Mytilus edulis.

    PubMed

    Booth, Andrew M; Scarlett, Alan G; Lewis, C Anthony; Belt, Simon T; Rowland, Steven J

    2008-11-01

    Previously, comprehensive two-dimensional gas chromatography-time of flight-mass-spectrometry (GCxGC-ToF-MS) revealed that the unresolved complex mixtures (UCMs) of contaminant hydrocarbons accumulated by health-affected mussels Mytilus edulis (up to 125 microg g dry weight(-1)) collected from around U.K. coasts, included many isomeric branched alkyl benzenes (BABs). A commercial mixture of BABs (C12-C14) was toxic to mussels in laboratorytests (tissue effective concentration EC(20)10.5 microg g dry tissue(-1)). Branched alkyl indanes (BINs) and branched alkyl tetralins (BATs) were also tentatively identified in the wild mussels, but no commercial sources of BINs or BATs were available for compound confirmation or toxicity testing. In the present study, we synthesized 14 isomeric BINs and BATs, investigated their chromatographic and mass spectral properties and measured their toxicity to mussels (Mytilus edulis). Comparison of the results of GCxGC-ToF-MS analysis of the synthesized compounds with those of complex mixtures of BINs and BATs in wild mussels confirmed the previous tentative identifications. Toxicity assays showed that in 72 h exposures, each of the synthetic BINs and BATs and a mixture of all were toxic to mussels at concentrations comparable to the BABs investigated previously (EC(20)13 microg g dry tissue(-1)). A further 5 day recovery period in clean water resulted in incomplete depuration of the accumulated body burden of BINs and BATs by the mussels. We suggest that monitoring of hydrocarbon contaminants in mussels should include an assessment of the concentrations of aromatic UCMs and ideally identification and measurement of the concentrations of BABs, BINs, and BATs and other toxic UCM components in order that the effects of these toxicants are not overlooked. PMID:19031912

  1. Role of alkyl group in the aromatic extraction using pyridinium-based ionic liquids.

    PubMed

    Kim, Min Ji; Shin, Seung Hoon; Kim, Young Jin; Cheong, Minserk; Lee, Je Seung; Kim, Hoon Sik

    2013-11-27

    The performance of N-alkylpyridinium-based ionic liquids with a SCN anion (PyILs) was evaluated for the selective extraction of aromatics from aliphatic hydrocarbons. The aromatic extraction ability of PyILs was greatly enhanced by the presence of a methyl group on the pyridinium ring at the 3- or 4-position, whereas the solubility of the aromatics in the PyILs decreased with increasing the number of methyl groups on the benzene ring. The FT-IR studies revealed that the solubility of an aromatic compound in a PyIL is closely correlated with the degree of aromatic C-H bending frequency shift observed during the dissolution of the aromatic compound in the PyIL: the larger the shift, the higher the solubility. The computational calculations on the dispersion interactions between aromatics and PyILs demonstrated that the anion-aromatic interaction is much more important than the cation-aromatic interaction in determining the aromatic solubility in PyILs, and such anion-aromatic interaction can be enhanced by introducing a methyl group at the carbon atom of the pyridinium ring. PMID:24180561

  2. Biodegradation of alkyl derivatives of aromatic hydrocarbons and cell surface properties of a strain of Pseudomonas stutzeri.

    PubMed

    Kaczorek, Ewa; Sałek, Karina; Guzik, Urszula; Jesionowski, Teofil; Cybulski, Zefiryn

    2013-01-01

    Pseudomonas stutzeri strain 9 was isolated from petroleum-contaminated soil. The main purpose of this study was to investigate how the long-term contact of this strain with diesel oil influences its surface and biodegradation properties. The experiments showed that the tested strain was able to degrade aromatic alkyl derivatives (butylbenzene, sec-butylbenzene, tert-butylbenzene and isobutylbenzene) and that the storage conditions had an influence on the cell surface properties. Also greater agglomeration of the cells was observed in the scanning electron microscope (SEM) micrographs and confirmed in particle size distribution results. The results also indicated that the addition of rhamnolipids to the hydrocarbons led to modification of the surface properties of P. stutzeri strain 9, which could be observed in the zeta potential and hydrophobicity values. PMID:22925424

  3. On the Cyclo-Depolymerization of Alkyl Aromatic Polyesters and the in Situ Polymerization of the Cyclic Oligomers Produced

    NASA Astrophysics Data System (ADS)

    Alessi, M.; Stagnaro, P.; Conzatti, L.; Scafati, S. Tagliatatela; Hodge, P.

    2008-08-01

    Macrocyclic oligomers (MCOs) of some commercial alkyl aromatic polyesters (PET, PTT, PBT) were prepared by cyclo-depolymerization (CDP) of the polymers in refluxing 1, 2-dichlorobenzene with di-n-butyltin oxide as a transesterification catalyst. The mixtures of MCOs and residual polymer obtained at varying polymer/solvent ratios were separated and characterized by thorough GPC and DSC analyses. The higher the initial polymer concentration the lower was the yield of MCOs, and vice versa. Rheological measurements carried out on polymer/MCO mixtures showed a decrease in the melt viscosity with increasing amount of MCOs. Moreover, the MCOs present in these systems easily underwent entropically-driven ring-opening polymerizations (ED-ROPs) to reform the parent polyesters.

  4. Parent, Alkylated, and Sulfur/Oxygen-Containing Polycyclic Aromatic Hydrocarbons in Mainstream Smoke from 13 Brands of Chinese Cigarettes.

    PubMed

    Gao, Bo; Du, Xueqing; Wang, Xinming; Tang, Jianhui; Ding, Xiang; Zhang, Yanli; Bi, Xinhui; Zhang, Gan

    2015-08-01

    China has the world's largest population of smokers with serious health consequences, yet we know a very limited spectrum of hazardous chemicals in cigarette smoke even for carcinogenic polycyclic aromatic hydrocarbons (PAHs). Here, we chose 13 popular cigarette brands sold in China markets, collected particulate matters in mainstream smoke using filter pads and an automatic smoking machine, and analyzed 56 PAHs, including 31 parent, 18 alkylated, and 7 sulfur/oxygen-containing PAHs (S/O PAHs). The 56 PAHs in mainstream smoke totaled from 244.2 ± 28.5 to 10254.8 ± 481.5 ng cig(-1); parent, alkylated, and S/O PAHs shared 16-23%, 64-74%, and 6-18%, respectively. Benzo[a]pyrene (BaP) ranged 1.1-41.6 ng cig(-1), while BaP equivalent concentrations (BaPeq) ranged 3.6-120.2 ng cig(-1), but contributions to BaPeq by individual carcinogenic PAH species varied with cigarette brands. When these cigarette smoke source profiles were pooled together with those of other combustion ones available in the literature, we found that widely used diagnostic ratios of parent PAHs failed to distinguish cigarette smoke from other combustion sources, except that the ratio indeno[1,2,3-cd]pyrene/(indeno[1,2,3-cd]pyrene + benzo[g,h,i]perylene) can largely separate cigarette smoke from vehicular emissions and that the ratio of Retene/(Retene + chrysene) can further discriminate cigarette smoke from coal combustion when alkylated PAHs are involved. PMID:26119395

  5. Polycyclic aromatic hydrocarbons (PAHs) and alkylated PAHs in the coastal seawater, surface sediment and oyster from Dalian, Northeast China.

    PubMed

    Hong, Wen-Jun; Jia, Hongliang; Li, Yi-Fan; Sun, Yeqing; Liu, Xianjie; Wang, Luo

    2016-06-01

    A total of 46 polycyclic aromatic hydrocarbons (PAHs, 21 parent and 25 alkylated) were determined in seawater, surface sediment and oyster from coastal area of Dalian, North China. The concentration of Σ46PAHs in seawater, sediment, and oyster were 136-621 ng/L, 172-4700 ng/g dry weight (dw) and 60.0-129 ng/g wet weight (ww) in winter, and 65.0-1130 ng/L, 71.1-1090 ng/g dw and 72.8-216 ng/g ww in summer, respectively. High PAH levels were found in industrial area both in winter and summer. Selected PAH levels in sediments were compared with Sediments Quality Guidelines (ERM-ERL, TEL-PEL indexes) for evaluation probable toxic effects on marine organism and the results indicate that surface sediment from all sampling sites have a low to medium ecotoxicological risk. Daily intake of PAHs via oyster as seafood by humans were estimated and the results indicated that oyster intake would not pose a health risk to humans even 30 days after a oil spill accident near by. Water-sediment exchange analysis showed that, both in winter and summer, the fluxes for most high molecular weight PAHs were from seawater to sediment, while for low molecular weight PAHs, an equilibrium was reached between seawater and sediment. PMID:26874984

  6. Retention behavior of alkylated polycyclic aromatic sulfur heterocycles on immobilized ionic liquid stationary phases.

    PubMed

    Antle, Patrick; Zeigler, Christian; Robbat, Albert

    2014-09-26

    Polycyclic aromatic sulfur heterocycles (PASH) are prevalent components of fossil fuel-based pollutants, and their accurate analysis is of critical importance in risk assessment and hazardous waste site remediation. PASH, however, have a wide range of volatilities and polarities and, as such, often coelute with one another and other sample components on the non-polar gas chromatography (GC) columns commonly used in their analysis. Immobilized ionic liquid (IL)-based stationary phases have been shown to provide better separation of polar compounds than non-polar columns, while withstanding higher temperatures than typical polar columns. In this way, they offer the opportunity of improved performance in the analysis of PASH in complex environmental samples and as the "more polar" column in GC×GC/MS analyses. In this study, the retention behavior of 119 PASH on four commercially-available IL stationary phases is reported and compared to behavior on three polydimethylsiloxane-based columns of varying polarities (DB-5, DB-17, and DB-200). Additionally, the utility of IL columns in GC×GC analyses of PASH-containing coal tar samples is examined. PMID:25155062

  7. Rate and pathways for the reaction of OH with the biogenic p-cymene, an alkylated aromatic

    NASA Astrophysics Data System (ADS)

    Strekowski, R.; Rayez, M.-T.; Rayez, J.-C.; Zetzsch, C.

    2009-04-01

    Aromatics are known to contribute strongly to tropospheric formation of ozone, and p-cymene (4-isopropyltoluene) is one of only a few biogenic, volatile aromatic hydrocarbons. In spite of its symmetry, this molecule (CH3 - °-CH(CH3)2) has a multitude of potential pathways of its reaction with OH radicals. Addition of OH is well-known to be the predominating primary step in the tropospheric transformation of aromatic hydrocarbons. The addition is expected to occur preferably at a non-occupied position, where four positions are available: two equivalent ones ortho to the methyl group and two equivalent ones ortho to the isopropyl group. Furthermore, various C-H bonds (4 aromatic and 10 aliphatic) are available for abstraction, leading to benzyl-type radicals in two cases. The present study combines theoretical calculations with kinetic experiments in the gas phase. The theoretical calculations are based on electronic quantum chemistry DFT method for the investigation of the possible pathways in the potential energy surface of the reaction. The experiments are carried out by the flash photolysis/resonance fluorescence technique. OH radicals are produced by pulsed vacuum-UV photolysis of H2O (> 115 nm) in the presence of p-cymene in a slow flow of He as carrier gas. Their pseudo-first-order decays are monitored by resonance fluorescence, storing the photon counts by multichannel scaling in a PC and accumulating 50 decays each; see Koch et al. (2007) for details of the technique and evaluation of data. The temperature was varied between room temperature (295 K) and 345K, the He pressure was 250 mbar, and the level of p-cymene was increased stepwise, up to 3 x 1013 molecules/cm3. The decays of OH were observed to be exponential at room temperature, becoming clearly biexponential at higher temperatures, thus indicating reversible addition of OH according to the equilibration OH + p-cymene ⇔ p-cymene-OH (1, -1) These reactions might be accompanied by various

  8. Solid-Phase synthesis of a library constructed of aromatic phosphate, long alkyl chains and tryptophane components, and identification of potent dipeptide telomerase inhibitors.

    PubMed

    Sasaki, S; Ehara, T; Alam, M R; Fujino, Y; Harada, N; Kimura, J; Nakamura, H; Maeda, M

    2001-10-01

    Telomerase inhibitors are expected as a new candidate of therapeutic agents for cancer. Recently, we have found novel inhibitors based on the bisindole skeleton. In this study, solid-phase synthesis was applied to construct a library of inhibitors having aromatic phosphate, long alkyl chain and tryptophane components, from which a D,D-ditryptophane derivative has been identified as a new potent telomerase inhibitor with IC(50) values of 0.3 microM. A hypothetical binding model for the new inhibitors has been proposed based on the structure-activity relationship. PMID:11551754

  9. An efficient nitration of light alkanes and the alkyl side-chain of aromatic compounds with nitrogen dioxide and nitric acid catalyzed by N-hydroxyphthalimide.

    PubMed

    Nishiwaki, Yoshiki; Sakaguchi, Satoshi; Ishii, Yasutaka

    2002-08-01

    Nitration of light alkanes and the alkyl side-chain of aromatic compounds with NO(2) and HNO(3) was successfully achieved by the use of N-hydroxyphthalimide (NHPI) as a catalyst under relatively mild conditions. For example, the nitration of propane with NO(2) catalyzed by NHPI at 100 degrees C for 14 h gave 2-nitropropane in good yield without formation of 1-nitropropane and cleaved products such as nitroethane and nitromethane. Various aliphatic nitroalkanes, which are difficult to prepare by conventional methods, could be selectively obtained by means of the present methodology by using NHPI as the key catalyst. In addition, the side-chain nitration of alkylbenzenes such as toluene was selectively carried out to lead to alpha-nitrotoluene without the ring nitration. The present reaction provides an efficient selective method for the nitration of light alkanes and alkylbenzenes, which has been very difficult to carry out so far. PMID:12153265

  10. Evaluation of O-alkyl and aryl sulfonyl aromatic and heteroaromatic amidoximes as novel potent DNA photo-cleavers.

    PubMed

    Papastergiou, A; Perontsis, S; Gritzapis, P; Koumbis, A E; Koffa, M; Psomas, G; Fylaktakidou, K C

    2016-03-01

    Several stable O-alkyl and aryl sulfonyl conjugated p-nitro-Ph and o-, m-, p-pyridine N'-hydroxy imidamides, were subjected to UV irradiation at 312 nm with supercoiled circular plasmid DNA pBluescript KS II. The generated amidinyl and sulfonyloxyl radicals led to effective DNA photo-cleavage. Both alkyl and aryl sulfonyl derivatives were active and the order p-pyridine > p-nitro-Ph > o-pyridine > m-pyridine was schematized for the N'-hydroxy imidamides moiety. Calf thymus-DNA affinity studies which comprised UV interactions, viscosity experiments and competitive studies with ethidium bromide showed good to excellent affinity of the compounds. These properties revealed sulfonyl amidoximes as novel effective DNA-photo-cleavers and may serve in the discovery of new leads for "on demand" biotechnological and medical applications. PMID:26959855

  11. Monthly variation and vertical distribution of parent and alkyl polycyclic aromatic hydrocarbons in estuarine water column: Role of suspended particulate matter.

    PubMed

    Wang, Xiaowei; Yuan, Ke; Chen, Baowei; Lin, Li; Huang, Bensheng; Luan, Tiangang

    2016-09-01

    The distribution and interaction of parent and alkyl polycyclic aromatic hydrocarbons (EPA-34 PAHs) among the multiple phases were investigated in estuarine water column of Humen outlet over a 12-months period. The water column was divided into 5 vertical layers, and each layer included dissolved phase, large- and small-size suspended particular matter (SPM). Regarding to EPA-34 PAHs, alkyl homologues were abundant, especially in the dissolved phase and small-size SPM. Moreover, SPM contributed a large proportion of EPA-34 PAHs in the water column especially for the large-size SPM, which therefore play an important role for the transportation of these pollutants. The EPA-34 PAHs concentrations in water column during wet season were higher than those in the dry season due to the decreasing of KD values which were affected by TSS and salinity obviously. Generally, the EPA-34 PAHs concentrations in the water column increased with the increasing of water depth, most of the highest concentrations of EPA-34 PAHs were found in the near-bottom layer due to the rapid sinking of large-size SPM and sediment resuspension. Additionally, during the ebb-flood tide period, the EPA-34 PAHs concentrations in different phases of the water column fluctuated oppositely based on the effects of hydrodynamic conditions. PMID:27318544

  12. Characteristics of oxidative homolytic alkylation of imidazoles and organic-inorganic hybrid extended networks from large aromatic building blocks

    NASA Astrophysics Data System (ADS)

    Li, Kunhao

    The discovery of the dramatic in vitro antimalarial activity of 2-iodo-L-histidine and 2-fluoro-L-histidine, as well as their in vivo limitations, has prompted a systematic search for novel 2-substituted imidazoles and bioimidazoles as agents against human malaria. Previous research has shown that the regioselective alkyl free radical substitution on imidazoles and bioimidazoles could serve as a simple and efficient route to a wide variety of 2-alkylimidazoles. In this research, this methodology was successfully extended to include alkyl radicals substituted with various functional groups such as amide or ester. While this novel methodology should be of some synthetic utility when tertiary radicals are used, poorer yields are usually encountered in the cases of primary radicals. In the second part of this dissertation, a series of novel ligands containing multiple ortho-bis(organothio) groups were synthesized and their coordination and network forming properties were studied in the context of crystalline organic-inorganic hybrid extended networks. For the syntheses of HRTTs [2,3,6,7,10,11-hexakis(alkylthio)triphenylenes], a simpler, safer and higher yielding one-pot process was developed. Quenching the hexa-anions (formed when sodium methylthiolate was refluxed with hexabromotriphenylene) with alkyl halides or acid chlorides afforded HRTTs. This newly developed process was also successfully expanded to the pyrene system. In the syntheses of unsymmetrically substituted triphenlyenes, it was shown for the first time that the oxidative cyclization process is applicable to thioether containing systems, pointing to a novel strategy for the preparation of this type of unsymmetrically substituted triphenlyenes. Treating these novel ligands with various metal salts [i.e. bismuth(III) chloride and bismuth(III) bromide] under carefully controlled conditions resulted in a series of air-stable semiconductive coordination networks. Their single crystal structures were

  13. Selective extraction of genotoxic impurities and structurally alerting compounds using polymeric ionic liquid sorbent coatings in solid-phase microextraction: Alkyl halides and aromatics.

    PubMed

    Ho, Tien D; Joshi, Manishkumar D; Silver, Mark A; Anderson, Jared L

    2012-06-01

    A series of polymeric ionic liquids (PILs) possessing varied chemical makeup and composition were applied as selective solid-phase microextraction (SPME) sorbent coatings for the analysis of genotoxic impurities (GTIs) and related structurally alerting compounds, namely, alkyl halides and aromatics. In addition to exploiting two previously synthesized PILs as selective coatings, two new PILs, namely, N,N-didecyl-N-methyl-D-glucaminium poly(2-methyl-acrylic acid 2-[1-(3-{2-[2-(3-trifluoromethanesulfonylamino-propoxy)-ethoxy]-ethoxy}-propylamino)-vinylamino]-ethyl ester) (poly([DDMGlu][MTFSI])), and poly(1-vinyl-3-propylphenylimidazolium) chloride (poly([VPPIM][Cl])), were designed, synthesized, and their selectivity examined in the extraction of the selected analytes. The glucaminium-based coating was developed to exploit the hydrogen bond-acidic hydroxyl groups within the carbohydrate moiety of the PIL in addition to dispersive capabilities resulting from the cation and anion. The poly([VPPIM][Cl]) coating was tailored to possess π-π interaction capabilities through the phenyl functionality while also containing the hydrogen bond-basic chloride anion. Calibration studies were performed via headspace extraction to determine the sensitivity and limit of detection (LOD) for all analytes with respect to each PIL-based sorbent coating and compared to the polyacrylate (PA) and polydimethylsiloxane (PDMS) sorbent coatings. PILs containing the chloride anion exhibited high selectivity for aniline-based compounds. The glucaminium-based PIL exhibited good sensitivity for larger aliphatic alkyl halides. The poly(1-4-vinylbenzyl-3-hexadecylimidazolium) bis[(trifluoromethyl)sulfonyl] imide (poly([VBHDIM][NTf₂])) PIL coating demonstrated superior selectivity for larger aliphatic/aromatic analytes. The LODs of both commercial and PIL-based coatings for the two classes of GTIs ranged from low part-per-billion (ppb) to mid part-per-trillion (ppt) levels. Recovery studies were

  14. Role of Delamination in Zeolite-Catalyzed Aromatic Alkylation: UCB‑3 versus 3‑D Al-SSZ-70

    SciTech Connect

    Runnebaum, Ron C.; Ouyang, Xiaoying; Edsinga, Jeffrey A.; Rea, Thomas; Arslan, Ilke; Hwang, Son-Jong; Zones, Stacey I.; Katz, Alexander

    2014-07-03

    Delaminated zeolite UCB-3 exhibits 2.4-fold greater catalytic activity relative to its three-dimensional (3D) zeolite counterpart, Al-SSZ-70, and 2.0-fold greater activity (per catalyst mass) when compared with industrial catalyst MCM-22, for the alkylation of toluene with propylene at 523 K. The former increase is nearly equal to the observed relative increase in external surface area and acid sites upon delamination. However, at 423 K for the same reaction, UCB-3 exhibits a 3.5-fold greater catalytic activity relative to 3D Al-SSZ-70. The higher relative rate enhancement for the delaminated material at lower temperature can be elucidated on the basis of increased contributions from internal acid sites. Evidence of possible contributions from such acid sites is obtained by performing catalysis after silanation treatment, which demonstrates that although virtually all catalysis in MCM-22 occurs on the external surface, catalysis also occurs on internal sites for 3D Al-SSZ-70. The additional observed enhancement at low temperatures can therefore be rationalized by greater access to internal active sites as a result of sheet breakage during delamination. Such breakage leads to shorter characteristic internal diffusion paths and was visualized using TEM comparisons of UCB-3 and 3D Al-SSZ-70.

