Sample records for aqueous polar aromatic

  1. Fibrous adsorbent for removal of aqueous aromatic hydrocarbons. (United States)

    Jung, Yong-Jun; Kiso, Yoshiaki; Oguchi, Tatsuo; Yamada, Toshiro; Takagi, Hiroo; Nishimura, Kazuyuki


    Bundles of a strongly hydrophobic fibrous material (p-phenylene-2,6-benzobisoxazole; PBO; Zylon) were employed as an adsorbent for the removal of aqueous aromatic compounds, because the PBO fibers are too rigid to be woven and did not entrap suspended solids. The removal performance for nine kinds of polyaromatic hydrocarbons (PAHs) and di-(2-ethylhexyl) phthalate (DEHP) was evaluated. PAHs and DEHP at initial concentrations of 50 microg L(-1) were removed at 72.5-99.9% and ca. 95%, respectively, although the removal efficiencies were affected by the phase ratio (fiber weight/solution volume). The logarithm of the partition coefficient (log K) for planar PAHs was linearly correlated with the logarithm of the n-octanol/water partition coefficient (log P), but nonplanar PAHs, such as cis-stilbene, p-terphenyl, and o-terphenyl, showed significantly lower adsorption performance. The adsorbed PAHs were not desorbed effectively with CH3CN, CH2Cl2, and toluene. On the other hand, DEHP was effectively desorbed with methanol.

  2. Aqueous leaching of polycyclic aromatic hydrocarbons from bitumen and asphalt. (United States)

    Brandt, H C; de Groot, P C


    The application of bitumen in, e.g. asphalt roads, roofs and hydraulic applications will lead to the leaching of compounds from the bitumen/asphalt into the environment. Because polycyclic aromatic hydrocarbons (PAHs) are present in bitumen, static and dynamic leach tests have been performed to study the leaching behaviour of this class of compounds. Nine petroleum bitumens covering a representative range of commercially available products and one asphalt made from one of the bitumens have been tested in a static leach test. The asphalt has been also subjected to a dynamic leach test. The main conclusions are that a 30h dynamic leach test is sufficient to determine the equilibrium concentration that will be reached after bitumen or asphalt has been in contact with the water for more than 3-6 days. As an alternative to performing a leach test, this concentration can be calculated from the PAH concentrations in the bitumen, and their distribution coefficients, as calculated here, or from their aqueous solubilities. The equilibrium PAH concentrations in the leach water from bitumens stay well below the surface water limits that exist in several EEC-countries and are also more than an order of magnitude lower than the current EEC limits for potable water.

  3. Oxidative aromatization of Hantzsch 1,4-dihydropyridines by aqueous hydrogen peroxide-acetic acid

    Institute of Scientific and Technical Information of China (English)


    A simple method for the oxidative aromatization of Hantzsch 1,4-dihydropyridines to the corresponding pyridines is achieved by using hydrogen peroxide as green oxidant and acetic acid as catalyst in aqueous solution.

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

    NARCIS (Netherlands)

    Zakzeski, J.; Weckhuysen, B.M.


    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 compo

  5. Effect of Polarity of Activated Carbon Surface, Solvent and Adsorbate on Adsorption of Aromatic Compounds from Liquid Phase. (United States)

    Goto, Tatsuru; Amano, Yoshimasa; Machida, Motoi; Imazeki, Fumio


    In this study, introduction of acidic functional groups onto a carbon surface and their removal were carried out through two oxidation methods and outgassing to investigate the adsorption mechanism of aromatic compounds which have different polarity (benzene and nitrobenzene). Adsorption experiments for these aromatics in aqueous solution and n-hexane solution were conducted in order to obtain the adsorption isotherms for commercial activated carbon (BAC) as a starting material, its two types of oxidized BAC samples (OXs), and their outgassed samples at 900 °C (OGs). Adsorption and desorption kinetics of nitrobenzene for the BAC, OXs and OGs in aqueous solution were also examined. The results showed that the adsorption of benzene molecules was significantly hindered by abundant acidic functional groups in aqueous solution, whereas the adsorbed amount of nitrobenzene on OXs gradually increased as the solution concentration increased, indicating that nitrobenzene can adsorb favourably on a hydrophilic surface due to its high dipole moment, in contrast to benzene. In n-hexane solution, it was difficult for benzene to adsorb on any sample owing to the high affinity between benzene and n-hexane solvent. On the other hand, adsorbed amounts of nitrobenzene on OXs were larger than those of OGs in n-hexane solution, implying that nitrobenzene can adsorb two adsorption sites, graphene layers and surface acidic functional groups. The observed adsorption and desorption rate constants of nitrobenzene on the OXs were lower than those on the BAC due to disturbance of diffusion by the acidic functional groups.

  6. Dechlorination of Aromatic Chlorides in Aqueous System Catalyzed by Functionalized MontK10 Supported Palladium-tin

    Institute of Scientific and Technical Information of China (English)


    A novel bisupporter bimetal catalyst PVP-PdCl2-SnCl4/MontK10-PEG400, using for dehalogenation of insoluable aromatic halides in aqueous system, has shown high dechlorination activity and selectivity, without any organic solvent or phase transfer catalyst. The conversion of aromatic chlorides can reach 100%. The catalyst is easy to prepare and has good reusability.

  7. Potentiometric online detection of aromatic hydrocarbons in aqueous phase using carbon nanotube-based sensors. (United States)

    Washe, Alemayehu P; Macho, Santiago; Crespo, Gastón A; Rius, F Xavier


    Surfaces made of entangled networks of single-walled carbon nanotubes (SWCNTs) display a strong adsorption affinity for aromatic hydrocarbons. Adsorption of these compounds onto the walls of SWCNTs changes the electrical characteristics of the SWCNT-solution interface. Using these features, we have developed a potentiometric sensor to detect neutral aromatic species. Specifically, we can detect online aromatic hydrocarbons in industrial coolant water. Our chromatographic results confirm the adsorption of toluene onto the walls of carbon nanotubes, and our impedance spectroscopy data show the change in the double layer capacitance of the carbon nanotube-solution interface upon addition of toluene, thus confirming the proposed sensing mechanism. The sensor showed a toluene concentration dependent EMF response that follows the shape of an adsorption isotherm and displayed an immediate response to the presence of toluene with a detection limit of 2.1 ppm. The sensor does not respond to other nonaromatic hydrocarbons that may coexist with aromatic hydrocarbons in water. It shows a qualitative sensitivity and selectivity of 100% and 83%, respectively, which confirms its ability to detect aromatic hydrocarbons in aqueous solutions. The sensor showed an excellent ability to immediately detect the presence of toluene in actual coolant water. Its operational characteristics, including its fast response, low cost, portability, and easy use in online industrial applications, improve those of current chromatographic or spectroscopic techniques.

  8. Is uracil aromatic? The enthalpies of hydrogenation in the gaseous and crystalline phases, and in aqueous solution, as tools to obtain an answer. (United States)

    Galvão, Tiago L P; Rocha, Inês M; da Silva, Maria D M C Ribeiro; da Silva, Manuel A V Ribeiro


    The enthalpy of hydrogenation of uracil was derived from the experimental enthalpies of formation, in the gaseous phase, of uracil and 5,6-dihydrouracil, in order to analyze its aromaticity. The enthalpy of formation of 5,6-dihydrouracil was obtained from combustion calorimetry, Knudsen effusion technique and Calvet microcalorimetry results. High-level computational methods were tested for the enthalpy of hydrogenation of uracil, but only with G3 was possible to obtain results in agreement with the experimental ones. It was found that uracil possesses 30.0% of aromatic character in the gaseous phase. Using both implicit, explicit, and hybrid solvation methods, it was possible to obtain a reference value for the enthalpy of hydrogenation of uracil in the aqueous solution and the effect of polarity and hydrogen bonds on the aromaticity of uracil was analyzed. The value of the hydrogenation enthalpy of uracil in aqueous solution was compared with the experimental value in the crystal phase, also dominated by polarity and hydrogen bonds, derived from combustion calorimetry results. The supramolecular effects on the crystal lattice were explored by the computational simulation of π-π staking dimers and hydrogen bonded dimers.

  9. Unexpectedly Enhanced Solubility of Aromatic Amino Acids and Peptides in an Aqueous Solution of Divalent Transition-Metal Cations (United States)

    Shi, Guosheng; Dang, Yaru; Pan, Tingting; Liu, Xing; Liu, Hui; Li, Shaoxian; Zhang, Lijuan; Zhao, Hongwei; Li, Shaoping; Han, Jiaguang; Tai, Renzhong; Zhu, Yiming; Li, Jichen; Ji, Qing; Mole, R. A.; Yu, Dehong; Fang, Haiping


    We experimentally observed considerable solubility of tryptophan (Trp) in a CuCl2 aqueous solution, which could reach 2-5 times the solubility of Trp in pure water. Theoretical studies show that the strong cation-π interaction between Cu2 + and the aromatic ring in Trp modifies the electronic distribution of the aromatic ring to enhance significantly the water affinity of Trp. Similar solubility enhancement has also been observed for other divalent transition-metal cations (e.g., Zn2 + and Ni2 + ), another aromatic amino acid (phenylalanine), and three aromatic peptides (Trp-Phe, Phe-Phe, and Trp-Ala-Phe).

  10. Adsorption of polar aromatic hydrocarbons on synthetic calcite

    DEFF Research Database (Denmark)

    Madsen, Lene; Grahl-Madsen, Laila; Grøn, Christian


    studied by adsorption experiments. The results clearly demonstrate the differences in the adsorption behaviour between probes with different functional groups of varying polarity and acidity. The maximum adsorption decreases in the order: benzoic acid, benzyl alcohol and benzylamine. The order...... of magnitude of Delta G degrees for the adsorption process implies the formation of a strong bond between the calcite surface and the adsorbate molecules. Copyright (C) 1996 Elsevier Science Ltd....

  11. A novel cloud-point extraction process for preconcentrating selected polycyclic aromatic hydrocarbons in aqueous solution

    Energy Technology Data Exchange (ETDEWEB)

    Bai, D.; Li, J.; Chen, S.B.; Chen, B.-H. [National University of Singapore (Singapore). Dept. of Chemical and Environmental Engineering


    Polycyclic aromatic hydrocarbons (PAHs) released in such processes as incomplete coal combustion and during the disposal of coal tar, are subject to strict emission controls in which the determination of PAHs has to be addressed. PAHs have low aqueous solubility which necessitates preconcentration prior to the analytical determination of PAHs. A novel but simple cloud-point extraction (CPE) process is developed to preconcentrate the trace of selected polycyclic aromatic hydrocarbons (PAHs) with the use of the readily biodegradable nonionic surfactant of secondary ethyoxylated alcohol Tergitol 15-S-7 as extractant. The concentrations of PAHs, mixtures of naphthalene and phenanthrene as well as pyrene in the spiked samples were determined with the new CPE process at ambient temperature (23{degree}C) followed by high performance liquid chromatography (HPLC) with fluorescence detection. More than 80% of phenanthrene and pyrene, respectively, and 96% of naphthalene initially present in the aqueous solutions with concentrations near or below their aqueous solubilities were recovered using this new CPE process. Importantly Tergitol 15-S-7 does not give any fluorometric signal to interfere with fluorescence detection of PAHs in the UV range. No special washing step is, thus, required to remove surfactant before HPLC analyses. Different experimental conditions were studied. The optimum conditions for the preconcentration and determination of these selected PAHs at ambient temperature have been established as the following: (1) 3 wt% surfactant; (2) addition of 0.5 M Na{sub 2}SO{sub 4}; (3) 10 min for equilibration time; and (4) 3000 rpm for centrifugal speed with duration of 10 min. 50 refs., 7 figs.

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

    Energy Technology Data Exchange (ETDEWEB)

    Chen Baoliang, E-mail: [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)


    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

  13. Adsorption of polar, nonpolar, and substituted aromatics to colloidal graphene oxide nanoparticles. (United States)

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


    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 1,3-dichlorobenzene) and model polar compounds (1-naphthol, 1-naphthylamine, 2,4-dichlorophenol, and 2,4-dinitrotoluene). GONPs exhibited strong adsorption affinities for all the test compounds, with distribution coefficients on the order of 10(3)-10(6) L/kg. Adsorption to GONPs is much more linear than to carbon nanotubes (CNTs) and C60, likely because GO nanoflakes are essentially individually dispersed (rendering adsorption sites of similar adsorption energy) whereas CNT/C60 are prone to bundling/aggregation. For a given compound GONPs and CNTs often exhibit different adsorption affinities, which is attributable to the differences in both the morphology and surface chemistry between the two nanomaterials. Particularly, the high surface O-content of GONPs enables strong H-bonding and Lewis acid-base interactions with hydroxyl- and amino-substituted aromatics.

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

    Energy Technology Data Exchange (ETDEWEB)

    Sato, Sanae; Yoshihara, Kazuya; Moriyama, Koji [Faculty of Engineering, Chiba University, Yayoi-cho 1-33, Inage-ku, Chiba 263-8522 (Japan); Machida, Motoi [Graduate School of Engineering, Chiba University, Yayoi-cho 1-33, Inage-ku, Chiba 263-8522 (Japan)], E-mail:; Tatsumoto, Hideki [Graduate School of Engineering, Chiba University, Yayoi-cho 1-33, Inage-ku, Chiba 263-8522 (Japan)


    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 C{pi}-cation interaction for the heavy metals adsorption, and from some kind of oxygen-aromatics interaction to {pi}-{pi} dispersion for the aromatics.

  15. Aromatic quinoxaline as corrosion inhibitor for bronze in aqueous chloride solution

    Indian Academy of Sciences (India)

    N Saoudi; A Bellaouchou; A Guenbour; A Ben Bachir; E M Essassi; M El Achouri


    A new corrosion inhibitor, viz. 3-ethyl-6-méthyl-quinoxalin-2-one, 1-benzyl-6-methyl-quinoxalin- 2-one, 2-benzyloxy-3,6-dimethyl-quinoxaline, 1-benzyl-3-methyl-quinoxalin-2-one, were synthesized in the laboratory. Their influence on the inhibition on corrosion of bronze in aqueous chloride solution (3% NaCl) was studied by electrochemical polarization methods and weight-loss measurements. The impact of temperature on the effectiveness of the substances mentioned above has been determined between 20 and 60°C. The results showed that the corrosion resistance was greatly enhanced in the presence of inhibitor and that the effectiveness depends on some physicochemical properties of the molecule, related to its functional groups. These compounds act through the formation of a protective film on the surface of the alloy.

  16. pH-switchable structural evolution in aqueous surfactant-aromatic dibasic acid system. (United States)

    Rose J, Linet; Tata, B V R; Aswal, V K; Hassan, P A; Talmon, Yeshayahu; Sreejith, Lisa


    Structural transitions triggered by pH in an aqueous micellar system comprising of a cationic surfactant (cetylpyridinium chloride) and an aromatic dibasic acid (phthalic acid) was investigated. Reversible switching between liquid-like and gel-like states was exhibited by the system on adjusting the solution pH. Self-assembled structures, responsible for the changes in flow properties were identified using rheology, light scattering techniques and cryogenic Transmission Electron Microscopy (cryo-TEM). High-viscosity, shear-thinning behavior and Maxwell-type dynamic rheology shown by the system at certain pH values suggested the growth of spheroidal/short cylindrical micelles into long and entangled structures. Light scattering profiles also supported the notion of pH-induced microstructural transitions in the solution. Cryo-TEM images confirmed the presence of spheroidal/short cylindrical micelles in the low-viscosity sample whereas very long and entangled thread-like micelles in the peak viscosity sample. pH-dependent changes in the micellar binding ability of phthalic acid is proposed as the key factor regulating the morphological transformations and related flow properties of the system.

  17. Correlation of the solubility of several aromatics and terpenes in aqueous hydroxypropyl-beta-cyclodextrin with steric and hydrophobicity parameters. (United States)

    Demian, B A


    The solubility isotherms of nineteen aromatics and terpenes in aqueous hydroxypropyl-beta-cyclodextrin were determined to be straight lines. This is explained by the host-guest complexation which is characteristic for the whole class of cyclodextrins and derivatives. The slopes of the solubility isotherms correlate with Sterimol L and log P(ow) as descriptors of the steric fit and hydrophobicity match, in accord with the qualitative representation of the phenomenon.

  18. ReCl(CO)5-catalyzed Reactions of Aromatic Compounds with 1,3,5-Trioxane or Aqueous Formaldehyde Affording Diarylmethanes

    Institute of Scientific and Technical Information of China (English)

    HUA,Rui-Mao; HE,Jun-Yi; SUN,Hong-Bin


    ReCl(CO)5 catalyzed the dehydration reaction of aromatic compounds with 1,3,5-trioxane or aqueous formaldehyde (37 wt%) under air. The reactions of a variety of aromatic compounds bearing electron-donating group(s)with 1,3,5-trioxane afforded the corresponding diarylmethanes in moderate to good yields.

  19. A DFT-based toxicity QSAR study of aromatic hydrocarbons to Vibrio fischeri: Consideration of aqueous freely dissolved concentration. (United States)

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


    In the present study, quantitative structure-activity relationship (QSAR) techniques based on toxicity mechanism and density functional theory (DFT) descriptors were adopted to develop predictive models for the toxicity of alkylated and parent aromatic hydrocarbons to Vibrio fischeri. The acute toxicity data of 17 aromatic hydrocarbons from both literature and our experimental results were used to construct QSAR models by partial least squares (PLS) analysis. With consideration of the toxicity process, the partition of aromatic hydrocarbons between water phase and lipid phase and their interaction with the target biomolecule, the optimal QSAR model was obtained by introducing aqueous freely dissolved concentration. The high statistical values of R(2) (0.956) and Q(CUM)(2) (0.942) indicated that the model has good goodness-of-fit, robustness and internal predictive power. The average molecular polarizability (α) and several selected thermodynamic parameters reflecting the intermolecular interactions played important roles in the partition of aromatic hydrocarbons between the water phase and biomembrane. Energy of the highest occupied molecular orbital (E(HOMO)) was the most influential descriptor which dominated the toxicity of aromatic hydrocarbons through the electron-transfer reaction with biomolecules. The results demonstrated that the adoption of freely dissolved concentration instead of nominal concentration was a beneficial attempt for toxicity QSAR modeling of hydrophobic organic chemicals.

  20. Aqueous stability of Ga- and N-polar gallium nitride. (United States)

    Foster, Corey M; Collazo, Ramon; Sitar, Zlatko; Ivanisevic, Albena


    The stability of III-nitride semiconductors in various solutions becomes important as researchers begin to integrate them into sensing platforms. This study quantitatively compares the stability of GaN surfaces with different polarities. This type of quantification is important because it represents the first step toward designing semiconductor material interfaces compatible with solution conditions. A stability study of Ga- and N-polar GaN was conducted by immersion of the surfaces in deionized H(2)O, pH 5, pH 9, and H(2)O(2) solutions for 7 days. Inductively coupled plasma mass spectrometry of the solutions was conducted to determine the amount of gallium leached from the surface. X-ray photoelectron spectroscopy and atomic force microscopy were used to compare the treated surfaces to untreated surfaces. The results show that both gallium nitride surface types exhibit the greatest stability in acidic and neutral solutions. Gallium polar surfaces were found to exhibit superior stability to nitrogen polar surfaces in the solutions studied. Our findings highlight the need for further research on surface passivation and functionalization techniques for polar III-nitride semiconductors.

  1. Accounting for Electronic Polarization Effects in Aqueous Sodium Chloride via Molecular Dynamics Aided by Neutron Scattering. (United States)

    Kohagen, Miriam; Mason, Philip E; Jungwirth, Pavel


    Modeled ions, described by nonpolarizable force fields, can suffer from unphysical ion pairing and clustering in aqueous solutions well below their solubility limit. The electronic continuum correction takes electronic polarization effects of the solvent into account in an effective way by scaling the charges on the ions, resulting in a much better description of the ionic behavior. Here, we present parameters for the sodium ion consistent with this effective polarizability approach and in agreement with experimental data from neutron scattering, which could be used for simulations of complex aqueous systems where polarization effects are important.

  2. Prediction of Intramolecular Polarization of Aromatic Amino Acids Using Kriging Machine Learning. (United States)

    Fletcher, Timothy L; Davie, Stuart J; Popelier, Paul L A


    Present computing power enables novel ways of modeling polarization. Here we show that the machine learning method kriging accurately captures the way the electron density of a topological atom responds to a change in the positions of the surrounding atoms. The success of this method is demonstrated on the four aromatic amino acids histidine, phenylalanine, tryptophan, and tyrosine. A new technique of varying training set sizes to vastly reduce training times while maintaining accuracy is described and applied to each amino acid. Each amino acid has its geometry distorted via normal modes of vibration over all local energy minima in the Ramachandran map. These geometries are then used to train the kriging models. Total electrostatic energies predicted by the kriging models for previously unseen geometries are compared to the true energies, yielding mean absolute errors of 2.9, 5.1, 4.2, and 2.8 kJ mol(-1) for histidine, phenylalanine, tryptophan, and tyrosine, respectively.

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

    Energy Technology Data Exchange (ETDEWEB)

    Riddar Johnson, Jakob, E-mail: [Work Environment Chemistry, Stockholm University, P.O. Box 460, 281 24 Haessleholm (Sweden); Karlsson, Daniel; Dalene, Marianne; Skarping, Gunnar [Work Environment Chemistry, Stockholm University, P.O. Box 460, 281 24 Haessleholm (Sweden)


    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 {mu}L 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 {mu}g mL{sup -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.


    Institute of Scientific and Technical Information of China (English)

    Chao Long; Quan-xing Zhang; Ai-min Li; Jin-long Chen


    The adsorption equilibrium isotherms of three aromatic sulfonic acid compounds, 2-naphthalenesulfonic acid, ptoluenesulfonic acid and p-chlorobenzenesulfonic acid, from aqueous solutions by macroporous weak base anion exchanger within the temperature range of 293 K-313 K were obtained. Several isotherm equations were correlated with the equilibrium data, and the experimental data was found to fit the three-parameter Redlich-Peterson equation best within the entire range of concentrations. The study showed that the hydrophobicity of solute has distinct influence on adsorption capacity of the anion exchanger for the aromatic sulfonic acid. Moreover, estimations of the isosteric enthalpy, free energy,and entropy change of adsorption were also reported. The positive isosteric enthalpy and entropy change for adsorption indicate an endothermic and entropy driven process in the present study.

  5. Determination of polar aromatic amines using newly synthesized sol-gel titanium (IV) butoxide cyanopropyltriethoxysilane as solid phase extraction sorbent. (United States)

    Miskam, Mazidatulakmam; Abu Bakar, Nor Kartini; Mohamad, Sharifah


    A solid phase extraction (SPE) method has been developed using a newly synthesized titanium (IV) butoxide-cyanopropyltriethoxysilane (Ti-CNPrTEOS) sorbent for polar selective extraction of aromatic amines in river water sample. The effect of different parameters on the extraction recovery was studied using the SPE method. The applicability of the sorbents for the extraction of polar aromatic amines by the SPE was extensively studied and evaluated as a function of pH, conditioning solvent, sample loading volume, elution solvent and elution solvent volume. The optimum experimental conditions were sample at pH 7, dichloromethane as conditioning solvent, 10 mL sample loading volume and 5 mL of acetonitrile as the eluting solvent. Under the optimum conditions, the limit of detection (LOD) and limit of quantification (LOQ) for solid phase extraction using Ti-CNPrTEOS SPE sorbent (0.01-0.2; 0.03-0.61 µg L(-1)) were lower compared with those achieved using Si-CN SPE sorbent (0.25-1.50; 1.96-3.59 µg L(-1)) and C18 SPE sorbent (0.37-0.98; 1.87-2.87 µg L(-1)) with higher selectivity towards the extraction of polar aromatic amines. The optimized procedure was successfully applied for the solid phase extraction method of selected aromatic amines in river water, waste water and tap water samples prior to the gas chromatography-flame ionization detector separation.

  6. 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.


    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.

  7. 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


    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 1,3-dichlorobenz

  8. Electrochemical transformation of trichloroethylene in aqueous solution by electrode polarity reversal. (United States)

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


    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.

  9. Ultrafast adsorption and selective desorption of aqueous aromatic dyes by graphene sheets modified by graphene quantum dots (United States)

    Ying, Yulong; He, Peng; Ding, Guqiao; Peng, Xinsheng


    Graphene modified by graphene quantum dots (GQDs) has been employed to remove toxic organic dyes. An excellent removal capacity (497 mg g-1) and record-breaking adsorption rate (475 mg g-1 min-1 at 20 °C) were demonstrated for Rhodamine B. The enhancement in performance by nearly a factor of three compared to that of graphene was ascribed to the greatly increased accessible surface area of graphene in aqueous solution as well as the increase in surface charges with the modification with GQDs. Besides, this unique adsorption behavior of the modified graphene was expanded to other typical toxic aqueous aromatic dyes such as Evans Blue, Methyl Orange, Malachite Green and Rose Bengal. What is more, a unique desorption behavior of dyes was first observed when employing different solvents, which enabled the GQD-modified graphene to be exploited for selective extraction of dyes and recycling of the adsorbent. The adsorption and desorption mechanism were further investigated. Combining high removal capacity, rapid adsorption kinetics, good recyclability and unique selective desorption, GQD-modified graphene has potential applications in both water purification and separation of aromatic dyes.

  10. Polar polycyclic aromatic compounds from different coal types show varying mutagenic potential, EROD induction and bioavailability depending on coal rank. (United States)

    Meyer, Wiebke; Seiler, Thomas-Benjamin; Schwarzbauer, Jan; Püttmann, Wilhelm; Hollert, Henner; Achten, Christine


    Investigations of the bioavailability and toxicity of polycyclic aromatic compounds (PAC) have rarely considered the heterogeneity of coals and the impact of more polar PAC besides polycyclic aromatic hydrocarbons (PAH). Earlier, we investigated the toxicity of eight heterogeneous coals and their extracts. In the present study, the hazard potential with respect to mechanism-specific toxicity of polar fractions of dichloromethane extracts from coals was studied. Polar extract fractions of all coal types except for anthracite induced EROD activity (determined in RTL-W1 cells), independent of coal type (Bio-TEQs between 23 ± 16 and 52 ± 22 ng/g). The polar fractions of all bituminous coal extracts revealed mutagenic activity (determined using the Ames Fluctuation test). No significant mutation induction was detected for the polar extract fractions from the lignite, sub-bituminous coal and anthracite samples, which indicates a higher dependency on coal type for polar PAC here. Additionally, information on bioavailability was derived from a bioaccumulation test using the deposit-feeding oligochaete Lumbriculus variegatus which was exposed for 28 days to ground coal samples. Despite the high toxic potential of most coal extracts and a reduced biomass of Lumbriculus in bituminous coal samples, bioaccumulation of PAH and mortality after 28 days were found to be low. Limited bioaccumulation of PAH (up to 3.6 ± 3.8 mg/kg EPA-PAH) and polar PAC were observed for all coal samples. A significant reduction of Lumbriculus biomass was observed in the treatments containing bituminous coals (from 0.019 ± 0.004 g to 0.046 ± 0.011 g compared to 0.080 ± 0.025 g per replicate in control treatments). We conclude that bioavailability of native PAC from coals including polar PAC is low for all investigated coal types. In comparison to lignite, sub-bituminous coals and anthracite, the bioavailability of PAC from bituminous coals is slightly increased.

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

    DEFF Research Database (Denmark)

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


    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...

  12. Polar-solvation classical density-functional theory for electrolyte aqueous solutions near a wall (United States)

    Warshavsky, Vadim; Marucho, Marcelo


    A precise description of the structural and dielectric properties of liquid water is critical to understanding the physicochemical properties of solutes in electrolyte solutions. In this article, a mixture of ionic and dipolar hard spheres is considered to account for water crowding and polarization effects on ionic electrical double layers near a uniformly charged hard wall. As a unique feature, solvent hard spheres carrying a dipole at their centers were used to model water molecules at experimentally known concentration, molecule size, and dipolar moment. The equilibrium ionic and dipole density profiles of this electrolyte aqueous model were calculated using a polar-solvation classical density-functional theory (PSCDFT). These profiles were used to calculate the charge density distribution, water polarization, dielectric permittivity function, and mean electric potential profiles as well as differential capacitance, excess adsorptions, and wall-fluid surface tension. These results were compared with those corresponding to the pure dipolar model and unpolar primitive solvent model of electrolyte aqueous solutions to understand the role that water crowding and polarization effects play on the structural and thermodynamic properties of these systems. Overall, PSCDFT predictions are in agreement with available experimental data.

  13. Polycyclic aromatic hydrocarbons (PAHs) in Antarctic Martian meteorites, carbonaceous chondrites, and polar ice

    Energy Technology Data Exchange (ETDEWEB)

    Becker, L. [Univ. of California, San Diego, La Jolla, CA (United States)]|[National Aeronautics and Space Administration, Moffett Field, CA (United States); Glavin, D.P.; Bada, J.L. [Univ. of California, San Diego, La Jolla, CA (United States)


    Recent analyses of the carbonate globules present in the Martian meteorite ALH84001 have detected polycyclic aromatic hydrocarbons (PAHs) at the ppm level. The distribution of PAHs observed in ALH84001 was interpreted as being inconsistent with a terrestrial origin and were claimed to be indigenous to the meteorite, perhaps derived from an ancient martian biota. We have examined PAHs in the Antarctic shergottite EETA79001, which is also considered to be from Mars, as well as several Antarctic carbonaceous chondrites. We have found that many of the same PAHs detected in the ALH84001 carbonate globules are present in Antarctic carbonaceous chondrites and in both the matrix and carbonate (druse) component of EETA79001. We also investigated PAHs in polar ice and found that carbonate is an effective scavenger of PAHs in ice meltwater. Moreover, the distribution of PAHs in the carbonate extract of Antarctic Allan Hills ice is remarkably similar to that found in both EETA79001 and ALH84001. The reported presence of L-amino acids of apparent terrestrial origin in the EETA79001 druse material suggests that this meteorite is contaminated with terrestrial organics probably derived from Antarctic ice meltwater that had percolated through the meteorite. Our data suggests that the PAHs observed in both ALH84001 and EETA79001 are derived from either the exogenous delivery of organics to Mars or extraterrestrial and terrestrial PAHs present in the ice meltwater or, more likely, from a mixture of these sources. It would appear that PAHs are not useful biomarkers in the search for extinct or extant life on Mars. 33 refs., 3 figs., 1 tab.

  14. The reaction-field effect on the chemical potentials of polar aprotic non-aromatic liquids 1. Vapour pressure (United States)

    Rosseinsky, D. R.; Stead, K.; Mowforth, C. W.


    The reaction field for the interaction of a molecule with its identical neighbours is shown to be a major determinant of the chemical potential of many dipolar liquids. The electrostatic potential w, derived for immersion of the dipolar molecule in its own kind, and notably comprising solely static and hf permittivities, is equated with the difference between the polar-liquid chemical potential and that of an isostructural non-polar hydrocarbon. For all the 26 non-aromatic Onsager liquids for which the requisite data are available, acceptable conformity is established of the vapour pressure calculated from w with that observed, fluorocarbons excepted. If w turns out to be small, vapour pressures of (these 12) dipolars approximate quite closely to those of the isostructural non-polars, as expected. For ketones and nitroalkanes varied-temperature data are available and well reproduced via w: thus calculated vaporization enthalpies equal the observed.

  15. Enhanced sorption of polycyclic aromatic hydrocarbons from aqueous solution by modified pine bark. (United States)

    Li, Yungui; Chen, Baoliang; Zhu, Lizhong


    To enhance removal efficiency of natural sorbent with polycyclic aromatic hydrocarbons (PAHs), single-solute and bi-solute sorption of phenanthrene and pyrene onto raw and modified pine bark were investigated. Pine bark was modified using Soxhlet extraction, saponification and acid hydrolysis, yielding six bark fractions with different chemical compositions. Raw pine bark exhibited high affinities with PAHs, and sorption was dominated by partitioning. The relatively nonlinear sorption isotherms of modified bark were attributed to the specific interaction between sorbate and aromatic core of sorbent. Comparison with lipid and suberin, lignin was the most powerful sorption medium, but which was almost completely suppressed by coexisting polysaccharide. After consuming polysaccharide by acid hydrolysis, sorption of pine bark fractions was notably increased (4-17 folds); and sorption of pyrene just decreased 16-34% with phenanthrene as a competitor. These observations suggest that pine bark is of great potential for PAHs removal and can be significantly promoted by acid hydrolysis for environmental application.

  16. Polarity, selectivity and performance of hydrophilic organic/salt-containing aqueous two-phase system on counter-current chromatography for polar compounds. (United States)

    Liu, Dan; Hong, Zhilai; Gao, Mingzhe; Wang, Zhixin; Gu, Ming; Zhang, Xiaozhe; Xiao, Hongbin


    The essential attributes of a solvent system for separation polar compounds on CCC are polarity, selectively and performance. Here, hydrophilic organic/salt-containing aqueous two-phase system (HO/S TPS) was evaluated as an alternative solvent system for CCC separation of polar compounds. Polarity measurements based on Rohrschneider-Snyder parameter was developed as quantitative assessing the polarity of HO/S TPS and comparing with an organic/aqueous system. All investigated 1-butanol/ethanol/saturated ammonium sulfate solution/water (BEAsWat) and 1-butanol/ethanol/saturated dipotassium hydrogen phosphate solution/water (BEDhpWat) systems with polarity values of organic phase from 4.5 to 6.8, were more polar than chloroform/methanol/water (1/1/1). The considerable water content of BEAsWat and BEDhpWat (0/1/1/1/) was 45.4 and 42.6% (w%) of hydrophilic organic phase, and 66.4 and 51.2% (w%) of salt-containing aqueous phase, respectively, closed to conventional aqueous two-phase system. Therefore, the polarity of HO/S TPS is in the middle of organic/aqueous and aqueous two-phase system. The LogKC values of twenty four polar compounds as model mixture confirmed that the polarities of HO/S TPSs were matched to that of the polar compounds and shown to be a very selective technique capable of separating positional isomers. Moreover, BEAsWat and BEDhpWat systems can be easily retained in CCC column with suitable elution mode. The hydrodynamic behavior reversion of HO/S TPS on hydrodynamic CCC was observed and was tentatively explained based on the density difference. Finally, caffeoylquinic acid isomers and dihydroxybenzoic acid isomers were successfully separated with HO/S TPS on CCC, respectively. Those results demonstrate that HO/S TPS on CCC is a performant and stable way to separate polar compounds from natural products.

  17. Sorption effects interfering with the analysis of polycyclic aromatic hydrocarbons (PAH) in aqueous samples. (United States)

    Krüger, Oliver; Kalbe, Ute; Meißner, Kerstin; Sobottka, Sebastian


    Polycyclic aromatic hydrocarbons (PAH) are severe environmental pollutants that are analyzed frequently. The risk assessment of PAH impact to groundwater can be performed using leaching tests. Therby a liquid-solid separation step including centrifugation may be required, which in turn might lead to loss of analytes due to sorption on the equipment. Thus we determined the PAH recoveries from various container materials (polyethylene (PE), polypropylene (PP), polytetraflourethylene (PTFE), stainless steel (ES), and perflouroalkoxy (PFA)) and compared them to selected PAH properties. We found the best recoveries for PFA (68%) and PTFE (65%) containers. We found good negative correlations (-0.93 and better) between PAH recovery and log partition coefficient organic carbon-water (logKOC) for PFA, PTFE, and ES containers.

  18. Responses of polar organic compounds to different ionic environments in aqueous media are interrelated. (United States)

    Ferreira, L A; Chervenak, A; Placko, S; Kestranek, A; Madeira, P P; Zaslavsky, B Y


    Solubilities of 17 polar organic compounds in aqueous solutions of Na2SO4, NaCl, NaClO4, and NaSCN at the salt concentrations of up to 1.0-2.0 M were determined and the Setschenow constant, ksalt, values were estimated. It was found that NaClO4 may display both salting-in and salting-out effects depending on the particular compound structure. The Setschenow constant values for all the polar compounds examined in different salt solutions are found to be interrelated. Similar relationships were observed for partition coefficients of nonionic organic compounds in aqueous polyethylene glycol-sodium sulfate two-phase systems in the presence of different salt additives reported previously [Ferreira et al., J. Chromatogr. A, 2011, 1218, 5031], and for the effects of different salts on optical rotation of amino acids reported by Rossi et al. [J. Phys. Chem. B, 2007, 111, 10510]. In order to explain the observed relationships it is suggested that all the effects observed originate as responses of the compounds to the presence of a given ionic environment and its interaction with the compounds by forming direct or solvent-separated ionic pairs. The response is compound-specific and its strength is determined by the compound structure and the type (and concentration) of ions inducing the response.

  19. Dehalogenation of aromatics by nucleophilic aromatic substitution. (United States)

    Sadowsky, Daniel; McNeill, Kristopher; Cramer, Christopher J


    Nucleophilic aromatic substitution has been implicated as a mechanism for both the biotic and abiotic hydrodehalogenation of aromatics. Two mechanisms for the aqueous dehalogenation of aromatics involving nucleophilic aromatic substitution with hydride as a nucleophile are investigated using a validated density functional and continuum solvation protocol. For chlorinated and brominated aromatics, nucleophilic addition ortho to carbon-halogen bonds via an anionic intermediate is predicted to be the preferred mechanism in the majority of cases, while concerted substitution is predicted to be preferred for most fluorinated aromatics. Nucleophilic aromatic substitution reactions with the hydroxide and hydrosulfide anions as nucleophiles are also investigated and compared.

  20. QSAR for Predicting Biodegradation Rates of Polycyclic Aromatic Hydrocarbons in Aqueous Systems

    Institute of Scientific and Technical Information of China (English)

    XU Xiang; LI Xian-Guo


    The relationship between chemical structures and biodegradation rates (k b) of 22 polycyclic aromatic hydrocarbons (PAHs) was studied using density functional theory (DFT) and stepwise multiple linear regression analysis (SMLR) method.The equilibrium geometries and vibration frequency have been investigated at the B3LYP/6-31+G(d,p) level by thinking Solvent effects using a selfconsistent reaction field (SCRF) based on the polarizable continuum model (PCM).It was concluded that the biodegradation rate was closely related to its molecular structure,and there is one high correlation coefficient between the in-plane bending vibration frequency of the conjugated ring of PAHs (Freq) and k b.By means of regression analysis,the main factors affecting the biodegradation rate were obtained and the equation of quantitative structure-activity relationship (QSAR) was successfully established kb =-0.653+0.001Freq+0.068CQ+0.049N1.Statistical evaluation of the developed QSAR showed that the relationships were statistically significant and the model had good predictive ability.The fact that a bending frequency is more important than the HOMO or LUMO energies in predicting k b suggests that the bending of benzene ring might play an important role in the enzymatic catalysis of the initial oxidation step.

  1. Polar organic solvent added to an aqueous solution changes hydrolytic property of lipase. (United States)

    Tsuzuki, Wakako; Ue, Akemi; Nagao, Akihiko


    For developing further uses of lipase as a biocatalyst, its hydrolytic activity toward some esters was investigated in a miscible solution composed of a buffer and a polar organic solvent. Twenty percent dimethylformamide, 35% dimethylsulfoxide, 15% 1,4-dioxane, 15% dimethoxyethane, and 2% diethoxyethane promoted the hydrolysis by a lipase from Rhizomucor miehei toward some hydrophobic substrates, 4-methylumbelliferyl oleate, 4-methylumbelliferyl palmitate, and monoolein. While hydrolysis by this lipase toward the substrates with a relatively weak hydrophobicity (4-metylumbelliferyl heptanoate and 4-methylumbelliferyl nanoate) was suppressed by these solvents. A fluorometric analysis showed that the polar organic solvent in the buffer induced some conformational change around a tryptophan residue of R. miehei lipase. In addition to the influence of the miscible solvent on the solubility of the substrates, the conformational change of the protein induced by the miscible solvent would also affect the reactive properties of the lipase. Adding a polar organic solvent to an aqueous solution will be an efficient method for changing hydrolytic performance of lipases.

  2. Enhanced aqueous solubility of polycyclic aromatic hydrocarbons by green diester-linked cationic gemini surfactants and their binary solutions (United States)

    Panda, Manorama; Fatma, Nazish; Kabir-ud-Din


    Three homologues of a novel biodegradable diester-linked cationic gemini surfactant series, CmH2m+1 (CH3)2N+(CH2COOCH2)2N+(CH3)2CmH2m+1.2Cl- (m-E2-m; m = 12, 14, 16), were used for investigation of the solubilization of polycyclic aromatic hydrocarbons (PAHs) such as naphthalene, anthracene and pyrene in single as well as binary surfactant solutions. Physicochemical parameters of the pure/mixed systems were derived by conductivity and surface tension measurements. Dissolution capacity of the equimolar binary surfactant solutions towards the PAHs was studied from the molar solubilization ratio (MSR), micelle-water partition coefficient (Km) and free energy of solubilization (ΔGs0) of the solubilizates. Influence of hydrophobic chain length of the dimeric surfactants on solubilization was characterized. Aqueous solubility of the PAHs was enhanced linearly with concentration of the surfactant in all the pure and mixed gemini-gemini surfactant systems.

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



    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 benzophenone...

  4. Biosorption and biodegradation of polycyclic aromatic hydrocarbons in aqueous solutions by a consortium of white-rot fungi. (United States)

    Chen, Baoliang; Wang, Yinshan; Hu, Dingfei


    Bioremediation is a popular approach used to abate polycyclic aromatic hydrocarbons (PAHs) in the environment. A consortium of white-rot fungi (CW-1) isolated from wood pieces was used for studying their potential of bioremediation of PAHs. Biosorption and biodegradation of PAHs by live and heat-killed white-rot fungi (CW-1) were investigated to elucidate the bio-dissipation mechanisms of PAHs. Sorption isotherms of naphthalene, acenaphthene, fluorene, phenanthrene and pyrene to heat-killed fungal biomass were linear and non-competitive, indicating the primary mechanism of biosorption to be by partition. The carbon-normalized partition coefficients (K(oc)) were linearly correlated with octanol-water partition coefficients (K(ow)), i.e., log K(oc)=1.13 log K(ow)-0.84 (n=5, r(2)=0.996). Biosorption and biodegradation of phenanthrene and pyrene by live white-rot fungi were quantified. In 1 week, the removal efficiency of phenanthrene (70-80%) and pyrene (90%) by live fungi from aqueous solution were comparable to those by heat-killed fungi. However, approximately 40-65% of phenanthrene and 60-85% of pyrene were still stored in organismal bodies. Biosorption might restrict biodegradation while nutrient limitation and presence of a PAH mixture might stimulate biodegradation. The apparent partition coefficients (K(d)(*)) in live fungal systems and the K(d) of heat-killed fungi without biodegradation were compared, and then the K(d)(*)/K(d) ratios were employed to illustrate the relative contributions of biosorption and biodegradation under different nutrient conditions.

  5. Anion-π aromatic neutral tweezers complexes: are they stable in polar solvents? (United States)

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


    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.

  6. Circularly Polarized Persistent Room-Temperature Phosphorescence from Metal-Free Chiral Aromatics in Air. (United States)

    Hirata, Shuzo; Vacha, Martin


    Circularly polarized room-temperature phosphorescence (RTP) with persistent emission characteristics was observed from metal-free chiral binaphthyl structures. Enantiomers of the binaphthyl compounds doped into an amorphous hydroxylated steroid matrix produced blue fluorescence and yellow persistent RTP in air. The lifetime and quantum yield of the yellow persistent RTP were 0.67 s and 2.3%, respectively. The dissymmetry factors of circular dichroism (CD) in the first absorption band, circularly polarized fluorescence (CPF), and circularly polarized persistent RTP were |1.1 × 10(-3)|, |4.5 × 10(-4)|, and |2.3 × 10(-3)|, respectively. A comparison between the experimental data and calculations by time-dependent density functional theory for transient CD spectra confirmed that the binaphthyl conformations in the lowest singlet excited state (S1) and the lowest triplet state (T1) were different. The large difference in the dissymmetry factors for the CPF and the circularly polarized persistent RTP was likely caused by this conformational change between S1 and T1.

  7. Polar aromatic biomarkers of Miocene-aged Chukurovo resinite and correlation with a progenitor macrofossil

    Energy Technology Data Exchange (ETDEWEB)

    Stefanova, Maya [Institute of Organic Chemistry, Bulgarian Academy of Sciences, Sofia 1113 (Bulgaria); Simoneit, Bernd R.T. [Department of Chemistry, Oregon State University, Corvallis, Oregon 97331 (United States)


    Functionalised aromatic constituents of Chukurovo resinite are compared here with the chemical composition of a macrofossil assigned paleobotanically as Taxodium dubium (Sternb.) Heer. Terpenoids and lipids of fossil wood tissue embedded in a clay sediment were extracted and analyzed for comparison. The information was interpreted in relation to the biomarker compositions of different conifer families, as well as to the effects of contamination by inward migration of organic matter from the adjacent sediments. Many of identified geolipids, i.e., alkanes, alkanols, alkan-2-ones, and steranes/triterpanes have no chemosystematic value because they are ubiquitous in the plant kingdom. Ferruginol, sugiol, and products of their diagenetic transformations were identified as the dominant specific biomarkers in the resinite. Ferruginol and its analogues were the most abundant diterpenoids in Taxodium dubium sample. Thus, the biomarker composition of the extractable matter of the resinite strongly suggests that species of Cupressaceae contributed significantly to the Chukurovo paleoenvironment. (author)

  8. Polar metabolites of polycyclic aromatic compounds from fungi are potential soil and groundwater contaminants. (United States)

    Boll, Esther S; Johnsen, Anders R; Christensen, Jan H


    This study investigated the sorption to soil of water-soluble metabolites from polycyclic aromatic compounds (PACs). The soil fungus Cunninghamella elegans was used to produce PAC metabolites from two un-substituted PACs (phenanthrene, pyrene), three alkyl-substituted PACs (2-methylnaphthalene, 1-methylphenanthrene, 1-methylpyrene), and one sulfur-containing heterocyclic PAC (dibenzothiophene). Fifty-eight metabolites were tentatively identified; metabolites from the un-substituted PACs were hydroxylated and sulfate conjugated, whereas metabolites from alkyl-substituted PACs were sulfate conjugated and either hydroxylated or oxidized to carboxylic acids at the methyl group. The metabolism of the sulfur-containing heterocyclic PAC resulted in sulfate conjugates. The sorption of the PAC metabolites to three soils was determined using a batch equilibrium method, and partition coefficients (Kd's) were calculated for fourteen representative metabolites. Sulfate conjugated metabolites displayed Kd's below 70 whereas the metabolites with both a sulfate and a carboxylic acid group had Kd's below 2.8. The low Kd's of water-soluble PAC metabolites indicate high mobility in soil and a potential for leaching to surface- and groundwaters.

  9. Thermodynamic constrains for life based on non-aqueous polar solvents on free-floating planets. (United States)

    Badescu, Viorel


    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.

  10. 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


    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.

  11. Characterization and deposit-forming tendency of polar compounds in cracked components of gasoline. Identification of phenols and aromatic sulfur compounds

    Energy Technology Data Exchange (ETDEWEB)

    Martin, P.; McCarty, F.; Ehrmann, U.; Lima, L. de; Carvajal, N.; Rojas, A. (INTEVEP S.A., Caracas (Venezuela))


    Acidic compounds in cracked components of gasoline, isolated by extraction with aqueous solutions of sodium bicarbonate and sodium hydroxide, were identified as phenol and its mono-, di-, tri- and tetramethyl- derivatives. Aromatic sulfur compounds separated as the hexane and benzene fractions by chromatography on an alumina column were identified as thiophene, its mono-, di- and trimethyl- derivatives, ethylthiophene, benzothiophene and methylbenzothiophene. The identification of the phenolic compounds was achieved by IR, hydrogen-1 and carbon-13 NMR spectroscopy and GC-MS. Additionally, for complete identification of sulfur compounds a GC equipped with a selective sulfur detector was used. ISD Induction System Deposit (ISD) tests showed a decreased deposit-forming tendency for phenol compounds and no significant deposit formation for aromatic sulfur compounds or other fractions isolated. 10 refs., 6 figs., 4 tabs.

  12. Aqueous and Tissue Residue-Based Interspecies Correlation Estimation Models Provide Conservative Hazard Estimates for Aromatic Compounds (United States)

    Interspecies correlation estimation (ICE) models were developed for 30 nonpolar aromatic compounds to allow comparison of prediction accuracy between 2 data compilation approaches. Type 1 models used data combined across studies, and type 2 models used data combined only within s...

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

    Lin, Shu-Ling; Wang, Chih-Chieh; Fuh, Ming-Ren


    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.

  14. Sol-gel immobilized cyano-polydimethylsiloxane coating for capillary microextraction of aqueous trace analytes ranging from polycyclic aromatic hydrocarbons to free fatty acids. (United States)

    Kulkarni, Sameer; Fang, Li; Alhooshani, Khalid; Malik, Abdul


    Sol-gel coating containing highly polar cyanopropyl and nonpolar poly(dimethylsiloxane) components (sol-gel CN-PDMS coating) was developed for capillary microextraction (CME). The sol-gel chemistry provided an efficient means to immobilize the CN-PDMS coating by establishing chemical anchorage between the coating and the fused silica capillary inner surface. This chemical bond provided excellent thermal and solvent stability to the created sol-gel coating. For the extraction of polar and nonpolar analytes, the upper allowable conditioning temperatures were 330 degrees C and 350 degrees C, respectively. To our knowledge, this is the first time when a CN-PDMS thick coating survived such a high operation temperature. The prepared sol-gel CN-PDMS coating provided effective extraction of polar and nonpolar analytes simultaneously from aqueous samples. The cyanopropyl moiety in sol-gel CN-PDMS coatings provided effective extraction of highly polar analytes such as free fatty acids, alcohols, and phenols without requiring derivatization, pH adjustment or salting out procedures. The PDMS moiety, on the other hand, provided efficient extraction of nonpolar analytes. The extraction properties of the sol-gel CN-PDMS coatings can be fine tuned via manipulation of relative proportions of 3-cyanopropyltriethoxysilane and hydroxy-terminated PDMS in the sol solution used to create the coatings. Detection limits of nanogram/liter (ng/L) were achieved for both highly polar and nonpolar analytes directly extracted from aqueous media using sol-gel CN-PDMS coated microextraction capillaries followed by GC analysis.

  15. Prediction and application in QSPR of aqueous solubility of sulfur-containing aromatic esters using GA-based MLR with quantum descriptors. (United States)

    Yin, Chunsheng; Liu, Xinhui; Guo, Weimin; Lin, Teng; Wang, Xiaodong; Wang, Liansheng


    Quantitative structure-property relationships (QSPR) were developed using a genetic algorithm (GA)-based variable-selection approach with quantum chemical descriptors derived from AM1-based calculations (MOPAC7.0). With the QSPR models, the aqueous solubility of 71 aromatic sulfur-containing carboxylates, including phenylthio, and phenylsulfonyl carboxylates were efficiently estimated and predicted. Using GA-based multivariate linear regression (MLR) with cross-validation procedure, the most important descriptors were selected from a pool of 28 quantum chemical semi-empirical descriptors, including steric and electronic types, to build QSPR models. The molecular descriptors included molecular surface (SA), charges on carboxyl group (Q(oc)), the magnitude of the difference between E(HOMO) of the solute and ELUMO of water, divided by 100 (E(B)), which were main factors affecting the aqueous solubility of the compounds of interest. The resulted coefficients R and R2 of 0.9571 and 0.9161 and the prediction residual error sum of squares (PRESS) of 13.1768, revealed that it was accurate and reliable for the model to predict the aqueous solubility of the investigated organic compounds. If two outliers were omitted from the dataset, the resulted coefficients R = 0.9619, R2 = 0.9253, and PRESS = 10.3875 were significantly improved. Compared with stepwise regression analysis, the results obtained in this work were better and more reasonable. The best QSPR model were obtained by GA-based MLR. Reasonable mechanisms for aqueous solubility of the sulfur-containing carboxylates were investigated and interpreted.

  16. Self-Assembled Templates of Aromatic Pentapeptides for Synthesis of CdS Quantum-Dots to Detect the Trace Amounts of Hg(2+) in Aqueous Solutions. (United States)

    Meng, Min; Dou, Yingying; Xu, Wenlong; Hao, Jingcheng


    Molecular self-assembly has become a popular tool to prepare nanomaterials with potential applications, such as ion-responsive detection of Hg(2+) in aqueous solutions. In this study, FFACD aromatic pentapeptides, whose N-terminuses were protected by carboxyl (Ac-FFACD) or a 9-fluorenylmethoxycarbonyl group (Fmoc-FFACD), were chosen as building blocks to produce nanostructures in solutions. Based on the preliminary determination of the critical aggregation concentration (CAC) of Ac-FFACD and Fmoc-FFACD aromatic pentapeptides in water, the order of magnitude of which is 10(-5) mol·L(-1), self-assembled spiral and networked nanowires can be easily obtained over a range of concentrations. These nanowires were characterized by transmission electron microscopy (TEM), scanning electron microscopy (SEM), and atomic force microscopy (AFM). The self-assembled spiral and networked nanowires were designed to be used as templates for preparing CdS quantum dots (QDs) in-situ at room temperature. The peptide-functionalized, nanowire-encapsulated CdS QDs can be used for rapid, sensitive, and selective detection of trace amounts of mercuric ions (Hg(2+)) in aqueous solutions. This method enables rapid, linear detection (the linear correlation coefficients are 0.9972 of ΔF = 257.09 + 3.58 cHg(2+) for Ac-FFACD and 0.9994 of ΔF = 48.13 + 32.96 cHg(2+) for Fmoc-FFACD) with the Hg(2+) limit of detection at 300.85 ng·L(-1) and 32.09 ng·L(-1) for Ac-FFACD and Fmoc-FFACD, respectively. The supramolecular, self-assembled nanowires, fabricated from the two aromatic pentapeptides and having encapsulated QDs, exhibit superior properties attributable to the large loading capacity and the coordination sites of these peptides with Hg(2+). These structures can serve as novel Hg(2+) sensors and have possible applications for detection of various targets in scientific and engineering systems.

