WorldWideScience

Sample records for aqueous polar aromatic

  1. Adsorption of aromatic hydrocarbons and ozone at environmental aqueous surfaces.

    Science.gov (United States)

    Vácha, Robert; Cwiklik, Lukasz; Rezác, Jan; Hobza, Pavel; Jungwirth, Pavel; Valsaraj, Kalliat; Bahr, Stephan; Kempter, Volker

    2008-06-05

    Adsorption of environmentally important aromatic molecules on a water surface is studied by means of classical and ab initio molecular dynamics simulations and by reflection-absorption infrared spectroscopy. Both techniques show strong activity and orientational preference of these molecules at the surface. Benzene and naphthalene, which bind weakly to water surface with a significant contribution of dispersion interactions, prefer to lie flat on water but retain a large degree of orientational flexibility. Pyridine is more rigid at the surface. It is tilted with the nitrogen end having strong hydrogen bonding interactions with water molecules. The degree of adsorption and orientation of aromatic molecules on aqueous droplets has atmospheric implications for heterogeneous ozonolysis, for which the Langmuir-Hinshelwood kinetics mechanism is discussed. At higher coverages of aromatic molecules the incoming ozone almost does not come into contact with the underlying aqueous phase. This may rationalize the experimental insensitivity of the ozonolysis on the chemical nature of the substrate on which the aromatic molecules adsorb.

  2. A combined chemical + enzymatic method to remove selected aromatics from aqueous streams

    International Nuclear Information System (INIS)

    Xu, X.; John, V.

    1993-01-01

    Aromatics are major pollutants found in aqueous environments and in sediments. While there are many chemical and biochemical processes to remove and/or destroy these contaminants, they have to be considered in light of the economics and the time-scales for treatment. We describe our initial work on a hybrid chemical + enzymatic technique to remove aromatics from aqueous stream. The aromatic is first converted to the corresponding phenol through classical Fenton type chemistry involving catalysis by Fe(II). The phenol is subsequently polymerized through an enzymatic mechanism, using horseradish peroxidase as the oxidative enzyme. The polymer is insoluble in water and can be easily recovered. In addition, such phenolic polymers are useful products with varied applications in coatings and resin technologies. Thus, the pollutants can be eventually converted to useful products

  3. Distributions of Polycyclic Aromatic Hydrocarbons, Aromatic Ketones, Carboxylic Acids, and Trace Metals in Arctic Aerosols: Long-Range Atmospheric Transport, Photochemical Degradation/Production at Polar Sunrise.

    Science.gov (United States)

    Singh, Dharmendra Kumar; Kawamura, Kimitaka; Yanase, Ayako; Barrie, Leonard A

    2017-08-15

    The distributions, correlations, and source apportionment of aromatic acids, aromatic ketones, polycyclic aromatic hydrocarbons (PAHs), and trace metals were studied in Canadian high Arctic aerosols. Nineteen PAHs including minor sulfur-containing heterocyclic PAH (dibenzothiophene) and major 6 carcinogenic PAHs were detected with a high proportion of fluoranthene followed by benzo[k]fluoranthene, pyrene, and chrysene. However, in the sunlit period of spring, their concentrations significantly declined likely due to photochemical decomposition. During the polar sunrise from mid-March to mid-April, benzo[a]pyrene to benzo[e]pyrene ratios significantly dropped, and the ratios diminished further from late April to May onward. These results suggest that PAHs transported over the Arctic are subjected to strong photochemical degradation at polar sunrise. Although aromatic ketones decreased in spring, concentrations of some aromatic acids such as benzoic and phthalic acids increased during the course of polar sunrise, suggesting that aromatic hydrocarbons are oxidized to result in aromatic acids. However, PAHs do not act as the major source for low molecular weight (LMW) diacids such as oxalic acid that are largely formed at polar sunrise in the arctic atmosphere because PAHs are 1 to 2 orders of magnitude less abundant than LMW diacids. Correlations of trace metals with organics, their sources, and the possible role of trace transition metals are explained.

  4. [Effectiveness of aqueous extracts of aromatic and medicinal plants against tomato grey mould in Morocco].

    Science.gov (United States)

    Kasmi, Manal; Aourach, Mohammed; El Boukari, Mohammed; Barrijal, Said; Essalmani, Haiat

    2017-08-01

    Grey mould is a major disease threatening the Moroccan tomato; this disease is often controlled by fungicides. However, the latter are a real danger to human health and environment. Thus, this study is part of the research of harmless alternatives such extracts of aromatic and medicinal plants (Lavandula officinalis, Thymus vulgaris, Cymbopogon citratus, and Melissa officinalis). In this study, the extracts of four medicinal and aromatic plants were tested for their antifungal potency in vitro and in vivo in order to select the most effective. The results show that, in vitro, the Lavandula officinalis, Thymus vulgaris and Cymbopogon citratus aqueous extracts all possess significant antifungal activity, whereas Melissa officinalis shows the least effective. Also in vivo only the aqueous extract of Cymbopogon citratus proves most effective against B. cinerea on tomato fruit. The test of the plants confirms that aqueous extracts of Cymbopogon citratus and Thymus vulgaris are most effective, while the aqueous extracts of Melissa officinalis and Lavandula officinalis always seem to be the least effective. Therefore, the aqueous extracts of Cymbopogon citratus and Thymus vulgaris are the most envisaged for the biological control of grey mould. Copyright © 2017 Académie des sciences. Published by Elsevier Masson SAS. All rights reserved.

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

    NARCIS (Netherlands)

    Zakzeski, J.|info:eu-repo/dai/nl/326160256; Weckhuysen, B.M.|info:eu-repo/dai/nl/285484397

    2011-01-01

    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

  6. Influence of activated carbon surface acidity on adsorption of heavy metal ions and aromatics from aqueous solution

    International Nuclear Information System (INIS)

    Sato, Sanae; Yoshihara, Kazuya; Moriyama, Koji; Machida, Motoi; Tatsumoto, Hideki

    2007-01-01

    Adsorption of toxic heavy metal ions and aromatic compounds onto activated carbons of various amount of surface C-O complexes were examined to study the optimum surface conditions for adsorption in aqueous phase. Cadmium(II) and zinc(II) were used as heavy metal ions, and phenol and nitrobenzene as aromatic compounds, respectively. Activated carbon was de-ashed followed by oxidation with nitric acid, and then it was stepwise out-gassed in helium flow up to 1273 K to gradually remove C-O complexes introduced by the oxidation. The oxidized activated carbon exhibited superior adsorption for heavy metal ions but poor performance for aromatic compounds. Both heavy metal ions and aromatics can be removed to much extent by the out-gassed activated carbon at 1273 K. Removing C-O complexes, the adsorption mechanisms would be switched from ion exchange to Cπ-cation interaction for the heavy metals adsorption, and from some kind of oxygen-aromatics interaction to π-π dispersion for the aromatics

  7. Detection of Polarized Infrared Emission by Polycyclic Aromatic Hydrocarbons in the MWC 1080 Nebula

    International Nuclear Information System (INIS)

    Zhang, Han; Telesco, Charles M.; Pantin, Eric; Barnes, Peter; Hoang, Thiem; Li, Aigen; Wright, Christopher M.; Li, Dan

    2017-01-01

    Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous in astrophysical environments, as revealed by their pronounced emission features at 3.3, 6.2, 7.7, 8.6, 11.3, and 12.7 μ m commonly ascribed to the C–H and C–C vibrational modes. Although these features have long been predicted to be polarized, previous searches for PAH polarization led to null or, at best, tentative detections. Here we report the definite detection of polarized PAH emission at 11.3 μ m in the nebula associated with the Herbig Be star MWC 1080. We measure a polarization degree of 1.9% ± 0.2%, which is unexpectedly high compared to models. This poses a challenge in the current understanding of the alignment of PAHs, which is required to polarize the PAH emission but thought to be substantially suppressed. PAH alignment with a magnetic field via a resonance paramagnetic relaxation process may account for such a high level of polarization.

  8. Detection of Polarized Infrared Emission by Polycyclic Aromatic Hydrocarbons in the MWC 1080 Nebula

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Han; Telesco, Charles M.; Pantin, Eric; Barnes, Peter [Department of Astronomy, University of Florida, Gainesville, FL 32611 (United States); Hoang, Thiem [Korea Astronomy and Space Science Institute 776, Daedeokdae-ro, Yuseong-gu, Daejeon 34055 (Korea, Republic of); Li, Aigen [Department of Physics and Astronomy, University of Missouri, Columbia, MO 65211 (United States); Wright, Christopher M. [School of Physical, Environmental and Mathematical Sciences, UNSW Canberra, P.O. Box 7916, Canberra BC 2610 (Australia); Li, Dan, E-mail: hanzh0420@ufl.edu [Department of Physics and Astronomy, University of Pennsylvania, Philadelphia, PA 19104 (United States)

    2017-07-20

    Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous in astrophysical environments, as revealed by their pronounced emission features at 3.3, 6.2, 7.7, 8.6, 11.3, and 12.7 μ m commonly ascribed to the C–H and C–C vibrational modes. Although these features have long been predicted to be polarized, previous searches for PAH polarization led to null or, at best, tentative detections. Here we report the definite detection of polarized PAH emission at 11.3 μ m in the nebula associated with the Herbig Be star MWC 1080. We measure a polarization degree of 1.9% ± 0.2%, which is unexpectedly high compared to models. This poses a challenge in the current understanding of the alignment of PAHs, which is required to polarize the PAH emission but thought to be substantially suppressed. PAH alignment with a magnetic field via a resonance paramagnetic relaxation process may account for such a high level of polarization.

  9. Process for preparing organoclays for aqueous and polar-organic systems

    Science.gov (United States)

    Chaiko, David J.

    2001-01-01

    A process for preparing organoclays as thixotropic agents to control the rheology of water-based paints and other aqueous and polar-organic systems. The process relates to treating low-grade clay ores to achieve highly purified organoclays and/or to incorporate surface modifying agents onto the clay by adsorption and/or to produce highly dispersed organoclays without excessive grinding or high shear dispersion. The process involves the treatment of impure, or run-of-mine, clay using an aqueous biphasic extraction system to produce a highly dispersed clay, free of mineral impurities and with modified surface properties brought about by adsorption of the water-soluble polymers used in generating the aqueous biphasic extraction system. This invention purifies the clay to greater than 95%.

  10. Chemically induced dynamic electron polarization. Pulse radiolysis of aqueous solutions of alcohols

    International Nuclear Information System (INIS)

    Trifunac, A.D.; Thurnauer, M.C.

    1975-01-01

    The radical pair model of chemically induced dynamic electron polarization (CIDEP) is experimentally verified. Aqueous solutions of alcohols were irradiated with 3 MeV electrons and observed with time resolved electron paramagnetic resonance (EPR) spectroscopy. Relative line intensities of the polarized EPR spectra of radicals from methanol and especially ethylene glycol, alone and in the presence of radicals from compounds containing halogens, illustrates the polarization dependence on the g-factor differences between the radical pair components. The observation of the relative polarization enhancement in the various lines of the multiline EPR spectra illustrates the polarization dependence on the hyperfine terms. Intrinsic enhancements are calculated and are shown to be proportional to the observed enhancement, showing that the radical pair model of CIDEP is qualitatively correct

  11. Determination of aromatic amines in aqueous extracts of polyurethane foam using hydrophilic interaction liquid chromatography and mass spectrometry

    International Nuclear Information System (INIS)

    Riddar Johnson, Jakob; Karlsson, Daniel; Dalene, Marianne; Skarping, Gunnar

    2010-01-01

    A method is presented for the determination of aromatic amines in aqueous extracts of polyurethane (PUR) foam. The method is based on the extraction of PUR foam using aqueous acetic acid (0.1%, w/v) followed by determination of extracted aromatic amines using hydrophilic interaction liquid chromatography (HILIC) and tandem mass spectrometry (MS/MS) with positive electrospray ionisation. The injections of volumes up to 5 μL of aqueous solutions were made possible by on-column focusing with partially filled loop injections. The fragmentation patterns for 2,4- and 2,6-toluene diamine (TDA) and 4,4'-methylene dianiline (MDA) were clarified by performing a hydrogen-deuterium exchange study. TDA and MDA were determined using trideuterated 2,4- and 2,6-TDA and dideuterated 4,4'-MDA as internal standards. Linear calibration graphs were obtained over the range 0.025-0.5 μg mL -1 with correlation coefficients >0.996 and the instrumental detection limit for each compound was <50 fmol. The stability of the amines was influenced by the matrix, so their concentrations decreased over time. Agreement was observed between the results of analyses of PUR foam extracts by HILIC-MS/MS and results obtained by ethyl chloroformate derivatisation and reversed phase (RP) liquid chromatography-mass spectrometry (LC-MS/MS). TDA was observed to be unstable in extracts of foam but not in pure solutions.

  12. Determination of heavy polycyclic aromatic hydrocarbons by non-aqueous reversed phase liquid chromatography: Application and limitation in refining streams.

    Science.gov (United States)

    Panda, Saroj K; Muller, Hendrik; Al-Qunaysi, Thunayyan A; Koseoglu, Omer R

    2018-01-19

    The heavy polycyclic aromatic hydrocarbons (HPAHs) cause detrimental effects to hydrocracker operations by deactivating the catalysts and depositing in the downstream of the reactor/ exchangers. Therefore, it is essential to continuously monitor the accumulation of HPAHs in a hydrocracker unit. To accurately measure the concentration of HPAHs, the development of a fast and reliable analytical method is inevitable. In this work, an analytical method based on non-aqueous reversed phase chromatography in combination with high resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) was developed. As a first step, five different types of stationary phases were evaluated for the separation of HPAHs in non-aqueous mode and the best suited phase was further used for the fractionation of HPAHs in a fractionator bottom sample obtained from a refinery hydrocracker unit. The eight major fractions or peaks obtained from the separation were further characterized by UV spectroscopy and FT-ICR MS and the compounds in the fractions were tentatively confirmed as benzoperylene, coronene, methylcoronene, naphthenocoronene, benzocoronene, dibenzoperylene, naphthocoronene and ovalene. The developed liquid chromatography method can be easily adapted in a refinery laboratory for the quantitation of HPAHs in hydrocracking products. The method was further tested to check the interference of sulfur aromatics and/or large alkylated aromatic hydrocarbons on the determination of HPAHs in hydrocracking products. Copyright © 2017 Elsevier B.V. All rights reserved.

  13. Electrochemical transformation of trichloroethylene in aqueous solution by electrode polarity reversal.

    Science.gov (United States)

    Rajic, Ljiljana; Fallahpour, Noushin; Yuan, Songhu; Alshawabkeh, Akram N

    2014-12-15

    Electrode polarity reversal is evaluated for electrochemical transformation of trichloroethylene (TCE) in aqueous solution using flow-through reactors with mixed metal oxide electrodes and Pd catalyst. The study tests the hypothesis that optimizing electrode polarity reversal will generate H2O2 in Pd presence in the system. The effect of polarity reversal frequency, duration of the polarity reversal intervals, current intensity and TCE concentration on TCE removal rate and removal mechanism were evaluated. TCE removal efficiencies under 6 cycles h(-1) were similar in the presence of Pd catalyst (50.3%) and without Pd catalyst (49.8%), indicating that Pd has limited impact on TCE degradation under these conditions. The overall removal efficacies after 60 min treatment under polarity reversal frequencies of 6, 10, 15, 30 and 90 cycles h(-1) were 50.3%, 56.3%, 69.3%, 34.7% and 23.4%, respectively. Increasing the frequency of polarity reversal increases TCE removal as long as sufficient charge is produced during each cycle for the reaction at the electrode. Electrode polarity reversal shifts oxidation/reduction and reduction/oxidation sequences in the system. The optimized polarity reversal frequency (15 cycles h(-1) at 60 mA) enables two reaction zones formation where reduction/oxidation occurs at each electrode surface. Published by Elsevier Ltd.

  14. Aromatic-Aromatic Interactions in Biological System: Structure Activity Relationships

    International Nuclear Information System (INIS)

    Rajagopal, Appavu; Deepa, Mohan; Govindaraju, Munisamy

    2016-01-01

    While, intramolecular hydrogen bonds have attracted the greatest attention in studies of peptide conformations, the recognition that several other weakly polar interactions may be important determinants of folded structure has been growing. Burley and Petsko provided a comprehensive overview of the importance of weakly polar interactions, in shaping protein structures. The interactions between aromatic rings, which are spatially approximate, have attracted special attention. A survey of the proximal aromatic residue pairs in proteins, allowed Burley and Petsko to suggest that, “phenyl ring centroids are separated by a preferential distance of between 4.5 and 7 Å, and dihedral angles approximately 90° are most common”

  15. Aromatic-Aromatic Interactions in Biological System: Structure Activity Relationships

    Energy Technology Data Exchange (ETDEWEB)

    Rajagopal, Appavu; Deepa, Mohan [Molecular Biophysics Unit, Indian Institute of Sciences-Bangalore, Karnataka (India); Govindaraju, Munisamy [Bio-Spatial Technology Research Unit, Department of Environmental Biotechnology, School of Environmental Sciences, Bharathidasan University, Tiruchirappalli, Tamil Nadu (India)

    2016-02-26

    While, intramolecular hydrogen bonds have attracted the greatest attention in studies of peptide conformations, the recognition that several other weakly polar interactions may be important determinants of folded structure has been growing. Burley and Petsko provided a comprehensive overview of the importance of weakly polar interactions, in shaping protein structures. The interactions between aromatic rings, which are spatially approximate, have attracted special attention. A survey of the proximal aromatic residue pairs in proteins, allowed Burley and Petsko to suggest that, “phenyl ring centroids are separated by a preferential distance of between 4.5 and 7 Å, and dihedral angles approximately 90° are most common”.

  16. 1H NMR analysis of complexation of hydrotropic agents nicotinamide and caffeine with aromatic biologically active molecules in aqueous solution

    Science.gov (United States)

    Lantushenko, Anastasia O.; Mukhina, Yulia V.; Veselkov, Kyrill A.; Davies, David B.; Veselkov, Alexei N.

    2004-07-01

    NMR spectroscopy has been used to elucidate the molecular mechanism of solubilization action of hydrotropic agents nicotinamide (NA) and caffeine (CAF). Hetero-association of NA with riboflavine-mononucleotide (FMN) and CAF with low soluble in aqueous solution synthetic analogue of antibiotic actinomycin D, actinocyl-bis-(3-dimethylaminopropyl) amine (Actill), has been investigated by 500 MHz 1H NMR spectroscopy. Concentration and temperature dependences of proton chemical shifts have been analysed in terms of a statistical-thermodynamic model of indefinite self- and heteroassociation of aromatic molecules. The obtained results enable to conclude that NA-FMN and CAF-Actill intermolecular complexes are mainly stabilized by the stacking interactions of the aromatic chromophores. Hetero-association of the investigated molecules plays an important role in solubilization of aromatic drugs by hydrotropic agents nicotinamide and caffeine.

  17. Effects of solution P H on the adsorption of aromatic compounds from aqueous solutions by activated carbon

    International Nuclear Information System (INIS)

    Nouri, S.; Haghseresht, F.; Lu, M.

    2002-01-01

    Absorption of p-Cresol, Benzoic acid and Nitro Benzene by activated carbon from dilute aqueous solutions was carried out under controlled ph conditions at 310 k. In acidic conditions, well below the pK a of all solutes, it was observed that the adsorbate solubility and the electron density of its aromatic ring were the influencing factors on the extent of the adsorption by affecting the extent of London dispersion forces. In higher solution ph conditions, on the other hand, it was found that the electrostatic forces played a significant role on the extent of adsorption. The Effect of ph must be considered from its combined effects on the carbon surface and on the solute molecules. It was found that the uptake of the molecular forms of the aromatic solutes was dependent on the substituents of the aromatic ring. Adsorption of the solutes in higher P H values was found to be dependent on the concentration of anionic form of the solutes. All isotherms were fitted into Freundlich Isotherm Equations

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

    Science.gov (United States)

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

    1983-09-20

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

  19. The Homocoupling Reaction of Aromatic Terminal Alkynes by a Highly Active Palladium(II)/AgNO₃ Cocatalyst in Aqueous Media Under Aerobic Conditions.

    Science.gov (United States)

    Guo, Mengping; Chen, Bo; Lv, Meiyun; Zhou, Xiuling; Wen, Yongju; Shen, Xiuli

    2016-05-10

    A new and efficient Pd(II)/AgNO₃-cocatalyzed homocoupling of aromatic terminal alkynes is described. Various symmetrical 1,4-disubstituted-1,3-diynes are obtained in good to excellent yields. This protocol employs a loading with relatively low palladium(II) in aqueous media under aerobic conditions.

  20. Determination of Polar Compounds in Guava Leaves Infusions and Ultrasound Aqueous Extract by HPLC-ESI-MS

    Directory of Open Access Journals (Sweden)

    Elixabet Díaz-de-Cerio

    2015-01-01

    Full Text Available Literature lacks publications about polar compounds content in infusion or guava leaves tea. Because of that, a comparison between different times of infusion and a conventional ultrasound aqueous extract was carried out. Several polar compounds have been identified by HPLC-ESI-MS and their antioxidant activity was evaluated by FRAP and ABTS assays. Four different classes of phenolic compounds (gallic and ellagic acid derivatives, flavonols, flavanones, and flavan-3-ols and some benzophenones were determined. The quantification results reported that the order, in terms of concentration of the classes of polar compounds in all samples, was flavonols > flavan-3-ols > gallic and ellagic acid derivatives > benzophenones > flavanones. As expected, the aqueous extract obtained by sonication showed the highest content in the compounds studied. Significative differences were noticed about the different times of infusion and five minutes was the optimal time to obtain the highest content in polar compounds using this culinary method. All the identified compounds, except HHDP isomers and naringenin, were positively correlated with antioxidant activity.

  1. Detection of chlorinated aromatic compounds

    Science.gov (United States)

    Ekechukwu, A.A.

    1996-02-06

    A method for making a composition for measuring the concentration of chlorinated aromatic compounds in aqueous fluids, and an optical probe for use with the method are disclosed. The composition comprises a hydrophobic polymer matrix, preferably polyamide, with a fluorescent indicator uniformly dispersed therein. The indicator fluoresces in the presence of the chlorinated aromatic compounds with an intensity dependent on the concentration of these compounds in the fluid of interest, such as 8-amino-2-naphthalene sulfonate. The probe includes a hollow cylindrical housing that contains the composition in its distal end. The probe admits an aqueous fluid to the probe interior for exposure to the composition. An optical fiber transmits excitation light from a remote source to the composition while the indicator reacts with chlorinated aromatic compounds present in the fluid. The resulting fluorescence light signal is reflected to a second optical fiber that transmits the light to a spectrophotometer for analysis. 5 figs.

  2. Long-Term Charge/Discharge Cycling Stability of MnO2 Aqueous Supercapacitor under Positive Polarization

    KAUST Repository

    Ataherian, Fatemeh; Wu, Nae-Lih

    2011-01-01

    The long-term charge/discharge cycling stability of MnO 2 electrode under positive polarization in aqueous KCl electrolyte has been studied over different potential windows spanning from the open circuit potential to varied higher-end potential

  3. Diffusion of aqueous solutions of ionic, zwitterionic, and polar solutes

    Science.gov (United States)

    Teng, Xiaojing; Huang, Qi; Dharmawardhana, Chamila Chathuranga; Ichiye, Toshiko

    2018-06-01

    The properties of aqueous solutions of ionic, zwitterionic, and polar solutes are of interest to many fields. For instance, one of the many anomalous properties of aqueous solutions is the behavior of water diffusion in different monovalent salt solutions. In addition, solutes can affect the stabilities of macromolecules such as proteins in aqueous solution. Here, the diffusivities of aqueous solutions of sodium chloride, potassium chloride, tri-methylamine oxide (TMAO), urea, and TMAO-urea are examined in molecular dynamics simulations. The decrease in the diffusivity of water with the concentration of simple ions and urea can be described by a simple model in which the water molecules hydrogen bonded to the solutes are considered to diffuse at the same rate as the solutes, while the remainder of the water molecules are considered to be bulk and diffuse at almost the same rate as pure water. On the other hand, the decrease in the diffusivity of water with the concentration of TMAO is apparently affected by a decrease in the diffusion rate of the bulk water molecules in addition to the decrease due to the water molecules hydrogen bonded to TMAO. In other words, TMAO enhances the viscosity of water, while urea barely affects it. Overall, this separation of water molecules into those that are hydrogen bonded to solute and those that are bulk can provide a useful means of understanding the short- and long-range effects of solutes on water.

  4. Parsing of the free energy of aromatic-aromatic stacking interactions in solution

    Energy Technology Data Exchange (ETDEWEB)

    Kostjukov, Viktor V.; Khomytova, Nina M. [Department of Physics, Sevastopol National Technical University, Sevastopol 99053, Crimea (Ukraine); Hernandez Santiago, Adrian A.; Tavera, Anna-Maria Cervantes; Alvarado, Julieta Salas [Faculty of Chemical Sciences, Autonomous University of Puebla, Puebla (Mexico); Evstigneev, Maxim P., E-mail: max_evstigneev@mail.ru [Department of Physics, Sevastopol National Technical University, Sevastopol 99053, Crimea (Ukraine)

    2011-10-15

    Graphical abstract: Highlights: > A protocol for decomposition of the free energy of aromatic stacking is developed. > The factors stabilizing/destabilizing stacking of aromatic molecules are defined. > Hydrophobic contribution is found to be dominant. - Abstract: We report an analysis of the energetics of aromatic-aromatic stacking interactions for 39 non-covalent reactions of self- and hetero-association of 12 aromatic molecules with different structures and charge states. A protocol for computation of the contributions to the total energy from various energetic terms has been developed and the results are consistent with experiment in 92% of all the systems studied. It is found that the contributions from hydrogen bonds and entropic factors are always unfavorable, whereas contributions from van-der-Waals, electrostatic and/or hydrophobic effects may lead to stabilizing or destabilizing factors depending on the system studied. The analysis carried out in this work provides an answer to the questions 'What forces stabilize/destabilize the stacking of aromatic molecules in aqueous-salt solution and what are their relative importance?'

  5. Parsing of the free energy of aromatic-aromatic stacking interactions in solution

    International Nuclear Information System (INIS)

    Kostjukov, Viktor V.; Khomytova, Nina M.; Hernandez Santiago, Adrian A.; Tavera, Anna-Maria Cervantes; Alvarado, Julieta Salas; Evstigneev, Maxim P.

    2011-01-01

    Graphical abstract: Highlights: → A protocol for decomposition of the free energy of aromatic stacking is developed. → The factors stabilizing/destabilizing stacking of aromatic molecules are defined. → Hydrophobic contribution is found to be dominant. - Abstract: We report an analysis of the energetics of aromatic-aromatic stacking interactions for 39 non-covalent reactions of self- and hetero-association of 12 aromatic molecules with different structures and charge states. A protocol for computation of the contributions to the total energy from various energetic terms has been developed and the results are consistent with experiment in 92% of all the systems studied. It is found that the contributions from hydrogen bonds and entropic factors are always unfavorable, whereas contributions from van-der-Waals, electrostatic and/or hydrophobic effects may lead to stabilizing or destabilizing factors depending on the system studied. The analysis carried out in this work provides an answer to the questions 'What forces stabilize/destabilize the stacking of aromatic molecules in aqueous-salt solution and what are their relative importance?'

  6. Removal of polycyclic aromatic hydrocarbons from aqueous solution using plant residue materials as a biosorbent

    Energy Technology Data Exchange (ETDEWEB)

    Chen Baoliang, E-mail: blchen@zju.edu.cn [Department of Environmental Science, Zhejiang University, Hangzhou, Zhejiang 310028 (China); Zhejiang Provincial Key Laboratory of Organic Pollution Process and Control, Zhejiang University, Hangzhou, Zhejiang 310028 (China); Yuan Miaoxin; Liu Hao [Department of Environmental Science, Zhejiang University, Hangzhou, Zhejiang 310028 (China); Zhejiang Provincial Key Laboratory of Organic Pollution Process and Control, Zhejiang University, Hangzhou, Zhejiang 310028 (China)

    2011-04-15

    Graphical abstract: The structure-effect relationship provides a reference to select and modify plant residues as a biosorbent with high efficiency to tackle organic pollutants. Research highlights: {yields} Polycyclic aromatic hydrocarbons are effectively removed by plant residues. {yields} Biosorption mechanism of plant residues to abate PAHs is a partitioning process. {yields} Partition coefficients are negatively related with sugar contents of biosorbent. {yields} The aromatic component and K{sub ow} exhibit positive effects on biosorption. {yields} The structure-effect relationship guides plant residue using as a biosorbent. - Abstract: To elucidate biosorption mechanism and removal efficiency of plant residues as a biosorbent to abate polycyclic aromatic hydrocarbons (PAHs) in wastewater, sorption of PAHs onto wood chips (WC), ryegrass roots (RR), orange peels (OP), bamboo leaves (BL), and pine needles (PN) were investigated. The structural characterization of the biosorbents was analyzed by elemental composition, BET-N{sub 2} surface area, and Fourier transform infrared spectroscopy. PAHs sorption to the selected biosorbents were compared and correlated with their structures. Biosorption isotherms fit well with Freundlich equation and the mechanism was dominated by partition process. The magnitude of phenanthrene partition coefficients (K{sub d}) followed the order of PN > BL > OP > RR > WC, ranged from 2484 {+-} 24.24 to 5306 {+-} 92.49 L/kg. Except the WC sample, the K{sub d} values were negatively correlated with sugar content, polar index [(N + O)/C] of the biosorbents, while the aromatic component exhibited positive effects. For a given biosorbent of bamboo leaves, the carbon-normalized partition coefficients (K{sub oc}) were linearly correlated with octanol-water partition coefficients (K{sub ow}) of PAHs, i.e., log K{sub oc} = 1.16 log K{sub ow} - 1.21. The structure-effect relationship provides a reference to select and modify plant residues as a

  7. Solid-phase extraction element based on epoxy polymer monolith for determination of polar organic compounds in aqueous media.

    Science.gov (United States)

    Takahashi, Tadashi; Odagiri, Kayo; Watanabe, Atsushi; Watanabe, Chuichi; Kubo, Takuya; Hosoya, Ken

    2011-10-01

    A solid-phase extraction element based on epoxy polymer monolith was fabricated for sorptive enrichment of polar compounds from liquid and gaseous samples. After ultrasonication of the element in an aqueous solution for a given period of time, the thermal desorption (TD) using a pyrolyzer with gas chromatography/mass spectrometry (GC/MS), in which TD temperature was programmed from 50 to 250 °C for the analytes absorbed in the element, was used to evaluate the element for basic extraction performance using the aqueous standard mixtures consisting of compounds having varied polarities such as hexanol, isoamyl acetate, linalool, furfural and decanoic acid, in concentrations ranging from 10 μg/L to 1 mg/L. Excellent linear relationships were observed for all compounds in the standard mixture, except decanoic acid. In the extraction of beverages such as red wine, the extraction element showed stronger adsorption characteristics for polar compounds such as alcohols and acids than a non-polar polydimethylsiloxane-based element. This feature is derived from the main polymer structure along with hydroxyl and amino groups present in the epoxy-based monolith polymer matrix. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Cathodic electrogenerated chemiluminescence of aromatic Tb(III) chelates at polystyrene-graphite composite electrodes

    International Nuclear Information System (INIS)

    Salminen, Kalle; Grönroos, Päivi; Tuomi, Sami; Kulmala, Sakari

    2017-01-01

    Tb(III) chelates exhibit intense hot electron-induced electrogenerated chemiluminescence during cathodic polarization of metal/polystyrene-graphite (M/PG) electrodes in fully aqueous solutions. The M/PG working electrode provides a sensitive means for the determination of aromatic Tb(III) chelates at nanomolar concentration levels with a linear log-log calibration curve spanning more than five orders of magnitude. The charge transport and other properties of these novel electrodes were studied by electrochemiluminescence measurements and cyclic voltammetry. The present composite electrodes can by utilized both under pulse polarization and DC polarization unlike oxide-coated metal electrodes which do not tolerate cathodic DC polarization. The present cost-effective electrodes could be utilized e.g. in immunoassays where polystyrene is extensively used as a solid phase for various bioaffinity assays by using electrochemiluminescent Tb(III) chelates or e.g. Ru(bpy) 3 2+ as labels. - Highlights: • Generation of hydrated electrons at Polystyrene-graphite electrodes. • The insulating polystyrene layer on the outer electrode surface seems necessary. • Hydrated electrons are able to produce chemiluminescence. • Strongest signal and lowest std. dev. achieved at same graphite weight fraction.

  9. Removal of polycyclic aromatic hydrocarbons in aqueous environment by chemical treatments: a review.

    Science.gov (United States)

    Rubio-Clemente, Ainhoa; Torres-Palma, Ricardo A; Peñuela, Gustavo A

    2014-04-15

    Due to their carcinogenic, mutagenic and teratogenic potential, the removal of polycyclic aromatic hydrocarbons (PAHs) from aqueous environment using physical, biological and chemical processes has been studied by several researchers. This paper reviews the current state of knowledge concerning PAHs including their physico-chemical properties, input sources, occurrence, adverse effects and conventional and alternative chemical processes applied for their removal from water. The mechanisms and reactions involved in each treatment method are reported, and the effects of various variables on the PAH degradation rate as well as the extent of degradation are also discussed. Extensive literature analysis has shown that an effective way to perform the conversion and mineralization of this type of substances is the application of advanced oxidation processes (AOPs). Furthermore, combined processes, particularly AOPs coupled with biological treatments, seem to be one of the best solutions for the treatment of effluents containing PAHs. Copyright © 2013 Elsevier B.V. All rights reserved.

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

    Science.gov (United States)

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

    1982-03-31

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

  11. Reactions of H-radicals with aromatic halogeno compounds in aqueous solutions

    International Nuclear Information System (INIS)

    Lichtscheidl, J.; Getoff, N.

    1979-01-01

    The spectroscopic and kinetic data of the short lived intermediates obtained by the attack of H-radicals on fluoro-, chloro-, bromobenzene, benzylchloride and phenethylchloride in aqueous solutions were studied by pulse radiolysis technique. The first three yield cyclohexadienylradicals (k equals 1-1.5 x 10 9 dm 3 mol -1 s -1 ) with chatacteristic absorption maxima in the region 220-330 nm. In the case of benzylchloride a quantitative abstraction of chlorine by the H-atoms is observed (k = 9.5 x 10 8 dm 3 mol -1 s -1 ) leading to the formation of the benzylradical (Λsub(max)=257, 303, 317.5 nm). The attack of H-atoms on phenethylchloride can occur on the aromatic ring forming also a cyclohexadienylradical (k = 2.0 x 10 9 dm 3 mol -1 s -1 , lambdasub(max)=317, 323 nm) as well as on the side chain (k = 1.5 x 10 8 dm 3 mol -1 s -1 ) yielding H 2 . The intermediates decay according to a second order reaction with k = 2 to 4.6 x 10 9 dm 3 mol -1 s -1 . To elucidate reaction mechanisms, steady state radiolysis experiments on the same systems were performed. (auth.)

  12. Basicity comparison for di-substituted 4-nitropyridine derivatives in polar non-aqueous media

    International Nuclear Information System (INIS)

    Gurzynski, Lukasz; Puszko, Aniela; Chmurzynski, Lech

    2007-01-01

    Acid dissociation, as well as cationic homoconjugation equilibria have been studied potentiometrically in systems involving four di-substituted 4-nitropyridines and conjugate cationic acids in the polar non-aqueous solvents - aprotic protophobic acetonitrile (AN) and propylene carbonate (PC), the amphiprotic methanol (MeOH), and in the aprotic protophilic dimethyl sulfoxide (DMSO). The influence of solvent effect on the obtained acidity constants has been discussed. The acidity constants (expressed as pK a values) were compared with those previously determined in another polar protophobic aprotic solvent - acetone (AC), and obtained for the unsubstituted pyridine (Py). A comparison of the acid dissociation constants determined in all media studied has proved that the strength of the cationic acids increases on going from acetonitrile through propylene carbonate, acetone, and methanol to dimethyl sulfoxide. Furthermore, the values of acidity constants in the non-aqueous media have shown that in all the solvents studied they change according to the substituent effects. It has been also found that substituted 4-nitropyridine derivatives studied exhibit no tendency towards cationic homoconjugation in acetonitrile, propylene carbonate, and methanol and dimethyl sulfoxide. Moreover, it has been demonstrated that the acid dissociation constants determined by potentiometric titration method in all the solutions investigated correlate well with the calculated energy parameters of the protonation reactions in the gaseous phase

  13. Basicity comparison for di-substituted 4-nitropyridine derivatives in polar non-aqueous media

    Energy Technology Data Exchange (ETDEWEB)

    Gurzynski, Lukasz [Department of General and Inorganic Chemistry, University of Gdansk, Sobieskiego 18, 80-952 Gdansk (Poland); Puszko, Aniela [Department of Organic Chemistry, School of Economics, Wroclaw (Poland); Chmurzynski, Lech [Department of General and Inorganic Chemistry, University of Gdansk, Sobieskiego 18, 80-952 Gdansk (Poland)], E-mail: lech@chemik.chem.univ.gda.pl

    2007-12-15

    Acid dissociation, as well as cationic homoconjugation equilibria have been studied potentiometrically in systems involving four di-substituted 4-nitropyridines and conjugate cationic acids in the polar non-aqueous solvents - aprotic protophobic acetonitrile (AN) and propylene carbonate (PC), the amphiprotic methanol (MeOH), and in the aprotic protophilic dimethyl sulfoxide (DMSO). The influence of solvent effect on the obtained acidity constants has been discussed. The acidity constants (expressed as pK{sub a} values) were compared with those previously determined in another polar protophobic aprotic solvent - acetone (AC), and obtained for the unsubstituted pyridine (Py). A comparison of the acid dissociation constants determined in all media studied has proved that the strength of the cationic acids increases on going from acetonitrile through propylene carbonate, acetone, and methanol to dimethyl sulfoxide. Furthermore, the values of acidity constants in the non-aqueous media have shown that in all the solvents studied they change according to the substituent effects. It has been also found that substituted 4-nitropyridine derivatives studied exhibit no tendency towards cationic homoconjugation in acetonitrile, propylene carbonate, and methanol and dimethyl sulfoxide. Moreover, it has been demonstrated that the acid dissociation constants determined by potentiometric titration method in all the solutions investigated correlate well with the calculated energy parameters of the protonation reactions in the gaseous phase.

  14. Prediction of environmental parameters of polycyclic aromatic hydrocarbons with COSMO-RS

    NARCIS (Netherlands)

    Schröder, B.; Santos, L.M.N.B.F.; Alves da Rocha, M.A.; Oliveira, M.B.; Marrucho, I.M.; Coutinho, J.A.P.

    2010-01-01

    The methodology for the prediction of properties of environmental relevance of polycyclic aromatic hydrocarbons based on the conductor-like screening model for real solvents (COSMO-RS/COSMOtherm) is presented and evaluated, with a special focus on the aqueous solubility of polycyclic aromatic

  15. Heat capacities of aqueous polar aromatic compounds over a wide range of conditions. Part I: phenol, cresols, aniline, and toluidines

    International Nuclear Information System (INIS)

    Censky, Miroslav; Hnedkovsky, Lubomir; Majer, Vladimir

    2005-01-01

    The heat capacities of dilute aqueous solutions of phenol (hydroxybenzene), three cresols (2-, 3- and 4-methylhydroxybenzene), aniline (aminobenzene) and three toluidines (2-, 3- and 4-methylaminobenzene) were determined using a modified flow Picker-type high temperature calorimeter. The measurements were performed at temperatures between (303 and 623) K or 573 K for compounds containing hydroxy or amino group, respectively, and at several pressures up to 30 MPa. Standard heat capacities (partial molar heat capacities at infinite dilution) obtained from the experimental data exhibit a strong increase with temperature above 500 K consistent with the evolution of the standard volumes reported earlier. The data for aqueous phenol were used for testing several semiempiric models proposed for description of the standard thermodynamic properties of aqueous solutes. Their ability to reproduce the temperature and pressure dependence of standard heat capacities and to extrapolate towards higher conditions were examined

  16. Extraction of Lanthanide and Actinide Ions from Aqueous Mixtures Using a Carboxylic Acid-Functionalized Porous Aromatic Framework

    Science.gov (United States)

    2016-01-01

    Porous aromatic frameworks (PAFs) incorporating a high concentration of acid functional groups possess characteristics that are promising for use in separating lanthanide and actinide metal ions, as required in the treatment of radioactive waste. These materials have been shown to be indefinitely stable to concentrated acids and bases, potentially allowing for multiple adsorption/stripping cycles. Additionally, the PAFs combine exceptional features from MOFs and inorganic/activated carbons giving rise to tunable pore surfaces and maximum chemical stability. Herein, we present a study of the adsorption of selected metal ions, Sr2+, Fe3+, Nd3+, and Am3+, from aqueous solutions employing a carbon-based porous aromatic framework, BPP-7 (Berkeley Porous Polymer-7). This material displays high metal loading capacities together with excellent adsorption selectivity for neodymium over strontium based on Langmuir adsorption isotherms and ideal adsorbed solution theory (IAST) calculations. Based in part upon X-ray absorption spectroscopy studies, the stronger adsorption of neodymium is attributed to multiple metal ion and binding site interactions resulting from the densely functionalized and highly interpenetrated structure of BPP-7. Recyclability and combustibility experiments demonstrate that multiple adsorption/stripping cycles can be completed with minimal degradation of the polymer adsorption capacity. PMID:27163056

  17. Evaluation and application of microwave-assisted extraction and dispersive liquid-liquid microextraction followed by high-performance liquid chromatography for the determination of polar heterocyclic aromatic amines in hamburger patties.

    Science.gov (United States)

    Aeenehvand, Saeed; Toudehrousta, Zahra; Kamankesh, Marzieh; Mashayekh, Morteza; Tavakoli, Hamid Reza; Mohammadi, Abdorreza

    2016-01-01

    This study developed an analytical method based on microwave-assisted extraction and dispersive liquid-liquid microextraction followed by high-performance liquid chromatography for the determination of three polar heterocyclic aromatic amines from hamburger patties. Effective parameters controlling the performance of the microextraction process, such as the type and volume of extraction and disperser solvents, microwave time, nature of alkaline aqueous solution, pH and salt amount, were optimized. The calibration graphs were linear in the range of 1-200 ng g(-1), with a coefficient of determination (R(2)) better than 0.9993. The relative standard deviations (RSD) for seven analyses were between 3.2% and 6.5%. The recoveries of those compounds in hamburger patties were from 90% to 105%. Detection limits were between 0.06 and 0.21 ng g(-1). A comparison of the proposed method with the existing literature demonstrates that it is a simple, rapid, highly selective and sensitive, and it gives good enrichment factors and detection limits for determining HAAs in real hamburger patties samples. Copyright © 2015 Elsevier Ltd. All rights reserved.

  18. Enhanced adsorbability and photocatalytic activity of TiO2-graphene composite for polycyclic aromatic hydrocarbons removal in aqueous phase.

    Science.gov (United States)

    Bai, Hongzhen; Zhou, Jun; Zhang, Hongjian; Tang, Guping

    2017-02-01

    Photodegradation via titanium dioxide (TiO 2 ) has been used to remove polycyclic aromatic hydrocarbons (PAHs) from environmental media broadly. In this study, a series of TiO 2 -graphene composites (P25-GR) with different GR weight ratios were synthesized via hydrothermal reaction of graphene oxide (GO) and P25. Their structures were characterized and the proprieties were tested in aqueous phase. Phenanthrene (PHE), fluoranthene (FLAN), and benzo[a]pyrene (BaP) were selected as models of PAHs. The experiment indicated that P25-2.5%GR exhibited enhancement in both adsorption and photodegradation, ∼80% of PAHs were removed after 2h photocatalysis. The influence of photodegradation rate was studied, including PAHs initial concentration and pH. Aromatic intermediates were identified during the reaction process and the degradation pathways were portrayed. This work explored the enhanced photocatalysis performance was attributed to the PAH-selective adsorbability and the strong electron transfer ability of the composite. The analysis of the degradation intermediates confirmed that the reaction proceeded with the formation of free radicals, leading to the gradual PAH mineralization. Copyright © 2016 Elsevier B.V. All rights reserved.

  19. Fluorescence quenching of polycyclic aromatic hydrocarbons within deep eutectic solvents and their aqueous mixtures

    Energy Technology Data Exchange (ETDEWEB)

    Pandey, Ashish; Yadav, Anita; Bhawna; Pandey, Siddharth, E-mail: sipandey@chemistry.iitd.ac.in

    2017-03-15

    Two common and popular deep eutectic solvents (DESs) composed of the salt choline chloride and H-bond donors glycerol and urea in 1:2 mol ratio named glyceline and reline, respectively, are investigated for the analysis of polycyclic aromatic hydrocarbons (PAHs) using quenching of both steady-state and time-resolved fluorescence of ten different PAHs by nitromethane at 30 °C. Based on their quenching efficiencies, the PAHs are divided into two groups – group 1 is constituted of the five PAHs whose fluorescence are quenched less effectively by nitromethane whereas the other five exhibiting high quenching efficiency are associated to group 2. Quenching of steady-state fluorescence of group 1 PAHs by nitromethane, albeit not very significant, follow a simple Stern-Volmer behavior. The excited-state emission intensity decay of these PAHs, in both absence and presence of nitromethane, fit best to a single exponential model with small but monotonic decrease in lifetimes. The decrease in lifetime also follows Stern-Volmer behavior, however, the quenching constants (K{sub D}) are lower than those obtained from steady-state fluorescence (K{sub SV}). This is ascribed to the possible formation of charge-transfer complex between the PAH and the nitromethane. Steady-state fluorescence quenching of group 2 PAHs exhibit distinct upward curvature from linear Stern-Volmer behavior implying highly efficient quenching. The intensity decay fits best to a double exponential decay model with longer of the decay times following simple Stern-Volmer behavior. Formation of a complex or the presence of nitromethane within the quenching sphere of action of the PAH having short decay time is proposed. Quenching behavior was found to be similar irrespective of the identity of the DES. A representative group 2 PAH, pyrene, is employed to investigate diffusion dynamics within aqueous mixtures of the two DESs. The bimolecular quenching rate constant (k{sub q}) is found to increase linearly with

  20. Control of π-Electron Rotations in Chiral Aromatic Molecules Using Intense Laser Pulses

    Science.gov (United States)

    Kanno, Manabu; Kono, Hirohiko; Fujimura, Yuichi

    Our recent theoretical studies on laser-induced π-electron rotations in chiral aromatic molecules are reviewed. π electrons of a chiral aromatic molecule can be rotated along its aromatic ring by a nonhelical, linearly polarized laser pulse. An ansa aromatic molecule with a six-membered ring, 2,5-dichloro[n](3,6) pyrazinophane, which belongs to a planar-chiral molecule group, and its simplified molecule 2,5-dichloropyrazine are taken as model molecules. Electron wavepacket simulations in the frozen-molecular-vibration approximation show that the initial direction of π-electron rotation depends on the polarization direction of a linearly polarized laser pulse applied. Consecutive unidirectional rotation can be achieved by applying a sequence of linearly polarized pump and dump pulses to prevent reverse rotation. Optimal control simulations of π-electron rotation show that another controlling factor for unidirectional rotation is the relative optical phase between the different frequency components of an incident pulse in addition to photon polarization direction. Effects of nonadiabatic coupling between π-electron rotation and molecular vibrations are also presented, where the constraints of the frozen approximation are removed. The angular momentum gradually decays mainly owing to nonadiabatic coupling, while the vibrational amplitudes greatly depend on their rotation direction. This suggests that the direction of π-electron rotation on an attosecond timescale can be identified by detecting femtosecond molecular vibrations.

  1. Identification of genotoxic compounds in crude oil using fractionation according to distillation, polarity and Kow.

    Science.gov (United States)

    Park, Shin Yeong; Lee, Hyo Jin; Khim, Jong Seong; Kim, Gi Beum

    2017-01-30

    We examined the degree of DNA damage caused by fractions of crude oil in accordance with the boiling points, polarity and log K ow . Relatively high DNA damage was observed in the aromatic fraction (290-330°C) and resin and polar fraction (350-400°C). The resin and polar fraction showed relatively high genotoxicity compared with the aliphatic and aromatic fraction at the 1-4 log K ow range. At the 6-7 log K ow range, the aromatic fraction showed relatively high DNA damage compared with the aliphatic and resin and polar fraction. In particular, every detailed fraction in accordance with the log K ow values (aliphatic and aromatic (310-320°C) and resins and polar fractions (370-380°C)) showed one or less than one DNA damage. However, the fractions before separation in accordance with log K ow values (aliphatic and aromatic (310-320°C) and resin and polar (370-380°C) fractions) showed high DNA damage. Thus, we confirm the synergistic action between the detailed compounds. Copyright © 2016 Elsevier Ltd. All rights reserved.

  2. Adsorption of polar, nonpolar, and substituted aromatics to colloidal graphene oxide nanoparticles

    NARCIS (Netherlands)

    Wang, Fang; Haftka, Joris J H; Sinnige, Theo L.; Hermens, Joop L M; Chen, Wei

    2014-01-01

    We conducted batch adsorption experiments to understand the adsorptive properties of colloidal graphene oxide nanoparticles (GONPs) for a range of environmentally relevant aromatics and substituted aromatics, including model nonpolar compounds (pyrene, phenanthrene, naphthalene, and

  3. Adsorption of polynuclear aromatic hydrocarbons from aqueous solution: Agrowaste-modified kaolinite vs surfactant modified bentonite

    Directory of Open Access Journals (Sweden)

    E. I. Unuabonah

    2017-01-01

    Full Text Available The adsorption efficiency of a new hybrid clay adsorbent for polynuclear aromatic hydrocarbons (PAHs is compared with known modified clay adsorbents. The new hybrid clay adsorbent (HYCA showed far higher adsorption capacities for the adsorption of various PAH molecules compared with sodium dodecyl sulfate modified and humic acid modified Bentonite clay adsorbents. With the new hybrid clay adsorbent (HYCA, the adsorption of some of the larger PAH molecules was complete in the first 1 h as compared with ≈ 62% and ≈ 76% observed for both humic acid modified and sodium dodecyl sulfate modified Bentonite clay adsorbents respectively. In 24 h adsorption of the PAHs was complete for all adsorbents with HYCA adsorbent showing better efficiency in the removal of the PAH molecules from aqueous solutions. No significant change was observed with increase in time up to 48 h. The adsorption was observed to be more spontaneous with HYCA adsorbent than with either modified Bentonite adsorbents. The enthalpy of adsorption did not follow any specific order and were not consistent for all PAH molecules considered.

  4. Ligand adsorption on an activated carbon for the removal of chromate ions from aqueous solutions.

    Science.gov (United States)

    García-Martín, J; López-Garzón, R; Godino-Salido, M Luz; Gutiérrez-Valero, M Dolores; Arranz-Mascarós, P; Cuesta, R; Carrasco-Marín, F

    2005-07-19

    The results presented in this work are related to the design of a guideline to develop specific properties at the surface of an activated carbon (AC). For this, two model aromatic compounds have been synthesized and their electrolytic behavior in aqueous solutions was studied by a potentiometric method. The textural characteristics of the activated carbon were determined by porosimetry methods. The nature of oxygen-carrying functions and the acid-base behavior of the AC surface were characterized by TPD and potentiometric titration methods, respectively. The adsorption and desorption equilibria of the aromatic compounds on activated carbon were measured in aqueous solutions, and the hysteresis between adsorption and desorption, which reveals irreversible adsorption, was discussed on the basis of the frontier orbital theory. HOMO and LUMO orbitals of the adsorbent and adsorbates were calculated, and irreversible adsorption was attributed to the small energy difference between HOMO and LUMO of the aromatic adsorbates and the adsorbent. Adsorption equilibria of K2CrO4 in aqueous solution on the AC alone and on the AC-aromatic ligand adsorbents, respectively, prove the efficient development of specific chemical functions at the carbon surface provided by the adsorbed aromatic compounds.

  5. Chromatographic selectivity of poly(alkyl methacrylate-co-divinylbenzene) monolithic columns for polar aromatic compounds by pressure-driven capillary liquid chromatography

    Energy Technology Data Exchange (ETDEWEB)

    Lin, Shu-Ling; Wang, Chih-Chieh; Fuh, Ming-Ren, E-mail: msfuh@scu.edu.tw

    2016-10-05

    In this study, divinylbenzene (DVB) was used as the cross-linker to prepare alkyl methacrylate (AlMA) monoliths for incorporating π-π interactions between the aromatic analytes and AlMA-DVB monolithic stationary phases in capillary LC analysis. Various AlMA/DVB ratios were investigated to prepare a series of 30% AlMA-DVB monolithic stationary phases in fused-silica capillaries (250-μm i.d.). The physical properties (such as porosity, permeability, and column efficiency) of the synthesized AlMA-DVB monolithic columns were investigated for characterization. Isocratic elution of phenol derivatives was first employed to evaluate the suitability of the prepared AlMA-DVB columns for small molecule separation. The run-to-run (0.16–1.20%, RSD; n = 3) and column-to-column (0.26–2.95%, RSD; n = 3) repeatabilities on retention times were also examined using the selected AlMA-DVB monolithic columns. The π-π interactions between the aromatic ring and the DVB-based stationary phase offered better recognition on polar analytes with aromatic moieties, which resulted in better separation resolution of aromatic analytes on the AlMA-DVB monolithic columns. In order to demonstrate the capability of potential environmental and/or food safety applications, eight phenylurea herbicides with single benzene ring and seven sulfonamide antibiotics with polyaromatic moieties were analyzed using the selected AlMA-DVB monolithic columns. - Highlights: • First investigation on chromatographic selectivity of AlMA-DVB monolithic columns. • Good run-to-run/column-to-column repeatability (<3%) on AlMA-DVB monolithic columns. • Efficient separation of phenylurea herbicides and sulfonamides on AlMA-DVB columns.

  6. Electrogenerated chemiluminescence induced by sequential hot electron and hole injection into aqueous electrolyte solution

    Energy Technology Data Exchange (ETDEWEB)

    Salminen, Kalle; Kuosmanen, Päivi; Pusa, Matti [Aalto University, Department of Chemistry, Laboratory of Analytical Chemistry, P.O. Box 16100, FI-00076 Aalto (Finland); Kulmala, Oskari [University of Helsinki, Department of Physics, P.O. Box 64, FI-00014 (Finland); Håkansson, Markus [Aalto University, Department of Chemistry, Laboratory of Analytical Chemistry, P.O. Box 16100, FI-00076 Aalto (Finland); Kulmala, Sakari, E-mail: sakari.kulmala@aalto.fi [Aalto University, Department of Chemistry, Laboratory of Analytical Chemistry, P.O. Box 16100, FI-00076 Aalto (Finland)

    2016-03-17

    Hole injection into aqueous electrolyte solution is proposed to occur when oxide-coated aluminum electrode is anodically pulse-polarized by a voltage pulse train containing sufficiently high-voltage anodic pulses. The effects of anodic pulses are studied by using an aromatic Tb(III) chelate as a probe known to produce intensive hot electron-induced electrochemiluminescence (HECL) with plain cathodic pulses and preoxidized electrodes. The presently studied system allows injection of hot electrons and holes successively into aqueous electrolyte solutions and can be utilized in detecting electrochemiluminescent labels in fully aqueous solutions, and actually, the system is suggested to be quite close to a pulse radiolysis system providing hydrated electrons and hydroxyl radicals as the primary radicals in aqueous solution without the problems and hazards of ionizing radiation. The analytical power of the present excitation waveforms are that they allow detection of electrochemiluminescent labels at very low detection limits in bioaffinity assays such as in immunoassays or DNA probe assays. The two important properties of the present waveforms are: (i) they provide in situ oxidation of the electrode surface resulting in the desired oxide film thickness and (ii) they can provide one-electron oxidants for the system by hole injection either via F- and F{sup +}-center band of the oxide or by direct hole injection to valence band of water at highly anodic pulse amplitudes. - Highlights: • Hot electrons injected into aqueous electrolyte solution. • Generation of hydrated electrons. • Hole injection into aqueous electrolyte solution. • Generation of hydroxyl radicals.

  7. Steam stripping of polycyclic aromatics from simulated high-level radioactive waste

    International Nuclear Information System (INIS)

    Lambert, D.P.; Shah, H.B.; Young, S.R.; Edwards, R.E.; Carter, J.T.

    1992-01-01

    The Defense Waste Processing Facility (DWPF) at the Savannah River Site (SRS) will be the United States' first facility to process High Level radioactive Waste (HLW) into a borosilicate glass matrix. The removal of aromatic precipitates by hydrolysis, evaporation, liquid-liquid extraction and decantation will be a key step in the processing of the HLW. This step, titled the Precipitate Hydrolysis Process, has been demonstrated by the Savannah River Technology Center with the Precipitate Hydrolysis Experimental Facility (PHEF). The mission of the PHEF is to demonstrate processing of simulated high level radioactive waste which contains tetraphenylborate precipitates and nitrite. Aqueous washing or nitrite destruction is used to reduce nitrite. Formic acid with a copper catalyst is used to hydrolyze tetraphenylborate (TPB). The primary offgases are benzene, carbon dioxide, nitrous oxide, and nitric oxide. Hydrolysis of TPB in the presence of nitrite results in the production of polycyclic aromatics and aromatic amines (referred as high boiling organics) such as biphenyl, diphenylamine, terphenyls etc. The decanter separates the organic (benzene) and aqueous phase, but the high boiling organic separation is difficult. This paper focuses on the evaluation of the operating strategies, including steam stripping, to maximize the removal of the high boiling organics from the aqueous stream. Two areas were investigated, (1) a stream stripping comparison of the late wash flowsheet to the HAN flowsheet and (2) the extraction performance of the original decanter to the new decanter. The focus of both studies was to minimize the high boiling organic content of the Precipitate Hydrolysis Aqueous (PHA) product in order to minimize downstream impacts caused by organic deposition

  8. Synthesis of polydopamine-functionalized magnetic graphene and carbon nanotubes hybrid nanocomposites as an adsorbent for the fast determination of 16 priority polycyclic aromatic hydrocarbons in aqueous samples.

    Science.gov (United States)

    Chen, Kun; Jin, Rongrong; Luo, Chen; Song, Guoxin; Hu, Yaoming; Cheng, Hefa

    2018-04-01

    A novel adsorbent made of polydopamine-functionalized magnetic graphene and carbon nanotubes hybrid nanocomposite was synthesized and applied to determine 16 priority polycyclic aromatic hydrocarbons by magnetic solid phase extraction in water samples. FTIR spectroscopy, transmission electron microscopy, scanning electron microscopy, and Raman spectroscopy consistently indicate that the synthesized adsorbents are made of core-shell nanoparticles well dispersed on the surface of graphene and carbon nanotubes. The major factors affecting the extraction efficiency, including the pH value of samples, the amount of adsorbent, adsorption time and desorption time, type and volume of desorption solvent, were systematically optimized. Under the optimum extraction conditions, a linear response was obtained for polycyclic aromatic hydrocarbons between concentrations of 10 and 500 ng/L with the correlation coefficients ranging from 0.9958 to 0.9989, and the limits of detection (S/N = 3) were between 0.1 and 3.0 ng/L. Satisfactory results were also obtained when applying these magnetic graphene/carbon nanotubes/polydopamine hybrid nanocomposites to detect polycyclic aromatic hydrocarbons in several environmental aqueous samples. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Relationship between total polar components and polycyclic aromatic hydrocarbons in fried edible oil.

    Science.gov (United States)

    An, Ke-Jing; Liu, Yu-Lan; Liu, Hai-Lan

    2017-09-01

    Deep-fried dough sticks (a Chinese traditional breakfast) were fried individually in peanut, sunflower, rapeseed, rice bran, soybean and palm oil without any time lag for 32 h (64 batches fried, each for 30 min) and fried oil samples were obtained every 2 h. The frying-induced changes in the levels of total polar compounds (TPC) and polycyclic aromatic hydrocarbons (PAHs) were investigated by edible oil polar compounds (EOPC) fast separation chromatographic system and gas chromatography-mass spectrometry (GC-MS), respectively. The correlations were analysed of TPC with benzo[a]pyrene (BaP), TPC and PAH4 (benzo[a]anthracene, chrysene, benzo[b]fluoranthene and benzo[a]pyrene) as well as TPC with PAH16 (USEPA 16 PAHs). The results revealed that the levels of TPC and PAHs in fried oil considerably increased with frying time, and the type of oil affected their formation, which could inform the choice of oil for frying. The total BaP equivalents (∑BaPeq) concentrations in fresh oil and in oil whose TPC exceeded 27% were 2.14-13.48 and 5.78-10.80 μg kg -1 , respectively, which means that the carcinogenic potency of frying oil was more pronounced than that of fresh oil. In addition, the TPC concentration was significantly correlated with the concentrations of the sum of the 16 PAHs, PAH4 and BaP, so that the levels of PAHs could be predicted according to the levels of TPC in fried oil. In European standards, the rejection point for TPC in frying oil should be recalculated when considered PAHs. In all, the concentration of PAHs is a vital factor for ensuring the safety of frying oil.

  10. Study on the polarity, solubility, and stacking characteristics of asphaltenes

    KAUST Repository

    Zhang, Long-li

    2014-07-01

    The structure and transformation of fused aromatic ring system in asphaltenes play an important role in the character of asphaltenes, and in step affect the properties of heavy oils. Polarity, solubility and structural characteristics of asphaltenes derived from Tahe atmospheric residue (THAR) and Tuo-826 heavy crude oil (Tuo-826) were analyzed for study of their internal relationship. A fractionation method was used to separate the asphaltenes into four sub-fractions, based on their solubility in the mixed solvent, for the study of different structural and physical-chemical properties, such as polarity, solubility, morphology, stacking characteristics, and mean structural parameters. Transmission electron microscope (TEM) observation can present the intuitive morphology of asphaltene molecules, and shows that the structure of asphaltenes is in local order as well as long range disorder. The analysis results showed that n-heptane asphaltenes of THAR and Tuo-826 had larger dipole moment values, larger fused aromatic ring systems, larger mean number of stacking layers, and less interlayer spacing between stacking layers than the corresponding n-pentane asphaltenes. The sub-fractions that were inclined to precipitate from the mixture of n-heptane and tetrahydrofuran had larger polarity and less solubility. From the first sub-fraction to the fourth sub-fraction, polarity, mean stacking numbers, and average layer size from the TEM images follow a gradual decrease. The structural parameters derived from TEM images could reflect the largest fused aromatic ring system in asphaltene molecule, yet the parameters derived from 1H NMR data reflected the mean message of poly-aromatic ring systems. The structural parameters derived from TEM images were more consistent with the polarity variation of sub-fractions than those derived from 1H NMR data, which indicates that the largest fused aromatic ring system will play a more important role in the stacking characteristics of

  11. Measurement and prediction of aromatic solute distribution coefficients for aqueous-organic solvent systems. Final report

    Energy Technology Data Exchange (ETDEWEB)

    Campbell, J.R.; Luthy, R.G.

    1984-06-01

    Experimental and modeling activities were performed to assess techniques for measurement and prediction of distribution coefficients for aromatic solutes between water and immiscible organic solvents. Experiments were performed to measure distribution coefficients in both clean water and wastewater systems, and to assess treatment of a wastewater by solvent extraction. The theoretical portions of this investigation were directed towards development of techniques for prediction of solute-solvent/water distribution coefficients. Experiments were performed to assess treatment of a phenolic-laden coal conversion wastewater by solvent extraction. The results showed that solvent extraction for recovery of phenolic material offered several wastewater processing advantages. Distribution coefficients were measured in clean water and wastewater systems for aromatic solutes of varying functionality with different solvent types. It was found that distribution coefficients for these compounds in clean water systems were not statistically different from distribution coefficients determined in a complex coal conversion process wastewater. These and other aromatic solute distribution coefficient data were employed for evaluation of modeling techniques for prediction of solute-solvent/water distribution coefficients. Eight solvents were selected in order to represent various chemical classes: toluene and benzene (aromatics), hexane and heptane (alkanes), n-octanol (alcohols), n-butyl acetate (esters), diisopropyl ether (ethers), and methylisobutyl ketone (ketones). The aromatic solutes included: nonpolar compounds such as benzene, toluene and naphthalene, phenolic compounds such as phenol, cresol and catechol, nitrogenous aromatics such as aniline, pyridine and aminonaphthalene, and other aromatic solutes such as naphthol, quinolinol and halogenated compounds. 100 references, 20 figures, 34 tables.

  12. Trapping of polycyclic aromatic hydrocarbons by amphiphilic cyclodextrin functionalized polypropylene nonwovens

    DEFF Research Database (Denmark)

    Lumholdt, Ludmilla; Nielsen, Ronnie Bo Højstrup; Larsen, Kim Lambertsen

    of the textile fibers. In this study we present the ability of amphiphilic CD coated polypropylene nonwovens to trap 8 different polycyclic aromatic hydrocarbons/endocrine disruptors from aqueous solutions thus demonstrating the potential of using the amphiphilic cyclodextrins for water purification....

  13. Removal of Congo Red and Methylene Blue from Aqueous Solutions by Vermicompost-Derived Biochars

    Science.gov (United States)

    Yang, Gang; Wu, Lin; Xian, Qiming; Shen, Fei; Wu, Jun; Zhang, Yanzong

    2016-01-01

    Biochars, produced by pyrolyzing vermicompost at 300, 500, and 700°C were characterized and their ability to adsorb the dyes Congo red (CR) and Methylene blue (MB) in an aqueous solution was investigated. The physical and chemical properties of biochars varied significantly based on the pyrolysis temperatures. Analysis of the data revealed that the aromaticity, polarity, specific surface area, pH, and ash content of the biochars increased gradually with the increase in pyrolysis temperature, while the cation exchange capacity, and carbon, hydrogen, nitrogen and oxygen contents decreased. The adsorption kinetics of CR and MB were described by pseudo-second-order kinetic models. Both of Langmuir and Temkin model could be employed to describe the adsorption behaviors of CR and MB by these biochars. The biochars generated at higher pyrolysis temperature displayed higher CR adsorption capacities and lower MB adsorption capacities than those compared with the biochars generated at lower pyrolysis temperatures. The biochar generated at the higher pyrolytic temperature displayed the higher ability to adsorb CR owing to its promoted aromaticity, and the cation exchange is the key factor that positively affects adsorption of MB. PMID:27144922

  14. Microbial transformation of chlorinated aromatics in sediments

    OpenAIRE

    Beurskens, J.E.M.

    1995-01-01

    Numerous contaminants like heavy metals, polycyclic aromatic hydrocarbons (PAHs), chlorinated benzenes (CBs), polychlorinated biphenyls (PCBs), polychlorinated dibenzo- p -dioxins (PCDDs) and polychlorinated furans (PCDFs) are detected in the major rivers in the Netherlands. These contaminants have relatively low aqueous solubilities and bind substantially to the suspended solids in river water. Due to decreasing stream velocities in the downstream stretches of a...

  15. Correlation between the solubility of aromatic hydrocarbons in water and micellar solutions, with their normal boiling points

    International Nuclear Information System (INIS)

    Almgren, M.; Grieser, F.; Powell, J.R.; Thomas, J.K.

    1979-01-01

    A linear correlation between the logarithm of the solubility in water of aromatic hydrocarbons and their normal boiling points is shown. Similarly, the logarithm of the distribution ratio of aromatic hydrocarbons in aqueous micellar solution is shown to be linearly related to the boiling points of the hydrocarbons. 2 figures, 2 tables

  16. A highly sensitive monoclonal antibody based biosensor for quantifying 3–5 ring polycyclic aromatic hydrocarbons (PAHs in aqueous environmental samples

    Directory of Open Access Journals (Sweden)

    Xin Li

    2016-03-01

    Full Text Available Immunoassays based on monoclonal antibodies (mAbs are highly sensitive for the detection of polycyclic aromatic hydrocarbons (PAHs and can be employed to determine concentrations in near real-time. A sensitive generic mAb against PAHs, named as 2G8, was developed by a three-step screening procedure. It exhibited nearly uniformly high sensitivity against 3-ring to 5-ring unsubstituted PAHs and their common environmental methylated PAHs, with IC50 values between 1.68 and 31 μg/L (ppb. 2G8 has been successfully applied on the KinExA Inline Biosensor system for quantifying 3–5 ring PAHs in aqueous environmental samples. PAHs were detected at a concentration as low as 0.2 μg/L. Furthermore, the analyses only required 10 min for each sample. To evaluate the accuracy of the 2G8-based biosensor, the total PAH concentrations in a series of environmental samples analyzed by biosensor and GC–MS were compared. In most cases, the results yielded a good correlation between methods. This indicates that generic antibody 2G8 based biosensor possesses significant promise for a low cost, rapid method for PAH determination in aqueous samples. Keywords: Monoclonal antibody, PAH, Pore water, Biosensor, Pyrene

  17. Degradation and utilization of polycyclic aromatic hydrocarbons by indigenous soil bacteria

    International Nuclear Information System (INIS)

    Stetzenbach, L.D.A.

    1986-01-01

    The persistence of industrially derived polycyclic aromatic hydrocarbons in the subsurface may be significantly affected by the metabolism of soil bacteria. This study was conducted to determine the ability of indigenous soil bacteria to decrease the concentration of four polycyclic aromatic hydrocarbons (naphthalene, fluorene, anthracene, and pyrene) and to utilize the compounds as a substrate for growth. Soil cores from petroleum contaminated and noncontaminated sites contained 10 5 -10 7 viable microorganisms per gram dryweight of soil. Gram negative rod-shaped bacteria predominated. Decreases in the concentration of the four polycyclic aromatic hydrocarbons were observed during incubation with bacterial isolates in aqueous suspension by the use of high performance liquid chromatography. Corresponding increases in bacterial numbers indicated utilization of the compounds as a carbon source. Soil samples from the contaminated sites contained greater numbers of bacteria utilizing anthracene and pyrene than soil samples from uncontaminated sites. Degradation rates of the four polycyclic aromatic hydrocarbons were related to the compound, its concentration, and the bacterium. Biodegradation of pyrene was positively correlated with the presence of oxygen. Pyrene was biodegraded by an Acinetobacter sp. under aerobic conditions but not under anaerobic or microaerophilic conditions. Studies with radiolabeled 14 C-anthracene demonstrated utilization of the labeled carbon as a source of carbon by viable bacterial cells in aqueous suspension. Incorporation of 14 C into cellular biomass however was not observed during incubation of 14 C-anthracene in soil

  18. Multicore Magnetic Nanoparticles Coated with Oligomeric Micelles: Characterization and Potential for the Extraction of Contaminants over a Wide Polarity Range.

    Science.gov (United States)

    Naous, Mohamed; García-Gómez, Diego; López-Jiménez, Francisco José; Bouanani, Farida; Lunar, María Loreto; Rubio, Soledad

    2017-01-17

    Oligomeric micelles from sodium undecylenate (oSUD) were chemisorbed to magnetic iron oxide nanoparticles (MNPs) through a single-step synthetic route involving the simultaneous nanoparticle formation and functionalization in an aqueous medium. The resulting spherical nanoparticles (MNPs-oSUD) consisted of a concatenation of iron oxide cores, with an average size of 7.7 nm, bound by oSUD micelles (particle average diameter of ca. 200 nm). Micellar coverage was ∼50% of the MNP-oSUD (by weight) and offered multiple retention mechanisms (e.g., dispersion, hydrogen bonding, polar, and ionic) for solute solubilization while keeping it intact during analyte elution. The high density of micelles and variety of interactions provided by this sorbent rendered it highly efficient for the extraction of aromatic amines in a wide polarity range (log K ow values from -0.80 to 4.05) from textiles, urine, and wastewater. Extraction took 5 min, no cleanup or evaporation of the extracts was needed and the method, based on LC-MS/MS quantitation, proved matrix-independent. Recoveries for 17 aromatic amines in samples were in the range of 93%-123% while those with negative log K ow values were in the range of 69%-87%. Detection limits for aromatic amines in textiles (0.007-2 mg kg -1 ) were well below the limits legislated by the European Union (EU) (30 mg kg -1 ) and those in urine and wastewater (0.004-1.5 μg L -1 ) were at the level usually found in real-world applications. All the analyzed samples were positive in aromatic amines. The easy synthesis and excellent extraction properties of MNPs-oSUD anticipate their high potential not only for multiresidue analysis but also in other fields such as water remediation.

  19. Exploring Redox Properties of Aromatic Amino Acids in Water: Contrasting Single Photon vs Resonant Multiphoton Ionization in Aqueous Solutions.

    Science.gov (United States)

    Roy, Anirban; Seidel, Robert; Kumar, Gaurav; Bradforth, Stephen E

    2018-04-12

    Direct measurements of the valence ionization energies and the reorganization energies of the three aromatic amino acids, l-tyrosine, l-tryptophan, and l-phenylalanine, in aqueous solution using the liquid microjet technique and two different photoemission methods-X-ray photoelectron spectroscopy (XPS) at 175 eV photon energy and resonant two-photon ionization (R2PI) using 2 × 267 nm (2 × 4.64 eV) UV laser light-are reported. l-Tryptophan has the lowest vertical ionization energy, 7.3 eV, followed by tyrosine (7.8 eV) and phenylalanine (∼8.7 eV). Essentially, no variation in recovered orbital energies is observed comparing near threshold ionization to X-ray ionization. Superior sensitivity of the (background-free) R2PI scheme for solutions with very low solute concentration (<2 mM) is demonstrated in contrast to the single-photon XPS measurements, which often requires solute concentrations of 0.1-1 molar. This higher sensitivity along with chemical selectivity of the R2PI technique can be exploited for both spectroscopic assignment and as an analytical tool. The nature of the adiabatic ionization energy for the three aromatic amino acids has been explored by the R2PI approach and by empirically formulating the correlation between the estimated ionization onset with electronic and nuclear relaxation on the excited state surface. Our results have implications for understanding one-electron transfer within enzymes and in redox situations where (ir)reversible deprotonation occurs such as those manifest in the biochemistry of oxidation damage.

  20. Highly Conductive Aromatic Functionalized Multi-Walled Carbon Nanotube for Inkjet Printable High Performance Supercapacitor Electrodes.

    Directory of Open Access Journals (Sweden)

    Sanjeev K Ujjain

    Full Text Available We report the functionalization of multiwalled carbon nanotubes (MWCNT via the 1,3-dipolar [3+2] cycloaddition of aromatic azides, which resulted in a detangled CNT as shown by transmission electron microscopy (TEM. Carboxylic moieties (-COOH on aromatic azide result in highly stable aqueous dispersion (max. conc. ~ 10 mg/mL H2O, making the suitable for inkjet printing. Printed patterns on polyethylene terephthalate (PET flexible substrate exhibit low sheet resistivity ~65 Ω. cm, which is attributed to enhanced conductivity. Fabricated Supercapacitors (SC assembled using these printed substrates exhibit good electrochemical performance in organic as well as aqueous electrolytes. High energy and power density (57.8 Wh/kg and 0.85 kW/kg in 1M H2SO4 aqueous electrolyte demonstrate the excellent performance of the proposed supercapacitor. Capacitive retention varies from ~85-94% with columbic efficiency ~95% after 1000 charge/discharge cycles in different electrolytes, demonstrating the excellent potential of the device for futuristic power applications.

  1. Primary processes of the radiation-induced cationic polymerization of aromatic olefins studied by pulse radiolysis

    International Nuclear Information System (INIS)

    Brede, O.; Boes, J.; Helmstreit, W.; Mehnert, R.

    1982-01-01

    By pulse radiolysis of solutions of aromatic olefins (styrene, 1-methylstyrene, 1,1-diphenylethylene) in non-polar solvents (cyclohexane, carbon tetrachloride, n-butylchloride) the mechanism and kinetics of primary processes of radiation-induced cationic polymerization were investigated. In cyclohexane, radical cations of the olefins are generated by charge transfer from solvent cations. These cations dimerize in a diffusion-controlled reaction. The next step of chain-growth is slower by 3 to 4 orders of magnitude. In carbon tetrachloride and in n-butyl chloride growing olefin cations are produced by a reaction of radical cations with solvent as well as by addition of solvent carbonium ions to the monomer. In strongly acidic aqueous solution of olefins radical cations produced indirectly from hydroxycyclohexadienyl radicals dimerize and react in a subsequent step by deprotonation forming non-saturated dimer radicals. The reaction mechanism established shows that in the case of radiation-induced cationic polymerization it is not possible to define a uniform first step of the chain reaction. (author)

  2. Bioremediation of PAH-contamined soils: Consequences on formation and degradation of polar-polycyclic aromatic compounds and microbial community abundance.

    Science.gov (United States)

    Biache, Coralie; Ouali, Salma; Cébron, Aurélie; Lorgeoux, Catherine; Colombano, Stéfan; Faure, Pierre

    2017-05-05

    A bioslurry batch experiment was carried out over five months on three polycyclic aromatic compound (PAC) contaminated soils to study the PAC (PAH and polar-PAC) behavior during soil incubation and to evaluate the impact of PAC contamination on the abundance of microbial communities and functional PAH-degrading populations. Organic matter characteristics and reactivity, assessed through solvent extractable organic matter and PAC contents, and soil organic matter mineralization were monitored during 5 months. Total bacteria and fungi, and PAH-ring hydroxylating dioxygenase genes were quantified. Results showed that PAHs and polar-PACs were degraded with different degradation dynamics. Differences in degradation rates were observed among the three soils depending on PAH distribution and availability. Overall, low molecular weight compounds were preferentially degraded. Degradation selectivity between isomers and structurally similar compounds was observed which could be used to check the efficiency of bioremediation processes. Bacterial communities were dominant over fungi and were most likely responsible for PAC degradation. Abundance of PAH-degrading bacteria increased during incubations, but their proportion in the bacterial communities tended to decrease. The accumulation of some oxygenated-PACs during the bioslurry experiment underlines the necessity to monitor these compounds during application of remediation treatment on PAH contaminated soils. Copyright © 2017 Elsevier B.V. All rights reserved.