  15. Metabolism of an Alkylated Polycyclic Aromatic Hydrocarbon 5-Methylchrysene in Human Hepatoma (HepG2) Cells.

    PubMed

    Huang, Meng; Zhang, Li; Mesaros, Clementina; Hackfeld, Linda C; Hodge, Richard P; Blair, Ian A; Penning, Trevor M

    2015-10-19

    Exposure to polycyclic aromatic hydrocarbons (PAHs) in the food chain is the major human health hazard associated with the Deepwater Horizon oil spill. C1-chrysenes are representative PAHs present in the crude oil and have been detected in contaminated sea food in amounts that exceed their permissible safety thresholds. We describe the metabolism of the most carcinogenic C1-chrysene regioisomer, 5-methylchrysene (5-MC), in human HepG2 cells. The structures of the metabolites were identified by HPLC-UV-fluorescence detection and LC-MS/MS. 5-MC-tetraol, a signature metabolite of the diol-epoxide pathway, was identified as reported previously. Novel O-monosulfonated-5-MC-catechol isomers and O-monomethyl-O-monosulfonated-5-MC-catechol were discovered, and evidence for their precursor ortho-quinones was obtained. The identities of O-monosulfonated-5-MC-1,2-catechol, O-monomethyl-O-monosulfonated-5-MC-1,2-catechol, and 5-MC-1,2-dione were validated by comparison to authentic synthesized standards. Dual metabolic activation of 5-MC involving the formation of bis-electrophiles, i.e., a mono-diol-epoxide and a mono-ortho-quinone within the same structure, bis-diol-epoxides, and bis-ortho-quinones is reported for the first time. Evidence was also obtained for minor metabolic conversion of 5-MC to form monohydroxylated-quinones and bis-phenols. The identification of 5-MC-tetraol, O-monosulfonated-5-MC-1,2-catechol, O-monomethyl-O-monosulfonated-5-MC-1,2-catechol, and 5-MC-1,2-dione supports metabolic activation of 5-MC by P450 and AKR isozymes followed by metabolic detoxification of the ortho-quinone through interception of redox cycling by COMT and SULT isozymes. The major metabolites, O-monosulfonated-catechols and tetraols, could be used as biomarkers of human exposure to 5-MC resulting from oil spills. PMID:26395544

  16. Polycyclic aromatic hydrocarbons (PAHs) and their derivatives (alkyl-PAHs, oxygenated-PAHs, nitrated-PAHs and azaarenes) in urban road dusts from Xi'an, Central China.

    PubMed

    Wei, Chong; Bandowe, Benjamin A Musa; Han, Yongming; Cao, Junji; Zhan, Changlin; Wilcke, Wolfgang

    2015-09-01

    Urban road dusts are carriers of polycyclic aromatic compounds (PACs) and are therefore considered to be a major source of contamination of other environmental compartments and a source of exposure to PACs for urban populations. We determined the occurrence, composition pattern and sources of several PACs (29 alkyl- and parent-PAHs, 15 oxygenated-PAHs (OPAHs), 4 azaarenes (AZAs), and 11 nitrated-PAHs (NPAHs)) in twenty urban road dusts and six suburban surface soils (0-5cm) from Xi'an, central China. The average concentrations of ∑29PAHs, ∑4AZAs, ∑15OPAHs, and ∑11NPAHs were 15767, 673, 4754, and 885 n gg(-1) in road dusts and 2067, 784, 854, and 118 ng g(-1) in surface soils, respectively. The concentrations of most individual PACs were higher in street dusts than suburban soils, particularly for PACs with molecular weight>192 g mol(-1). The enrichment factors of individual PACs were significantly positively correlated with log KOA and log KOW, indicating an increasing deposition and co-sorption of the PACs in urban dusts with decreasing volatility and increasing hydrophobicity. Significant correlations between the concentrations of individual and sum of PACs, carbon fractions (soot and char), and source-characteristic PACs (combustion-derived PAHs and retene, etc.), indicated that PAHs, OPAHs and AZAs were mostly directly emitted from combustion activities and had similar post-emission fates, but NPAHs were possibly more intensely photolyzed after deposition as well as being emitted from vehicle exhaust sources. The incremental lifetime cancer risk (ILCR) resulting from exposure to urban dust bound-PACs was higher than 10(-6), indicating a non-negligible cancer risk to residents of Xi'an. PMID:25543159

  17. Mechanism of the alkylation of benzene with propylene in the presence of an aluminosilicate catalyst modified by reaction of aluminum chloride with aromatic hydrocarbons. Catalyst promotion

    SciTech Connect

    Kolesnikov, I.M.; Zaitseva, T.V.

    1985-09-01

    The authors investigated the gas-liquid phase alkylation reaction of benzene with propylene in the presence of aluminosilicate catalysts which have been activated by treatment with varying amounts of the complex derived from aluminum chloride and polyalkylbenzene, and also studied the viability of various compounds as complex promoters. It was established that catalyst activity is enhanced by modification with the complex. The optimum concentration of complex (in the modified catalyst) is 15. wt. %. It was also established that isobutyl chloride added to the reaction mixture in the presence of the modified catalyst acts as a promoter and increases the activity of the catalyst twofold, to an acceptable level. The value of the energy of activation of the alkylation reaction was determined by kinetic analysis of the experimental data to be 38,300 J/mole.

  18. Genomic Phenotyping by Barcode Sequencing Broadly Distinguishes between Alkylating Agents, Oxidizing Agents, and Non-Genotoxic Agents, and Reveals a Role for Aromatic Amino Acids in Cellular Recovery after Quinone Exposure

    PubMed Central

    Svensson, J. Peter; Quirós Pesudo, Laia; McRee, Siobhan K.; Adeleye, Yeyejide; Carmichael, Paul; Samson, Leona D.

    2013-01-01

    Toxicity screening of compounds provides a means to identify compounds harmful for human health and the environment. Here, we further develop the technique of genomic phenotyping to improve throughput while maintaining specificity. We exposed cells to eight different compounds that rely on different modes of action: four genotoxic alkylating (methyl methanesulfonate (MMS), N-Methyl-N-nitrosourea (MNU), N,N′-bis(2-chloroethyl)-N-nitroso-urea (BCNU), N-ethylnitrosourea (ENU)), two oxidizing (2-methylnaphthalene-1,4-dione (menadione, MEN), benzene-1,4-diol (hydroquinone, HYQ)), and two non-genotoxic (methyl carbamate (MC) and dimethyl sulfoxide (DMSO)) compounds. A library of S. cerevisiae 4,852 deletion strains, each identifiable by a unique genetic ‘barcode’, were grown in competition; at different time points the ratio between the strains was assessed by quantitative high throughput ‘barcode’ sequencing. The method was validated by comparison to previous genomic phenotyping studies and 90% of the strains identified as MMS-sensitive here were also identified as MMS-sensitive in a much lower throughput solid agar screen. The data provide profiles of proteins and pathways needed for recovery after both genotoxic and non-genotoxic compounds. In addition, a novel role for aromatic amino acids in the recovery after treatment with oxidizing agents was suggested. The role of aromatic acids was further validated; the quinone subgroup of oxidizing agents were extremely toxic in cells where tryptophan biosynthesis was compromised. PMID:24040048

  19. Pressurized liquid extraction using water/isopropanol coupled with solid-phase extraction cleanup for semivolatile organic compounds, polycyclic aromatic hydrocarbons (PAH), and alkylated PAH homolog groups in sediment

    USGS Publications Warehouse

    Burkhardt, M.R.; Zaugg, S.D.; Burbank, T.L.; Olson, M.C.; Iverson, J.L.

    2005-01-01

    Polycyclic aromatic hydrocarbons (PAH) are recognized as environmentally relevant for their potential adverse effects on human and ecosystem health. This paper describes a method to determine the distribution of PAH and alkylated homolog groups in sediment samples. Pressurized liquid extraction (PLE), coupled with solid-phase extraction (SPE) cleanup, was developed to decrease sample preparation time, to reduce solvent consumption, and to minimize background interferences for full-scan GC-MS analysis. Recoveries from spiked Ottawa sand, environmental stream sediment, and commercially available topsoil, fortified at 1.5-15 ??g per compound, averaged 94.6 ?? 7.8%, 90.7 ?? 5.8% and 92.8 ?? 12.8%, respectively. Initial method detection limits for single-component compounds ranged from 20 to 302 ??g/kg, based on 25 g samples. Results from 28 environmental sediment samples, excluding homologs, show 35 of 41 compounds (85.4%) were detected in at least one sample with concentrations ranging from 20 to 100,000 ??g/kg. The most frequently detected compound, 2,6-dimethylnaphthalene, was detected in 23 of the 28 (82%) environmental samples with a concentration ranging from 15 to 907 ??g/kg. The results from the 28 environmental sediment samples for the homolog series showed that 27 of 28 (96%) samples had at least one homolog series present at concentrations ranging from 20 to 89,000 ??g/kg. The most frequently detected homolog series, C2-alkylated naphthalene, was detected in 26 of the 28 (93%) environmental samples with a concentration ranging from 25 to 3900 ??g/kg. Results for a standard reference material using dichloromethane Soxhlet-based extraction also are compared. ?? 2005 Elsevier B.V. All rights reserved.

  20. New and extended parameterization of the thermodynamic model AIOMFAC: calculation of activity coefficients for organic-inorganic mixtures containing carboxyl, hydroxyl, carbonyl, ether, ester, alkenyl, alkyl, and aromatic functional groups

    NASA Astrophysics Data System (ADS)

    Zuend, A.; Marcolli, C.; Booth, A. M.; Lienhard, D. M.; Soonsin, V.; Krieger, U. K.; Topping, D. O.; McFiggans, G.; Peter, T.; Seinfeld, J. H.

    2011-09-01

    We present a new and considerably extended parameterization of the thermodynamic activity coefficient model AIOMFAC (Aerosol Inorganic-Organic Mixtures Functional groups Activity Coefficients) at room temperature. AIOMFAC combines a Pitzer-like electrolyte solution model with a UNIFAC-based group-contribution approach and explicitly accounts for interactions between organic functional groups and inorganic ions. Such interactions constitute the salt-effect, may cause liquid-liquid phase separation, and affect the gas-particle partitioning of aerosols. The previous AIOMFAC version was parameterized for alkyl and hydroxyl functional groups of alcohols and polyols. With the goal to describe a wide variety of organic compounds found in atmospheric aerosols, we extend here the parameterization of AIOMFAC to include the functional groups carboxyl, hydroxyl, ketone, aldehyde, ether, ester, alkenyl, alkyl, aromatic carbon-alcohol, and aromatic hydrocarbon. Thermodynamic equilibrium data of organic-inorganic systems from the literature are critically assessed and complemented with new measurements to establish a comprehensive database. The database is used to determine simultaneously the AIOMFAC parameters describing interactions of organic functional groups with the ions H+, Li+, Na+, K+, NH4+, Mg2+, Ca2+, Cl-, Br-, NO3-, HSO4-, and SO42-. Detailed descriptions of different types of thermodynamic data, such as vapor-liquid, solid-liquid, and liquid-liquid equilibria, and their use for the model parameterization are provided. Issues regarding deficiencies of the database, types and uncertainties of experimental data, and limitations of the model, are discussed. The challenging parameter optimization problem is solved with a novel combination of powerful global minimization algorithms. A number of exemplary calculations for systems containing atmospherically relevant aerosol components are shown. Amongst others, we discuss aqueous mixtures of ammonium sulfate with

  1. New and extended parameterization of the thermodynamic model AIOMFAC: calculation of activity coefficients for organic-inorganic mixtures containing carboxyl, hydroxyl, carbonyl, ether, ester, alkenyl, alkyl, and aromatic functional groups

    NASA Astrophysics Data System (ADS)

    Zuend, A.; Marcolli, C.; Booth, A. M.; Lienhard, D. M.; Soonsin, V.; Krieger, U. K.; Topping, D. O.; McFiggans, G.; Peter, T.; Seinfeld, J. H.

    2011-05-01

    We present a new and considerably extended parameterization of the thermodynamic activity coefficient model AIOMFAC (Aerosol Inorganic-Organic Mixtures Functional groups Activity Coefficients) at room temperature. AIOMFAC combines a Pitzer-like electrolyte solution model with a UNIFAC-based group-contribution approach and explicitly accounts for interactions between organic functional groups and inorganic ions. Such interactions constitute the salt-effect, may cause liquid-liquid phase separation, and affect the gas-particle partitioning of aerosols. The previous AIOMFAC version was parameterized for alkyl and hydroxyl functional groups of alcohols and polyols. With the goal to describe a wide variety of organic compounds found in atmospheric aerosols, we extend here the parameterization of AIOMFAC to include the functional groups carboxyl, hydroxyl, ketone, aldehyde, ether, ester, alkenyl, alkyl, aromatic carbon-alcohol, and aromatic hydrocarbon. Thermodynamic equilibrium data of organic-inorganic systems from the literature are critically assessed and complemented with new measurements to establish a comprehensive database. The database is used to determine simultaneously the AIOMFAC parameters describing interactions of organic functional groups with the ions H+, Li+, Na+, K+, NH4+, Mg2+, Ca2+, Cl-, Br-, NO3-, HSO4-, and SO42-. Detailed descriptions of different types of thermodynamic data, such as vapor-liquid, solid-liquid, and liquid-liquid equilibria, and their use for the model parameterization are provided. Issues regarding deficiencies of the database, types and uncertainties of experimental data, and limitations of the model, are discussed. The challenging parameter optimization problem is solved with a novel combination of powerful global minimization algorithms. A number of exemplary calculations for systems containing atmospherically relevant aerosol components are shown. Amongst others, we discuss aqueous mixtures of ammonium sulfate with

  2. Lithium perchlorate-nitromethane-promoted alkylation of anilines with arylmethanols.

    PubMed

    Zhou, Jun; Mao, Hai-Feng; Wang, Lu; Zou, Jian-Ping; Zhang, Wei

    2011-11-01

    A new application of lithium perchlorate-nitromethane (LPNM) for the formation of aromatic C-N and C-C bonds is introduced. LPNM-promoted reactions of anilines with diarylmethanols selectively generate N-alkylated anilines or mono and double Friedel-Crafts alkylation products under different conditions by changing the reaction time, reaction temperature, and the ratio of the reactants. This method does not require the use of transition metal catalysts to prepare alkylated aniline derivatives. PMID:21547437

  3. Bacterial Degradation of Aromatic Compounds

    PubMed Central

    Seo, Jong-Su; Keum, Young-Soo; Li, Qing X.

    2009-01-01

    Aromatic compounds are among the most prevalent and persistent pollutants in the environment. Petroleum-contaminated soil and sediment commonly contain a mixture of polycyclic aromatic hydrocarbons (PAHs) and heterocyclic aromatics. Aromatics derived from industrial activities often have functional groups such as alkyls, halogens and nitro groups. Biodegradation is a major mechanism of removal of organic pollutants from a contaminated site. This review focuses on bacterial degradation pathways of selected aromatic compounds. Catabolic pathways of naphthalene, fluorene, phenanthrene, fluoranthene, pyrene, and benzo[a]pyrene are described in detail. Bacterial catabolism of the heterocycles dibenzofuran, carbazole, dibenzothiophene, and dibenzodioxin is discussed. Bacterial catabolism of alkylated PAHs is summarized, followed by a brief discussion of proteomics and metabolomics as powerful tools for elucidation of biodegradation mechanisms. PMID:19440284

  4. Distance-Dependent Attractive and Repulsive Interactions of Bulky Alkyl Groups.

    PubMed

    Hwang, Jungwun; Li, Ping; Smith, Mark D; Shimizu, Ken D

    2016-07-01

    The stabilizing and destabilizing effects of alkyl groups on an aromatic stacking interaction were experimentally measured in solution. The size (Me, Et, iPr, and tBu) and position (meta and para) of the alkyl groups were varied in a molecular balance model system designed to measure the strength of an intramolecular aromatic interaction. Opposite stability trends were observed for alkyl substituents at different positions on the aromatic rings. At the closer meta-position, smaller groups were stabilizing and larger groups were destabilizing. Conversely, at the farther para-position, the larger alkyl groups were systematically more stabilizing with the bulky tBu group forming the strongest stabilizing interaction. X-ray crystal structures showed that the stabilizing interactions of the small meta-alkyl and large para-alkyl groups were due to their similar distances and van der Waals contact areas with the edge of opposing aromatic ring. PMID:27159670

  5. Method for making aromatic ethers using diorganoamino pyridinium salt catalyst

    SciTech Connect

    Brunelle, D. J.; Singleton, D. A.

    1985-04-23

    A method is provided for making aromatic ethers by effecting the displacement of reactive radicals on an activated aromatic nucleus such as a phthalimide with a mono or bisalkali metal phenoxide in the presence of an organic solvent and a dialkylamino branched alkyl substituted pyridinium salt as a phase transfer catalyst. Improved yields of bis(aromatic ethers) are achieved without the production of undesirable by-products, such as alkylated phenols.

  6. Catalytic alkylation apparatus

    SciTech Connect

    Hann, P.D.; VanPool, J.

    1989-09-05

    This patent describes an apparatus. It comprises alkylation reactor means for producing alkylate product; acid catalyst settler means having an upper portion, an intermediate portion and a lower portion; means for withdrawing alkylate product from the alkylation reactor means and for providing alkylate product from the alkylation reactor means to a point of introduction in the intermediate portion of the acid catalyst settler means; and means for establishing a temperature gradient in the upper the gas lines to the detector so that a flow rate of a sample gas passing through the detector is constant.

  7. Alkylating potential of oxetanes.

    PubMed

    Gómez-Bombarelli, Rafael; Palma, Bernardo Brito; Martins, Célia; Kranendonk, Michel; Rodrigues, Antonio S; Calle, Emilio; Rueff, José; Casado, Julio

    2010-07-19

    Small, highly strained heterocycles are archetypical alkylating agents (oxiranes, beta-lactones, aziridinium, and thiirinium ions). Oxetanes, which are tetragonal ethers, are higher homologues of oxiranes and reduced counterparts of beta-lactones, and would therefore be expected to be active alkylating agents. Oxetanes are widely used in the manufacture of polymers, especially in organic light-emitting diodes (OLEDs), and are present, as a substructure, in compounds such as the widely used antimitotic taxol. Whereas the results of animal tests suggest that trimethylene oxide (TMO), the parent compound, and beta,beta-dimethyloxetane (DMOX) are active carcinogens at the site of injection, no studies have explored the alkylating ability and genotoxicity of oxetanes. This work addresses the issue using a mixed methodology: a kinetic study of the alkylation reaction of 4-(p-nitrobenzyl)pyridine (NBP), a trap for alkylating agents with nucleophilicity similar to that of DNA bases, by three oxetanes (TMO, DMOX, and methyloxetanemethanol), and a mutagenicity, genotoxicity, and cell viability study (Salmonella microsome test, BTC E. coli test, alkaline comet assay, and MTT assay). The results suggest either that oxetanes lack genotoxic capacity or that their mode of action is very different from that of epoxides and beta-lactones. PMID:20550097

  8. Discovery and identification of a series of alkyl decalin isomers in petroleum geological samples.

    PubMed

    Wang, Huitong; Zhang, Shuichang; Weng, Na; Zhang, Bin; Zhu, Guangyou; Liu, Lingyan

    2015-07-01

    The comprehensive two-dimensional gas chromatography/time-of-flight mass spectrometry (GC × GC/TOFMS) has been used to characterize a crude oil and a source rock extract sample. During the process, a series of pairwise components between monocyclic alkanes and mono-aromatics have been discovered. After tentative assignments of decahydronaphthalene isomers, a series of alkyl decalin isomers have been synthesized and used for identification and validation of these petroleum compounds. From both the MS and chromatography information, these pairwise compounds were identified as 2-alkyl-decahydronaphthalenes and 1-alkyl-decahydronaphthalenes. The polarity of 1-alkyl-decahydronaphthalenes was stronger. Their long chain alkyl substituent groups may be due to bacterial transformation or different oil cracking events. This systematic profiling of alkyl-decahydronaphthalene isomers provides further understanding and recognition of these potential petroleum biomarkers. PMID:25945366

  9. Potential Metabolic Activation of a Representative C2-Alkylated Polycyclic Aromatic Hydrocarbon 6-Ethylchrysene Associated with the Deepwater Horizon Oil Spill in Human Hepatoma (HepG2) Cells

    PubMed Central

    2016-01-01

    Exposure to polycyclic aromatic hydrocarbons (PAHs) is the major human health hazard associated with the Deepwater Horizon oil spill. C2-Chrysenes are representative PAHs present in crude oil and could contaminate the food chain. We describe the metabolism of a C2-chrysene regioisomer, 6-ethylchrysene (6-EC), in human HepG2 cells. The structures of the metabolites were identified by HPLC-UV-fluorescence detection and LC-MS/MS. 6-EC-tetraol isomers were identified as signature metabolites of the diol-epoxide pathway. O-Monomethyl-O-monosulfonated-6-EC-catechol, its monohydroxy products, and N-acetyl-l-cysteine(NAC)-6-EC-ortho-quinone were discovered as signature metabolites of the ortho-quinone pathway. Potential dual metabolic activation of 6-EC involving the formation of bis-electrophiles, i.e., a mono-diol-epoxide and a mono-ortho-quinone within the same structure, bis-diol-epoxides, and bis-ortho-quinones was observed as well. The identification of 6-EC-tetraol, O-monomethyl-O-monosulfonated-6-EC-catechol, its monohydroxy products, and NAC-6-EC-ortho-quinone supports potential metabolic activation of 6-EC by P450 and AKR enzymes followed by metabolic detoxification of the ortho-quinone through interception of its redox cycling capability by catechol-O-methyltransferase and sulfotransferase enzymes. The tetraols and catechol conjugates could be used as biomarkers of human exposure to 6-EC resulting from oil spills. PMID:27054409

  10. Potential Metabolic Activation of a Representative C2-Alkylated Polycyclic Aromatic Hydrocarbon 6-Ethylchrysene Associated with the Deepwater Horizon Oil Spill in Human Hepatoma (HepG2) Cells.