  17. 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


    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.

  18. Adsorptive micro-extraction techniques--novel analytical tools for trace levels of polar solutes in aqueous media. (United States)

    Neng, N R; Silva, A R M; Nogueira, J M F


    A novel enrichment technique, adsorptive μ-extraction (AμE), is proposed for trace analysis of polar solutes in aqueous media. The preparation, stability tests and development of the analytical devices using two geometrical configurations, i.e. bar adsorptive μ-extraction (BAμE) and multi-spheres adsorptive μ-extraction (MSAμE) is fully discussed. From the several sorbent materials tested, activated carbons and polystyrene divinylbenzene phases demonstrated the best stability, robustness and to be the most suitable for analytical purposes. The application of both BAμE and MSAμE devices proved remarkable performance for the determination of trace levels of polar solutes and metabolites (e.g. pesticides, disinfection by-products, drugs of abuse and pharmaceuticals) in water matrices and biological fluids. By comparing AμE techniques with stir bar sorptive extraction based on polydimethylsiloxane phase, great effectiveness is attained overcoming the limitations of the latter enrichment approach regarding the more polar solutes. Furthermore, convenient sensitivity and selectivity is reached through AμE techniques, since the great advantage of this new analytical technology is the possibility to choose the most suitable sorbent to each particular type of application. The enrichment techniques proposed are cost-effective, easy to prepare and work-up, demonstrating robustness and to be a remarkable analytical tool for trace analysis of priority solutes in areas of recognized importance such as environment, forensic and other related life sciences.

  19. 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. (United States)

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


    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.

  20. High extraction efficiency for polar aromatic compounds in natural water samples using multiwalled carbon nanotubes/Nafion solid-phase microextraction coating. (United States)

    Chen, Wenfeng; Zeng, Jingbin; Chen, Jinmei; Huang, Xiaoli; Jiang, Yaqi; Wang, Yiru; Chen, Xi


    A novel solid-phase microextraction (SPME) fiber coated with multiwalled carbon nanotubes (MWCNTs)/Nafion was developed and applied for the extraction of polar aromatic compounds (PACs) in natural water samples. The characteristics and the application of this fiber were investigated. Electron microscope photographs indicated that the MWCNTs/Nafion coating with average thickness of 12.5microm was homogeneous and porous. The MWCNTs/Nafion coated fiber exhibited higher extraction efficiency towards polar aromatic compounds compared to an 85microm commercial PA fiber. SPME experimental conditions, such as fiber coating, extraction time, stirring rate, desorption temperature and desorption time, were optimized in order to improve the extraction efficiency. The calibration curves were linear from 0.01 to 10microgmL(-1) for five PACs studied except p-nitroaniline (from 0.005 to 10microgmL(-1)) and m-cresol (from 0.001 to 10microgmL(-1)), and detection limits were within the range of 0.03-0.57ngmL(-1). Single fiber and fiber-to-fiber reproducibility were less than 7.5 (n=7) and 10.0% (n=5), respectively. The recovery of the PACs spiked in natural water samples at 1microgmL(-1) ranged from 83.3 to 106.0%.

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

    NARCIS (Netherlands)

    Asaad, N; den Otter, MJ; Engberts, JBFN; Otter, Marie Jetta den


    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 solu

  2. Bupivacaine salts of diflunisal and other aromatic hydroxycarboxylic acids: aqueous solubility and release characteristics from solutions and suspensions using a rotating dialysis cell model. (United States)

    Østergaard, Jesper; Larsen, Susan W; Parshad, Henrik; Larsen, Claus


    In the search for poorly soluble bupivacaine salts potentially enabling prolonged postoperative pain relief after local joint administration in the form of suspensions the solubility of bupivacaine salts of diflunisal and other aromatic hydroxycarboxylic acids were investigated together with the release characteristics of selected 1:1 salts from solutions and suspensions using a rotating dialysis cell model. The poorest soluble bupivacaine salts were obtained from the aromatic ortho-hydroxycarboxylic acids diflunisal, 5-iodosalicylic acid, and salicylic acid (aqueous solubilities: 0.6-1.9 mM at 37 degrees C). Diffusant appearance rates in the acceptor phase upon instillation of solutions of various salts in the donor cell applied to first-order kinetics. Calculated permeability coefficients for bupivacaine and the counterions diflunisal, 5-iodosalicylic acid, and mandelic acid were found to be correlated with the molecular size of the diffusants. Release experiments at physiological pH involving suspensions of the bupivacaine-diflunisal salt revealed that at each sampling point the diflunisal concentration exceeded that of bupivacaine in the acceptor phase. However, after an initial lag period, a steady state situation was attained resulting in equal and constant fluxes of the two diffusants controlled by the permeability coefficients in combination with the solubility product of the salt. Due to the fact that the saturation solubility of the bupivacaine-salicylic acid salt in water exceeded that of bupivacaine at pH 7.4, suspensions of the latter salt were unable to provide simultaneous release of the cationic and anionic species at pH 7.4. The release profiles were characterised by a rapid release of salicylate accompanied by a much slower appearance of bupivacaine in the acceptor phase caused by precipitation of bupivacaine base from the solution upon dissolution of the salt in the donor cell.

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

    KAUST Repository

    Ataherian, Fatemeh


    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.

  4. Strong Circularly Polarized Luminescence from Highly Emissive Terbium Complexes in Aqueous Solution

    Energy Technology Data Exchange (ETDEWEB)

    Samuel, Amanda; Lunkley, Jamie; Muller, Gilles; Raymond, Kenneth


    Two luminescent terbium(III) complexes have been prepared from chiral ligands containing 2-hydroxyisophthalamide (IAM) antenna chromophores and their non-polarized and circularly-polarized luminescence properties have been studied. These tetradentate ligands, which form 2:1 ligand/Tb{sup III} complexes, utilize diaminocyclohexane (cyLI) and diphenylethylenediamine (dpenLI) backbones, which we reasoned would impart conformational rigidity and result in Tb{sup III} complexes that display both large luminescence quantum yield ({phi}) values and strong circularly polarized luminescence (CPL) activities. Both Tb{sup III} complexes are highly emissive, with {phi} values of 0.32 (dpenLI-Tb) and 0.60 (cyLI-Tb). Luminescence lifetime measurements in H{sub 2}O and D{sub 2}O indicate that while cyLI-Tb exists as a single species in solution, dpenLI-Tb exists as two species: a monohydrate complex with one H{sub 2}O molecule directly bound to the Tb{sup III} ion and a complex with no water molecules in the inner coordination sphere. Both cyLI-Tb and dpenLI-Tb display increased CPL activity compared to previously reported Tb{sup III} complexes made with chiral IAM ligands. The CPL measurements also provide additional confirmation of the presence of a single emissive species in solution in the case of cyLI-Tb, and multiple emissive species in the case of dpenLI-Tb.

  5. Purge-assisted headspace solid-phase microextraction combined with gas chromatography/mass spectrometry for the determination of trace nitrated polycyclic aromatic hydrocarbons in aqueous samples. (United States)

    Hung, Cheng-Han; Ho, Hsin-Pin; Lin, Mei-Tzu; Chen, Chung-Yu; Shu, Youn-Yuen; Lee, Maw-Rong


    This study describes a new procedure, namely, purge-assisted headspace solid phase microextraction combined with gas chromatography/negative ion chemical ionization mass spectrometry (PA/HS-SPME-GC/NICI-MS), which is used to determine seven nitrated polycyclic aromatic hydrocarbons (NPAHs) in aqueous samples. High extraction efficiency was obtained with PA/HS-SPME with polydimethylsiloxane (PDMS) fiber coating. A programmable temperature vaporizing (PTV) inlet was used in the desorption process. Selected ion monitoring (SIM) was used for quantitative and qualitative purposes. The linear range of detection of the proposed method was 5-5000 pg/mL with coefficients of determination between 0.995 and 0.999. Limits of detection (LODs) for seven NPAHs were 0.01-0.06 pg/mL. The relative standard deviation was below 12.7% at a concentration of 50 pg/mL. Compared with headspace-solid phase microextraction (HS-SPME), the purge procedure enhanced the extraction efficiency for high boiling point analytes, such as 7-nitrobenz[a]anthracene (7-NBA) and 6-nitrochrysene (6-NC). The proposed method provides a sensitive method for NPAH analysis at the pg/mL level. The application of the proposed method for the determination of trace NPAHs in real samples was investigated by analyzing aqueous samples from rivers. The concentrations of NPAHs detected from the samples ranged from 5.2 to 7.5 pg/mL. This method was applied successfully in the analysis of trace NPAHs in river samples.

  6. Analysis of binary mixtures of aqueous aromatic hydrocarbons with low-phase-noise shear-horizontal surface acoustic wave sensors using multielectrode transducer designs. (United States)

    Bender, Florian; Mohler, Rachel E; Ricco, Antonio J; Josse, Fabien


    The present work investigates a compact sensor system that provides rapid, real-time, in situ measurements of the identities and concentrations of aromatic hydrocarbons at parts-per-billion concentrations in water through the combined use of kinetic and thermodynamic response parameters. The system uses shear-horizontal surface acoustic wave (SH-SAW) sensors operating directly in the liquid phase. The 103 MHz SAW sensors are coated with thin sorbent polymer films to provide the appropriate limits of detection as well as partial selectivity for the analytes of interest, the BTEX compounds (benzene, toluene, ethylbenzene, and xylenes), which are common indicators of fuel and oil accidental releases in groundwater. Particular emphasis is placed on benzene, a known carcinogen and the most challenging BTEX analyte with regard to both regulated levels and its solubility properties. To demonstrate the identification and quantification of individual compounds in multicomponent aqueous samples, responses to binary mixtures of benzene with toluene as well as ethylbenzene were characterized at concentrations below 1 ppm (1 mg/L). The use of both thermodynamic and kinetic (i.e., steady-state and transient) responses from a single polymer-coated SH-SAW sensor enabled identification and quantification of the two BTEX compounds in binary mixtures in aqueous solution. The signal-to-noise ratio was improved, resulting in lower limits of detection and improved identification at low concentrations, by designing and implementing a type of multielectrode transducer pattern, not previously reported for chemical sensor applications. The design significantly reduces signal distortion and root-mean-square (RMS) phase noise by minimizing acoustic wave reflections from electrode edges, thus enabling limits of detection for BTEX analytes of 9-83 ppb (calculated from RMS noise); concentrations of benzene in water as low as ~100 ppb were measured directly. Reliable quantification of BTEX

  7. A comparative QSPR study on aqueous solubility of polycyclic aromatic hydrocarbons by GA-SVM, GA-RBFNN and GA-PLS

    Institute of Scientific and Technical Information of China (English)

    Jun QI; Jia WEI; Changhong SUN; Tao PAN


    A novel method to develop quantitative structure-property relationship(QSPR)models of organic contaminants was proposed based on genetic algorithm (GA)and support vector machine(SVM).GA was used to perform the variable selection and SVM was used to construct QSPR models.In this study,GA-SVM was applied to develop the QSPR model for aqueous solubility (Sw,mol·L-1)of polycyclic aromatic hydrocarbons (PAHs).The R2(0.98)of the model developed by GASVM indicated a good predictive precision for 1g Sw values of PAHs.According to leave-one-out(LOO)cross validation,the results of GA-SVM were compared with those of genetic algorithm-radial based function neural network(GA-RBFNN)and genetic algorithm-partial leastsquares(GA-PLS)regression.The comparisons showed that the cross validation correlation coefficient(Q2LOO =0.92)and root mean square error of LOO cross validation (RMSELoo =0.49)of GA-SVM were the highest and lowest,respectively,which illustrated that GA-SVM was more suitable to develop QSPR model for the lg Sw values of PAHs than GA-RBFNN and GA-PLS.

  8. Kinetics and thermodynamics of adsorption of ionizable aromatic compounds from aqueous solutions by as-prepared and oxidized multiwalled carbon nanotubes. (United States)

    Sheng, G D; Shao, D D; Ren, X M; Wang, X Q; Li, J X; Chen, Y X; Wang, X K


    The adsorption of 1-naphthylamine, 1-naphthol and phenol on as-prepared and oxidized multiwalled carbon nanotubes (MWCNTs) has been investigated. The results illustrated that both as-prepared and oxidized MWCNTs showed high adsorption capacity for the three ionizable aromatic compounds (IACs) studied. Oxidation of MWCNTs increased the surface area and the pore volume, and introduced oxygen-containing functional groups to the surfaces of MWCNTs, which depressed the adsorption of IACs on MWCNTs. Both Langmuir and Freundlich models described the adsorption isotherms very well and the adsorption thermodynamic parameters (DeltaG degrees, DeltaH degrees and DeltaS degrees) were measured. The adsorption for 1-naphthylamine, 1-naphthol and phenol is general spontaneous and thermodynamically favorable. The adsorption of phenol is an exothermic process, whereas the adsorption of 1-naphthylamine and 1-naphthol is an endothermic process. Results of this work are of great significance for the environmental application of MWCNTs for the removal of IACs from large volume of aqueous solutions.

  9. Complexation of uranium(VI) with aromatic acids in aqueous solution. A comparison of hydroxamic acids and benzoic acid

    Energy Technology Data Exchange (ETDEWEB)

    Glorius, M.; Moll, H.; Bernhard, G. [Forschungszentrum Dresden-Rossendorf e.V., Dresden (Germany). Inst. fuer Radiochemie


    The complex formation of uranium(VI) with salicylhydroxamic,benzohydroxamic, and benzoic acid in 0.1 M NaClO{sub 4} was studied by UV-vis spectroscopy at pH 3 and 4. Uranium(VI) species of the type M{sub p}L{sub q}H{sub r} were identified from the UV-vis spectra in all three systems. An increase in the absorption combined with a blue shift of the absorption maxima in comparison to the bands of the free uranyl ion of 22.5 {+-} 2 nm was observed in the uranium (VI)-salicylhydroxamic acid-system. Besides indications for a 1:2 complex, the formation of a 1:1 complex with a stability constant of log {beta}{sub 111} = 17.12 {+-} 0.10 could be demonstrated by its individual absorption spectrum and molar absorption coefficient. Also in the uranium(VI)-benzohydroxamic acid-system a blue shift of the absorption maxima in comparison to the bands of the free uranyl ion of 27 {+-} 1.4 nm indicate the complex formation. The stability constants are log {beta}{sub 110} = 7.96 {+-} 0.05 for UO{sub 2}[C{sub 6}H{sub 4}CONHO]{sup +} and log {beta}{sub 120} = 15.25 {+-} 0.11 for UO{sub 2}[C{sub 6}H{sub 4}CONHO]{sub 2}. In contrast to the hydroxamic acids, benzoic acid shows a red shift of the absorption maxima of 2.5 {+-} 2 nm. Only the 1:1 complex UO{sub 2}[C{sub 6}H{sub 4}COO]{sup +} with a stability constant of log {beta}{sub 110} = 3.37 {+-} 0.14 is existent. An estimate is made in order to discuss the dependencies observed in the absorption spectra in relation to possible coordination modes of uranium(VI). The strength of the complex formation between uranyl and the three aromatic acids is discussed. (orig.)

  10. Characterization of the properties of stationary phases for liquid chromatography in aqueous mobile phases using aromatic sulphonic acids as the test compounds. (United States)

    Jandera, P; Bocian, S; Molíková, M; Buszewski, B


    We investigated the effects of the concentration of naphthalene sulphonic acids (NSAs) as anionic test compounds in the injected sample and of the salt additives to the mobile phase on ion-exclusion. The retention behaviour of NSAs sensitively reflects even minor changes in the ionic and hydrophobic interactions and can be useful for predicting the effects of the stationary phases in reversed-phase chromatography of polar and ionic compounds, both small ones and biopolymers, e.g., oligonucleotides. We studied chromatographic properties of several stationary phases intended for separations in aqueous mobile phases: a C18 column end-capped with polar hydrophilic groups, a densely bonded C8 column doubly end-capped with short alkyl groups, a short alkyl stationary phase designed to keep full pore accessibility in highly-aqueous mobile phases and a Bidentate column with "bridged" C18 groups attached to the silica hydride support. The chemistry and pore structure of various types of column packing materials and of the salt additives to the mobile phase affect the proportion of the pore volume non-accessible to anions due to ion-exclusion and consequently the peak asymmetry and hydrophobic selectivity in reversed-phase chromatography of organic acids. We also addressed the problems connected with the determination of column hold-up volume in aqueous mobile phases. The accessibility of the stationary phase for anionic compounds in contact with the sample zone is affected by ion-exclusion due to repulsive interactions with the negatively charged surface in the pores of the stationary phase. The accessible part of the stationary phase increases and consequently the migration velocity along the column decreases with increasing concentration of the sample in the zone moving along the column. Because of a limited access to the stationary phase, its capacity can be easily overloaded. The combination of the column overload and ion-exclusion effects may result in fronting or

  11. Determination of octanol-water partition coefficients of polar polycyclic aromatic compounds (N-PAC) by high performance liquid chromatography

    DEFF Research Database (Denmark)

    Helweg, C.; Nielsen, T.; Hansen, P.E.


    Prediction of 1-octanol water partition coefficients for a range of polar N-PAC from HPLC capacity coefficients has been investigated. Two commercially available columns, an ODS column and a Diol column were tested with water-methanol eluents. The best prediction of log K-ow for N-PAC was achieve...

  12. Dynamics of polar aromatic molecules confined in a nanocavity of δ-phase of syndiotactic polystyrene as studied by dielectric spectroscopy (United States)

    Kobayashi, Hideo; Urakawa, Osamu; Kaneko, Fumitoshi; Inoue, Tadashi


    Rotational dynamics was examined in detail for four polar aromatic molecules, benzonitrile (BN), p-methylbenzonitrile (p-MBN), o-methylbenzonitrile (o-MBN), and m-methylbenzonitrile (m-MBN), accommodated in a nano-cavity regularly arranged inside the crystalline region (δ-form) of syndiotactic polystyrene (sPS) by means of dielectric relaxation measurements. Except for m-MBN, for which the co-crystalline structure was monoclinic δ-intercalate and no dielectric relaxation process arising from the crystalline region appeared, other three polar guests in the monoclinic δ-clathrate form exhibited the specific dielectric relaxation process. The relaxation times of o-MBN, BN, and p-MBN at room temperature were ranged from 10-7 s to 10-1 s, and in the order of o-MBN < BN < p-MBN. From the analysis of dielectric intensity data as functions of temperature, new insights about the stable and quasi-stable states of the guest molecules inside the cavity were obtained based on the two site model.

  13. Bioremediation of PAH-contamined soils: Consequences on formation and degradation of polar-polycyclic aromatic compounds and microbial community abundance. (United States)

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


    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.

  14. Preparation of Mg-Al layered double hydroxides intercalated with 1,3,6-naphthalenetrisulfonate and 3-amino-2,7-naphthalenedisulfonate and assessment of their selective uptake of aromatic compounds from aqueous solutions (United States)

    Kameda, Tomohito; Yamazaki, Takashi; Yoshioka, Toshiaki


    Mg-Al layered double hydroxides (Mg-Al LDHs) intercalated with 1,3,6-naphthalenetrisulfonate (NTS 3-) and 3-amino-2,7-naphthalenedisulfonate (ANDS 2-) ions were prepared by coprecipitation and were characterized by X-ray diffraction and chemical analyses. Based on X-ray diffraction patterns, the naphthalene rings of NTS 3- and ANDS 2- were most likely oriented parallel to the brucite-like host layers of the Mg-Al LDH, midway between layers. The prepared Mg-Al LDHs were able to selectively take up aromatics from aqueous solutions, and the order of percentage uptake was as follows: 1,3-dinitrobenzene > nitrobenzene > benzaldehyde > N,N-dimethylaniline > anisole > 1,2-dimethoxybenzene. The differences in the extent of π-π stacking interactions occurring between the benzene rings of the aromatics and the naphthalene ring of the intercalated NTS 3- and ANDS 2- probably resulted in these differences among the absorbed quantities of the various aromatics.

  15. 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


    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...

  16. 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:; 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)


    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. A rotating disk apparatus for assessing the biodegradation of polycyclic aromatic hydrocarbons transferring from a non-aqueous phase liquid to solutions of surfactant Brij 35


    Bernardez, Letícia Alonso


    Texto completo: acesso restrito. p. 415-424 A rotating disk apparatus was used to investigate the biodegradation of PAHs from non-aqueous phase liquids to solutions of Brij 35. The mass transfer of PAHs in absence of surfactant solution was not large enough to replenish the degraded PAHs. The addition of surfactant resulted in an overall enhancement of biodegradation rates compared to that observed in pure aqueous solution. This is because surfactant partition significant amount of PAHs in...

  18. The Synthesis and Characterization of Aromatic Hybrid Anderson-Evans POMs and their Serum Albumin Interactions: The Shift from Polar to Hydrophobic Interactions. (United States)

    Al-Sayed, Emir; Blazevic, Amir; Roller, Alexander; Rompel, Annette


    Four aromatic hybrid Anderson polyoxomolybdates with Fe(3+) or Mn(3+) as the central heteroatom have been synthesized by using a pre-functionalization protocol and characterized by using single-crystal X-ray diffraction, FTIR, ESI-MS, (1) H NMR spectroscopy, and elemental analysis. Structural analysis revealed the formation of (TBA)3 [FeMo6 O18 {(OCH2 )3 CNHCOC6 H5 }2 ]⋅3.5 ACN (TBA-FeMo6 -bzn; TBA=tetrabutylammonium, ACN=acetonitrile, bzn=TRIS-benzoic acid alkanolamide, TRISR=(HOCH2 )3 CR)), (TBA)3 [FeMo6 O18 {(OCH2 )3 CNHCOC8 H7 }2 ]⋅2.5 ACN (TBA-FeMo6 -cin; cin=TRIS-cinnamic acid alkanolamide), (TBA)3 [MnMo6 O18 {(OCH2 )3 CNHCOC6 H5 }2 ]⋅3.5 ACN (TBA-MnMo6 -bzn), and (TBA)3 [MnMo6 O18 {(OCH2 )3 CNHCOC8 H7 }2 ]⋅2.5 ACN (TBA-MnMo6 -cin). To make these four compounds applicable in biological systems, an ion exchange was performed that gave the water-soluble (up to 80 mM) sodium salts Na3 [FeMo6 O18 {(OCH2 )3 CNHCOC6 H5 }2 ] (Na-FeMo6 -bzn), Na3 [FeMo6 O18 {(OCH2 )3 CNHCOC8 H7 }2 ] (Na-FeMo6 -cin), Na3 [MnMo6 O18 {(OCH2 )3 CNHCOC6 H5 }2 ] (Na-MnMo6 -bzn), and Na3 [MnMo6 O18 {(OCH2 )3 CNHCOC8 H7 }2 ] (Na-MnMo6 -cin). The hydrolytic stability of the sodium salts was examined by applying ESI-MS in the pH range of 4 to 9. Sodium dodecylsulfate-polyacrylamide gel electrophoresis (SDS-PAGE) showed that human and bovine serum albumin (HSA and BSA) remain intact in solutions that contain up to 100 equivalents of the sodium salts over more than 4 d at 20 °C. Tryptophan (Trp) fluorescence quenching was applied to study the interactions between the sodium salts and HSA and BSA at pH 5.5 and 7.4. The quenching constants were extracted by using Stern-Volmer analysis, which suggested the formation of a 1:1 POM-protein complex in all samples. It is suggested that the aromatic hybrid POM approaches subdomain IIA of HSA and exhibits hydrophobic interactions with its hydrophobic tails, whereas the Anderson core is stabilized through electrostatic

  19. Application of acetone acetals as water scavengers and derivatization agents prior to the gas chromatographic analysis of polar residual solvents in aqueous samples. (United States)

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


    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.

  20. Catalytic hydrogenation of aromatic nitro compounds by functionalized ionic liquids-stabilized nickel nanoparticles in aqueous phase:The influence of anions

    Institute of Scientific and Technical Information of China (English)


    Two kinds of nickel nanoparticles (NPs) well-dispersed in aqueous phase have been conveniently prepared by reducing nickel(II) salt with hydrazine in the presence of amino group (-NH2) functionalized ionic liquids:1-(3-aminopropyl)-2,3-dimethylimidazolium bromide ([AMMIM][Br]) and 1-(3-aminopropyl)-2,3-dimethylimidazolium acetate ([AMMIM][AcO]).The Ni(0) particles are composed of smaller ones which assemble in a blackberry-like shape.The Ni nanoparticles stabilized with [AMMIM][AcO] are much larger than those stabilized with [AMMIM][Br],and the former unexpectedly give much higher activity in the selective hydrogenation of citral and nitrobenzene (NB) in aqueous phase.The Ni(0) nanocatalysts dispersed in aqueous phase are stable enough to be reused at least five times without significant loss of catalytic activity and selectivity during the catalytic recycles.

  1. Spirocyclic aromatic hydrocarbon-based organic nanosheets for eco-friendly aqueous processed thin-film non-volatile memory devices. (United States)

    Lin, Zong-Qiong; Liang, Jin; Sun, Peng-Ju; Liu, Feng; Tay, Yee-Yan; Yi, Ming-Dong; Peng, Kun; Xia, Xian-Hai; Xie, Ling-Hai; Zhou, Xin-Hui; Zhao, Jian-Feng; Huang, Wei


    Supramolecular steric hindrance designs make pyrene-functionalized spiro[fluorene-9,7'-dibenzo[c,h]acridine]-5'-one (Py-SFDBAO) assemble into 2D nanostructures that facilitate aqueous phase large-area synthesis of high-quality and uniform crystalline thin films. Thin-film diodes using aqueous nanosheets as active layers exhibit a non-volatile bistable electrical switching feature with ON/OFF ratios of 6.0 × 10(4) and photoswitching with conductive gains of 10(2) -10(3). Organic nanosheets are potentially key components for eco-friendly aqueous dispersed organic nano-inks in the application of printed and flexible electronics.

  2. Effects of humic acid fractions with different polarities on photodegradation of 2, 4-D in aqueous environments

    Institute of Scientific and Technical Information of China (English)

    Chunyan YU; Xie QUAN; Xiaoxia OU; Shuo CHEN


    Four fractions (A, B, C, and D) of humic acids (HAs) were separated based on the polarity from weak to strong. UV-vis absorption and Fourier transform infrared spectroscopy (FTIR) analysis show that the fractions C and D possessed morearomatic C=C content. The influences of HAs and their fractions on the photolysis were investigated by the photodegradation-of 2, 4-D solutions under simu-lated solar light irradiation. The degradation rate of 2, 4-D was found to decrease in the presence of bulk HAs or their fractions especially at high HAs concentration. The frac-tions of strong polarity C and D retarded the degradation rate more than the fractions of weak polarity A and B. This could be attributed to the different absorption intensity of the four HAs fractions in the order of D≥C>A>B, and the stronger π-π electron donor-acceptor interactions between the strong polar fractions and 2, 4-D.

  3. Determination of polar organophosphorus pesticides in aqueous samples by direct injection using liquid chromatography : tandem mass spectrometry

    NARCIS (Netherlands)

    Ingelse, B.A.; Dam, R.C.J. van; Vreeken, R.J.; Mol, H.G.J.; Steijger, O.M.


    It was demonstrated that four out of six of the very polar organophosphorus pesticides (OPs), i.e. acephate, methamidophos, monocrotophos, omethoate, oxydemeton-methyl and vamidothion, could not be extracted from water using commonly available SPE cartridges. In addition, GC analysis on all six comp

  4. Influence of non-aqueous phase liquid configuration on induced polarization parameters: Conceptual models applied to a time-domain field case study (United States)

    Johansson, Sara; Fiandaca, Gianluca; Dahlin, Torleif


    Resistivity and induced polarization (IP) measurements on soil contaminated with non-aqueous phase liquids (NAPLs) show a great variety in results in previous research. Several laboratory studies have suggested that the presence of NAPLs in soil samples generally decrease the magnitude of the IP-effect, while others have indicated the opposite. A number of conceptual models have been proposed suggesting that NAPLs can alter the pore space in different ways, e.g. by coating the grain surfaces and thus inhibiting grain polarization, or by changing the pore throat size and thus affecting the membrane polarization mechanism. The main aim of this paper is to review previously published conceptual models and to introduce some new concepts of possible residual NAPL configurations in the pore space. Time domain induced polarization measurements were performed at a NAPL contaminated field site, and the data were inverted using the Constant Phase Angle (CPA) model and the Cole-Cole model respectively. No significant phase anomalies were observed in the source area of the contamination when the CPA inverted profiles were compared with soil sampling results of free-phase contaminant concentrations. However, relatively strong phase and normalized phase anomalies appeared next to the source area, where residual free-phase presence could be expected according to the chemical data. We conclude that depending on the NAPL configuration, different spectral IP responses can be expected. In previous research, the NAPL configurations in different samples or field sites are often unknown, and this may to some extent explain why different results have been achieved by different authors. In our field case, we believe that the NAPL forms a more or less continuous phase in the pore space of the source zone leading to an absence of IP anomalies. The increase in phase and normalized phase angle observed next to the source zone is interpreted as a degradation zone. The ongoing biodegradation

  5. 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)


    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”.

  6. Estimating the physicochemical properties of polyhalogenated aromatic and aliphatic compounds using UPPER: part 2. Aqueous solubility, octanol solubility and octanol-water partition coefficient. (United States)

    Admire, Brittany; Lian, Bo; Yalkowsky, Samuel H


    The UPPER (Unified Physicochemical Property Estimation Relationships) model uses additive and non-additive parameters to estimate 20 biologically relevant properties of organic compounds. The model has been validated by Lian and Yalkowsky (2014) on a data set of 700 hydrocarbons. Recently, Admire et al. (2014) expanded the model to predict the boiling and melting points of 1288 polyhalogenated benzenes, biphenyls, dibenzo-p-dioxins, diphenyl ethers, anisoles and alkanes. In this work, 19 new group descriptors are determined and used to predict the aqueous solubilities, octanol solubilities and the octanol-water coefficients.

  7. Determination of the distribution constants of aromatic compounds and steroids in biphasic micellar phosphonium ionic liquid/aqueous buffer systems by capillary electrokinetic chromatography. (United States)

    Lokajová, Jana; Railila, Annika; King, Alistair W T; Wiedmer, Susanne K


    The distribution constants of some analytes, closely connected to the petrochemical industry, between an aqueous phase and a phosphonium ionic liquid phase, were determined by ionic liquid micellar electrokinetic chromatography (MEKC). The phosphonium ionic liquids studied were the water-soluble tributyl(tetradecyl)phosphonium with chloride or acetate as the counter ion. The retention factors were calculated and used for determination of the distribution constants. For calculating the retention factors the electrophoretic mobilities of the ionic liquids were required, thus, we adopted the iterative process, based on a homologous series of alkyl benzoates. Calculation of the distribution constants required information on the phase-ratio of the systems. For this the critical micelle concentrations (CMC) of the ionic liquids were needed. The CMCs were calculated using a method based on PeakMaster simulations, using the electrophoretic mobilities of system peaks. The resulting distribution constants for the neutral analytes between the ionic liquid and the aqueous (buffer) phase were compared with octanol-water partitioning coefficients. The results indicate that there are other factors affecting the distribution of analytes between phases, than just simple hydrophobic interactions.

  8. Triacontyl modified silica gel as a sorbent for the preconcentration of polycyclic aromatic hydrocarbons in aqueous samples prior to gas chromatographic-mass spectrometry determination

    Institute of Scientific and Technical Information of China (English)



    Triacontyl modified silica gel as a sorbent coupled with gas chromatography-mass spectrometry (GC-MS) was developed to determine EPA prior 16 polycyclic aromatic hydrocarbons (PAHs) in water samples. Various parameters of solid-phase extraction such as organic modifier solvent, eluent, sample flow rate and volume were optimized. The developed method was found to yield a linear calibration curve in the concentration range of 0.05-8 μg/L with respect to naphthalene, acenaphthylene, acenaphthene and 0.01-8μg/L for dibenz[a,h]anthracene and 0.05-14 μg/L for fluorene, phenanthrene, anthracene and 0.01-14 μg/L for the rest of analytes. Furthermore, the good accuracy and repeatability of the method made sure the requirements for achieving reliable analysis of PAHs in the environmental water samples, and the recoveries of optimal method were in the range of 80-120% except to higher volatility PAHs. C30-bonded silica was proved to be an efficient sorbent for extraction of high molecular weight PAHs.

  9. Thermodynamic origin of the solubility profile of drugs showing one or two maxima against the polarity of aqueous and nonaqueous mixtures: niflumic acid and caffeine. (United States)

    Bustamante, Pilar; Navarro, J; Romero, S; Escalera, B


    The purpose of this work was to investigate the origin of the different solubility profiles of drugs against the polarity of solvent mixtures with a common cosolvent. Niflumic acid and caffeine where chosen as model drugs. The solubilities were measured at five or six temperatures in aqueous (ethanol-water) and nonaqueous (ethyl acetate-ethanol) mixtures. The enthalpies of solution were obtained at the harmonic mean of the experimental temperature. Solid phase changes were analyzed using differential scanning calorimetry and thermomicroscopy. A single solubility maximum was obtained for niflumic acid against the solubility parameter of both mixtures that is not related to solid phase changes. In contrast, caffeine displays two maxima and anhydrous-hydrate transition occurs at the solubility peak in the amphiprotic mixture. The apparent enthalpies of solution of both drugs show endothermic maxima against solvent composition that are related to hydrophobic hydration. A general explanation for the cosolvent action in aqueous mixtures is proposed. The dominant mechanism shifts from entropy to enthalpy at a certain cosolvent ratio dependent on the hydrophobicity and the solubility parameter of the drug. Niflumic acid and caffeine show enthalpy-entropy compensation in ethanol-water, and this relationship is demonstrated for the first time in nonaqueous mixtures. The results support that enthalpy-entropy compensation is a general effect for the solubility of drugs in solvent mixtures. The shape of the solubility curves is correlated with the compensation plots. The solubility peaks separate different enthalpy-entropy relationships that also differentiate the solubility behavior of the hydrate and the anhydrous forms of caffeine.

  10. Coupling of homogeneous liquid-liquid extraction and dispersive liquid-liquid microextraction for the extraction and preconcentration of polycyclic aromatic hydrocarbons from aqueous samples followed by GC with flame ionization detection. (United States)

    Farajzadeh, Mir Ali; Khiavi, Elahe Behboudi; Khorram, Parisa; Mogaddam, Mohammad Reza Afshar


    In the present study, a simple and rapid method for the extraction and preconcentration of some polycyclic aromatic hydrocarbons in water samples has been developed. In this method, two sample preparation methods were combined to obtain high extraction recoveries and enrichment factors for sensitive analysis of the selected analytes. In the first stage of the method, a homogeneous solution containing an aqueous solution and cyclohexyl amine is broken by the addition of a salt. After centrifugation, the upper collected phase containing the extracted analytes is subjected to the following dispersive liquid-liquid microextraction method. Rapid injection of the mixture of cyclohexyl amine resulted from the first stage and 1,1,2-trichloroethane (as an extraction solvent) into an acetic acid solution is led to form a cloudy solution. After centrifuging, the fine droplets of the extraction solvent are settled down in the bottom of the test tube, and an aliquot of it is analyzed by gas chromatography. Under the optimum extraction conditions, enrichment factors and limits of detection for the studied analytes were obtained in the ranges of 616-752 and 0.08-0.20 μg/L, respectively. The simplicity, high extraction efficiency, short sample preparation time, low cost, and safety demonstrated the efficiency of this method relative to other approaches.

  11. Development and application of a simultaneous SPE-method for polycyclic aromatic hydrocarbons (PAHs), alkylated PAHs, heterocyclic PAHs (NSO-HET) and phenols in aqueous samples from German Rivers and the North Sea. (United States)

    Siemers, Anne-Kathrin; Mänz, Jan Sebastian; Palm, Wolf-Ulrich; Ruck, Wolfgang K L


    Polycyclic aromatic hydrocarbons (PAHs), heterocyclic PAHs (NSO-HETs), alkylated PAHs and phenols are known as the prevailing contaminants in groundwater at tar contaminated sites. Besides these local sources, the concentrations and the distribution in particular of NSO-HETs in environmental samples, such as rivers, have received notably less attention. To investigate their occurrence in river basins two sensitive analytical methods for the simultaneous extraction of 86 substances including NSO-HETs, classical EPA-PAHs, alkylated PAHs and phenols were developed: liquid-liquid extraction for the whole water phase and solid phase extraction for the dissolved water phase only. Solely GC-MS or additionally LC-MSMS for fractionated basic nitrogen heterocycles (N-HETs) were used for quantification. Limits of quantification were in the low ngL(-1) range. Concentrations were determined in 29 aqueous samples from 8 relatively large rivers located in Lower Saxony (Germany) and the North Sea. NSO-HETs had comparable or even higher sum concentrations than EPA-PAHs. N-HETs, especially acridine and quinolines with concentrations of up to 20ngL(-1) per substance, were predominant.

  12. Anthracene and pyrene photolysis kinetics in aqueous, organic, and mixed aqueous-organic phases (United States)

    Grossman, Jarod N.; Stern, Adam P.; Kirich, Makena L.; Kahan, Tara F.


    Condensed phases in the atmosphere, such as cloud droplets and aerosols, often contain both water and organic matter (OM). Reactivity can differ significantly between aqueous and organic phases. We have measured photolysis kinetics of the polycyclic aromatic hydrocarbons (PAHs) anthracene and pyrene in several organic solvents and in water, as well as in miscible and phase-separated aqueous-organic mixtures at atmospherically-relevant wavelengths. Photolysis rate constants generally increased with increasing solvent polarity; photolysis of both PAHs was more than ten times faster in water than in octanol. Local polarity had a much greater effect on PAH photolysis kinetics than changes in PAH absorptivity or singlet oxygen concentrations. Photolysis kinetics in homogeneous aqueous-organic mixtures varied monotonically with2 OM volume fraction. Kinetics in immiscible (phase-separated) solutions were more complex, with different dependences on OM content observed in stagnant and turbulent solutions. Our results suggest that OM could greatly affect the photochemical lifetimes of PAHs in atmospheric condensed phases such as aerosols, even if the OM does not itself absorb photons.

  13. Transport of Polycyclic Aromatic Hydrocarbons in Unsaturated Porous Media (United States)

    Chahal, Maninder; Flury, Markus


    Polycyclic aromatic hydrocarbons (PAHs) are complex organic molecules containing 2 or more fused benzene rings. Being hydrophobic and non-polar, PAHs tend to partition to the organic matter in the soil from bulk aqueous phase. Though transport of these contaminants has been well studied in saturated environment, interactive mechanisms of these fluorescent compounds in unsaturated (identified by presence of air-water interface) porous media is still not well understood. We studied is the transport of fluoranthene in unsaturated porous media as facilitated by moving air-water interfaces. Confocal microscopy was used to visualize the interactions of fluoranthene particles in a glass channel packed with quartz glass beads. The packed glass channel was used to mimic a porous media and effects of an advancing and receding capillary fringe on the detachment of fluoranthene.

  14. Aromatic graphene (United States)

    Das, D. K.; Sahoo, S.


    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.


    Neville, O.K.


    A selective complexing organic solvent extraction process is presented for the separation of uranium values from an aqueous nitric acid solution of neutron irradiated thorium. The process comprises contacting the solution with an organic aromatic dithiccarbamaie and recovering the resulting urancdithiccarbamate complex with an organic solvent such as ethyl acetate.

  16. The role of weakly polar and H-bonding interactions in the stabilization of the conformers of FGG, WGG, and YGG: an aqueous phase computational study. (United States)

    Csontos, József; Murphy, Richard F; Lovas, Sándor


    The energetics of intramolecular interactions on the conformational potential energy surface of the terminally protected N-Ac-Phe-Gly-Gly-NHMe (FGG), N-Ac-Trp-Gly-Gly-NHMe (WGG), and N-Ac-Tyr-Gly-Gly-NHMe (YGG) tripeptides was investigated. To identify the representative conformations, simulated annealing molecular dynamics (MD) and density functional theory (DFT) methods were used. The interaction energies were calculated at the BHandHLYP/aug-cc-pVTZ level of theory. In the global minima, 10%, 31%, and 10% of the stabilization energy come from weakly polar interactions, respectively, in FGG, WGG, and YGG. In the prominent cases 46%, 62%, and 46% of the stabilization energy is from the weakly polar interactions, respectively, in FGG, WGG, and YGG. On average, weakly polar interactions account for 15%, 34%, and 9% of the stabilization energies of the FGG, WGG, and YGG conformers, respectively. Thus, weakly polar interactions can make an important energetic contribution to protein structure and function.

  17. Simply enhancing throughput of free-flow electrophoresis via organic-aqueous environment for purification of weak polarity solute of phenazine-1-carboxylic acid in fermentation of Pseudomonas sp. M18. (United States)

    Yang, Jing-Hua; Shao, Jing; Wang, Hou-Yu; Dong, Jing-Yu; Fan, Liu-Yin; Cao, Cheng-Xi; Xu, Yu-Quan


    Herein, a simple novel free-flow electrophoresis (FFE) method was developed via introduction of organic solvent into the electrolyte system, increasing the solute solubility and throughput of the sample. As a proof of concept, phenazine-1-carboxylic acid (PCA) from Pseudomonas sp. M18 was selected as a model solute for the demonstration on feasibility of novel FFE method on account of its faint solubility in aqueous circumstance. In the developed method, the organic solvent was added into not only the sample buffer to improve the solubility of the solute, but also the background buffer to construct a uniform aqueous-organic circumstance. These factors of organic solvent percentage and types as well as pH value of background buffer were investigated for the purification of PCA in the FFE device via CE. The experiments revealed that the percentage and the types of organic solvent exerted major influence on the purification of PCA. Under the optimized conditions (30 mM phosphate buffer in 60:40 (v/v) water-methanol at an apparent pH 7.0, 3.26 mL/min background flux, 10-min residence time of injected sample, and 400 V), PCA could be continuously purified from its impurities. The flux of sample injection was 10.05 μL/min, and the recovery was up to 93.7%. An 11.9-fold improvement of throughput was found with a carrier buffer containing 40% (v/v) methanol, compared with the pure aqueous phase. The developed procedure is of evident significance for the purification of weak polarity solute via FFE.

  18. Photoinduced electron transfer and fluorescence mechanisms in covalently linked polynuclear aromatic-nucleotide complexes

    Energy Technology Data Exchange (ETDEWEB)

    Geacintov, N.E.; Mao, Bing; Zhao, Rushen; Chen, Junxin; Liu, Tong Ming; Ya, Nai-Qi [New York Univ., NY (United States). Dept. of Chemistry; France, L.L.; Sutherland, J.D. [Brookhaven National Lab., Upton, NY (United States)


    The fluorescence of polycyclic aromatic hydrocarbon-nucleic acid complexes is quenched by photoinduced electron transfer mechanisms in aqueous solutions at ambient temperatures. These effects are illustrated with the biologically important compound benzo[a]pyrene-7,8-diol-9,10-epoxide (BPDE), a mutagenic and carcinogenic metabolite of the environmental pollutant benzo[a]pyrene, which forms covalent mutagenic lesions with 2{prime}-deoxyguanosine (dG) residues in DNA. The dependence of the fluroescence yeild and fluorescence decay times of the covalent model adduct (+)-trans-BPDE-N{sup 2}-dG as a function of temperature and methanol/water composition are described. Because of the sensitivity of the fluorescence of the pyrenyl residue to the polarity of the microenvironment, the magnitude of the fluorescence yield can be used to distinguish between highly hydrophobic (e.g. intercalation) and other more solvent-exposed BPDE-nucleic acid binding sites.

  19. Photoinduced electron transfer and fluorescence mechanisms in covalently linked polynuclear aromatic-nucleotide complexes

    Energy Technology Data Exchange (ETDEWEB)

    Geacintov, N.E.; Mao, Bing; Zhao, Rushen; Chen, Junxin; Liu, Tong Ming; Ya, Nai-Qi (New York Univ., NY (United States). Dept. of Chemistry); France, L.L.; Sutherland, J.D. (Brookhaven National Lab., Upton, NY (United States))


    The fluorescence of polycyclic aromatic hydrocarbon-nucleic acid complexes is quenched by photoinduced electron transfer mechanisms in aqueous solutions at ambient temperatures. These effects are illustrated with the biologically important compound benzo(a)pyrene-7,8-diol-9,10-epoxide (BPDE), a mutagenic and carcinogenic metabolite of the environmental pollutant benzo(a)pyrene, which forms covalent mutagenic lesions with 2{prime}-deoxyguanosine (dG) residues in DNA. The dependence of the fluroescence yeild and fluorescence decay times of the covalent model adduct (+)-trans-BPDE-N{sup 2}-dG as a function of temperature and methanol/water composition are described. Because of the sensitivity of the fluorescence of the pyrenyl residue to the polarity of the microenvironment, the magnitude of the fluorescence yield can be used to distinguish between highly hydrophobic (e.g. intercalation) and other more solvent-exposed BPDE-nucleic acid binding sites.

  20. Aromatization of Ethanol Over Desilicated ZSM-5 Zeolites: Effect of Pore Size in the Mesoporous Region. (United States)

    Jun, Jong Won; Hasan, Zubair; Kim, Chul-Ung; Jeong, Soon-Yong; Jhung, Sung Hwa


    Mesoporous ZSM-5 zeolites were obtained from microporous ZSM-5 by desilication using aqueous NaOH solutions, and their catalytic activity in the aromatization of ethanol was investigated in order to understand the effects of pore size, in the mesoporous region, on the product distribution and stability of the catalysts. Mesopores generally enhanced the selectivities towards aromatics and stability for aromatization. Mesopores with a maximum pore diameter of around 13 nm were the most effective in the aromatization process (especially for benzene and toluene), suggesting that pore-diameter optimization is necessary for efficient catalysis such as aromatization.

  1. Study of different HILIC, mixed-mode, and other aqueous normal-phase approaches for the liquid chromatography/mass spectrometry-based determination of challenging polar pesticides. (United States)

    Vass, Andrea; Robles-Molina, José; Pérez-Ortega, Patricia; Gilbert-López, Bienvenida; Dernovics, Mihaly; Molina-Díaz, Antonio; García-Reyes, Juan F


    The aim of the study was to evaluate the performance of different chromatographic approaches for the liquid chromatography/mass spectrometry (LC-MS(/MS)) determination of 24 highly polar pesticides. The studied compounds, which are in most cases unsuitable for conventional LC-MS(/MS) multiresidue methods were tested with nine different chromatographic conditions, including two different hydrophilic interaction liquid chromatography (HILIC) columns, two zwitterionic-type mixed-mode columns, three normal-phase columns operated in HILIC-mode (bare silica and two silica-based chemically bonded columns (cyano and amino)), and two standard reversed-phase C18 columns. Different sets of chromatographic parameters in positive (for 17 analytes) and negative ionization modes (for nine analytes) were examined. In order to compare the different approaches, a semi-quantitative classification was proposed, calculated as the percentage of an empirical performance value, which consisted of three main features: (i) capacity factor (k) to characterize analyte separation from the void, (ii) relative response factor, and (iii) peak shape based on analytes' peak width. While no single method was able to provide appropriate detection of all the 24 studied species in a single run, the best suited approach for the compounds ionized in positive mode was based on a UHPLC HILIC column with 1.8 μm particle size, providing appropriate results for 22 out of the 24 species tested. In contrast, the detection of glyphosate and aminomethylphosphonic acid could only be achieved with a zwitterionic-type mixed-mode column, which proved to be suitable only for the pesticides detected in negative ion mode. Finally, the selected approach (UHPLC HILIC) was found to be useful for the determination of multiple pesticides in oranges using HILIC-ESI-MS/MS, with limits of quantitation in the low microgram per kilogram in most cases. Graphical Abstract HILIC improves separation of multiclass polar pesticides.

  2. 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: [Department of Physics, Sevastopol National Technical University, Sevastopol 99053, Crimea (Ukraine)


    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?'

  3. Reforming Biomass Derived Pyrolysis Bio-oil Aqueous Phase to Fuels

    Energy Technology Data Exchange (ETDEWEB)

    Mukarakate, Calvin; Evans, Robert J.; Deutch, Steve; Evans, Tabitha; Starace, Anne K.; ten Dam, Jeroen; Watson, Michael J.; Magrini, Kim


    Fast pyrolysis and catalytic fast pyrolysis (CFP) of biomass produce a liquid product stream comprised of various classes of organic compounds having different molecule size and polarity. This liquid, either spontaneously in the case of catalytic fast pyrolysis or by water addition for the non-catalytic process separates into a non-polar organic-rich fraction and a highly polar water-rich fraction. The organic fraction can be used as a blendstock or feedstock for further processing in a refinery while, in the CFP process design, the aqueous phase is currently sent to wastewater treatment, which results in a loss of residual biogenic carbon present in this stream. This work focuses on the catalytic conversion of the biogenic carbon in pyrolysis aqueous phase streams to produce hydrocarbons using a vertical micro-reactor coupled to a molecular beam mass spectrometer (MBMS). The MBMS provides real-time analysis of products while also tracking catalyst deactivation. The catalyst used in this work was HZSM-5, which upgraded the oxygenated organics in the aqueous fraction to fuels comprising small olefins and aromatic hydrocarbons. During processing the aqueous bio-oil fraction the HZSM-5 catalyst exhibited higher activity and coke resistance than those observed in similar experiments using biomass or whole bio-oils. Reduced coking is likely due to ejection of coke precursors from the catalyst pores that was enhanced by excess process water available for steam stripping. The water reacted with coke precursors to form phenol, methylated phenols, naphthol, and methylated naphthols. Conversion data shows that up to 40 wt% of the carbon in the feed stream is recovered as hydrocarbons.

  4. 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...

  5. 有机硅表面活性剂对水体中多环芳烃的浊点萃取研究%Cloud Point Extraction of Polycyclic Aromatic Hydrocarbons in Aqueous Solution with Silicone Surfactants

    Institute of Scientific and Technical Information of China (English)

    姚炳佳; 杨立; 胡琼; Shigendo Akita


    Cloud point extraction (CPE) processes with two silicone suffactants, Dow Corning DC-190 and DC-193, were studied as preconcentration and treatment for the water polluted by three trace polycyclic aromatic hydrocarbons (PAHs): anthracene, phenanthrene and pyrene. For all cases, the volumes of suffactant-rich phase obtained by two silicone suffactants were very small, i.e. a lower water content in the surfactant-rich phase was obtained. For example, less than 3% of the initial solution was obtained in a 1% (by mass) surfactant solution, which was much smaller than that of TX-114 in the same surfactant concentration. And TX-114 is known as a high compact surfactant-rich phase among most nonionic surfactants, thus the comparison showed that an excellent enrichment was ensured in the analysis application by the CPE process with the silicone surfactants, and the lower water content obtained in the surfactant-rich phase is also important in the large scale water treatment. The influences of additives and phase separation methodology on the recovery of PAHs were discussed. Comparing with DC-193,DC-190 has a lower cloud point and a higher recovery (near 100%) of all the three PAHs in same surfactant concentration, which was required for application as a preconcentration process prior to HPLC system. However the DC-190 solution is hard to be phase separated only by heating, whereas DC-193 has a relative higher phase separating speed by heating, but a high cloud point (around 360K) limits its application. Due to the phase separation by heating is the only method of CPE suitable to the large scale water treatment, the mixtures of two silicone surfacrants solutions were investigated in this study. A solution containing 1% of mixed DC-190 and DC-193 (in the ratio of 90∶10) removed anthracene, phenanthrene and pyrene near 100% with a relative low cloud point and quick phase separating speed.

  6. Interfacial forces in aqueous media

    CERN Document Server

    van Oss, Carel J


    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

  7. Enzyme catalytic nitration of aromatic compounds. (United States)

    Kong, Mingming; Wang, Kun; Dong, Runan; Gao, Haijun


    Nitroaromatic compounds are important intermediates in organic synthesis. The classic method used to synthesize them is chemical nitration, which involves the use of nitric acid diluted in water or acetic acid, both harmful to the environment. With the development of green chemistry, environmental friendly enzyme catalysis is increasingly employed in chemical processes. In this work, we adopted a non-aqueous horseradish peroxidase (HRP)/NaNO2/H2O2 reaction system to study the structural characteristics of aromatic compounds potentially nitrated by enzyme catalysis, as well as the relationship between the charges on carbon atoms in benzene ring and the nitro product distribution. Investigation of various reaction parameters showed that mild reaction conditions (ambient temperature and neutral pH), plus appropriate use of H2O2 and NaNO2 could prevent inactivation of HRP and polymerization of the substrates. Compared to aqueous-organic co-solvent reaction media, the aqueous-organic two-liquid phase system had great advantages in increasing the dissolved concentration of substrate and alleviating substrate inhibition. Analysis of the aromatic compounds' structural characteristics indicated that substrates containing substituents of NH2 or OH were readily catalyzed. Furthermore, analysis of the relationship between natural bond orbital (NBO) charges on carbon atoms in benzene ring, as calculated by the density functional method, and the nitro product distribution characteristics, demonstrated that the favored nitration sites were the ortho and para positions of substituents in benzene ring, similar to the selectivity of chemical nitration.

  8. Synthesis of coenzyme A thioesters using methyl acyl phosphates in an aqueous medium. (United States)

    Pal, Mohan; Bearne, Stephen L


    Regioselective S-acylation of coenzyme A (CoA) is achieved under aqueous conditions using various aliphatic and aromatic carboxylic acids activated as their methyl acyl phosphate monoesters. Unlike many hydrophobic activating groups, the anionic methyl acyl phosphate mixed anhydride is more compatible with aqueous solvents, making it useful for conducting acylation reactions in an aqueous medium.

  9. 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: [Aalto University, Department of Chemistry, Laboratory of Analytical Chemistry, P.O. Box 16100, FI-00076 Aalto (Finland)


    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.