  3. Interfacial forces in aqueous media

    CERN Document Server

    van Oss, Carel J

    2006-01-01

    Thoroughly revised and reorganized, the second edition of Interfacial Forces in Aqueous Media examines the role of polar interfacial and noncovalent interactions among biological and nonbiological macromolecules as well as biopolymers, particles, surfaces, cells, and both polar and apolar polymers. The book encompasses Lifshitz-van der Waals and electrical double layer interactions, as well as Lewis acid-base interactions between colloidal entities in polar liquids such as water. New in this Edition: Four previously unpublished chapters comprising a new section on interfacial propertie

  4. The influence of non-polar lipids on tear film dynamics

    KAUST Repository

    Bruna, M.

    2014-04-04

    © 2014 Cambridge University Press. In this paper we examine the effect that physiological non-polar lipids, residing on the surface of an aqueous tear film, have on the film evolution. In our model we track the evolution of the thickness of the non-polar lipid layer, the thickness of the aqueous layer and the concentration of polar lipids which reside at the interface between the two. We also utilise a force balance in the non-polar lipid layer in order to determine its velocity. We show how to obtain previous models in the literature from our model by making particular choices of the parameters. We see the formation of boundary layers in some of these submodels, across which the concentration of polar lipid and the non-polar lipid velocity and film thickness vary. We solve our model numerically for physically realistic parameter values, and we find that the evolution of the aqueous layer and the polar lipid layer are similar to that described by previous authors. However, there are interesting dynamics for the non-polar lipid layer. The effects of altering the key parameters are highlighted and discussed. In particular, we see that the Marangoni number plays a key role in determining how far over the eye the non-polar lipid spreads.

  5. Adsorption of Polycyclic Aromatic Hydrocarbons (PAHS from Aqueous Solutions on Different Sorbents

    Directory of Open Access Journals (Sweden)

    Smol Marzena

    2014-12-01

    Full Text Available This paper presents the results of the possibility and effectiveness of PAHs removal from a model aqueous solution, during the sorption on the selected sorbents. Six PAHs (naphthalene, acenaphthylene, acenaphthene, fluorene, phenanthrene, anthracene listed by EPA for the analysis in the environmental samples were determined. Model aqueous solution was prepared with RESTEK 610 mix PAHs standard. After the sorption process, decrease in the concentration of individual hydrocarbons was observed. The removal percentage was dependent on the type of sorbent (quartz sand, mineral sorbent, activated carbon. The highest efficiency (98.1% was observed for activated carbon.. The results shows that the sorption processes can be used in aqueous solutions treatment procedures.

  6. Differential immunomodulatory responses to nine polycyclic aromatic hydrocarbons applied by passive dosing

    DEFF Research Database (Denmark)

    Oostingh, Gertie J.; Smith, Kilian E. C.; Tischler, Ulrike

    2015-01-01

    Studying the effects of hydrophobic chemicals using in vitro cell based methods is hindered by the difficulty in bringing and keeping these chemicals in solution. Their effective concentrations are often lower than their nominal concentrations. Passive dosing is one approach that provides defined...... and stable dissolved concentrations during in vitro testing, and was applied to control and maintain freely dissolved concentrations of polycyclic aromatic hydrocarbons (PAHs) at levels up to their aqueous solubility limit. The immunomodulatory effects of 9 different PAHs at aqueous solubility on human...

  7. Enhanced diffusion of polycyclic aromatic hydrocarbons in artificial and natural aqueous solutions

    DEFF Research Database (Denmark)

    Mayer, Philipp; Fernqvist, M.M.; Christensen, P.S.

    2007-01-01

    Uptake of hydrophobic organic compounds into organisms is often limited by the diffusive transport through a thin boundary layer. Therefore, a microscale diffusion technique was applied to determine the diffusive mass transfer of 12 polycyclic aromatic hydrocarbons through water, air, surfactant...

  8. Polarization switching and patterning in self-assembled peptide tubular structures

    Science.gov (United States)

    Bdikin, Igor; Bystrov, Vladimir; Delgadillo, Ivonne; Gracio, José; Kopyl, Svitlana; Wojtas, Maciej; Mishina, Elena; Sigov, Alexander; Kholkin, Andrei L.

    2012-04-01

    Self-assembled peptide nanotubes are unique nanoscale objects that have great potential for a multitude of applications, including biosensors, nanotemplates, tissue engineering, biosurfactants, etc. The discovery of strong piezoactivity and polar properties in aromatic dipeptides [A. Kholkin, N. Amdursky, I. Bdikin, E. Gazit, and G. Rosenman, ACS Nano 4, 610 (2010)] opened up a new perspective for their use as biocompatible nanoactuators, nanomotors, and molecular machines. Another, as yet unexplored functional property is the ability to switch polarization and create artificial polarization patterns useful in various electronic and optical applications. In this work, we demonstrate that diphenylalanine peptide nanotubes are indeed electrically switchable if annealed at a temperature of about 150 °C. The new orthorhombic antipolar structure that appears after annealing allows for the existence of a radial polarization component, which is directly probed by piezoresponse force microscopy (PFM) measurements. Observation of the relatively stable polarization patterns and hysteresis loops via PFM testifies to the local reorientation of molecular dipoles in the radial direction. The experimental results are complemented with rigorous molecular calculations and create a solid background of electric-field induced deformation of aromatic rings and corresponding polarization switching in this emergent material.

  9. High proton polarization at high temperature with single crystals of aromatic molecules

    International Nuclear Information System (INIS)

    Iinuma, M.; Takahashi, Y.; Shake, I.; Oda, M.; Masaike, A.; Yabuzaki, T.; Shimizu, H.M.

    2004-01-01

    Protons in single crystals of naphthalene doped with pentacene and p-terphenyl doped with pentacene have been polarized up to 32% and 18%, respectively. Such polarization has been achieved at liquid nitrogen temperature in a magnetic field of 3 kG by means of microwave-induced optical nuclear polarization. We also measured the polarization by the neutron transmission method. The relaxation time at 77 K in 7 G was found to be about 3 h and the enhancement of the obtained polarization compared with thermal polarization reached 8x10 4 . This method is applicable to neutron experiments

  10. SHPOLSKII FLUOROMETRIC-DETERMINATION OF POLYCYCLIC AROMATIC-HYDROCARBONS IN COMPLEX ENVIRONMENTAL-SAMPLES

    NARCIS (Netherlands)

    ARIESE, F; GOOIJER, C; Velthorst, N.H.; Hofstraat, J.W.

    1991-01-01

    High-resolution fluorimetry in low-temperature n-alkane Shpol'skii matrices is a powerful technique for the analysis of rigid, non-polar compounds like polycyclic aromatic hydrocarbons. Because of the method's sensitivity and selectivity, sample clean-up, preconcentration and even chromatographic

  11. Biofiltration of paint solvent mixtures in two reactor types: overloading by polar components.

    Science.gov (United States)

    Paca, Jan; Halecky, Martin; Misiaczek, Ondrej; Kozliak, Evguenii I; Jones, Kim

    2012-01-01

    Steady-state performances of a trickle bed reactor (TBR) and a biofilter (BF) in loading experiments with increasing inlet concentrations of polar solvents, acetone, methyl ethyl ketone, methyl isobutyl ketone and n-butyl acetate, were investigated, along with the system's dynamic responses. Throughout the entire experimentation time, a constant loading rate of aromatic components of 4 g(c)·m(-3)·h(-1) was maintained to observe the interactions between the polar substrates and aromatic hydrocarbons. Under low combined substrate loadings, the BF outperformed TBR not only in the removal of aromatic hydrocarbons but also in the removal of polar substrates. However, increasing the loading rate of polar components above the threshold value of 31-36 g(c)·m(-3)·h(-1) resulted in a steep and significant drop in the removal efficiencies of both polar (except for butyl acetate) and hydrophobic components, which was more pronounced in the BF; so the relative TBR/BF efficiency became reversed under such overloading conditions. A step-drop of the overall OL(POLAR) (combined loading by polar air pollutants) from overloading values to 7 g(c)·m(-3)·h(-1) resulted in an increase of all pollutant removal efficiencies, although in TBR the recovery was preceded by lag periods lasting between 5 min (methyl ethyl ketone) to 3.7 h (acetone). The occurrence of lag periods in the TBR recovery was, in part, due to the saturation of mineral medium with water-soluble polar solvents, particularly, acetone. The observed bioreactor behavior was consistent with the biological steps being rate-limiting.

  12. Sorption of polar and nonpolar organic contaminants by oil-contaminated soil.

    Science.gov (United States)

    Chen, Hong; Chen, Shuo; Quan, Xie; Zhao, Huimin; Zhang, Yaobin

    2008-12-01

    Sorption of nonpolar (phenanthrene and butylate) and polar (atrazine and diuron) organic chemicals to oil-contaminated soil was examined to investigate oil effects on sorption of organic chemicals and to derive oil-water distribution coefficients (K(oil)). The resulting oil-contaminated soil-water distribution coefficients (K(d)) for phenanthrene demonstrated sorption-enhancing effects at both lower and higher oil concentrations (C(oil)) but sorption-reducing (competitive) effects at intermediate C(oil) (approximately 1 g kg(-1)). Rationalization of the different dominant effects was attempted in terms of the relative aliphatic carbon content which determines the accessibility of the aromatic cores to phenanthrene. Little or no competitive effect occurred for butylate because its sorption was dominated by partitioning. For atrazine and diuron, the changes in K(d) at C(oil) above approximately 1 g kg(-1) were negligible, indicating that the presently investigated oil has little or no effect on the two tested compounds even though the polarity of the oil is much less than soil organic matter (SOM). Therefore, specific interactions with the active groups (aromatic and polar domains) are dominantly responsible for the sorption of polar sorbates, and thus their sorption is controlled by available sorption sites. This study showed that the oil has the potential to be a dominant sorptive phase for nonpolar pollutants when compared to SOM, but hardly so for polar compounds. The results may aid in a better understanding of the role of the aliphatic and aromatic domains in sorption of nonpolar and polar organic pollutants.

  13. In situ STM investigation of aromatic poly(azomethine) arrays constructed by "on-site" equilibrium polymerization.

    Science.gov (United States)

    Tanoue, Ryota; Higuchi, Rintaro; Ikebe, Kiryu; Uemura, Shinobu; Kimizuka, Nobuo; Stieg, Adam Z; Gimzewski, James K; Kunitake, Masashi

    2012-10-02

    Two-dimensional (2D) arrays of π-conjugated aromatic polymers produced by surface-selective Schiff base coupling reactions between an aromatic diamine and an aromatic dialdehyde were investigated in detail using in situ scanning tunneling microscopy. Surface-selective coupling was achieved for almost all diamine/dialdehyde combinations attempted, although several combinations did not proceed even in homogeneous aqueous alkaline solution. Most of the combinations of an aromatic diamine and a dialdehyde, except the combinations of 4,4'-azodianiline with mono/bithiophenedicarboxaldehyde, formed highly ordered π-conjugated polymer arrays on an iodine-modified Au(111) surface in aqueous solution at a suitable pH. The simplest polymer of the various combinations tested, obtained from the combination of 1,4-diaminobenzene with terephthaldicarboxaldehyde, gave a 2D array consisting of linearly connected benzene units. Poly(azomethine) adlayers caused a positive shift in the electrochemical potential of the butterfly shaped oxidative adsorption and reductive desorption of iodine. The acceleration of the reductive desorption of iodine suggests the existence of a weak interaction between the polymer layer and iodine. Not only the first polymer adlayers but also partially adsorbed secondary adlayers with "on-top" epitaxial behavior were frequently observed for all polymer systems. The alignment of the polymer chains in the adlayers possessed a certain regularity in terms of a regular interval between polymer chains because of repulsive interpolymer interactions.

  14. Towards water compatible MIPs for sensing in aqueous media.

    Science.gov (United States)

    Horemans, F; Weustenraed, A; Spivak, D; Cleij, T J

    2012-06-01

    When synthesizing molecularly imprinted polymers (MIPs), a few fundamental principles should be kept in mind. There is a strong correlation between porogen polarity, MIP microenvironment polarity and the imprinting effect itself. The combination of these parameters eventually determines the overall binding behavior of a MIP in a given solvent. In addition, it is shown that MIP binding is strongly influenced by the polarity of the rebinding solvent. Because the use of MIPs in biomedical environments is of considerable interest, it is important that these MIPs perform well in aqueous media. In this article, various approaches are explored towards a water compatible MIP for the target molecule l-nicotine. To this end, the imprinting effect together with the MIP matrix polarity is fine-tuned during MIP synthesis. The binding behavior of the resulting MIPs is evaluated by performing batch rebinding experiments that makes it possible to select the most suitable MIP/non-imprinted polymer couple for future application in aqueous environments. One method to achieve improved compatibility with water is referred to as porogen tuning, in which porogens of varying polarities are used. It is demonstrated that, especially when multiple porogens are mixed, this approach can lead to superior performance in aqueous environments. Another method involves the incorporation of polar or non-polar comonomers in the MIP matrix. It is shown that by carefully selecting these monomers, it is also possible to obtain MIPs, which can selectively bind their target in water. Copyright © 2012 John Wiley & Sons, Ltd.

  15. Secondary organic aerosol formation through cloud processing of aromatic VOCs

    Science.gov (United States)

    Herckes, P.; Hutchings, J. W.; Ervens, B.

    2010-12-01

    Field observations have shown substantial concentrations (20-5,500 ng L-1) of aromatic volatile organic compounds (VOC) in cloud droplets. The potential generation of secondary organic aerosol mass through the processing of these anthropogenic VOCs was investigated through laboratory and modeling studies. Under simulated atmospheric laboratory conditions, in idealized solutions, benzene, toluene, ethylbenzene, and xylene (BTEX) degraded quickly in the aqueous phase. The degradation process yielded less volatile products which would contribute to new aerosol mass upon cloud evaporation. However, when realistic cloud solutions containing natural organic matter were used in the experiments, the reaction rates decreased with increasing organic carbon content. Kinetic data derived from these experiments were used as input to a multiphase box model in order to evaluate the secondary organic aerosol (SOA) mass formation potential of cloud processing of BTEX. Model results will be presented that quantify the SOA amounts from these aqueous phase pathways. The efficiency of this multiphase SOA source will be compared to SOA yields from the same aromatics as treated in traditional SOA models that are restricted to gas phase oxidation and subsequent condensation on particles.

  16. Photolysis of aromatic pollutants in clean and dirty ice

    Science.gov (United States)

    Kahan, T.; Malley, P.; Stathis, A.

    2015-12-01

    Anthropogenic aromatic pollutants such as polycyclic aromatic hydrocarbons (PAHs) and substituted benzenes often become more toxic following atmospheric oxidation. Photolysis of these pollutants in ice can be much faster than that in aqueous solution, which might lead to higher carcinogenic loadings in snow-covered regions. In this work we investigate two things. First, we investigate whether toluene, which has been detected at very elevated concentrations near hydraulic fracturing operations, can undergo photolysis at ice surfaces. Toluene in aqueous solution does not absorb sunlight, so photolysis has not been considered a potential atmospheric fate. However, benzene was recently demonstrated to undergo a significant red shift in its absorbance at ice surfaces, leading to photolysis under environmentally-relevant conditions. Here we show that toluene also undergoes photolysis at ice surfaces. In a second set of experiments, we have investigated the effects of organic matter on the photolysis kinetics ofPAHs in ice and at ice surfaces. We found that very small loadings of hydrophobic organics such as octanol can significantly suppress PAH photolysis kinetics in ice, but that the primary effect of the more soluble fulvic acid is competitive photon absorption. Our results show that photochemistry of anthropogenic pollutants can follow very different mechanisms and kinetics in ice than in aqueous solution, and that the photochemical fate of these pollutants depends strongly on the composition of the snow. These results have implications for pollutant fate and human health in a wide range of snow-covered environments including remote areas, cities, and regions near gas and oil extraction operations.

  17. Effects of fulvic acid concentration and origin on photodegradation of polycyclic aromatic hydrocarbons in aqueous solution: Importance of active oxygen

    International Nuclear Information System (INIS)

    Xia Xinghui; Li Gongchen; Yang Zhifeng; Chen Yumin; Huang, Gordon H.

    2009-01-01

    With an Xe arc lamp house as simulated sunlight, the influences of fulvic acid (FA) concentration and origins on photodegradation of acenaphthene, fluorine, phenanthrene, fluoranthene and pyrene in aqueous solution have been studied. Similar effects of FAs, collected from five places around China, on polycyclic aromatic hydrocarbon (PAH) photodegradation have been observed. Active oxygen was of significance in PAH photodegradation with the presence of FAs. For systems with 1.25 mg L -1 FAs, the contributions of ·OH to PAH photodegradation rates were from 33% to 69%. FAs had two opposite effects, i.e., stimulating the generation of active oxygen and advancing PAH photodegradation; competing with PAHs for energy and photons and restraining PAH photodegradation. Generally, photodegradation rates of the 5 PAHs decreased with the increase of FAs concentration; except fluoranthene and pyrene were advanced in solutions with low FA concentration. The influences of FA concentration on PAH photodegradation were more significant than FA origin. - Influences of fulvic acid (FA) concentration on PAH photodegradation were more significant than FA origin, and active oxygen played an important role in PAH photodegradation

  18. Larvicidal effects of mineral turpentine, low aromatic white spirits, aqueous extracts of Cassia alata, and aqueous extracts, ethanolic extracts and essential oil of betel leaf (Piper betle) on Chrysomya megacephala.

    Science.gov (United States)

    Kumarasinghe, Sujith Prasad W; Karunaweera, Nadira D; Ihalamulla, Ranjan L; Arambewela, Lakshmi S R; Dissanayake, Roshinie D S C T

    2002-12-01

    Many methods have been employed, with variable success, in the treatment of cutaneous myiasis caused by Chrysomya species. Experiment 1: to assess the larvicidal effect of mineral turpentine (MT) and the main ingredient of MT, low aromatic white spirits (LAWS), on Chrysomya megacephala larvae in vitro. Experiment 2: to assess the larvicidal effects of aqueous extracts of winged senna (Cassia alata), and aqueous extracts, ethanolic extracts and essential oil of betel leaf (Piper betle). In experiment 1, two samples of LAWS were obtained from two industrialists (samples 1 and 2). Adult flies of C. megacephala were bred in the insectory of the Department of Parasitology, Faculty of Medicine, University of Colombo. Petri dishes were prepared with pads of cotton wool. These cotton pads were soaked separately in MT, LAWS samples 1 and 2, and normal saline as a control. Ten larvae were placed in each Petri dish. The activity of the larvae was observed and recorded half-hourly. MT and the two samples of LAWS were analyzed by chromatography. In experiment 2, volatile essential oil of betel was prepared using a standard steam distillation process. An ethanolic extract of betel was obtained after boiling the crushed leaf with water, and mixing the stock with ethanol. Betel oil dilutions of 1-4% were prepared using 1% Tween 80 (v/v aq) as a solvent, with 0.05 g/100 mL sodium lauryl sulphate (as stabilizer) and 0.01 g/100 mL methyl paraben (as a preservative). Cotton wool swabs soaked in 1, 2, 3 and 4% essential oil of betel in 1% Tween 80 (v/v aq) prepared as above, 1, 2, 3 and 4% ethanolic extract of betel, 50 and 25% aqueous extract of C. alata, and 50 and 25% aqueous extract of betel were placed in separate Petri dishes. Ten larvae were placed in each Petri dish. 1% Tween 80 solvent with the stabilizer and the preservative, but without betel essential oil, was used as a negative control and MT was used as a positive control. Larval motility was assessed as before. MT and

  19. Orientation of aromatic residues in amyloid cores: Structural insights into prion fiber diversity

    KAUST Repository

    Reymer, Anna; Frederick, Kendra K.; Rocha, Sandra; Beke-Somfai, Tamá s; Kitts, Catherine C.; Lindquist, Susan; Nordé n, Bengt

    2014-01-01

    Sup35 with respect to angular orientation of tyrosines using polarized light spectroscopy. By applying a combination of alignment methods the degree of fiber orientation can be assessed, which allows a relatively accurate determination of the aromatic

  20. Thickening agent for flood water in secondary recovery of oil and for other aqueous salt solutions

    Energy Technology Data Exchange (ETDEWEB)

    Roth, H H

    1966-04-14

    Alkenyl-aromatic polymer sulfonates are good thickeners for some aqueous solutions, but addition of salts to such solutions reduces the desirable viscosity. High-molecular, water-soluble alkenyl-aromatic polymers which carry sulfonic acid or sulfonate groups substituted at the aromatic nuclei yield thickened solutions (e.g., for waterflooding) which are not influenced by the presence of water-soluble salts. Such polymers are derivatives of polyvinyltoluene, alone or in combination with about 5% acrylonitrile. It was also found that such thickening agents are less adsorbed on the rock matrix in a waterflood formation. (1 claim)

  1. Long-Term Charge/Discharge Cycling Stability of MnO2 Aqueous Supercapacitor under Positive Polarization

    KAUST Repository

    Ataherian, Fatemeh

    2011-01-01

    The long-term charge/discharge cycling stability of MnO 2 electrode under positive polarization in aqueous KCl electrolyte has been studied over different potential windows spanning from the open circuit potential to varied higher-end potential limited by O 2 evolution. Cycling up to 1.2 V (vs Ag/AgCl (aq)) causes partial (35) capacitance fading to a plateau value within the initial cycles, accompanied by morphological reconstruction, reduction of surface Mn ions and oxygen evolution. The surface Mn-ion reduction has been attributed to a two-step oxidation-reduction mechanism involving OH oxidation in electrolyte, based on electrochemical analysis. When cycling potential extends to 1.4 V, extensive oxygen evolution takes place. The combination of surface passivation of current collector and extensive gas bubbling, which deteriorates electrical contact among the constituent particles within the electrode, results in further monotonic capacitance reduction. © 2011 The Electrochemical Society.

  2. Radiolysis of anthraquinone dyes in aqueous solutions

    International Nuclear Information System (INIS)

    Vysotskaya, N.A.; Bortun, L.N.; Ogurtsov, N.A.; Migdalovich, E.A.; Revina, A.A.; Volodko, V.V.; AN SSSR, Moscow. Inst. Ehlektrokhimii)

    1986-01-01

    The commercial anthraquinone dyes (Dark Blue, Light Blue, Green) in aqueous solutions were shown to be decoloured and degrade under the action of ionizing radiation. The degree of decolouration and degradation of aromatic rings was found to increase in presence of oxygen. Hydroxyl radicals were shown to play the key role in the degradation of the dyes under irradiation. The radiolysis intermediate products were studied using the pulse radiolysis technique. (author)

  3. Preparation of a novel bioavailable curcuminoid formulation (Cureit™) using Polar-Nonpolar-Sandwich (PNS) technology and its characterization and applications

    Energy Technology Data Exchange (ETDEWEB)

    Amalraj, Augustine; Jude, Shintu; Varma, Karthik; Jacob, Joby [R& D Centre, Aurea Biolabs (P) Ltd, Kolenchery, Cochin, 682 311, Kerala (India); Gopi, Sreeraj, E-mail: sreeraj.gopi@plantlipids.com [R& D Centre, Aurea Biolabs (P) Ltd, Kolenchery, Cochin, 682 311, Kerala (India); Oluwafemi, Oluwatobi S. [Department of Applied Chemistry, University of Johannesburg, Doornfontein Campus, P.O. Box 17011, Doornfontein, 2028 Johannesburg (South Africa); Centre for Nanomaterials Science Research, University of Johannesburg, Johannesburg (South Africa); Thomas, Sabu [School of Chemical Sciences, Mahatma Gandhi University, Kottayam (India)

    2017-06-01

    Health benefits of curcuminoid are highly limited due to their poor aqueous solubility, very low systemic bioavailability, fast metabolic alterations and rapid elimination. In this study, a novel bioavailable curcuminoid formulation Cureit™ was prepared by using Polar-Nonpolar-Sandwich (PNS) technology with complete natural turmeric matrix (CNTM). The synthesized bioavailable curcuminoid formulation Cureit™ was characterizations by Nuclear magnetic resonance spectroscopy (NMR), scanning electron microscopy (SEM), X-ray diffraction (XRD), Fourier transform infra-red (IR), current-voltage (I-V) study, Quadrupole Time-of-Flight Mass Spectrometry (Q-TOF), differential scanning calorimeter (DSC) and thermogravimetric analysis (TGA). NMR study showed the presence of hydrogen bonding interactions with curcuminoids, polar and non-polar compounds in the PNS technology. SEM images indicated that Cureit™ was almost spherical and well dispersed with rough morphology, and separated with three layers of PNS formulation. The chemical profile of Cureit™ was analyzed by Q-TOF confirmed the presence of curcuminoids (curcumin, demethoxycurcumin and bismethoxycurcumin), lactones, sesquiterpenes and their derivatives derived from polar layer, aromatic turmerone, dihydroturmerone, turmeronol, curdione and bisacurone derived from non-polar layer. IR, XRD, DSC and TGA also confirmed the presence of curcuminoids with high stability in the PNS formulation. Various biological activities of Cureit™ were also discussed. - Highlights: • A novel bioavailable curcuminoid formulation Cureit™ was prepared. • Polar-Nonpolar-Sandwich technology is used with complete natural turmeric matrix. • Cureit™ was analyzed and predicted by NMR, SEM, XRD, IR, I-V, Q-TOF, DSC and TGA. • Cureit™ exhibited 10 fold higher bioavailable curcuminoid than pure curcuminoid.

  4. Preparation of a novel bioavailable curcuminoid formulation (Cureit™) using Polar-Nonpolar-Sandwich (PNS) technology and its characterization and applications

    International Nuclear Information System (INIS)

    Amalraj, Augustine; Jude, Shintu; Varma, Karthik; Jacob, Joby; Gopi, Sreeraj; Oluwafemi, Oluwatobi S.; Thomas, Sabu

    2017-01-01

    Health benefits of curcuminoid are highly limited due to their poor aqueous solubility, very low systemic bioavailability, fast metabolic alterations and rapid elimination. In this study, a novel bioavailable curcuminoid formulation Cureit™ was prepared by using Polar-Nonpolar-Sandwich (PNS) technology with complete natural turmeric matrix (CNTM). The synthesized bioavailable curcuminoid formulation Cureit™ was characterizations by Nuclear magnetic resonance spectroscopy (NMR), scanning electron microscopy (SEM), X-ray diffraction (XRD), Fourier transform infra-red (IR), current-voltage (I-V) study, Quadrupole Time-of-Flight Mass Spectrometry (Q-TOF), differential scanning calorimeter (DSC) and thermogravimetric analysis (TGA). NMR study showed the presence of hydrogen bonding interactions with curcuminoids, polar and non-polar compounds in the PNS technology. SEM images indicated that Cureit™ was almost spherical and well dispersed with rough morphology, and separated with three layers of PNS formulation. The chemical profile of Cureit™ was analyzed by Q-TOF confirmed the presence of curcuminoids (curcumin, demethoxycurcumin and bismethoxycurcumin), lactones, sesquiterpenes and their derivatives derived from polar layer, aromatic turmerone, dihydroturmerone, turmeronol, curdione and bisacurone derived from non-polar layer. IR, XRD, DSC and TGA also confirmed the presence of curcuminoids with high stability in the PNS formulation. Various biological activities of Cureit™ were also discussed. - Highlights: • A novel bioavailable curcuminoid formulation Cureit™ was prepared. • Polar-Nonpolar-Sandwich technology is used with complete natural turmeric matrix. • Cureit™ was analyzed and predicted by NMR, SEM, XRD, IR, I-V, Q-TOF, DSC and TGA. • Cureit™ exhibited 10 fold higher bioavailable curcuminoid than pure curcuminoid.

  5. Conformational switching of ethano-bridged Cu,H2-bis-porphyrin induced by aromatic amines.

    Science.gov (United States)

    Bettini, Simona; Maglie, Emanuela; Pagano, Rosanna; Borovkov, Victor; Inoue, Yoshihisa; Valli, Ludovico; Giancane, Gabriele

    2015-01-01

    Cu,H2-bis-porphyrin (Cu,H2-Por2), in which copper porphyrin and free-base porphyrin are linked together by an ethano-bridge, was dissolved in chloroform and spread at the air/liquid subphase interface of a Langmuir trough. The bis-porphyrin derivative, floating film was characterized by reflection spectroscopy and the surface pressure of the floating film was studied as a function of the mean area per molecule. When aromatic amines are dissolved in the subphase, an evident interaction between the bis-porphyrin host and the aromatic amine guest is observed. A clear-cut variation of the profile of surface pressure vs area per molecule curve is observed. Reflection spectroscopy highlights that the aromatic amines dissolved in the subphase are able to induce the syn-to-anti conformational switching in the bis-porphyrin derivative. The Langmuir-Schaefer technique has been used to transfer the floating bis-porphyrin film (when using pure water as a subphase) to a surface plasmon resonance (SPR) substrate and the resulting device was able to detect the presence of aniline at concentrations as low as 1 nM in aqueous solution. The high selectivity of the SPR sensing device has been verified by checking the spectral response of the active layer towards other analytes dissolved in the aqueous solutions.

  6. Conformational switching of ethano-bridged Cu,H2-bis-porphyrin induced by aromatic amines

    Directory of Open Access Journals (Sweden)

    Simona Bettini

    2015-11-01

    Full Text Available Cu,H2-bis-porphyrin (Cu,H2-Por2, in which copper porphyrin and free-base porphyrin are linked together by an ethano-bridge, was dissolved in chloroform and spread at the air/liquid subphase interface of a Langmuir trough. The bis-porphyrin derivative, floating film was characterized by reflection spectroscopy and the surface pressure of the floating film was studied as a function of the mean area per molecule. When aromatic amines are dissolved in the subphase, an evident interaction between the bis-porphyrin host and the aromatic amine guest is observed. A clear-cut variation of the profile of surface pressure vs area per molecule curve is observed. Reflection spectroscopy highlights that the aromatic amines dissolved in the subphase are able to induce the syn-to-anti conformational switching in the bis-porphyrin derivative. The Langmuir–Schaefer technique has been used to transfer the floating bis-porphyrin film (when using pure water as a subphase to a surface plasmon resonance (SPR substrate and the resulting device was able to detect the presence of aniline at concentrations as low as 1 nM in aqueous solution. The high selectivity of the SPR sensing device has been verified by checking the spectral response of the active layer towards other analytes dissolved in the aqueous solutions.

  7. The formation of quasi-alicyclic rings in alkyl-aromatic compounds

    Science.gov (United States)

    Straka, Pavel; Buryan, Petr; Bičáková, Olga

    2018-02-01

    The alkyl side chains of n-alkyl phenols, n-alkyl benzenes and n-alkyl naphthalenes are cyclised, as demonstrated by GC measurements, FTIR spectroscopy and molecular mechanics calculations. Cyclisation occurs due to the intramolecular interaction between an aromatic ring (-δ) and a hydrogen of the terminal methyl group (+δ) of an alkyl chain. In fact, conventional molecules are not aliphatic-aromatic, but quasi-alicyclic-aromatic. With the aromatic molecules formed with a quasi-alicyclic ring, the effect of van der Waals attractive forces increases not only intramolecularly but also intermolecularly. This effect is strong in molecules with propyl and higher alkyl substituents. The increase of intermolecular van der Waals attractive forces results in bi-linearity in the GC retention time of the compounds in question, observed in the dependence of the logarithm of the relative retention time on the number of carbons in a molecule in both polar and nonpolar stationary phases with both capillary and packed columns. The role of van der Waals forces has been demonstrated using the potential energies of covalent and noncovalent interactions for 2-n-alkyl phenols, n-alkyl benzenes and 1-n-alkyl- and 2-n-alkyl naphthalenes.

  8. Aromatic amino acids and ultraviolet induced photoelectric effects in bilayer membranes

    Energy Technology Data Exchange (ETDEWEB)

    Huebner, J S; Arrieta, R T [University of North Florida, Jacksonville (USA); Naval Medical Research Inst., Bethesda, MD (USA))

    1982-04-01

    Ultraviolet light flashes induced voltage transients across bilayer lipid membranes when aromatic amino acids were adsorbed to one side of the membrane. These photo-effects varied with the chromophore structure, the aqueous solution salt concentration, pH and oxygen partial pressure. These photo-effects are attributed to the migration of electrically charged photochemical intermediates in the membrane, and provide a new method for studying the effects of UV light on membranes.

  9. Spin-trapping and ESR studies of the direct photolysis of aromatic amino acids, dipeptides, tripeptides and polypeptides in aqueous solutions-II. Tyrosine and related compounds

    Energy Technology Data Exchange (ETDEWEB)

    Lion, Y; Kuwabara, M; Riesz, P [National Cancer Inst., Bethesda, MD (USA)

    1982-01-01

    The UV-photolysis of peptides containing tyrosine (Tyr) was investigated in aqueous solutions at room temperature at 220 and 265 nm. The short-lived free radicals formed during photolysis were spin-trapped by t-nitrosobutane and identified by electron spin resonance. For N-acetyl-and N-formyl-L-Tyr and for peptides containing L-Tyr as the middle residue, photolysis at 265 nm under neutral conditions produced mainly spin-adducts due to the scission between the alpha carbon and the methylene group attached to the aromatic ring, while at 220 nm decarboxylation radicals were spin-trapped. Photolysis of di- and tripeptides at 275 nm in alkaline solutions predominantly generated deamination radicals. The radicals produced in the photolysis of the oxidized A chain of insulin were tentatively characterized by comparison with the results for di- and tripeptides.

  10. Potentiometric titrations of para and nitro substituted aromatic acids and their mixtures in methylethyl ketone

    International Nuclear Information System (INIS)

    Ozeroglu, C.; Karahan, M.

    2011-01-01

    In this study, it was the purpose to examine the potentiometric titrations of para and nitro substituted aromatic acids in methylethyl ketone (MEK) as a non-aqueous solvent. Good analytical results were obtained in determining the amount of each acid and the amounts of acids in their ternary mixtures by using 0.0964 N tetrabuthylammoniumhydroxyde (TBAH) as a standard titrant. Methylethyl ketone (MEK) which is a good solvent for many organic compounds and has a convenient liquid range of -86 to 80 deg. C was used for titration of the para and nitro substituted aromatic acids. A linear relationship has been found between pKa values of the para and nitro substituted aromatic acids in water and the half neutralization potential (HNP) values determined by potentiometric titration curves of the same acids in MEK. (author)

  11. The Effect of n vs. iso Isomerization on the Thermophysical Properties of Aromatic and Non-aromatic Ionic Liquids.

    Science.gov (United States)

    Rodrigues, Ana S M C; Almeida, Hugo F D; Freire, Mara G; Lopes-da-Silva, José A; Coutinho, João A P; Santos, Luís M N B F

    2016-09-15

    This work explores the n vs. iso isomerization effects on the physicochemical properties of different families of ionic liquids (ILs) with variable aromaticity and ring size. This study comprises the experimental measurements, in a wide temperature range, of the ILs' thermal behavior, heat capacities, densities, refractive indices, surface tensions, and viscosities. The results here reported show that the presence of the iso -alkyl group leads to an increase of the temperature of the glass transition, T g . The iso- pyrrolidinium (5 atoms ring cation core) and iso -piperidinium (6 atoms ring cation core) ILs present a strong differentiation in the enthalpy and entropy of melting. Non-aromatic ILs have higher molar heat capacities due to the increase of the atomic contribution, whereas it was not found any significant differentiation between the n and iso -alkyl isomers. A small increase of the surface tension was observed for the non-aromatic ILs, which could be related to their higher cohesive energy of the bulk, while the lower surface entropy observed for the iso isomers indicates a structural resemblance between the IL bulk and surface. The significant differentiation between ILs with a 5 and 6 atoms ring cation in the n -alkyl series (where 5 atoms ring cations have higher surface entropy) is an indication of a more efficient arrangement of the non-polar region at the surface in ILs with smaller cation cores. The ILs constituted by non-aromatic piperidinium cation, and iso -alkyl isomers were found to be the most viscous among the studied ILs due to their higher energy barriers for shear stress.

  12. Carotamine, a Unique Aromatic Amide from Daucus Carota L. Var Biossieri (Apiaceae

    Directory of Open Access Journals (Sweden)

    Mohamed M. El-Azizi

    2002-06-01

    Full Text Available The unique aromatic peptide 4-(p-aminobenzoylamino-2-aminobenzoic acid, carotamine, together with 2,4-diaminobenzoic acid, isolated for the first time from a plant source, were identified from the aqueous alcoholic extract of the aerial parts of Daucus carota L. var. boissieri (Apiaceae. The structures were determined through conventional methods of analysis and confirmed by LC-ESI/MS and NMR spectral analysis.

  13. Aqueous CO2 vs. aqueous extraction of soils as a preparative procedure for acute toxicity testing

    International Nuclear Information System (INIS)

    Yates, G.W.; Burks, S.L.

    1994-01-01

    This study was to determine if contaminated soils extracted with supercritical CO 2 (SFE) would yield different results from soils extracted with an aqueous media. Soil samples from an abandoned oil refinery were subjected to aqueous and SFE extraction. Uncontaminated control sites were compared with contaminated sites. Each extract was analyzed for 48 hour acute Ceriodaphnia LC50s and Microtox reg-sign EC50s. Comparisons were then made between the aqueous extracts and the SFE extracts. An additional study was made with HPLC chromatographs of the SFE contaminated site extracts to determine if there was a correlation between LC50 results and peak area of different sections of the chromatograph. The 48 hour Ceriodaphnia LC50 of one contaminated site showed a significant increase in toxicity with the supercritical extract compared to the aqueous extract. All contaminated sites gave toxic responses with the supercritical procedure. The Microtox reg-sign assay showed a toxic response with 2 of the 3 contaminated sites for both aqueous and SFE extracts. Results indicate that the Ceriodaphnia assays were more sensitive than Microtox reg-sign to contaminants found in the refinery soil. SFE controls did not show adverse effects with the Ceriodaphnia, but did have a slight effect with Microtox reg-sign. The best correlation (r 2 > 0.90) between the Ceriodaphnia LC50s and the peak areas of the chromatographs was obtained for sections with an estimated log K ow of 1 to 5. SFE extraction provided a fast, efficient and inexpensive method of collecting and testing moderately non-polar to strongly non-polar organic contaminants from contaminated soils

  14. Dispersions of Goethite Nanorods in Aprotic Polar Solvents

    Directory of Open Access Journals (Sweden)

    Delphine Coursault

    2017-10-01

    Full Text Available Colloidal suspensions of anisotropic nanoparticles can spontaneously self-organize in liquid-crystalline phases beyond some concentration threshold. These phases often respond to electric and magnetic fields. At lower concentrations, usual isotropic liquids are observed but they can display very strong Kerr and Cotton-Mouton effects (i.e., field-induced particle orientation. For many examples of these colloidal suspensions, the solvent is water, which hinders most electro-optic applications. Here, for goethite (α-FeOOH nanorod dispersions, we show that water can be replaced by polar aprotic solvents, such as N-methyl-2-pyrrolidone (NMP and dimethylsulfoxide (DMSO, without loss of colloidal stability. By polarized-light microscopy, small-angle X-ray scattering and electro-optic measurements, we found that the nematic phase, with its field-response properties, is retained. Moreover, a strong Kerr effect was also observed with isotropic goethite suspensions in these polar aprotic solvents. Furthermore, we found no significant difference in the behavior of both the nematic and isotropic phases between the aqueous and non-aqueous dispersions. Our work shows that goethite nanorod suspensions in polar aprotic solvents, suitable for electro-optic applications, can easily be produced and that they keep all their outstanding properties. It also suggests that this solvent replacement method could be extended to the aqueous colloidal suspensions of other kinds of charged anisotropic nanoparticles.

  15. Salting out the polar polymorph: analysis by alchemical solvent transformation.

    Science.gov (United States)

    Duff, Nathan; Dahal, Yuba Raj; Schmit, Jeremy D; Peters, Baron

    2014-01-07

    We computationally examine how adding NaCl to an aqueous solution with α- and γ-glycine nuclei alters the structure and interfacial energy of the nuclei. The polar γ-glycine nucleus in pure aqueous solution develops a melted layer of amorphous glycine around the nucleus. When NaCl is added, a double layer is formed that stabilizes the polar glycine polymorph and eliminates the surface melted layer. In contrast, the non-polar α-glycine nucleus is largely unaffected by the addition of NaCl. To quantify the stabilizing effect of NaCl on γ-glycine nuclei, we alchemically transform the aqueous glycine solution into a brine solution of glycine. The alchemical transformation is performed both with and without a nucleus in solution and for nuclei of α-glycine and γ-glycine polymorphs. The calculations show that adding 80 mg/ml NaCl reduces the interfacial free energy of a γ-glycine nucleus by 7.7 mJ/m(2) and increases the interfacial free energy of an α-glycine nucleus by 3.1 mJ/m(2). Both results are consistent with experimental reports on nucleation rates which suggest: J(α, brine) transformation approach can predict the results for both polar and non-polar polymorphs. The results suggest a general "salting out" strategy for obtaining polar polymorphs and also a general approach to computationally estimate the effects of solvent additives on interfacial free energies for nucleation.

  16. Study on the polarity, solubility, and stacking characteristics of asphaltenes

    KAUST Repository

    Zhang, Long-li; Yang, Guo-hua; Wang, Ji-Qian; Li, Yan; Li, Li; Yang, Chao-he

    2014-01-01

    The structure and transformation of fused aromatic ring system in asphaltenes play an important role in the character of asphaltenes, and in step affect the properties of heavy oils. Polarity, solubility and structural characteristics of asphaltenes

  17. Nonadiabatic Response Model of Laser-Induced Ultrafast π-Electron Rotations in Chiral Aromatic Molecules

    International Nuclear Information System (INIS)

    Kanno, Manabu; Kono, Hirohiko; Fujimura, Yuichi; Lin, Sheng H.

    2010-01-01

    We theoretically investigated the nonadiabatic couplings between optically induced π-electron rotations and molecular vibrations in a chiral aromatic molecule irradiated by a nonhelical, linearly polarized laser pulse. The results of wave packet dynamics simulation show that the vibrational amplitudes strongly depend on the initial rotation direction, clockwise or counterclockwise, which is controlled by the polarization direction of the incident pulse. This suggests that attosecond π-electron rotations can be observed by spectroscopic detection of femtosecond molecular vibrations.

  18. Retardation effect of nitrogen compounds and condensed aromatics on shale oil catalytic cracking processing and their characterization.

    Science.gov (United States)

    Li, Nan; Chen, Chen; Wang, Bin; Li, Shaojie; Yang, Chaohe; Chen, Xiaobo

    Untreated shale oil, shale oil treated with HCl aqueous solution and shale oil treated with HCl and furfural were used to do comparative experiments in fixed bed reactors. Nitrogen compounds and condensed aromatics extracted by HCl and furfural were characterized by electrospray ionization Fourier transform cyclotron resonance mass spectrometry and gas chromatography and mass spectrometry, respectively. Compared with untreated shale oil, the conversion and yield of liquid products increased considerably after removing basic nitrogen compounds by HCl extraction. Furthermore, after removing nitrogen compounds and condensed aromatics by both HCl and furfural, the conversion and yield of liquid products further increased. In addition, N 1 class species are predominant in both basic and non-basic nitrogen compounds, and they are probably indole, carbazole, cycloalkyl-carbazole, pyridine and cycloalkyl-pyridine. As for the condensed aromatics, most of them possess aromatic rings with two to three rings and zero to four carbon atom.

  19. Halogenating reaction activity of aromatic organic compounds during disinfection of drinking water

    International Nuclear Information System (INIS)

    Guo Gaimei; Chen Xiaodong

    2009-01-01

    The halogenating reactions of five aromatic organic compounds (AOCs) with aqueous chlorine (HOCl/OCl - ) and aqueous bromine (HOBr/OBr - ) were studied with an aim to compare the formation properties of haloacetic acids (HAAs) for the corresponding chlorination or bromination reactions of AOCs, respectively. The experiment results indicated that the HAAs substitution efficiency for the bromination reactions of AOCs was greater than that for the chlorination reactions, and the formation of HAAs had a strong dependence on the chemical structure of AOCs. The chlorination or bromination reaction activities for the AOCs with electron donating functional groups were higher than that for them with electron withdrawing functional groups. The kinetic experiments indicated that the reactions of aqueous bromine with phenol were faster than those of aqueous chlorine with phenol and the halogen consumption exhibited rapid initial and slower consumption stages for the reactions of phenol with aqueous chlorine and bromine, respectively. In addition, the HAAs production for the chlorination reaction of phenol decreased with the increase of pH. These conclusions could provide the valuable information for the effective control of the disinfection by-products during drinking water treatment operation

  20. Sorption of Aromatic Compounds with Copolymer Sorbent Materials Containing β-Cyclodextrin

    OpenAIRE

    Wilson, Lee D.; Mohamed, Mohamed H.; Berhaut, Christopher L.

    2011-01-01

    Urethane copolymer sorbent materials that incorporate β-cyclodextrin (CD) have been prepared and their sorption properties with chlorinated aromatic compounds (i.e., pentachlorophenol, 2,4-dichlorophenol and 2,4-dichlorophenoxy acetic acid) have been evaluated. The sorption properties of granular activated carbon (GAC) were similarly compared in aqueous solution at variable pH conditions. The sorbents displayed variable BET surface areas as follows: MDI-X copolymers (< 101 m2/g), CDI-X cop...

  1. Unexpected solvent effects on the UV/Vis absorption spectra of o-cresol in toluene and benzene: in contrast with non-aromatic solvents.

    Science.gov (United States)

    Zheng, Dong; Yuan, Xiang-Ai; Ma, Haibo; Li, Xiaoxiong; Wang, Xizhang; Liu, Ziteng; Ma, Jing

    2018-03-01

    Cresol is a prototype molecule in understanding intermolecular interactions in material and biological systems, because it offers different binding sites with various solvents and protonation states under different pH values. It is found that the UV/Vis absorption spectra of o -cresol in aromatic solvents (benzene, toluene) are characterized by a sharp peak, unlike the broad double-peaks in 11 non-aromatic solvents. Both molecular dynamics simulations and electronic structure calculations revealed the formation of intermolecular π-complexation between o -cresol and aromatic solvents. The thermal movements of solvent and solute molecules render the conformations of o -cresol changing between trans and cis isomers. The π-interaction makes the cis configuration a dominant isomer, hence leading to the single keen-edged UV/Vis absorption peak at approximately 283 nm. The free conformation changes between trans and cis in aqueous solution rationalize the broader absorption peaks in the range of 260-280 nm. The pH dependence of the UV/Vis absorption spectra in aqueous solutions is also rationalized by different protonation states of o -cresol. The explicit solvent model with long-ranged interactions is vital to describe the effects of π-complexation and electrostatic interaction on the UV/Vis absorption spectra of o -cresol in toluene and alkaline aqueous (pH > 10.3) solutions, respectively.

  2. One-Pot Synthesis of Some New Pyrido[2,3-d]pyrimidine Derivatives Catalyzed by Sodium Lauryl Sulfate in Aqueous Media

    Directory of Open Access Journals (Sweden)

    Sheng-Hui Li

    2010-01-01

    Full Text Available A series of pyrido[2,3-d]pyrimidine derivatives were synthesized by the three-component reaction of aromatic aldehyde, malononitrile and 6-amino-4-hydroxy-2-mercaptopyrimidine catalyzed by sodium lauryl sulfate (SDS in aqueous media. It was interesting that further aromatization took place automatically. This method provides several advantages such as easier work-up, milder reaction conditions and environmental friendly.

  3. Formic-acid-induced depolymerization of oxidized lignin to aromatics

    Science.gov (United States)

    Rahimi, Alireza; Ulbrich, Arne; Coon, Joshua J.; Stahl, Shannon S.

    2014-11-01

    Lignin is a heterogeneous aromatic biopolymer that accounts for nearly 30% of the organic carbon on Earth and is one of the few renewable sources of aromatic chemicals. As the most recalcitrant of the three components of lignocellulosic biomass (cellulose, hemicellulose and lignin), lignin has been treated as a waste product in the pulp and paper industry, where it is burned to supply energy and recover pulping chemicals in the operation of paper mills. Extraction of higher value from lignin is increasingly recognized as being crucial to the economic viability of integrated biorefineries. Depolymerization is an important starting point for many lignin valorization strategies, because it could generate valuable aromatic chemicals and/or provide a source of low-molecular-mass feedstocks suitable for downstream processing. Commercial precedents show that certain types of lignin (lignosulphonates) may be converted into vanillin and other marketable products, but new technologies are needed to enhance the lignin value chain. The complex, irregular structure of lignin complicates chemical conversion efforts, and known depolymerization methods typically afford ill-defined products in low yields (that is, less than 10-20wt%). Here we describe a method for the depolymerization of oxidized lignin under mild conditions in aqueous formic acid that results in more than 60wt% yield of low-molecular-mass aromatics. We present the discovery of this facile C-O cleavage method, its application to aspen lignin depolymerization, and mechanistic insights into the reaction. The broader implications of these results for lignin conversion and biomass refining are also considered.

  4. Pyridyl-alanine as a Hydrophilic, Aromatic Element in Peptide Structural Optimization.

    Science.gov (United States)

    Mroz, Piotr A; Perez-Tilve, Diego; Liu, Fa; Gelfanov, Vasily; DiMarchi, Richard D; Mayer, John P

    2016-09-08

    Glucagon (Gcg) 1 serves a seminal physiological role in buffering against hypoglycemia, but its poor biophysical properties severely complicate its medicinal use. We report a series of novel glucagon analogues of enhanced aqueous solubility and stability at neutral pH, anchored by Gcg[Aib16]. Incorporation of 3- and 4-pyridyl-alanine (3-Pal and 4-Pal) enhanced aqueous solubility of glucagon while maintaining biological properties. Relative to native hormone, analogue 9 (Gcg[3-Pal6,10,13, Aib16]) demonstrated superior biophysical character, better suitability for medicinal purposes, and comparable pharmacology against insulin-induced hypoglycemia in rats and pigs. Our data indicate that Pal is a versatile surrogate to natural aromatic amino acids and can be employed as an alternative or supplement with isoelectric adjustment to refine the biophysical character of peptide drug candidates.

  5. Aqueous citric acid as green reaction media for the synthesis of octahydroxanthenes

    Directory of Open Access Journals (Sweden)

    Camilo A. Navarro D.

    2013-08-01

    Full Text Available A simple, convenient and environmentally friendly one-pot procedure for the synthesis of 1,8-dioxo-octahydroxanthenes by the reaction of dimedone and aromatic aldehydes in aqueous citric acid is described. In this green synthetic protocol promoted by the reaction media, the use of any other catalysts and hazardous organic solvents are avoided, making the work up procedure greener and easier. The isolation of the products, obtained in good yields, is readily performed by filtration and crystallization from ethanol when required and the aqueous acidic media can be easily recycled and reused several times without significant loss of catalytic activity.

  6. Application of the cubic-plus-association (CPA) equation of state to complex mixtures with aromatic hydrocarbons

    DEFF Research Database (Denmark)

    Folas, Georgios; Kontogeorgis, Georgios; Michelsen, Michael Locht

    2006-01-01

    The cubic-plus-association (CPA) equation of state is applied to phase equilibria of mixtures containing alcohols, glycols, water, and aromatic or olefinic hydrocarbons. Previously, CPA has been successfully used for mixtures containing various associating compounds (alcohols, glycols, amines......, organic acids, and water) and aliphatic hydrocarbons. We show in this work that the model can be satisfactorily extended to complex vapor-liquid-liquid equilibria with aromatic or olefinic hydrocarbons. The solvation between aromatics/olefinics and polar compounds is accounted for. This is particularly...... important for mixtures containing water and glycols, but less so for mixtures with alcohols. For water/hydrocarbons, a single binary interaction parameter which accounts for the solvation is fitted to the experimental liquid-liquid equilibria (LLE) data. The interaction parameter of the physical term...

  7. High-resolution gas chromatographic analysis of polycyclic aromatic hydrocarbons and aliphatic hydrocarbons

    International Nuclear Information System (INIS)

    Perez, M.; Gonzalez, D.

    1988-01-01

    A study of the analysis by gas chromatography of aromatic polycyclic hydrocarbons and aliphatic hydrocarbons is presented. The separation has been carried out by glass and fused silica capillary column in two different polar stationary phases OV-1 and SE-54. The limitation and the advantages of the procedure are discussed in terms of separation, sensitivity and precision. (Author) 20 refs

  8. Biodegradation Of Polycyclic Aromatic Hydrocarbons In Petroleum Oil Contaminating The Environment

    International Nuclear Information System (INIS)

    Partila, A.M.

    2013-01-01

    Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous pollutants in urban atmospheres (Chen et al., 2013). PAHs enter the environment via incomplete combustion of fossil fuels and accidental leakage of petroleum products, and as components of products such as creosote (Muckian et al., 2009). Due to PAHs carcinogenic activity, they have been included in the European Union (EU) and the Environmental Protection Agency (EPA) priority pollutant lists. Human exposure to PAHs occurs in three ways, inhalation, dermal contact and consumption of contaminated foods, which account for 88-98% of such contamination; in other words, diet is the major source of human exposure to these contaminants (Rey-Salgueiro et al., 2008). Both the World Health Organization and the UK Expert Panel on Air Quality Standards (EPAQS) have considered benzo(a)pyrene (BaP) as a marker of the carcinogenic potency of the polycyclic aromatic hydrocarbons (PAH) mixture (Delgado-Saborit et al., 2011). Polycyclic aromatic and heavier aliphatic hydrocarbons, which have a stable recalcitrant molecular structure, exhibit high hydrophobicity and low aqueous solubility, are not readily removed from soil through leaching and volatilization (Brassington et al., 2007). The hydrophobicity of PAHs limits desorption to the aqueous phase (Donlon et al., 2002). Six main ways of dissipation, i.e. disappearance, are recognized in the environment: volatilization, photooxidation, Aim of the Work chemical oxidation, sorption, leaching and biodegradation. Microbial degradation is considered to be the main process involved in the dissipation of PAH (Yuan et al., 2002). Thus, more and more research interests are turning to the biodegradation of PAHs. Some microorganisms can utilize PAHs as a source of carbon and energy so that PAHs can be degraded to carbon dioxide and water, or transformed to other nontoxic or low-toxic substances (Perelo, 2010). Compared with other physical and chemical methods such as combustion

  9. Prediction of aqueous and nonaqueous solubilities of chemicals with environmental interest by UNIFAC

    International Nuclear Information System (INIS)

    Kan, A.T.; Tomson, M.B.

    1995-01-01

    This paper is to investigate the accuracy and precision of predicting the aqueous and non-aqueous solubilities of a vast number of chemicals with significant environmental roles using the latest version of UNIFAC group interaction parameters. A few critical measurements to test specific UNIFAC calculations of nonaqueous solubilities are also reported. The chemicals included in the calculation have aqueous solubilities that span eleven orders of magnitude. Good agreement was observed between the UNIFAC predicted and literature reported aqueous solubilities for eleven groups of compounds. Similarly, UNIFAC successfully predicts the co-solvency of PCB in methanol/water solutions. The error between predicted and literature reported aqueous solubilities was larger for three groups of chemicals: long chain alkanes, phthalates, and chlorinated alkenes. The average absolute error in UNIFAC precision of aqueous solubilities is about 0.5 log units, but the average absolute error is only about 0.2 log units for chlorinated aromatic compounds in organic solvents. The application of UNIFAC approach to predict the fate of hydrocarbons and PCBs in soil column flushing, cosolvency and in natural gas pipeline liquids will be discussed

  10. Mechanism of aromatic hydroxylation of lidocaine at a Pt electrode under acidic conditions

    International Nuclear Information System (INIS)

    Gul, Turan; Bischoff, Rainer; Permentier, Hjalmar P.

    2017-01-01

    Aromatic hydroxylation reactions, which are mainly catalyzed by cytochrome P450 (CYP) enzymes in vivo, are some of the most important reactions of Phase I metabolism, because insertion of a hydroxyl group into a lipophilic drug compound increases its hydrophilicity and prepares it for subsequent Phase II metabolic conjugation reactions as a prerequisite to excretion. Aromatic hydroxylation metabolites of pharmaceuticals may be obtained through various synthetic and enzymatic methods Electrochemical oxidation is an alternative with advantages in terms of mild reaction conditions and less hazardous chemicals. In the present study, we report that aromatic hydroxylation metabolites of lidocaine can be readily obtained electrochemically under aqueous acidic conditions at platinum electrodes. Our results show that the dominant N-dealkylation reaction can be suppressed by decreasing the solution pH below 0.5 resulting in selective 3-hydroxylidocaine, which is an in vivo metabolite of lidocaine. Experiments in 18 O labelled water indicated that water is the primary source of oxygen, while dissolved molecular oxygen contributes to a minor extent to the hydroxylation reaction.

  11. Aromatic hydrocarbons

    International Nuclear Information System (INIS)

    Roder, M.

    1985-01-01

    Papers dealing with radiolysis of aromatic hydrocarbons of different composition (from benzene to terphenyls and hydrocarbons with condensed rings) as well as their mixtures (with alkanes, alkenes, other aromatic hydrocarbons) are reviewed. High radiation stability of aromatic hydrocarbons in condensed phases associated with peculiarities of molecular structure of compounds is underlined. Mechanisms of radiolytic processes, vaues of product yields are considered

  12. Liquid-liquid extraction and separation of VIII group elements, especially ruthenium, by synergic combinations or aromatic polyimines and micellar cationic exchangers

    International Nuclear Information System (INIS)

    Vitart, X.

    1991-01-01

    This thesis aims to characterize and to quantify the chemical equilibria involved in d-elements liquid-liquid extraction systems, especially elements belonging to the VIII group (Fe, Ni, Co, Ru, Rh, Pd, Pt). These systems are composed of synergic combination of aromatic polyimines and micellar cationic exchangers. Substitutions are first performed in aqueous acidic media by aromatic polyimines; then extractions are operated using micellic canionic exchangers. Chemical equilibria, selectivity effects, especially those due to ion-pair formations, kinetics, extractant behaviour are analysed and quantified [fr

  13. Dissolution of lignin in green urea aqueous solution

    Science.gov (United States)

    Wang, Jingyu; Li, Ying; Qiu, Xueqing; Liu, Di; Yang, Dongjie; Liu, Weifeng; Qian, Yong

    2017-12-01

    The dissolution problem is the main obstacle for the value-added modification and depolymerization of industrial lignin. Here, a green urea aqueous solution for complete dissolution of various lignin is presented and the dissolution mechanism is analyzed by AFM, DLS and NMR. The results show that the molecular interaction of lignin decreases from 32.3 mN/m in pure water to 11.3 mN/m in urea aqueous solution. The immobility of 1H NMR spectra and the shift of 17O NMR spectra of urea in different lignin/urea solutions indicate that the oxygen of carbonyl in urea and the hydrogen of hydroxyl in lignin form new hydrogen bonds and break the original hydrogen bonds among lignin molecules. The shift of 1H NMR spectra of lignin and the decrease of interactions in model compound polystyrene indicate that urea also breaks the π-π interactions between aromatic rings of lignin. Lignin dissolved in urea aqueous has good antioxidant activity and it can scavenge at least 63% free radicals in 16 min.

  14. Metabolism and genotoxicity of aromatic amines in aquatic organisms

    International Nuclear Information System (INIS)

    Knezovich, J.P.; Krauter, P.W.; Lawton, M.P.; Harrison, F.L.

    1987-01-01

    Marine mussels (Mytilus edulis) and bullfrog tadpoles (Rana catesbeiana) were used to investigate the comparative metabolism and genotoxicity of aromatic amines in vivo. These organisms were selected because they possess distinctly different metabolic capabilities: mussels lack an active mixed-function-oxidase enzyme system that is present in most other organisms, including amphibians. Using 14 C-labeled chemical probes (o- and p-toluidine, 2-aminofluorene (2-AF), and 2-acetylaminofluorene (2-AAF)), mussels and tadpoles well dosed with individual compounds by direct immersion in aqueous solutions. The identities of metabolites were then determined by HPLC and GC/MS methods. Results indicate that the N-conjugating pathways used by mussels result primarily in the detoxification of aromatic amines by limiting the amount of primary amine available for activation. The tadpoles excreted a number of 2-AAF metabolites but did form DNA and protein adducts in the liver. Induction of micronuclei in the peripheral red blood cells was also demonstrated. The tadpole was shown to be a sensitive biological indicator of pollution in aquatic ecosystems

  15. Stochastic models (cooperative and non-cooperative) for NMR analysis of the hetero-association of aromatic molecules in aqueous solution

    Energy Technology Data Exchange (ETDEWEB)

    Evstigneev, Maxim P. [Department of Physics, Sevastopol National Technical University, Sevastopol 99053, Crimea (Ukraine)], E-mail: max_evstigneev@mail.ru; Davies, David B. [School of Biological and Chemical Sciences, Birkbeck College, University of London, Malet Street, London WC1E 7HX (United Kingdom); Veselkov, Alexei N. [Department of Physics, Sevastopol National Technical University, Sevastopol 99053, Crimea (Ukraine)

    2006-01-25

    Stochastic cooperative (STOCH-C) and non-cooperative (STOCH-NC) models have been developed for NMR analysis of the hetero-association of aromatic compounds in solution, in order to take into account all physically meaningful association reactions of molecules in which there are no limitations on the lengths of the aggregates and complexes. These algorithmical approaches are compared with previously published basic (BASE) and generalized (GEN) analytical statistical thermodynamical models of hetero-association of biologically active aromatic molecules using the same sets of published NMR data measured under the same solution conditions (0.1 M phosphate buffer, pD = 7.1, T = 298 K). It is shown that, within experimental errors, the BASE analytical model may be used to describe molecular systems characterized by relatively small contributions of hetero-association reactions, whereas the GEN model may be applied to hetero-association reactions of any aromatic compound with different self-association properties. The STOCH-C computational algorithm enabled the effect on hetero-association of the interactions of molecules with different cooperativity parameters of self-association to be estimated for the first time and it is proposed that the algorithm for the stochastic models has great potential for detailed investigation and understanding of the interactions of aromatic molecules in solution.

  16. Stochastic models (cooperative and non-cooperative) for NMR analysis of the hetero-association of aromatic molecules in aqueous solution

    International Nuclear Information System (INIS)

    Evstigneev, Maxim P.; Davies, David B.; Veselkov, Alexei N.

    2006-01-01

    Stochastic cooperative (STOCH-C) and non-cooperative (STOCH-NC) models have been developed for NMR analysis of the hetero-association of aromatic compounds in solution, in order to take into account all physically meaningful association reactions of molecules in which there are no limitations on the lengths of the aggregates and complexes. These algorithmical approaches are compared with previously published basic (BASE) and generalized (GEN) analytical statistical thermodynamical models of hetero-association of biologically active aromatic molecules using the same sets of published NMR data measured under the same solution conditions (0.1 M phosphate buffer, pD = 7.1, T = 298 K). It is shown that, within experimental errors, the BASE analytical model may be used to describe molecular systems characterized by relatively small contributions of hetero-association reactions, whereas the GEN model may be applied to hetero-association reactions of any aromatic compound with different self-association properties. The STOCH-C computational algorithm enabled the effect on hetero-association of the interactions of molecules with different cooperativity parameters of self-association to be estimated for the first time and it is proposed that the algorithm for the stochastic models has great potential for detailed investigation and understanding of the interactions of aromatic molecules in solution

  17. Spectroscopic Diagnosis of Excited-State Aromaticity: Capturing Electronic Structures and Conformations upon Aromaticity Reversal.

    Science.gov (United States)

    Oh, Juwon; Sung, Young Mo; Hong, Yongseok; Kim, Dongho

    2018-03-06

    Aromaticity, the special energetic stability derived from cyclic [4 n + 2]π-conjugated electronic structures, has been the topic of intense interest in chemistry because it plays a critical role in rationalizing molecular stability, reactivity, and physical/chemical properties. Recently, the pioneering work by Colin Baird on aromaticity reversal, postulating that aromatic (antiaromatic) character in the ground state reverses to antiaromatic (aromatic) character in the lowest excited triplet state, has attracted much scientific attention. The completely reversed aromaticity in the excited state provides direct insight into understanding the photophysical/chemical properties of photoactive materials. In turn, the application of aromatic molecules to photoactive materials has led to numerous studies revealing this aromaticity reversal. However, most studies of excited-state aromaticity have been based on the theoretical point of view. The experimental evaluation of aromaticity in the excited state is still challenging and strenuous because the assessment of (anti)aromaticity with conventional magnetic, energetic, and geometric indices is difficult in the excited state, which practically restricts the extension and application of the concept of excited-state aromaticity. Time-resolved optical spectroscopies can provide a new and alternative avenue to evaluate excited-state aromaticity experimentally while observing changes in the molecular features in the excited states. Time-resolved optical spectroscopies take advantage of ultrafast laser pulses to achieve high time resolution, making them suitable for monitoring ultrafast changes in the excited states of molecular systems. This can provide valuable information for understanding the aromaticity reversal. This Account presents recent breakthroughs in the experimental assessment of excited-state aromaticity and the verification of aromaticity reversal with time-resolved optical spectroscopic measurements. To

  18. Application of acetone acetals as water scavengers and derivatization agents prior to the gas chromatographic analysis of polar residual solvents in aqueous samples.

    Science.gov (United States)

    van Boxtel, Niels; Wolfs, Kris; Van Schepdael, Ann; Adams, Erwin

    2015-12-18

    The sensitivity of gas chromatography (GC) combined with the full evaporation technique (FET) for the analysis of aqueous samples is limited due to the maximum tolerable sample volume in a headspace vial. Using an acetone acetal as water scavenger prior to FET-GC analysis proved to be a useful and versatile tool for the analysis of high boiling analytes in aqueous samples. 2,2-Dimethoxypropane (DMP) was used in this case resulting in methanol and acetone as reaction products with water. These solvents are relatively volatile and were easily removed by evaporation enabling sample enrichment leading to 10-fold improvement in sensitivity compared to the standard 10μL FET sample volumes for a selection of typical high boiling polar residual solvents in water. This could be improved even further if more sample is used. The method was applied for the determination of residual NMP in an aqueous solution of a cefotaxime analogue and proved to be considerably better than conventional static headspace (sHS) and the standard FET approach. The methodology was also applied to determine trace amounts of ethylene glycol (EG) in aqueous samples like contact lens fluids, where scavenging of the water would avoid laborious extraction prior to derivatization. During this experiment it was revealed that DMP reacts quantitatively with EG to form 2,2-dimethyl-1,3-dioxolane (2,2-DD) under the proposed reaction conditions. The relatively high volatility (bp 93°C) of 2,2-DD makes it possible to perform analysis of EG using the sHS methodology making additional derivatization reactions superfluous. Copyright © 2015 Elsevier B.V. All rights reserved.

  19. Sorption of Aromatic Compounds with Copolymer Sorbent Materials Containing β-Cyclodextrin.

    Science.gov (United States)

    Wilson, Lee D; Mohamed, Mohamed H; Berhaut, Christopher L

    2011-08-29

    Urethane copolymer sorbent materials that incorporate β-cyclodextrin (CD) have been prepared and their sorption properties with chlorinated aromatic compounds (i.e., pentachlorophenol, 2,4-dichlorophenol and 2,4-dichlorophenoxy acetic acid) have been evaluated. The sorption properties of granular activated carbon (GAC) were similarly compared in aqueous solution at variable pH conditions. The sorbents displayed variable BET surface areas as follows: MDI-X copolymers (granular activated carbon (GAC ~10³ m²/g). The sorption capacities for the copolymers sorbents are listed in descending order, as follows: GAC > CDI-3 copolymer ≈ MDI-3 copolymer. The sorption capacity for the aromatic adsorbates with each sorbent are listed in descending order, as follows: 2,4-dichlorophenol > 2,4-dichlorophenoxy acetic acid > pentachlorophenol. In general, the differences in the sorption properties of the copolymer sorbents with the chlorinated organics were related to the following factors: (i) surface area of the sorbent; (ii) CD content and accessibility; and (iii) and the chemical nature of the sorbent material.

  20. Anion-π aromatic neutral tweezers complexes: are they stable in polar solvents?

    Science.gov (United States)

    Sánchez-Lozano, Marta; Otero, Nicolás; Hermida-Ramón, Jose M; Estévez, Carlos M; Mandado, Marcos

    2011-03-17

    The impact of the solvent environment on the stabilization of the complexes formed by fluorine (T-F) and cyanide (T-CN) substituted tweezers with halide anions has been investigated theoretically. The study was carried out using computational methodologies based on density functional theory (DFT) and symmetry adapted perturbation theory (SAPT). Interaction energies were obtained at the M05-2X/6-31+G* level. The obtained results show a large stability of the complexes in solvents with large dielectric constant and prove the suitability of these molecular tweezers as potential hosts for anion recognition in solution. A detailed analysis of the effects of the solvent on the electron withdrawing ability of the substituents and its influence on the complex stability has been performed. In particular, the interaction energy in solution was split up into intermonomer and solvent-complex terms. In turn, the intermonomer interaction energy was partitioned into electrostatic, exchange, and polarization terms. Polar resonance structures in T-CN complexes are favored by polar solvents, giving rise to a stabilization of the intermonomer interaction, the opposite is found for T-F complexes. The solvent-complex energy increases with the polarity of the solvent in T-CN complexes, nonetheless the energy reaches a maximum and then decreases slowly in T-F complexes. An electron density analysis was also performed before and after complexation, providing an explanation to the trends followed by the interaction energies and their different components in solution.

  1. On the mechanism of dechlorination of polychlorinated biphenyls (PCBs) induced by electron beam irradiation in aqueous and aqueous micellar solutions, transformer oil, and sediment

    International Nuclear Information System (INIS)

    Chaychian, M.; Silverman, J.; Al-Sheirkhly, M.

    2011-01-01

    Complete text of publication follows. The widespread release of PCBs into the environment presents a serious problem due to their persistence and toxicity. Ionizing radiation, such as gamma rays and high-energy electron beam, is remarkably effective in dechlorinating PCBs into biphenyls. The kinetics of the reductive dechlorination of PCBs in aqueous and aqueous micellar solutions and in transformer oil is being studied by pulse radiolysis and steady-state radiolysis. In aqueous micellar solutions, dichlori-, tetrachloro-, and decachlorobiphenyl congeners were solubilized in water using a commercially available non-ionic surfactant, Triton X-100, and subsequently pulse irradiated by electron accelerator using optical detection method. The reaction rate constant between decachlorobiphenyl and aqueous electrons e aq ·- , and Triton with e aq ·- in the 2% Triton solution, were measured as 2.6 x 10 9 Lmol -1 s -1 and 1.2 x 10 7 Lmol -1 s -1 , respectively. We have also measured in aqueous solutions, the reaction rate constant of e aq ·- with dichlorobiphenyl as 3.8 x 10 9 Lmol -1 s -1 . In aqueous-propanol, the reaction rate constants of e aq ·- with dichlorobiphenyl, tetrachlorobiphenyl, and dechachlorobiphenyl are 2 x 10 9 Lmol -1 s -1 , 3 x 10 9 Lmol -1 s -1 , and 7 x 10 9 Lmol -1 s -1 , respectively. In addition to the presence of PCBs as high-dielectric component, transformer oil contains many aromatic hydrocarbons; the most abundant being biphenyl, fluorine, and phenanthrene. Solvated electrons formed by irradiation of the oil react either with PCB to lead to dechlorination or with the aromatic hydrocarbons present in the oil to form radical anions. These species are shown to transfer an electron to chlorinated biphenyls relative rapidly, leading to dechlorination. The rate constants for several such reactions, determined in 2-propanol solutions, are in the range of 10 7 - 10 8 Lmol -1 s -1 . These rapid reactions explain why PCB can be dechlorinated in oil

  2. Exciplex fluorescence emission from simple organic intramolecular constructs in non-polar and highly polar media as model systems for DNA-assembled exciplex detectors.

    Science.gov (United States)

    Bichenkova, Elena V; Sardarian, Ali R; Wilton, Amanda N; Bonnet, Pascal; Bryce, Richard A; Douglas, Kenneth T

    2006-01-21

    Organic intramolecular exciplexes, N-(4-dimethylaminobenzyl)-N-(1-pyrenemethyl)amine (1) and N'-4-dimethylaminonaphthyl-N-(1-pyrenemethyl)amine (2), were used as model systems to reveal major factors affecting their exciplex fluorescence, and thus lay the basis for developing emissive target-assembled exciplexes for DNA-mounted systems in solution. These models with an aromatic pyrenyl hydrocarbon moiety as an electron acceptor appropriately connected to an aromatic dimethylamino electron donor component (N,N-dimethylaminophenyl or N,N-dimethylaminonaphthyl) showed strong intramolecular exciplex emission in both non-polar and highly polar solvents. The effect of dielectric constant on the maximum wavelength for exciplex emission was studied, and emission was observed for 1 and 2 over the full range of solvent from non-polar hydrocarbons up to N-methylformamide with a dielectric constant of 182. Quantum yields were determined for these intramolecular exciplexes in a range of solvents relative to that for Hoechst 33,258. Conformational analysis of 1 was performed both computationally and via qualitative 2D NMR using (1)H-NOESY experiments. The results obtained indicated the contribution of pre-folded conformation(s) to the ground state of 1 conducive to exciplex emission. This research provides the initial background for design of self-assembled, DNA-mounted exciplexes and underpins further development of exciplex-based hybridisation bioassays.

  3. 1H NMR analysis of the heteroassociation of antitumor antibiotics novotrone and actinomycin D in aqueous solution

    International Nuclear Information System (INIS)

    Evstigneev, M.P.; Rozvadovskaya, A.O.; Kisurkin, D.V.; Dehvis, D.B.; Veselkov, A.N.

    2004-01-01

    The heteroassociation of antitumor antibiotics novotrone (NOV) and actinomycin D (AMD) in aqueous solution has been studied by one- and two-dimensional 1 H-NMR spectroscopy (500 MHz) in order to elucidate the molecular mechanism of the action of antibiotics in combination. It has been shown that heterocomplexes become predominant in the mixed solution at r > 12. It is concluded that aromatic antibiotics (e. g. novotrone and actinomycin D) may form energetically stable heteroassociation complexes in aqueous solution and hence affect their medical-biological activity

  4. The leachability of carbon-14-labelled 3,4-benzopyrene from coal ash into aqueous systems

    NARCIS (Netherlands)

    Besemer, A.C.; Kanij, J.

    1984-01-01

    The leachability of polycyclic aromatic hydrocarbons from coal ash into aqueous systems was studied. Carbon-14-labeled 3,4-Benzopyrene (BaP) was deposited on coal fly ash by adsorption from the liquid phase in quantities of about 10 ??g/g ash. After a thermal treatment in air at 120??C for 2 hours

  5. Phenolic carbonyls undergo rapid aqueous photodegradation to form low-volatility, light-absorbing products

    Science.gov (United States)

    Smith, Jeremy D.; Kinney, Haley; Anastasio, Cort

    2016-02-01

    We investigated the aqueous photochemistry of six phenolic carbonyls - vanillin, acetovanillone, guaiacyl acetone, syringaldehyde, acetosyringone, and coniferyl aldehyde - that are emitted from wood combustion. The phenolic carbonyls absorb significant amounts of solar radiation and decay rapidly via direct photodegradation, with lifetimes (τ) of 13-140 min under Davis, CA winter solstice sunlight at midday (solar zenith angle = 62°). The one exception is guaiacyl acetone, where the carbonyl group is not directly connected to the aromatic ring: This species absorbs very little sunlight and undergoes direct photodegradation very slowly (τ > 103 min). We also found that the triplet excited states (3C*) of the phenolic carbonyls rapidly oxidize syringol (a methoxyphenol without a carbonyl group), on timescales of 1-5 h for solutions containing 5 μM phenolic carbonyl. The direct photodegradation of the phenolic carbonyls, and the oxidation of syringol by 3C*, both efficiently produce low volatility products, with SOA mass yields ranging from 80 to 140%. Contrary to most aliphatic carbonyls, under typical fog conditions we find that the primary sink for the aromatic phenolic carbonyls is direct photodegradation in the aqueous phase. In areas of significant wood combustion, phenolic carbonyls appear to be small but significant sources of aqueous SOA: over the course of a few hours, nearly all of the phenolic carbonyls will be converted to SOA via direct photodegradation, enhancing the POA mass from wood combustion by approximately 3-5%.