    PubMed

    Huang, Meng; Mesaros, Clementina; Zhang, Suhong; Blair, Ian A; Penning, Trevor M

    2016-06-20

    Exposure to polycyclic aromatic hydrocarbons (PAHs) is the major human health hazard associated with the Deepwater Horizon oil spill. C2-Chrysenes are representative PAHs present in crude oil and could contaminate the food chain. We describe the metabolism of a C2-chrysene regioisomer, 6-ethylchrysene (6-EC), in human HepG2 cells. The structures of the metabolites were identified by HPLC-UV-fluorescence detection and LC-MS/MS. 6-EC-tetraol isomers were identified as signature metabolites of the diol-epoxide pathway. O-Monomethyl-O-monosulfonated-6-EC-catechol, its monohydroxy products, and N-acetyl-l-cysteine(NAC)-6-EC-ortho-quinone were discovered as signature metabolites of the ortho-quinone pathway. Potential dual metabolic activation of 6-EC involving the formation of bis-electrophiles, i.e., a mono-diol-epoxide and a mono-ortho-quinone within the same structure, bis-diol-epoxides, and bis-ortho-quinones was observed as well. The identification of 6-EC-tetraol, O-monomethyl-O-monosulfonated-6-EC-catechol, its monohydroxy products, and NAC-6-EC-ortho-quinone supports potential metabolic activation of 6-EC by P450 and AKR enzymes followed by metabolic detoxification of the ortho-quinone through interception of its redox cycling capability by catechol-O-methyltransferase and sulfotransferase enzymes. The tetraols and catechol conjugates could be used as biomarkers of human exposure to 6-EC resulting from oil spills. PMID:27054409

  11. Cobalt-Catalyzed N-Alkylation of Amines with Alcohols.

    PubMed

    Zhang, Guoqi; Yin, Zhiwei; Zheng, Shengping

    2016-01-15

    A well-defined nonprecious metal cobalt(II) catalyst based on a pincer PNP ligand has been employed for the efficient N-alkylation of both aromatic and aliphatic amines with alcohols. A subtle change of reaction conditions (simply adding 4 Å molecular sieves) was observed to readily switch the resulting products (amines vs imines) with high chemoselectivity. A range of alcohols and amines including both aromatic and aliphatic substrates were efficiently converted to secondary amines in good-to-excellent yields when 2 mol % cobalt catalyst was used. Additional experiments indicate that a hydrogen-borrowing mechanism is responsible for the tandem acceptorless dehydrogenation/condensation/hydrogenation process. PMID:26695594

  12. Novel Approach for Evaluating Secondary Organic Aerosol from Aromatic Hydrocarbons: SOA Yield and Chemical Composition

    NASA Astrophysics Data System (ADS)

    Li, Lijie; Tang, Ping; Nakao, Shunsuke; Qi, Li; Kacarab, Mary; Cocker, David

    2016-04-01

    Aromatic hydrocarbons account for 20%-30% of urban atmospheric VOCs and are major contributors to anthropogenic secondary organic aerosol (SOA). However, prediction of SOA from aromatic hydrocarbons as a function of structure, NOx concentration, and OH radical levels remains elusive. Innovative SOA yield and chemical composition evaluation approaches are developed here to investigate SOA formation from aromatic hydrocarbons. SOA yield is redefined in this work by adjusting the molecular weight of all aromatic precursors to the molecular weight of benzene (Yield'= Yieldi×(MWi/MWBenzene); i: aromatic hydrocarbon precursor). Further, SOA elemental ratio is calculated on an aromatic ring basis rather than the classic mole basis. Unified and unique characteristics in SOA formed from aromatic hydrocarbons with different alkyl groups (varying in carbon number and location on aromatic ring) are explored by revisiting fifteen years of UC Riverside/CE-CERT environmental chamber data on 129 experiments from 17 aromatic precursors at urban region relevant low NOx conditions (HC:NO 11.1-171 ppbC:ppb). Traditionally, SOA mass yield of benzene is much greater than that of other aromatic species. However, when adjusting for molecular weight, a similar yield is found across the 17 different aromatic precursors. More importantly, four oxygens per aromatic ring are observed in the resulting SOA regardless of the alkyl substitutes attached to the ring, which majorly affect H/C ratio in SOA. Therefore, resulting SOA bulk composition from aromatic hydrocarbons can be predicted as C6+nH6+2nO4 (n: alkyl substitute carbon number). Further, the dominating role of the aromatic ring carbons is confirmed by studying the chemical composition of SOA formed from the photooxidation of an aromatic hydrocarbon with a 13C isotopically labeled alkyl carbon. Overall, this study unveils the similarity in SOA formation from aromatic hydrocarbons enhancing the understanding of SOA formation from

  13. Supramolecular aromaticity

    NASA Astrophysics Data System (ADS)

    Karabıyık, Hande; Sevinçek, Resul; Karabıyık, Hasan

    2014-05-01

    We report experimental and theoretical evidences for supramolecular aromaticity as a new concept to be widely used in researches about molecular crystals. CSD survey regarding frequently encountered resonance-assisted H-bonds (RAHBs) in formic acid, formamide, formimidamide, formic acid-formamide, and formamide-formimidamide dimers shows that supramolecular quasirings formed by RAHBs have remarkable electronic delocalization within themselves, which is reminiscent of aromaticity at supramolecular level. This study criticizes and reevaluates the validity of conventional judgment which states that ring systems formed by intermolecular H-bonds cannot be aromatic. Thus, the term aromaticity can be extended to supramolecular systems formed by RAHBs. Supramolecular aromaticity has a multi-fold nature involving both σ- and π-delocalization, and σ-delocalization through RAHBs takes on a task of compensating σ-deficiency within quasirings. Atomic composition in donor-acceptor set of the dimers is descriptive for supramolecular aromaticity. We revised bond-valence parameters for RAHBs and they suggest that hypervalent character of H atoms is more pronounced than their hypovalent character in RAHBs. The σ-delocalized bonding within H-bonded quasirings necessitates hypervalent character of H atoms. Quantum chemical calculations based on adiabatic Hydrogen Atom Transfer (HAT) between the monomers reveal that topological parameters at ring critical points (RCPs) of the quasirings correlate well with Shannon's entropic aromaticity index. The presence of additional LP orbital on O atoms implying more diffused LP-orbitals in donor-acceptor set leads to the formation of resonance-disabling states reducing supramolecular aromaticity of a quasiring and energetic cost of the electron transfer between the monomers. There is a nonignorable electron transfer between the monomers even in the cases where H atoms are close to donor or acceptor atom. NBO analyses have revealed that

  14. Method of making alkyl esters

    DOEpatents

    Elliott, Brian

    2010-09-14

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

  15. 40 CFR 721.9595 - Alkyl benzene sulfonic acids and alkyl sulfates, amine salts (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Alkyl benzene sulfonic acids and alkyl... Significant New Uses for Specific Chemical Substances § 721.9595 Alkyl benzene sulfonic acids and alkyl...) The chemical substances identified generically as alkyl benzene sulfonic acids and alkyl...

  16. 40 CFR 721.9595 - Alkyl benzene sulfonic acids and alkyl sulfates, amine salts (generic).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Alkyl benzene sulfonic acids and alkyl... Significant New Uses for Specific Chemical Substances § 721.9595 Alkyl benzene sulfonic acids and alkyl...) The chemical substances identified generically as alkyl benzene sulfonic acids and alkyl...

  17. 40 CFR 721.9595 - Alkyl benzene sulfonic acids and alkyl sulfates, amine salts (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Alkyl benzene sulfonic acids and alkyl... Significant New Uses for Specific Chemical Substances § 721.9595 Alkyl benzene sulfonic acids and alkyl...) The chemical substances identified generically as alkyl benzene sulfonic acids and alkyl...

  18. 40 CFR 721.9595 - Alkyl benzene sulfonic acids and alkyl sulfates, amine salts (generic).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Alkyl benzene sulfonic acids and alkyl... Significant New Uses for Specific Chemical Substances § 721.9595 Alkyl benzene sulfonic acids and alkyl...) The chemical substances identified generically as alkyl benzene sulfonic acids and alkyl...

  19. 40 CFR 721.9595 - Alkyl benzene sulfonic acids and alkyl sulfates, amine salts (generic).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Alkyl benzene sulfonic acids and alkyl... Significant New Uses for Specific Chemical Substances § 721.9595 Alkyl benzene sulfonic acids and alkyl...) The chemical substances identified generically as alkyl benzene sulfonic acids and alkyl...

  20. Mechanism of aromatic hydrocarbon formation in FCC naphtha

    SciTech Connect

    Mota, C.J.A.; Rawet, R.

    1995-12-01

    A microactivity test study of the FCC naphtha composition at increasing conversions was carried out. At low conversions (ca. 10--20%), the naphtha is rich in olefinic and aromatic hydrocarbons. As the conversion increases, the composition changes dramatically. The olefins initially increase and then decrease sharply. The paraffins increase continually, and the aromatics initially decrease and then increase slightly. The naphthenics remain constant in the conversion range studied. These results indicate that, at low conversions, the aromatics in the gasoline are mainly formed by dealkylation of heavy aromatic molecules present in the feed. At higher conversions, however, the aromatics in the naphtha are mainly formed by cyclization followed by hydrogen transfer of the olefins formed during cracking. This reaction also increases the relative concentration of paraffinic hydrocarbons. The distribution of C9 aromatics showed that, as the conversion increases, there occurs an isomerization of the alkyl chain, to increase the branching of the ring.

  1. Polyimides with pendant alkyl groups

    NASA Technical Reports Server (NTRS)

    Jensen, B. J.; Young, P. R.

    1982-01-01

    The effect on selected polyimide properties when pendant alkyl groups were attached to the polymer backbone was investigated. A series of polymers were prepared using benzophenone tetracarboxylic acid dianhydride (BTDA) and seven different p-alkyl-m,p'-diaminobenzophenone monomers. The alkyl groups varied in length from C(1) (methyl) to C(9) (nonyl). The polyimide prepared from BTDA and m,p'-diaminobenzophenone was included as a control. All polymers were characterized by various chromatographic, spectroscopic, thermal, and mechanical techniques. Increasing the length of the pendant alkyl group resulted in a systematic decrease in glass transition temperature (Tg) for vacuum cured films. A 70 C decrease in Tg to 193 C was observed for the nonyl polymer compared to the Tg for the control. A corresponding systematic increase in Tg indicative of crosslinking, was observed for air cured films. Thermogravimetric analysis revealed a slight sacrifice in thermal stability with increasing alkyl length. No improvement in film toughness was observed.

  2. Aromatic graphene

    NASA Astrophysics Data System (ADS)

    Das, D. K.; Sahoo, S.

    2016-04-01

    In recent years graphene attracts the scientific and engineering communities due to its outstanding electronic, thermal, mechanical and optical properties and many potential applications. Recently, Popov et al. [1] have studied the properties of graphene and proved that it is aromatic but without fragrance. In this paper, we present a theory to prepare graphene with fragrance. This can be used as scented pencils, perfumes, room and car fresheners, cosmetics and many other useful household substances.

  3. Visible-light-promoted iminyl radical formation from vinyl azides: synthesis of 6-(fluoro)alkylated phenanthridines.

    PubMed

    Sun, Xiaoyang; Yu, Shouyun

    2016-09-18

    An efficient strategy assisted by visible-light-promoted iminyl radical formation has been developed for the synthesis of 6-(fluoro)alkylated phenanthridine derivatives. In the reactions, addition of alkyl and trifluoromethyl radicals onto vinyl azides gives iminyl radicals, which then undergo intramolecular homolytic aromatic substitution leading to phenanthridines. These reactions can be carried out under mild conditions with high chemical yields and broad substrate scope. PMID:27530901

  4. 40 CFR 721.1875 - Boric acid, alkyl and substituted alkyl esters (generic name).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Boric acid, alkyl and substituted... Significant New Uses for Specific Chemical Substances § 721.1875 Boric acid, alkyl and substituted alkyl... chemical substance boric acid, alkyl and substituted alkyl esters (PMN P-86-1252) is subject to...

  5. 40 CFR 721.1875 - Boric acid, alkyl and substituted alkyl esters (generic name).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Boric acid, alkyl and substituted... Significant New Uses for Specific Chemical Substances § 721.1875 Boric acid, alkyl and substituted alkyl... chemical substance boric acid, alkyl and substituted alkyl esters (PMN P-86-1252) is subject to...

  6. 40 CFR 721.1875 - Boric acid, alkyl and substituted alkyl esters (generic name).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Boric acid, alkyl and substituted... Significant New Uses for Specific Chemical Substances § 721.1875 Boric acid, alkyl and substituted alkyl... chemical substance boric acid, alkyl and substituted alkyl esters (PMN P-86-1252) is subject to...

  7. 40 CFR 721.1875 - Boric acid, alkyl and substituted alkyl esters (generic name).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Boric acid, alkyl and substituted... Significant New Uses for Specific Chemical Substances § 721.1875 Boric acid, alkyl and substituted alkyl... chemical substance boric acid, alkyl and substituted alkyl esters (PMN P-86-1252) is subject to...

  8. 40 CFR 721.1875 - Boric acid, alkyl and substituted alkyl esters (generic name).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Boric acid, alkyl and substituted... Significant New Uses for Specific Chemical Substances § 721.1875 Boric acid, alkyl and substituted alkyl... chemical substance boric acid, alkyl and substituted alkyl esters (PMN P-86-1252) is subject to...

  9. Alkylation and acylation of cyclotriphosphazenes.

    PubMed

    Benson, Mark A; Zacchini, Stefano; Boomishankar, Ramamoorthy; Chan, Yuri; Steiner, Alexander

    2007-08-20

    Phosphazenes (RNH)6P3N3 (R = n-propyl, isobutyl, isopropyl, cyclohexyl, tert-butyl, benzyl) are readily alkylated at ring N sites by alkyl halides forming N-alkyl phosphazenium cations. Alkylation of two ring N sites occurred after prolonged heating in the presence of methyl iodide or immediately at room temperature with methyl triflate yielding N,N'-dimethyl phosphazenium dications. Geminal dichloro derivatives Cl2(RNH)4P3N3 are methylated by methyl iodide at the ring N site adjacent to both P centers carrying four RNH groups. X-ray crystal structures showed that the alkylation of ring N sites leads to substantial elongation of the associated P-N bonds. Both N-alkyl and N,N'-dialkyl phosphazenium salts form complex supramolecular networks in the solid state via NH...X interactions. Systems carrying less-bulky RNH groups show additional NH...N bonds between N-alkyl phosphazenium ions. N-Alkyl phosphazenium halides form complexes with silver ions upon treatment with silver nitrate. Depending on the steric demand of RNH substituents, either one or both of the vacant ring N sites engage in coordination to silver ions. Treatment of (RNH)6P3N3 (R = isopropyl) with acetyl chloride and benzoyl chloride, respectively, yielded N-acyl phosphazenium ions. X-ray crystal structures revealed that elongation of P-N bonds adjacent to the acylated ring N site is more pronounced than it is in the case of N-alkylated species. Salts containing N-alkyl phosphazenium ions are stable toward water and other mild nucleophiles, while N,N'-dialkyl and N-acyl phosphazenium salts are readily hydrolyzed. The reaction of (RNH)6P3N3 with bromoacetic acid led to N-alkylation at one ring N site in addition to formation of an amide via condensation of an adjacent RNH substituent with the carboxylic acid group. The resulting bromide salt contains mono cations of composition (RNH)5P3N3CH2CONR in which a CH2-C(O) unit is embedded between a ring N and an exocyclic N site of the phosphazene. PMID

  10. Mild Catalytic methods for Alkyl-Alkyl Bond Formation

    SciTech Connect

    Vicic, David A

    2009-08-10

    Overview of Research Goals and Accomplishments for the Period 07/01/06 – 06/30/07: Our overall research goal is to transform the rapidly emerging synthetic chemistry involving alkyl-alkyl cross-couplings into more of a mechanism-based field so that that new, rationally-designed catalysts can be performed under energy efficient conditions. Our specific objectives for the previous year were 1) to obtain a proper electronic description of an active catalyst for alkyl-alkyl cross-coupling reactions and 2) to determine the effect of ligand structure on the rate, scope, selectivity, and functional group compatibility of C(sp3)-C(sp3) cross-coupling catalysis. We have completed both of these initial objectives and established a firm base for further studies. The specific significant achievements of the current grant period include: 1) we have performed magnetic and computational studies on (terpyridine)NiMe, an active catalyst for alkyl-alkyl cross couplings, and have discovered that the unpaired electron resides heavily on the terpyridine ligand and that the proper electronic description of this nickel complex is a Ni(II)-methyl cation bound to a reduced terpyridine ligand; 2) we have for the first time shown that alkyl halide reduction by terpyridyl nickel catalysts is substantially ligand based; 3) we have shown by isotopic labeling studies that the active catalyst (terpyridine)NiMe is not produced via a mechanism that involves the formation of methyl radicals when (TMEDA)NiMe2 is used as the catalyst precursor; 4) we have performed an extensive ligand survey for the alkyl-alkyl cross-coupling reactions and have found that electronic factors only moderately influence reactivity in the terpyridine-based catalysis and that the most dramatic effects arise from steric and solubility factors; 5) we have found that the use of bis(dialkylphosphino)methanes as ligands for nickel does not produce active catalysts for cross-coupling but rather leads to bridging hydride

  11. Transformations of Aromatic Compounds by Nitrosomonas europaea

    PubMed Central

    Keener, William K.; Arp, Daniel J.

    1994-01-01

    Benzene and a variety of substituted benzenes inhibited ammonia oxidation by intact cells of Nitrosomonas europaea. In most cases, the inhibition was accompanied by transformation of the aromatic compound to a more oxidized product or products. All products detected were aromatic, and substituents were often oxidized but were not separated from the benzene ring. Most transformations were enhanced by (NH4)2SO4 (12.5 mM) and were prevented by C2H2, a mechanism-based inactivator of ammonia monooxygenase (AMO). AMO catalyzed alkyl substituent hydroxylations, styrene epoxidation, ethylbenzene desaturation to styrene, and aniline oxidation to nitrobenzene (and unidentified products). Alkyl substituents were preferred oxidation sites, but the ring was also oxidized to produce phenolic compounds from benzene, ethylbenzene, halobenzenes, phenol, and nitrobenzene. No carboxylic acids were identified. Ethylbenzene was oxidized via styrene to two products common also to oxidation of styrene; production of styrene is suggestive of an electron transfer mechanism for AMO. Iodobenzene and 1,2-dichlorobenzene were oxidized slowly to halophenols; 1,4-dichlorobenzene was not transformed. No 2-halophenols were detected as products. Several hydroxymethyl (-CH2OH)-substituted aromatics and p-cresol were oxidized by C2H2-treated cells to the corresponding aldehydes, benzaldehyde was reduced to benzyl alcohol, and o-cresol and 2,5-dimethylphenol were not depleted. PMID:16349282

  12. Overview of Polycyclic Aromatic Compounds (PAC)

    PubMed Central

    Achten, Christine; Andersson, Jan T.

    2015-01-01

    The chemical group of polycyclic aromatic compounds (PAC), including the better-known subgroup of polycyclic aromatic hydrocarbons (PAH) and the heterocyclic aromatic compounds (NSO-PAC, heterocycles), comprise several thousand individual compounds. It is hard to find a comprehensive overview in the literature of these PACs that includes a substantial amount of relevant properties. Here an attempt is made to summarize the most studied but also some less well-known PACs. In addition to basic data such as recommended names, abbreviations, CAS numbers, molecular formulas, chemical structures, and exact mono-isotopic molecular weights, physico-chemical properties taken from the literature like boiling points, vapor pressures, water solubilities, Henry's Law constants, n-octanol-water partition coefficients (log KOW), and pKa are summarized. Selected toxicological data are listed indicating carcinogenic and mutagenic activity or effects on different organisms. PAC nomenclature is a complex topic, so suggestions for practical use are made. Regarding available data, estimated (instead of measured) values should be used with caution because considerable deviations from experimentally determined values can occur. For an enhanced understanding of the behavior of single PACs in comparison with each other, some of the properties mentioned above are plotted vs. the number of rings or the degree of alkylation. Also, some physico-chemical data are correlated with different functional groups as substituents of the PAHs. This article reveals that rather little is known about the less common PACs, e.g., higher molecular weight compounds, alkylated or otherwise substituted aromatics, for instance, keto-, oxo-, amino-, nitro-, cyano-PAHs, or some heterocyclic aromatic compounds, including their derivatives. It mirrors the limited state of knowledge about the variety of PACs that do not belong to the 16 EPA PAHs. PMID:26823644

  13. The high-temperature oxidation of aromatic hydrocarbons

    NASA Technical Reports Server (NTRS)

    Brezinsky, K.

    1986-01-01

    Chemical mechanisms of the atmospheric pressure, high-temperature (875-1500 K) gas-phase oxidation of benzene, toluene, ethylbenzene, and propylbenzene are described and discussed. Oxidation trends evident from turbulent flow reactor experiments serve as the basis for the mechanisms of the oxidation of benzene and alkylated aromatics. The potential effects of very high temperatures and pressures on the chemistry of oxidation of aromatics are described. The oxidation of benzene and phenyl radical has been found to proceed in a stepwise C6-C5-C4 sequence. Species profiles obtained from flow-reactor experiments suggest that the oxidation of benzene and phenyl radical follows the generalized route via phenoxy, cyclopentadienyl and butadienyl radical. The oxidation of the C4 species branches into multiple pathways that yield copious amounts of ethylene and acetylene. Certain major trends are evident: the alkylated aromatics on initial attack either form styrene, benzyl radical or benzene. The styrene reacts further to produce a benzyl radical or benzene. The oxidation of an alkylated aromatic hydrocarbon appears eventually to reduce to the oxidation of either phenyl radical or benzene.

  14. Alkylation of toluene with ethanol

    SciTech Connect

    Walendziewski, J.; Trawczynski, J.

    1996-10-01

    A series of Y and ZSM-5 zeolite based catalysts was prepared. Zeolites were cation exchanged and formed with 50% of aluminum hydroxide as a binder, and the obtained catalysts were finally thermally treated. Activity tests in alkylation of toluene with ethanol were carried out in the temperature range of 325--400 C, in nitrogen or hydrogen stream, and a pressure up to 3 MPa. The feed consisted of toluene and ethanol mixed in a mole ratio 1/1 or 2/1. The obtained results showed that among the studied catalysts the highest activity in the alkylation reaction was attained by ZSM-5 zeolite based catalyst with a moderate acidity and medium silica to alumina ratio, i.e., {approximately}50. Activity and selectivity of the most active catalyst as well as conversion of the feed components were similar to those reported in other papers. The content of p-ethyltoluene in alkylation products attained ca. 60%.

  15. From lignin to cycloparaffins and aromatics: directional synthesis of jet and diesel fuel range biofuels using biomass.

    PubMed

    Bi, Peiyan; Wang, Jicong; Zhang, Yajing; Jiang, Peiwen; Wu, Xiaoping; Liu, Junxu; Xue, He; Wang, Tiejun; Li, Quanxin

    2015-05-01

    The continual growth in commercial aviation fuels and more strict environmental legislations have led to immense interest in developing green aviation fuels from biomass. This paper demonstrated a controllable transformation of lignin into jet and diesel fuel range hydrocarbons, involving directional production of C8-C15 aromatics by the catalytic depolymerization of lignin into C6-C8 low carbon aromatic monomers coupled with the alkylation of aromatics, and the directional production of C8-C15 cycloparaffins by the hydrogenation of aromatics. The key step, the production of the desired C8-C15 aromatics with the selectivity up to 94.3%, was achieved by the low temperature alkylation reactions of the lignin-derived monomers using ionic liquid. The synthetic biofuels basically met the main technical requirements of conventional jet fuels. The transformation potentially provides a useful way for the development of cycloparaffinic and aromatic components in jet fuels using renewable lignocellulose biomass. PMID:25710678

  16. A biological source of oceanic alkyl nitrates

    NASA Astrophysics Data System (ADS)

    Dahl, E. E.; Lewis, C. B.; Velasco, F. L.; Escobar, C.; Kellogg, D.; Velcamp, M.