  10. Self-assembly of aromatic-functionalized amphiphiles: The role and consequences of aromatic-aromatic noncovalent interactions in building supramolecular aggregates and novel assemblies

    Energy Technology Data Exchange (ETDEWEB)

    Whitten, D.G.; Chen, L.; Geiger, H.C.; Perlstein, J.; Song, X. [Los Alamos National Lab., NM (United States). Chemical Science and Technology Div.]|[Univ. of Rochester, NY (United States)


    This feature article presents an overview of a study of several different aromatic-functionalized amphiphiles-fatty acid and phospholipid derivatives. These amphiphiles form organized assemblies when the fatty acids are spread as monolayers at the air-water interface or when the phospholipids are dispersed in aqueous solutions. For a wide range of aromatic chromophores--trans-stilbene derivatives and a series of vinylogues (1,4-diphenyl-1,3-butadiene and 1,6-diphenyl-1,3,5-hexatriene), diphenylacetylenes, and azobenzenes such as phenyl, biphenyl, and terphenyl derivatives and modified stilbenes (styryl thiophenes and styryl naphthalenes)--assembly formation is accompanied by formation of aggregates of the aromatic groups. Results of experimental studies and simulations indicate that in many cases the aromatics form a small, stable unit aggregate characterized by strong noncovalent edge-to-face interactions among adjacent aromatics. Although the unit aggregates exhibit characteristic spectral shifts and strong induced circular dichroism indicating a chiral pinwheel aggregate structure, they may be packed together in pure films or dispersions to form an extended glide or herringbone structure. Although the pinwheel unit aggregate and the extended glide or herringbone structure. Although the pinwheel unit aggregate and the extended glide structure is favored for the majority of aromatics studied, for certain aromatics (styrenes, styrylthiophenes, and {alpha}-styrylnaphthalenes) a translation layer, characterized by face-to-face noncovalent interactions, is preferred. The glide or herringbone aggregates are readily distinguished from the translation aggregates by different spectral signatures and different photochemical and photophysical behavior. Factors controlling the type of aggregate and hence extended structure formed from different aromatic functionalized aromatics include shape and steric factors and strength of the competing noncovalent edge-face and face


    Directory of Open Access Journals (Sweden)

    Yonghong Deng,


    Full Text Available Sodium lignosulfonate (SL fractions with narrow molecular weight distribution and known salt content were used to investigate – stacking of the aromatic groups in SL. Results show that the charge-free aromatic groups of SL tend to form oriented – stacking with the spectroscopic characteristics of J–aggregates. The formation of J–aggregates in SL are recognized by a significant spectral red shift in fluorescent excitation spectra. The other effects that may cause spectral shift, such as the SL species, solvent effect, and the impurities, are investigated to confirm that the formation of J-aggregates is the only viable explanation for the significant spectral redshift of SL. Salt causes molecular shrinkage of SL polyelectrolytes, but has no influence on J–aggregates of the aromatic groups as detected by lack of spectral shift, indicating that the aromatic groups are charge-free. This suggests that not all the aromatic groups but only the charge-free aromatic groups can form – stacking. This work demonstrates the presence of J–aggregation in aqueous SL solutions for the first time, which gives an insight in understanding the preferred orientation of the aromatic groups in lignin-based biopolymers.

  12. Aqueous thermal degradation of gallic acid (United States)

    Snow Boles, Jennifer; Crerar, David A.; Grissom, Grady; Key, Tonalee C.


    Aqueous thermal degradation experiments show gallic acid, a naturally occurring aromatic carboxylic compound, decomposes rapidly at temperatures between 105° and 150°C, with an activation energy of 22.9 or 27.8 kcal/ mole, depending on pH of the starting solution. Pyrogallol is the primary product identified, indicating degradation via decarboxylation and a carbanion transition state. Relatively rapid degradation of vanillic, phthalic, ellagic and tannic acids has also been observed, suggesting that these and perhaps other aromatic acids could be short-lived in deep formation waters.

  13. Aqueous reactions of chlorine dioxide with hydrocarbons

    Energy Technology Data Exchange (ETDEWEB)

    Rav-Acha, C.; Choshen, E.


    In contrast to mechanisms proposed earlier in the literature, according to which chlorine dioxide (ClO/sub 2/) reacts with various hydrocarbons in aqueous media by abstracting allylic or benzylic hydrogens, it is shown that ClO/sub 2/ reacts with olefins through initial electron transfer. Hydrocarbons that can undergo facile oxidation, such as polycyclic aromatic hydrocarbons (PAH) and some olefins, react with ClO/sub 2/ quite rapidly, while saturated aliphatic hydrocarbons, some aromatic hydrocarbons, and olefins substituted with electron-withdrawing groups remain unreactive. This was substantiated by comparing the reactivities toward ClO/sub 2/ of a variety of hydrocarbons, including aliphatic and aromatic hydrocarbons, saturated and unsaturated acids, PAH, or cyclic and acyclic olefins. The results were supported by a detailed kinetic and product study of the reaction between ClO/sub 2/ and some model compounds.

  14. Non-Aqueous Capillary Electrophoresis (United States)

    Szumski, Michał; Buszewski, Bogusław

    Non-aqueous capillary electrophoresis and capillary electrochromatography are special variants of these techniques. Here, organic solvents or their mixtures with or without dissolved electrolytes are used as separation buffer or mobile phase, respectively. The most important features of non-aqueous systems are: better solubility of more hydrophobic ionic substances (many natural products) than in water, much less current and Joule heating allows for using highly concentrated buffers and/or larger capillary internal diameters, polar interactions are enhanced in organic solvents which is often highly advantageous in chiral separation systems. This chapter presents most frequently used solvents, their properties, as well as shows pH* scale which is often used in non-aqueous systems.

  15. Removal of Congo Red and Methylene Blue from Aqueous Solutions by Vermicompost-Derived Biochars. (United States)

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


    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.

  16. Characterization of cadmium removal from aqueous solution by biochar produced from a giant Miscanthus at different pyrolytic temperatures. (United States)

    Kim, Woong-Ki; Shim, Taeyong; Kim, Yong-Seong; Hyun, Seunghun; Ryu, Changkook; Park, Young-Kwon; Jung, Jinho


    The objective of this study was to investigate the feasibility of biochar for removing Cd from aqueous solution. Biochars were produced from a Miscanthus sacchariflorus via slow pyrolysis at 300, 400, 500 and 600°C. Higher pyrolytic temperature resulted in biochar with a higher aromatic structure and fewer polar functional groups. In particular, pH and surface area of biochar increased greatly at pyrolytic temperatures ≥ 500°C, which increased Cd sorption capacity up to 13.24 mgg(-1). The diffuse-controlled Cd removal was likely due to a surface sorption or a precipitation reaction depending on pH. A simulation with the visual MINTEQ program indicated that the precipitate was Cd(OH)2. In addition, biochar treatment significantly removed the acute toxicity of Cd toward Daphnia magna, resulting in increase of EC50 (50% effective concentration) value from 0.16 to 0.76 mgL(-1).

  17. Structure–property relationships of ‘safe’ aromatic oil based passenger car tire tread rubber compounds

    NARCIS (Netherlands)

    Rathi, A.; Hernández, M.; Dierkes, W.K.; Bergmann, C.; Trimbach, J.; Blume, A.


    In this study, the effect of Treated Distillate Aromatic Extract (TDAE) was investigated in medium styrene/high vinyl solution styrene butadiene rubber (S-SBR) and high cis-polybutadiene rubber (BR). Three properties were evaluated: (i) molecular structure (polarity/aromaticity), (ii) molecular weig

  18. Aromaticity Competition in Differentially Fused Borepin-Containing Polycyclic Aromatics. (United States)

    Messersmith, Reid E; Siegler, Maxime A; Tovar, John D


    This report describes the synthesis and characterization of a series of borepin-based polycyclic aromatics bearing two different arene fusions. The borepin synthesis features streamlined Ti-mediated alkyne reduction, leading to Z-olefins, followed by direct lithiation and borepin formation. These molecules allow for an assessment of aromatic competition between the fused rings and the central borepin core. Crystallographic, magnetic, and computational studies yielded insights about the aromaticity of novel, differentially fused [b,f]borepins and allowed for comparison to literature compounds. Multiple borepin motifs were also incorporated into polycyclic aromatics with five or six rings in the main backbone, and their properties were also evaluated.

  19. Nonlinear Spectroscopu of Nanoparticle/Aqueous Interface (United States)


    experiments at air/water interfaces have measured:polarity at a polystyrene sulfonate /water interface,acid-base equilibria at polystyrene nanoparticle...water interface. 2009, Abstracts, 238th ACS National Meeting, Washington, D.C. Polarity of polystyrene colloid/aqueous interface with second harmonic...electrostatic potential, the pH, and the acid-base equilibrium of the carboxyl (-COOH) functional group fixed at the surface of polystyrene carboxyl

  20. The Nature of Intermolecular Interactions Between Aromatic Amino Acid Residues

    Energy Technology Data Exchange (ETDEWEB)

    Gervasio, Francesco; Chelli, Riccardo; Procacci, Piero; Schettino, Vincenzo


    The nature of intermolecular interactions between aromatic amino acid residues has been investigated by a combination of molecular dynamics and ab initio methods. The potential energy surface of various interacting pairs, including tryptophan, phenilalanine, and tyrosine, was scanned for determining all the relevant local minima by a combined molecular dynamics and conjugate gradient methodology with the AMBER force field. For each of these minima, single-point correlated ab initio calculations of the binding energy were performed. The agreement between empirical force field and ab initio binding energies of the minimum energy structures is excellent. Aromatic-aromatic interactions can be rationalized on the basis of electrostatic and van der Waals interactions, whereas charge transfer or polarization phenomena are small for all intermolecular complexes and, particularly, for stacked structures.

  1. Contorted polycyclic aromatics. (United States)

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


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

  2. Petrochemistry - Aromatics; Petrochimie - Aromatiques

    Energy Technology Data Exchange (ETDEWEB)



    The assignment of Unipetrol chemical activities to the Czech group Agrofert by the Polish PKN Orlen is suspended and would be renegotiated. Oman Oil Company (OOC) is joining in the Korean LG International and in its subsidiary company Oman Refinery Company (ORC) for the construction of its new aromatics complex on its site of Sohar (Oman). This plan represents an investment of one milliard of dollars; it will produce 800000 t/year of para-xylene and 210000 t/year of benzene. The unit would be operational at the third trimester 2008. (O.M.)

  3. Fluorinated aromatic diamine (United States)

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


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

  4. Potential application of aromatic plant extracts to prevent cheese blowing. (United States)

    Librán, C M; Moro, A; Zalacain, A; Molina, A; Carmona, M; Berruga, M I


    This study aimed to inhibit the growth of Escherichia coli and Clostridium tyrobutyricum, common bacteria responsible for early and late cheese blowing defects respectively, by using novel aqueous extracts obtained by dynamic solid-liquid extraction and essential oils obtained by solvent free microwave extraction from 12 aromatic plants. In terms of antibacterial activity, a total of 13 extracts inhibited one of the two bacteria, and only two essential oils, Lavandula angustifolia Mill. and Lavandula hybrida, inhibited both. Four aqueous extracts were capable of inhibiting C. tyrobutyricum, but none were effective against E. coli. After extracts' chemical composition identification, relationship between the identified compounds and their antibacterial activity were performed by partial least square regression models revealing that compounds such as 1,8 cineole, linalool, linalyl acetate, β-phellandrene or verbene (present in essential oils), pinocarvone, pinocamphone or coumaric acid derivate (in aqueous extracts) were compounds highly correlated to the antibacterial activity.

  5. "Carbo-aromaticity" and novel carbo-aromatic compounds. (United States)

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


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

  6. Bacterial Degradation of Aromatic Compounds

    Directory of Open Access Journals (Sweden)

    Qing X. Li


    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.

  7. Field effect transistors based on polycyclic aromatic hydrocarbons for the detection and classification of volatile organic compounds. (United States)

    Bayn, Alona; Feng, Xinliang; Müllen, Klaus; Haick, Hossam


    We show that polycyclic aromatic hydrocarbon (PAH) based field effect transistor (FET) arrays can serve as excellent chemical sensors for the detection of volatile organic compounds (VOCs) under confounding humidity conditions. Using these sensors, w/o complementary pattern recognition methods, we study the ability of PAH-FET(s) to: (i) discriminate between aromatic and non-aromatic VOCs; (ii) distinguish polar and non-polar non-aromatic compounds; and to (iii) identify specific VOCs within the subgroups (i.e., aromatic compounds, polar non-aromatic compounds, non-polar non-aromatic compounds). We further study the effect of water vapor on the sensor array's discriminative ability and derive patterns that are stable when exposed to different constant values of background humidity. Patterns based on different independent electronic features from an array of PAH-FETs may bring us one step closer to creating a unique fingerprint for individual VOCs in real-world applications in atmospheres with varying levels of humidity.

  8. Folding dynamics of flavin adenine dinucleotide (FAD) inside non-aqueous and aqueous reverse micelles (United States)

    Sengupta, Abhigyan; Gavvala, Krishna; Koninti, Raj Kumar; Chaudhuri, Haribandhu; Hazra, Partha


    Present Letter describes dynamics of FAD in non-aqueous and aqueous reverse micelles (RMs). FAD in non-aqueous reverse micelles (containing MeOH, glycerol, formamide or DMF) shows a prominent rise of quantum yield with increasing solvent loading, whereas in water RM FAD shows a rise in quantum yield only up to w0 = 10 and afterwards drops sharply up to bulk. A relative difference in polarity of dry AOT to solvent loaded RMs can be attributed to the opposite trend of changes in emission. This Letter of FAD in different RMs and its preferential orientation might be useful for understanding FAD dynamics inside flavoproteins.

  9. Safety of water treatment by chlorine dioxide oxidation of aromatic hydrocarbons commonly found in water

    Energy Technology Data Exchange (ETDEWEB)

    Taymaz, K.; Williams, D.T.; Benoit, F.M.


    The safety of water treatment by chlorine dioxide oxidation of aromatic hydrocarbons commonly found in water and industrial wastewaters in the US was studied by observing the reactions of naphthalene and methylnaphthalenes in essentially chlorine-free, aqueous chlorine dioxide solutions. Naphthalene and methylnaphthalenes yielded chlorinated derivatives and oxidation products. Further research is recommended.

  10. Polarization, political

    NARCIS (Netherlands)

    M. Wojcieszak


    Polarization has been studied in three different forms: on a social, group, and individual level. This entry first focuses on the undisputed phenomenon of elite polarization (i.e., increasing adherence of policy positions among the elites) and also outlines different approaches to assessing mass pol

  11. Polar Codes (United States)


    QPSK Gaussian channels . .......................................................................... 39 vi 1. INTRODUCTION Forward error correction (FEC...Capacity of BSC. 7 Figure 5. Capacity of AWGN channel . 8 4. INTRODUCTION TO POLAR CODES Polar codes were introduced by E. Arikan in [1]. This paper...Under authority of C. A. Wilgenbusch, Head ISR Division EXECUTIVE SUMMARY This report describes the results of the project “More reliable wireless

  12. Polarization holography

    DEFF Research Database (Denmark)

    Nikolova, L.; Ramanujam, P.S.

    Current research into holography is concerned with applications in optically storing, retrieving, and processing information. Polarization holography has many unique properties compared to conventional holography. It gives results in high efficiency, achromaticity, and special polarization...... properties. This books reviews the research carried out in this field over the last 15 years. The authors provide basic concepts in polarization and the propagation of light through anisotropic materials, before presenting a sound theoretical basis for polarization holography. The fabrication...... and characterization of azobenzene based materials, which remain the most efficient for the purpose, is described in detail. This is followed by a description of other materials that are used in polarization holography. An in-depth description of various applications, including display holography and optical storage...

  13. Photochemical degradation of hydroxy PAHs in ice: Implications for the polar areas. (United States)

    Ge, Linke; Li, Jun; Na, Guangshui; Chen, Chang-Er; Huo, Cheng; Zhang, Peng; Yao, Ziwei


    Hydroxyl polycyclic aromatic hydrocarbons (OH-PAHs) are derived from hydroxylated PAHs as contaminants of emerging concern. They are ubiquitous in the aqueous and atmospheric environments and may exist in the polar snow and ice, which urges new insights into their environmental transformation, especially in ice. In present study the simulated-solar (λ > 290 nm) photodegradation kinetics, products and pathways of four OH-PAHs (9-Hydroxyfluorene, 2-Hydroxyfluorene, 1-Hydroxypyrene and 9-Hydroxyphenanthrene) in ice were investigated, and the corresponding implications for the polar areas were explored. It was found that the kinetics followed the pseudo-first-order kinetics with the photolysis quantum yields (Φs) ranging from 7.48 × 10(-3) (1-Hydroxypyrene) to 4.16 × 10(-2) (2-Hydroxyfluorene). These 4 OH-PAHs were proposed to undergo photoinduced hydroxylation, resulting in multiple hydroxylated intermediates, particularly for 9-Hydroxyfluorene. Extrapolation of the lab data to the real environment is expected to provide a reasonable estimate of OH-PAH photolytic half-lives (t1/2,E) in mid-summer of the polar areas. The estimated t1/2,E values ranged from 0.08 h for 1-OHPyr in the Arctic to 54.27 h for 9-OHFl in the Antarctic. In consideration of the lower temperature and less microorganisms in polar areas, the photodegradation can be a key factor in determining the fate of OH-PAHs in sunlit surface snow/ice. To the best of our knowledge, this is the first report on the photodegradation of OH-PAHs in polar areas.

  14. Correlation and prediction of adsorption capacity and affinity of aromatic compounds on carbon nanotubes. (United States)

    Wu, Wenhao; Yang, Kun; Chen, Wei; Wang, Wendi; Zhang, Jie; Lin, Daohui; Xing, Baoshan


    Adsorption of 22 nonpolar and polar aromatic compounds on 10 carbon nanotubes (CNTs) with various diameters, lengths and surface oxygen-containing group contents was investigated to develop predictive correlations for adsorption, using the isotherm fitting of Polanyi theory-based Dubinin-Ashtakhov (DA) model. Adsorption capacity of aromatic compounds on CNTs is negatively correlated with melting points of aromatic compounds, and surface oxygen-containing group contents and surface area ratios of mesopores to total pores of CNTs, but positively correlated with total surface area of CNTs. Adsorption affinity is positively correlated with solvatochromic parameters of aromatic compounds, independent of tube lengths and surface oxygen-containing group contents of CNTs, but negatively correlated with surface area ratios of mesopores to total pores of CNTs. The correlations of adsorption capacity and adsorption affinity with properties of both aromatic compounds and CNTs clearly have physical significance, can be used successfully with DA model to predict adsorption of aromatic compounds on CNTs from the well-known physiochemical properties of aromatic compounds (i.e., solvatochromic parameters, melting points) and CNTs (i.e., surface area and total acidic group contents), and thus can facilitate the environmental application of CNTs as sorbents and environmental risk assessment of both aromatic contaminants and CNTs.

  15. pH-resistant titania hybrid organic-inorganic sol-gel coating for solid-phase microextraction of polar compounds. (United States)

    Li, Xiujuan; Gao, Jie; Zeng, Zhaorui


    A novel titania-hydroxy-terminated silicone oil (titania-OH-TSO) sol-gel coating was developed for solid-phase microextraction of polar compounds. In general, titania-based sol-gel reaction is very fast and need to be decelerated by the use of suitable chelating agents. But in the present work, a judiciously designed sol solution ingredients was used to create the titania-OH-TSO coating without the addition of any chelating agent, which simplified the sol-gel procedure. Thanks to the variety of titania's adsorption sites and their acid-base characteristics, aromatic amines, phenols and polycyclic aromatic hydrocarbons were efficiently extracted and preconcentrated from aqueous samples followed by thermal desorption and GC analysis. The newly developed sol-gel hybrid titania coating demonstrated excellent pH stability, and retained its extraction characteristics intact even after continuous rinsing with a 3 M HCl or NaOH solution for 12 h. Furthermore, it could withstand temperatures as high as 320 degrees C. Practical application was demonstrated through the analysis of six aromatic amines in dye process wastewater. A linearity of four orders of magnitude was obtained with correlation coefficient better than 0.9982. The detection limits ranged from 0.22 to 0.84 microg L(-1) and the repeatability of the measurements was <7.0%. The recoveries of these compounds studied in the wastewater were in the ranges 83.6-101.4%, indicating the method accuracy.

  16. Advances towards aromatic oligoamide foldamers

    DEFF Research Database (Denmark)

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


    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...

  17. Polarizing cues. (United States)

    Nicholson, Stephen P


    People categorize themselves and others, creating ingroup and outgroup distinctions. In American politics, parties constitute the in- and outgroups, and party leaders hold sway in articulating party positions. A party leader's endorsement of a policy can be persuasive, inducing co-partisans to take the same position. In contrast, a party leader's endorsement may polarize opinion, inducing out-party identifiers to take a contrary position. Using survey experiments from the 2008 presidential election, I examine whether in- and out-party candidate cues—John McCain and Barack Obama—affected partisan opinion. The results indicate that in-party leader cues do not persuade but that out-party leader cues polarize. This finding holds in an experiment featuring President Bush in which his endorsement did not persuade Republicans but it polarized Democrats. Lastly, I compare the effect of party leader cues to party label cues. The results suggest that politicians, not parties, function as polarizing cues.

  18. Bioassay of polycyclic aromatic hydrocarbons

    Energy Technology Data Exchange (ETDEWEB)

    Van Kirk, E.A.


    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.

  19. Polycyclic Aromatic Hydrocarbons (United States)

    Salama, Farid


    Carbonaceous materials play an important role in space. Polycyclic Aromatic Hydrocarbons (PAHs) are a ubiquitous component of the carbonaceous materials. PAHs are the best-known candidates to account for the IR emission bands. They are also thought to be among the carriers of the diffuse interstellar absorption bands (DIBs). PAH ionization states reflect the ionization balance of the medium while PAH size, composition, and structure reflect the energetic and chemical history of the medium. A major challenge is to reproduce in the laboratory the physical conditions that exist in the emission and absorption interstellar zones. The harsh physical conditions of the ISM -low temperature, collisionless, strong UV radiation fields- are simulated in the laboratory by associating a molecular beam with an ionizing discharge to generate a cold plasma expansion. PAH ions and radicals are formed from the neutral precursors in an isolated environment at low temperature and probed with high-sensitivity cavity ringdown spectroscopy in the NUV-NIR range. Carbon nanoparticles are also formed during the short residence time of the precursors in the plasma and are characterized with time-offlight mass spectrometry. These experiments provide unique information on the spectra of large carbonaceous molecules and ions in the gas phase that can now be directly compared to interstellar and circumstellar observations (IR emission bands, DIBs, extinction curve). These findings also hold great potential for understanding the formation process of interstellar carbonaceous grains. We will review recent progress in the experimental and theoretical studies of PAHs, compare the laboratory data with astronomical observations and discuss the global implications.

  20. Characterization of nitrogen-rich biomaterial-derived biochars and their sorption for aromatic compounds. (United States)

    Zhang, Meng; Shu, Liang; Shen, Xiaofang; Guo, Xiaoying; Tao, Shu; Xing, Baoshan; Wang, Xilong


    Biochars from nitrogen-rich biomaterials (i.e., α-amylase, chitin and zein) were produced at different temperatures (i.e. 170, 250, 350 and 450 °C) and characterized, and their sorption for phenanthrene, naphthalene and 1-naphthol was investigated. The organic carbon content normalized-sorption coefficient (Koc) of the tested compounds by biochars increased with increasing charring temperature, attributed to the reduction of O-containing polar moieties especially the O-alkyl components, and the newly created aromatic carbon domains. The N-heterocyclic ring structure formed during charring process may enhance π-π interactions between aromatics and the aromatic components in the resulting biochars. However, π-π interactions did not dominate sorption of aromatics by N-rich biochars. Sorption of the tested compounds by N-rich biochars was predominantly controlled by the hydrophobic interactions between these chemicals and the aromatic components in biochars. Both N- and O-containing polar moieties at the biochar surfaces negatively affected their sorption for aromatics.

  1. Bacterial degradation of monocyclic aromatic amines

    Directory of Open Access Journals (Sweden)

    Pankaj Kumar Arora


    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.


    Directory of Open Access Journals (Sweden)

    N. Ia. Mokshina


    Full Text Available The extraction of phenylalanine, tyrosine and tryptophan from aqueous salt solutions by water soluble polymer - poly-N-vinylpyrrolidone having a molecular weight of 3,500 has been studied. Under identical conditions set quantitative characteristics extraction has been established, general scheme of analysis has been developed. Effect the volume ratio of aqueous and organic phases to the recovery of phenylalanine, tryptophan and tyrosine has been studied. The dependence of solution viscosity of the polymer and the speed of lamination systems the molecular weight and concentration of the extractant has been set. It was established that the most studied aromatic amino fully extracted solution of PVP-3500 at a concentration of 0,12 g/cm3, while the ratio of the equilibrium amounts of aqueous and organic phases 10:4. Optimized conditions for the almost complete extraction of phenylalanine, tyrosine and tryptophan from aqueous salt solutions. The technique of extraction-spectrophotometer determination of aromatic amino acids in aqueous solution. Based highs proposed scheme of interaction with PVP-3500 extractable substances. We have developed a technique characterized by express (analysis time 30 - 40 min, accuracy (relative error within 7%, ecology (and lack of toxic extragants "green extraction". Learned extraction systems applicable to practically complete extraction of phenylalanine, tyrosine and tryptophan from aqueous solutions.

  3. A feasibility study on identification of Basmati (aromatic) rice using SAR data

    Indian Academy of Sciences (India)

    Varunika Jain; C Patnaik; S Panigrahy


    Rice areas in India are being mapped for acreage estimation using Synthetic Aperture Radar (SAR) data under forecasting agricultural output using space, agrometeorology and land-based observations (FASAL) program for over a decade now. Under this study, an attempt was made to segregate rice areas based on variety in parts of Punjab state. Data acquisition was done at critical stages of rice growth. The shift in transplantation in temporal domain and difference in canopy volume formed the basis of characterization of rice crop into two different varieties namely aromatic and non-aromatic. Multitemporal HH polarization data along with rate of change of cross polarization ratio (HH/HV) from July to September 2011 was used. The aromatic rice could be separated from normal rice with 91% accuracy.

  4. Molecular transformations of phenolic SOA during photochemical aging in the aqueous phase: competition among oligomerization, functionalization, and fragmentation (United States)

    Yu, Lu; Smith, Jeremy; Laskin, Alexander; George, Katheryn M.; Anastasio, Cort; Laskin, Julia; Dillner, Ann M.; Zhang, Qi


    Organic aerosol is formed and transformed in atmospheric aqueous phases (e.g., cloud and fog droplets and deliquesced airborne particles containing small amounts of water) through a multitude of chemical reactions. Understanding these reactions is important for a predictive understanding of atmospheric aging of aerosols and their impacts on climate, air quality, and human health. In this study, we investigate the chemical evolution of aqueous secondary organic aerosol (aqSOA) formed during reactions of phenolic compounds with two oxidants - the triplet excited state of an aromatic carbonyl (3C∗) and hydroxyl radical (•OH). Changes in the molecular composition of aqSOA as a function of aging time are characterized using an offline nanospray desorption electrospray ionization mass spectrometer (nano-DESI MS) whereas the real-time evolution of SOA mass, elemental ratios, and average carbon oxidation state (OSC) are monitored using an online aerosol mass spectrometer (AMS). Our results indicate that oligomerization is an important aqueous reaction pathway for phenols, especially during the initial stage of photooxidation equivalent to ˜ 2 h irradiation under midday winter solstice sunlight in Northern California. At later reaction times functionalization (i.e., adding polar oxygenated functional groups to the molecule) and fragmentation (i.e., breaking of covalent bonds) become more important processes, forming a large variety of functionalized aromatic and open-ring products with higher OSC values. Fragmentation reactions eventually dominate the photochemical evolution of phenolic aqSOA, forming a large number of highly oxygenated ring-opening molecules with carbon numbers (nC) below 6. The average nC of phenolic aqSOA decreases while average OSC increases over the course of photochemical aging. In addition, the saturation vapor pressures (C∗) of dozens of the most abundant phenolic aqSOA molecules are estimated. A wide range of C∗ values is observed, varying

  5. Cation-π Interaction between the Aromatic Organic Counterion and DTAB Micelle in Mixed Solvents

    Institute of Scientific and Technical Information of China (English)

    DENG,Dong-Shun(邓东顺); LI,Hao-Ran(李浩然); LIU,Di-Xia(刘迪霞); HAN,Shi-Jun(韩世钧)


    The cation-π interaction between the aromatic organic counterion potassium hydrogen phthalate (KHP) and DTAB micelle in aqueous mixture of EG was investigated, using the techniques of conductivity measurements, UV absorption spectrum and NMR spectrum. The conductivity and UV spectrum studies were with respect to the effect of KHP on DTAB and that of DTAB micelle on KHP, respectively. According to the chemical shift changes of the aromatic ring and the surfactant methylene protons, it can be assumed that KHP penetrated into DTAB micelle with its carboxylic group protruding out of the micellar surface. And the strength of the interaction became weaker with the content of EG in the mixed solvent increasing.

  6. Polarized Campuses. (United States)

    Parr, Susan Resneck


    On college campuses, the climate is polarized because of intolerance and discrimination, censorship, factionalism, and anger among students and faculty. As a result, the campus is in danger of becoming dominated by political issues and discouraging the exchange of ideas characteristic of a true liberal arts education. (MSE)

  7. Adsorption of aromatic compounds by carbonaceous adsorbents: a comparative study on granular activated carbon, activated carbon fiber, and carbon nanotubes. (United States)

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


    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.

  8. Polarized light propagation through tissue and tissue phantoms

    Energy Technology Data Exchange (ETDEWEB)

    Sankaran, V; Walsh, J T JR; Maitland, D J


    We show that standard tissue phantoms can be used to mimic the intensity and polarization properties of tissue. Polarized light propagation through biologic tissue is typically studied using tissue phantoms consisting of dilute aqueous suspensions of microspheres. The dilute phantoms can empirically match tissue polarization and intensity properties. One discrepancy between the dilute phantoms and tissue exist: common tissue phantoms, such as dilute Intralipid and dilute 1-{micro}m-diameter polystyrene microsphere suspensions, depolarize linearly polarized light more quickly than circularly polarized light. In dense tissue, however, where scatterers are often located in close proximity to one another, circularly polarized light is depolarized similar to or more quickly than linearly polarized light. We also demonstrate that polarized light propagates differently in dilute versus densely packed microsphere suspensions, which may account for the differences seen between polarized light propagation in common dilute tissue phantoms versus dense biologic tissue.

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

    KAUST Repository

    Zhang, Long-li


    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

  10. Sol-gel methyl coating in capillary microextraction hyphenated on-line with high-performance liquid chromatography Counterintuitive extraction behavior for polar analytes. (United States)

    Segro, Scott S; Malik, Abdul


    A sol-gel coating with anchored methyl groups was developed for capillary microextraction hyphenated on-line with high-performance liquid chromatography (HPLC). This was accomplished by using methyltrimethoxysilane as the sol-gel precursor. The methyl group on the sol-gel precursor ultimately turned into a pendant group on the created sol-gel coating and was primarily responsible for the extraction of nonpolar analytes. A 40-cm segment of 0.25mm I.D. fused silica capillary containing the sol-gel methyl coating on the inner surface was installed as a sampling loop in an HPLC injection port. The analytes were extracted by the coating when an aqueous sample containing the analytes was passed through this capillary. The extracted analytes were then transferred to the HPLC column using isocratic elution with an acetonitrile/water mobile phase. This capillary demonstrated excellent extraction capability for polycyclic aromatic hydrocarbons and ketones. Unexpectedly, this coating also provided good extraction for polar analytes, including aromatic phenols, alcohols, and amines. Considering the fact that the methyl group is nonpolar in nature, such an extraction behavior of sol-gel methyl coating toward polar analytes is counterintuitive. Thus, sol-gel sorbents with short alkyl side chains have the potential to offer a polymer-free alternative to traditional sol-gel capillary microextraction (CME) media commonly prepared with the use of polymers in the sol solution. Elimination of polymers from the sol-gel coating solution is conducive to improving thermal stability and solvent tolerance of the created sol-gel extracting phase. This also makes the preparation of sol-gel coatings facile and cost-effective. Possessing excellent solvent stability, such sol-gel coatings offer the opportunity for effective on-line hyphenation of capillary microextraction with HPLC and other liquid-phase separation techniques that employ organo-aqueous mobile phases.

  11. Aromaticity of group 14 organometallics: experimental aspects. (United States)

    Lee, Vladimir Ya; Sekiguchi, Akira


    The long story of aromatic compounds has extended over almost two centuries, since the discovery by Faraday of "bicarburet of hydrogen", or C(6)H(6), now called benzene. Since then, the chemistry of aromatic compounds has been developed extensively; this is reflected in the synthesis of novel classes of aromatic derivatives including charged species, nonclassical (Möbius, three-dimensional, homo-, metalla-) aromatics, and fullerenes. The theory of aromaticity has also undergone a spectacular evolution since the first definition of aromaticity by Hückel; the classification of aromaticity now requires the consideration of versatile criteria: energetic, structural, magnetic, among others. In this Review, we discuss the current state of affairs in the chemistry of aromatic compounds of the heavier Group 14 elements, the latest experimental achievements, as well as future prospects in the field.

  12. Towards water compatible MIPs for sensing in aqueous media. (United States)

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


    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.

  13. Design of a coil satellite centrifuge and its performance on counter-current chromatographic separation of 4-methylumbelliferyl sugar derivatives with polar organic-aqueous two-phase solvent systems. (United States)

    Shinomiya, Kazufusa; Tokura, Koji; Kimura, Emiru; Takai, Midori; Harikai, Naoki; Yoshida, Kazunori; Yanagidaira, Kazuhiro; Ito, Yoichiro


    A new high-speed counter-current chromatograph, named coil satellite centrifuge (CSC), was designed and fabricated in our laboratory. The CSC apparatus produces the satellite motion such that the coiled column simultaneously rotates around the sun axis (the angular velocity, ω1), the planet axis (ω2) and the satellite axis (the central axis of the column) (ω3). In order to achieve this triplicate rotary motion without twisting of the flow tube, the rotation of each axis was determined by the following formula: ω1=ω2+ω3. This relation enabled to lay out the flow tube without twisting by the simultaneous rotation of three axes. The flow tube was introduced from the bottom side of the apparatus into the sun axis of the first rotary frame reaching the upper side of the planet axis and connected to the column in the satellite axis. The performance of the apparatus was examined on separation of 4-methylumbelliferyl (MU) sugar derivatives as test samples with organic-aqueous two-phase solvent systems composed of ethyl acetate/1-butanol/water (3:2:5, v/v) for lower phase mobile and (1:4:5, v/v) for upper phase mobile. With lower phase mobile, five 4-MU sugar derivatives including β-D-cellobioside (Cel), β-D-glucopyranoside, α-D-mannopyranoside, β-D-fucopyranoside and α-L-fucopyranoside (α-L-Fuc) were separated with the combined rotation around each axis at counterclockwise (CCW) (ω1) - CCW (ω2) - CCW (ω3) by the flow tube distribution. With upper phase mobile, three 4-MU sugar derivatives including α-L-Fuc, β-D-galactopyranoside and Cel were separated with the combined rotation around each axis at clockwise (CW) (ω1) - CW (ω2) - CW (ω3) by the flow tube distribution. A series of experiments on peak resolution and stationary phase retention revealed that better partition efficiencies were obtained at the flow rate of 0.5 mL/min (column 1) and 0.8 mL/min (column 2) for lower phase mobile and 0.2 mL/min (column 1) and 0.4 mL/min (column 2) for upper phase

  14. Polar Diving (United States)


    3 July 2006 This Mars Global Surveyor (MGS) Mars Orbiter Camera (MOC) image shows layers exposed by erosion in a trough within the north polar residual cap of Mars, diving beneath a younger covering of polar materials. The layers have, since the Mariner 9 mission in 1972, been interpreted to be composed of a combination of dust and ice in unknown proportions. In this scene, a layer of solid carbon dioxide, which was deposited during the previous autumn and winter, blankets the trough as well as the adjacent terrain. Throughout northern spring, the carbon dioxide will be removed; by summer, the layers will be frost-free. Location near: 81.4oN, 352.2oW Image width: 3 km (1.9 mi) Illumination from: lower left Season: Northern Spring

  15. Formic-acid-induced depolymerization of oxidized lignin to aromatics. (United States)

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


    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.

  16. [Spectrophotometric determination of aromatic amino compounds with J-acid]. (United States)

    Yin, Xiao-hang; Shi, Wen-jian; Shen, Xin; Ma, Jun-tao; Li, Liang


    The problems such as chromogenic reaction selectivity, reaction rate, sensitivity and water-solubility of azo compounds were considered. The molecular structures of coupling components were theoretically designed and screened in the present research The reaction conditions and methods of chromogenic reaction were investigated. J-Acid (2-amino-5-naphthol-7-sulfonic acid) as a coupling reagent to determine aromatic amino compounds was established. In the presence of potassium bromide, at room temperature, nitrite reacted with aromatic amino compounds in the medium of thin hydrochloric acid. Then diazonium salt reacted with J-Acid in the aqueous solution of sodium carbonate, forming coloured azo dye, which had a maximum adsorption at 480 nm. The molar adsorption coeffcients of aniline, 4-aminobenzene sulfonic acid and 1-naphthylamine were 3. 95 X 10(4), 3. 24 X 10(4) and 3. 91 X 10(4) L . mol-1 . cm-1 , respectively. Experimental results showed that common coexisting ions on the surface water did not affect the results of determination. J-Acid of spectrophotometry was used to determine the samples of Shanghai Fu Xing Dao canal. Meanwhile, recovery experiments by standard addition method were done. Experiment results showed that the recoveries of aniline were in the range of 98. 5%-102. 1%, and RSD was 2. 08%. J-Acid is a common organic reagent. It is soluble in water and low volatile, and its toxicity is much lower than N-ethylenediamine. spectrophotometric determination of aromatic amino compounds by J-Acid has the advantage of high sensitivity, good selectivity, simple rapid operation and accurate results, and thus it can be used for the determination of trace aromatic amino compounds in the environmental water.

  17. Formic-acid-induced depolymerization of oxidized lignin to aromatics (United States)

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


    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.

  18. Photolysis of aromatic pollutants in clean and dirty ice (United States)

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


    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.

  19. Study on biodegradable aromatic/aliphatic copolyesters

    Energy Technology Data Exchange (ETDEWEB)

    Yiwang Chen; Licheng Tan; Lie Chen; Yan, Yang; Xiaofeng Wang [Nanchang University, Nanchang (China). School of Materials Science and Engineering. Inst. of Polymer Materials]. E-mail:


    Progress on biodegradable aromatic/aliphatic copolyesters based on aliphatic and aromatic diacids, diols and ester monomers was reviewed. The aromatic/aliphatic copolyesters combined excellent mechanical properties with biodegradability. Physical properties and biodegradability of copolyesters varied with chain length of the aliphatic polyester segment and atacticity of copolyesters. The process ability of copolyesters could be improved significantly after incorporating a stiff chain segment through copolymerization of aliphatic polyesters with an aromatic liquid crystal element. The aromatic/aliphatic copolyesters as a new type of biodegradable materials could replace some general plastics in certain applications, namely biomedical and environmental friendly fields. (author)

  20. Use of Ionic Liquid-filled Semipermeable Membrane for Extraction of Polycyclic Aromatic Hydrocarbons in Water

    Institute of Scientific and Technical Information of China (English)

    Wen Yan ZHAO; Meng HAN; Shu Gui DAI; Xia ZHONG


    A novel and facile sample preparation method was developed for the extraction of polycyclic aromatic hydrocarbons (PAHs) in aqueous sample solution using 1-butyl-3-methylimidazolium hexafluorophosphate ([C4MIM] [PF6]) - filled semipermeable membrane. For24 hrs extraction of naphthalene, 1-methylnaphthalene, 2-chloronaphthalene, phenanthrene, the result showed that the extraction efficiency, correlation coefficient (R2) and RSD (n=5) were in the range of 67-102 %, 0.9870-0.9962, and 2.1-5.3 %, respectively.

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

    Directory of Open Access Journals (Sweden)

    Mohamed M. El-Azizi


    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.


    Directory of Open Access Journals (Sweden)

    Y. I. Korenman


    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.


    Institute of Scientific and Technical Information of China (English)

    LIN Qinghuang; WANG Huifen; LIU Deshan; ZHOU Qixiang


    Several novel aromatic liquid crystalline copolyesters with regular sequence structure were prepared by melt Schotten-Baumann polycondensation via complex monomer. Polarizing microscope with hot stage,thermal analysis and X-ray diffraction were used to investigate the structure and properties of the copolyesters . The effects of structural units, such as flexible spacer, noncolinear meta-linked phenylene unit, crankshaft unit, kink with flexible bridging unit and various substituted benzene rings on melting temperature of aromatic copolyesters were studied and discussed on the basis of crystalline structure of the polymers.

  4. Nucleophilic fluorination of aromatic compounds

    Energy Technology Data Exchange (ETDEWEB)

    Satyamurthy, Nagichettiar; Barrio, Jorge R


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

  5. Alkylation of organic aromatic compounds (United States)

    Smith, L.A. Jr.


    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.

  6. MIPs in Aqueous Environments. (United States)

    Wan, Ying-chun; Ma, Hui-ting; Lu, Bin


    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.

  7. Solubilization isotherms of aromatic solutes in surfactant aggregates

    Energy Technology Data Exchange (ETDEWEB)

    Gadelle, F.; Koros, W.J.; Schechter, R.S. (Univ. of Texas, Austin, TX (United States). Dept. of Chemical Engineering)


    Several factors affecting solubilization of aromatic solutes in surfactant micelles have been investigated. Solubilization isotherms of benzene, toluene, and chlorobenzene in various aqueous micellar solutions were determined using head space gas chromatography. Cationic surfactants such as cetylpyridinium chloride or cetyltrimethylammonium bromide present high solubilization capacities. Comparable anionic surfactants exhibit lower solubilization and a greater tendency to precipitate. It was observed that nonionic surfactants show high solubilization on a molar basis. Solubilization in mixed cationic-anionic micelles was also investigated. It also appears that the molecular size of the solute determines the extent of the solubilization. Finally, the shape of the different isotherms indicates that knowing the amount solubilized at saturation of the micellar solution is not sufficient to estimate solubilization at solute concentrations lower than the solute aqueous solubility. Solubilization of organics in surfactant micelles is of major importance in many applications. One new application is micellar-enhanced ultrafiltration. Another application of interest is the surfactant-enhanced aquifer remediation, a process in which a micellar aqueous solution is flushed into contaminated groundwaters to enhance recovery of pollutants by micellar solubilization.

  8. Polycyclic aromatic hydrocarbons (PAHs) removal by sorption: A review. (United States)

    Lamichhane, Shanti; Bal Krishna, K C; Sarukkalige, Ranjan


    Polycyclic aromatic hydrocarbons (PAHs) are organic micro pollutants which are persistent compounds in the environment due to their hydrophobic nature. Concerns over their adverse effects in human health and environment have resulted in extensive studies on various types of PAHs removal methods. Sorption is one of the widely used methods as PAHs possess a great sorptive ability into the solid media and their low aqueous solubility property. Several adsorbent media such as activated carbon, biochar, modified clay minerals have been largely used to remove PAHs from aqueous solution and to immobilise PAHs in the contaminated soils. According to the past studies, very high removal efficiency could be achieved using the adsorbents such as removal efficiency of activated carbon, biochar and modified clay mineral were 100%, 98.6% and >99%, respectively. PAHs removal efficiency or adsorption/absorption capacity largely depends on several parameters such as particle size of the adsorbent, pH, temperature, solubility, salinity including the production process of adsorbents. Although many studies have been carried out to remove PAHs using the sorption process, the findings have not been consolidated which potentially hinder to get the correct information for future study and to design the sorption method to remove PAHs. Therefore, this paper summarized the adsorbent media which have been used to remove PAHs especially from aqueous solutions including the factor affecting the sorption process reported in 142 literature published between 1934 and 2015.

  9. Calcined eggshell (CES): An efficient natural catalyst for Knoevenagel condensation under aqueous condition

    Indian Academy of Sciences (India)

    Suresh Patil; Swati D Jadhav; M B Deshmukh


    A convenient, eco-friendly and economic method for Knoevenagel condensation of aromatic aldehydes with active methylene compounds using calcined eggshell (CES) as an efficient natural catalyst in aqueous medium has been reported. CES is a new, ecologically safe and inexpensive green catalyst obtained from renewable resources.

  10. Extraction of toluene, o-xylene from heptane and benzyl alcohol from toluene with aqueous cyclodextrins

    NARCIS (Netherlands)

    Meindersma, G.W.; Schoonhoven, van T.; Kuzmanovic, B.; Haan, de A.B.


    The separation of aromatic compounds (toluene and o-xylene) from heptane and of benzyl alcohol from toluene with aqueous solutions of cyclodextrins has been experimentally investigated, because cyclodextrins and its derivatives can selectively incorporate several organic compounds, whereas the separ

  11. Derivatization in gas chromatographic determination of phenol and aniline traces in aqueous media (United States)

    Gruzdev, I. V.; Zenkevich, I. G.; Kondratenok, B. M.


    Substituted anilines and phenols are the most common hydrophilic organic environmental toxicants. The principles of gas chromatographic determination of trace amounts of these compounds in aqueous media at concentrations extractive preconcentration and selective chromatographic detection. Among the known reactions, this condition is best met by electrophilic halogenation of compounds at the aromatic moiety. The bibliography includes 177 references.

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

    NARCIS (Netherlands)

    Besemer, A.C.; Kanij, J.


    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 t

  13. 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)


    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.

  14. Deuterated polycyclic aromatic hydrocarbons: Revisited

    CERN Document Server

    Doney, Kirstin D; Mori, Tamami; Onaka, Takashi; Tielens, A G G M


    The amount of deuterium locked up in polycyclic aromatic hydrocarbons (PAHs) has to date been an uncertain value. We present a near-infrared (NIR) spectroscopic survey of HII regions in the Milky Way, Large Magellanic Cloud (LMC), and Small Magellanic Cloud (SMC) obtained with AKARI, which aims to search for features indicative of deuterated PAHs (PAD or Dn-PAH) to better constrain the D/H ratio of PAHs. Fifty-three HII regions were observed in the NIR (2.5-5 {\\mu}m), using the Infrared Camera (IRC) on board the AKARI satellite. Through comparison of the observed spectra with a theoretical model of deuterated PAH vibrational modes, the aromatic and (a)symmetric aliphatic C-D stretch modes were identified. We see emission features between 4.4-4.8 {\\mu}m, which could be unambiguously attributed to deuterated PAHs in only six of the observed sources, all of which are located in the Milky Way. In all cases, the aromatic C-D stretching feature is weaker than the aliphatic C-D stretching feature, and, in the case o...

  15. Noncomparative scaling of aromaticity through electron itinerancy

    Energy Technology Data Exchange (ETDEWEB)

    Paul, Satadal [Department of Chemistry, University of North Bengal, Raja Rammohunpur, Darjeeling 734013, West Bengal (India); Darjeeling Polytechnic, Kurseong, Darjeeling 734203, West Bengal (India); Goswami, Tamal; Misra, Anirban, E-mail: [Department of Chemistry, University of North Bengal, Raja Rammohunpur, Darjeeling 734013, West Bengal (India)


    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.

  16. Polar Shapelets

    CERN Document Server

    Massey, R; Massey, Richard; Refregier, Alexandre


    The shapelets method for astronomical image analysis is based around the decomposition of localised objects into a series of orthogonal components with particularly convenient mathematical properties. We extend the "Cartesian shapelet" formalism from earlier work, and construct "polar shapelet" basis functions that separate an image into components with explicit rotational symmetries. This provides a more compact representation of typical galaxy shapes, and its physical interpretation is frequently more intuitive. Linear coordinate transformations can be simply expressed using this basis set, and shape measures (including object photometry, astrometry and galaxy morphology estimators) take a naturally elegant form. Particular attention is paid to the analysis of astronomical survey images, and we test shapelet techniques with real data from the Hubble Space Telescope. We present a practical method to automatically optimise the quality of an arbitrary shapelet decomposition in the presence of noise, pixellisat...

  17. Partition of polycyclic aromatic hydrocarbons on organobentonites

    Institute of Scientific and Technical Information of China (English)


    A series of organobentonites synthesized by exchanging organiccation such as dodecyltri-methylammonium (DTMA),benzyldimethyltetradecylammonium (BDTDA), cetyltrimethyl-ammonium (CTMA), octodeyltrimethylammonium (OTMA) on bentonite. The optimal condition, properties and mechanisms for the organobentonites to sorb phenanthrene, anthracene, naphthalene, acenaphthene in water were investigated in detail. The partition behavior was determined for four polycyclic aromatic hydrocarbons (PAHs), such as naphthalene, phenanthrene, anthracene and acenaphthene, from water to a series of organobentonites. The interlayer spacings and organic carbon contents of organobentonites, removal rate and sorption capacities for organobentonites to treat phenanthrene,anthracene, naphthalene, acenaphthene were correlated to the length of alkyl chains and the amounts of cation surfactant exchanged on Foundation item: the bentonite. Phenanthrene, anthracene, naphthalene, and acenaphthene sorption to organobentonites were characterized by linear isotherms, indicating solute partition between water and the organic phase composed of the large alkyl functional groups of quaternary ammonium cations. PAHs distribution coefficients (Kd)between organobentonites and water were proportional to the organic carbon contents of organobentonites. However, the partition coefficients (Koc) were nearly constants for PAHs in the system of organobentonite-water. The Koc of phenanthrene, anthracene,naphthalene, acenaphthene were 2.621x105, 2.106x105, 2.247x104,5.085x104, respectively. The means Koc values on the organobentonites are about ten to twenty times larger than the values on the soils/sediments, what is significant prerequisite for organobentonite to apply to remediation of pollution soil and groundwater. The sorption mechanism was also evaluated from octanol-water partition coefficients and aqueous solubility of PAHs. The correlations between lgKoc and 1gkow, 1gKoc and 1gS for PAHs in the system of water

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


    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, Tg. 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. PMID:27682333

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


    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, Tg. 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.

  20. Compactness Aromaticity of Atoms in Molecules

    Directory of Open Access Journals (Sweden)

    Mihai V. Putz


    Full Text Available A new aromaticity definition is advanced as the compactness formulation through the ratio between atoms-in-molecule and orbital molecular facets of the same chemical reactivity property around the pre- and post-bonding stabilization limit, respectively. Geometrical reactivity index of polarizability was assumed as providing the benchmark aromaticity scale, since due to its observable character; with this occasion new Hydrogenic polarizability quantum formula that recovers the exact value of 4.5 a03 for Hydrogen is provided, where a0 is the Bohr radius; a polarizability based–aromaticity scale enables the introduction of five referential aromatic rules (Aroma 1 to 5 Rules. With the help of these aromatic rules, the aromaticity scales based on energetic reactivity indices of electronegativity and chemical hardness were computed and analyzed within the major semi-empirical and ab initio quantum chemical methods. Results show that chemical hardness based-aromaticity is in better agreement with polarizability based-aromaticity than the electronegativity-based aromaticity scale, while the most favorable computational environment appears to be the quantum semi-empirical for the first and quantum ab initio for the last of them, respectively.

  1. Ultra resolution chemical fingerprinting of dense non-aqueous phase liquids from manufactured gas plants by reversed phase comprehensive two-dimensional gas chromatography. (United States)

    McGregor, Laura A; Gauchotte-Lindsay, Caroline; Daéid, Niamh Nic; Thomas, Russell; Daly, Paddy; Kalin, Robert M


    Ultra resolution chemical fingerprinting of dense non-aqueous phase liquids (DNAPLs) from former manufactured gas plants (FMGPs) was investigated using comprehensive two-dimensional gas chromatography coupled with time of flight mass spectrometry (GC×GC TOFMS). Reversed phase GC×GC (i.e. a polar primary column coupled to a non-polar secondary column) was found to significantly improve the separation of polycyclic aromatic hydrocarbons (PAHs) and their alkylated homologues. Sample extraction and cleanup was performed simultaneously using accelerated solvent extraction (ASE), with recovery rates between 76% and 97%, allowing fast, efficient extraction with minimal solvent consumption. Principal component analysis (PCA) of the GC×GC data was performed in an attempt to differentiate between twelve DNAPLs based on their chemical composition. Correlations were discovered between DNAPL composition and historic manufacturing processes used at different FMGP sites. Traditional chemical fingerprinting methods generally follow a tiered approach with sample analysis on several different instruments. We propose ultra resolution chemical fingerprinting as a fast, accurate and precise method of obtaining more chemical information than traditional tiered approaches while using only a single analytical technique.

  2. Aqueous Corrosion Behavior of Iron aluminide Intermetallics (United States)

    Sharma, Garima; Singh, P. R.; Sharma, R. K.; Gaonkar, K. B.; Ramanujan, R. V.


    Iron aluminide intermetallics based on DO3 ordered structure are being developed for use as structural materials and cladding material for conventional engineering alloys. Aqueous corrosion behavior of iron aluminides has been studied extensively by electrochemical techniques. Studies were carried out on pure Fe (99.9%), Fe-28Al (at.%), Fe-28Al-3Cr (at.%), and AISI SS 304 so as to compare and contrast their behavior in same experimental condition. Polarization behavior under different pH conditions was examined to evaluate their performance in acidic, basic, and neutral solutions. Pitting behavior was also studied in solution containing Cl-1 ions. The stability of the passive film formed was studied by current time transients and potential decay profiles. The presence of 3 at.% Cr in iron aluminides was found to improve the aqueous corrosion resistance and makes it comparable to AISI SS 304.

  3. 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;


    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...... of the model (the Soave-Redlich-Kwong (SRK) equation of state) can be obtained from mixtures with aliphatic hydrocarbons. For mixtures of glycols with aromatic hydrocarbons, two parameters have been fitted to experimental data, one in the physical (SRK) part and one in the association part of the model...