  6. Evaluation of Extraction Protocols for Simultaneous Polar and Non-Polar Yeast Metabolite Analysis Using Multivariate Projection Methods

    Directory of Open Access Journals (Sweden)

    Nicolas P. Tambellini

    2013-07-01

    Full Text Available Metabolomic and lipidomic approaches aim to measure metabolites or lipids in the cell. Metabolite extraction is a key step in obtaining useful and reliable data for successful metabolite studies. Significant efforts have been made to identify the optimal extraction protocol for various platforms and biological systems, for both polar and non-polar metabolites. Here we report an approach utilizing chemoinformatics for systematic comparison of protocols to extract both from a single sample of the model yeast organism Saccharomyces cerevisiae. Three chloroform/methanol/water partitioning based extraction protocols found in literature were evaluated for their effectiveness at reproducibly extracting both polar and non-polar metabolites. Fatty acid methyl esters and methoxyamine/trimethylsilyl derivatized aqueous compounds were analyzed by gas chromatography mass spectrometry to evaluate non-polar or polar metabolite analysis. The comparative breadth and amount of recovered metabolites was evaluated using multivariate projection methods. This approach identified an optimal protocol consisting of 64 identified polar metabolites from 105 ion hits and 12 fatty acids recovered, and will potentially attenuate the error and variation associated with combining metabolite profiles from different samples for untargeted analysis with both polar and non-polar analytes. It also confirmed the value of using multivariate projection methods to compare established extraction protocols.

  7. Polarization-Sensitive Resonance CSRS of Deoxy- and Oxyhaemoglobin

    NARCIS (Netherlands)

    Voroshilov, A.; Voroshilov, Artemy; Lucassen, Gerald; Lucassen, Gerald W.; Otto, Cornelis; Greve, Jan

    1995-01-01

    Polarization-sensitive coherent Stokes Raman scattering (CSRS) measurements of oxy- and deoxyhaemoglobin in aqueous solutions are reported. The excitation wavelengths used were chosen in the region of the Q absorption bands to achieve twofold electronic resonance. The dispersion profiles of all

  8. Synthesis and ATRP of novel fluorinated aromatic monomer with pendant sulfonate group

    DEFF Research Database (Denmark)

    Dimitrov, Ivaylo; Jankova Atanasova, Katja; Hvilsted, Søren

    2013-01-01

    Novel, fluorinated monomer with pendant sulfonate group was synthesized utilizing a two-step derivatization of 2,3,4,5,6-pentafluorostyrene (FS). The first step was a nucleophilic substitution of the fluorine atom in para position by hydroxyl group followed by sulfopropylation. The monomer...... was polymerized under aqueous ATRP conditions to yield phenyl-fluorinated aromatic homopolymer bearing pendant sulfonates on each repeating unit. Furthermore, this polymer was used as macroinitiator for the ATRP of poly(ethylene glycol) methacrylate. The polymers were characterized by 1H NMR, SEC and FTIR...

  9. Voltammetry study of quinoxaline in aqueous electrolytes

    International Nuclear Information System (INIS)

    Milshtein, Jarrod D.; Su, Liang; Liou, Catherine; Badel, Andres F.; Brushett, Fikile R.

    2015-01-01

    Organic compounds have recently received considerable attention as active materials in redox flow batteries (RFBs) due to their good electrochemical reversibility, high theoretical energy densities, and promise for low cost production. Until now, organic active material candidates for aqueous RFBs have been limited to the quinone family, a set of aromatic-derived organic molecules, distinguished by an even number of ketone (R−C(=O)−R′) groups. This work aims to elucidate and optimize the electrochemical behavior of quinoxaline, an organic molecule consisting of fused benzene and pyrazine rings, in aqueous electrolytes. More than 30 electrolytes are screened by cyclic voltammetry, and the five most promising electrolytes are investigated further using rotating disk voltammetry. Electrochemical behavior of quinoxaline shows pH dependent thermodynamics and reaction mechanisms, while chloride-containing supporting electrolytes greatly enhance solubility. This study sheds light on the promising characteristics of quinoxaline as a low potential compound for aqueous RFBs; quinoxaline has a redox potential of E° ≈ −0.02 V vs. RHE, is soluble up to ∼4.5 M in water, exhibits a two-electron transfer capability, and possesses a low molecular weight (130.15 g mol"−"1), resulting in a theoretical capacity of 410 mAh g"−"1.

  10. Aromatic chemical feedstocks from coal

    Energy Technology Data Exchange (ETDEWEB)

    Collin, G

    1982-06-01

    Liquid byproducts of coal carbonization meet some 25% of the world demand for aromatic chemicals, currently at approx. 30 million t/a, in particular 15% of the demand for benzene and over 95% of the demand for condensed aromatics and heteroaromatics. Industrial processing of the aromatic byproducts of coal pressure gasification is carried out to only a minor extent. Other methods that may be employed in future to obtain carbochemical aromatic compounds are solvolysis and supercritical gas extraction, the catalytic liquid-phase hydrogenation and hydropyrolysis of coal, which also permit recovery of benzene and homologues, phenols, and condensed and partially hydrogenated aromatics, and the synthesis of aromatics using methanol as the key compound. As with the present means of obtaining aromatic chemicals from coal, the processes that may in the future be applied on an industrial scale to obtain pure aromatics will only be economically feasible if linked with the manufacture of other mass products and combined with the present production of carbochemical aromatics.

  11. Aromatic raw materials from coal

    Energy Technology Data Exchange (ETDEWEB)

    Collin, G

    1982-06-01

    Liquid byproducts of coal carbonization meet some 25% of the world demand for aromatic chemicals, currently at approx. 30 million t/a, in particular 15% of the demand for benzene and over 95% of the demand for condensed aromatics and heteroaromatics. Industrial processing of the aromatic byproducts of coal pressure gasification is carried out to only a minor extent. Other methods that may be employed in future to obtain carbochemical aromatic compounds are solvolysis and supercritical gas extraction, the catalytic liquid-phase hydrogenation and hydropyrolysis of coal, which also permit recovery of benzene and homologues, phenols, and condensed and partially hydrogenated aromatics, and the synthesis of aromatics using methanol as the key compound. As with the present means of obtaining aromatic chemicals from coal, the processes that may in future be applied on an industrial scale to obtain pure aromatics will only be economically feasible if linked with the manufacture of other mass products and combined with the present production of carbochemical aromatics. (In German)

  12. Backflush HPLC for the isolation of polycyclic aromatic compounds - a comparative study

    Energy Technology Data Exchange (ETDEWEB)

    Oestman, C.E.; Colmsjoe, A.L.

    1987-12-01

    Semipreparative HPLC utilizing a polar bonded phase was applied to the isolation of polycyclic aromatic compounds (PAC) from complex samples using a backflush technique. Aminopropyl- and cyanopropyl-modified silica was tested. Aminopropyl-modified silica was found to be superior in achieving rapid, selective and non discriminating isolation of PAC. This was compared with the most commonly used isolation methods, dimethylsulfoxide (DMSO), dimethylformamide (DMF) and nitromethane liquid-liquid extractions, and silica and SephadexLH-20 open column chromatography. Strong discrimination of alkylated PAC and polycyclic aromatic nitrogen heterocyclics (PANH) was found for the liquid-liquid extractions and the LH-20 column chromatography. These comparisons were made using both standard compounds and a sample of used crank-case oil, indicating the necessity of using a real sample for evaluation of extraction methods. Recoveries of 42 PACs are reported.

  13. Biotransformation of polycyclic aromatic hydrocarbons in marine polychaetes

    DEFF Research Database (Denmark)

    Jørgensen, Anne; Giessing, Anders; Rasmussen, Lene Juel

    2008-01-01

    Deposit-feeding polychaetes constitute the dominant macrofauna in marine environments that tend to be depositional centers for organic matter and contaminants. Polychaetes are known to accumulate polycyclic aromatic hydrocarbons (PAHs) from both particulate and dissolved phases but less is known...... about the mechanisms underlying elimination of accumulated PAHs. An important pathway of elimination is through biotransformation which results in increased aqueous solubility of the otherwise hydrophobic PAHs. Biotransformation in marine polychaetes proceeds in a two phased process similar to those...... well studied in vertebrates, phase I enzymes belonging to the Cytochrome P450 (CYP) enzyme family, along with a few phase II enzymes have been identified in marine polychaetes. In this review we aim at highlighting advances in the mechanistic understanding of PAH biotransformation in marine polychaetes...

  14. Prenatal exposure to polycyclic aromatic hydrocarbons/aromatics, BDNF and child development

    International Nuclear Information System (INIS)

    Perera, Frederica; Phillips, David H.; Wang, Ya; Roen, Emily; Herbstman, Julie; Rauh, Virginia; Wang, Shuang; Tang, Deliang

    2015-01-01

    Objectives: Within a New York City (NYC) birth cohort, we assessed the associations between polycyclic aromatic hydrocarbon (PAH) and other aromatic DNA adducts and brain derived neurotrophic factor (BDNF) concentrations in umbilical cord blood, and neurodevelopment at age 2 years and whether BDNF is a mediator of the associations between PAH/aromatic-DNA adducts and neurodevelopment. Methods: PAH/aromatic-DNA adduct concentrations in cord blood were measured in 505 children born to nonsmoking African-American and Dominican women residing in NYC, and a subset was assessed for neurodevelopment at 2 years using the Bayley Scales of Infant Development Mental Development Index (MDI). A spectrum of PAH/aromatic-DNA adducts was measured using the 32 P-postlabeling assay; DNA adducts formed by benzo[a]pyrene (B[a]P), a representative PAH, were measured by High Performance Liquid Chromatography (HPLC)/fluorescence. BDNF mature protein in cord blood plasma was quantified by an ELISA. Multivariate regression analysis, adjusting for potential confounders, was conducted. Results: PAH/aromatic-DNA adduct concentration measured by postlabeling was inversely associated with BDNF concentration (p=0.02) and with MDI scores at 2 years (p=0.04). BDNF level was positively associated with MDI scores (p=0.003). Restricting to subjects having all three measures (PAH/aromatic-DNA adducts by postlabeling, MDI, and BDNF), results were similar but attenuated (p=0.13, p=0.05, p=0.01, respectively). Associations between B[a]P-DNA adducts and BDNF and B[a]P-DNA adducts and MDI at age 2 years were not significant. At age 3 years, the positive association of BDNF with MDI was not observed. Conclusions: The results at age 2 suggest that prenatal exposure to a spectrum of PAH/aromatic pollutants may adversely affect early neurodevelopment, in part by reducing BDNF levels during the fetal period. However, the same relationship was not seen at age 3. - Highlights: • Cord blood Polycyclic Aromatic

  15. Prenatal exposure to polycyclic aromatic hydrocarbons/aromatics, BDNF and child development

    Energy Technology Data Exchange (ETDEWEB)

    Perera, Frederica, E-mail: fpp1@columbia.edu [Department of Environmental Health Sciences, Mailman School of Public Health, Columbia University, 722 W. 168th St., New York, NY 10032 (United States); Columbia Center for Children' s Environmental Health, Columbia University, 722 W. 168th St., New York, NY 10032 (United States); Phillips, David H. [Analytical and Environmental Sciences Division, MRC-PHE Centre for Environment and Health, King' s College London, Franklin-Wilkins Building, London SE1 9NH (United Kingdom); Wang, Ya [Columbia Center for Children' s Environmental Health, Columbia University, 722 W. 168th St., New York, NY 10032 (United States); Department of Biostatistics, Mailman School of Public Health, Columbia University, 722 W. 168th St., New York, NY 10032 (United States); Roen, Emily; Herbstman, Julie [Department of Environmental Health Sciences, Mailman School of Public Health, Columbia University, 722 W. 168th St., New York, NY 10032 (United States); Columbia Center for Children' s Environmental Health, Columbia University, 722 W. 168th St., New York, NY 10032 (United States); Rauh, Virginia [Columbia Center for Children' s Environmental Health, Columbia University, 722 W. 168th St., New York, NY 10032 (United States); The Heilbrunn Department of Population and Family Health, Columbia University, 60 Haven Avenue, New York, NY 10032 (United States); Wang, Shuang [Columbia Center for Children' s Environmental Health, Columbia University, 722 W. 168th St., New York, NY 10032 (United States); Department of Biostatistics, Mailman School of Public Health, Columbia University, 722 W. 168th St., New York, NY 10032 (United States); Tang, Deliang [Department of Environmental Health Sciences, Mailman School of Public Health, Columbia University, 722 W. 168th St., New York, NY 10032 (United States); Columbia Center for Children' s Environmental Health, Columbia University, 722 W. 168th St., New York, NY 10032 (United States)

    2015-10-15

    Objectives: Within a New York City (NYC) birth cohort, we assessed the associations between polycyclic aromatic hydrocarbon (PAH) and other aromatic DNA adducts and brain derived neurotrophic factor (BDNF) concentrations in umbilical cord blood, and neurodevelopment at age 2 years and whether BDNF is a mediator of the associations between PAH/aromatic-DNA adducts and neurodevelopment. Methods: PAH/aromatic-DNA adduct concentrations in cord blood were measured in 505 children born to nonsmoking African-American and Dominican women residing in NYC, and a subset was assessed for neurodevelopment at 2 years using the Bayley Scales of Infant Development Mental Development Index (MDI). A spectrum of PAH/aromatic-DNA adducts was measured using the {sup 32}P-postlabeling assay; DNA adducts formed by benzo[a]pyrene (B[a]P), a representative PAH, were measured by High Performance Liquid Chromatography (HPLC)/fluorescence. BDNF mature protein in cord blood plasma was quantified by an ELISA. Multivariate regression analysis, adjusting for potential confounders, was conducted. Results: PAH/aromatic-DNA adduct concentration measured by postlabeling was inversely associated with BDNF concentration (p=0.02) and with MDI scores at 2 years (p=0.04). BDNF level was positively associated with MDI scores (p=0.003). Restricting to subjects having all three measures (PAH/aromatic-DNA adducts by postlabeling, MDI, and BDNF), results were similar but attenuated (p=0.13, p=0.05, p=0.01, respectively). Associations between B[a]P-DNA adducts and BDNF and B[a]P-DNA adducts and MDI at age 2 years were not significant. At age 3 years, the positive association of BDNF with MDI was not observed. Conclusions: The results at age 2 suggest that prenatal exposure to a spectrum of PAH/aromatic pollutants may adversely affect early neurodevelopment, in part by reducing BDNF levels during the fetal period. However, the same relationship was not seen at age 3. - Highlights: • Cord blood Polycyclic

  16. Substrate specific hydrolysis of aromatic and aromatic-aliphatic esters in orchid tissue cultures

    Directory of Open Access Journals (Sweden)

    Agnieszka Mironowicz

    2014-01-01

    Full Text Available We found that tissue cultures of higher plants were able, similarly as microorganisms, to transform low-molecular-weight chemical compounds. In tissue cultures of orchids (Cymbidium 'Saint Pierre' and Dendrobium phalaenopsis acetates of phenols and aromatic-aliphatic alcohols were hydrolyzed, whereas methyl esters of aromatic and aromatic-aliphatic acids did not undergo this reaction. Acetates of racemic aromatic-aliphatic alcohols were hydrolyzed with distinct enantiospecificity.

  17. EXTRACTION-CHROMATOGRAPHIC DETERMINATION OF GLUCOSE AND FRUCTOSE IN THE PRESENCE OF AROMATIC AMINO ACIDS

    Directory of Open Access Journals (Sweden)

    Y. I. Korenman

    2012-01-01

    Full Text Available The extraction of glucose and fructose from aqueous salt solutions containing aromatic amino acids (phenylalanine, tryptophan, tyrosine, hydrophilic solvents (aliphatic alcohols, alkyl acetates, ketones have been studied. The quantitative characteric of the process (the distribution coefficients, the degree of extraction, separation factors are calculeted. The dependence of distribution ratios of monosaccharides from the amino acid content in the solution has been established. A mobile phase for analysis of the concentrate by ascending thin layer chromatography have been developed.

  18. Sorption of Aromatic Compounds with Copolymer Sorbent Materials Containing β-Cyclodextrin

    Directory of Open Access Journals (Sweden)

    Lee D. Wilson

    2011-08-01

    Full Text Available Urethane copolymer sorbent materials that incorporate β-cyclodextrin (CD have been prepared and their sorption properties with chlorinated aromatic compounds (i.e., pentachlorophenol, 2,4-dichlorophenol and 2,4-dichlorophenoxy acetic acid have been evaluated. The sorption properties of granular activated carbon (GAC were similarly compared in aqueous solution at variable pH conditions. The sorbents displayed variable BET surface areas as follows: MDI-X copolymers (< 101 m2/g, CDI-X copolymers (< 101 m2/g, and granular activated carbon (GAC ~103 m2/g. The sorption capacities for the copolymers sorbents are listed in descending order, as follows: GAC > CDI-3 copolymer ≈ MDI-3 copolymer. The sorption capacity for the aromatic adsorbates with each sorbent are listed in descending order, as follows: 2,4-dichlorophenol > 2,4-dichlorophenoxy acetic acid > pentachlorophenol. In general, the differences in the sorption properties of the copolymer sorbents with the chlorinated organics were related to the following factors: (i surface area of the sorbent; (ii CD content and accessibility; and (iii and the chemical nature of the sorbent material.

  19. Ultrasonic Assisted Synthesis of Chromenes Catalyzed by Sodium Carbonate in Aqueous Media.

    Science.gov (United States)

    Sabbaghan, Maryam; Sofalgar, Pegah

    2015-01-01

    A simple, efficient, and environmentally benign procedure for the synthesis of 2-amino-4H-chromene ring has been achieved by the three-component reaction of an aromatic aldehyde, malononitrile and diverse enolizable C-H activated compound under ultrasound irradiation using sodium carbonate as a catalyst in aqueous media. Sodium carbonate as a natural salt, being available as an inexpensive catalyst combined with ultrasound method promoted this protocol in comparison to other methods and catalysts.

  20. A simple and efficient synthesis of imidazolo[1,2-a]pyridines using MgO in aqueous medium

    Directory of Open Access Journals (Sweden)

    S.V. Patil

    2016-11-01

    Full Text Available Various imidazolo[1,2-a]pyridines were synthesized from amino pyridines and aromatic phenacyl bromides by one step process in the presence of MgO in aqueous medium at room temperature. The salient feature of this method includes mild conditions, short reaction time, high yields, easy purification and simple procedure.

  1. Hydrogen Bonded Supramolecular Polymers in Both Apolar and Aqueous Media: Self-Assembly and Reversible Conversion of Vesicles and Gels%Hydrogen Bonded Supramolecular Polymers in Both Apolar and Aqueous Media: Self-Assembly and Reversible Conversion of Vesicles and Gels

    Institute of Scientific and Technical Information of China (English)

    杜平; 孔军; 王贵涛; 赵新; 李光玉; 蒋锡夔; 黎占亭

    2011-01-01

    In a preliminary letter (Tetrahedron Lett. 2010, 51, 188), we reported two new hydrazide-based quadruple hydrogen-bonding motifs, this is, two monopodal (la and lb) and five dipodal (2a, 2b and 3a--3c) aromatic hydrazide derivatives, and the formation of supramolecular polymers and vesicles from the dipodal motifs in hydrocarbons. In this paper, we present a full picture on the properties of these hydrogen-bonding motifs with an emphasis on their self-assembling behaviors in aqueous media. SEM, AFM, TEM and fluorescent micrographs indicate that all the dipodal compounds also form vesicles in polar methanol and water-methanol (up to 50% of water) mixtures. Control experiments show that lb does not form vesicles in same media. Addition of lb to the solution of the dipodal compounds inhibits the latter's capacity of forming vesicles. At high concentrations, 3b and 3c also gelate discrete solvents, including hydrocarbons, esters, methanol, and methanol-water mixture. Concentration-dependent SEM investigations reveal that the vesicles of 3b and 3c fuse to form gels and the gel of 3c can de-aggregate to form the vesicles reversibly.

  2. Aromatic Side Chain Water-to-Lipid Transfer Free Energies Show a Depth Dependence across the Membrane Normal.

    Science.gov (United States)

    McDonald, Sarah K; Fleming, Karen G

    2016-06-29

    Quantitating and understanding the physical forces responsible for the interactions of biomolecules are fundamental to the biological sciences. This is especially challenging for membrane proteins because they are embedded within cellular bilayers that provide a unique medium in which hydrophobic sequences must fold. Knowledge of the energetics of protein-lipid interactions is thus vital to understand cellular processes involving membrane proteins. Here we used a host-guest mutational strategy to calculate the Gibbs free energy changes of water-to-lipid transfer for the aromatic side chains Trp, Tyr, and Phe as a function of depth in the membrane. This work reveals an energetic gradient in the transfer free energies for Trp and Tyr, where transfer was most favorable to the membrane interfacial region and comparatively less favorable into the bilayer center. The transfer energetics follows the concentration gradient of polar atoms across the bilayer normal that naturally occurs in biological membranes. Additional measurements revealed nearest-neighbor coupling in the data set are influenced by a network of aromatic side chains in the host protein. Taken together, these results show that aromatic side chains contribute significantly to membrane protein stability through either aromatic-aromatic interactions or placement at the membrane interface.

  3. Engineering Aromatic-Aromatic Interactions To Nucleate Folding in Intrinsically Disordered Regions of Proteins.

    Science.gov (United States)

    Balakrishnan, Swati; Sarma, Siddhartha P

    2017-08-22

    Aromatic interactions are an important force in protein folding as they combine the stability of a hydrophobic interaction with the selectivity of a hydrogen bond. Much of our understanding of aromatic interactions comes from "bioinformatics" based analyses of protein structures and from the contribution of these interactions to stabilizing secondary structure motifs in model peptides. In this study, the structural consequences of aromatic interactions on protein folding have been explored in engineered mutants of the molten globule protein apo-cytochrome b 5 . Structural changes from disorder to order due to aromatic interactions in two variants of the protein, viz., WF-cytb5 and FF-cytb5, result in significant long-range secondary and tertiary structure. The results show that 54 and 52% of the residues in WF-cytb5 and FF-cytb5, respectively, occupy ordered regions versus 26% in apo-cytochrome b 5 . The interactions between the aromatic groups are offset-stacked and edge-to-face for the Trp-Phe and Phe-Phe mutants, respectively. Urea denaturation studies indicate that both mutants have a C m higher than that of apo-cytochrome b 5 and are more stable to chaotropic agents than apo-cytochrome b 5 . The introduction of these aromatic residues also results in "trimer" interactions with existing aromatic groups, reaffirming the selectivity of the aromatic interactions. These studies provide insights into the aromatic interactions that drive disorder-to-order transitions in intrinsically disordered regions of proteins and will aid in de novo protein design beyond small peptide scaffolds.

  4. Pro-aromatic and anti-aromatic π-conjugated molecules: an irresistible wish to be diradicals

    KAUST Repository

    Zeng, Zebing

    2015-01-01

    © 2015 The Royal Society of Chemistry. Aromaticity is an important concept to understand the stability and physical properties of π-conjugated molecules. Recent studies on pro-aromatic and anti-aromatic molecules revealed their irresistible tendency to become diradicals in the ground state. Diradical character thus becomes another very important concept and it is fundamentally correlated to the physical (optical, electronic and magnetic) properties and chemical reactivity of most of the organic optoelectronic materials. Molecules with distinctive diradical character show unique properties which are very different from those of traditional closed-shell π-conjugated systems, and thus they have many potential applications in organic electronics, spintronics, non-linear optics and energy storage. This critical review first introduces the fundamental electronic structure of Kekulé diradicals within the concepts of anti-aromaticity and pro-aromaticity in the context of Hückel aromaticity and diradical character. Then recent research studies on various stable/persistent diradicaloids based on pro-aromatic and anti-aromatic compounds are summarized and discussed with regard to their synthetic chemistry, physical properties, structure-property relationships and potential material applications. A summary and personal perspective is given at the end.

  5. Redox shuttles for overcharge protection of lithium batteries

    Science.gov (United States)

    Amine, Khalil; Chen, Zonghai; Wang, Qingzheng

    2010-12-14

    The present invention is generally related to electrolytes containing novel redox shuttles for overcharge protection of lithium-ion batteries. The redox shuttles are capable of thousands hours of overcharge tolerance and have a redox potential at about 3-5.5 V vs. Li and particularly about 4.4-4.8 V vs. Li. Accordingly, in one aspect the invention provides electrolytes comprising an alkali metal salt; a polar aprotic solvent; and a redox shuttle additive that is an aromatic compound having at least one aromatic ring with four or more electronegative substituents, two or more oxygen atoms bonded to the aromatic ring, and no hydrogen atoms bonded to the aromatic ring; and wherein the electrolyte solution is substantially non-aqueous. Further there are provided electrochemical devices employing the electrolyte and methods of making the electrolyte.

  6. Electrochemical behavior of uranyl in anhydrous polar organic media

    Energy Technology Data Exchange (ETDEWEB)

    Burn, Adam G.; Nash, Kenneth L. [Washington State Univ., Pullmann, WA (United States). Dept. of Chemistry

    2017-09-01

    Weak complexes between pentavalent and hexavalent actinyl cations have been reported to exist in acidic, non-complexing high ionic strength aqueous media. Such ''cation-cation complexes'' were first identified in the context of actinide-actinide redox reactions in acidic aqueous media relevant to solvent extraction-based separation systems, hence their characterization is of potential interest for advanced nuclear fuel reprocessing. This chemistry could be relevant to efforts to develop advanced actinide separations based on the upper oxidation states of americium, which are of current interest. In the present study, the chemical behavior of pentavalent uranyl was examined in non-aqueous, aprotic polar organic solvents (propylene carbonate and acetonitrile) to determine whether UO{sub 2}{sup +} cations generated at the reducing working electrode surface would interact with the UO{sub 2}{sup 2+} cations in the bulk phase to form cation-cation complexes in such media. In magnesium perchlorate media, the electrolyte adsorbed onto the working electrode surface and interfered with the uranyl reduction/diffusion process through an ECE (electron transfer/chemical reaction/electron transfer) mechanism. In parallel studies of uranyl redox behavior in tetrabutylammonium hexafluorophosphate solutions, an EC (electron transfer/chemical reaction) mechanism was observed in the cyclic voltammograms. Ultimately, no conclusive electrochemical evidence demonstrated uranyl cation-cation interactions in the non-aqueous, aprotic polar organic solvent solutions, though the results reported do not completely rule out the presence of UO{sub 2}{sup +}.UO{sub 2}{sup 2+} complexes.

  7. Bacterial degradation of monocyclic aromatic amines

    Directory of Open Access Journals (Sweden)

    Pankaj Kumar Arora

    2015-08-01

    Full Text Available Aromatic amines are an important group of industrial chemicals, which are widely used for manufacturing of dyes, pesticides, drugs, pigments, and other industrial products. These compounds have been considered highly toxic to human beings due to their carcinogenic nature. Three groups of aromatic amines have been recognized: monocyclic, polycyclic and heterocyclic aromatic amines. Bacterial degradation of several monocyclic aromatic compounds has been studied in a variety of bacteria, which utilizes monocyclic aromatic amines as their sole source of carbon and energy. Several degradation pathways have been proposed and the related enzymes and genes have also been characterized. Many reviews have been reviewed toxicity of monocyclic aromatic amines; however, there is lack of review on biodegradation of monocyclic aromatic amines. The aim of this review is to summarize bacterial degradation of monocyclic aromatic amines. This review will increase our current understanding of biochemical and molecular basis of bacterial degradation of monocyclic aromatic amines.

  8. Thermodynamic constrains for life based on non-aqueous polar solvents on free-floating planets.

    Science.gov (United States)

    Badescu, Viorel

    2011-02-01

    Free-floating planets (FFPs) might originate either around a star or in solitary fashion. These bodies can retain molecular gases atmospheres which, upon cooling, have basal pressures of tens of bars or more. Pressure-induced opacity of these gases prevents such a body from eliminating its internal radioactive heat and its surface temperature can exceed for a long term the melting temperature of a life-supporting solvent. In this paper two non-aqueous but still polar solvents are considered: hydrogen sulfide and ammonia. Thermodynamic requirements to be fulfilled by a hypothetic gas constituent of a life-supporting FFP's atmosphere are studied. The three gases analyzed here (nitrogen, methane and ethane) are candidates. We show that bodies with ammonia oceans are possible in interstellar space. This may happen on FFPs of (significantly) smaller or larger mass than the Earth. Generally, in case of FFP smaller in size than the Earth, the atmosphere exhibits a convective layer near the surface and a radiative layer at higher altitudes while the atmosphere of FFPs larger in size than Earth does not exhibit a convective layer. The atmosphere mass of a life-hosting FFP of Earth size is two or three orders of magnitude larger than the mass of Earth atmosphere. For FFPs larger than the Earth and specific values of surface pressure and temperature, there are conditions for condensation (in the ethane atmosphere). Some arguments induce the conclusion than the associated surface pressures and temperatures should be treated with caution as appropriate life conditions.

  9. Analysis of aromatic amines in water samples by liquid-liquid-liquid microextraction with hollow fibers and high-performance liquid chromatography.

    Science.gov (United States)

    Zhao, Limian; Zhu, Lingyan; Lee, Hian Kee

    2002-07-19

    Liquid-liquid-liquid microextraction (LLLME) with hollow fibers in high-performance liquid chromatography (HPLC) has been applied as a rapid and sensitive quantitative method for the detection of four aromatic amines (3-nitroaniline, 4-chloroaniline, 4-bromoaniline and 3,4-dichloroaniline) in environmental water samples. The preconcentration procedure was induced by the pH difference inside and outside the hollow fiber. The target compounds were extracted from 4-ml aqueous sample (donor solution, pH approximately 13) through a microfilm of organic solvent (di-n-hexyl ether), immobilized in the pores of a hollow fiber (1.5 cm length x 0.6 mm I.D.), and finally into 4 microl of acid acceptor solution inside the fiber. After a prescribed period of time, the acceptor solution inside the fiber was withdrawn into the microsyringe and directly injected into the HPLC system for analysis. Factors relevant to the extraction procedure were studied. Up to 500-fold enrichment of analytes could be obtained under the optimized conditions (donor solution: 0.1 M sodium hydroxide solution with 20% sodium chloride and 2% acetone; organic phase: di-n-hexyl ether; acceptor solution: 0.5 M hydrochloric acid and 500 mM 18-crown-6 ether; extraction time of 30 min; stirring at 1,000 rev./min). The procedure also served as a sample clean-up step. The influence of humic acid on the extraction efficiency was also investigated, and more than 85% relative recoveries of the analytes at two different concentrations (20 and 100 microg/l) were achieved at various concentration of humic acid. This technique is a low cost, simple and fast approach to the analysis of polar compounds in aqueous samples.

  10. Activity-Based Approach for Teaching Aqueous Solubility, Energy, and Entropy

    Science.gov (United States)

    Eisen, Laura; Marano, Nadia; Glazier, Samantha

    2014-01-01

    We describe an activity-based approach for teaching aqueous solubility to introductory chemistry students that provides a more balanced presentation of the roles of energy and entropy in dissolution than is found in most general chemistry textbooks. In the first few activities, students observe that polar substances dissolve in water, whereas…

  11. Polar Compounds Isolated from the Leaves of Albertisia delagoensis (Menispermaceae

    Directory of Open Access Journals (Sweden)

    Jia Li

    2011-11-01

    Full Text Available Aqueous infusions of the leaves of the shrub Albertisia delagoensis (Menispermaceae are used in South Africa in traditional Zulu medicine to alleviate a variety of symptoms, including fever, and intestinal problems. We report the analysis of such an aqueous extract using the HPLC-NMR technique. A number of polar compounds were identified, including proto-quercitol, nicotinic acid, allantoic acid, 3,4-dihydroxy-benzoic acid, phthalic acid and the aporphine alkaloid derivative roemrefidine. Allantoic acid and roemrefidine have been fully characterised by 1H- and 13C-NMR and mass spectrometry. Earlier reports of antiplasmodial activity of roemrefidine and of A. delagoensis extracts are correlated with this study and with the antipyretic properties of neutral aqueous extracts.

  12. Theoretical studies of the structures and local aromaticity of conjugated polycyclic hydrocarbons using three aromatic indices

    Science.gov (United States)

    Sakai, Shogo; Kita, Yuki

    2013-07-01

    The structures and local aromaticity of some conjugated polycyclic hydrocarbons (from the butadienoid, acene, and phenylene series) are studied using ab initio MO and density functional methods. The aromaticities of the molecules are estimated using three indices: the nucleus-independent chemical shift (NICS), the harmonic oscillator model of aromaticity (HOMA), and the index of deviation from aromaticity (IDA). Assessment of the relationships between the structures and the aromatic indices shows that the IDA values correspond best to the characteristics of the conjugated polycyclic hydrocarbon structures.

  13. Adsorption of aromatic compounds by carbonaceous adsorbents: a comparative study on granular activated carbon, activated carbon fiber, and carbon nanotubes.

    Science.gov (United States)

    Zhang, Shujuan; Shao, Ting; Kose, H Selcen; Karanfil, Tanju

    2010-08-15

    Adsorption of three aromatic organic compounds (AOCs) by four types of carbonaceous adsorbents [a granular activated carbon (HD4000), an activated carbon fiber (ACF10), two single-walled carbon nanotubes (SWNT, SWNT-HT), and a multiwalled carbon nanotube (MWNT)] with different structural characteristics but similar surface polarities was examined in aqueous solutions. Isotherm results demonstrated the importance of molecular sieving and micropore effects in the adsorption of AOCs by carbonaceous porous adsorbents. In the absence of the molecular sieving effect, a linear relationship was found between the adsorption capacities of AOCs and the surface areas of adsorbents, independent of the type of adsorbent. On the other hand, the pore volume occupancies of the adsorbents followed the order of ACF10 > HD4000 > SWNT > MWNT, indicating that the availability of adsorption site was related to the pore size distributions of the adsorbents. ACF10 and HD4000 with higher microporous volumes exhibited higher adsorption affinities to low molecular weight AOCs than SWNT and MWNT with higher mesopore and macropore volumes. Due to their larger pore sizes, SWNTs and MWNTs are expected to be more efficient in adsorption of large size molecules. Removal of surface oxygen-containing functional groups from the SWNT enhanced adsorption of AOCs.

  14. Cyano-containing ionic liquids for the extraction of aromatic hydrocarbons from an aromatic/aliphatic mixture

    NARCIS (Netherlands)

    Meindersma, G.W.; Haan, de A.B.

    2012-01-01

    Ionic liquids can replace conventional solvents in aromatic/aliphatic extractions, if they have higher aromatic distribution coefficients and higher or similar aromatic/aliphatic selectivities. Also physical properties, such as density and viscosity, must be taken into account if a solvent is

  15. The influence of non-polar lipids on tear film dynamics

    KAUST Repository

    Bruna, M.; Breward, C.  J.  W.

    2014-01-01

    © 2014 Cambridge University Press. In this paper we examine the effect that physiological non-polar lipids, residing on the surface of an aqueous tear film, have on the film evolution. In our model we track the evolution of the thickness of the non

  16. Bacterial Degradation of Aromatic Compounds

    Directory of Open Access Journals (Sweden)

    Qing X. Li

    2009-01-01

    Full Text Available 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.

  17. Sorption behavior of charged and neutral polar organic compounds on solid phase extraction materials: which functional group governs sorption?

    NARCIS (Netherlands)

    Bäuerlein, P.S.; Mansell, J.E.; ter Laak, T.L.; de Voogt, P.

    2012-01-01

    Numerous polar anthropogenic organic chemicals have been found in the aqueous environment. Solid phase extraction (SPE) has been applied for the isolation of these from aqueous matrices, employing various materials. Nevertheless, little is known about the influence of functional groups on the

  18. Aromater i drikkevand

    DEFF Research Database (Denmark)

    Nyeland, B. A.; Hansen, A. B.

    DMU har den 10. Juni 1997 afholdt en præstationsprøvning: Aromater i drikkevand. Der deltog 21 laboratorier i præstationsprøvningen. Prøvningen omfattede 6 vandige prøver og 6 ampuller indeholdende 6 aromater. Laboratorierne spikede de tilsendte vandprøver med indholdet fra ampullerne...

  19. Investigation of the atmospheric behavior of dicarboxylic acids and other polar organic aerosol constituents

    International Nuclear Information System (INIS)

    Limbeck, A.

    2001-05-01

    The objective of the present work was to improve the present knowledge about the atmospheric behavior of polar organic aerosol constituents with special respect to dicarboxylic acids. To enable the simultaneous determination of polar organic compounds in atmospheric samples like aerosol or precipitation samples (atmospheric hydrometeors) a new GCMS method was developed. Almost all classes of oxygenated organic compounds like mono- and dicarboxylic acids, aldehydes, alcohols or polar aromatic compounds like phthalates could be determined with only one sample preparation scheme. The separation into two classes of organic compounds with different polarity was performed using solid phase extraction. After a sample pre-treatment of the derived fractions, including esterification of the acids and extraction with cyclohexane, the samples were analyzed with a GCMS system. The new method was applied for the analysis of simultaneously collected interstitial aerosol and cloud water samples from a continental background site in Central Europe (Sonnblick Observatory, located at 3106-m elevation in the Austrian Alps). In all samples a large variety of mono- and dicarboxylic acids were identified and quantified, together with some aldehydes, alcohols and aromatic compounds. Using the obtained data set, for the first time in-cloud scavenging efficiencies for dicarboxylic acids, monocarboxylic acids, and other polar organic compounds were calculated. The results were compared to sulfate, which exhibited an average scavenging efficiency of 0.94. In the last part of the present work the results from laboratory and field investigations conducted with the intention to yield an improved sampling technique for the correction of the positive sampling artifact (adsorption of gas phase organics onto the filter substrate) were presented. (author)

  20. Photochemical coupling of 5-bromouracil to tryptophan, tyrosine and histidine, peptide-like derivatives in aqueous fluid solution

    International Nuclear Information System (INIS)

    Dietz, T.M.; Koch, T.H.

    1987-01-01

    Direct irradiation of 5-bromouracil (BU) in aqueous fluid solution in the presence of tryptophan (trp), tyrosine (tyr) or histidine (his) derivatives using a XeCl excimer laser at 308 nm yielded photocoupling of BU to the aromatic ring of each amino acid. Irradiation of BU at 308 nm most likely results in excitation of the n-π* transition, intersystem crossing to the triplet manifold, and coupling via electron transfer from the aromatic amino acid. The coupling observed was regiospecific between the 5-position of uracil (U) and the 2-position of the indole and phenol rings and the 5-position of the imidazole ring of the respective amino acids. Quantum yields of photocoupling to BU ranged from 1 x 10 -3 to 7 x 10 -3 and paralleled known rates of electron transfer and ionization potentials of the aromatic rings. The photocoupling between BU and some of the aromatic amino acid peptide-like derivatives possibly mimics photocrosslinking of BU-DNA to associated proteins, a potentially useful photoreaction for studying nucleic acid-protein interactions. Formation of crosslinks of the type proposed here might be detected by the characteristic fluorescence emission of the uracil amino acid adducts. (author)

  1. Fluorescence method for enzyme analysis which couples aromatic amines with aromatic aldehydes

    Science.gov (United States)

    Smith, R.E.; Dolbeare, F.A.

    1980-10-21

    Analysis of proteinases is accomplished using conventional amino acid containing aromatic amine substrates. Aromatic amines such as 4-methoxy-2-naphthylamine (4M2NA), 2-naphthylamine, aminoisophthalic acid dimethyl ester, p-nitroaniline, 4-methoxy-1-aminofluorene and coumarin derivatives resulting from enzymatic hydrolysis of the substrate couples with aromatic aldehydes such as 5-nitrosalicylaldehyde (5-NSA), benzaldehyde and p-nitrobenzaldehyde to produce Schiff-base complexes which are water insoluble. Certain Schiff-base complexes produce a shift from blue to orange-red (visible) fluorescence. Such complexes are useful in the assay of enzymes. No Drawings

  2. Detection of Microbial Growth on Polycyclic Aromatic Hydrocarbons in Microtiter Plates by Using the Respiration Indicator WST-1

    OpenAIRE

    Johnsen, Anders R.; Bendixen, Karen; Karlson, Ulrich

    2002-01-01

    We have developed a microtiter plate method for screening a large number of bacterial isolates for the ability to grow on different crystalline polycyclic aromatic hydrocarbons (PAHs). Growth on PAHs cannot easily be determined with standard growth assays because of the very low aqueous solubility and bioavailability of the PAHs. Our microtiter plate assay utilizes a new water-soluble respiration indicator, WST-1 {4-[3-(4-iodophenyl)-2-(4-nitrophenyl)-2H-5-tetrazolio]-1,3-benzene disulfonate}...

  3. Production of a transparent lavender flavour nanocapsule aqueous solution and pyrolysis characteristics of flavour nanocapsule

    OpenAIRE

    Zhu, Guangyong; Xiao, Zuobing; Zhou, Rujun; Feng, Nienie

    2014-01-01

    Flavour plays an important role and has been widely used in many products. Usually, the components of flavour are volatile and the sensory perception can be changed as a result of volatilization, heating, oxidation and chemical interactions. Encapsulation can prevent the loss of volatile aromatic ingredients, provide protection and enhance the stability of the core materials. This work concentrated on production of a transparent lavender flavour nanocapsule aqueous solution. The results showe...

  4. Influence of Tunisian aromatic plants on the prevention of oxidation in soybean oil under heating and frying conditions.

    Science.gov (United States)

    Saoudi, Salma; Chammem, Nadia; Sifaoui, Ines; Bouassida-Beji, Maha; Jiménez, Ignacio A; Bazzocchi, Isabel L; Silva, Sandra Diniz; Hamdi, Moktar; Bronze, Maria Rosário

    2016-12-01

    The aim of this study was to improve the oxidative stability of soybean oil by using aromatic plants. Soybean oil flavored with rosemary (ROS) and soybean oil flavored with thyme (THY) were subjected to heating for 24h at 180°C. The samples were analyzed every 6h for their total polar compounds, anisidine values, oxidative stability and polyphenols content. The tocopherols content was determined and volatile compounds were also analyzed. After 24h of heating, the incorporation of these plants using a maceration process reduced the polar compounds by 69% and 71% respectively, in ROS and THY compared to the control. Until 6h of heating, the ROS kept the greatest oxidative stability. The use of the two extracts preserves approximately 50% of the total tocopherols content until 18h for the rosemary and 24h for the thyme flavored oils. Volatile compounds known for their antioxidant activity were also detected in the formulated oils. Aromatic plants added to the soybean oil improved the overall acceptability of potato crisps (p<0.05) until the fifteenth frying. Copyright © 2016 Elsevier Ltd. All rights reserved.

  5. Efficient and Selective Reduction of Aromatic Nitro Compounds to Aromatic Amines by NbCl{sub 5}/Indium System

    Energy Technology Data Exchange (ETDEWEB)

    Yoo, Byung Woo; Kim, Duckil; Kim, Hyung Min; Kang, Sung Ho [Korea Univ., Seoul (Korea, Republic of)

    2012-09-15

    -selective reduction of aromatic nitro compounds in the presence of the above-mentioned functional groups. After screening the reaction conditions, THF has been found to be the most suitable solvent for the reaction in terms of reaction time and yield. We investigated that the use of NbCl{sub 5}/Zn in place of NbCl{sub 5}/In is also equally effective but require slight longer reaction time and lower yield as compared to NbCl{sub 5}/In (Table 1). Thus, we have been able to demonstrate the utility of easily accessible NbCl{sub 5}/In system as a convenient reagent for effecting chemo-selective reduction of aromatic nitro compounds. Although the role of niobium(V) chloride is still not clarified, it is assumed that reduction of niobium(V) chloride with indium provides low-valent niobium species, which are involved in complexation with the substrates. The reduction probably proceeds by a reductive cleavage of polarized N.O bonds through a single electron transfer from indium metal to the niobium-substrate complex due to the high oxophilic nature of the niobium species. The reducing property exhibited by metal-metal salt combinations proceeds through transfer of one electron from the metal surface to the substrate. We believe that the present procedure using NbCl{sub 5}/In system proceeds through a SET (single electron transfer) process. The notable advantages of this methodology are mild reaction condition, simple manipulation, high yield, and tolerance of various functional groups. In conclusion, we have demonstrated that the NbCl{sub 5}/In system mediates an efficient and mild reduction of aromatic nitro compounds to the corresponding amines. Although the scope and limitations were not fully established, the present method could be a practical alternative to the conventional method. Further work on the application of the NbCl{sub 5}/In system is currently in progress.

  6. Some aspects of synergistic extraction of actinides and lanthanides from mixed aqueous-organic media

    International Nuclear Information System (INIS)

    Shukla, J.P.; Subramanian, M.S.

    1981-01-01

    Various aspects of the synergistic extraction and separation of actinides and lanthanides from mixed aqueous-organic solutions (polar media) have been reviewed. Notable recent developments as well as its current status in solvent extraction systems where the aqueous acidic phase contains an organic solvent which is completely miscible with water, are presented briefly. In general, extraction increases in the presence of an organic component. The less polar the additive, the higher is the tendency to form neutral metal complexes which ultimately brings about an increase in the extraction. In a polar media, synergism has mostly been observed, though antagonism is not uncommon. An attempt has been made to classify the factors that play an important role in polar phase extractions. Also, their influence particularly on the extractability of actinides and lanthanides is discussed. The discussion is limited to the factors affecting the extraction equilibria, effect of dielectric constant of the polar medium, solvation of the extracting agent and to the composition and stability of the metal complex in the organic phase. Hydroxyl (OHsup(-)) bearing organic additives, e.g. alcohols, and solvents not containing the hydroxyl group such as acetone, dimethylsulphoxide, tetrahydrofuran, amides and acetonitrile etc. are the two major classes of organic additives considered in these studies. Generally, synergistic effect in extraction of the ion-association (TBP, TOPO, sulphoxides etc.) or anion exchange (amines etc.) type is relatively more pronounced compared to other extractions. A tabular summary concerning extraction of actinides and lanthanides from polar media is appended for ready reference. (author)

  7. Designer solvents for the extraction of glycols and alcohols from aqueous streams

    NARCIS (Netherlands)

    Garcia Chavez, L.Y.

    2013-01-01

    The separation of polar compounds from aqueous streams is one of the most energy intensive operations within the chemical industry, because of the formation of hydrogen bonds that should be broken and the high heat of vaporization of water. Important bulk chemicals like glycols and alcohols produced

  8. Hofmeister effect on the interfacial free energy of aliphatic and aromatic surfaces studied by chemical force microscopy.

    Science.gov (United States)

    Patete, Jonathan; Petrofsky, John M; Stepan, Jeffery; Waheed, Abdul; Serafin, Joseph M

    2009-01-15

    This work describes chemical force microscopy (CFM) studies of specific-ion effects on the aqueous interfacial free energy of hydrophobic monolayers. CFM measurements allow for the characterization of interfacial properties on length scales below 100 nm. The ions chosen span the range of the Hofmeister series, from the kosmotropic Na(2)SO(4) to the chaotropic NaSCN. The salt concentrations used are typical of many laboratory processes such as protein crystallization, 2-3 M. Both aliphatic (terminal methyl) and aromatic (terminal phenyl) monolayers were examined, and rather pronounced differences were observed between the two cases. The specific-ion dependence of the aliphatic monolayer closely follows the Hofmeister series, namely the chaotropic ions lowered the interfacial free energy and the kosmotropic ions increased the interfacial free energy. However, the aromatic monolayer had significant deviations from the Hofmeister series. Possible origins for this difference are discussed.

  9. Specific determination of 20 primary aromatic amines in aqueous food simulants by liquid chromatography-electrospray ionization-tandem mass spectrometry

    DEFF Research Database (Denmark)

    Mortensen, Sarah Kelly; Trier, Xenia Thorsager; Foverskov, Annie

    2005-01-01

    A multi-analyte method without any pre-treatment steps using reversed-phase liquid chromatography-electrospray ionization-tandem mass spectrometry (LC-ESI-MS/MS) was developed and applied for the determination of 20 primary aromatic amines (PAA) associated with polyurethane (PUR) products or azo...

  10. Noncomparative scaling of aromaticity through electron itinerancy

    International Nuclear Information System (INIS)

    Paul, Satadal; Goswami, Tamal; Misra, Anirban

    2015-01-01

    Aromaticity is a multidimensional concept and not a directly observable. These facts have always stood in the way of developing an appropriate theoretical framework for scaling of aromaticity. In the present work, a quantitative account of aromaticity is developed on the basis of cyclic delocalization of π-electrons, which is the phenomenon leading to unique features of aromatic molecules. The stabilization in molecular energy, caused by delocalization of π-electrons is obtained as a second order perturbation energy for archetypal aromatic systems. The final expression parameterizes the aromatic stabilization energy in terms of atom to atom charge transfer integral, onsite repulsion energy and the population of spin orbitals at each site in the delocalized π-electrons. An appropriate computational platform is framed to compute each and individual parameter in the derived equation. The numerical values of aromatic stabilization energies obtained for various aromatic molecules are found to be in close agreement with available theoretical and experimental reports. Thus the reliable estimate of aromaticity through the proposed formalism renders it as a useful tool for the direct assessment of aromaticity, which has been a long standing problem in chemistry

  11. Three-dimensional aromatic networks.

    Science.gov (United States)

    Toyota, Shinji; Iwanaga, Tetsuo

    2014-01-01

    Three-dimensional (3D) networks consisting of aromatic units and linkers are reviewed from various aspects. To understand principles for the construction of such compounds, we generalize the roles of building units, the synthetic approaches, and the classification of networks. As fundamental compounds, cyclophanes with large aromatic units and aromatic macrocycles with linear acetylene linkers are highlighted in terms of transannular interactions between aromatic units, conformational preference, and resolution of chiral derivatives. Polycyclic cage compounds are constructed from building units by linkages via covalent bonds, metal-coordination bonds, or hydrogen bonds. Large cage networks often include a wide range of guest species in their cavity to afford novel inclusion compounds. Topological isomers consisting of two or more macrocycles are formed by cyclization of preorganized species. Some complicated topological networks are constructed by self-assembly of simple building units.

  12. Passivation behavior of Type 304 stainless steel in a non-aqueous alkyl carbonate solution containing LiPF6 salt

    International Nuclear Information System (INIS)

    Myung, Seung-Taek; Sasaki, Yusuke; Saito, Takamitsu; Sun, Yang-Kook; Yashiro, Hitoshi

    2009-01-01

    Passivation behavior of type 304 stainless steel in a non-aqueous alkyl carbonate solution containing LiPF 6 salt was studied using electrochemical polarization, X-ray photoelectron spectroscopy (XPS) and time of flight-secondary ion mass spectroscopy (ToF-SIMS). Cathodic polarization to 0 V vs. Li/Li + resulted in most but not complete reduction of the air-formed film from oxides to metal on the stainless steel, as confirmed by XPS. For complete elimination of the air-formed film, the surface of the stainless steel was scratched under anodic polarization conditions. At 3 V vs. Li/Li + where an anodic current peak appeared, only an indistinct layer was recognized on the newly scratched surface, according to ToF-SIMS analysis. Above 4 V vs. Li/Li + , substantial passive films were formed, which were composed of oxides and fluorides of iron and chromium. The origin of oxide was due to water contained in the non-aqueous alkyl carbonate solution, and that of fluorides were the result of the decomposition of electrolytic salt, LiPF 6 , especially at higher potential. The resultant passive films were stable in the non-aqueous alkyl carbonate solution containing LiPF 6 salt.

  13. Aromatic acids in a Eurasian Arctic ice core: a 2600-year proxy record of biomass burning

    Science.gov (United States)

    Grieman, Mackenzie M.; Aydin, Murat; Fritzsche, Diedrich; McConnell, Joseph R.; Opel, Thomas; Sigl, Michael; Saltzman, Eric S.

    2017-04-01

    Wildfires and their emissions have significant impacts on ecosystems, climate, atmospheric chemistry, and carbon cycling. Well-dated proxy records are needed to study the long-term climatic controls on biomass burning and the associated climate feedbacks. There is a particular lack of information about long-term biomass burning variations in Siberia, the largest forested area in the Northern Hemisphere. In this study we report analyses of aromatic acids (vanillic and para-hydroxybenzoic acids) over the past 2600 years in the Eurasian Arctic Akademii Nauk ice core. These compounds are aerosol-borne, semi-volatile organic compounds derived from lignin combustion. The analyses were made using ion chromatography with electrospray mass spectrometric detection. The levels of these aromatic acids ranged from below the detection limit (0.01 to 0.05 ppb; 1 ppb = 1000 ng L-1) to about 1 ppb, with roughly 30 % of the samples above the detection limit. In the preindustrial late Holocene, highly elevated aromatic acid levels are observed during three distinct periods (650-300 BCE, 340-660 CE, and 1460-1660 CE). The timing of the two most recent periods coincides with the episodic pulsing of ice-rafted debris in the North Atlantic known as Bond events and a weakened Asian monsoon, suggesting a link between fires and large-scale climate variability on millennial timescales. Aromatic acid levels also are elevated during the onset of the industrial period from 1780 to 1860 CE, but with a different ratio of vanillic and para-hydroxybenzoic acid than is observed during the preindustrial period. This study provides the first millennial-scale record of aromatic acids. This study clearly demonstrates that coherent aromatic acid signals are recorded in polar ice cores that can be used as proxies for past trends in biomass burning.

  14. Polar and non-polar organic aerosols from large-scale agricultural-waste burning emissions in Northern India: Implications to organic mass-to-organic carbon ratio.

    Science.gov (United States)

    Rajput, Prashant; Sarin, M M

    2014-05-01

    This study focuses on characteristics of organic aerosols (polar and non-polar) and total organic mass-to-organic carbon ratio (OM/OC) from post-harvest agricultural-waste (paddy- and wheat-residue) burning emissions in Northern India. Aerosol samples from an upwind location (Patiala: 30.2°N, 76.3°E) in the Indo-Gangetic Plain were analyzed for non-polar and polar fractions of organic carbon (OC1 and OC2) and their respective mass (OM1 and OM2). On average, polar organic aerosols (OM2) contribute nearly 85% of the total organic mass (OM) from the paddy- and wheat-residue burning emissions. The water-soluble-OC (WSOC) to OC2 ratio, within the analytical uncertainty, is close to 1 from both paddy- and wheat-residue burning emissions. However, temporal variability and relatively low WSOC/OC2 ratio (Av: 0.67±0.06) is attributed to high moisture content and poor combustion efficiency during paddy-residue burning, indicating significant contribution (∼30%) of aromatic carbon to OC2. The OM/OC ratio for non-polar (OM1/OC1∼1.2) and polar organic aerosols (OM2/OC2∼2.2), hitherto unknown for open agricultural-waste burning emissions, is documented in this study. The total OM/OC ratio is nearly identical, 1.9±0.2 and 1.8±0.2, from paddy- and wheat-residue burning emissions. Copyright © 2013 Elsevier Ltd. All rights reserved.

  15. Polycyclic aromatic hydrocarbons, tobacco smoke, and epigenetic remodeling in asthma

    Science.gov (United States)

    Klingbeil, E. C.; Hew, K. M.; Nygaard, U. C.; Nadeau, K. C.

    2014-01-01

    Environmental determinants including aerosolized pollutants such as polycyclic aromatic hydrocarbons (PAHs) and tobacco smoke have been associated with exacerbation and increased incidence of asthma. The influence of aerosolized pollutants on the development of immune dysfunction in asthmatics has been suggested to be mediated through epigenetic remodeling. Genome accessibility and transcription are regulated primarily through DNA methylation, histone modification, and microRNA transcript silencing. Epigenetic remodeling has been shown in studies to be associated with Th2 polarization and associated cytokine and chemokine regulation in the development of asthma. This review will present evidence for the contribution of the aerosolized pollutants PAH and environmental tobacco smoke to epigenetic remodeling in asthma. PMID:24760221

  16. The spectral properties of (--epigallocatechin 3-O-gallate (EGCG fluorescence in different solvents: dependence on solvent polarity.

    Directory of Open Access Journals (Sweden)

    Vladislav Snitsarev

    Full Text Available (--Epigallocatechin 3-O-gallate (EGCG a molecule found in green tea and known for a plethora of bioactive properties is an inhibitor of heat shock protein 90 (HSP90, a protein of interest as a target for cancer and neuroprotection. Determination of the spectral properties of EGCG fluorescence in environments similar to those of binding sites found in proteins provides an important tool to directly study protein-EGCG interactions. The goal of this study is to examine the spectral properties of EGCG fluorescence in an aqueous buffer (AB at pH=7.0, acetonitrile (AN (a polar aprotic solvent, dimethylsulfoxide (DMSO (a polar aprotic solvent, and ethanol (EtOH (a polar protic solvent. We demonstrate that EGCG is a highly fluorescent molecule when excited at approximately 275 nm with emission maxima between 350 and 400 nm depending on solvent. Another smaller excitation peak was found when EGCG is excited at approximately 235 nm with maximum emission between 340 and 400 nm. We found that the fluorescence intensity (FI of EGCG in AB at pH=7.0 is significantly quenched, and that it is about 85 times higher in an aprotic solvent DMSO. The Stokes shifts of EGCG fluorescence were determined by solvent polarity. In addition, while the emission maxima of EGCG fluorescence in AB, DMSO, and EtOH follow the Lippert-Mataga equation, its fluorescence in AN points to non-specific solvent effects on EGCG fluorescence. We conclude that significant solvent-dependent changes in both fluorescence intensity and fluorescence emission shifts can be effectively used to distinguish EGCG in aqueous solutions from EGCG in environments of different polarity, and, thus, can be used to study specific EGCG binding to protein binding sites where the environment is often different from aqueous in terms of polarity.

  17. Cr(VI) adsorption on functionalized amorphous and mesoporous silica from aqueous and non-aqueous media

    International Nuclear Information System (INIS)

    Perez-Quintanilla, Damian; Hierro, Isabel del; Fajardo, Mariano; Sierra, Isabel

    2007-01-01

    A mesoporous silica (SBA-15) and amorphous silica (SG) have been chemically modified with 2-mercaptopyridine using the homogeneous route. This synthetic route involved the reaction of 2-mercaptopyridine with 3-chloropropyltriethoxysilane prior to immobilization on the support. The resulting material has been characterized by powder X-ray diffraction, nitrogen gas sorption, FT-IR and MAS NMR spectroscopy, thermogravimetry and elemental analysis. The solid was employed as a Cr(VI) adsorbent from aqueous and non-aqueous solutions at room temperature. The effect of several variables (stirring time, pH, metal concentration and solvent polarity) has been studied using the batch technique. The results indicate that under the optimum conditions, the maximum adsorption value for Cr(VI) was 1.83 ± 0.03 mmol/g for MP-SBA-15, whereas the adsorption capacity of the MP-SG was 0.86 ± 0.02 mmol/g. On the basis of these results, it can be concluded that it is possible to modify chemically SBA-15 and SG with 2-mercaptopyridine and to use the resulting modified silicas as effective adsorbents for Cr(VI)

  18. Strong CH/O interactions between polycyclic aromatic hydrocarbons and water: Influence of aromatic system size.

    Science.gov (United States)

    Veljković, Dušan Ž

    2018-03-01

    Energies of CH/O interactions between water molecule and polycyclic aromatic hydrocarbons with a different number of aromatic rings were calculated using ab initio calculations at MP2/cc-PVTZ level. Results show that an additional aromatic ring in structure of polycyclic aromatic hydrocarbons significantly strengthens CH/O interactions. Calculated interaction energies in optimized structures of the most stable tetracene/water complex is -2.27 kcal/mol, anthracene/water is -2.13 kcal/mol and naphthalene/water is -1.97 kcal/mol. These interactions are stronger than CH/O contacts in benzene/water complex (-1.44 kcal/mol) while CH/O contacts in tetracene/water complex are even stronger than CH/O contacts in pyridine/water complexes (-2.21 kcal/mol). Electrostatic potential maps for different polycyclic aromatic hydrocarbons were calculated and used to explain trends in the energies of interactions. Copyright © 2017 Elsevier Inc. All rights reserved.

  19. Constraint on the polarization of electric dipole emission from spinning dust

    Energy Technology Data Exchange (ETDEWEB)

    Hoang, Thiem; Martin, P. G. [Canadian Institute for Theoretical Astrophysics, University of Toronto, 60 St. George Street, Toronto, ON M5S 3H8 (Canada); Lazarian, A. [Department of Astronomy, University of Wisconsin-Madison, Madison, WI 53705 (United States)

    2013-12-20

    Planck results have revealed that the electric dipole emission from polycyclic aromatic hydrocarbons (PAHs) is the most reliable explanation for the anomalous microwave emission that interferes with cosmic microwave background (CMB) radiation experiments. The emerging question is to what extent this emission component contaminates the polarized CMB radiation. We present constraints on polarized dust emission for the model of grain-size distribution and grain alignment that best fits the observed extinction and polarization curves. Two stars with a prominent polarization feature at λ = 2175 Å—HD 197770 and HD 147933-4—are chosen for our study. For HD 197770, we find that the model with aligned silicate grains plus weakly aligned PAHs can successfully reproduce the 2175 Å polarization feature; in contrast, for HD 147933-4, we find that the alignment of only silicate grains can account for that feature. The alignment function of PAHs for the best-fit model to the HD 197770 data is used to constrain polarized spinning dust emission. We find that the degree of polarization of spinning dust emission is about 1.6% at frequency ν ≈ 3 GHz and declines to below 0.9% for ν > 20 GHz. We also predict the degree of polarization of thermal dust emission at 353 GHz to be P {sub em} ≈ 11% and 14% for the lines of sight to the HD 197770 and HD 147933-4 stars, respectively.

  20. Determination of uptake kinetics (sampling rates) by lipid-containing semipermeable membrane devices (SPMDs) for polycyclic aromatic hydrocarbons (PAHs) in water

    Science.gov (United States)

    Huckins, J.N.; Petty, J.D.; Orazio, C.E.; Lebo, J.A.; Clark, R.C.; Gibson, V.L.; Gala, W.R.; Echols, K.R.

    1999-01-01

    The use of lipid-containing semipermeable membrane devices (SPMDs) is becoming commonplace, but very little sampling rate data are available for the estimation of ambient contaminant concentrations from analyte levels in exposed SPMDs. We determined the aqueous sampling rates (R(s)s; expressed as effective volumes of water extracted daily) of the standard (commercially available design) 1-g triolein SPMD for 15 of the priority pollutant (PP) polycyclic aromatic hydrocarbons (PAHs) at multiple temperatures and concentrations. Under the experimental conditions of this study, recovery- corrected R(s) values for PP PAHs ranged from ???1.0 to 8.0 L/d. These values would be expected to be influenced by significant changes (relative to this study) in water temperature, degree of biofouling, and current velocity- turbulence. Included in this paper is a discussion of the effects of temperature and octanol-water partition coefficient (K(ow)); the impacts of biofouling and hydrodynamics are reported separately. Overall, SPMDs responded proportionally to aqueous PAH concentrations; i.e., SPMD R(s) values and SPMD-water concentration factors were independent of aqueous concentrations. Temperature effects (10, 18, and 26 ??C) on Rs values appeared to be complex but were relatively small.The use of lipid-containing semipermeable membrane devices (SPMDs) is becoming commonplace, but very little sampling rate data are available for the estimation of ambient contaminant concentrations from analyte levels in exposed SPMDs. We determined the aqueous sampling rates (Rss; expressed as effective volumes of water extracted daily) of the standard (commercially available design) 1-g triolein SPMD for 15 of the priority pollutant (PP) polycyclic aromatic hydrocarbons (PAHs) at multiple temperatures and concentrations. Under the experimental conditions of this study, recovery-corrected Rs values for PP PAHs ranged from ???1.0 to 8.0 L/d. These values would be expected to be influenced by

  1. Rapid determination of 9 aromatic amines in mainstream cigarette smoke by modified dispersive liquid liquid microextraction and ultraperformance convergence chromatography tandem mass spectrometry.

    Science.gov (United States)

    Deng, Huimin; Yang, Fei; Li, Zhonghao; Bian, Zhaoyang; Fan, Ziyan; Wang, Ying; Liu, Shanshan; Tang, Gangling

    2017-07-21

    Aromatic amines in mainstream cigarette smoke have long been monitored due to their carcinogenic toxicity. In this work, a reliable and rapid method was developed for the simultaneous determination of 9 aromatic amines in mainstream cigarette smoke by modified dispersive liquid liquid microextraction (DLLME) and ultraperformance convergence chromatography tandem mass spectrometry (UPC 2 -MS/MS). Briefly, the particulate phase of the cigarette smoke was captured by a Cambridge filter pad, and diluted hydrogen chloride aqueous solution is employed to extract the aromatic amines under mechanical shaking. After alkalization with sodium hydroxide solution, small amount of toluene was introduced to further extract and enrich aromatic amines by modified DLLME under vortexing. After centrifugation, toluene phase was purified by a universal QuEChERS cleanup kit and was finally analyzed by UPC 2 -MS/MS. Attributing to the superior performance of UPC 2 -MS/MS, this novel approach allowed the separation and determination of 9 aromatic amines within 5.0min with satisfactory resolution and sensitivity. The proposed method was finally validated using Kentucky reference cigarette 3R4F, and emission levels of targeted aromatic amines determined were comparable to previously reported methods At three different spiked levels, the recoveries of most analytes were ranged from 74.01% to 120.50% with relative standard deviation (RSD) less than 12%, except that the recovery of p-toluidine at low spiked level and 3-aminobiphenyl at medium spiked level was 62.77% and 69.37% respectively. Thus, this work provides a novel alternative method for the simultaneous analysis of 9 aromatic amines in mainstream cigarette smoke. Copyright © 2017 Elsevier B.V. All rights reserved.

  2. Phytochemical profiles and antimicrobial activity of aromatic Malaysian herb extracts against food-borne pathogenic and food spoilage microorganisms.

    Science.gov (United States)

    Aziman, Nurain; Abdullah, Noriham; Noor, Zainon Mohd; Kamarudin, Wan Saidatul Syida Wan; Zulkifli, Khairusy Syakirah

    2014-04-01

    Preliminary phytochemical and flavonoid compounds of aqueous and ethanolic extracts of 6 aromatic Malaysian herbs were screened and quantified using Reverse-Phase High Performance Liquid Chromatography (RP-HPLC). The herbal extracts were tested for their antimicrobial activity against 10 food-borne pathogenic and food spoilage microorganisms using disk diffusion assay. The minimum inhibitory concentration (MIC) and minimum bactericidal concentration (MBC)/minimum fungicidal concentration (MFC) of herbal extracts were determined. In the phytochemical screening process, both aqueous and ethanolic extracts of P. hydropiper exhibited presence of all 7 tested phytochemical compounds. Among all herbal extracts, the aqueous P. hydropiper and E. elatior extracts demonstrated the highest antibacterial activity against 7 tested Gram-positive and Gram-negative bacteria with diameter ranging from 7.0 to 18.5 mm and 6.5 to 19 mm, respectively. The MIC values for aqueous and ethanolic extracts ranged from 18.75 to 175 mg/mL and 0.391 to 200 mg/mL, respectively while the MBC/MFC values for aqueous and ethanolic extracts ranged from 25 to 200 mg/mL and 3.125 to 50 mg/mL, respectively. Major types of bioactive compounds in aqueous P. hydropiper and E. elatior extracts were identified using RP-HPLC instrument. Flavonoids found in these plants were epi-catechin, quercetin, and kaempferol. The ability of aqueous Persicaria hydropiper (L.) H. Gross and Etlingera elatior (Jack) R.M. Sm. extracts to inhibit the growth of bacteria is an indication of its broad spectrum antimicrobial potential. Hence these herbal extracts may be used as natural preservative to improve the safety and shelf-life of food and pharmaceutical products. © 2014 Institute of Food Technologists®

  3. Pulse shape discrimination in non-aromatic plastics

    Energy Technology Data Exchange (ETDEWEB)

    Paul Martinez, H.; Pawelczak, Iwona; Glenn, Andrew M.; Leslie Carman, M.; Zaitseva, Natalia; Payne, Stephen

    2015-01-21

    Recently it has been demonstrated that plastic scintillators have the ability to distinguish neutrons from gamma rays by way of pulse shape discrimination (PSD). This discovery has lead to new materials and new capabilities. Here we report our work with the effects of aromatic, non-aromatic, and mixed aromatic/non-aromatic matrices have on the performance of PSD plastic scintillators.

  4. Quantum coherent π-electron rotations in a non-planar chiral molecule induced by using a linearly polarized UV laser pulse

    Science.gov (United States)

    Mineo, Hirobumi; Fujimura, Yuichi

    2015-06-01

    We propose an ultrafast quantum switching method of π-electron rotations, which are switched among four rotational patterns in a nonplanar chiral aromatic molecule (P)-2,2’- biphenol and perform the sequential switching among four rotational patterns which are performed by the overlapped pump-dump laser pulses. Coherent π-electron dynamics are generated by applying the linearly polarized UV pulse laser to create a pair of coherent quasidegenerated excited states. We also plot the time-dependent π-electron ring current, and discussed ring current transfer between two aromatic rings.

  5. Determination of descriptors for polycyclic aromatic hydrocarbons and related compounds by chromatographic methods and liquid-liquid partition in totally organic biphasic systems.

    Science.gov (United States)

    Ariyasena, Thiloka C; Poole, Colin F

    2014-09-26

    Retention factors on several columns and at various temperatures using gas chromatography and from reversed-phase liquid chromatography on a SunFire C18 column with various mobile phase compositions containing acetonitrile, methanol and tetrahydrofuran as strength adjusting solvents are combined with liquid-liquid partition coefficients in totally organic biphasic systems to calculate descriptors for 23 polycyclic aromatic hydrocarbons and eighteen related compounds of environmental interest. The use of a consistent protocol for the above measurements provides descriptors that are more self consistent for the estimation of physicochemical properties (octanol-water, air-octanol, air-water, aqueous solubility, and subcooled liquid vapor pressure). The descriptor in this report tend to have smaller values for the L and E descriptors and random differences in the B and S descriptors compared with literature sources. A simple atom fragment constant model is proposed for the estimation of descriptors from structure for polycyclic aromatic hydrocarbons. The new descriptors show no bias in the prediction of the air-water partition coefficient for polycyclic aromatic hydrocarbons unlike the literature values. Copyright © 2014 Elsevier B.V. All rights reserved.

  6. Effect of Ultrasound on the Decomposition of Sodium Dodecylbenzene Sulfonate in Aqueous Solution

    International Nuclear Information System (INIS)

    Yim, Bong Been

    2004-01-01

    The influence of ultrasound frequency, dissolved gases, and initial concentration on the decomposition of sodium dodecylbenzene sulfonate(DBS) aqueous solution was investigated using ultrasound generator with 200 W ultrasound power. The decomposition rates at three frequencies(50, 200, and 600 kHz) examined under argon atmosphere were highest at 200 kHz. The highest observed decomposition rate at 200 kHz occurred in the presence of oxygen followed by air and argon, helium, and nitrogen. The effect of initial concentration of DBS on the ultrasonic decomposition was decreased with increasing initial concentration and would depend upon the formation of micelle in aqueous solution. It appears that the ultrasound frequency, dissolved gases, and initial concentration play an important role on the sonolysis of DBS. Sonolysis of DBS mainly take place at the interfacial region of cavitation bubbles by both OH radical attack and pyrolysis to alkyl chain, aromatic ring, and headgroup

  7. Chromatographic separation and spectro-analytical characterization of a natural African mineral dye

    Directory of Open Access Journals (Sweden)

    G.B. Adebayo

    2007-08-01

    Full Text Available Chromatographic fractionation and spectroscopic characterization of a natural African mineral dye have been carried out. The chromatographic separation of the dyes made use of column and thin layer chromatographic techniques. Some physicochemical properties of the dye including solubility in polar and non-polar solvents, pH, ash and organic contents were determined. The spectro-analytical techniques used for characterization included energy dispersive X-ray fluorescence (EDXRF, X-ray diffractometry (XRD, Optical microscopy, infrared (IR and UV-VIS spectroscopy. Four different fractions having colours yellow, grey, orange and purple were obtained from the chromatographic separation. All the fractions were found to contain aromatic nucleus based on IR and UV-VIS spectroscopic data. Other functional groups detected are Ar-NH2, -CONH2, C=C, C-C and metal-carbon chelate rings. The presence of aromatic amine in the dye provides strong evidence for its use as hair dye. The dye was found to be soluble in both aqueous and non-aqueous solvents. The pH of the dye's aqueous solution was found to be 8.6, and the ash and organic content of the raw dye were 49 % and 51 % respectively. The XRF revealed that the dye contains twenty elements with concentrations ranging from major to ultra-trace levels. The XRD also showed that the sample contains about forty-six mineral phases which include both inorganic and organic components. The maximum absorption wavelength (λmax in UV-VIS of the aqueous solution was found to be 464 nm. The optical microscopic investigation gave indication that the dyes are likely to be of the marine origin.

  8. Potentiodynamic polarization studies of bulk amorphous alloy Zr57Cu15.4Ni12.6Al10Nb5 and Zr59Cu20Ni8Al10Ti3 in aqueous HNO3 media

    International Nuclear Information System (INIS)

    Sharma, Poonam; Dhawan, Anil; Jayraj, J.; Kamachi Mudali, U.

    2013-01-01

    The potentiodynamic polarization studies were carried out on Zr based bulk amorphous alloy Zr 57 Cu 15.4 Ni 12.6 Al 10 Nb 5 and Zr 59 Cu 20 Ni 8 Al 10 Ti 3 in solutions of 1 M, 6 M and 11.5 M HNO 3 aqueous media at room temperature. As received specimens of Zr 57 Cu 15.4 Ni 12.6 Al 10 Nb 5 (5 mm diameter rod) and Zr 59 Cu 20 Ni 8 Al 10 Ti 3 (3 mm diameter rod) were polished with SiC paper before testing them for potentiodynamic polarization studies. The amorphous nature of the specimens was checked by X-ray diffraction. The bulk amorphous alloy Zr 59 Cu 20 Ni 8 Al 10 Ti 3 shows the better corrosion resistance than Zr 57 Cu 15.4 Ni 12.6 Al 10 Nb 5 alloy in the aqueous HNO 3 media as the value of the corrosion current density (I corr ) for Zr 57 Cu 15.4 Ni 12.6 Al 10 Nb 5 alloy were found to be more than Zr 59 Cu 20 Ni 8 Al 10 Ti 3 alloy in aqueous HNO 3 media. The improved corrosion resistance of Zr 59 Cu 20 Ni 8 Al 10 Ti 3 alloy is possibly due to the presence of Ti and formation of TiO 2 during anodic oxidation. Both Zr based bulk amorphous alloys shows wider passive range at lower concentration of nitric acid and the passive region gets narrowed down with the increase in concentration. A comparison of data obtained from both the Zr-based bulk amorphous alloys is made and results are discussed in the paper. (author)

  9. Polarized Emission of Wholly Aromatic Bio-Based Copolyesters of a Liquid Crystalline Nature

    Directory of Open Access Journals (Sweden)

    Daisaku Kaneko

    2011-05-01

    Full Text Available A novel thermotropic liquid crystalline polymers poly{3-benzylidene amino-4-hydroxybenzoic acid (3,4-BAHBA-co-trans-4-hydroxycinnamic acid (4HCA: trans-coumaric acid} (Poly(3,4-BAHBA-co-4HCA, was synthesized by the thermal polycondensation of 4HCA and 3,4-BAHBA, which was synthesized by a reaction of 3-amino-4-hydroxybenzoic acid (3,4-AHBA with benzaldehyde. When the 4HCA compositions of Poly(3,4-BAHBA-co-4HCAs were above 55 mol%, the copolymers showed a nematic, liquid crystalline phase. Differential scanning calorimetry (DSC measurements of the copolymers showed a high glass transition temperature of more than 100 °C, sufficient for use in engineering plastics. Furthermore, the copolymers showed photoluminescence in an N-methylpyrrolidone (NMP solution under ultraviolet (UV light with a wavelength of 365 nm. Oriented film of Poly(3,4-BAHBA-co-4HCA with a 4HCA composition of 75 mol% emitted polarized light, which was confirmed by fluorescent spectroscopy equipped with parallel and crossed polarizers.

  10. Dynamic nuclear-polarization studies of paramagnetic species in solution

    International Nuclear Information System (INIS)

    Glad, W.E.

    1982-07-01

    Dynamic Nuclear Polarization (DNP) was used to measure the electron spin lattice relaxation times, T 1 , of transition metal ions in aqueous solution. Saturation which is induced in the electron spin system is transferred to the solvent proton spins by dipole-dipole interactions. The change in the polarization of the proton spins is much larger than it is in the electron spins. The change in proton polarization is easily measured by proton Nuclear Magnetic Resonance (NMR). In one experimental arrangement the sample solution was continuously flowed through a microwave cavity to the NMR coil. The NMR was observed with a continuous wave NMR spectrometer. In a second arrangement the whole sample tube was moved from within the microwave cavity to the NMR coil in less than 40 ms by a blast of compressed air. The NMR was then observed with a pulse-Fourier-transform spectrometer. With the second arrangement a mean-square microwave magnetic field at the sample of more than 10 G 2 is obtainable with 14 W of microwave power. Measurements of DNP at 9 GHz were made on aqueous solutions of VO 2+ , Mn 2+ , Cr(CN) 6 3- , Cu 2+ and Cu(ethylenediamine) 2 (H 2 0) 2 2+ ions from 3 to 60 0 C. It was also possible to observe DNP on resolved proton resonances from mixed water-acetonitrile solutions of VO 2+ and Cr(CN) 6 3- ions

  11. Non-aqueous electrolytes for lithium ion batteries

    Science.gov (United States)

    Chen, Zonghai; Amine, Khalil

    2015-11-12

    The present invention is generally related to electrolytes containing anion receptor additives to enhance the power capability of lithium-ion batteries. The anion receptor of the present invention is a Lewis acid that can help to dissolve LiF in the passivation films of lithium-ion batteries. Accordingly, one aspect the invention provides electrolytes comprising a lithium salt; a polar aprotic solvent; and an anion receptor additive; and wherein the electrolyte solution is substantially non-aqueous. Further there are provided electrochemical devices employing the electrolyte and methods of making the electrolyte.