    2013-12-01

    Alkyl nitrates are an important component of reactive nitrogen in the troposphere. The oceans are a source of alkyl nitrates to the atmosphere, however the source of alkyl nitrates in the oceans is unknown. It has been demonstrated that the reaction of alkyl peroxy radicals (ROO) with nitric oxide (NO) produces alkyl nitrates in the aqueous phase. We hypothesize that alkyl nitrates may be formed by organisms through the same reaction and therefore biological production could be a source of alkyl nitrates to the troposphere. This work focuses on the production of alkyl nitrates by the diatoms Chaetoceros muelleri and Thalassiosira weisfloggi. Using chemostats, we measure alkyl nitrates formed under nitrate limited conditions. We also use triggers and inhibitors of nitric oxide formation to determine if alkyl nitrate formation is affected by changes in NO production. To date, the rates of production of alkyl nitrates in our cultures, lead us to estimate a production rate on the order of femtomolar/day for C1-C3 alkyl nitrates by diatom species in the equatorial Pacific Ocean. This suggests that diatoms may contribute to the overall ocean source of alkyl nitrates; however, it is possible that other types of phytoplankton, such as cyanobacteria, that are more abundant in the open ocean, may contribute to a greater extent.

  17. Phosphine-alkene ligand-mediated alkyl-alkyl and alkyl-halide elimination processes from palladium(II).

    PubMed

    Tuxworth, Luke; Baiget, Lise; Phanopoulos, Andreas; Metters, Owen J; Batsanov, Andrei S; Fox, Mark A; Howard, Judith A K; Dyer, Philip W

    2012-10-28

    N-Diphenylphosphino-7-aza-benzobicyclo[2.2.1]hept-2-ene (2) behaves as a chelating phosphine-alkene ligand for Pd(0) and Pd(II), promoting direct alkyl-alkyl and indirect alkyl-halide reductive elimination reactions due to the stabilisation of the resulting bis(phosphine-alkene)Pd(0) complex. PMID:22986447

  18. Novel Approach for Evaluating Secondary Organic Aerosol from Aromatic Hydrocarbons: Unified Method for Predicting Aerosol Composition and Formation.

    PubMed

    Li, Lijie; Tang, Ping; Nakao, Shunsuke; Kacarab, Mary; Cocker, David R

    2016-06-21

    Innovative secondary organic aerosol (SOA) composition analysis methods normalizing aerosol yield and chemical composition on an aromatic ring basis are developed and utilized to explore aerosol formation from oxidation of aromatic hydrocarbons. SOA yield and chemical composition are revisited using 15 years of University of California, Riverside/CE-CERT environmental chamber data on 17 aromatic hydrocarbons with HC:NO ranging from 11.1 to 171 ppbC:ppb. SOA yield is redefined in this work by normalizing the molecular weight of all aromatic precursors to the molecular weight of the aromatic ring [Formula: see text], where i is the aromatic hydrocarbon precursor. The yield normalization process demonstrates that the amount of aromatic rings present is a more significant driver of aerosol formation than the vapor pressure of the precursor aromatic. Yield normalization also provided a basis to evaluate isomer impacts on SOA formation. Further, SOA elemental composition is explored relative to the aromatic ring rather than on a classical mole basis. Generally, four oxygens per aromatic ring are observed in SOA, regardless of the alkyl substitutes attached to the ring. Besides the observed SOA oxygen to ring ratio (O/R ∼ 4), a hydrogen to ring ratio (H/R) of 6 + 2n is observed, where n is the number of nonaromatic carbons. Normalization of yield and composition to the aromatic ring clearly demonstrates the greater significance of aromatic ring carbons compared with alkyl carbon substituents in determining SOA formation and composition. PMID:27177154

  19. 40 CFR 721.9892 - Alkylated urea.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Alkylated urea. 721.9892 Section 721... Alkylated urea. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as an alkylated urea (PMN P-93-1649) is subject to reporting under...

  20. 40 CFR 721.9892 - Alkylated urea.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Alkylated urea. 721.9892 Section 721... Alkylated urea. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as an alkylated urea (PMN P-93-1649) is subject to reporting under...

  1. 40 CFR 721.9892 - Alkylated urea.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Alkylated urea. 721.9892 Section 721... Alkylated urea. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as an alkylated urea (PMN P-93-1649) is subject to reporting under...

  2. 40 CFR 721.9892 - Alkylated urea.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Alkylated urea. 721.9892 Section 721... Alkylated urea. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as an alkylated urea (PMN P-93-1649) is subject to reporting under...

  3. 40 CFR 721.9892 - Alkylated urea.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Alkylated urea. 721.9892 Section 721... Alkylated urea. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as an alkylated urea (PMN P-93-1649) is subject to reporting under...

  4. Oil compositions containing alkyl amine or alkyl mercaptan derivatives of copolymers of an alpha olefin or an alkyl vinyl ether

    SciTech Connect

    Le, H.T.

    1990-02-13

    This patent describes an oil composition. It comprises a major amount of an oil selected from a crude oil or fuel oil and a minor amount of an alkyl amine or alkyl mercaptan derivative of an alpha olefin or alkyl vinyl ether and an unsaturated alpha, beta-dicarboxylic compound copolymer having pour point depressant ;properties. The copolymer comprising the reaction product of an alpha olefin having from about 2 to about 30 carbon atoms or mixtures of alpha olefins having from about 2 to about 30 carbon atoms or an alkyl vinyl ether or mixture of alkyl vinyl ethers.

  5. Application of liquid clathrates for separation of aromatic hydrocarbons from synthetic fuels

    SciTech Connect

    Wilson, M.F.; Zaworotko, M.J.; Fisher, I.P.

    1988-08-01

    The high aromaticity of synthetic crudes from upgraded tar sands degrades mid-distillate fuel quality and incurs high costs through refining by hydrotreating. Recent work has demonstrated that a class of complex ionic liquids liquid clathrates may be used to extract aromatic components from synthetic fuels at ambient temperatures. Liquid clathrates are formed by matching large organic cations, e.g., alkyl ammonium and alkyl pyridinium with air stable anions Al/sub 2/Cl/sub 7/minus// and AlCl/sub 4/minus// in the presence of an aromatic component. Such ternary mixtures typically form two liquid phases; the lower phase is salt-rich and contains a high concentration of aromatic components. Experimental details are given together with preparation procedures and extraction results determined by mass spectrometry and NMR spectroscopy.

  6. Methods of making alkyl esters

    DOEpatents

    Elliott, Brian

    2010-08-03

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

  7. PREPARATION OF ALKYL PYROPHOSPHATE EXTRACTANTS

    DOEpatents

    Levine, C.A.; Skiens, W.E.; Moore, G.R.

    1960-08-01

    A process for providing superior solvent extractants for metal recovery processes is given wherein the extractant comprises an alkyl pyrophosphoric acid ester dissolved in an organic solvent diluent. Finely divided solid P/sub 2/O/ sub 5/ is slurried in an organic solvent-diluent selected from organic solvents such as kerosene, benzene, chlorobenzene, toluene, etc. An alcohol selected from the higher alcohols having 4 to 17 carbon atoms. e.g.. hexanol-1. heptanol-3, octanol-1. 2.6-dimethyl-heptanol-4, and decanol-1, is rapidly added to the P/sub 2/O/sub 5/ slurry in the amount of about 2 moles of alcohol to 1 mole of P/sub 2/ O/sub 5/. The temperature is maintained below about 110 deg C during the course of the P/sub 2/O/sub 5/-alcohol reaction. An alkyl pyrophosphate extractant compound is formed as a consequence of the reaction process. The alkyl pyrophosphate solvent-diluent extractant phase is useful in solvent extraction metal recovery processes.

  8. Lewis Acid Assisted Nickel-Catalyzed Cross-Coupling of Aryl Methyl Ethers by C-O Bond-Cleaving Alkylation: Prevention of Undesired β-Hydride Elimination.

    PubMed

    Liu, Xiangqian; Hsiao, Chien-Chi; Kalvet, Indrek; Leiendecker, Matthias; Guo, Lin; Schoenebeck, Franziska; Rueping, Magnus

    2016-05-10

    In the presence of trialkylaluminum reagents, diverse aryl methyl ethers can be transformed into valuable products by C-O bond-cleaving alkylation, for the first time without the limiting β-hydride elimination. This new nickel-catalyzed dealkoxylative alkylation method enables powerful orthogonal synthetic strategies for the transformation of a variety of naturally occurring and easily accessible anisole derivatives. The directing and/or activating properties of aromatic methoxy groups are utilized first, before they are replaced by alkyl chains in a subsequent coupling process. PMID:27062726

  9. 40 CFR 721.8673 - [(Disubstituted phenyl)]azo dihydro hydroxy alkyl oxo alkyl-substituted-pyridines (generic name).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false azo dihydro hydroxy alkyl oxo alkyl... Significant New Uses for Specific Chemical Substances § 721.8673 azo dihydro hydroxy alkyl oxo alkyl...) The chemical substances identified generically as azo dihydro hydroxy alkyl oxo...

  10. 40 CFR 721.8673 - [(Disubstituted phenyl)]azo dihydro hydroxy alkyl oxo alkyl-substituted-pyridines (generic name).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false azo dihydro hydroxy alkyl oxo alkyl... Significant New Uses for Specific Chemical Substances § 721.8673 azo dihydro hydroxy alkyl oxo alkyl...) The chemical substances identified generically as azo dihydro hydroxy alkyl oxo...

  11. 40 CFR 721.8673 - [(Disubstituted phenyl)]azo dihydro hydroxy alkyl oxo alkyl-substituted-pyridines (generic name).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false azo dihydro hydroxy alkyl oxo alkyl... Significant New Uses for Specific Chemical Substances § 721.8673 azo dihydro hydroxy alkyl oxo alkyl...) The chemical substances identified generically as azo dihydro hydroxy alkyl oxo...

  12. Chemotopic Representations of Aromatic Odorants in the Rat Olfactory Bulb

    PubMed Central

    Farahbod, Haleh; Johnson, Brett A.; Minami, S. Sakura; Leon, Michael

    2008-01-01

    Our laboratory has characterized spatial patterns of evoked neural activity across the entire glomerular layer of the rat olfactory bulb using primarily aliphatic odorants that differ systematically in functional groups and hydrocarbon structures. To represent more fully the true range of odorant chemistry, we have investigated aromatic compounds, which have a more rigid molecular structure than most aliphatic compounds and are particularly salient olfactory stimuli for humans. We first investigated glomerular patterns of 2-deoxyglucose uptake in response to aromatic compounds that differ in the nature and position of their functional groups (e.g., xylenes, trimethylbenzenes, tolualdehydes, benzaldehydes, methyl toluates, and anisaldehydes). We also studied the effects of systematic increases in the number and length of alkyl substituents. We found that most aromatic compounds activated glomeruli in the dorsal part of the bulb. Within this general area, aromatic odorants with oxygen-containing substituents favored activation of more rostral regions, and aromatic hydrocarbons activated more posterior regions. The nature of substituents greatly affected the pattern of glomerular activation, whereas isomers differing in substitution position evoked very similar overall patterns. These relationships between the structure of aromatic compounds and their spatial representation in the bulb are contrasted with our previous findings with aliphatic odorants. PMID:16736464

  13. Occupational asthma due to alkyl cyanoacrylate

    SciTech Connect

    Nakazawa, T. )

    1990-08-01

    A case of bronchial asthma induced by occupational exposure to alkyl cyanoacrylate, an adhesive, occurred in an assembly operation. Provocative exposure testing induced immediate and delayed asthmatic responses. Alkyl cyanoacrylate seemed to act as an allergen or as an irritant, resulting in the development of asthma.

  14. Stabilized dialkyl aluminum complexes as alkylating agents

    SciTech Connect

    Blum, J.; Baidossi, W.; Rosenfeld, A.

    1995-12-31

    Although trialkylaluminum derivatives are widely used as Ziegler-Natta polymerization co-catalysts, their application as routine alkylating agents is limited owing to their pyrophoric nature. The authors have now found that substitution of one of the alkyl moieties by a chelating group reduces the sensitivity of the organoaluminum compounds to air, and enables one to utilize them under normal laboratory conditions.

  15. Source identification of aromatic hydrocarbons in sediments using GC/MS

    SciTech Connect

    Sporstoel, S.; Gjos, N.; Lichtenthaler, R.G.; Gustavsen, K.O.; Urdal, K.; Oreld, F.; Skel, J.

    1983-01-01

    A method that may distinguish between input of polycyclic aromatic hydrocarbons (PAH) from petroleum and combustion sources is demonstrated on sediment samples. Selected series of aromatics (unsubstituted compounds and their C/sub 1/-C/sub 3/ alkyl homologues) are quantified by computerized GC/MS. The alkyl homologue distribution (AHD) within each series and the sum of components in each series relative to the sum of all components measured (relative amount of each aromatic series (RAA)) are graphically visualized. In combination these parameters give a first-order indication of the PAH source. Pyrene/fluoranthene AHD series appear to be especially sensitive as an indicator for detecting PAH from combustion sources. Interestingly the dibenzothiophene AHD series does not discriminate between crude oil and soot samples. The method is demonstrated on sediments from the North Sea and from Norwegian and Swedish fjords.

  16. C-Alkylation by Hydrogen Autotransfer Reactions.

    PubMed

    Obora, Yasushi

    2016-04-01

    The development of practical, efficient, and atom-economical methods for the formation of carbon-carbon bonds remains a topic of considerable interest in current synthetic organic chemistry. In this review, we have summarized selected topics from the recent literature with particular emphasis on C-alkylation processes involving hydrogen transfer using alcohols as alkylation reagents. This review includes selected highlights concerning recent progress towards the modification of catalytic systems for the α-alkylation of ketones, nitriles, and esters. Furthermore, we have devoted a significant portion of this review to the methylation of ketones, alcohols, and indoles using methanol. Lastly, we have also documented recent advances in β-alkylation methods involving the dimerization of alcohols (Guerbet reaction), as well as new developments in C-alkylation methods based on sp (3) C-H activation. PMID:27573136

  17. Theory Of Alkyl Terminated Silicon Quantum Dots

    SciTech Connect

    Reboredo, F; Galli, G

    2004-08-19

    We have carried out a series of ab-initio calculations to investigate changes in the optical properties of Si quantum dots as a function of surface passivation. In particular, we have compared hydrogen passivated dots with those having alkyl groups at the surface. We find that, while on clusters with reconstructed surfaces a complete alkyl passivation is possible, steric repulsion prevents full passivation of Si dots with unreconstructed surfaces. In addition, our calculations show that steric repulsion may have a dominant effect in determining the surface structure, and eventually the stability of alkyl passivated clusters, with results dependent on the length of the carbon chain. Alkyl passivation weakly affects optical gaps of silicon quantum dots, while it substantially decreases ionization potentials and electron affinities and affect their excited state properties. On the basis of our results we propose that alkyl terminated quantum dots may be size selected taking advantage of the change in ionization potential as a function of the cluster size.

  18. Alkylating reactivity and herbicidal activity of chloroacetamides.

    PubMed

    Jablonkai, Istvan

    2003-04-01

    The relationship between S- and N-alkylating reactivity and herbicidal activity within a series of chloroacetamides, including several commercial herbicides and newly synthesised analogues was studied. The S-alkylating reactivity of selected chloroacetamides, as well as those of atrazine and chlorfenprop-methyl, was determined by in vitro GSH conjugation at a ratio of GSH to alkylating agent of 25:1. A spectrophotometric reaction using 4-(4-nitrobenzyl)pyridine was used to characterise the N-alkylating reactivity of the chemicals. Our results indicate that a reduced level of N-alkylating reactivity correlates with an improved herbicidal efficacy at a practical rate. However, the phytoxicity of the molecules is not simply dependent on chemical reactivities, but strictly related to the molecular structure, indicating that lipophilicity, uptake, mobility and induction of detoxifying enzymes may also be decisive factors in the mode of action. PMID:12701706

  19. DNA-damaging disinfection byproducts: alkylation mechanism of mutagenic mucohalic acids.

    PubMed

    Gómez-Bombarelli, Rafael; González-Pérez, Marina; Arenas-Valgañón, Jorge; Céspedes-Camacho, Isaac Fabián; Calle, Emilio; Casado, Julio

    2011-10-15

    Hydroxyhalofuranones form a group of genotoxic disinfection byproduct (DBP) of increasing interest. Among them, mucohalic acids (3,4-dihalo-5-hydroxyfuran-2(5H)-one, MXA) are known mutagens that react with nucleotides, affording etheno, oxaloetheno, and halopropenal derivatives. Mucohalic acids have also found use in organic synthesis due to their high functionalization. In this work, the alkylation kinetics of mucochloric and mucobromic acids with model nucleophiles aniline and NBP has been studied experimentally. Also, the alkylation mechanism of nucleosides by MXA has been studied in silico. The results described allow us to reach the following conclusions: (i) based on the kinetic and computational evidence obtained, a reaction mechanism was proposed, in which MXA react directly with amino groups in nucleotides, preferentially attacking the exocyclic amino groups over the endocyclic aromatic nitrogen atoms; (ii) the suggested mechanism is in agreement with both the product distribution observed experimentally and the mutational pattern of MXA; (iii) the limiting step in the alkylation reaction is addition to the carbonyl group, subsequent steps occurring rapidly; and (iv) mucoxyhalic acids, the hydrolysis products of MXA, play no role in the alkylation reaction by MXA. PMID:21910489

  20. PAH phototoxicity: Identification of sensitive marine infaunal crustaceans and the effects of alkylation

    SciTech Connect

    Boese, B.; Swartz, R.; Lamberson, J.

    1995-12-31

    The toxicity of some polycyclic aromatic hydrocarbons (PAHs) has been shown to be greatly enhanced in the presence of UV light. The objectives of the research were to: (1) test for PAH phototoxicity using seven marine infaunal crustacean species, (2) determine if the sensitivity to PAH phototoxicity was related to their potential exposure to sunlight in nature, and (3) determine if alkylation alters PAH phototoxicity. The first objective was accomplished by exposing test species to fluoranthene in 4-day, water-only bioassays. Survivors of the tests were then exposed to UV light in an exposure chamber for one hour. The differences between EC50s (the ability to bury in sediment) before and after UV exposure were used to access phototoxicity. The results indicated that species having the greatest potential for natural exposure to sunlight were the least sensitive UV-enhanced fluoranthene toxicity. The amphipod, Rhepoxynius abronius, which in nature has the least potential for exposure to sunlight among the organisms tested, was the most sensitive. Rhepoxynius abronius was subsequently used in a series of tests to determine if alkylation of PAHs alters phototoxicity. This was done by conducting standard 10-day sediment bioassay using alkylated and unalkylated PAHs. As in the water-only tests, EC{sub 50}s were determined before and after UV light exposures. The results indicated that alkylation of PAHs, in general, did not alter phototoxicity.

  1. Nucleophilic Aromatic Substitution.

    ERIC Educational Resources Information Center

    Avila, Walter B.; And Others

    1990-01-01

    Described is a microscale organic chemistry experiment which demonstrates one feasible route in preparing ortho-substituted benzoic acids and provides an example of nucleophilic aromatic substitution chemistry. Experimental procedures and instructor notes for this activity are provided. (CW)

  2. Motor fuel alkylation process utilizing low acid

    SciTech Connect

    Kocal, J.A.; Imai, T.

    1987-01-06

    A process is described for the alkylation of an isoparaffin with an olefin acting agent comprising contacting the isoparaffin with the olefin acting agent at alkylation conditions in the presence of a catalyst. The catalyst consists essentially of an anhydrous, nonalcoholic mixture of from about 5 to 15 wt. % methyl tert-butyl ether and from 85 to 95 wt. % hydrofluoric acid. The volumetric ratio of hydrofluoric acid to isoparaffin and olefin acting agent is less than 0.75.

  3. Trimerization of aromatic nitriles

    NASA Technical Reports Server (NTRS)

    Hsu, L. C. (Inventor)

    1977-01-01

    Triazine compounds and cross-linked polymer compositions were made by heating aromatic nitriles to a temperature in the range of about 100 C to about 700 C, in the presence of a catalyst or mixture of catalysts. Aromatic nitrile-modified (terminated and/or appended) imide, benzimidazole, imidazopyrrolone, quinoxaline, and other condensation type prepolymers or their precopolymers were made which were trimerized with or without a filler by the aforementioned catalytic trimerization process.

  4. Thermally induced alkylation of diamond.

    PubMed

    Hoeb, Marco; Auernhammer, Marianne; Schoell, Sebastian J; Brandt, Martin S; Garrido, Jose A; Stutzmann, Martin; Sharp, Ian D

    2010-12-21

    We present an approach for the thermally activated formation of alkene-derived self-assembled monolayers on oxygen-terminated single and polycrystalline diamond surfaces. Chemical modification of the oxygen and hydrogen plasma-treated samples was achieved by heating in 1-octadecene. The resulting layers were characterized using X-ray photoelectron spectroscopy, thermal desorption spectroscopy, atomic force microscopy, Fourier transform infrared spectroscopy, and water contact angle measurements. This investigation reveals that alkenes selectively attach to the oxygen-terminated sites via covalent C-O-C bonds. The hydrophilic oxygen-terminated diamond is rendered strongly hydrophobic following this reaction. The nature of the process limits the organic layer growth to a single monolayer, and FTIR measurements reveal that such monolayers are dense and well ordered. In contrast, hydrogen-terminated diamond sites remain unaffected by this process. This method is thus complementary to the UV-initiated reaction of alkenes with diamond, which exhibits the opposite reactivity contrast. Thermal alkylation increases the range of available diamond functionalization strategies and provides a means of straightforwardly forming single organic layers in order to engineer the surface properties of diamond. PMID:21090790

  5. Aromatic Polyimide Foam

    NASA Technical Reports Server (NTRS)

    Weiser, Erik S. (Inventor); St.Clair, Terry L. (Inventor); Echigo, Yoshiaki (Inventor); Kaneshiro, Hisayasu (Inventor)

    2000-01-01

    A mechanically undensified aromatic polyimide foam is made from an aromatic polyimide precursor solid residuum and has the following combination of properties: a density according to ASTM D-3574A of about 0.5 pounds/cu.ft to about 20 pounds/cu.ft; a compression strength according to ASTM D-3574C of about 1.5 psi to about 1500 psi; and a limiting oxygen index according to ASTM D-2863 of about 35% oxygen to about 75% oxygen at atmospheric pressure. The aromatic polyimide foam has no appreciable solid inorganic contaminants which are residues of inorganic blowing agents. The aromatic polyimide which constitutes the aromatic polyimide foam has a glass transition temperature (Tg) by differential scanning calorimetry of about 235 C to about 400 C; and a thermal stability of 0 to about 1% weight loss at 204 C as determined by thermogravinietric analysis (TGA). The aromatic polyimide foam has utility as foam insulation and as structural foam, for example, for aeronautical, aerospace and maritime applications.