  4. Characterization of transient species in laser photolysis of aromatic amino acids using acetone as photosensitizer

    Institute of Scientific and Technical Information of China (English)

    宋钦华; 徐业平; 俞书勤; 陈从香; 马兴孝; 王文锋; 姚思德; 林念芸


    The photochemical processes of aromatic amino acids were investigated in aqueous solution using acetone as photosensitizer by KrF (248 nm) laser flash photolysis. Laser-induced transient species were characterized according to kinetic analysis and quenching experiments. The intermediates recorded were assigned to the excited triplet state of tryptophan, the radicals of tryptophan and tyrosine. The excited triplet state of tryptophan produced via a triplet-triplet excitation transfer and the radicals arising from electron transfer reaction has been identified. Neither electron transfer nor energy transfer between triplet acetone and phenylalanine can occur in photolysis of phenylalanine aqueous solution which contains acetone. Furthermore, triplet acetone-induced radical transformation: Trp/N-Tyr→Trp-Tyr/O was observed directly in photolysis of dipeptide (Trp-Tyr) aqueous solution containing acetone, and the transformation resulting from intramolecular electron transfer was suggested.

  5. Sorption of polycyclic aromatic hydrocarbons to polystyrene nanoplastic. (United States)

    Liu, Lijing; Fokkink, Remco; Koelmans, Albert A


    Microplastic has become an emerging contaminant of global concern. Bulk plastic can degrade to form smaller particles down to the nanoscale (nanoplastics. Because of their high surface area, nanoplastic may bind hydrophobic chemicals very effectively, increasing their hazard when such nanoplastics are taken up by biota. The present study reports distribution coefficients for sorption of polycyclic aromatic hydrocarbons (PAHs) to 70 nm polystyrene in freshwater, and PAH adsorption isotherms spanning environmentally realistic aqueous concentrations of 10(-5)  μg/L to 1 μg/L. Nanopolystyrene aggregate state was assessed using dynamic light scattering. The adsorption isotherms were nonlinear, and the distribution coefficients at the lower ends of the isotherms were very high, with values up to 10(9) L/kg. The high and nonlinear sorption was explained from π-π interactions between the planar PAHs and the surface of the aromatic polymer polystyrene and was higher than for micrometer-sized polystyrene. Reduction of nanopolystyrene aggregate sizes had no significant effect on sorption, which suggests that the PAHs could reach the sorption sites on the pristine nanoparticles regardless of the aggregation state. Pre-extraction of the nanopolystyrene with C18 polydimethylsiloxane decreased sorption of PAHs, which could be explained by removal of the most hydrophobic fraction of the nanopolystyrene. Environ Toxicol Chem 2016;35:1650-1655. © 2015 SETAC.

  6. Reconfigurable thz polarizer

    DEFF Research Database (Denmark)


    The present invention provides a polarizer. The polarizer comprises a first membrane having a first polarization region comprising a first plurality of membrane perforations; a second membrane having a second polarization region comprising a second plurality of membrane perforations; and a support...... with one or more membrane perforations in the second plurality of perforations in a direction normal to the first polarization region or normal to the second polarization region, resulting in corresponding one or more openings in said direction....

  7. Birds and polycyclic aromatic hydrocarbons (United States)

    Albers, P.H.


    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.

  8. Hückel's Rule of Aromaticity Categorizes Aromatic Closo Boron Hydride Clusters


    Poater i Teixidor, Jordi; Solà i Puig, Miquel; Viñas, Clara; Teixidor, Francesc


    A direct connection is established between tridimensional aromatic closo boron hydride clusters and planar aromatic [n]annulenes for medium and large size boron clusters. In particular, our results prove the existence of a link between the two-dimensional Hückel rule followed by aromatic [n]-annulenes and Wade-Mingos' rule of three-dimensional aromaticity applied to the aromatic [BnHn]2- closo boron hydride clusters. Our results show that closo boron hydride clusters can be categorized into d...

  9. Beyond organic chemistry: aromaticity in atomic clusters. (United States)

    Boldyrev, Alexander I; Wang, Lai-Sheng


    We describe joint experimental and theoretical studies carried out collaboratively in the authors' labs for understanding the structures and chemical bonding of novel atomic clusters, which exhibit aromaticity. The concept of aromaticity was first discovered to be useful in understanding the square-planar unit of Al4 in a series of MAl4(-) bimetallic clusters that led to discoveries of aromaticity in many metal cluster systems, including transition metals and similar cluster motifs in solid compounds. The concept of aromaticity has been found to be particularly powerful in understanding the stability and bonding in planar boron clusters, many of which have been shown to be analogous to polycyclic aromatic hydrocarbons in their π bonding. Stimulated by the multiple aromaticity in planar boron clusters, a design principle has been proposed for stable metal-cerntered aromatic molecular wheels of the general formula, M@Bn(k-). A series of such borometallic aromatic wheel complexes have been produced in supersonic cluster beams and characterized experimentally and theoretically, including Ta@B10(-) and Nb@B10(-), which exhibit the highest coordination number in two dimensions.

  10. Heterogeneous photocatalytic reactions of sulfur aromatic compounds. (United States)

    Samokhvalov, Alexander


    Sulfur aromatic compounds, such as mono-, di-, tri-, and tetraalkyl-substituted thiophene, benzothiophenes, dibenzothiophenes, are the molecular components of many fossils (petroleum, oil shale, tar sands, bitumen). Structural units of natural, cross-linked heteroaromatic polymers present in brown coals, turf, and soil are similar to those of sulfur aromatic compounds. Many sulfur aromatic compounds are found in the streams of petroleum refining and upgrading (naphthas, gas oils) and in the consumer products (gasoline, diesel, jet fuels, heating fuels). Besides fossils, the structural fragments of sulfur aromatic compounds are present in molecules of certain organic semiconductors, pesticides, small molecule drugs, and in certain biomolecules present in human body (pheomelanin pigments). Photocatalysis is the frontier area of physical chemistry that studies chemical reactions initiated by absorption of photons by photocatalysts, that is, upon electronic rather than thermal activation, under "green" ambient conditions. This review provides systematization and critical review of the fundamental chemical and physicochemical information on heterogeneous photocatalysis of sulfur aromatic compounds accumulated in the last 20-30 years. Specifically, the following topics are covered: physicochemical properties of sulfur aromatic compounds, major classes of heterogeneous photocatalysts, mechanisms and reactive intermediates of photocatalytic reactions of sulfur aromatic compounds, and the selectivity of these reactions. Quantum chemical calculations of properties and structures of sulfur aromatic compounds, their reactive intermediates, and the structure of adsorption complexes formed on the surface of the photocatalysts are also discussed.

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

    Energy Technology Data Exchange (ETDEWEB)

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


    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.

  12. An amino acid at position 142 in nitrilase from Rhodococcus rhodochrous ATCC 33278 determines the substrate specificity for aliphatic and aromatic nitriles. (United States)

    Yeom, Soo-Jin; Kim, Hye-Jung; Lee, Jung-Kul; Kim, Dong-Eun; Oh, Deok-Kun


    Nitrilase from Rhodococcus rhodochrous ATCC 33278 hydrolyses both aliphatic and aromatic nitriles. Replacing Tyr-142 in the wild-type enzyme with the aromatic amino acid phenylalanine did not alter specificity for either substrate. However, the mutants containing non-polar aliphatic amino acids (alanine, valine and leucine) at position 142 were specific only for aromatic substrates such as benzonitrile, m-tolunitrile and 2-cyanopyridine, and not for aliphatic substrates. These results suggest that the hydrolysis of substrates probably involves the conjugated pi-electron system of the aromatic ring of substrate or Tyr-142 as an electron acceptor. Moreover, the mutants containing charged amino acids such as aspartate, glutamate, arginine and asparagine at position 142 displayed no activity towards any nitrile, possibly owing to the disruption of hydrophobic interactions with substrates. Thus aromaticity of substrate or amino acid at position 142 in R. rhodochrous nitrilase is required for enzyme activity.

  13. Direct photolysis of nitroaromatic compounds in aqueous solutions

    Institute of Scientific and Technical Information of China (English)

    CHEN Bing; YANG Chun; GOH Ngoh Khang


    The direct photolysis of nitrobenzene and nitrophenols in aqueous solutions irradiated by polychromatic light were investigated.Several aromatic intermediates were identified as three nitrophenol isomers, nitrohydroquinone, nitrosobenzene, nitrocatechol, catechol and phenol. Nitrite and nitrate ions were also detected in the irradiated solution indicating direct photolysis of nitrobenzene or nitrophenols.The degradation of nitrobenzene and nitrophenols and the formation of three nitrophenol isomers were observed to follow zero-order kinetics. The quantum yields for nitrobenzene and nitrophenols removal are about 10-3 and 10-3-10-4 respectively. The mechanism for nitrobenzene degradation was suggested to follow mainly nitro-nitrite intramolecular arrangement.

  14. Treatment of Aqueous Solutions

    NARCIS (Netherlands)

    Van Spronsen, J.; Witkamp, G.J.


    The invention is directed to a process for the recovery or removal of one or more crystallizable compounds from an aqueous solution containing, apart from the said crystallizable compounds, one or more organic or inorganic scale- forming or scale-inducing materials having a lower solubility in water

  15. π-Hydrogen Bonding of Aromatics on the Surface of Aerosols: Insights from Ab Initio and Molecular Dynamics Simulation. (United States)

    Feng, Ya-Juan; Huang, Teng; Wang, Chao; Liu, Yi-Rong; Jiang, Shuai; Miao, Shou-Kui; Chen, Jiao; Huang, Wei


    Molecular level insight into the interaction between volatile organic compounds (VOCs) and aerosols is crucial for improvement of atmospheric chemistry models. In this paper, the interaction between adsorbed toluene, one of the most significant VOCs in the urban atmosphere, and the aqueous surface of aerosols was studied by means of combined molecular dynamics simulations and ab initio quantum chemistry calculations. It is revealed that toluene can be stably adsorbed on the surface of aqueous droplets via hydroxyl-π hydrogen bonding between the H atoms of the water molecules and the C atoms in the aromatic ring. Further, significant modifications on the electrostatic potential map and frontier molecular orbital are induced by the solvation effect of surface water molecules, which would affect the reactivity and pathway of the atmospheric photooxidation of toluene. This study demonstrates that the surface interactions should be taken into consideration in the atmospheric chemical models on oxidation of aromatics.

  16. Removal of crude oil polycyclic aromatic hydrocarbons via organoclay-microbe-oil interactions. (United States)

    Ugochukwu, Uzochukwu C; Fialips, Claire I


    Clay minerals are quite vital in biogeochemical processes but the effect of organo-clays in the microbial degradation of crude oil polycyclic aromatic hydrocarbons is not well understood. The role of organo-saponite and organo-montmorillonite in comparison with the unmodified clays in crude oil polycyclic aromatic hydrocarbons (PAHs) removal via adsorption and biodegradation was studied by carrying out microcosm experiments in aqueous clay/oil systems with a hydrocarbon degrading microbial community that is predominantly alcanivorax spp. Montmorillonite and saponite samples were treated with didecyldimethylammonium bromide to produce organo-montmorillonite and organo-saponite used in this study. Obtained results indicate that clays with high cation exchange capacity (CEC) such as montmorillonite produced organo-clay (organomontmorillonite) that was not stimulatory to biodegradation of crude oil polycyclic aromatic compounds, especially the low molecular weight (LMW) ones, such as dimethylnaphthalenes. It is suggested that interaction between the organic phase of the organo-clay and the crude oil PAHs which is hydrophobic in nature must have reduced the availability of the polycyclic aromatic hydrocarbons for biodegradation. Organo-saponite did not enhance the microbial degradation of dimethylnaphthalenes but enhanced the biodegradation of some other PAHs such as phenanthrene. The unmodified montmorillonite enhanced the microbial degradation of the PAHs and is most likely to have done so as a result of its high surface area that allows the accumulation of microbes and nutrients enhancing their contact.

  17. Conservation of medicinal and aromatic plants

    Directory of Open Access Journals (Sweden)

    Šveistytė, Laima


    Full Text Available The conservation of medicinal and aromatic plants includes ex situ and in situ methods. The genetic recourses of medicinal and aromatic plants are stored, studied and constantly maintained in the field collections of the Institute of Botany of Nature Research Centre, Kaunas Botanical Garden of Vytautas Magnus University and Aleksandras Stulginskis University of Agriculture. Presently seeds of 214 accessions representing 38 species of medicinal and aromatic plants are stored in a long-term storage in the Plant Gene Bank. The data about national genetic resources are collected and stored in the Central Database of the Plant Gene Bank.

  18. 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.

  19. WFPC2 Polarization Calibration (United States)

    Biretta, J.; McMaster, M.


    We derive a detailed calibration for WFPC2 polarization data which is accurate to about 1.5%. We begin by computing polarizer flats, and show how they are applied to data. A physical model for the polarization effects of the WFPC2 optics is then created using Mueller matricies. This model includes corrections for the instrumental polarization (diattenuation and phase retardance) of the pick-off mirror, as well as the high cross-polarization transmission of the polarizer filter. We compare this model against the on-orbit observations of polarization calibrators, and show it predicts relative counts in the different polarizer/aperture settings to 1.5% RMS accuracy. We then show how this model can be used to calibrate GO data, and present two WWW tools which allow observers to easily calibrate their data. Detailed examples are given illustrationg the calibration and display of WFPC2 polarization data. In closing we describe future plans and possible improvements.

  20. Metasurface polarization splitter

    CERN Document Server

    Slovick, Brian A; Yu, Zhi Gang; Kravchenckou, Ivan I; Briggs, Dayrl P; Moitra, Parikshit; Krishnamurthy, Srini; Valentine, Jason


    Polarization beam splitters, devices that separate the two orthogonal polarizations of light into different propagation directions, are one of the most ubiquitous optical elements. However, traditionally polarization splitters rely on bulky optical materials, while emerging optoelectronic and photonic circuits require compact, chip-scale polarization splitters. Here we show that a subwavelength rectangular lattice of cylindrical silicon Mie resonators functions as a polarization splitter, efficiently reflecting one polarization while transmitting the other. We show that the polarization splitting arises from the anisotropic permittivity and permeability of the metasurface due to the two-fold rotational symmetry of the rectangular unit cell. The high polarization efficiency, low loss, and low profile make these metasurface polarization splitters ideally suited for monolithic integration with optoelectronic and photonic circuits.

  1. Determination of aromatic amines from textiles using dispersive liquid-liquid microextraction. (United States)

    Yang, Lu; Yiwei, Wang; Caiying, Lou; Yan, Zhu


    A dispersive liquid-liquid microextraction procedure coupled with GC-MS is described for preconcentration and determination of banned aromatic amines from textile samples. Experimental conditions affecting the microextraction procedure were optimized. A mixture of 30 μL chlorobenzene (extraction solvent) and 800 μL ACN (disperser solvent), 5 min extraction time, and 5 mL aqueous sample volume were chosen for the best extraction efficiency by the proposed procedure. Satisfactory linearity (with correlation coefficients >0.9962) and repeatability (<9.78%) were obtained for all 20 aromatic amines; detection limits attained were much lower than the standardized liquid-liquid method. The proposed method has advantages of being quicker and easier to operate, and lower consumption of organic solvent.

  2. 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


    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.

  3. Comments on Coulomb pairing in aromatic hydrocarbons

    CERN Document Server

    Huber, D L


    Recently reported anomalies in the double-photonionization spectra of aromatic molecules such as benzene, naphthalene, anthracene and coronene are attributed to Coulomb-pair resonances of pi electrons.

  4. Silicone elastomers with aromatic voltage stabilizers

    DEFF Research Database (Denmark)

    A Razak, Aliff Hisyam; Skov, Anne Ladegaard

    modifications. In order to increase the electrical breakdown strength of polymers for e.g. the cable industry, additives like aromatic voltage stabilizers are used. Earlier works on using voltage stabilizers in polymers have mainly focused on polyethylene with the purpose of reducing power loss for high voltage...... insulation cables.3–5 As an alternative to utilise additives as voltage stabilizers, grafting aromatic compounds to silicone backbones may overcome the common problem of insolubility of the aromatic voltage stabilizer in the silicone elastomers due to phase separation. Preventing phase separation during...... via hydrosilylation by a vinyl-functional crosslinker. The mechanism 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...

  5. Graphite Oxide and Aromatic Amines : Size Matters

    NARCIS (Netherlands)

    Spyrou, Konstantinos; Calvaresi, Matteo; Diamanti, Evmorfi A. K.; Tsoufis, Theodoros; Gournis, Dimitrios; Rudolf, Petra; Zerbetto, Francesco


    Experimental and theoretical studies are performed in order to illuminate, for first time, the intercalation mechanism of polycyclic aromatic molecules into graphite oxide. Two representative molecules of this family, aniline and naphthalene amine are investigated. After intercalation, aniline molec

  6. Volatilisation of aromatic hydrocarbons from soil

    DEFF Research Database (Denmark)

    Lindhardt, B.; Christensen, T.H.


    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...

  7. Infrared Spectra of Polycyclic Aromatic Hydrocarbons (PAHs) (United States)

    Bauschlicher, Charles W., Jr.; Bakes, E. L. O.


    We have computed the synthetic infrared spectra of some polycyclic aromatic hydrocarbons containing up to 54 carbon atoms. The species studied include ovalene, circumcoronene, dicoronylene, and hexabenzocoronene. We report spectra for anions, neutrals, cations, and multiply charged cations.

  8. The Industrial Reduction of Aromatic Nitro Compounds. (United States)

    Gilbert, G.


    Describes methods for enriching an A-level chemistry course with a series of chemical company visits. The rationale is discussed for an emphasis of the visits on the industrial reduction of aromatic nitro compounds. (CS)

  9. Activity relationships for aromatic crown ethers

    CERN Document Server

    Wilson, M J


    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...

  10. Geographical Income Polarization

    DEFF Research Database (Denmark)

    Azhar, Hussain; Jonassen, Anders Bruun

    In this paper we estimate the degree, composition and development of geographical income polarization based on data at the individual and municipal level in Denmark from 1984 to 2002. Rising income polarization is reconfirmed when applying new polarization measures, the driving force being greater...... inter municipal income inequality. Counter factual simulations show that rising property prices to a large part explain the rise in polarization. One side-effect of polarization is tendencies towards a parallel polarization of residence location patterns, where low skilled individuals tend to live...

  11. Dehydrogenative Aromatization of Saturated Aromatic Compounds by Graphite Oxide and Molecular Sieves

    Institute of Scientific and Technical Information of China (English)

    张轩; 徐亮; 王希涛; 马宁; 孙菲菲


    Graphite oxide (GO) has attracted much attention of material and catalysis chemists recently. Here we describe a combination of GO and molecular sieves for the dehydrogenative aromatization. GO prepared through improved Hummers method showed high oxidative activity in this reaction. Partially or fully saturated aromatic compounds were converted to their corresponding dehydrogenated aromatic products with fair to excellent conversions and selectivities. As both GO and molecular sieves are easily available, cheap, lowly toxic and have good tolerance to various functional groups, this reaction provides a facile approach toward aromatic compounds from their saturated precursors

  12. Hydrodynamic resistance of concentration polarization boundary layers in ultrafiltration

    NARCIS (Netherlands)

    Wijmans, J.G.; Nakao, S.; Berg, van den J.W.A.; Troelstra, F.R.; Smolders, C.A.


    The influence of concentration polarization on the permeate flux in the ultrafiltration of aqueous Dextran T70 solutions can be described by (i) the osmotic pressure model and (ii) the boundary layer resistance model. In the latter model the hydrodynamic resistance of the non-gelled boundary layer i

  13. Thoughts on Optimization of Aromatic Feedstock

    Institute of Scientific and Technical Information of China (English)

    Cao Jian


    This article refers to four cases of process unit combinations with different throughputs of aromatics unit for production of 450 kt/a paraxylene at a certain petrochemical complex in order to against a representative case (provided with an 800-kt/a CCR unit and a 600-kt/a disproportionation unit) and the feasibility and advantage of using prolysis gasoline as aromatic feedstock is studied.

  14. Aromatic amines sources, environmental impact and remediation


    Pereira, Luciana; Mondal, P. K.; Alves, M. M.


    Aromatic amines are widely used industrial chemicals as their major sources in the environment include several chemical industry sectors such as oil refining, synthetic polymers, dyes, adhesives, rubbers, perfume, pharmaceuticals, pesticides and explosives. They result also from diesel exhaust, combustion of wood chips and rubber and tobacco smoke. Some types of aromatic amines are generated during cooking, special grilled meat and fish, as well. The intensive use and production of these comp...

  15. Reactive Extraction of Alcohols from Apolar Hydrocarbons with Aqueous Solutions

    Institute of Scientific and Technical Information of China (English)


    The aqueous solutions are evaluated as sustainable reactive extraction solvents for the recovery of monohydroxyl alcohols (benzyl alcohol, 1-hexanol, cyclohexanol) present in few-percent concentrations in apolar hydrocarbons (toluene, n-hexane, and cyclohexane) by considering two approaches. An aqueous solution containing a reactive extractant, like borate salts, borate complexes, a monosalt of dicarboxylic acid,hydroxypropyl-cyclodextrins, and silver nitrate, shows limited potential to be used. Another approach, in which the alcohol is chemically modified prior to the extraction into an easy-extractable form, in this case a monoesterlcarboxylic acid, shows much more potential. An environmentally benign aqueous solution of sodium hydrogen carbonate can provide a distribution ratio of benzyl alcohol up to 200, leaving the solubility of the organic solvent in the aqueous solution unchanged relative to pure water and therefore increasing the selectivity with two orders of magnitude. The modification of aromatic, cyclo-aliphatic, and linear aliphatic alcohols can be performed efficiently in the apolar organic solvent without need for a catalyst. The recovery of the modified alcohol can be performed by back-extraction in combination with a spontaneous hydrolysis.

  16. Crystalline fibrillar gel formation in aqueous surfactant-antioxidant system. (United States)

    Joseph, Linet Rose; Tata, B V R; Sreejith, Lisa


    Cetyltrimethylammonium bromide (CTAB) is a well-known cationic surfactant capable to micellize into diverse morphologies in aqueous medium. We observed the formation of an opaque gel state from aqueous CTAB solution in the presence of the aromatic additive, para-coumaric acid (PCA). Optical microscopic images revealed the presence of large fibrils in the system at room temperature. Gel nature of the fibrils was confirmed by rheological measurements. Presence of interstitial water in the fibrils was recognized with Raman spectroscopy. On heating the sample above 30 (°) C, the fibrillar gel state changes to a transparent liquid state with Newtonian flow properties. Dynamic light scattering study hinted the presence of small micelles in the solution above 30 (°) C. Thus the system showed a temperature-dependent structural transition from opaque water-swollen gel to transparent micellar liquid. The formation of water-swollen fibrillar network is attributed to surfactant-additive intermolecular interactions in aqueous medium. Transition to micelle phase above 30 (°) C is related to Kraft transition which is observed at significantly lower temperature for CTAB in the absence of PCA. The structural features of PCA play a key role in promoting fibrillar network formation and elevating the Kraft transition in aqueous solution of CTAB.

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

    Directory of Open Access Journals (Sweden)

    Camilo A. Navarro D.


    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.

  18. A Translational Polarization Rotator

    CERN Document Server

    Chuss, David T; Pisano, Giampaolo; Ackiss, Sheridan; U-Yen, Kongpop; Ng, Ming wah


    We explore a free-space polarization modulator in which a variable phase introduction between right- and left-handed circular polarization components is used to rotate the linear polarization of the outgoing beam relative to that of the incoming beam. In this device, the polarization states are separated by a circular polarizer that consists of a quarter-wave plate in combination with a wire grid. A movable mirror is positioned behind and parallel to the circular polarizer. As the polarizer-mirror distance is separated, an incident linear polarization will be rotated through an angle that is proportional to the introduced phase delay. We demonstrate a prototype device that modulates Stokes Q and U over a 20% bandwidth.

  19. NESDIS VIIRS Polar Winds (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — This dataset contains the Level 3 Polar Winds Northern and Southern Hemisphere datasets. The Level 3 Polar Winds data from VIIRS for the Arctic and Antarctic from 65...

  20. Use of Cyclic Allylic Bromides in the Zinc–Mediated Aqueous Barbier–Grignard Reaction

    Directory of Open Access Journals (Sweden)

    Suzanne M. Perala


    Full Text Available The zinc–mediated aqueous Barbier–Grignard reaction of cyclic allylic bromide substrates with various aldehydes and ketones to afford homoallylic alcohols was investigated. Aromatic aldehydes and ketones afforded adducts in good yields (66–90% and with good diastereoselectivities. Non–aromatic aldehydes also reacted well under these conditions, but only poor yields were obtained with non–aromatic ketones. Regioselectivity was high when some substituted cyclic allylic bromides were investigated.

  1. Solubilization of benzene, toluene, and xylene (BTX) in aqueous micellar solutions of amphiphilic imidazolium ionic liquids. (United States)

    Łuczak, Justyna; Jungnickel, Christian; Markiewicz, Marta; Hupka, Jan


    Water-soluble ionic liquids may be considered analogues to cationic surfactants with a corresponding surface activity and ability to create organized structures in aqueous solutions. For the first time, the enhanced solubility of the aromatic hydrocarbons, benzene, toluene, and xylene, in aqueous micellar systems of 1-alkyl-3-methylimidazolium chlorides was investigated. Above a critical micelle concentration, a gradual increase in the concentration of aromatic hydrocarbons in the miceller solution was observed. This phenomenon was followed by means of the molar solubilization ratio, the micellar/water partition coefficient, and the number of solubilizate molecules per IL micelle. The molar solubilization ratio for ionic liquid micelles was found to be significantly higher when compared to that of ionic surfactants of similar chain length. The incorporation of the hydrocarbon into the micelle affects also an increase of the aggregation number.

  2. Chemical modification of amino acids by atmospheric-pressure cold plasma in aqueous solution (United States)

    Takai, Eisuke; Kitamura, Tsuyoshi; Kuwabara, Junpei; Ikawa, Satoshi; Yoshizawa, Shunsuke; Shiraki, Kentaro; Kawasaki, Hideya; Arakawa, Ryuichi; Kitano, Katsuhisa


    Plasma medicine is an attractive new research area, but the principles of plasma modification of biomolecules in aqueous solution remain elusive. In this study, we investigated the chemical effects of atmospheric-pressure cold plasma on 20 naturally occurring amino acids in aqueous solution. High-resolution mass spectrometry revealed that chemical modifications of 14 amino acids were observed after plasma treatment: (i) hydroxylation and nitration of aromatic rings in tyrosine, phenylalanine and tryptophan; (ii) sulfonation and disulfide linkage formation of thiol groups in cysteine; (iii) sulfoxidation of methionine and (iv) amidation and ring-opening of five-membered rings in histidine and proline. A competitive reaction experiment using 20 amino acids demonstrated that sulfur-containing and aromatic amino acids were preferentially decreased by the plasma treatment. These data provide fundamental information for elucidating the mechanism of protein inactivation for biomedical plasma applications.

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

    DEFF Research Database (Denmark)

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

    Recently, there has been an augmented focus on the increasing amount of pesticides, drug residues and endocrine disruptors present in waste and drinking water1. These pollutants represent a challenge in water purification since they may be hazardous to human health even in low doses2. Cyclodextrins...... 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....

  4. Inclusion of poly-aromatic hydrocarbon (PAH) molecules in a functionalized layered double hydroxide

    Indian Academy of Sciences (India)

    L Mohanambe; S Vasudevan


    The internal surface of an Mg-Al layered double hydroxide has been functionalized by anchoring carboxy-methyl derivatized -cyclodextrin cavities to the gallery walls. Neutral polyaromatic hydrocarbon (PAH) molecules have been included within the functionalized solid by driving the hydrophobic aromatic molecules from a polar solvent into the less polar interior of the anchored cyclodextrin cavities by a partitioning process. The optical (absorption and emission) properties of the PAH molecules included within the functionalized Mg-Al layered double hydroxide solid are similar to that of dilute solutions of the PAH in non-polar solvents. The unique feature of these hybrid materials is that they are thermally stable over a wide temperature range with their emission properties practically unaltered.

  5. Structure of water and the thermodynamics of aqueous solutions

    Energy Technology Data Exchange (ETDEWEB)

    Nemethy, G.


    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.

  6. ExBox: a polycyclic aromatic hydrocarbon scavenger. (United States)

    Barnes, Jonathan C; Juríček, Michal; Strutt, Nathan L; Frasconi, Marco; Sampath, Srinivasan; Giesener, Marc A; McGrier, Psaras L; Bruns, Carson J; Stern, Charlotte L; Sarjeant, Amy A; Stoddart, J Fraser


    A template-directed protocol, which capitalizes on donor-acceptor interactions, is employed to synthesize a semi-rigid cyclophane (ExBox(4+)) that adopts a box-like geometry and is comprised of π-electron-poor 1,4-phenylene-bridged ("extended") bipyridinium units (ExBIPY(2+)). ExBox(4+) functions as a high-affinity scavenger of an array of different polycyclic aromatic hydrocarbons (PAHs), ranging from two to seven fused rings, as a result of its large, accommodating cavity (approximately 3.5 Å in width and 11.2 Å in length when considering the van der Waals radii) and its ability to form strong non-covalent bonding interactions with π-electron-rich PAHs in either organic or aqueous media. In all, 11 PAH guests were observed to form inclusion complexes with ExBox(4+), with coronene being the largest included guest. Single-crystal X-ray diffraction data for the 11 inclusion complexes ExBox(4+)⊂PAH as well as UV/vis spectroscopic data for 10 of the complexes provide evidence of the promiscuity of ExBox(4+) for the various PAHs. Nuclear magnetic resonance spectroscopy and isothermal titration calorimetric analyses of 10 of the inclusion complexes are employed to further characterize the host-guest interactions in solution and determine the degree with which ExBox(4+) binds each PAH compound. As a proof-of-concept, a batch of crude oil from Saudi Arabia was subjected to extraction with the water-soluble form of the PAH receptor, ExBox·4Cl, resulting in the isolation of different aromatic compounds after ExBox·4Cl was regenerated.

  7. The influence of chemical composition of aliphatic-aromatic copolyesters on their properties

    Energy Technology Data Exchange (ETDEWEB)

    Wojtczak, Malgorzata; Galeski, Andrzej; Piorkowska, Ewa [Centre of Molecular and Macromolecular Studies, Polish Academy of Sciences, Sienkiewicza 112, 90-363 Lodz (Poland); Dutkiewicz, Slawomir [Institute of Biopolymers and Chemical Fibres, Marii Sklodowskiej-Curie 19/27, 90-570 Lodz (Poland)


    The chain microstructure and properties of a series of aliphatic-aromatic copolyesters in a range of compositions from 10 to 100% of aromatic components were studied by examining melting and crystallization behaviors, dynamic mechanical response, morphology, wide- (WAXS) and small-angle X-ray scattering (SAXS), and tensile deformation. Chain microstructure was analyzed by {sup 1}H NMR. The results indicate that most of copolyesters used in this study have essentially random distribution of comonomers. Copolyesters with more than 30 mol% of aromatic part crystallize with a crystal structure characteristic for homopolymer poly(butylene terephthalate) (PBT). However, some of the reflections from crystal planes are shifted towards lower diffraction angles as compared to butylene terephthalate homoplymer. The phase transition temperatures decrease with increasing aliphatic content. By means of polarized light microscopy (PLM), small-angle light scattering (SALS) and SAXS, crystallization behavior of a selected aliphatic-aromatic copolyester was further explored. Selected copolyester crystallizes in the form of thin fibrous crystals, few nanometers thick, which is the main factor influencing the depression of its melting temperature.

  8. Graphing Polar Curves (United States)

    Lawes, Jonathan F.


    Graphing polar curves typically involves a combination of three traditional techniques, all of which can be time-consuming and tedious. However, an alternative method--graphing the polar function on a rectangular plane--simplifies graphing, increases student understanding of the polar coordinate system, and reinforces graphing techniques learned…

  9. Plasma polarization spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Fujimoto, Takashi [Department of Engineering Physics and Mechanics, Graduate School of Engineering, Kyoto University, Kyoto (Japan)


    Polarization of radiation emitted from a plasma reflects the anisotropic properties of the plasma, especially the angular anisotropic distribution of electron velocities. Polarization has been observed on impurity ion lines from the WT-3 tokamak and the GAMMA-10 tandem mirror machines. The soft x-ray laser line from the neonlike germanium was also found polarized. (author)

  10. Polarity at Many Levels (United States)

    Flannery, Maura C.


    An attempt is made to find how polarity arises and is maintained, which is a central issue in development. It is a fundamental attribute of living things and cellular polarity is also important in the development of multicellular organisms and controversial new work indicates that polarization in mammals may occur much earlier than previously…

  11. Effect of interlayer cations of montmorillonite on the biodegradation and adsorption of crude oil polycyclic aromatic compounds. (United States)

    Ugochukwu, Uzochukwu C; Manning, David A C; Fialips, Claire I


    Cation exchange capacity, surface acidity and specific surface area are surface properties of clay minerals that make them act as catalysts or supports in most biogeochemical processes hence making them play important roles in environmental control. However, the role of homoionic clay minerals during the biodegradation of polycyclic aromatic compounds is not well reported. In this study, the effect of interlayer cations of montmorillonites in the removal of some crude oil polycyclic aromatic compounds during biodegradation was investigated in aqueous clay/oil microcosm experiments with a hydrocarbon degrading microorganism community. The homoionic montmorillonites were prepared via cation exchange reactions by treating the unmodified montmorillonite with the relevant metallic chloride. The study indicated that potassium-montmorillonite and zinc-montmorillonite did not enhance the biodegradation of the polycyclic aromatic hydrocarbons whereas calcium-montmorillonite, and ferric-montmorillonite enhanced their biodegradation significantly. Adsorption of polycyclic aromatic hydrocarbons was significant during biodegradation with potassium- and zinc-montmorillonite where there was about 45% removal of the polycyclic aromatic compounds by adsorption in the experimental microcosm containing 5:1 ratio (w/w) of clay to oil.

  12. Aqueous leaching of di-2-ethylhexyl phthalate and "green" plasticizers from poly(vinyl chloride). (United States)

    Kastner, Joshua; Cooper, David G; Marić, Milan; Dodd, Patrick; Yargeau, Viviane


    A method was developed to assess leaching of several poly(vinyl chloride) (PVC) plasticizers in aqueous media using gas chromatography (GC), and compared to a gravimetric standard test method (ASTM Method D1239). The GC method was a more direct measurement of plasticizer concentration in the aqueous phase. The leaching of commercial plasticizers, as well as several series of "green" candidate plasticizers, were assessed as a function of their molecular characteristics and compared to the industry standard PVC plasticizer, di-2-ethylhexyl phthalate (DEHP). It was found that plasticizers containing longer alkyl chains or non-polar branching emanating from polar structural units, increased the hydrophobicity of the molecule and reduced its aqueous leaching rate. Several "green" plasticizer candidates were found to minimize aqueous leaching to rates ten times below that of DEHP; notably dioctyl succinate (DOS), dihexyl maleate (DHM), methyl cyclohexyl diester (MCDE), diethylhexyl succinate (DEHS), hexanediol dibenzoate (C6), and the commercially available Hexamoll® DINCH.

  13. Aromatic metabolism of filamentous fungi in relation to the presence of aromatic compounds in plant biomass. (United States)

    Mäkelä, Miia R; Marinović, Mila; Nousiainen, Paula; Liwanag, April J M; Benoit, Isabelle; Sipilä, Jussi; Hatakka, Annele; de Vries, Ronald P; Hildén, Kristiina S


    The biological conversion of plant lignocellulose plays an essential role not only in carbon cycling in terrestrial ecosystems but also is an important part of the production of second generation biofuels and biochemicals. The presence of the recalcitrant aromatic polymer lignin is one of the major obstacles in the biofuel/biochemical production process and therefore microbial degradation of lignin is receiving a great deal of attention. Fungi are the main degraders of plant biomass, and in particular the basidiomycete white rot fungi are of major importance in converting plant aromatics due to their ability to degrade lignin. However, the aromatic monomers that are released from lignin and other aromatic compounds of plant biomass are toxic for most fungi already at low levels, and therefore conversion of these compounds to less toxic metabolites is essential for fungi. Although the release of aromatic compounds from plant biomass by fungi has been studied extensively, relatively little attention has been given to the metabolic pathways that convert the resulting aromatic monomers. In this review we provide an overview of the aromatic components of plant biomass, and their release and conversion by fungi. Finally, we will summarize the applications of fungal systems related to plant aromatics.

  14. Water-soluble constituents of caraway: aromatic compound, aromatic compound glucoside and glucides. (United States)

    Matsumura, Tetsuko; Ishikawa, Toru; Kitajima, Junichi


    From the water-soluble portion of the methanolic extract of caraway (fruit of Carum carvi L.), an aromatic compound, an aromatic compound glucoside and a glucide were isolated together with 16 known compounds. Their structures were clarified as 2-methoxy-2-(4'-hydroxyphenyl)ethanol, junipediol A 2-O-beta-D-glucopyranoside and L-fucitol, respectively.

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

    KAUST Repository

    Bruna, M.


    © 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.

  16. Polarization effects. Volume 2

    Energy Technology Data Exchange (ETDEWEB)

    Courant, E.


    The use of polarized proton beams in ISABELLE is important for several general reasons: (1) With a single longitudinally polarized proton beam, effects involving parity violation can be identified and hence processes involving weak interactions can be separated from those involving strong and electromagnetic interactions. (2) Spin effects are important in the strong interactions and can be useful for testing QCD. The technique for obtaining polarized proton beams in ISABELLE appears promising, particularly in view of the present development of a polarized proton beam for the AGS. Projections for the luminosity in ISABELLE for collisions of polarized protons - one or both beams polarized with longitudinal or transverse polarization - range from 1/100 to 1 times the luminosity for unpolarized protons.

  17. Polarity inversion in polar-nonpolar-polar heterostructures. (United States)

    Cho, S; Youn, S J; Kim, Y; DiVenere, A; Wong, G K; Freeman, A J; Ketterson, J B


    We have observed an epilayer-thickness-dependent polarity inversion for the growth of CdTe on Sb(Bi)/CdTe(111)B. For films with Sb(Bi) thicknesses of less than 40 A (15 A), the CdTe layer shows a B (Te-terminated) face, but it switches to an A (Cd-terminated) face for thicker layers. On the other hand, a CdTe layer grown on Bi(Sb)/CdTe(111)A always shows the A face regardless of Sb or Bi layer thicknesses. In order to address the observations we have performed ab initio calculations, which suggest that the polarity of a polar material on a nonpolar one results from the binding energy difference between the two possible surface configurations.


    Institute of Scientific and Technical Information of China (English)

    Shou-xi Chen; Hua-chun Zhai; Yong-ze Jin


    A new spherulite-like structure of main chain thermotropic aromatic copolyesters formed in solution cast specimens was observed and was studied by means of polarizing microscopy, X-ray diffraction,SEM and IR spectrometry. Results indicate that the spherulite-like structure of main chain thermotropic aromatic copolyesters formed from the casting solution (phenol/Cl2CH2CH2Cl2) is not a real crystal but only a high oriented arrangement of the macromolecular chains as a spherulite. This resulted from the interaction between the needle-like crystal of phenol and the rigid mesomorphic groups of molecular chain. The parallel packing of extended copolyester molecules along the needle-like crystal of phenol leads to the formation of the spherulite-like structure.

  19. Probing Aromaticity of Borozene Through Optical and Dielectric Response: A Theoretical Study

    CERN Document Server

    Sahu, Sridhar


    In this work, we report electronic structure calculations aimed at computing the linear optical absorption spectrum, and static dipole polarizablity of a newly proposed boron-based planar aromatic compound borozene (B_12H_6$. For the purpose, we use the semiempirical INDO model Hamiltonian, accompanied by large-scale correlation calculations using the multi-reference singles-doubles configuration-interaction (MRSDCI) approach. We present detailed predictions about the energetics, polarization properties, and the nature of many-particle states contributing to various peaks in the linear absorption spectrum. Our results can be used to characterize this material in future optical absorption experiments. We also argue that one can deduce the aromaticity of the cluster from the optical absorption and static polarizability results.

  20. Cross polarization, magic-angle spinning /sup 13/C nuclear magnetic resonance spectroscopy of soil humic fractions

    Energy Technology Data Exchange (ETDEWEB)

    Saiz-Jimenez, C.; Hawkins, B.L.; Maciel, G.E.


    Cross polarization, magic-angle spinning /sup 13/C nuclear magnetic resonance spectroscopy was used to characterize humic fractions isolated from different soils. The humic acid fractions are more aromatic than the humin fractions, probably due to the higher polysaccharide content of humins. However, fulvic acid fractions are more aromatic than the corresponding humic acid and humin fractions. These results can be interpreted in terms of the isolation procedure, because the high affinity of Polyclar AT for phenols results in higher aromaticities as compared with other isolation methods (e.g. charcoal).

  1. 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


    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.

  2. Thermochemical factors affecting the dehalogenation of aromatics. (United States)

    Sadowsky, Daniel; McNeill, Kristopher; Cramer, Christopher J


    Halogenated aromatics are one of the largest chemical classes of environmental contaminants, and dehalogenation remains one of the most important processes by which these compounds are degraded and detoxified. The thermodynamic constraints of aromatic dehalogenation reactions are thus important for understanding the feasibility of such reactions and the redox conditions necessary for promoting them. Accordingly, the thermochemical properties of the (poly)fluoro-, (poly)chloro-, and (poly)bromobenzenes, including standard enthalpies of formation, bond dissociation enthalpies, free energies of reaction, and the redox potentials of Ar-X/Ar-H couples, were investigated using a validated density functional protocol combined with continuum solvation calculations when appropriate. The results highlight the fact that fluorinated aromatics stand distinct from their chloro- and bromo- counterparts in terms of both their relative thermodynamic stability toward dehalogenation and how different substitution patterns give rise to relevant properties, such as bond strengths and reduction potentials.

  3. Asymmetric chemical reactions by polarized quantum beams (United States)

    Takahashi, Jun-Ichi; Kobayashi, Kensei

    One of the most attractive hypothesis for the origin of homochirality in terrestrial bio-organic compounds (L-amino acid and D-sugar dominant) is nominated as "Cosmic Scenario"; a chiral impulse from asymmetric excitation sources in space triggered asymmetric reactions on the surfaces of such space materials as meteorites or interstellar dusts prior to the existence of terrestrial life. 1) Effective asymmetric excitation sources in space are proposed as polarized quantum beams, such as circularly polarized light and spin polarized electrons. Circularly polarized light is emitted as synchrotron radiation from tightly captured electrons by intense magnetic field around neutron stars. In this case, either left-or right-handed polarized light can be observed depending on the direction of observation. On the other hand, spin polarized electrons is emitted as beta-ray in beta decay from radioactive nuclei or neutron fireballs in supernova explosion. 2) The spin of beta-ray electrons is longitudinally polarized due to parity non-conservation in the weak interaction. The helicity (the the projection of the spin onto the direction of kinetic momentum) of beta-ray electrons is universally negative (left-handed). For the purpose of verifying the asymmetric structure emergence in bio-organic compounds by polarized quantum beams, we are now carrying out laboratory simulations using circularly polarized light from synchrotron radiation facility or spin polarized electron beam from beta-ray radiation source. 3,4) The target samples are solid film or aqueous solution of racemic amino acids. 1) K.Kobayashi, K.Kaneko, J.Takahashi, Y.Takano, in Astrobiology: from simple molecules to primitive life; Ed. V.Basiuk; American Scientific Publisher: Valencia, 2008. 2) G.A.Gusev, T.Saito, V.A.Tsarev, A.V.Uryson, Origins Life Evol. Biosphere. 37, 259 (2007). 3) J.Takahashi, H.Shinojima, M.Seyama, Y.Ueno, T.Kaneko, K.Kobayashi, H.Mita, M.Adachi, M.Hosaka, M.Katoh, Int. J. Mol. Sci. 10, 3044

  4. Constraint on the Polarization of Electric Dipole Emission from Spinning Dust

    CERN Document Server

    Hoang, Thiem; Martin, P G


    Planck results have revealed that the electric dipole emission from polycyclic aromatic hydrocarbons (PAHs) is the most likely explanation for anomalous microwave emission that interferes with cosmic microwave background (CMB) radiation experiments. The emerging question is to what extent this emission component contaminates to the polarized CMB radiation. We present constraints on polarized dust emission for the model of grain size distribution and grain alignment that best fits to observed extinction and polarization data. Two stars with a prominent polarization excess at 2175 Angstrom, 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 reproduce the 2175 Angstrom polarization feature; whereas, for HD 147933-4, we find that the alignment by silicate grains only can account for that feature. The alignment function of PAHs for the best fit model to the HD 197770 data is employed to constrain polarized spinning du...

  5. Production of aromatics from di- and polyoxygenates

    Energy Technology Data Exchange (ETDEWEB)

    Beck, Taylor; Blank, Brian; Jones, Casey; Woods, Elizabeth; Cortright, Randy


    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 Group VIII metal and a crystalline alumina support.

  6. Production of aromatics from di- and polyoxygenates

    Energy Technology Data Exchange (ETDEWEB)

    Beck, Taylor; Blank, Brian; Jones, Casey; Woods, Elizabeth; Cortright, Randy


    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.

  7. Global aromatics supply. Today and tomorrow

    Energy Technology Data Exchange (ETDEWEB)

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


    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.)

  8. Assessing aromaticity and the degree of aromatic condensation of pyrogenic carbon (United States)

    Wiedemeier, D. B.; Abiven, S.; Hockaday, W. C.; Keiluweit, M.; Kleber, M.; Masiello, C. A.; McBeath, A. V.; Nico, P. S.; Pyle, L. A.; Schneider, M. P.; Smernik, R. J.; Wiesenberg, G. L.; Schmidt, M. W.


    Fire-derived, pyrogenic carbon (PyC) is a persistent organic carbon fraction in soils because it is relatively resistant against chemical and biological degradation. PyC thus represents a carbon sequestration potential in the global carbon cycle and was also reported to be potentially beneficial for soil fertility. PyC is naturally added to soils during wildfires and anthropogenically in the form of biochar, after organic waste is pyrolyzed. Aromaticity and the degree of aromatic condensation are the two main quality properties of PyC that probably determine its persistence against degradation. Consequently, the two properties largely influence the PyC's carbon sequestration potential as well as the duration, during which it can provide benefits to the soil. Aromaticity and the degree of aromatic condensation of PyC should theoretically be dependent on pyrolysis conditions, such as highest heating temperature or pyrolysis time, and also depend on the feedstock. In this study, we used two different pyrolysis procedures and four different feedstocks to produce four thermosequences of 38 chars in total, with highest heating temperatures ranging from 100 - 1000° C. The chars were then analyzed with an extensive suite of seven different methods: solid state 13C nuclear magnetic resonance (13C NMR), diffuse infrared Fourier transform spectroscopy (DRIFT), synchrotron-based near-edge X-ray absorption fine structure analysis (NEXAFS), benzene polycarboxylic acid analysis (BPCA), lipid analysis, elemental analysis and helium pycnometry. These methods allowed to infer the aromaticity and the degree of aromatic condensation of the differently pyrolyzed materials. Using multivariate statistical methods, aromaticity and the degree of aromatic condensation could successfully be linked to highest heating temperature and other pyrolysis conditions because characteristic patterns of the two aromatic properties could be observed by different methods throughout all four

  9. Fluorescence method for enzyme analysis which couples aromatic amines with aromatic aldehydes (United States)

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


    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

  10. Fluorescence method for enzyme analysis which couples aromatic amines with aromatic aldehydes (United States)

    Smith, Robert E.; Dolbeare, Frank A.


    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, 5-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.

  11. Solubilization and biodegradation of polycyclic aromatic hydrocarbons in microemulsions

    Energy Technology Data Exchange (ETDEWEB)

    Wong, J.W.C.; Zhao, Z.Y.; Yang, J.; Wong, S.Y. [Hong Kong Baptist Univ., Hong Kong (China). Sino-Forest Applied Research Centre for Pearl River Delta Environment, Dept. of Biology


    This study investigated the feasibility of using microemulsions to enhance the biodegradation of polycyclic aromatic hydrocarbons (PAHs). Microemulsions are commonly used in soil washing as a means of enhancing the solubility of hydrophobic pollutants. The microemulsions were composed of Tween-80, 1-pentanol and linseed oil. Phenanthrene (PHE) was dissolved in dichloromethane and added to a glass vial. Microemulsions were added separately to the vials. A high performance liquid chromatograph (HPLC) was used to determine PHE concentrations. The vials were inoculated with an isolated PAH degradative bacterium Bacillus subtilis B-UM. Soil collected from abandoned shipyards in Hong Kong were then spiked with the mixtures and aged for 3 months. One way analysis of variance (ANOVA) analyses were conducted. Results of the study showed that a microemulsion composed of 0.4 Tween-80, 0.1 per cent 1-pentanol, and 0.05 linseed oil effectively enhanced the biodegradation of PHE in the aqueous phase. It was concluded that microemulsions can be used to remediate soils contaminated by PAHs. 26 refs., 2 tabs., 4 figs.

  12. Contamination of rivers in Tianjin, China by polycyclic aromatic hydrocarbons

    Energy Technology Data Exchange (ETDEWEB)

    Shi, Z.; Tao, S.; Pan, B.; Fan, W.; He, X.C.; Zuo, Q.; Wu, S.P.; Li, B.G.; Cao, J.; Liu, W.X.; Xu, F.L.; Wang, X.J.; Shen, W.R.; Wong, P.K. [Peking University, Beijing (China). College of Environmental Science


    Abstract: Tianjin urban/industrial complex is highly polluted by some persistent organic pollutants. In this study, the levels of 16 priority polycyclic aromatic hydrocarbons (PAHs) were tested in sediment, water, and suspended particulate matter (SPM) samples in 10 rivers in Tianjin. The total concentration of 16 PAHs varied from 0.787 to 1943 {mu}g/g dry weight in sediment, from 45.81 to 1272 ng/L in water, and from 0.938 to 64.2 {mu}g/g dry weight in SPM. The levels of PAHs in these media are high in comparison with values reported from other river and marine systems. Variability of total concentrations of PAHs in sediment, water, and SPM from nine different rivers is consistent with each other. No obvious trends of total PAHs concentration variations were found between upstream and downstream sediment, water, and SPM samples for most rivers, which indicate local inputs and disturbances along these rivers. The spatial distributions of three-phase PAHs are very similar to each other, and they are also similar to those found in topsoil. However, their chemical profiles are significantly different from that of topsoil. The change of profiles is consistent with the different aqueous transport capability of 16 PAHs. Low molecular weight PAHs predomination suggests a relatively recent local source and coal combustion source of PAHs in the study area.

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

    Directory of Open Access Journals (Sweden)

    M.A. Cremasco


    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.

  14. The impact of multiphase reactions of NO2 with aromatics: a modelling approach

    Directory of Open Access Journals (Sweden)

    N. Lahoutifard


    Full Text Available The impact of multiphase reactions involving nitrogen dioxide (NO2 and aromatic compounds was simulated in this study. A mechanism (CAPRAM 2.4, MODAC Mechanism was applied for the aqueous phase reactions, whereas RACM was applied for the gas phase chemistry. Liquid droplets were considered as monodispersed with a mean radius of 0.1 µm and a liquid content (LC of 50 µg m-3. The multiphase mechanism has been further extended to the chemistry of aromatics, i.e. reactions involving benzene, toluene, xylene, phenol and cresol have been added. In addition, reaction of NO2 with dissociated hydroxyl substituted aromatic compounds has also been implemented. These reactions proceed through charge exchange leading to nitrite ions and therefore to nitrous acid formation. The strength of this source was explored under urban polluted conditions. It was shown that it may increase gas phase HONO levels under some conditions and that the extent of this effect is strongly pH dependent. Especially under moderate acidic conditions (i.e. pH above 4 this source may represent more than 75% of the total HONO/NO2 - production rate, but this contribution drops down close to zero in acidic droplets (as those often encountered in urban environments.

  15. Spinning dust emission from ultrasmall silicates: emissivity and polarization spectrum

    CERN Document Server

    Hoang, Thiem; Lan, Nguyen Quynh


    Anomalous microwave emission (AME) is an important Galactic foreground of Cosmic Microwave Background (CMB) radiation. It is believed that the AME arises from rotational emission by spinning polycyclic aromatic hydrocarbons (PAHs) in the interstellar medium (ISM). In this paper, we assume that a population of ultrasmall silicate grains may exist in the ISM, and quantify rotational emissivity from these tiny particles and its polarization spectrum. We found that spinning silicate nanoparticles can produce strong rotational emission when those small grains follow a log-normal size distribution. The polarization fraction of spinning dust emission from tiny silicates increases with decreasing the dipole moment per atom ($\\beta$) and can reach $P\\sim 20\\%$ for $\\beta\\sim 0.1$D at grain temperature of 60 K. We identify a parameter space $(\\beta,Y_{Si})$ for silicate nanoparticles in which its rotational emission can adequately reproduce both the observed AME and the polarization of the AME, without violating the ob...

  16. Polar varieties revisited


    Piene, Ragni


    We recall the definition of classical polar varieties, as well as those of affine and projective reciprocal polar varieties. The latter are defined with respect to a non-degenerate quadric, which gives us a notion of orthogonality. In particular we relate the reciprocal polar varieties to the "Euclidean geometry" in projective space. The Euclidean distance degree and the degree of the focal loci can be expressed in terms of the ranks, i.e., the degrees of the classical polar varieties, and he...

  17. Polarization at SLC

    Energy Technology Data Exchange (ETDEWEB)

    Swartz, M.L.


    The SLAC Linear Collider has been designed to readily accommodate polarized electron beams. Considerable effort has been made to implement a polarized source, a spin rotation system, and a system to monitor the beam polarization. Nearly all major components have been fabricated. At the current time, several source and polarimeter components have been installed. The installation and commissioning of the entire system will take place during available machine shutdown periods as the commissioning of SLC progresses. It is expected that a beam polarization of 45% will be achieved with no loss in luminosity. 13 refs., 15 figs.

  18. Polarized negative ions

    Energy Technology Data Exchange (ETDEWEB)

    Haeberli, W.