  12. Catalytic Oxidation and Depolymerization of Lignin in Aqueous Ionic Liquid

    Energy Technology Data Exchange (ETDEWEB)

    Das, Lalitendu [Biosystems and Agricultural Engineering, University of Kentucky, Lexington, KY (United States); Xu, Siquan [Biosystems and Agricultural Engineering, University of Kentucky, Lexington, KY (United States); College of Chemical Engineering, Nanjing Forestry University, Nanjing (China); Shi, Jian, E-mail: j.shi@uky.edu [Biosystems and Agricultural Engineering, University of Kentucky, Lexington, KY (United States)

    2017-08-10

    Lignin is an integral part of the plant cell wall, which provides rigidity to plants, also contributes to the recalcitrance of the lignocellulosic biomass to biochemical and biological deconstruction. Lignin is a promising renewable feedstock for aromatic chemicals; however, an efficient and economic lignin depolymerization method needs to be developed to enable the conversion. In this study, we investigated the depolymerization of alkaline lignin in aqueous 1-ethyl-3-methylimidazolium acetate [C{sub 2}C{sub 1}Im][OAc] under oxidizing conditions. Seven different transition metal catalysts were screened in presence of H{sub 2}O{sub 2} as oxidizing agent in a batch reactor. CoCl{sub 2} and Nb{sub 2}O{sub 5} proved to be the most effective catalysts in degrading lignin to aromatic compounds. A central composite design was used to optimize the catalyst loading, H{sub 2}O{sub 2} concentration, and temperature for product formation. Results show that lignin was depolymerized, and the major degradation products found in the extracted oil were guaiacol, syringol, vanillin, acetovanillone, and homovanillic acid. Lignin streams were characterized by Fourier transform infrared spectroscopy and gel permeation chromatography to determine effects of the experimental parameters on lignin depolymerization. The weight-average molecular weight (M{sub w}) of liquid stream lignin after oxidation, for CoCl{sub 2} and Nb{sub 2}O{sub 5} catalysts were 1,202 and 1,520 g mol{sup −1}, respectively, lower than that of Kraft lignin. Polydispersity index of the liquid stream lignin increased as compared with Kraft lignin, indicating wide span of the molecular weight distribution as a result of lignin depolymerization. Results from this study provide insights into the role of oxidant and transition metal catalysts and the oxidative degradation reaction sequence of lignin toward product formation in presence of aqueous ionic liquid.

  13. Catalytic Oxidation and Depolymerization of Lignin in Aqueous Ionic Liquid

    International Nuclear Information System (INIS)

    Das, Lalitendu; Xu, Siquan; Shi, Jian

    2017-01-01

    Lignin is an integral part of the plant cell wall, which provides rigidity to plants, also contributes to the recalcitrance of the lignocellulosic biomass to biochemical and biological deconstruction. Lignin is a promising renewable feedstock for aromatic chemicals; however, an efficient and economic lignin depolymerization method needs to be developed to enable the conversion. In this study, we investigated the depolymerization of alkaline lignin in aqueous 1-ethyl-3-methylimidazolium acetate [C 2 C 1 Im][OAc] under oxidizing conditions. Seven different transition metal catalysts were screened in presence of H 2 O 2 as oxidizing agent in a batch reactor. CoCl 2 and Nb 2 O 5 proved to be the most effective catalysts in degrading lignin to aromatic compounds. A central composite design was used to optimize the catalyst loading, H 2 O 2 concentration, and temperature for product formation. Results show that lignin was depolymerized, and the major degradation products found in the extracted oil were guaiacol, syringol, vanillin, acetovanillone, and homovanillic acid. Lignin streams were characterized by Fourier transform infrared spectroscopy and gel permeation chromatography to determine effects of the experimental parameters on lignin depolymerization. The weight-average molecular weight (M w ) of liquid stream lignin after oxidation, for CoCl 2 and Nb 2 O 5 catalysts were 1,202 and 1,520 g mol −1 , respectively, lower than that of Kraft lignin. Polydispersity index of the liquid stream lignin increased as compared with Kraft lignin, indicating wide span of the molecular weight distribution as a result of lignin depolymerization. Results from this study provide insights into the role of oxidant and transition metal catalysts and the oxidative degradation reaction sequence of lignin toward product formation in presence of aqueous ionic liquid.

  14. Advances towards aromatic oligoamide foldamers

    DEFF Research Database (Denmark)

    Hjelmgaard, Thomas; Plesner, Malene; Dissing, Mette Marie

    2014-01-01

    We have efficiently synthesized 36 arylopeptoid dimers with ortho-, meta-, and para-substituted aromatic backbones and tert-butyl or phenyl side chains. The dimers were synthesized by using a "submonomer method" on solid phase, by applying a simplified common set of reaction conditions. X......-ray crystallographic analysis of two of these dimers disclosed that the tert-butyl side chain invokes a cis amide conformation with a comparatively more closely packed structure of the surrounding aromatic backbone while the phenyl side chain results in a trans amide conformation with a more open, extended structure...... of the surrounding aromatic backbone. Investigation of the X-ray structures of two arylopeptoid dimers disclosed that the tert-butyl side chain invokes a cis amide conformation with a closely packed structure of the surrounding aromatic backbone while the phenyl side chain results in a trans amide conformation...

  15. Solvent-free functionalization of fullerene C{sub 60} and pristine multi-walled carbon nanotubes with aromatic amines

    Energy Technology Data Exchange (ETDEWEB)

    Ramírez-Calera, Itzel J. [Centro de Ciencias Aplicadas y Desarrollo Tecnológico, Universidad Nacional Autónoma de México, Circuito Exterior C. U., 04510, México, D.F. (Mexico); Meza-Laguna, Victor [Instituto de Ciencias Nucleares, Universidad Nacional Autónoma de México, Circuito Exterior C. U., 04510 México, D.F. (Mexico); Gromovoy, Taras Yu. [O.O. Chuiko Institute of Surface Chemistry, National Academy of Sciences of the Ukraine, Gen. Naumova 17, 03164 Kiev (Ukraine); Chávez-Uribe, Ma. Isabel [Instituto de Química, Universidad Nacional Autónoma de México, Circuito Exterior C. U., 04510 México, D.F. (Mexico); Basiuk, Vladimir A., E-mail: basiuk@nucleares.unam.mx [Instituto de Ciencias Nucleares, Universidad Nacional Autónoma de México, Circuito Exterior C. U., 04510 México, D.F. (Mexico); Basiuk, Elena V., E-mail: elbg1111@gmail.com [Centro de Ciencias Aplicadas y Desarrollo Tecnológico, Universidad Nacional Autónoma de México, Circuito Exterior C. U., 04510, México, D.F. (Mexico)

    2015-02-15

    Highlights: • Pristine multi-walled carbon nanotubes were functionalized with aromatic amines. • The amines add onto nanotube defects, likewise they add onto fullerene C{sub 60}. • The addition takes place at elevated temperature and without organic solvents. • Functionalized nanotubes were characterized by a number of instrumental techniques. - Abstract: We employed a direct one-step solvent-free covalent functionalization of solid fullerene C{sub 60} and pristine multi-walled carbon nanotubes (MWCNTs) with aromatic amines 1-aminopyrene (AP), 2-aminofluorene (AF) and 1,5-diaminonaphthalene (DAN). The reactions were carried out under moderate vacuum, in a wide temperature range of 180–250 °C, during relatively short time of about 2 h. To confirm successful amine attachment, a large number of analytical techniques were used (depending on the nanomaterial functionalized) such as Fourier transform infrared, Raman, X-ray photoelectron, {sup 13}C cross-polarization magic angle spinning NMR spectroscopy, thermogravimetric analysis, laser-desorption ionization time-of-flight mass spectrometry, temperature-programmed desorption with mass spectrometric detection, as well as scanning and transmission electron microscopy. The nucleophilic addition of the aromatic amines to C{sub 60} molecule was studied theoretically by using density functional theory (PBE GGA functional with Grimme dispersion correction in conjunction with the DNP basis set). In the case of crystalline C{sub 60}, the solvent-free technique has a limited applicability due to poor diffusion of vaporous aromatic amines into the bulk. Nevertheless, the approach proposed allows for a facile preparation of aromatic amine-functionalized pristine MWCNTs without contamination with other chemical reagents, detergents and solvents, which is especially important for a vast variety of nanotube applications spanning from nanoelectronics to nanomedicine.

  16. Proton polarization in photo-excited aromatic molecule at room temperature enhanced by intense optical source and temperature control

    Energy Technology Data Exchange (ETDEWEB)

    Sakaguchi, S., E-mail: sakaguchi@phys.kyushu-u.ac.jp [Department of Physics, Kyushu University, Fukuoka 812-8581 (Japan); Uesaka, T. [RIKEN Nishina Center, Saitama 351-0198 (Japan); Kawahara, T. [Department of Physics, Toho University, Chiba 274-8510 (Japan); Ogawa, T. [RIKEN Advanced Science Institute, Saitama 351-0198 (Japan); Tang, L. [Center for Nuclear Study, University of Tokyo, Tokyo 113-0001 (Japan); Teranishi, T. [Department of Physics, Kyushu University, Fukuoka 812-8581 (Japan); Urata, Y.; Wada, S. [RIKEN Advanced Science Institute, Saitama 351-0198 (Japan); Wakui, T. [Cyclotron and Radioisotope Center (CYRIC), Tohoku University, Miyagi 980-8578 (Japan)

    2013-12-15

    Highlights: • Proton polarization in p-terphenyl at room-temperature is enhanced by a factor of 3. • Intense laser and temperature control are critically important for high polarization. • Optimization of time structure of laser pulse is effective for further improvement. -- Abstract: Proton polarization at room temperature, produced in a p-terphenyl crystal by using electron population difference in a photo-excited triplet state of pentacene, was enhanced by utilizing an intense laser with an average power of 1.5 W. It was shown that keeping the sample temperature below 300 K is critically important to prevent the rise of the spin–lattice relaxation rate caused by the laser heating. It is also reported that the magnitude of proton polarization strongly depends on the time structure of the laser pulse such as its width and the time interval between them.

  17. The development of a cholesterol biosensor using a liquid crystal/aqueous interface in a SDS-included β-cyclodextrin aqueous solution

    Energy Technology Data Exchange (ETDEWEB)

    Munir, Sundas; Park, Soo-Young, E-mail: psy@knu.ac.kr

    2015-09-17

    Sodium dodecyl sulphate (SDS) including β-cyclodextrin (β-CD) (β-CD{sub SDS}) was used to detect cholesterol at the 4-cyano-4′-pentylbiphenyl (5CB)/aqueous interface in transmission electron microscopy (TEM) grid cells. The β-CD acts as a host for SDS (guest). The guest SDS enclosed within the β-CD cavity was replaced with cholesterol by injecting cholesterol solution into the TEM cell at concentrations greater than 3 μM. The replacement of SDS with cholesterol was confirmed by pH measurement and high performance liquid chromatography (HPLC). The SDS excluded from the β-CD altered the planar orientation of the 5CB confined within the TEM grid cell to a homeotropic orientation. This planar-to-homeotropic transition was observed using a polarized optical microscope under crossed polarizers. This convenient TEM grid cell provides a new method for the selective detection of cholesterol without immobilization of the detecting receptors (enzyme, antibody, or aptamer) or the use of sophisticated instruments. - Highlights: • β-CD-SDS inclusion was used for the detection of cholesterol at 5CB/aqueous interface. • The SDS enclosed within the β-CD cavity was replaced by cholesterol. • The released SDS from the β-CD caused homeotropic orientation of 5CB. • The cholesterol was detected from planar-to-homeotropic transition of 5CB. • This convenient TEM grid cell provides a new method for the selective detection of cholesterol.

  18. The development of a cholesterol biosensor using a liquid crystal/aqueous interface in a SDS-included β-cyclodextrin aqueous solution

    International Nuclear Information System (INIS)

    Munir, Sundas; Park, Soo-Young

    2015-01-01

    Sodium dodecyl sulphate (SDS) including β-cyclodextrin (β-CD) (β-CD_S_D_S) was used to detect cholesterol at the 4-cyano-4′-pentylbiphenyl (5CB)/aqueous interface in transmission electron microscopy (TEM) grid cells. The β-CD acts as a host for SDS (guest). The guest SDS enclosed within the β-CD cavity was replaced with cholesterol by injecting cholesterol solution into the TEM cell at concentrations greater than 3 μM. The replacement of SDS with cholesterol was confirmed by pH measurement and high performance liquid chromatography (HPLC). The SDS excluded from the β-CD altered the planar orientation of the 5CB confined within the TEM grid cell to a homeotropic orientation. This planar-to-homeotropic transition was observed using a polarized optical microscope under crossed polarizers. This convenient TEM grid cell provides a new method for the selective detection of cholesterol without immobilization of the detecting receptors (enzyme, antibody, or aptamer) or the use of sophisticated instruments. - Highlights: • β-CD-SDS inclusion was used for the detection of cholesterol at 5CB/aqueous interface. • The SDS enclosed within the β-CD cavity was replaced by cholesterol. • The released SDS from the β-CD caused homeotropic orientation of 5CB. • The cholesterol was detected from planar-to-homeotropic transition of 5CB. • This convenient TEM grid cell provides a new method for the selective detection of cholesterol.

  19. Solvent polarity scale on the fluorescence spectra of a dansyl monomer copolymerizable in aqueous media

    Science.gov (United States)

    Ren, Biye; Gao, Feng; Tong, Zhen; Yan, Yu

    1999-06-01

    A copolymerizable fluorescent monomer N-[2-[[[5-(N,N-dimethylamino)-1-naphthalenyl]sulfonyl]-amino]ethyl]-2-propenamide (DANSAEP) was synthesized, which exhibits dual fluorescence due to the twisted intramolecular charge transfer in the excited state. The emission maximum λem shifts from 463.3 nm in n-hexane to 530.0 nm in water, showing solvent polarity dependence. The relations between λem and the conventional solvent polarity parameters ET(30) or Z are linear, dividing solvents into protic and aprotic groups. Kamlet's linear solvation energy relationship gives a good description for λem as a solvent polarity scale. The increment of dipole moment Δ μ at the excited state was estimated as 5.09 D with the solvatochromic analysis.

  20. Use of aqueous and solvent extraction to assess risk and bioavailability of contaminated soil

    International Nuclear Information System (INIS)

    Bordelon, N.; Huebner, H.; Washburn, K.; Donnelly, K.C.

    1995-01-01

    Contaminated media at Superfund sites typically consist of complex mixtures of organic and inorganic chemicals. These mixtures are difficult to characterize, both analytically and toxicologically, especially the complex mixtures of polycyclic aromatic hydrocarbons. The current approach to risk assessment assumes that all contaminants in the soil are available for human exposure. EPA protocol uses solvent extraction to remove chemicals from the soil as a basis for estimating risk to the human population. However, contaminants that can be recovered with a solvent extract may not represent chemicals that are available for exposure. A system using aqueous extraction provides a more realistic picture of what chemicals are bioavailable through leaching and ingestion. A study was conducted with coal tar contaminated soil spiked with benzo(a)pyrene, and trinitrotoluene. Samples were extracted with hexane:acetone and water titrated to pH 2 and pH 7. HPLC analysis demonstrated up to 35% and 29% recovery of contaminants from aqueous extracts with an estimated cancer risk one order of magnitude less than that for solvent extracts. Analysis using the Salmonella/microsome assay showed that solvent extracts were genotoxic with metabolic activation while aqueous extracts showed no genotoxicity. These results suggest that aqueous extraction may be useful in determining what contaminants are available for human exposure, as well as what compounds may pose a risk to human health

  1. Converting lignin to aromatics: step by step

    NARCIS (Netherlands)

    Strassberger, Z.I.

    2014-01-01

    Lignin, the glue that holds trees together, is the most abundant natural resource of aromatics. In that respect, it is a far more advanced resource than crude oil. This is because lignin already contains the aromatic functional groups. Thus, catalytic conversion of lignin to high-value aromatics is

  2. Exfoliation of graphite into graphene in polar solvents mediated by amphiphilic hexa-peri-hexabenzocoronene.

    Science.gov (United States)

    Kabe, Ryota; Feng, Xinliang; Adachi, Chihaya; Müllen, Klaus

    2014-11-01

    A water-soluble surfactant consisting of hexa-peri-hexabenzocoronene (HBC) as hydrophobic aromatic core and hydrophilic carboxy substituents was synthesized. It exhibited a self-assembled nanofiber structure in the solid state. Profiting from the π interactions between the large aromatic core of HBC and graphene, the surfactant mediated the exfoliation of graphite into graphene in polar solvents, which was further stabilized by the bulky hydrophilic carboxylic groups. A graphene dispersion with a concentration as high as 1.1 mg L(-1) containing 2-6 multilayer nanosheets was obtained. The lateral size of the graphene sheets was in the range of 100-500 nm based on atomic force microscope (AFM) and transmission electron microscope (TEM) measurements. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. High atmosphere–ocean exchange of semivolatile aromatic hydrocarbons

    KAUST Repository

    González-Gaya, Belén

    2016-05-16

    Polycyclic aromatic hydrocarbons, and other semivolatile aromatic-like compounds, are an important and ubiquitous fraction of organic matter in the environment. The occurrence of semivolatile aromatic hydrocarbons is due to anthropogenic sources such as incomplete combustion of fossil fuels or oil spills, and other biogenic sources. However, their global transport, fate and relevance for the carbon cycle have been poorly assessed, especially in terms of fluxes. Here we report a global assessment of the occurrence and atmosphere-ocean fluxes of 64 polycyclic aromatic hydrocarbons analysed in paired atmospheric and seawater samples from the tropical and subtropical Atlantic, Pacific and Indian oceans. The global atmospheric input of polycyclic aromatic hydrocarbons to the global ocean is estimated at 0.09 Tg per month, four times greater than the input from the Deepwater Horizon spill. Moreover, the environmental concentrations of total semivolatile aromatic-like compounds were 10 2 -10 3 times higher than those of the targeted polycyclic aromatic hydrocarbons, with a relevant contribution of an aromatic unresolved complex mixture. These concentrations drive a large global deposition of carbon, estimated at 400 Tg C yr -1, around 15% of the oceanic CO2 uptake. © 2016 Macmillan Publishers Limited.

  4. Structure of water and the thermodynamics of aqueous solutions

    Energy Technology Data Exchange (ETDEWEB)

    Nemethy, G.

    1970-10-26

    This report represents the summary of a series of lectures held at the Istituto Superiore di Sanita, Laboratori di Fisica, from 18 September to 26 October 1970. The topics discussed were: Intermolecular forces, the individual water molecule and the hydrogen bond, the structures of the solid phases of water, experimental information on the strucuture of liquid water, theoretical models of water structure, experimental properties and theoretical models of aqueous solutions of nonpolar solutes, polar solutes, and electrolytes, the conformational stability of biological macromolecules.

  5. Development of linear free energy relationships for aqueous phase radical-involved chemical reactions.

    Science.gov (United States)

    Minakata, Daisuke; Mezyk, Stephen P; Jones, Jace W; Daws, Brittany R; Crittenden, John C

    2014-12-02

    Aqueous phase advanced oxidation processes (AOPs) produce hydroxyl radicals (HO•) which can completely oxidize electron rich organic compounds. The proper design and operation of AOPs require that we predict the formation and fate of the byproducts and their associated toxicity. Accordingly, there is a need to develop a first-principles kinetic model that can predict the dominant reaction pathways that potentially produce toxic byproducts. We have published some of our efforts on predicting the elementary reaction pathways and the HO• rate constants. Here we develop linear free energy relationships (LFERs) that predict the rate constants for aqueous phase radical reactions. The LFERs relate experimentally obtained kinetic rate constants to quantum mechanically calculated aqueous phase free energies of activation. The LFERs have been applied to 101 reactions, including (1) HO• addition to 15 aromatic compounds; (2) addition of molecular oxygen to 65 carbon-centered aliphatic and cyclohexadienyl radicals; (3) disproportionation of 10 peroxyl radicals, and (4) unimolecular decay of nine peroxyl radicals. The LFERs correlations predict the rate constants within a factor of 2 from the experimental values for HO• reactions and molecular oxygen addition, and a factor of 5 for peroxyl radical reactions. The LFERs and the elementary reaction pathways will enable us to predict the formation and initial fate of the byproducts in AOPs. Furthermore, our methodology can be applied to other environmental processes in which aqueous phase radical-involved reactions occur.

  6. Arginine-aromatic interactions and their effects on arginine-induced solubilization of aromatic solutes and suppression of protein aggregation

    KAUST Repository

    Shah, Dhawal

    2011-09-21

    We examine the interaction of aromatic residues of proteins with arginine, an additive commonly used to suppress protein aggregation, using experiments and molecular dynamics simulations. An aromatic-rich peptide, FFYTP (a segment of insulin), and lysozyme and insulin are used as model systems. Mass spectrometry shows that arginine increases the solubility of FFYTP by binding to the peptide, with the simulations revealing the predominant association of arginine to be with the aromatic residues. The calculations further show a positive preferential interaction coefficient, Γ XP, contrary to conventional thinking that positive Γ XP\\'s indicate aggregation rather than suppression of aggregation. Simulations with lysozyme and insulin also show arginine\\'s preference for aromatic residues, in addition to acidic residues. We use these observations and earlier results reported by us and others to discuss the possible implications of arginine\\'s interactions with aromatic residues on the solubilization of aromatic moieties and proteins. Our results also highlight the fact that explanations based purely on Γ XP, which measures average affinity of an additive to a protein, could obscure or misinterpret the underlying molecular mechanisms behind additive-induced suppression of protein aggregation. © 2011 American Institute of Chemical Engineers (AIChE).

  7. Arginine-aromatic interactions and their effects on arginine-induced solubilization of aromatic solutes and suppression of protein aggregation

    KAUST Repository

    Shah, Dhawal; Li, Jianguo; Shaikh, Abdul Rajjak; Rajagopalan, Raj

    2011-01-01

    We examine the interaction of aromatic residues of proteins with arginine, an additive commonly used to suppress protein aggregation, using experiments and molecular dynamics simulations. An aromatic-rich peptide, FFYTP (a segment of insulin), and lysozyme and insulin are used as model systems. Mass spectrometry shows that arginine increases the solubility of FFYTP by binding to the peptide, with the simulations revealing the predominant association of arginine to be with the aromatic residues. The calculations further show a positive preferential interaction coefficient, Γ XP, contrary to conventional thinking that positive Γ XP's indicate aggregation rather than suppression of aggregation. Simulations with lysozyme and insulin also show arginine's preference for aromatic residues, in addition to acidic residues. We use these observations and earlier results reported by us and others to discuss the possible implications of arginine's interactions with aromatic residues on the solubilization of aromatic moieties and proteins. Our results also highlight the fact that explanations based purely on Γ XP, which measures average affinity of an additive to a protein, could obscure or misinterpret the underlying molecular mechanisms behind additive-induced suppression of protein aggregation. © 2011 American Institute of Chemical Engineers (AIChE).

  8. Facile synthesis of “green” gold nanocrystals using cynarin in an aqueous solution

    Energy Technology Data Exchange (ETDEWEB)

    Katircioğlu, Zeynep; Şakalak, Hüseyin [Department of Metallurgical and Materials Engineering, Selcuk University, Konya 42075 (Turkey); Nanobiotechnology Laboratory, Advanced Technology Research and Application Center, Selcuk University, Konya 42075 (Turkey); Ulaşan, Mehmet [Nanobiotechnology Laboratory, Advanced Technology Research and Application Center, Selcuk University, Konya 42075 (Turkey); Department of Chemistry, Selcuk University, Konya 42075 (Turkey); Gören, Ahmet Ceyhan, E-mail: ahmetceyhan.goren@tubitak.gov.tr [TÜBİTAK UME, Chemistry Group, Organic Chemistry Laboratories, 41470 Gebze, Kocaeli (Turkey); Yavuz, Mustafa Selman, E-mail: selmanyavuz@selcuk.edu.tr [Department of Metallurgical and Materials Engineering, Selcuk University, Konya 42075 (Turkey); Nanobiotechnology Laboratory, Advanced Technology Research and Application Center, Selcuk University, Konya 42075 (Turkey)

    2014-11-01

    Highlights: • The first time a remarkably simple, versatile, environmentally friendly, one-pot and biogenic fabrication and aqueous synthesis of monodisperse gold nanoparticles by using cynarin. • Cynarin as a reductant and capping agent. • Exclusion of extra reducing agents or reductant. • Fabrication of Pd and Ag nanoparticles using cynarin in aqueous media. - Abstract: Herein we describe a water-based protocol that generates Au nanoparticles (AuNPs) by mixing aqueous solutions of HAuCl4 and cynarin (a natural product extract from artichoke leaf). Based on the observations from {sup 1}H NMR spectrum of AuNPs, a polyol oxidation mechanism by metal ions which eventually results in AuNPs formation, is proposed. Basically, the aromatic alcohol groups (1,2-benzenediol) of cynarin are oxidized to α-hydroxy ketone intermediate product, and then further oxidized to the vicinal diketone final product while the Au{sup 3+} ions are reduced to its atomic form (Au{sup 0}) which leads the generation of Au nanoparticles. This new protocol has also been employed to prepare multiply twinned Pd nanoparticles and Ag cubical aggregates. Due to exclusion of organic solvent, surfactant, or stabilizer for all these synthesis, this protocol may provide a simple, versatile, and environmentally benign route to fabricate noble-metal nanoparticles having various compositions and morphologies.

  9. Facile synthesis of “green” gold nanocrystals using cynarin in an aqueous solution

    International Nuclear Information System (INIS)

    Katircioğlu, Zeynep; Şakalak, Hüseyin; Ulaşan, Mehmet; Gören, Ahmet Ceyhan; Yavuz, Mustafa Selman

    2014-01-01

    Highlights: • The first time a remarkably simple, versatile, environmentally friendly, one-pot and biogenic fabrication and aqueous synthesis of monodisperse gold nanoparticles by using cynarin. • Cynarin as a reductant and capping agent. • Exclusion of extra reducing agents or reductant. • Fabrication of Pd and Ag nanoparticles using cynarin in aqueous media. - Abstract: Herein we describe a water-based protocol that generates Au nanoparticles (AuNPs) by mixing aqueous solutions of HAuCl4 and cynarin (a natural product extract from artichoke leaf). Based on the observations from 1 H NMR spectrum of AuNPs, a polyol oxidation mechanism by metal ions which eventually results in AuNPs formation, is proposed. Basically, the aromatic alcohol groups (1,2-benzenediol) of cynarin are oxidized to α-hydroxy ketone intermediate product, and then further oxidized to the vicinal diketone final product while the Au 3+ ions are reduced to its atomic form (Au 0 ) which leads the generation of Au nanoparticles. This new protocol has also been employed to prepare multiply twinned Pd nanoparticles and Ag cubical aggregates. Due to exclusion of organic solvent, surfactant, or stabilizer for all these synthesis, this protocol may provide a simple, versatile, and environmentally benign route to fabricate noble-metal nanoparticles having various compositions and morphologies

  10. Benzo-thia-fused [n]Thienoacenequinodimethanes with Small to Moderate Diradical Characters: The Role of Pro-aromaticity versus Anti-aromaticity

    KAUST Repository

    Shi, Xueliang

    2016-01-19

    Open-shell singlet diradicaloids recently have received much attention due to their unique optical, electronic and magnetic properties and promising applications in materials science. Among various diradicaloids, quinoidal π-conjugated molecules have become the prevailing designs. However, there still lacks fundamental understanding on how the fusion mode and pro-aromaticity/anti-aromaticity affect their diradical character and physical properties. In this work, a series of pro-aromatic benzo-thia-fused [n]thienoacenequinodimethanes (Thn-TIPS (n=1-3) and BDTh-TIPS) were synthesized and compared with the previously reported anti-aromatic bisindeno-[n]thienoacenes (Sn-TIPS, n=1-4). The ground-state geometric and electronic structures of these new quinoidal molecules were systematically investigated by X-ray crystallographic analysis, variable temperature NMR, ESR, SQUID, Raman, and electronic absorption spectroscopy, assisted by DFT calculations. It was found that the diradical character index (y0) increased from nearly zero for Th1-TIPS to 2.4% for Th2-TIPS, 18.2% for Th3-TIPS, and 38.2% for BDTh-TIPS, due to the enhanced aromatic stabilization. Consequently, with the extension of molecular size, the one-photon absorption spectra are gradually red-shifted, the two-photon absorption (TPA) cross section values increase, and the singlet excited state lifetimes decrease. By comparison with the corresponding anti-aromatic analogues Sn-TIPS (n=1-3), the pro-aromatic Thn-TIPS (n=1-3) exhibit larger diradical character, longer singlet excited state lifetime and larger TPA cross section value. At the same time, they display distinctively different electronic absorption spectra and improved electrochemical amphotericity. Spectroelectrochemical studies revealed a good linear relationship between the optical energy gaps and the molecular length in the neutral, radical cationic and dicationic forms. Our research work disclosed the significant difference between the pro-aromatic

  11. Benzo-thia-fused [n]Thienoacenequinodimethanes with Small to Moderate Diradical Characters: The Role of Pro-aromaticity versus Anti-aromaticity

    KAUST Repository

    Shi, Xueliang; Quintero, EstefanÍ a; Lee, Sangsu; Jing, Linzhi; Herng, Tun Seng; Zheng, Bin; Huang, Kuo-Wei; Ló pez Navarrete, Juan T.; Ding, Jun; Kim, Dongho; Casado, Juan; Chi, Chunyan

    2016-01-01

    Open-shell singlet diradicaloids recently have received much attention due to their unique optical, electronic and magnetic properties and promising applications in materials science. Among various diradicaloids, quinoidal π-conjugated molecules have become the prevailing designs. However, there still lacks fundamental understanding on how the fusion mode and pro-aromaticity/anti-aromaticity affect their diradical character and physical properties. In this work, a series of pro-aromatic benzo-thia-fused [n]thienoacenequinodimethanes (Thn-TIPS (n=1-3) and BDTh-TIPS) were synthesized and compared with the previously reported anti-aromatic bisindeno-[n]thienoacenes (Sn-TIPS, n=1-4). The ground-state geometric and electronic structures of these new quinoidal molecules were systematically investigated by X-ray crystallographic analysis, variable temperature NMR, ESR, SQUID, Raman, and electronic absorption spectroscopy, assisted by DFT calculations. It was found that the diradical character index (y0) increased from nearly zero for Th1-TIPS to 2.4% for Th2-TIPS, 18.2% for Th3-TIPS, and 38.2% for BDTh-TIPS, due to the enhanced aromatic stabilization. Consequently, with the extension of molecular size, the one-photon absorption spectra are gradually red-shifted, the two-photon absorption (TPA) cross section values increase, and the singlet excited state lifetimes decrease. By comparison with the corresponding anti-aromatic analogues Sn-TIPS (n=1-3), the pro-aromatic Thn-TIPS (n=1-3) exhibit larger diradical character, longer singlet excited state lifetime and larger TPA cross section value. At the same time, they display distinctively different electronic absorption spectra and improved electrochemical amphotericity. Spectroelectrochemical studies revealed a good linear relationship between the optical energy gaps and the molecular length in the neutral, radical cationic and dicationic forms. Our research work disclosed the significant difference between the pro-aromatic

  12. Research progress of anti-icing/deicing technologies for polar ships and offshore platforms

    Directory of Open Access Journals (Sweden)

    XIE Qiang

    2017-01-01

    Full Text Available The polar regions present adverse circumstances of high humidity and strong air-sea exchange. As such, the surfaces of ships and platforms (oil exploiting and drilling platforms serving in polar regions can easily be frozen by ice accretion, which not only affects the operation of the equipment but also threatens safety. This paper summarizes the status of the anti-icing/deicing technologies of both China and abroad for polar ships and offshore platforms, and introduces the various effects of ice accretion on polar ships and offshore platforms, and the resulting safety impacts. It then reviews existing anti-icing/deicing technologies and methods of both China and abroad, including such active deicing methods as electric heating, infrared heating and ultrasonic guided wave deicing, as well as such passive deicing methods as super hydrophobic coating, sacrificial coating, aqueous lubricating layer coating and low cross-link density (with interfacial slippage coating, summarizes their applicability to polar ships and offshore platforms, and finally discusses their advantages/disadvantages.

  13. Development of a screening method for the determination of total polynuclear aromatic hydrocarbons (PAH) in water and wastewater

    International Nuclear Information System (INIS)

    Riggin, R.; Strup, P.; Billets, S.

    1983-01-01

    Polynuclear aromatic hydrocarbons (PAHs) represent an important class of organic compounds from an environmental standpoint, due to known human carcinogenicity of some members. Consequently, there is a great need for monitoring the PAH concentration of a variety of media, including water and industrial wastewater. Recently, the United States Environmental Protection Agency (U.S. EPA) developed a sensitive analytical method, designated Test Method 610, for the determination of priority pollutant PAHs in aqueous industrial discharges. This method employs reversed phase high performance liquid chromatography (HPLC) with ultraviolet (UV) and fluorescence detection to determine all sixteen priority pollutant PAHs in a single chromatographic separation

  14. Paracetamol degradation in aqueous solution by non-thermal plasma

    Science.gov (United States)

    Baloul, Yasmine; Aubry, Olivier; Rabat, Hervé; Colas, Cyril; Maunit, Benoît; Hong, Dunpin

    2017-08-01

    This study deals with paracetamol degradation in water using a non-thermal plasma (NTP) created by a dielectric barrier discharge (DBD). The effects of the NTP operating conditions on the degradation were studied, showing that the treatment efficiency of the process was highly dependent on the electrical parameters and working gas composition in the reactor containing the aqueous solution. A conversion rate higher than 99% was reached with an energy yield of 12 g/kWh. High resolution mass spectrometry (HRMS) measurements showed that the main species produced in water during the process were nitrogen compounds, carboxylic acids and aromatic compounds. Contribution to the topical issue "The 15th International Symposium on High Pressure Low Temperature Plasma Chemistry (HAKONE XV)", edited by Nicolas Gherardi and Tomáš Hoder

  15. Energy transfer from triplet aromatic hydrocarbons to Tb3+ and Eu3+ in aqueous micellar solutions

    International Nuclear Information System (INIS)

    Almgren, M.; Grieser, F.; Thomas, J.K.

    1979-01-01

    The sensitization of Tb 3+ and Eu 3+ luminescence by energy transfer from aromatic triplet donors like naphthalene, bromonaphthalene, biphenyl, and phenanthrene in micellar sodium lauryl sulfate solution has been studied. Formal second-order rate constants for the energy transfer process in the micellar solutions were determined as 5 x 10 5 and 1.8 x 10 5 M -1 S -1 for transfer from biphenyl to Tb 3+ . The method of converting these rate constants to second-order constants pertaining to the micellar microenvironment is discussed; it is estimated that the transfer process at the micelles is charaterized by rate constants about one order of magnitude smaller than the formal ones. The transfer process is thus extremely slow. 7 figures

  16. Photochemical reaction between triclosan and nitrous acid in the atmospheric aqueous environment

    Science.gov (United States)

    Ma, Jianzhong; Zhu, Chengzhu; Lu, Jun; Lei, Yu; Wang, Jizhong; Chen, Tianhu

    2017-05-01

    Nitrous acid (HONO) is an important tropospheric pollutant and a major source of hydroxyl radical in the atmospheric gas phase. However, studies on the role of HONO in atmospheric aqueous phase chemistry processes are relatively few. The present work investigated the photochemical reaction of HONO with triclosan (TCS), which is an emerging contaminant, using a combination of laser flash photolysis spectrometry and gas chromatography mass spectrometry. With these techniques, the reaction pathway of HONO with TCS was proposed by directly monitoring the transient species and detecting the stable products. ·OH was generated from the photodissociation of the HONO aqueous solution and attacked TCS molecules on different sites to produce the TCS-OH adducts with a second-order rate constant of 1.11 × 109 L mol-1 s-1. The ·OH added a C atom adjacent to the ether bond in the aromatic ring of TCS and self-decayed when the ether bond broke. The intermediates generated from the addition of ·OH to the benzene ring of the TCS molecular structure were immediately nitrated by HONO, which played a key role in the formation process of nitrocompounds. An atmospheric model suggests that the aqueous oxidation of TCS by ·OH is a major reaction at high liquid water concentrations, and the photolysis of TCS dominates under low-humidity conditions.

  17. Micellar Enhanced Ultrafiltration for the Removal of Polycyclic Aromatic Hydrocarbons (PAHs Mixtures in Underground Contaminated Water in Oman

    Directory of Open Access Journals (Sweden)

    Mohamed Aoudia

    2011-12-01

    Full Text Available In an attempt to analyze polycyclic aromatic hydrocarbons (PAHs in diesel contaminated underground water in Oman (Rustaq, Gas chromatography-Mass spectrometry was first used to determine the different concentrations in a standard mixture containing 16 PAHs. Retention time and calibration curves were obtained for all aromatic compounds and were used to identify a given analyte as well as its concentration in the contaminated underground water. Micellar enhanced ultrafiltration (MEUF was then used to treat standard aqueous solution of PAHs at low concentration (~ 1 ppb using an edible nonionic surfactant (Tween 80. The totality of the mixture components was completely rejected. Within the experimental detection limit (± 0.01 ppb, the residual PAH concentrations were less than 0.01 ppb in accord with the allowed concentrations in drinking water. Likewise, excellent rejections of PAHs in MEUF treatment of diesel contaminated underground water at an Omani site (Rustaq were observed. The concentration of PAHs was reduced to less than 0.01 ppb, the accepted limit for the most toxic member of the PAH group (benzo(apyrene.

  18. Survey of benzene and aromatics in Canadian Gasoline - 1994

    International Nuclear Information System (INIS)

    Tushingham, M.

    1996-01-01

    A comprehensive database of the benzene and aromatics levels of gasoline produced in or imported into Canada during 1994, was presented. Environment Canada conducted a survey that requested refineries and importers to report quarterly on benzene and aromatics levels in gasoline. Benzene, which has been declared toxic by the Canadian Environmental Protection Act, is found in gasoline and is formed during the combustion of the aromatic components of gasoline. It was shown that benzene and aromatics levels differ regionally and seasonally. There are also variations in benzene levels between batches of gasoline produced at any one refinery. This report listed the responses to the benzene/aromatics survey. It also described the analytical procedures used to measure benzene and aromatics levels in gasoline, and provided guidelines for reporting gasoline benzene and total aromatics data. 7 tabs., 21 figs

  19. Modeling the fate of polynuclear aromatic hydrocarbons in the rhizosphere

    International Nuclear Information System (INIS)

    Santharam, S.K.; Erickson, L.E.; Fan, L.T.

    1994-01-01

    Polynuclear aromatic hydrocarbons (PAHs) are major contaminants associated with wastes from manufactured gas plants, wood treating operations, and petroleum refining; they are potentially carcinogenic and mutagenic. It has been known that vegetation can enhance the rate and extent of degradation of PAHs in contaminated soil. Plant roots release exudates capable of supplying carbon and energy to microflora for degrading PAHs. It has also been well established that the population of microorganisms in the rhizosphere is significantly greater than that in the non-vegetated soil; these microorganisms are apparently responsible for the enhanced biodegradation of PAHs. A model has been derived for describing the rate of disappearance of a non-aqueous phase contaminant in the rhizosphere, which takes into account dissolution, adsorption, desorption and biodegradation of the contaminant, without neglecting the size distribution of the organic-phase droplets; the rate of biodegradation is expressed in terms of the Monod kinetics. The model is validated with the available experimental data for pyrene

  20. Bicyclic Baird-type aromaticity

    Science.gov (United States)

    Cha, Won-Young; Kim, Taeyeon; Ghosh, Arindam; Zhang, Zhan; Ke, Xian-Sheng; Ali, Rashid; Lynch, Vincent M.; Jung, Jieun; Kim, Woojae; Lee, Sangsu; Fukuzumi, Shunichi; Park, Jung Su; Sessler, Jonathan L.; Chandrashekar, Tavarekere K.; Kim, Dongho

    2017-12-01

    Classic formulations of aromaticity have long been associated with topologically planar conjugated macrocyclic systems. The theoretical possibility of so-called bicycloaromaticity was noted early on. However, it has yet to be demonstrated by experiment in a simple synthetic organic molecule. Conjugated organic systems are attractive for studying the effect of structure on electronic features. This is because, in principle, they can be modified readily through dedicated synthesis. As such, they can provide useful frameworks for testing by experiment with fundamental insights provided by theory. Here we detail the synthesis and characterization of two purely organic non-planar dithienothiophene-bridged [34]octaphyrins that permit access to two different aromatic forms as a function of the oxidation state. In their neutral forms, these congeneric systems contain competing 26 and 34 π-electronic circuits. When subject to two-electron oxidation, electronically mixed [4n+1]/[4n+1] triplet biradical species in the ground state are obtained that display global aromaticity in accord with Baird's rule.

  1. Multi-q pattern classification of polarization curves

    Science.gov (United States)

    Fabbri, Ricardo; Bastos, Ivan N.; Neto, Francisco D. Moura; Lopes, Francisco J. P.; Gonçalves, Wesley N.; Bruno, Odemir M.

    2014-02-01

    Several experimental measurements are expressed in the form of one-dimensional profiles, for which there is a scarcity of methodologies able to classify the pertinence of a given result to a specific group. The polarization curves that evaluate the corrosion kinetics of electrodes in corrosive media are applications where the behavior is chiefly analyzed from profiles. Polarization curves are indeed a classic method to determine the global kinetics of metallic electrodes, but the strong nonlinearity from different metals and alloys can overlap and the discrimination becomes a challenging problem. Moreover, even finding a typical curve from replicated tests requires subjective judgment. In this paper, we used the so-called multi-q approach based on the Tsallis statistics in a classification engine to separate the multiple polarization curve profiles of two stainless steels. We collected 48 experimental polarization curves in an aqueous chloride medium of two stainless steel types, with different resistance against localized corrosion. Multi-q pattern analysis was then carried out on a wide potential range, from cathodic up to anodic regions. An excellent classification rate was obtained, at a success rate of 90%, 80%, and 83% for low (cathodic), high (anodic), and both potential ranges, respectively, using only 2% of the original profile data. These results show the potential of the proposed approach towards efficient, robust, systematic and automatic classification of highly nonlinear profile curves.

  2. A critical evaluation of magnetic activated carbon's potential for the remediation of sediment impacted by polycyclic aromatic hydrocarbons.

    Science.gov (United States)

    Han, Zhantao; Sani, Badruddeen; Akkanen, Jarkko; Abel, Sebastian; Nybom, Inna; Karapanagioti, Hrissi K; Werner, David

    2015-04-09

    Addition of activated carbon (AC) or biochar (BC) to sediment to reduce the chemical and biological availability of organic contaminants is a promising in-situ remediation technology. But concerns about leaving the adsorbed pollutants in place motivate research into sorbent recovery methods. This study explores the use of magnetic sorbents. A coal-based magnetic activated carbon (MAC) was identified as the strongest of four AC and BC derived magnetic sorbents for polycyclic aromatic hydrocarbons (PAHs) remediation. An 8.1% MAC amendment (w/w, equal to 5% AC content) was found to be as effective as 5% (w/w) pristine AC in reducing aqueous PAHs within three months by 98%. MAC recovery from sediment after three months was 77%, and incomplete MAC recovery had both, positive and negative effects. A slight rebound of aqueous PAH concentrations was observed following the MAC recovery, but aqueous PAH concentrations then dropped again after six months, likely due to the presence of the 23% unrecovered MAC. On the other hand, the 77% recovery of the 8.1% MAC dose was insufficient to reduce ecotoxic effects of fine grained AC or MAC amendment on the egestion rate, growth and reproduction of the AC sensitive species Lumbriculus variegatus. Copyright © 2014 Elsevier B.V. All rights reserved.

  3. Picosecond absorption studies of photoinduced charge separation in polyelectrolyte bound aromatic chromophores

    Science.gov (United States)

    Shand, M. A.; Rodgers, M. A. J.; Webber, S. E.

    1991-02-01

    Picosecond absorption studies of photoinduced electron transfer between aromatic chromophores bound to polymethacrylic acid (P) and methylviologen (MV 2+ have been carried out in aqueous solution. The diphenylanthracene copolymer/viologen system at pH 2.8 shows the corresponding redox products DPA + rad and MV + rad arising from the singlet state of DPA with a forward rate constant of electron transfer of 2.6 × 10 9 s -1. At pH 9.0 the quenching of the S 1 state of DPA occurs with no charge separated products being observed. The pyrene copolymer shows no evidence of charge separated products at any pH in the range 2.8-9.0. It is proposed that the differences in the radical pair kinetics arise from differences in the degree of binding of the ground state complexes formed by the donor and acceptor species.

  4. Mutagenic hazards of complex polycyclic aromatic hydrocarbon mixtures in contaminated soil

    Energy Technology Data Exchange (ETDEWEB)

    Lemieux, C.L.; Lambert, A.B.; Lundstedt, S.; Tysklind, M.; White, P.A. [Health Canada, Ottawa, ON (Canada). Safe Environment Program

    2008-04-15

    The objective of the present study was to evaluate hazard/risk assessment methods for complex environmental mixtures that involve a targeted, priority chemical approach based on the cumulative hazard/risk of known mixture components or analyses of sufficiently similar mixtures. Ten polycyclic aromatic hydrocarbon (PAH)-contaminated soils were separated into nonpolar and semipolar fractions, and both fractions elicited positive responses on the Salmonella reverse mutation assay. Targeted and nontargeted methods of hazard prediction routinely overestimated mutagenic activities for the nonpolar soil fractions, suggesting nonadditive interactions of PAHs in complex mixtures. This suggests that current risk assessment methods for complex mixtures may provide conservative estimates regarding soils contaminated with priority PAHs alone. Significant underestimations of total risk, however, will be obtained if the soils also contain unidentified PAHs as well as polycyclic aromatic compounds and related compounds that contribute to the total mutagenic activity. Furthermore, estimates of excess lifetime cancer risk associated with the nondietary ingestion of the PAH-contaminated soils studied here indicate that a traditional risk assessment model based on identified priority PAHs and an assumption of additivity generally underestimates the risk associated with the nonpolar soil fractions (in comparison to bioassay-derived risk estimates). Additional cancer risk may be associated with the more polar compounds that also are found at these contaminated sites and that rarely are included in the standard risk assessment methodology.

  5. Volatilisation of aromatic hydrocarbons from soil

    DEFF Research Database (Denmark)

    Lindhardt, B.; Christensen, T.H.

    1996-01-01

    The non-steady-state fluxes of aromatic hydrocarbons were measured in the laboratory from the surface of soils contaminated with coal tar Four soil samples from a former gasworks site were used for the experiments. The fluxes were quantified for 11 selected compounds, 4 mono- and 7 polycyclic...... aromatic hydrocarbons, for a period of up to 8 or 16 days. The concentrations of the selected compounds in the soils were between 0.2 and 3,100 mu g/g. The study included the experimental determination of the distribution coefficient of the aromatic hydrocarbons between the sorbed phase and the water under...... saturated conditions. The determined distribution coefficients showed that the aromatic hydrocarbons were more strongly sorbed to the total organic carbon including the coal tar pitch - by a factor of 8 to 25 - than expected for natural organic matter. The fluxes were also estimated using an analytical...

  6. Development of selective colorimetric probes for hydrogen sulfide based on nucleophilic aromatic substitution.

    Science.gov (United States)

    Montoya, Leticia A; Pearce, Taylor F; Hansen, Ryan J; Zakharov, Lev N; Pluth, Michael D

    2013-07-05

    Hydrogen sulfide is an important biological signaling molecule and an important environmental target for detection. A major challenge in developing H2S detection methods is separating the often similar reactivity of thiols and other nucleophiles from H2S. To address this need, the nucleophilic aromatic substitution (SNAr) reaction of H2S with electron-poor aromatic electrophiles was developed as a strategy to separate H2S and thiol reactivity. Treatment of aqueous solutions of nitrobenzofurazan (7-nitro-1,2,3-benzoxadiazole, NBD) thioethers with H2S resulted in thiol extrusion and formation of nitrobenzofurazan thiol (λmax = 534 nm). This reactivity allows for unwanted thioether products to be converted to the desired nitrobenzofurazan thiol upon reaction with H2S. The scope of the reaction was investigated using a Hammett linear free energy relationship study, and the determined ρ = +0.34 is consistent with the proposed SN2Ar reaction mechanism. The efficacy of the developed probes was demonstrated in buffer and in serum with associated submicromolar detection limits as low as 190 nM (buffer) and 380 nM (serum). Furthermore, the sigmoidal response of nitrobenzofurazan electrophiles with H2S can be fit to accurately quantify H2S. The developed detection strategy offers a manifold for H2S detection that we foresee being applied in various future applications.

  7. Solvent effects on extraction of polycyclic aromatic hydrocarbons in ambient aerosol samples

    Directory of Open Access Journals (Sweden)

    Flasch Mira

    2016-01-01

    Full Text Available Polycyclic Aromatic Hydrocarbons (PAHs in the ambient particulate matter pose one of the most important issues in the focus of environmental management. The concentration of their representative, Benzo(apyrene (BaP, undergoes limitations according to European Union directive. However, a successful control over the pollution levels and their sources is limited by the high uncertainty of analytical and statistical approaches used for their characterization. Here we compare differences in PAH concentrations related to the use of different solvents in the course of ultrasonic extraction of a certified reference material (PM10-like PAH mixture and filter samples of ambient particulate matter collected in Austria for the CG-MS PAH analysis. Using solvents of increasing polarity: Cyclohexane (0,006, Toluene (0,099, Dichloromethane (0,309, Acetone (0,43 and Acetonitrile (0,460, as well as mixtures of those, filters representing high and low concentrations of particulate matter were investigated. Although some scatter of the obtained concentrations was observed no trend related to the polarity of the solvent became visible. Regarding the reproducibility, which can be expected of PAH analysis no significant difference between the different solvents was determined. This result is valid for all compounds under investigation.

  8. Bioassay of polycyclic aromatic hydrocarbons

    Energy Technology Data Exchange (ETDEWEB)

    Van Kirk, E.A.

    1980-08-01

    A positive relationship was found between the photodynamic activity of 24 polycyclic aromatic hydrocarbons versus published results on the mutagenicity, carcinogenicity, and initiation of unscheduled DNA synthesis. Metabolic activation of benzo(a)pyrene resulted in detection of increased mutagenesis in Paramecium tetraurelia as found also in the Ames Salmonella assay. The utility of P. tetraurelia as a biological detector of hazardous polycyclic aromatic hydrocarbons is discussed.

  9. How non-conventional feedstocks will affect aromatics technologies

    Energy Technology Data Exchange (ETDEWEB)

    Koehler, E. [Clariant Produkte (Deutschland) GmbH, Muenchen (Germany)

    2013-11-01

    The abundance of non-conventional feedstocks such as coal and shale gas has begun to affect the availability of traditional base chemicals such as propylene and BTX aromatics. Although this trend is primarily fueled by the fast growing shale gas economy in the US and the abundance of coal in China, it will cause the global supply and demand situation to equilibrate across the regions. Lower demand for gasoline and consequently less aromatics rich reformate from refineries will further tighten the aromatics markets that are expected to grow at healthy rates, however. Refiners can benefit from this trend by abandoning their traditional fuel-oriented business model and becoming producers of petrochemical intermediates, with special focus on paraxylene (PX). Cheap gas from coal (via gasification) or shale reserves is an advantaged feedstock that offers a great platform to make aromatics in a cost-competitive manner, especially in regions where naphtha is in short supply. Gas condensates (LPG and naphtha) are good feedstocks for paraffin aromatization, and methanol from coal or (shale) gas can be directly converted to BTX aromatics (MTA) or alkylated with benzene or toluene to make paraxylene. Most of today's technologies for the production and upgrading of BTX aromatics and their derivatives make use of the unique properties of zeolites. (orig.)

  10. Vanillic and syringic acids from biomass burning: Behaviour during Fenton-like oxidation in atmospheric aqueous phase and in the absence of light

    Energy Technology Data Exchange (ETDEWEB)

    Santos, Gabriela T.A.D.; Santos, Patrícia S.M., E-mail: patricia.santos@ua.pt; Duarte, Armando C.

    2016-08-05

    Highlights: • The rate of oxidation of small aromatic acids increase with the pH decrease. • With the oxidation of aromatic acids are formed new small aromatic compounds. • The initial and formed compounds are not totally degraded during the night period. • The substituents and their positions in ring affect the oxidation of aromatic acids. • The OH radical attack to vanillic and syringic acids is different in atmospheric waters. - Abstract: Biomass combustion is a threat to the environment since it emits to the atmosphere organic compounds, which may react and originate others more aggressive. This work studied the behaviours of vanillic and syringic acids, small aromatic tracers of biomass burning, during Fenton-like oxidation in aqueous phase and absence of light. For both compounds, the extent of oxidation increased with pH decrease from neutral to acid in atmospheric waters, but for vanillic acid the neutral pH was not able of promoting the oxidation. With the oxidation of both acids were formed chromophoric compounds, and the formation rate increased with the degree of electron-donator substituents in benzene ring. The initial and produced compounds were not totally degraded up to 24 h of reaction at pH 4.5, suggesting that the night period may be not sufficient for their full degradation in atmospheric waters. The major compounds formed were the 3,4-dihydroxybenzoic acid for vanillic acid, and the 1,4-dihydroxy-2,6-dimethoxybenzene for syringic acid. These findings suggest the occurrence of an ipso attack by the hydroxyl radical preferential to the methoxy and carboxyl groups of vanillic and syringic acids, respectively. It is important to highlight that for both aromatic acids the main compounds produced are also small aromatic compounds.

  11. Metabolism and Biomarkers of Heterocyclic Aromatic Amines in Molecular Epidemiology Studies: Lessons Learned from Aromatic Amines

    Science.gov (United States)

    2011-01-01

    Aromatic amines and heterocyclic aromatic amines (HAAs) are structurally related classes of carcinogens that are formed during the combustion of tobacco or during the high-temperature cooking of meats. Both classes of procarcinogens undergo metabolic activation by N-hydroxylation of the exocyclic amine group, to produce a common proposed intermediate, the arylnitrenium ion, which is the critical metabolite implicated in toxicity and DNA damage. However, the biochemistry and chemical properties of these compounds are distinct and different biomarkers of aromatic amines and HAAs have been developed for human biomonitoring studies. Hemoglobin adducts have been extensively used as biomarkers to monitor occupational and environmental exposures to a number of aromatic amines; however, HAAs do not form hemoglobin adducts at appreciable levels and other biomarkers have been sought. A number of epidemiologic studies that have investigated dietary consumption of well-done meat in relation to various tumor sites reported a positive association between cancer risk and well-done meat consumption, although some studies have shown no associations between well-done meat and cancer risk. A major limiting factor in most epidemiological studies is the uncertainty in quantitative estimates of chronic exposure to HAAs and, thus, the association of HAAs formed in cooked meat and cancer risk has been difficult to establish. There is a critical need to establish long-term biomarkers of HAAs that can be implemented in molecular epidemioIogy studies. In this review article, we highlight and contrast the biochemistry of several prototypical carcinogenic aromatic amines and HAAs to which humans are chronically exposed. The biochemical properties and the impact of polymorphisms of the major xenobiotic-metabolizing enzymes on the biological effects of these chemicals are examined. Lastly, the analytical approaches that have been successfully employed to biomonitor aromatic amines and HAAs, and

  12. Aromatization of n-octane over Pd/C catalysts

    KAUST Repository

    Yin, Mengchen; Natelson, Robert H.; Campos, Andrew A.; Kolar, Praveen; Roberts, William L.

    2013-01-01

    Gas-phase aromatization of n-octane was investigated using Pd/C catalyst. The objectives were to: (1) determine the effects of temperature (400-600 °C), weight hourly space velocity (WHSV) (0.8-∞), and hydrogen to hydrocarbon molar ratio (MR) (0-6) on conversion, selectivity, and yield (2) compare the activity of Pd/C with Pt/C and Pt/KL catalysts and (3) test the suitability of Pd/C for aromatization of different alkanes including n-hexane, n-heptane, and n-octane. Pd/C exhibited the best aromatization performance, including 54.4% conversion and 31.5% aromatics yield at 500 °C, WHSV = 2 h-1, and a MR of 2. The Pd/C catalyst had higher selectivity towards the preferred aromatics including ethylbenzene and xylenes, whereas Pt/KL had higher selectivity towards benzene and toluene. The results were somewhat consistent with adsorbed n-octane cyclization proceeding mainly through the six-membered ring closure mechanism. In addition, Pd/C was also capable of catalyzing aromatization of n-hexane and n-heptane. © 2012 Elsevier Ltd. All rights reserved.

  13. Proximate Composition, Mineral Content and Fatty Acids Analyses of Aromatic and Non-Aromatic Indian Rice

    Directory of Open Access Journals (Sweden)

    Deepak Kumar Verma

    2017-01-01

    Full Text Available Awareness on nutritive value and health benefits of rice is of vital importance in order to increase the consumption of rice in daily diet of the human beings. In this study, a total of six aromatic and two non-aromatic rice accessions grown in India were analysed for their nutritional quality attributes including proximate composition, mineral contents and fatty acids. Data with three replications were used to measure Pearson's simple correlation co-efficient in order to establish the relationship among various nutritional quality attributes. The result on proximate composition showed that Govind Bhog had the highest moisture (13.57% and fat (0.92% content, which signifies its tasty attribute. Badshah Bhog exhibited the highest fibre content (0.85%, carbohydrate content (82.70% and food energy (365.23 kCal per 100 g. Among the minerals, the higher Ca (98.75 mg/kg, Zn (17.00 mg/kg and Fe (31.50 mg/kg were in Gopal Bhog, whereas the highest Na (68.85 mg/kg was in Badshah Bhog, the highest K (500.00 mg/kg was in Swetganga, Khushboo and Sarbati. The highest contents of unsaturated fatty acids viz. oleic acid (49.14%, linoleic acid (46.99% and linolenic acid (1.27% were found in Sarbati, whereas the highest content of saturated fatty acids viz. myristic acid (4.60% and palmitic acid (31.91% were found in Govind Bhog and stearic acid (6.47% in Todal. The identified aromatic rice accessions Gopal Bhog, Govind Bhog and Badshah Bhog and non-aromatic rice accession Sarbati were found nutritionally superior among all eight tested accessions. The nutritional quality oriented attributes in this study were competent with recognized prominent aromatic and non-aromatic rice accessions as an index of their nutritional worth and recommend to farmers and consumers which may be graded as export quality rice with good unique nutritional values in international market.

  14. Four groups of new aromatic halogenated disinfection byproducts: effect of bromide concentration on their formation and speciation in chlorinated drinking water.

    Science.gov (United States)

    Pan, Yang; Zhang, Xiangru

    2013-02-05

    Bromide is naturally present in source waters worldwide. Chlorination of drinking water can generate a variety of chlorinated and brominated disinfection byproducts (DBPs). Although substantial efforts have been made to examine the effect of bromide concentration on the formation and speciation of halogenated DBPs, almost all previous studies have focused on trihalomethanes and haloacetic acids. Given that about 50% of total organic halogen formed in chlorination remains unknown, it is still unclear how bromide concentration affects the formation and speciation of the new/unknown halogenated DBPs. In this study, chlorinated drinking water samples with different bromide concentrations were prepared, and a novel approach-precursor ion scan using ultra performance liquid chromatography/electrospray ionization-triple quadrupole mass spectrometry-was adopted for the detection and identification of polar halogenated DBPs in these water samples. With this approach, 11 new putative aromatic halogenated DBPs were identified, and they were classified into four groups: dihalo-4-hydroxybenzaldehydes, dihalo-4-hydroxybenzoic acids, dihalo-salicylic acids, and trihalo-phenols. A mechanism for the formation of the four groups of new aromatic halogenated DBPs was proposed. It was found that increasing the bromide concentration shifted the entire polar halogenated DBPs as well as the four groups of new DBPs from being less brominated to being more brominated; these new aromatic halogenated DBPs might be important intermediate DBPs formed in drinking water chlorination. Moreover, the speciation of the four groups of new DBPs was modeled: the speciation patterns of the four groups of new DBPs well matched those determined from the model equations, and the reactivity differences between HOBr and HOCl in reactions forming the four groups of new DBPs were larger than those in reactions forming trihalomethanes and haloacetic acids.

  15. Enhanced Photocatalytic Activity of TiO2 Nanoparticles Supported on Electrically Polarized Hydroxyapatite.

    Science.gov (United States)

    Zhang, Xuefei; Yates, Matthew Z

    2018-05-23

    Fast recombination of photogenerated charge carriers in titanium dioxide (TiO 2 ) remains a challenging issue, limiting the photocatalytic activity. This study demonstrates increased photocatalytic performance of TiO 2 nanoparticles supported on electrically polarized hydroxyapatite (HA) films. Dense and thermally stable yttrium and fluorine co-doped HA films with giant internal polarization were synthesized as photocatalyst supports. TiO 2 nanoparticles deposited on the support were then used to catalyze the photochemical reduction of aqueous silver ions to produce silver nanoparticles. It was found that significantly more silver nanoparticles were produced on polarized HA supports than on depolarized HA supports. In addition, the photodegradation of methyl orange with TiO 2 nanoparticles on polarized HA supports was found to be much faster than with TiO 2 nanoparticles on depolarized HA supports. It is proposed that separation of photogenerated electrons and holes in TiO nanoparticles is promoted by the internal polarization of the HA support, and consequently, the recombination of charge carriers is mitigated. The results imply that materials with large internal polarization can be used in strategies for enhancing quantum efficiency of photocatalysts.

  16. Estimating release of polycyclic aromatic hydrocarbons from coal tar at manufactured-gas plant sites

    International Nuclear Information System (INIS)

    Loehr, R.C.; Rao, P.S.C.; Lee, L.S.; Okuda, I.

    1992-08-01

    One component of the EPRI's research on Envirorunental Behavior of Organic Substances (EBOS) consists of developing information and models to predict releases of monocyclic and polycyclic aromatic hydrocarbons (MAHs and PAHs) to groundwater from coal tars and contaminated soils at MGP sites. The results of this report focus primarily on release of PAHs from coal tars. There are at least two approaches to predicting the release of organic chemicals from coal tar to water. The simplest method to estimate aqueous concentrations is to assume that water solubility of a PAH compound released from the tar can be defined by equilibrium precipitation-dissolution reactions. Application of Raoult's law is another method to predict aqueous concentrations, which requires the assumption of ''ideal'' behavior for partitioning of PAHs between the tar and water phases. To evaluate the applicability of these two methods for predicting PAH releases, laboratory experiments were conducted with eight coal tar samples from former MGP sites across the country. Migration of chemicals in the environment and resulting contaminant plumes in groundwater are determined by leachate concentrations of the chemicals. The use of equilibrium precipitation-dissolution reactions will usually result in an overestimation of PAH concentrations in the leachate from a coal tar source, and thus the resulting PAH concentrations in groundwater. Raoult's law appears to be a more accurate approach to predicting the release of several PAHs from coal tars. Furthermore, if nonequilibrium conditions prevail, aqueous-phase PAH concentrations will be even lower than those predicted using Raoult's law

  17. Sorption of polycyclic aromatic hydrocarbons on particulate organic matters

    International Nuclear Information System (INIS)

    Guo Xueyan; Luo Lei; Ma Yibing; Zhang Shuzhen

    2010-01-01

    Particulate organic matter (POM) is a key organic matter fraction which can influence soil fertility. Its interactions with hydrophobic organic pollutants (HOCs) have not been characterized and the mechanisms of retention of HOCs by POM remain unclear. In the present study, sorption behaviors of polycyclic aromatic hydrocarbons (PAHs) naphthalene (NAP), phenanthrene (PHE), and pyrene (PYR) by POMs separated from different soils were examined and the POMs were characterized by elemental analysis, solid state 13 C NMR, and Fourier transform infrared spectroscopy (FT-IR). The results indicated that POMs were mainly composed of aliphatic components with high polarity. The different original POMs showed similar chemical composition and configuration. Sorption behaviors of PAHs indicated that there was no significant difference in sorption capacity among the POMs. Sorption of NAP and PHE by POMs displayed a nonlinear isotherm, while sorption of PYR yielded a linear isotherm. No significant hysteresis and ionic strength effect were observed for PAH desorption from the POMs.

  18. Speeding up the self-assembly of a DNA nanodevice using a variety of polar solvents

    Science.gov (United States)

    Kang, Di; Duan, Ruixue; Tan, Yerpeng; Hong, Fan; Wang, Boya; Chen, Zhifei; Xu, Shaofang; Lou, Xiaoding; Wei, Wei; Yurke, Bernard; Xia, Fan

    2014-11-01

    The specific recognition and programmable assembly properties make DNA a potential material for nanodevices. However, the more intelligent the nanodevice is, the more complicated the structure of the nanodevice is, which limits the speed of DNA assembly. Herein, to address this problem, we investigate the performance of DNA Strand Displacement Reaction (DSDR) in a mixture of polar organic solvents and aqueous buffer and demonstrate that the organic polar solvent can speed up DNA self-assembly efficiently. Taking DSDR in 20% ethanol as an example, first we have demonstrated that the DSDR is highly accelerated in the beginning of the reaction and it can complete 60% of replacement reactions (160% enhancement compared with aqueous buffer) in the first 300 seconds. Secondly, we calculated that the ΔΔG of the DSDR in 20% ethanol (-18.2 kcal mol-1) is lower than that in pure aqueous buffer (-32.6 kcal mol-1), while the activation energy is lowered by introducing ethanol. Finally, we proved that the DSDR on the electrode surface can also be accelerated using this simple strategy. More importantly, to test the efficacy of this approach in nanodevices with a complicated and slow DNA self-assembly process, we apply this strategy in the hybridization chain reaction (HCR) and prove the acceleration is fairly obvious in 20% ethanol, which demonstrates the feasibility of the proposed strategy in DNA nanotechnology and DNA-based biosensors.The specific recognition and programmable assembly properties make DNA a potential material for nanodevices. However, the more intelligent the nanodevice is, the more complicated the structure of the nanodevice is, which limits the speed of DNA assembly. Herein, to address this problem, we investigate the performance of DNA Strand Displacement Reaction (DSDR) in a mixture of polar organic solvents and aqueous buffer and demonstrate that the organic polar solvent can speed up DNA self-assembly efficiently. Taking DSDR in 20% ethanol as an

  19. AN AROMATIC INVENTORY OF THE LOCAL VOLUME

    International Nuclear Information System (INIS)

    Marble, A. R.; Engelbracht, C. W.; Block, M.; Van Zee, L.; Dale, D. A.; Cohen, S. A.; Schuster, M. D.; Smith, J. D. T.; Gordon, K. D.; Wu, Y.; Lee, J. C.; Kennicutt, R. C.; Skillman, E. D.; Johnson, L. C.; Calzetti, D.; Lee, H.

    2010-01-01

    Using infrared photometry from the Spitzer Space Telescope, we perform the first inventory of aromatic feature emission (also commonly referred to as polycyclic aromatic hydrocarbon emission) for a statistically complete sample of star-forming galaxies in the local volume. The photometric methodology involved is calibrated and demonstrated to recover the aromatic fraction of the Infrared Array Camera 8 μm flux with a standard deviation of 6% for a training set of 40 SINGS galaxies (ranging from stellar to dust dominated) with both suitable mid-infrared Spitzer Infrared Spectrograph spectra and equivalent photometry. A potential factor of 2 improvement could be realized with suitable 5.5 μm and 10 μm photometry, such as what may be provided in the future by the James Webb Space Telescope. The resulting technique is then applied to mid-infrared photometry for the 258 galaxies from the Local Volume Legacy (LVL) survey, a large sample dominated in number by low-luminosity dwarf galaxies for which obtaining comparable mid-infrared spectroscopy is not feasible. We find the total LVL luminosity due to five strong aromatic features in the 8 μm complex to be 2.47 x 10 10 L sun with a mean volume density of 8.8 x 10 6 L sun Mpc -3 . Twenty-four of the LVL galaxies, corresponding to a luminosity cut at M B = -18.22, account for 90% of the aromatic luminosity. Using oxygen abundances compiled from the literature for 129 of the 258 LVL galaxies, we find a correlation between metallicity and the aromatic-to-total infrared emission ratio but not the aromatic-to-total 8 μm dust emission ratio. A possible explanation is that metallicity plays a role in the abundance of aromatic molecules relative to the total dust content, but other factors, such as star formation and/or the local radiation field, affect the excitation of those molecules.

  20. Water-Soluble Pd8L4 Self-assembled Molecular Barrel as an Aqueous Carrier for Hydrophobic Curcumin.

    Science.gov (United States)

    Bhat, Imtiyaz Ahmad; Jain, Ruchi; Siddiqui, Mujahuddin M; Saini, Deepak K; Mukherjee, Partha Sarathi

    2017-05-01

    A tetrafacial water-soluble molecular barrel (1) was synthesized by coordination driven self-assembly of a symmetrical tetrapyridyl donor (L) with a cis-blocked 90° acceptor [cis-(en)Pd(NO 3 ) 2 ] (en = ethane-1,2-diamine). The open barrel structure of (1) was confirmed by single crystal X-ray diffraction. The presence of a hydrophobic cavity with large windows makes it an ideal candidate for encapsulation and carrying hydrophobic drug like curcumin in an aqueous medium. The barrel (1) encapsulates curcumin inside its molecular cavity and protects highly photosensitive curcumin from photodegradation. The photostability of encapsulated curcumin is due to the absorption of a high proportion of the incident photons by the aromatic walls of 1 with a high absorption cross-sectional area, which helps the walls to shield the guest even against sunlight/UV radiations. As compared to free curcumin in water, we noticed a significant increase in solubility as well as cellular uptake of curcumin upon encapsulation inside the water-soluble molecular barrel (1) in aqueous medium. Fluorescence imaging confirmed that curcumin was delivered into HeLa cancer cells by the aqueous barrel (1) with the retention of its potential anticancer activity. While free curcumin is inactive toward cancer cells in aqueous medium at room temperature due to negligible solubility, the determined IC 50 value of ∼14 μM for curcumin in aqueous medium in the presence of the barrel (1) reflects the efficiency of the barrel as a potential curcumin carrier in aqueous medium without any other additives. Thus, two major challenges of increasing the bioavailability and stability of curcumin in aqueous medium even in the presence of UV light have been addressed by using a new supramolecular water-soluble barrel (1) as a drug carrier.

  1. Electrochemical degradation of aromatic amines on BDD electrodes

    International Nuclear Information System (INIS)

    Pacheco, M.J.; Santos, V.; Ciriaco, L.; Lopes, A.

    2011-01-01

    The electrochemical oxidation of four aromatic amines, with different substituent groups, 3-amino-4-hydroxy-5-nitrobenzenesulfonic acid (A1), 5-amino-2-methoxybenzenesulfonic acid (A2), 2,4-dihydroxyaniline hydrochloride (A3) and benzene-1,4-diamine (A4), was performed using as anode a boron-doped diamond electrode, commercially available at Adamant Technologies. Tests were run at room temperature with model solutions of the different amines, with concentrations of 200 ppm, using as electrolyte 0.035 M Na 2 SO 4 aqueous solutions, in a batch cell with recirculation, at different current densities (200 and 300 A m -2 ). The following analyses were performed with the samples collected during the assays: UV-Vis spectrophotometry, chemical oxygen demand (COD), total organic carbon (TOC), total Kjeldahl nitrogen, ammonia nitrogen, nitrates and HPLC. Results have shown a good electrodegradation of all the amines tested, with COD removals, after 6 h assays, higher than 90% and TOC removals between 60 and 80%. Combustion efficiency (η C ), which measures the tendency to convert organic carbon to CO 2 , was also determined for all the amines, being η CA1 CA2 CA3 CA4 = 0.99.

  2. Degradation of polycyclic aromatic hydrocarbons : model simulation for bioavailability and biodegradation

    Energy Technology Data Exchange (ETDEWEB)

    Owabor, C.N.; Ogbeide, S.E. [Benin Univ. (Nigeria). Dept. of Chemical Engineering; Susu, A.A. [Lagos Univ. (Nigeria). Dept. of Chemical Engineering

    2010-04-15

    Research has indicated that the biodegradation of polycyclic aromatic hydrocarbons (PAHs) is influenced by the molecular size of the PAHs as well as by soil properties. This study presented a model for a 1-D convective-dispersive solute transport in a soil matrix. The model was designed to consider the gas-liquid interface film and the biofilm between the liquid and solid interface as well as to account for interparticle; intraparticle, and interphase mass transport. A soil microcosm reactor was used to evaluate substrate bioavailability and biodegradation in a contaminated aqueous solids system. The numerical model involved the discretization of depth, radial distance, and time into mesh or grid points with constant intervals. Dimensionless variables were defined using a backward finite difference (BFD) method. Results of the study suggested that PAH occlusion occurred in the micropores of the soil particle. The non-steady state model adequately predicted the concentration profiles of PAHs within the soil matrix. 26 refs., 5 tabs., 7 figs.

  3. Fused aromatic thienopyrazines: structure, properties and function

    KAUST Repository

    Mondal, Rajib; Ko, Sangwon; Bao, Zhenan

    2010-01-01

    Recent development of a fused aromatic thieno[3.4-b]pyrazine system and their application in optoelectronic devices are reviewed. Introduction of a fused aromatic unit followed by side chain engineering, dramatically enhanced the charge carrier

  4. Open Circuit Potential Changes upon Protonation/Deprotonation of ω-Functionalized Alkanethiols on Au: Determination of Surface pK {sub 1/2} in Aqueous and Non-Aqueous System

    Energy Technology Data Exchange (ETDEWEB)

    Yoo, Seung Ryul; Park, Kyung Soon; Jang, Jae Won; Hwang, Seong Pil [Korea Univ., Sejong (Korea, Republic of)

    2016-09-15

    The controlled assembly of functional nanomaterials has been drawing significant interest for making devices by integration of nanomaterials. The building blocks of functional nanomaterials might be confined spatially on the chemically patterned surface through both covalent and non-covalent bonds. Potentiometric measurement is affordable technique for various researchers because it requires only voltmeter and reference electrode. Moreover, it can be applied to various polar solvent such as methanol and ethanol. The open circuit potential (OCP) is measured indicating the potential difference between reference electrode and working electrode. The potential of working electrode might be affected by redox chemical reaction and charge state/separation. Our results provide the simple and affordable method to investigate pK {sub 1/2} of thin film both in aqueous phase and in non-aqueous phase, which has significant role in colloidal chemistry, nanochemistry, surface chemistry, electrochemistry, and others.

  5. IR SPECTRAL MAPPING OF THE MARTIAN SOUTH POLAR RESIDUAL CAP USING CRISM

    Directory of Open Access Journals (Sweden)

    J. Campbell

    2016-06-01

    Full Text Available Polycyclic aromatic hydrocarbons (PAHs are considered to be important in theories of abiogenesis (Allamandola, 2011 . There is evidence that PAHs have been detected on two icy Saturnian satellites using the Visual and Infrared Mapping Spectrometer (VIMS on the Cassini spacecraft (Cruikshank et al., 2007. The hypothesised presence of PAHs in Mars south polar cap has not been systematically examined even though the Mars south polar cap may allow the preservation of organic molecules that are typically destroyed at the Martian surface by UV radiation (Dartnell et al. 2012. This hypothesis is supported by recent analyses of South Polar Residual Cap (SPRC structural evolution (Thomas et al., 2009 that suggest the possibility that seasonal and long term sublimation may excavate dust particles from within the polar ice. Periodic sublimation is believed to be responsible for the formation of so-called “Swiss Cheese Terrain”, a unique surface feature found only in the Martian south polar residual cap consisting of flat floored, circular depressions (Byrne, 2009. We show the first examples of work towards the detection of PAHs in Swiss Cheese Terrain, using data from the Compact Reconnaissance Imaging Spectrometer for Mars (CRISM, on board NASA’s Mars Reconnaissance Orbiter (MRO. CRISM is designed to search for mineralogical indications of past and present water, thus providing extensive coverage of the south polar cap. In this work, we discuss whether CRISM infrared spectra can be used to detect PAHs in Swiss Cheese Terrain and demonstrate a number of maps showing shifts in spectral profiles over the SPRC.

  6. Comparison of 13C Nuclear Magnetic Resonance and Fourier Transform Infrared spectroscopy for estimating humification and aromatization of soil organic matter

    Science.gov (United States)

    Rogers, K.; Cooper, W. T.; Hodgkins, S. B.; Verbeke, B. A.; Chanton, J.