  6. N-Alkylation by Hydrogen Autotransfer Reactions.

    PubMed

    Ma, Xiantao; Su, Chenliang; Xu, Qing

    2016-06-01

    Owing to the importance of amine/amide derivatives in all fields of chemistry, and also the green and environmentally benign features of using alcohols as alkylating reagents, the relatively high atom economic dehydrative N-alkylation reactions of amines/amides with alcohols through hydrogen autotransfer processes have received much attention and have developed rapidly in recent decades. Various efficient homogeneous and heterogeneous transition metal catalysts, nano materials, electrochemical methods, biomimetic methods, asymmetric N-alkylation reactions, aerobic oxidative methods, and even certain transition metal-free, catalyst-free, or autocatalyzed methods, have also been developed in recent years. With a brief introduction to the background and developments in this area of research, this chapter focuses mainly on recent progress and technical and conceptual advances contributing to the development of this research in the last decade. In addition to mainstream research on homogeneous and heterogeneous transition metal-catalyzed reactions, possible mechanistic routes for hydrogen transfer and alcohol activation, which are key processes in N-alkylation reactions but seldom discussed in the past, the recent reports on computational mechanistic studies of the N-alkylation reactions, and the newly emerged N-alkylation methods based on novel alcohol activation protocols such as air-promoted reactions and transition metal-free methods, are also reviewed in this chapter. Problems and bottlenecks that remained to be solved in the field, and promising new research that deserves greater future attention and effort, are also reviewed and discussed. PMID:27573267

  7. The effect of the cation alkyl chain branching on mutual solubilities with water and toxicities.

    PubMed

    Kurnia, Kiki A; Sintra, Tânia E; Neves, Catarina M S S; Shimizu, Karina; Canongia Lopes, José N; Gonçalves, Fernando; Ventura, Sónia P M; Freire, Mara G; Santos, Luís M N B F; Coutinho, João A P

    2014-10-01

    The design of ionic liquids has been focused on the cation-anion combinations but other more subtle approaches can be used. In this work the effect of the branching of the cation alkyl chain on the design of ionic liquids (ILs) is evaluated. The mutual solubilities with water and toxicities of a series of bis(trifluoromethylsulfonyl)-based ILs, combined with imidazolium, pyridinium, pyrrolidinium, and piperidinium cations with linear or branched alkyl chains, are reported. The mutual solubility measurements were carried out in the temperature range from (288.15 to 323.15) K. From the obtained experimental data, the thermodynamic properties of the solution (in the water-rich phase) were determined and discussed. The COnductor like Screening MOdel for Real Solvents (COSMO-RS) was used to predict the liquid-liquid equilibrium. Furthermore, molecular dynamic simulations were also carried out aiming to get a deeper understanding of these fluids at the molecular level. The results show that the increase in the number of atoms at the cation ring (from five to six) leads to a decrease in the mutual solubilities with water while increasing their toxicity, and as expected from the well-established relationship between toxicities and hydrophobicities of ILs. The branching of the alkyl chain was observed to decrease the water solubility in ILs, while increasing the ILs solubility in water. The inability of COSMO-RS to correctly predict the effect of branching alkyl chains toward water solubility on them was confirmed using molecular dynamic simulations to be due to the formation of nano-segregated structures of the ILs that are not taken into account by the COSMO-RS model. In addition, the impact of branched alkyl chains on the toxicity is shown to be not trivial and to depend on the aromatic nature of the ILs. PMID:25119425

  8. The effect of the cation alkyl chain branching on mutual solubilities with water and toxicities

    PubMed Central

    Kurnia, Kiki A.; Sintra, Tânia E.; Neves, Catarina M. S. S.; Shimizu, Karina; Lopes, José N. Canongia; Gonçalves, Fernando; Ventura, Sónia P. M.; Freire, Mara G.; Santos, Luís M. N. B. F.; Coutinho, João A. P.

    2014-01-01

    The design of ionic liquids has been focused on the cation-anion combinations but other more subtle approaches can be used. In this work the effect of the branching of the cation alkyl chain on the design of ionic liquids (ILs) is evaluated. The mutual solubilities with water and toxicities of a series of bis(trifluoromethylsulfonyl)-based ILs, combined with imidazolium, pyridinium, pyrrolidinium, and piperidinium cations with linear or branched alkyl chains, are reported. The mutual solubility measurements were carried out in the temperature range from (288.15 to 323.15) K. From the obtained experimental data, the thermodynamic properties of the solution (in the water-rich phase) were determined and discussed. The COnductor like Screening MOdel for Real Solvents (COSMO-RS) was used to predict the liquid-liquid equilibrium. Furthermore, molecular dynamic simulations were also carried out aiming to get a deeper understanding of these fluids at the molecular level. The results show that the increase in the number of atoms at the cation ring (from five to six) leads to a decrease in the mutual solubilities with water while increasing their toxicity, and as expected from the well-established relationship between toxicities and hydrophobicities of ILs. The branching of the alkyl chain was observed to decrease the water solubility in ILs, while increasing the ILs solubility in water. The inability of COSMO-RS to correctly predict the effect of branching alkyl chains toward water solubility on them was confirmed using molecular dynamic simulations to be due to the formation of nano-segregated structures of the ILs that are not taken into account by the COSMO-RS model. In addition, the impact of branched alkyl chains on the toxicity is shown to be not trivial and to depend on the aromatic nature of the ILs. PMID:25119425

  9. Blend of alkyl phenol ethoxylates and alkyl phenol glycoxylates and their use as surfactants

    SciTech Connect

    Grolitzer, M. A.

    1985-11-12

    Nonionic surfactant compositions useful in forming stable emulsions with oil in saline solutions comprising a blend of: at least one alkyl phenol ethoxylate and at least one alkyl phenol glycoxylate. These surfactant compositions may be employed in enhanced oil recovery processes and other applications where good emulsification and high salinity tolerances are required such as textiles, leather, dairy, concrete grinding aids and drilling muds.

  10. Alkyl rearrangement processes in organozirconium complexes. Observation of internal alkyl complexes during hydrozirconation

    SciTech Connect

    Chirik, P.J.; Day, M.W.; Labinger, J.A.; Bercaw, J.E.

    1999-11-10

    Isotopically labeled alkyl zirconocene complexes of the form (CpR{sub n}){sub 2}Zr(CH{sub 2}CDR{sub 2}{prime})(X) (CpR{sub n} = alkyl-substituted cyclopentadienyl; R{prime} = H, alkyl group; X = H, D, Me) undergo isomerization of the alkyl ligand as well as exchange with free olefin in solution under ambient conditions. Increasing the substitution on the Cp ring results in slower isomerization reactions, but these steric effects are small. In contrast, changing X has a very large effect on the rate of isomerization. Pure {sigma}-bonding ligands such as methyl and hydride promote rapid isomerization, whereas {pi}-donor ligands inhibit {beta}-H elimination and hence alkyl isomerization. For ({eta}{sup 5}-C{sub 5}H{sub 5}){sub 2}Zr(R)(Cl), internal alkyl complexes have been observed for the first time. The rate of isomerization depends on the length of the alkyl group: longer alkyl chains (heptyl, hexyl) isomerize faster than shorter chains (butyl). The transient intermediate species have been identified by a combination of isotopic labeling and {sup 1}H, {sup 2}H, and {sup 13}C NMR experiments. The solid-state structure of the zirconocene cyclopentyl chloride complex, Cp{sub 2}Zr(cyclo-C{sub 5}H{sub 9})(Cl), has been determined by X-ray diffraction.

  11. Alkylation of isobutane with light olefins: Yields of alkylates for different olefins

    SciTech Connect

    Albright, L.F.; Kranz, K.E.; Masters, K.R.

    1993-12-01

    For alkylation of isobutane with C{sub 3}-C{sub 5} olefins using sulfuric acid as the catalyst, the yields of alkylates with different olefins are compared as the operating conditions are changed. The results of recent pilot plant experiments with propylene, C{sub 4} olefins, and C{sub 5} olefins permit such comparisons. The yields expressed as weight of alkylate produced per 100 wt of olefin consumed varied from about 201:100 to 220:100. Weight ratios of the isobutane consumed per olefin consumed vary from about 101:100 to 120:100. differences of yield values are explained by the changes in the overall chemistry. The procedure employed to calculate yields with good accuracy is based on the analysis of the alkylate and the amount of conjunct polymers produced. Based on literature data, yields are also reported for alkylations using HF as the catalyst.

  12. Alkyl phosphonic acids and sulfonic acids in the Murchison meteorite

    NASA Technical Reports Server (NTRS)

    Cooper, George W.; Onwo, Wilfred M.; Cronin, John R.

    1992-01-01

    Homologous series of alkyl phosphonic acids and alkyl sulfonic acids, along with inorganic orthophosphate and sulfate, are identified in water extracts of the Murchison meteorite after conversion to their t-butyl dimethylsilyl derivatives. The methyl, ethyl, propyl, and butyl compounds are observed in both series. Five of the eight possible alkyl phosphonic acids and seven of the eight possible alkyl sulfonic acids through C4 are identified. Abundances decrease with increasing carbon number as observed of other homologous series indigenous to Murchison. Concentrations range downward from approximately 380 nmol/gram in the alkyl sulfonic acid series, and from 9 nmol/gram in the alkyl phosphonic acid series.

  13. Organic Modification of a Layered Silicate by Co-Ion Exchange of an Alkyl Ammonium and a Mono-Protonated Diamine

    NASA Technical Reports Server (NTRS)

    Campbell, Sandi G. (Inventor)

    2004-01-01

    Co-Ion exchange of the interlayer cations of a layered silicate with a mono-protonated aromatic diamine and an alkyl ammonium ion into the silicate galleries. The presence of the alkyl ammonium ion provides low oligomer melt viscosity during processing. The presence of the diamine allows chemical reaction between the silicate surface modification and the monomers. This reaction strengthens the polymer silicate interface, and ensures irreversible separation of the individual silicate layers. Improved polymer thermal oxidative stability and mechanical properties are obtained.

  14. Formation of α-keto alkyl radical in the photoreduction of chromone as studied by the laser photolysis—ESR technique

    NASA Astrophysics Data System (ADS)

    Igarashi, Masatoshi; Sakaguchi, Yoshio; Hayashi, Hisaharu; I'Haya, Yasumasa J.

    1991-06-01

    In the photochemical hydrogen abstraction reactions of chromone in 2-propanol at room temperature, beside its ketyl radical, the α-keto alkyl radical from chromone was observed, with the aid of the time-resolved electron spin resonance technique. When tri- n-butylin hydride was used as a hydrogen donor, the α-keto alkyl radical was produced predominantly from the lowest ππ* triplet state. The formation of such a non-ketyl radical in the hydrogen abstraction reaction with both of the hydrogen donors indicates the popularity of the hydrogen abstraction reactions from the ππ* triplet state of aromatic carbonyl compounds.

  15. Magnetic criteria of aromaticity.

    PubMed

    Gershoni-Poranne, Renana; Stanger, Amnon

    2015-09-21

    This review describes the current state of magnetic criteria of aromaticity. The introduction contains the fundamentals of ring currents in aromatic and antiaromatic systems, followed by a brief description of experimental and computational tools: NMR, diamagnetic susceptibility exaltation, current density analyses (CDA) and nucleus independent chemical shifts (NICS). This is followed by more comprehensive chapters: NMR - focusing on the work of R. Mitchell - NICS and CDA - describing the progress and development of the methods to their current state and presenting some examples of representative work. PMID:26035305

  16. Classical density functional theory & simulations on a coarse-grained model of aromatic ionic liquids.

    PubMed

    Turesson, Martin; Szparaga, Ryan; Ma, Ke; Woodward, Clifford E; Forsman, Jan

    2014-05-14

    A new classical density functional approach is developed to accurately treat a coarse-grained model of room temperature aromatic ionic liquids. Our major innovation is the introduction of charge-charge correlations, which are treated in a simple phenomenological way. We test this theory on a generic coarse-grained model for aromatic RTILs with oligomeric forms for both cations and anions, approximating 1-alkyl-3-methyl imidazoliums and BF₄⁻, respectively. We find that predictions by the new density functional theory for fluid structures at charged surfaces are very accurate, as compared with molecular dynamics simulations, across a range of surface charge densities and lengths of the alkyl chain. Predictions of interactions between charged surfaces are also presented. PMID:24718295

  17. Polybenzimidazole via aromatic nucleophilic displacement

    NASA Technical Reports Server (NTRS)

    Connell, John W. (Inventor); Hergenrother, Paul M. (Inventor); Smith, Joseph G. (Inventor)

    1994-01-01

    Di(hydroxyphenyl)benzimidazole monomers were prepared from phenyl-4-hydroxybenzoate and aromatic bis(o-diamine)s. These monomers were used in the synthesis of soluble polybenzimidazoles. The reaction involved the aromatic nucleophilic displacement of various di(hydroxyphenyl)benzimidazole monomers with activated aromatic dihalides or activated aromatic dinitro compounds in the presence of an alkali metal base. These polymers exhibited lower glass transition temperatures, improved solubility, and better compression moldability over their commercial counterparts.

  18. Field validation of polyethylene passive air samplers for parent and alkylated PAHs in Alexandria, Egypt.

    PubMed

    Khairy, Mohammed A; Lohmann, Rainer

    2012-04-01

    Polyethylene samplers (PEs) were deployed at 11 locations in Alexandria, Egypt during summer and winter to test and characterize them as passive samplers for concentrations, sources, and seasonal variations of atmospheric concentrations of polycyclic aromatic hydrocarbons (PAHs). PE-air equilibrium was attained faster for a wider range of PAHs during the winter season possibly due to increased wind speeds. Calculated PE-air partitioning constants, K(PE-A), in our study [Log K(PE-A) = 0.9426 × Log K(OA) - 0.022 (n = 12, R(2) = 0.99, Std error = 0.053)] agreed with literature values within <46%. For parent (except naphthalene), mono- and dialkylated PAHs, active sampling based concentrations of PAHs were within an average factor of 1.4 (1.0-5.6) compared to the PE based values. For C(3-4) alkylated PAHs, K(PE-A) values were lower than predicted, on average by ~0.8 log units per carbon in the alkylation. Enthalpies of vaporization (ΔH(vap)) accurately corrected K(PE-A)s for temperature differences between winter and summer sampling. PAH profiles were dominated by naphthalene, phenanthrene, and alkylated phenanthrenes. Calculated diagnostic ratios indicated that PAHs originated mainly from vehicle emissions. PMID:22397460

  19. Microbial Degradation of Alkyl Carbazoles in Norman Wells Crude Oil

    PubMed Central

    Fedorak, Phillip M.; Westlake, Donald W. S.

    1984-01-01

    Norman Wells crude oil was fractionated by sequential alumina and silicic acid column chromatography methods. The resulting nitrogen-rich fraction was analyzed by gas chromatography-mass spectrometry and showed 26 alkyl (C1 to C5) carbazoles to be the predominant compounds. An oil-degrading mixed bacterial culture was enriched on carbazole to enhance its ability to degrade nitrogen heterocycles. This culture was used to inoculate a series of flasks of mineral medium and Norman Wells crude oil. Residual oil was recovered from these cultures after incubation at 25°C for various times. The nitrogen-rich fraction was analyzed by capillary gas chromatography, using a nitrogen-specific detector. Most of the C1-, C2-, and C3- carbazoles and one of the C4-isomers were degraded within 8 days. No further degradation occurred when incubation was extended to 28 days. The general order of susceptibility of the isomers to biodegradation was C1 > C2 > C3 > C4. The carbazole-enriched culture was still able to degrade n-alkanes, isoprenoids, aromatic hydrocarbons, and sulfur heterocycles in the crude soil. PMID:16346524

  20. Enhancement of alkylation catalysts for improved supercritical fluid regeneration

    DOEpatents

    Ginosar, Daniel M.; Petkovic, Lucia

    2009-09-22

    A method of modifying an alkylation catalyst to reduce the formation of condensed hydrocarbon species thereon. The method comprises providing an alkylation catalyst comprising a plurality of active sites. The plurality of active sites on the alkylation catalyst may include a plurality of weakly acidic active sites, intermediate acidity active sites, and strongly acidic active sites. A base is adsorbed to a portion of the plurality of active sites, such as the strongly acidic active sites, selectively poisoning the strongly acidic active sites. A method of modifying the alkylation catalyst by providing an alkylation catalyst comprising a pore size distribution that sterically constrains formation of the condensed hydrocarbon species on the alkylation catalyst or by synthesizing the alkylation catalyst to comprise a decreased number of strongly acidic active sites is also disclosed, as is a method of improving a regeneration efficiency of the alkylation catalyst.

  1. Enhancement of alkylation catalysts for improved supercritical fluid regeneration

    DOEpatents

    Ginosar, Daniel M.; Petkovic, Lucia M.

    2010-12-28

    A method of modifying an alkylation catalyst to reduce the formation of condensed hydrocarbon species thereon. The method comprises providing an alkylation catalyst comprising a plurality of active sites. The plurality of active sites on the alkylation catalyst may include a plurality of weakly acidic active sites, intermediate acidity active sites, and strongly acidic active sites. A base is adsorbed to a portion of the plurality of active sites, such as the strongly acidic active sites, selectively poisoning the strongly acidic active sites. A method of modifying the alkylation catalyst by providing an alkylation catalyst comprising a pore size distribution that sterically constrains formation of the condensed hydrocarbon species on the alkylation catalyst or by synthesizing the alkylation catalyst to comprise a decreased number of strongly acidic active sites is also disclosed, as is a method of improving a regeneration efficiency of the alkylation catalyst.

  2. Solid and liquid charge-transfer complex formation between 1-methylnaphthalene and 1-alkyl-cyanopyridinium bis{(trifluoromethyl)sulfonyl}imide ionic liquids.

    PubMed

    Hardacre, Christopher; Holbrey, John D; Mullan, Claire L; Nieuwenhuyzen, Mark; Youngs, Tristan G A; Bowron, Daniel T; Teat, Simon J

    2010-02-28

    Liquid charge-transfer (CT) complexes were observed to form on contacting electron-rich aromatics with electron withdrawing group appended 1-alkyl-4-cyanopyridinium ionic liquids (ILs). Cooling below the melting point of the ionic liquid resulted in crystallisation of ionic liquid from the complex for 2-cyano and 3-cyano pyridinium isomers and in the formation of a 1 : 1 IL : aromatic crystalline CT-complex with the 4-cyanopyridinium isomer. The liquid structure of a 1 : 1 mixture of 1-methyl-4-cyanopyridinium bis{(trifluoromethyl)sulfonyl}imide with 1-methylnaphthalene has been probed by neutron diffraction experiments and molecular dynamics simulations. A high degree of correlation between the experimental data and the simulations was found with a significant displacement of the anions from around the cation by the aromatic species and the resulting structure having pi-pi stacks between the cations and the aromatic. PMID:20145851

  3. 40 CFR 721.3485 - Hydrofluorocarbon alkyl ether.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Hydrofluorocarbon alkyl ether. 721... Substances § 721.3485 Hydrofluorocarbon alkyl ether. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as a hydrofluorocarbon alkyl...

  4. 40 CFR 721.3485 - Hydrofluorocarbon alkyl ether.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Hydrofluorocarbon alkyl ether. 721... Substances § 721.3485 Hydrofluorocarbon alkyl ether. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as a hydrofluorocarbon alkyl...

  5. 40 CFR 721.10053 - Alkyl silane methacrylate (generic).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Alkyl silane methacrylate (generic... Specific Chemical Substances § 721.10053 Alkyl silane methacrylate (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as alkyl...

  6. 40 CFR 721.10053 - Alkyl silane methacrylate (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Alkyl silane methacrylate (generic... Specific Chemical Substances § 721.10053 Alkyl silane methacrylate (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as alkyl...

  7. 40 CFR 721.10053 - Alkyl silane methacrylate (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Alkyl silane methacrylate (generic... Specific Chemical Substances § 721.10053 Alkyl silane methacrylate (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as alkyl...

  8. 40 CFR 721.10053 - Alkyl silane methacrylate (generic).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Alkyl silane methacrylate (generic... Specific Chemical Substances § 721.10053 Alkyl silane methacrylate (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as alkyl...

  9. 40 CFR 721.10053 - Alkyl silane methacrylate (generic).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Alkyl silane methacrylate (generic... Specific Chemical Substances § 721.10053 Alkyl silane methacrylate (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as alkyl...

  10. 40 CFR 721.555 - Alkyl amino nitriles (generic).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... Substances § 721.555 Alkyl amino nitriles (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substances identified generically as alkyl amino nitriles (PMNs P-96... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Alkyl amino nitriles (generic)....

  11. IONIC LIQUID-CATALYZED ALKYLATION OF ISOBUTANE WITH 2-BUTENE

    EPA Science Inventory

    A detailed study of the alkylation of isobutane with 2-butene in ionic liquid media has been conducted using 1-alkyl-3-methylimidazolium halides?aluminum chloride encompassing various alkyl groups (butyl-, hexyl-, and octyl-) and halides (Cl, Br, and I) on its cations and anions,...

  12. 40 CFR 721.2825 - Alkyl ester (generic name).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Alkyl ester (generic name). 721.2825... Substances § 721.2825 Alkyl ester (generic name). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance alkyl ester (PMN P-84-968) is subject to reporting under this...

  13. 40 CFR 721.2825 - Alkyl ester (generic name).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Alkyl ester (generic name). 721.2825... Substances § 721.2825 Alkyl ester (generic name). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance alkyl ester (PMN P-84-968) is subject to reporting under this...

  14. 40 CFR 721.2420 - Alkoxylated dialkyldiethylenetriamine, alkyl sulfate salt.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ..., alkyl sulfate salt. 721.2420 Section 721.2420 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.2420 Alkoxylated dialkyldiethylenetriamine, alkyl sulfate salt. (a... generically as an alkoxylated dialkyldiethylenetriamine, alkyl sulfate salt (PMN P-91-288) is subject...

  15. 40 CFR 721.2420 - Alkoxylated dialkyldiethylenetriamine, alkyl sulfate salt.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ..., alkyl sulfate salt. 721.2420 Section 721.2420 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.2420 Alkoxylated dialkyldiethylenetriamine, alkyl sulfate salt. (a... generically as an alkoxylated dialkyldiethylenetriamine, alkyl sulfate salt (PMN P-91-288) is subject...

  16. 40 CFR 721.575 - Substituted alkyl halide.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Substituted alkyl halide. 721.575... Substances § 721.575 Substituted alkyl halide. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as substituted alkyl halide (PMN P-83-1222)...

  17. 40 CFR 721.1878 - Alkali metal alkyl borohydride (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Alkali metal alkyl borohydride... Specific Chemical Substances § 721.1878 Alkali metal alkyl borohydride (generic). (a) Chemical substance... alkali metal alkyl borohydride (PMN P-00-1089) is subject to reporting under this section for...

  18. 40 CFR 721.1878 - Alkali metal alkyl borohydride (generic).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Alkali metal alkyl borohydride... Specific Chemical Substances § 721.1878 Alkali metal alkyl borohydride (generic). (a) Chemical substance... alkali metal alkyl borohydride (PMN P-00-1089) is subject to reporting under this section for...