    This paper presents a survey of methods, commonly in use or under development, to produce beams of polarized negative ions for injection into accelerators. A short summary recalls how the hyperfine interaction is used to obtain nuclear polarization in beams of atoms. Atomic-beam sources for light ions are discussed. If the best presently known techniques are incorporated in all stages of the source, polarized H/sup -/ and D/sup -/ beams in excess of 10 can probably be achieved. Production of polarized ions from fast (keV) beams of polarized atoms is treated separately for atoms in the H(25) excited state (Lamb-Shift source) and atoms in the H(1S) ground state. The negative ion beam from Lamb-Shift sources has reached a plateau just above 1, but this beam current is adequate for many applications and the somewhat lower beam current is compensated by other desirable characteristics. Sources using fast polarized ground state atoms are in a stage of intense development. The next sections summarize production of polarized heavy ions by the atomic beam method, which is well established, and by optical pumping, which has recently been demonstrated to yield very large nuclear polarization. A short discussion of proposed ion sources for polarized /sup 3/He/sup -/ ions is followed by some concluding remarks.

  19. Aromatic compound glucosides, alkyl glucoside and glucide from the fruit of anise. (United States)

    Fujimatu, Eiko; Ishikawa, Toru; Kitajima, Junichi


    From the polar portion of the methanolic extract of the fruit of anise (Pimpinella anisum L.), which has been used as a spice and medicine since antiquity, four aromatic compound glucosides, an alkyl glucoside and a glucide were isolated together with 24 known compounds. The structures of the new compounds were clarified as (E)-3-hydroxyanethole beta-D-glucopyranoside, (E)-1'-(2-hydroxy-5-methoxyphenyl)propane beta-D-glucopyranoside, 3-hydroxyestragole beta-D-glucopyranoside, methyl syringate 4-O-beta-D-glucopyranoside, hexane-1,5-diol 1-O-beta-D-glucopyranoside and 1-deoxy-L-erythritol 3-O-beta-D-glucopyranoside by spectral investigation.

  20. QSAR for Photodegradation Activity of Polycyclic Aromatic Hydrocarbons in Aqueous Systems

    Institute of Scientific and Technical Information of China (English)

    XU Xiang; LI Xianguo


    The relationship between chemical structures and photodegradation activity of 12 PAHs is studied using DFT and HF methods, and stepwise multiple linear regression analysis method. The equilibrium geometries and vibration frequency have been investigated by considering Solvent effects using a selfconsistent reaction field based on the polarizable continuum model. With DFT and HF methods, different quantum chemical structural descriptors are obtained by quantum chemical calculation and the results with DFT method are better for QSAR model. It is concluded that the photodegradation activity is closely related to its molecular structure. In the regression analysis, the main factors affecting photodegradation rate include the energy of the highest occupied orbital EHOMO and the number of six-carbon benzene ring N1, and the QSAR model successfully established is logkb=6.046 + 54.830EHOMO +0.272N1. Statistical evaluation of the developed QSAR shows that the relationships are statistically significant and the model has good predictive ability. EHOMO is the most important factor influcing the photodegradation of PAHs, because the higher EHOMO is, the more easily electron will be excited and the more easily molecular will be degraded. Comparison of the photodegradation of PAHs with their biodegradation shows that the committed step of biodegradation is that the effects of microorganisms make the chemical bond break, while in the committed step of photodegradation PAHs eject electrons.

  1. Bacterial formation of hydroxylated aromatic compounds.

    NARCIS (Netherlands)

    Tweel, van den W.J.J.


    As stated in the introduction of this thesis, hydroxylated aromatic compounds in general are of great importance for various industries as for instance pharmaceutical, agrochemical and petrochemical industries. Since these compounds can not be isolated in sufficient amounts from natural resources, t


    Institute of Scientific and Technical Information of China (English)

    HUANG Zhitang


    This review is a concise survey about the works in our laboratory on the polymerization of aromatic and heterocyclic dinitriles, including the polymerization kinetics and mechanism, synthesis of heterocyclic dinitriles, the structure of polymers, and the correlation between the structures of dinitriles and polymerization rates and thermal performances of polymers.

  3. Fused aromatic thienopyrazines: structure, properties and function

    KAUST Repository

    Mondal, Rajib


    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.

  4. Fate and biodegradability of sulfonated aromatic amines

    NARCIS (Netherlands)

    Tan, N.C.G.; Leeuwen, van A.; Voorthuizen, van E.M.; Slenders, P.; Prenafeta, F.X.; Temmink, H.; Lettinga, G.; Field, J.A.


    Ten sulfonated aromatic amines were tested for their aerobic and anaerobic biodegradability and toxicity potential in a variety of environmental inocula. Of all the compounds tested, only two aminobenzenesulfonic acid (ABS) isomers, 2- and 4-ABS, were degraded. The observed degradation occurred only

  5. Electronic Aromaticity Index for Large Rings

    CERN Document Server

    Matito, Eduard


    We introduce a new electronic aromaticity index, AV1245, consisting in the average of the 4-center MCI values along the ring that keep a positional relationship of 1,2,4,5. AV1245 measures the extent of transferability of the delocalized electrons between bonds 1-2 and 4-5, which is expected to be large in conjugated circuits and, therefore, in aromatic molecules. A new algorithm for the calculation of MCI for large rings is also introduced and used to produce the data for the calibration of the new aromaticity index. AV1245 does not rely on reference values, does not suffer from large numerical precision errors, and it does not present any limitation on the nature of atoms, the molecular geometry or the level of calculation. It is a size-extensive measure with a small computational cost that grows linearly with the number of ring members. Therefore, it is specially suitable to study the aromaticity of large molecular rings as those occurring in belt-shaped M\\"obius structures or porphyrins.

  6. Micellar and vesicular nanoassemblies of triazole-based amphiphilic probes triggered by mercury(II) ions in a 100% aqueous medium. (United States)

    Kim, Inhye; Lee, Na-Eun; Jeong, Yoo-Jeong; Chung, Young-Ho; Cho, Byoung-Ki; Lee, Eunji


    ABA-type amphiphiles bearing a triazole-based aromatic block were easily synthesized using click chemistry, which act as fluorescent turn-off Hg(2+)-chemoprobes in an aqueous solution. Interestingly, the metal-binding process of amphiphiles induced nanoassemblies even below the CMCs, and the binding stoichiometry affected the morphologies of the resultant nanostructures.

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

    Directory of Open Access Journals (Sweden)

    Simona Bettini


    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.

  8. 40 CFR 721.2673 - Aromatic epoxide resin (generic). (United States)


    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Aromatic epoxide resin (generic). 721... Substances § 721.2673 Aromatic epoxide resin (generic). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as aromatic epoxide resin (PMN...

  9. 40 CFR 721.5762 - Aromatic aldehyde phenolic resin (generic). (United States)


    ... 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...

  10. 40 CFR 721.2925 - Brominated aromatic ester. (United States)


    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Brominated aromatic ester. 721.2925... Substances § 721.2925 Brominated aromatic ester. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified generically as a brominated aromatic ester (PMN...

  11. Polar or apolar--the role of polarity for urea-induced protein denaturation.

    Directory of Open Access Journals (Sweden)

    Martin C Stumpe


    Full Text Available Urea-induced protein denaturation is widely used to study protein folding and stability; however, the molecular mechanism and driving forces of this process are not yet fully understood. In particular, it is unclear whether either hydrophobic or polar interactions between urea molecules and residues at the protein surface drive denaturation. To address this question, here, many molecular dynamics simulations totalling ca. 7 micros of the CI2 protein in aqueous solution served to perform a computational thought experiment, in which we varied the polarity of urea. For apolar driving forces, hypopolar urea should show increased denaturation power; for polar driving forces, hyperpolar urea should be the stronger denaturant. Indeed, protein unfolding was observed in all simulations with decreased urea polarity. Hyperpolar urea, in contrast, turned out to stabilize the native state. Moreover, the differential interaction preferences between urea and the 20 amino acids turned out to be enhanced for hypopolar urea and suppressed (or even inverted for hyperpolar urea. These results strongly suggest that apolar urea-protein interactions, and not polar interactions, are the dominant driving force for denaturation. Further, the observed interactions provide a detailed picture of the underlying molecular driving forces. Our simulations finally allowed characterization of CI2 unfolding pathways. Unfolding proceeds sequentially with alternating loss of secondary or tertiary structure. After the transition state, unfolding pathways show large structural heterogeneity.

  12. 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


    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.

  13. Planetary polarization nephelometer

    NARCIS (Netherlands)

    Banfield, D.; Dissly, R.; Mishchenko, M.; Muñoz, O.; Roos-Serote, M.; Stam, D.M.; Volten, H.; Wilson, A.


    We have proposed to develop a polarization nephelometer for use on future planetary descent probes. It will measure both the scattered intensity and polarization phase functions of the aerosols it encounters descending through an atmosphere. These measurements will be taken at two wavelengths separa

  14. Polarization modulators for CMBPol

    Energy Technology Data Exchange (ETDEWEB)

    Ade, P A R; Savini, G [Cardiff University, School of Physics and Astronomy, Queens Buildings, The Parade, Cardiff, CF24 3AA (United Kingdom); Chuss, D T [NASA Goddard Space Flight Center, Code 665, Greenbelt, MD, 20771 (United States); Hanany, S [School of Physics and Astronomy, University of Minnesota/Twin Cities, Minneapolis, MN, 55455 (United States); Haynes, V; Pisano, G [University of Manchester, School of Physics and Astronomy - Alan Turing Building, Upper Brooke street, Manchester, M13 4PL (United Kingdom); Keating, B G [Department of Physics, University of California, San Diego, La Jolla, CA 92093-0424 (United States); Kogut, A [Code 665 Goddard Space Flight Center, Greenbelt, MD 20771 (United States); Ruhl, J E [Physics Department, Case Western Reserve University, Cleveland, OH, 44106 (United States); Wollack, E J [Observational Cosmology Laboratory, NASA/GSFC, Greenbelt, MD 20771 (United States)


    We review a number of technologies that are candidates for active polarization modulators for CMBPol. The technologies are appropriate for instruments that use bolometric detectors and include birefringent crystal-based and metal-mesh-based half-wave plates, variable phase polarization modulator, Faraday rotator, and photolithographed modulators. We also give a current account of the status of millimeter-wave orthomode transducers.

  15. Polar Code Validation (United States)


    SUMMARY OF POLAR ACHIEVEMENTS ..... .......... 3 3. POLAR CODE PHYSICAL MODELS ..... ............. 5 3.1 PL- ASMA Su ^"ru5 I1LS SH A...of this problem. 1.1. The Charge-2 Rocket The Charge-2 payload was launched on a Black Brant VB from White Sands Mis- sile Range in New Mexico in

  16. Plasma polarization spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Iwamae, Atsushi; Inoue, Takeru; Tanaka, Akihiro; Kawakami, Kazuki; Fujimoto, Takashi [Kyoto Univ., Dept. of Engineering Physics, Kyoto (Japan)


    Polarization of radiation emitted from plasma reflects the anisotropic properties of the plasma, especially the angular isotropic distribution of electron velocities. Polarization has been observed on impurity ion lines from the WT-3 tokamak and GAMMA 10 tandem mirror device. (author)

  17. Polar Cap Patch Dynamics (United States)


    cap arcs Citation: Hosokawa, K., J. I. Moen, K. Shiokawa, and Y. Otsuka ( 2011 ), Motion of polar cap arcs , J. Geophys. Res. , 116 , A01305, doi...K., J. I. Moen, K. Shiokawa, and Y. Otsuka , (2011), Decay of polar cap patch, J. Geophys. Res., 116, A05308, doi:10.1029/2010JA016287, Abstract. We

  18. Polarized Light: Three Demonstrations. (United States)

    Goehmann, Ruth; Welty, Scott


    Describes three demonstrations used in the Chicago Museum of Science and Industry polarized light show. The procedures employed are suitable for the classroom by using smaller polarizers and an overhead projector. Topic areas include properties of cellophane tape, nondisappearing arrows, and rope through a picket fence. (JN)

  19. 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)


    -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.

  20. Parallel Polarization State Generation (United States)

    She, Alan; Capasso, Federico


    The control of polarization, an essential property of light, is of wide scientific and technological interest. The general problem of generating arbitrary time-varying states of polarization (SOP) has always been mathematically formulated by a series of linear transformations, i.e. a product of matrices, imposing a serial architecture. Here we show a parallel architecture described by a sum of matrices. The theory is experimentally demonstrated by modulating spatially-separated polarization components of a laser using a digital micromirror device that are subsequently beam combined. This method greatly expands the parameter space for engineering devices that control polarization. Consequently, performance characteristics, such as speed, stability, and spectral range, are entirely dictated by the technologies of optical intensity modulation, including absorption, reflection, emission, and scattering. This opens up important prospects for polarization state generation (PSG) with unique performance characteristics with applications in spectroscopic ellipsometry, spectropolarimetry, communications, imaging, and security.

  1. Parallel Polarization State Generation

    CERN Document Server

    She, Alan


    The control of polarization, an essential property of light, is of wide scientific and technological interest. The general problem of generating arbitrary time-varying states of polarization (SOP) has always been mathematically formulated by a series of linear transformations, i.e. a product of matrices, imposing a serial architecture. Here we show a parallel architecture described by a sum of matrices. The theory is experimentally demonstrated by modulating spatially-separated polarization components of a laser using a digital micromirror device that are subsequently beam combined. This method greatly expands the parameter space for engineering devices that control polarization. Consequently, performance characteristics, such as speed, stability, and spectral range, are entirely dictated by the technologies of optical intensity modulation, including absorption, reflection, emission, and scattering. This opens up important prospects for polarization state generation (PSG) with unique performance characteristi...

  2. Interactions of helquats with chiral acidic aromatic analytes investigated by partial-filling affinity capillary electrophoresis. (United States)

    Růžička, Martin; Koval, Dušan; Vávra, Jan; Reyes-Gutiérrez, Paul E; Teplý, Filip; Kašička, Václav


    Noncovalent molecular interactions between helquats, a new class of dicationic helical extended diquats, and several chiral acidic aromatic drugs and catalysts have been investigated using partial-filling affinity capillary electrophoresis (PF-ACE). Helquats dissolved at 1mM concentration in the aqueous background electrolyte (40mM Tris, 20mM acetic acid, pH 8.1) were introduced as ligand zones of variable length (0-130mm) into the hydroxypropylcellulose coated fused silica capillary whereas 0.1mM solutions of negatively charged chiral drugs or catalysts (warfarin, ibuprofen, mandelic acid, etodolac, binaphthyl phosphate and 11 other acidic aromatic compounds) were applied as a short analyte zone at the injection capillary end. After application of electric field, analyte and ligand migrated against each other and in case of their interactions, migration time of the analyte was increasing with increasing length of the ligand zone. From the tested compounds, only isomers of those exhibiting helical chirality and/or possessing conjugated aromatic systems were enantioselectively separated through their differential interactions with helquats. Some compounds with conjugated aromatic groups interacted with helquats moderately strongly but non-enantiospecifically. Small compounds with single benzene ring exhibited no or very weak non-enantiospecific interactions. PF-ACE method allowed to determine binding constants of the analyte-helquat complexes from the changes of migration times of the analytes. Binding constants of the weakest complexes of the analytes with helquats were less than 50L/mol, whereas binding constants of the strongest complexes were in the range 1 000-1 400L/mol.

  3. Microwave-assisted synthesis of α-hydroxy aromatic ketones from α-bromo aromatic ketones in water

    Institute of Scientific and Technical Information of China (English)

    Xiang Liu; Hai Bo Chen; Zheng Guang Pan; Jian He Xu; He Xing Li


    A reaction of α-bromo aromatic ketones in water with microwave irradiation gave the corresponding α-hydroxy aromatic ketones in good yields.The use of microwaves was found to significantly improve yields and shorten the reaction time.This reaction afforded a very clean,convenient method for the synthesis of α-hydroxy aromatic ketones.

  4. Aqueous humor changes after experimental filtering surgery. (United States)

    Radius, R L; Herschler, J; Claflin, A; Fiorentino, G


    We studied aqueous humor of rhesus and owl monkeys for its effect on the growth of subconjunctival fibroblasts in tissue culture. Aqueous humor samples obtained before glaucoma surgery inhibited the initiation of growth of fibroblasts. However, postoperative aqueous humor samples supported growth of fibroblasts. The change in aqueous humor physiology lasted for up to two months after glaucoma surgery. Our study indicated that possibly material added to the postoperative aqueous humor inactivates an inhibitor normally present in primary aqueous humor. An alternative explanation would be that primary aqueous humor, in contrast to secondary aqueous humor, lacks sufficient nutrient material to support fibroblast growth in tissue culture.

  5. Development and validation of a hydrophilic interaction liquid chromatographic method for determination of aromatic amines in environmental water. (United States)

    Li, Ruiping; Zhang, Yi; Lee, Charles C; Lu, Rongrong; Huang, Yingping


    A simple, precise, and accurate hydrophilic interaction liquid chromatographic (HILIC) method has been developed for the determination of five aromatic amines in environmental water samples. Chromatography was carried out on a bare silica column, using a mixture of acetonitrile and a buffer of NaH(2)PO(4)-H(3)PO(4) (pH 1.5, containing 10mM NaH(2)PO(4)) (85:15, v/v) as a mobile phase at a flow rate of 1 mL min(-1). Aromatic amines were detected by UV absorbance at 254 nm. The linear range of amines was good (r(2)>0.998) and limit of detection (LOD) within 0.02-0.2 mg L(-1) (S/N=3). The retention mechanism for the analytes under the optimum conditions was determined to be a combination of adsorption, partition and ionic interactions. The proposed method was applied to the environmental water samples. Aromatic amines were isolated from aqueous samples using solid-phase extraction (SPE) with Oasis HLB cartridges. Recoveries of greater than 75% with precision (RSD) less than 12% were obtained at amine concentrations of 5-50 microg L(-1) from 100mL river water and influents from a wastewater treatment plant (WWTP). The present HILIC technique proved to be a viable method for the analysis of aromatic amines in the environmental water samples.

  6. Hydrophobic contribution to the free energy of complexation of aromatic ligands with DNA

    Directory of Open Access Journals (Sweden)

    Evstigneev M. P.


    Full Text Available The hydrophobic component of complexation energy of double-stranded DNA with biologically active aromatic compounds was calculated using two semi-empirical methods – correlations of hydrophobic energy with changes of a heat capacity (DCp and solvent-accessible surface area (SASA. These surface areas were calculated for free ligands and DNA oligomers, unwound DNA duplexes and DNA-ligand complexes. The changes of polar and non-polar SASAs of molecules upon binding ligands to DNA were found. The hydrophobic contribution at both complexation stages were calculated. It was shown that the calculation of hydrophobic energy by SASA method is more correct than (DCp method for DNA-binding ligands.

  7. Activity-Based Approach for Teaching Aqueous Solubility, Energy, and Entropy (United States)

    Eisen, Laura; Marano, Nadia; Glazier, Samantha


    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…

  8. Influence of polarization extinction ratio on distributed polarization coupling detection

    Institute of Scientific and Technical Information of China (English)

    XU Tian-hua; TANG Feng; JING Wen-cai; ZHANG Hong-xia; JIA Da-gong; YU Chang-song; ZHOU Ge; ZHANG Yi-mo


    Distributed polarization coupling in polarization-maintaining fibers can be detected by using a white light Michelsonin terferorneter. This technique usually requires that only one polarization mode is excited. However, in practical measurement,the injection polarization direction could not be exactly aligned to one of the principal axes of the PMF, so the influence of the polarization extinction ratio should be considered. Based on the polarization coupling theory, the influence of theincident polarization extinction on the measurement result is evaluated and analyzed, and a method for distributed polarization coupling detection is developed when both two orthogonal eigenmodes are excited.


    Institute of Scientific and Technical Information of China (English)

    刘剑洪; 刘冬; 任祥忠; 田德余


    Pyrene was used as a fluorescent probe to investigate the polarity and stability of the micelle of anionic aqueous polyurethane dispersion(AAPUD).Results indicated that the micelle is non-polar or weak polar,and the polarity is greatly dependent on the hydrophilicity of the main chain of polyurethane and the pH value of the medium.The polarized value of the polarized fluorescent of pyrene in the AAPUD was measured, and the results show that the stability of the micelle could be characterized by the polarized value.

  10. Aqueous adsorption and removal of organic contaminants by carbon nanotubes. (United States)

    Yu, Jin-Gang; Zhao, Xiu-Hui; Yang, Hua; Chen, Xiao-Hong; Yang, Qiaoqin; Yu, Lin-Yan; Jiang, Jian-Hui; Chen, Xiao-Qing


    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.

  11. Mars Aqueous Processing System Project (United States)

    National Aeronautics and Space Administration — Mars Aqueous Processing System (MAPS) is an innovative method to produce useful building materials from Martian regolith. Acids and bases produced from the regolith...

  12. Mars Aqueous Processing System Project (United States)

    National Aeronautics and Space Administration — The Mars Aqueous Processing System (MAPS) is a novel technology for recovering oxygen, iron, and other constituents from lunar and Mars soils. The closed-loop...

  13. Aromatic characterization of pot distilled kiwi spirits. (United States)

    López-Vázquez, Cristina; García-Llobodanin, Laura; Pérez-Correa, José Ricardo; López, Francisco; Blanco, Pilar; Orriols, Ignacio


    This study contributes fundamental knowledge that will help to develop a distillate of kiwi wine, made from kiwis of the Hayward variety grown in the southwest of Galicia (Spain). Two yeast strains, L1 (Saccharomyces cerevisiae ALB-6 from the EVEGA yeast collection) and L2 (S. cerevisiae Uvaferm BDX from Lallemand) were assessed to obtain a highly aromatic distillate. The kiwi spirits obtained were compared with other fruit spirits, in terms of higher alcohols, minor alcohols, monoterpenols, and other minor compounds, which are relevant in determining the quality and taste of the kiwi spirits. It was found that the kiwi juice fermented with yeast L1 produced a more aromatic distillate. In addition, kiwi distillates produced with both yeasts had the same ratio of trans-3-hexen-1-ol and cis-3-hexen-1-ol, which is lower than that found in other fruit distillates.

  14. Polyimides derived from non-aromatic monomers

    Energy Technology Data Exchange (ETDEWEB)

    Volksen, W.; Sanchez, M.I.; Cha, Hyuk-Jin; Yoon, D.Y. [IBM Almaden Research Center, San Jose, CA (United States)


    In recent years the shift in emphasis on high performance polymers, such as polyimides for microelectronic applications, has led to the search for other potential applications utilizing the unique properties of this class of polymers. In this context, polyimides incorporating non-aromatic units in the polymer backbone have been shown to exhibit excellent optical properties as well as significantly lower refractive indices. This lowering in the refractive index, of course, is also reflected in a lower dielectric constant of the material. For this reason, we have initiated a study of new polyimides, in which the traditional aromatic character is diluted with cycloaliphatic structures. One such example is the polyimide derived from hexafluoroisopropylidene diphthalic anhydride (6FDA) and 1,4-diaminocyclohexane (DACH). Preliminary data with respect to the preparation and solution behavior of the polyimide precursor as well as the characterization of relevant physical properties of the final polyimide will be presented.

  15. Side Chain Cyclized Aromatic Amino Acids

    DEFF Research Database (Denmark)

    Van der Poorten, Olivier; Knuhtsen, Astrid; Sejer Pedersen, Daniel


    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....

  16. Aromatic compounds from three Brazilian Lauraceae species

    Energy Technology Data Exchange (ETDEWEB)

    Batista, Andrea Nastri de Luca; Batista Junior, Joao Marcos; Lopez, Silvia Noeli; Furlan, Maysa; Cavalheiro, Alberto Jose; Silva, Dulce Helena Siqueira; Bolzani, Vanderlan da Silva [UNESP, Araraquara, SP (Brazil). Inst. de Quimica. Dept. de Quimica Organica; Nunomura, Sergio Massayoshi [Instituto Nacional de Pesquisa da Amazonia (INPA), Manaus, AM (Brazil). Dept. de Produtos Naturais; Yoshida, Massayoshi [Centro de Biotecnologia da Amazonia, Manaus, AM (Brazil)


    Phytochemical investigations on three Brazilian Lauraceae species from the Cerrado region of Sao Paulo State, Ocotea corymbosa (Meins) Mez., O. elegans Mez. and Persea pyrifolia Nees and Mart. ex Nees resulted in the isolation of flavonoids, an ester of the 4-O-E-caffeoylquinic acid, an aromatic sesquiterpene besides furofuran lignans. This is the first chemical study on the leaves of Ocotea elegans and O. corymbosa as well as the first report of non-volatile compounds from Persea pyrifolia. (author)

  17. Allylation of Aromatic Aldehyde under Microwave Irradiation

    Institute of Scientific and Technical Information of China (English)

    ZHANG,Yu-Mei; JIA,Xue-Feng; WANG,Jin-Xian


    @@ Allylation of carbonyl compounds is one of the most interesting processes for the preparation of homoallylic alcohols. Over the past few decades, many reagents have been developed for such reactions[1~3]. In this paper, we first report allylic zinc reagent 1, which can be prepared from zinc dust and allyl bromide conveniently in THF, and reacted with aromatic aldehyde to give homo-allylic alcohols under microwave irradiation.

  18. Aromatics Oxidation and Soot Formation in Flames

    Energy Technology Data Exchange (ETDEWEB)

    Howard, J. B.; Richter, H.


    This project is concerned with the kinetics and mechanisms of aromatics oxidation and the growth process to polycyclic aromatic hydrocarbons (PAH) of increasing size, soot and fullerenes formation in flames. The overall objective of the experimental aromatics oxidation work is to extend the set of available data by measuring concentration profiles for decomposition intermediates such as phenyl, cyclopentadienyl, phenoxy or indenyl radicals which could not be measured with molecular-beam mass spectrometry to permit further refinement and testing of benzene oxidation mechanisms. The focus includes PAH radicals which are thought to play a major role in the soot formation process while their concentrations are in many cases too low to permit measurement with conventional mass spectrometry. The radical species measurements are used in critical testing and improvement of a kinetic model describing benzene oxidation and PAH growth. Thermodynamic property data of selected species are determined computationally, for instance using density functional theory (DFT). Potential energy surfaces are explored in order to identify additional reaction pathways. The ultimate goal is to understand the conversion of high molecular weight compounds to nascent soot particles, to assess the roles of planar and curved PAH and relationships between soot and fullerenes formation. The specific aims are to characterize both the high molecular weight compounds involved in the nucleation of soot particles and the structure of soot including internal nanoscale features indicative of contributions of planar and/or curved PAH to particle inception.

  19. Dynamic nuclear spin polarization

    Energy Technology Data Exchange (ETDEWEB)

    Stuhrmann, H.B. [GKSS-Forschungszentrum Geesthacht GmbH (Germany)


    Polarized neutron scattering from dynamic polarized targets has been applied to various hydrogenous materials at different laboratories. In situ structures of macromolecular components have been determined by nuclear spin contrast variation with an unprecedented precision. The experiments of selective nuclear spin depolarisation not only opened a new dimension to structural studies but also revealed phenomena related to propagation of nuclear spin polarization and the interplay of nuclear polarisation with the electronic spin system. The observation of electron spin label dependent nuclear spin polarisation domains by NMR and polarized neutron scattering opens a way to generalize the method of nuclear spin contrast variation and most importantly it avoids precontrasting by specific deuteration. It also likely might tell us more about the mechanism of dynamic nuclear spin polarisation. (author) 4 figs., refs.

  20. Coordenadas polares: curvas maravillosas


    Norberto Jaime Chau Pérez; Roy Wil Sánchez Gutiérrez


    Se presenta una actividad colaborativa en la que se trabaja el tema coordenadas polares. Se presentan los objetivos de aprendizaje, el desarrollo de la actividad, los conocimientos previos necesarios y recomendaciones para una aplicación posterior.

  1. Time Domain Induced Polarization

    DEFF Research Database (Denmark)

    Fiandaca, Gianluca; Auken, Esben; Christiansen, Anders Vest


    Time-domain-induced polarization has significantly broadened its field of reference during the last decade, from mineral exploration to environmental geophysics, e.g., for clay and peat identification and landfill characterization. Though, insufficient modeling tools have hitherto limited the use...... of time-domaininduced polarization for wider purposes. For these reasons, a new forward code and inversion algorithm have been developed using the full-time decay of the induced polarization response, together with an accurate description of the transmitter waveform and of the receiver transfer function......%. Furthermore, the presence of low-pass filters in time-domain-induced polarization instruments affects the early times of the acquired decays (typically up to 100 ms) and has to be modeled in the forward response to avoid significant loss of resolution. The developed forward code has been implemented in a 1D...

  2. Experimental determination of the temperature dependence of water activities for a selection of aqueous organic solutions

    Directory of Open Access Journals (Sweden)

    G. Ganbavale


    Full Text Available This work presents experimental data of the temperature dependence of water activity in aqueous organic solutions relevant for tropospheric conditions (200–273 K. Water activity (aw at low temperatures (T is a crucial parameter for predicting homogeneous ice nucleation. We investigated temperature dependent water activities, ice freezing and melting temperatures of solutions, and vapour pressures of a selection of atmospherically relevant aqueous organic systems. To measure aw over a wide composition range and with a focus on low temperatures, we use various aw measurement techniques and instruments: a dew point water activity meter, an electrodynamic balance (EDB, differential scanning calorimetry (DSC, and a setup to measure the total gas phase pressure at equilibrium over aqueous solutions. Water activity measurements were performed for aqueous multicomponent and multifunctional organic mixtures containing the functional groups typically found in atmospheric organic aerosols, such as hydroxyl, carboxyl, ketone, ether, ester, and aromatic groups. The aqueous organic systems studied at several fixed compositions over a considerable temperature range differ significantly in their temperature dependence. Aqueous organic systems of 1,4-butanediol and methoxyacetic acid show a moderate decrease in aw with decreasing temperature. The aqueous M5 system (a multicomponent system containing five different dicarboxylic acids and aqueous 2-(2-ethoxyethoxyethanol solutions both show a strong increase of water activity with decreasing temperature at high solute concentrations for TTaw can be reversed at low temperatures and that linear extrapolations of high temperature data may lead to erroneous predictions. To avoid this, experimentally determined aw at low temperature are needed to improve thermodynamic models towards lower temperatures and for improved predictions of the ice nucleation ability of organic–water systems.

  3. A Simple One-pot Synthesis of 3,5-Dicyano-1,2-dihydropyrid-2-ones in Aqueous Media

    Institute of Scientific and Technical Information of China (English)

    ZHUANG, Qi-Ya; XU, Jia-Ning; TU, Shu-Jiang; JIA, Run-Hong; ZHANG, Jun-Yong; LI, Chun-Mei; ZHOU, Dian-Xiang


    A simple and clean synthesis of 3,5-dicyano-1,2-dihydropyrid-2-ones by a one-pot three-component reaction of malononitrile, aromatic aldehydes and 2-cyanoacetamide or 2-cyanothioacetamide has been achieved in an aqueous solution with potassium carbonate as a base under microwave irradiation without a phase transfer reagent. This protocol has the advantages of short reaction time (5-8 min) and convenient work-up.

  4. Political Competition and Polarization

    DEFF Research Database (Denmark)

    Schultz, Christian

    This paper considers political competition and the consequences of political polarization when parties are better informed about how the economy functions than voters are. Specifically, parties know the cost producing a public good, voters do not. An incumbent's choice of policy acts like a signal...... for costs before an upcoming election. It is shown that the more polarized the political parties the more distorted the incumbent's policy choice....

  5. Polar Warming Drivers (United States)

    McDunn, T. L.; Bougher, S. W.; Mischna, M. A.; Murphy, J. R.


    Polar warming is a dynamically induced temperature enhancement over mid-to-high latitudes that results in a reversed (poleward) meridional temperature gradient. This phenomenon was recently characterized over the 40-90 km altitude region [1] based on nearly three martian years of Mars Climate Sounder observations [2, 3]. Here we investigate which forcing mechanisms affect the magnitude and distribution of the observed polar warming by conducting simulations with the Mars Weather Research and Forecasting General Circulation Model [4, 5]. We present simulations confirming the influence topography [6] and dust loading [e.g., 7] have upon polar warming. We then present simulations illustrating the modulating influence gravity wave momentum deposition exerts upon polar warming, consistent with previous modeling studies [e.g., 8]. The results of this investigation suggest the magnitude and distribution of polar warming in the martian middle atmosphere is modified by gravity wave activity and that the characteristics of the gravity waves that most significantly affect polar warming vary with season. References: [1] McDunn, et al., 2012 (JGR), [2]Kleinböhl, et al., 2009 (JGR), [3] Kleinböhl, et al., 2011 (JQSRT), [4] Richardson, et al., 2007 (JGR), [5] Mischna, et al., 2011 (Planet. Space Sci.), [6] Richardson and Wilson, 2002 (Nature), [7] Haberle, et al., 1982 (Icarus), [8] Barnes, 1990 (JGR).

  6. Phytochemical profiles and antimicrobial activity of aromatic Malaysian herb extracts against food-borne pathogenic and food spoilage microorganisms. (United States)

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


    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.

  7. Polarization properties of linearly polarized parabolic scaling Bessel beams (United States)

    Guo, Mengwen; Zhao, Daomu


    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.

  8. Novel Application of Cyclolipopeptide Amphisin: Feasibility Study as Additive to Remediate Polycyclic Aromatic Hydrocarbon (PAH Contaminated Sediments

    Directory of Open Access Journals (Sweden)

    Anne Groboillot


    Full Text Available To decontaminate dredged harbor sediments by bioremediation or electromigration processes, adding biosurfactants could enhance the bioavailability or mobility of contaminants in an aqueous phase. Pure amphisin from Pseudomonas fluorescens DSS73 displays increased effectiveness in releasing polycyclic aromatic hydrocarbons (PAHs strongly adsorbed to sediments when compared to a synthetic anionic surfactant. Amphisin production by the bacteria in the natural environment was also considered. DSS73’s growth is weakened by three model PAHs above saturation, but amphisin is still produced. Estuarine water feeding the dredged material disposal site of a Norman harbor (France allows both P. fluorescens DSS73 growth and amphisin production.

  9. Polarization switching and patterning in self-assembled peptide tubular structures (United States)

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


    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.

  10. Sorption of polycyclic aromatic hydrocarbons (PAHs) on glass surfaces. (United States)

    Qian, Yuan; Posch, Tjorben; Schmidt, Torsten C


    Sorption of polycyclic aromatic hydrocarbons (PAHs) to glass commonly used in laboratories was studied. Sorption coefficients (Kd) of five selected PAHs to borosilicate glass surfaces were measured using column chromatography. A linear relationship between log Kd and the corresponding water solubility of the subcooled liquid (log Sw) of the investigated PAHs was observed. Based on the determined sorption coefficients our data revealed that mass loss caused by sorption on glass walls strongly depends on the ratio of solution volume to contacted surface area (V/S). The influence of solution chemistry such as ionic strength, solution pH, presence of cosolvent, and the influence of temperature on the sorption process were investigated. In the presence of ionic strength, sorption coefficients concurrently increased but less than a factor of 2 up to 0.005 M calcium chloride concentration. However, further increasing ionic strength had no influence on Kd. The cosolvent reduced sorption at a concentration of methanol in water above 0.5% (v/v); however, for benzo[a]pyrene even with 10% (v/v) methanol the mass loss would be still higher than 10% (with a V/S ratio less than 0.25). Significant effects of the solution pH and temperature were not observed. These results suggest that van der Waal's forces dominate the sorption process. In the analysis of highly hydrophobic PAHs in aqueous samples, mass loss due to sorption on glass walls should be accounted for in the final result if untreated glass is used. The presented relationship between log Kd and log Sw may help to decide if such a correction is necessary. Furthermore, the frequently used silanization of glass surfaces may not be sufficient to suppress sorption for large PAHs.

  11. Polarized Light Microscopy (United States)

    Frandsen, Athela F.


    Polarized light microscopy (PLM) is a technique which employs the use of polarizing filters to obtain substantial optical property information about the material which is being observed. This information can be combined with other microscopy techniques to confirm or elucidate the identity of an unknown material, determine whether a particular contaminant is present (as with asbestos analysis), or to provide important information that can be used to refine a manufacturing or chemical process. PLM was the major microscopy technique in use for identification of materials for nearly a century since its introduction in 1834 by William Fox Talbot, as other techniques such as SEM (Scanning Electron Microscopy), FTIR (Fourier Transform Infrared spectroscopy), XPD (X-ray Powder Diffraction), and TEM (Transmission Electron Microscopy) had not yet been developed. Today, it is still the only technique approved by the Environmental Protection Agency (EPA) for asbestos analysis, and is often the technique first applied for identification of unknown materials. PLM uses different configurations in order to determine different material properties. With each configuration additional clues can be gathered, leading to a conclusion of material identity. With no polarizing filter, the microscope can be used just as a stereo optical microscope, and view qualities such as morphology, size, and number of phases. With a single polarizing filter (single polars), additional properties can be established, such as pleochroism, individual refractive indices, and dispersion staining. With two polarizing filters (crossed polars), even more can be deduced: isotropy vs. anisotropy, extinction angle, birefringence/degree of birefringence, sign of elongation, and anomalous polarization colors, among others. With the use of PLM many of these properties can be determined in a matter of seconds, even for those who are not highly trained. McCrone, a leader in the field of polarized light microscopy, often

  12. Phenolic carbonyls undergo rapid aqueous photodegradation to form low-volatility, light-absorbing products (United States)

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


    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%.

  13. Biological applications of confocal fluorescence polarization microscopy (United States)

    Bigelow, Chad E.

    Fluorescence polarization microscopy is a powerful modality capable of sensing changes in the physical properties and local environment of fluorophores. In this thesis we present new applications for the technique in cancer diagnosis and treatment and explore the limits of the modality in scattering media. We describe modifications to our custom-built confocal fluorescence microscope that enable dual-color imaging, optical fiber-based confocal spectroscopy and fluorescence polarization imaging. Experiments are presented that indicate the performance of the instrument for all three modalities. The limits of confocal fluorescence polarization imaging in scattering media are explored and the microscope parameters necessary for accurate polarization images in this regime are determined. A Monte Carlo routine is developed to model the effect of scattering on images. Included in it are routines to track the polarization state of light using the Mueller-Stokes formalism and a model for fluorescence generation that includes sampling the excitation light polarization ellipse, Brownian motion of excited-state fluorophores in solution, and dipole fluorophore emission. Results from this model are compared to experiments performed on a fluorophore-embedded polymer rod in a turbid medium consisting of polystyrene microspheres in aqueous suspension. We demonstrate the utility of the fluorescence polarization imaging technique for removal of contaminating autofluorescence and for imaging photodynamic therapy drugs in cell monolayers. Images of cells expressing green fluorescent protein are extracted from contaminating fluorescein emission. The distribution of meta-tetrahydroxypheny1chlorin in an EMT6 cell monolayer is also presented. A new technique for imaging enzyme activity is presented that is based on observing changes in the anisotropy of fluorescently-labeled substrates. Proof-of-principle studies are performed in a model system consisting of fluorescently labeled bovine

  14. Solvent-free functionalization of fullerene C60 and pristine multi-walled carbon nanotubes with aromatic amines (United States)

    Ramírez-Calera, Itzel J.; Meza-Laguna, Victor; Gromovoy, Taras Yu.; Chávez-Uribe, Ma. Isabel; Basiuk, Vladimir A.; Basiuk, Elena V.


    We employed a direct one-step solvent-free covalent functionalization of solid fullerene C60 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, 13C 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 C60 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 C60, 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.

  15. [Polar and non polar notations of refraction]. (United States)

    Touzeau, O; Gaujoux, T; Costantini, E; Borderie, V; Laroche, L


    Refraction can be expressed by four polar notations which correspond to four different combinations of spherical or cylindrical lenses. Conventional expressions of refraction (plus and minus cylinder notation) are described by sphere, cylinder, and axis. In the plus cylinder notation, the axis visualizes the most powerful meridian. The axis usually corresponds to the bow tie axis in curvature maps. Plus cylinder notation is also valuable for all relaxing procedures (i.e., selective suture ablation, arcuate keratotomy, etc.). In the cross-cylinder notation, two orthogonal cylinders can describe (without the sphere component) the actual refraction of both the principal meridians. This notation must be made before performing the vertex calculation. Using an association of a Jackson cross-cylinder and a spherical equivalent, refraction can be broken down into two pure components: astigmatism and sphere. All polar notations of refraction may perfectly characterize a single refraction but are not suitable for statistical analysis, which requires nonpolar expression. After doubling the axis, a rectangular projection breaks down the Jackson cross-cylinder, which has a polar axis, into two Jackson cross-cylinders on the 0 degrees /90 degrees and 45 degrees /135 degrees axis. This procedure results in the loss of the directional nature of the data. Refraction can be written in a nonpolar notation by three rectangular coordinates (x,y,z), which can also represent the spherocylinder by one point in a dioptric space. These three independent (orthogonal) variables have a concrete optical significance: a spherical component, a direct/inverse (WTR/ATR) component, and an oblique component of the astigmatism. Finally, nonpolar notations are useful for statistical analysis and graphical representation of refraction.

  16. Polarized nuclear target based on parahydrogen induced polarization

    Energy Technology Data Exchange (ETDEWEB)

    D. Budker, M.P. Ledbetter, S. Appelt, L.S. Bouchard, B. Wojtsekhowski


    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 ({approx}100 HZ) polarization oscillation (akin to polarization reversal), and operation with large intensity of an electron beam.

  17. Cylindrically Polarized Nondiffracting Optical Pulses

    CERN Document Server

    Ornigotti, Marco; Szameit, Alexander


    We extend the concept of radially and azimuthally polarized optical beams to the polychromatic domain by introducing cylindrically polarized nondiffracting optical pulses. In particular, we discuss in detail the case of cylindrically polarized X-waves, both in the paraxial and nonparaxial regime. The explicit expressions for the electric and magnetic fields of cylindrically polarized X-waves is also reported.

  18. Sequential Polarity-Reversing Circuit (United States)

    Labaw, Clayton C.


    Proposed circuit reverses polarity of electric power supplied to bidirectional dc motor, reversible electro-mechanical actuator, or other device operating in direction depending on polarity. Circuit reverses polarity each time power turned on, without need for additional polarity-reversing or direction signals and circuitry to process them.

  19. Qualitative Characterization of the Aqueous Fraction from Hydrothermal Liquefaction of Algae Using 2D Gas Chromatography with Time-of-flight Mass Spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Maddi, Balakrishna; Panisko, Ellen; Albrecht, Karl; Howe, Daniel


    Two-dimensional gas chromatography coupled with time of flight mass spectrometry is a powerful tool for identifying and quantifying components in complex mixtures. It has been used to analyze gasoline, jet fuel, diesel, bio-diesel and organic fraction of bio-crude/bio-oil. In these experiments, the first dimension of separation was non-polar, followed by a polar separation. Aqueous fractions of bio-crude and other aqueous samples have been examined with similar column combinations. However, sample preparation techniques such as derivatization, solvent extraction, and solid-phase extraction were necessary prior to analysis. In this study, aqueous fraction obtained from hydrothermal liquefaction of algae was characterized by two-dimensional gas chromatography coupled with time of flight mass spectrometry without prior sample preparation techniques using a polar separation in the first dimension followed by a non-polar separation. Two-dimensional plots from this analysis were compared with those obtained from the more traditional column combination. Results from qualitative characterization aqueous fractions of algal bio-crude are discussed in detail. The advantages of using a polar separation followed by a non-polar separation for characterization of organics in aqueous samples by two-dimensional gas chromatography coupled with time of flight mass spectrometry are highlighted.

  20. Bioavailability and biodegradation of polycyclic aromatic hydrocarbons.

    NARCIS (Netherlands)

    Volkering, F.


    One of the main problems in biological soil remediation is the slow or incomplete degradation of hydrophobic organic pollutants. The principal reason for this problem is the fact that these compounds bind strongly to the soil matrix or occur as a separate non- aqueous phase in the soil. As most micr

  1. Polar low monitoring (United States)

    Bobylev, Leonid; Zabolotskikh, Elizaveta; Mitnik, Leonid


    Polar lows are intense mesoscale atmospheric low pressure weather systems, developing poleward of the main baroclinic zone and associated with high surface wind speeds. Small size and short lifetime, sparse in-situ observations in the regions of their development complicate polar low study. Our knowledge of polar lows and mesocyclones has come almost entirely during the period of satellite remote sensing since, by virtue of their small horizontal scale, it was rarely possible to analyse these lows on conventional weather charts using only the data from the synoptic observing network. However, the effects of intense polar lows have been felt by coastal communities and seafarers since the earliest times. These weather systems are thought to be responsible for the loss of many small vessels over the centuries, although the nature of the storms was not understood and their arrival could not be predicted. The actuality of the polar low research is stipulated by their high destructive power: they are a threat to such businesses as oil and gas exploration, fisheries and shipping. They could worsen because of global warming: a shrinking of sea ice around the North Pole, which thawed to its record minimum in the summer of 2007, is likely to give rise to more powerful storms that form only over open water and can cause hurricane-strength winds. Therefore, study of polar lows, their timely detection, tracking and forecasting represents a challenge for today meteorology. Satellite passive microwave data, starting from Special Sensor Microwave Imager (SSM/I) onboard Defense Meteorological Satellite Program (DMSP) satellite, remain invaluable source of regularly available remotely sensed data to study polar lows. The sounding in this spectral range has several advantages in comparison with observations in visible and infrared ranges and Synthetic Aperture Radar (SAR) data: independence on day time and clouds, regularity and high temporal resolution in Polar Regions. Satellite

  2. Polarization twist in perovskite ferrielectrics (United States)

    Kitanaka, Yuuki; Hirano, Kiyotaka; Ogino, Motohiro; Noguchi, Yuji; Miyayama, Masaru; Moriyoshi, Chikako; Kuroiwa, Yoshihiro


    Because the functions of polar materials are governed primarily by their polarization response to external stimuli, the majority of studies have focused on controlling polar lattice distortions. In some perovskite oxides, polar distortions coexist with nonpolar tilts and rotations of oxygen octahedra. The interplay between nonpolar and polar instabilities appears to play a crucial role, raising the question of how to design materials by exploiting their coupling. Here, we introduce the concept of ‘polarization twist’, which offers enhanced control over piezoelectric responses in polar materials. Our experimental and theoretical studies provide direct evidence that a ferrielectric perovskite exhibits a large piezoelectric response because of extended polar distortion, accompanied by nonpolar octahedral rotations, as if twisted polarization relaxes under electric fields. The concept underlying the polarization twist opens new possibilities for developing alternative materials in bulk and thin-film forms.

  3. Polarization twist in perovskite ferrielectrics. (United States)

    Kitanaka, Yuuki; Hirano, Kiyotaka; Ogino, Motohiro; Noguchi, Yuji; Miyayama, Masaru; Moriyoshi, Chikako; Kuroiwa, Yoshihiro


    Because the functions of polar materials are governed primarily by their polarization response to external stimuli, the majority of studies have focused on controlling polar lattice distortions. In some perovskite oxides, polar distortions coexist with nonpolar tilts and rotations of oxygen octahedra. The interplay between nonpolar and polar instabilities appears to play a crucial role, raising the question of how to design materials by exploiting their coupling. Here, we introduce the concept of 'polarization twist', which offers enhanced control over piezoelectric responses in polar materials. Our experimental and theoretical studies provide direct evidence that a ferrielectric perovskite exhibits a large piezoelectric response because of extended polar distortion, accompanied by nonpolar octahedral rotations, as if twisted polarization relaxes under electric fields. The concept underlying the polarization twist opens new possibilities for developing alternative materials in bulk and thin-film forms.

  4. Polarization twist in perovskite ferrielectrics (United States)

    Kitanaka, Yuuki; Hirano, Kiyotaka; Ogino, Motohiro; Noguchi, Yuji; Miyayama, Masaru; Moriyoshi, Chikako; Kuroiwa, Yoshihiro


    Because the functions of polar materials are governed primarily by their polarization response to external stimuli, the majority of studies have focused on controlling polar lattice distortions. In some perovskite oxides, polar distortions coexist with nonpolar tilts and rotations of oxygen octahedra. The interplay between nonpolar and polar instabilities appears to play a crucial role, raising the question of how to design materials by exploiting their coupling. Here, we introduce the concept of ‘polarization twist’, which offers enhanced control over piezoelectric responses in polar materials. Our experimental and theoretical studies provide direct evidence that a ferrielectric perovskite exhibits a large piezoelectric response because of extended polar distortion, accompanied by nonpolar octahedral rotations, as if twisted polarization relaxes under electric fields. The concept underlying the polarization twist opens new possibilities for developing alternative materials in bulk and thin-film forms. PMID:27586824

  5. Spectrometric study of α-methylene aromatic araminenone and aminoketone

    Institute of Scientific and Technical Information of China (English)


    Thirteen α-methylene aromatic araminenone and four α-methylene aromatic aminoketones were prepared by modified Mannich reaction. On the basis of isotopic labeling, a plausible way of cleavage was proposed for the formation of the M+- 17 fragment peak in the MS of the α-methylene aromatic araminenone and aminoketones. The characteristic chemical shift of the olefinic protons in 1H NMR is also discussed.

  6. Monobromination of Activated Aromatic Compounds withPolyvinylbenzyltriphenylphosphonium Supported Tribromide

    Institute of Scientific and Technical Information of China (English)

    WU Ming-Hu; YANG Gui-Chun; CHEN Zu-Xing


    Chloromethylated crosslinked co-polyvinylbenzene-divinylber-zene (2% DVB) was treated with triphenylphospbhie and then with sodium bromate and hydrobromic acid to afford red col-ored insoluble polyvinylbenzyltriphenylphosphon supportedtribromide.This reagent could be used as a mild and efficient monobrominating reagent for activated aromatic compounds such as phenols,aromatic,aromatic amines and acety-lanilines with good yields and high para-selectivity.

  7. Implementation of polarization processes in a charge transport model applied on poly(ethylene naphthalate) films (United States)

    Hoang, M.-Q.; Le Roy, S.; Boudou, L.; Teyssedre, G.


    One of the difficulties in unravelling transport processes in electrically insulating materials is the fact that the response, notably charging current transients, can have mixed contributions from orientation polarization and from space charge processes. This work aims at identifying and characterizing the polarization processes in a polar polymer in the time and frequency-domains and to implement the contribution of the polarization into a charge transport model. To do so, Alternate Polarization Current (APC) and Dielectric Spectroscopy measurements have been performed on poly(ethylene naphthalene 2,6-dicarboxylate) (PEN), an aromatic polar polymer, providing information on polarization mechanisms in the time- and frequency-domain, respectively. In the frequency-domain, PEN exhibits 3 relaxation processes termed β, β* (sub-glass transitions), and α relaxations (glass transition) in increasing order of temperature. Conduction was also detected at high temperatures. Dielectric responses were treated using a simplified version of the Havriliak-Negami model (Cole-Cole (CC) model), using 3 parameters per relaxation process, these parameters being temperature dependent. The time dependent polarization obtained from the CC model is then added to a charge transport model. Simulated currents issued from the transport model implemented with the polarization are compared with the measured APCs, showing a good consistency between experiments and simulations in a situation where the response comes essentially from dipolar processes.

  8. Polar metabolites of polycyclic aromatic compounds from fungi are potential soil and groundwater contaminants

    DEFF Research Database (Denmark)

    Boll, Esther Sørensen; Johnsen, Anders R.; Christensen, Jan H.


    and either hydroxylated or oxidized to carboxylic acids at the methyl group. The metabolism of the sulfur-containing heterocyclic PAC resulted in sulfate conjugates. The sorption of the PAC metabolites to three soils was determined using a batch equilibrium method, and partition coefficients (Kd's) were...

  9. Phenylnaphthalenes: sublimation equilibrium, conjugation, and aromatic interactions. (United States)

    Lima, Carlos F R A C; Rocha, Marisa A A; Schröder, Bernd; Gomes, Lígia R; Low, John N; Santos, Luís M N B F


    In this work, the interplay between structure and energetics in some representative phenylnaphthalenes is discussed from an experimental and theoretical perspective. For the compounds studied, the standard molar enthalpies, entropies and Gibbs energies of sublimation, at T = 298.15 K, were determined by the measurement of the vapor pressures as a function of T, using a Knudsen/quartz crystal effusion apparatus. The standard molar enthalpies of formation in the crystalline state were determined by static bomb combustion calorimetry. From these results, the standard molar enthalpies of formation in the gaseous phase were derived and, altogether with computational chemistry at the B3LYP/6-311++G(d,p) and MP2/cc-pVDZ levels of theory, used to deduce the relative molecular stabilities in various phenylnaphthalenes. X-ray crystallographic structures were obtained for some selected compounds in order to provide structural insights, and relate them to energetics. The thermodynamic quantities for sublimation suggest that molecular symmetry and torsional freedom are major factors affecting entropic differentiation in these molecules, and that cohesive forces are significantly influenced by molecular surface area. The global results obtained support the lack of significant conjugation between aromatic moieties in the α position of naphthalene but indicate the existence of significant electron delocalization when the aromatic groups are in the β position. Evidence for the existence of a quasi T-shaped intramolecular aromatic interaction between the two outer phenyl rings in 1,8-di([1,1'-biphenyl]-4-yl)naphthalene was found, and the enthalpy of this interaction quantified on pure experimental grounds as -(11.9 ± 4.8) kJ·mol(-1), in excellent agreement with the literature CCSD(T) theoretical results for the benzene dimer.