    2017-12-01

    Solid state direct polarization 13C NMR spectroscopy (DP-NMR) is generally considered the most quantitatively reliable method for soil organic matter (SOM) characterization, including determination of the relative abundances of carbon functional groups. These functional abundances can then be used to calculate important soil parameters such as degree of humification and extent of aromaticity that reveal differences in reactivity or compositional changes along gradients (e.g. thaw chronosequence in permafrost). Unfortunately, the 13C NMR DP-NMR experiment is time-consuming, with a single sample often requiring over 24 hours of instrument time. Alternatively, solid state cross polarization 13C NMR (CP-NMR) can circumvent this problem, reducing analyses times to 4-6 hours but with some loss of quantitative reliability. Attenuated Total Reflectance Fourier Transform Infrared spectroscopy (ATR-FTIR) is a quick and relatively inexpensive method for characterizing solid materials, and has been suggested as an alternative to NMR for analysis of soil organic matter and determination of humification (HI) and aromatization (AI) indices. However, the quantitative reliability of ATR-FTIR for SOM analyses has never been verified, nor have any ATR-FTIR data been compared to similar measurements by NMR. In this work we focused on FTIR vibrational bands that correspond to the three functional groups used to calculate HI and AI values: carbohydrates (1030 cm-1), aromatics (1510, 1630 cm-1), and aliphatics (2850, 2920 cm-1). Data from ATR-FTIR measurements were compared to analogous quantitation by DP- and CP-NMR using peat samples from Sweden, Minnesota, and North Carolina. DP- and CP-NMR correlate very strongly, although the correlations are not always 1:1. Direct comparison of relative abundances of the three functional groups determined by NMR and ATR-FTIR yielded satisfactory results for carbohydrates (r2= 0.78) and aliphatics (r2=0.58), but less so for aromatics (r2= 0

  7. Electrochemical corrosion study of Mg–Al–Zn–Mn alloy in aqueous ethylene glycol containing chloride ions

    Directory of Open Access Journals (Sweden)

    Harish Medhashree

    2017-01-01

    Full Text Available Nowadays most of the automobiles use magnesium alloys in the components of the engine coolant systems. These engine coolants used are mainly composed of aqueous ethylene glycol along with some inhibitors. Generally the engine coolants are contaminated by environmental anions like chlorides, which would enhance the rate of corrosion of the alloys used in the coolant system. In the present study, the corrosion behavior of Mg–Al–Zn–Mn alloy in 30% (v/v aqueous ethylene glycol containing chloride anions at neutral pH was investigated. Electrochemical techniques, such as potentiodynamic polarization method, cyclic polarization and electrochemical impedance spectroscopy (EIS were used to study the corrosion behavior of Mg–Al–Zn–Mn alloy. The surface morphology, microstructure and surface composition of the alloy were studied by using the scanning electron microscopy (SEM, optical microscopy and energy dispersion X-ray (EDX analysis, respectively. Electrochemical investigations show that the rate of corrosion increases with the increase in chloride ion concentration and also with the increase in medium temperature.

  8. Prediction of aliphatic and aromatic oil-water interfacial tension at temperatures >100 °C using COSMO-RS

    DEFF Research Database (Denmark)

    Andersson, Martin Peter; Eckert, F.; Reinisch, J.

    2017-01-01

    As a contribution to the 9th Industrial Fluid Property Simulation Challenge on predicting interfacial tension between water and a set of non-polar oils at temperatures up to 170 °C we have used our first-principles based model, which is based on density functional theory and uses COSMO-RS implicit...... solvent model thermodynamics. Our calculations predict that the oil-water interfacial tension starts to drop significantly for alkanes at temperatures above ∼100 °C, and the oil-water interfacial tension drops significantly with increased temperature already above ∼25 °C for aromatic oils. In the range...

  9. A method of refining aromatic hydrocarbons from coal chemical production

    Energy Technology Data Exchange (ETDEWEB)

    Zieborak, K.; Koprowski, A.; Ratajczak, W.

    1979-10-01

    A method is disclosed for refining aromatic hydrocarbons of coal chemical production by contact of liquid aromatic hydrocarbons and their mixtures with a strongly acid macroporous sulfocationite in the H-form at atmospheric pressure and high temperature. The method is distinguished in that the aromatic hydrocarbons and their mixtures, from which alkali compounds have already been removed, are supplied for refinement with the sulfocationite with simultaneous addition of olefin derivatives of aromatic hydrocarbons, followed by separation of pure hydrocarbons by rectification. Styrene or alpha-methylstyrene is used as the olefin derivatives of the aromatic hydrocarbons. The method is performed in several stages with addition of olefin derivatives of aromatic hydrocarbons at each stage.

  10. Sorption characteristics and mechanisms of organic contaminant to carbonaceous biosorbents in aqueous solution

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    A series of carbonaceous biosorbents was prepared by pyrolyzing pine needles,a model biomass,at various temperatures (100-700℃) under an oxygen-limited condition for 6h. The elemental composi-tions and the specific surface areas (BET-N2) of the biosorbents were analyzed. Sorption properties of 4-nitrotoluene to the biosorbents and their mechanisms were investigated,and then correlated with the structures of the biosorbents. The result shows that with the increase of the pyrolytic temperature,the aromaticity of the carbonaceous biosorbents increases dramatically and the polarity (the (N+O)/C atomic ratio) decreases sharply. Correspondingly,conformations of the organic matter in the biosor-bents transform gradually from a "soft-state" to a "hard-state" and the specific surface areas of the resultant biosorbents extend rapidly. The sorption isotherms fit well with the Freundlich equation. The regression parameters (i.e.,N and lgKf) are linearly related to the aromaticity indices (the H/C atomic ratio). Contributions of adsorption and partition to total sorption of the carbonaceous biosorbents are quantified. The adsorption of the carbonaceous biosorbents increases quickly with the increase of the pyrolytic temperature. The saturated adsorption amounts (Qmax) increase linearly with the increase of the specific surface areas (SA) of the biosorbents. For the carbonaceous biosorbents with hard-state carbon,the calculated normalized-Qmax values by SA are comparable to the theoretical estimation (2.45 μmol/m2). In comparison,for the carbonaceous sorbents with soft-state carbon,the calculated nor-malized-Qmax values by SA are much higher than the theoretical estimation. The partition coefficients (Kom) increase with the decrease of the polarity of the biosorbents,reaching a maximum,and then de-crease sharply with further decreasing the polarity,suggesting that partition mechanism be dominated by the compatibility and accessibility of the sorbent medium with organic

  11. The kinetics of dye formation by pulse radiolysis of pararosaniline cyanide in aqueous or organic solution

    International Nuclear Information System (INIS)

    McLaughlin, W.L.; Holcman, J.; Sehested, K.; Kosanic, M.M.

    1979-11-01

    The radiation-induced conversion of the leucocyanide of pararosaniline dye to the highly colored salt-isomer of the dye in acidic aqueous solution (wavelength of maximum absorption lambda sub(max)=540 nm) or polar organic solution (lambda sub(max)=550 nm), takes place in two separate processes. The first is very fast (within 3 s -1 to 10 6 s -1 , as the acidity or concentration of an oxidizing agent increases. In oxygen-free acidic aqueous or organic solutions (argon saturated) there is an unstable transient species (lambdasub(max)=380 nm). When using O 2 or N 2 O-saturated aqueous or organic solution, there is no intermediate absorption band at 380 nm, but the slow process of dye formation at 540 or 550 nm is still sequential to the initial fast process having somewhat faster kinetics than in Ar-saturated solution. (author)

  12. International congress on aromatic and medicinal plants

    International Nuclear Information System (INIS)

    2009-01-01

    Full Text : In Morocco, medicinal and aromatic plants occupy an important place in the traditional care system of a large number of local people. They are also economically strong potential, but unfortunately they are not valued enough. Indeed, Morocco by its privileged geographical position in the Mediterranean basin and its floristic diversity (with a total of over 4,200 species and subspecies of which over 500 are recognized as medicinal and aromatic plants), is a leading provider of traditional global market. In this context and given the back label of the natural global, group research and studies on Aromatic and Medicinal Plants (GREPAM), the Faculty of Semlalia and University Cadi Ayyad, organize: the International Congress on Medicinal and Aromatic Plants CIPAM 2009. The organization of this conference is part of scientific research developed by the GREPAM. [fr

  13. Hexacoordinate bonding and aromaticity in silicon phthalocyanine.

    Science.gov (United States)

    Yang, Yang

    2010-12-23

    Si-E bondings in hexacoordinate silicon phthalocyanine were analyzed using bond order (BO), energy partition, atoms in molecules (AIM), electron localization function (ELF), and localized orbital locator (LOL). Bond models were proposed to explain differences between hexacoordinate and tetracoordinate Si-E bondings. Aromaticity of silicon phthalocyanine was investigated using nucleus-independent chemical shift (NICS), harmonic oscillator model of aromaticity (HOMA), conceptual density functional theory (DFT), ring critical point (RCP) descriptors, and delocalization index (DI). Structure, energy, bonding, and aromaticity of tetracoordinate silicon phthalocyanine were studied and compared with hexacoordinate one.

  14. 40 CFR 721.5762 - Aromatic aldehyde phenolic resin (generic).

    Science.gov (United States)

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Aromatic aldehyde phenolic resin... Specific Chemical Substances § 721.5762 Aromatic aldehyde phenolic resin (generic). (a) Chemical substance... aromatic aldehyde phenolic resin (PMN P-01-573) is subject to reporting under this section for the...

  15. Hydroxypropyl cyclic β-(1 → 2)-D-glucans and epichlorohydrin β-cyclodextrin dimers as effective carbohydrate-solubilizers for polycyclic aromatic hydrocarbons.

    Science.gov (United States)

    Choi, Jae Min; Jeong, Daham; Piao, Jinglan; Kim, Kyoungtea; Nguyen, Andrew Bao Loc; Kwon, Nak-Jung; Lee, Mi-Kyung; Lee, Im Soon; Yu, Jae-Hyuk; Jung, Seunho

    2015-01-12

    The removal of polycyclic aromatic hydrocarbons by soil washing using water is extremely difficult due to their intrinsic hydrophobic nature. In this study, the effective aqueous solubility enhancements of seven polycyclic aromatic hydrocarbons by chemically modified hydroxypropyl rhizobial cyclic β-(1 → 2)-D-glucans and epichlorohydrin β-cyclodextrin dimer have been investigated for the first time. In the presence of hydroxypropyl cyclic β-(1 → 2)-D-glucans, the solubility of benzo[a]pyrene is increased up to 38 fold of its native solubility. The solubility of pyrene and phenanthrene dramatically increased up to 160 and 359. Coronene, chrysene, perylene, and fluoranthene also show an increase of 11, 23, 23, and 97 fold, respectively, of enhanced solubility by complexation with synthetic epichlorohydrin β-cyclodextrin dimer. The physicochemical properties of the complex are characterized by Fourier-transform infrared spectra and differential scanning calorimetry. Utilizing a scanning electron microscopy, the morphological structures of native benzo[a]pyrene, pyrene, phenanthrene, coronene, chrysene, perylene, fluoranthene and their complex with novel carbohydrate-solubilizers are studied. These results elucidate that polycyclic aromatic hydrocarbons are able to form an efficient complex with hydroxypropyl cyclic β-(1 → 2)-D-glucans and β-cyclodextrin dimer, suggesting the potential usage of chemically modified novel carbohydrate-solubilizers. Copyright © 2014 Elsevier Ltd. All rights reserved.

  16. Aromatic VOCs global influence in the ozone production

    Science.gov (United States)

    Cabrera-Perez, David; Pozzer, Andrea

    2016-04-01

    Aromatic hydrocarbons are a subgroup of Volatile Organic Compounds (VOCs) of special interest in the atmosphere of urban and semi-urban areas. Aromatics form a high fraction of VOCs, are highly reactive and upon oxidation they are an important source of ozone. These group of VOCs are released to the atmosphere by processes related to biomass burning and fossil fuel consumption, while they are removed from the atmosphere primarily by OH reaction and by dry deposition. In addition, a branch of aromatics (ortho-nitrophenols) produce HONO upon photolysis, which is responsible of certain amount of the OH recycling. Despite their importance in the atmosphere in anthropogenic polluted areas, the influence of aromatics in the ozone production remains largely unknown. This is of particular relevance, being ozone a pollutant with severe side effects on air quality, health and climate. In this work the atmospheric impacts at global scale of the most emitted aromatic VOCs in the gas phase (benzene, toluene, xylenes, ethylbenzene, styrene, phenol, benzaldehyde and trimethylbenzenes) are analysed and assessed. Specifically, the impact on ozone due to aromatic oxidation is estimated, as this is of great interest in large urban areas and can be helpful for developing air pollution control strategies. Further targets are the quantification of the NOx loss and the OH recycling due to aromatic oxidation. In order to investigate these processes, two simulations were performed with the numerical chemistry and climate simulation ECHAM/MESSy Atmospheric Chemistry (EMAC) model. The simulations compare two cases, one with ozone concentrations when aromatics are present or the second one when they are missing. Finally, model simulated ozone is compared against a global set of observations in order to better constrain the model accuracy.

  17. Recent Advances in Microbial Production of Aromatic Chemicals and Derivatives.

    Science.gov (United States)

    Noda, Shuhei; Kondo, Akihiko

    2017-08-01

    Along with the development of metabolic engineering and synthetic biology tools, various microbes are being used to produce aromatic chemicals. In microbes, aromatics are mainly produced via a common important precursor, chorismate, in the shikimate pathway. Natural or non-natural aromatics have been produced by engineering metabolic pathways involving chorismate. In the past decade, novel approaches have appeared to produce various aromatics or to increase their productivity, whereas previously, the targets were mainly aromatic amino acids and the strategy was deregulating feedback inhibition. In this review, we summarize recent studies of microbial production of aromatics based on metabolic engineering approaches. In addition, future perspectives and challenges in this research area are discussed. Copyright © 2017 Elsevier Ltd. All rights reserved.

  18. Analogs of solid nanoparticles as precursors of aromatic hydrocarbons

    Science.gov (United States)

    Gadallah, K. A. K.; Mutschke, H.; Jäger, C.

    2013-06-01

    Context. Aromatic =CH and C=C vibrational bands have been observed within shocked interstellar regions, indicating the presence of aromatic emission carriers such as PAHs, which may have been created from adjacent molecular cloud material by interaction with a shock front. Aims: We investigate the evolution of the aromatic =CH and C=C vibrational modes at 3.3 and 6.2 μm wavelength in heated HAC materials, PAHs and mixed PAHs and HACs, respectively, aiming at an explanation of the evolution of carbonaceous dust grains in the shocked regions. Methods: Materials used in these analogs (HAC and PAH materials) were prepared by the laser ablation and the laser pyrolysis methods, respectively. The transmission electron microscopy (TEM) in high-resolution mode was used as an analytical technique to characterize the aromatic layers in HACs. Spectroscopic analysis was prformed in the mid-IR range. Results: A remarkable destruction of aliphatic structures in HACs has been observed with the thermal processing, while aromatic structures become dominating by increasing the diameters of the graphene layers. The aromatic bands at 3.3 and 6.2 μm, observed in the laboratory spectra of PAHs and of the combination of the PAHs and HAC materials, are also clearly observed in the spectrum of the heated HACs. These bands agree with those of aromatic bands observed in astronomical observations. Conclusions: Aromatization of HACs could be a pre-stage in the decomposition process of hydrocarbons that form PAH-clusters in such hot interstellar medium.

  19. Reactivity of silicon and germanium doped CNTs toward aromatic sulfur compounds: A theoretical approach

    International Nuclear Information System (INIS)

    Galano, Annia; Francisco-Marquez, Misaela

    2008-01-01

    Adsorption processes of thiophene and benzothiophene on pristine carbon nanotubes (CNTs), and on CNTs doped with Si or Ge, have been modeled with Density Functional. This is the first study on the chemical reactivity of such doped tubes. The calculated data suggest that the presence of silicon or germanium atoms in CNTs increases their reactivity toward thiophene, and benzothiophene. The adsorption of these species on pristine CNTs seems very unlikely to occur, while the addition products involving doped CNTs were found to be very stable, with respect to the isolated reactants, in terms of Gibbs free energy. Several of these adsorption processes were found to be significantly exergonic (ΔG < 0) in non-polar liquid phase. The results reported in this work suggest that Si and Ge defects on CNTs increase their reactivity toward unsaturated species, and could make them useful in the removal processes of aromatic sulfur compounds from oil-hydrocarbons. However, according to our results, CNTs doped with Si atoms are expected to be more efficient as aromatic sulfur compounds scavengers than those doped with Ge. These results also suggest that the presence of silicon and germanium atoms in the CNTs structures enhances their reactivity toward nucleophilic molecules, compared to pristine carbon nanotubes

  20. Adsorption of aromatic amino acids in a fixed bed column

    Directory of Open Access Journals (Sweden)

    Cremasco M.A.

    2003-01-01

    Full Text Available Phenylalanine (Phe and tyrosine (Tyr are two of the twenty amino acids in proteins; they are classified as aromatic amino acids, because both have a benzene ring in their structures. These amino acids are important in the synthesis of several biologically active amines, such as beta-endorphin, a neurotransmitter. Amino acids can be separated by ion-exchange chromatography. In this case, it is important that fixed-bed adsorber design adequately predict the breakthrough curve. This work presents a mathematical model for both fluid and porous phases. In the solution proposed for this model the liquid-phase concentration inside the particles is solved analytically and is related to the liquid-phase concentration in the bed using Duhamel's theorem. The solution for liquid-phase concentration in the bed is then solved numerically instead of analytically. The basic mass transfer parameters are from the literature. The results from the model are compared with those obtained experimentally using Phe and Tyr diluted in aqueous solutions in a fixed bed of PVP (poly-4-vinylpyridine resin.

  1. Analysis of polycyclic aromatic hydrocarbons in water and beverages using membrane-assisted solvent extraction in combination with large volume injection-gas chromatography-mass spectrometric detection.

    Science.gov (United States)

    Rodil, Rosario; Schellin, Manuela; Popp, Peter

    2007-09-07

    Membrane-assisted solvent extraction (MASE) in combination with large volume injection-gas chromatography-mass spectrometry (LVI-GC-MS) was applied for the determination of 16 polycyclic aromatic hydrocarbons (PAHs) in aqueous samples. The MASE conditions were optimized for achieving high enrichment of the analytes from aqueous samples, in terms of extraction conditions (shaking speed, extraction temperature and time), extraction solvent and composition (ionic strength, sample pH and presence of organic solvent). Parameters like linearity and reproducibility of the procedure were determined. The extraction efficiency was above 65% for all the analytes and the relative standard deviation (RSD) for five consecutive extractions ranged from 6 to 18%. At optimized conditions detection limits at the ng/L level were achieved. The effectiveness of the method was tested by analyzing real samples, such as river water, apple juice, red wine and milk.

  2. Silver colloidal effects on excited-state structure and intramolecular charge transfer of p-N, N-dimethylaminobenzoic acid in aqueous cyclodextrin solutions

    International Nuclear Information System (INIS)

    Choi, Jung Kwon; Kim, Yang Hee; Yoon, Min Joong; Lee, Seung Joon; Kim, Kwan; Jeoung, Sae Chae

    2001-01-01

    The silver colloidal effects on the excited-state structure and intramolecular charge transfer (ICT) of p-N,N-dimethylaminobenzoic acid (DMABA) in aqueous cyclodextrin (CD) solutions have been investigated by UV-VIS absorption, steady-state and time-resolved fluorescence, and transient Raman spectroscopy. As the concentration of silver colloids increases, the ratio of the ICT emission to the normal emission (I a /I b ) of DMABA in the aqueous α-CD solutions are greatly decreased while the I a /I b values in the aqueous β-CD solutions are significantly enhanced. It is also noteworthy that the ICT emission maxima are red-shifted by 15-40 nm upon addition of silver colloids, implying that DMABA encapsulated in α-CD or β-CD cavity is exposed to more polar environment. The transient resonance Raman spectra of DMABA in silver colloidal solutions demonstrate that DMABA in the excited-state is desorbed from silver colloidal surfaces as demonstrated by the disappearance of v s (CO 2 - )(1380 cm -1 ) with appearance of v (C-OH)(1280 cm -1 ) band, respectively. Thus, in the aqueous β-CD solutions the carboxylic acid group of DMABA in the excited-state can be readily hydrogen bonded with the secondary hydroxyl group of β-CD while in aqueous and α-CD solutions the carboxylic acid group of DMABA has the hydrogen-bonding interaction with water. Consequently, in the aqueous β-CD solutions the enhancement of the I a /I b value arises from the intermolecular hydrogen-bonding interaction between DMABA and the secondary hydroxyl group of β-CD as well as the lower polarity of the rim of the β-CD cavity compared to bulk water. This is also supported by the increase of the association constant for DMABA/β-CD complex in the presence of silver colloids

  3. Protonation sites of aromatic compounds in (+) atmospheric pressure photoionization

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Sung Hwan; Ahmed, Arif [Dept. of Chemistry, Kyungpoo k National University, Daegu (Korea, Republic of)

    2017-02-15

    Reaction enthalpy of hydrogen transfer reactions of aromatic compounds has been observed to be greatly affected by the exact location of the protonation site. Therefore, to clearly identify the protonation location, each candidate protonation site for 43 aromatic compounds were theoretically determined and their location was compared with that determined based on experimental MS data. Only the basic nitrogen atom is favorable as a protonation site for pyridine-type aromatic compounds, whereas carbon atoms are preferable for the protonation of pyrrole-type compounds. The most favorable protonation sites for aniline or methylated aniline-type aromatic compounds are either the nitrogen atom in the amine group or the carbon atom at the para-position to the amine group. Like pyrrole-type compounds, aromatic compounds with amine groups also favor protonation at the carbon atom instead of at the nitrogen atom. In addition, hydrocarbons having an anthracene structural motif without heteroatoms produced higher or equal percentages of protonated ions compared to that achieved with molecular ions. The results of this study can be used to improve the analyses of aromatic compounds.

  4. Anodic polarization behavior and film breakdown potential of pure copper in the simulated geological environment containing carbonate

    International Nuclear Information System (INIS)

    Kawasaki, Manabu; Taniguchi, Naoki; Naito, Morimasa

    2009-01-01

    In order to clarify the influence of environmental factors on the corrosion behavior of copper overpacks in oxidizing environment, potentiodynamic and potentiostatic anodic polarization tests were performed in carbonate aqueous solutions at 80degC. As the results, the passivation was promoted and film breakdown was suppressed in higher carbonate concentrations, in lower chloride ion concentrations, and in higher pH conditions. The sulfate ion tended to promote the film breakdown of copper. The effects of the composition of the test solutions on the anodic polarization curve of copper in bentonite/sand mixture were quite smaller than those in simple aqueous solution. By comparison with previous data for lower temperature condition, it was clarified that passivation of copper was promoted in higher temperature condition, but breakdown potential, Eb was independent of temperature. The Eb, was expressed as a function of the ratio of aggressive ion and inhibiting ion such as [Cl - ]/[HCO 3 - ] and [SO 4 2- ]/[HCO 3 - ], and it was confirmed that the Eb was lowered with increasing the ratio. When the ratio exceeds a certain value, the Eb was no longer able to be determined since the anodic polarization curve becomes active dissolution type. The lower limit of Eb in passive type region was estimated to be about -200 mV vs. SCE. The results of potentiostatic tests showed that pitting corrosion or non-uniform corrosion was observed at the potentials over Eb or second current peak potentials in anodic polarization curve. (author)

  5. Magnetic ionic liquids as non-conventional extraction solvents for the determination of polycyclic aromatic hydrocarbons.

    Science.gov (United States)

    Trujillo-Rodríguez, María J; Nacham, Omprakash; Clark, Kevin D; Pino, Verónica; Anderson, Jared L; Ayala, Juan H; Afonso, Ana M

    2016-08-31

    This work describes the applicability of magnetic ionic liquids (MILs) in the analytical determination of a group of heavy polycyclic aromatic hydrocarbons. Three different MILs, namely, benzyltrioctylammonium bromotrichloroferrate (III) (MIL A), methoxybenzyltrioctylammonium bromotrichloroferrate (III) (MIL B), and 1,12-di(3-benzylbenzimidazolium) dodecane bis[(trifluoromethyl)sulfonyl)]imide bromotrichloroferrate (III) (MIL C), were designed to exhibit hydrophobic properties, and their performance examined in a microextraction method for hydrophobic analytes. The magnet-assisted approach with these MILs was performed in combination with high performance liquid chromatography and fluorescence detection. The study of the extraction performance showed that MIL A was the most suitable solvent for the extraction of polycyclic aromatic hydrocarbons and under optimum conditions the fast extraction step required ∼20 μL of MIL A for 10 mL of aqueous sample, 24 mmol L(-1) NaOH, high ionic strength content of NaCl (25% (w/v)), 500 μL of acetone as dispersive solvent, and 5 min of vortex. The desorption step required the aid of an external magnetic field with a strong NdFeB magnet (the separation requires few seconds), two back-extraction steps for polycyclic aromatic hydrocarbons retained in the MIL droplet with n-hexane, evaporation and reconstitution with acetonitrile. The overall method presented limits of detection down to 5 ng L(-1), relative recoveries ranging from 91.5 to 119%, and inter-day reproducibility values (expressed as relative standard derivation) lower than 16.4% for a spiked level of 0.4 μg L(-1) (n = 9). The method was also applied for the analysis of real samples, including tap water, wastewater, and tea infusion. Copyright © 2016 Elsevier B.V. All rights reserved.

  6. Photodegradation of emamectin benzoate in aqueous solutions

    International Nuclear Information System (INIS)

    Mushtaq, M.; Chukwudebe, A.C.; Wrzesinski, C.; Allen, L.R.S.; Luffer-Atlas, D.; Arison, B.H.

    1998-01-01

    The half-life of [ 14 C]4'-deoxy-4'-(epi-methylamino)avermectin B1a (MAB1a) benzoate (1 ppm) photodegradation in buffer (pH 7), natural pond water, and sensitized buffer (1% acetone in pH 7 buffer) determined at Three Bridges, NJ (latitude approximately 40 degrees N) during the fall season under natural sunlight was 22, 7, and 1 days, respectively. The half-life of [ 14 C]MAB1a benzoate (10-12 ppm) photodegradation in buffer (pH 7) containing 1% (v/v) acetonitrile, ethanol, or acetone as cosolvent under continuous exposure with a xenon lamp was 64.5, 8.5, or 0.5 days, respectively. The photoisomer 8,9-Z-MAB1a, 8a-hydroxy-MAB1a, and unknown polar residues were found in light-exposed samples of MAB1a in buffer and natural pond water. In light-exposed sensitized buffer samples, 8a-oxo-MAB1a and MAB1a-10,11-14,15-diepoxide were additional products. Very polar residues found in the organic and aqueous phases after extraction increased with time, and their formation followed the order sensitized buffer natural pond water buffer. (author)

  7. The mutagenic potential of high flash aromatic naphtha.

    Science.gov (United States)

    Schreiner, C A; Edwards, D A; McKee, R H; Swanson, M; Wong, Z A; Schmitt, S; Beatty, P

    1989-06-01

    Catalytic reforming is a refining process that converts naphthenes to aromatics by dehydrogenation to make higher octane gasoline blending components. A portion of this wide boiling range hydrocarbon stream can be separated by distillation and used for other purposes. One such application is a mixture of predominantly 9-carbon aromatic molecules (C9 aromatics, primarily isomers of ethyltoluene and trimethylbenzene), which is removed and used as a solvent--high-flash aromatic naphtha. A program was initiated to assess the toxicological properties of high-flash aromatic naphtha since there may be human exposure through inhalation or external body contact. The current study was conducted partly to assess the potential for mutagenic activity and also to assist in an assessment of carcinogenic potential. The specific tests utilized included the Salmonella/mammalian microsome mutagenicity assay, the hypoxanthine-guanine phosphoribosyl transferase (HGPRT) forward mutation assay in CHO cells, in vitro chromosome aberration and sister chromatid exchange (SCE) assays in CHO cells, and an in vivo chromosome aberration assay in rat bone marrow.

  8. EXTRACTION AND SORPTION BENZOIC ACID FROM AQUEOUS SOLUTIONS OF POLYMERS BASED ON N-VINYLAMIDES

    Directory of Open Access Journals (Sweden)

    A. G. Savvina

    2015-01-01

    Full Text Available The widespread use of aromatic acids (benzoic acid, salicylic as preservatives necessitates their qualitative and quantitative determination in food. Effective and common way to separation and concentration of aromatic acids liquid extraction. Biphasic system of water-soluble polymers based on (poly-N-vinyl pyrrolidone, and poly-N-vinylcaprolactam satisfy the requirements of the extraction system. When sorption concentration improved definition of the metrological characteristics, comply with the requirements for sensitivity and selectivity definition appears possible, use of inexpensive and readily available analytical equipment. When studying the adsorption of benzoic acid used as a sorbent crosslinked polymer based on N-vinyl pyrrolidone, obtained by radical polymerisation of a functional monomer and crosslinker. In the extraction of benzoic acid to maximize the allocation of water and the organic phase of the polymer used salt solutions with concentrations close to saturation. Regardless of the nature of the anion salt is used as salting-out agent, aromatic acids sorption increases with the size of the cations. In the experiment the maximum recovery rate (80% benzoic acid obtained in the PVP (0.2 weight%. Ammonium sulphate. The dependence stepepni benzoic acid extraction from time sorption sorbent mass and the pH of the aqueous phase. To establish equilibrium in the system, for 20 minutes. The dependence of the degree of extraction of the acid pH indicates that the acid is extracted into the molecular form. The maximum adsorption is reached at pH 3,5, with its efficiency decreases symbatically reduce the amount of undissociated acid molecules in solution.

  9. Effects of halogenated aromatics/aliphatics and nitrogen(N)-heterocyclic aromatics on estimating the persistence of future pharmaceutical compounds using a modified QSAR model.

    Science.gov (United States)

    Lim, Seung Joo; Fox, Peter

    2014-02-01

    The effects of halogenated aromatics/aliphatics and nitrogen(N)-heterocyclic aromatics on estimating the persistence of future pharmaceutical compounds were investigated using a modified half life equation. The potential future pharmaceutical compounds investigated were approximately 2000 pharmaceutical drugs currently undergoing the United States Food and Drug Administration (US FDA) testing. EPI Suite (BIOWIN) model estimates the fates of compounds based on the biodegradability under aerobic conditions. While BIOWIN considered the biodegradability of a compound only, the half life equation used in this study was modified by biodegradability, sorption and cometabolic oxidation. It was possible that the potential future pharmaceutical compounds were more accurately estimated using the modified half life equation. The modified half life equation considered sorption and cometabolic oxidation of halogenated aromatic/aliphatics and nitrogen(N)-heterocyclic aromatics in the sub-surface, while EPI Suite (BIOWIN) did not. Halogenated aliphatics in chemicals were more persistent than halogenated aromatics in the sub-surface. In addition, in the sub-surface environment, the fates of organic chemicals were much more affected by halogenation in chemicals than by nitrogen(N)-heterocyclic aromatics. © 2013.

  10. Solid-state surface luminescence of polycyclic aromatic hydrocarbons adsorbed on cellulose diacetate matrices

    Science.gov (United States)

    Rogacheva, Svetlana M.; Shipovskaya, Anna B.; Volkova, Elena V.; Khurshudyan, Grachia N.; Suska-Malawska, Malgorzata; Gubina, Tamara I.

    2018-04-01

    The spectral-kinetic characteristics of luminescence of 17 polycyclic aromatic hydrocarbons (PAH) sorbed from a "water-organic solvent" medium on cellulose diacetate (CDA) matrices were studied. A significant increase in the fluorescence signal on the CDA matrix was observed for 13 PAHs in comparison with aqueous solutions. The highest detection sensitivity was found for pyrene, benzo(a)pyrene, and benzo(k)fluoranthene. The fluorescence spectra of two PAH indicator pairs (anthracene-phenanthrene and pyrene-fluoranthene) used to control toxicant emission sources were studied with the simultaneous presence of isomers in the analyte, depending on the excitation wavelength. For both isomer pairs, it has been found that the spectra of their solid-state luminescence overlap insignificantly, the characteristic peaks do not coincide and do not overlap, the sensitivities of detection are close to each other, which makes it possible to consider this technique as promising to control PAH contamination sources.

  11. Application of calculated NMR parameters, aromaticity indices and wavefunction properties for evaluation of corrosion inhibition efficiency of pyrazine inhibitors

    Science.gov (United States)

    Behzadi, Hadi; Manzetti, Sergio; Dargahi, Maryam; Roonasi, Payman; Khalilnia, Zahra

    2018-01-01

    In light of the importance of developing novel corrosion inhibitors, a series of quantum chemical calculations were carried out to evaluate 15N chemical shielding CS tensors as well as aromaticity indexes including NICS, HOMA, FLU, and PDI of three pyrazine derivatives, 2-methylpyrazine (MP), 2-aminopyrazine (AP) and 2-amino-5-bromopyrazine (ABP). The NICS parameters have been shown in previous studies to be paramount to the prediction of anti-corrosion properties, and have been combined here with HOMA, FLU and PDI and detailed wavefunction analysis to determine the effects from bromination and methylation on pyrazine. The results show that the electron density around the nitrogens, represented by CS tensors, can be good indicators of anti-corrosion efficiency. Additionally, the NICS, FLU and PDI, as aromaticity indicators of molecule, are well correlated with experimental corrosion inhibition efficiencies of the studied inhibitors. Bader sampling and detailed wavefunction analysis shows that the major effects from bromination on the pyrazine derivatives affect the Laplacian of the electron density of the ring, delocalizing the aromatic electrons of the carbon atoms into lone pairs and increasing polarization of the Laplacian values. This feature is well agreement with empirical studies, which show that ABP is the most efficient anti-corrosion compound followed by AP and MP, a property which can be attributed and predicted by derivation of the Laplacian of the electron density of the ring nuclei. This study shows the importance of devising DFT methods for development of new corrosion inhibitors, and the strength of electronic and nuclear analysis, and depicts most importantly how corrosion inhibitors composed of aromatic moieties may be modified to increase anti-corrosive properties.

  12. Bio-Based Aromatic Epoxy Monomers for Thermoset Materials

    Directory of Open Access Journals (Sweden)

    Feifei Ng

    2017-01-01

    Full Text Available The synthesis of polymers from renewable resources is a burning issue that is actively investigated. Polyepoxide networks constitute a major class of thermosetting polymers and are extensively used as coatings, electronic materials, adhesives. Owing to their outstanding mechanical and electrical properties, chemical resistance, adhesion, and minimal shrinkage after curing, they are used in structural applications as well. Most of these thermosets are industrially manufactured from bisphenol A (BPA, a substance that was initially synthesized as a chemical estrogen. The awareness on BPA toxicity combined with the limited availability and volatile cost of fossil resources and the non-recyclability of thermosets implies necessary changes in the field of epoxy networks. Thus, substitution of BPA has witnessed an increasing number of studies both from the academic and industrial sides. This review proposes to give an overview of the reported aromatic multifunctional epoxide building blocks synthesized from biomass or from molecules that could be obtained from transformed biomass. After a reminder of the main glycidylation routes and mechanisms and the recent knowledge on BPA toxicity and legal issues, this review will provide a brief description of the main natural sources of aromatic molecules. The different epoxy prepolymers will then be organized from simple, mono-aromatic di-epoxy, to mono-aromatic poly-epoxy, to di-aromatic di-epoxy compounds, and finally to derivatives possessing numerous aromatic rings and epoxy groups.

  13. Frozen Acrylamide Gels as Dynamic Nuclear Polarization Matrices.

    KAUST Repository

    Viger-Gravel, Jasmine; Berruyer, Pierrick; Gajan, David; Basset, Jean-Marie; Lesage, Anne; Tordo, Paul; Ouari, Olivier; Emsley, Lyndon

    2017-01-01

    We show that aqueous acrylamide gels can be used to provide dynamic nuclear polarization (DNP) NMR signal enhancements of around 200 at 9.4 T and 100 K. The enhancements are shown to increase with cross linker concentration and low concentrations of the AMUPol biradical. We show that this DNP matrix can be used in situations where conventional incipient wetness methods fail, such as to obtain DNP surface enhanced NMR spectra from inorganic nanoparticles. In particular, we obtain 113Cd spectra from CdTe-COOH NPs in minutes. The spectra clearly indicate a highly-disordered cadmium rich surface.

  14. Frozen Acrylamide Gels as Dynamic Nuclear Polarization Matrices.

    KAUST Repository

    Viger-Gravel, Jasmine

    2017-05-24

    We show that aqueous acrylamide gels can be used to provide dynamic nuclear polarization (DNP) NMR signal enhancements of around 200 at 9.4 T and 100 K. The enhancements are shown to increase with cross linker concentration and low concentrations of the AMUPol biradical. We show that this DNP matrix can be used in situations where conventional incipient wetness methods fail, such as to obtain DNP surface enhanced NMR spectra from inorganic nanoparticles. In particular, we obtain 113Cd spectra from CdTe-COOH NPs in minutes. The spectra clearly indicate a highly-disordered cadmium rich surface.

  15. Comparison between Different Extraction Methods for Determination of Primary Aromatic Amines in Food Simulant

    Directory of Open Access Journals (Sweden)

    Morteza Shahrestani

    2018-01-01

    Full Text Available The primary aromatic amines (PAAs are food contaminants which may exist in packaged food. Polyurethane (PU adhesives which are used in flexible packaging are the main source of PAAs. It is the unreacted diisocyanates which in fact migrate to foodstuff and then hydrolyze to PAAs. These PAAs include toluenediamines (TDAs and methylenedianilines (MDAs, and the selected PAAs were 2,4-TDA, 2,6-TDA, 4,4′-MDA, 2,4′-MDA, and 2,2′-MDA. PAAs have genotoxic, carcinogenic, and allergenic effects. In this study, extraction methods were applied on a 3% acetic acid as food simulant which was spiked with the PAAs under study. Extraction methods were liquid-liquid extraction (LLE, dispersive liquid-liquid microextraction (DLLME, and solid-phase extraction (SPE with C18 ec (octadecyl, HR-P (styrene/divinylbenzene, and SCX (strong cationic exchange cartridges. Extracted samples were detected and analyzed by HPLC-UV. In comparison between methods, recovery rate of SCX cartridge showed the best adsorption, up to 91% for polar PAAs (TDAs and MDAs. The interested PAAs are polar and relatively soluble in water, so a cartridge with cationic exchange properties has the best absorption and consequently the best recoveries.

  16. Aromatic Plants as a Source of Bioactive Compounds

    Directory of Open Access Journals (Sweden)

    Panagiota Florou-Paneri

    2012-09-01

    Full Text Available Aromatic plants, also known as herbs and spices, have been used since antiquity as folk medicine and as preservatives in foods. The best known aromatic plants, such as oregano, rosemary, sage, anise, basil, etc., originate from the Mediterranean area. They contain many biologically active compounds, mainly polyphenolics, which have been found to possess antimicrobial, antioxidant, antiparasitic, antiprotozoal, antifungal, and anti-inflammatory properties. Currently, the demand for these plants and their derivatives has increased because they are natural, eco-friendly and generally recognized as safe products. Therefore, aromatic plants and their extracts have the potential to become new generation substances for human and animal nutrition and health. The purpose of this review is to provide an overview of the literature surrounding the in vivo and in vitro use of aromatic plants.

  17. Fe(III)-solar light induced degradation of diethyl phthalate (DEP) in aqueous solutions.

    Science.gov (United States)

    Mailhot, G; Sarakha, M; Lavedrine, B; Cáceres, J; Malato, S

    2002-11-01

    The degradation of diethyl phthalate (DEP) photoinduced by Fe(III) in aqueous solutions has been investigated under solar irradiation in the compound parabolic collector reactor at Plataforma Solar de Almeria. Hydroxyl radicals *OH, responsible of the degradation, are formed via an intramolecular photoredox process in the excited state of Fe(III) aquacomplexes. The primary step of the reaction is mainly due to the attack of *OH radicals on the aromatic ring. For prolonged irradiations DEP and its photoproducts are completely mineralized due to the regeneration of the absorbing species and the continuous formation of *OH radicals that confers a catalytic aspect to the process. Consequently, the degradation photoinduced by Fe(III) could be an efficient method of DEP removal from water.

  18. By-products formation during degradation of isoproturon in aqueous solution. II: Chlorination.

    Science.gov (United States)

    Mascolo, G; Lopez, A; James, H; Fielding, M

    2001-05-01

    After a previous study in which the considered oxidant was ozone (Part I), a laboratory investigation has been carried out to study the degradation of the herbicide isoproturon during its reaction with another oxidant, i.e. chlorine, in aqueous solution (Part II; this paper). The specific aim was to identify the by-products formed. The effects of pH and the presence of bromide ions were studied. Reactions have been carried out at room temperature, in phosphate buffered aqueous solutions, at four pHs (6, 7, 8 and 9). By-products identification was first performed using relatively high initial reagent concentrations which were analytically convenient ([isoproturon] = 40 mg/l, [HClO + ClO-] = 160 mg Cl/l, [Br-] = 80 mg/l). In follow-up studies, the by-products identified during this preliminary step were searched for when using concentration values closer to those actually encountered at real water treatment plants ([isoproturon] = 0.4 and 0.004 mg/l, [HClO + ClO-] = 1.6 mg Cl/l, [Br-] = 0.8 and 0.008 mg/l). Under all of the studied conditions, the results showed that isoproturon is completely degraded and that it decays much faster in the presence of bromide. The pH has a negligible influence when bromide ions are absent. On the contrary, if bromide ions are present, the isoproturon decay is slower at higher pH values. High-performance liquid chromatography-mass spectrometry (HPLC-MS) analyses have led to the identification of several by-products as a result of simultaneous oxidation and substitution reactions, both occurring on the aromatic ring of the herbicide. However, the more abundant by-products are those resulting from the oxidation of the isoproturon aromatic ring. As far as halogenated by-products are concerned, the higher the bromide ion concentration the higher the ratio of brominated to chlorinated by-products. On the basis of the analytical results, a pathway for isoproturon degradation under the studied conditions is proposed.

  19. Cyclodextrin-functionalized mesostructured silica nanoparticles for removal of polycyclic aromatic hydrocarbons.

    Science.gov (United States)

    Topuz, Fuat; Uyar, Tamer

    2017-07-01

    Polycyclic aromatic hydrocarbons (PAHs) are the byproducts of the incomplete combustion of carbon-based fuels, and have high affinity towards DNA strands, ultimately exerting their carcinogenic effects. They are ubiquitousenvironmental contaminants,and can accumulate on tissues due to their lipophilic nature. In this article, we describe a novel concept for PAH removal from aqueous solutions using cyclodextrin-functionalized mesostructured silica nanoparticles (CDMSNs) and pristine mesostructured silica nanoparticles (MSNs). The adsorption applications of MSNs are greatly restricted due to the absence of surface functional groups on such particles. In this regard, cyclodextrins can serve as ideal functional molecules with their toroidal, cone-type structure, capable of inclusion-complex formation with many hydrophobic molecules, including genotoxic PAHs. The CDMSNs were synthesized by the surfactant-templated, NaOH-catalyzed condensation reactions of tetraethyl orthosilicate (TEOS) in the presence of two different types of cyclodextrin (i.e. hydroxypropyl-β-cyclodextrin (HP-β-CD) and native β-cyclodextrin (β-CD)). The physical incorporation of CD moieties was supported by XPS, FT-IR, NMR, TGA and solid-state 13 C NMR. The CDMSNs were treated with aqueous solutions of five different PAHs (e.g. pyrene, anthracene, phenanthrene, fluorene and fluoranthene). The functionalization of MSNs with cyclodextrin moieties significantly boosted the sorption capacity (q) of the MSNs up to ∼2-fold, and the q ranged between 0.3 and 1.65mg per gram CDMSNs, of which the performance was comparable to that of the activated carbon. Copyright © 2017 Elsevier Inc. All rights reserved.

  20. Aqueous solutions that model the cytosol : studies on polarity, chemical reactivity and enzyme kinetics

    NARCIS (Netherlands)

    Asaad, N.; den Otter, M.J.; Engberts, J.B.F.N.

    2004-01-01

    Concentrated solutions of a series of organic compounds have been prepared and the effects of these solutes on the properties of the solvent system assessed as a function of their concentration and nature. Polarity, as measured by Reichardt's E-T(30) probe, exhibits a linear variation with both

  1. The formation of aromatics and PAH's in laminar flames

    International Nuclear Information System (INIS)

    Marinov, N M; Pitz, W J; Westbrook, C K

    1999-01-01

    The formation of aromatics and PAH's is an important problem in combustion. These compounds are believed to contribute to the formation of soot whose emission from diesel engines is regulated widely throughout the industrial world. Additionally, the United States Environmental Protection Agency regulates the emission of many aromatics and PAH species from stationary industrial burners, under the 1990 Clean Air Act Amendments. The above emission regulations have created much interest in understanding how these species are formed in combustion systems. Much previous work has been done on aromatics and PAH's. The work is too extensive to review here, but is reviewed in Reference 1. A few recent developments are highlighted here. McEnally, Pfefferle and coworkers have studied aromatic, PAH and soot formation in a variety of non-premixed flames with hydrocarbon additives[2-4]. They found additives that contain a C5 ring increase the concentration of aromatics and soot[4]. Howard and coworkers have studied the formation of aromatic and PAH's in low pressure, premixed, laminar hydrocarbon flames. They found the cyclopentadienyl radical to be a key species in naphthalene formation in a fuel-rich, benzene/Ar/O2 flame[5

  2. Aromatic hydrocarbon concentrations in sediments of Placentia Bay, Newfoundland

    International Nuclear Information System (INIS)

    Kiceniuk, J.W.

    1992-01-01

    A study was conducted to examine the potential for contamination of recent sediments with polycyclic aromatic hydrocarbons due to tanker and refinery activity in Placentia Bay, Newfoundland, an area without large local anthropogenic sources of aromatics. Sediment samples were taken from the vicinity of the Come By Chance refinery, Woody Island, Wild Cove, and Port Royal Arm, all in the north end of the bay. The samples were extracted by two methods, dichloromethane extraction of dried sediment for determination of total aromatic hydrocarbon content and hexane extraction of wet sediment for estimation of the bioavailability of hydrocarbons and determination of more volatile compounds. Class analysis of aromatic hydrocarbons was conducted on a NH 2 column with detection at 255 nm. Total concentrations of di-tricyclic aromatics were highest at the Woody Island site (0.6 μg/g). The sediments from the Come By Chance site, Wild Cove, and Port Royal Arm sediments contained 0.3, 0.1, and 0.2 μg/g respectively. The hexane extracts from Come By Chance were lowest in di-tricyclic aromatics (0.007 μg/g), with the other sites being equal in concentration (0.01 μg/g). It is evident from the study that aromatic hydrocarbon concentrations in Placentia Bay are elevated in some parts of the bay in the absence of local combustion sources, and that the most likely source is petroleum. 12 refs., 5 figs., 2 tabs

  3. Monomers for thermosetting and toughening epoxy resins. [glycidyl amine derivatives, propargyl-containing amines, and mutagenic testing of aromatic diamines

    Science.gov (United States)

    Pratt, J. R.

    1981-01-01

    Eight glycidyl amines were prepared by alkylating the parent amine with epichlorohydrin to form chlorohydrin, followed by cyclization with aqueous NaOH. Three of these compounds contained propargyl groups with postcuring studies. A procedure for quantitatively estimating the epoxy content of these glycidyl amines was employed for purity determination. Two diamond carbonates and several model propargly compounds were prepared. The synthesis of three new diamines, two which contain propargyloxy groups, and another with a sec-butyl group is in progress. These materials are at the dinitro stage ready for the final hydrogenation step. Four aromatic diamines were synthesized for mutagenic testing purposes. One of these compounds rapidly decomposes on exposure to air.

  4. Water flow in carbon-based nanoporous membranes impacted by interactions between hydrated ions and aromatic rings.

    Science.gov (United States)

    Liu, Jian; Shi, Guosheng; Fang, Haiping

    2017-02-24

    Carbon-based nanoporous membranes, such as carbon nanotubes (CNTs), graphene/graphene oxide and graphyne, have shown great potential in water desalination and purification, gas and ion separation, biosensors, and lithium-based batteries, etc. A deep understanding of the interaction between hydrated ions in an aqueous solution and the graphitic surface in systems composed of water, ions and a graphitic surface is essential for applications with carbon-based nanoporous membrane platforms. In this review, we describe the recent progress of the interaction between hydrated ions and aromatic ring structures on the carbon-based surface and its applications in the water flow in a carbon nanotube. We expect that these works can be extended to the understanding of water flow in other nanoporous membranes, such as nanoporous graphene, graphyne and stacked sheets of graphene oxide.

  5. Fused aromatic thienopyrazines: structure, properties and function

    KAUST Repository

    Mondal, Rajib

    2010-01-01

    Recent development of a fused aromatic thieno[3.4-b]pyrazine system and their application in optoelectronic devices are reviewed. Introduction of a fused aromatic unit followed by side chain engineering, dramatically enhanced the charge carrier mobility in thin film transistor devices and mobilities up to 0.2 cm2/Vs were achieved. The optoelectronic properties of these fused aromatic thienopyrazine polymers (Eg = 1.3 to 1.6 eV, HOMO = -4.9 to -5.2 V) were tuned by introduction of various fused aromatic rings within thienopyrazine. By balancing the fundamental properties of these polymers, both high charge carrier mobilities and moderate PCEs in solar cells were achieved. Further, effects of copolymerizing units are discussed. Low band gap semiconducting polymer (Eg ∼ 1 eV) with high field effect mobility (0.044 cm2/Vs) was obtained using cyclopentadithiophene as copolymerizing unit. Finally, a molecular design approach to enhance the absorption coefficients is discussed, which resulted in improved power conversion efficiency in bulk heterojunction solar cells. © 2010 The Royal Society of Chemistry.

  6. Chronic toxicity of selected polycyclic aromatic hydrocarbons to algae and crustaceans using passive dosing.

    Science.gov (United States)

    Bragin, Gail E; Parkerton, Thomas F; Redman, Aaron D; Letinksi, Daniel J; Butler, Josh D; Paumen, Miriam Leon; Sutherland, Cary A; Knarr, Tricia M; Comber, Mike; den Haan, Klaas

    2016-12-01

    Because of the large number of possible aromatic hydrocarbon structures, predictive toxicity models are needed to support substance hazard and risk assessments. Calibration and evaluation of such models requires toxicity data with well-defined exposures. The present study has applied a passive dosing method to generate reliable chronic effects data for 8 polycyclic aromatic hydrocarbons (PAHs) on the green algae Pseudokirchneriella subcapitata and the crustacean Ceriodaphnia dubia. The observed toxicity of these substances on algal growth rate and neonate production were then compared with available literature toxicity data for these species, as well as target lipid model and chemical activity-based model predictions. The use of passive dosing provided well-controlled exposures that yielded more consistent data sets than attained by past literature studies. Results from the present study, which were designed to exclude the complicating influence of ultraviolet light, were found to be well described by both target lipid model and chemical activity effect models. The present study also found that the lack of chronic effects for high molecular weight PAHs was consistent with the limited chemical activity that could be achieved for these compounds in the aqueous test media. Findings from this analysis highlight that variability in past literature toxicity data for PAHs may be complicated by both poorly controlled exposures and photochemical processes that can modulate both exposure and toxicity. Environ Toxicol Chem 2016;35:2948-2957. © 2016 SETAC. © 2016 SETAC.

  7. Secondary organic aerosol (trans)formation through aqueous phase guaiacol photonitration: a kinetic study

    Science.gov (United States)

    Kroflič, Ana; Grgić, Irena

    2014-05-01

    It is well known that atmospheric aerosols play a crucial role in the Earth's climate and public health (Pöschl 2005). Despite a great effort invested in the studies of secondary organic aerosol (SOA) budget, composition, and its formation mechanisms, there is still a gap between field observations and atmospheric model predictions (Heald et al. 2005, Hallquist et al. 2009, and Lim et al. 2010). The insisting uncertainties surrounding SOA formation and aging thus gained an increasing interest in atmospheric aqueous phase chemistry; they call for more complex and time consuming studies at the environmentally relevant conditions allowing confident extrapolation to desired ambient conditions. In addition to the adverse health effects of atmospheric particulate matter (PM) as such, toxicity is also attributed to nitro-aromatic and other organic compounds which have already been detected in real aerosol samples (Traversi et al. 2009). Moreover, low-volatility aromatic derivatives are believed to form at least partly in the aerosol aqueous phase and not only in the gas phase from where they partition into water droplets (Ervens et al. 2011). Two nitro derivatives of biomass burning tracer guaiacol have recently been found in winter PM10 samples from the city of Ljubljana, Slovenia, and aqueous photonitration reaction was proposed as their possible production pathway (Kitanovski et al. 2012). In this study the kinetics of guaiacol nitration in aqueous solution was investigated in the presence of H2O2 and NO2¯ upon simulated solar irradiation (Xenon lamp, 300 W). During the experiment the DURAN® flask with the reaction mixture was held in the thermostated bath and thoroughly mixed. The reaction was monitored for 44 hours at different temperatures. Guaiacol and its main nitro-products (4-nitroguaiacol, 4-NG; 6-nitroguaiacol, 6-NG; and 4,6-dinitroguaiacol, 4,6-DNG) were quantified in every aliquot, taken from the reaction mixture, by use of high pressure liquid

  8. Enantiopure distorted ribbon-shaped nanographene combining two-photon absorption-based upconversion and circularly polarized luminescence.

    Science.gov (United States)

    Cruz, Carlos M; Márquez, Irene R; Mariz, Inês F A; Blanco, Victor; Sánchez-Sánchez, Carlos; Sobrado, Jesús M; Martín-Gago, José A; Cuerva, Juan M; Maçôas, Ermelinda; Campaña, Araceli G

    2018-04-28

    Herein we describe a distorted ribbon-shaped nanographene exhibiting unprecedented combination of optical properties in graphene-related materials, namely upconversion based on two-photon absorption (TPA-UC) together with circularly polarized luminescence (CPL). The compound is a graphene molecule of ca. 2 nm length and 1 nm width with edge defects that promote the distortion of the otherwise planar lattice. The edge defects are an aromatic saddle-shaped ketone unit and a [5]carbohelicene moiety. This system is shown to combine two-photon absorption and circularly polarized luminescence and a remarkably long emission lifetime of 21.5 ns. The [5]helicene is responsible for the chiroptical activity while the push-pull geometry and the extended network of sp 2 carbons are factors favoring the nonlinear absorption. Electronic structure theoretical calculations support the interpretation of the results.

  9. Stable dielectric response of low-loss aromatic polythiourea thin films on Pt/SiO2 substrate

    Directory of Open Access Journals (Sweden)

    A. Eršte

    2016-03-01

    Full Text Available We have investigated dielectric properties of aromatic polythiourea (ArPTU, a polar polymer containing high dipolar moments with very low defect levels thin films that were developed on Pt/SiO2 substrate. The detected response is compared to the response of commercially available polymers, such as high density polyethylene (HDPE and polypropylene (PP, which are at present used in foil capacitors. Stable values of the dielectric constant ε′≈5 (being twice higher than in HDPE and PP over broad temperature and frequency ranges and dielectric losses as low as in commercial systems suggest ArPTU as a promising candidate for future use in a variety of applications.

  10. An ethnopharmacological study of aromatic Uyghur medicinal plants in Xinjiang, China.

    Science.gov (United States)

    Zhao, Lu; Tian, Shuge; Wen, E; Upur, Halmuart

    2017-12-01

    An ethnobotanical survey was completed in a remote village and surrounding country of Xinjiang, where most Uyghur medicinal plants could be collected. This work clarifies and increases ethnobotanical data. We surveyed and organized aromatic medicinal plants that are commonly used in clinical settings to provide a significant reference for studying new medical activities. In the survey, informants who have traditional knowledge on aromatic Uyghur medicinal plants were interviewed between March 2014 and September 2014. Aromatic medicinal plant species and pertinent information were collected. Some therapeutic methods and modes of preparation of traditional aromatic medicinal plants were found. A total of 86 aromatic medicinal plant species belonging to 36 families were included in our study. We identified 34 plant species introduced from different regions such as Europe, India and Mediterranean areas. Fruits and whole plants were the most commonly used parts of plant, and most aromatic medicinal plants could be applied as medicine and food. We assigned the medicinal plants a use value (UV). Knowing the UV of species is useful in determining the use reliability and pharmacological features of related plants. Xinjiang is an area in which indigenous aromatic medicinal plants are diversely used and has therefore established a sound dimensional medical healthcare treatment system. Some aromatic Uyghur medicinal plants are on the verge of extinction. Hence, further strategies for the conservation of these aromatic medicinal plants should be prioritized.

  11. Spectrofluorimetric study of the aromatic carbohydrates of Noriisk petroleum

    Energy Technology Data Exchange (ETDEWEB)

    Alekseeva, T.A.; Lekveishvili, E.G.; Melikadze, L.D.; Teplitskaia, T.A.; Tevdorashvili, M.N.

    1979-01-01

    Investigation was made of the specimens of aromatic hydrocarbons which were produced by photochemical decomposition of the products of photocondensation with maleicanhydride of narrow aromatic fractions separated by a system of methods from a high temperature part of Noriisk petroleum. Use was made of a standard spectrofluorimeter of low resolution. A series of aromatic hydrocarbons, naphthalene, benzofluorene, phenantrene, chrizene, pyrene, tetraphene, and 3,4-benzophenantrene were installed in the machine.

  12. Polarization measurement for internal polarized gaseous targets

    International Nuclear Information System (INIS)

    Ye Zhenyu; Ye Yunxiu; Lv Haijiang; Mao Yajun

    2004-01-01

    The authors present an introduction to internal polarized gaseous targets, polarization method, polarization measurement method and procedure. To get the total nuclear polarization of hydrogen atoms (including the polarization of the recombined hydrogen molecules) in the target cell, authors have measured the parameters relating to atomic polarization and polarized hydrogen atoms and molecules. The total polarization of the target during our measurement is P T =0.853 ± 0.036. (authors)

  13. The cisproline(i - 1)-aromatic(i) interaction: Folding of the Ala-cisPro-Tyr peptide characterized by NMR and theoretical approaches

    Energy Technology Data Exchange (ETDEWEB)

    Nardi, Frederico; Kemmink, Johan; Sattler, Michael; Wade, Rebecca C. [European Molecular Biology Laboratory (Germany)

    2000-05-15

    Cisproline(i-1)-aromatic(i) interactions have been detected in several short peptides in aqueous solution by analysis of anomalous chemical shifts measured by {sup 1}H-NMR spectroscopy. This formation of local structure is of importance for protein folding and binding properties. To obtain an atomic-detail characterisation of the cisproline(i-1)-aromatic(i) interaction in terms of structure, energetics and dynamics, we studied the minimal peptide unit, blocked Ala-cisPro-Tyr, using computational and experimental techniques. Structural database analyses and a systematic search revealed two groups of conformations displaying a cisproline(i-1)-aromatic(i) interaction. These conformations were taken as seeds for molecular dynamics simulations in explicit solvent at 278 K. During a total of 33.6 ns of simulation, all the 'folded' conformations and some 'unfolded' states were sampled. {sup 1}H- and {sup 13}C-chemical shifts and {sup 3}J-coupling constants were measured for the Ala-Pro-Tyr peptide. Excellent agreement was found between all the measured and computed NMR properties, showing the good quality of the force field. We find that under the experimental and simulation conditions, the Ala-cisPro-Tyr peptide is folded 90% of the time and displays two types of folded conformation which we denote 'a' and 'b'. The type a conformations are twice as populated as the type b conformations. The former have the tyrosine ring interacting with the alanine {alpha} proton and are enthalpically stabilised. The latter have the aromatic ring interacting with the proline side chain and are entropically stabilised. The combined and complementary use of computational and experimental techniques permitted derivation of a detailed scenario of the 'folding' of this peptide.

  14. Quaternary ammonium-functionalized silica sorbents for the solid-phase extraction of aromatic amines under normal phase conditions.

    Science.gov (United States)

    Vidal, Lorena; Robin, Orlane; Parshintsev, Jevgeni; Mikkola, Jyri-Pekka; Riekkola, Marja-Liisa

    2013-04-12

    Quaternary ammonium-functionalized silica materials were synthesized and applied for solid-phase extraction (SPE) of aromatic amines, which are classified as priority pollutants by US Environmental Protection Agency. Hexamethylenetetramine used for silica surface modification for the first time was employed as SPE sorbent under normal phase conditions. Hexaminium-functionalized silica demonstrated excellent extraction efficiencies for o-toluidine, 4-ethylaniline and quinoline (recoveries 101-107%), while for N,N-dimethylaniline and N-isopropylaniline recoveries were from low to moderate (14-46%). In addition, the suitability of 1-alkyl-3-(propyl-3-sulfonate) imidazolium-functionalized silica as SPE sorbent was tested under normal phase conditions. The recoveries achieved for the five aromatic amines ranged from 89 to 99%. The stability of the sorbent was evaluated during and after 150 extractions. Coefficients of variation between 4.5 and 10.2% proved a high stability of the synthesized sorbent. Elution was carried out using acetonitrile in the case of hexaminium-functionalized silica and water for 1-alkyl-3-(propyl-3-sulfonate) imidazolium-functionalized silica sorbent. After the extraction the analytes were separated and detected by liquid chromatography ultraviolet detection (LC-UV). The retention mechanism of the materials was primarily based on polar hydrogen bonding and π-π interactions. Comparison made with activated silica proved the quaternary ammonium-functionalized materials to offer different selectivity and better extraction efficiencies for aromatic amines. Finally, 1-alkyl-3-(propyl-3-sulfonate) imidazolium-functionalized silica sorbent was successfully tested for the extraction of wastewater and soil samples. Copyright © 2013 Elsevier B.V. All rights reserved.

  15. Extraction of aromatics from naphtha with ionic liquids

    NARCIS (Netherlands)

    Meindersma, G.W.

    2005-01-01

    The objective of this study was the development of a separation technology for the selective recovery and purification of aromatic compounds benzene, toluene, ethylbenzene and xylenes (BTEX) from liquid ethylene cracker feeds. Most ethylene cracker feeds contain 10 ¿ 25% of aromatic components,

  16. Critical point measurement of some polycyclic aromatic hydrocarbons

    International Nuclear Information System (INIS)

    Nikitin, Eugene D.; Popov, Alexander P.

    2015-01-01

    Highlights: • Critical properties of five polycyclic aromatic hydrocarbons were measured. • These hydrocarbons decompose at near-critical temperatures. • Pulse-heating method with short residence times was used. - Abstract: The critical temperatures and the critical pressures of five polycyclic aromatic compounds, namely, acenaphthene, fluorene, anthracene, phenanthrene, and pyrene have been measured. All the compounds studied decompose at near-critical temperatures. A pulse-heating technique applicable to measuring the critical properties of thermally unstable compounds has been used. The times from the beginning of a heating pulse to the moment of reaching the critical temperature were from (0.06 to 0.85) ms. The short residence times provide little degradation of the substances in the course of the experiments. The experimental critical parameters of the polycyclic aromatic compounds have been compared with those estimated by five predictive methods. The acentric factors of polycyclic aromatic compounds studied have been calculated

  17. Self-assembled electrical materials from contorted aromatics

    Science.gov (United States)

    Xiao, Shengxiong

    This thesis describes the design, synthesis, self-assembly and electrical properties of new types of contorted polycyclic aromatic hydrocarbons. These topologically interesting contorted aromatics show promising transistor characteristics as new building blocks for organic field-effect transistors (OFETs) at different length scales. In chapter 2, a class of pentacenes that are substituted along their long edges with aromatic rings were synthesized. Their solid-state assemblies were studied by X-ray crystallography. Their performance as thin film transistors (TFTs) and single crystal field effect transistors (SCFETs) were systematically evaluated. A structure-property relationship between these highly phenylated pentacenes was found. Chapter 3 explores the new concept of whether a non-planar aromatic core could yield efficacious electronic materials, as the ultimate success in the organic electronics will require a holistic approach to creating new building blocks. Synthesis, functionalization and assembly of a new type of contorted hexabenzocoronene (HBC) whose aromatic core is heavily distorted away from planarity due to the steric congestion around its proximal carbons were discussed. Structural studies by X-ray crystallography showed that these HBC molecules stack into columnar structures in the solid state, which are ideal for conduction. Chapter 4 describes that microscale liquid crystalline thin film OFETs of tetradodecyloxy HBC showed the best transistor properties of all discotic columnar materials. Chapter 5 details the fabrication and characterization of nanoscale single crystalline fiber OFETs of octadodecyloxyl HBC. In Chapter 6 we show that a molecular scale monolayer of HBC acid chlorides could be self-assembled on SiO2 insulating layer and could be organized laterally between the ends of 2 nm carbon nanotube gaps to form high quality FETs that act as environmental and chemical sensors. Chapter 7 details the enforced one-dimensional photoconductivity

  18. Effect of pyrolysis temperature on polycyclic aromatic hydrocarbons toxicity and sorption behaviour of biochars prepared by pyrolysis of paper mill effluent treatment plant sludge.

    Science.gov (United States)

    Devi, Parmila; Saroha, Anil K

    2015-09-01

    The polycyclic aromatic hydrocarbons (PAHs) toxicity and sorption behaviour of biochars prepared from pyrolysis of paper mill effluent treatment plant (ETP) sludge in temperature range 200-700 °C was studied. The sorption behaviour was found to depend on the degree of carbonization where the fractions of carbonized and uncarbonized organic content in the biochar act as an adsorption media and partition media, respectively. The sorption and partition fractions were quantified by isotherm separation method and isotherm parameters were correlated with biochar properties (aromaticity, polarity, surface area, pore volume and ash content). The risk assessment for the 16 priority EPA PAHs present in the biochar matrix was performed and it was found that the concentrations of the PAHs in the biochar were within the permissible limits prescribed by US EPA (except BC400 and BC500 for high molecular weight PAHs). Copyright © 2015 Elsevier Ltd. All rights reserved.

  19. Multi-layer solid-phase extraction and evaporation-enrichment methods for polar organic chemicals from aqueous matrices.

    Science.gov (United States)

    Köke, Niklas; Zahn, Daniel; Knepper, Thomas P; Frömel, Tobias

    2018-03-01

    Analysis of polar organic chemicals in the aquatic environment is exacerbated by the lack of suitable and widely applicable enrichment methods. In this work, we assessed the suitability of a novel combination of well-known solid-phase extraction (SPE) materials in one cartridge as well as an evaporation method and for the enrichment of 26 polar model substances (predominantly log D evaporation method were investigated for the recovery and matrix effects of the model substances and analyzed with hydrophilic interaction liquid chromatography-tandem mass spectrometry (HILIC-MS/MS). In total, 65% of the model substances were amenable (> 10% recovery) to the mlSPE method with a mean recovery of 76% while 73% of the model substances were enriched with the evaporation method achieving a mean recovery of 78%. Target and non-target screening comparison of both methods with a frequently used reversed-phase SPE method utilizing "hydrophilic and lipophilic balanced" (HLB) material was performed. Target analysis showed that the mlSPE and evaporation method have pronounced advantages over the HLB method since the HLB material retained only 30% of the model substances. Non-target screening of a ground water sample with the investigated enrichment methods showed that the median retention time of all detected features on a HILIC system decreased in the order mlSPE (3641 features, median t R 9.7 min), evaporation (1391, 9.3 min), HLB (4414, 7.2 min), indicating a higher potential of the described methods to enrich polar analytes from water compared with HLB-SPE. Graphical abstract Schematic of the method evaluation (recovery and matrix effects) and method comparison (target and non-target analysis) of the two investigated enrichment methods for very polar chemicals in aqueousmatrices.

  20. Kinetics and Mechanism of Oxidation of Aromatic Aldehydes by Imidazolium Dichromate in Aqueous Acetic Acid Medium

    Directory of Open Access Journals (Sweden)

    S. Sheik Mansoor

    2009-01-01

    Full Text Available The kinetics of oxidation of benzaldehyde (BA and para-substituted benzaldehydes by imidazolium dichromate (IDC has been studied in aqueous acetic acid medium in the presence of perchloric acid. The reaction is first order each in [IDC], [Substrate] and [H+]. The reaction rates have been determined at different temperatures and the activation parameters calculated. Electron withdrawing substituents are found to increase the reaction and electron releasing substituents are found to retard the rate of the reaction and the rate data obey the Hammett relationship. The products of the oxidation are the corresponding acids. The rate decreases with the increase in the water content of the medium. A suitable mechanism is proposed.

  1. Anaerobic catabolism of aromatic compounds: a genetic and genomic view.

    Science.gov (United States)

    Carmona, Manuel; Zamarro, María Teresa; Blázquez, Blas; Durante-Rodríguez, Gonzalo; Juárez, Javier F; Valderrama, J Andrés; Barragán, María J L; García, José Luis; Díaz, Eduardo

    2009-03-01

    Aromatic compounds belong to one of the most widely distributed classes of organic compounds in nature, and a significant number of xenobiotics belong to this family of compounds. Since many habitats containing large amounts of aromatic compounds are often anoxic, the anaerobic catabolism of aromatic compounds by microorganisms becomes crucial in biogeochemical cycles and in the sustainable development of the biosphere. The mineralization of aromatic compounds by facultative or obligate anaerobic bacteria can be coupled to anaerobic respiration with a variety of electron acceptors as well as to fermentation and anoxygenic photosynthesis. Since the redox potential of the electron-accepting system dictates the degradative strategy, there is wide biochemical diversity among anaerobic aromatic degraders. However, the genetic determinants of all these processes and the mechanisms involved in their regulation are much less studied. This review focuses on the recent findings that standard molecular biology approaches together with new high-throughput technologies (e.g., genome sequencing, transcriptomics, proteomics, and metagenomics) have provided regarding the genetics, regulation, ecophysiology, and evolution of anaerobic aromatic degradation pathways. These studies revealed that the anaerobic catabolism of aromatic compounds is more diverse and widespread than previously thought, and the complex metabolic and stress programs associated with the use of aromatic compounds under anaerobic conditions are starting to be unraveled. Anaerobic biotransformation processes based on unprecedented enzymes and pathways with novel metabolic capabilities, as well as the design of novel regulatory circuits and catabolic networks of great biotechnological potential in synthetic biology, are now feasible to approach.

  2. Determination of major aromatic constituents in vanilla using an on-line supercritical fluid extraction coupled with supercritical fluid chromatography.

    Science.gov (United States)

    Liang, Yanshan; Liu, Jiaqi; Zhong, Qisheng; Shen, Lingling; Yao, Jinting; Huang, Taohong; Zhou, Ting

    2018-04-01

    An on-line supercritical fluid extraction coupled with supercritical fluid chromatography method was developed for the determination of four major aromatic constituents in vanilla. The parameters of supercritical fluid extraction were systematically investigated using single factor optimization experiments and response surface methodology by a Box-Behnken design. The modifier ratio, split ratio, and the extraction temperature and pressure were the major parameters which have significant effects on the extraction. While the static extraction time, dynamic extraction time, and recycle time had little influence on the compounds with low polarity. Under the optimized conditions, the relative extraction efficiencies of all the constituents reached 89.0-95.1%. The limits of quantification were in the range of 1.123-4.747 μg. The limits of detection were in the range of 0.3368-1.424 μg. The recoveries of the four analytes were in the range of 76.1-88.9%. The relative standard deviations of intra- and interday precision ranged from 4.2 to 7.6%. Compared with other off-line methods, the present method obtained higher extraction yields for all four aromatic constituents. Finally, this method has been applied to the analysis of vanilla from different sources. On the basis of the results, the on-line supercritical fluid extraction-supercritical fluid chromatography method shows great promise in the analysis of aromatic constituents in natural products. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Hydrocarbons (aliphatic and aromatic) in the snow-ice cover in the Arctic

    International Nuclear Information System (INIS)

    Nemirovskaya, I.A.; Novigatsky, A.N.; Kluvitkin, A.A.

    2002-01-01

    This paper presented the concentration and composition of aliphatic hydrocarbons and polycyclic aromatic hydrocarbons (PAHs) in snow and ice-infested waters in the France-Victoria trough in the northern Barents Sea and in the Mendeleev ridge in the Amerasian basin of the Arctic Ocean. Extreme conditions such as low temperatures, ice sheets and the polar nights render the arctic environment susceptible to oil spills. Hydrocarbons found in these northern seas experience significant transformations. In order to determine the sources, pathways and transformations of the pollutants, it is necessary to know their origin. Hydrocarbon distributions is determined mostly by natural hydrobiological and geochemical conditions. The regularity of migration is determined by natural factors such as formation and circulation of air and ice drift. There is evidence suggesting that the hydrocarbons come from pyrogenic sources. It was noted that hydrocarbons could be degraded even at low temperatures. 17 refs., 1 tab

  4. Separation of aromatics by vapor permeation through solvent swollen membrane

    Energy Technology Data Exchange (ETDEWEB)

    Ito, A.; Adachi, K.; Feng, Y. [Niigata University, Niigata (Japan)

    1995-12-20

    A vapor permeation process for aromatics separation from a hydrocarbon mixture was studied by means of the simultaneous permeation of dimethylsulfoxide vapor as an agent for membrane swelling and preferential permeation of aromatics. The separation performance of the process was demonstrated by a polyvinylalcohol membrane for mixed vapors of benzene/cyclohexane, xylene/octane and a model gasoline. The aromatic vapors preferentially permeated from these mixed vapor feeds. The separation factor was over 10. The separation mechanism of the process mainly depends on the relative salability of the vapors between aromatics and other hydrocarbons in dimethylsulfoxide. 14 refs., 9 figs., 1 tab.

  5. Does the concept of Clar's aromatic sextet work for dicationic forms of polycyclic aromatic hydrocarbons?--testing the model against charged systems in singlet and triplet states.

    Science.gov (United States)

    Dominikowska, Justyna; Palusiak, Marcin

    2011-07-07

    The concept of Clar's π-electron aromatic sextet was tested against a set of polycyclic aromatic hydrocarbons in neutral and doubly charged forms. Systems containing different types of rings (in the context of Clar's concept) were chosen, including benzene, naphthalene, anthracene, phenanthrene and triphenylene. In the case of dicationic structures both singlet and triplet states were considered. It was found that for singlet state dicationic structures the concept of aromatic sextet could be applied and the local aromaticity could be discussed in the context of that model, whereas in the case of triplet state dicationic structures Clar's model rather failed. Different aromaticity indices based on various properties of molecular systems were applied for the purpose of the studies. The discussion about the interdependence between the values of different aromaticity indices applied to neutral and charged systems in singlet and triplet states is also included. This journal is © the Owner Societies 2011

  6. Deuteration of benzen derivatives and condensed aromatics

    International Nuclear Information System (INIS)

    Ichikawa, Masaru.

    1970-01-01

    A process for the deuteration of aromatic compounds (benzene derivatives having one or more cyano, halogeno, nitro or other electron attractive groups, and condensed ring aromatics) is provided. The process comprises reducing said aromatic compound with an alkali metal (preferably K, Rb or Cs) in a solvent (dimethoxyethane, tetrahydrofuran, etc.) to provide an electron-acceptor-donor complex, which is followed by introducing gaseous deuterium into the solution. The deuteration takes place selectively at the position of highest electron density in accordance with nature of the substituent, regardless of steric hindrance. The process is applicable to a wide variety of aromatics to give deuterated compounds in high yields. In one example, 5x10 -3 mole of anthracene (An) was reacted with 2g of metallic potassium in 80cc of dimethoxyethane in a N 2 atmosphere. Into the resulting solution of An=2K + was introduced D 2 gas (30 cmHg) at 25 0 C. After decomposition with air and washing with alcohol, the precipitate was recrystallized from benzene. Yield of recovered AN: more than 90%. Yield of deuteration: 100%. Position of deuteration: 9 and 10 (revealed by NMR and mass spectroscopy). (Kaichi, S.)

  7. Synthesis and bioelectrochemical behavior of aromatic amines.

    Science.gov (United States)

    Shabbir, Muhammad; Akhter, Zareen; Ahmad, Iqbal; Ahmed, Safeer; Bolte, Michael; McKee, Vickie

    2017-12-01

    Four aromatic amines 1-amino-4-phenoxybenzene (A 1 ), 4-(4-aminophenyloxy) biphenyl (A 2 ), 1-(4-aminophenoxy) naphthalene (A 3 ) and 2-(4-aminophenoxy) naphthalene (A 4 ) were synthesized and characterized by elemental, spectroscopic (FTIR, NMR), mass spectrometric and single crystal X-ray diffraction methods. The compounds crystallized in monoclinic crystal system with space group P2 1 . Intermolecular hydrogen bonds were observed between the amine group and amine/ether acceptors of neighboring molecules. Electrochemical investigations were done using cyclic voltammetry (CV), square wave voltammetry (SWV) and differential pulse voltammetry (DPV). CV studies showed that oxidation of aromatic amines takes place at about 0.9 V (vs. Ag/AgCl) and the electron transfer (ET) process has irreversible nature. After first scan reactive intermediate were generated electrochemically and some other cathodic and anodic peaks also appeared in the succeeding scans. DPV study revealed that ET process is accompanied by one electron. DNA binding study of aromatic amines was performed by CV and UV-visible spectroscopy. These investigations revealed groove binding mode of interaction of aromatic amines with DNA. Copyright © 2017 Elsevier Inc. All rights reserved.

  8. Oxidative decomposition of aromatic hydrocarbons by electron beam irradiation

    Science.gov (United States)

    Han, Do-Hung; Stuchinskaya, Tatiana; Won, Yang-Soo; Park, Wan-Sik; Lim, Jae-Kyong

    2003-05-01

    Decomposition of aromatic volatile organic compounds (VOCs) under electron beam irradiation was studied in order to examine the kinetics of the process, to characterize the reaction product distribution and to develop a process of waste gas control technology. Toluene, ethylbenzene, o-, m-, p-xylenes and chlorobenzene were used as target materials. The experiments were carried out at doses ranging from 0.5 to 10 kGy, using a flow reactor utilized under electron beam irradiation. Maximum degrees of decomposition carried out at 10 kGy in air environment were 55-65% for “non-chlorinated” aromatic VOC and 85% for chlorobenzene. It was found that a combination of aromatic pollutants with chlorobenzene would considerably increase the degradation value up to nearly 50% compared to the same compounds in the absence of chlorine groups. Based on our experimental observation, the degradation mechanism of the aromatic compounds combined with chloro-compound suggests that a chlorine radical, formed from EB irradiation, induces a chain reaction, resulting in an accelerating oxidative destruction of aromatic VOCs.