  19. 40 CFR 721.1878 - Alkali metal alkyl borohydride (generic).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Alkali metal alkyl borohydride... Specific Chemical Substances § 721.1878 Alkali metal alkyl borohydride (generic). (a) Chemical substance... alkali metal alkyl borohydride (PMN P-00-1089) is subject to reporting under this section for...

  20. 40 CFR 721.1878 - Alkali metal alkyl borohydride (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Alkali metal alkyl borohydride... Specific Chemical Substances § 721.1878 Alkali metal alkyl borohydride (generic). (a) Chemical substance... alkali metal alkyl borohydride (PMN P-00-1089) is subject to reporting under this section for...

  1. 40 CFR 721.555 - Alkyl amino nitriles (generic).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... Substances § 721.555 Alkyl amino nitriles (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substances identified generically as alkyl amino nitriles (PMNs P-96... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Alkyl amino nitriles (generic)....

  2. 40 CFR 721.10506 - Alkylated phenols (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Alkylated phenols (generic). 721.10506... Substances § 721.10506 Alkylated phenols (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substances identified generically as alkylated phenols (PMNs...

  3. 40 CFR 721.5769 - Mixture of nitrated alkylated phenols.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Mixture of nitrated alkylated phenols... Substances § 721.5769 Mixture of nitrated alkylated phenols. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as a mixture of nitrated alkylated...

  4. 40 CFR 721.5769 - Mixture of nitrated alkylated phenols.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Mixture of nitrated alkylated phenols... Substances § 721.5769 Mixture of nitrated alkylated phenols. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as a mixture of nitrated alkylated...

  5. 40 CFR 721.5769 - Mixture of nitrated alkylated phenols.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Mixture of nitrated alkylated phenols... Substances § 721.5769 Mixture of nitrated alkylated phenols. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as a mixture of nitrated alkylated...

  6. 40 CFR 721.5769 - Mixture of nitrated alkylated phenols.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Mixture of nitrated alkylated phenols... Substances § 721.5769 Mixture of nitrated alkylated phenols. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as a mixture of nitrated alkylated...

  7. 40 CFR 721.5769 - Mixture of nitrated alkylated phenols.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Mixture of nitrated alkylated phenols... Substances § 721.5769 Mixture of nitrated alkylated phenols. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as a mixture of nitrated alkylated...

  8. 40 CFR 721.10506 - Alkylated phenols (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Alkylated phenols (generic). 721.10506... Substances § 721.10506 Alkylated phenols (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substances identified generically as alkylated phenols (PMNs...

  9. 40 CFR 721.4136 - Alkyl heteropolycyclic-aniline (generic).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Alkyl heteropolycyclic-aniline... Specific Chemical Substances § 721.4136 Alkyl heteropolycyclic-aniline (generic). (a) Chemical substance... alkyl heteropolycyclic-aniline (PMN P-00-0067) is subject to reporting under this section for...

  10. 40 CFR 721.4136 - Alkyl heteropolycyclic-aniline (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Alkyl heteropolycyclic-aniline... Specific Chemical Substances § 721.4136 Alkyl heteropolycyclic-aniline (generic). (a) Chemical substance... alkyl heteropolycyclic-aniline (PMN P-00-0067) is subject to reporting under this section for...

  11. 40 CFR 721.4136 - Alkyl heteropolycyclic-aniline (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Alkyl heteropolycyclic-aniline... Specific Chemical Substances § 721.4136 Alkyl heteropolycyclic-aniline (generic). (a) Chemical substance... alkyl heteropolycyclic-aniline (PMN P-00-0067) is subject to reporting under this section for...

  12. 40 CFR 721.4136 - Alkyl heteropolycyclic-aniline (generic).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Alkyl heteropolycyclic-aniline... Specific Chemical Substances § 721.4136 Alkyl heteropolycyclic-aniline (generic). (a) Chemical substance... alkyl heteropolycyclic-aniline (PMN P-00-0067) is subject to reporting under this section for...

  13. 40 CFR 721.4136 - Alkyl heteropolycyclic-aniline (generic).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Alkyl heteropolycyclic-aniline... Specific Chemical Substances § 721.4136 Alkyl heteropolycyclic-aniline (generic). (a) Chemical substance... alkyl heteropolycyclic-aniline (PMN P-00-0067) is subject to reporting under this section for...

  14. 40 CFR 721.2410 - Alkoxylated alkyldiethylenetriamine, alkyl sulfate salts.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ..., alkyl sulfate salts. 721.2410 Section 721.2410 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.2410 Alkoxylated alkyldiethylenetriamine, alkyl sulfate salts. (a... generically as alkoxylated dialkyldiethylenetriamine, alkyl sulfate salts (PMN P-94-325, 326, and 327)...

  15. 40 CFR 721.2420 - Alkoxylated dialkyldiethylenetriamine, alkyl sulfate salt.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ..., alkyl sulfate salt. 721.2420 Section 721.2420 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.2420 Alkoxylated dialkyldiethylenetriamine, alkyl sulfate salt. (a... generically as an alkoxylated dialkyldiethylenetriamine, alkyl sulfate salt (PMN P-91-288) is subject...

  16. 40 CFR 721.2410 - Alkoxylated alkyldiethylenetriamine, alkyl sulfate salts.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ..., alkyl sulfate salts. 721.2410 Section 721.2410 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.2410 Alkoxylated alkyldiethylenetriamine, alkyl sulfate salts. (a... generically as alkoxylated dialkyldiethylenetriamine, alkyl sulfate salts (PMN P-94-325, 326, and 327)...

  17. 40 CFR 721.2410 - Alkoxylated alkyldiethylenetriamine, alkyl sulfate salts.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ..., alkyl sulfate salts. 721.2410 Section 721.2410 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.2410 Alkoxylated alkyldiethylenetriamine, alkyl sulfate salts. (a... generically as alkoxylated dialkyldiethylenetriamine, alkyl sulfate salts (PMN P-94-325, 326, and 327)...

  18. 40 CFR 721.2410 - Alkoxylated alkyldiethylenetriamine, alkyl sulfate salts.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ..., alkyl sulfate salts. 721.2410 Section 721.2410 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.2410 Alkoxylated alkyldiethylenetriamine, alkyl sulfate salts. (a... generically as alkoxylated dialkyldiethylenetriamine, alkyl sulfate salts (PMN P-94-325, 326, and 327)...

  19. 40 CFR 721.2410 - Alkoxylated alkyldiethylenetriamine, alkyl sulfate salts.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ..., alkyl sulfate salts. 721.2410 Section 721.2410 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.2410 Alkoxylated alkyldiethylenetriamine, alkyl sulfate salts. (a... generically as alkoxylated dialkyldiethylenetriamine, alkyl sulfate salts (PMN P-94-325, 326, and 327)...

  20. 40 CFR 721.2420 - Alkoxylated dialkyldiethylenetriamine, alkyl sulfate salt.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ..., alkyl sulfate salt. 721.2420 Section 721.2420 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.2420 Alkoxylated dialkyldiethylenetriamine, alkyl sulfate salt. (a... generically as an alkoxylated dialkyldiethylenetriamine, alkyl sulfate salt (PMN P-91-288) is subject...

  1. 40 CFR 721.2420 - Alkoxylated dialkyldiethylenetriamine, alkyl sulfate salt.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ..., alkyl sulfate salt. 721.2420 Section 721.2420 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.2420 Alkoxylated dialkyldiethylenetriamine, alkyl sulfate salt. (a... generically as an alkoxylated dialkyldiethylenetriamine, alkyl sulfate salt (PMN P-91-288) is subject...

  2. 40 CFR 721.1852 - Di-alkyl borane (generic).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Di-alkyl borane (generic). 721.1852... Substances § 721.1852 Di-alkyl borane (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as di-alkyl borane (PMN P-00-1087) is...

  3. 40 CFR 721.10087 - Substituted alkyl phosphine oxide (generic).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Substituted alkyl phosphine oxide... Specific Chemical Substances § 721.10087 Substituted alkyl phosphine oxide (generic). (a) Chemical... as substituted alkyl phosphine oxide (PMN P-06-332) is subject to reporting under this section...

  4. 40 CFR 721.10087 - Substituted alkyl phosphine oxide (generic).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Substituted alkyl phosphine oxide... Specific Chemical Substances § 721.10087 Substituted alkyl phosphine oxide (generic). (a) Chemical... as substituted alkyl phosphine oxide (PMN P-06-332) is subject to reporting under this section...

  5. 40 CFR 721.9720 - Disubstituted alkyl triazines (generic name).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Disubstituted alkyl triazines (generic... Specific Chemical Substances § 721.9720 Disubstituted alkyl triazines (generic name). (a) Chemical... as disubstituted alkyl triazines (PMNs P-85-932 and P-85-933) are subject to reporting under...

  6. Poly(ethyleneoxide) functionalization through alkylation

    SciTech Connect

    Sivanandan, Kulandaivelu; Eitouni, Hany Basam; Li, Yan; Pratt, Russell Clayton

    2015-04-21

    A new and efficient method of functionalizing high molecular weight polymers through alkylation using a metal amide base is described. This novel procedure can also be used to synthesize polymer-based macro-initiators containing radical initiating groups at the chain-ends for synthesis of block copolymers.

  7. Synthesis and characterization of chitosan alkyl urea.

    PubMed

    Wang, Jing; Jiang, Ji-Zhou; Chen, Wei; Bai, Zheng-Wu

    2016-07-10

    Chitosan is a versatile material employed for various purposes in many fields including the development of chiral stationary phases for enantioseparation. Chitosan alkyl urea is a kind of intermediate used to prepare enantioseparation materials. In order to synthesize the intermediates, in the present work, a new way to prepare chitosan alkyl urea has been established: chitosan was first reacted with methyl chloroformate yielding N-methoxyformylated chitosan, which was then converted to chitosan alkyl urea through amine-ester exchange reaction. With a large excess of methyl chloroformate and primary amine of low stereohindrance, the amino group in chitosan could be almost completely converted to ureido group. The as-prepared chitosan alkyl urea derivatives were characterized by IR, (1)H NMR, (13)C NMR,(1)H-(1)H COSY and (1)H-(13)C HSQC NMR spectra. The chemical shifts of hydrogen and carbon atoms of glucose unit were assigned. It was found that the degree of substitution was obviously lower if cyclopropyl amine, aniline, tert-butyl amine and diethyl amine were used as reactants for the amine-ester exchange reaction. The reason was explained with the aid of theoretical calculations. PMID:27106154

  8. Separate olefin processing in sulfuric acid alkylation

    SciTech Connect

    Imhoff, S.A.; Graves, D.C.

    1995-09-01

    This paper will discuss the effects of alkylating propylene, butylenes and amylenes together and suggest alternative processing schemes which will minimize the negative synergies, improve octane and/or minimize acid consumption. The first option will show the impact of segregating the propylene and amylenes. In the second option, the benefit of alkylating the individual olefins at their optimal acid strengths will be presented. Additionally, each olefin`s optimal reaction conditions will be examined. Unfortunately, many refiners may not have the existing flexibility to take advantage of separate olefin processing. First, the majority of the propylene, butylenes and amylenes must be separate upon entry to the alkylation unit. If the olefins cannot be segregated upstream, separate olefin processing will not be as beneficial. If this is the case, then the benefits of separate olefin processing will have to be weighed versus the capital and energy costs required to separate them. In addition, small units may not have sufficient numbers of Contactors and settlers to achieve adequate segregation. Later in this paper, the modifications required in the alkylation unit for separate olefin processing will be discussed.

  9. Polygas spells relief from alkylation ills

    SciTech Connect

    Weismantel, G.E.

    1980-06-16

    Tight supplies and soaring prices of isobutane (for olefin alkylation), are causing renewed interest in the olefin ''polymerization'' (i.e., dimerization), route to high-octane gasoline-blending components. Modern polymerization processes, intended to supplement rather than replace alkylation offer considerable energy and capital savings, compared with alkylation-only schemes. In addition to the Institut Francais du Petrole's Dimersol ''polymerization'' tecnique which is already being used or will be used by 1981 in at least five U.S. refineries, with six more units in the planning stage, a low-cost process to ''polymerize'' excess refinery olefins, developed by International Energy Consultants Inc., is nearing commercialization. A third route to process C/sub 3//C/sub 4/ refinery streams with high conversion rates has been proposed by UOP Inc. The low motor octane number (MON) of the product gasoline (approx. 13 numbers lower than a typical alkylate), was recently confirmed in Total Petroleum Inc.'s studies, but Good Hope Refineries Inc. plans to increase its polymer gasoline MON by adding methyl tert.-butyl ether.

  10. The chemistry of aromatic osmacycles.

    PubMed

    Cao, Xiao-Yu; Zhao, Qianyi; Lin, Zhiqun; Xia, Haiping

    2014-02-18

    Aromatic compounds, such as benzene and its derivatives, porphyrins, fullerenes, carbon nanotubes, and graphene, have numerous applications in biomedicine, materials science, energy science, and environmental science. Metalla-aromatics are analogues of conventional organic aromatic molecules in which one of the (hydro)carbon segments is formally replaced by an isolobal transition-metal fragment. Researchers have studied these transition-metal-containing aromatic molecules for the past three decades, particularly the synthesis and reactivity of metallabenzenes. Another focus has been the preparation and characterization of other metalla-aromatics such as metallafurans, metallapyridines, metallabenzynes, and more. Despite significant advances, remaining challenges in this field include the limited number of convenient and versatile synthetic methods to construct stable and fully characterized metalla-aromatics, and the relative shortage of new topologies. To address these challenges, we have developed new methods for preparing metalla-aromatics, especially those possessing new topologies. Our synthetic efforts have led to a large family of closely related metalla-aromatics known as aromatic osmacycles. This Account summarizes the synthesis and reactivity of these compounds, with a focus on features that are different from those of compounds developed by other groups. These osmacycles can be synthesized from simple precursors under mild conditions. Using these efficient methods, we have synthesized aromatic osmacycles such as osmabenzene, osmabenzyne, isoosmabenzene, osmafuran, and osmanaphthalene. Furthermore, these methods have also created a series of new topologies, such as osmabenzothiazole and osmapyridyne. Our studies of the reactivity of these osma-aromatics revealed unprecedented reaction patterns, and we demonstrated the interconversion of several osmacycles. Like other metalla-aromatics, osma-aromatics have spectroscopic features of aromaticity, such as

  11. Dichloromethyl alkyl ethers and sulfides in the Reformatskii reaction

    SciTech Connect

    Lapkin, I.I.; Fotin, V.V.

    1986-09-10

    A study was carried out on the reaction of dichloromethyl alkyl ethers and sulfides with ..cap alpha..-brominated esters in the presence of zinc resulting in the formation of either ..cap alpha..-alkyl-..beta..-alkoxyacrylates (or ..cap alpha..-alkyl-..beta..-alkylthioacrylates) or ..cap alpha..,..cap alpha..,..cap alpha..',..cap alpha..'-tetramethyl-..beta..-alkoxyglutaric acid (or ..cap alpha..,..cap alpha..,..cap alpha..',..cap alpha..'-tetramethyl-..beta..-alkylthioglutaric acid) depending on the structure of the starting bromoester. PMR and IR spectroscopy indicates the geometry of the ..cap alpha..-alkyl-..beta..-alkoxyacrylates and ..cap alpha..-alkyl-..beta..-alkylthioacrylates.

  12. Method for continuous production of aromatic carboxylic acid

    SciTech Connect

    Abrams, K.J.

    1988-12-20

    This patent describes a method for the continuous production of an aromatic carboxylic acid product in a pressurized oxidation reactor by liquid-phase, exothermic oxidation of an aromatic alkyl feed with an oxygen-containing gas, in the presence of an aromatic alkyl feed with an oxygen-containing gas, in the presence of an oxidation catalyst and in an aqueous monocarboxylic C/sub 2/ to C/sub 6/ aliphatic acid solvent medium, wherein the heat generated during the course of the oxidation is removed from the reactor by vaporization of a portion of the reaction medium and water, wherein the resulting vapors are condensed in part in a reflux loop externally of the oxidation reactor to produce a condensate and a gaseous phase, and wherein at least a portion of the condensate is returned to the oxidation reactor, the improvement comprising a method for controlling within desired limits the concentration of water in the oxidation reactor, which comprises: partitioning the vapors into a parallel condensate having a relatively lesser water-to-solvent weight ratio and a vapor phase having a relatively greater water-to-solvent weight ratio; returning the partial condensate directly to the oxidation reactor as a direct reflux stream; withdrawing the vapor phase from the reflux loop as a vapor stream; subjecting the withdrawn vapor stream to heat exchange while decreasing the vapor stream pressure to less than the oxidation reactor pressure to thereby produce an aqueous aliphatic acid stream having a water-to-solvent weight ratio greater than that of the direct reflux stream.

  13. Effects of alkylate fuel on exhaust emissions and secondary aerosol formation of a 2-stroke and a 4-stroke scooter

    NASA Astrophysics Data System (ADS)

    Zardini, Alessandro A.; Platt, Stephen M.; Clairotte, Michael; El Haddad, Imad; Temime-Roussel, Brice; Marchand, Nicolas; Ježek, Irena; Drinovec, Luka; Močnik, Griša; Slowik, Jay G.; Manfredi, Urbano; Prévôt, André S. H.; Baltensperger, Urs; Astorga, Covadonga

    2014-09-01

    Regulated and unregulated emissions from a 2-stroke and a 4-stroke scooter were characterized during a legislative driving cycle in a certified laboratory. Scooter exhaust was analyzed at the tailpipe, in a dilution tunnel, and partly collected in a mobile smog chamber for photochemical ageing. We present evidence that the photochemically aged exhaust from a 2-stroke and a 4-stroke scooter produces considerable amounts of secondary organic aerosol: from 1.5 to 22.0 mg/km, and from 5.5 to 6.6 mg/km, respectively. Tests were repeated after replacing the standard petrol and synthetic lube oil with an alkylate fuel (with low content of aromatic compounds) and ultra-clean lube oil (low ash forming potential). We observed emission reduction (with some exceptions) for several gaseous and particulate phase species, in particular for carbon monoxide (from 8% up to 38% and from 31% to 50%, for the 2-stroke and the 4-stroke scooters, respectively), particulate mass (from 32% up to 75% for the 2-stroke scooter), aromatic compounds (89% and 97% for the 2-stroke and the 4-stroke scooter, respectively), and secondary organic aerosol (from 87% to 100% and 99% for the 2-stroke and the 4-stroke scooters, respectively). We attribute the organic aerosol reduction to the low content of aromatics in the alkylate fuel.

  14. Direct, one-pot reductive alkylation of anilines with functionalized acetals mediated by triethylsilane and TFA. Straightforward route for unsymmetrically substituted ethylenediamine.

    PubMed

    Righi, Marika; Bedini, Annalida; Piersanti, Giovanni; Romagnoli, Federica; Spadoni, Gilberto

    2011-01-21

    A new, robust, and reliable method has been developed for the selective reductive N-alkylation of primary and secondary aromatic amines with some functionalized acetals using TFA/Et(3)SiH as a reagent combination. A variety of unsymmetrically substituted ethylenediamines can be synthesized in a one-pot procedure in excellent yields at room temperature. This new procedure offers significant advantages over previous synthetic approaches, including brevity, mild reaction conditions, excellent yields, and high functional group tolerance. PMID:21175194

  15. Ultra-bright alkylated graphene quantum dots

    NASA Astrophysics Data System (ADS)

    Feng, Lan; Tang, Xing-Yan; Zhong, Yun-Xin; Liu, Yue-Wen; Song, Xue-Huan; Deng, Shun-Liu; Xie, Su-Yuan; Yan, Jia-Wei; Zheng, Lan-Sun

    2014-10-01

    Highly efficient and stable photoluminescence (PL) are urgently desired for graphene quantum dots (GQDs) to facilitate their prospective applications as optical materials. Here, we report the facile and straightforward synthesis of alkylated graphene quantum dots (AGQDs) via the solvothermal reaction of propagatively alkylated graphene sheets (PAGenes). In contrast to most GQDs reported so far, the synthesized AGQDs process pH-independent and ultra-bright PL with a relative quantum yield of up to 65%. Structural and chemical composition characterization demonstrated that the synthesized AGQDs are nearly oxygen-defect-free with alkyl groups decorated on edges and basal plane, which may contribute to their greatly improved pH tolerance and high quantum efficiency. The photocatalytic performance of AGQDs-P25 nanocomposites was evaluated by the degradation of Rhodamine B under visible light. The photocatalytic rate is ca. 5.9 times higher than that of pure P25, indicating that AGQDs could harness the visible spectrum of sunlight for energy conversion or environmental therapy.Highly efficient and stable photoluminescence (PL) are urgently desired for graphene quantum dots (GQDs) to facilitate their prospective applications as optical materials. Here, we report the facile and straightforward synthesis of alkylated graphene quantum dots (AGQDs) via the solvothermal reaction of propagatively alkylated graphene sheets (PAGenes). In contrast to most GQDs reported so far, the synthesized AGQDs process pH-independent and ultra-bright PL with a relative quantum yield of up to 65%. Structural and chemical composition characterization demonstrated that the synthesized AGQDs are nearly oxygen-defect-free with alkyl groups decorated on edges and basal plane, which may contribute to their greatly improved pH tolerance and high quantum efficiency. The photocatalytic performance of AGQDs-P25 nanocomposites was evaluated by the degradation of Rhodamine B under visible light. The

  16. On the Extraction of Aromatic Compounds from Hydrocarbons by Imidazolium Ionic Liquids

    PubMed Central

    Cassol, Cláudia C.; Umpierre, Alexandre P.; Ebeling, Günter; Ferrera, Bauer; Chiaro, Sandra S. X.; Dupont, Jairton

    2007-01-01

    The liquid-liquid equilibrium for the ternary system formed by n-octane and aromatic (alkylbenzenes) and heteroaromatic compounds (nitrogen and sulfur containing heterocyles) and 1-alkyl-3-methylimidazolium ionic liquids (ILs) associated with various anions has been investigated. The selectivity on the extraction of a specific aromatic compound is influenced by anion volume, hydrogen bond strength between the anion and the imidazolium cation and the length of the 1-methyl-3-alkylimidazolium alkyl side chain. The interaction of alkylbenzenes and sulfur heterocyles with the IL is preferentially through CH-π hydrogen bonds and the quantity of these aromatics in the IL phase decreases with the increase of the steric hindrance imposed by the substituents on the aromatic nucleus. In the case of nitrogen heterocycles the interaction occurs preferentially through N(heteroaromatic)-H(imidazolium) hydrogen bonds and the extraction process is largely controlled by the nitrogen heterocycle pKa. Competitive extraction experiments suggest that benzene, pyridine and dibenzothiophene do not compete for the same hydrogen bond sites of the IL.