  10. Aromatic plant production on metal contaminated soils

    Energy Technology Data Exchange (ETDEWEB)

    Zheljazkov, Valtcho D. [Mississippi State, Department of Plant and Soil Sciences and North Mississippi Research and Extension Center, 5421 Highway 145 South, Verona, MS 38879 (United States)], E-mail:; Craker, Lyle E.; Xing Baoshan [Department of Plant and Soil Sciences, 12 Stockbridge Hall, University of Massachusetts, Amherst, MA 01003 (United States); Nielsen, Niels E. [Plant Nutrition and Soil Fertility Lab, Department of Agricultural Sciences, Royal Veterinary and Agricultural University, Thorvaldsensvej 40, DK1871, Copenhagen (Denmark); Wilcox, Andrew [Harper Adams University College, Newport, Shropshire, TF10 8NB (United Kingdom)


    Field and container experiments were conducted to assess the feasibility of growing aromatic crops in metal contaminated areas and the effect of metals on herbage and oil productivity. The field experiments were conducted in the vicinities of the Non-Ferrous Metals Combine (Zn-Cu smelter) near Plovdiv, Bulgaria using coriander, sage, dill, basil, hyssop, lemon balm, and chamomile grown at various distances from the smelter. Herbage essential oil yields of basil, chamomile, dill, and sage were reduced when they were grown closer to the smelter. Metal removal from the site with the harvestable plant parts was as high as 180 g ha{sup -1} for Cd, 660 g ha{sup -1} for Pb, 180 g ha{sup -1} for Cu, 350 g ha{sup -1} for Mn, and 205 g ha{sup -1} for Zn. Sequential extraction of soil demonstrated that metal fractionation was affected by the distance to the smelter. With decreasing distance to the smelter, the transfer factor (TF) for Cu and Zn decreased but increased for Cd, while the bioavailability factor (BF) for Cd, Pb, Cu, Mn, and Zn decreased. Scanning electron microscopy and X-ray microanalyses of contaminated soil verified that most of the Pb, Cd, Mn, Cu, and Zn were in the form of small (< 1 {mu}m) particles, although there were larger particles (1-5 {mu}m) with high concentrations of individual metals. This study demonstrated that high concentrations of heavy metals in soil or growth medium did not result in metal transfer into the essential oil. Of the tested metals, only Cu at high concentrations may reduce oil content. Our results demonstrated that aromatic crops may not have significant phytoremediation potential, but growth of these crops in metal contaminated agricultural soils is a feasible alternative. Aromatic crops can provide economic return and metal-free final product, the essential oil.

  11. A lunar polar expedition (United States)

    Dowling, Richard; Staehle, Robert L.; Svitek, Tomas


    Advanced exploration and development in harsh environments require mastery of basic human survival skill. Expeditions into the lethal climates of Earth's polar regions offer useful lessons for tommorrow's lunar pioneers. In Arctic and Antarctic exploration, 'wintering over' was a crucial milestone. The ability to establish a supply base and survive months of polar cold and darkness made extensive travel and exploration possible. Because of the possibility of near-constant solar illumination, the lunar polar regions, unlike Earth's may offer the most hospitable site for habitation. The World Space Foundation is examining a scenario for establishing a five-person expeditionary team on the lunar north pole for one year. This paper is a status report on a point design addressing site selection, transportation, power, and life support requirements.

  12. On polarization in biomembranes

    DEFF Research Database (Denmark)

    Zecchi, Karis Amata

    close to physiological conditions, making these effects biologically relevant. In this work, we consider the case of asymmetric membranes which can display spontaneous polarization in the absence of a field. Close to the phase transition, we find that the membrane displays piezoelectric, flexoelectric...... and thermoelectric behaviour. In particular, the membrane capacitance is a nonlinear function of the applied voltage. Furthermore, in the presence of spontaneous polarization, our thermodynamical description is able to explain the outward rectified current-voltage relationship measured on synthetic lipid bilayers....... Due to the nonlinear dependence of the membrane capacitance and conductance on voltage and the presence of spontaneous polarization, the traditional equivalent circuit of the membrane is not an accurate description in physiological conditions. An updated equivalent circuit of the lipid bilayer is here...

  13. [Polar body diagnosis]. (United States)

    Montag, M; van der Ven, K; van der Ven, H


    Polar body diagnosis (PBD) is a diagnostic method for the indirect genetic analysis of oocytes. Polar bodies are by-products of the meiotic cell cycle which have no influence on further embryo development. The biopsy of polar bodies can be accomplished either by zona drilling or laser drilling within a very short time period. The paternal contribution to the genetic constitution of the developing embryo cannot be diagnosed by PBD. The major application of PBD is the detection of maternally derived chromosomal aneuploidies and translocations in oocytes. For these indications, PBD may offer a viable alternative to blastomere biopsy as the embryo's integrity remains unaffected in contrast to preimplantation genetic diagnosis by blastomere biopsy. The fast development in the field of molecular diagnostics will also influence PBD and probably allow a more general diagnosis in the future.

  14. Metabolism of aromatic compounds by Caulobacter crescentus

    Energy Technology Data Exchange (ETDEWEB)

    Chatterjee, D.K.; Bourquin, A.W.


    Cultures of Caulobacter crescentus were found to grow on a variety of aromatic compounds. Degradation of benzoate, p-hydroxybenzoate, and phenol was found to occur via ..beta..-ketoadipate. The induction of degradative enzymes such as benzoate 1,2-dioxygenase, the ring cleavage enzyme catechol 1,2-dioxygenase, and cis,cis-muconate lactonizing enzyme appeared similar to the control mechanism present in Pseudomonas spp. Both benzoate 1,2-dioxygenase and catechol 1,2-dioxygenase had stringent specificities, as revealed by their action toward substituted benzoates and substituted catechols, respectively.

  15. Aromatics oxidation and soot formation in flames

    Energy Technology Data Exchange (ETDEWEB)

    Howard, J.B.; Pope, C.J.; Shandross, R.A.; Yadav, T. [Massachusetts Institute of Technology, Cambridge (United States)


    This project is concerned with the kinetics and mechanisms of aromatics oxidation and soot and fullerenes formation in flames. The scope includes detailed measurements of profiles of stable and radical species concentrations in low-pressure one-dimensional premixed flames. Intermediate species identifications and mole fractions, fluxes, and net reaction rates calculated from the measured profiles are used to test postulated reaction mechanisms. Particular objectives are to identify and to determine or confirm rate constants for the main benzene oxidation reactions in flames, and to characterize fullerenes and their formation mechanisms and kinetics.

  16. Photoinduced dynamics in protonated aromatic amino acid

    CERN Document Server

    Grégoire, Gilles; Barat, Michel; Fayeton, Jacqueline; Dedonder-Lardeux, Claude; Jouvet, Christophe


    UV photoinduced fragmentation of protonated aromatics amino acids have emerged the last few years, coming from a situation where nothing was known to what we think a good understanding of the optical properties. We will mainly focus this review on the tryptophan case. Three groups have mostly done spectroscopic studies and one has mainly been involved in dynamics studies of the excited states in the femtosecond/picosecond range and also in the fragmentation kinetics from nanosecond to millisecond. All these data, along with high level ab initio calculations, have shed light on the role of the different electronic states of the protonated molecules upon the fragmentation mechanisms.

  17. Selection of ionic liquids for the extraction of aromatic hydrocarbons from aromatic/aliphatic mixtures

    NARCIS (Netherlands)

    Meindersma, G. Wytze; Podt, Anita (J.G.); Haan, de André B.


    The separation of aromatic hydrocarbons (benzene, toluene, ethyl benzene and xylenes) from C4 to C10 aliphatic hydrocarbon mixtures is challenging since these hydrocarbons have boiling points in a close range and several combinations form azeotropes. In this work, we investigated the separation of t

  18. New compact neutron polarizer (United States)

    Krist, Th; Kennedy, S. J.; Hicks, T. J.; Mezei, F.

    A new type of a neutron polarizing bender was developed in co-operation with BENSC and ANSTO. It is based upon bent thin silicon wafers coated on one side with SiFeCo polarizing supermirrors and on the other side with Gd. Initial tests at BENSC in a 300 Oe magnetic field yielded a transmission of spin-up neutrons of about 55% over an angle range of 0.75° and flipping ratios > 30. Subsequent tests at ANSTO at 1200 Oe yielded a transmission of 48% with a flipping ratio > 45.

  19. Internal polarized targets

    Energy Technology Data Exchange (ETDEWEB)

    Kinney, E.R.; Coulter, K.; Gilman, R.; Holt, R.J.; Kowalczyk, R.S.; Napolitano, J.; Potterveld, D.H.; Young, L. (Argonne National Lab., IL (USA)); Mishnev, S.I.; Nikolenko, D.M.; Popov, S.G.; Rachek, I.A.; Temnykh, A.B.; Toporkov, D.K.; Tsentalovich, E.P.; Wojtsekhowski, B.B. (AN SSSR, Novosibirsk (USSR). Inst. Yadernoj Fiziki)


    Internal polarized targets offer a number of advantages over external targets. After a brief review of the basic motivation and principles behind internal polarized targets, the technical aspects of the atomic storage cell will be discussed in particular. Sources of depolarization and the means by which their effects can be ameliorated will be described, especially depolarization by the intense magnetic fields arising from the circulating particle beam. The experience of the Argonne Novosibirsk collaboration with the use of a storage cell in a 2 GeV electron storage ring will be the focus of this technical discussion. 17 refs., 11 figs.

  20. Microwave Frequency Polarizers (United States)

    Ha, Vien The; Mirel, Paul; Kogut, Alan J.


    This article describes the fabrication and analysis of microwave frequency polarizing grids. The grids are designed to measure polarization from the cosmic microwave background. It is effective in the range of 500 to 1500 micron wavelength. It is cryogenic compatible and highly robust to high load impacts. Each grid is fabricated using an array of different assembly processes which vary in the types of tension mechanisms to the shape and size of the grids. We provide a comprehensive study on the analysis of the grids' wire heights, diameters, and spacing.

  1. Role of glyoxal in SOA formation from aromatic hydrocarbons: gas-phase reaction trumps reactive uptake

    Directory of Open Access Journals (Sweden)

    S. Nakao


    Full Text Available This study evaluates the significance of glyoxal acting as an intermediate species leading to SOA formation from aromatic hydrocarbon photooxidation under humid conditions. Rapid SOA formation from glyoxal uptake onto aqueous (NH42SO4 seed particles is observed; however, glyoxal did not partition to SOA or SOA coated aqueous seed during all aromatic hydrocarbon experiments (RH up to 80%. Glyoxal is found to only influence SOA formation by raising hydroxyl (OH radical concentrations. Four experimental approaches supporting this conclusion are presented in this paper: (1 increased SOA formation and decreased SOA volatility in the toluene + NOx photooxidation system with additional glyoxal was reproduced by matching OH radical concentrations through H2O2 addition; (2 glyoxal addition to SOA seed formed from toluene + NOx photooxidation did not increase observed SOA volume; (3 SOA formation from toluene + NOx photooxidation with and without deliquesced (NH42SO4 seed resulted in similar SOA growth, consistent with a coating of SOA preventing glyoxal uptake onto deliquesced (NH42SO4 seed; and (4 the fraction of a C4H9+ fragment (observed by Aerodyne High Resolution Time-of-Flight Aerosol Mass Spectrometer, HR-ToF-AMS from SOA formed by 2-tert-butylphenol (BP oxidation was unchanged in the presence of additional glyoxal despite enhanced SOA formation. This study suggests that glyoxal uptake onto aerosol is minor when the surface (and near-surface of aerosols are primarily composed of secondary organic compounds.

  2. Dermal permeation of biocides and aromatic chemicals in three generic formulations of metalworking fluids. (United States)

    Vijay, Vikrant; White, Eugene M; Kaminski, Michael D; Riviere, Jim E; Baynes, Ronald E


    Metalworking fluids (MWF) are complex mixtures consisting of a variety of components and additives. A lack of scientific data exists regarding the dermal permeation of its components, particularly biocides. The aim of this study was to evaluate the dermal permeation of biocides and other aromatic chemicals in water and in three generic soluble oil, semi-synthetic, and synthetic MWF types in order to evaluate any differences in their permeation profiles. An in vitro flow-through diffusion cell study was performed to determine dermal permeation. An infinite dose of different groups of chemicals (6 biocides and 29 aromatic chemicals) was applied to porcine skin, with perfusate samples being collected over an 8-h period. Perfusate samples were analyzed by gas chromatography/mass spectrometry (GC-MS) and ultra-performance liquid chromatography/mass spectroscopy (UPLC-MS), and permeability was calculated from the analysis of the permeated chemical concentration-time profile. In general, the permeation of chemicals was highest in aqueous solution, followed by synthetic, semi-synthetic, and soluble oil MWF. The absorption profiles of most of the chemicals including six biocides were statistically different among the synthetic and soluble oil MWF formulations, with reduced permeation occurring in oily formulations. Permeation of almost all chemicals was statistically different between aqueous and three MWF formulation types. Data from this study show that permeation of chemicals is higher in a generic synthetic MWF when compared to a soluble oil MWF. This indicates that a soluble oil MWF may be safer than a synthetic MWF in regard to dermal permeation of chemicals to allow for an increased potential of systemic toxicity. Therefore, one may conclude that a synthetic type of formulation has more potential to produce contact dermatitis and induce systemic toxicological effects. The dilution of these MWF formulations with water may increase dermal permeability of biocides

  3. 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.


    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.

  4. Terahertz absorption of dilute aqueous solutions. (United States)

    Heyden, Matthias; Tobias, Douglas J; Matyushov, Dmitry V


    Absorption of terahertz (THz) radiation by aqueous solutions of large solutes reports on the polarization response of their hydration shells. This is because the dipolar relaxation of the solute is dynamically frozen at these frequencies, and most of the solute-induced absorption changes, apart from the expulsion of water, are caused by interfacial water. We propose a model expressing the dipolar response of solutions in terms of a single parameter, the interface dipole moment induced in the interfacial water by electromagnetic radiation. We apply this concept to experimental THz absorption of hydrated sugars, amino acids, and proteins. None of the solutes studied here follow the expectations of dielectric theories, which predict a negative projection of the interface dipole on the external electric field. We find that this prediction is not able to describe the available experimental data, which instead suggests a nearly zero interface dipole for sugars and a more diverse pattern for amino acids. Hydrophobic amino acids, similarly to sugars, give rise to near zero interface dipoles, while strongly hydrophilic ones are best described by a positive projection of the interface dipole on the external field. The sign of the interface dipole is connected to the slope of the absorption coefficient with the solute concentration. A positive slope, implying an increase in the solution polarity relative to water, mirrors results frequently reported for protein solutions. We therefore use molecular dynamics simulations of hydrated glucose and lambda repressor protein to calculate the interface dipole moments of these solutes and the concentration dependence of the THz absorption. The absorption at THz frequencies increases with increasing solute concentration in both cases, implying a higher polarity of the solution compared to bulk water. The structure of the hydration layer, extracted from simulations, is qualitatively similar in both cases, with spatial correlations

  5. Rheology of nanocrystalline cellulose aqueous suspensions. (United States)

    Shafiei-Sabet, Sadaf; Hamad, Wadood Y; Hatzikiriakos, Savvas G


    The rheological properties and microstructure of nanocrystalline cellulose (NCC) aqueous suspensions have been investigated at different concentrations. The suspension is isotropic up to 3 wt %, and phase separates to liquid crystalline and isotropic domains at higher concentrations where the samples exhibit a fingerprint texture and the viscosity profile shows a three-region behavior, typical of liquid crystals. The suspension behaves as a rheological gel at even higher concentrations where the viscosity profile shows a single shear thinning behavior over the whole range of shear rates investigated. The effects of ultrasound energy and temperature on the rheological properties and structure of these suspensions were studied using polarized optical microscopy and rheometry. Our results indicate that the amount of applied ultrasound energy affects the microstructure of the suspensions and the pitch of the chiral nematic domains. The viscosity profile is changed significantly at low shear rates, whereas the viscosity of biphasic suspensions at intermediate and high shear rates decreased with increasing temperature. This suggests that, between 30 and 40 °C, structural rearrangement takes place. At higher concentrations of about 10 wt %, the temperature has no significant effect on viscosity; however, a marked increase in viscosity has been observed at around 50 °C. Finally, the Cox-Merz rule was found to fail after a critical concentration, thereby implying significant structural formation. This critical concentration is much higher for sonicated compared to unsonicated suspensions.

  6. Multicenter bond index analysis of influence of metal cations on the aromaticity of aromatic amino acids: Phenylalanine and tyrosine (United States)

    Pakiari, A. H.; Farrokhnia, M.; Azami, S. M.


    In order to provide insight into the influence of metal cations on the aromaticity of amino acids, evaluation of six-center delocalization indices is accomplished in the context of quantum theory of atoms in molecules (QTAIM). Aromaticity of two amino acids, phenylalanine and tyrosine, is investigated as typical amino acids containing aromatic ring in their isolated state and complexed by some metal cations. The results showed that the metal cations affect the most important three connectivities differently. Also, it is shown that the existence of metal cations can increase two-center delocalization in certain parts of the aromatic rings.

  7. Antimutagenicity of coriander (Coriandrum sativum) juice on the mutagenesis produced by plant metabolites of aromatic amines. (United States)

    Cortés-Eslava, Josefina; Gómez-Arroyo, Sandra; Villalobos-Pietrini, Rafael; Espinosa-Aguirre, Jesús Javier


    Aromatic amines are metabolically activated into mutagenic compounds by both animal and plant systems. The 4-nitro-o-phenylenediamine (NOP) is a well-known direct-acting mutagen whose mutagenic potential can be enhanced by plant metabolism; m-phenylenediamine (m-PDA) is converted to mutagenic products detected by the Salmonella typhimurium TA98 strain, and 2-aminofluorene (2-AF) is the plant-activated promutagen most extensively studied. Plant cells activate both 2-AF and m-PDA into potent mutagens producing DNA frameshift mutations. Coriander (Coriandrum sativum) is a common plant included in the Mexican diet, usually consumed uncooked. The antimutagenic activity of coriander juice against the mutagenic activity of 4-nitro-o-phenylenediamine, m-phenylenediamine and 2-aminofluorene was investigated using the Ames reversion mutagenicity assay (his- to his+) with the S. typhimurium TA98 strain as indicator organism. The plant cell/microbe coincubation assay was used as the activating system for aromatic transformation and plant extract interaction. Aqueous crude coriander juice significantly decreased the mutagenicity of metabolized aromatic amines (AA) in the following order: 2-AF (92.43%) > m-PDA (87.14%) > NOP (83.21%). The chlorophyll content in vegetable juice was monitored and its concentration showed a positive correlation with the detected antimutagenic effect. Protein content and peroxidase activity were also determined. The concentration of coriander juice (50-1000 microl/coincubation flask) was neither toxic nor mutagenic. The similar shape of the antimutagenic response curves obtained with coriander juice and chlorophyllin (used as a subrogate molecule of chlorophyll) indicated that comparable mechanisms of mutagenic inhibition could be involved. The negative correlation between chlorophyll content and mutagenic response of the promutagenic and direct-acting used amines allows us to deduce that a chemical interaction takes place between the two molecules

  8. A green, inexpensive and efficient organocatalyzed procedure for aqueous aldol condensations

    Energy Technology Data Exchange (ETDEWEB)

    Abaee, M. Saeed; Mojtahedi, Mohammad M.; Forghani, Soudabeh; Sharifi, Roholah [Chemistry and Chemical Engineering Research Center of Iran, Tehran (Iran, Islamic Republic of). Faculty of Organic Chemistry and Natural Products; Ghandchi, Nafiseh M. [Islamic Azad University, Tehran (Iran, Islamic Republic of). Dept. of Chemistry; Forouzani, Mehdi; Chaharnazm, Behnam [Payam Noor University, Sari (Iran, Islamic Republic of)


    A facile and general procedure is presented for diethylamine-catalyzed double crossed aldol condensation of cyclic ketones with various aromatic aldehydes under aqueous conditions. Excellent yields of 3,5-bisarylmethylidenes of homocyclic and heterocyclic ketones are achieved in a one-pot procedure. Furthermore, the methodology is efficiently applied to the synthesis of chalcones from their corresponding methyl ketones. In the majority of the cases studied, products precipitate from the reaction mixtures and the medium is recycled in subsequent several reactions without significant loss of activity. (author)

  9. Nano-Aluminum Powder Mediated Allylation of Carbonyl Compounds in Aqueous Media

    Institute of Scientific and Technical Information of China (English)

    YUAN Shi-Zhen; LIU Jin


    A new and effective Barbier-Grignard allylation of aldehydes or ketones has been carried out with nano-aluminum powder in aqueous 0.1 mol·L-1 NH4Cl (aq.) under an atmosphere of nitrogen. Aromatic carbonyl compounds gave homoallylic alcohols in good yields. The effectiveness of reaction was strongly influenced by the steric environment surrounding the carbonyl group. Aliphatic carbonyl compounds proceeded in low yields. The dominant stereoisomer was an erythro-isomer when an ortho-hydroxyl carbonyl compound was reacted under such a reaction condition.

  10. The physics of polarization (United States)

    Landi Degl'Innocenti, Egidio

    This course is intended to give a description of the basic physical concepts which underlie the study and the interpretation of polarization phenomena. Apart from a brief historical introduction (Sect. 1), the course is organized in three parts. A first part (Sects. 2 - 6) covers the most relevant facts about the polarization phenomena that are typically encountered in laboratory applications and in everyday life. In Sect. 2, the modern description of polarization in terms of the Stokes parameters is recalled, whereas Sect. 3 is devoted to introduce the basic tools of laboratory polarimetry, such as the Jones calculus and the Mueller matrices. The polarization phenomena which are met in the reflection and refraction of a beam of radiation at the separation surface between two dielectrics, or between a dielectric and a metal, are recalled in Sect. 4. Finally, Sect. 5 gives an introduction to the phenomena of dichroism and of anomalous dispersion and Sect. 6 summarizes the polarization phenomena that are commonly encountered in everyday life. The second part of this course (Sects. 7-14) deals with the description, within the formalism of classical physics, of the spectro-polarimetric properties of the radiation emitted by accelerated charges. Such properties are derived by taking as starting point the Liénard and Wiechert equations that are recalled and discussed in Sect. 7 both in the general case and in the non-relativistic approximation. The results are developed to find the percentage polarization, the radiation diagram, the cross-section and the spectral characteristics of the radiation emitted in different phenomena particularly relevant from the astrophysical point of view. The emission of a linear antenna is derived in Sect. 8. The other Sections are devoted to Thomson scattering (Sect. 9), Rayleigh scattering (Sect. 10), Mie scattering (Sect. 11), bremsstrahlung radiation (Sect. 12), cyclotron radiation (Sect. 13), and synchrotron radiation (Sect. 14

  11. Effect of testosterone and its aliphatic and aromatic dimers on DNA morphology. (United States)

    Chanphai, P; Agudelo, D; Vesper, A R; Bérubé, G; Tajmir-Riahi, H A


    Conjugation of DNA with testosterone and it aliphatic dimer (alip) and aromatic dimer (arom) was investigated in aqueous solution at pH 7.4. Multiple spectroscopic methods, transmission electron microscopy (TEM) and molecular modeling were used to characterize steroid-DNA binding and DNA morphology. Spectroscopic analysis showed that testosterone binds DNA via A7, A16, A17, T8, T15 and T18 nucleobases with overall binding constants Ktest-DNA=1.8 (±0.4)×10(4)M(-1), Ktest-dimeralip-DNA=5.7 (±0.7)×10(4)M(-1) and Ktest-dimer-arom-DNA=7.3 (±0.9)×10(4)M(-1). The binding affinity increases in this order: testosterone dimer-aromatic>testosterone dimer-aliphatic>testosterone. The steroid loading efficacy was 40-50%. Transmission electron microscopy showed major changes in DNA morphology as testosterone-DNA interaction occurred with increase in the diameter of the DNA aggregate, indicating encapsulation of testosterone by DNA. Modeling showed the presence of several nucleobases attached to testosterone with the free binding energy of -4.93Kcal/mol.

  12. Simultaneous biodegradation of creosote-polycyclic aromatic hydrocarbons by a pyrene-degrading Mycobacterium

    Energy Technology Data Exchange (ETDEWEB)

    Lopez, Z.; Vila, J.; Grifoll, M. [Barcelona Univ. (Spain). Dept. de Microbiologia; Ortega-Calvo, J.J. [C.S.I.C., Seville (Spain). Inst. de Recursos Naturales y Agrobiologia


    When incubated with a creosote-polycyclic aromatic hydrocarbons (PAHs) mixture, the pyrene-degrading strain Mycobacterium sp. AP1 acted on three- and four-ring components, causing the simultaneous depletion of 25% of the total PAHs in 30 days. The kinetics of disappearance of individual PAHs was consistent with differences in aqueous solubility. During the incubation, a number of acid metabolites indicative of distinctive reactions carried out by high-molecular-weight PAH-degrading mycobacteria accumulated in the medium. Most of these metabolites were dicarboxylic aromatic acids formed as a result of the utilization of growth substrates (phenanthrene, pyrene, or fluoranthene) by multibranched pathways including meta- and ortho-ring-cleavage reactions: phthalic acid, naphthalene-1,8-dicarboxylic acid, phenanthrene-4,5-dicarboxylic acid, diphenic acid, Z-9-carboxymethylenefluorene-1-carboxylic acid, and 6,6'-dihydroxy-2,2'-biphenyl dicarboxylic acid. Others were dead-end products resulting from cometabolic oxidations on nongrowth substrates (fluorene meta-cleavage product). These results contribute to the general knowledge of the biochemical processes that determine the fate of the individual components of PAH mixtures in polluted soils. The identification of the partially oxidized compounds will facilitate to develop analytical methods to determine their potential formation and accumulation in contaminated sites. (orig.)

  13. Oxidation of polycyclic aromatic hydrocarbons using partially purified laccase from residual compost of agaricus bisporus

    Energy Technology Data Exchange (ETDEWEB)

    Mayolo-Deloisa, K. [Center for Biotechnology Research, Autonomous University of Morelos State, Cuernavaca, Morelos (Mexico); Center for Biotechnology-FEMSA, Monterrey Institute of Technology, Campus Monterrey, Monterrey (Mexico); Machin-Ramirez, C. [Center for Biotechnology Research, Autonomous University of Morelos State, Cuernavaca, Morelos (Mexico); Faculty of Chemical Sciences and Engineering, Autonomous University of Morelos State, Cuernavaca, Morelos (Mexico); Rito-Palomares, M. [Center for Biotechnology-FEMSA, Monterrey Institute of Technology, Campus Monterrey, Monterrey (Mexico); Trejo-Hernandez, M.R. [Center for Biotechnology Research, Autonomous University of Morelos State, Cuernavaca, Morelos (Mexico)


    Laccase partially purified from residual compost of Agaricus bisporus by an aqueous two-phase system (Lac ATPS) was used in degrading polycyclic aromatic hydrocarbons: fluorene (Flu), phenanthrene (Phe), anthracene (Ant), benzo[a]pyrene (BaP), and benzo[a]anthracene (BaA). The capacity of the enzyme to oxidize polyaromatic compounds was compared to that of the crude laccase extract (CE). After treatment of 72 h, Lac ATPS and CE were not capable of oxidizing Flu and Phe, while Ant, BaP, and BaA were oxidized, resulting in percentages of oxidation of 11.2 {+-} 1, 26 {+-} 2, and 11.7 {+-} 4 % with CE, respectively. When Lac ATPS was used, the following percentages of oxidation were obtained: 11.4 {+-} 3 % for Ant, 34 {+-} 0.1 % for BaP, and 13.6 {+-} 2 % for BaA. The results reported here demonstrate the potential application of Lac ATPS for the oxidation of polycyclic aromatic hydrocarbons. (Copyright copyright 2011 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  14. Polarized Proton Collisions at RHIC

    CERN Document Server

    Bai, Mei; Alekseev, Igor G; Alessi, James; Beebe-Wang, Joanne; Blaskiewicz, Michael; Bravar, Alessandro; Brennan, Joseph M; Bruno, Donald; Bunce, Gerry; Butler, John J; Cameron, Peter; Connolly, Roger; De Long, Joseph; Drees, Angelika; Fischer, Wolfram; Ganetis, George; Gardner, Chris J; Glenn, Joseph; Hayes, Thomas; Hseuh Hsiao Chaun; Huang, Haixin; Ingrassia, Peter; Iriso, Ubaldo; Laster, Jonathan S; Lee, Roger C; Luccio, Alfredo U; Luo, Yun; MacKay, William W; Makdisi, Yousef; Marr, Gregory J; Marusic, Al; McIntyre, Gary; Michnoff, Robert; Montag, Christoph; Morris, John; Nicoletti, Tony; Oddo, Peter; Oerter, Brian; Osamu, Jinnouchi; Pilat, Fulvia Caterina; Ptitsyn, Vadim; Roser, Thomas; Satogata, Todd; Smith, Kevin T; Svirida, Dima; Tepikian, Steven; Tomas, Rogelio; Trbojevic, Dejan; Tsoupas, Nicholaos; Tuozzolo, Joseph; Vetter, Kurt; Wilinski, Michelle; Zaltsman, Alex; Zelenski, Anatoli; Zeno, Keith; Zhang, S Y


    The Relativistic Heavy Ion Collider~(RHIC) provides not only collisions of ions but also collisions of polarized protons. In a circular accelerator, the polarization of polarized proton beam can be partially or fully lost when a spin depolarizing resonance is encountered. To preserve the beam polarization during acceleration, two full Siberian snakes were employed in RHIC to avoid depolarizing resonances. In 2003, polarized proton beams were accelerated to 100~GeV and collided in RHIC. Beams were brought into collisions with longitudinal polarization at the experiments STAR and PHENIX by using spin rotators. RHIC polarized proton run experience demonstrates that optimizing polarization transmission efficiency and improving luminosity performance are significant challenges. Currently, the luminosity lifetime in RHIC is limited by the beam-beam effect. The current state of RHIC polarized proton program, including its dedicated physics run in 2005 and efforts to optimize luminosity production in beam-beam limite...

  15. Initial microbial degradation of polycyclic aromatic hydrocarbons

    Directory of Open Access Journals (Sweden)

    Milić Jelena


    Full Text Available The group of polycyclic aromatic hydrocarbons (PAHs are very hazardous environmental pollutants because of their mutagenic, carcinogenic and toxic effects on living systems. The aim of this study was to examine and compare the ability and efficiency of selected bacterial isolates obtained from oil-contaminated areas to biodegrade PAHs. The potential of the bacteria to biodegrade various aromatic hydrocarbons was assessed using the 2,6-dichlorophenol-indophenol assay. Further biodegradation of PAHs was monitored by gravimetric and gas-chromatographic analysis. Among the eight bacterial isolates, identified on the basis of 16S rDNA sequences, two isolates, Planomicrobium sp. RNP01 and Rhodococcus sp. RNP05, had the ability to grow on and utilize almost all examined hydrocarbons. Those isolates were further examined for biodegradation of phenanthrene and pyrene, as single substrates, and as a mixture, in vitro for ten days. After three days, both isolates degraded a significant amount phenanthrene, which has a simpler chemical structure than pyrene. Planomicrobium sp.RNP01 commenced biodegradation of pyrene in the PAH mixture only after it had almost completly degraded phenanthrene. The isolated and characterized bacteria, Planomicrobium sp. RNP01 and Rhodococcus sp. RNP05, have shown high bioremediation potential and are likely candidates to be used for degradation of highly toxic PAHs in contaminated areas. [Projekat Ministarstva nauke Republike Srbije, br. III43004

  16. An Aromatic Inventory of the Local Volume

    CERN Document Server

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


    Using infrared photometry from the Spitzer Space Telescope, we perform the first inventory of aromatic feature emission (AFE, but also commonly referred to as PAH 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 IRAC 8 micron 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 IRS spectra and equivalent photometry. A potential factor of two improvement could be realized with suitable 5.5 and 10 micron photometry, such as what may be provided in the future by JWST. 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 lum...

  17. Catalytic C-H imidation of aromatic cores of functional molecules: ligand-accelerated Cu catalysis and application to materials- and biology-oriented aromatics. (United States)

    Kawakami, Takahiro; Murakami, Kei; Itami, Kenichiro


    Versatile imidation of aromatic C-H bonds was accomplished. In the presence of copper bromide and 6,6'-dimethyl-2,2'-bipyridyl, a range of aromatics, such as polycyclic aromatic hydrocarbons, aromatic bowls, porphyrins, heteroaromatics, and natural products, can be imidated by N-fluorobenzenesulfonimide. A dramatic ligand-accelerated copper catalysis and an interesting kinetic profile were uncovered.

  18. No More Polarization, Please!

    DEFF Research Database (Denmark)

    Hansen, Mia Reinholt

    The organizational science literature on motivation has for long been polarized into two main positions; the organizational economic position focusing on extrinsic motivation and the organizational behavior position emphasizing intrinsic motivation. With the rise of the knowledge economy and the ......The organizational science literature on motivation has for long been polarized into two main positions; the organizational economic position focusing on extrinsic motivation and the organizational behavior position emphasizing intrinsic motivation. With the rise of the knowledge economy...... and the increasing levels of complexities it entails, such polarization is not fruitful in the attempt to explain motivation of organizational members. This paper claims that a more nuanced perspective on motivation, acknowledging the co-existence of intrinsic and extrinsic motivation, the possible interaction...... between the two as well as different types of motivations filling in the gap between the two polar types, is urgently needed in the organizational science literature. By drawing on the research on intrinsic and extrinsic motivation conducted in social psychology and combining this with contributions from...

  19. Variable polarity arc welding (United States)

    Bayless, E. O., Jr.


    Technological advances generate within themselves dissatisfactions that lead to further advances in a process. A series of advances in welding technology which culminated in the Variable Polarity Plasma Arc (VPPA) Welding Process and an advance instituted to overcome the latest dissatisfactions with the process: automated VPPA welding are described briefly.

  20. Saturn's Polar Atmosphere

    CERN Document Server

    Sayanagi, Kunio M; Dyudina, Ulyana A; Fletcher, Leigh N; Sánchez-Lavega, Agustin; West, Robert A


    This book chapter, Saturn's Polar Atmosphere, is to be published by Cambridge University Press as part of a multi-volume work edited by Kevin Baines, Michael Flasar, Norbert Krupp, and Thomas Stallard, entitled "Saturn in the 21st Century." This chapter reviews the state of our knowledge about Saturn's polar atmosphere that has been revealed through Earth- and space-based observation as well as theoretical and numerical modeling. In particular, the Cassini mission to Saturn, which has been in orbit around the ringed planet since 2004, has revolutionized our understanding of the planet. The current review updates a previous review by Del Genio et al (2009; Saturn Atmospheric Structure and Dynamics, Chapter 7 of "Saturn from Cassini-Huygens"), written after Cassini's primary mission phase that ended in 2008, by focusing on the north polar region of Saturn and comparing it to the southern high latitudes. Two prominent features in the northern high latitudes are the northern hexagon and the north polar vortex; we...

  1. Polarized parton distributions

    Energy Technology Data Exchange (ETDEWEB)

    de Florian, D.; Epele, L.N.; Fanchiotti, H.; Garcia Canal, C.A.; Sassot, R. (Laboratorio de Fisica Teorica, Departamento de Fisica, Universidad Nacional de La Plata, C.C. 67-1900 La Plata (Argentina))


    We analyze spin-dependent parton distributions consistent with the most recent measurements of the spin-dependent deep inelastic scattering structure functions and obtained in the framework of the spin dilution model. Predictions for the doubly polarized proton-proton Drell-Yan asymmetry, for the high [ital p][sub [ital T

  2. 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: [Instituto de Ciencias Nucleares, Universidad Nacional Autónoma de México, Circuito Exterior C. U., 04510 México, D.F. (Mexico); Basiuk, Elena V., E-mail: [Centro de Ciencias Aplicadas y Desarrollo Tecnológico, Universidad Nacional Autónoma de México, Circuito Exterior C. U., 04510, México, D.F. (Mexico)


    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.

  3. Aqueous solubility data for pressurized hot water extraction for solid heterocyclic analogs of anthracene, phenanthrene and fluorene. (United States)

    Karásek, Pavel; Planeta, Josef; Roth, Michal


    We report the aqueous solubilities of phenanthrene and several solid three-ring aromatic heterocycles (phenanthridine, acridine, phenazine, thianthrene, phenothiazine, phenoxathiin, phenoxazine, carbazole, dibenzofuran, dibenzothiophene, and 4,6-dimethyldibenzothiophene) at temperatures ranging from 313K to the solute melting point and at a pressure of 5MPa. The data were measured by dynamic saturation method using an in-house-assembled apparatus for pressurized hot water extraction (PHWE). The solute from a known mass of the saturated aqueous solution was transferred to an organic solvent (hexane or toluene), and the organic phase was analyzed by GC/MS. In any of the solutes, the GC/MS records did not indicate any noticeable decomposition within the temperature range of the measurements. The resultant solubilities were converted to activity coefficients of the individual solutes in saturated aqueous solutions, and the results are discussed in terms of temperature and type/number of heteroatoms.

  4. Chemical reactions at aqueous interfaces (United States)

    Vecitis, Chad David


    Interfaces or phase boundaries are a unique chemical environment relative to individual gas, liquid, or solid phases. Interfacial reaction mechanisms and kinetics are often at variance with homogeneous chemistry due to mass transfer, molecular orientation, and catalytic effects. Aqueous interfaces are a common subject of environmental science and engineering research, and three environmentally relevant aqueous interfaces are investigated in this thesis: 1) fluorochemical sonochemistry (bubble-water), 2) aqueous aerosol ozonation (gas-water droplet), and 3) electrolytic hydrogen production and simultaneous organic oxidation (water-metal/semiconductor). Direct interfacial analysis under environmentally relevant conditions is difficult, since most surface-specific techniques require relatively `extreme' conditions. Thus, the experimental investigations here focus on the development of chemical reactors and analytical techniques for the completion of time/concentration-dependent measurements of reactants and their products. Kinetic modeling, estimations, and/or correlations were used to extract information on interfacially relevant processes. We found that interfacial chemistry was determined to be the rate-limiting step to a subsequent series of relatively fast homogeneous reactions, for example: 1) Pyrolytic cleavage of the ionic headgroup of perfluorooctanesulfonate (PFOS) and perfluorooctanoate (PFOA) adsorbed to cavitating bubble-water interfaces during sonolysis was the rate-determining step in transformation to their inorganic constituents carbon monoxide, carbon dioxide, and fluoride; 2) ozone oxidation of aqueous iodide to hypoiodous acid at the aerosol-gas interface is the rate-determining step in the oxidation of bromide and chloride to dihalogens; 3) Electrolytic oxidation of anodic titanol surface groups is rate-limiting for the overall oxidation of organics by the dichloride radical. We also found chemistry unique to the interface, for example: 1

  5. Polarized nuclear target based on parahydrogen induced polarization

    Energy Technology Data Exchange (ETDEWEB)

    Budker, D., E-mail: [Department of Physics, University of California at Berkeley, Berkeley, CA 94720-7300 (United States); Nuclear Science Division, Lawrence Berkeley National Laboratory, Berkeley, CA 94720 (United States); Ledbetter, M.P. [Department of Physics, University of California at Berkeley, Berkeley, CA 94720-7300 (United States); Appelt, S. [Central Institute for Electronics, Research Center Juelich, D-52425 Juelich (Germany); Bouchard, L.S. [Department of Chemistry and Biochemistry, California NanoSystems Institute, Biomedical Engineering IDP, Jonsson Comprehensive Cancer Center, University of California, Los Angeles, CA 90095 (United States); Wojtsekhowski, B. [Thomas Jefferson National Accelerator Facility, Newport News, VA 23606 (United States)


    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 ({approx}100Hz) polarization oscillation (akin to polarization reversal), and operation with large intensity of an electron beam. -- Highlights: Black-Right-Pointing-Pointer Novel concept for polarized nuclear targets. Black-Right-Pointing-Pointer The target features fast reversal and operates at near-zero magnetic field. Black-Right-Pointing-Pointer Based on the technique of parahydrogen induced polarization that is revolutionizing NMR and enables NMR/MRI without magnets. Black-Right-Pointing-Pointer Competitive figure-of-merit for polarized targets.

  6. Degradation of atrazine in aqueous medium by electrocatalytically generated hydroxyl radicals. A kinetic and mechanistic study. (United States)

    Balci, Beytul; Oturan, Nihal; Cherrier, Richard; Oturan, Mehmet A


    Oxidative degradation of atrazine by hydroxyl radicals (()OH) was studied in aqueous medium. ()OH were formed in situ from electrochemically generating Fenton's reagent by an indirect electrochemical advanced oxidation process. Identification and evolution of seven main aromatic metabolites and four short-chain carboxylic acids were performed by using liquid chromatography analyses. Total organic carbon (TOC) and ionic chromatography were used in order to evaluate the mineralization efficiency of treated aqueous solutions. A high mineralization rate of 82% (never reported until now) was obtained. The oxidative degradation of cyanuric acid, the ultimate product of atrazine degradation, was highlighted for the first time. The absolute rate constant of the reaction between atrazine and hydroxyl radicals was evaluated by competition kinetics method as (2.54+/-0.22)x10(9)M(-1)s(-1). Considering all oxidation reaction intermediates and end products a general reaction sequence for atrazine degradation by hydroxyl radicals was proposed.

  7. Reaction mechanism of 3-chlorophenol with OH, H in aqueous solution. (United States)

    Zhu, Jie; Chen, Ye-Fei; Dong, Wen-Bo; Pan, Xun-Xi; Hou, Hui-Qi


    The reaction mechanism of 3-chlorophenol with OH, H in aqueous solution was studied by transient technology. The 3-chlorophenol aqueous solutions have been saturated with air or N2 previously. Under alkaline condition, the reaction of OH radical with 3-chlorophenol produces 3-chlorinated phenoxyl radical, with the absorption peaks at 400 nm and 417 nm. Under neutral condition, the reaction of OH radical with 3-chlorophenol produces OH-adduct with the maximal absorption at about 340 nm. And in acid solution, the reaction of H with 3-chlorophenol produces H-adduct with the maximal absorption at about 320 nm. 3-chlorophenol is compared with 4-and 2-chlorophenols from the free radical pathways. The results show that the positions of chlorine on the aromatic ring strongly influence the dehalogenation and degradation process.

  8. Biocompatible sodium alginate fibers by aqueous processing and physical crosslinking. (United States)

    Shen, Wei; Hsieh, You-Lo


    Sodium alginate (SA) hybrid fibers have been robustly fabricated by electrospinning of aqueous mixtures containing as high as 60% SA in the presence of polyvinyl alcohol (PVA). Solution viscosities of SA, PVA and their mixtures showed fiber spinning to be strongly influenced by the balance between SA-PVA and PVA-PVA intermolecular polar interaction and SA-SA repulsion. Low viscosity SAl (50 mPas at 1%) enabled higher SA loadings without significantly increasing mixture viscosities, producing more cylindrical fibers. All aqueous mixtures containing 33.3-60% SAl (5.68-7.15% total SAl-PVA) had viscosities ranging from 530 to 3600 mPas and could be electrospun continuously for at least 48 h. The SA-PVA hybrid fibers had diameters ranging from ca. 140 to 350 nm and were rendered stable in water via simultaneous ionic-crosslinking SA and crystallization of PVA (5% CaCl2 in 75% EtOH for 30 min). This aqueous electrospinning and physical crosslinking approach is a green and highly efficient alternative to create alginate hybrid fibers that are biologically compatible and ingestible for potential biomedical, food and other applications.

  9. Positioning lipid membrane domains in giant vesicles by micro-organization of aqueous cytoplasm mimic. (United States)

    Cans, Ann-Sofie; Andes-Koback, Meghan; Keating, Christine D


    We report localization of lipid membrane microdomains to specific "poles" of asymmetric giant vesicles (GVs) in response to local internal composition. Interior aqueous microdomains were generated in a simple model cytoplasm composed of a poly(ethyleneglycol) (PEG)/dextran aqueous two-phase system (ATPS) encapsulated in the vesicles. The GV membrane composition used here was a modification of a DOPC/DPPC/cholesterol mixture known to form micrometer-scale liquid ordered and liquid disordered domains; we added lipids with PEG 2000 Da-modified headgroups. Osmotically induced budding of the ATPS-containing GVs led to structures where the PEG-rich and dextran-rich interior aqueous phases were in contact with different regions of the vesicle membrane. Liquid ordered (L o) membrane domains rich in PEG-terminated lipids preferentially coated the PEG-rich aqueous phase vesicle "body", while coexisting liquid disordered (L d) membrane domains coated the dextran-rich aqueous phase "bud". Membrane domain positioning resulted from interactions between lipid headgroups and the interior aqueous polymer solutions, e.g., PEGylated headgroups with PEG and dextran polymers. Heating resulted first in patchy membranes where L o and L d domains no longer showed any preference for coating the PEG-rich vs dextran-rich interior aqueous volumes, and eventually complete lipid mixing. Upon cooling lipid domains again coated their preferred interior aqueous microvolume. This work shows that nonspecific interactions between interior aqueous contents and the membrane that encapsulates them can drive local chemical heterogeneity, and offers a primitive experimental model for membrane and cytoplasmic polarity in biological cells.

  10. Products Distribution of Meta-Oriented Aromatic Polyamide Needs Improvement

    Institute of Scientific and Technical Information of China (English)

    Sun Maojian


    @@ Capacity holding the second place in the world Metaoriented aromatic polya-mide fiber was first developed by DuPont of the United States. Commercial production began in the late 1960s.Today the world's capacity to produce meta-oriented aromatic polyamide fiber is 28 150t/a, and DuPont holds a 78% market share.

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


    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.

  12. High atmosphere–ocean exchange of semivolatile aromatic hydrocarbons

    KAUST Repository

    González-Gaya, Belén


    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.

  13. Bis-perfluoroalkylation of aromatic compounds with sodium perfluoroalkanesulfinates

    Institute of Scientific and Technical Information of China (English)

    LIU, Jin-Tao(刘金涛); LU, He-Jun(吕贺军)


    Bis-perfluoroalkylation of aromatic compounds such as dimethoxybenzenes (2,4,6), anisole (8), pyridine (10) and quinoline (13) was accomplished by reaction with excess sodium perfluoroalkanesulfinates, RFSO2Na (1), in the presence of Mn(OAc)3·2H2O under mild conditions. The reaction provides a facile method for the synthesis of bis-perfluoroalkylated aromatic compounds.

  14. C-Nucleosides Derived from Simple Aromatic Hydrocarbons. (United States)

    Chaudhuri, Narayan C; Ren, Rex X-F; Kool, Eric T


    We describe the synthesis, structure and DNA incorporation of a class of novel aromatic C-deoxynucleosides in which benzenes and larger polycyclic aromatics serve as DNA base analogs. Novel approaches have been developed for glycosidic bond formation and for epimenzation of the anomeric substitutents to β-configuration, and we describe some of the properties of such compounds in DNA.

  15. High atmosphere-ocean exchange of semivolatile aromatic hydrocarbons (United States)

    González-Gaya, Belén; Fernández-Pinos, María-Carmen; Morales, Laura; Méjanelle, Laurence; Abad, Esteban; Piña, Benjamin; Duarte, Carlos M.; Jiménez, Begoña; Dachs, Jordi


    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 102-103 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.

  16. Non-polar lipids characterization of Quinoa (Chenopodium quinoa) seed by comprehensive two-dimensional gas chromatography with flame ionization/mass spectrometry detection and non-aqueous reversed-phase liquid chromatography with atmospheric pressure chemical ionization mass spectrometry detection. (United States)

    Fanali, Chiara; Beccaria, Marco; Salivo, Simona; Tranchida, Peter; Tripodo, Giusy; Farnetti, Sara; Dugo, Laura; Dugo, Paola; Mondello, Luigi


    A chemical characterization of major lipid components, namely, triacylglycerols, fatty acids and the unsaponifiable fraction, in a Quinoa seed lipids sample is reported. To tackle such a task, non-aqueous reversed-phase high-performance liquid chromatography with mass spectrometry detection was employed. The latter was interfaced with atmospheric pressure chemical ionization for the analysis of triacylglycerols. The main triacylglycerols (>10%) were represented by OLP, OOL and OLL (P = palmitoyl, O = oleoyl, L = linoleoyl); the latter was present in the oil sample at the highest percentage (18.1%). Furthermore, fatty acid methyl esters were evaluated by gas chromatography with flame ionization detection. 89% of the total fatty acids was represented by unsaturated fatty acid methyl esters with the greatest percentage represented by linoleic and oleic acids accounting for approximately 48 and 28%, respectively. An extensive characterization of the unsaponifiable fraction of Quinoa seed lipids was performed for the first time, by using comprehensive two-dimensional gas chromatography with dual mass spectrometry/flame ionization detection. Overall, 66 compounds of the unsaponifiable fraction were tentatively identified, many constituents of which (particularly sterols) were confirmed by using gas chromatography with high-resolution time-of-flight mass spectrometry.

  17. Fabrication of semi-aromatic polyamide/spherical mesoporous silica nanocomposite reverse osmosis membrane with superior permeability (United States)

    Li, Qiang; Yu, Hui; Wu, Feiyang; Song, Jie; Pan, Xianhui; Zhang, Meng


    Semi-aromatic polyamide (SAP)/spherical mesoporous silica nanocomposite reverse osmosis (RO) membrane was successfully fabricated using m-phenylene diamine aqueous solution and cyclohexane-1,3,5-tricarbonyl chloride/mesoporous-silica-sphere (MSS) organic solution as main raw materials. The experimental suggests that the microstructures and surface features are significantly different from those of the contrast samples (the full- and semi-aromatic polyamide membranes), including the surface morphology, polymer framework structure, surface charge density, hydrophilicity, and the thickness of barrier layer. It was observed that many MSSs with ca. 1.5 nm of pore size are evenly embedded on the surface of the fabricated SAP/MSS RO membrane. Furthermore, the separation performance testing results indicate that the permeabilities range from 62.53 to 72.73 L/m2 h with the increase of the introduced MSSs from 0.02 to 0.08 w/v % under 1.5 MPa operating pressure and 2000 mg/L NaCl solution, which is obviously better than the contrast samples. Simultaneously, their salt rejections can be still maintained at a comparable level (94.78-91.46%). The excellent separation performance of the nanocomposite RO membrane is closely related to the higher-freedom-degree semi-aromatic framework, the incorporation of MSSs, the improved surface hydrophilicity, the thinner barrier layer, and the enhanced surface negative charge density.

  18. 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)


    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.


    NARCIS (Netherlands)



    Just as He-3 --> can be approximately characterized as a polarized neutron target, polarized Li-6D has been advocated as a good isoscalar nuclear target for the extraction of the polarized gluon content of the nucleon. The original argument rests upon a presumed ''alpha + deuteron'' picture of Li-6,

  20. Neutral Diboron Analogues of Archetypal Aromatic Species by Spontaneous Cycloaddition. (United States)

    Arrowsmith, Merle; Böhnke, Julian; Braunschweig, Holger; Celik, Mehmet Ali; Claes, Christina; Ewing, William C; Krummenacher, Ivo; Lubitz, Katharina; Schneider, Christoph


    Among the numerous routes organic chemists have developed to synthesize benzene derivatives and heteroaromatic compounds, transition-metal-catalyzed cycloaddition reactions are the most elegant. In contrast, cycloaddition reactions of heavier alkene and alkyne analogues, though limited in scope, proceed uncatalyzed. In this work we present the first spontaneous cycloaddition reactions of lighter alkene and alkyne analogues. Selective addition of unactivated alkynes to boron-boron multiple bonds under ambient conditions yielded diborocarbon equivalents of simple aromatic hydrocarbons, including the first neutral 6 π-aromatic diborabenzene compound, a 2 π-aromatic triplet biradical 1,3-diborete, and a phosphine-stabilized 2 π-homoaromatic 1,3-dihydro-1,3-diborete. DFT calculations suggest that all three compounds are aromatic and show frontier molecular orbitals matching those of the related aromatic hydrocarbons, C6 H6 and C4 H4 (2+) , and homoaromatic C4 H5 (+) .

  1. (Hetero)aromatics from dienynes, enediynes and enyne-allenes. (United States)

    Raviola, Carlotta; Protti, Stefano; Ravelli, Davide; Fagnoni, Maurizio


    The construction of aromatic rings has become a key objective for organic chemists. While several strategies have been developed for the functionalization of pre-formed aromatic rings, the direct construction of an aromatic core starting from polyunsaturated systems is yet a less explored field. The potential of such reactions in the formation of aromatics increased at a regular pace in the last few years. Nowadays, there are reliable and well-established procedures to prepare polyenic derivatives, such as dienynes, enediynes, enyne-allenes and hetero-analogues. This has stimulated their use in the development of innovative cycloaromatizations. Different examples have recently emerged, suggesting large potential of this strategy in the preparation of (hetero)aromatics. Accordingly, this review highlights the recent advancements in this field and describes the different conditions exploited to trigger the process, including thermal and photochemical activation, as well as the use of transition metal catalysis and the addition of electrophiles/nucleophiles or radical species.

  2. North Polar Cap (United States)


    [figure removed for brevity, see original site] This week we will be looking at five examples of laminar wind flow on the north polar cap. On Earth, gravity-driven south polar cap winds are termed 'catabatic' winds. Catabatic winds begin over the smooth expanse of the cap interior due to temperature differences between the atmosphere and the surface. Once begun, the winds sweep outward along the surface of the polar cap toward the sea. As the polar surface slopes down toward sealevel, the wind speeds increase. Catabatic wind speeds in the Antartic can reach several hundreds of miles per hour. In the images of the Martian north polar cap we can see these same type of winds. Notice the streamers of dust moving downslope over the darker trough sides, these streamers show the laminar flow regime coming off the cap. Within the trough we see turbulent clouds of dust, kicked up at the trough base as the winds slow down and enter a chaotic flow regime. The horizontal lines in these images are due to framelet overlap and lighting conditions over the bright polar cap. Image information: VIS instrument. Latitude 86.5, Longitude 64.5 East (295.5 West). 40 meter/pixel resolution. Note: this THEMIS visual image has not been radiometrically nor geometrically calibrated for this preliminary release. An empirical correction has been performed to remove instrumental effects. A linear shift has been applied in the cross-track and down-track direction to approximate spacecraft and planetary motion. Fully calibrated and geometrically projected images will be released through the Planetary Data System in accordance with Project policies at a later time. NASA's Jet Propulsion Laboratory manages the 2001 Mars Odyssey mission for NASA's Office of Space Science, Washington, D.C. The Thermal Emission Imaging System (THEMIS) was developed by Arizona State University, Tempe, in collaboration with Raytheon Santa Barbara Remote Sensing. The THEMIS investigation is led by Dr. Philip Christensen

  3. Density functional theory based study of magnetic interaction in bis-oxoverdazyl diradicals connected by different aromatic couplers. (United States)

    Bhattacharya, Debojit; Misra, Anirban


    We design and investigate 11 different bis-oxoverdazyl diradicals connected by various aromatic couplers for their magnetic properties. The intramolecular magnetic exchange coupling constants (J) have been calculated using a broken symmetry approach in DFT framework. The J values are explained using spin polarization maps and magnetic orbitals. Isotropic hyperfine coupling constants (hfcc's) have been calculated for all the species in vacuum. The computed hfcc values also support intramolecular magnetic interactions. It has been found that some of the diradicals have ferromagnetic character while the others are antiferromagnetic in nature.