  9. Microbial degradation of aliphatic and aliphatic-aromatic co-polyesters.

    Science.gov (United States)

    Shah, Aamer Ali; Kato, Satoshi; Shintani, Noboru; Kamini, Numbi Ramudu; Nakajima-Kambe, Toshiaki

    2014-04-01

    Biodegradable plastics (BPs) have attracted much attention since more than a decade because they can easily be degraded by microorganisms in the environment. The development of aliphatic-aromatic co-polyesters has combined excellent mechanical properties with biodegradability and an ideal replacement for the conventional nondegradable thermoplastics. The microorganisms degrading these polyesters are widely distributed in various environments. Although various aliphatic, aromatic, and aliphatic-aromatic co-polyester-degrading microorganisms and their enzymes have been studied and characterized, there are still many groups of microorganisms and enzymes with varying properties awaiting various applications. In this review, we have reported some new microorganisms and their enzymes which could degrade various aliphatic, aromatic, as well as aliphatic-aromatic co-polyesters like poly(butylene succinate) (PBS), poly(butylene succinate)-co-(butylene adipate) (PBSA), poly(ε-caprolactone) (PCL), poly(ethylene succinate) (PES), poly(L-lactic acid) (PLA), poly(3-hydroxybutyrate) and poly(3-hydoxybutyrate-co-3-hydroxyvalterate) (PHB/PHBV), poly(ethylene terephthalate) (PET), poly(butylene terephthalate) (PBT), poly(butylene adipate-co-terephthalate (PBAT), poly(butylene succinate-co-terephthalate) (PBST), and poly(butylene succinate/terephthalate/isophthalate)-co-(lactate) (PBSTIL). The mechanism of degradation of aliphatic as well as aliphatic-aromatic co-polyesters has also been discussed. The degradation ability of microorganisms against various polyesters might be useful for the treatment and recycling of biodegradable wastes or bioremediation of the polyester-contaminated environments.

  10. Anion bridges drive salting out of a simple amphiphile from aqueous solution

    International Nuclear Information System (INIS)

    Bowron, D.T.; Finney, J.L.

    2002-01-01

    Neutron diffraction with isotope substitution has been used to determine the structural changes that occur on the addition of a simple salting-out agent to a dilute aqueous alcohol solution. The striking results obtained demonstrate a relatively simple process occurs in which interamphiphile anionic salt bridges are formed between the polar groups of the alcohol molecules. These ion bridges drive an increase in the exposure of the alcohol molecule nonpolar surface to the solvent water and hence point the way to their eventual salting out by the hydrophobic effect

  11. Which kind of aromatic structures are produced during biomass charring? New insights provided by modern solid-state NMR spectroscopy

    Science.gov (United States)

    Knicker, Heike; Paneque-Carmona, Marina; Velasco-Molina, Marta; de la Rosa, José Maria; León-Ovelar, Laura Regina; Fernandez-Boy, Elena

    2017-04-01

    Intense research on biochar and charcoal of the last years has revealed that depending on the production conditions, the chemical and physical characteristics of their aromatic network can greatly vary. Since such variations are determining the behavior and stability of charred material in soils, a better understanding of the structural changes occurring during their heating and the impact of those changes on their function is needed. One method to characterize pyrogenic organic matter (PyOM) represents solid-state 13C NMR spectroscopy applying the cross polarization (CP) magic angle spinning technique (MAS). A drawback of this technique is that the quantification of NMR spectra of samples with highly condensed and proton-depleted structures is assumed to be bias. Typical samples with such attributes are charcoals produced at temperatures above 700°C under pyrolytic conditions. Commonly their high condensation degree leads to graphenic structures that are not only reducing the CP efficiency but create also a conductive lattice which acts as a shield and prevents the entering of the excitation pulse into the sample during the NMR experiments. Since the latter can damage the NMR probe and in the most cases the obtained NMR spectra show only one broad signal assignable to aromatic C, this technique is rarely applied for characterizing high temperature chars or soot. As a consequence, a more detailed knowledge of the nature of the aromatic ring systems is still missing. The latter is also true for the aromatic domains of PyOM produced at lower temperatures, since older NMR instruments operating at low magnetic fields deliver solid-state 13C NMR spectra with low resolution which turns a more detailed analysis of the aromatic chemical shift region into a challenging task. In order to overcome this disadvantages, modern NMR spectroscopy offers not only instruments with greatly improved resolution but also special pulse sequences for NMR experiments which allow a more

  12. Oxidation of nitride films in aqueous solution: Correlation between surface analysis and electrochemical studies

    International Nuclear Information System (INIS)

    Brown, R.; Alias, M.N.

    1994-01-01

    Ac impedance and dc polarization tests of 304 stainless steels coated by cathodic arc plasma deposition (CAPD) titanium nitride and zirconium nitride were conducted in aqueous chloride solution. Cyclic polarization data suggested passive films were formed over the nitride coatings which are most likely hydrated titanium oxide and zirconium oxides. ESCA analysis of fresh samples and samples exposed during impedance tests indicated a layer rich in oxygen over the ZrN coating after exposure but not over TiN coating. Chemical shifts in the Zr 3d 5/2 core electrons indicate transformation from ZrN to its oxide; the shifts in Ti 2P 3/2 did not support the change from TiN to its oxide. The influence of these shifts on corrosion protection is documented

  13. Formation and occurrence of new polar iodinated disinfection byproducts in drinking water.

    Science.gov (United States)

    Pan, Yang; Li, Wenbin; An, Hao; Cui, Hao; Wang, Ying

    2016-02-01

    During drinking water disinfection, iodinated disinfection byproducts (I-DBPs) can be generated through reactions between iodide, disinfectants, and natural organic matter. Drinking water I-DBPs have been increasingly attracting attention as emerging organic pollutants as a result of their significantly higher toxicity and growth inhibition than their chloro- and bromo-analogues. In this study, by adopting ultra performance liquid chromatography/electrospray ionization-triple quadrupole mass spectrometry precursor ion scan, multiple reaction monitoring, and product ion scan analyses, 11 new polar I-DBPs with confirmed structures and eight new polar I-DBPs with proposed structures were detected in simulated drinking water samples. Chloramination of simulated raw waters containing natural organic matter with higher aromaticity produced higher levels of new phenolic I-DBPs. Formation of new polar I-DBPs and total organic iodine (TOI) was most favored in chloramination, followed by chlorine dioxide treatment, and relatively minor in chlorination. Lower pH in chloramination substantially enhanced the formation of new polar I-DBPs and TOI. NH2Cl and dissolved organic nitrogen could be important nitrogen sources and precursors for formation of the two new nitrogenous phenolic I-DBPs. Notably, in tap water samples collected from nine major cities located in the Yangtze River Delta region of China, seven of the 11 new polar I-DBPs with confirmed structures were detected at levels from 0.11 to 28 ng/L, and the two new nitrogenous phenolic I-DBPs were ubiquitous with concentrations from 0.12 to 24 ng/L, likely due to the relatively high dissolved organic nitrogen levels in regional source waters. Copyright © 2015 Elsevier Ltd. All rights reserved.

  14. Escherichia coli as a potential hydrocarbon conversion microorganism. Oxidation of aliphatic and aromatic compounds by recombinant E. coli in two-liquid phase (aqueous-organic) systems

    NARCIS (Netherlands)

    Favre-Bulle, Olivier

    1992-01-01

    The increased interest in the study of hydrocarbon utilizing microorganisms in recent years has been stimulated by the possibility of using their monooxygenases in the selective oxidation of aliphatic and aromatic compounds. As an example, long chain (>C16) n-alkanes are converted to dicarboxylic

  15. Detection of biologically important anions in aqueous media by dicationic azaborines bearing ammonio or phosphonio groups.

    Science.gov (United States)

    Agou, Tomohiro; Sekine, Masaki; Kobayashi, Junji; Kawashima, Takayuki

    2009-01-01

    New cationic triarylboranes bearing ammonio or phosphonio groups on the periphery were synthesized from a common intermediate, a dibromodibenzoazaborine. These cationic molecules are soluble in highly polar organic solvents as well as water, and they exhibit strong light absorption and photoluminescence emission in water. Complexation of the cationic azaborines with fluoride and cyanide ions in aqueous media proceeded and could be monitored by NMR, UV/Vis, and fluorescence spectroscopy.

  16. Spectral behaviour of eosin Y in different solvents and aqueous surfactant media

    Science.gov (United States)

    Chakraborty, Moumita; Panda, Amiya Kumar

    2011-10-01

    Photophysical behaviour of the anionic xanthene dye, eosin Y (EY) was investigated in solvents of different polarities as well as in the presence of aqueous cationic surfactants. From the correlation between ET(30) and Kosower Z values of EY in different solvents, subsequent parameters for EY were determined in the presence of surfactants. A red shift, both in the absorption and emission spectra of EY, was observed with decreasing solvent polarity. Dimerisation of EY was found to be dependent on solvent polarity. Cationic surfactants retarded the process of dimerisation, which were evident from the lower dimerisation constant ( KD) values, compared to that of in pure water. Dye-surfactant interaction constants were determined at different temperatures (298-318 K) and subsequently the thermodynamic parameters, viz., Δ G°, Δ H° and Δ S° were evaluated using the interaction constant values. The fluorescence spectra of EY followed the same trend as in the absorption spectra, although with lesser extents. Stokes shifts were calculated and correlated with the polarity of the medium. Fluorescence of EY was initially quenched by the cationic surfactants in their pre-micellar region, which then followed a red shift with intensity enhancement. Fluorescence quenching was found to be of Stern-Volmer type where the excited state lifetime of EY remained unchanged in different surfactant media. However, the anisotropy value of EY was changed in the post micellar region of surfactants.

  17. Effects of humic acid and heavy metals on the sorption of polar and apolar organic pollutants onto biochars.

    Science.gov (United States)

    Wang, Fei; Sun, Hongwen; Ren, Xinhao; Liu, Yarui; Zhu, Hongkai; Zhang, Peng; Ren, Chao

    2017-12-01

    The effects of humic acid (HA) and heavy metals (Cu 2+ and Ag + ) on the sorption of polar and apolar organic pollutants onto biochars that were produced at temperatures of 200 °C (BC200) and 700 °C (BC700) were studied. Due to the plentiful polar functional groups on BC200, cationic propranolol exhibited higher levels of sorption than naphthalene on BC200 while naphthalene and propranolol showed similar sorption capacities on BC700. HA changed the characteristics of biochars and generally inhibited the sorption of target organic pollutants on biochars; however, enhancement occurred in some cases depending on the pollutants involved and their concentrations, biochars used and the addition sequences and concentrations of HA. On BC200, HA modifications mainly influenced sorption by decreasing its polarity and increasing its aromaticity, while on BC700, the surface area and pore volume greatly decreased due to the pore-blocking effects of HA. Residue dissolved HA in solution may also contribute to sorption inhibition. Complexation between polar functional groups on BC200 and heavy metals slightly enhanced the sorption of neutral naphthalene and significantly enhanced that of anionic 4-nitro-1-naphtol, while limited the sorption of cationic propranolol. Heavy metals together with their associated water molecules decreased the sorption of target chemicals on BC700 via pore-filling or pore-mouth-covering. Inhibition of heavy metals for 4-nitro-1-naphthol was found to be the weakest due to the bridge effects of heavy metals between 4-nitro-1-naphtol and BC700. The higher polarizability of Ag + led to the increase of its sorption on biochars in the presence of organic aromatic pollutants. The results of the present study shed light on the sorption mechanisms of bi-solute systems and enable us to select suitable biochar sorbents when chemicals co-exist. Copyright © 2017. Published by Elsevier Ltd.

  18. Aromatic graphene

    Energy Technology Data Exchange (ETDEWEB)

    Das, D. K., E-mail: gour.netai@gmail.com [Department of Metallurgical and Material Science Engineering, National Institute of Technology Durgapur-713209, West Bengal (India); Sahoo, S., E-mail: sukadevsahoo@yahoo.com [Department of Physics, National Institute of Technology Durgapur-713209, West Bengal (India)

    2016-04-13

    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.

  19. Aromatic graphene

    International Nuclear Information System (INIS)

    Das, D. K.; Sahoo, S.

    2016-01-01

    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.

  20. Quantitation of chlorophylls and 22 of their colored degradation products in culinary aromatic herbs by HPLC-DAD-MS and correlation with color changes during the dehydration process.

    Science.gov (United States)

    Lafeuille, Jean-Louis; Lefèvre, Stéphane; Lebuhotel, Julie

    2014-02-26

    Chlorophylls and their green and olive-brown derivatives were successfully separated from culinary herb extracts by HPLC with photodiode-array and mass spectrometry detection. The method involved a ternary gradient elution and reverse-phase separation conditions capable of resolving 24 different pigments (2 chlorophylls and 22 of their derivatives) of different polarities within 28 min. The method was applied to monitor color changes in 50 samples of culinary aromatic herbs subjected to five different drying treatments. Of the 24 pigments, 14 were key to understanding the differences between the primary degradation pathways of chlorophyll a and chlorophyll b in culinary herbs during drying processes. A color degradation ladder based on the total molar percentage of all the remaining green pigments was also proposed as a tool to measure the impact of drying treatments on aromatic herb visual aspects.

  1. Global simulation of aromatic volatile organic compounds in the atmosphere

    Science.gov (United States)

    Cabrera Perez, David; Taraborrelli, Domenico; Pozzer, Andrea

    2015-04-01

    Among the large number of chemical compounds in the atmosphere, the organic group plays a key role in the tropospheric chemistry. Specifically the subgroup called aromatics is of great interest. Aromatics are the predominant trace gases in urban areas due to high emissions, primarily by vehicle exhausts and fuel evaporation. They are also present in areas where biofuel is used (i.e residential wood burning). Emissions of aromatic compounds are a substantial fraction of the total emissions of the volatile organic compounds (VOC). Impact of aromatics on human health is very important, as they do not only contribute to the ozone formation in the urban environment, but they are also highly toxic themselves, especially in the case of benzene which is able to trigger a range of illness under long exposure, and of nitro-phenols which cause detrimental for humans and vegetation even at very low concentrations. The aim of this work is to assess the atmospheric impacts of aromatic compounds on the global scale. The main goals are: lifetime and budget estimation, mixing ratios distribution, net effect on ozone production and OH loss for the most emitted aromatic compounds (benzene, toluene, xylenes, ethylbenzene, styrene and trimethylbenzenes). For this purpose, we use the numerical chemistry and climate simulation ECHAM/MESSy Atmospheric Chemistry (EMAC) model to build the global atmospheric budget for the most emitted and predominant aromatic compounds in the atmosphere. A set of emissions was prepared in order to include biomass burning, vegetation and anthropogenic sources of aromatics into the model. A chemical mechanism based on the Master Chemical Mechanism (MCM) was developed to describe the chemical oxidation in the gas phase of these aromatic compounds. MCM have been reduced in terms of number of chemical equation and species in order to make it affordable in a 3D model. Additionally other features have been added, for instance the production of HONO via ortho

  2. Radiolysis of paracetamol in dilute aqueous solution

    International Nuclear Information System (INIS)

    Szabó, László; Tóth, Tünde; Homlok, Renáta; Takács, Erzsébet; Wojnárovits, László

    2012-01-01

    Using radiolytic experiments hydroxyl radical (main reactant in advanced oxidation processes) was shown to effectively destroy paracetamol molecules. The basic reaction is attachment to the ring. The hydroxy-cyclohexadienyl radical produced in the further reactions may transform to hydroxylated paracetamol derivatives or to quinone type molecules and acetamide. The initial efficiency of aromatic ring destruction in the absence of dissolved O 2 is c.a. 10%. The efficiency is 2–3 times higher in the presence of O 2 due to its reaction with intermediate hydroxy-cyclohexadienyl radical and the subsequent ring destruction reactions through peroxi radical. Upon irradiation the toxicity of solutions at low doses increases with the dose and then at higher doses it decreases. This is due to formation of compounds with higher toxicity than paracetamol (e.g. acetamide, hidroquinone). These products, however, are highly sensitive to irradiation and degrade easily. - Highlights: ► Paracetamol is easily degraded in aqueous solution by low dose irradiation. ► Main degradation products are hydroxylated molecules, acetamide and hydroquinone. ► Toxicity of solutions goes through a maximum as a function of dose.

  3. Radiolysis of paracetamol in dilute aqueous solution

    Energy Technology Data Exchange (ETDEWEB)

    Szabo, Laszlo [Institute of Isotopes, Hungarian Academy of Sciences, Budapest (Hungary); Budapest University of Technology and Economics, Budapest (Hungary); Toth, Tuende [Budapest University of Technology and Economics, Budapest (Hungary); Homlok, Renata [Institute of Isotopes, Hungarian Academy of Sciences, Budapest (Hungary); Takacs, Erzsebet [Institute of Isotopes, Hungarian Academy of Sciences, Budapest (Hungary); Wojnarovits, Laszlo [Institute of Isotopes, Hungarian Academy of Sciences, Budapest (Hungary)

    2012-09-15

    Using radiolytic experiments hydroxyl radical (main reactant in advanced oxidation processes) was shown to effectively destroy paracetamol molecules. The basic reaction is attachment to the ring. The hydroxy-cyclohexadienyl radical produced in the further reactions may transform to hydroxylated paracetamol derivatives or to quinone type molecules and acetamide. The initial efficiency of aromatic ring destruction in the absence of dissolved O{sub 2} is c.a. 10%. The efficiency is 2-3 times higher in the presence of O{sub 2} due to its reaction with intermediate hydroxy-cyclohexadienyl radical and the subsequent ring destruction reactions through peroxi radical. Upon irradiation the toxicity of solutions at low doses increases with the dose and then at higher doses it decreases. This is due to formation of compounds with higher toxicity than paracetamol (e.g. acetamide, hidroquinone). These products, however, are highly sensitive to irradiation and degrade easily. - Highlights: Black-Right-Pointing-Pointer Paracetamol is easily degraded in aqueous solution by low dose irradiation. Black-Right-Pointing-Pointer Main degradation products are hydroxylated molecules, acetamide and hydroquinone. Black-Right-Pointing-Pointer Toxicity of solutions goes through a maximum as a function of dose.

  4. Effects of an electric field on interaction of aromatic systems.

    Science.gov (United States)

    Youn, Il Seung; Cho, Woo Jong; Kim, Kwang S

    2016-04-30

    The effect of uniform external electric field on the interactions between small aromatic compounds and an argon atom is investigated using post-HF (MP2, SCS-MP2, and CCSD(T)) and density functional (PBE0-D3, PBE0-TS, and vdW-DF2) methods. The electric field effect is quantified by the difference of interaction energy calculated in the presence and absence of the electric field. All the post-HF methods describe electric field effects accurately although the interaction energy itself is overestimated by MP2. The electric field effect is explained by classical electrostatic models, where the permanent dipole moment from mutual polarization mainly determines its sign. The size of π-conjugated system does not have significant effect on the electric field dependence. We found out that PBE0-based methods give reasonable interaction energies and electric field response in every case, while vdW-DF2 sometimes shows spurious artifact owing to its sensitivity toward the real space electron density. © 2015 Wiley Periodicals, Inc.

  5. Global aromatics supply. Today and tomorrow

    Energy Technology Data Exchange (ETDEWEB)

    Bender, M. [BASF SE, Ludwigshafen (Germany)

    2013-11-01

    Aromatics are the essential building blocks for some of the largest petrochemical products in today's use. To the vast majority they are consumed to produce intermediates for polymer products and, hence, contribute to our modern lifestyle. Their growth rates are expected to be in line with GDP growth in future. This contrasts the significantly lower growth rates of the primary sources for aromatics - fuel processing and steam cracking of naphtha fractions. A supply gap can be expected to open up in future for which creative solutions will be required. (orig.)

  6. Silicone elastomers with aromatic voltage stabilizers

    DEFF Research Database (Denmark)

    A Razak, Aliff Hisyam; Skov, Anne Ladegaard

    of electron-trapping by aromatic compounds grafted to silicone backbones in a crosslinked PDMS is illustrated in Fig. 1. The electrical breakdown strength, the storage modulus and the loss modulus of the elastomer were investigated, as well as the excitation energy from the collision between electron carriers...... and benzene rings in PDMS-PPMS copolymer was measured by UV-vis spectroscopy. The developed elastomers were inherently soft with enhanced electrical breakdown strength due to delocalized pi-electrons of aromatic rings attached to the silicone backbone. The dielectric relative permittivity of PDMS...

  7. Equilibrium studies of the adsorption of aromatic disulfonates by Mg-Al oxide

    Science.gov (United States)

    Kameda, Tomohito; Umetsu, Mami; Kumagai, Shogo; Yoshioka, Toshiaki

    2018-03-01

    The removal of m-benzenedisulfonate (BDS2-) and 2,6-naphthalenedisulfonate (NDS2-) anions by Mg-Al oxide was investigated. Langmuir model best describes the adsorption of both aromatic disulfonate anions, with the maximum amount of uptake higher for BDS2-. Mg-Al oxide reacts easier with the aromatic disulfonate anion with higher charge density, a trend that is the opposite of that observed in aromatic sulfonate anions. After increasing the charge from -1 to -2, the removal of aromatic disulfonates by Mg-Al oxide is controlled by electrostatic interactions, instead of hydrophobic interactions that are dominant for aromatic sulfonate anions.

  8. Micropore engineering of carbonized porous aromatic framework (PAF-1) for supercapacitors application.

    Science.gov (United States)

    Li, Yanqiang; Roy, Soumyajit; Ben, Teng; Xu, Shixian; Qiu, Shilun

    2014-07-07

    Micropore engineering of porous carbons on the effect of capacitance was explored using a carbonized porous aromatic framework (PAF-1). The porous carbons obtained through different carbonization methods show different pore structures enabling us to do this. The capacitance was measured both in aqueous electrolyte and different organic electrolytes. The porous carbons prepared by KOH activation show both high microporous volume, which is beneficial for charge storage, and mesoporous volume, which is devoted to fast ion diffusion in the pores; properties which are highly desirable. It shows a capacitance as high as 280 F g(-1) and 203 F g(-1) at a current density of 1 A g(-1) in 6.0 M KOH and 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (EMImTFSI), respectively. We also demonstrate the effect of diffusion and that of geometric packing of the electrolyte ions in the pores, where a commensurate match of the electrolyte ions with the pores of carbonized materials control and influence significantly the capacitance of these materials.

  9. Sorption kinetics of polycyclic aromatic hydrocarbons removal using granular activated carbon: Intraparticle diffusion coefficients

    International Nuclear Information System (INIS)

    Valderrama, C.; Gamisans, X.; Heras, X. de las; Farran, A.; Cortina, J.L.

    2008-01-01

    Granular activated carbon (GAC) was evaluated as a suitable sorbent for polycyclic aromatic hydrocarbons (PAHs) removal from aqueous solutions. For this purpose, kinetic measurements on the extraction of a family of six PAHs were taken. A morphology study was performed by means of a scanning electron microscopy (SEM) analysis of GAC samples. Analyses of the batch rate data for each PAH were carried out using two kinetic models: the homogenous particle diffusion model (HPDM) and the shell progressive model (SPM). The process was controlled by diffusion rate the solutes (PAHs) that penetrated the reacted layer at PAH concentrations in the range of 0.2-10 mg L -1 . The effective particle diffusion coefficients (D eff ) derived from the two models were determined from the batch rate data. The Weber and Morris intraparticle diffusion model made a double contribution to the surface and pore diffusivities in the sorption process. The D eff values derived from both the HPMD and SPM equations varied from 1.1 x 10 -13 to 6.0 x 10 -14 m 2 s -1 . The simplest model, the pore diffusion model, was applied first for data analysis. The model of the next level of complexity, the surface diffusion model, was applied in order to gain a deeper understanding of the diffusion process. This model is able to explain the data, and the apparent surface diffusivities are in the same order of magnitude as the values for the sorption of functionalized aromatic hydrocarbons (phenols and sulphonates) that are described in the literature

  10. Ion beam irradiation effects on aromatic polymers

    International Nuclear Information System (INIS)

    Shukushima, Satoshi; Ueno, Keiji

    1995-01-01

    We studied the optical and thermal properties of aromatic polymer films which had been irradiated with 1 MeV H + , H 2 + and He + ions. The examined aromatic polymers were polyetherether ketone(PEEK), polyetherimide(PEI), polyether sulfon(PES), polysulfon(PSF), and polyphenylene sulfide(PPS). The optical densities at 300nm of PES and PSF greatly increased after the irradiation. The optical densities at 400nm of all the examined polymer lineally increased with the irradiation dose. The PEEK film which had been irradiated with 1 MeV H + was not deformed above melting point. This demonstrates that cross-linking occurs in PEEK films by ion beam irradiation. As for the effects, depending on the mass of the irradiated ions, it was found that the ions with a high mass induced larger effects on the aromatic polymers for the same absorption energy. (author)

  11. Determination of aromatic and PAH (polycyclic aromatic hydrocarbons) content of oily wastewaters

    Energy Technology Data Exchange (ETDEWEB)

    Lysyj, I.; Russell, E.C.

    1978-08-01

    An analytical scheme was developed for determining the total organic content and hydrocarbon concentration from a one-liter portion of a wastewater sample, and determining the volatile, suspended, and water-soluble fractions from a second, two-liter portion. Analyses of untreated and treated bilge wastewater from the U.S. Army Fort Eustis, Va., facility showed 10-300 ppm suspended organics and 10-300 ppm dissolved organics in the untreated bilge, and no suspended matter, but 700-2000 ppm dissolved organics, in the treated bilge wastewaters. Of the dissolved organics in untreated and treated wastewater, 70 and 10%, respectively, were extracted with chloroform; the organics in the treated water were probably biologically derived from petroleum degradation. Gas chromatographic/mass spectroscopic and high-pressure liquid chromatographic analyses of the chloroform extracts showed about equal parts of phenolic compounds and aromatic hydrocarbons, small amounts of heterocyclics, and traces of polycyclic aromatics in the untreated wastewater, and mainly phenolics in the treated water.

  12. Infrared Spectroscopy of Matrix-Isolated Polycyclic Aromatic Nitrogen Heterocycles (PANHs)

    Science.gov (United States)

    Mattioda, A. L.; Hudgins, D. M.; Bauschlicher, C. W.; Allamandola, L. J.; Biemesderfer, C. D.; Rosi, M.

    2002-01-01

    The mid-infrared spectra of the nitrogen-containing heterocyclic polycyclic aromatic compounds 1-azabenz[a]-anthracene; 2-azabenz[a]anthracene; 1-azachrysene; 2-azachrysene; 4-azachrysene; 2-azapyrene, and 7,8 benzoquinoline in their neutral and cation forms were investigated. The spectra of these species isolated in an argon matrix have been measured. Band frequencies and intensities were tabulated and these data compared with spectra computed using density functional theory at the B3LYP level. The overall agreement between experiment and theory is quite good, in keeping with earlier results on homonuclear polycyclic aromatic hydrocarbons. The differences between the spectral properties of nitrogen bearing aromatics and non-substituted, neutral polycyclic aromatic hydrocarbons will be discussed.

  13. SEDIMENT-ASSOCIATED REACTIONS OF AROMATIC AMINES. 2. QSAR DEVELOPMENT

    Science.gov (United States)

    The fate of aromatic amines in soils and sediments is dominated by irreversible binding through nucleophilic addition and oxidative radical coupling. Despite the common occurrence of the aromatic amine functional group in organic chemicals, the molecular properties useful for pr...

  14. Aromatic products from reaction of lignin model compounds with UV-alkaline peroxide

    International Nuclear Information System (INIS)

    Sun, Y.P.; Wallis, A.F.A.; Nguyen, K.L.

    1997-01-01

    A series of guaiacyl and syringyl lignin model compounds and their methylated analogues were reacted with alkaline hydrogen peroxide while irradiating with UV light at 254 nm. The aromatic products obtained were investigated by gas chromatography-mass spectrometry (GC-MS). Guaiacol, syringol and veratrol gave no detectable aromatic products. However, syringol methyl ether gave small amounts of aromatic products, resulting from ring substitution and methoxyl displacement by hydroxyl radicals. Reaction of vanillin and syringaldehyde gave the Dakin reaction products, methoxy-1,4-hydroquinones, while reaction of their methyl ethers yielded benzoic acids. Acetoguaiacone, acetosyringone and their methyl ethers afforded several hydroxylated aromatic products, but no aromatic products were identified in the reaction mixtures from guaiacylpropane and syringylpropane. In contrast, veratrylpropane gave a mixture from which 17 aromatic hydroxylated compounds were identified. It is concluded that for phenolic lignin model compounds, particularly those possessing electrondonating aromatic ring substituents, ring-cleavage reactions involving superoxide radical anions are dominant, whereas for non-phenolic lignin models, hydroxylation reactions through attack of hydroxyl radicals prevail

  15. One-step extraction of polar drugs from plasma by Parallel Artificial Liquid Membrane Extraction

    DEFF Research Database (Denmark)

    Pilařová, Veronika; Sultani, Mumtaz; Ask, Kristine Skoglund

    2017-01-01

    in the pores of a thin polymeric membrane, a well-known extraction principle also used in hollow fiber liquid-phase microextraction (HF-LPME). However, the new PALME technique offers a more user-friendly setup in which the supported liquid membrane is incorporated in a 96 well plate system. Thus, high......The new microextraction technique named parallel artificial liquid membrane extraction (PALME) was introduced as an alternative approach to liquid-liquid extraction of charged analytes from aqueous samples. The concept is based on extraction of analytes across a supported liquid membrane sustained...... for extraction of polar basic drugs was developed in the present work. The basic drugs hydralazine, ephedrine, metaraminol, salbutamol, and cimetidine were used as model analytes, and were extracted from alkalized human plasma into an aqueous solution via the supported liquid membrane. The extraction...

  16. Orientation of aromatic residues in amyloid cores: Structural insights into prion fiber diversity

    KAUST Repository

    Reymer, Anna

    2014-11-17

    Structural conversion of one given protein sequence into different amyloid states, resulting in distinct phenotypes, is one of the most intriguing phenomena of protein biology. Despite great efforts the structural origin of prion diversity remains elusive, mainly because amyloids are insoluble yet noncrystalline and therefore not easily amenable to traditional structural-biology methods. We investigate two different phenotypic prion strains, weak and strong, of yeast translation termination factor Sup35 with respect to angular orientation of tyrosines using polarized light spectroscopy. By applying a combination of alignment methods the degree of fiber orientation can be assessed, which allows a relatively accurate determination of the aromatic ring angles. Surprisingly, the strains show identical average orientations of the tyrosines, which are evenly spread through the amyloid core. Small variations between the two strains are related to the local environment of a fraction of tyrosines outside the core, potentially reflecting differences in fibril packing.

  17. A Review of Polycyclic Aromatic Hydrocarbons and Heavy Metal ...

    African Journals Online (AJOL)

    A Review of Polycyclic Aromatic Hydrocarbons and Heavy Metal Contamination of Fish from Fish Farms. ... Journal of Applied Sciences and Environmental Management ... Polycyclic aromatic hydrocarbons (PAHs) and heavy metals contribute to pollutants in aquaculture facilities and thus need to be further investigated.

  18. Metal Triflates for the Production of Aromatics from Lignin

    NARCIS (Netherlands)

    Deuss, Peter J.; Lahive, Ciaran W.; Lancefield, Christopher S.; Westwood, Nicholas J.; Kamer, Paul C. J.; Barta, Katalin; de Vries, Johannes G.

    2016-01-01

    The depolymerization of lignin into valuable aromatic chemicals is one of the key goals towards establishing economically viable biorefineries. In this contribution we present a simple approach for converting lignin to aromatic monomers in high yields under mild reaction conditions. The methodology

  19. Reduction of Aromatic and Heterocyclic Aromatic N-Hydroxylamines by Human Cytochrome P450 2S1

    Science.gov (United States)

    Wang, Kai; Guengerich, F. Peter

    2013-01-01

    Many aromatic amines and heterocyclic aromatic amines (HAAs) are known carcinogens for animals and there is also strong evidence for some in human cancer. The activation of these compounds, including some arylamine drugs, involves N-hydroxylation, usually by cytochrome P450 enzymes (P450) in Family 1 (1A2, 1A1, and 1B1). We previously demonstrated that the bioactivation product of the anti-cancer agent 2-(4-amino-3-methylphenyl)-5-fluorobenzothiazole (5F 203), an N-hydroxylamine, can be reduced by P450 2S1 to its amine precursor under anaerobic conditions and, to a lesser extent, under aerobic conditions (Wang, K., and Guengerich, F. P. (2012) Chem. Res. Toxicol. 25, 1740–1751). In the present study, we tested the hypothesis that P450 2S1 is involved in the reductive biotransformation of known carcinogenic aromatic amines and HAAs. The N-hydroxylamines of 4-aminobiphenyl (4-ABP), 2-naphthylamine (2-NA), and 2-aminofluorene (2-AF) were synthesized and found to be reduced by P450 2S1 under both anaerobic and aerobic conditions. The formation of amines due to P450 2S1 reduction also occurred under aerobic conditions but was less apparent because the competitive disproportionation reactions (of the N-hydroxylamines) also yielded amines. Further, some nitroso and nitro derivatives of the arylamines could also be reduced by P450 2S1. None of the amines tested were oxidized by P450 2S1. These results suggest that P450 2S1 may be involved in the reductive detoxication of several of the activated products of carcinogenic aromatic amines and HAAs. PMID:23682735

  20. Global atmospheric budget of simple monocyclic aromatic compounds

    Directory of Open Access Journals (Sweden)

    D. Cabrera-Perez

    2016-06-01

    Full Text Available The global atmospheric budget and distribution of monocyclic aromatic compounds is estimated, using an atmospheric chemistry general circulation model. Simulation results are evaluated with an ensemble of surface and aircraft observations with the goal of understanding emission, production and removal of these compounds.Anthropogenic emissions provided by the RCP database represent the largest source of aromatics in the model (≃ 23 TgC year−1 and biomass burning from the GFAS inventory the second largest (≃ 5 TgC year−1. The simulated chemical production of aromatics accounts for  ≃ 5 TgC year−1. The atmospheric burden of aromatics sums up to 0.3 TgC. The main removal process of aromatics is photochemical decomposition (≃ 27 TgC  year−1, while wet and dry deposition are responsible for a removal of  ≃ 4 TgC year−1.Simulated mixing ratios at the surface and elsewhere in the troposphere show good spatial and temporal agreement with the observations for benzene, although the model generally underestimates mixing ratios. Toluene is generally well reproduced by the model at the surface, but mixing ratios in the free troposphere are underestimated. Finally, larger discrepancies are found for xylenes: surface mixing ratios are not only overestimated but also a low temporal correlation is found with respect to in situ observations.

  1. Biodegradation of Various Aromatic Compounds by Enriched Bacterial Cultures: Part A-Monocyclic and Polycyclic Aromatic Hydrocarbons.

    Science.gov (United States)

    Oberoi, Akashdeep Singh; Philip, Ligy; Bhallamudi, S Murty

    2015-08-01

    Present study focused on the screening of bacterial consortium for biodegradation of monocyclic aromatic hydrocarbon (MAH) and polycyclic aromatic hydrocarbons (PAHs). Target compounds in the present study were naphthalene, acenaphthene, phenanthrene (PAHs), and benzene (MAH). Microbial consortia enriched with the above target compounds were used in screening experiments. Naphthalene-enriched consortium was found to be the most efficient consortium, based on its substrate degradation rate and its ability to degrade other aromatic pollutants with significantly high efficiency. Substrate degradation rate with naphthalene-enriched culture followed the order benzene > naphthalene > acenaphthene > phenanthrene. Chryseobacterium and Rhodobacter were discerned as the predominant species in naphthalene-enriched culture. They are closely associated to the type strain Chryseobacterium arthrosphaerae and Rhodobacter maris, respectively. Single substrate biodegradation studies with naphthalene (PAH) and benzene (MAH) were carried out using naphthalene-enriched microbial consortium (NAPH). Phenol and 2-hydroxybenzaldehyde were identified as the predominant intermediates during benzene and naphthalene degradation, respectively. Biodegradation of toluene, ethyl benzene, xylene, phenol, and indole by NAPH was also investigated. Monod inhibition model was able to simulate biodegradation kinetics for benzene, whereas multiple substrate biodegradation model was able to simulate biodegradation kinetics for naphthalene.

  2. Solid-Phase Microextraction Coupled to Capillary Atmospheric Pressure Photoionization-Mass Spectrometry for Direct Analysis of Polar and Nonpolar Compounds.

    Science.gov (United States)

    Mirabelli, Mario F; Zenobi, Renato

    2018-04-17

    A novel capillary ionization source based on atmospheric pressure photoionization (cAPPI) was developed and used for the direct interfacing between solid-phase microextraction (SPME) and mass spectrometry (MS). The efficiency of the source was evaluated for direct and dopant-assisted photoionization, analyzing both polar (e.g., triazines and organophosphorus pesticides) and nonpolar (polycyclic aromatic hydrocarbons, PAHs) compounds. The results show that the range of compound polarity, which can be addressed by direct SPME-MS can be substantially extended by using cAPPI, compared to other sensitive techniques like direct analysis in real time (DART) and dielectric barrier discharge ionization (DBDI). The new source delivers a very high sensitivity, down to sub parts-per-trillion (ppt), making it a viable alternative when compared to previously reported and less comprehensive direct approaches.

  3. Rationalization and Prediction of the Equivalent Alkane Carbon Number (EACN) of Polar Hydrocarbon Oils with COSMO-RS σ-Moments.

    Science.gov (United States)

    Lukowicz, Thomas; Benazzouz, Adrien; Nardello-Rataj, Véronique; Aubry, Jean-Marie

    2015-10-20

    The equivalent alkane carbon numbers (EACNs) of 20 polar hydrocarbon oils are determined by the fishtail method. These values supplemented by 43 already reported EACNs of other hydrocarbons are rationalized by using the COSMO-RS σ-moments as descriptors for a QSPR analysis. A reliable model, with only two meaningful physicochemical parameters, namely the surface area (M0(X)) and the overall polarity (M2(X)) of the oil X, is able to predict the EACN values of a large variety of oils including (cyclo)alkanes, (cyclo)alkenes, terpenes, aromatics, alkynes, and chloroalkanes and to rationalize structural effects on EACNs. Furthermore, the dependence of the EACN of homologous oils on the chain length provides some molecular insight into how the different oils penetrate into the interfacial film of surfactants.

  4. Aromatics saturation, opening and cleavage technology for middle distillates

    Energy Technology Data Exchange (ETDEWEB)

    Oballa, M.C.; Simanzhenkov, V.; Kim, G. [NOVA Chemicals Corp., Calgary, AB (Canada)

    2009-07-01

    In order to address environmental concerns, there is a need to develop technologies to reformulate or adjust the quality of transportation fuels. The purpose is to reduce the concentration of the compounds which negatively affect the air that people breathe. One of those targeted is the aromatics content of diesel, because high aromatics content results in low cetane number of diesel, as well as higher emission of particulate matter. Less conventional sources of hydrocarbon feedstock such as oil from oil sands and/or shale oil are being exploited in Alberta. These feeds contain multiple fused aromatic ring compounds. NOVA Chemicals would like to use these potentially abundant liquids as feed, but they must first be transformed into a more user friendly state. This paper discussed the development of a process technology that could saturate the aromatic rings, open up the saturated rings and cleave them to get smaller paraffinic molecules. The products then comprised of lower paraffins are suitable as feed to steam crackers for the production of ethylene and propylene, higher paraffins suitable for blending into gasoline and mono aromatic ring compounds which may be further treated through alkylation of benzene to ethylbenzene and dealkylation to styrene. The paper discussed the process steps and highlighted the catalysts. Research results were also shown. It was concluded that the critical technology gaps, as well as solutions, which would enable overcoming the challenges related to handling of aromatic bitumen feedstock, entail the development of two different catalysts, which are on two different technology platforms. 7 refs., 3 tabs., 5 figs.

  5. Polar constituents isolated from Green River oil shale

    Energy Technology Data Exchange (ETDEWEB)

    Anders, D.E.; Doolittle, F.G.; Robinson, W.E.

    1975-01-01

    The mass spectrometric, ir absorption, and NMR data were interpreted for 22 compounds obtained from a polar fraction of Green River shale. The major constituents analyzed are believed to be of the following compositional types: C/sub n/H/sub 2n/O (cyclohexanols and chain isoprenoid ketones), C/sub n/H/sub 2n-10/O (tetralones and indanones), C/sub n/H/sub 2n-7/N (tetrahydroquinolines), C/sub n/H/sub 2n-11/N(quinolines), C/sub n/H/sub 2n-1/NO (alkoxypyrrolines), C/sub n/H/sub 2n-5/NO/sub 2/ (maleimides), C/sub n/H/sub 2n-8/ (tetralins), C/sub n/H/sub 2n-12/ (naphthalenes) and C/sub n/H/sub 2n-14/ (benzylbenzenes). This work expands the present information about nitrogen, oxygen and aromatic constituents indigenous to Green River shale.

  6. Application of aromatization catalyst in synthesis of carbon nanotubes

    Indian Academy of Sciences (India)

    In a typical chemical vapour deposition (CVD) process for synthesizing carbon nanotubes (CNTs), it was found that the aromatization catalysts could promote effectively the formation of CNT. The essence of this phenomenon was attributed to the fact that the aromatization catalyst can accelerate the ...

  7. Alkylation of organic aromatic compounds

    Science.gov (United States)

    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.

  8. Alkylation of organic aromatic compounds

    Science.gov (United States)

    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.

  9. Flow of Aqueous Humor

    Science.gov (United States)

    ... Home Flow of Aqueous Humor Flow of Aqueous Humor Most, but not all, forms of glaucoma are ... remains normal when some of the fluid (aqueous humor) produced by the eye's ciliary body flows out ...

  10. Substituted Phthalic Anhydrides from Biobased Furanics : A New Approach to Renewable Aromatics

    NARCIS (Netherlands)

    Thiyagarajan, Shanmugam; Genuino, Homer C.|info:eu-repo/dai/nl/371571685; Sliwa, Michal; van der Waal, Jan C.; de Jong, Ed; van Haveren, Jacco; Weckhuysen, Bert M.|info:eu-repo/dai/nl/285484397; Bruijnincx, Pieter C. A.|info:eu-repo/dai/nl/33799529X; van Es, Daan S.

    2015-01-01

    A novel route for the production of renewable aromatic chemicals, particularly substituted phthalic acid anhydrides, is presented. The classical two-step approach to furanics-derived aromatics via Diels-Alder (DA) aromatization has been modified into a three-step procedure to address the general

  11. Cation Radical Accelerated Nucleophilic Aromatic Substitution via Organic Photoredox Catalysis.

    Science.gov (United States)

    Tay, Nicholas E S; Nicewicz, David A

    2017-11-15

    Nucleophilic aromatic substitution (S N Ar) is a direct method for arene functionalization; however, it can be hampered by low reactivity of arene substrates and their availability. Herein we describe a cation radical-accelerated nucleophilic aromatic substitution using methoxy- and benzyloxy-groups as nucleofuges. In particular, lignin-derived aromatics containing guaiacol and veratrole motifs were competent substrates for functionalization. We also demonstrate an example of site-selective substitutive oxygenation with trifluoroethanol to afford the desired trifluoromethylaryl ether.

  12. Catalytic oxidation of o-aminophenols and aromatic amines by mushroom tyrosinase.

    Science.gov (United States)

    Muñoz-Muñoz, Jose Luis; Garcia-Molina, Francisco; Garcia-Ruiz, Pedro Antonio; Varon, Ramon; Tudela, Jose; Rodriguez-Lopez, Jose N; Garcia-Canovas, Francisco

    2011-12-01

    The kinetics of tyrosinase acting on o-aminophenols and aromatic amines as substrates was studied. The catalytic constants of aromatic monoamines and o-diamines were both low, these results are consistent with our previous mechanism in which the slow step is the transfer of a proton by a hydroxyl to the peroxide in oxy-tyrosinase (Fenoll et al., Biochem. J. 380 (2004) 643-650). In the case of o-aminophenols, the hydroxyl group indirectly cooperates in the transfer of the proton and consequently the catalytic constants in the action of tyrosinase on these compounds are higher. In the case of aromatic monoamines, the Michaelis constants are of the same order of magnitude than for monophenols, which suggests that the monophenols bind better (higher binding constant) to the enzyme to facilitate the π-π interactions between the aromatic ring and a possible histidine of the active site. In the case of aromatic o-diamines, both the catalytic and Michaelis constants are low, the values of the catalytic constants being lower than those of the corresponding o-diphenols. The values of the Michaelis constants of the aromatic o-diamines are slightly lower than those of their corresponding o-diphenols, confirming that the aromatic o-diamines bind less well (lower binding constant) to the enzyme. Copyright © 2011 Elsevier B.V. All rights reserved.

  13. Palladium-catalysed electrophilic aromatic C-H fluorination

    Science.gov (United States)

    Yamamoto, Kumiko; Li, Jiakun; Garber, Jeffrey A. O.; Rolfes, Julian D.; Boursalian, Gregory B.; Borghs, Jannik C.; Genicot, Christophe; Jacq, Jérôme; van Gastel, Maurice; Neese, Frank; Ritter, Tobias

    2018-02-01

    Aryl fluorides are widely used in the pharmaceutical and agrochemical industries, and recent advances have enabled their synthesis through the conversion of various functional groups. However, there is a lack of general methods for direct aromatic carbon-hydrogen (C-H) fluorination. Conventional methods require the use of either strong fluorinating reagents, which are often unselective and difficult to handle, such as elemental fluorine, or less reactive reagents that attack only the most activated arenes, which reduces the substrate scope. A method for the direct fluorination of aromatic C-H bonds could facilitate access to fluorinated derivatives of functional molecules that would otherwise be difficult to produce. For example, drug candidates with improved properties, such as increased metabolic stability or better blood-brain-barrier penetration, may become available. Here we describe an approach to catalysis and the resulting development of an undirected, palladium-catalysed method for aromatic C-H fluorination using mild electrophilic fluorinating reagents. The reaction involves a mode of catalysis that is unusual in aromatic C-H functionalization because no organometallic intermediate is formed; instead, a reactive transition-metal-fluoride electrophile is generated catalytically for the fluorination of arenes that do not otherwise react with mild fluorinating reagents. The scope and functional-group tolerance of this reaction could provide access to functional fluorinated molecules in pharmaceutical and agrochemical development that would otherwise not be readily accessible.

  14. Effect of polar and non-polar surfaces of ZnO nanostructures on photocatalytic properties

    International Nuclear Information System (INIS)

    Yang Jinghai; Wang Jian; Li Xiuyan; Lang Jihui; Liu Fuzhu; Yang Lili; Zhai Hongju; Gao Ming; Zhao Xiaoting

    2012-01-01

    Highlights: ► Large-scale arrayed ZnO nanocrystals including ZnO hexagonal platforms and hamburger-like samples have been successfully fabricated by a simple hydrothermal method. ► ZnO with hexagonal platform-like morphology exhibited higher photocatalytic activity compared with that of the hamburger-like ZnO nanostructures. ► The theories of expose surfaces and oxygen vacancies were utilized to explain the photocatalytic mechanism. - Abstract: Large-scale arrayed ZnO nanocrystals with two different expose surfaces, including ZnO hexagonal nanoplatforms with the major expose plane of (0 0 0 1) and hamburger-like samples with the nonpolar planes of {101 ¯ 0} mainly exposed, were successfully fabricated by a simple hydrothermal method. Mechanisms for compare the photocatalytic activity of two typical ZnO nanostructures were systematic explained as the key point in the paper. Compared with the hamburger-like ZnO nanostructures, the ZnO with hexagonal platform-like morphology exhibited improved ability on the photocatalytic degradation of Rhodamine B (RhB) in aqueous solution under UV radiation. The relative higher photocatalytic activity of the ZnO hexagonal nanoplatforms was attributed to the exposed polar surfaces and the content of oxygen vacancy on the nanostructures surface. The Zn-terminated (0 0 0 1) polar face and the surface defects are facile to adsorb O 2− and OH − ions, resulting in a greater production rate of O 2 · − and OH· − , hence promoting the photocatalysis reaction.

  15. Photocathalytic degradation of organic micropollutants in aqueous phase

    International Nuclear Information System (INIS)

    Driussi, D.

    2009-01-01

    The aim of this study was to design, construct and test a small system for the photo catalytic degradation of organic micropollutants in aqueous phase using solar radiation. The system is a parabolic linear trough type with automatic one-axis (N-S) tracking of the apparent movement of the sun. The tracking algorithm foresees two dispositions of the collector named horizontal and polar, the last is necessary for installations in locations that are higher than 50 o in latitude. The idea that brought to mind this project was to offer the possibility of treat herbicides polluted waters by means of a simple system without using particular oxidizing chemicals (for example hydrogen peroxide) or components (for example mercury vapour UV lamps) and therefore in an eco-sustainable way. [it

  16. Extraction of Aromatics from Heavy Naphtha Using Different Solvents

    International Nuclear Information System (INIS)

    EI-Bassuoni, A.A.; Esmael, K.K.

    2004-01-01

    Aromatic hydrocarbons are very important to the petrochemical industry. Among these are benzene, toluene and xylene (BTX), which are basic raw materials for the production of a number of important petrochemicals. There are many processes used to separate aromatic from non aromatic such as fractionation, azeotropic distillation and liquid I liquid extraction, etc. Liquid - liquid extraction is unique, efficiently used for heat sensitive, close boiling components and for separation of components not possible by other unit operations and it could be done at ambient temperature makes it more energy efficient. The choice of solvent depends on the properties and boiling range of the feedstock. Through the years, a lot of selective solvents has been proposed and selected for the physical separation of aromatics in liquid liquid extraction. Among the selection criteria are the stability,. chemical compatibility, availability, environmental hazards and price of the solvent. But the basic solvent properties that make it efficient are selectivity and capacity

  17. Aqueous Extract of Annona macroprophyllata: A Potential α-Glucosidase Inhibitor

    Science.gov (United States)

    Brindis, F.; González-Trujano, M. E.; González-Andrade, M.; Aguirre-Hernández, E.; Villalobos-Molina, R.

    2013-01-01

    Annona genus contains plants used in folk medicine for the treatment of diabetes. In the present study, an aqueous extract prepared from Annona macroprophyllata (Annonaceae, also known as A. diversifolia) leaves was evaluated on both the activity of yeast α-glucosidase (an in vitro assay) and sucrose tolerance in Wistar rats. The results have shown that the aqueous extract from A. macroprophyllata inhibits the yeast α-glucosidase with an IC50 = 1.18 mg/mL, in a competitive manner with a K i = 0.97 mg/mL, a similar value to that of acarbose (K i = 0.79 mg/mL). The inhibitory activity of A. macroprophyllata was reinforced by its antihyperglycemic effect, at doses of 100, 300, and 500 mg/kg in rats. Chromatographic analysis identified the flavonoids rutin and isoquercitrin in the most polar fractions of A. macroprophyllata crude extract, suggesting that these flavonoids are part of the active constituents in the plant. Our results support the use of A. macroprophyllata in Mexican folk medicine to control postprandial glycemia in people with diabetes mellitus, involving active constituents of flavonoid nature. PMID:24298552

  18. Radiolytic degradation of gallic acid and its derivatives in aqueous solution

    International Nuclear Information System (INIS)

    Melo, R.; Leal, J.P.; Takacs, E.; Wojnarovits, L.

    2009-01-01

    Polyphenols, like gallic acid (GA) released in the environment in larger amount, by inducing some unwanted oxidations, may constitute environmental hazard: their concentration in wastewater should be controlled. Radiolytic degradation of GA was investigated by pulse radiolysis and final product techniques in dilute aqueous solution. Subsidiary measurements were made with 3,4,5-trimethoxybenzoic acid (TMBA) and 3,4,5-trihydroxy methylbenzoate (MGA). The hydroxyl radical and hydrogen atom intermediates of water radiolysis react with the solute molecules yielding cyclohexadienyl radicals. The radicals formed in GA and MGA solutions in acid/base catalyzed water elimination decay to phenoxyl radicals. This reaction is not observed in TMBA solution. The hydrated electron intermediate of water decomposition adds to the carbonyl oxygen, the anion thus formed protonates on the ring forming cyclohexadienyl radical or on the carbonyl group forming carbonyl centred radical. The GA intermediates formed during reaction with primary water radicals in presence of oxygen transform to non-aromatic molecules, e.g., to aliphatic carboxylic acids.

  19. Radiolytic degradation of gallic acid and its derivatives in aqueous solution

    Energy Technology Data Exchange (ETDEWEB)

    Melo, R. [Instituto Tecnologico e Nuclear, UCQR, Estrada Nacional No. 10, Apartado 21, 2686-953, Sacavem (Portugal); Leal, J.P. [Instituto Tecnologico e Nuclear, UCQR, Estrada Nacional No. 10, Apartado 21, 2686-953, Sacavem (Portugal); Centro Quimica e Bioquimica, Faculdade de Ciencias da Universidade de Lisboa, 1749-016 Lisboa (Portugal); Takacs, E., E-mail: takacs@iki.kfki.hu [Institute of Isotopes, Hungarian Academy of Sciences, P.O. Box 77, H-1525 Budapest (Hungary); Wojnarovits, L. [Institute of Isotopes, Hungarian Academy of Sciences, P.O. Box 77, H-1525 Budapest (Hungary)

    2009-12-30

    Polyphenols, like gallic acid (GA) released in the environment in larger amount, by inducing some unwanted oxidations, may constitute environmental hazard: their concentration in wastewater should be controlled. Radiolytic degradation of GA was investigated by pulse radiolysis and final product techniques in dilute aqueous solution. Subsidiary measurements were made with 3,4,5-trimethoxybenzoic acid (TMBA) and 3,4,5-trihydroxy methylbenzoate (MGA). The hydroxyl radical and hydrogen atom intermediates of water radiolysis react with the solute molecules yielding cyclohexadienyl radicals. The radicals formed in GA and MGA solutions in acid/base catalyzed water elimination decay to phenoxyl radicals. This reaction is not observed in TMBA solution. The hydrated electron intermediate of water decomposition adds to the carbonyl oxygen, the anion thus formed protonates on the ring forming cyclohexadienyl radical or on the carbonyl group forming carbonyl centred radical. The GA intermediates formed during reaction with primary water radicals in presence of oxygen transform to non-aromatic molecules, e.g., to aliphatic carboxylic acids.

  20. Transformations of Aromatic Compounds by Nitrosomonas europaea

    OpenAIRE

    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 monoo...

  1. The direct aromatization of methane

    Energy Technology Data Exchange (ETDEWEB)

    Marcelin, G.; Oukaci, R.; Migone, R.A.; Kazi, A.M. [Altamira Instruments, Pittsburgh, PA (United States)

    1995-12-31

    The thermal decomposition of methane shows significant potential as a process for the production of higher unsaturated and aromatic hydrocarbons when the extent of the reaction is limited. Thermodynamic calculations have shown that when the reaction is limited to the formation of C{sub 2} to C{sub 10} products, yields of aromatics can exceed 40% at temperatures of 1200{degrees}C. Preliminary experiments have shown that when the reaction is limited to the formation of C{sub 2} to C{sub 10} products, yields of aromatics can exceed 40% at temperatures of 1200{degrees}C. Preliminary experiments have shown that cooling the product and reacting gases as the reaction proceeds can significantly reduce or eliminate the formation of solid carbon and heavier (C{sub 10+}) materials. Much work remains to be done in optimizing the quenching process and this is one of the goals of this program. Means to lower the temperature of the reaction are being studied as this result in a more feasible commercial process due to savings realized in energy and material of construction costs. The use of free-radical generators and catalysts will be investigated as a means of lowering the reaction temperature thus allowing faster quenching. It is highly likely that such studies will lead to a successful direct methane to higher hydrocarbon process.

  2. NMR detects molecular interactions of graphene with aromatic and aliphatic hydrocarbons in water

    Science.gov (United States)

    Bichenkova, Elena V.; Raju, Arun P. A.; Burusco, Kepa K.; Kinloch, Ian A.; Novoselov, Kostya S.; Clarke, David J.

    2018-03-01

    Polyaromatic carbon is widely held to be strongly diamagnetic and hydrophobic, with textbook van der Waals and ‘π-stacked’ binding of hydrocarbons, which disrupt their self-assembled supramolecular structures. The NMR of organic molecules sequestered by polyaromatic carbon is expected to be dominated by shielding from the orbital diamagnetism of π electrons. We report the first evidence of very different polar and magnetic behavior in water, wherein graphene remained well-dispersed after extensive dialysis and behaved as a 1H-NMR-silent ghost. Magnetic effects dominated the NMR of organic structures which interacted with graphene, with changes in spin-spin coupling, vast increase in relaxation, line broadening and decrease in NMR peak heights when bound to graphene. However, the interactions were weak, reversible and did not disrupt organic self-assemblies reliant on hydrophobic ‘π-stacking’, even when substantially sequestered on the surface of graphene by the high surface area available. Interacting assemblies of aromatic molecules retained their strongly-shielded NMR signals and remained within self-assembled structures, with slower rates of diffusion from association with graphene, but with no further shielding from graphene. Binding to graphene was selective for positively-charged organic assemblies, weaker for non-aromatic and negligible for strongly-negatively-charged molecules, presumably repelled by a negative zeta potential of graphene in water. Stronger binders, or considerable excess of weaker binders readily reversed physisorption, with no evidence of structural changes from chemisorption. The fundamental nature of these different electronic interactions between organic and polyaromatic carbon is considered with relevance to electronics, charge storage, sensor, medical, pharmaceutical and environmental research.

  3. Study of polarization curves from AlSi12, AlSi5Mg and AlMg5 alloys due to corrosion problems in telecomunication equipment

    International Nuclear Information System (INIS)

    Silva, J.R.A. da

    1984-01-01

    The corrosion behaviour of three aluminium based alloys (AlSi 12, AlMg5 and AlSi 5Mg) when exposed to aqueous media containing chloride is investigated; these alloys are used in the manufacturing of telecomunication equipment. Accelerated corrosion testing and salt spray tests were carried out. The results include polarization curves obtained with three kinds of aqueous solutions (the first containing only 3% NaCl and the others, 3% NaCl and small amounts of Fe 3+ and Cu 2+ ions). (C.L.B.) [pt

  4. Alkyne Benzannulation Reactions for the Synthesis of Novel Aromatic Architectures.

    Science.gov (United States)

    Hein, Samuel J; Lehnherr, Dan; Arslan, Hasan; J Uribe-Romo, Fernando; Dichtel, William R

    2017-11-21

    Aromatic compounds and polymers are integrated into organic field effect transistors, light-emitting diodes, photovoltaic devices, and redox-flow batteries. These compounds and materials feature increasingly complex designs, and substituents influence energy levels, bandgaps, solution conformation, and crystal packing, all of which impact performance. However, many polycyclic aromatic hydrocarbons of interest are difficult to prepare because their substitution patterns lie outside the scope of current synthetic methods, as strategies for functionalizing benzene are often unselective when applied to naphthalene or larger systems. For example, cross-coupling and nucleophilic aromatic substitution reactions rely on prefunctionalized arenes, and even directed metalation methods most often modify positions near Lewis basic sites. Similarly, electrophilic aromatic substitutions access single regioisomers under substrate control. Cycloadditions provide a convergent route to densely functionalized aromatic compounds that compliment the above methods. After surveying cycloaddition reactions that might be used to modify the conjugated backbone of poly(phenylene ethynylene)s, we discovered that the Asao-Yamamoto benzannulation reaction is notably efficient. Although this reaction had been reported a decade earlier, its scope and usefulness for synthesizing complex aromatic systems had been under-recognized. This benzannulation reaction combines substituted 2-(phenylethynyl)benzaldehydes and substituted alkynes to form 2,3-substituted naphthalenes. The reaction tolerates a variety of sterically congested alkynes, making it well-suited for accessing poly- and oligo(ortho-arylene)s and contorted hexabenzocoronenes. In many cases in which asymmetric benzaldehyde and alkyne cycloaddition partners are used, the reaction is regiospecific based on the electronic character of the alkyne substrate. Recognizing these desirable features, we broadened the substrate scope to include silyl

  5. STUDY OF FACTORS AFFECTING DEVELOPMENT OF FOOD AROMATIZATION

    Directory of Open Access Journals (Sweden)

    Н.Ye. Dubova

    2017-10-01

    Full Text Available The specific understanding of food philosophy according to the facts of development of cooking technologies and growth rate of food range is given. As it has been proven by historical stages of production of flavorings, aroma is one of the important organoleptic ingredients for food developers. A review of food production based on development of nanotechnologies, as well as promising and cautioning publications on nanotechnologies in the food sector is presented. On the basis of the literary analysis, the future impact of nanotechnologies on the evolution of the aromatization process of food products is predicted. It has been determined that the peculiarity of the development mentioned above lies in the use of plant enzymes and / or flavor precursors in the nanoscale range. The example of enzymatic breakdown of polyunsaturated fatty acids of plant cell membranes as one of the ways of creating fresh flavor of many fruits, namely C6-C9 aldehydes and alcohols, is considered. It is noted that green fresh aromatic ingredients are needed to improve the organoleptic profile of foods from heat-treated vegetables, melons and gourds. The following factors affecting the development of food aromatization are defined: the decreased differentiation of principles of healthy nutrition and fast food, repetition of natural processes of aroma formation, application of wild green leafy vegetables, and evolution of medical nutrition. The information on food aromatization by packing with autonomous mixing and their approximate assortment is given. The innovations in food aromatization are aimed at quality nutrition, time saving, recreation and entertainment, meeting specific needs (vegetarian dishes, restrictive diets.

  6. Experimental and theoretical studies on electropolymerization of polar amino acids on platinum electrode

    Energy Technology Data Exchange (ETDEWEB)

    Alhedabi, Taleb [Nanomedicine Lab EA4662, Bat. E, Université de Bourgogne Franche-Comté, UFR Sciences & Techniques, 16 route de Gray, 25030 Besançon Cedex (France); Department of Chemistry, College of Science, University of Thi-qar, Thi-qar (Iraq); Cattey, Hélène [Institut ICMUB - CNRS 6302, Université de Bourgogne Franche-Comté, UFR Sciences et Techniques Mirande, 9 Avenue Alain Savary, 21000 Dijon (France); Roussel, Christophe [Ecole Polytechnique Fédérale de Lausanne, Section of Chemistry and Chemical Engineering, Station 6, CH-1015 Lausanne (Switzerland); Blondeau-Patissier, Virginie [Institut FEMTO-ST, UMR CNRS 6174, Department Time-Frequency, 26, Chemin de l' épitaphe, 25030 Besançon Cedex (France); Gharbi, Tijani [Nanomedicine Lab EA4662, Bat. E, Université de Bourgogne Franche-Comté, UFR Sciences & Techniques, 16 route de Gray, 25030 Besançon Cedex (France); Herlem, Guillaume, E-mail: guillaume.herlem@univ-fcomte.fr [Nanomedicine Lab EA4662, Bat. E, Université de Bourgogne Franche-Comté, UFR Sciences & Techniques, 16 route de Gray, 25030 Besançon Cedex (France)

    2017-01-01

    The anodic oxidation of polar amino acids (L-serine, L-threonine, L-asparagine, and L-glutamine) in aqueous electrolyte on smooth platinum electrode was carried out by cyclic voltammetry coupled to electrochemical quartz crystal microbalance (EQCM). pH (zwitterion, acidic and alkaline) effects on their electrochemical behavior were examined. The maximum current values are measured for zwitterion species. In addition, the current increases with increasing of concentration and scan rate, and decreases with increasing pH. The resulting passivation was studied by spectroscopic analysis such as attenuated total reflection FT infrared spectroscopy (ATR-FTIR), X-ray photoelectron spectroscopy (XPS) and mass spectroscopy (MALDI-TOF). From thin film coatings observed on the electrode surface, peptide bonds are found, and are in favor of electropolymerization of these polar amino acids into poly-L-amino acids in an irreversible way. Scanning electronic microscopy was also used to study the morphology of these electrodeposited L-amino acids. The electrodeposited poly-L-amino acids on Pt electrode were tested as bioinspired transducer for pH sensing purposes. - Highlights: • Anodic oxidation of polar amino acids with uncharged R group on platinum electrode. • Polypeptide bonds revealed by ATR-IR and XPS spectroscopies. • The film growth depends on the chemistry of the polar amino acid.

  7. Polarization of lanthanum nucleus by dynamic polarization method

    International Nuclear Information System (INIS)

    Adachi, Toshikazu; Ishimoto, Shigeru; Masuda, Yasuhiro; Morimoto, Kimio

    1989-01-01

    Preliminary studies have been carried out concerning the application of a dynamic polarization method to polarizing lanthanum fluoride single crystal to be employed as target in experiments with time reversal invariance. The present report briefly outlines the dynamic polarization method and describes some preliminary studies carried out so far. Dynamic polarization is of particular importance because no techniques are currently available that can produce highly polarized static nucleus. Spin interaction between electrons and protons (nuclei) plays a major role in the dynamic polarization method. In a thermal equilibrium state, electrons are polarized almost completely while most protons are not polarized. Positively polarized proton spin is produced by applying microwave to this system. The most hopeful candidate target material is single crystal of LaF 3 containing neodymium because the crystal is chemically stable and easy to handle. The spin direction is of great importance in experiments with time reversal invariance. The spin of neutrons in the target can be cancelled by adjusting the external magnetic field applied to a frozen polarized target. In a frozen spin state, the polarity decreases slowly with a relaxation time that depends on the external magnetic field and temperature. (N.K.)

  8. A double isotope dilution method for assaying of polycyclic aromatic hydrocarbons in cigarette smoke condensate

    International Nuclear Information System (INIS)

    Bechtold, W.E.; Chen, B.T.

    1988-01-01

    This report describes a double isotope dilution method for analysis of the polycyclic aromatic hydrocarbons (PAH) phenanthrene, fluor-anthene, pyrene, and benzo[a]pyrene in cigarette smoke particulates. The first isotope dilution used deuterated analogues of the first three PAH as internal standards. The second isotope dilution, for benzo[a]pyrene, used the tritiated analogue as an internal standard. The PAH were isolated from extracts of cigarette smoke particulates using a two-step procedure based on selective extraction from aqueous dimethyl sulfoxide (DMSO) followed by chromatography on silica gel extraction columns. After isolation, aliquots of the samples were analyzed for phenanthrene, pyrene, and fluoranthene by gas chromatography with mass spectrometric detection (GC/MS). Separate aliquots of the samples were analyzed for benzo[a]pyrene by high pressure liquid chromatography with fluorescence detection followed by liquid scintillation spectrometry. PAH levels from cigarette smoke condensates collected from different exposure modes were compared; no exposure-related differences were found. (author)

  9. Polarized neutrons

    International Nuclear Information System (INIS)

    Williams, W.G.

    1988-01-01

    The book on 'polarized neutrons' is intended to inform researchers in condensed matter physics and chemistry of the diversity of scientific problems that can be investigated using polarized neutron beams. The contents include chapters on:- neutron polarizers and instrumentation, polarized neutron scattering, neutron polarization analysis experiments and precessing neutron polarization. (U.K.)

  10. Ambient aromatic hydrocarbon measurements at Welgegund, South Africa

    Science.gov (United States)

    Jaars, K.; Beukes, J. P.; van Zyl, P. G.; Venter, A. D.; Josipovic, M.; Pienaar, J. J.; Vakkari, V.; Aaltonen, H.; Laakso, H.; Kulmala, M.; Tiitta, P.; Guenther, A.; Hellén, H.; Laakso, L.; Hakola, H.

    2014-07-01

    Aromatic hydrocarbons are associated with direct adverse human health effects and can have negative impacts on ecosystems due to their toxicity, as well as indirect negative effects through the formation of tropospheric ozone and secondary organic aerosol, which affect human health, crop production and regional climate. Measurements of aromatic hydrocarbons were conducted at the Welgegund measurement station (South Africa), which is considered to be a regionally representative background site. However, the site is occasionally impacted by plumes from major anthropogenic source regions in the interior of South Africa, which include the western Bushveld Igneous Complex (e.g. platinum, base metal and ferrochrome smelters), the eastern Bushveld Igneous Complex (platinum and ferrochrome smelters), the Johannesburg-Pretoria metropolitan conurbation (> 10 million people), the Vaal Triangle (e.g. petrochemical and pyrometallurgical industries), the Mpumalanga Highveld (e.g. coal-fired power plants and petrochemical industry) and also a region of anticyclonic recirculation of air mass over the interior of South Africa. The aromatic hydrocarbon measurements were conducted with an automated sampler on Tenax-TA and Carbopack-B adsorbent tubes with heated inlet for 1 year. Samples were collected twice a week for 2 h during daytime and 2 h during night-time. A thermal desorption unit, connected to a gas chromatograph and a mass selective detector was used for sample preparation and analysis. Results indicated that the monthly median (mean) total aromatic hydrocarbon concentrations ranged between 0.01 (0.011) and 3.1 (3.2) ppb. Benzene levels did not exceed the local air quality standard limit, i.e. annual mean of 1.6 ppb. Toluene was the most abundant compound, with an annual median (mean) concentration of 0.63 (0.89) ppb. No statistically significant differences in the concentrations measured during daytime and night-time were found, and no distinct seasonal patterns were

  11. Activated carbon as catalyst for microwave-assisted wet peroxide oxidation of aromatic hydrocarbons.

    Science.gov (United States)

    Garcia-Costa, Alicia L; Lopez-Perela, Lucia; Xu, Xiyan; Zazo, Juan A; Rodriguez, Juan J; Casas, Jose A

    2018-05-21

    This paper addresses the removal of four aromatic hydrocarbons typically found in petrochemical wastewater: benzene (B), toluene (T), o-xylene (X), and naphthalene (N), by microwave-assisted catalytic wet peroxide oxidation (MW-CWPO) using activated carbon (AC) as catalyst. Under the studied conditions, complete pollutant elimination (B, 1.28 mM; T, 1.09 mM; X, 0.94 mM; and N, 0.78 mM) was achieved, with more than 90% TOC removal after only 15-min reaction time, working at 120 °C, pH 0  = 3, AC at 1 g L -1 , and H 2 O 2 at the stoichiometric dose. Furthermore, in the case of toluene, naphthalene, and xylene, the hydroxylation and breakdown of the ring is very rapid and toxic intermediates were not detected. The process follows two steps: (i) pollutant adsorption onto AC followed by (ii) adsorbed compounds oxidation. Thus, MW-CWPO with AC as catalyst appears a promising way for a fast and effective process for B, T, X, and N removal in aqueous phase.

  12. Removal of polycyclic aromatic hydrocarbons from aged-contaminated soil using cyclodextrins: Experimental study

    International Nuclear Information System (INIS)

    Viglianti, Christophe; Hanna, Khalil; Brauer, Christine de; Germain, Patrick

    2006-01-01

    The removal of polycyclic aromatic hydrocarbons (PAHs) from soil using water as flushing agent is relatively ineffective due to their low aqueous solubility. However, addition of cyclodextrin (CD) in washing solutions has been shown to increase the removal efficiency several times. Herein are investigated the effectiveness of cyclodextrin to remove PAH occurring in industrially aged-contaminated soil. β-Cyclodextrin (BCD), hydroxypropyl-β-cyclodextrin (HPCD) and methyl-β-cyclodextrin (MCD) solutions were used for soil flushing in column test to evaluate some influent parameters that can significantly increase the removal efficiency. The process parameters chosen were CD concentration, ratio of washing solution volume to soil weight, and temperature of washing solution. These parameters were found to have a significant and almost linear effect on PAH removal from the contaminated soil, except the temperature where no significant enhancement in PAH extraction was observed for temperature range from 5 to 35 o C. The PAHs extraction enhancement factor compared to water was about 200. - An innovative method using a biodegradable and non-toxic flushing agent for the depollution of industrially aged-contaminated soil

  13. Volatile Profiling of Aromatic Traditional Medicinal Plant, Polygonum minus in Different Tissues and Its Biological Activities

    Directory of Open Access Journals (Sweden)

    Rafidah Ahmad

    2014-11-01

    Full Text Available The aim of this research was to identify the volatile metabolites produced in different organs (leaves, stem and roots of Polygonum minus, an important essential oil producing crop in Malaysia. Two methods of extraction have been applied: Solid Phase Microextraction (SPME and hydrodistillation coupled with Gas Chromatography-Mass Spectrometry (GC-MS. Approximately, 77 metabolites have been identified and aliphatic compounds contribute significantly towards the aroma and flavour of this plant. Two main aliphatic compounds: decanal and dodecanal were found to be the major contributor. Terpenoid metabolites were identified abundantly in leaves but not in the stem and root of this plant. Further studies on antioxidant, total phenolic content, anticholinesterase and antimicrobial activities were determined in the essential oil and five different extracts. The plant showed the highest DPPH radical scavenging activity in polar (ethanol extract for all the tissues tested. For anti-acetylcholinesterase activity, leaf in aqueous extract and methanol extract showed the best acetylcholinesterase inhibitory activities. However, in microbial activity, the non-polar extracts (n-hexane showed high antimicrobial activity against Methicillin-resistant Staphylococcus aureus (MRSA compared to polar extracts. This study could provide the first step in the phytochemical profiles of volatile compounds and explore the additional value of pharmacology properties of this essential oil producing crop Polygonum minus.

  14. Applications of electrochemically-modulated liquid chromatography (EMLC): Separations of aromatic amino acids and polycyclic aromatic hydrocarbons

    Energy Technology Data Exchange (ETDEWEB)

    Deng, Li [Iowa State Univ., Ames, IA (United States)

    1998-03-27

    The research in this thesis explores the separation capabilities of a new technique termed electrochemically-modulated liquid chromatography (EMLC). The thesis begins with a general introduction section which provides a literature review of this technique as well as a brief background discussion of the two research projects in each of the next two chapters. The two papers which follow investigate the application of EMLC to the separation of a mixture of aromatic amino acids and of a mixture of polycyclic aromatic hydrocarbons (PAHs). The last section presents general conclusions and summarizes the thesis. References are compiled in the reference section of each chapter. The two papers have been removed for separate processing.

  15. Study of lanthanide tri-cations in aqueous solution by molecular dynamic

    International Nuclear Information System (INIS)

    Duvail, M.

    2007-11-01

    This is essentially a lanthanide tri-cation hydration study by means of classical molecular dynamics (CLMD) simulations using explicit polarization. Explicit polarization is calculated with a Car-Parrinello type of dynamics on induced dipoles, which decreases the CPU time as compared to the self-consistent resolution. Several pair interaction potentials are parametrized from ab initio calculations (MP2) and tested for the La 3+ -OH 2 interaction. The best results are obtained with an exponential-6 Buckingham potential. Next, the La 3+ -OH 2 interaction potential parameters are extrapolated to the other Ln 3+ -OH 2 interactions, only by using the ionic radii. The CLMD results reproduce the reliable experimental data (EXAFS distances), and the sigmoidal variation of the coordination number (with S shape), from 9 for La 3+ to 8 for Lu 3+ . This variation is explained by the linear variation of DrG0 (9,298) vs. atomic number. Insights are also given on the Co 2+ hydration, CPMD simulations, reconstruction of EXAFS signal from MD simulations, and OH - complexation of La 3+ in aqueous solution. (author)

  16. Nucleophilic addition of amines to the activated ethylene bond in non-aqueous media

    International Nuclear Information System (INIS)

    Perepichka, Igor F.; Popov, Anatolii F.

    1995-01-01

    The kinetics of addition of a number of primary and secondary aliphatic amines to trans-(2-furyl) nitro ethylene (1) has been studied in solvents of various polarities (from acetonitrile, ε 37.5, to heptane, ε 1.89). It has been shown that the reaction is catalysed both by the amine reagent and by tertiary amines. On the basis of analyzing the observed kinetic regularities a stepwise reaction mechanism has been proposed which involves formation of zwitterionic intermediate (3) at the first equilibrium step (k 1 , K 1 ) which is then converted into the reaction product by means of proton transfer in parallel routes, the non-catalytic one (k 2 ) and that catalysed by the initial (K 3 ) or tertiary (K 4 ) amine. The observed high values of the deuterium isotope effects in the reaction (K H /K D ∼ 2.3 - 8.9) confirm that proton transfer occurs in the rate-limiting step of the reaction (primary kinetic isotope effect). The third order by amine kinetic route is observed in low polar media which is due to participation of amine dimers (R 2 NH HNR 2 ) in the reaction. The observed kinetic regularities are compared with those for the nucleophilic aromatic substitution reactions in low-polar media, and the conclusion has been made that the reaction route of the third order by amine proceeds as reversible nucleophilic attack by amine dimer and following base-catalysed transformation of the intermediate into the product. (author)

  17. Water absorption in PEEK and PEI matrices. Contribution to the understanding of water-polar group interactions

    Science.gov (United States)

    Courvoisier, E.; Bicaba, Y.; Colin, X.