  17. Zinc-thiolate complexes of the bis(pyrazolyl)(thioimidazolyl)hydroborate tripods for the modeling of thiolate alkylating enzymes.

    PubMed

    Ji, Mian; Benkmil, Boumahdi; Vahrenkamp, Heinrich

    2005-05-16

    The new tripod ligands bis(pyrazolyl)(3-tert-butyl-2-thioimidazol-1-yl)hydroborate (L(1)) and bis(pyrazolyl)(3-isopropyl-2-thioimidazol-1-yl)hydroborate (L(2)), together with zinc nitrate or zinc chloride and the corresponding thiolates, have yielded a total of 17 zinc-thiolate complexes. These comprise aliphatic as well as aromatic thiolates and a cysteine derivative. Structure determinations have confirmed the tetrahedral ZnN(2)S(2) coordination in the complexes. Upon reaction with methyl iodide, the species L(1).Zn-SR are slowly converted to L(1).Zn-I and the free thioethers CH(3)SR. A kinetic analysis has shown these alkylations to be about 1 order of magnitude slower than those of the tris(pyrazolyl)borate complexes Tp(Ph,Me)Zn-SR. Alkylations with trimethyl phosphate were found to proceed very slowly even in DMSO at 80 degrees C. PMID:15877434

  18. PROCESS FOR PRODUCING ALKYL ORTHOPHOSPHORIC ACID EXTRACTANTS

    DOEpatents

    Grinstead, R.R.

    1962-01-23

    A process is given for producing superior alkyl orthophosphoric acid extractants for use in solvent extraction methods to recover and purify various metals such as uranium and vanadium. The process comprises slurrying P/sub 2/O/ sub 5/ in a solvent diluent such as kerosene, benzene, isopropyl ether, and the like. An alipbatic alcohol having from nine to seventeen carbon atoms, and w- hcrein ihc OH group is situated inward of the terminal carbon atoms, is added to the slurry while the reaction temperature is mainiained below 60 deg C. The alcohol is added in the mole ratio of about 2 to l, alcohol to P/sub 2/O/sub 5/. A pyrophosphate reaotion product is formed in the slurry-alcohol mixture. Subsequently, the pyrophosphate reaction product is hydrolyzed with dilute mineral acid to produce the desired alkyl orthophosphoric aeid extractant. The extraetant may then be separated and utilized in metal-recovery, solvent- extraction processes. (AEC)

  19. Polyimidazoles via aromatic nucleophilic displacement

    NASA Technical Reports Server (NTRS)

    Connell, John W. (Inventor); Hergenrother, Paul M. (Inventor)

    1991-01-01

    Polyimidazoles (Pl) are prepared by the aromatic nucleophilic displacement reaction of di(hydroxyphenyl)imidazole monomers with activated aromatic dihalides or activated aromatic dinitro compounds. The reactions are carried out in polar aprotic solvents such as N,N-dimethylacetamide, sulfolane, N-methylpyrroldinone, dimethylsulfoxide, or diphenylsulfone using alkali metal bases such as potassium carbonate at elevated temperature under nitrogen. The di(hydroxyphenyl)imidazole monomers are prepared by reacting an aromatic aldehyde with a dimethoxybenzil or by reacting an aromatic dialdehyde with a methoxybenzil in the presence of ammonium acetate. The di(methoxyphenyl)imidazole is subsequently treated with aqueous hydrobromic acid to give the di(hydroxyphenyl)imidazole monomer. This synthetic route has provided high molecular weight Pl of new chemical structure, is economically and synthetically more favorable than other routes, and allows for facile chemical structure variation due to the availability of a large variety of activated aromatic dihalides and dinitro compounds.

  20. Polyimidazoles via aromatic nucleophilic displacement

    NASA Technical Reports Server (NTRS)

    Connell, John W. (Inventor); Hergenrother, Paul M. (Inventor)

    1992-01-01

    Polyimidazoles (PI) are prepared by the aromatic nucleophilic displacement reaction of di(hydroxyphenyl) imidazole monomers with activated aromatic dihalides or activated aromatic dinitro compounds. The reactions are carried out in polar aprotic solvents such as N,N-dimethyl acetamide, sulfolane, N-methylpyrrolidinone, dimethylsulfoxide, or diphenylsulfone using alkali metal bases such as potassium carbonate at elevated temperatures under nitrogen. The di(hydroxyphenyl) imidazole monomers are prepared by reacting an aromatic aldehyde with a dimethoxybenzil or by reacting an aromatic dialdehyde with a methoxybenzil in the presence of ammonium acetate. The di(methoxyphenyl) imidazole is subsequently treated with aqueous hydrobromic acid to give the di(hydroxphenyl) imidazole monomer. This synthetic route has provided high molecular weight PI of new chemical structure, is economically and synthetically more favorable than other routes, and allows for facile chemical structure variation due to the availability of a large variety of activated aromatic dihalides and dinitro compounds.

  1. Examining spatial patterns in polycyclic aromatic compounds measured in stream macroinvertebrates near a small subarctic oil and gas operation.

    PubMed

    Korosi, J B; Eickmeyer, D C; Chin, K S; Palmer, M J; Kimpe, L E; Blais, J M

    2016-03-01

    The Cameron River runs through a small, remote petrochemical development in the Cameron Hills (Northwest Territories, Canada). In order to evaluate the exposure of aquatic biota to contaminants from oil and gas activities, we measured polycyclic aromatic compounds (PACs) in macroinvertebrates collected from sites and tributaries along the Cameron River, including upstream and downstream of the development, and sites located near drilled wells (developed). Macroinvertebrate tissue PAC burdens ranged from 0.2-2.8 μg g(-1) lipid for unsubstituted compounds, and from 4.2-63.2 μg g(-1) lipid for alkylated compounds, relatively low compared to similar studies from more industrialized regions in North America. There was no significant difference in tissue PAC burdens between upstream, downstream, or developed sites (p = 0.12), although alkyl PACs in five out of seven developed sites were higher than the regional average. Petrogenic PACs were dominant in most samples, including alkyl fluorines, alkyl phenanthrene/anthracenes, and alkyl dibenzothiophenes. Minimal changes in PAC composition in macroinvertebrate tissues were detected along the Cameron River, with the exception of the two sites furthest downstream that had high concentrations of C3-C4 naphthalene. Overall, our results suggest that oil and gas development in the Cameron Hills has not resulted in substantial increases in PAC bioaccumulation in stream macroinvertebrates, although the potential that alkyl naphthalenes are being transported downstream from the development warrants further attention. PMID:26911593

  2. ALKYL PYROPHOSPHATE METAL SOLVENT EXTRACTANTS AND PROCESS

    DOEpatents

    Long, R.L.

    1958-09-30

    A process is presented for the recovery of uranium from aqueous mineral acidic solutions by solvent extraction. The extractant is a synmmetrical dialkyl pyrophosphate in which the alkyl substituents have a chain length of from 4 to 17 carbon atoms. Mentioned as a preferred extractant is dioctyl pyrophosphate. The uranium is precipitated irom the organic extractant phase with an agent such as HF, fluoride salts. alcohol, or ammonia.

  3. In pursuit of homoleptic actinide alkyl complexes.

    PubMed

    Seaman, Lani A; Walensky, Justin R; Wu, Guang; Hayton, Trevor W

    2013-04-01

    This Forum Article describes the pursuit of isolable homoleptic actinide alkyl complexes, starting with the pioneering work of Gilman during the Manhattan project. The initial reports in this area suggested that homoleptic uranium alkyls were too unstable to be isolated, but Wilkinson demonstrated that tractable uranium alkyls could be generated by purposeful "ate" complex formation, which serves to saturate the uranium coordination sphere and provide the complexes with greater kinetic stability. More recently, we reported the solid-state molecular structures of several homoleptic uranium alkyl complexes, including [Li(THF)4][U(CH2(t)Bu)5], [Li(TMEDA)]2[UMe6], [K(THF)]3[K(THF)2][U(CH2Ph)6]2, and [Li(THF)4][U(CH2SiMe3)6], by employing Wilkinson's strategy. Herein, we describe our attempts to extend this chemistry to thorium. The treatment of ThCl4(DME)2 with 5 equiv of LiCH2(t)Bu or LiCH2SiMe3 at -25 °C in THF affords [Th(CH2(t)Bu)5] (1) and [Li(DME)2][Th(CH2SiMe3)5 (2), respectively, in moderate yields. Similarly, the treatment of ThCl4(DME)2 with 6 equiv of K(CH2Ph) produces [K(THF)]2[Th(CH2Ph)6] (3), in good yield. Complexes 1-3 have been fully characterized, while the structures of 1 and 3 were confirmed by X-ray crystallography. Additionally, the electronic properties of 1 and 3 were explored by density functional theory. PMID:22716022

  4. Contorted polycyclic aromatics.

    PubMed

    Ball, Melissa; Zhong, Yu; Wu, Ying; Schenck, Christine; Ng, Fay; Steigerwald, Michael; Xiao, Shengxiong; Nuckolls, Colin

    2015-02-17

    CONSPECTUS: This Account describes a body of research in the design, synthesis, and assembly of molecular materials made from strained polycyclic aromatic molecules. The strain in the molecular subunits severely distorts the aromatic molecules away from planarity. We coined the term "contorted aromatics" to describe this class of molecules. Using these molecules, we demonstrate that the curved pi-surfaces are useful as subunits to make self-assembled electronic materials. We have created and continue to study two broad classes of these "contorted aromatics": discs and ribbons. The figure that accompanies this conspectus displays the three-dimensional surfaces of a selection of these "contorted aromatics". The disc-shaped contorted molecules have well-defined conformations that create concave pi-surfaces. When these disc-shaped molecules are substituted with hydrocarbon side chains, they self-assemble into columnar superstructures. Depending on the hydrocarbon substitution, they form either liquid crystalline films or macroscopic cables. In both cases, the columnar structures are photoconductive and form p-type, hole- transporting materials in field effect transistor devices. This columnar motif is robust, allowing us to form monolayers of these columns attached to the surface of dielectrics such as silicon oxide. We use ultrathin point contacts made from individual single-walled carbon nanotubes that are separated by a few nanometers to probe the electronic properties of short stacks of a few contorted discs. We find that these materials have high mobility and can sense electron-deficient aromatic molecules. The concave surfaces of these disc-shaped contorted molecules form ideal receptors for the molecular recognition and assembly with spherical molecules such as fullerenes. These interfaces resemble ball-and-socket joints, where the fullerene nests itself in the concave surface of the contorted disc. The tightness of the binding between the two partners can be

  5. Ultra-bright alkylated graphene quantum dots.

    PubMed

    Feng, Lan; Tang, Xing-Yan; Zhong, Yun-Xin; Liu, Yue-Wen; Song, Xue-Huan; Deng, Shun-Liu; Xie, Su-Yuan; Yan, Jia-Wei; Zheng, Lan-Sun

    2014-11-01

    Highly efficient and stable photoluminescence (PL) are urgently desired for graphene quantum dots (GQDs) to facilitate their prospective applications as optical materials. Here, we report the facile and straightforward synthesis of alkylated graphene quantum dots (AGQDs) via the solvothermal reaction of propagatively alkylated graphene sheets (PAGenes). In contrast to most GQDs reported so far, the synthesized AGQDs process pH-independent and ultra-bright PL with a relative quantum yield of up to 65%. Structural and chemical composition characterization demonstrated that the synthesized AGQDs are nearly oxygen-defect-free with alkyl groups decorated on edges and basal plane, which may contribute to their greatly improved pH tolerance and high quantum efficiency. The photocatalytic performance of AGQDs-P25 nanocomposites was evaluated by the degradation of Rhodamine B under visible light. The photocatalytic rate is ca. 5.9 times higher than that of pure P25, indicating that AGQDs could harness the visible spectrum of sunlight for energy conversion or environmental therapy. PMID:25192187

  6. 40 CFR 721.7200 - Perfluoroalkyl aromatic carbamate modified alkyl methacrylate copolymer.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... for cancer; 1.0 percent for other effects), (f), (g)(1)(ii), (g)(2)(ii), and (g)(5). In addition, the... substance may cause lung effects. (ii) Industrial, commercial, and consumer activities. Requirements...

  7. Radiolytic crosslinking and chain scission in aliphatic and alkyl-aromatic polyamides—II

    NASA Astrophysics Data System (ADS)

    Lyons, Bernard J.; Glover, Leon C.

    Regression analysis of the radiation parameters of nine aliphatic polyamides exposed to ionizing radiation leads to the conclusion that the decline in the ratio of chain scission to crosslinking in higher aliphatic polyamides is best related to the linear increase in the methylene content of, or the number of methylene groups in, the polyamide repeat unit. G(crosslink) [ G(X)] and G(chain scission) [ G(CS)] values, however, do not correlate well with either of these parameters. Rather it is found that the major determinant of yields [about 80-85% of the variation for G(X), 70% for G(CS)] is the number of hydrogen atoms or methylene groups in the amine residue. A minor determinant [15% of the variation for G(X) and 30% for G(CS)] is the number of hydrogen atoms or methylene groups in the acid residue of the repeat unit. Significantly, although there was little sign of a decrease in G(CS) in the higher aliphatic homologues (up to 11 methylene residues per amide group), G(CS) is found to be positively related to the number of methylene groups in the amine residue but negatively related to the number of methylene groups in the acid residue. Thus although the amine residue dominates the radiolytic response, the acid residue plays a critical if lesser role in determining chain scission yields in polyamides. Thus a polyamide with the repeat unit —(CH 2) 3 nCONH(CH 2) nNHCO— would be predicted to have a very low or zero G(CS) and, if n is 10 or more, a G(X) comparable to that of polyethylene. Although, logically, the yields of crosslinks and chain scissions in polyamides would be expected to tend to that of polyethylene as the number of methylene groups in the repeat unit increases, use of two models assuming an exponential trend to the G(X) value characteristic of polyethylene in the analysis did not provide better fits to the data than the simple linear model referred to above. Indeed, the assumption of a significant exponential trend factor led to a marked drop in the goodness of fit.

  8. 40 CFR 721.7200 - Perfluoroalkyl aromatic carbamate modified alkyl methacrylate copolymer.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... for cancer; 1.0 percent for other effects), (f), (g)(1)(ii), (g)(2)(ii), and (g)(5). In addition, the... substance may cause lung effects. (ii) Industrial, commercial, and consumer activities. Requirements...

  9. 40 CFR 721.7200 - Perfluoroalkyl aromatic carbamate modified alkyl methacrylate copolymer.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... for cancer; 1.0 percent for other effects), (f), (g)(1)(ii), (g)(2)(ii), and (g)(5). In addition, the... substance may cause lung effects. (ii) Industrial, commercial, and consumer activities. Requirements...

  10. 40 CFR 721.7200 - Perfluoroalkyl aromatic carbamate modified alkyl methacrylate copolymer.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... for cancer; 1.0 percent for other effects), (f), (g)(1)(ii), (g)(2)(ii), and (g)(5). In addition, the... substance may cause lung effects. (ii) Industrial, commercial, and consumer activities. Requirements...

  11. Aromatic molecules as spintronic devices

    SciTech Connect

    Ojeda, J. H.; Orellana, P. A.; Laroze, D.

    2014-03-14

    In this paper, we study the spin-dependent electron transport through aromatic molecular chains attached to two semi-infinite leads. We model this system taking into account different geometrical configurations which are all characterized by a tight binding Hamiltonian. Based on the Green's function approach with a Landauer formalism, we find spin-dependent transport in short aromatic molecules by applying external magnetic fields. Additionally, we find that the magnetoresistance of aromatic molecules can reach different values, which are dependent on the variations in the applied magnetic field, length of the molecules, and the interactions between the contacts and the aromatic molecule.

  12. Fluorinated aromatic diamine

    NASA Technical Reports Server (NTRS)

    Jones, Robert J. (Inventor); O'Rell, Michael K. (Inventor); Hom, Jim M. (Inventor)

    1980-01-01

    This invention relates to a novel aromatic diamine and more particularly to the use of said diamine for the preparation of thermally stable high-molecular weight polymers including, for example, polyamides, polyamideimides, polyimides, and the like. This diamine is obtained by reacting a stoichometric amount of a disodium salt of 2,2-bis(4-hydroxyphenyl) hexafluoropropane with 4-chloronitrobenzene to obtain an intermediate, 2,2-bis[4-(4-nitrophenoxy)phenyl] hexafluoropropane, which is reduced to the corresponding 2,2-bis[4-(4-aminophenoxy)phenyl] hexafluoropropane.

  13. Controlling the Adsorption of Aromatic Compounds on Pt(111) with Oxygenate Substituents: From DFT to Simple Molecular Descriptors.

    PubMed

    Réocreux, Romain; Huynh, Minh; Michel, Carine; Sautet, Philippe

    2016-06-01

    Aromatic chemistry on metallic surfaces is involved in many processes within the contexts of biomass valorization, pollutant degradation, or corrosion protection. Albeit theoretically and experimentally challenging, knowing the structure and the stability of aromatic compounds on such surfaces is essential to understand their properties. To gain insights on this topic, we performed periodic ab initio calculations on Pt(111) to determine a set of simple molecular descriptors that predict both the stability and the structure of aromatic adsorbates substituted with alkyl and alkoxy (or hydroxy) groups. While the van der Waals (vdW) interaction is controlled by the molecular weight and the deformation energy by both the nature and the relative position of the substituents to the surface, the chemical bonding can be correlated to the Hard and Soft Acids and Bases (HSAB) interaction energy. This work gives general insights on the interaction of aromatic compounds with the Pt(111) surface. PMID:27206155

  14. One-pot synthesis of S-alkyl dithiocarbamates via the reaction of N-tosylhydrazones, carbon disulfide and amines.

    PubMed

    Sha, Qiang; Wei, Yun-Yang

    2013-09-14

    A new, convenient and efficient transition metal-free synthesis of S-alkyl dithiocarbamates through one-pot reaction of N-tosylhydrazones, carbon disulfide and amines is reported. Tosylhydrazones derived from various aromatic and aliphatic ketones or aldehydes were tested and gave dithiocarbamates in good to excellent yields. The tosylhydrazones can be generated in situ without isolation, which provides a simpler one-pot method to synthesize dithiocarbamates via the reaction of carbonyl compounds, carbon disulfide and amines in the presence of 4-methylbenzenesulfonohydrazide. PMID:23863979

  15. The effects of CYP1A inhibition on alkyl-phenanthrene metabolism and embryotoxicity in marine medaka (Oryzias melastigma).

    PubMed

    Mu, Jingli; Jin, Fei; Wang, Juying; Wang, Ying; Cong, Yi

    2016-06-01

    Alkylated polycyclic aromatic hydrocarbons (alkyl-PAHs) are the predominant form of PAHs in crude oils, of which, 3-5 ring alkyl-PAH may cause dioxin-like toxicity to early life stages of fish. Retene (7-isopropyl-1-methylphenanthrene), a typical alkyl-phenanthrene compound, can be more toxic than phenanthrene, and the mechanism of retene toxicity is likely related to its rapid biotransformation by cytochrome P450 (CYP) enzymes to metabolites with a wide array of structures and potential toxicities. Here, we investigated how α-naphthoflavone (ANF), a cytochrome P450 1A (CYP1A) inhibitor, affected the embryotoxicity of retene and the role that CYP1A inhibition may play in the interactions. Marine medaka (Oryzias melastigma) embryos were exposed, separately or together, to 200 μg/L retene with 0, 5, 10, 100, and 200 μg/L ANF for 14 days. The results showed that ANF significantly inhibited the induction of CYP1A activity by retene; however, ANF interacted with retene to induce significant developmental toxicity and genotoxicity at 10, 100, and 200 μg/L (p < 0.01). Tissue concentrations of retene and its metabolites and lipid hydroperoxide (LPO) activity also increased, whereas the inhibition of the glutathione S-transferase (GST) activity and the alteration in metabolic profiles of retene were observed. The interactions of retene with ANF indicate that CYP1A inhibition was possibly act through different mechanisms to produce similar developmental effects and genotoxicity. Retene metabolites and altered metabolic profile were likely responsible for retene embryotoxicity to marine medaka. Therefore, elevated toxicity of alkyl-phenanthrene under CYP1A inhibitor suggested that the ecotoxicity of PAHs in coastal water may have underestimated the threat of PAHs to fish or ecosystem. PMID:26924701

  16. "Carbo-aromaticity" and novel carbo-aromatic compounds.

    PubMed

    Cocq, Kévin; Lepetit, Christine; Maraval, Valérie; Chauvin, Remi

    2015-09-21

    While the concept of aromaticity is being more and more precisely delineated, the category of "aromatic compounds" is being more and more expanded. This is illustrated by an introductory highlight of the various types of "aromaticity" previously invoked, and by a focus on the recently proposed "aromatic character" of the "two-membered rings" of the acetylene and butatriene molecules. This serves as a general foundation for the definition of "carbo-aromaticity", the relevance of which is surveyed through recent results in the synthetic, physical, and theoretical chemistry of carbo-mers and in particular macrocyclic-polycyclic representatives constituting a natural family of "novel aromatic compounds". With respect to their parent molecules, carbo-mers are constitutionally defined as "carbon-enriched", and can also be functionally regarded as "π-electron-enriched". This is exemplified by recent experimental and theoretical results on functional, aromatic, rigid, σ,π-macrocyclic carbo-benzene archetypes of various substitution patterns, with emphasis on the quadrupolar pattern. For the purpose of comparison, several types of non-aromatic references of carbo-benzenes are then considered, i.e. freely rotating σ,π-acyclic carbo-n-butadienes and flexible σ-cyclic, π-acyclic carbo-cyclohexadienes, and to "pro-aromatic" congeners, i.e. rigid σ,π-macrocyclic carbo-quinoids. It is shown that functional carbo-mers are entering the field of "molecular materials" for properties such as linear or nonlinear optical properties (e.g. dichromism and two-photon absorption) and single molecule conductivity. Since total or partial carbo-mers of aromatic carbon-allotropes of infinite size such as graphene (graphynes and graphdiynes) and graphite ("graphitynes") have long been addressed at the theoretical or conceptual level, recent predictive advances on the electrical, optical and mechanical properties of such carbo-materials are surveyed. Very preliminary experimental results

  17. Electronic Structure Principles and Aromaticity

    ERIC Educational Resources Information Center

    Chattaraj, P. K.; Sarkar, U.; Roy, D. R.

    2007-01-01

    The relationship between aromaticity and stability in molecules on the basis of quantities such as hardness and electrophilicity is explored. The findings reveal that aromatic molecules are less energetic, harder, less polarizable, and less electrophilic as compared to antiaromatic molecules, as expected from the electronic structure principles.