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

    KAUST Repository

    Zeng, Zebing


    © 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. Kinetics study of aqueous sorption of phenanthrene to humic acids and sediments

    Institute of Scientific and Technical Information of China (English)

    LIU Rui-xia; TANG Hong-xiao


    The sorption behavior was determined for a model polycyclic aromatic hydrocarbon(PAH), i.e., phenanthrene(PHN), from water to three humic acids(HAs) and three sediments in different reacting time. The chemical compositions of HA samples were measured using cross polarization magic angle spinning carbon-13(CPMAS 13C) NMR along with elemental analysis. The dissolved humic substances dissociating from solid HAs and sediments were characterized by 1H NMR. The experiments indicated that the sorption modes and mechanisms of natural sorbents for PHN varied significantly between short(<7 d) and long contact time and the reaction time should be taken into consideration in studying the overall sorption process. The sorption capacity() and exponent() might be relative to the properties of dissolved humic materials in initial stage but the solid aromatic organic matter after long time reaction. According to the experiments performed in this investigation and the previous researches, a conceptive sorption model was established.

  6. Chlorination of 2-phenoxypropanoic acid with NCP in aqueous acetic acid: using a novel ortho-para relationship and the para/meta ratio of substituent effects for mechanism elucidation. (United States)

    Segurado, Manuel A P; Reis, João Carlos R; de Oliveira, Jaime D Gomes; Kabilan, Senthamaraikannan; Shanthi, Manohar


    Rate constants were measured for the oxidative chlorodehydrogenation of (R,S)-2-phenoxypropanoic acid and nine ortho-, ten para- and five meta-substituted derivatives using (R,S)-1-chloro-3-methyl-2,6-diphenylpiperidin-4-one (NCP) as chlorinating agent. The kinetics was run in 50% (v/v) aqueous acetic acid acidified with perchloric acid under pseudo-first-order conditions with respect to NCP at temperature intervals of 5 K between 298 and 318 K, except at the highest temperature for the meta derivatives. The dependence of rate constants on temperature was analyzed in terms of the isokinetic relationship (IKR). For the 20 reactions studied at five different temperatures, the isokinetic temperature was estimated to be 382 K, which suggests the preferential involvement of water molecules in the rate-determining step. The dependence of rate constants on meta and para substitution was analyzed using the tetralinear extension of the Hammett equation. The parameter lambda for the para/meta ratio of polar substituent effects was estimated to be 0.926, and its electrostatic modeling suggests the formation of an activated complex bearing an electric charge near the oxygen atom belonging to the phenoxy group. A new approach is introduced for examining the effect of ortho substituents on reaction rates. Using IKR-determined values of activation enthalpies for a set of nine pairs of substrates with a given substituent, a linear correlation is found between activation enthalpies of ortho and para derivatives. The correlation is interpreted in terms of the selectivity of the reactant toward para- or ortho-monosubstituted substrates, the slope of which being related to the ortho effect. This slope is thought to be approximated by the ratio of polar substituent effects from ortho and para positions in benzene derivatives. Using the electrostatic theory of through-space interactions and a dipole length of 0.153 nm, this ratio was calculated at various positions of a charged reaction

  7. Polarization singularity anisotropy: determining monstardom

    CERN Document Server

    Dennis, Mark R


    C points, that is isolated points of circular polarization in transverse fields of varying polarization, are classified morphologically into three distinct types, known as lemons, stars and monstars. These morphologies are interpreted here according to two natural parameters associated with the singularity, namely the anisotropy of the C point, and the polarization azimuth on the anisotropy axis. In addition to providing insight into singularity morphology, this observation applies to the densities of the various morphologies in isotropic random polarization speckle fields.

  8. Surfactant-enhanced desorption and biodegradation of polycyclic aromatic hydrocarbons in contaminated soil. (United States)

    Zhu, Hongbo; Aitken, Michael D


    We evaluated two nonionic surfactants, one hydrophobic (Brij 30) and one hydrophilic (C(12)E(8)), for their ability to enhance the biodegradation of polycyclic aromatic hydrocarbons (PAHs) in contaminated soil after it had been treated in an aerobic bioreactor. The effects of each surfactant were evaluated at doses corresponding to equilibrium aqueous-phase concentrations well above the surfactant's critical micelle concentration (CMC), slightly above the CMC, and below the CMC. The concentrations of all 3- and 4-ring PAHs were significantly lower in the soil amended with Brij 30 at the two lower doses compared to controls, whereas removal of only the 3-ring PAHs was significantly enhanced at the highest Brij 30 dose. In contrast, C(12)E(8) did not enhance PAH removal at any dose. In the absence of surfactant, PAH desorbed from the soil over an 18 day period. Brij 30 addition at the lowest dose significantly increased the desorption of most PAHs, whereas the addition of C(12)E(8) at the lowest dose actually decreased the desorption of all PAHs. These findings suggest that the effects of the two surfactants on PAH biodegradation could be explained by their effects on PAH bioavailability. Overall, this study demonstrates that the properties of the surfactant and its dose relative to the corresponding aqueous-phase concentration are important factors in designing systems for surfactant-enhanced bioremediation of PAH-contaminated soils in which PAH bioavailability is limited.

  9. Differential immunomodulatory responses to nine polycyclic aromatic hydrocarbons applied by passive dosing. (United States)

    Oostingh, Gertie J; Smith, Kilian E C; Tischler, Ulrike; Radauer-Preiml, Isabella; Mayer, Philipp


    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 bronchial epithelial cells were determined by analysing the cytokine promoter expression of 4 different inflammatory cytokines using stably transfected recombinant A549 cell lines. Diverse immunomodulatory responses were found with the highest induction observed for the most hydrophobic PAHs chrysene, benzo(a)antracene and benzo(a)pyrene. Cytokine promoter expression was then studied in dose response experiments with acenaphthene, phenanthrene and benzo(a)anthracene. The strongest induction was observed for benzo(a)anthracene. Cell viability analysis was performed and showed that none of the PAHs induced cytotoxicity at any of the concentrations tested. Overall, this study shows that (1) immunomodulatory effects of PAHs can be studied in vitro at controlled freely dissolved concentrations, (2) the most hydrophobic PAHs were the strongest inducers and (3) induction was often higher at lower exposure levels and decreased then with concentration despite the apparent absence of cytotoxicity.

  10. Extraction-photometric determination of toxic aromatic hydroxy compounds in water

    Energy Technology Data Exchange (ETDEWEB)

    Korenman, Y.I.; Bortnikova, R.N.; Bolotov, V.M.; Taldykina, S.N.; Sel' manshchuk, N.N.; Tishchenko, Y.M.


    A rapid (1 hr) and accurate method with the use of simple equipment was developed to determine phenol and its derivatives in water. The method was tested on purified waste water from phenol-producing plants not containing other aromatic compounds and on water from the Oka River collected near Dzerzhinsk. The following conditions are recommended: 180 g of anhydrous Na/sub 2/SO/sub 4/ is added to 1 liter of water to be analyzed; this is acidified to pH 2 with HCl. Samples containing nitrophenols should be acidified to pH 0-0.5. An organic solvent with a distribution coefficient not below 30-40 (e.g., butyl acetate) is used to which 20 mol.% tributyl phosphate or camphor has been added. Under these conditions a 100-fold concentration is obtained.Further extraction with alkalinized aqueous solutions of the photometric reagent (p-nitroaniline or diazoticized sulfanilic acid) produces an additional three-fold concentration. Test data on determining phenol in aqueous solutions containing sodium sulfate with the use of butyl acetate plus 20 mol.% tributyl phosphate showed a high degree of concentration (about 330) and the possibility of determining phenol in maximum allowable concentrations (about 0.001 mg/liter).

  11. Prediction of mono- and polycyclic aromatic hydrocarbon degradation in spiked soils using cyclodextrin extraction

    Energy Technology Data Exchange (ETDEWEB)

    Allan, Ian J. [School of Environmental Sciences, University of East Anglia, Norwich NR4 7TJ (United Kingdom); Semple, Kirk T. [Department of Environmental Sciences, Lancaster University, LA1 4YQ (United Kingdom); Hare, Rina [Alcontrol Laboratories, Chester CH5 3US (United Kingdom); Reid, Brian J. [Alcontrol Laboratories, Chester CH5 3US (United Kingdom)]. E-mail:


    In this study, an aqueous-based hydroxypropyl-{beta}-cyclodextrin (HPCD) extraction technique was assessed for its capacity to determine the microbially degradable fraction of mono- and polycyclic aromatic hydrocarbons in four dissimilar soils. A linear relationship (slope = 0.90; R {sup 2} = 0.89), approaching 1:1 between predicted and observed phenanthrene mineralization, was demonstrated for the cyclodextrin extraction; however, the water only extraction underestimated the microbially available fraction by a factor of three (slope = 3.35; R {sup 2} = 0.64). With respect to determining the mineralizable fraction of p-cresol in soils, the cyclodextrin extraction (slope = 0.94; R {sup 2} = 0.84) was more appropriate than the water extraction (slope = 1.50; R {sup 2} = 0.36). Collectively, these results suggested that the cyclodextrin extraction technique was suitable for the prediction of the mineralizable fraction of representative PAHs and phenols present in dissimilar soils following increasing soil-contaminant contact times. The assessment of the microbial availability of contaminants in soils is important for a more representative evaluation of soil contamination. - An aqueous-based HPCD extraction technique was more appropriate than the water extraction in prediction of the mineralizable fraction of phenanthrene and p-cresol present in a range of dissimilar soils.

  12. Cadmium-109 Radioisotope Adsorption onto Polypyrrole Coated Sawdust of Dryobalanops aromatic: Kinetics and Adsorption Isotherms Modelling (United States)

    Olatunji, Michael Adekunle; Khandaker, Mayeen Uddin; Amin, Yusoff Mohd; Mahmud, Habibun Nabi Muhammad Ekramul


    A radiotracer study was conducted to investigate the removal characteristics of cadmium (109Cd) from aqueous solution by polypyrrole/ sawdust composite. Several factors such as solution pH, sorbent dosage, initial concentration, contact time, temperature and interfering metal ions were found to have influence on the adsorption process. The kinetics of adsorption was relatively fast, reaching equilibrium within 3 hours. A lowering of the solution pH reduced the removal efficiency from 99.3 to ~ 46.7% and an ambient temperature of 25°C was found to be optimum for maximum adsorption. The presence of sodium and potassium ions inhibited 109Cd removal from its aqueous solution. The experimental data for 109Cd adsorption showed a very good agreement with the Langmuir isotherm and a pseudo-first order kinetic model. The surface condition of the adsorbent before and after cadmium loading was investigated using BET, FESEM and FTIR. Considering the low cost of the precursor’s materials and the toxicity of 109Cd radioactive metal, polypyrrole synthesized on the sawdust of Dryobalanops aromatic could be used as an efficient adsorbent for the removal of 109Cd radioisotope from radionuclide-containing effluents. PMID:27706232

  13. Synchronized aromaticity as an enthalpic driving force for the aromatic Cope rearrangement. (United States)

    Babinski, David J; Bao, Xiaoguang; El Arba, Marie; Chen, Bo; Hrovat, David A; Borden, Weston Thatcher; Frantz, Doug E


    We report herein experimental and theoretical evidence for an aromatic Cope rearrangement. Along with several successful examples, our data include the first isolation and full characterization of the putative intermediate that is formed immediately after the initial [3,3] sigmatropic rearrangement. Calculations at the B3LYP/6-31G(d) level of theory predict reaction energy barriers in the range 22-23 kcal/mol for the [3,3]-rearrangement consistent with the exceptionally mild reaction conditions for these reactions. The experimental and computational results support a significant enthalpic contribution of the concomitant pyrazole ring formation that serves as both a kinetic and thermodynamic driving force for the aromatic Cope rearrangement.

  14. Polarization of a Helium-Neon Laser. (United States)

    Jones, Edwin R.


    Describes an experiment that involves measuring the intensity of laser light passed by a linear polarizer. Discusses polarization effects, orthogonal polarizations, instrumentation, and further experiments. (JRH)

  15. Polyenamines from aromatic diacetylenic diketones and diamines (United States)

    Hergenrother, Paul M. (Inventor); Bass, Robert G. (Inventor); Sinsky, Mark S. (Inventor); Connell, John W. (Inventor)


    The synthesis and characterization of several polyenamine ketones are discussed wherein conjugated diacetylenic diketones and aromatic diamines are used as a route to the formation of high molecular weight polyenamine ketones which exhibit good mechanical properties and can be cast into creasible films. Typical polymerization conditions involved the reaction of stoichiometric amounts of 1,4- or 1,3-PPPO and a diamine at 60 to 130 C in m-cresol at (w/w) solids content of 8 to 26% for a specified period of time under a nitrogen atmosphere. Novel polyenamine ketones were prepared with inherent viscosities as high as 1.99 dl/g and tough, clear amber films with tensile strengths of 12,400 psi and tensile moduli of 397,000 psi were cast from solutions of the polymers in chloroform. In most cases, the elemental analyses for the polyenamine ketones agree within + or - 0.3% of the theoretical values.

  16. Structural Evolution of Interstellar Polycyclic Aromatic Hydrocarbons (United States)

    Hammonds, Mark; Candian, Alessandra; Mori, Tamami; Usui, Fumihiko; Onaka, Takashi


    Polycyclic Aromatic Hydrocarbons (PAHs) are an important reservoir for molecular carbon in the interstellar medium (ISM), and investigations into their chemistry and behaviour may be important to the understanding of how carbon is processed from simple forms into complex prebiotic molecules such as those detected in chondritic meteorites. In this study, infrared astronomical data from AKARI and other observatories are used together with laboratory and theoretical data to study variations in the structure of emitting PAHs in interstellar environments using spectroscopic decomposition techniques and bands arising from carbon-hydrogen bond vibrations at wavelengths from 3 - 14 microns. Results and inferences are discussed in terms of the processing of large carbonaceous molecules in astrophysical environments.

  17. The biodegradation vs. biotransformation of fluorosubstituted aromatics. (United States)

    Kiel, Martina; Engesser, Karl-Heinrich


    Fluoroaromatics are widely and--in recent years--increasingly used as agrochemicals, starting materials for chemical syntheses and especially pharmaceuticals. This originates from the special properties the carbon-fluorine bond is imposing on organic molecules. Hence, fluoro-substituted compounds more and more are considered to be important potential environmental contaminants. On the other hand, the microbial potentials for their transformation and mineralization have received less attention in comparison to other haloaromatics. Due to the high electronegativity of the fluorine atom, its small size, and the extraordinary strength of the C-F bond, enzymes and mechanisms known to facilitate the degradation of chloro- or bromoarenes are not necessarily equally active with fluoroaromatics. Here, we review the literature on the microbial degradation of ring and side-chain fluorinated aromatic compounds under aerobic and anaerobic conditions, with particular emphasis being placed on the mechanisms of defluorination reactions.

  18. Photochemically induced oscillations of aromatic pentazadienes

    Energy Technology Data Exchange (ETDEWEB)

    Kunz, T.; Hahn, C.; Wokaun, A. [Paul Scherrer Inst. (PSI), Villigen (Switzerland)


    Aromatic pentazadienes are used to enhance the laser induced ablation of standard polymers with low absorption in the UV. Therefore the photochemistry of substituted 1,5-diaryl-3-alkyl-1,4-pentazadiene monomers was studied with a pulsed excimer laser as irradiation source. The net photochemical reaction proceeds in an overall one-step pathway A{yields}B. Quantum yields for the laser decomposition were determined to be up to 10%. An oscillating behaviour of the absorption was found during the dark period following the irradiation. The temperature dependence of this dark reaction has been studied. An attempt to model this behaviour in terms of a non-linear coupling between heat released, heat transfer, and reaction kinetics will be described. (author) 4 figs., 4 refs.

  19. Planar cell polarity signaling: a common mechanism for cellular polarization. (United States)

    Jenny, Andreas; Mlodzik, Marek


    Epithelial cells frequently display--in addition to the common apical-basolateral polarity--a polarization within the plane of the epithelium. This is commonly referred to as planar cell polarity (PCP) or tissue polarity. Examples of vertebrate PCP include epithelial patterning in the skin and inner ear, and also the morphogenetic movements of mesenchymal cells during convergent extension at gastrulation. In Drosophila, all adult epithelial structures of the cuticle are polarized within the plane. This review presents recent results and new insights into the molecular mechanisms underlying the establishment of PCP, and compares and contrasts the intriguing similarities between PCP signaling in Drosophila and vertebrates.

  20. Polarized electrogowdy spacetimes censored

    Energy Technology Data Exchange (ETDEWEB)

    Nungesser, Ernesto, E-mail: ernesto.nungesser@aei.mpg.d [Max-Planck-Institut fuer Gravitationsphysik, Albert-Einstein-Institut, Am Muehlenberg 1, 14476 Potsdam (Germany)


    A sketch of the proof of strong cosmic censorship is presented for a class of solutions of the Einstein-Maxwell equations, those with polarized Gowdy symmetry. A key element of the argument is the observation that by means of a suitable choice of variables the central equations in this problem can be written in a form where they are identical to the central equations for general (i.e. non-polarized) vacuum Gowdy spacetimes. Using this it is seen that the results of Ringstroem on strong cosmic censorship in the vacuum case have implications for the Einstein-Maxwell case. Working out the geometrical meaning of these analytical results leads to the main conclusion.

  1. Galactic Diffuse Polarized Emission

    Indian Academy of Sciences (India)

    Ettore Carretti


    Diffuse polarized emission by synchrotron is a key tool to investigate magnetic fields in the Milky Way, particularly the ordered component of the large scale structure. Key observables are the synchrotron emission itself and the RM is by Faraday rotation. In this paper the main properties of the radio polarized diffuse emission and its use to investigate magnetic fields will be reviewed along with our current understanding of the galactic magnetic field and the data sets available. We will then focus on the future perspective discussing RM-synthesis – the new powerful instrument devised to unlock the information encoded in such an emission – and the surveys currently in progress like S-PASS and GMIMS.

  2. Measuring Polarization with DASI

    CERN Document Server

    Leitch, E M; Pryke, C L; Reddall, B; Sandberg, E S; Dragovan, M; Carlstrom, J E; Halverson, N W; Holzapfel, W L


    We describe an experiment to measure the polarization of the Cosmic Microwave Background (CMB) with the Degree Angular Scale Interferometer (DASI), a compact microwave interferometer optimized to detect CMB anisotropy at multipoles 140 to 900. The telescope has operated at the Amundsen-Scott South Pole research station since 2000 January. The telescope was retrofit as a polarimeter during the 2000--2001 austral summer, and throughout the 2001 and 2002 austral winters has made observations of the CMB with sensitivity to all four Stokes parameters. The telescope performance has been extensively characterized through observations of artificial sources, the Moon, and polarized and unpolarized Galactic sources. In 271 days of observation, DASI has differenced the CMB fluctuations in two fields to an rms noise level of 2.8 uK.

  3. Polarization Diffusion from Spacetime Uncertainty

    CERN Document Server

    Contaldi, Carlo; Philpott, Lydia


    A model of Lorentz invariant random fluctuations in photon polarization is presented. The effects are frequency dependent and affect the polarization of photons as they propagate through space. We test for this effect by confronting the model with the latest measurements of polarization of Cosmic Microwave Background (CMB) photons.

  4. Alternating-Polarity Arc Welding (United States)

    Schwinghamer, R. J.


    Brief reversing polarity of welding current greatly improves quality of welds. NASA technical memorandum recounts progress in art of variable-polarity plasma-arc (VPPA) welding, with emphasis on welding of aluminum-alloy tanks. VPPA welders offer important advantages over conventional single-polarity gas/tungsten arc welders.

  5. Polarization losses in reflector antennas (United States)

    Safak, M.; Yazgan, E.


    Various definitions for polarization-loss efficiency of Cassegrainian and front-fed reflectors are compared. The effects of flare angle, feed taper and the feed pattern asymmetry on the polarization-loss efficiency are investigated. The definitions based on aperture fields are shown to be inadequate and far fields must be used for calculating the polarization losses.

  6. Environmental Remediation: Removal of polycyclic aromatic hydrocarbons

    Energy Technology Data Exchange (ETDEWEB)

    Nkansah, Marian Asantewah


    Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous persistent semi-volatile organic compounds. They are contaminants that are resistant to degradation and can remain in the environment for long periods due to their high degree of conjugation, and aromaticity. PAHs are present in industrial effluents as products of incomplete combustion processes of organic compounds. Petroleum, coal and shale oil contain extremely complex mixtures of these PAHs, and their transport and refining process can also result in the release of PAHs. It is therefore prudent that such effluents are treated before discharge into the environment. In this project, different approaches to the treatment of PAHs have been investigated. Hydrous pyrolysis has been explored as a potential technique for degrading PAHs in water using anthracene as a model compound. The experiments were performed under different conditions of temperature, substrate, redox systems and durations. The conditions include oxidising systems comprising pure water, hydrogen peroxide and Nafion-SiO2 solid catalyst in water; and reducing systems of formic acid and formic acid / Nafion-SiO2 / Pd-C catalysts to assess a range of reactivities. Products observed in GCMS analysis of the extract from the water phase include anthrone, anthraquinone, xanthone and multiple hydro-anthracene derivatives (Paper I). In addition a modified version of the Nafion-SiO2 solid catalyst in water oxidising system was tested; and reducing systems of formic acid and formic acid / Nafion-SiO2 / Pd-C catalysts were adopted for the conversion of a mixture of anthracene, fluorene and fluoranthene. The rate of conversion in the mixture was high as compared to that of only anthracene (Paper II). Also the use of LECA (Lightweight expanded clay aggregates) as an adsorbent (Paper III) for PAHs (phenanthrene, fluoranthene and pyrene) removal from water has been.(Author)

  7. Polarization induced doped transistor

    Energy Technology Data Exchange (ETDEWEB)

    Xing, Huili (Grace); Jena, Debdeep; Nomoto, Kazuki; Song, Bo; Zhu, Mingda; Hu, Zongyang


    A nitride-based field effect transistor (FET) comprises a compositionally graded and polarization induced doped p-layer underlying at least one gate contact and a compositionally graded and doped n-channel underlying a source contact. The n-channel is converted from the p-layer to the n-channel by ion implantation, a buffer underlies the doped p-layer and the n-channel, and a drain underlies the buffer.

  8. Transverse polarization in ; production

    Indian Academy of Sciences (India)

    Saurabh D Rindani


    With the use of transverse polarization (TP), a CP-odd and T-odd observable can be constructed when the final-state particles are self-conjugate. In the case of production, this observable can be used to probe a certain effective four-point + - CP-violating coupling, not accessible without TP. Effective CP-violating coupling does not contribute to this observable. A similar observable in production can be used to probe + - four-point couplings.

  9. Development of linear free energy relationships for aqueous phase radical-involved chemical reactions. (United States)

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


    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.

  10. Release behavior and formation mechanism of polycyclic aromatic hydrocarbons during coal pyrolysis. (United States)

    Gao, Meiqi; Wang, Yulong; Dong, Jie; Li, Fan; Xie, Kechang


    Polycyclic aromatic hydrocarbons (PAHs) are major environmental pollutants. They have attracted considerable attention due to their severe potential carcinogenic, mutagenic and genotoxic effects on human health. In this study, five different rank coals from China were pyrolyzed using pyro-probe CDS 5250 and the release behavior of 16 PAHs under different pyrolysis conditions were studied by Gas Chromatography-Mass Spectrometer (GC-MS). The structural characteristics of the five coals were determined by Cross-Polarization/Magic Angle Spinning Carbon-13 Nuclear Magnetic Resonance (CP/MAS (13)C NMR) spectroscopy, and then the factors influencing the formation of PAHs during coal pyrolysis were discussed together with the coal structural data. It was shown that the amount of PAHs generated during coal pyrolysis was largely related to coal rank and followed the order of medium metamorphic coal > low metamorphic coal > high metamorphic coal. The amount of total PAHs varied as the temperature was increased from 400 °C to 1200 °C, which showed a trend of first increasing and then decreasing, with the maximum value at 800 °C. Moreover, the species of PAHs released varied with pyrolysis temperatures. When the temperature was lower than 800 °C, the small ring PAHs were the most abundant, while the proportion of heavy rings increased at higher temperature. The results indicate that the formation of PAHs during coal pyrolysis depends on the structure of the coal. The species and amounts of PAHs generated during coal pyrolysis are closely related to the contents of protonated aromatic carbons and bridging ring junction aromatic carbons present in the coal structure.

  11. Inhibitory effects of polycyclic aromatic hydrocarbons (PAHs) on photosynthetic performance are not related to their aromaticity. (United States)

    Jajoo, Anjana; Mekala, Nageswara Rao; Tomar, Rupal Singh; Grieco, Michele; Tikkanen, Mikko; Aro, Eva-Mari


    Polycyclic aromatic hydrocarbons (PAHs) are very toxic and highly persistent environmental pollutants which accumulate in soil and affect growth of the plants adversely. This study aims to investigate inhibitory effects of 3 major PAH particularly on photosynthetic processes in Arabidopsis thaliana grown in soil treated with PAH. The 3 PAH chosen differ from each other in aromaticity (number of rings) comprising their structure (2 rings: naphthalene, 3 rings: anthracene and 4 rings: pyrene). Several growth parameters and Chlorophyll a fluorescence was monitored in PAH treated plants. BN-PAGe analysis was done in order to get information about change in the protein conformation. PAH treatment led to increased value of Fo which collaborated with increase in the amount of free LHC as seen through BN-Page analysis. Thus PAH were found to inhibit PS II photochemistry and caused distinct change in pigment composition. However the results led us to infer that 3-ring anthracence is more inhibitory as compared to 2-ring naphthalene and 4-ring pyrene. This indicates that aromaticity of PAH is unrelated to their response on photosynthetic processes.

  12. Exploring aromatic chemical space with NEAT: novel and electronically equivalent aromatic template. (United States)

    Tu, Meihua; Rai, Brajesh K; Mathiowetz, Alan M; Didiuk, Mary; Pfefferkorn, Jeffrey A; Guzman-Perez, Angel; Benbow, John; Guimarães, Cristiano R W; Mente, Scot; Hayward, Matthew M; Liras, Spiros


    In this paper, we describe a lead transformation tool, NEAT (Novel and Electronically equivalent Aromatic Template), which can help identify novel aromatic rings that are estimated to have similar electrostatic potentials, dipoles, and hydrogen bonding capabilities to a query template; hence, they may offer similar bioactivity profiles. In this work, we built a comprehensive heteroaryl database, and precalculated high-level quantum mechanical (QM) properties, including electrostatic potential charges, hydrogen bonding ability, dipole moments, chemical reactivity, and othe properties. NEAT bioisosteric similarities are based on the electrostatic potential surface calculated by Brood, using the precalculated QM ESP charges and other QM properties. Compared with existing commercial lead transformation software, (1) NEAT is the only one that covers the comprehensive heteroaryl chemical space, and (2) NEAT offers a better characterization of novel aryl cores by using high-evel QM properties that are relevant to molecular interactions. NEAT provides unique value to medicinal chemists quickly exploring the largely uncharted aromatic chemical space, and one successful example of its application is discussed herein.

  13. PEPPo: Using a Polarized Electron Beam to Produce Polarized Positrons

    Energy Technology Data Exchange (ETDEWEB)

    Adeyemi, Adeleke H. [Hampton Univ., Hampton, VA (United States); et al.


    Polarized positron beams have been identified as either an essential or a significant ingredient for the experimental program of both the present and next generation of lepton accelerators (JLab, Super KEK B, ILC, CLIC). An experiment demonstrating a new method for producing polarized positrons has been performed at the Continuous Electron Beam Accelerator Facility at Jefferson Lab. The PEPPo (Polarized Electrons for Polarized Positrons) concept relies on the production of polarized e⁻/e⁺ pairs from the bremsstrahlung radiation of a longitudinally polarized electron beam interacting within a high-Z conversion target. PEPPo demonstrated the effective transfer of spin-polarization of an 8.2 MeV/c polarized (P~85%) electron beam to positrons produced in varying thickness tungsten production targets, and collected and measured in the range of 3.1 to 6.2 MeV/c. In comparison to other methods this technique reveals a new pathway for producing either high-energy or thermal polarized positron beams using a relatively low polarized electron beam energy (~10MeV) .This presentation will describe the PEPPo concept, the motivations of the experiment and high positron polarization achieved.

  14. Polar Business Design

    Directory of Open Access Journals (Sweden)

    Sébastien Caisse


    Full Text Available Polar business design aims to enable entrepreneurs, managers, consultants, researchers, and business students to better tackle model-based analysis, creation, and transformation of businesses, ventures, and, more generically, collective endeavors of any size and purpose. It is based on a systems-thinking approach that builds on a few interrelated core concepts to create holistic visual frameworks. These core concepts act as poles linked by meaningful dyads, flows, and faces arranged in geometric shapes. The article presents two such polar frameworks as key findings in an ongoing analytic autoethnography: the three-pole Value−Activity−Stakeholder (VAS triquetra and the four-pole Offer−Creation−Character−Stakeholder (OCCS tetrahedron. The VAS triquetra is a more aggregated model of collective endeavors. The OCCS tetrahedron makes a trade-off between a steeper learning curve and deeper, richer representation potential. This article discusses how to use these two frameworks as well as their limits, and explores the potential that polar business design offers for future research.

  15. 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.


    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)

  16. Metabolism of mutagenic polycyclic aromatic hydrocarbons by photosynthetic algal species. (United States)

    Schoeny, R; Cody, T; Warshawsky, D; Radike, M


    Polycyclic aromatic hydrocarbons (PAH) known to produce carcinogenic and mutagenic effects have been shown to contaminate waters, sediments and soils. While it is accepted that metabolites of these compounds are responsible for most of their biological effects in mammals, their metabolism, and to a large extent their bioactivity, in aquatic plants have not been explored. Cultures of photosynthetic algal species were assayed for their ability to metabolize benzo[a]pyrene (BaP), a carcinogenic PAH under conditions which either permitted (white light) or disallowed (gold light) photooxidation of the compound. Growth of Selenastrum capricornutum, a fresh-water green alga, was completely inhibited when incubated in white light with 160 micrograms BaP/l medium. By contrast concentrations at the upper limit of BaP solubility in aqueous medium had no effect on algal growth when gold light was used. BaP quinones and phenol derivatives were found to inhibit growth of Selenastrum under white light incubation. BaP phototoxicity and metabolism were observed to be species-specific. All 3 tested species of the order Chlorococcales were growth-inhibited by BaP in white light whereas neither the green alga Chlamydomonas reinhardtii nor a blue-green, a yellow-green or an euglenoid alga responded in this fashion. Assays of radiolabeled BaP metabolism in Selenastrum showed that the majority of radioactivity associated with BaP was found in media as opposed to algal cell pellets, that the extent of metabolism was BaP concentration dependent, and that the proportion of various metabolites detected was a function of the light source. After gold light incubation, BaP diols predominated while after white light treatment at equal BaP concentrations, the 3,6-quinone was found in the highest concentration. Extracted material from algal cell pellets and from media was tested for mutagenicity in a forward mutation suspension assay in Salmonella typhimurium using resistance to 8-azaguanine for

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

    Energy Technology Data Exchange (ETDEWEB)

    Galano, Annia [Departamento de Quimica, Universidad Autonoma Metropolitana-Iztapalapa, San Rafael Atlixco 186, Col. Vicentina. Iztapalapa, C.P. 09340 Mexico D.F. (Mexico); Instituto Mexicano del Petroleo, Eje Central Lazaro Cardenas 152, 07730 Mexico D.F. (Mexico)], E-mail:; Francisco-Marquez, Misaela [Departamento de Quimica, Universidad Autonoma Metropolitana-Iztapalapa, San Rafael Atlixco 186, Col. Vicentina. Iztapalapa, C.P. 09340 Mexico D.F. (Mexico); Instituto Mexicano del Petroleo, Eje Central Lazaro Cardenas 152, 07730 Mexico D.F. (Mexico)


    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 ({delta}G < 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.

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

    KAUST Repository

    Reymer, Anna


    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.

  19. Highly selective hydrogenation of halonitroaromatics to aromatic haloamines by ligand modified Ni-based catalysts

    Institute of Scientific and Technical Information of China (English)

    Chun Shan Lu; Jing Hui Lv; Lei Ma; Qun Feng Zhang; Feng Feng; Xiao Nian Li


    Ligand modification of Ni-based catalysts by coordination of dicyandiamide to Ni metal leads to enhanced selectivity for the selective hydrogenation of halonitroaromatics.The selectivity of above 99.9% to aromatic haloamines can be achieved at the conversion of 100%.The results of H2-TPD and FT-IR experiments show that Ni-H+ species possessing the properties of Lewis acid site on the surface of Raney Ni could be responsible for the hydrodehalogenation.When Raney Ni was treated by dicyandiamide,Ni-H+ species interacted with N atom from the dicyandiamide.This interaction was stable even at reaction temperature,which reduced the possibility to form the intermediate state of Ar-Cl …H+Ni-.And then C-Cl bond could not be polarized and activated.The hydrodechlorination process was suppressed effectively.

  20. Structure-Activity Relationships in Nitro-Aromatic Compounds (United States)

    Vogt, R. A.; Rahman, S.; Crespo-Hernández, C. E.

    Many nitro-aromatic compounds show mutagenic and carcinogenic properties, posing a potential human health risk. Despite this potential health hazard, nitro-aromatic compounds continue to be emitted into ambient air from municipal incinerators, motor vehicles, and industrial power plants. As a result, understanding the structural and electronic factors that influence mutagenicity in nitro-aromatic compounds has been a long standing objective. Progress toward this goal has accelerated over the years, in large part due to the synergistic efforts among toxicology, computational chemistry, and statistical modeling of toxicological data. The concerted influence of several structural and electronic factors in nitro-aromatic compounds makes the development of structure-activity relationships (SARs) a paramount challenge. Mathematical models that include a regression analysis show promise in predicting the mutagenic activity of nitro-aromatic compounds as well as in prioritizing compounds for which experimental data should be pursued. A major challenge of the structure-activity models developed thus far is their failure to apply beyond a subset of nitro-aromatic compounds. Most quantitative structure-activity relationship papers point to statistics as the most important confirmation of the validity of a model. However, the experimental evidence shows the importance of the chemical knowledge in the process of generating models with reasonable applicability. This chapter will concisely summarize the structural and electronic factors that influence the mutagenicity in nitro-aromatic compounds and the recent efforts to use quantitative structure-activity relationships to predict those physicochemical properties.

  1. How non-conventional feedstocks will affect aromatics technologies

    Energy Technology Data Exchange (ETDEWEB)

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


    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.)

  2. Epoxy Coenzyme A Thioester pathways for degradation of aromatic compounds. (United States)

    Ismail, Wael; Gescher, Johannes


    Aromatic compounds (biogenic and anthropogenic) are abundant in the biosphere. Some of them are well-known environmental pollutants. Although the aromatic nucleus is relatively recalcitrant, microorganisms have developed various catabolic routes that enable complete biodegradation of aromatic compounds. The adopted degradation pathways depend on the availability of oxygen. Under oxic conditions, microorganisms utilize oxygen as a cosubstrate to activate and cleave the aromatic ring. In contrast, under anoxic conditions, the aromatic compounds are transformed to coenzyme A (CoA) thioesters followed by energy-consuming reduction of the ring. Eventually, the dearomatized ring is opened via a hydrolytic mechanism. Recently, novel catabolic pathways for the aerobic degradation of aromatic compounds were elucidated that differ significantly from the established catabolic routes. The new pathways were investigated in detail for the aerobic bacterial degradation of benzoate and phenylacetate. In both cases, the pathway is initiated by transforming the substrate to a CoA thioester and all the intermediates are bound by CoA. The subsequent reactions involve epoxidation of the aromatic ring followed by hydrolytic ring cleavage. Here we discuss the novel pathways, with a particular focus on their unique features and occurrence as well as ecological significance.

  3. Polarized Matrix Infrared Spectra of Cyclopentadienone (United States)

    Ormond, Thomas K.; Scheer, Adam M.; Ellison, G. Barney; Nimlos, Mark R.; Daily, John W.; Stanton, John F.


    We are developing a resistively-heated SiC μtubular reactor with a 100 μsec residence time to study the thermal cracking of biomass monomers. The decomposition products are identified by two independent techniques: 118.2 nm VUV photoionization mass spectrometry (PIMS) and matrix infrared spectroscopy. Many lignins thermally crack to produce cyclopentadienone (m/z 80) and its derivatives. Subsequent decomposition of these cyclopentadienones results in formation of substituted acetylenes which are known precursors to polycyclic aromatic hydrocarbons and soot. Due to its anitaromatic character, cyclopentadienone is highly reactive and presents an interesting spectroscopic system. Pyrolysis of {o}-phenylene sulfite (m/z 156) is a convenient precursor for cyclopentadienone. In this work we report the polarized matrix infrared absorption spectra of cyclopentadienone and d_4-cyclopentadienone. The PIMS results corroborate the thermal decomposition steps of phenylene sulfite. {Ab initio} coupled-cluster anharmonic force field calculations are used to guide the vibrational assignments. A. M. Scheer, C. Murkarakate, D. J. Robichaud, M. R. Nimlos, and G. B. Ellison J. Phys. Chem. A 115, 13381 (2011)

  4. Polarized Emission from Interstellar Dust

    CERN Document Server

    Vaillancourt, J E


    Observations of far-infrared (FIR) and submillimeter (SMM) polarized emission are used to study magnetic fields and dust grains in dense regions of the interstellar medium (ISM). These observations place constraints on models of molecular clouds, star-formation, grain alignment mechanisms, and grain size, shape, and composition. The FIR/SMM polarization is strongly dependent on wavelength. We have attributed this wavelength dependence to sampling different grain populations at different temperatures. To date, most observations of polarized emission have been in the densest regions of the ISM. Extending these observations to regions of the diffuse ISM, and to microwave frequencies, will provide additional tests of grain and alignment models. An understanding of polarized microwave emission from dust is key to an accurate measurement of the polarization of the cosmic microwave background. The microwave polarization spectrum will put limits on the contributions to polarized emission from spinning dust and vibrat...

  5. Elite Polarization and Public Opinion

    DEFF Research Database (Denmark)

    Robison, Joshua; Mullinix, Kevin


    Elite polarization has reshaped American politics and is an increasingly salient aspect of news coverage within the United States. As a consequence, a burgeoning body of research attempts to unravel the effects of elite polarization on the mass public. However, we know very little about how...... polarization is communicated to the public by news media. We report the results of one of the first content analyses to delve into the nature of news coverage of elite polarization. We show that such coverage is predominantly critical of polarization. Moreover, we show that unlike coverage of politics focused...... on individual politicians, coverage of elite polarization principally frames partisan divisions as rooted in the values of the parties rather than strategic concerns. We build on these novel findings with two survey experiments exploring the influence of these features of polarization news coverage on public...

  6. Optimization of polarization lidar structure (United States)

    Abramochkin, Alexander I.; Kaul, Bruno V.; Tikhomirov, Alexander A.


    The problems of the polarization lidar transceiver optimization are considered. The basic features and the optimization criteria of lidar polarization units are presented and the comparative analysis of polarization units is fulfilled. We have analyzed optical arrangements of the transmitter to form the desired polarization state of sounding radiation. We have also considered various types of lidar receiving systems: (1) one-channel, providing measurement of Stocks parameters at a successive change of position of polarization analyzers in the lidar receiver, and (2) multichannel, where each channel has a lens, an analyzer, and a photodetector. In the latter case measurements of Stocks parameters are carried out simultaneously. The optimization criteria of the polarization lidar considering the atmospheric state are determined with the purpose to decrease the number of polarization devices needed.

  7. The Effect of Liquid Crystalline Structures on Antiseizure Properties of Aqueous Solutions of Ethoxylated Alcohols



    Aqueous solutions of ethoxylated alcohols which form lyotropic liquid crystals at high concentrations (40–80%) were selected as model lubricating substances. Microscopic studies under polarized light and viscosity measurements were carried out in order to confirm the presence of liquid crystalline structures in the case of alcohol solutions with ethoxylation degrees of 3, 5, 7 and 10. Microscopic images and viscosity coefficient values characteristic of various mesophases were obtained. As ex...

  8. Understanding surface interactions in aqueous miscible organic solvent treated layered double hydroxides.


    Erastova, Valentina; Degiacomi, Matteo T.; O'Hare, Dermot; Greenwell, H. Chris


    Layered materials are of interest for use in a wealth of technological applications, many of which require a high surface area for optimal properties and performance. Recently, an industrially scalable method to create high surface area layered double hydroxide (LDH) materials, which may be readily dispersed in non-polar solvents, has been developed. This method involves treatment of LDHs with aqueous miscible organic (AMO) solvents. Here, molecular modeling is exploited to elucidate the AMO ...


    Institute of Scientific and Technical Information of China (English)

    D.Q. Peng; X.D. Bai; Q.G. Zhou; X.W. Chen; R.H. Yu; X.Y. Liu


    In order to study the influence of cerium ion implantation on the aqueous corrosion behavior of zirconium, specimens were implanted by cerium ions with a dosage range from 1 ×1016 to 1 ×1017 ions/cm2 at about 150℃, using MEWA source at an acceler ative voltage of 40kV. The valence of the surface layer was analyzed by X-ray photoelectron spectroscopy (XPS); Three-sweep potentiodynamic polarization measurement was employed to value the aqueous corrosion resistance of zirconium in a 0.5mol/L H2SO4 solution. It was found that a remarkable decline in the aqueous corrosion behavior of zirconium implanted with cerium ions compared with that of the as-received zirconium. Finally, the mechanism of the corrosion resistance decline of the cerium-implanted zirconium is discussed.

  10. Phase-transition and aggregation characteristics of a thermoresponsive dextran derivative in aqueous solutions. (United States)

    Shi, Huan-Ying; Zhang, Li-Ming


    Grafting of poly(N-vinylcaprolactam) side chains onto a hydrophilic dextran backbone was found to provide the dextran with new, thermoresponsive properties in aqueous solutions. Depending on its solution concentration, the resulting dextran derivative could exhibit a temperature-induced phase-transition and critical transition temperature (T(c)). Different anions and cations of added salts, including five potassium salts and five alkali-metal chlorides, were observed to influence the T(c) value of its aqueous solution. Except for potassium iodide, all added salts were found to lower the T(c) value. The addition of the surfactant, cationic cetyltrimethylammonium bromide or anionic sodium dodecyl sulfate, resulted in an increase of the T(c) value. With the help of the Coomassie Brilliant Blue dye as a polarity probe, the formation of hydrophobic aggregates above the T(c) was revealed for this new dextran derivative in aqueous solution.

  11. β-CD assisted dissolution of quaternary ammonium permanganates in aqueous medium. (United States)

    Bank, Suraj Prakash; Guru, Partha Sarathi; Dash, Sukalyan


    The non-polar internal cavity of β-cyclodextrin (β-CD) has been exploited for the entrapment of the hydrophobic tails of two water insoluble quaternary ammonium permanganates (QAPs): cetyltrimethylammonium permanganate (CTAP) and tetrabutylammonium permanganate (TBAP), for solubilization in aqueous medium. The solubilization and organizational behavior of the QAPs in aqueous β-CD solution have been determined from the comparison of their rates of self-oxidation in presence and in absence of β-CD. Effect of QAP concentration on their observed rate constants (k(obs)) at a fixed β-CD concentration, phase solubility analysis in varying β-CD concentration, impact of quaternary ammonium bromides (QABs) on the kobs values of CTAP and TBAP at fixed QAP and β-CD concentrations, and the temperature effect have been reported. A scheme to explain the solvation of QAPs in aqueous β-CD has been proposed based on dynamic light scattering (DLS) analysis of the samples.

  12. Preparation,characterization and properties studies of quinine-imprinted polymer in the aqueous phase

    Institute of Scientific and Technical Information of China (English)

    He Jianfeng; Liu Lan; Yang Guilan; Deng Qinying


    The uniform-sized spherical molecularly imprinted polymers were successfully prepared through molecular imprinting technology by two-step seed swelling and mini-emulsion polymerization in the aqueous condition using quinine as template molecules and methacrylic acid (MAA)as functional monomer.The polymers were characterized by IR spectra,thermal-weight analysis,scanning electron microscope and laser particle size analysis.The properties of imprinted polymers were investigated in different organic phases and aqueous media.In the organic media,results suggested that polar interactions(hydrogen bonding,ionic interactions)between acidic monomer/polymer and template molecules are mainly responsible for the binding and recognition;whereas in the aqueous medium,a considerable recognition effect was also obtained where the ionic(electrostatic)interaction and hydrophobic interaction play an important role.The experiments of binding different substrates indicated that the MIPs possessed an excellent rebinding ability and inherent selectivity to quinine.

  13. Aqueous solubility of a simple (single-carbon) organic molecule as a function of its size & dipole moment. (United States)

    Al-Malah, Kamal I


    The aqueous solubility of a single-carbon organic molecule as a function of its size & dipole moment was investigated. The molecular dipole moment was chosen to represent the polar character of a poly-atomic molecule. It is hypothesized here that at a given pH, temperature, and pressure, the solubility of a single-carbon organic molecule in water will be a function of its polar character; namely, dipole moment and of its molecular size. Different forms of the solubility function were tested; it was found that the solubility model, given by Eq. 1, which is based on the polar character and the molecular volume, adequately described the aqueous solubility of single-carbon organic moieties. The aqueous solubility of single-carbon organic solutes exhibits maximum at the condition of high polar character (large dipole moment) and low molecular volume. The general trend of the solubility of single-carbon organic solutes, based on the proposed model (Eq. 1) could be explained in terms of the trade-off between the driving force (degree of polar character of the solute) for solubilization versus the resistance to be solubilized as a result of the entropic effects which increase with increasing molecular volume of the organic moiety.

  14. Theoretical study of aromaticity in inorganic tetramer clusters

    Indian Academy of Sciences (India)

    Sandeep Nigam; Chiranjib Majumder; S K Kulshreshtha


    Ground state geometry and electronic structure of M$^{2-}_{4}$ cluster (M = B, Al, Ga) have been investigated to evaluate their aromatic properties. The calculations are performed by employing the Density Functional Theory (DFT) method. It is found that all these three clusters adopt square planar configuration. Results reveal that square planar M$^{2-}_{4}$ dianion exhibits characteristics of multifold aromaticity with two delocalised -electrons. In spite of the unstable nature of these dianionic clusters in the gas phase, their interaction with the sodium atoms forms very stable dipyramidal M4Na2 complexes while maintaining their square planar structure and aromaticity.

  15. Aromatic oligoamides with a rare ortho-connectivity

    DEFF Research Database (Denmark)

    Hjelmgaard, T.; Nielsen, John


    Even though aromatic oligoamides composed of aromatic amino acids in a "one-way sequence" attract ever increasing research interest, backbones connected through ortho-linked aromatics remain rare. Herein, we present the first synthesis and study of N-alkylated ortho-aminomethyl- benzamides termed...... studies indicated a more restricted rotation about the amide bonds in ortho-arylopeptoids, presumably due to a more congested backbone structure resulting from the ortho-connectivity pattern. Intriguingly, tert-butyl and phenyl side chains offer complete control over the amide conformations; whereas...

  16. Degradation/oxidation susceptibility of organic photovoltaic cells in aqueous solutions. (United States)

    Habib, K; Husain, A; Al-Hazza, A


    A criterion of the degradation/oxidation susceptibility of organic photovoltaic (OPV) cells in aqueous solutions was proposed for the first time. The criterion was derived based on calculating the limit of the ratio value of the polarization resistance of an OPV cell in aqueous solution (Rp(s)) to the polarization resistance of the OPV cell in air (Rp(air)). In other words, the criterion lim(Rp(s)/Rp(air)) = 1 was applied to determine the degradation/oxidation of the OPV cell in the aqueous solution when Rp(air) became equal (increased) to Rp(s) as a function of time of the exposure of the OPV cell to the aqueous solution. This criterion was not only used to determine the degradation/oxidation of different OPV cells in a simulated operational environment but also it was used to determine the electrochemical behavior of OPV cells in deionized water and a polluted water with fine particles of sand. The values of Rp(s) were determined by the electrochemical impedance spectroscopy at low frequency. In addition, the criterion can be applied under diverse test conditions with a predetermined period of OPV operations.

  17. Polar Direct Drive (United States)

    Skupsky, S.


    Direct drive offers the potential of higher target gain on the National Ignition Facility (NIF) than x-ray drive: The initial direct-drive target design had a 1-D gain of 45 and consisted primarily of a pure cryogenic DT shell. Using the expected levels of target and laser nonuniformities for the NIF, two-dimensional (2-D) hydrodynamic simulations predicted target gains around 30.(P.W. McKenty et al.), Phys. Plasmas 8, 2315 (2001). More-recent designs have shown that higher target gains could be obtained by replacing a portion of the DT shell with ``wetted'' CH foam and by using adiabat shaping: (1) Higher-Z material (C) in the foam increases laser absorption by about 40% (from 60% absorption to 85%).(S. Skupsky et al.), in Inertial Fusion Sciences and Applications 2001, edited by K. Tanaka et al. (Elsevier, Paris, 2002), p. 240. (2) Adiabat shaping allows the main portion of the fuel to be placed on a lower adiabat without compromising target stability.(V.N. Goncharov et al.), Phys. Plasmas 10, 1906 (2003). These direct-drive concepts can be tested on the NIF, long before that facility is converted to a direct-drive (spherically symmetric) irradiation configuration. Using the NIF x-ray-drive beam configuration, some of the near-polar beams could be pointed to better illuminate the target's equator. These more-oblique, equatorial beams will have lower absorption and reduced drive efficiency than the polar beams. One strategy to compensate for the difference in polar and equatorial drive is to reduce the irradiation at the poles and employ different pulse shapes to accommodate the time-dependent variations in drive and absorption. This concept of polar direct drive (PDD) has been studied using the 2-D hydrocode DRACO to determine the requirements for achieving ignition and moderate target gain for the NIF. Experiments on the OMEGA laser will examine the effects of oblique irradiation on target drive. Results of simulations for different direct-drive target designs

  18. Polar Cap Retreat (United States)


    13 August 2004 This red wide angle Mars Global Surveyor (MGS) Mars Orbiter Camera (MOC) image shows a view of the retreating seasonal south polar cap in the most recent spring in late 2003. Bright areas are covered with frost, dark areas are those from which the solid carbon dioxide has sublimed away. The center of this image is located near 76.5oS, 28.2oW. The scene is large; it covers an area about 250 km (155 mi) across. The scene is illuminated by sunlight from the upper left.

  19. Circularly polarized antennas

    CERN Document Server

    Gao, Steven; Zhu, Fuguo


    This book presents a comprehensive insight into the design techniques for different types of CP antenna elements and arrays In this book, the authors address a broad range of topics on circularly polarized (CP) antennas. Firstly, it introduces to the reader basic principles, design techniques and characteristics of various types of CP antennas, such as CP patch antennas, CP helix antennas, quadrifilar helix antennas (QHA), printed quadrifilar helix antennas (PQHA), spiral antenna, CP slot antennas, CP dielectric resonator antennas, loop antennas, crossed dipoles, monopoles and CP horns. Adva

  20. Normalized polarization ratios for the analysis of cell polarity.

    Directory of Open Access Journals (Sweden)

    Raz Shimoni

    Full Text Available The quantification and analysis of molecular localization in living cells is increasingly important for elucidating biological pathways, and new methods are rapidly emerging. The quantification of cell polarity has generated much interest recently, and ratiometric analysis of fluorescence microscopy images provides one means to quantify cell polarity. However, detection of fluorescence, and the ratiometric measurement, is likely to be sensitive to acquisition settings and image processing parameters. Using imaging of EGFP-expressing cells and computer simulations of variations in fluorescence ratios, we characterized the dependence of ratiometric measurements on processing parameters. This analysis showed that image settings alter polarization measurements; and that clustered localization is more susceptible to artifacts than homogeneous localization. To correct for such inconsistencies, we developed and validated a method for choosing the most appropriate analysis settings, and for incorporating internal controls to ensure fidelity of polarity measurements. This approach is applicable to testing polarity in all cells where the axis of polarity is known.

  1. Influence of polar cap currents on pulsar polarization

    CERN Document Server

    Kumar, D


    We have developed a model for the polarization of curvature radiation for pulsars by taking into account the polar cap induced perturbation on the nonrotating (slowly rotating) dipolar magnetic field, where the rotation effects such as aberration and retardation can be ignored. We have simulated a set of typical pulse profiles to understand the role of induced magnetic field on radio emission of pulsars, and found to be significantly influencing the profile structure and polarization. Our model indicates that the intensity components and the polarization angle inflection point can get shifted to either leading or trailing side depending upon the prevailing conditions in the viewing geometry, the non-uniformity in source distribution (modulation) and the polar cap current induced perturbation. Also, we find an evidence for the origin of symmetric type circular polarization in addition to antisymmetric type. Our model predicts for a stronger trailing component compared to that on leading side of a given cone.

  2. Affinity of four polar neurotransmitters for lipid bilayer membranes

    DEFF Research Database (Denmark)

    Wang, Chunhua; Ye, Fengbin; Valardez, Gustavo F.


    interacts unfavorably with DMPC and is thus preferentially excluded from the membrane's hydration layer. Conversely, the zwitterionic neurotransmitters are attracted to membranes with 10% anionic lipid and their local concentration at the interface is 5-10 times larger than in the aqueous bulk....... The simulations suggest that this attraction mainly relies on electrostatic interactions of the amino group of the neurotransmitter and the lipid phosphate. We conclude that moderate attraction to lipid membranes occurs for some polar neurotransmitters and hence that one premise for a theory of bilayer...