    2016-05-01

    The water absorption in two aromatic linear polymers (PEEK and PEI) was studied between 10% and 90% RH at 30, 50 and 70°C. It was found that these polymers display classical Henry and Fick's behaviors. Moreover, they have very close values of equilibrium water concentration C∞ and water diffusivity D presumably because their respective polar groups establish molecular interactions of the same nature with water. This assumption was checked from a literature compilation of values of C∞ and D for a large variety of linear and tridimensional polymers containing a single type of polar group. It was then evidenced that almost all types of carbonyl group (in particular, those belonging to imides, amides and ketones) have the same molar contribution to water absorption, except those belonging to esters which are much less hydrophilic. Furthermore, hydroxyl and sulfone groups are much more hydrophilic than carbonyl groups so that their molar contribution is located on another master curve. On this basis, semi-empirical structure/water transport property relationships were proposed. It was found that C∞ increases exponentially with the concentration of polar groups (presumably because water is doubly bonded), but also with the intensity of their molecular interactions with water. In contrast, D is inversely proportional to C∞, which means that polar group-water interactions slow down the rate of water diffusion.

  18. Effects of humic acid and heavy metals on the sorption of polar and apolar organic pollutants onto biochars

    International Nuclear Information System (INIS)

    Wang, Fei; Sun, Hongwen; Ren, Xinhao; Liu, Yarui; Zhu, Hongkai; Zhang, Peng; Ren, Chao

    2017-01-01

    The effects of humic acid (HA) and heavy metals (Cu 2+ and Ag + ) on the sorption of polar and apolar organic pollutants onto biochars that were produced at temperatures of 200 °C (BC200) and 700 °C (BC700) were studied. Due to the plentiful polar functional groups on BC200, cationic propranolol exhibited higher levels of sorption than naphthalene on BC200 while naphthalene and propranolol showed similar sorption capacities on BC700. HA changed the characteristics of biochars and generally inhibited the sorption of target organic pollutants on biochars; however, enhancement occurred in some cases depending on the pollutants involved and their concentrations, biochars used and the addition sequences and concentrations of HA. On BC200, HA modifications mainly influenced sorption by decreasing its polarity and increasing its aromaticity, while on BC700, the surface area and pore volume greatly decreased due to the pore-blocking effects of HA. Residue dissolved HA in solution may also contribute to sorption inhibition. Complexation between polar functional groups on BC200 and heavy metals slightly enhanced the sorption of neutral naphthalene and significantly enhanced that of anionic 4-nitro-1-naphtol, while limited the sorption of cationic propranolol. Heavy metals together with their associated water molecules decreased the sorption of target chemicals on BC700 via pore-filling or pore-mouth-covering. Inhibition of heavy metals for 4-nitro-1-naphthol was found to be the weakest due to the bridge effects of heavy metals between 4-nitro-1-naphtol and BC700. The higher polarizability of Ag + led to the increase of its sorption on biochars in the presence of organic aromatic pollutants. The results of the present study shed light on the sorption mechanisms of bi-solute systems and enable us to select suitable biochar sorbents when chemicals co-exist. - Highlights: • Polar functional groups on low-temperature biochar enhanced propranolol sorption. • Humic acid

  19. Corrosion behavior of aluminum doped diamond-like carbon thin films in NaCl aqueous solution.

    Science.gov (United States)

    Khun, N W; Liu, E

    2010-07-01

    Aluminum doped diamond-like carbon (DLC:Al) thin films were deposited on n-Si(100) substrates by co-sputtering a graphite target under a fixed DC power (650 W) and an aluminum target under varying DC power (10-90 W) at room temperature. The structure, adhesion strength and surface morphology of the DLC:Al films were characterized by X-ray photoelectron spectroscopy (XPS), micro-scratch testing and atomic force microscopy (AFM), respectively. The corrosion performance of the DLC:Al films was investigated by means of potentiodynamic polarization testing in a 0.6 M NaCl aqueous solution. The results showed that the polarization resistance of the DLC:Al films increased from about 18 to 30.7 k(omega) though the corrosion potentials of the films shifted to more negative values with increased Al content in the films.

  20. Volatile Compounds in Dry Dog Foods and Their Influence on Sensory Aromatic Profile

    Directory of Open Access Journals (Sweden)

    Koushik Adhikari

    2013-02-01

    Full Text Available The aim of this study was to determine volatile compounds in dry dog foods and their possible influence on sensory aromatic profile. Grain-free dry dog foods were compared to dry dog foods manufactured with grain, but also with different protein sources for their aromatic volatiles. Solid-phase microextraction/gas chromatography/mass spectrometry was used to determine the aromatic compounds present in the headspace of these samples. Partial Least Squares regression was performed to correlate the instrumental aromatic data with the descriptive aroma analysis data. A total of 54 aromatic compounds were tentatively identified in the dry dog food samples, with aldehydes and ketones being the most represented organic volatiles group. Grain-added products were on the average higher in total volatiles than grain-free products. Partial Least Squares regression analysis indicated possible connections with sensory aromatic profile and grain-added samples, such as rancid aroma and aldehydes, especially hexanal. The results of this study showed that dry dog foods are products with complex odor characteristics and that grain-free products are less aromatic.

  1. Production of a transparent lavender flavour nanocapsule aqueous solution and pyrolysis characteristics of flavour nanocapsule.

    Science.gov (United States)

    Zhu, Guangyong; Xiao, Zuobing; Zhou, Rujun; Feng, Nienie

    2015-07-01

    Flavour plays an important role and has been widely used in many products. Usually, the components of flavour are volatile and the sensory perception can be changed as a result of volatilization, heating, oxidation and chemical interactions. Encapsulation can prevent the loss of volatile aromatic ingredients, provide protection and enhance the stability of the core materials. This work concentrated on production of a transparent lavender flavour nanocapsule aqueous solution. The results showed that a transparent lavender flavour microcapsule aqueous solution can be produced using hydroxypropyl-β-cyclodextrin (HP-β-CD) as wall material. The combination and interaction of flavour and wall materials were investigated by pyrolysis. Pyrolysis characteristics and kinetic parameters of the flavour nanocapsule were determined. During thermal degradation of blank HP-β-CD and flavour-HP-β-CD inclusion complex, three main stages can be distinguished. Due to the vaporization of lavender flavour encapsulated in HP-β-CD, the thermogravimetric (TG) curve of blank HP-β-CD shows a leveling-off from room temperature to 269 °C, while the TG curve of flavour-HP-β-CD inclusion complex is downward sloping in this temperature range. The kinetic parameters are helpful in understanding the mechanism of molecular recognition between hosts and guests.

  2. Complexation of some trivalent lanthanides, scandium(III) and thorium(IV) by benzylidenepyruvates in aqueous solution

    International Nuclear Information System (INIS)

    Marques, R.N.; Moraes, M. de; Ionashiro, M.

    1997-01-01

    The protonation constants of 4-methylbenzylidenepyruvate (4Me-BP) and 4-isopropylbenzylidenepyruvate (4IP-BP) as well as the stability constants of their binary 1:1 complexes with Cu(II), La(III), Pr(III), Sm(III), Eu(III), Yb(III), Sc(III) and Th(IV) have been determined spectrophotometrically in aqueous solution at 25 C and ionic strength 0.500 M, maintained with sodium perchlorate. For all metal ions considered, the stability changes move in the same direction as the pK a of the ligands. Linear free energy relationships, as applied to oxygen donor substances, suggest the -COCOO - moiety as the metal binding site of the ligands. The results are discussed mainly taking into account that benzylidenepyruvates, besides the α-keto canonical form, may display other forms in aqueous solution with changing pH and the possible occurrence of extra intra-ligand charge polarization, induced by metal ions. (orig.)

  3. Effects of surface condition on aqueous corrosion and environmental embrittlement of iron aluminides

    Energy Technology Data Exchange (ETDEWEB)

    Perrin, R.L.; Buchanan, R.A. [Univ. of Tennessee, Knoxville, TN (United States)

    1996-08-01

    Effects of retained high-temperature surface oxides, produced during thermomechanical processing and/or heat treatment, on the aqueous-corrosion and environmental-embrittlement characteristics of Fe{sub 3}Al-based iron aluminides (FA-84, FA-129 and FAL-Mo), a FeAl-based iron aluminide (FA-385), and a disordered low-aluminum Fe-Al alloy (FAPY) were evaluated. All tests were conducted at room temperature in a mild acid-chloride solution. In cyclic-anodic-polarization testing for aqueous-corrosion behavior, the surface conditions examined were: as-received (i.e., with the retained high-temperature oxides), mechanically cleaned and chemically cleaned. For all materials, the polarization tests showed the critical pitting potentials to be significantly lower in the as-received condition than in the mechanically-cleaned and chemically-cleaned conditions. These results indicate detrimental effects of the retained high-temperature oxides in terms of increased susceptibilities to localized corrosion. In 200-hour U-bend stress-corrosion-cracking tests for environmental-embrittlement behavior, conducted at open-circuit corrosion potentials and at a hydrogen-charging potential of {minus}1500 mV (SHE), the above materials (except FA-385) were examined with retained oxides and with mechanically cleaned surfaces. At the open-circuit corrosion potentials, none of the materials in either surface condition underwent cracking. At the hydrogen-charging potential, none of the materials with retained oxides underwent cracking, but FA-84, FA-129 and FAL-Mo in the mechanically cleaned condition did undergo cracking. These results suggest beneficial effects of the retained high-temperature oxides in terms of increased resistance to environmental hydrogen embrittlement.

  4. Classification of Malaysia aromatic rice using multivariate statistical analysis

    Energy Technology Data Exchange (ETDEWEB)

    Abdullah, A. H.; Adom, A. H.; Shakaff, A. Y. Md; Masnan, M. J.; Zakaria, A.; Rahim, N. A. [School of Mechatronic Engineering, Universiti Malaysia Perlis, Kampus Pauh Putra, 02600 Arau, Perlis (Malaysia); Omar, O. [Malaysian Agriculture Research and Development Institute (MARDI), Persiaran MARDI-UPM, 43400 Serdang, Selangor (Malaysia)

    2015-05-15

    Aromatic rice (Oryza sativa L.) is considered as the best quality premium rice. The varieties are preferred by consumers because of its preference criteria such as shape, colour, distinctive aroma and flavour. The price of aromatic rice is higher than ordinary rice due to its special needed growth condition for instance specific climate and soil. Presently, the aromatic rice quality is identified by using its key elements and isotopic variables. The rice can also be classified via Gas Chromatography Mass Spectrometry (GC-MS) or human sensory panels. However, the uses of human sensory panels have significant drawbacks such as lengthy training time, and prone to fatigue as the number of sample increased and inconsistent. The GC–MS analysis techniques on the other hand, require detailed procedures, lengthy analysis and quite costly. This paper presents the application of in-house developed Electronic Nose (e-nose) to classify new aromatic rice varieties. The e-nose is used to classify the variety of aromatic rice based on the samples odour. The samples were taken from the variety of rice. The instrument utilizes multivariate statistical data analysis, including Principal Component Analysis (PCA), Linear Discriminant Analysis (LDA) and K-Nearest Neighbours (KNN) to classify the unknown rice samples. The Leave-One-Out (LOO) validation approach is applied to evaluate the ability of KNN to perform recognition and classification of the unspecified samples. The visual observation of the PCA and LDA plots of the rice proves that the instrument was able to separate the samples into different clusters accordingly. The results of LDA and KNN with low misclassification error support the above findings and we may conclude that the e-nose is successfully applied to the classification of the aromatic rice varieties.

  5. Classification of Malaysia aromatic rice using multivariate statistical analysis

    Science.gov (United States)

    Abdullah, A. H.; Adom, A. H.; Shakaff, A. Y. Md; Masnan, M. J.; Zakaria, A.; Rahim, N. A.; Omar, O.

    2015-05-01

    Aromatic rice (Oryza sativa L.) is considered as the best quality premium rice. The varieties are preferred by consumers because of its preference criteria such as shape, colour, distinctive aroma and flavour. The price of aromatic rice is higher than ordinary rice due to its special needed growth condition for instance specific climate and soil. Presently, the aromatic rice quality is identified by using its key elements and isotopic variables. The rice can also be classified via Gas Chromatography Mass Spectrometry (GC-MS) or human sensory panels. However, the uses of human sensory panels have significant drawbacks such as lengthy training time, and prone to fatigue as the number of sample increased and inconsistent. The GC-MS analysis techniques on the other hand, require detailed procedures, lengthy analysis and quite costly. This paper presents the application of in-house developed Electronic Nose (e-nose) to classify new aromatic rice varieties. The e-nose is used to classify the variety of aromatic rice based on the samples odour. The samples were taken from the variety of rice. The instrument utilizes multivariate statistical data analysis, including Principal Component Analysis (PCA), Linear Discriminant Analysis (LDA) and K-Nearest Neighbours (KNN) to classify the unknown rice samples. The Leave-One-Out (LOO) validation approach is applied to evaluate the ability of KNN to perform recognition and classification of the unspecified samples. The visual observation of the PCA and LDA plots of the rice proves that the instrument was able to separate the samples into different clusters accordingly. The results of LDA and KNN with low misclassification error support the above findings and we may conclude that the e-nose is successfully applied to the classification of the aromatic rice varieties.

  6. Classification of Malaysia aromatic rice using multivariate statistical analysis

    International Nuclear Information System (INIS)

    Abdullah, A. H.; Adom, A. H.; Shakaff, A. Y. Md; Masnan, M. J.; Zakaria, A.; Rahim, N. A.; Omar, O.

    2015-01-01

    Aromatic rice (Oryza sativa L.) is considered as the best quality premium rice. The varieties are preferred by consumers because of its preference criteria such as shape, colour, distinctive aroma and flavour. The price of aromatic rice is higher than ordinary rice due to its special needed growth condition for instance specific climate and soil. Presently, the aromatic rice quality is identified by using its key elements and isotopic variables. The rice can also be classified via Gas Chromatography Mass Spectrometry (GC-MS) or human sensory panels. However, the uses of human sensory panels have significant drawbacks such as lengthy training time, and prone to fatigue as the number of sample increased and inconsistent. The GC–MS analysis techniques on the other hand, require detailed procedures, lengthy analysis and quite costly. This paper presents the application of in-house developed Electronic Nose (e-nose) to classify new aromatic rice varieties. The e-nose is used to classify the variety of aromatic rice based on the samples odour. The samples were taken from the variety of rice. The instrument utilizes multivariate statistical data analysis, including Principal Component Analysis (PCA), Linear Discriminant Analysis (LDA) and K-Nearest Neighbours (KNN) to classify the unknown rice samples. The Leave-One-Out (LOO) validation approach is applied to evaluate the ability of KNN to perform recognition and classification of the unspecified samples. The visual observation of the PCA and LDA plots of the rice proves that the instrument was able to separate the samples into different clusters accordingly. The results of LDA and KNN with low misclassification error support the above findings and we may conclude that the e-nose is successfully applied to the classification of the aromatic rice varieties

  7. Asymmetric transfer hydrogenation of ketones in aqueous solution catalyzed by Rhodium(III) complexes with C2-symmetric fluorene-ligands containing chiral (1R,2R)-cyclohexane-1,2-diamine

    International Nuclear Information System (INIS)

    Montalvo-Gonzalez, Ruben; Chavez, Daniel; Aguirre, Gerardo; Parra-Hake, Miguel; Somanathan, Ratnasamy

    2010-01-01

    Two C 2 -symmetric bis(sulfonamide) ligands containing fluorene-chiral (1R, 2R)-cyclohexane-1,2-diamine were complexed to Rh III (Cp * ) and used as catalyst to reduce aromatic ketones. The corresponding chiral secondary alcohols were obtained in 87-100% ee and 85-99% yield, under asymmetric transfer hydrogenation (ATH) conditions using aqueous sodium formate as the hydride source. With acetophenone, 94% ee and 86-97% yield was achieved with substrate/catalyst (S/C) ratio of 10,000. (author)

  8. Polycyclic Aromatic Hydrocarbons as Plausible Prebiotic Membrane Components

    Science.gov (United States)

    Groen, Joost; Deamer, David W.; Kros, Alexander; Ehrenfreund, Pascale

    2012-08-01

    Aromatic molecules delivered to the young Earth during the heavy bombardment phase in the early history of our solar system were likely to be among the most abundant and stable organic compounds available. The Aromatic World hypothesis suggests that aromatic molecules might function as container elements, energy transduction elements and templating genetic components for early life forms. To investigate the possible role of aromatic molecules as container elements, we incorporated different polycyclic aromatic hydrocarbons (PAH) in the membranes of fatty acid vesicles. The goal was to determine whether PAH could function as a stabilizing agent, similar to the role that cholesterol plays in membranes today. We studied vesicle size distribution, critical vesicle concentration and permeability of the bilayers using C6-C10 fatty acids mixed with amphiphilic PAH derivatives such as 1-hydroxypyrene, 9-anthracene carboxylic acid and 1,4 chrysene quinone. Dynamic Light Scattering (DLS) spectroscopy was used to measure the size distribution of vesicles and incorporation of PAH species was established by phase-contrast and epifluorescence microscopy. We employed conductimetric titration to determine the minimal concentration at which fatty acids could form stable vesicles in the presence of PAHs. We found that oxidized PAH derivatives can be incorporated into decanoic acid (DA) vesicle bilayers in mole ratios up to 1:10 (PAH:DA). Vesicle size distribution and critical vesicle concentration were largely unaffected by PAH incorporation, but 1-hydroxypyrene and 9-anthracene carboxylic acid lowered the permeability of fatty acid bilayers to small solutes up to 4-fold. These data represent the first indication of a cholesterol-like stabilizing effect of oxidized PAH derivatives in a simulated prebiotic membrane.

  9. Aromatic claw: A new fold with high aromatic content that evades structural prediction: Aromatic Claw

    Energy Technology Data Exchange (ETDEWEB)

    Sachleben, Joseph R. [Biomolecular NMR Core Facility, University of Chicago, Chicago Illinois; Adhikari, Aashish N. [Department of Chemistry, University of Chicago, Chicago Illinois; Gawlak, Grzegorz [Department of Biochemistry and Molecular Biology, University of Chicago, Chicago Illinois; Hoey, Robert J. [Department of Biochemistry and Molecular Biology, University of Chicago, Chicago Illinois; Liu, Gaohua [Northeast Structural Genomics Consortium (NESG), Department of Molecular Biology and Biochemistry, School of Arts and Sciences, and Department of Biochemistry and Molecular Biology, Robert Wood Johnson Medical School, and Center for Advanced Biotechnology and Medicine, Rutgers, The State University of New Jersey, Piscataway New Jersey; Joachimiak, Andrzej [Department of Biochemistry and Molecular Biology, University of Chicago, Chicago Illinois; Biological Sciences Division, Argonne National Laboratory, Argonne Illinois; Montelione, Gaetano T. [Northeast Structural Genomics Consortium (NESG), Department of Molecular Biology and Biochemistry, School of Arts and Sciences, and Department of Biochemistry and Molecular Biology, Robert Wood Johnson Medical School, and Center for Advanced Biotechnology and Medicine, Rutgers, The State University of New Jersey, Piscataway New Jersey; Sosnick, Tobin R. [Department of Biochemistry and Molecular Biology, University of Chicago, Chicago Illinois; Koide, Shohei [Department of Biochemistry and Molecular Biology, University of Chicago, Chicago Illinois; Department of Biochemistry and Molecular Pharmacology and the Perlmutter Cancer Center, New York University School of Medicine, New York New York

    2016-11-10

    We determined the NMR structure of a highly aromatic (13%) protein of unknown function, Aq1974 from Aquifex aeolicus (PDB ID: 5SYQ). The unusual sequence of this protein has a tryptophan content five times the normal (six tryptophan residues of 114 or 5.2% while the average tryptophan content is 1.0%) with the tryptophans occurring in a WXW motif. It has no detectable sequence homology with known protein structures. Although its NMR spectrum suggested that the protein was rich in β-sheet, upon resonance assignment and solution structure determination, the protein was found to be primarily α-helical with a small two-stranded β-sheet with a novel fold that we have termed an Aromatic Claw. As this fold was previously unknown and the sequence unique, we submitted the sequence to CASP10 as a target for blind structural prediction. At the end of the competition, the sequence was classified a hard template based model; the structural relationship between the template and the experimental structure was small and the predictions all failed to predict the structure. CSRosetta was found to predict the secondary structure and its packing; however, it was found that there was little correlation between CSRosetta score and the RMSD between the CSRosetta structure and the NMR determined one. This work demonstrates that even in relatively small proteins, we do not yet have the capacity to accurately predict the fold for all primary sequences. The experimental discovery of new folds helps guide the improvement of structural prediction methods.

  10. High-resolution gas chromatographic analysis of polycyclic aromatic hydrocarbons and aliphatic hydrocarbons; Separacion por cromatografia de gases de alta eficiencia de hidrocarburos aromaticos policiclicos, (PAH) y alifaticos (AH) ambientales, empleado como fases estacionarias OV-1 y SE-54

    Energy Technology Data Exchange (ETDEWEB)

    Perez, M.; Gonzalez, D.

    1988-07-01

    A study of the analysis by gas chromatography of aromatic polycyclic hydrocarbons and aliphatic hydrocarbons is presented. The separation has been carried out by glass and fused silica capillary column in two different polar stationary phases OV-1 and SE-54. The limitation and the advantages of the procedure are discussed in terms of separation, sensitivity and precision. (Author) 20 refs.

  11. Metal Triflates for the Production of Aromatics from Lignin.

    Science.gov (United States)

    Deuss, Peter J; Lahive, Ciaran W; Lancefield, Christopher S; Westwood, Nicholas J; Kamer, Paul C J; Barta, Katalin; de Vries, Johannes G

    2016-10-20

    The depolymerization of lignin into valuable aromatic chemicals is one of the key goals towards establishing economically viable biorefineries. In this contribution we present a simple approach for converting lignin to aromatic monomers in high yields under mild reaction conditions. The methodology relies on the use of catalytic amounts of easy-to-handle metal triflates (M(OTf) x ). Initially, we evaluated the reactivity of a broad range of metal triflates using simple lignin model compounds. More advanced lignin model compounds were also used to study the reactivity of different lignin linkages. The product aromatic monomers were either phenolic C2-acetals obtained by stabilization of the aldehyde cleavage products by reaction with ethylene glycol or methyl aromatics obtained by catalytic decarbonylation. Notably, when the method was ultimately tested on lignin, especially Fe(OTf) 3 proved very effective and the phenolic C2-acetal products were obtained in an excellent, 19.3±3.2 wt % yield. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. A neurotoxicity assessment of high flash aromatic naphtha.

    Science.gov (United States)

    Douglas, J F; McKee, R H; Cagen, S Z; Schmitt, S L; Beatty, P W; Swanson, M S; Schreiner, C A; Ulrich, C E; Cockrell, B Y

    1993-01-01

    Catalytic reforming is a refining process that converts naphthenes to aromatics by dehydrogenation to make higher octane gasoline blending components. A portion of this wide-boiling range hydrocarbon stream can be separated by distillation and used for other purposes. One such application is a mixture of predominantly 9-carbon aromatic molecules (C9 Aromatics, primarily isomers of ethyltoluene and trimethylbenzene), which is removed and used as a solvent also known as High Flash Aromatic Naphtha (HFAN). A program was initiated to assess the toxicological properties of HFAN since there may be human exposure, especially in the workplace. The current study was conducted to assess the potential for neurotoxicity in the rat. Adult male Sprague-Dawley rats of approximately 300 grams body weight, in groups of twenty, were exposed by inhalation to HFAN for 90 days at concentrations of 0, 100, 500, and 1500 ppm. During this period the animals were tested monthly for motor activity and in a functional observation battery. After three months of exposure, for 6 hours/day, 5 days/week, 10 animals/group/sex were sacrificed and selected nervous system tissue was examined histopathologically. No signs of neurotoxicity were seen in any of the evaluated parameters, nor was there evidence of pathologic changes in any of the examined tissues.

  13. Performance Evaluation of Ozonation Combined with Persulfate Application for Removal of Furfural from Aqueous Solutions

    Directory of Open Access Journals (Sweden)

    Alireza Rahmani

    2017-03-01

    Full Text Available Background: Furfural is an organic compound which derived from a variety industrial, including petrochemicals, pulping, pharmaceutical, food. Also is a main agent in many industries and aromatic organic compounds entrance in the environment. There are several methods of treating including physical, chemical, biological and physicochemical for remove this matter. Among advanced oxidation methods can be combined ozonation process with persulfate catalytic are noted. The purpose of this study was to evaluate the efficiency of ozonation process with the use of persulfate in removal furfural from aqueous solution. Materials and Methods: In this study, the efficiency of the process with a concentration furfural 5 to 30 mg/L, concentration persulfate 4 to 15 mM, pH = 3-11 and reaction time of 35 minutes in the semi-continuous reactor with a capacity of one liter was obtained. Results: The results of this study have been shown in  conditions of operation optimal , pH =,3 persulfate dosage 12 mM, ozone dosage of 1 g/min and the initial concentration of furfural  5 mg/L, this process is capable  remove of %93/34 percent Furfural and %70 of the initial COD. Conclusion: The results of this study showed that the ozone/persulfate process can be a suitable process for the removal of organic aromatic compounds including pollutants of interest.

  14. Activity relationships for aromatic crown ethers

    International Nuclear Information System (INIS)

    Wilson, Mark James

    1998-01-01

    This thesis involves an investigation of aromatic crown ethers and a study of their binding constants for alkali metals. The study was motivated by the current needs of the semiconductor industry to improve the scavenging of mobile ions from fabricated circuits. A number of aromatic crown ethers have been sulphonated in an attempt to improve their water solubility and cation binding activity. These materials have been extensively studied and their binding activity determined. In collaboration with a molecular modelling study, the effect of ionisable sulphonate groups on the macrocycles' behaviour has been investigated. The broader issue of the effect of substituents in aromatic crown ethers has also been studied with the preparation of a wide range of substituted crown ethers. The cation binding activity of these materials has been found to bear a simple relationship to the electron withdrawing nature of the aromatic substituents. This relationship can be accurately monitored using electronic charge densities from molecular modelling and this rational has been applied to the study of proton ionisable and lariating crown ethers. The incorporation of crown ethers into polyamic acid and polyimide frameworks has also been investigated, where the resulting materials have been found to exhibit unusual cation binding and uptake properties. These results imply that the combination of the crown ethers' macrocycle and adjacent carboxylic acid residues, from the polyamic acids, are conducive to effective cationic binding. NMR measurements, in conjunction with molecular modelling, have been used to explore the geometry changes encountered as the crown ether goes from it's uncomplexed to its complexed state. The energy requirement for these geometry changes has subsequently been used to examine the cation selectivity of these materials. The electronic charge changes associated with the complexation have also been investigated and correlated with the theoretical results. (author)

  15. Synthesis of new annulated pyrano[2,3-d]pyrimidine derivatives using organo catalyst (DABCO in aqueous media

    Directory of Open Access Journals (Sweden)

    Ajmal R. Bhat

    2017-01-01

    Full Text Available A selective method for the synthesis of annulated pyrano[2,3-d]pyrimidines has been developed. It was shown that base catalysis is more efficient in this reaction, rather than acid catalysis as it is believed that 1,4-diazabicyclo[2.2.2]octane (DABCO is N-type base catalyst used for the synthesis of pyrano[2,3-d]pyramidine derivatives via one-pot three component condensation reactions of various aromatic aldehydes, active methylene compounds and barbituric acid in aqueous ethanol carried at normal temperature. The potential application of DABCO in organic synthesis increasing rapidly because of its reaction simplicity, less pollution, and minimum reaction time, high yields of the biological active products, uses less toxic solvents and low cost chemicals.

  16. The molecular characteristics of pyrogenic organic materials and their aqueous leachates

    Science.gov (United States)

    Wozniak, A. S.; Hatcher, P.; Mitra, S.; Bostick, K. W.; Zimmerman, A. R.

    2016-12-01

    Pyrogenic organic matter (Py-OM), or black carbon, is known to impact soil chemistry, pollutant transport, regional and global carbon cycling, and climate. Py-OM is incorporated into soils via atmospheric deposition (e.g., from biomass, fossil fuel combustion) or direct applications by humans (e.g., biochars applied for agricultural production). Due to its presumed refractory and immobile nature, soil Py-OM is thought to be efficiently buried, sequestering atmospheric CO2. However, tracers of dissolved Py-OM (Py-DOM) have been detected in appreciable quantities in riverine, estuarine, and oceanic waters suggesting that Py-OM is more mobile in the environment than expected. The molecular characteristics of Py-OM are likely to be a controlling factor in the quantities and impacts of Py-DOM released to aqueous systems. Yet, little is known about the detailed molecular composition of these materials, let alone how those molecular characteristics vary with combustion conditions or are altered by environmental processes. Here, we examine oak and grass Py-OM (combusted over a range of temperatures), natural Py-OM (chars aged in the environment for variable lengths of time), and their Py-DOM leachates via nuclear magnetic resonance spectroscopy (NMR) and Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS). Multi-CP 13C NMR analyses of Py-OM materials and 1H NMR analyses of corresponding Py-DOM leachates reveal that Py-OM combustion temperature, environmental exposure, and molecular characteristics are reflected in Py-DOM quantities and characteristics. The relative amounts of aromatic C in Py-OM 1) decreases with environmental exposure, the relative oxygen-content in both Py-OM and Py-DOM, and the amount of Py-DOC released per g of Py-OC but 2) is positively correlated with combustion temperature and the relative contributions of acetate and aliphatic hydrogens (CH2) in Py-DOM. Preliminary FTICR-MS analyses show Py-DOM produced from oak at 400 °C to

  17. Workshop on polarized neutron filters and polarized pulsed neutron experiments

    International Nuclear Information System (INIS)

    Itoh, Shinichi

    2004-07-01

    The workshop was held in KEK by thirty-three participants on April 26, 2004. The polarized neutron filter method was only discussed. It consists of three parts; the first part was discussed on the polarized neutron methods, the second part on the polarized neutron experiments and the third on the pulse neutron spectrometer and polarized neutron experiments. The six papers were presented such as the polarized 3 He neutron spin filter, neutron polarization by proton polarized filter, soft master and neutron scattering, polarized neutron in solid physics, polarization experiments by chopper spectroscope and neutron polarization system in superHRPD. (S.Y.)

  18. Silicone elastomers with covalently incorporated aromatic voltage stabilisers

    DEFF Research Database (Denmark)

    A Razak, Aliff Hisyam; Skov, Anne Ladegaard

    2017-01-01

    to the incorporationof an aromatic voltage stabiliser, were prepared by cross-linking synthesised polydimethylsiloxane–polyphenylmethylsiloxane (PDMS–PPMS) copolymers. PPMS possesses voltage stabilisation capabilitiesbut is immiscible in PDMS, and thus the copolymerisation of the two components was necessary...... forhomogeneity. Concentrations of the voltage stabiliser were varied by changing the molecular weights ofthe PPMS in the copolymer. The developed elastomers were inherently soft with enhanced electricalbreakdown strengths, due to delocalisedp-electrons of the aromatic constituent. An optimumconcentration...

  19. Biodegradation of polycyclic aromatic hydrocarbons: Using microbial bioelectrochemical systems to overcome an impasse.

    Science.gov (United States)

    Kronenberg, Maria; Trably, Eric; Bernet, Nicolas; Patureau, Dominique

    2017-12-01

    Polycyclic aromatic hydrocarbons (PAHs) are hardly biodegradable carcinogenic organic compounds. Bioremediation is a commonly used method for treating PAH contaminated environments such as soils, sediment, water bodies and wastewater. However, bioremediation has various drawbacks including the low abundance, diversity and activity of indigenous hydrocarbon degrading bacteria, their slow growth rates and especially a limited bioavailability of PAHs in the aqueous phase. Addition of nutrients, electron acceptors or co-substrates to enhance indigenous microbial activity is costly and added chemicals often diffuse away from the target compound, thus pointing out an impasse for the bioremediation of PAHs. A promising solution is the adoption of bioelectrochemical systems. They guarantee a permanent electron supply and withdrawal for microorganisms, thereby circumventing the traditional shortcomings of bioremediation. These systems combine biological treatment with electrochemical oxidation/reduction by supplying an anode and a cathode that serve as an electron exchange facility for the biocatalyst. Here, recent achievements in polycyclic aromatic hydrocarbon removal using bioelectrochemical systems have been reviewed. This also concerns PAH precursors: total petroleum hydrocarbons and diesel. Removal performances of PAH biodegradation in bioelectrochemical systems are discussed, focussing on configurational parameters such as anode and cathode designs as well as environmental parameters like porosity, salinity, adsorption and conductivity of soil and sediment that affect PAH biodegradation in BESs. The still scarcely available information on microbiological aspects of bioelectrochemical PAH removal is summarised here. This comprehensive review offers a better understanding of the parameters that affect the removal of PAHs within bioelectrochemical systems. In addition, future experimental setups are proposed in order to study syntrophic relationships between PAH

  20. Influence of aqueous phase on electrochemical biocorrosion tests in diesel/water systems

    Energy Technology Data Exchange (ETDEWEB)

    Bento, F.M. [Dept. of Soils, Faculty of Agronomy, UFRGS, 7712 Bento Goncalves Avenue, CEP: 91540-001, POA, RS (Brazil); Englert, G.E.; Muller, I.L. [Dept. of Metallurgy, Biocorrosion and Biofilms Lab, UFRGS, 99 Osvaldo Aranha Avenue s.615D, CEP: 90035-190, POA, RS (Brazil); Gaylarde, C.C. [Dept. of Biophisics, UFRGS POA, RS (Brazil)

    2004-08-01

    Storage tanks containing microbially contaminated diesel oil are susceptible to corrosion. This process may be evaluated electrochemically in the laboratory using simulated storage systems containing diesel oil and an aqueous phase. The simulated aqueous phase must supply mineral nutrients for microbial growth, together with adequate electrical conductivity, without, however, being too corrosive, so as to allow the aggressive nature of the microbial metabolites to be detected. In this investigation, microbial growth was measured in six electrically conductive media overlaid with metropolitan diesel oil containing an additive package. The microorganisms were the filamentous fungi, Hormoconis resinae, Paecilomyces variotii and Aspergillus fumigatus, the bacterium Bacillus subtilis and the yeast Candida silvicola, all previously isolated from contaminated diesel oil. After 60 days incubation with pure or mixed inocula of these microorganisms, pH, conductivity and viable microorganisms were measured. The electrochemical behaviour of carbon steel ASTM 283-93-C was determined in each of the six media (uninoculated) and in selected inoculated medium via measurements of open circuit potential and potentiostatic polarization curves. The uptake of phosphate (corrosion inhibitor), microbial growth, pH, conductivity and anodic and cathodic polarization curves were assessed in the water phase after 30 and 60 days of incubation with each single species Aspergillus fumigatus and Hormoconis resinae and with the consortium. The medium which proved most appropriate was Bushnell-Haas medium modified by the omission of chlorides, which allowed satisfactory microbial growth and had low aggressivity towards the steel. The performance of electrochemical tests in aerated, rather than deaerated, electrolyte solutions is suggested to be important to allow the detection of microbial influence on passive film formation and stability. (Abstract Copyright [2004], Wiley Periodicals, Inc.)

  1. Aqueous adsorption and removal of organic contaminants by carbon nanotubes

    International Nuclear Information System (INIS)

    Yu, Jin-Gang; Zhao, Xiu-Hui; Yang, Hua; Chen, Xiao-Hong; Yang, Qiaoqin; Yu, Lin-Yan; Jiang, Jian-Hui; Chen, Xiao-Qing

    2014-01-01

    Organic contaminants have become one of the most serious environmental problems, and the removal of organic contaminants (e.g., dyes, pesticides, and pharmaceuticals/drugs) and common industrial organic wastes (e.g., phenols and aromatic amines) from aqueous solutions is of special concern because they are recalcitrant and persistent in the environment. In recent years, carbon nanotubes (CNTs) have been gradually applied to the removal of organic contaminants from wastewater through adsorption processes. This paper reviews recent progress (145 studies published from 2010 to 2013) in the application of CNTs and their composites for the removal of toxic organic pollutants from contaminated water. The paper discusses removal efficiencies and adsorption mechanisms as well as thermodynamics and reaction kinetics. CNTs are predicted to have considerable prospects for wider application to wastewater treatment in the future. - Highlights: • We summarize the most recent research progress of CNTs for removal of organics. • Adsorption mechanisms between CNTs and organics were elucidated in detail. • The developing trends and prospects of CNTs for removal of organics were discussed

  2. Aqueous adsorption and removal of organic contaminants by carbon nanotubes

    Energy Technology Data Exchange (ETDEWEB)

    Yu, Jin-Gang, E-mail: yujg@csu.edu.cn [College of Chemistry and Chemical Engineering, Central South University, Changsha, Hunan 410083 (China); College of Chemistry and Chemical Engineering, Hunan University, Changsha, Hunan 410082 (China); Key Laboratory of Resources Chemistry of Nonferrous Metals, Ministry of Education, Central South University, Changsha, Hunan 410083 (China); Zhao, Xiu-Hui; Yang, Hua [College of Chemistry and Chemical Engineering, Central South University, Changsha, Hunan 410083 (China); Key Laboratory of Resources Chemistry of Nonferrous Metals, Ministry of Education, Central South University, Changsha, Hunan 410083 (China); Chen, Xiao-Hong [Collaborative Innovation Center of Resource-conserving and Environment-friendly Society and Ecological Civilization, Changsha, Hunan 410083 (China); Yang, Qiaoqin [Department of Mechanical Engineering, University of Saskatchewan, Saskatoon, SK S7N 5A9 (Canada); Yu, Lin-Yan [College of Chemistry and Chemical Engineering, Central South University, Changsha, Hunan 410083 (China); Key Laboratory of Resources Chemistry of Nonferrous Metals, Ministry of Education, Central South University, Changsha, Hunan 410083 (China); Jiang, Jian-Hui [College of Chemistry and Chemical Engineering, Hunan University, Changsha, Hunan 410082 (China); Chen, Xiao-Qing, E-mail: xqchen@csu.edu.cn [College of Chemistry and Chemical Engineering, Central South University, Changsha, Hunan 410083 (China); Key Laboratory of Resources Chemistry of Nonferrous Metals, Ministry of Education, Central South University, Changsha, Hunan 410083 (China)

    2014-06-01

    Organic contaminants have become one of the most serious environmental problems, and the removal of organic contaminants (e.g., dyes, pesticides, and pharmaceuticals/drugs) and common industrial organic wastes (e.g., phenols and aromatic amines) from aqueous solutions is of special concern because they are recalcitrant and persistent in the environment. In recent years, carbon nanotubes (CNTs) have been gradually applied to the removal of organic contaminants from wastewater through adsorption processes. This paper reviews recent progress (145 studies published from 2010 to 2013) in the application of CNTs and their composites for the removal of toxic organic pollutants from contaminated water. The paper discusses removal efficiencies and adsorption mechanisms as well as thermodynamics and reaction kinetics. CNTs are predicted to have considerable prospects for wider application to wastewater treatment in the future. - Highlights: • We summarize the most recent research progress of CNTs for removal of organics. • Adsorption mechanisms between CNTs and organics were elucidated in detail. • The developing trends and prospects of CNTs for removal of organics were discussed.

  3. Organic compounds in radiation fogs in Davis (California)

    Science.gov (United States)

    Herckes, Pierre; Hannigan, Michael P.; Trenary, Laurie; Lee, Taehyoung; Collett, Jeffrey L.

    New stainless steel active fogwater collectors were designed and used in Davis (CA, USA) to collect fogwater for the speciation of organic matter. Organic compounds in fog samples were extracted by liquid-liquid extraction and analyzed by gas chromatography coupled to mass spectrometry. Numerous organic compounds, including various alkanes, polycyclic aromatic hydrocarbons (PAH) and alkanoic acids, have been identified in the fogwater samples. Higher molecular weight (MW) compounds are preferentially associated with an insoluble phase inside the fog drops, whereas lower molecular weight and more polar compounds are found predominantly in the dissolved phase. Concentrations in the dissolved phase were sometimes much higher than estimated by the compounds' aqueous solubilities.

  4. Phytotoxic activity of crude aqueous extracts and fractions of young leaves of Sapindus saponaria L. (Sapindaceae

    Directory of Open Access Journals (Sweden)

    Patrícia Umeda Grisi

    2013-03-01

    Full Text Available The aim of this study was to evaluate the phytotoxic potential of aqueous extract of young leaves of Sapindus saponaria L. (soapberry on the diaspore germination and seedling growth Lactuca sativa L. (lettuce and Allium cepa L. (onion, as well as to determine, by bioassay-guided fractioning, whether the fractionated extracts of those leaves are phytotoxic to Triticum aestivum L. (wheat coleoptiles. The aqueous extract was prepared using 100 g of dried plant material dissolved in 1000 ml of distilled water, resulting in a concentration of 10.0%. Distilled water was added in order to obtain dilutions of 7.5%, 5.0%, and 2.5%. The extraction was carried out with young leaves (in powder form and organic solvents of various polarities. We fractioned the ethyl acetate extract using column chromatography. The phytotoxic potential of the aqueous extract of young leaves S. saponaria varied according to the receiving species and the concentration-dependent inhibitory effect. The ethyl acetate extract, specifically fraction 6 (57-70, had the greatest inhibitory effect on the elongation of wheat coleoptiles, indicating that the compounds responsible for the phytotoxic effect reside within this fraction.

  5. Solubilization of Polycyclic Aromatic Hydrocarbons by Single and Binary Mixed Rhamnolipid-Sophorolipid Biosurfactants.

    Science.gov (United States)

    Song, Dandan; Liang, Shengkang; Yan, Lele; Shang, Yujun; Wang, Xiuli

    2016-07-01

    Biosurfactants are promising additives for surfactant enhanced remediation (SER) technologies due to their low toxicity and high biodegradability. To develop green and efficient additives for SER, the aqueous solubility enhancements of polycyclic aromatic hydrocarbons (PAHs; naphthalene, phenanthrene, and pyrene) by rhamnolipid (RL) and sophorolipid (SL) biosurfactants were investigated in single and binary mixed systems. The solubilization capacities were quantified in terms of the solubility enhancement factor, molar solubilization ratio (MSR), and micelle-water partition coefficient (). Rughbin's model was applied to evaluate the interaction parameters (β) in the mixed RL-SL micelles. The solubility of the PAHs increased linearly with the glycolipid concentration above the critical micelle concentration (CMC) in both single and mixed systems. Binary RL-SL mixtures exhibited greater solubilization than individual glycolipids. At a SL molar fraction of 0.7 to 0.8, the solubilization capacity was the greatest, and the MSR and reached their maximum values, and β values became positive. These results suggest that the two biosurfactants act synergistically to increase the solubility of the PAHs. The solubilization capacity of the RL-SL mixtures increased with increasing temperature and decreased with increasing salinity. The aqueous solubility of phenanthrene reached a maximum value at pH of 5.5. Moreover, the mixed RL-SL systems exhibited a strong ability to solubilize PAHs, even in the presence of heavy metal ions. These mixed biosurfactant systems have the potential to improve the performance of SER technologies using biosurfactants to solubilize hydrophobic organic contaminants by decreasing the applied biosurfactant concentration, which reduces the costs of remediation. Copyright © by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America, Inc.

  6. Aliphatic-aromatic separation using deep eutectic solvents as extracting agents

    NARCIS (Netherlands)

    Rodriguez Rodriguez, Nerea; Fernandez Requejo, Patricia; Kroon, Maaike

    2015-01-01

    The separation of aliphatic and aromatic compounds is a great challenge for chemical engineers. There is no efficient separation process for mixtures with compositions lower than 20 wt % in aromatics. In this work, the feasibility of two different deep eutectic solvents (DESs) as novel extracting

  7. Neutron polarization in polarized 3He targets

    International Nuclear Information System (INIS)

    Friar, J.L.; Gibson, B.F.; Payne, G.L.; Bernstein, A.M.; Chupp, T.E.

    1990-01-01

    Simple formulas for the neutron and proton polarizations in polarized 3 He targets are derived assuming (1) quasielastic final states; (2) no final-state interactions; (3) no meson-exchange currents; (4) large momentum transfers; (5) factorizability of 3 He SU(4) response-function components. Numerical results from a wide variety of bound-state solutions of the Faddeev equations are presented. It is found that this simple model predicts the polarization of neutrons in a fully polarized 3 He target to be 87%, while protons should have a slight residual polarization of -2.7%. Numerical studies show that this model works very well for quasielastic electron scattering

  8. Degradation of aromatic compounds in plants grown under aseptic conditions

    Energy Technology Data Exchange (ETDEWEB)

    Mithaishvili, T.; Ugrekhelidze, D.; Tsereteli, B.; Sadunishvili, T.; Kvesitadze, G. [Durmishidze Inst. of Biochemistry and Biotechnology, Academy of Sciences of Georgia, Tbilisi (Georgia); Scalla, R. [Lab. des Xenobiotiques, INRA, Toulouse (France)

    2005-02-01

    The aim of the work is to investigate the ability of higher plants to absorb and detoxify environmental pollutants - aromatic compounds via aromatic ring cleavage. Transformation of {sup 14}C specifically labelled benzene derivatives, [1-6-{sup 14}C]-nitrobenzene, [1-6-{sup 14}C]-aniline, [1-{sup 14}C]- and [7-{sup 14}C]-benzoic acid, in axenic seedlings of maize (Zea mays L.), kidney bean (Phaseolus vulgaris L.), pea (Pisum sativum L.) and pumpkin (Cucurbita pepo L.) were studied. After penetration in plants, the above xenobiotics are transformed by oxidative or reductive reactions, conjugation with cell endogenous compounds, and binding to biopolymers. The initial stage of oxidative degradation consists in hydroxylation reactions. The aromatic ring can then be cleaved and degraded into organic acids of the Krebs cycle. Ring cleavage is accompanied by {sup 14}CO{sub 2} evolution. Aromatic ring cleavage in plants has thus been demonstrated for different xenobiotics carrying different substitutions on their benzene ring. Conjugation with low molecular peptides is the main pathway of aromatic xenobiotics detoxification. Peptide conjugates are formed both by the initial xenobiotics (except nitrobenzene) and by intermediate transformation products. The chemical nature of the radioactive fragment and the amino acid composition of peptides participating in conjugation were identified. (orig.)

  9. The future role of aromatics in refining and petrochemistry. Proceedings of the DGMK-Conference (Authors' manuscripts)

    Energy Technology Data Exchange (ETDEWEB)

    Emig, G.; Rupp, M.; Weitkamp, J. [eds.

    1999-07-01

    Topic of this conference has been the furure role of aromatics in the refinign industry. The articles deal with the following topics: Refining; legal aspects in the aromatics market; transportation fuels; dearomatization; catalytic reforming and aromatics; separation processes for aromatics; oxidation and ammoxidation of aromatics; electrophilic substitution of aromatics; hydrogenation of benzene; zeolites. (orig./sr)

  10. Interaction between Carbon Nanotubes and Aromatic Hydrocarbon-degrading Microbes and its Effect on Carbon Nanotubes Transformation

    Science.gov (United States)

    You, Y.; Wang, L.; Poulson, S.; Wang, X.; Xing, B.; Yang, Y.

    2015-12-01

    Due to their unique electrical, optical and mechanical properties, carbon nanotubes (CNTs) have been substantially produced and widely applied during the past decades, leading to their increased probability of entering the environment. Some estimation suggests that CNTs are accumulated in agricultural systems with their soil concentration increasing by 0.4-157 ng/kg/year. This has raised concerns about environmental impacts of these emerging contaminants including their ecotoxicity. Meanwhile, transformation of CNTs in the environment can significantly affect their transport, bioavailability and thereby ecotoxicity. So far, environmental biodegradation of CNTs remains obscure. Given the high diversity of soil microorganisms and their metabolic potentials, it is important to investigate microbial biodegradation of CNTs under various environmental conditions. This study focuses on an aromatic hydrocarbon-degrading bacterium, Mycobacterium vanbaalenii PYR-1, as a model microorganism capable of ring cleavage. We hypothesize that bacterial activities could transform CNTs to more hydrophilic forms, increasing their aqueous stability and environmental reactivity. We incubated M. vanbaalenii PYR-1 with 13C-labeded multiwall carbon nanotubes (MWCNTs) for 30 days, monitored δ13C in the system, characterized MWCNTs before and after the reaction, and compared the results with culture-negative controls. To investigate effects of various environmental conditions, including the presence of extracellular oxidative enzymes from white-rot fungi, additional experiments will be conducted and results compared will be compared among different setups. Moreover, we will measure adverse impacts of CNTs on the metabolic activities of M. vanbaalenii PYR-1, particularly its biodegradation of polycyclic aromatic hydrocarbons.

  11. When measured spin polarization is not spin polarization

    International Nuclear Information System (INIS)

    Dowben, P A; Wu Ning; Binek, Christian

    2011-01-01

    Spin polarization is an unusually ambiguous scientific idiom and, as such, is rarely well defined. A given experimental methodology may allow one to quantify a spin polarization but only in its particular context. As one might expect, these ambiguities sometimes give rise to inappropriate interpretations when comparing the spin polarizations determined through different methods. The spin polarization of CrO 2 and Cr 2 O 3 illustrate some of the complications which hinders comparisons of spin polarization values. (viewpoint)

  12. Ambient aromatic hydrocarbon measurements at Welgegund, South Africa

    Energy Technology Data Exchange (ETDEWEB)

    Jaars, K.; Beukes, J. P.; van Zyl, P. G.; Venter, A. D.; Josipovic, M.; Pienaar, J. J.; Vakkari, Ville; Aaltonen, H.; Laakso, H.; Kulmala, M.; Tiitta, P.; Guenther, Alex B.; Hellen, H.; Laakso, L.; Hakola, H.

    2014-07-11

    Aromatic hydrocarbons are associated with direct adverse human health effects and can have negative impacts on ecosystems due to their toxicity, as well as indirect negative effects through the formation of tropospheric ozone and secondary organic aerosol that affect human health, crop production and regional climate. Measurements were conducted at the Welgegund measurement station (South Africa) that is considered to be a regionally representative background site. However, the site is occasionally impacted by plumes from major anthropogenic source regions in the interior of South Africa, which include the western Bushveld Igneous Complex (e.g. platinum, base metal and ferrochrome smelters), the eastern Bushveld Igneous Complex (platinum and ferrochrome smelters), the Johannesburg-Pretoria metropolitan conurbation (>10 million people), the Vaal Triangle (e.g. petrochemical and industries), the Mpumalanga Highveld (e.g. coal-fired power plants and petrochemical industry) and also a region of anti-cyclonic recirculation of air mass over the interior of South Africa. The aromatic hydrocarbon measurements were conducted with an automated sampler on Tenax-TA and Carbopack-B adsorbent tubes with heated inlet for one year. Samples were collected twice a week for two hours during daytime and two hours 1 during night-time. A thermal desorption unit, connected to a gas chromatograph and a mass 2 selective detector was used for sample preparation and analysis. Results indicated that the 3 monthly median total aromatic hydrocarbon concentrations ranged between 0.01 to 3.1 ppb. 4 Benzene levels did not exceed local air quality standards. Toluene was the most abundant 5 species, with an annual median concentration of 0.63 ppb. No statistically significant 6 differences in the concentrations measured during daytime and night-time were found and no distinct seasonal patterns were observed. Air mass back trajectory analysis proved that the lack of seasonal cycles could be

  13. Continuous Flow Nucleophilic Aromatic Substitution with Dimethylamine Generated in Situ by Decomposition of DMF

    DEFF Research Database (Denmark)

    Petersen, Trine P; Larsen, Anders Foller; Ritzén, Andreas

    2013-01-01

    A safe, practical, and scalable continuous flow protocol for the in situ generation of dimethylamine from DMF followed by nucleophilic aromatic substitution of a broad range of aromatic and heteroaromatic halides is reported.......A safe, practical, and scalable continuous flow protocol for the in situ generation of dimethylamine from DMF followed by nucleophilic aromatic substitution of a broad range of aromatic and heteroaromatic halides is reported....

  14. Intra-molecular selectivity of muonium towards chlorinated aromatic compounds

    International Nuclear Information System (INIS)

    Venkateswaran, K.; Stadlbauer, J.M.; Laing, M.E.; Klugkist, J.; Chong, D.P.; Porter, G.B.; Walker, D.C.

    1994-01-01

    Muon resonance studies show that muonium atoms (Mu) in ethanol add selectively to certain C-sites of aromatic compounds containing -Cl and -OH substituents. The sites chosen seem to be those carrying the lowest electron density. This helps to characterize Mu as a nucleophile in addition reactions and, in this respect, Mu differs from ordinary H-atoms. The study shows no apparent inter-molecular selectivity between a pair of aromatic solutes in an equimolar mixture, but strong intra-molecular selectivity in an ether composed of those two aromatic rings. This difference between intra- and inter-molecular selectivity is interpreted as kinetic in origin - arising from the 'caging effect' of the solvent and peculiar to reactions close to the diffusion-controlled limit. (orig.)

  15. Photocatalytic oxidation of aromatic amines using MnO2@g ...

    Science.gov (United States)

    An efficient and direct oxidation of aromatic amines to aromatic azo-compounds has been achieved using a MnO2@g-C3N4 catalyst under visible light as a source of energy at room temperature Prepared for submission to the journal, Advanced Materials Letters.

  16. A Simple Alternative Method for the Synthesis of Aromatic Dialdehydes

    OpenAIRE

    KOZ, Gamze; ASTLEY, Demet; ASTLEY, Stephen

    2011-01-01

    Aromatic dialdehydes were synthesized from 5-t-butylsalicylaldehyde and o-vanilline in good yields using paraformaldehyde, hydrobromic acid and catalytic amounts of sulfuric acid in one step which was previously unavailable with present methods. Key Words: aromatic dialdehydes, bromomethylation, 5-t-butylsalicylaldehyde, o-vanilline. 

  17. A Simple Alternative Method for the Synthesis of Aromatic Dialdehydes

    OpenAIRE

    KOZ, Gamze; ASTLEY, Demet; ASTLEY, Stephen Thomas

    2012-01-01

    Aromatic dialdehydes were synthesized from 5-t-butylsalicylaldehyde and o-vanilline in good yields using paraformaldehyde, hydrobromic acid and catalytic amounts of sulfuric acid in one step which was previously unavailable with present methods. Key Words: aromatic dialdehydes, bromomethylation, 5-t-butylsalicylaldehyde, o-vanilline. 

  18. MIPs in Aqueous Environments.

    Science.gov (United States)

    Wan, Ying-chun; Ma, Hui-ting; Lu, Bin

    2015-01-01

    When organic solvent-compatible molecularly imprinted polymers (MIPs) are used in aqueous environment, how to reduce nonspecific binding is a major challenge. By modifying the binding solvents and introducing appropriate washing and elution steps, even relatively hydrophobic MIPs can gain optimal rebinding selectivity in aqueous conditions. Furthermore, water-compatible MIPs that can be used to treat aqueous samples directly have been prepared. The use of hydrophilic co-monomers, the controlled surface modification through controlled radical polymerization, and the new interfacial molecular imprinting methods are different strategies to prepare water-compatible MIPs. By combining MIPs with other techniques, both organic solvent-compatible and water-compatible MIPs can display better functional performances in aqueous conditions. Intensive studies on MIPs in aqueous conditions can provide new MIPs with much-improved compatibilities that will lead to more interesting applications in biomedicine and biotechnology.

  19. Toxicity of Aromatic Ketone to Yeast Cell and Improvement of the Asymmetric Reduction of Aromatic Ketone Catalyzed by Yeast Cell with the Introduction of Resin Adsorption

    Directory of Open Access Journals (Sweden)

    Zhong-Hua Yang

    2008-01-01

    Full Text Available Asymmetric reduction of the prochiral aromatic ketone catalyzed by yeast cells is one of the most promising routes to produce its corresponding enantiopure aromatic alcohol, but the space-time yield does not meet people’s expectations. Therefore, the toxicity of aromatic ketone and aromatic alcohol to the yeast cell is investigated in this work. It has been found that the aromatic compounds are poisonous to the yeast cell. The activity of yeast cell decreases steeply when the concentration of acetophenone (ACP is higher than 30.0 mmol/L. Asymmetric reduction of acetophenone to chiral S-α-phenylethyl alcohol (PEA catalyzed by the yeast cell was chosen as the model reaction to study in detail the promotion effect of the introduction of the resin adsorption on the asymmetric reduction reaction. The resin acts as the substrate reservoir and product extraction agent in situ. It has been shown that this reaction could be remarkably improved with this technique when the appropriate kind of resin is applied. The enantioselectivity and yield are acceptable even though the initial ACP concentration reaches 72.2 mmol/L.

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

    Science.gov (United States)

    Hoang, Trung Q.

    Upgrading of light oxygenates derived from biomass conversion, such as propanal and glycerol, to more valuable aromatics for biofuels has been demonstrated on zeolite catalysts. Aromatics with a high ratio of C 9/(C8+C7) and little benzene are produced at much higher yield from oxygenates than from olefins at mild conditions over HZSM-5. It is proposed that C9 aromatics are predominantly produced via acid-catalyzed aldol condensation. This reaction pathway is different from the pathway of propylene and other hydrocarbon aromatization that occurs via a hydrocarbon pool at more severe conditions with major aromatic products C6 and C7. In fact, investigation on the effect of crystallite size HZSM-5 has shown a higher ratio of C9/(C8+C 7) aromatics on small crystallite. This is due to faster removal of products from the shorter diffusion path length. As a result, a longer catalyst lifetime, less isomerization, and less cracking were observed on small crystallites. Beside crystallite size, pore geometry of zeolites was also found to significantly affect aromatic production for both conversion of propanal and glycerol. It is shown that the structure of the HZSM-22, with a one-dimensional and narrower channel system, restricts the formation of aromatics. In contrast, a higher yield of aromatic products is observed over HZSM-5 with its three-dimensional channel system. By increasing channel dimension and connectivity of the channels, increasing catalyst activity was also observed due to more accessible acid sites. It was also found that glycerol is highly active for dehydration on zeolites to produce high yields of acrolein (propenal), a high value chemical. To maximize aromatics from glycerol conversion, HZSM-5 and HY were found to be effective. A two-bed reactor of Pd/ZnO and HZSM-5 was used to first deoxygenate/hydrogenate glycerol over Pd/ZnO to intermediate oxygenates that can further aromatize on HZSM-5. The end results are very promising with significant improvement

  1. Rapid quantification of polycyclic aromatic hydrocarbons in hydroxypropyl-{beta}-cyclodextrin (HPCD) soil extracts by synchronous fluorescence spectroscopy (SFS)

    Energy Technology Data Exchange (ETDEWEB)

    Guoxiong, Hua [School of Biology and Psychology, Institute for Research on Environment and Sustainability, Newcastle University, Newcastle upon Tyne NE1 7RU (United Kingdom); Broderick, John [School of Biology and Psychology, Institute for Research on Environment and Sustainability, Newcastle University, Newcastle upon Tyne NE1 7RU (United Kingdom); Semple, Kirk T [Department of Environmental Science, Faculty of Science and Technology, University of Lancaster, Lancaster LA1 4YQ (United Kingdom); Killham, Ken [School of Biological Sciences, University of Aberdeen, Aberdeen AB24 3UU (United Kingdom); Singleton, Ian [School of Biology and Psychology, Institute for Research on Environment and Sustainability, Newcastle University, Newcastle upon Tyne NE1 7RU (United Kingdom)

    2007-07-15

    Synchronous fluorescence spectroscopy (SFS) was directly applied to rapidly quantify selected polycyclic aromatic hydrocarbons (PAHs: benzo[a]pyrene and pyrene) in aqueous hydroxypropyl-{beta}-cyclodextrin (HPCD) soil extract solutions from a variety of aged contaminated soils containing four different PAHs. The method was optimized and validated. The results show that SFS can be used to analyse benzo[a]pyrene and pyrene in HPCD based soil extracts with high sensitivity and selectivity. The linear calibration ranges were 4.0 x 10{sup -6}-1.0 x 10{sup -3} mM for benzo[a]pyrene and 6.0 x 10{sup -6}-1.2 x 10{sup -3} mM for pyrene in 10 mM HPCD aqueous solution alone. The detection limits according to the error propagation theory for benzo[a]pyrene and pyrene were 3.9 x 10{sup -6} and 5.4 x 10{sup -6} mM, respectively. A good agreement between SFS and HPLC was reached for both determinations of PAHs in HPCD alone and in soil HPCD extracts. Hence, SFS is a potential means to simplify the present non-exhaustive hydroxypropyl-{beta}-cyclodextrin (HPCD)-based extraction technique for the evaluation of PAH bioavailability in soil. - SFS can be used to rapidly quantify selected PAHs in soil extracts and to simplify the non-exhaustive HPCD-based extraction technique for the evaluation of PAH bioavailability.

  2. Rapid quantification of polycyclic aromatic hydrocarbons in hydroxypropyl-β-cyclodextrin (HPCD) soil extracts by synchronous fluorescence spectroscopy (SFS)

    International Nuclear Information System (INIS)

    Hua Guoxiong; Broderick, John; Semple, Kirk T.; Killham, Ken; Singleton, Ian

    2007-01-01

    Synchronous fluorescence spectroscopy (SFS) was directly applied to rapidly quantify selected polycyclic aromatic hydrocarbons (PAHs: benzo[a]pyrene and pyrene) in aqueous hydroxypropyl-β-cyclodextrin (HPCD) soil extract solutions from a variety of aged contaminated soils containing four different PAHs. The method was optimized and validated. The results show that SFS can be used to analyse benzo[a]pyrene and pyrene in HPCD based soil extracts with high sensitivity and selectivity. The linear calibration ranges were 4.0 x 10 -6 -1.0 x 10 -3 mM for benzo[a]pyrene and 6.0 x 10 -6 -1.2 x 10 -3 mM for pyrene in 10 mM HPCD aqueous solution alone. The detection limits according to the error propagation theory for benzo[a]pyrene and pyrene were 3.9 x 10 -6 and 5.4 x 10 -6 mM, respectively. A good agreement between SFS and HPLC was reached for both determinations of PAHs in HPCD alone and in soil HPCD extracts. Hence, SFS is a potential means to simplify the present non-exhaustive hydroxypropyl-β-cyclodextrin (HPCD)-based extraction technique for the evaluation of PAH bioavailability in soil. - SFS can be used to rapidly quantify selected PAHs in soil extracts and to simplify the non-exhaustive HPCD-based extraction technique for the evaluation of PAH bioavailability

  3. Aqueous electrolytes for redox flow battery systems

    Science.gov (United States)

    Liu, Tianbiao; Li, Bin; Wei, Xiaoliang; Nie, Zimin; Wang, Wei; Liu, Jun; Sprenkle, Vincent L.

    2017-10-17

    An aqueous redox flow battery system includes an aqueous catholyte and an aqueous anolyte. The aqueous catholyte may comprise (i) an optionally substituted thiourea or a nitroxyl radical compound and (ii) a catholyte aqueous supporting solution. The aqueous anolyte may comprise (i) metal cations or a viologen compound and (ii) an anolyte aqueous supporting solution. The catholyte aqueous supporting solution and the anolyte aqueous supporting solution independently may comprise (i) a proton source, (ii) a halide source, or (iii) a proton source and a halide source.

  4. Spectral Induced Polarization Response of Biofilm Formation in Hanford Vadose Zone Sediment

    Science.gov (United States)

    Garcia, A.; Katsenovich, Y.; Lee, B.; Whitman, D.

    2017-12-01

    As a result of the U.S. Nuclear weapons program during the second world war and the cold war, there now exists a significant amount of uranium contamination at the U.S. Department of Energy Hanford site located in Washington state. In-situ immobilization of mobile uranium via injections of a soluble sodium tripolyphosphate amendment may prove effective in the formation of insoluble uranyl phosphate mineral, autunite. However, the injected polyphosphate undergoes hydrolysis in aqueous solutions to form orthophosphate, which serves as a readily available nutrient for the various microorganisms in the sediment. Sediment-filled column experiments conducted under saturated oxygen restricted conditions using geophysical Spectral Induced Polarization technique have shown the impact of microbes on the dissolution of autunite, a calcium uranyl phosphate mineral. Spectral Induced Polarization may be an effective way to track changes indicative of bacterial activities on the surrounding environment. This method can be a cost-effective alternative to the drilling of boreholes at a field scale.

  5. Development of a yeast cell factory for production of aromatic products

    DEFF Research Database (Denmark)

    Rodriguez Prado, Edith Angelica; Kildegaard, Kanchana Rueksomtawin; Li, Mingji

    2014-01-01

    There is much interest in aromatic chemicals in the chemical industry as these can be used for production of dyes, anti-oxidants, nutraceuticals and food ingredients. Yeast is a widely used cell factory and it is particularly well suited for production of aromatic chemicals via complex biosynthetic...... routes involving P450 enzymes. In Saccharomyces cerevisiae the fluxes towards aromatic acids (L-tryptophan, L-tyrosine and L-phenylalanine) are strictly controlled on transcriptional and kinetic levels and therefore are difficult to manipulate. We engineered S. cerevisiae for increased production...... of aromatic compounds by eliminating degradation, up-regulating the key enzyme encoding genes, and removing feed-back inhibition in the pathway. In order to test the strain performance we overexpressed heterologous pathway for coumaric acid production. We obtained 4-fold higher concentrations of coumaric acid...

  6. Organic superalkalis with closed-shell structure and aromaticity

    Science.gov (United States)

    Srivastava, Ambrish Kumar

    2018-06-01

    Benzene (C6H6) and polycyclic hydrocarbons such as naphthalene (C10H8), anthracene (C14H10) and coronene (C24H12) are well known aromatic organic compounds. We study the substitution of Li replacing all H-atoms in these hydrocarbons using density functional method. The vertical ionisation energy of such lithiated species, i.e. C6Li6, C10Li8, C14Li10 and C24Li12 ranges 4.24-4.50 eV, which is lower than the ionisation energy (IE) of Li atom. Thus, these species may behave as superalkalis due to their lower IE than alkali metal. However, these lithiated species possess planar and closed-shell structure, unlike typical superalkalis. Furthermore, all Li-substituted species are aromatic although their degree of aromaticity is reduced as compared to corresponding hydrocarbon analogues. We have further explored the structure of C6Li6 as star-like, unlike its inorganic analogue B3N3Li6, which appears as fan-like structure. We have also demonstrated that the interaction of C6Li6 with a superhalogen (such as BF4) is similar to that of a typical superalkali (such as OLi3). This may further suggest that the proposed lithiated species may form a new class of closed-shell organic superalkalis with aromaticity.

  7. Asymmetric transfer hydrogenation of ketones in aqueous solution catalyzed by Rhodium(III) complexes with C2-symmetric fluorene-ligands containing chiral (1R,2R)-cyclohexane-1,2-diamine

    Energy Technology Data Exchange (ETDEWEB)

    Montalvo-Gonzalez, Ruben [Universidad Autonoma de Nayarit, Tepic, Nay (Mexico). Unidad Academica de Ciencias Quimico Biologicas y Farmaceuticas; Chavez, Daniel; Aguirre, Gerardo; Parra-Hake, Miguel; Somanathan, Ratnasamy, E-mail: somanatha@sundown.sdsu.ed [Instituto Tecnologico de Tijuana, B.C. (Mexico). Centro de Graduados e Investigacion

    2010-07-01

    Two C{sub 2}-symmetric bis(sulfonamide) ligands containing fluorene-chiral (1R, 2R)-cyclohexane-1,2-diamine were complexed to Rh{sup III}(Cp{sup *}) and used as catalyst to reduce aromatic ketones. The corresponding chiral secondary alcohols were obtained in 87-100% ee and 85-99% yield, under asymmetric transfer hydrogenation (ATH) conditions using aqueous sodium formate as the hydride source. With acetophenone, 94% ee and 86-97% yield was achieved with substrate/catalyst (S/C) ratio of 10,000. (author)

  8. Biosorption of aqueous lead (II) on rice straws (oryza sativa) by flash column process

    International Nuclear Information System (INIS)

    Khalid, H.N.; Hassan, M.U.; Jamil, N.; Ahmad, D.; Bushra, H.; Khatoon, S.

    2010-01-01

    Biosorption of Pb (II) on rice straws has been studied with the variation in the parameters and on modified rice straws by flash column process. Different parameters like particle size of adsorbent, initial concentration of metal ions, length and width of columns were studied. A comparative study of modification of adsorbent was also done for which rice straws were modified with EDTA, acids, bases, and volatile organic solvents. Base modified adsorbents have shown an increase in adsorption capacity while acid modified adsorbents proved to be the poor adsorbents for metal ions similarly ash of rice straws used as adsorbent given higher adsorption and EDTA modified adsorbents have shown least adsorption of metal ions. Polar volatile organic solvents modified adsorbent gave less adsorption efficiency and non polar adsorbent shown no influence on Pb (II) uptake capacity of rice straws. Rice straws proved to be the best biosorbent for Pb(II) in aqueous solution. The biosorption characteristics fit well with Langmuir and Freundlich isotherm. (author)

  9. Design and screening of ASIC inhibitors based on aromatic diamidines for combating neurological disorders.

    Science.gov (United States)

    Chen, Xuanmao; Orser, Beverley A; MacDonald, John F

    2010-12-01

    Acid sensing ion channels (ASICs) are implicated in various brain functions including learning and memory and are involved in a number of neurological disorders such as pain, ischemic stroke, depression, and multiple sclerosis. We have recently defined ASICs as one of receptor targets of aromatic diamidines in neurons. Aromatic diamidines are DNA-binding agents and have long been used in the treatment of leishmaniasis, trypanosomiasis, pneumocystis pneumonia and babesiosis. Moreover, some aromatic diamidines are used as skin-care and baby products and others have potential to suppress tumor growth or to combat malaria. A large number of aromatic diamidines or analogs have been synthesized. Many efforts are being made to optimize the therapeutic spectrum of aromatic diamidines, i.e. to reduce toxicity, increase oral bioavailability and enhance their penetration of the blood-brain barrier. Aromatic diamidines therefore provide a shortcut of screening for selective ASIC inhibitors with therapeutic potential. Intriguingly nafamostat, a protease inhibitor for treating acute pancreatitis, also inhibits ASIC activities. Aromatic diamidines and nafamostat have many similarities although they belong to distinct classes of medicinal agents for curing different diseases. Here we delineate background, clinical application and drug development of aromatic diamidines that could facilitate the screening for selective ASIC inhibitors for research purposes. Further studies may lead to a drug with therapeutic value and extend the therapeutic scope of aromatic diamidines to combat neurological diseases. Copyright © 2010 Elsevier B.V. All rights reserved.

  10. Presence and potential significance of aromatic-ketone groups in aquatic humic substances

    Science.gov (United States)

    Leenheer, J.A.; Wilson, M.A.; Malcolm, R.L.

    1987-01-01

    Aquatic humic- and fulvic-acid standards of the International Humic Substances Society were characterized, with emphasis on carbonyl-group nature and content, by carbon-13 nuclear-magnetic-resonance spectroscopy, proton nuclear-magnetic-resonance spectroscopy, and infrared spectroscopy. After comparing spectral results of underivatized humic and fulvic acids with spectral results of chemically modified derivatives, that allow improved observation of the carbonyl group, the data clearly indicated that aromatic ketone groups comprised the majority of the carbonyl-group content. About one ketone group per monocyclic aromatic ring was determined for both humic and fulvic acids. Aromatic-ketone groups were hypothesized to form by photolytic rearrangements and oxidation of phenolic ester and hydrocarbon precursors; these groups have potential significance regarding haloform formation in water, reactivity resulting from active hydrogen of the methyl and methylene adjacent to the ketone groups, and formation of hemiketal and lactol structures. Aromatic-ketone groups also may be the point of attachment between aliphatic and aromatic moieties of aquatic humic-substance structure. ?? 1987.

  11. Identification and quantification of seven fused aromatic rings C26H14 peri-condensed benzenoid polycyclic aromatic hydrocarbons in a complex mixture of polycyclic aromatic hydrocarbons from coal tar.

    Science.gov (United States)

    Oña-Ruales, Jorge O; Ruiz-Morales, Yosadara; Wise, Stephen A

    2016-04-15

    A methodology for the characterization of groups of polycyclic aromatic hydrocarbons (PAHs) using a combination of normal phase liquid chromatography with ultraviolet-visible spectroscopy (NPLC/UV-vis) and gas chromatography with mass spectrometry (GC/MS) was used for the identification and quantification of seven fused aromatic rings C26H14 peri-condensed benzenoid polycyclic aromatic hydrocarbons, PAHs, in standard reference material (SRM) 1597a, complex mixture of PAHs from coal tar. The NPLC/UV-vis isolated the fractions based on the number of aromatic carbons and the GC/MS allowed the identification and quantification of five of the nine C26H14 PAH isomers; naphtho[1,2,3,4-ghi]perylene, dibenzo[b,ghi]perylene, dibenzo[b,pqr]perylene, naphtho[8,1,2-bcd]perylene, and dibenzo[cd,lm]perylene using a retention time comparison with authentic reference standards. For the other four benzenoid isomers with no available reference standards the following two approaches were used. First, the annellation theory was used to achieve the potential identification of benzo[qr]naphtho[3,2,1,8-defg]chrysene, and second, the elution distribution in the GC fractions was used to support the potential identification of benzo[qr]naphtho[3,2,1,8-defg]chrysene and to reach the tentative identifications of dibenzo[a,ghi]perylene, naphtho[7,8,1,2,3-pqrst]pentaphene, and anthra[2,1,9,8-opqra]naphthacene. It is the first time that naphtho[1,2,3,4-ghi]perylene, dibenzo[b,ghi]perylene, dibenzo[b,pqr]perylene, naphtho[8,1,2-bcd]perylene, and dibenzo[cd,lm]perylene are quantified, and the first time that benzo[qr]naphtho[3,2,1,8-defg]chrysene is potentially identified, in any sample, in any context. Copyright © 2016 Elsevier B.V. All rights reserved.

  12. Research on generating various polarization-modes in polarized illumination system

    Science.gov (United States)

    Huang, Jinping; Lin, Wumei; Fan, Zhenjie

    2013-08-01

    With the increase of the numerical aperture (NA), the polarization of light affects the imaging quality of projection lens more significantly. On the contrary, according to the mask pattern, the resolution of projection lens can be improved by using the polarized illumination. That is to say, using the corresponding polarized beam (or polarization-mode) along with the off-axis illumination will improve the resolution and the imaging quality of the of projection lens. Therefore, the research on the generation of various polarization modes and its conversion methods become more and more important. In order to realize various polarization modes in polarized illumination system, after read a lot of references, we provide a way that fitting for the illumination system with the wavelength of 193nm.Six polarization-modes and a depolarized mode are probably considered. Wave-plate stack is used to generate linearly polarization-mode, which have a higher degree polarization. In order to generate X-Y and Y-X polarization mode, the equipment consisting of four sectors of λ/2 wave plate was used. We combined 16 sectors of λ/2 wave plate which have different orientations of the "slow" axis to generate radial and azimuthal polarization. Finally, a multi-polarization control device was designed. Using the kind of multi-polarization control device which applying this method could help to choose the polarization modes conveniently and flexibility for the illumination system.

  13. Polarization properties of linearly polarized parabolic scaling Bessel beams

    Energy Technology Data Exchange (ETDEWEB)

    Guo, Mengwen; Zhao, Daomu, E-mail: zhaodaomu@yahoo.com

    2016-10-07

    The intensity profiles for the dominant polarization, cross polarization, and longitudinal components of modified parabolic scaling Bessel beams with linear polarization are investigated theoretically. The transverse intensity distributions of the three electric components are intimately connected to the topological charge. In particular, the intensity patterns of the cross polarization and longitudinal components near the apodization plane reflect the sign of the topological charge. - Highlights: • We investigated the polarization properties of modified parabolic scaling Bessel beams with linear polarization. • We studied the evolution of transverse intensity profiles for the three components of these beams. • The intensity patterns of the cross polarization and longitudinal components can reflect the sign of the topological charge.

  14. Photocatalytic oxidation of polycyclic aromatic hydrocarbons: Intermediates identification and toxicity testing

    International Nuclear Information System (INIS)

    Woo, O.T.; Chung, W.K.; Wong, K.H.; Chow, Alex T.; Wong, P.K.

    2009-01-01

    Polycyclic aromatic hydrocarbons (PAHs) are hydrophobic pollutants and their low water solubility limits their degradation in aqueous solution. The presence of water-miscible solvent such as acetone can increase the water solubility of PAHs, however acetone will also affect the degradation of PAH. In this study the effects of acetone on the photocatalytic degradation efficiency and pathways of 5 selected PAHs, namely naphthalene (2 rings), acenaphthylene (3 rings), phenanthrene (3 rings), anthracene (3 rings) and benzo[a]anthracene (4 rings) were investigated. The Microtox toxicity test was used to determine whether the PCO system can completely detoxify the parental PAHs and its intermediates. The addition of 16% acetone can greatly alter the degradation pathway of naphthalene and anthracene. Based on intermediates identified from degradation of the 5 PAHs, the location of parental PAHs attacked by reactive free radicals can be correlated with the localization energies of different positions of the compound. For toxicity analysis, irradiation by UV light was found to induce acute toxicity by generating intermediates/degradation products from PAHs and possibly acetone. Lastly, all PAHs (10 mg l -1 ) can be completely detoxified by titanium dioxide (100 mg l -1 ) within 24 h under UVA irradiation (3.9 mW cm -2 ).

  15. HPLC and MS/MS study of polar contaminants in a wetland adjoining a sour-gas plant

    International Nuclear Information System (INIS)

    Dickson, L.C.; Headley, J.V.; Peru, K.; Spiegel, K.; Gandrass, J.