  18. Degradation and formation of polycyclic aromatic compounds during bioslurry treatment of an aged gasworks soil.

    PubMed

    Lundstedt, Staffan; Haglund, Peter; Oberg, Lars

    2003-07-01

    The goals of this study were to investigate the relative degradation rates of polycyclic aromatic compounds (PACs) in contaminated soil, and to assess whether persistent oxidation products are formed during their degradation. Samples were taken on five occasions during a pilot-scale bioslurry treatment of soil from a former gasworks site. More than 100 PACs were identified in the soil, including unsubstituted polycyclic aromatic hydrocarbons (PAHs), alkylated PAHs (alkyl-PAHs), heterocyclic PACs, and oxygenated PAHs (oxy-PAHs), such as ketones, quinones, and coumarins. During the treatment, the low molecular weight PAHs and heterocyclics were degraded faster than the high molecular weight compounds. The unsubstituted PAHs also appear to have degraded more quickly than the corresponding alkyl-PAHs and nitrogen-containing heterocyclics. No new oxidation products that were not present in the untreated soil were identified after the soil treatment. However, oxy-PAHs that were present in the untreated soil were generally degraded more slowly than the parent compounds, suggesting that they were formed during the treatment or that they are more persistent. Two oxidation products, 1-acenaphthenone and 4-oxapyrene-5-one, were found at significantly higher concentrations at the end of the study. Because oxy-PAHs can be acutely toxic, mutagenic, or carcinogenic, we suggest that this group of compounds should also be monitored during the treatment of PAH-contaminated soil. PMID:12836964

  19. Determining cysteine oxidation status using differential alkylation

    NASA Astrophysics Data System (ADS)

    Schilling, Birgit; Yoo, Chris B.; Collins, Christopher J.; Gibson, Bradford W.

    2004-08-01

    Oxidative damage to proteins plays a major role in aging and in the pathology of many degenerative diseases. Under conditions of oxidative stress, reactive oxygen and nitrogen species can modify key redox sensitive amino acid side chains leading to altered biological activities or structures of the targeted proteins. This in turn can affect signaling or regulatory control pathways as well as protein turnover and degradation efficiency in the proteasome. Cysteine residues are particularly susceptible to oxidation, primarily through reversible modifications (e.g., thiolation and nitrosylation), although irreversible oxidation can lead to products that cannot be repaired in vivo such as sulfonic acid. This report describes a strategy to determine the overall level of reversible cysteine oxidation using a stable isotope differential alkylation approach in combination with mass spectrometric analysis. This method employs 13C-labeled alkylating reagents, such as N-ethyl-[1,4-13C2]-maleimide, bromo-[1,2-13C2]-acetic acid and their non-labeled counterparts to quantitatively assess the level of cysteine oxidation at specific sites in oxidized proteins. The differential alkylation protocol was evaluated using standard peptides and proteins, and then applied to monitor and determine the level of oxidative damage induced by diamide, a mild oxidant. The formation and mass spectrometric analysis of irreversible cysteine acid modification will also be discussed as several such modifications have been identified in subunits of the mitochondrial electron transport chain complexes. This strategy will hopefully contribute to our understanding of the role that cysteine oxidation plays in such chronic diseases such as Parkinson's disease, where studies in animal and cell models have shown oxidative damage to mitochondrial Complex I to be a specific and early target.

  20. Alkyl Chlorides as Hydrogen Bond Acceptors

    SciTech Connect

    Nadas, Janos I; Vukovic, Sinisa; Hay, Benjamin

    2012-01-01

    To gain an understanding of the role of an alkyl chloride as a hydrogen bond acceptor, geometries and interaction energies were calculated at the MP2/aug-cc-pVDZ level of theory for complexes between ethyl chloride and representative hydrogen donor groups. The results establish that these donors, which include hydrogen cyanide, methanol, nitrobenzene, pyrrole, acetamide, and N-methylurea, form X-H {hor_ellipsis} Cl hydrogen bonds (X = C, N, O) of weak to moderate strength, with {Delta}E values ranging from -2.8 to -5.3 kcal/mol.

  1. Characterizing PUF disk passive air samplers for alkyl-substituted PAHs: Measured and modelled PUF-AIR partition coefficients with COSMO-RS.

    PubMed

    Parnis, J Mark; Eng, Anita; Mackay, Donald; Harner, Tom

    2016-02-01

    Isomers of alkyl-substituted polycyclic aromatic hydrocarbons (PAHs) and dibenzothiophenes are modelled with COSMO-RS theory to determine the effectiveness and accuracy of this approach for estimation of isomer-specific partition coefficients between air and polyurethane foam (PUF), i.e., KPUF-AIR. Isomer-specific equilibrium partitioning coefficients for a series of 23 unsubstituted and isomeric alkyl-substituted PAHs and dibenzothiophenes were measured at 22 °C. This data was used to determine the accuracy of estimated values using COSMO-RS, which is isomer specific, and the Global Atmospheric Passive Sampling (GAPS) template approach, which treats all alkyl-substitutions as a single species of a given side-chain carbon number. A recently developed oligomer-based model for PUF was employed, which consisted of a 1:1 condensed pair of 2,4-toluene-diisocyanide and glycerol. The COSMO-RS approach resulted in a significant reduction in the RMS error associated with simple PAHs and dibenzothiophene compared with the GAPS template approach. When used with alkylated PAHs and dibenzothiophenes grouped into carbon-number categories, the GAPS template approach gave lower RMS error (0.72) compared to the COSMO-RS result (0.87) when the latter estimates were averaged within the carbon-number-based categories. When the isomer-specific experimental results were used, the COSMO-RS approach resulted in a 21% reduction in RMS error with respect to the GAPS template approach, with a 0.57 RMS error for all alkylated PAHs and dibenzothiophenes studied. The results demonstrate that COSMO-RS theory is effective in generating isomer-specific PUF-air partition coefficients, supporting the application of PUF-based passive samplers for monitoring and research studies of polycyclic aromatic compounds (PACs) in air. PMID:26692513

  2. 40 CFR 721.10218 - 2-Propenoic acid, 2-mehtyl-, C12-15-branched and linear alkyl esters, telomers with alkyl 2...

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ...-branched and linear alkyl esters, telomers with alkyl 2- thio]-2-alkanoate, aminoalkyl methacrylate and alkyl methacrylate, tert-Bu 2-ethylhexanoperoxoate-initiated (generic). 721.10218 Section 721.10218...-alkanoate, aminoalkyl methacrylate and alkyl methacrylate, tert-Bu 2-ethylhexanoperoxoate-initiated...

  3. 40 CFR 721.10218 - 2-Propenoic acid, 2-mehtyl-, C12-15-branched and linear alkyl esters, telomers with alkyl 2...

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ...-branched and linear alkyl esters, telomers with alkyl 2- thio]-2-alkanoate, aminoalkyl methacrylate and alkyl methacrylate, tert-Bu 2-ethylhexanoperoxoate-initiated (generic). 721.10218 Section 721.10218...-alkanoate, aminoalkyl methacrylate and alkyl methacrylate, tert-Bu 2-ethylhexanoperoxoate-initiated...

  4. 40 CFR 721.10218 - 2-Propenoic acid, 2-mehtyl-, C12-15-branched and linear alkyl esters, telomers with alkyl 2...

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ...-branched and linear alkyl esters, telomers with alkyl 2- thio]-2-alkanoate, aminoalkyl methacrylate and alkyl methacrylate, tert-Bu 2-ethylhexanoperoxoate-initiated (generic). 721.10218 Section 721.10218...-alkanoate, aminoalkyl methacrylate and alkyl methacrylate, tert-Bu 2-ethylhexanoperoxoate-initiated...

  5. 40 CFR 721.10218 - 2-Propenoic acid, 2-mehtyl-, C12-15-branched and linear alkyl esters, telomers with alkyl 2...

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ...-branched and linear alkyl esters, telomers with alkyl 2- thio]-2-alkanoate, aminoalkyl methacrylate and alkyl methacrylate, tert-Bu 2-ethylhexanoperoxoate-initiated (generic). 721.10218 Section 721.10218...-alkanoate, aminoalkyl methacrylate and alkyl methacrylate, tert-Bu 2-ethylhexanoperoxoate-initiated...

  6. Geochemical markers and polycyclic aromatic hydrocarbons in solvent extracts from diesel engine particulate matter.

    PubMed

    Fabiańska, Monika; Kozielska, Barbara; Bielaczyc, Piotr; Woodburn, Joseph; Konieczyński, Jan

    2016-04-01

    Exhaust particulate from compression ignition (CI) engines running on engine and chassis dynamometers was studied. Particulate dichloromethane extracts were qualitatively and quantitatively analyzed for polycyclic aromatic hydrocarbons (PAHs) and biomarkers by gas chromatography with flame ionization detector (GC-FID) and gas chromatography-mass spectrometry (GC-MS). PAH group profiles were made and the PAH group shares according to the number of rings (2 or 3; 4; 5 or more) as well as diagnostic indices were calculated. Values of geochemical ratios of selected biomarkers and alkyl aromatic hydrocarbons were compared with literature values. A geochemical interpretation was carried out using these values and biomarker and alkyl aromatic hydrocarbon distributions. It has been shown that geochemical features are unequivocally connected to the emission of fossil fuels and biofuels burned in CI engines. The effect of the exothermic combustion process is limited to low-molecular-weight compounds, which shows that the applied methodology permits source identification of PAHs coexisting in the particulate emitted. PMID:26728284

  7. The photodissociation dynamics of alkyl radicals

    SciTech Connect

    Giegerich, Jens; Fischer, Ingo

    2015-01-28

    The photodisscociation dynamics of the alkyl radicals i-propyl (CH(CH{sub 3}){sub 2}) and t-butyl (C(CH{sub 3}){sub 3}) are investigated by H-atom photofragment imaging. While i-propyl is excited at 250 nm, the photodynamics of t-butyl are explored over a large energy range using excitation wavelengths between 347 nm and 233 nm. The results are compared to those obtained previously for ethyl, CH{sub 3}CH{sub 2}, and to those reported for t-butyl using 248 nm excitation. The translational energy (E{sub T}) distribution of the H-atom photofragments is bimodal and appears rather similar for all three radicals. The low E{sub T} part of the distribution shows an isotropic photofragment angular distribution, while the high E{sub T} part is associated with a considerable anisotropy. Thus, for t-butyl, two H-atom loss channels of roughly equal importance have been identified in addition to the CH{sub 3}-loss channel reported previously. A mechanism for the photodissociation of alkyl radicals is suggested that is based on interactions between Rydberg- and valence states.

  8. ESCHERICHIA COLI Gene Induction by Alkylation Treatment

    PubMed Central

    Volkert, Michael R.; Nguyen, Dinh C.; Beard, K. Christopher

    1986-01-01

    Searches for alkylation-inducible (aid) genes of Escherichia coli have been conducted by screening random fusions of the Mu-dl(ApR lac) phage for fusions showing increased β-galactosidase activity after treatment with methylating agents, but not after treatments with UV-irradiation. In this report we describe gene fusions that are specifically induced by alkylation treatments. Nine new mutants are described, and their properties are compared with the five mutants described previously. The total of 14 fusion mutants map at five distinct genetic loci. They can be further subdivided on the basis of their induction by methyl methanesulfonate (MMS) and N-methyl-N'-nitro-N-nitrosoguanidine (MNNG). alkA, aidB and aidD are induced by both agents and appear to be regulated by ada. Neither aidC nor aidI is regulated by ada. Moreover, since aidC is induced only by MNNG and aidI is induced only by MMS, these two genes are likely to be individually regulated. Thus, there appear to be at least three different regulatory mechanisms controlling aid genes. PMID:3080354

  9. The photodissociation dynamics of alkyl radicals

    NASA Astrophysics Data System (ADS)

    Giegerich, Jens; Fischer, Ingo

    2015-01-01

    The photodisscociation dynamics of the alkyl radicals i-propyl (CH(CH3)2) and t-butyl (C(CH3)3) are investigated by H-atom photofragment imaging. While i-propyl is excited at 250 nm, the photodynamics of t-butyl are explored over a large energy range using excitation wavelengths between 347 nm and 233 nm. The results are compared to those obtained previously for ethyl, CH3CH2, and to those reported for t-butyl using 248 nm excitation. The translational energy (ET) distribution of the H-atom photofragments is bimodal and appears rather similar for all three radicals. The low ET part of the distribution shows an isotropic photofragment angular distribution, while the high ET part is associated with a considerable anisotropy. Thus, for t-butyl, two H-atom loss channels of roughly equal importance have been identified in addition to the CH3-loss channel reported previously. A mechanism for the photodissociation of alkyl radicals is suggested that is based on interactions between Rydberg- and valence states.

  10. 40 CFR 721.10038 - Trimellitic anhydride, polymer with substituted glycol, alkyl phenols and ethoxylated nonylphenol...

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... substituted glycol, alkyl phenols and ethoxylated nonylphenol (generic). 721.10038 Section 721.10038... Trimellitic anhydride, polymer with substituted glycol, alkyl phenols and ethoxylated nonylphenol (generic... identified generically as trimellitic anhydride, polymer with substituted glycol, alkyl phenols...

  11. 40 CFR 721.10038 - Trimellitic anhydride, polymer with substituted glycol, alkyl phenols and ethoxylated nonylphenol...

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... substituted glycol, alkyl phenols and ethoxylated nonylphenol (generic). 721.10038 Section 721.10038... Trimellitic anhydride, polymer with substituted glycol, alkyl phenols and ethoxylated nonylphenol (generic... identified generically as trimellitic anhydride, polymer with substituted glycol, alkyl phenols...

  12. 40 CFR 721.10038 - Trimellitic anhydride, polymer with substituted glycol, alkyl phenols and ethoxylated nonylphenol...

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... substituted glycol, alkyl phenols and ethoxylated nonylphenol (generic). 721.10038 Section 721.10038... Trimellitic anhydride, polymer with substituted glycol, alkyl phenols and ethoxylated nonylphenol (generic... identified generically as trimellitic anhydride, polymer with substituted glycol, alkyl phenols...

  13. Synthesis of aromatic secondary diamines

    NASA Technical Reports Server (NTRS)

    Wolfe, J. F.; Greenwood, T. D.; Kahley, R. A.

    1979-01-01

    A series of N-methyl substituted aromatic polyamides derived from the secondary aromatic diamines, 4,4'-bis(methylamino)diphenylmethane, 3,3'-bis(methylamino) diphenylmethane, 4,4'-bis(methylamino)benzophenone or 3,3'-bis(methylamino)benzophenone and isophthaloyl dichloride, terphthaloyl dichloride or 3,3'diphenylmethane dicarboxylic acid dichloride was prepared by high temperature solution polymerization in s-tetrachloroethane. Compared to analogous unsubstituted and partially N-methylated aromatic polyamides, the full N-methylated polyamides exhibited significantly lower glass transition temperatures, reduced crystallinity, improved thermal stability and good solubility in chlorinated solvents.

  14. Lignin solubilization and aqueous phase reforming for the production of aromatic chemicals and hydrogen.

    PubMed

    Zakzeski, Joseph; Weckhuysen, Bert M

    2011-03-21

    The solubilization and aqueous phase reforming of lignin, including kraft, soda, and alcell lignin along with sugarcane bagasse, at low temperatures (T≤498 K) and pressures (P≤29 bar) is reported for the first time for the production of aromatic chemicals and hydrogen. Analysis of lignin model compounds and the distribution of products obtained during the lignin aqueous phase reforming revealed that lignin was depolymerized through disruption of the abundant β-O-4 linkages and, to a lesser extent, the 5-5' carbon-carbon linkages to form monomeric aromatic compounds. The alkyl chains contained on these monomeric compounds were readily reformed to produce hydrogen and simple aromatic platform chemicals, particularly guaiacol and syringol, with the distribution of each depending on the lignin source. The methoxy groups present on the aromatic rings were subject to hydrolysis to form methanol, which was also readily reformed to produce hydrogen and carbon dioxide. The composition of the isolated yields of monomeric aromatic compounds and overall lignin conversion based on these isolated yields varied from 10-15% depending on the lignin sample, with the balance consisting of gaseous products and residual solid material. Furthermore, we introduce the use of a high-pressure autoclave with optical windows and an autoclave with ATR-IR sentinel for on-line in situ spectroscopic monitoring of biomass conversion processes, which provides direct insight into, for example, the solubilization process and aqueous phase reforming reaction of lignin. PMID:21246746

  15. Current-voltage characteristics of a homologous series of polycyclic aromatic hydrocarbons.

    PubMed

    Böhme, Thilo; Simpson, Christopher D; Müllen, Klaus; Rabe, Jürgen P

    2007-01-01

    A novel alkyl-substituted polycyclic aromatic hydrocarbon (PAH) with D(2h) symmetry and 78 carbon atoms in the aromatic core (C78) was synthesized, thereby completing a homologous series of soluble PAH compounds with increasing size of the aromatic pi system (42, 60, and 78 carbon atoms). The optical band gaps were determined by UV/Vis and fluorescence spectroscopy in solution. Scanning tunneling microscopy (STM) and spectroscopy (STS) revealed diode-like current versus voltage (I-V) characteristics through individual aromatic cores in monolayers at the interface between the solution and the basal plane of graphite. The asymmetry of the current-voltage (I-V) characteristics increases with the increasing size of the aromatic core, and the concomitantly decreasing HOMO-LUMO gap. This is attributed to resonant tunneling through the HOMO of the adsorbed molecule, and an asymmetric position of the molecular species in the tunnel junction. Consistently, submolecularly resolved STM images at negative substrate bias are in good agreement with the calculated pattern for the electron densities of the HOMOs. The analysis provides the basis for tailoring rectification with a single molecule in an STM junction. PMID:17579898

  16. Degradable Polymer Composites Fabricated from Starch and Alkyl Cyanoacrylate Monomer

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Degradable polymer composites are fabricated from alkyl cyanoacrylate monomer and starch without special equipment. Alkyl cyanoacrylate, which is a major component of “super glue”, is a monomer that polymerizes at room temperature in the presence of initiators. During the fabrication of polymer com...

  17. 40 CFR 721.8700 - Halogenated alkyl pyridine.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Halogenated alkyl pyridine. 721.8700 Section 721.8700 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) TOXIC SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.8700 Halogenated alkyl...

  18. 40 CFR 721.2825 - Alkyl ester (generic name).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Alkyl ester (generic name). 721.2825 Section 721.2825 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) TOXIC SUBSTANCES... Substances § 721.2825 Alkyl ester (generic name). (a) Chemical substance and significant new uses subject...

  19. 40 CFR 721.2825 - Alkyl ester (generic name).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Alkyl ester (generic name). 721.2825 Section 721.2825 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) TOXIC SUBSTANCES... Substances § 721.2825 Alkyl ester (generic name). (a) Chemical substance and significant new uses subject...

  20. 40 CFR 721.2560 - Alkylated diphenyl oxide (generic name).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Alkylated diphenyl oxide (generic name). 721.2560 Section 721.2560 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) TOXIC... Substances § 721.2560 Alkylated diphenyl oxide (generic name). (a) Chemical substance and significant...

  1. 40 CFR 721.9720 - Disubstituted alkyl triazines (generic name).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Disubstituted alkyl triazines (generic name). 721.9720 Section 721.9720 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED... Specific Chemical Substances § 721.9720 Disubstituted alkyl triazines (generic name). (a)...

  2. 40 CFR 721.2560 - Alkylated diphenyl oxide (generic name).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Alkylated diphenyl oxide (generic name). 721.2560 Section 721.2560 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) TOXIC... Substances § 721.2560 Alkylated diphenyl oxide (generic name). (a) Chemical substance and significant...

  3. 40 CFR 721.2825 - Alkyl ester (generic name).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Alkyl ester (generic name). 721.2825 Section 721.2825 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) TOXIC SUBSTANCES... Substances § 721.2825 Alkyl ester (generic name). (a) Chemical substance and significant new uses subject...

  4. 21 CFR 176.120 - Alkyl ketene dimers.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 21 Food and Drugs 3 2014-04-01 2014-04-01 false Alkyl ketene dimers. 176.120 Section 176.120 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) INDIRECT FOOD ADDITIVES: PAPER AND PAPERBOARD COMPONENTS Substances for Use Only as Components of Paper and Paperboard § 176.120 Alkyl ketene dimers....

  5. 40 CFR 721.1878 - Alkali metal alkyl borohydride (generic).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ...) TOXIC SUBSTANCES CONTROL ACT SIGNIFICANT NEW USES OF CHEMICAL SUBSTANCES Significant New Uses for Specific Chemical Substances § 721.1878 Alkali metal alkyl borohydride (generic). (a) Chemical substance... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Alkali metal alkyl...

  6. Clinical applications of quinone-containing alkylating agents.

    PubMed

    Begleiter, A

    2000-11-01

    Quinone-containing alkylating agents are a class of chemical agents that have received considerable interest as anticancer drugs. These agents contain a quinone moiety that can be reduced and an alkylating group that can form covalent bonds with a variety of cellular components. The oxidation state of the quinone element can modulate the activity of the alkylating element, and reduction of the quinone is required for activation of the alkylating activity of many of these agents. The quinone element may also contribute to the cytotoxic activity of quinone-containing alkylating agents through the formation of reactive oxygen species during redox cycling. The natural product, mitomycin C, has been the most widely used quinone-containing alkylating agent in the clinic, but other quinone-containing alkylating agents like porfiromycin, diaziquone, carbazilquinone, triaziquone and EO9 have also been used in the clinic for the treatment of cancer. In addition, many other quinone-containing alkylating agents have been tested in preclinical studies and the development of new agents is being actively pursued. This chapter describes the current and past clinical uses of these agents in the treatment of cancer and discusses new agents that are currently in clinical trials. PMID:11056078

  7. 40 CFR 721.10073 - Modified alkyl acrylamide (generic).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Modified alkyl acrylamide (generic... Specific Chemical Substances § 721.10073 Modified alkyl acrylamide (generic). (a) Chemical substance and... acrylamide (PMN P-05-536) is subject to reporting under this section for the significant new uses...

  8. 40 CFR 721.840 - Alkyl substituted diaromatic hydrocarbons.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... hydrocarbons. 721.840 Section 721.840 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED... Specific Chemical Substances § 721.840 Alkyl substituted diaromatic hydrocarbons. (a) Chemical substance... alkyl substituted di-aro-matic hydrocarbons (PMN P-91-710) is subject to reporting under this...

  9. 40 CFR 721.840 - Alkyl substituted diaromatic hydrocarbons.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... hydrocarbons. 721.840 Section 721.840 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED... Specific Chemical Substances § 721.840 Alkyl substituted diaromatic hydrocarbons. (a) Chemical substance... alkyl substituted di-aro-matic hydrocarbons (PMN P-91-710) is subject to reporting under this...

  10. 40 CFR 721.840 - Alkyl substituted diaromatic hydrocarbons.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... hydrocarbons. 721.840 Section 721.840 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED... Specific Chemical Substances § 721.840 Alkyl substituted diaromatic hydrocarbons. (a) Chemical substance... alkyl substituted di-aro-matic hydrocarbons (PMN P-91-710) is subject to reporting under this...