  3. A simple method for the synthesis of a polar-embedded and polar-endcapped reversed-phase chromatographic packing with low activity of residue silanols. (United States)

    Liu, Hai-yan; Li, Zhi-yong; Liu, Dan; Xue, Ying-wen; Shi, Zhi-guo


    Octadecyl bonded silica (ODS) is the most popular packing for reversed-phase chromatography. However, it generally demonstrates bad resolution for polar analytes because of the residue silanols and its poor stability in aqueous mobile phase. To address the problem, a new reversed-phase packing containing both polar-embedded and polar-endcapped moieties was proposed. It was prepared by a very simple method, in which the epoxide addition reaction of 3-glycidoxypropyltrimethoxysilane with 1-octadecanethiol proceeded simultaneously with the reaction of silane coupling onto silica particles. By controlling the molecular ratio of 3-glycidoxypropyltrimethoxysilane to 1-octadecanethiol higher than 1.0 (1.56 for the present study), both polar-embedded and polar-endcapped moieties were achieved onto the packing. The performance of the packing was evaluated in detail. The results demonstrated that neutral, acidic and basic analytes were well separated on the packing. The column efficiency for phenanthrene was 34,200 theoretical plates per meter. In addition, four nucleotides can be separated in 100% phosphate buffered saline solution with good reproducibility, which indicates the packing has good stability in aqueous mobile phase. Amitriptyline, a typical basic analytes, was eluted out with relatively symmetric peak shape (asymmetry factor of 1.36), which implies that the packing has not suffered from the negative effect of residue silanols significantly. Good stability in buffer solution of pH ranging from 2.0 to 10.0 was also documented for the packing.

  4. Micellar electrokinetic chromatography of aromatic anions and non-ionic aromatic compounds with stepwise changes of the concentration of cetyltrimethylammonium chloride. (United States)

    Esaka, Yukihiro; Kobayashi, Miki; Murakami, Hiroya; Uno, Bunji


    Micellar electrokinetic chromatography in which the concentration of cetyltrimetylammmonium chloride (CTAC) was sequentially changed in the separation system was investigated using 10 aromatic anions and 11 non-ionic aromatic compounds as model analytes. All separations were performed in the absence of electroosmotic flow (EOF), and thus, analytes were detected in the order of their strength of interaction with micelles in the system. In isocratic elutions without EOF, the model analytes could be separated better with lower concentrations of CTAC but migration times of the analytes possessing relatively higher polarities increased markedly, and thus, long analysis times were required. Therefore, we attempted to increase the concentration of CTAC during a single measurement to reduce the analysis time without hindering the resultant separation of analytes obtained with lower concentrations. Briefly, the present surfactant stepwise elution can be performed by a sequential increase in CTAC concentrations of the running solution in the anodic reservoir from 30 to 50mM for the anions and from 20 to 50 mM for the non-ionic compounds. Additionally, to perform expected gradient separations with good reproducibility, each running solution with a different CTAC concentration was treated with tetraethylammmonium chloride as an additive to adjust electric conductivities of each running solution to be equal. Under this condition, CTAC micelles of each zone of different CTAC concentrations would migrate with practically the same velocity. Consequently, by the present stepwise method, both the 10 anionic analytes and the 11 non-ionic analytes were well separated within reasonable periods which corresponded approximately to two-third and less than half of those by the isocratic elutions, respectively.

  5. Six-Membered Aromatic Polyazides: Synthesis and Application

    Directory of Open Access Journals (Sweden)

    Sergei V. Chapyshev


    Full Text Available Aromatic polyazides are widely used as starting materials in organic synthesis and photochemical studies, as well as photoresists in microelectronics and as cross-linking agents in polymer chemistry. Some aromatic polyazides possess high antitumor activity, while many others are of considerable interest as high-energy materials and precursors of high-spin nitrenes and C3N4 carbon nitride nanomaterials. The use of aromatic polyazides in click-reactions may be a new promising direction in the design of various supramolecular systems possessing interesting chemical, physical and biological properties. This review is devoted to the synthesis, properties and applications of six-membered aromatic compounds containing three and more azido groups in the ring.

  6. Prenyl transfer to aromatic substrates: genetics and enzymology. (United States)

    Heide, Lutz


    Aromatic prenyltransferases catalyze the transfer of prenyl moieties to aromatic acceptor molecules and give rise to an astounding diversity of primary and secondary metabolites in plants, fungi and bacteria. Significant progress has been made in the biochemistry and genetics of this heterogeneous group of enzymes in the past years. After 30 years of extensive research on plant prenylflavonoid biosynthesis, finally the first aromatic prenyltransferases involved in the formation of these compounds have been cloned. In bacteria, investigations of the newly discovered family of ABBA prenyltransferases revealed a novel type of protein fold, the PT barrel. In fungi, a group of closely related indole prenyltransferase was found to carry out aromatic prenylations with different substrate specificity and regiospecificity, and to catalyze both regular and reverse prenylations.

  7. Biodegradation Rates of Aromatic Contaminants in Biofilm Reactors

    DEFF Research Database (Denmark)

    Arcangeli, Jean-Pierre; Arvin, Erik


    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, chlorophe......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...

  8. [Inhibition of aromatics on ammonia-oxidizing activity of sediment]. (United States)

    Dong, Chun-hong; Hu, Hong-ying; Wei, Dong-bin; Huang, Xia; Qian, Yi


    The inhibition of 24 aromatics on ammonia-oxidizing activity of nitrifying bacteria in sediment was measured. The effects of the kind, number and position of substituted groups on ammonia-oxidizing activity of nitrifying bacteria were discussed. The inhibition of mono-substituted benzenes on ammonia-oxidizing activity of nitrifying bacteria were in order of -OH > -NO2 > -NH2 > -Cl > -CH3 > -H. The position of substituted groups of di-substituted benzenes also affected the inhibition, and the inhibitions of dimethylbenzenes(xylene) were in order of meta-> ortho-> para-. The increase in number of substituted group on benzene-ring enhanced the inhibition of aromatics studied in this study on nitrifying bacteria. There was a linear relationship between inhibition (IC50, mumol.L-1) of aromatics on ammonia-oxidizing activity and total electronegativity (sigma E) of aromatics: lgIC50 = 14.72 - 0.91 sigma E.

  9. Six-Membered Aromatic Polyazides: Synthesis and Application. (United States)

    Chapyshev, Sergei V


    Aromatic polyazides are widely used as starting materials in organic synthesis and photochemical studies, as well as photoresists in microelectronics and as cross-linking agents in polymer chemistry. Some aromatic polyazides possess high antitumor activity, while many others are of considerable interest as high-energy materials and precursors of high-spin nitrenes and C₃N₄ carbon nitride nanomaterials. The use of aromatic polyazides in click-reactions may be a new promising direction in the design of various supramolecular systems possessing interesting chemical, physical and biological properties. This review is devoted to the synthesis, properties and applications of six-membered aromatic compounds containing three and more azido groups in the ring.

  10. Assessing Uncertainty of Interspecies Correlation Estimation Models for Aromatic Compounds (United States)

    We developed Interspecies Correlation Estimation (ICE) models for aromatic compounds containing 1 to 4 benzene rings to assess uncertainty in toxicity extrapolation in two data compilation approaches. ICE models are mathematical relationships between surrogate and predicted test ...

  11. Aromatic Plants as a Source of Bioactive Compounds

    Directory of Open Access Journals (Sweden)

    Panagiota Florou-Paneri


    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.

  12. Application of aromatization catalyst in synthesis of carbon nanotubes

    Indian Academy of Sciences (India)

    Song Rongjun; Yang Yunpeng; Ji Qing; Li Bin


    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 dehydrogenation–cyclization and condensation reaction of carbon source, which belongs to a necessary step in the formation of CNTs. In this work, aromatization catalysts, H-beta zeolite, HZSM-5 zeolite and organically modified montmorillonite (OMMT) were chosen to investigate their effects on the formation of multi-walled carbon nanotubes (MWCNTs) via pyrolysis method when polypropylene and 1-hexene as carbon source and Ni2O3 as the charring catalyst. The results demonstrated that the combination of those aromatization catalysts with nickel catalyst can effectively improve the formation of MWCNTs.

  13. Affinity labelling enzymes with esters of aromatic sulfonic acids (United States)

    Wong, Show-Chu; Shaw, Elliott


    Novel esters of aromatic sulfonic acids are disclosed. The specific esters are nitrophenyl p- and m-amidinophenylmethanesulfonate. Also disclosed is a method for specific inactivation of the enzyme, thrombin, employing nitrophenyl p-amidinophenylmethanesulfonate.


    Directory of Open Access Journals (Sweden)



    Full Text Available The aim of research is to achieve chemical modifications of corn starch. Therefore, the present study focuses on its chemical modifications, in order to increase its aqueous solubility and to ameliorate its adsorption properties for one hydrophobic pollutant, belonging to Polycyclic Aromatic Hydrocarbons (PAHs, benzo[a]pyrene (BaP, as a model. Starch chemical modifications are realized by alkylation reactions using ether (propylene oxide or ester (succinic anhydride alkyl agents. Starches obtained are characterized by 1H NMR technique in order to verify the alkylation procedure. Water solubility of the obtained product was determined and its capacity to adsorb the considered model pollutant was studied. According to the registered results, starch modification with succinic anhydride conducts to an aqueous solubility of 34.00 g·L-1, significantly increased in comparison with the solubility of native corn starch which is insoluble in water at room temperature. With this modified starch, promising results for BaP aqueous solubilisation were obtained.

  15. Enhanced sorption of polycyclic aromatic hydrocarbons to tetra-alkyl ammonium modified smectites via cation-pi interactions. (United States)

    Qu, Xiaolei; Liu, Ping; Zhu, Dongqiang


    The objective of this study was to characterize molecular sorptive interactions of polycyclic aromatic hydrocarbons (PAHs) by organoclays modified with quaternary ammonium cations. Three PAHs, naphthalene (NAPH), phenanthrene (PHEN), and pyrene (PYR), and three chlorobenzenes, 1,2-dichlorobenzene (DCB), 1,2,4,5-tetrachlorobenzene (TeCB), and pentachlorobenzene (PtCB), were sorbed from aqueous solution to reference montmorillonite clays (SWy-2) exchanged respectively with tetramethyl ammonium (TMA), tetraethyl ammonium (TEA), tetra-n-butyl ammonium (TBA), and hexadecyltrimethyl ammonium (HDTMA) cations. Solute hydrophobicities are compared between PAHs and chlorobenzenes using the solute n-octanol-water partition coefficient, n-hexadecane-water partition coefficient, and polyethylene-water distribution coefficient. The PAHs show several- to more than 10-fold greater sorption than the chlorobenzenes having close hydrophobicities but fewer delocalized pi electrons (NAPH/DCB, PHEN/TeCB, and PYR/ PtCB) by TEA-, TBA-, and HDTMA-clays. Furthermore, the PAHs show greater trends of solubility enhancement than the compared chlorobenzenes by TMA, TEA, and TBA in aqueous solution. The enhanced sorption and aqueous solubility of PAHs are best described by cation-pi interactions between ammonium cations and PAHs relative to chlorobenzenes that are incapable of such interactions. Cation-pi complexation between PAHs and tetra-alkyl ammonium cations in chloroform was verified by ring-current-induced upfield chemical shifts of the alkyl groups of cations in the 1H NMR spectrum.

  16. Characterization of Selective Antibacterial Peptides by Polarity Index

    Directory of Open Access Journals (Sweden)

    C. Polanco


    Full Text Available In the recent decades, antibacterial peptides have occupied a strategic position for pharmaceutical drug applications and became subject of intense research activities since they are used to strengthen the immune system of all living organisms by protecting them from pathogenic bacteria. This work proposes a simple and easy statistical/computational method through a peptide polarity index measure by which an antibacterial peptide subgroup can be efficiently identified, that is, characterized by a high toxicity to bacterial membranes but presents a low toxicity to mammal cells. These peptides also have the feature not to adopt to an alpha-helicoidal structure in aqueous solution. The double-blind test carried out to the whole Antimicrobial Peptide Database (November 2011 showed an accuracy of 90% applying the polarity index method for the identification of such antibacterial peptide groups.

  17. Characterization of Selective Antibacterial Peptides by Polarity Index (United States)

    Polanco, C.; Samaniego, J. L.; Buhse, T.; Mosqueira, F. G.; Negron-Mendoza, A.; Ramos-Bernal, S.; Castanon-Gonzalez, J. A.


    In the recent decades, antibacterial peptides have occupied a strategic position for pharmaceutical drug applications and became subject of intense research activities since they are used to strengthen the immune system of all living organisms by protecting them from pathogenic bacteria. This work proposes a simple and easy statistical/computational method through a peptide polarity index measure by which an antibacterial peptide subgroup can be efficiently identified, that is, characterized by a high toxicity to bacterial membranes but presents a low toxicity to mammal cells. These peptides also have the feature not to adopt to an alpha-helicoidal structure in aqueous solution. The double-blind test carried out to the whole Antimicrobial Peptide Database (November 2011) showed an accuracy of 90% applying the polarity index method for the identification of such antibacterial peptide groups. PMID:22611416

  18. Biodegradation aspects of polycyclic aromatic hydrocarbons (PAHs): a review. (United States)

    Haritash, A K; Kaushik, C P


    PAHs are aromatic hydrocarbons with two or more fused benzene rings with natural as well as anthropogenic sources. They are widely distributed environmental contaminants that have detrimental biological effects, toxicity, mutagenecity and carcinogenicity. Due to their ubiquitous occurrence, recalcitrance, bioaccumulation potential and carcinogenic activity, the PAHs have gathered significant environmental concern. Although PAH may undergo adsorption, volatilization, photolysis, and chemical degradation, microbial degradation is the major degradation process. PAH degradation depends on the environmental conditions, number and type of the microorganisms, nature and chemical structure of the chemical compound being degraded. They are biodegraded/biotransformed into less complex metabolites, and through mineralization into inorganic minerals, H(2)O, CO(2) (aerobic) or CH(4) (anaerobic) and rate of biodegradation depends on pH, temperature, oxygen, microbial population, degree of acclimation, accessibility of nutrients, chemical structure of the compound, cellular transport properties, and chemical partitioning in growth medium. A number of bacterial species are known to degrade PAHs and most of them are isolated from contaminated soil or sediments. Pseudomonas aeruginosa, Pseudomons fluoresens, Mycobacterium spp., Haemophilus spp., Rhodococcus spp., Paenibacillus spp. are some of the commonly studied PAH-degrading bacteria. Lignolytic fungi too have the property of PAH degradation. Phanerochaete chrysosporium, Bjerkandera adusta, and Pleurotus ostreatus are the common PAH-degrading fungi. Enzymes involved in the degradation of PAHs are oxygenase, dehydrogenase and lignolytic enzymes. Fungal lignolytic enzymes are lignin peroxidase, laccase, and manganese peroxidase. They are extracellular and catalyze radical formation by oxidation to destabilize bonds in a molecule. The biodegradation of PAHs has been observed under both aerobic and anaerobic conditions and the rate

  19. Biodegradation aspects of Polycyclic Aromatic Hydrocarbons (PAHs): A review

    Energy Technology Data Exchange (ETDEWEB)

    Haritash, A.K., E-mail: [Department of Environmental Science and Engineering, Guru Jambheshwar University of Science and Technology, Hisar, Haryana (India); Kaushik, C.P. [Department of Environmental Science and Engineering, Guru Jambheshwar University of Science and Technology, Hisar, Haryana (India)


    PAHs are aromatic hydrocarbons with two or more fused benzene rings with natural as well as anthropogenic sources. They are widely distributed environmental contaminants that have detrimental biological effects, toxicity, mutagenecity and carcinogenicity. Due to their ubiquitous occurrence, recalcitrance, bioaccumulation potential and carcinogenic activity, the PAHs have gathered significant environmental concern. Although PAH may undergo adsorption, volatilization, photolysis, and chemical degradation, microbial degradation is the major degradation process. PAH degradation depends on the environmental conditions, number and type of the microorganisms, nature and chemical structure of the chemical compound being degraded. They are biodegraded/biotransformed into less complex metabolites, and through mineralization into inorganic minerals, H{sub 2}O, CO{sub 2} (aerobic) or CH{sub 4} (anaerobic) and rate of biodegradation depends on pH, temperature, oxygen, microbial population, degree of acclimation, accessibility of nutrients, chemical structure of the compound, cellular transport properties, and chemical partitioning in growth medium. A number of bacterial species are known to degrade PAHs and most of them are isolated from contaminated soil or sediments. Pseudomonas aeruginosa, Pseudomons fluoresens, Mycobacterium spp., Haemophilus spp., Rhodococcus spp., Paenibacillus spp. are some of the commonly studied PAH-degrading bacteria. Lignolytic fungi too have the property of PAH degradation. Phanerochaete chrysosporium, Bjerkandera adusta, and Pleurotus ostreatus are the common PAH-degrading fungi. Enzymes involved in the degradation of PAHs are oxygenase, dehydrogenase and lignolytic enzymes. Fungal lignolytic enzymes are lignin peroxidase, laccase, and manganese peroxidase. They are extracellular and catalyze radical formation by oxidation to destabilize bonds in a molecule. The biodegradation of PAHs has been observed under both aerobic and anaerobic conditions

  20. Optimization of low ring polycylic aromatic biodegradation (United States)

    Othman, N.; Abdul-Talib, S.; Tay, C. C.


    Polycyclic aromatic hydrocarbons (PAHs) are recalcitrance and persistence that finally turn into problematic environmental contaminants. Microbial degradation is considered to be the primary mechanism of PAHs removal from the environment due to its organic criteria. This study is carried out to optimize degradation process of low ring PAHs. Bacteria used in this study was isolated from sludge collected from Kolej Mawar, Universiti Teknologi MARA, Shah Alam, Selangor. Working condition namely, substrate concentration, bacteria concentration, pH and temperature were optimized. PAHs in the liquid sample was extracted by using solid phase microextractio equipped with a 7 µm polydimethylsiloxane (PDMS) SPME fibr. Removal of PAHs were assessed by measuring PAHs concentration using GC-FID. Results from the optimization study of biodegradation indicated that maximum rate of PAHs removal occurred at 100 mgL-1 of PAHs, 10% bacteria concentration, pH 7.0 and 30°C. These working condition had proved the effectiveness of using bacteria in biodegradation process of PAHs.

  1. Biodegradation of aliphatic and aromatic polycarbonates. (United States)

    Artham, Trishul; Doble, Mukesh


    Polycarbonate is one of the most widely used engineering plastics because of its superior physical, chemical, and mechanical properties. Understanding the biodegradation of this polymer is of great importance to answer the increasing problems in waste management of this polymer. Aliphatic polycarbonates are known to biodegrade either through the action of pure enzymes or by bacterial whole cells. Very little information is available that deals with the biodegradation of aromatic polycarbonates. Biodegradation is governed by different factors that include polymer characteristics, type of organism, and nature of pretreatment. The polymer characteristics such as its mobility, tacticity, crystallinity, molecular weight, the type of functional groups and substituents present in its structure, and plasticizers or additives added to the polymer all play an important role in its degradation. The carbonate bond in aliphatic polycarbonates is facile and hence this polymer is easily biodegradable. On the other hand, bisphenol A polycarbonate contains benzene rings and quaternary carbon atoms which form bulky and stiff chains that enhance rigidity. Even though this polycarbonate is amorphous in nature because of considerable free volume, it is non-biodegradable since the carbonate bond is inaccessible to enzymes because of the presence of bulky phenyl groups on either side. In order to facilitate the biodegradation of polymers few pretreatment techniques which include photo-oxidation, gamma-irradiation, or use of chemicals have been tested. Addition of biosurfactants to improve the interaction between the polymer and the microorganisms, and blending with natural or synthetic polymers that degrade easily, can also enhance the biodegradation.


    Institute of Scientific and Technical Information of China (English)

    罗斌杰; 李新宇


    Crude oils from different basins in China ,Australia and New Zealand were analyzed to character-ize aromatic hydrocarbons produced in different environments by means of GC/MS .The distributions of some common compounds such as naphthalene, phenanthrene, chrysene,pyrene, fluoranthene, fluorine,dibenzothiophene and dibenzofuran were found to be related to sedimentary environments.Especially the relative contents of fluorenes ,dibenzofurans and dibenzothiophenes can be used to di-vide the oils into three types(1) saline or marine carbonate environment;(2) fresh-brackish water lake;(3) swamp and coal-bearing sequence.A romatic biomarkers (e.g.retene, nor-abietene,derivatives of lupeol and β-amyrin)represent higher plant inpults with respect to the precursors of crude oils. High contents of sulphur-containing compounds like benzothiophene and dibenzothiophene series indicate a reducing sulphur-abundant diagenetic condition .The benzohopane series (C32-C35) was identified both in hypersaline and coal-bearing basins, and it is postulated to be the result of strong bacteria activity.In all the sam-ples, a complete series of alkyl benzenes was analyzed .The similarity of its carbon-number distrbu-tion with that of n-alkanes probably suggests their genetic relationship. The distribution of the methylphenanthrene series reflects the evolution degree of crude oils,MPI holding a positive correlation with C29-sterane 20S/(20S+20R).

  3. Porphyrins Fused with Unactivated Polycyclic Aromatic Hydrocarbons

    KAUST Repository

    Diev, Vyacheslav V.


    A systematic study of the preparation of porphyrins with extended conjugation by meso,β-fusion with polycyclic aromatic hydrocarbons (PAHs) is reported. The meso-positions of 5,15-unsubstituted porphyrins were readily functionalized with PAHs. Ring fusion using standard Scholl reaction conditions (FeCl 3, dichloromethane) occurs for perylene-substituted porphyrins to give a porphyrin β,meso annulated with perylene rings (0.7:1 ratio of syn and anti isomers). The naphthalene, pyrene, and coronene derivatives do not react under Scholl conditions but are fused using thermal cyclodehydrogenation at high temperatures, giving mixtures of syn and anti isomers of the meso,β-fused porphyrins. For pyrenyl-substituted porphyrins, a thermal method gives synthetically acceptable yields (>30%). Absorption spectra of the fused porphyrins undergo a progressive bathochromic shift in a series of naphthyl (λ max = 730 nm), coronenyl (λ max = 780 nm), pyrenyl (λ max = 815 nm), and perylenyl (λ max = 900 nm) annulated porphyrins. Despite being conjugated with unsubstituted fused PAHs, the β,meso-fused porphyrins are more soluble and processable than the parent nonfused precursors. Pyrenyl-fused porphyrins exhibit strong fluorescence in the near-infrared (NIR) spectral region, with a progressive improvement in luminescent efficiency (up to 13% with λ max = 829 nm) with increasing degree of fusion. Fused pyrenyl-porphyrins have been used as broadband absorption donor materials in photovoltaic cells, leading to devices that show comparatively high photovoltaic efficiencies. © 2011 American Chemical Society.

  4. Synthesis and characterization of organosoluble aromatic copolyimids

    Institute of Scientific and Technical Information of China (English)

    YANG Jintian; HUANG Wei; ZHOU Yongfeng; YAN Deyue


    A series of aromatic copolyimides was success fully synthesized from the commercial pyromellitic dianhy dride (PMDA) with a commercial diamine p-phenyldiamine (PDA) and a diamine 4,4'-methylenebis-(2-tert-butylaniline)(MBTBA) specially designed by the authors.The copoly imides were characterized by Infra-red (IR),Nuclear Magnetic Resonance (NMR),Gel Permeation Chromato graphy (GPC),Ultraviolet Visual (UV-Vis),Thermogra vimetic Analysis (TGA) and Dynamic Mechanical Analysis (DMA).The copolyimide was precipitated in m-cresol in the polymerization process when the molar ratio of MBTBA and PDA was lower than 6/4.The number-average molecular weight of the soluble copolyimides measured by GPC was larger than 4.0 x 104,and the polydispersity index was higher than 1.5.Only one glass transition temperature of these copolyimdies was detected around 360℃ by DMA.The copolyimides did not show appreciable decomposition up to 500℃ under N2,and the thermal stability of the copolyimide increased a little with the introduction of PDA into the polyimide main chain.

  5. Highly Energetic, Low Sensitivity Aromatic Peroxy Acids. (United States)

    Gamage, Nipuni-Dhanesha H; Stiasny, Benedikt; Stierstorfer, Jörg; Martin, Philip D; Klapötke, Thomas M; Winter, Charles H


    The synthesis, structure, and energetic materials properties of a series of aromatic peroxy acid compounds are described. Benzene-1,3,5-tris(carboperoxoic) acid is a highly sensitive primary energetic material, with impact and friction sensitivities similar to those of triacetone triperoxide. By contrast, benzene-1,4-bis(carboperoxoic) acid, 4-nitrobenzoperoxoic acid, and 3,5-dinitrobenzoperoxoic acid are much less sensitive, with impact and friction sensitivities close to those of the secondary energetic material 2,4,6-trinitrotoluene. Additionally, the calculated detonation velocities of 3,5-dinitrobenzoperoxoic acid and 2,4,6-trinitrobenzoperoxoic acid exceed that of 2,4,6-trinitrotoluene. The solid-state structure of 3,5-dinitrobenzoperoxoic acid contains intermolecular O-H⋅⋅⋅O hydrogen bonds and numerous N⋅⋅⋅O, C⋅⋅⋅O, and O⋅⋅⋅O close contacts. These attractive lattice interactions may account for the less sensitive nature of 3,5-dinitrobenzoperoxoic acid.

  6. Atmospheric polycyclic aromatic hydrocarbons in Seoul, Korea (United States)

    Park, Seung S.; Kim, Young J.; Kang, Chang H.

    Daily particulate- and vapor-phase polycyclic aromatic hydrocarbons (PAH) samples were collected at an urban site in Seoul, Korea, during five intensive sampling campaigns between October 1998 and December 1999. PAH samples collected on quartz fiber filters and PUF plugs were first extracted using dichloromethane with ultrasonication and supercritical fluid extraction methods, respectively, and then analyzed by GC/MSD/SIM. Seasonal trends in atmospheric PAH concentrations in the study area were highly influenced by fossil fuel usage for domestic heating, boundary layer height, and air temperature. The relative benzo[a]pyrene amount and particulate organic to elemental carbon ratio calculated from the measurement results suggested that photo-oxidation is not an important factor in the variation of PAH concentrations during the summer sampling periods. Correlation studies between specific PAH of the individual factors identified by principal component factor analysis and meteorological parameters revealed that both temperature and relative humidity gave greater effects on the semi-volatile PAH, PHEN and FLT, rather than on the heavier PAH, B(b+k)F and BghiP.

  7. Structure and Aromaticity of AlCO-substituted Semibullvalene

    Institute of Scientific and Technical Information of China (English)

    YAO Wen-Zhi; WU Hai-Shun


    The structures, energies and aromaticity (the nuclear-independent chemical shifts,NICS) of AlCO-substituted semibullvalenes were investigated at the B3LYP/6-311+G** level.Similar to BCO-substituted analogues, [2,6]-AlCO-semibullvalene is neutral bishomoaromatic.The NICS values reveal that the aromaticity of AlCO-substituted structures is smaller than that of BCO analogues.

  8. Engineered biosynthesis of bacterial aromatic polyketides in Escherichia coli


    Zhang, Wenjun; Li, Yanran; Tang, Yi


    Bacterial aromatic polyketides are important therapeutic compounds including front line antibiotics and anticancer drugs. It is one of the last remaining major classes of natural products of which the biosynthesis has not been reconstituted in the genetically superior host Escherichia coli. Here, we demonstrate the engineered biosynthesis of bacterial aromatic polyketides in E. coli by using a dissected and reassembled fungal polyketide synthase (PKS). The minimal PKS of the megasynthase PKS4...

  9. Environmental Remediation: Removal of polycyclic aromatic hydrocarbons Dissertation


    Nkansah, Marian Asantewah


    Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous persistent semi-volatile organic compounds. They are contaminants that are resistant to degradation and can remain in the environment for long periods due to their high degree of conjugation, and aromaticity. PAHs are present in industrial effluents as products of incomplete combustion processes of organic compounds. Petroleum, coal and shale oil contain extremely complex mixtures of these PAHs, and their transport and refi...

  10. Transient Crystallization of an Aromatic Polyetherimide: Effect of Annealing (United States)


    on the annealing behavior of an aromatic polyetherimide ( Ultem 5001). Although crystallization from the melt did not occur, crystallinity was LARC-TPI. 10-’ 3 Ultem aromatic polyetherimide, first reported by Serfaty, 15 is an amorphous thermoplastic with the following structure for a...commercially available Ultem 1000. 0 0 0n Our studies have been carried out on Ultem 5001-based materials which is a new aro- matic polyetherimide with


    Institute of Scientific and Technical Information of China (English)

    CHEN Shouxi


    The kinetics of mesophase formation of a lyotropic aromatic polyamide from isotropic state has been studied by means of depolarized light intensity. Avrami type analysis of the data gives an exponent close to 1, which suggests the nucleation followed by one-dimensional growth. No influence of blending flexible chain from nylon 6 to the aromatic polyamide on the kinetics of mesophase formation was observed.


    Institute of Scientific and Technical Information of China (English)

    ZHANG Jian; SUN Qiushi; HOU Xiaohuai


    Six aromatic polyesters were prepared for gas separation membranes, and their permeation properties for hydrogen, oxygen, nitrogen, carbon dioxide, and methane were measured at 30℃ and 1 atmosphere by low pressure manometric method. The correlation between the gas transport behavior and molecular structure of aromatic polyester membrane is discussed. These data are interpreted qualitatively in terms of the calculated packing density, gas-polymer interaction, concentration of aryl bromine on backbone, and effect of silane group on main chain of polymer.

  13. Terahertz Spectroscopy of Biochars and Related Aromatic Compounds (United States)

    Lepodise, L. M.; Horvat, J.; Lewis, R. A.


    A recent application of terahertz spectroscopy is to biochar, the agricultural charcoal produced by pyrolysis of various organic materials. Biochars simultaneously improve soil fertility and assist in carbon sequestration. Terahertz spectroscopy allows different biochars to be distinguished. However, the origin of the absorption features observed has not been clear. Given that biochar-based fertilizers are rich in aromatic compounds, we have investigated simple aromatic compounds as an approach to unravelling the complex biochar spectrum.

  14. Catalytic co-aromatization of ethanol and methane

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Aiguo; He, Peng; Yung, Matthew; Zeng, Hongbo; Qian, Hui; Song, Hua


    This study demonstrates the technical feasibility of simultaneously converting ethanol and methane into liquid hydrocarbons at mild reaction conditions (400 degrees C and 1 atm) over silver and/or zinc modified zeolite catalysts. After GC-MS analysis, it is worth noting that aromatics are the major compounds contained in the liquid product collected from the run when 1%Ag/ZSM-5, particularly after H2 pretreatment, is charged. Compared to the performance exhibited from the run with pure HZSM-5 support engaged, Ag addition into the HZSM-5 framework favors aromatics formation, which might be closely associated with better Ag dispersion and more abundance of strong surface acidic sites where aromatization might take place while Zn loading exerts a detrimental effect on the production of aromatics but promotes the ether generation possibly through dehydration reaction. Referred to that from its N2 counterpart, the increased aromatics formation of the collected liquid product when methane is present indicates that methane existence might facilitate ethanol aromatization. Moreover, combined with the increased carbon number in the formed aromatics from CH4 run when H2 run is referred and zero liquid formation from CH4-alone test as well as more prominent endothermic feature of methane run and more importantly the notably increased 13C signals in 13C NMR spectra of the liquid product collected during ethanol conversion under 13CH4 environment, all the observations suggest that methane might be activated nonoxidatively and converted into higher hydrocarbons, preferentially into aromatics if suitable catalyst is charged under the assistance of co-existing oxygenated hydrocarbon. The reported synergetic effect could potentially lead to the more economic utilization of abundant natural gas and cellulosic ethanol.

  15. Aromatic VOCs global influence in the ozone production (United States)

    Cabrera-Perez, David; Pozzer, Andrea


    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.

  16. Terahertz Spectroscopy of Biochars and Related Aromatic Compounds (United States)

    Lepodise, L. M.; Horvat, J.; Lewis, R. A.


    A recent application of terahertz spectroscopy is to biochar, the agricultural charcoal produced by pyrolysis of various organic materials. Biochars simultaneously improve soil fertility and assist in carbon sequestration. Terahertz spectroscopy allows different biochars to be distinguished. However, the origin of the absorption features observed has not been clear. Given that biochar-based fertilizers are rich in aromatic compounds, we have investigated simple aromatic compounds as an approach to unravelling the complex biochar spectrum.

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


    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.

  18. Spectral induced polarization signature of contaminated soil (United States)

    Schwartz, N.; Huisman, J. A.; Shefer, I.; Furman, A.


    Spectral induced polarization (SIP) signatures of porous media contaminated with non aqueous phase liquids (NAPL) were measured using an accurate impedance meter. The samples were prepared by mixing air-dried sand with 15% by weight of bentonite clay, tap water and either diesel fuel or motor oil. Next, the soil was packed in a column and left for 24 hr before electrical measurements were performed. For all the samples, water saturation was constant (Sw = 0.47) and the NAPL saturation was 0 (control), 5, or 15 percent. Counter-intuitively, the results show that addition of NAPL to the porous media resulted in an increase of the real part of the complex conductivity. Evidently, for each type of contaminant, an increase in the contaminant saturation resulted in an increase in the real part of the conductivity. The imaginary part of the complex conductivity showed a reversed behavior: higher NAPL saturation resulted in a reduction of the imaginary part of the complex conductivity. For both the real and the imaginary part of the complex conductivity, the effect of NAPL on the complex electrical conductivity was more significant for motor oil than for diesel fuel. In addition to the electrical measurements, we also performed an extraction experiment to examine the effect of the presence of NAPL on the electrical conductivity (EC) of the pore water. The results from the extraction experiment showed that addition of NAPL to the porous media resulted in an increase of the pore water EC. We argue that this increase in the real part of the complex conductivity is related to adsorption of organic polar compounds from the NAPL onto the mineral surface and the associated release of inorganic ions from the mineral surface to the pore water. These exchange processes affect both the surface and the pore water conductivity. In addition, we suggest that the decrease in polarization (associated with the imaginary part of the complex conductivity) of the NAPL contaminated porous media

  19. Photochemical Studies on Aqueous Carboplatin

    Institute of Scientific and Technical Information of China (English)

    刘伟平; 杨懿昆; 阙振寰; 熊惠周


    The photochemical products,quantum yields and mechanisms of aqueous Carboplatin havebeen studied at 313 and 254 nm irradiation.Excitation in the ligand field bands 1A1→1A2 and 1A1→1E leads tosubstitution reactions,giving diaquodiammineplatinum and tetraaquoplatinum.And then these complexesundergo thermally hydrolysis and polymerization producing polymeric hydroxo-bridged complexes.Oxygen isnot involved in the reactions.Excitation in the charge-transfer band 1A1→1A2u results in redox reaction.Metallic platinum and diaquodiammineplatinum are formed,respectively,in the absence and the presence ofoxygen.

  20. Polarized proton collider at RHIC (United States)

    Alekseev, I.; Allgower, C.; Bai, M.; Batygin, Y.; Bozano, L.; Brown, K.; Bunce, G.; Cameron, P.; Courant, E.; Erin, S.; Escallier, J.; Fischer, W.; Gupta, R.; Hatanaka, K.; Huang, H.; Imai, K.; Ishihara, M.; Jain, A.; Lehrach, A.; Kanavets, V.; Katayama, T.; Kawaguchi, T.; Kelly, E.; Kurita, K.; Lee, S. Y.; Luccio, A.; MacKay, W. W.; Mahler, G.; Makdisi, Y.; Mariam, F.; McGahern, W.; Morgan, G.; Muratore, J.; Okamura, M.; Peggs, S.; Pilat, F.; Ptitsin, V.; Ratner, L.; Roser, T.; Saito, N.; Satoh, H.; Shatunov, Y.; Spinka, H.; Syphers, M.; Tepikian, S.; Tominaka, T.; Tsoupas, N.; Underwood, D.; Vasiliev, A.; Wanderer, P.; Willen, E.; Wu, H.; Yokosawa, A.; Zelenski, A. N.


    In addition to heavy ion collisions (RHIC Design Manual, Brookhaven National Laboratory), RHIC will also collide intense beams of polarized protons (I. Alekseev, et al., Design Manual Polarized Proton Collider at RHIC, Brookhaven National Laboratory, 1998 [2]), reaching transverse energies where the protons scatter as beams of polarized quarks and gluons. The study of high energy polarized protons beams has been a long term part of the program at BNL with the development of polarized beams in the Booster and AGS rings for fixed target experiments. We have extended this capability to the RHIC machine. In this paper we describe the design and methods for achieving collisions of both longitudinal and transverse polarized protons in RHIC at energies up to s=500 GeV.

  1. Polarization and Polarimetry: A Review

    CERN Document Server

    Trippe, S


    Polarization is a basic property of light and is fundamentally linked to the internal geometry of a source of radiation. Polarimetry complements photometric, spectroscopic, and imaging analyses of sources of radiation and has made possible multiple astrophysical discoveries. In this article I review (i) the physical basics of polarization: electromagnetic waves, photons, and parameterizations; (ii) astrophysical sources of polarization: scattering, synchrotron radiation, active media, and the Zeeman, Goldreich-Kylafis, and Hanle effects, as well as interactions between polarization and matter (like birefringence, Faraday rotation, or the Chandrasekhar-Fermi effect); (iii) observational methodology: on-sky geometry, influence of atmosphere and instrumental polarization, polarization statistics, and observational techniques for radio, optical, and X/gamma wavelengths; and (iv) science cases for astronomical polarimetry: solar and stellar physics, planetary system bodies, interstellar matter, astrobiology, astro...

  2. Formation of polar ring galaxies

    CERN Document Server

    Bournaud, F


    Polar ring galaxies are peculiar systems in which a gas rich, nearly polar ring surrounds an early-type or elliptical host galaxy. Two formation scenarios for these objects have been proposed: they are thought to form either in major galaxy mergers or by tidal accretion of the polar material from a gas rich donor galaxy. Both scenarios are studied through N-body simulations including gas dynamics and star formation. Constraints on physical parameters are drawn out, in order to determine which scenario is the most likely to occur. Polar ring galaxies from each scenario are compared with observations and we discuss whether the accretion scenario and the merging scenario account for observational properties of polar ring galaxies. The conclusion of this study is that the accretion scenario is both the most likely and the most supported by observations. Even if the merging scenario is rather robust, most polar ring galaxies are shown to be the result of tidal gas accretion events.

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

    KAUST Repository

    Yin, Mengchen


    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.

  4. Bond length alternation and aromaticity in large annulenes (United States)

    Choi, Cheol Ho; Kertesz, Miklos


    Properties of [4n] and [4n+2]annulenes were studied as a function of n for up to [66]annulene using Hartree-Fock and density functional theory in the generalized gradient approximation (DFT-GGA). In the 4n+2 series a "transition" from delocalized to localized structures occurs at 4n+2=30. Various indices of aromaticity, including NMR chemical shifts, bond localization, and aromatic stabilization energy (ASE) were monitored. π-bond localization occurs not due to a dramatic decrease of ASE as n increases, but rather as a result of a pseudo-Jahn-Teller (PJT) effect that sets in as the HOMO-LUMO gap decreases with increasing size. The NMR measures of aromaticity (difference between inner and outer 1H chemical shielding constants and the nucleus-independent chemical shifts, NICS) are reduced in the localized structures in comparison to the delocalized ones. The gradual nature of this "transition" is also implied by the relatively large values of the NMR measures of aromaticity that approach zero only gradually for larger size annulenes. Therefore intermediate size annulenes, such as [30]annulene are predicted to have a localized structure and aromatic properties at the same time showing the delocalized structure is not a necessary condition to be aromatic.

  5. Bio-Based Aromatic Epoxy Monomers for Thermoset Materials. (United States)

    Ng, Feifei; Couture, Guillaume; Philippe, Coralie; Boutevin, Bernard; Caillol, Sylvain


    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.

  6. Bio-Based Aromatic Epoxy Monomers for Thermoset Materials

    Directory of Open Access Journals (Sweden)

    Feifei Ng


    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.

  7. Polarized Electrons for Linear Colliders

    CERN Document Server

    Clendenin, J E; Garwin, E L; Kirby, R E; Luh, D A; Maruyama, T; Prescott, C Y; Sheppard, J C; Turner, J; Prepost, R


    Future electron-positron linear colliders require a highly polarized electron beam with a pulse structure that depends primarily on whether the acceleration utilizes warm or superconducting rf structures. The International Linear Collider (ILC) will use cold structures for the main linac. It is shown that a dc-biased polarized photoelectron source such as successfully used for the SLC can meet the charge requirements for the ILC micropulse with a polarization approaching 90%.

  8. Cell Polarity Signaling in Arabidopsis


    Yang, Zhenbiao


    Cell polarization is intimately linked to plant development, growth, and responses to the environment. Major advances have been made in our understanding of the signaling pathways and networks that regulate cell polarity in plants owing to recent studies on several model systems, e.g., tip growth in pollen tubes, cell morphogenesis in the leaf epidermis, and polar localization of PINs. From these studies we have learned that plant cells use conserved mechanisms such as Rho family GTPases to i...

  9. An innovative approach to molecularly imprinted capillaries for polar templates by grafting polymerization. (United States)

    Giovannoli, Cristina; Passini, Cinzia; Baravalle, Patrizia; Anfossi, Laura; Giraudi, Gianfranco; Baggiani, Claudio


    Molecularly imprinted polymers have been successfully used as selective stationary phases in capillary electrophoresis. Notwithstanding, this technique suffers from several drawbacks as the loss of molecular recognition properties in aqueous media and the lack of feasibility for imprinted systems directed towards highly polar templates soluble in aqueous environments only. Thus, the preparation of imprinted polymers for highly polar, water-soluble analytes, represents a challenge. In this work, we present an innovative approach to overcome these drawbacks. It is based on a surface molecular imprinting technique that uses preformed macromonomers as both functional recognition elements and cross-linking agents. A poly-2-hydroxyethyl-co-methacrylic acid linear polymer was grafted from the surface of silica capillaries. The grafted polymer was exhaustively esterified with methacrylic anhydride to obtain polyethylendimethacrylate-co-methacrylic acid linear chains. Then, as a proof of concept, an adequate amount of a very polar template like penicillin V was added in a hydro-organic mixture, and a thin layer of imprinted polymer was obtained by cross-linking the polymer linear chains. The binding behaviour of the imprinted and non-imprinted capillaries was evaluated in different separation conditions in order to assess the presence of template selectivity and molecular recognition effects. The experimental results clearly show that this innovative kind of imprinted material can be easily obtained in very polar polymerization environments and that it is characterized by enhanced molecular recognition properties in aqueous buffers and good selectivity towards the template and strictly related molecules.

  10. Improved AIOMFAC model parameterisation of the temperature dependence of activity coefficients for aqueous organic mixtures

    Directory of Open Access Journals (Sweden)

    G. Ganbavale


    Full Text Available This study presents a new, improved parameterisation of the temperature dependence of activity coefficients in the AIOMFAC (Aerosol Inorganic–Organic Mixtures Functional groups Activity Coefficients model applicable for aqueous as well as water-free organic solutions. For electrolyte-free organic and organic–water mixtures the AIOMFAC model uses a group-contribution approach based on UNIFAC (UNIversal quasi-chemical Functional-group Activity Coefficients. This group-contribution approach explicitly accounts for interactions among organic functional groups and between organic functional groups and water. The previous AIOMFAC version uses a simple parameterisation of the temperature dependence of activity coefficients, aimed to be applicable in the temperature range from ~275 to ~400 K. With the goal to improve the description of a wide variety of organic compounds found in atmospheric aerosols, we extend the AIOMFAC parameterisation for the functional groups carboxyl, hydroxyl, ketone, aldehyde, ether, ester, alkyl, aromatic carbon-alcohol, and aromatic hydrocarbon to atmospherically relevant low temperatures with the introduction of a new temperature dependence parameterisation. The improved temperature dependence parameterisation is derived from classical thermodynamic theory by describing effects from changes in molar enthalpy and heat capacity of a multicomponent system. Thermodynamic equilibrium data of aqueous organic and water-free organic mixtures from the literature are carefully assessed and complemented with new measurements to establish a comprehensive database, covering a wide temperature range (~190 to ~440 K for many of the functional group combinations considered. Different experimental data types and their processing for the estimation of AIOMFAC model parameters are discussed. The new AIOMFAC parameterisation for the temperature dependence of activity coefficients from low to high temperatures shows an overall improvement of

  11. Reduction of Aromatic α-Keto Esters by Commercially Available Zinc Dust and Ammonium Formate:Formation of Aromatic a-Hydroxy Esters

    Institute of Scientific and Technical Information of China (English)

    CHEN Gang; YAO Guo-xin; SONG Guang-wei; ZHU Jin-tao


    Various aromatic α-keto esters were rapidly and selectively reduced to aromatic α-hydroxy esters by commercially available zinc dust and ammonium formate in the presence of other functional groups such as halogens,methoxy and esters.

  12. Corrosion behavior of bulk metallic glasses in different aqueous solutions

    Institute of Scientific and Technical Information of China (English)


    The corrosion behavior of as-cast fully amorphous, structural relaxed amorphous and crystallized Fe65.5Cr4Mo4Ga4P12C5B5.5 bulk metallic glasses (BMGs) in NaCl, HCl and NaOH solutions was investigated by electrochemical polarization and immersion methods. X-ray photoelectron spectroscopy measurements was used to analyze the changes of the elements on the alloy surface before and after immersion in various solutions. The corrosion resistance of the Fe65.5Cr4Mo4Ga4P12C5B5.5 BMG was better than its structural relaxation/crystallization counterparts and common alloys (such as stainless steel, carbonized steel, and steel) in the selected aqueous solutions. The high corrosion resistance of this alloy in corrosive solutions leads to the formation of Fe-, Cr- and Mo-enriched protective thin surface films.

  13. Experimental study on thermophoresis of colloids in aqueous surfactant solutions (United States)

    Dong, Ruo-Yu; Zhou, Yi; Yang, Chun; Cao, Bing-Yang


    Thermophoresis refers to the motion of particles under a temperature gradient and it is one of the particle manipulation techniques. Regarding the thermophoresis of particles in liquid media, however, many open questions still remain, especially the role of the interfacial effect. This work reports on a systematic experimental investigation of surfactant effects, especially the induced interfacial effect, on the thermophoresis of colloids in aqueous solutions via a microfluidic approach. Two kinds of commonly used surfactants, sodium dodecyl sulfate (SDS) and cetyltrimethylammonium bromide (CTAB), are selected and the results show that from relatively large concentrations, the two surfactants can greatly enhance the thermophilic mobilities. Specifically, it is found that the colloid-water interfaces modified with more polar end groups can potentially lead to a stronger thermophilic tendency. Due to the complex effects of surfactants, further theoretical model development is needed to quantitatively describe the dependence of thermophoresis on the interface characteristics.

  14. The RHIC polarized source upgrade

    Energy Technology Data Exchange (ETDEWEB)

    Zelenski, A.; Atoian, G.; Davydenko, V.; Ivanov, A.; Kolmogorov, A.; Ritter, J.; Steski, D.; Zubets, V.


    The RHIC polarized H{sup -} ion source is being upgraded to higher intensity (5-10 mA) and polarization for use in the RHIC polarization physics program at enhanced luminosity RHIC operation. The higher beam peak intensity will allow reduction of the transverse beam emittance at injection to AGS to reduce polarization losses in AGS. There is also a planned RHIC luminosity upgrade by using the electron beam lens to compensate the beam-beam interaction at collision points. This upgrade is also essential for future BNL plans for a high-luminosity electron - proton (ion) Collider eRHIC.

  15. Magnet polarities in the LHC

    CERN Document Server

    McAteer, M; Maclean, E; Persson, T; Steinhagen, R; Tomas, R


    We report the results of extensive tests to verify the polarities of Landau damping octupoles (MOF, MOD) and octupole spool correctors (MCO), arc trim skew sextupoles (MSS), and triplet sextupole correctors (MCSX and MCSSX). All octupole circuits that were measured were found to have the expected polarity. All arc skew sextupoles MSS and triplet sextupole correctors MCSX and MCSSX that were measured were found to have reversed polarity with respect to MADX. It is also noted that the triplet quadrupole trims ktqx2, as well as MQS and MQSX, have reversed polarity with respect to MADX.

  16. Majorization of quantum polarization distributions

    CERN Document Server

    Luis, Alfredo


    Majorization provides a rather powerful partial-order classification of probability distributions depending only on the spread of the statistics, and not on the actual numerical values of the variable being described. We propose to apply majorization as a meta-measure of quantum polarization fluctuations, this is to say of the degree of polarization. We compare the polarization fluctuations of the most relevant classes of quantum and classical-like states. In particular we test the Lieb's conjecture regarding classical-like states as the most polarized and a complementary conjecture that the most unpolarized pure states are the most nonclassical.

  17. Polarization-preserving holey fibers

    DEFF Research Database (Denmark)

    Broeng, Jes; Mogilevtsev, Dmitri; Libori, Stig E. Barkou


    In this work we suggest and discuss a microstructure of air capillaries with elliptical cross-section in a tread of glass that gives opportunity for Creation of polarization-preserving fiber with very small beat length between the fundamental modes of different polarization......In this work we suggest and discuss a microstructure of air capillaries with elliptical cross-section in a tread of glass that gives opportunity for Creation of polarization-preserving fiber with very small beat length between the fundamental modes of different polarization...

  18. Urban Air Pollution from Ethanol (E85) in the Presence of Aqueous Aerosols and Fog (United States)

    Ginnebaugh, D. L.; Jacobson, M. Z.


    This is a study to examine the effect of ethanol (E85) versus gasoline on urban air pollution in the presence of aqueous aerosols and fog. In previous work, we analyzed the temperature-dependence of ethanol and gasoline exhaust chemistry and its impact on urban air pollution considering only gas-phase chemistry. We used the near-explicit Master Chemical Mechanism (MCM, version 3.1, LEEDS University) with the SMVGEAR II chemical ordinary differential solver to provide the speed necessary to simulate explicit chemistry. The MCM has over 13,500 organic reactions and 4,600 species. SMVGEAR II is a sparse-matrix Gear solver that reduces the computation time significantly while maintaining any specified accuracy. We found that the average ozone concentrations through the range of temperatures tested could be higher with E85 than with gasoline by up to 8 parts per billion volume (ppbv) at room temperature but much higher at cold temperatures and low sunlight (winter conditions) for a region with a high nitrogen oxide (NOx) to non-methane organic gases (NMOG) ratio. We also found that the solution to chemistry in a 3-D urban airshed model was practical. We now extend our study to include aqueous chemistry in the presence of aerosols and fog. We combine the Chemical Aqueous Phase Radical Mechanism, CAPRAM 3.0 with the MCM 3.1 and gas-particle transfer in box model calculations. CAPRAM treats aqueous phase chemistry among 390 species and 829 reactions (including 51 gas-to-aqueous phase reactions). We investigate the impact aqueous reactions have on unburned ethanol and acetaldehyde mixing ratios in the atmosphere in particular because acetaldehyde is an ozone precursor and carcinogen, and aqueous oxidation has potential to speed the conversion of unburned ethanol to acetaldehyde. Acetaldehyde also forms acetic acid in aqueous solution. Acetic acid vapor is an eye, nose, and lung irritant, so both species contribute negatively to human health. We look at the impact of aerosol

  19. Influence of propylene glycol on aqueous silica dispersions and particle-stabilized emulsions. (United States)

    Binks, Bernard P; Fletcher, Paul D I; Thompson, Michael A; Elliott, Russell P


    We have studied the influence of adding propylene glycol to both aqueous dispersions of fumed silica nanoparticles and emulsions of paraffin liquid and water stabilized by the same particles. In the absence of oil, aerating mixtures of aqueous propylene glycol and particles yields either stable dispersions, aqueous foams, climbing particle films, or liquid marbles depending on the glycol content and particle hydrophobicity. The presence of glycol in water promotes particles to behave as if they are more hydrophilic. Calculations of their contact angle at the air-aqueous propylene glycol surface are in agreement with these findings. In the presence of oil, particle-stabilized emulsions invert from water-in-oil to oil-in-water upon increasing either the inherent hydrophilicity of the particles or the glycol content in the aqueous phase. Stable multiple emulsions occur around phase inversion in systems of low glycol content, and completely stable, waterless oil-in-propylene glycol emulsions can also be prepared. Accounting for the surface energies at the respective interfaces allows estimation of the contact angle at the oil-polar phase interface; reasonable agreement between measured and calculated phase inversion conditions is found assuming no glycol adsorption on particle surfaces.

  20. Mechanism of formation of oil by the hot aqueous alkaline digestion of cellulose

    Energy Technology Data Exchange (ETDEWEB)

    Molten, P.M.; Miller, R.K.; Donovan, J.M.; Demmitt, T.F.


    The overall mechanism of cellulose converson in hot aqueous alkali appears to be one of degradation through glucose to low molecular weight saccharinic acids, dihydroxybutyric acid, glycolic acid, and carbonyl products such as acetone, acetaldehyde, formaldehyde, and similar compounds. Although the products identified in the present report were fairly complex furans, carbocyclic ketones, unsaturated hydrocarbons, and aromatic compounds, nevertheless, in most cases, they could have been formed from simple carbonyl compounds through a series of condensations involving carbanion intermediates. It is conceivable that residual alkali in the oil during acetone extraction could have given rise to diacetone alcohol as an artifact. This is refuted by examination of an aqueous residue which was extracted with diethyl ether and which was never exposed to any acetone: Compounds derived from diacetone alcohol (such as mesityl oxide or 4-methyl-3-penten-2-one) were also identified in the diethyl ether extract of the aqueous phase. Other compounds were identified in the oil acetone extract which could not have been derived from acetone or diacetone alcohol, but which could have been formed from other carbonyl compounds by the same mechanism. Hence, diacetone alcohol is a genuine product of cellulose conversion although apparently not an intermediate in further synthesis of other products. The further reaction of the postulated cyclic intermediates, and the route to formation of unsaturated hydrocarbons of high molecular weight is intended to be the next subject of investigation in the current work. The fundamental difference in the mechanism of cellulose conversion to oil by pyrolysis and by aqueous alkaline digestion predicted by theory is therefore confirmed. Pyrolysis products may be explained generally by carbonium ion and free radical reactions (in fact, cellulose decomposition is acid-catalyzed), while in aqueous alkali, nucleophilic carbanion reactions are favored.