    1995-01-01

    An analytical methodology was developed for target analyses and broad spectrum characterization of polar contaminants such as nitrogenous and organosulfur compounds in wetlands using the complementary techniques of HPLC with electrochemical (EC) detection and tandem MS with probe and electrospray ionization. Tandem MS was well suited for the identification and quantification of mixtures of polar compounds in water samples and soil extracts, while HPLC-EC provided sensitive detection of compounds transparent to MS detection and conventional methods. The usefulness of the methodology is demonstrated by studying the removal of polar contaminants from a wetland in western Canada affected by releases of hydrocarbon-rich condensate and free product from an adjoining sour-gas plant. The concern is that the mobile water-soluble polar contaminants may not be as efficiently attenuated by volatilization or adsorption processes as the more hydrophobic hydrocarbons and that some of the polar toxic compounds may break through to contaminate groundwater and surface waters. Samples of groundwater, surface water, and aqueous soil extracts were analyzed to quantify levels of polar contaminants in the presence of high concentrations of hydrocarbons. The use of water extracts reduced the background interference from hydrocarbons and other non-polar compounds that were present in the soil samples. HPLC-EC was used to quantify the target compounds that included monoethanolamine, diethanolamine and methyldiethanolamine and sulfolane-derived compounds while tandem MS was used to identify related compounds and degradation products. Influent concentrations were in the ppm range and discharge concentrations were in the ppb range

  16. Effects of sulfur and aromatic contents in gasoline on motorcycle emissions

    Science.gov (United States)

    Yao, Yung-Chen; Tsai, Jiun-Horng; Chang, An-Lin; Jeng, Fu-Tien

    By investigating the effect of sulfur and aromatic contents in gasoline on the criteria pollutant emissions [CO, total hydrocarbons (THCs), and NO x] and on air toxics in the exhaust from a non-catalyst four-stroke motorcycle engine, inferences can be made concerning the effect of fuel composition on motorcycle emissions. The fuels were blended with different contents of sulfur (40 and 150 ppmw) and aromatics (20 and 30 vol%). The data indicate that the sulfur content does not correlate with the emissions of the criteria pollutants from the catalyst free engine. Instead, lowering aromatic content in gasoline reduced the THC emission by over 30%, especially in the cruising test. The NO x emission, however, showed an inverse correlation with the aromatic content in gasoline. While a reduction of aromatic content in gasoline may decrease emissions of benzene and toluene, it will increase the emission of aldehyde. Since the percentage changes of emission factor of THC and air toxics in the motorcycle were larger than those in passenger cars, the benefit of emission reduction due to fuel composition changes in motorcycles may have significant impacts in health risk analysis.

  17. Development of aromatic giant-embryo rice by molecular marker-assisted selection

    Directory of Open Access Journals (Sweden)

    ZHU Yingdong

    2013-12-01

    Full Text Available Aromatic rice is loved for its distinctive aroma when cooking and eating.In this research,aromatic normal-embryo rice and non-aromatic giant-embryo rice,"Shangshida No.5",both bred by our laboratory,were selected as the parents for the hybridization.We used conventional breeding techniques as well as fragrance gene marker-assisted selection to derive new aromatic giant-embryo rice "Shangshida No.8".By comparing the agronomic and yield characters of "Shangshida No.5" and "Shangshida No.8",the average of filled grains per panicle of "Shangshida No.5" exceeds "Shangshida No.8" very significantly,while the average of effective panicles of "Shangshida No.8" is slightly more than "Shangshida No.5".Also,in the weight of thousand grains "Shangshida No.8" is slightly heavier than "Shangshida No.5".Thus,their grain weights per plant are close,29.10 g and 28.92 g respectively.By comparing the traits of rice embryo,there is no significant difference in embryo weight and volume.Also,there is no significant difference in weight ratio and volume ratio of embryo.This research has laid a solid foundation for further market development and application of aromatic giant-embryo rice.

  18. Aromatic Amino Acids-Guanidinium Complexes through Cation-π Interactions

    Directory of Open Access Journals (Sweden)

    Cristina Trujillo

    2015-05-01

    Full Text Available Continuing with our interest in the guanidinium group and the different interactions than can establish, we have carried out a theoretical study of the complexes formed by this cation and the aromatic amino acids (phenylalanine, histidine, tryptophan and tyrosine using DFT methods and PCM-water solvation. Both hydrogen bonds and cation-π interactions have been found upon complexation. These interactions have been characterized by means of the analysis of the molecular electron density using the Atoms-in-Molecules approach as well as the orbital interactions using the Natural Bond Orbital methodology. Finally, the effect that the cation-π and hydrogen bond interactions exert on the aromaticity of the corresponding amino acids has been evaluated by calculating the theoretical NICS values, finding that the aromatic character was not heavily modified upon complexation.

  19. Computer Simulations Reveal Multiple Functions for Aromatic Residues in Cellulase Enzymes (Fact Sheet)

    Energy Technology Data Exchange (ETDEWEB)

    2012-07-01

    NREL researchers use high-performance computing to demonstrate fundamental roles of aromatic residues in cellulase enzyme tunnels. National Renewable Energy Laboratory (NREL) computer simulations of a key industrial enzyme, the Trichoderma reesei Family 6 cellulase (Cel6A), predict that aromatic residues near the enzyme's active site and at the entrance and exit tunnel perform different functions in substrate binding and catalysis, depending on their location in the enzyme. These results suggest that nature employs aromatic-carbohydrate interactions with a wide variety of binding affinities for diverse functions. Outcomes also suggest that protein engineering strategies in which mutations are made around the binding sites may require tailoring specific to the enzyme family. Cellulase enzymes ubiquitously exhibit tunnels or clefts lined with aromatic residues for processing carbohydrate polymers to monomers, but the molecular-level role of these aromatic residues remains unknown. In silico mutation of the aromatic residues near the catalytic site of Cel6A has little impact on the binding affinity, but simulation suggests that these residues play a major role in the glucopyranose ring distortion necessary for cleaving glycosidic bonds to produce fermentable sugars. Removal of aromatic residues at the entrance and exit of the cellulase tunnel, however, dramatically impacts the binding affinity. This suggests that these residues play a role in acquiring cellulose chains from the cellulose crystal and stabilizing the reaction product, respectively. These results illustrate that the role of aromatic-carbohydrate interactions varies dramatically depending on the position in the enzyme tunnel. As aromatic-carbohydrate interactions are present in all carbohydrate-active enzymes, the results have implications for understanding protein structure-function relationships in carbohydrate metabolism and recognition, carbon turnover in nature, and protein engineering

  20. Organic high ionic strength aqueous two-phase solvent system series for separation of ultra-polar compounds by spiral high-speed counter-current chromatography

    Science.gov (United States)

    Zeng, Yun; Liu, Gang; Ma, Ying; Chen, Xiaoyuan; Ito, Yoichiro

    2011-01-01

    Existing two-phase solvent systems for high-speed countercurrent chromatography cover the separation of hydrophobic to moderately polar compounds, but often fail to provide suitable partition coefficient values for highly polar compounds such as sulfonic acids, catecholamines and zwitter ions. The present paper introduces a new solvent series which can be applied for the separation of these polar compounds. It is composed of 1-butanol, ethanol, saturated ammonium sulfate and water at various volume ratios and consists of a series of 10 steps which are arranged according to the polarity of the solvent system so that the two-phase solvent system with suitable K values for the target compound(s) can be found in a few steps. Each solvent system gives proper volume ratio and high density difference between the two phases to provide a satisfactory level of retention of the stationary phase in the spiral column assembly. The method is validated by partition coefficient measurement of four typical polar compounds including methyl green (basic dye), tartrazine (sulfonic acid), tyrosine (zwitter ion) and epinephrine (a catecholamine), all of which show low partition coefficient values in the polar 1-butanol-water system. The capability of the method is demonstrated by separation of three catecholamines. PMID:22033108

  1. Removal of polycyclic aromatic hydrocarbons in soil spiked with model mixtures of petroleum hydrocarbons and heterocycles using biosurfactants from Rhodococcus ruber IEGM 231.

    Science.gov (United States)

    Ivshina, Irina; Kostina, Ludmila; Krivoruchko, Anastasiya; Kuyukina, Maria; Peshkur, Tatyana; Anderson, Peter; Cunningham, Colin

    2016-07-15

    Removal of polycyclic aromatic hydrocarbons (PAHs) in soil using biosurfactants (BS) produced by Rhodococcus ruber IEGM 231 was studied in soil columns spiked with model mixtures of major petroleum constituents. A crystalline mixture of single PAHs (0.63g/kg), a crystalline mixture of PAHs (0.63g/kg) and polycyclic aromatic sulfur heterocycles (PASHs), and an artificially synthesized non-aqueous phase liquid (NAPL) containing PAHs (3.00g/kg) dissolved in alkanes C10-C19 were used for spiking. Percentage of PAH removal with BS varied from 16 to 69%. Washing activities of BS were 2.5 times greater than those of synthetic surfactant Tween 60 in NAPL-spiked soil and similar to Tween 60 in crystalline-spiked soil. At the same time, amounts of removed PAHs were equal and consisted of 0.3-0.5g/kg dry soil regardless the chemical pattern of a model mixture of petroleum hydrocarbons and heterocycles used for spiking. UV spectra for soil before and after BS treatment were obtained and their applicability for differentiated analysis of PAH and PASH concentration changes in remediated soil was shown. The ratios A254nm/A288nm revealed that BS increased biotreatability of PAH-contaminated soils. Copyright © 2016 Elsevier B.V. All rights reserved.

  2. Estimating release of polycyclic aromatic hydrocarbons from coal-tar contaminated soil at manufactured gas plant sites. Final report

    International Nuclear Information System (INIS)

    Lee, L.S.

    1998-04-01

    One of EPRI's goals regarding the environmental behavior of organic substances consists of developing information and predictive tools to estimate the release potential of polycyclic aromatic hydrocarbons (PAHs) from contaminated soils at manufactured gas (MGP) plant sites. A proper assessment of the distribution of contaminants under equilibrium conditions and the potential for mass-transfer constraints is essential in evaluating the environmental risks of contaminants in the subsurface at MGP sites and for selecting remediation options. The results of this research provide insights into estimating maximum release concentrations of PAHs from MGP soils that have been contaminated by direct contact with the tar or through years of contact with contaminated groundwater. Attention is also given to evaluating the use of water-miscible cosolvents for estimating aqueous phase concentrations, and assessing the role of mass-transfer constraints in the release of PAHs from MGP site soils

  3. Porous Aromatic Framework 48/Gel Hybrid Material Coated Solid-Phase Microextraction Fiber for the Determination of the Migration of Styrene from Polystyrene Food Contact Materials.

    Science.gov (United States)

    Jin, Yuanyuan; Li, Zhongyue; Yang, Lei; Xu, Jun; Zhao, Le; Li, Zhonghao; Niu, Jiajia

    2017-01-17

    A novel solid-phase microextraction (SPME) fiber was fabricated by a porous aromatic framework 48 (PAF-48)/gel hybrid material through a sol-gel process. PAF-48 is a porous organic framework (POF) material that was polymerized from 1,3,5-triphenylbenzene. The uniform pore structure, high surface area, continuous conjugate network, and hydrophobicity make PAF-48 expected to have special abilities to absorb and extract styrene as well as some other harmful volatile aromatic compounds (VACs). The PAF-48/gel-coated fiber was explored for the extraction of styrene and six VACs (benzene, toluene, ethylbenzene, and xylenes) from aqueous food simulants followed by gas chromatography (GC) separation. The fiber was found to be very sensitive for the determination of the target molecules with wide linear ranges (0.1-200 or 500 μg·kg -1 ), low limits of detection (LODs, 0.003-0.060 μg·kg -1 ), acceptable precisions (intraday relative standard deviation, RSD 200 times). Particularly for styrene, the PAF-48/gel-coated fiber exhibited a much lower LOD (0.006 μg·kg -1 ) compared with most of the reported fibers. Moreover, the PAF-48/gel-coated fiber had a high extraction selectivity for styrene and VACs over alcohols, phenols, aromatic amines, and alkanes and show a molecular sieving effect for the different molecule sizes. Finally, the PAF-48/gel-coated SPME fiber was successfully applied in GC for the determination of the specific migrations of styrene and VACs from polystyrene (PS) plastic food contact materials (FCMs).

  4. Progress in aqueous rechargeable batteries

    OpenAIRE

    Jilei Liu; Chaohe Xu; Zhen Chen; Shibing Ni; Ze Xiang Shen

    2018-01-01

    Over the past decades, a series of aqueous rechargeable batteries (ARBs) were explored, investigated and demonstrated. Among them, aqueous rechargeable alkali-metal ion (Li+, Na+, K+) batteries, aqueous rechargeable-metal ion (Zn2+, Mg2+, Ca2+, Al3+) batteries and aqueous rechargeable hybrid batteries are standing out due to peculiar properties. In this review, we focus on the fundamental basics of these batteries, and discuss the scientific and/or technological achievements and challenges. B...

  5. Electrochemical measurements for the corrosion inhibition of mild steel in 1 M hydrochloric acid by using an aromatic hydrazide derivative

    Directory of Open Access Journals (Sweden)

    P. Preethi Kumari

    2017-07-01

    Full Text Available The influence of an aromatic hydrazide derivative, 2-(3,4,5-trimethoxybenzylidene hydrazinecarbothioamide (TMBHC as corrosion inhibitor on mild steel in 1 M hydrochloric acid was studied by Tafel polarization and electrochemical impedance spectroscopy (EIS technique. The results showed that the inhibition efficiency (% IE of TMBHC increased with increasing inhibitor concentrations and also with increase in temperatures. TMBHC acted as a mixed type of inhibitor and its adsorption on mild steel surface was found to follow Langmuir’s adsorption isotherm. The evaluation of thermodynamic and activation parameters indicated that the adsorption of TMBHC takes place through chemisorption. The formation of protective film was further confirmed by scanning electron microscopy (SEM.

  6. Accelerated simulations of aromatic polymers: application to polyether ether ketone (PEEK)

    Science.gov (United States)

    Broadbent, Richard J.; Spencer, James S.; Mostofi, Arash A.; Sutton, Adrian P.

    2014-10-01

    For aromatic polymers, the out-of-plane oscillations of aromatic groups limit the maximum accessible time step in a molecular dynamics simulation. We present a systematic approach to removing such high-frequency oscillations from planar groups along aromatic polymer backbones, while preserving the dynamical properties of the system. We consider, as an example, the industrially important polymer, polyether ether ketone (PEEK), and show that this coarse graining technique maintains excellent agreement with the fully flexible all-atom and all-atom rigid bond models whilst allowing the time step to increase fivefold to 5 fs.

  7. Polarized nuclear target based on parahydrogen induced polarization

    OpenAIRE

    Budker, D.; Ledbetter, M. P.; Appelt, S.; Bouchard, L. S.; Wojtsekhowski, B.

    2012-01-01

    We discuss a novel concept of a polarized nuclear target for accelerator fixed-target scattering experiments, which is based on parahydrogen induced polarization (PHIP). One may be able to reach a 33% free-proton polarization in the ethane molecule. The potential advantages of such a target include operation at zero magnetic field, fast ($\\sim$100 Hz) polarization reversal, and operation with large intensity of an electron beam.

  8. Biodegradation Rates of Aromatic Contaminants in Biofilm Reactors

    DEFF Research Database (Denmark)

    Arcangeli, Jean-Pierre; Arvin, Erik

    1995-01-01

    This study has shown that microorganisms can adapt to degrade mixtures of aromatic pollutants at relatively high rates in the μg/l concentration range. The biodegradation rates of the following compounds were investigated in biofilm systems: aromatic hydrocarbons, phenol, methylphenols......-reducing conditions, toluene was easily biodegraded. The xylenes and ethylbenzene were degraded cometabolically if toluene was used as a primary carbon source; their removal was influenced by competitive inhibition with toluene. These interaction phenomena are discussed in this paper and a kinetic model taking...

  9. HP-SPME of volatile polycyclic aromatic hydrocarbons from water using multiwalled carbon nanotubes coated on a steel fiber through electrophoretic deposition

    Energy Technology Data Exchange (ETDEWEB)

    Maghsoudi, S.; Noroozian, E. [Shahid Bahonar Univ., Kerman (Iran, Islamic Republic of). Dept. of Chemistry

    2012-08-15

    A headspace solid-phase microextraction (SPME) method using a stainless steel wire electrophoretically coated with dodecylsulfate modified multiwalled carbon nanotubes was used for the gas chromatographic (GC) determination of polycyclic aromatic hydrocarbons (PAHs) in aqueous samples. Electrophoretic deposition was easily carried out from an aqueous sodium dodecylsulfate medium. The effects of various parameters on the efficiency of SPME process, such as extraction time, extraction temperature, ionic strength, desorption time, and desorption temperature were studied. Under optimized conditions, the detection limits for the various PAHs studied varied from 0.03 to 0.07 ng mL{sup -1}. The inter-day and intra-day relative standard deviations at a 10 ng mL{sup -1} concentration level (n = 7) using a single-fiber were from 5.5 to 9.7 and 4.1 to 8.5 %, respectively. The fiber-to-fiber RSD% (n = 3) was between 7.3 and 11.1 %. The linear ranges were between 0.1 and 100 ng mL{sup -1}. The method was successfully applied to the analysis of a real sample with the recoveries from 88 to 105 % for 5 ng mL{sup -1} and 89 to 101 % for 0.5 ng mL{sup -1} samples. (orig.)

  10. Zirconacyclopentadiene-annulated polycyclic aromatic hydrocarbons

    International Nuclear Information System (INIS)

    Kiel, Gavin R.; Ziegler, Micah S.; Tilley, T. Don

    2017-01-01

    Syntheses of large polycyclic aromatic hydrocarbons (PAHs) and graphene nanostructures demand methods that are capable of selectively and efficiently fusing large numbers of aromatic rings, yet such methods remain scarce. Herein, we report a new approach that is based on the quantitative intramolecular reductive cyclization of an oligo(diyne) with a low-valent zirconocene reagent, which gives a PAH with one or more annulated zirconacyclopentadienes (ZrPAHs). The efficiency of this process is demonstrated by a high-yielding fivefold intramolecular coupling to form a helical ZrPAH with 16 fused rings (from a precursor with no fused rings). Several other PAH topologies are also reported. Protodemetalation of the ZrPAHs allowed full characterization (including by X-ray crystallography) of PAHs containing one or more appended dienes with the ortho-quinodimethane (o-QDM) structure, which are usually too reactive for isolation and are potentially valuable for the fusion of additional rings by Diels-Alder reactions. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

  11. Zirconacyclopentadiene-annulated polycyclic aromatic hydrocarbons

    Energy Technology Data Exchange (ETDEWEB)

    Kiel, Gavin R.; Ziegler, Micah S.; Tilley, T. Don [Department of Chemistry, University of California, Berkeley, CA (United States)

    2017-04-18

    Syntheses of large polycyclic aromatic hydrocarbons (PAHs) and graphene nanostructures demand methods that are capable of selectively and efficiently fusing large numbers of aromatic rings, yet such methods remain scarce. Herein, we report a new approach that is based on the quantitative intramolecular reductive cyclization of an oligo(diyne) with a low-valent zirconocene reagent, which gives a PAH with one or more annulated zirconacyclopentadienes (ZrPAHs). The efficiency of this process is demonstrated by a high-yielding fivefold intramolecular coupling to form a helical ZrPAH with 16 fused rings (from a precursor with no fused rings). Several other PAH topologies are also reported. Protodemetalation of the ZrPAHs allowed full characterization (including by X-ray crystallography) of PAHs containing one or more appended dienes with the ortho-quinodimethane (o-QDM) structure, which are usually too reactive for isolation and are potentially valuable for the fusion of additional rings by Diels-Alder reactions. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

  12. Birds and polycyclic aromatic hydrocarbons

    Science.gov (United States)

    Albers, P.H.

    2006-01-01

    Polycyclic aromatic hydrocarbons (PAH) are present throughout the global environment and are produced naturally and by activities of humans. Effects of PAH on birds have been determined by studies employing egg injection, egg immersion, egg shell application, single and multiple oral doses, subcutaneous injection, and chemical analysis of field-collected eggs and tissue. The four-to six-ring aromatic compounds are the most toxic to embryos, young birds, and adult birds. For embryos, effects include death, developmental abnormalities, and a variety of cellular and biochemical responses. For adult and young birds, effects include reduced egg production and hatching, increased clutch or brood abandonment, reduced growth, increased organweights, and a variety of biochemical responses. Trophic level accumulation is unlikely. Environmental exposure to PAH in areas of high human population or habitats affected by recent petroleum spills might be sufficient to adversely affect reproduction. Evidence of long-term effects of elevated concentrations of environmental PAH on bird populations is very limited and the mechanisms of effect are unclear.

  13. Aqueous lithium air batteries

    Science.gov (United States)

    Visco, Steven J.; Nimon, Yevgeniy S.; De Jonghe, Lutgard C.; Petrov, Alexei; Goncharenko, Nikolay

    2017-05-23

    Aqueous Li/Air secondary battery cells are configurable to achieve high energy density and prolonged cycle life. The cells include a protected a lithium metal or alloy anode and an aqueous catholyte in a cathode compartment. The aqueous catholyte comprises an evaporative-loss resistant and/or polyprotic active compound or active agent that partakes in the discharge reaction and effectuates cathode capacity for discharge in the acidic region. This leads to improved performance including one or more of increased specific energy, improved stability on open circuit, and prolonged cycle life, as well as various methods, including a method of operating an aqueous Li/Air cell to simultaneously achieve improved energy density and prolonged cycle life.

  14. Production of aromatics from di- and polyoxygenates

    Energy Technology Data Exchange (ETDEWEB)

    Beck, Taylor; Blank, Brian; Jones, Casey; Woods, Elizabeth; Cortright, Randy

    2017-07-04

    Methods, catalysts, and reactor systems for producing in high yield aromatic chemicals and liquid fuels from a mixture of oxygenates comprising di- and polyoxygenates are disclosed. Also disclosed are methods, catalysts, and reactor systems for producing aromatic chemicals and liquid fuels from oxygenated hydrocarbons such as carbohydrates, sugars, sugar alcohols, sugar degradation products, and the like; and methods, catalysts, and reactor systems for producing the mixture of oxygenates from oxygenated hydrocarbons such as carbohydrates, sugars, sugar alcohols, sugar degradation products, and the like. The disclosed catalysts for preparing the mixture of oxygenates comprise a Ni.sub.nSn.sub.m alloy and a crystalline alumina support.

  15. Redox shuttles having an aromatic ring fused to a 1,1,4,4-tetrasubstituted cyclohexane ring

    Science.gov (United States)

    Weng, Wei; Zhang, Zhengcheng; Amine, Khalil

    2015-12-01

    An electrolyte includes an alkali metal salt; an aprotic solvent; and a redox shuttle additive including an aromatic compound having at least one aromatic ring fused with at least one non-aromatic ring, the aromatic ring having two or more oxygen or phosphorus-containing substituents.

  16. Aromaticity of benzene in condensed phases. A case of a benzene-water system

    Science.gov (United States)

    Zborowski, Krzysztof K.

    2014-05-01

    A theoretical Density Functional Theory study was performed for a benzene molecule in water cages. Two DFT functionals (B3LYP and BLYP) were employed. The optimized geometries of the studied clusters were used to calculate the aromaticity of benzene in a condensed phase using the aromaticity indices: HOMA, NICS, PDI, and H. The results were compared with aromaticity of a single benzene molecule in the gas phase and in the solvent environment provided by the PCM continuum model. It is argued that high aromaticity of benzene in the gas phase is retained in the water environment.

  17. Experimental and Theoretical Investigation of the Aromatic-Aromatic Interaction in Isolated Capped Dipeptides

    Czech Academy of Sciences Publication Activity Database

    Gloaguen, E.; Valdés, H.; Pagliarulo, F.; Pollet, R.; Tardivel, B.; Hobza, Pavel; Piuzzi, F.; Mons, M.

    2010-01-01

    Roč. 114, č. 9 (2010), s. 2973-2982 ISSN 1089-5639 R&D Projects: GA MŠk LC512 Institutional research plan: CEZ:AV0Z40550506 Keywords : aromatic residues interactions * Ac-Phe-Phe-NH2 dipeptides * Ac-Phe-D-Phe-NH2 dipeptides * correlated ab initio calculations Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.732, year: 2010

  18. Exploring the aqueous vertical ionization of organic molecules by molecular simulation and liquid microjet photoelectron spectroscopy.

    Science.gov (United States)

    Tentscher, Peter R; Seidel, Robert; Winter, Bernd; Guerard, Jennifer J; Arey, J Samuel

    2015-01-08

    To study the influence of aqueous solvent on the electronic energy levels of dissolved organic molecules, we conducted liquid microjet photoelectron spectroscopy (PES) measurements of the aqueous vertical ionization energies (VIEaq) of aniline (7.49 eV), veratrole alcohol (7.68 eV), and imidazole (8.51 eV). We also reanalyzed previously reported experimental PES data for phenol, phenolate, thymidine, and protonated imidazolium cation. We then simulated PE spectra by means of QM/MM molecular dynamics and EOM-IP-CCSD calculations with effective fragment potentials, used to describe the aqueous vertical ionization energies for six molecules, including aniline, phenol, veratrole alcohol, imidazole, methoxybenzene, and dimethylsulfide. Experimental and computational data enable us to decompose the VIEaq into elementary processes. For neutral compounds, the shift in VIE upon solvation, ΔVIEaq, was found to range from ≈-0.5 to -0.91 eV. The ΔVIEaq was further explained in terms of the influence of deforming the gas phase solute into its solution phase conformation, the influence of solute hydrogen-bond donor and acceptor interactions with proximate solvent molecules, and the polarization of about 3000 outerlying solvent molecules. Among the neutral compounds, variability in ΔVIEaq appeared largely controlled by differences in solute-solvent hydrogen-bonding interactions. Detailed computational analysis of the flexible molecule veratrole alcohol reveals that the VIE is strongly dependent on molecular conformation in both gas and aqueous phases. Finally, aqueous reorganization energies of the oxidation half-cell ionization reaction were determined from experimental data or estimated from simulation for the six compounds aniline, phenol, phenolate, veratrole alcohol, dimethylsulfide, and methoxybenzene, revealing a surprising constancy of 2.06 to 2.35 eV.

  19. Development of second generation gold-supported palladium material with low-leaching and recyclable characteristics in aromatic amination.

    Science.gov (United States)

    Al-Amin, Mohammad; Arai, Satoshi; Hoshiya, Naoyoki; Honma, Tetsuo; Tamenori, Yusuke; Sato, Takatoshi; Yokoyama, Mami; Ishii, Akira; Takeuchi, Masashi; Maruko, Tomohiro; Shuto, Satoshi; Arisawa, Mitsuhiro

    2013-08-02

    An improved process for the preparation of sulfur-modified gold-supported palladium material [SAPd, second generation] is presented. The developed preparation method is safer and generates less heat (aqueous Na2S2O8 and H2SO4) for sulfur fixation on a gold surface, and it is superior to the previous method of preparing SAPd (first generation), which requires the use of the more heat-generating and dangerous piranha solution (concentrated H2SO4 and 35% H2O2) in the sulfur fixation step. This safer and improved preparation method is particularly important for the mass production of SAPd (second generation) for which the catalytic activity was examined in ligand-free Buchwald-Hartwig cross-coupling reactions. The catalytic activities were the same between the first and second generation SAPds in aromatic aminations, but the lower palladium leaching properties and safer preparative method of second generation SAPd are a significant improvement over the first generation SAPd.

  20. Adsorption and Oxidation of Aromatic Amines on Metal(II Hexacyanocobaltate(III Complexes: Implication for Oligomerization of Exotic Aromatic Compounds

    Directory of Open Access Journals (Sweden)

    Rachana Sharma

    2017-03-01

    Full Text Available Based on the hypothesis on the presence of double metal cyanides in the primordial oceans, a series of nano-sized metal(II hexacyanocobaltate(III (MHCCo with the general formula: M3[Co(CN6]2•xH2O (where M = Zn, Fe, Ni and Mn has been synthesized. Surface interaction of aromatic amines, namely aniline, 4-chloroaniline, 4-methylaniline and 4-methoxyaniline with MHCCo particles has been carried out at the concentration range of 100–400 μM at pH~7.0. The percentage binding of aromatic amines on MHCCo surface was found to be in the range of 84%–44%. The trend in adsorption was in accordance to the relative basicity of the studied amines. At the experimental pH, amines reacted rapidly with the surface of the iron(II hexacyanocobaltate, producing colored products that were analyzed by Gas Chromatography Mass Spectroscopy (GC-MS. GC-MS analysis of the colored products demonstrated the formation of dimers of the studied aromatic amines. Surface interaction of aromatic amines with MHCCo was studied by Fourier Transform Infrared (FT-IR spectroscopy and Field Emission Scanning Electron Microscopy (FE-SEM. The change in amine characteristic frequencies, as observed by FT-IR, suggests that interaction took place through the NH2 group on amines with metal ions of hexacyanocobaltate complexes. FE-SEM studies revealed the adherence of 4-methoxyaniline on zinc hexacyanocobaltate particles surface. We proposed that MHCCo might have been formed under the conditions on primitive Earth and may be regarded as an important candidate for concentrating organic molecules through the adsorption process.

  1. In situ electro-osmotic cleanup of tar contaminated soil—Removal of polycyclic aromatic hydrocarbons

    KAUST Repository

    Lima, Ana T.

    2012-12-01

    An in situ electro-osmosis experiment was set up in a tar contaminated clay soil in Olst, the Netherlands, at the site of a former asphalt factory. The main goal of this experiment was to remove polycyclic aromatic hydrocarbons (PAHs) from the contaminated clay layer by applying an electric gradient of 12 V m-1 across the soil over an electrode distance of 1 m. With the movement of water by electro-osmosis and the addition of a non-ionic surfactant (Tween 80), the non-polar PAHs were dragged along by convection and removed from the fine soil fraction. Soil samples were taken at the start and after 159 days at the end of the experiment. Water at the electrode wells was sampled regularly during the course of the experiment. The results reflect the heterogeneity of the soil characteristics and show the PAH concentrations within the experimental set up. After first having been released into the anolyte solution due to extraction by Tween 80 and subsequent diffusion, PAH concentrations increased significantly in the electrode reservoirs at the cathode side after 90 days of experiment. Although more detailed statistical analysis is necessary to quantify the efficiency of the remediation, it can be concluded that the use of electro-osmosis together with a non-ionic surfactant is a feasible technique to mobilize non-polar organic contaminants in clayey soils. Crown Copyright © 2011 Published by Elsevier Ltd. All rights reserved.

  2. Radioluminescence of aromatic molecule solutions in atactic and isotactic polystyrene

    International Nuclear Information System (INIS)

    Lisovskaya, I.A.; Alfimov, M.V.; Milinchuk, V.K.; Skvortsov, V.G.

    1975-01-01

    The generation of excited states of naphthalene-d 8 and carbazole molecules in polystyrene (PS) under X-ray illumination was investigated using luminescence method. A comparison of the concentration dependences of radioluminescence of the aromatic additives to solid PS and to toluene as well as the pattern of concentration versus photoluminescence of naphthalene-d 8 in PS demonstrates that unlike toluene there is no singlet-triplet conversion in PS owing to the formation of excimers. It is shown that the excited ststes of the aromatic additives in PS are populated under radiolysis via an energy transfer from singlet to triplet molecules of the matrix. Under the radiolysis the excited states of PS molecules may generate upon charge recombination. A comparison of radio luminescence spectra of the corresponding aromatic additives in two isomeric PS structures (atacting and isotactic) shows different processes with charge participation. The difference detected in the radioluminescence spectra of aromatic additives in the atactic and isotactic PS explained by the greater number of defects in atactic PS competing with the polymer molecule ion for charge capture

  3. Tuning aromaticity in trigonal alkaline earth metal clusters and their alkali metal salts.

    Science.gov (United States)

    Jiménez-Halla, J Oscar C; Matito, Eduard; Blancafort, Lluís; Robles, Juvencio; Solà, Miquel

    2009-12-01

    In this work, we analyze the geometry and electronic structure of the [X(n)M(3)](n-2) species (M = Be, Mg, and Ca; X = Li, Na, and K; n = 0, 1, and 2), with special emphasis on the electron delocalization properties and aromaticity of the cyclo-[M(3)](2-) unit. The cyclo-[M(3)](2-) ring is held together through a three-center two-electron bond of sigma-character. Interestingly, the interaction of these small clusters with alkali metals stabilizes the cyclo-[M(3)](2-) ring and leads to a change from sigma-aromaticity in the bound state of the cyclo-[M(3)](2-) to pi-aromaticity in the XM(3) (-) and X(2)M(3) metallic clusters. Our results also show that the aromaticity of the cyclo-[M(3)](2-) unit in the X(2)M(3) metallic clusters depends on the nature of X and M. Moreover, we explored the possibility for tuning the aromaticity by simply moving X perpendicularly to the center of the M(3) ring. The Na(2)Mg(3), Li(2)Mg(3), and X(2)Ca(3) clusters undergo drastic aromaticity alterations when changing the distance from X to the center of the M(3) ring, whereas X(2)Be(3) and K(2)Mg(3) keep its aromaticity relatively constant along this process. (c) 2009 Wiley Periodicals, Inc.

  4. Fusion of a polarized projectile with a polarized target

    International Nuclear Information System (INIS)

    Christley, J.A.; Johnson, R.C.; Thompson, I.J.

    1995-01-01

    The fusion cross sections for a polarized target with both unpolarized and polarized projectiles are studied. Expressions for the observables are given for the case when both nuclei are polarized. Calculations for fusion of an aligned 165 Ho target with 16 O and polarized 7 Li beams are presented

  5. The effects of polycyclic aromatic hydrocarbons on the immune system of fish: A review

    International Nuclear Information System (INIS)

    Reynaud, S.; Deschaux, P.

    2006-01-01

    Polycyclic aromatic hydrocarbons are an important class of environmental pollutants that are known to be carcinogenic and immunotoxic. This review summarizes the diverse literature on the effects of these pollutants on innate and acquired immunity in fish and the mechanism of PAH-induced immunotoxicity. Among innate immune parameters, many authors have focused on macrophage activities in fish exposed to polycyclic aromatic hydrocarbons. Macrophage respiratory burst appears especially sensitive to polycyclic aromatic hydrocarbons. Among acquired immune parameters, lymphocyte proliferation appears highly sensitive to polycyclic aromatic hydrocarbon exposure. However, the effects of polycyclic aromatic hydrocarbons on both specific and non-specific immunity are contradictory and depend on the mode of exposure, the dose used or the species studied. In contrast to mammals, fewer studies have been done in fish to determine the mechanism of polycyclic aromatic hydrocarbon-induced toxicity. This phenomenon seems to implicate different intracellular mechanisms such as metabolism by cytochrome P4501A, binding to the Ah-receptor, or increased intracellular calcium. Advances in basic knowledge of fish immunity should lead to improvements in monitoring fish health and predicting the impact of polycyclic aromatic hydrocarbons on fish populations, which is a fundamental ecotoxicological goal

  6. The effects of polycyclic aromatic hydrocarbons on the immune system of fish: A review

    Energy Technology Data Exchange (ETDEWEB)

    Reynaud, S. [Laboratoire d' Ecologie Alpine. UMR CNRS 5553. Universite Joseph Fourier. BP 53. 38041 Grenoble cedex 9 (France) and Laboratory of General and Comparative Immunophysiology, Science Teaching and Research Unit, 123, av. Albert Thomas, 87060 Limoges (France)]. E-mail: stephane.reynaud@ujf-grenoble.fr; Deschaux, P. [Laboratory of General and Comparative Immunophysiology, Science Teaching and Research Unit, 123, av. Albert Thomas, 87060 Limoges (France)

    2006-05-01

    Polycyclic aromatic hydrocarbons are an important class of environmental pollutants that are known to be carcinogenic and immunotoxic. This review summarizes the diverse literature on the effects of these pollutants on innate and acquired immunity in fish and the mechanism of PAH-induced immunotoxicity. Among innate immune parameters, many authors have focused on macrophage activities in fish exposed to polycyclic aromatic hydrocarbons. Macrophage respiratory burst appears especially sensitive to polycyclic aromatic hydrocarbons. Among acquired immune parameters, lymphocyte proliferation appears highly sensitive to polycyclic aromatic hydrocarbon exposure. However, the effects of polycyclic aromatic hydrocarbons on both specific and non-specific immunity are contradictory and depend on the mode of exposure, the dose used or the species studied. In contrast to mammals, fewer studies have been done in fish to determine the mechanism of polycyclic aromatic hydrocarbon-induced toxicity. This phenomenon seems to implicate different intracellular mechanisms such as metabolism by cytochrome P4501A, binding to the Ah-receptor, or increased intracellular calcium. Advances in basic knowledge of fish immunity should lead to improvements in monitoring fish health and predicting the impact of polycyclic aromatic hydrocarbons on fish populations, which is a fundamental ecotoxicological goal.

  7. Impact of using fishing boat fuel with high poly aromatic content on the emission of polycyclic aromatic hydrocarbons from the diesel engine

    Science.gov (United States)

    Lin, Yuan-Chung; Lee, Wen-Jhy; Li, Hsing-Wang; Chen, Chung-Ban; Fang, Guor-Cheng; Tsai, Perng-Jy

    Because of the fishery subsidy policy, the fishing boat fuel oil (FBFO) exemption from commodity taxes, business taxes and air pollution control fees, resulted in the price of FBFO was ˜50% lower than premium diesel fuel (PDF) in Taiwan. It is estimated that ˜650,000 kL FBFO was illegally used by traveling diesel-vehicles (TDVs) with a heavy-duty diesel engine (HDDE), which accounted for ˜16.3% of the total diesel fuel consumed by TDVs. In this study, sulfur, poly aromatic and total-aromatic contents in both FBFO and PDF were measured and compared. Exhaust emissions of polycyclic aromatic hydrocarbons (PAHs) and their carcinogenic potencies (BaP eq) from a HDDE under transient cycle testing for both FBFO and PDF were compared and discussed. Finally, the impact caused by the illegal use of FBFO on the air quality was examined. Results show that the mean sulfur-, poly aromatic and aromatic-contents in FBFO were 43.0, 3.89 and 1.04 times higher than that of PDF, respectively. Emission factors of total-PAHs and total-BaP eq obtained by utilizing FBFO were 51.5 and 0.235 mg L -1-Fuel, which were 3.41 and 5.82 times in magnitude higher than obtained by PDF, respectively. The estimated annual emissions of total-PAHs and total-BaP eq to the ambient environment due to the illegally used FBFO were 23.6 and 0.126 metric tons, respectively, which resulted in a 17.9% and a 25.0% increment of annual emissions from all mobile sources, respectively. These results indicated that the FBFO used illegally by TDVs had a significant impact on PAH emissions to the ambient environment.

  8. Physicochemical Mechanisms of Synergistic Biological Action of Combinations of Aromatic Heterocyclic Compounds

    OpenAIRE

    Evstigneev, Maxim P.

    2013-01-01

    The mechanisms of synergistic biological effects observed in the simultaneous use of aromatic heterocyclic compounds in combination are reviewed, and the specific biological role of heteroassociation of aromatic molecules is discussed.

  9. Irradiated aromatic polysulphones of increased flow resistance and molecular weight

    International Nuclear Information System (INIS)

    Staniland, P.A.; Jarrett, W.G.

    1976-01-01

    Aromatic polymers of increased resistance to flow and molecular weight are obtained by irradiation using β-rays or γ-rays at temperatures up to 400 0 C of an aromatic polymer whose molecular chains comprise benzenoid groups and bivalent linking groups, and where irradiation is γ-rays by heating subsequent to irradiation at 200 to 400 0 C

  10. Unleaded gasoline with reduction in benzene and aromatics

    International Nuclear Information System (INIS)

    Ahmed, I.

    2003-01-01

    The trend today is towards making gasoline more environment and human friendly or in other words making gasoline a really clean fuel. This paper covers the ill effects of benzene and aromatics and the driving force behind their reduction in gasoline worldwide. It addresses health concerns specifically, and the theme is unleaded gasoline without simultaneously addressing reduction in benzene and aromatics is more harmful. The paper cites worldwide case studies, and also the World Bank (WB), Government of Pakistan (GoP), and United Nations (UN) efforts in this area in Pakistan. (author)

  11. Update of the Polar SWIFT model for polar stratospheric ozone loss (Polar SWIFT version 2)

    Science.gov (United States)

    Wohltmann, Ingo; Lehmann, Ralph; Rex, Markus

    2017-07-01

    The Polar SWIFT model is a fast scheme for calculating the chemistry of stratospheric ozone depletion in polar winter. It is intended for use in global climate models (GCMs) and Earth system models (ESMs) to enable the simulation of mutual interactions between the ozone layer and climate. To date, climate models often use prescribed ozone fields, since a full stratospheric chemistry scheme is computationally very expensive. Polar SWIFT is based on a set of coupled differential equations, which simulate the polar vortex-averaged mixing ratios of the key species involved in polar ozone depletion on a given vertical level. These species are O3, chemically active chlorine (ClOx), HCl, ClONO2 and HNO3. The only external input parameters that drive the model are the fraction of the polar vortex in sunlight and the fraction of the polar vortex below the temperatures necessary for the formation of polar stratospheric clouds. Here, we present an update of the Polar SWIFT model introducing several improvements over the original model formulation. In particular, the model is now trained on vortex-averaged reaction rates of the ATLAS Chemistry and Transport Model, which enables a detailed look at individual processes and an independent validation of the different parameterizations contained in the differential equations. The training of the original Polar SWIFT model was based on fitting complete model runs to satellite observations and did not allow for this. A revised formulation of the system of differential equations is developed, which closely fits vortex-averaged reaction rates from ATLAS that represent the main chemical processes influencing ozone. In addition, a parameterization for the HNO3 change by denitrification is included. The rates of change of the concentrations of the chemical species of the Polar SWIFT model are purely chemical rates of change in the new version, whereas in the original Polar SWIFT model, they included a transport effect caused by the

  12. Separation of polar betalain pigments from cacti fruits of Hylocereus polyrhizus by ion-pair high-speed countercurrent chromatography.

    Science.gov (United States)

    Wybraniec, Sławomir; Stalica, Paweł; Jerz, Gerold; Klose, Bettina; Gebers, Nadine; Winterhalter, Peter; Spórna, Aneta; Szaleniec, Maciej; Mizrahi, Yosef

    2009-10-09

    Polar betacyanin pigments together with betaxanthins from ripe cactus fruits of Hylocereus polyrhizus (Cactaceae) were fractionated by means of preparative ion-pair high-speed countercurrent chromatography (IP-HSCCC) also using the elution-extrusion (EE) approach for a complete pigment recovery. HSCCC separations were operated in the classical 'head-to-tail' mode with an aqueous mobile phase. Different CCC solvent systems were evaluated in respect of influence and effectiveness of fractionation capabilities to separate the occurring pigment profile of H. polyrhizus. For that reason, the additions of two different volatile ion-pair forming perfluorinated carboxylic acids (PFCA) were investigated. For a direct comparison, five samples of Hylocereus pigment extract were run on preparative scale (900 mg) in 1-butanol-acetonitrile-aqueous TFA 0.7% (5:1:6, v/v/v) and the modified systems tert.-butyl methyl ether-1-butanol-acetonitrile-aqueous PFCA (2:2:1:5, v/v/v/v) using 0.7% and 1.0% trifluoroacetic acid (TFA) or heptafluorobutyric acid (HFBA) in the aqueous phase, respectively. The chemical affinity to the organic stationary CCC solvent phases and in consequence the retention of these highly polar betalain pigments was significantly increased by the use of the more lipophilic fluorinated ion-pair reagent HFBA instead of TFA. The HFBA additions separated more effectively the typical cacti pigments phyllocactin and hylocerenin from betanin as well as their iso-forms. Unfortunately, similar K(D) ratios and selectivity factors alpha around 1.0-1.1 in all tested solvent systems proved that the corresponding diastereomers, 15S-type pigments cannot be resolved from the 15R-epimers (iso-forms). Surprisingly, additions of the stronger ion-pair reagent (HFBA) resulted in a partial separation of hylocerenin from phyllocactin which were not resolved in the other solvent systems. The pigments were detected by means of HPLC-DAD and HPLC-electrospray ionization-MS using also

  13. Communication: Probing the absolute configuration of chiral molecules at aqueous interfaces

    Energy Technology Data Exchange (ETDEWEB)

    Lotze, Stephan, E-mail: lotze@amolf.nl; Versluis, Jan [FOM Institute for Atomic and Molecular Physics, Science Park 104, 1098 XG Amsterdam (Netherlands); Olijve, Luuk L. C.; Schijndel, Luuk van; Milroy, Lech G.; Voets, Ilja K. [Laboratory of Macromolecular and Organic Chemistry, Department of Chemical Engineering and Chemistry, and Institute for Complex Molecular Systems, Eindhoven University of Technology, P.O. Box 513, 5600 MB Eindhoven (Netherlands); Bakker, Huib J., E-mail: bakker@amolf.nl [FOM Institute AMOLF, Science Park 104, 1098 XG Amsterdam (Netherlands)

    2015-11-28

    We demonstrate that the enantiomers of chiral macromolecules at an aqueous interface can be distinguished with monolayer sensitivity using heterodyne-detected vibrational sum-frequency generation (VSFG). We perform VSFG spectroscopy with a polarization combination that selectively probes chiral molecular structures. By using frequencies far detuned from electronic resonances, we probe the chiral macromolecular structures with high surface specificity. The phase of the sum-frequency light generated by the chiral molecules is determined using heterodyne detection. With this approach, we can distinguish right-handed and left-handed helical peptides at a water-air interface. We thus show that heterodyne-detected VSFG is sensitive to the absolute configuration of complex, interfacial macromolecules and has the potential to determine the absolute configuration of enantiomers at interfaces.

  14. Aqueous Angiography: Real-Time and Physiologic Aqueous Humor Outflow Imaging.

    Directory of Open Access Journals (Sweden)

    Sindhu Saraswathy

    Full Text Available Trabecular meshwork (TM bypass surgeries attempt to enhance aqueous humor outflow (AHO to lower intraocular pressure (IOP. While TM bypass results are promising, inconsistent success is seen. One hypothesis for this variability rests upon segmental (non-360 degrees uniform AHO. We describe aqueous angiography as a real-time and physiologic AHO imaging technique in model eyes as a way to simulate live AHO imaging.Pig (n = 46 and human (n = 6 enucleated eyes were obtained, orientated based upon inferior oblique insertion, and pre-perfused with balanced salt solution via a Lewicky AC maintainer through a 1mm side-port. Fluorescein (2.5% was introduced intracamerally at 10 or 30 mm Hg. With an angiographer, infrared and fluorescent (486 nm images were acquired. Image processing allowed for collection of pixel information based on intensity or location for statistical analyses. Concurrent OCT was performed, and fixable fluorescent dextrans were introduced into the eye for histological analysis of angiographically active areas.Aqueous angiography yielded high quality images with segmental patterns (p<0.0001; Kruskal-Wallis test. No single quadrant was consistently identified as the primary quadrant of angiographic signal (p = 0.06-0.86; Kruskal-Wallis test. Regions of high proximal signal did not necessarily correlate with regions of high distal signal. Angiographically positive but not negative areas demonstrated intrascleral lumens on OCT images. Aqueous angiography with fluorescent dextrans led to their trapping in AHO pathways.Aqueous angiography is a real-time and physiologic AHO imaging technique in model eyes.

  15. Neutron polarization

    International Nuclear Information System (INIS)

    Firk, F.W.K.

    1976-01-01

    Some recent experiments involving polarized neutrons are discussed; they demonstrate how polarization studies provide information on fundamental aspects of nuclear structure that cannot be obtained from more traditional neutron studies. Until recently, neutron polarization studies tended to be limited either to very low energies or to restricted regions at higher energies, determined by the kinematics of favorable (p, vector n) and (d, vector n) reactions. With the advent of high intensity pulsed electron and proton accelerators and of beams of vector polarized deuterons, this is no longer the case. One has entered an era in which neutron polarization experiments are now being carried out, in a routine way, throughout the entire range from thermal energies to tens-of-MeV. The significance of neutron polarization studies is illustrated in discussions of a wide variety of experiments that include the measurement of T-invariance in the β-decay of polarized neutrons, a search for the effects of meson exchange currents in the photo-disintegration of the deuteron, the determination of quantum numbers of states in the fission of aligned 235 U and 237 Np induced by polarized neutrons, and the double- and triple-scattering of fast neutrons by light nuclei

  16. Amphiphilic invertible polymers: Self-assembly into functional materials driven by environment polarity

    Science.gov (United States)

    Hevus, Ivan

    Stimuli-responsive polymers adapt to environmental changes by adjusting their chain conformation in a fast and reversible way. Responsive polymeric materials have already found use in electronics, coatings industry, personal care, and bio-related areas. The current work aims at the development of novel responsive functional polymeric materials by manipulating environment-dependent self-assembly of a new class of responsive macromolecules strategically designed in this study,—amphiphilic invertible polymers (AIPs). Environment-dependent micellization and self-assembly of three different synthesized AIP types based on poly(ethylene glycol) as a hydrophilic fragment and varying hydrophobic constituents was demonstrated in polar and nonpolar solvents, as well as on the surfaces and interfaces. With increasing concentration, AIP micelles self-assemble into invertible micellar assemblies composed of hydrophilic and hydrophobic domains. Polarity-responsive properties of AIPs make invertible micellar assemblies functional in polar and nonpolar media including at interfaces. Thus, invertible micellar assemblies solubilize poorly soluble substances in their interior in polar and nonpolar solvents. In a polar aqueous medium, a novel stimuli-responsive mechanism of drug release based on response of AIP-based drug delivery system to polarity change upon contact with the target cell has been established using invertible micellar assemblies loaded with curcumin, a phytochemical drug. In a nonpolar medium, invertible micellar assemblies were applied simultaneously as nanoreactors and stabilizers for size-controlled synthesis of silver nanoparticles stable in both polar and nonpolar media. The developed amphiphilic nanosilver was subsequently used as seeds to promote anisotropic growth of CdSe semiconductor nanoparticles that have potential in different applications ranging from physics to medicine. Amphiphilic invertible polymers were shown to adsorb on the surface of silica

  17. Assessment of polycyclic aromatic hydrocarbons (PAHs) pollution in soil of suburban areas in Tianjin, China.

    Science.gov (United States)

    Lv, Jungang; Shi, Rongguang; Cai, Yanming; Liu, Yong

    2010-07-01

    Soil contamination with polycyclic aromatic hydrocarbons is an increasing problem and has aroused more and more concern in many countries, including China. In this study, representative soil samples (n = 87) of suburban areas in Tianjin (Xiqing, Dongli, Jinnan, Beichen) were evaluated for 16 polycyclic aromatic hydrocarbons. Surface soil samples were air-dried and sieved. Microwave assisted extraction was used for polycyclic aromatic hydrocarbons preparation prior to analysis with gas chromatography-mass spectrometry. The total concentrations of tested polycyclic aromatic hydrocarbons in Xiqing, Dongli, Jinnan, Beichen ranged in 58.5-2,748.3, 36.1-6,734.7, 58.5-4,502.5, 29.7-852.5 ng/g and the averages of total concentration of polycyclic aromatic hydrocarbons were 600.5, 933.6, 640.8, 257.3 ng/g, respectively. Spatial variation of polycyclic aromatic hydrocarbons in soil was illustrated; Pollution status and comparison to other cities were also investigated. Serious polycyclic aromatic hydrocarbons soil pollution was found in Dongli district, on the contrary, Bap in most sites in Beichen did not exceed relative standards and most sites in Beichen should be classified as non-contaminated soil. Principal component analysis was used to identify the possible sources of different districts. It turned out that coal combustion still was the most important sources in three districts except Beichen. Coking, traffic, cooking, biomass combustion also accounted for polycyclic aromatic hydrocarbons pollution to certain extent in different districts. These data can be further used to assess the health risk associated with soils polluted with polycyclic aromatic hydrocarbons and help local government find proper way to reduce polycyclic aromatic hydrocarbons pollution in soils.

  18. Metal-free hydration of aromatic haloalkynes to α-halomethyl ketones

    KAUST Repository

    Ye, Min

    2016-10-01

    A highly regioselective and efficient metal-free hydration of aromatic haloalkynes to alpha-halomethyl ketones using cheap tetrafluoroboric acid as catalyst is described. The protocol is conducted under convenient conditions and affords products in good to excellent yields, with broad substrate scope, including a variety of aromatic alkynyl chlorides, alkynyl bromides, and alkynyl iodides. (C) 2016 Elsevier Ltd. All rights reserved.

  19. Metal-free hydration of aromatic haloalkynes to α-halomethyl ketones

    KAUST Repository

    Ye, Min; Wen, Yuelu; Li, Huifang; Fu, Yejuan; Wang, Qinghao

    2016-01-01

    A highly regioselective and efficient metal-free hydration of aromatic haloalkynes to alpha-halomethyl ketones using cheap tetrafluoroboric acid as catalyst is described. The protocol is conducted under convenient conditions and affords products in good to excellent yields, with broad substrate scope, including a variety of aromatic alkynyl chlorides, alkynyl bromides, and alkynyl iodides. (C) 2016 Elsevier Ltd. All rights reserved.

  20. Three-photon polarization ququarts: polarization, entanglement and Schmidt decompositions

    International Nuclear Information System (INIS)

    Fedorov, M V; Miklin, N I

    2015-01-01

    We consider polarization states of three photons, propagating collinearly and having equal given frequencies but with arbitrary distributed horizontal or vertical polarizations of photons. A general form of such states is a superposition of four basic three-photon polarization modes, to be referred to as the three-photon polarization ququarts (TPPQ). All such states can be considered as consisting of one- and two-photon parts, which can be entangled with each other. The degrees of entanglement and polarization, as well as the Schmidt decomposition and Stokes vectors of TPPQ are found and discussed. (paper)

  1. Improved Separation of Complex Polycyclic Aromatic Hydrocarbon Mixtures Using Novel Column Combinations in GC×GC/ToF-MS

    Science.gov (United States)

    Manzano, Carlos; Hoh, Eunha; Simonich, Staci L. Massey

    2012-01-01

    Complex mixtures of polycyclic aromatic hydrocarbons (PAHs) are difficult to resolve because of the high degree of overlap in compound vapor pressures, boiling points and mass spectral fragmentation patterns. The objective of this research was to improve the separation of complex PAH mixtures (including 97 different parent, alkyl-, nitro-, oxy-, thio-, chloro-, bromo-, and high molecular weight PAHs) using GC×GC/ToF-MS by maximizing the orthogonality of different GC column combinations and improving the separation of PAHs from the sample matrix interferences, including unresolved complex mixtures (UCM). Four different combinations of non-polar, polar, liquid crystal and nano-stationary phase columns were tested. Each column combination was optimized and evaluated for orthogonality using a method based on conditional entropy that considers the quantitative peak distribution in the entire two-dimensional space. Finally, an atmospheric particulate matter with diameter column in the first dimension and a 1.2 m × 0.10 mm × 0.10 µm NSP-35 nano-stationary phase column in the second dimension. In addition, the use of this column combination in GC×GC/ToF-MS resulted in significantly shorter analysis times (176 min) for complex PAH mixtures compared to one-dimensional GC/MS (257 min), as well as potentially reduced sample preparation time. PMID:22769970

  2. Side Chain Cyclized Aromatic Amino Acids

    DEFF Research Database (Denmark)

    Van der Poorten, Olivier; Knuhtsen, Astrid; Sejer Pedersen, Daniel

    2016-01-01

    Constraining the conformation of flexible peptides is a proven strategy to increase potency, selectivity, and metabolic stability. The focus has mostly been on constraining the backbone dihedral angles; however, the correct orientation of the amino acid side chains (χ-space) that constitute...... the peptide pharmacophore is equally important. Control of χ-space utilizes conformationally constrained amino acids that favor, disfavor, or exclude the gauche (-), the gauche (+), or the trans conformation. In this review we focus on cyclic aromatic amino acids in which the side chain is connected...... to the peptide backbone to provide control of χ(1)- and χ(2)-space. The manifold applications for cyclized analogues of the aromatic amino acids Phe, Tyr, Trp, and His within peptide medicinal chemistry are showcased herein with examples of enzyme inhibitors and ligands for G protein-coupled receptors....

  3. Polarization splitter and polarization rotator designs based on transformation optics.

    Science.gov (United States)

    Kwon, Do-Hoon; Werner, Douglas H

    2008-11-10

    The transformation optics technique is employed in this paper to design two optical devices - a two-dimensional polarization splitter and a three-dimensional polarization rotator for propagating beams. The polarization splitter translates the TM- and the TE-polarized components of an incident beam in opposite directions (i.e., shifted up or shifted down). The polarization rotator rotates the polarization state of an incoming beam by an arbitrary angle. Both optical devices are reflectionless at the entry and exit interfaces. Design details and full-wave simulation results are provided.

  4. Role of Dehalogenases in Aerobic Bacterial Degradation of Chlorinated Aromatic Compounds

    Directory of Open Access Journals (Sweden)

    Pankaj Kumar Arora

    2014-01-01

    Full Text Available This review was conducted to provide an overview of dehalogenases involved in aerobic biodegradation of chlorinated aromatic compounds. Additionally, biochemical and molecular characterization of hydrolytic, reductive, and oxygenolytic dehalogenases was reviewed. This review will increase our understanding of the process of dehalogenation of chlorinated aromatic compounds.

  5. A Multistep Synthesis Incorporating a Green Bromination of an Aromatic Ring

    Science.gov (United States)

    Cardinal, Pascal; Greer, Brandon; Luong, Horace; Tyagunova, Yevgeniya

    2012-01-01

    Electrophilic aromatic substitution is a fundamental topic taught in the undergraduate organic chemistry curriculum. A multistep synthesis that includes a safer and greener method for the bromination of an aromatic ring than traditional bromination methods is described. This experiment is multifaceted and can be used to teach students about…

  6. Influence of trace aromatics on the chemical growth mechanisms of Titan aerosol analogues

    Science.gov (United States)

    Gautier, Thomas; Sebree, Joshua A.; Li, Xiang; Pinnick, Veronica T.; Grubisic, Andrej; Loeffler, Mark J.; Getty, Stephanie A.; Trainer, Melissa G.; Brinckerhoff, William B.

    2017-06-01

    The chemical structure and formation pathways of Titan aerosols remain largely unknown. In this work, we studied the effect of trace aromatics on the chemical composition and formation pathways of laboratory analogues of Titan's organic aerosols. The aerosol analogues were produced using four different trace aromatic molecules, comprised of one or two aromatic rings, each with or without a nitrogen heteroatom. Samples were then analyzed by laser desorption/ionization Mass Spectrometry (LDMS), revealing a high variability in the sample composition depending on the trace aromatic used. Our work reveals that the final chemical structure of the aerosols depends strongly on the number of aromatic rings in the trace molecule, leading either to a polymeric or to a random co-polymeric growth of the sample. These different chemical structures can affect the physical properties of the aerosol. Future analysis of Titan's aerosols using better resolution could potentially determine whether either of the growth hypotheses are preferred.

  7. Polycyclic Aromatic Hydrocarbons: A Critical Review of Environmental Occurrence and Bioremediation.

    Science.gov (United States)

    Alegbeleye, Oluwadara Oluwaseun; Opeolu, Beatrice Oluwatoyin; Jackson, Vanessa Angela

    2017-10-01

    The degree of polycyclic aromatic hydrocarbon contamination of environmental matrices has increased over the last several years due to increase in industrial activities. Interest has surrounded the occurrence and distribution of polycyclic aromatic hydrocarbons for many decades because they pose a serious threat to the health of humans and ecosystems. The importance of the need for sustainable abatement strategies to alleviate contamination therefore cannot be overemphasised, as daily human activities continue to create pollution from polycyclic aromatic hydrocarbons and impact the natural environment. Globally, attempts have been made to design treatment schemes for the remediation and restoration of contaminated sites. Several techniques and technologies have been proposed and tested over time, the majority of which have significant limitations. This has necessitated research into environmentally friendly and cost-effective clean-up techniques. Bioremediation is an appealing option that has been extensively researched and adopted as it has been proven to be relatively cost-effective, environmentally friendly and is publicly accepted. In this review, the physicochemical properties of some priority polycyclic aromatic hydrocarbons, as well as the pathways and mechanisms through which they enter the soil, river systems, drinking water, groundwater and food are succinctly examined. Their effects on human health, other living organisms, the aquatic ecosystem, as well as soil microbiota are also elucidated. The persistence and bioavailability of polycyclic aromatic hydrocarbons are discussed as well, as they are important factors that influence the rate, efficiency and overall success of remediation. Bioremediation (aerobic and anaerobic), use of biosurfactants and bioreactors, as well as the roles of biofilms in the biological treatment of polycyclic aromatic hydrocarbons are also explored.

  8. Polycyclic Aromatic Hydrocarbons: A Critical Review of Environmental Occurrence and Bioremediation

    Science.gov (United States)

    Alegbeleye, Oluwadara Oluwaseun; Opeolu, Beatrice Oluwatoyin; Jackson, Vanessa Angela

    2017-10-01

    The degree of polycyclic aromatic hydrocarbon contamination of environmental matrices has increased over the last several years due to increase in industrial activities. Interest has surrounded the occurrence and distribution of polycyclic aromatic hydrocarbons for many decades because they pose a serious threat to the health of humans and ecosystems. The importance of the need for sustainable abatement strategies to alleviate contamination therefore cannot be overemphasised, as daily human activities continue to create pollution from polycyclic aromatic hydrocarbons and impact the natural environment. Globally, attempts have been made to design treatment schemes for the remediation and restoration of contaminated sites. Several techniques and technologies have been proposed and tested over time, the majority of which have significant limitations. This has necessitated research into environmentally friendly and cost-effective clean-up techniques. Bioremediation is an appealing option that has been extensively researched and adopted as it has been proven to be relatively cost-effective, environmentally friendly and is publicly accepted. In this review, the physicochemical properties of some priority polycyclic aromatic hydrocarbons, as well as the pathways and mechanisms through which they enter the soil, river systems, drinking water, groundwater and food are succinctly examined. Their effects on human health, other living organisms, the aquatic ecosystem, as well as soil microbiota are also elucidated. The persistence and bioavailability of polycyclic aromatic hydrocarbons are discussed as well, as they are important factors that influence the rate, efficiency and overall success of remediation. Bioremediation (aerobic and anaerobic), use of biosurfactants and bioreactors, as well as the roles of biofilms in the biological treatment of polycyclic aromatic hydrocarbons are also explored.

  9. Polarization dynamics and polarization time of random three-dimensional electromagnetic fields

    International Nuclear Information System (INIS)

    Voipio, Timo; Setaelae, Tero; Shevchenko, Andriy; Friberg, Ari T.

    2010-01-01

    We investigate the polarization dynamics of random, stationary three-dimensional (3D) electromagnetic fields. For analyzing the time evolution of the instantaneous polarization state, two intensity-normalized polarization autocorrelation functions are introduced, one based on a geometric approach with the Poincare vectors and the other on energy considerations with the Jones vectors. Both approaches lead to the same conclusions on the rate and strength of the polarization dynamics and enable the definition of a polarization time over which the state of polarization remains essentially unchanged. For fields obeying Gaussian statistics, the two correlation functions are shown to be expressible in terms of quantities characterizing partial 3D polarization and electromagnetic coherence. The 3D degree of polarization is found to have the same meaning in the 3D polarization dynamics as the usual two-dimensional (2D) degree of polarization does with planar fields. The formalism is demonstrated with several examples, and it is expected to be useful in applications dealing with polarization fluctuations of 3D light.

  10. Dansyl-based fluorescent film sensor for nitroaromatics in aqueous solution

    International Nuclear Information System (INIS)

    Kang Jianping; Ding Liping; Lue Fengting; Zhang Shujuan; Fang Yu

    2006-01-01

    We demonstrate the preparation, characterization and performance evaluation of a fluorescent film sensor for the specific detection of nitroaromatics in aqueous solution. The film sensor was fabricated by covalent immobilization of a fluorophore, dansyl, on a glass slide surface via reaction with diaminopropane and then with an epoxide-terminated self-assembled monolayer. Nitroaromatics like nitrobenzene, 4-nitrotoluene, 3, 5-dinitrotoluene, and 2,4,6-trinitrotoluene, etc were found to strongly quench the fluorescence emission of the film while some other commonly-used quenchers like nitromethane, KI, acrylamide, etc showed no or slight quenching effect on the emission. The quenching mechanism was examined through fluorescence lifetime measurements and it was proved that the quenching is static in nature and may be caused by electron transfer from the fluorophore to the nitroaromatics. The presence of other aromatics like benzene, toluene, etc had little effect upon the sensing performance of the film to nitroaromatics. Solvent effect studies revealed that the conformations adopted by the spacer connecting the fluorophore and the substrate played a crucial role in the performance of the film sensor. Furthermore, the response of the film to nitroaromatics is fast and reversible

  11. Dansyl-based fluorescent film sensor for nitroaromatics in aqueous solution

    Energy Technology Data Exchange (ETDEWEB)

    Kang Jianping; Ding Liping; Lue Fengting; Zhang Shujuan; Fang Yu [Key Laboratory for Macromolecular Science of Shaanxi Province, School of Chemistry and Materials Science, Shaanxi Normal University, Xi' an 710062 (China)

    2006-12-07

    We demonstrate the preparation, characterization and performance evaluation of a fluorescent film sensor for the specific detection of nitroaromatics in aqueous solution. The film sensor was fabricated by covalent immobilization of a fluorophore, dansyl, on a glass slide surface via reaction with diaminopropane and then with an epoxide-terminated self-assembled monolayer. Nitroaromatics like nitrobenzene, 4-nitrotoluene, 3, 5-dinitrotoluene, and 2,4,6-trinitrotoluene, etc were found to strongly quench the fluorescence emission of the film while some other commonly-used quenchers like nitromethane, KI, acrylamide, etc showed no or slight quenching effect on the emission. The quenching mechanism was examined through fluorescence lifetime measurements and it was proved that the quenching is static in nature and may be caused by electron transfer from the fluorophore to the nitroaromatics. The presence of other aromatics like benzene, toluene, etc had little effect upon the sensing performance of the film to nitroaromatics. Solvent effect studies revealed that the conformations adopted by the spacer connecting the fluorophore and the substrate played a crucial role in the performance of the film sensor. Furthermore, the response of the film to nitroaromatics is fast and reversible.

  12. Dansyl-based fluorescent film sensor for nitroaromatics in aqueous solution

    Science.gov (United States)

    Kang, Jianping; Ding, Liping; Lü, Fengting; Zhang, Shujuan; Fang, Yu

    2006-12-01

    We demonstrate the preparation, characterization and performance evaluation of a fluorescent film sensor for the specific detection of nitroaromatics in aqueous solution. The film sensor was fabricated by covalent immobilization of a fluorophore, dansyl, on a glass slide surface via reaction with diaminopropane and then with an epoxide-terminated self-assembled monolayer. Nitroaromatics like nitrobenzene, 4-nitrotoluene, 3, 5-dinitrotoluene, and 2,4,6-trinitrotoluene, etc were found to strongly quench the fluorescence emission of the film while some other commonly-used quenchers like nitromethane, KI, acrylamide, etc showed no or slight quenching effect on the emission. The quenching mechanism was examined through fluorescence lifetime measurements and it was proved that the quenching is static in nature and may be caused by electron transfer from the fluorophore to the nitroaromatics. The presence of other aromatics like benzene, toluene, etc had little effect upon the sensing performance of the film to nitroaromatics. Solvent effect studies revealed that the conformations adopted by the spacer connecting the fluorophore and the substrate played a crucial role in the performance of the film sensor. Furthermore, the response of the film to nitroaromatics is fast and reversible.

  13. Degradation of diuron in aqueous solution by dielectric barrier discharge

    Energy Technology Data Exchange (ETDEWEB)

    Feng Jingwei [State Key Laboratory of Pollution Control and Resource Reuse, School of the Environment Nanjing University, Nanjing 210093 (China); Zheng Zheng [State Key Laboratory of Pollution Control and Resource Reuse, School of the Environment Nanjing University, Nanjing 210093 (China)], E-mail: zzheng@nju.edu.cn; Sun Yabing; Luan Jingfei; Wang Zhen; Wang Lianhong; Feng Jianfang [State Key Laboratory of Pollution Control and Resource Reuse, School of the Environment Nanjing University, Nanjing 210093 (China)

    2008-06-15

    Degradation of diuron in aqueous solution was conducted in a dielectric barrier discharge (DBD) reactor and the proposed degradation mechanism was investigated in detail. The factors that affect the degradation of diuron were examined. The degradation efficiency of diuron and the removal of total organic carbon (TOC) increased with increasing input power, and the degradation of diuron by DBD fitted first-order kinetics. Both strong acidic and alkaline solution conditions could improve diuron degradation efficiency and TOC removal rate. Degradation of diuron could be accelerated or inhibited in the presence of H{sub 2}O{sub 2} depending on the dosage. The degradation efficiency increased dramatically with adding Fe{sup 2+}. The removal of TOC and the amount of the detected Cl{sup -}, NO{sub 3}{sup -} and NH{sub 4}{sup +} were increased in the presence of Fe{sup 2+}. The concentrations of oxalic and acetic acids were almost the same in the absence and presence of Fe{sup 2+}, but high concentration of formic acid was accumulated in the presence of Fe{sup 2+}. The main degradation pathway of diuron by DBD involved a series of dechlorination-hydroxylation, dealkylation and oxidative opening of the aromatic ring processes.

  14. Drivers and applications of integrated clean-up technologies for surfactant-enhanced remediation of environments contaminated with polycyclic aromatic hydrocarbons (PAHs).

    Science.gov (United States)

    Liang, Xujun; Guo, Chuling; Liao, Changjun; Liu, Shasha; Wick, Lukas Y; Peng, Dan; Yi, Xiaoyun; Lu, Guining; Yin, Hua; Lin, Zhang; Dang, Zhi

    2017-06-01

    Surfactant-enhanced remediation (SER) is considered as a promising and efficient remediation approach. This review summarizes and discusses main drivers on the application of SER in removing polycyclic aromatic hydrocarbons (PAHs) from contaminated soil and water. The effect of PAH-PAH interactions on SER efficiency is, for the first time, illustrated in an SER review. Interactions between mixed PAHs could enhance, decrease, or have no impact on surfactants' solubilization power towards PAHs, thus affecting the optimal usage of surfactants for SER. Although SER can transfer PAHs from soil/non-aqueous phase liquids to the aqueous phase, the harmful impact of PAHs still exists. To decrease the level of PAHs in SER solutions, a series of SER-based integrated cleanup technologies have been developed including surfactant-enhanced bioremediation (SEBR), surfactant-enhanced phytoremediation (SEPR) and SER-advanced oxidation processes (SER-AOPs). In this review, the general considerations and corresponding applications of the integrated cleanup technologies are summarized and discussed. Compared with SER-AOPs, SEBR and SEPR need less operation cost, yet require more treatment time. To successfully achieve the field application of surfactant-based technologies, massive production of the cost-effective green surfactants (i.e. biosurfactants) and comprehensive evaluation of the drivers and the global cost of SER-based cleanup technologies need to be performed in the future. Copyright © 2017. Published by Elsevier Ltd.

  15. Manufacture of aromatic hydrocarbons from coal hydrogenation products

    Energy Technology Data Exchange (ETDEWEB)

    A.S. Maloletnev; M.A. Gyul' malieva [Institute for Fossil Fuels, Moscow (Russian Federation)

    2007-08-15

    The manufacture of aromatic hydrocarbons from coal distillates was experimentally studied. A flow chart for the production of benzene, ethylbenzene, toluene, and xylenes was designed, which comprised the hydrogen treatment of the total wide-cut (or preliminarily dephenolized) fraction with FBP 425{sup o}C; fractional distillation of the hydrotreated products into IBP-60, 60-180, 180-300, and 300-425{sup o}C fractions; the hydro-cracking of middle fractions for increasing the yield of gasoline fractions whenever necessary; the catalytic reform of the fractions with bp up to 180{sup o}C; and the extraction of aromatic hydrocarbons.

  16. OH-radical induced degradation of hydroxybenzoic- and hydroxycinnamic acids and formation of aromatic products-A gamma radiolysis study

    Energy Technology Data Exchange (ETDEWEB)

    Krimmel, Birgit; Swoboda, Friederike [University of Vienna, Department of Nutritional Sciences, Section Radiation Biology (Austria); Solar, Sonja, E-mail: sonja.solar@univie.ac.a [University of Vienna, Department of Nutritional Sciences, Section Radiation Biology (Austria); Reznicek, Gottfried [Department of Pharmacognosy, Althanstrasse 14, A-1090 Vienna (Austria)

    2010-12-15

    The OH-radical induced degradation of hydroxybenzoic acids (HBA), hydroxycinnamic acids (HCiA) and methoxylated derivatives, as well as of chlorogenic acid and rosmarinic acid was studied by gamma radiolysis in aerated aqueous solutions. Primary aromatic products resulting from an OH-radical attachment to the ring (hydroxylation), to the position occupied by the methoxyl group (replacement -OCH{sub 3} by -OH) as well as to the propenoic acid side chain of the cinnamic acids (benzaldehyde formations) were analysed by HPLC-UV and LC-ESI-MS. A comparison of the extent of these processes is given for 3,4-dihydroxybenzoic acid, vanillic acid, isovanillic acid, syringic acid, cinnamic acid, 4-hydroxycinnamic acid, caffeic acid, ferulic acid, isoferulic acid, chlorogenic acid, and rosmarinic acid. For all cinnamic acids and derivatives benzaldehydes were significant oxidation products. With the release of caffeic acid from chlorogenic acid the cleavage of a phenolic glycoside could be demonstrated. Reaction mechanisms are discussed.

  17. Polarized electron sources

    Energy Technology Data Exchange (ETDEWEB)

    Prepost, R. [Univ. of Wisconsin, Madison, WI (United States)

    1994-12-01

    The fundamentals of polarized electron sources are described with particular application to the Stanford Linear Accelerator Center. The SLAC polarized electron source is based on the principle of polarized photoemission from Gallium Arsenide. Recent developments using epitaxially grown, strained Gallium Arsenide cathodes have made it possible to obtain electron polarization significantly in excess of the conventional 50% polarization limit. The basic principles for Gallium and Arsenide polarized photoemitters are reviewed, and the extension of the basic technique to strained cathode structures is described. Results from laboratory measurements of strained photocathodes as well as operational results from the SLAC polarized source are presented.

  18. Polarized electron sources

    International Nuclear Information System (INIS)

    Prepost, R.

    1994-01-01

    The fundamentals of polarized electron sources are described with particular application to the Stanford Linear Accelerator Center. The SLAC polarized electron source is based on the principle of polarized photoemission from Gallium Arsenide. Recent developments using epitaxially grown, strained Gallium Arsenide cathodes have made it possible to obtain electron polarization significantly in excess of the conventional 50% polarization limit. The basic principles for Gallium and Arsenide polarized photoemitters are reviewed, and the extension of the basic technique to strained cathode structures is described. Results from laboratory measurements of strained photocathodes as well as operational results from the SLAC polarized source are presented

  19. Pitting morphologies of zirconium base alloys in aqueous and non aqueous chloride media

    International Nuclear Information System (INIS)

    Palit, G.C.; Gadiyar, H.S.

    1988-01-01

    Pitting morphology of zirconium and Zr-Cr alloys in aqueous chloride and nonaqueous methanol + 0.4 per cent HCl solution was investigated and observed to follow different modes in these two environments. While in aqueous chloride solution pitting was transgranular and randomly oriented, in methanol-chloride solution pits were observed to initiate and propagate along the grain boundaries. In aqueous chloride solution very irregular and sponge like zirconium metal was formed inside the pit while in methanol-chloride solution the pits were crystallographic in nature. Optical microscopy has revealed that pits preferentially initiate and propagate along scratch line in aqueous chloride solution, but such was not the case in nonaqueous methanol-chloride solution. The nature and the mechanism operating in the catastropic failure of these materials are investigated. (author). 10 refs., 11 figs

  20. Adsorption of Polycyclic aromatic hydrocarbons (fluoranthene and anthracenemethanol) by functional graphene oxide and removal by pH and temperature-sensitive coagulation.

    Science.gov (United States)

    Zhang, Caili; Wu, Lin; Cai, Dongqing; Zhang, Caiyun; Wang, Ning; Zhang, Jing; Wu, Zhengyan

    2013-06-12

    A new kind of functional graphene oxide with fine stability in water was fabricated by mixing graphene oxide (GO) and brilliant blue (BB) with a certain weight ratio. The adsorption performance of this mixture of BB and GO (BBGO) to polycyclic aromatic hydrocarbons (anthracenemethanol (AC) and fluoranthene (FL)) was investigated, and the results indicated BBGO possessed adsorption capacity of 1.676 mmol/g and removal efficiency of 72.7% as to AC and adsorption capacity of 2.212 mmol/g and removal efficiency of 93.2% as to FL. After adsorption, pH and temperature-sensitive coagulation (PTC) method was used to remove the AC/BBGO or FL/BBGO complex and proved to be an effective approach to flocculate the AC/BBGO or FL/BBGO complex into large flocs, which tended to be removed from the aqueous solution.